US20150101755A1 - Substrate processing apparatus - Google Patents
Substrate processing apparatus Download PDFInfo
- Publication number
- US20150101755A1 US20150101755A1 US14/573,654 US201414573654A US2015101755A1 US 20150101755 A1 US20150101755 A1 US 20150101755A1 US 201414573654 A US201414573654 A US 201414573654A US 2015101755 A1 US2015101755 A1 US 2015101755A1
- Authority
- US
- United States
- Prior art keywords
- containing gas
- gas supply
- supply system
- gas
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000001301 oxygen Substances 0.000 claims abstract description 83
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 69
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
- H01L21/0228—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67017—Apparatus for fluid treatment
- H01L21/67063—Apparatus for fluid treatment for etching
- H01L21/67069—Apparatus for fluid treatment for etching for drying etching
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- C—CHEMISTRY; METALLURGY
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C16/45531—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations specially adapted for making ternary or higher compositions
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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- C23C16/45544—Atomic layer deposition [ALD] characterized by the apparatus
- C23C16/45546—Atomic layer deposition [ALD] characterized by the apparatus specially adapted for a substrate stack in the ALD reactor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
- H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
- H01L21/02178—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing aluminium, e.g. Al2O3
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
- H01L21/02181—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing hafnium, e.g. HfO2
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
- H01L21/02186—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing titanium, e.g. TiO2
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
- H01L21/02189—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing zirconium, e.g. ZrO2
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/02227—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process
- H01L21/0223—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/02227—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process
- H01L21/02247—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by nitridation, e.g. nitridation of the substrate
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67017—Apparatus for fluid treatment
Definitions
- the present invention relates to a method of manufacturing a semiconductor device including a process of forming a thin film on a substrate, a method of processing a substrate, and a substrate processing apparatus.
- Processes of manufacturing a semiconductor device includes a process of forming an insulating film such as a silicon oxide (SiO 2 ) film or a silicon nitride (Si 3 N 4 ) film on a wafer such as a silicon wafer.
- the SiO 2 film is widely used as an insulating film or an interlayer film due to its excellent insulating property and low dielectric property.
- the Si 3 N 4 film is widely used as an insulating film, a mask film, a charge accumulating film, or a stress control film due to its excellent insulating property, corrosion-resistant property, dielectric property, and film stress controlling property, etc.
- Technology of adding carbon (C) to these insulating films is also well known in the art (for example, see Patent Document 1).
- the etching-resistant property of the insulating films may be enhanced by such technology.
- a substrate processing apparatus comprising: a process vessel configured to accommodate a substrate; an element-containing gas supply system configured to supply a gas containing an element into the process vessel; a carbon-containing gas supply system configured to supply a carbon-containing gas into the process vessel; a nitrogen-containing gas supply system configured to supply a nitrogen-containing gas into the process vessel; an oxygen-containing gas supply system configured to supply an oxygen-containing gas into the process vessel; a heater configured to heat the substrate in the process vessel; and a control unit configured to control the element-containing gas supply system, the carbon-containing gas supply system, the nitrogen-containing gas supply system, the oxygen-containing gas supply system and the heater to form an oxycarbonitride film on the substrate by performing a cycle a predetermined number of times, the cycle including: (a) performing a set a predetermined number of times, the set including: (a-1) supplying the gas containing the element to the substrate; (a-2) supplying the carbon-containing gas to the substrate; and (a
- a substrate processing apparatus comprising: a process vessel configured to accommodate a substrate; an element-containing gas supply system configured to supply a gas containing an element into the process vessel; a carbon-containing gas supply system configured to supply a carbon-containing gas into the process vessel; a nitrogen-containing gas supply system configured to supply a nitrogen-containing gas into the process vessel; an oxygen-containing gas supply system configured to supply an oxygen-containing gas into the process vessel; a heater configured to heat the substrate in the process vessel; and a control unit configured to control the element-containing gas supply system, the carbon-containing gas supply system, the nitrogen-containing gas supply system, the oxygen-containing gas supply system and the heater to form an oxycarbonitride film on the substrate by performing a cycle a predetermined number of times, the cycle including: (a) performing a set a predetermined number of times, the set including: (a-1) supplying the gas containing the element to the substrate; (a-2) supplying the carbon-containing gas to the substrate; (a-
- FIG. 1 is a configuration diagram schematically illustrating a vertical process furnace of a substrate processing apparatus preferably used in an exemplary embodiment of the present invention, illustrating a longitudinal cross section of the process furnace;
- FIG. 2 is a configuration diagram schematically illustrating the vertical process furnace of the substrate processing apparatus preferably used in the exemplary embodiment of the present invention, illustrating a cross section of the process furnace taken along line A-A of FIG. 1 ;
- FIG. 3 is a diagram illustrating gas supply timings in a first sequence according to an embodiment of the present invention
- FIG. 4 is a diagram illustrating gas supply timings in a modified example of the first sequence according to the embodiment of the present invention.
- FIG. 5 is a diagram illustrating gas supply timings in a second sequence according to the embodiment of the present invention.
- FIG. 6 is a diagram illustrating gas supply timings in a modified example of the second sequence according to the embodiment of the present invention.
- FIG. 1 is a configuration diagram schematically illustrating a vertical process furnace of a substrate processing apparatus preferably used in an exemplary embodiment of the present invention, illustrating a longitudinal cross section of the process furnace 202 .
- FIG. 2 is a configuration diagram schematically illustrating the vertical process furnace of the substrate processing apparatus preferably used in the exemplary embodiment of the present invention, illustrating a cross section of the process furnace 202 taken along line A-A of FIG. 1 .
- the process furnace 202 includes a heater 207 serving as a heating means (a heating device).
- the heater 207 has a cylindrical shape and is supported by a heater base (not shown) serving as a holding plate to be installed vertically.
- the heater 207 also functions as an activation device configured to activate gas by heat.
- a reaction tube 203 having a shape concentric with the heater 207 and constituting a reaction vessel (a process vessel) is installed inside the heater 207 .
- the reaction tube 203 is, for example, made of a heat-resistant material such as quartz (SiO 2 ) or silicon carbide (SiC).
- the reaction tube 203 has a cylindrical shape with its upper end closed and lower end open.
- a process chamber 201 is formed in a hollow cylindrical portion of the reaction tube 203 .
- the process chamber 201 is configured to accommodate wafers 200 serving as substrates in a horizontal posture in a state where the wafers 200 are vertically arranged in multiple stages by a boat 217 to be described below.
- a first nozzle 249 a , a second nozzle 249 b , a third nozzle 249 c , and a fourth nozzle 249 d are installed inside the process chamber 201 so as to pass through a lower portion of the reaction tube 203 .
- a first gas supply pipe 232 a , a second gas supply pipe 232 b , a third gas supply pipe 232 c , and a fourth gas supply pipe 232 d are connected to the first nozzle 249 a , the second nozzle 249 b , the third nozzle 249 c , and the fourth nozzle 249 d , respectively.
- the four nozzles 249 a , 249 b , 249 c , and 249 d and the four gas supply pipes 232 a . 232 b , 232 c , and 232 d are installed in the reaction tube 203 so that many kinds of gases, for example, four kinds of gases here, may be supplied into the process chamber 201 .
- a mass flow controller (MFC) 241 a which is a flow rate controller (a flow rate control unit), and a valve 243 a , which is an opening/closing valve, are installed in the first gas supply pipe 232 a in order from an upstream side thereof.
- a first inert gas supply pipe 232 e is connected to a downstream side of the valve 243 a of the first gas supply pipe 232 a .
- An MFC 241 e which is a flow rate controller (a flow rate control unit), and a valve 243 e , which is an opening/closing valve, are installed in the first inert gas supply pipe 232 e in order from an upstream side thereof.
- the above-described first nozzle 249 a is connected to a tip end portion of the first gas supply pipe 232 a .
- the first nozzle 249 a is vertically installed in an arc-shaped space between an inner wall of the reaction tube 203 and the wafers 200 in a stacking direction of the wafers 200 along an upper portion from a lower portion of the inner wall of the reaction tube 203 .
- the first nozzle 249 a is formed as an L-shaped long nozzle.
- a gas supply hole 250 a configured to supply a gas is installed on a side surface of the first nozzle 249 a .
- the gas supply hole 250 a is opened toward the center of the reaction tube 203 .
- a plurality of gas supply holes 250 a are installed from a lower portion to an upper portion of the reaction tube 203 to have the same opening area and the same opening pitch.
- a first gas supply system mainly includes the first gas supply pipe 232 a , the MFC 241 a , the valve 243 a , and the first nozzle 249 a .
- a first inert gas supply system mainly includes the first inert gas supply pipe 232 e , the MFC 241 e , and the valve 243 e.
- An MFC 241 b which is a flow rate controller (a flow rate control unit), and a valve 243 b , which is an opening/closing valve, are installed in the second gas supply pipe 232 b in order from an upstream side thereof.
- a second inert gas supply pipe 232 f is connected to a downstream side of the valve 243 b of the second gas supply pipe 232 b .
- An MFC 241 f which is a flow rate controller (a flow rate control unit), and a valve 243 f , which is an opening/closing valve, are installed in the second inert gas supply pipe 232 f in order from an upstream side thereof.
- the above-described second nozzle 249 b is connected to a tip end portion of the second gas supply pipe 232 b .
- the second nozzle 249 b is vertically installed in an arc-shaped space between an inner wall of the reaction tube 203 and the wafers 200 in a stacking direction of the wafers 200 along an upper portion from a lower portion of the inner wall of the reaction tube 203 .
- the second nozzle 249 b is formed as an L-shaped long nozzle.
- a gas supply hole 250 b configured to supply a gas is installed on a side surface of the second nozzle 249 b .
- the gas supply hole 250 b is opened toward the center of the reaction tube 203 .
- a plurality of gas supply holes 250 b are installed from a lower portion to an upper portion of the reaction tube 203 to have the same opening area and the same opening pitch.
- a second gas supply system mainly includes the second gas supply pipe 232 b , the MFC 241 b , the valve 243 b , and the second nozzle 249 b .
- a second inert gas supply system mainly includes the second inert gas supply pipe 232 f , the MFC 241 f , and the valve 243 f.
- An MFC 241 c which is a flow rate controller (a flow rate control unit), and a valve 243 c , which is an opening/closing valve, are installed in the third gas supply pipe 232 c in order from an upstream side thereof.
- a third inert gas supply pipe 232 g is connected to a downstream side of the valve 243 c of the third gas supply pipe 232 c .
- An MFC 241 g which is a flow rate controller (a flow rate control unit), and a valve 243 g , which is an opening/closing valve, are installed in the third inert gas supply pipe 232 g in order from an upstream side thereof.
- the above-described third nozzle 249 c is connected to a tip end portion of the third gas supply pipe 232 c .
- the third nozzle 249 c is vertically installed in an arc-shaped space between an inner wall of the reaction tube 203 and the wafers 200 in a stacking direction of the wafers 200 along an upper portion from a lower portion of the inner wall of the reaction tube 203 .
- the third nozzle 249 c is formed as an L-shaped long nozzle.
- a gas supply hole 250 c configured to supply a gas is installed on a side surface of the third nozzle 249 c .
- the gas supply hole 250 c is opened toward the center of the reaction tube 203 .
- a plurality of gas supply holes 250 c are installed from a lower portion to an upper portion of the reaction tube 203 to have the same opening area and the same opening pitch.
- a third gas supply system mainly includes the third gas supply pipe 232 c , the MFC 241 c , the valve 243 c , and the third nozzle 249 c .
- a third inert gas supply system mainly includes the third inert gas supply pipe 232 g , the MFC 241 g , and the valve 243 g.
- An MFC 241 d which is a flow rate controller (a flow rate control unit), and a valve 243 d , which is an opening/closing valve, are installed in the fourth gas supply pipe 232 d in order from an upstream side thereof.
- a fourth inert gas supply pipe 232 h is connected to a downstream side of the valve 243 d of the fourth gas supply pipe 232 d .
- An MFC 241 h which is a flow rate controller (a flow rate control unit), and a valve 243 h , which is an opening/closing valve, are installed in the fourth inert gas supply pipe 232 h in order from an upstream side thereof.
- the above-described fourth nozzle 249 d is connected to a tip end portion of the fourth gas supply pipe 232 d .
- the fourth nozzle 249 d is installed inside a buffer chamber 237 , which is a gas dispersing space.
- the buffer chamber 237 is installed in an arc-shaped space between an inner wall of the reaction tube 203 and the wafers 200 in a stacking direction of the wafers 200 from a lower portion to an upper portion of the inner wall of the reaction tube 203 .
- a gas supply hole 250 e configured to supply a gas is installed on an end portion of a wall of the buffer chamber 237 , which is adjacent to the wafers 200 .
- the gas supply hole 250 e is opened toward the center of the reaction tube 203 .
- a plurality of gas supply holes 250 e are installed from a lower portion to an upper portion of the reaction tube 203 to have the same opening area and the same opening pitch.
- the fourth nozzle 249 d is vertically installed at an end portion opposite to another end portion of the buffer chamber 237 in which the gas supply holes 250 e are installed, in a stacking direction of the wafers 200 along an upper portion from a lower portion of the inner wall of the reaction tube 203 .
- the fourth nozzle 249 d is formed as an L-shaped long nozzle.
- a gas supply hole 250 d configured to supply a gas is installed on a side surface of the fourth nozzle 249 d .
- the gas supply hole 250 d is opened toward the center of the buffer chamber 237 .
- a plurality of gas supply holes 250 d are installed from a lower portion to an upper portion of the reaction tube 203 .
- the plurality of gas supply holes 250 d may have the same opening area and the same opening pitch from an upstream side (a lower portion) to a downstream side (an upper portion). However, when the difference in pressure is large, each opening area may become larger or each opening pitch may become smaller as the opening area or the opening pitch span from an upstream side toward a downstream side.
- gases are injected at different flow velocities but at substantially the same flow rate through the gas supply holes 250 d of the fourth nozzle 249 d by adjusting the opening areas or opening pitches of the gas supply holes 250 d from an upstream side to a downstream side of the fourth nozzle 249 d as described above. Then, the gas injected through each of the gas supply holes 250 d is first introduced into the buffer chamber 237 , and the difference in the flow velocities of the gas in the buffer chamber 237 is uniformly adjusted.
- the gas that has been injected into the buffer chamber 237 through each of the gas supply holes 250 d of the fourth nozzle 249 d has uniform flow rate and flow velocity when the gas is injected into the process chamber 201 through each of the gas supply holes 250 e of the buffer chamber 237 .
- a fourth gas supply system mainly includes the fourth gas supply pipe 232 d , the MFC 241 d , the valve 243 d , the fourth nozzle 249 d , and the buffer chamber 237 . Also, in the fourth gas supply system, the buffer chamber 237 functions as a nozzle configured to supply a gas toward the wafers 200 .
- a fourth inert gas supply system mainly includes the fourth inert gas supply pipe 232 h , the MFC 241 h , and the valve 243 h.
- a silicon (Si) source gas i.e., a gas containing silicon (a silicon-containing gas)
- a silicon-containing gas a gas containing silicon
- HCD Hexachlorodisilane
- a liquid material such as HCD, which is in a liquid state at a normal temperature and under a normal pressure
- the liquid material is vaporized by a vaporizing system such as a vaporizer or a bubbler to be supplied as a source gas.
- a gas containing carbon (C) (a carbon-containing gas) is supplied into the process chamber 201 through the second gas supply pipe 232 b via the MFC 241 b , the valve 243 b , and the second nozzle 249 b .
- Propylene (C 3 H 6 ) gas for example, may be used as the carbon-containing gas.
- a gas containing hydrogen (H) (a hydrogen-containing gas) may be supplied into the process chamber 201 through the second gas supply pipe 232 b via the MFC 241 b , the valve 243 b , and the second nozzle 249 b .
- Hydrogen (H 2 ) gas for example, may be used as the hydrogen-containing gas.
- a gas containing nitrogen (N) (a nitrogen-containing gas) is supplied into the process chamber 201 through the third gas supply pipe 232 c via the MFC 241 c , the valve 243 c , and the third nozzle 249 c .
- Ammonia (NH 3 ) gas may be used as the nitrogen-containing gas.
- a gas containing oxygen (O) (an oxygen-containing gas) is supplied into the process chamber 201 through the fourth gas supply pipe 232 d via the MFC 241 d , the valve 243 d , the fourth nozzle 249 d , and the buffer chamber 237 .
- Oxygen (O 2 ) gas for example, may be used as the oxygen-containing gas.
- N 2 gas is supplied into the process chamber 201 through the inert gas supply pipes 232 e , 232 f , 232 g , and 232 h via the MFCs 241 e , 241 f , 241 g , and 241 h , the valves 243 e , 243 f , 243 g , and 243 h , the gas supply pipes 232 a , 232 b , 232 c , and 232 d , the gas nozzles 249 a , 249 b , 249 c , and 249 d , and the buffer chamber 237 .
- the first gas supply system constitutes a source gas supply system, i.e., a silicon-containing gas supply system (a silane-based gas supply system).
- the second gas supply system constitutes a carbon-containing gas supply system or a hydrogen-containing gas supply system.
- the third gas supply system constitutes a nitrogen-containing gas supply system.
- the fourth gas supply system constitutes an oxygen-containing gas supply system.
- the source gas supply system is also simply referred to as a source supply system.
- reaction gases When the carbon-containing gas, the hydrogen-containing gas, the nitrogen-containing gas, and the oxygen-containing gas are generally called reaction gases, the carbon-containing gas supply system, the hydrogen-containing gas supply system, the nitrogen-containing gas supply system, and the oxygen-containing gas supply system constitute a reaction gas supply system.
- a first rod-shaped electrode 269 i.e., a first electrode
- a second rod-shaped electrode 270 i.e., a second electrode, each of which has a thin and long structure
- Each of the first rod-shaped electrode 269 and the second rod-shaped electrode 270 is installed in parallel to the fourth nozzle 249 d .
- Each of the first rod-shaped electrode 269 and the second rod-shaped electrode 270 is covered and protected by an electrode protecting tube 275 , which is a protection tube configured to protect the electrodes from upper portions to lower portions thereof.
- a plasma source serving as a plasma generator mainly includes the first rod-shaped electrode 269 , the second rod-shaped electrode 270 , the electrode protecting tubes 275 , the matching transformer 272 , and the high-frequency power source 273 .
- the plasma source also functions as an activation device configured to activate gas by plasma.
- the electrode protecting tube 275 is configured such that each of the first rod-shaped electrode 269 and the second rod-shaped electrode 270 can be inserted into the buffer chamber 237 in a state where first rod-shaped electrode 269 and the second rod-shaped electrode 270 are separated from an atmosphere of the buffer chamber 237 .
- an interior of the electrode protecting tube 275 has the same atmosphere as an exterior air (atmosphere)
- the first rod-shaped electrode 269 and the second rod-shaped electrode 270 inserted respectively into the electrode protecting tubes 275 are oxidized by heat of the heater 207 .
- an inert gas purge mechanism charged or purged with an inert gas such as nitrogen, restrained to a sufficiently low oxygen concentration, and configured to prevent oxidation of the first rod-shaped electrode 269 or the second rod-shaped electrode 270 is installed in the interior of the electrode protecting tube 275 .
- An exhaust pipe 231 configured to exhaust an atmosphere in the process chamber 201 is installed in the reaction tube 203 .
- a vacuum pump 246 serving as a vacuum exhaust unit is connected to the exhaust pipe 231 via a pressure sensor 245 serving as a pressure detector (a pressure detecting unit) configured to detect a pressure in the process chamber 201 , and an auto pressure controller (APC) valve 244 serving as a pressure regulator (a pressure regulating unit).
- the vacuum pump 246 may vacuum-exhaust the process chamber 201 so that a pressure in the process chamber 201 becomes a predetermined pressure (vacuum degree).
- the APC valve 244 is an opening/closing valve that may vacuum-exhaust an interior of the process chamber 201 or stop the vacuum-exhausting of an interior of the process chamber 201 as it is opened and closed and may regulate a pressure in the process chamber 201 according to an opening degree of the valve 244 .
- An exhaust system mainly includes the exhaust pipe 231 , the APC valve 244 , the vacuum pump 246 , and the pressure sensor 245 .
- a seal cap 219 serving as a furnace port cover configured to hermetically seal a lower end opening of the reaction tube 203 is installed on a lower portion of the reaction tube 203 .
- the seal cap 219 is installed to vertically contact a lower end of the reaction tube 203 on the lower side of the reaction tube 203 .
- the seal cap 219 is made of a metal such as stainless steel and has a disk shape.
- An O-ring 220 serving as a seal member configured to contact the lower end of the reaction tube 203 is installed on an upper surface of the seal cap 219 .
- a boat rotating mechanism 267 configured to rotate the boat 217 is installed at an opposite side of the process chamber 201 with respect to a center of the seal cap 219 .
- a rotary shaft 255 of the boat rotating mechanism 267 passes through the seal cap 219 to be connected to the boat 217 to be described below.
- the wafers 200 are rotated by rotating the boat 217 .
- the seal cap 219 is configured to be vertically elevated by a boat elevator 115 serving as an elevation mechanism vertically installed outside the reaction tube 203 so that the boat 217 can be loaded into the process chamber 201 or unloaded from the process chamber 201 .
- the boat 217 serving as a substrate supporting tool is made of a heat-resistant material, for example, SiO 2 or SiC.
- the boat 217 is configured to concentrically align a plurality of wafers 200 in a horizontal posture and support the plurality of wafers 200 in multiple stages.
- an insulating member 218 made of a heat-resistant material such as SiO 2 or SiC is configured to be installed at a lower portion of the boat 217 so that heat from the heater 207 cannot be easily transferred to the seal cap 219 .
- the insulating member 218 may include a plurality of insulating plates made of a heat-resistant material such as SiO 2 or SiC, and an insulating plate holder configured to support the insulating plates in a horizontal posture in multiple stages.
- a temperature sensor 263 serving as a temperature detector is installed inside the reaction tube 203 .
- the process chamber 201 is configured to have a desired temperature distribution by regulating power supplied to the heater 207 based on temperature information detected by the temperature sensor 263 .
- the temperature sensor 263 is L-shaped similar to the nozzles 249 a , 249 b , 249 c , and 249 c and is installed along the inner wall of the reaction tube 203 .
- a controller 121 which is a control unit (a control means), is connected to the MFCs 241 a , 241 b , 241 c , 241 d , 241 e , 241 f , 241 g , and 241 h , the valves 243 a , 243 b , 243 c , 243 d , 243 e , 243 f , 243 g , and 243 h , the pressure sensor 245 , the APC valve 244 , the vacuum pump 246 , the heater 207 , the temperature sensor 263 , the boat rotating mechanism 267 , the boat elevator 115 , the high-frequency power source 273 , the matching transformer 272 , etc.
- the controller 121 controls flow rate regulating operations for various gases by the MFCs 241 a , 241 b , 241 c , 241 d , 241 e , 241 f , 241 g , and 241 h , opening/closing operations of the valves 243 a , 243 b , 243 c , 243 d , 243 e , 243 f , 243 g , and 243 h , opening/closing operations of the APC valve 244 , a pressure regulating operation of the APC valve 244 based on the pressure sensor 245 , a temperature regulating operation of the heater 207 based on the temperature sensor 263 , starting and stopping of the vacuum pump 246 , a rotating speed regulating operation of the boat rotating mechanism 267 , an elevating operation of the boat elevator 115 , etc., or controls power supply of the high-frequency power source 273 and an impedance of the matching transformer 272 .
- a sequence example of forming a silicon oxycarbonitride film (a SiOCN film) serving as an insulating film on a substrate will be described as a process of the processes of manufacturing a semiconductor device using the process furnace of the above-described substrate processing apparatus.
- the operations of the units constituting the substrate processing apparatus are also controlled by the controller 121 .
- a conventional chemical vapor deposition (CVD) method a plurality of gases containing a plurality of elements constituting a film to be formed are supplied together at the same time.
- a conventional atomic layer deposition (ALD) method a plurality of gases containing a plurality of elements constituting a film to be formed are alternately supplied. Then, a SiO 2 film or a Si 3 N 4 film is formed by controlling supply conditions such as a flow rate of a supplied gas, a gas supplying time, and a plasma power during the gas supply.
- the supply conditions are controlled so that, in the case of forming the SiO 2 film by the technology, a composition ratio of the SiO 2 film becomes a stoichiometric composition ratio of O/Si ⁇ 2, and in the case of forming the Si 3 N 4 film, a composition ratio of the Si 3 N 4 film becomes a stoichiometric composition ratio of N/Si ⁇ 1.33.
- a supply condition is controlled so that a composition ratio of a film to be formed becomes a stoichiometric composition ratio or a predetermined composition ratio different from the stoichiometric composition ratio.
- a supply condition is controlled such that at least one of a plurality of elements constituting a film to be formed becomes a more excessive than the other elements in terms of the stoichiometric composition ratio.
- FIG. 3 is a diagram illustrating gas supply timing in a first sequence according to the embodiment of the present invention.
- a SiOCN film having a predetermined thickness is formed on a wafer 200 by performing, a predetermined number of times (n times), a cycle including the steps of:
- SiO would be obtained instead of SiOCN by oxidizing SiCN. This is because the inventors thought that since a binding force of a Si—O bond is stronger than that of a Si—N bond or a Si—C bond of SiCN, the Si—N bond and the Si—C bond of SiCN would be broken and C and N from which Si is broken would be separated from the SiCN while a Si—O bond was formed in an oxidation process.
- SiOCN may be properly formed as C and N separated by oxidation may be left by controlling an oxidizing force (in particular, a dilution rate, a supply time, and a partial pressure of an oxygen-containing gas) during oxidation of SiCN.
- an oxidizing force in particular, a dilution rate, a supply time, and a partial pressure of an oxygen-containing gas
- the boat 217 supporting the plurality of wafers 200 is lifted by the boat elevator 115 and loaded into the process chamber 201 (boat loading).
- the seal cap 219 seals a lower end of the reaction tube 203 via the O-ring 220 .
- An interior of the process chamber 201 is vacuum-exhausted by the vacuum pump 246 such that a pressure in the process chamber 201 becomes a desired pressure (vacuum degree).
- the pressure in the process chamber 201 is measured by the pressure sensor 245 and the APC valve 244 is feedback-controlled based on measured pressure information (pressure regulation).
- an interior of the process chamber 201 is heated by the heater 207 so that an temperature in the process chamber 201 becomes a desired temperature.
- power supplied to the heater 207 is feedback-controlled based on temperature information detected by the temperature sensor 263 so that the interior of the process chamber 201 has a desired temperature distribution (temperature regulation).
- the wafers 200 are rotated when the boat 217 is rotated by the boat rotating mechanism 267 (wafer rotation). Thereafter, four steps to be described below are sequentially performed.
- the valve 243 a of the first gas supply pipe 232 a is opened to flow HCD gas into the first gas supply pipe 232 a .
- a flow rate of the HCD gas that flows in the first gas supply pipe 232 a is regulated by the MFC 241 a .
- the HCD gas whose flow rate has been regulated is supplied into the process chamber 201 through the gas supply hole 250 a of the first nozzle 249 a and is exhausted through the exhaust pipe 231 .
- the valve 243 e is opened to flow an inert gas such as N 2 gas into the inert gas supply pipe 232 e .
- a flow rate of the N 2 gas that flows in the inert gas supply pipe 232 e is regulated by the MFC 241 e .
- the N 2 gas whose flow rate has been regulated is supplied into the process chamber 201 together with the HCD gas and exhausted through the exhaust pipe 231 .
- a pressure in the process chamber 201 is set, for example, to a range of 10 to 1,000 Pa by properly regulating the APC valve 244 .
- a flow rate of supplied HCD gas controlled by the MFC 241 la is set, for example, to a range of 10 to 1,000 sccm.
- a flow rate of supplied N 2 gas controlled by the MFC 241 e is set, for example, to a range of 200 to 2,000 sccm.
- a time taken to expose the wafer 200 to the HCD gas i.e., a gas supply time (irradiation time), is set, for example, to a range of 1 to 120 seconds.
- a temperature of the heater 207 is set, for example, to a temperature at which a CVD reaction may be caused in the process chamber 201 , i.e., a temperature at which the wafer 200 has a temperature range of, for example, 300 to 650° C.
- a temperature at which the wafer 200 has a temperature range of, for example, 300 to 650° C When the temperature of the wafer 200 is less than 300° C., adsorption of HCD onto the wafer 200 is difficult. Also, when the temperature of the wafer 200 exceeds 650° C., uniformity is deteriorated due to a strong CVD reaction.
- the temperature of the wafer 200 is preferably set to a range of 300 to 650° C.
- a first layer including Si is formed on an underlayer film on a surface of the wafer 200 by supplying HCD gas. That is, a Si layer serving as a silicon-containing layer of less than one atomic layer to several atomic layers is formed on the wafer 200 (on the underlayer film).
- the silicon-containing layer may be a chemical adsorption layer of HCD.
- Si is an element that becomes solid by itself.
- the Si layer in addition to a continuous layer composed of Si, the Si layer includes a discontinuous layer or a thin film formed by overlaying the continuous layer and the discontinuous layer. Also, the continuous layer composed of Si is often referred to as a thin film.
- the chemical adsorption layer of HCD includes, in addition to a continuous chemical adsorption layer of HCD molecules, a discontinuous chemical adsorption layer of HCD molecules.
- a layer of less than one atomic layer means a discontinuously formed atomic layer.
- Si is deposited on the wafer 200 to form a Si layer under a condition where HCD gas is self-decomposed, whereas HCD is chemically adsorbed on the wafer 200 to form a chemical adsorption layer of HCD under a condition where HCD gas is not self-decomposed. It is more preferable to form a Si layer on the wafer 200 than to form a chemical adsorption layer of HCD on the wafer 200 in order to increase a film-forming rate.
- the valve 243 a is closed to stop supply of the HCD gas.
- the APC valve 244 of the exhaust pipe 231 is kept open to vacuum-exhaust the interior of the process chamber 201 using the vacuum pump 246 , and the residual HCD gas in the process chamber 201 which has not reacted or has contributed to formation of the silicon-containing layer is removed from the process chamber 201 .
- the valve 243 e is kept open to maintain supply of the N 2 gas into the process chamber 201 . Accordingly, the residual HCD gas in the process chamber 201 which has not reacted or has contributed to formation of the silicon-containing layer may be effectively removed from the process chamber 201 .
- the silicon-containing gas may be, in addition to the HCD gas, an organic source such as amino silane-based tetrakisdimethylaminosilane (Si[N(CH 3 ) 2 ] 4 , 4DMAS) gas, trisdimethylaminosilane (Si[N(CH 3 ) 2 ] 3 H, 3DMAS) gas, bisdiethylaminosilane (Si[N(C 2 H 5 ) 2 ] 2 H 2 , 2DEAS) gas, and bistertiarybutylaminosilane (SiH 2 [NH(C 4 H 9 )] 2 , BTBAS), as well as an inorganic source such as tetrachlorosilane (SiCl 4 , STC) gas, trichlorosilane (SiHCl 3 , TCS) gas, dichlorosilane (SiH 2 Cl 2 , DCS) gas, monochlorosilane (SiH 3 Cl, MCS) gas
- the valve 243 b of the second gas supply pipe 232 b is opened to flow C 3 H 6 gas into the second gas supply pipe 232 b .
- a flow rate of the C 3 H 6 gas that flows in the second gas supply pipe 232 b is regulated by the MFC 241 b .
- the C 3 H 6 gas whose flow rate has been regulated is supplied into the process chamber 201 through a gas supply hole 250 b of the second nozzle 249 b and is exhausted through the exhaust pipe 231 .
- the C 3 H 6 gas supplied into the process chamber 201 is thermally activated.
- valve 243 f is opened to flow N 2 gas into the inert gas supply pipe 232 f at the same time.
- the N 2 gas is supplied into the process chamber 201 together with C 3 H 6 gas and is exhausted through the exhaust pipe 231 .
- a pressure in the process chamber 201 is set, for example, to a range of 50 to 3,000 Pa by properly controlling the APC valve 244 .
- a flow rate of supplied C 3 H 6 gas controlled by the MFC 241 b is set, for example, to a range of 100 to 10,000 sccm.
- a flow rate of supplied N 2 gas controlled by the MFC 241 f is set, for example, to a range of 200 to 2,000 sccm.
- a partial pressure of the C 3 H 6 gas in the process chamber 201 is regulated to a range of 6 to 2,940 Pa.
- An exposure time of the C 3 H 6 gas to the wafer 200 i.e., a gas supply time (irradiation time) is set, for example, to a range of 1 to 120 seconds.
- a temperature of the heater 207 is set such that the temperature of the wafer 200 becomes 300° C. to 650° C. as in the first step. Since a soft reaction may be caused by thermally activating and supplying the C 3 H 6 gas, a carbon-containing layer to be described below may be easily formed.
- the gas flowing into the process chamber 201 is thermally activated C 3 H 6 gas, and HCD gas does not flow into the process chamber 201 .
- the C 3 H 6 gas does not cause a vapor phase reaction and is activated and supplied to the wafer 200 .
- a carbon-containing layer of less than one atomic layer i.e., a discontinuous carbon-containing layer, is formed on the silicon-containing layer formed on the wafer 200 in the first step.
- the second layer including Si and C is formed.
- the second layer including Si and C may be formed by reacting a portion of the silicon-containing layer with the C 3 H 6 gas and modifying (carbonizing) the silicon-containing layer depending on conditions.
- the carbon-containing layer formed on the silicon-containing layer may be a C layer or may be a chemical adsorption layer of a carbon-containing gas (C 3 H 6 ), that is, a chemical adsorption layer of a material (C x H y ) produced by decomposing C 3 H 6 .
- the carbon layer needs to be a discontinuous layer composed of C.
- the chemical adsorption layer of C x H y needs to be a discontinuous chemical adsorption layer of C x H y molecules.
- the carbon-containing layer formed on the silicon-containing layer is a continuous layer
- a continuous chemical adsorption layer of C x H y is formed on a silicon-containing layer with adsorption of C x H y onto the silicon-containing layer being in a saturated state
- a surface of the silicon-containing layer is entirely covered with the chemical adsorption layer of C x H y .
- silicon is not present on a surface of the second layer, nitriding the second layer in the third step to be described below is difficult. This is because N binds to Si but does not bind to C.
- adsorption of C x H y onto the silicon-containing layer is in an unsaturated state, and thus a surface of the second layer needs to be a state where silicon is exposed.
- the processing conditions in the second step may preferably be set to the above-described processing conditions. Furthermore, when the processing conditions in the second step are set to the following processing conditions, it becomes easy to make an adsorption state of C x H y onto a silicon-containing layer an unsaturated state.
- Temperature of wafer 500 to 630° C.
- valve 243 b of the second gas supply pipe 232 b is closed to stop supply of the C 3 H 6 gas.
- the APC valve 244 of the exhaust pipe 231 is kept open to vacuum-exhaust the interior of the process chamber 201 using the vacuum pump 246 , and the residual C 3 H 6 gas in the process chamber 201 which has not reacted or has contributed to formation of the carbon-containing layer is removed from the process chamber 201 .
- the valve 243 f is also kept open to maintain supply of the N 2 gas into the process chamber 201 . Accordingly, the residual C 3 H 6 gas in the process chamber 201 which has not reacted or has contributed to formation of the carbon-containing layer can be effectively removed from the process chamber 201 .
- the carbon-containing gas may be acetylene (C 2 H 2 ) gas or ethylene (C 2 H 4 ) gas in addition to C 3 H 6 gas.
- the valve 243 c of the third gas supply pipe 232 c is opened to flow NH 3 gas into the third gas supply pipe 232 c .
- a flow rate of the NH 3 gas that flows in the third gas supply pipe 232 c is regulated by the MFC 241 c .
- the NH 3 gas whose flow rate has been regulated is supplied into the process chamber 201 through a gas supply hole 250 c of the third nozzle 249 c and is exhausted through the exhaust pipe 231 .
- the NH 3 gas supplied into the process chamber 201 is thermally activated.
- the valve 243 g is opened to flow the N 2 gas into the inert gas supply pipe 232 g at the same time.
- the N 2 gas is supplied into the process chamber 201 together with the NH 3 gas and is exhausted through the exhaust pipe 231 .
- a pressure in the process chamber 201 is regulated, for example, to a range of 50 to 3,000 Pa by properly controlling the APC valve 244 .
- a flow rate of supplied NH 3 gas controlled by the MFC 241 c is set, for example, to a range of 100 to 10,000 sccm.
- a flow rate of supplied N 2 gas controlled by the MFC 241 g is set, for example, to a range of 200 to 2,000 sccm.
- a partial pressure of the NH 3 gas in the process chamber 201 is set to a range of 6 to 2,940 Pa.
- An exposure time of the NH 3 gas to the wafer 200 i.e., a gas supply time (irradiation time) is set, for example, to a range of 1 to 120 seconds.
- a temperature of the heater 207 is set such that a temperature of the wafer 200 becomes, for example, 300° C. to 650° C. as in the first step.
- the NH 3 gas may be thermally activated when the pressure in the process chamber 201 is relatively high as described above. Since a soft reaction may be caused by thermally activating and supplying the NH 3 gas, a nitridation reaction to be described below may be softly performed.
- the gas flowing in the process chamber 201 is thermally activated NH 3 gas, and neither HCD gas nor C 3 H 6 gas flows in the process chamber 201 .
- the NH 3 gas does not cause a vapor phase reaction
- the activated NH 3 gas reacts with a portion of a layer including Si and C which is the second layer formed on the wafer 200 in the second step.
- the second layer is thermally nitrided in a non-plasma environment so that the second layer is changed into the third layer including Si, C, and N, i.e., a silicon carbonitride layer (a SiCN layer).
- the nitridation reaction of the second layer is not allowed to be saturated.
- a Si layer of several atomic layers is formed in the first step and a carbon-containing layer of less than one atomic layer is formed in the second step
- a portion of the surface layer (one atomic layer of the surface) thereof is nitrided. That is, some or all portion of an area (an area where silicon is exposed) where nitridation may be caused of the surface layer thereof is nitrided.
- nitridation is performed under a condition where a nitridation reaction of the second layer is unsaturated so that the entire second layer cannot be nitrided.
- the surface layer of the second layer may be nitrided depending on conditions, only the surface layer is preferably nitrided to enhance the controllability of the composition ratio of the SiOCN film.
- a Si layer of one atomic layer or less than one atomic layer is formed in the first step and a carbon-containing layer of less than one atomic layer is formed in the second step, a portion of the surface layer thereof is nitrided likewise. Even in this case, nitridation is also performed under a condition where a nitridation reaction of the second layer is unsaturated so that the second layer cannot be entirely nitrided.
- the processing conditions in the third step preferably may be set to the above-described processing conditions. Furthermore, when processing conditions in the third step are set to the following processing conditions, it becomes easy to make a nitridation reaction of the second layer in an unsaturated state.
- Temperature of wafer 500 to 630° C.
- valve 243 c of the third gas supply pipe 232 c is closed to stop supply of the NH 3 gas.
- the APC valve 244 of the exhaust pipe 231 is kept open to vacuum-exhaust the interior of the process chamber using the vacuum pump 246 , and the residual NH 3 gas in the process chamber 201 which has not reacted or has contributed to the nitridation is removed from the process chamber 201 .
- the valve 243 g is also kept open to maintain supply of the N 2 gas into the process chamber 201 . Accordingly, the residual NH 3 gas in the process chamber 201 which has not reacted or has contributed to the nitridation may be effectively removed from the process chamber 201 .
- the nitrogen-containing gas may be diazine (N 2 H 2 ) gas, hydrazine (N 2 H 4 ) gas or N 3 H 8 gas in addition to NH 3 gas.
- valve 243 d of the fourth gas supply pipe 232 d and the valve 243 h of the fourth inert gas supply pipe 232 h are opened to flow the O 2 gas into the fourth gas supply pipe 232 d and flow the N 2 gas into the fourth inert gas supply pipe 232 h .
- a flow rate of the N 2 gas that flows in the fourth inert gas supply pipe 232 h is regulated by the MFC 241 h .
- a flow rate of the O 2 gas that flows in the fourth gas supply gas pipe 232 d is regulated by the MFC 241 d .
- the O 2 gas whose flow rate has been regulated is mixed with the N 2 gas whose flow rate has been regulated and is supplied into the buffer chamber 237 through the gas supply hole 250 d of the fourth nozzle 249 d .
- a high-frequency power is not applied between the first rod-shaped electrode 269 and the second rod-shaped electrode 270 .
- the O 2 gas supplied into the buffer chamber 237 is thermally activated, the O 2 gas is directed toward the wafer 200 and supplied into the process chamber 201 through the gas supply hole 250 e , and is exhausted through the exhaust chamber 231 .
- the O 2 gas supplied into the buffer chamber 237 may be activated using plasma by applying high-frequency power between the first rod-shaped electrode 269 and the second rod-shaped electrode 270 .
- a pressure in the process chamber 201 is set, for example, to a range of 1 to 3,000 Pa by properly regulating the APC valve 244 .
- a flow rate of supplied O 2 gas controlled by the MFC 241 d is set, for example, to a range of 100 to 5,000 sccm (0.1 to 5 slm).
- a flow rate of supplied N 2 gas controlled by the MFC 241 h is set, for example, to a range of 200 to 2,000 sccm (0.2 to 2 slm).
- a partial pressure of the O 2 gas in the process chamber 201 is set to a range of 6 to 2,940 Pa.
- An exposure time of the wafer 200 to the O 2 gas i.e., a gas supply time (irradiation time) is set, for example, to a range of 1 to 120 seconds.
- a temperature of the heater 207 is set such that a temperature of the wafer 200 falls within a range of 300 to 650° C. as in the first through third steps.
- the O 2 gas is thermally activated under the above-described conditions. Since a soft reaction may be caused by thermally activating and supplying the O 2 gas, an oxidation reaction to be described below may be softly performed.
- the gas flowing into the process chamber 201 is thermally activated O 2 gas, and none of the HCD gas, the C 3 H 6 gas, and the NH 3 gas flows in the process chamber 201 .
- the O 2 gas does not cause a vapor phase reaction
- the activated O 2 gas reacts with a portion of a SiCN layer serving as the third layer formed on the wafer 200 in the third step.
- the SiCN layer is thermally oxidized in a non-plasma environment so that the SiCN layer is changed into the fourth layer including Si, C, N, and O, i.e., a SiOCN layer.
- the oxidation reaction of the SiCN layer is not allowed to be saturated.
- a SiCN layer of several atomic layers is formed in the first through third steps, at least a portion of the surface layer (one atomic layer of the surface) thereof is oxidized.
- oxidation is performed under a condition where the oxidation reaction of the SiCN layer is unsaturated such that the SiCN layer cannot be entirely oxidized.
- several layers below the surface layer of the SiCN layer may be oxidized depending on conditions, only the surface layer is preferably oxidized to enhance controllability of the composition ratio of the SiOCN film.
- a SiCN layer of one atomic layer or less than one atomic layer is formed in the first through third steps, a portion of the surface layer thereof is oxidized likewise. Even in this case, oxidation is also performed under a condition where an oxidation reaction of the SiCN layer is unsaturated so that the SiCN layer cannot be entirely oxidized.
- the processing conditions in the fourth step preferably may be set to the above-described processing conditions. Furthermore, when processing conditions in the fourth step are set to the following processing conditions, it becomes easy to make an oxidation reaction of the second layer in an unsaturated state.
- Temperature of wafer 500 to 630° C.
- valve 243 d of the fourth gas supply pipe 232 d is closed to stop supply of the O 2 gas.
- the APC valve 244 of the exhaust pipe 231 is kept open to vacuum-exhaust the interior of the process chamber 201 using the vacuum pump 246 , and the residual O 2 gas in the process chamber 201 which has not reacted or has contributed to oxidation is removed from the process chamber 201 .
- the valve 243 h is kept open to maintain supply of the N 2 gas into the process chamber 201 . Accordingly, the residual O 2 gas in the process chamber 201 which has not reacted or has contributed to oxidation may be effectively removed from the process chamber 201
- the oxygen-containing gas may include, vapor (H 2 O) gas, nitrogen monoxide (NO) gas, nitrous oxide (N 2 O) gas, nitrogen dioxide (NO 2 ) gas, carbon monoxide (CO) gas, carbon dioxide (CO 2 ) gas, ozone (0.3) gas, a mixture of H 2 gas and O 2 gas, a mixture of H 2 gas and O 3 gas, etc., in addition to O 2 gas.
- vapor (H 2 O) gas nitrogen monoxide (NO) gas, nitrous oxide (N 2 O) gas, nitrogen dioxide (NO 2 ) gas, carbon monoxide (CO) gas, carbon dioxide (CO 2 ) gas, ozone (0.3) gas, a mixture of H 2 gas and O 2 gas, a mixture of H 2 gas and O 3 gas, etc., in addition to O 2 gas.
- a thin film including Si, C, N, and O, i.e., a SiOCN film, having a predetermined thickness may be formed on the wafer 200 by performing a cycle including the above-described first through fourth steps once or more.
- the above-described cycle is preferably repeatedly performed a plurality of times.
- ratios of each of the element components in the SiOCN layer i.e., a Si component, an O component, a C component and a N component, that is, a Si concentration, an O concentration, a C concentration and a N concentration may be regulated by controlling process conditions such as a pressure in the process chamber 201 or a gas supply time in the respective steps so that a composition ratio of the SiOCN film may be controlled.
- a SiOCN film having a predetermined thickness may be formed on the wafer 200 by performing, once or more, a cycle including a process of carrying out a set of steps including the above-described first through third steps once or more, and a process of carrying out the fourth step afterwards
- a SiOCN film having a predetermined thickness may be formed on a wafer 200 by performing, a predetermined number of times (n times), a cycle including steps of:
- FIG. 4 exemplifies formation of a SiOCN film having a predetermined thickness on the wafer 200 by performing, n times, a cycle which includes a process of carrying out a set of the first through third steps twice, and a process of carrying out the fourth step afterwards.
- the ratio of a Si component, a C component, and a N component to an O component of a SiOCN film may be controlled properly (in a rich direction) by performing, a predetermined number of times, a cycle including a process of carrying out a set of the first through third steps a predetermined number of times, and a process of carrying out the fourth step afterwards, and thereby the controllability of a composition ratio of the SiOCN film can be enhanced more.
- the number of SiCN layers formed per cycle may be increased as the set of steps is increased in number, making it possible to enhance a cycle rate. Accordingly, a film-forming rate may be enhanced.
- an inert gas such as N 2 gas is supplied into the process chamber 201 and then is exhausted such that the interior of the process chamber 201 is purged by the inert gas (gas purging). Thereafter, an atmosphere in the process chamber 201 is substituted with the inert gas (inert gas substitution), and a pressure in the process chamber 201 is returned to a normal pressure (returning to atmospheric pressure).
- the processed wafer 200 is unloaded (boat unloading) out of the reaction tube 203 from a lower end of the reaction tube 203 in a state where the processed wafer 200 is supported by the boat 217 . Thereafter, the processed wafer 200 is discharged from the boat 217 (wafer discharging).
- FIG. 5 is a timing diagram illustrating gas supply timing in a second sequence according to the embodiment of the present invention.
- a SiOCN film having a predetermined thickness is formed on the wafer 200 by performing, a predetermined number of times (n times), a cycle including the steps of: (a) supplying a silicon-containing gas into a process vessel accommodating the wafer 200 under a condition where a CVD reaction is caused to form a silicon-containing layer on the wafer 200 ;
- the second sequence is performed in the same manner as in the first second sequence until the wafer charging, the boat loading, the pressure regulation, the temperature regulation and the wafer rotation are performed. Thereafter, five steps to be described below are sequentially performed.
- the first step is performed in the same manner as in the first step of the first sequence. That is, processing conditions, a reaction to be caused, a layer to be formed, etc. of the first step are the same as those of the first step of the first sequence. That is, in this step, a silicon-containing layer is formed on a wafer 200 by supplying HCD gas into the process chamber 201 .
- the second step is performed in the same manner as in the second step of the first sequence. That is, processing conditions, a reaction to be caused, a layer to be formed, etc. of the second step are the same as those of the second step of the first sequence. That is, in this step, a first layer including Si and C is formed by supplying C 3 H 6 gas into the process chamber 201 and forming a carbon-containing layer on a silicon-containing layer.
- the third step is performed in the same manner as in the first step of the first sequence. That is, processing conditions, a reaction to be caused, a layer to be formed, etc. of the third step are the same as those of the first step of the first sequence. That is, in this step, a second layer including Si and C is formed by supplying HCD gas into the process chamber 201 and forming a silicon-containing layer on the first layer including Si and C.
- the fourth step is performed in the same manner as in the third step of the first sequence. That is, processing conditions, a reaction to be caused, a layer to be formed, etc. of the fourth step are the same as those of the third step of the first sequence. That is, in this step, a SiCN layer is formed by supplying NH 3 gas into the process chamber 201 and nitriding the second layer including Si and C to form a SiCN layer.
- the fifth step is performed in the same manner as in the fourth step of the first sequence. That is, processing conditions, a reaction to be caused, a layer to be formed, etc. of the fifth step are the same as those of the fourth step of the first sequence. That is, in this step, a SiOCN layer is formed by supplying O 2 gas into the process chamber 201 and oxidizing the SiCN layer.
- a SiOCN film having a predetermined thickness may be formed on the wafer 200 by performing a cycle including the above-described first through fifth steps once or more.
- the above-described cycle is preferably repeated a plurality of times.
- ratios of each of the element components in the SiOCN layer i.e., a Si component, an O component, a C component and a N component, that is, a Si concentration, an O concentration, a C concentration and a N concentration
- process conditions such as a pressure in the process chamber 201 or a gas supply time in the respective steps so that a composition ratio of the SiOCN film can be controlled.
- a SiOCN film having a predetermined thickness may be formed on the wafer 200 by performing, once or more, a cycle including a process of carrying out a set of steps including the above-described first through fourth steps once or more, and a process of carrying out the fifth step afterwards.
- a SiOCN film having a predetermined thickness may be formed on the wafer 200 by performing, a predetermined number of times (n times), a cycle including steps of:
- FIG. 6 exemplifies formation of a SiOCN film having a predetermined thickness on the wafer 200 by performing, n times, a cycle which includes a process of carrying out a set of the first through fourth steps twice, and a process of carrying out the fifth step afterwards.
- the ratio of a Si component, a C component, and a N component to an O component of a SiOCN film may be controlled properly (in a rich direction) by performing, a predetermined number of times, a cycle including a process of carrying out a set of the first through fourth steps a predetermined number of times, and a process of carrying out the fifth step afterwards, and thereby the controllability of a composition ratio of the SiOCN film can be enhanced more.
- the number of SiCN layers formed per cycle may be increased as the set of steps is increased in number, making it possible to enhance a cycle rate. Accordingly, a film-forming rate may be enhanced.
- HCD gas is supplied at least once per cycle (first step) to form at least one silicon layer per cycle.
- HCD gas may be supplied at least twice per cycle (first step and third step) to form at least two silicon layers per cycle. That is, according to the second sequence, an amount of Si adsorbed and deposited per cycle may be increased as compared with the first sequence (more than two times), making it possible to enhance a cycle rate.
- C i.e., C x H y
- Si is adsorbed and deposited in the third step, resulting in increased probability of forming a Si—C—Si bond.
- N i.e. NH 3 gas
- an attack of N is blocked by Si forming the Si—C—Si bond, and thus separation of C may be difficult and C may easily remain.
- an amount of C introduced to the SiCN i.e. a C concentration in the SiCN film, is enhanced.
- both adsorption of C x H y onto the Si layer in the second step and nitridation of the second layer by NH 3 gas in the third step need to be stopped when the adsorption and the nitridation are in an unsaturated state.
- nitridation of the second layer by NH 3 gas in the third step is saturated, a large amount of C is separated and a C concentration in the SiCN film is severely lowered.
- C x H y is adsorbed onto a Si layer in the second step and Si is adsorbed and deposited in the third step, causing a probability of forming a Si—C—Si bond to be increased so that the Si forming the Si—C—Si bond functions as a block layer of C against an attack of N in the fourth step.
- saturating nitridation of the third layer by NH 3 gas in the fourth step is possible. That is, a nitriding force may be increased and more uniform nitridation becomes possible while separation of C is being restrained. As a result, uniformity in a film thickness on a wafer surface of a SiCN film may be enhanced.
- the gas purging, the inert gas substitution, the returning to the atmospheric pressure, the boat unloading, and the wafer discharging are performed in the same manner as in the first sequence.
- the embodiment of the present invention has one or plural effects as follows.
- the first through fourth steps are sequentially performed in order, or after a set of steps, i.e., the first through third steps, is performed once or more, the fourth step is performed.
- a SiOCN film having a predetermined composition ratio and a predetermined thickness may be formed.
- the first through fifth steps are sequentially performed in order, or after a set of steps, i.e., the first through fourth steps, is performed once or more, the fifth step is performed.
- a SiOCN film having a predetermined composition ratio and a predetermined thickness may be formed.
- a SiOCN film having an excellent uniformity in film thickness in a wafer surface may be formed in any one of the first sequence and the second sequence.
- a SiOCN film formed through the first sequence or the second sequence of the embodiment of the present invention is used as an insulating film, it is possible to provide a uniform performance in a surface of the SiOCN film and to contribute to enhancing a performance of a semiconductor device or enhancing a production rate.
- ratios of each of the element components in the SiOCN layer may be regulated by controlling process conditions such as a pressure in the process chamber or a gas supply time in the respective steps so that a composition ratio of the SiOCN film can be controlled.
- a composition ratio of a formed thin film in order to control a composition ratio of a formed thin film, controlling the ratio of flow rates of supplied gases during supply of the gases can be considered for example.
- a composition ratio of a thin film cannot be controlled even by controlling supply conditions such as a temperature of a substrate, a pressure in the process chamber, and gas supply times during supply of gases.
- a plurality of kinds of gases containing a plurality of elements constituting a thin film to be formed are alternately supplied.
- controlling flow rates of supplied gases and gas supply times during supply of gases may be considered in order to control a composition ratio of a thin film to be formed.
- a source gas is supplied to be adsorbed and saturated onto a surface of a substrate, there is no need to control a pressure in the process chamber.
- the adsorption and saturation of a source gas may be achieved at any pressure. Accordingly, when a film is generally formed through the ALD method, the pressure in the process chamber is set to a pressure according to capability of exhausting a substrate processing apparatus with respect to an amount of supplied gas. When the pressure in the process chamber is varied, chemical adsorption of a source gas onto a surface of a substrate may be hampered or a reaction may be close to the CVD reaction, and thus film formation using the ALD method may not be properly performed.
- an ALD reaction saturated adsorption, and surface reaction
- deposition may become insufficient and deposition rate may not be sufficient.
- a composition ratio of a thin film is controlled by controlling a pressure in the process chamber or a gas supply time in respective steps in any of the sequences.
- a composition ratio of a thin film may also be controlled by controlling a pressure in the process chamber or the pressure and a gas supply time.
- composition ratio of a thin film When a composition ratio of a thin film is controlled by controlling a pressure in the process chamber in respective steps, effects caused by a difference between other substrate processing apparatuses may be reduced. That is, a composition ratio of a thin film may be controlled under the same control conditions and in the same manner even in the other substrate processing apparatuses. In this case, when a gas supply time is controlled in respective steps, a composition ratio of a thin film may be minutely regulated and a controllability of a composition ratio of the thin film may be enhanced. Also by controlling a pressure in the process chamber in respective steps, a composition ratio of a thin film may be controlled while raising a film-forming rate.
- a composition ratio of a thin film may be controlled by controlling a pressure in the process chamber, for example, while raising a growth rate of a silicon-containing layer formed in the first steps of the respective sequences.
- the composition ratio of the thin film may be controlled under the same control conditions and in the same manner even in the other substrate processing apparatuses, controllability of the composition ratio of the thin film may be enhanced, and the film formation rate, i.e. productivity may also be enhanced.
- a composition ratio of a thin film is controlled by controlling a flow rate of supplied gas and a gas supply time in respective steps, effects caused by a difference between other substrate processing apparatuses is increased. That is, the same control is performed to the other substrate processing apparatuses, a composition ratio of a thin film cannot be controlled in the same manner. For example, even when the flow rates of supplied gases and gas supply times in the other substrate processing apparatuses are set to the same flow rates and gas supply times, the pressures in the process chambers do not become the same value due to the difference between the other substrate processing apparatuses.
- composition ratios in the substrate processing apparatuses cannot be controlled in a desired manner.
- pressures in the process chambers of the substrate processing apparatuses are varied, chemical adsorption of a source gas onto a surface of a substrate may be hampered or reactions may be close to the CVD reactions, and thus a film cannot be properly formed using the ALD method.
- a SiOCN film of a predetermined composition ratio may be formed according to the embodiment of the present invention, an etching-resistant property, a dielectric constant, and an insulation-resistant property may be controlled. Therefore, a silicon insulating film having a low dielectric constant, an excellent etching-resistant property and a excellent insulation-resistant property may be formed, compared to those of the SiN film.
- the C 3 H 6 gas, the NH 3 gas, and the O 2 gas supplied into the process chamber 201 are thermally activated respectively and are supplied to a surface of the wafer 200 in the second through fourth steps of the first sequence of this embodiment and in the second, fourth, and fifth steps of the second sequence. Accordingly, since each of the above-described reactions may be softly caused, formation of the carbon-containing layer, nitridation and oxidation can be easily performed with excellent controllability.
- the silicon insulating film formed through the technique of the embodiment of the present invention may be used as a side wall spacer, providing a device forming technology with small leak current and excellent processing.
- the silicon insulating film formed through the technique of the embodiment of the present invention may be used as an etch stopper, providing a device forming technology with excellent processing.
- a silicon insulating film of an ideal stoichiometric ratio can be formed. Further, since a Si insulating film is formed without using plasma, the silicon insulating film may be applied to a process where plasma damage is concerned, for example, on an SADP film of DPT.
- the buffer chamber 237 may not be installed inside the process chamber 201 , but O 2 gas may be directly supplied into the process chamber 201 through the fourth nozzle 249 d .
- the O 2 gas may be directly supplied toward the wafer 200 through the fourth nozzle 249 d with the gas supply hole 250 d of the fourth nozzle 249 d facing the center of the reaction tube 203 .
- the fourth nozzle 249 d may not be installed, but only the buffer chamber 237 may be installed.
- the C 3 H 6 gas, NH 3 gas, and O 2 gas supplied into the process chamber 201 are not limited to be thermally activated, but, for example, may be activated using plasma.
- the gases may be plasma-excited using the plasma source serving as the above-described plasma generator.
- a hydrogen-containing gas may be supplied together with an oxygen-containing gas in the fourth step of the first sequence and the fifth step of the second sequence.
- an oxygen-containing gas and a hydrogen-containing gas are supplied into the process chamber under an atmosphere less than the atmospheric pressure (reduced pressure)
- the oxygen-containing gas and the hydrogen-containing gas react with each other in the process vessel to produce an oxidant (atomic oxygen etc.) including oxygen, and then the layers may be oxidized by the oxidant.
- oxidation can be performed with a higher oxidizing force than with that of a single oxygen-containing gas.
- the oxidation is performed in the absence of plasma under a reduced pressure atmosphere.
- H 2 gas may be used as the hydrogen-containing gas.
- the above-described hydrogen-containing gas supply system may be used.
- a SiOCN film (a semiconductor insulating film) including Si serving as a semiconductor element as an insulating film
- the present invention may also be applied to a case of forming a metal oxycarbonitride film (a metal insulating film) including a metal element such as titanium (Ti), zirconium (Zr), hafnium (Hf), tantalum (Ta), aluminum (Al), molybdenum (Mo), gallium (Ga), or germanium (Ge).
- the present invention may also be applied to a titanium oxycarbonitride film (a TiOCN film), a zirconium oxycarbonitride film (a ZrOCN film), a hafnium oxycarbonitride film (a HfOCN film), a tantalum oxycarbonitride film (a TaOCN film), an aluminum oxycarbonitride film (an AlOCN film), a molybdenum oxycarbonitride film (a MoOCN film), a gallium oxycarbonitride film (a GaOCN film), or a germanium oxycarbonitride film (a GeOCN film), or a metal oxycarbonitride film obtained by combination or mixture thereof.
- a TiOCN film titanium oxycarbonitride film
- a ZrOCN film zirconium oxycarbonitride film
- a hafnium oxycarbonitride film a HfOCN film
- a TaOCN film tantalum oxycarbonitride film
- a film may be formed though the same sequences (first sequence and second sequence) as in the above-described embodiments using Ti source gas, Zr source gas, Hf source gas.
- Ta source gas, Al source gas, Mo source gas, Ga source gas, or Ge source gas instead of the Si source gas.
- a metal oxycarbonitride film having a predetermined thickness is, for example, formed on a wafer in the first sequence by performing, a predetermined number of times (n times), a cycle including the steps of:
- the metal oxycarbonitride film having a predetermined thickness may be formed on the wafer by performing, once or more, a cycle which includes a process of carrying out a set of the first through third steps once or more, and a process of carrying out the fourth step afterwards.
- a metal oxycarbonitride film having a predetermined thickness may be formed on a wafer by performing, a predetermined number of times (n times), a cycle including steps of:
- a metal oxycarbonitride film having a predetermined thickness is, for example, formed on a wafer in the second sequence by performing, a predetermined number of times (n times), a cycle including the steps of:
- a metal oxycarbonitride film having a predetermined thickness may be formed on a wafer by performing, once or more, a cycle which includes a process of carrying out a set of the first through fourth steps once or more, and a process of carrying out the fifth step afterwards.
- a metal oxycarbonitride film having a predetermined thickness may be formed on a wafer by performing, a predetermined number of times (n times), a cycle including steps of:
- a source containing Ti may include an organic source such as tetrakisethylmethylaminotitanium (Ti[N(C 2 H 5 )(CH 3 )] 4 , TEMAT), tetrakisdimethylaminotitanium (Ti[N(CH 3 ) 2 ] 4 , TDMAT), and tetrakisdiethylaminotitanium (Ti[N(C 2 H 5 ) 2 ] 4 , TDEAT), or an inorganic source such as titanium tetrachloride (TiCl 4 ).
- an organic source such as tetrakisethylmethylaminotitanium (Ti[N(C 2 H 5 )(CH 3 )] 4 , TEMAT), tetrakisdimethylaminotitanium (Ti[N(CH 3 ) 2 ] 4 , TDMAT), and tetrakisdiethylaminotitanium (Ti[N(
- the same gases described in the embodiment of the present invention may be used as the carbon-containing gas, the nitrogen-containing gas, or the oxygen-containing gas.
- the processing conditions may be, for example, set to the same processing conditions as described in the embodiment of the present invention, but a temperature of the wafer is more preferably, for example, in a range of 100 to 500° C. and a pressure in the process chamber is more preferably in a range of 1 to 1,000 Pa.
- a source containing Zr may include an organic source such as tetrakisethylmethylaminozirconium (Zr[N(C 2 H 5 )(CH 3 )] 4 , TEMAZ), tetrakisdimethylaminozirconium (Zr[N(CH 3 ) 2 ] 4 , TDMAZ), and tetrakisdiethylaminozirconium (Zr[N(C 2 H 5 ) 2 ] 4 , TDEAZ), or an inorganic source such as zirconium tetrachloride (ZrCl 4 ).
- an organic source such as tetrakisethylmethylaminozirconium (Zr[N(C 2 H 5 )(CH 3 )] 4 , TEMAZ), tetrakisdimethylaminozirconium (Zr[N(CH 3 ) 2 ] 4 , TDMAZ), and tetrakisdieth
- the same gases described in the embodiment of the present invention may be used as the carbon-containing gas, the nitrogen-containing gas, or the oxygen-containing gas.
- the processing conditions may be, for example, set to the same processing conditions as described in the embodiment of the present invention, but a temperature of the wafer is more preferably, for example, in a range of 100 to 400° C. and a pressure in the process chamber is more preferably in a range of 1 to 1,000 Pa.
- a source containing Hf may include an organic source such as tetrakisethylmethylaminohafnium (Hf[N(C 2 H 5 )CH 3 )] 4 , TEMAH), tetrakisdimethylaminohafnium (Hf[N(CH 3 ) 2 ] 4 , TDMAH), and tetrakisdiethylaminohafnium (Hf[N(C 2 H 5 ) 2 ] 4 , TDEAH), or an inorganic source such as hafnium tetrachloride (HfCl 4 ).
- an organic source such as tetrakisethylmethylaminohafnium (Hf[N(C 2 H 5 )CH 3 )] 4 , TEMAH), tetrakisdimethylaminohafnium (Hf[N(CH 3 ) 2 ] 4 , TDMAH), and tetrakisdiethyla
- the same gas described in the embodiment of the present invention may be used as the carbon-containing gas, the nitrogen-containing gas, or the oxygen-containing gas.
- the processing conditions may be, for example, set to the same processing conditions as described in the embodiment of the present invention, but a temperature of the wafer is more preferably, for example, in a range of 100 to 400° C. and a pressure in the process chamber is more preferably in a range of 1 to 1,000 Pa.
- a source containing Al may include an organic source such as trimethylaluminum (Al(CH 3 ) 3 , TMA), or an inorganic source such as trichloroaluminum (AlCl 3 ).
- the same gas described in the embodiment of the present invention may be used as the carbon-containing gas, the nitrogen-containing gas, or the oxygen-containing gas.
- the processing conditions may be, for example, set to the same processing conditions as described in the embodiment of the present invention, but a temperature of the wafer is more preferably, for example, in a range of 100 to 400° C. and a pressure in the process chamber is more preferably in a range of 1 to 1,000 Pa.
- the present invention may be applied to formation of the metal oxycarbonitride film, in which case the same operations and effects as in the embodiment of the present invention can be obtained.
- the present invention may be applied to the case of forming a oxycarbonitride film containing a certain element such as a semiconductor element or a metal element.
- SiOCN films were formed while controlling composition ratios through the first sequence according to the above-described embodiment and the composition ratios of the SiOCN films and uniformity in film thicknesses in wafer surfaces were measured.
- HCD gas was used as the silicon-containing gas
- C 3 H 6 gas was used as the carbon-containing gas
- NH 3 gas was used as the nitrogen-containing gas
- O 2 gas was used as the oxygen-containing gas.
- the composition ratios were controlled by regulating factors for controlling the composition ratios, i.e., a pressure, or a pressure and gas supply time (irradiation time). In controlling the composition ratios, the higher the pressure is and the longer the gas supply time is, the higher the reaction is, and thus layers formed in the corresponding steps become thicker or an adsorption amount is increased. That is, the number of atoms given in the corresponding steps becomes larger. In the meantime, when the adsorption of reaction species or a reaction by the reaction species is saturated, there is a case that a film thickness may not become thick
- the pressure in the process chamber and the supply time of C 3 H 6 gas in the second step of the first sequence were regulated, and a SiOCN film having a C concentration of approximately 8 atoms % was formed on the wafer.
- the processing conditions then were set as follows.
- a SiOCN film having a C concentration of approximately 16 atoms % was obtained by changing a pressure in the process chamber from 133 Pa (1 Torr) to 2394 Pa (18 Torr) in the second step.
- a SiOCN film having a C ratio higher than that of a SiOCN film formed by the reference processing conditions may be formed. That is, it was confirmed that a SiOCN film having a high C ratio may be formed by setting a pressure in the process chamber in the second step to a higher pressure than a pressure in the process chamber with respect to the reference processing conditions. It was also confirmed that as C concentration increases, N concentration decreases.
- the processing conditions except for the pressure in the process chamber in the second step were set to the same conditions as in the reference processing conditions. That is, the processing conditions in this case were set as follows.
- the uniformity in film thickness on the wafer surface represents a deviation degree of film thickness distribution on the wafer surface, and as the deviation degree is smaller, the uniformity in film thickness distribution on the wafer surface is excellent.
- a SiOCN film having an excellent uniformity in film thickness on the wafer surface may be formed.
- a surface of the SiOCN film may be endowed with uniform performance, thereby contributing to enhanced performance of a semiconductor device or enhanced yield rate
- a SiOCN film was not formed on the wafer. That is, it was confirmed that when film formation was performed in the order of the first step, the second step, the fourth step, and the third step, a SiOCN film could not be obtained.
- the processing conditions in each step are set to the same processing conditions as the processing conditions (reference processing conditions) in each step of the embodiment.
- a method of manufacturing a semiconductor device including performing a cycle a predetermined number of times to form an oxycarbonitride film having a predetermined thickness on a substrate in a process vessel, wherein the cycle includes steps of:
- the carbonitride layer having the predetermined thickness is thermally oxidized under a condition where an oxidation reaction of the carbonitride layer having the predetermined thickness caused by the oxygen-containing gas is unsaturated.
- a discontinuous chemical adsorption layer is formed as the carbon-containing layer on the layer containing the element
- the layer including the element and the carbon is thermally nitrided under a condition where a nitridation reaction of the layer including the element and the carbon caused by the nitrogen-containing gas is unsaturated, and
- the carbonitride layer having the predetermined thickness is thermally oxidized under a condition where an oxidation reaction of the carbonitride layer having the predetermined thickness caused by the oxygen-containing gas is unsaturated.
- a deposition layer of the element is formed as the layer containing the element on the substrate,
- a discontinuous chemical adsorption layer is formed as the carbon-containing layer on the layer containing the element
- the layer including the element and the carbon is thermally nitrided under a condition where a nitridation reaction of the layer including the element and the carbon caused by the nitrogen-containing gas is unsaturated, and
- the carbonitride layer having the predetermined thickness is thermally oxidized under a condition where an oxidation reaction of the carbonitride layer having the predetermined thickness caused by the oxygen-containing gas is unsaturated.
- a composition of the oxycarbonitride film is adjusted by controlling a pressure in the process vessel, or the pressure and a gas supply time in at least one of the steps.
- At least one of concentrations of the element, the carbon, a nitrogen and an oxygen in the oxycarbonitride film is adjusted by controlling a pressure in the process vessel, or the pressure and a gas supply time in at least one of the steps.
- the element includes a semiconductor element or a metal element.
- the element is a silicon.
- a method of manufacturing a semiconductor device including performing a cycle a predetermined number of times to form a silicon oxycarbonitride film having a predetermined thickness on a substrate in a process vessel, wherein the cycle includes steps of:
- the silicon carbonitride layer having the predetermined thickness is thermally oxidized under a condition where an oxidation reaction of the silicon carbonitride layer having the predetermined thickness caused by the oxygen-containing gas is unsaturated.
- a discontinuous chemical adsorption layer is formed as the carbon-containing layer on the silicon-containing layer
- the layer including the silicon and the carbon is thermally nitrided under a condition where a nitridation reaction of the layer including the silicon and the carbon caused by the nitrogen-containing gas is unsaturated, and
- the silicon carbonitride layer having the predetermined thickness is thermally oxidized under a condition where an oxidation reaction of the silicon carbonitride layer having the predetermined thickness caused by the oxygen-containing gas is unsaturated.
- a deposition layer of the silicon is formed as the silicon-containing layer on the substrate,
- a discontinuous chemical adsorption layer is formed as the carbon-containing layer on the silicon-containing layer
- the layer including the silicon and the carbon is thermally nitrided under a condition where a nitridation reaction of the layer including the silicon and the carbon caused by the nitrogen-containing gas is unsaturated, and
- the silicon carbonitride layer having the predetermined thickness is thermally oxidized under a condition where an oxidation reaction of the silicon carbonitride layer having the predetermined thickness caused by the oxygen-containing gas is unsaturated.
- a composition of the silicon oxycarbonitride film is adjusted by controlling a pressure in the process vessel, or the pressure and a gas supply time in at least one of the steps.
- At least one of concentrations of the silicon, the carbon, a nitrogen and an oxygen in the silicon oxycarbonitride film is adjusted by controlling a pressure in the process vessel, or the pressure and a gas supply time in at least one of the steps.
- a method of manufacturing a semiconductor device including performing a cycle a predetermined number of times to form an oxycarbonitride film having a predetermined thickness on a substrate in a process vessel, wherein the cycle includes steps of:
- a method of manufacturing a semiconductor device including performing a cycle a predetermined number of times to form a silicon oxycarbonitride film having a predetermined thickness on a substrate in a process vessel, wherein the cycle includes steps of:
- a method of processing a substrate including performing a cycle a predetermined number of times to form an oxycarbonitride film having a predetermined thickness on a substrate in a process vessel, wherein the cycle includes steps of:
- a substrate processing apparatus including:
- a process vessel configured to accommodate a substrate
- a heater configured to heat the substrate in the process vessel
- an element-containing gas supply system configured to supply a gas containing an element into the process vessel
- a carbon-containing gas supply system configured to supply a carbon-containing gas into the process vessel
- a nitrogen-containing gas supply system configured to supply a nitrogen-containing gas into the process vessel
- an oxygen-containing gas supply system configured to supply an oxygen-containing gas into the process vessel
- a pressure regulating unit configured to regulate a pressure in the process vessel
- control unit configured to control the heater, the element-containing gas supply system, the carbon-containing gas supply system, the nitrogen-containing gas supply system, the oxygen-containing gas supply system and the pressure regulating unit such that an oxycarbonitride film having a predetermined thickness is formed on the substrate by performing a cycle a predetermined number of times wherein the cycle includes processes of: (a) performing a set of processes a predetermined number of times to form a carbonitride layer having a predetermined thickness on the substrate; and (b) supplying an oxygen-containing gas into the process vessel to oxidize the carbonitride layer having the predetermined thickness, thereby forming an oxycarbonitride layer,
- the set of processes includes: (a-1) supplying a gas containing an element into the process vessel accommodating the substrate under a condition where a CVD reaction is caused to form a layer containing the element on the substrate; (a-2) supplying a carbon-containing gas into the process vessel to form a carbon-containing layer on the layer containing the element, thereby forming a layer including the element and a carbon; and (a-3) supplying a nitrogen-containing gas into the process vessel to nitride the layer including the element and the carbon, thereby forming the carbonitride layer.
- a method of manufacturing a semiconductor device including performing a cycle a predetermined number of times to form an oxycarbonitride film having a predetermined thickness on a substrate in a process vessel, wherein the cycle includes steps of:
- a method of manufacturing a semiconductor device including performing a cycle a predetermined number of times to form an oxycarbonitride film having a predetermined thickness on a substrate in a process vessel, wherein the cycle includes steps of:
- a substrate processing apparatus including:
- a process vessel configured to accommodate a substrate
- a heater configured to heat the substrate in the process vessel
- an element-containing gas supply system configured to supply a gas containing an element into the process vessel
- a carbon-containing gas supply system configured to supply a carbon-containing gas into the process vessel
- a nitrogen-containing gas supply system configured to supply a nitrogen-containing gas into the process vessel
- an oxygen-containing gas supply system configured to supply an oxygen-containing gas into the process vessel
- a pressure regulating unit configured to regulate a pressure in the process vessel
- control unit configured to control the heater, the element-containing gas supply system, the carbon-containing gas supply system, the nitrogen-containing gas supply system, the oxygen-containing gas supply system and the pressure regulating unit such that an oxycarbonitride film having a predetermined thickness is formed on the substrate by performing a cycle a predetermined number of times wherein the cycle includes processes of: (a) performing a set of processes a predetermined number of times to form a carbonitride layer having a predetermined thickness on the substrate; and (b) supplying an oxygen-containing gas into the process vessel to oxidize the carbonitride layer having the predetermined thickness, thereby forming an oxycarbonitride layer,
- the set of processes includes: (a-1) supplying a gas containing an element into the process vessel accommodating the substrate under a condition where a CVD reaction is caused to form a layer containing the element on the substrate; (a-2) supplying a carbon-containing gas into the process vessel to form a carbon-containing layer on the layer containing the element, thereby forming a first layer including the element and a carbon; (a-3) supplying the gas containing the element into the process vessel under a condition where a CVD reaction is caused to form a layer containing the element on the first layer including the element and the carbon, thereby forming a second layer containing the element and the carbon; and (a-4) supplying a nitrogen-containing gas into the process vessel to nitride the second layer including the element and the carbon, thereby forming the carbonitride layer.
Abstract
An insulating film having features such as a low dielectric constant, a low etching rate and a high insulating property is formed. An oxycarbonitride film is formed on a substrate by performing a cycle a predetermined number of times, the cycle including: (a) supplying a gas containing an element to the substrate; (b) supplying a carbon-containing gas to the substrate; (c) supplying a nitrogen-containing gas to the substrate; and (d) supplying an oxygen-containing gas to the substrate.
Description
- This application is a divisional application of U.S. patent application Ser. No. 14/036,568 filed on Sep. 25, 2013, which is a divisional application of U.S. patent application Ser. No. 13/083,022, filed Apr. 8, 2011, which issued as U.S. Pat. No. 8,546,272 on Oct. 1, 2013, which claims priority under 35 U.S.C. §119 to Japanese Patent Application Nos. 2010-280421, filed Dec. 16, 2010, and 2010-091327, filed Apr. 12, 2010, in the Japanese Patent Office, the entire contents of which are hereby incorporated by reference.
- The present invention relates to a method of manufacturing a semiconductor device including a process of forming a thin film on a substrate, a method of processing a substrate, and a substrate processing apparatus.
- Processes of manufacturing a semiconductor device includes a process of forming an insulating film such as a silicon oxide (SiO2) film or a silicon nitride (Si3N4) film on a wafer such as a silicon wafer. The SiO2 film is widely used as an insulating film or an interlayer film due to its excellent insulating property and low dielectric property. Also, the Si3N4 film is widely used as an insulating film, a mask film, a charge accumulating film, or a stress control film due to its excellent insulating property, corrosion-resistant property, dielectric property, and film stress controlling property, etc. Technology of adding carbon (C) to these insulating films is also well known in the art (for example, see Patent Document 1). The etching-resistant property of the insulating films may be enhanced by such technology.
- 1. Japanese Patent Laid-Open Publication No. 2005-268699
- However, when C is added to an insulating film, an etching-resistant property of the insulating film is enhanced, but a dielectric constant is increased and a leak-resistant property is deteriorated. That is, since each conventional insulating film has both advantages and disadvantages, there has been no film having all features of a low dielectric constant, a low etching rate and a high insulating property.
- Therefore, it is an object of the present invention to provide a method of manufacturing a semiconductor device, a method of processing a substrate, and a substrate processing apparatus that are capable of forming an insulating film having features such as a low dielectric constant, a low etching rate, and a high insulating property.
- According to one aspect of the present invention, there is provided a substrate processing apparatus comprising: a process vessel configured to accommodate a substrate; an element-containing gas supply system configured to supply a gas containing an element into the process vessel; a carbon-containing gas supply system configured to supply a carbon-containing gas into the process vessel; a nitrogen-containing gas supply system configured to supply a nitrogen-containing gas into the process vessel; an oxygen-containing gas supply system configured to supply an oxygen-containing gas into the process vessel; a heater configured to heat the substrate in the process vessel; and a control unit configured to control the element-containing gas supply system, the carbon-containing gas supply system, the nitrogen-containing gas supply system, the oxygen-containing gas supply system and the heater to form an oxycarbonitride film on the substrate by performing a cycle a predetermined number of times, the cycle including: (a) performing a set a predetermined number of times, the set including: (a-1) supplying the gas containing the element to the substrate; (a-2) supplying the carbon-containing gas to the substrate; and (a-3) supplying the nitrogen-containing gas to the substrate; and (b) supplying the oxygen-containing gas to the substrate, wherein the steps (a-1) through (a-3) are non-simultaneously performed, and the steps (a) and (b) are non-simultaneously performed.
- According to another aspect of the present invention, there is provided a substrate processing apparatus comprising: a process vessel configured to accommodate a substrate; an element-containing gas supply system configured to supply a gas containing an element into the process vessel; a carbon-containing gas supply system configured to supply a carbon-containing gas into the process vessel; a nitrogen-containing gas supply system configured to supply a nitrogen-containing gas into the process vessel; an oxygen-containing gas supply system configured to supply an oxygen-containing gas into the process vessel; a heater configured to heat the substrate in the process vessel; and a control unit configured to control the element-containing gas supply system, the carbon-containing gas supply system, the nitrogen-containing gas supply system, the oxygen-containing gas supply system and the heater to form an oxycarbonitride film on the substrate by performing a cycle a predetermined number of times, the cycle including: (a) performing a set a predetermined number of times, the set including: (a-1) supplying the gas containing the element to the substrate; (a-2) supplying the carbon-containing gas to the substrate; (a-3) supplying the gas containing the element to the substrate; and (a-4) supplying the nitrogen-containing gas to the substrate; and (b) supplying the oxygen-containing gas to the substrate, wherein the steps (a-1) through (a-4) are non-simultaneously performed in order, and the steps (a) and (b) are non-simultaneously performed.
-
FIG. 1 is a configuration diagram schematically illustrating a vertical process furnace of a substrate processing apparatus preferably used in an exemplary embodiment of the present invention, illustrating a longitudinal cross section of the process furnace; -
FIG. 2 is a configuration diagram schematically illustrating the vertical process furnace of the substrate processing apparatus preferably used in the exemplary embodiment of the present invention, illustrating a cross section of the process furnace taken along line A-A ofFIG. 1 ; -
FIG. 3 is a diagram illustrating gas supply timings in a first sequence according to an embodiment of the present invention; -
FIG. 4 is a diagram illustrating gas supply timings in a modified example of the first sequence according to the embodiment of the present invention; -
FIG. 5 is a diagram illustrating gas supply timings in a second sequence according to the embodiment of the present invention; and -
FIG. 6 is a diagram illustrating gas supply timings in a modified example of the second sequence according to the embodiment of the present invention; - Hereinafter, exemplary embodiments of the present invention will be described with reference to the accompanying drawings.
- (1) Configuration of Substrate Processing Apparatus
-
FIG. 1 is a configuration diagram schematically illustrating a vertical process furnace of a substrate processing apparatus preferably used in an exemplary embodiment of the present invention, illustrating a longitudinal cross section of theprocess furnace 202.FIG. 2 is a configuration diagram schematically illustrating the vertical process furnace of the substrate processing apparatus preferably used in the exemplary embodiment of the present invention, illustrating a cross section of theprocess furnace 202 taken along line A-A ofFIG. 1 . - As shown in
FIG. 1 , theprocess furnace 202 includes aheater 207 serving as a heating means (a heating device). Theheater 207 has a cylindrical shape and is supported by a heater base (not shown) serving as a holding plate to be installed vertically. As will be described below, theheater 207 also functions as an activation device configured to activate gas by heat. - A
reaction tube 203 having a shape concentric with theheater 207 and constituting a reaction vessel (a process vessel) is installed inside theheater 207. Thereaction tube 203 is, for example, made of a heat-resistant material such as quartz (SiO2) or silicon carbide (SiC). Thereaction tube 203 has a cylindrical shape with its upper end closed and lower end open. Aprocess chamber 201 is formed in a hollow cylindrical portion of thereaction tube 203. Theprocess chamber 201 is configured to accommodatewafers 200 serving as substrates in a horizontal posture in a state where thewafers 200 are vertically arranged in multiple stages by aboat 217 to be described below. - A
first nozzle 249 a, asecond nozzle 249 b, athird nozzle 249 c, and afourth nozzle 249 d are installed inside theprocess chamber 201 so as to pass through a lower portion of thereaction tube 203. A firstgas supply pipe 232 a, a secondgas supply pipe 232 b, a thirdgas supply pipe 232 c, and a fourthgas supply pipe 232 d are connected to thefirst nozzle 249 a, thesecond nozzle 249 b, thethird nozzle 249 c, and thefourth nozzle 249 d, respectively. In this way, the fournozzles gas supply pipes 232 a. 232 b, 232 c, and 232 d are installed in thereaction tube 203 so that many kinds of gases, for example, four kinds of gases here, may be supplied into theprocess chamber 201. - A mass flow controller (MFC) 241 a, which is a flow rate controller (a flow rate control unit), and a
valve 243 a, which is an opening/closing valve, are installed in the firstgas supply pipe 232 a in order from an upstream side thereof. A first inertgas supply pipe 232 e is connected to a downstream side of thevalve 243 a of the firstgas supply pipe 232 a. AnMFC 241 e, which is a flow rate controller (a flow rate control unit), and avalve 243 e, which is an opening/closing valve, are installed in the first inertgas supply pipe 232 e in order from an upstream side thereof. The above-describedfirst nozzle 249 a is connected to a tip end portion of the firstgas supply pipe 232 a. Thefirst nozzle 249 a is vertically installed in an arc-shaped space between an inner wall of thereaction tube 203 and thewafers 200 in a stacking direction of thewafers 200 along an upper portion from a lower portion of the inner wall of thereaction tube 203. Thefirst nozzle 249 a is formed as an L-shaped long nozzle. Agas supply hole 250 a configured to supply a gas is installed on a side surface of thefirst nozzle 249 a. Thegas supply hole 250 a is opened toward the center of thereaction tube 203. A plurality ofgas supply holes 250 a are installed from a lower portion to an upper portion of thereaction tube 203 to have the same opening area and the same opening pitch. A first gas supply system mainly includes the firstgas supply pipe 232 a, the MFC 241 a, thevalve 243 a, and thefirst nozzle 249 a. A first inert gas supply system mainly includes the first inertgas supply pipe 232 e, the MFC 241 e, and thevalve 243 e. - An
MFC 241 b, which is a flow rate controller (a flow rate control unit), and avalve 243 b, which is an opening/closing valve, are installed in the secondgas supply pipe 232 b in order from an upstream side thereof. A second inertgas supply pipe 232 f is connected to a downstream side of thevalve 243 b of the secondgas supply pipe 232 b. AnMFC 241 f, which is a flow rate controller (a flow rate control unit), and avalve 243 f, which is an opening/closing valve, are installed in the second inertgas supply pipe 232 f in order from an upstream side thereof. The above-describedsecond nozzle 249 b is connected to a tip end portion of the secondgas supply pipe 232 b. Thesecond nozzle 249 b is vertically installed in an arc-shaped space between an inner wall of thereaction tube 203 and thewafers 200 in a stacking direction of thewafers 200 along an upper portion from a lower portion of the inner wall of thereaction tube 203. Thesecond nozzle 249 b is formed as an L-shaped long nozzle. Agas supply hole 250 b configured to supply a gas is installed on a side surface of thesecond nozzle 249 b. Thegas supply hole 250 b is opened toward the center of thereaction tube 203. A plurality of gas supply holes 250 b are installed from a lower portion to an upper portion of thereaction tube 203 to have the same opening area and the same opening pitch. A second gas supply system mainly includes the secondgas supply pipe 232 b, theMFC 241 b, thevalve 243 b, and thesecond nozzle 249 b. Also, a second inert gas supply system mainly includes the second inertgas supply pipe 232 f, theMFC 241 f, and thevalve 243 f. - An
MFC 241 c, which is a flow rate controller (a flow rate control unit), and avalve 243 c, which is an opening/closing valve, are installed in the thirdgas supply pipe 232 c in order from an upstream side thereof. A third inertgas supply pipe 232 g is connected to a downstream side of thevalve 243 c of the thirdgas supply pipe 232 c. AnMFC 241 g, which is a flow rate controller (a flow rate control unit), and avalve 243 g, which is an opening/closing valve, are installed in the third inertgas supply pipe 232 g in order from an upstream side thereof. The above-describedthird nozzle 249 c is connected to a tip end portion of the thirdgas supply pipe 232 c. Thethird nozzle 249 c is vertically installed in an arc-shaped space between an inner wall of thereaction tube 203 and thewafers 200 in a stacking direction of thewafers 200 along an upper portion from a lower portion of the inner wall of thereaction tube 203. Thethird nozzle 249 c is formed as an L-shaped long nozzle. Agas supply hole 250 c configured to supply a gas is installed on a side surface of thethird nozzle 249 c. Thegas supply hole 250 c is opened toward the center of thereaction tube 203. A plurality of gas supply holes 250 c are installed from a lower portion to an upper portion of thereaction tube 203 to have the same opening area and the same opening pitch. A third gas supply system mainly includes the thirdgas supply pipe 232 c, theMFC 241 c, thevalve 243 c, and thethird nozzle 249 c. Also, a third inert gas supply system mainly includes the third inertgas supply pipe 232 g, theMFC 241 g, and thevalve 243 g. - An
MFC 241 d, which is a flow rate controller (a flow rate control unit), and avalve 243 d, which is an opening/closing valve, are installed in the fourthgas supply pipe 232 d in order from an upstream side thereof. A fourth inertgas supply pipe 232 h is connected to a downstream side of thevalve 243 d of the fourthgas supply pipe 232 d. AnMFC 241 h, which is a flow rate controller (a flow rate control unit), and avalve 243 h, which is an opening/closing valve, are installed in the fourth inertgas supply pipe 232 h in order from an upstream side thereof. The above-describedfourth nozzle 249 d is connected to a tip end portion of the fourthgas supply pipe 232 d. Thefourth nozzle 249 d is installed inside abuffer chamber 237, which is a gas dispersing space. - The
buffer chamber 237 is installed in an arc-shaped space between an inner wall of thereaction tube 203 and thewafers 200 in a stacking direction of thewafers 200 from a lower portion to an upper portion of the inner wall of thereaction tube 203. Agas supply hole 250 e configured to supply a gas is installed on an end portion of a wall of thebuffer chamber 237, which is adjacent to thewafers 200. Thegas supply hole 250 e is opened toward the center of thereaction tube 203. A plurality of gas supply holes 250 e are installed from a lower portion to an upper portion of thereaction tube 203 to have the same opening area and the same opening pitch. - The
fourth nozzle 249 d is vertically installed at an end portion opposite to another end portion of thebuffer chamber 237 in which the gas supply holes 250 e are installed, in a stacking direction of thewafers 200 along an upper portion from a lower portion of the inner wall of thereaction tube 203. Thefourth nozzle 249 d is formed as an L-shaped long nozzle. Agas supply hole 250 d configured to supply a gas is installed on a side surface of thefourth nozzle 249 d. Thegas supply hole 250 d is opened toward the center of thebuffer chamber 237. Like the gas supply holes 250 e of thebuffer chamber 237, a plurality of gas supply holes 250 d are installed from a lower portion to an upper portion of thereaction tube 203. When a difference in pressure between the interior of thebuffer chamber 237 and the interior of theprocess chamber 201 is small, the plurality of gas supply holes 250 d may have the same opening area and the same opening pitch from an upstream side (a lower portion) to a downstream side (an upper portion). However, when the difference in pressure is large, each opening area may become larger or each opening pitch may become smaller as the opening area or the opening pitch span from an upstream side toward a downstream side. - In the embodiment of the present invention, gases are injected at different flow velocities but at substantially the same flow rate through the gas supply holes 250 d of the
fourth nozzle 249 d by adjusting the opening areas or opening pitches of the gas supply holes 250 d from an upstream side to a downstream side of thefourth nozzle 249 d as described above. Then, the gas injected through each of the gas supply holes 250 d is first introduced into thebuffer chamber 237, and the difference in the flow velocities of the gas in thebuffer chamber 237 is uniformly adjusted. - That is, after the particle velocity of the gas injected into the
buffer chamber 237 through the gas supply holes 250 d of thefourth nozzle 249 d is lowered in thebuffer chamber 237, the gas is injected into theprocess chamber 201 through the gas supply holes 250 e of thebuffer chamber 237. Accordingly, the gas that has been injected into thebuffer chamber 237 through each of the gas supply holes 250 d of thefourth nozzle 249 d has uniform flow rate and flow velocity when the gas is injected into theprocess chamber 201 through each of the gas supply holes 250 e of thebuffer chamber 237. - A fourth gas supply system mainly includes the fourth
gas supply pipe 232 d, theMFC 241 d, thevalve 243 d, thefourth nozzle 249 d, and thebuffer chamber 237. Also, in the fourth gas supply system, thebuffer chamber 237 functions as a nozzle configured to supply a gas toward thewafers 200. A fourth inert gas supply system mainly includes the fourth inertgas supply pipe 232 h, theMFC 241 h, and thevalve 243 h. - For example, a silicon (Si) source gas, i.e., a gas containing silicon (a silicon-containing gas), is supplied into the
process chamber 201 through the firstgas supply pipe 232 a via theMFC 241 a, thevalve 243 a, and thefirst nozzle 249 a. Hexachlorodisilane (Si2C6, HCD) gas, for example, may be used as the silicon-containing gas. When a liquid material, such as HCD, which is in a liquid state at a normal temperature and under a normal pressure is used, the liquid material is vaporized by a vaporizing system such as a vaporizer or a bubbler to be supplied as a source gas. - For example, a gas containing carbon (C) (a carbon-containing gas) is supplied into the
process chamber 201 through the secondgas supply pipe 232 b via theMFC 241 b, thevalve 243 b, and thesecond nozzle 249 b. Propylene (C3H6) gas, for example, may be used as the carbon-containing gas. Also, a gas containing hydrogen (H) (a hydrogen-containing gas) may be supplied into theprocess chamber 201 through the secondgas supply pipe 232 b via theMFC 241 b, thevalve 243 b, and thesecond nozzle 249 b. Hydrogen (H2) gas, for example, may be used as the hydrogen-containing gas. - For example, a gas containing nitrogen (N) (a nitrogen-containing gas) is supplied into the
process chamber 201 through the thirdgas supply pipe 232 c via theMFC 241 c, thevalve 243 c, and thethird nozzle 249 c. Ammonia (NH3) gas, for example, may be used as the nitrogen-containing gas. - For example, a gas containing oxygen (O) (an oxygen-containing gas) is supplied into the
process chamber 201 through the fourthgas supply pipe 232 d via theMFC 241 d, thevalve 243 d, thefourth nozzle 249 d, and thebuffer chamber 237. Oxygen (O2) gas, for example, may be used as the oxygen-containing gas. - For example, N2 gas is supplied into the
process chamber 201 through the inertgas supply pipes MFCs valves gas supply pipes gas nozzles buffer chamber 237. - For example, when the above-described gases flow through the gas supply pipes, the first gas supply system constitutes a source gas supply system, i.e., a silicon-containing gas supply system (a silane-based gas supply system). Also, the second gas supply system constitutes a carbon-containing gas supply system or a hydrogen-containing gas supply system. Also, the third gas supply system constitutes a nitrogen-containing gas supply system. In addition, the fourth gas supply system constitutes an oxygen-containing gas supply system. The source gas supply system is also simply referred to as a source supply system. When the carbon-containing gas, the hydrogen-containing gas, the nitrogen-containing gas, and the oxygen-containing gas are generally called reaction gases, the carbon-containing gas supply system, the hydrogen-containing gas supply system, the nitrogen-containing gas supply system, and the oxygen-containing gas supply system constitute a reaction gas supply system.
- As shown in
FIG. 2 , a first rod-shapedelectrode 269, i.e., a first electrode, and a second rod-shapedelectrode 270, i.e., a second electrode, each of which has a thin and long structure, are installed inside thebuffer chamber 237 along a stacking direction of thewafers 200 from a lower portion to an upper portion of thereaction tube 203. Each of the first rod-shapedelectrode 269 and the second rod-shapedelectrode 270 is installed in parallel to thefourth nozzle 249 d. Each of the first rod-shapedelectrode 269 and the second rod-shapedelectrode 270 is covered and protected by anelectrode protecting tube 275, which is a protection tube configured to protect the electrodes from upper portions to lower portions thereof. One of the first rod-shapedelectrode 269 and the second rod-shapedelectrode 270 is connected to a high-frequency power source 273 via amatching transformer 272, and the other is connected to a ground, which is a reference potential. As a result, plasma is produced in aplasma producing region 224 between the first rod-shapedelectrode 269 and the second rod-shapedelectrode 270. A plasma source serving as a plasma generator (a plasma generating unit) mainly includes the first rod-shapedelectrode 269, the second rod-shapedelectrode 270, theelectrode protecting tubes 275, the matchingtransformer 272, and the high-frequency power source 273. As described below, the plasma source also functions as an activation device configured to activate gas by plasma. - The
electrode protecting tube 275 is configured such that each of the first rod-shapedelectrode 269 and the second rod-shapedelectrode 270 can be inserted into thebuffer chamber 237 in a state where first rod-shapedelectrode 269 and the second rod-shapedelectrode 270 are separated from an atmosphere of thebuffer chamber 237. Here, when an interior of theelectrode protecting tube 275 has the same atmosphere as an exterior air (atmosphere), the first rod-shapedelectrode 269 and the second rod-shapedelectrode 270 inserted respectively into theelectrode protecting tubes 275 are oxidized by heat of theheater 207. Therefore, an inert gas purge mechanism charged or purged with an inert gas such as nitrogen, restrained to a sufficiently low oxygen concentration, and configured to prevent oxidation of the first rod-shapedelectrode 269 or the second rod-shapedelectrode 270 is installed in the interior of theelectrode protecting tube 275. - An
exhaust pipe 231 configured to exhaust an atmosphere in theprocess chamber 201 is installed in thereaction tube 203. Avacuum pump 246 serving as a vacuum exhaust unit is connected to theexhaust pipe 231 via apressure sensor 245 serving as a pressure detector (a pressure detecting unit) configured to detect a pressure in theprocess chamber 201, and an auto pressure controller (APC)valve 244 serving as a pressure regulator (a pressure regulating unit). Thevacuum pump 246 may vacuum-exhaust theprocess chamber 201 so that a pressure in theprocess chamber 201 becomes a predetermined pressure (vacuum degree). Also, theAPC valve 244 is an opening/closing valve that may vacuum-exhaust an interior of theprocess chamber 201 or stop the vacuum-exhausting of an interior of theprocess chamber 201 as it is opened and closed and may regulate a pressure in theprocess chamber 201 according to an opening degree of thevalve 244. An exhaust system mainly includes theexhaust pipe 231, theAPC valve 244, thevacuum pump 246, and thepressure sensor 245. - A
seal cap 219 serving as a furnace port cover configured to hermetically seal a lower end opening of thereaction tube 203 is installed on a lower portion of thereaction tube 203. Theseal cap 219 is installed to vertically contact a lower end of thereaction tube 203 on the lower side of thereaction tube 203. For example, theseal cap 219 is made of a metal such as stainless steel and has a disk shape. An O-ring 220 serving as a seal member configured to contact the lower end of thereaction tube 203 is installed on an upper surface of theseal cap 219. Aboat rotating mechanism 267 configured to rotate theboat 217 is installed at an opposite side of theprocess chamber 201 with respect to a center of theseal cap 219. Arotary shaft 255 of the boatrotating mechanism 267 passes through theseal cap 219 to be connected to theboat 217 to be described below. Thewafers 200 are rotated by rotating theboat 217. Theseal cap 219 is configured to be vertically elevated by aboat elevator 115 serving as an elevation mechanism vertically installed outside thereaction tube 203 so that theboat 217 can be loaded into theprocess chamber 201 or unloaded from theprocess chamber 201. - The
boat 217 serving as a substrate supporting tool is made of a heat-resistant material, for example, SiO2 or SiC. Theboat 217 is configured to concentrically align a plurality ofwafers 200 in a horizontal posture and support the plurality ofwafers 200 in multiple stages. Also, an insulatingmember 218 made of a heat-resistant material such as SiO2 or SiC is configured to be installed at a lower portion of theboat 217 so that heat from theheater 207 cannot be easily transferred to theseal cap 219. Also, the insulatingmember 218 may include a plurality of insulating plates made of a heat-resistant material such as SiO2 or SiC, and an insulating plate holder configured to support the insulating plates in a horizontal posture in multiple stages. - A
temperature sensor 263 serving as a temperature detector is installed inside thereaction tube 203. Theprocess chamber 201 is configured to have a desired temperature distribution by regulating power supplied to theheater 207 based on temperature information detected by thetemperature sensor 263. Thetemperature sensor 263 is L-shaped similar to thenozzles reaction tube 203. - A
controller 121, which is a control unit (a control means), is connected to theMFCs valves pressure sensor 245, theAPC valve 244, thevacuum pump 246, theheater 207, thetemperature sensor 263, the boatrotating mechanism 267, theboat elevator 115, the high-frequency power source 273, the matchingtransformer 272, etc. Thecontroller 121 controls flow rate regulating operations for various gases by theMFCs valves APC valve 244, a pressure regulating operation of theAPC valve 244 based on thepressure sensor 245, a temperature regulating operation of theheater 207 based on thetemperature sensor 263, starting and stopping of thevacuum pump 246, a rotating speed regulating operation of the boatrotating mechanism 267, an elevating operation of theboat elevator 115, etc., or controls power supply of the high-frequency power source 273 and an impedance of the matchingtransformer 272. - (2) Substrate Processing Process
- Next, a sequence example of forming a silicon oxycarbonitride film (a SiOCN film) serving as an insulating film on a substrate will be described as a process of the processes of manufacturing a semiconductor device using the process furnace of the above-described substrate processing apparatus. In the following description, the operations of the units constituting the substrate processing apparatus are also controlled by the
controller 121. - According to a conventional chemical vapor deposition (CVD) method, a plurality of gases containing a plurality of elements constituting a film to be formed are supplied together at the same time. According to a conventional atomic layer deposition (ALD) method, a plurality of gases containing a plurality of elements constituting a film to be formed are alternately supplied. Then, a SiO2 film or a Si3N4 film is formed by controlling supply conditions such as a flow rate of a supplied gas, a gas supplying time, and a plasma power during the gas supply. For example, the supply conditions are controlled so that, in the case of forming the SiO2 film by the technology, a composition ratio of the SiO2 film becomes a stoichiometric composition ratio of O/Si≈2, and in the case of forming the Si3N4 film, a composition ratio of the Si3N4 film becomes a stoichiometric composition ratio of N/Si≈1.33.
- According to the embodiment of the present invention, a supply condition is controlled so that a composition ratio of a film to be formed becomes a stoichiometric composition ratio or a predetermined composition ratio different from the stoichiometric composition ratio. For example, a supply condition is controlled such that at least one of a plurality of elements constituting a film to be formed becomes a more excessive than the other elements in terms of the stoichiometric composition ratio. Hereinafter, a sequence example of forming a film while controlling a ratio of the plurality of elements constituting a film to be formed, i.e., the composition ratio of the film to be formed, will be described.
- (First Sequence)
- First, a first sequence according to an embodiment of the present invention will be described.
FIG. 3 is a diagram illustrating gas supply timing in a first sequence according to the embodiment of the present invention. - In the first sequence according to the embodiment of the present invention, a SiOCN film having a predetermined thickness is formed on a
wafer 200 by performing, a predetermined number of times (n times), a cycle including the steps of: - (a) supplying a silicon-containing gas into a process vessel accommodating the
wafer 200 under a condition where a CVD reaction is caused to form a silicon-containing layer on thewafer 200; - (b) supplying a carbon-containing gas into the process vessel to form a carbon-containing layer on the silicon-containing layer, thereby forming a layer including Si and C;
- (c) supplying a nitrogen-containing gas into the process vessel to nitride the layer including Si and C, thereby forming a SiCN layer; and
- (d) supplying an oxygen-containing gas into the process vessel to oxidize the SiCN layer, thereby forming a SiOCN layer.
- When starting the study, the inventors thought that SiO would be obtained instead of SiOCN by oxidizing SiCN. This is because the inventors thought that since a binding force of a Si—O bond is stronger than that of a Si—N bond or a Si—C bond of SiCN, the Si—N bond and the Si—C bond of SiCN would be broken and C and N from which Si is broken would be separated from the SiCN while a Si—O bond was formed in an oxidation process.
- Accordingly, when starting the study, the inventors were planning to form SiOCN by alternately repeating deposition of SiCN onto a wafer and deposition of SiO onto SiCN and alternately stacking SiCN and SiO. However, the inventors have made much research and found that SiOCN may be properly formed as C and N separated by oxidation may be left by controlling an oxidizing force (in particular, a dilution rate, a supply time, and a partial pressure of an oxygen-containing gas) during oxidation of SiCN. The present invention is based on these facts acquired by the inventors.
- Hereinafter, the first sequence according to the embodiment of the present invention will be described in detail. Here, an example where a SiOCN film serving as an insulating film is formed on a substrate through the sequence of
FIG. 3 using HCD gas as a silicon-containing gas, C3H6 gas as a carbon-containing gas, NH3 gas as a nitrogen-containing gas, and O2 gas as an oxygen-containing gas will be described. - As shown in
FIG. 1 , when a plurality ofwafers 200 are charged onto the boat 217 (wafer charging), theboat 217 supporting the plurality ofwafers 200 is lifted by theboat elevator 115 and loaded into the process chamber 201 (boat loading). In this state, theseal cap 219 seals a lower end of thereaction tube 203 via the O-ring 220. - An interior of the
process chamber 201 is vacuum-exhausted by thevacuum pump 246 such that a pressure in theprocess chamber 201 becomes a desired pressure (vacuum degree). In this case, the pressure in theprocess chamber 201 is measured by thepressure sensor 245 and theAPC valve 244 is feedback-controlled based on measured pressure information (pressure regulation). Also, an interior of theprocess chamber 201 is heated by theheater 207 so that an temperature in theprocess chamber 201 becomes a desired temperature. In this case, power supplied to theheater 207 is feedback-controlled based on temperature information detected by thetemperature sensor 263 so that the interior of theprocess chamber 201 has a desired temperature distribution (temperature regulation). Subsequently, thewafers 200 are rotated when theboat 217 is rotated by the boat rotating mechanism 267 (wafer rotation). Thereafter, four steps to be described below are sequentially performed. - [First Step]
- The
valve 243 a of the firstgas supply pipe 232 a is opened to flow HCD gas into the firstgas supply pipe 232 a. A flow rate of the HCD gas that flows in the firstgas supply pipe 232 a is regulated by theMFC 241 a. The HCD gas whose flow rate has been regulated is supplied into theprocess chamber 201 through thegas supply hole 250 a of thefirst nozzle 249 a and is exhausted through theexhaust pipe 231. In this case, thevalve 243 e is opened to flow an inert gas such as N2 gas into the inertgas supply pipe 232 e. A flow rate of the N2 gas that flows in the inertgas supply pipe 232 e is regulated by theMFC 241 e. The N2 gas whose flow rate has been regulated is supplied into theprocess chamber 201 together with the HCD gas and exhausted through theexhaust pipe 231. - In this case, a pressure in the
process chamber 201 is set, for example, to a range of 10 to 1,000 Pa by properly regulating theAPC valve 244. A flow rate of supplied HCD gas controlled by the MFC 241 la is set, for example, to a range of 10 to 1,000 sccm. A flow rate of supplied N2 gas controlled by theMFC 241 e is set, for example, to a range of 200 to 2,000 sccm. A time taken to expose thewafer 200 to the HCD gas, i.e., a gas supply time (irradiation time), is set, for example, to a range of 1 to 120 seconds. In this case, a temperature of theheater 207 is set, for example, to a temperature at which a CVD reaction may be caused in theprocess chamber 201, i.e., a temperature at which thewafer 200 has a temperature range of, for example, 300 to 650° C. When the temperature of thewafer 200 is less than 300° C., adsorption of HCD onto thewafer 200 is difficult. Also, when the temperature of thewafer 200 exceeds 650° C., uniformity is deteriorated due to a strong CVD reaction. Thus, the temperature of thewafer 200 is preferably set to a range of 300 to 650° C. - A first layer including Si is formed on an underlayer film on a surface of the
wafer 200 by supplying HCD gas. That is, a Si layer serving as a silicon-containing layer of less than one atomic layer to several atomic layers is formed on the wafer 200 (on the underlayer film). The silicon-containing layer may be a chemical adsorption layer of HCD. Si is an element that becomes solid by itself. Here, in addition to a continuous layer composed of Si, the Si layer includes a discontinuous layer or a thin film formed by overlaying the continuous layer and the discontinuous layer. Also, the continuous layer composed of Si is often referred to as a thin film. The chemical adsorption layer of HCD includes, in addition to a continuous chemical adsorption layer of HCD molecules, a discontinuous chemical adsorption layer of HCD molecules. Also, a layer of less than one atomic layer means a discontinuously formed atomic layer. When a thickness of the silicon-containing layer formed on thewafer 200 exceeds that of several atomic layers, a nitriding operation in a third step to be described below does not affect the entire silicon-containing layer. Also, a minimum value of a silicon-containing layer, which may be formed on thewafer 200, is less than one atomic layer. Thus, a thickness of the silicon-containing layer is preferably set to less than one atomic layer to several atomic layers. Also, Si is deposited on thewafer 200 to form a Si layer under a condition where HCD gas is self-decomposed, whereas HCD is chemically adsorbed on thewafer 200 to form a chemical adsorption layer of HCD under a condition where HCD gas is not self-decomposed. It is more preferable to form a Si layer on thewafer 200 than to form a chemical adsorption layer of HCD on thewafer 200 in order to increase a film-forming rate. - After the silicon-containing layer is formed, the
valve 243 a is closed to stop supply of the HCD gas. In this case, theAPC valve 244 of theexhaust pipe 231 is kept open to vacuum-exhaust the interior of theprocess chamber 201 using thevacuum pump 246, and the residual HCD gas in theprocess chamber 201 which has not reacted or has contributed to formation of the silicon-containing layer is removed from theprocess chamber 201. In this case, thevalve 243 e is kept open to maintain supply of the N2 gas into theprocess chamber 201. Accordingly, the residual HCD gas in theprocess chamber 201 which has not reacted or has contributed to formation of the silicon-containing layer may be effectively removed from theprocess chamber 201. - The silicon-containing gas may be, in addition to the HCD gas, an organic source such as amino silane-based tetrakisdimethylaminosilane (Si[N(CH3)2]4, 4DMAS) gas, trisdimethylaminosilane (Si[N(CH3)2]3H, 3DMAS) gas, bisdiethylaminosilane (Si[N(C2H5)2]2H2, 2DEAS) gas, and bistertiarybutylaminosilane (SiH2[NH(C4H9)]2, BTBAS), as well as an inorganic source such as tetrachlorosilane (SiCl4, STC) gas, trichlorosilane (SiHCl3, TCS) gas, dichlorosilane (SiH2Cl2, DCS) gas, monochlorosilane (SiH3Cl, MCS) gas, and monosilane (SiH4) gas. The inert gas may include a noble gas such as Ar gas, He gas, Ne gas, and Xe gas, in addition to N2 gas.
- [Second Step]
- After the first step is completed and the residual gas in the
process chamber 201 is removed, thevalve 243 b of the secondgas supply pipe 232 b is opened to flow C3H6 gas into the secondgas supply pipe 232 b. A flow rate of the C3H6 gas that flows in the secondgas supply pipe 232 b is regulated by theMFC 241 b. The C3H6 gas whose flow rate has been regulated is supplied into theprocess chamber 201 through agas supply hole 250 b of thesecond nozzle 249 b and is exhausted through theexhaust pipe 231. Also, the C3H6 gas supplied into theprocess chamber 201 is thermally activated. In this case, thevalve 243 f is opened to flow N2 gas into the inertgas supply pipe 232 f at the same time. The N2 gas is supplied into theprocess chamber 201 together with C3H6 gas and is exhausted through theexhaust pipe 231. - In this case, a pressure in the
process chamber 201 is set, for example, to a range of 50 to 3,000 Pa by properly controlling theAPC valve 244. A flow rate of supplied C3H6 gas controlled by theMFC 241 b is set, for example, to a range of 100 to 10,000 sccm. A flow rate of supplied N2 gas controlled by theMFC 241 f is set, for example, to a range of 200 to 2,000 sccm. In this case, a partial pressure of the C3H6 gas in theprocess chamber 201 is regulated to a range of 6 to 2,940 Pa. An exposure time of the C3H6 gas to thewafer 200, i.e., a gas supply time (irradiation time), is set, for example, to a range of 1 to 120 seconds. In this case, a temperature of theheater 207 is set such that the temperature of thewafer 200 becomes 300° C. to 650° C. as in the first step. Since a soft reaction may be caused by thermally activating and supplying the C3H6 gas, a carbon-containing layer to be described below may be easily formed. - In this case, the gas flowing into the
process chamber 201 is thermally activated C3H6 gas, and HCD gas does not flow into theprocess chamber 201. Thus, the C3H6 gas does not cause a vapor phase reaction and is activated and supplied to thewafer 200. In this case, a carbon-containing layer of less than one atomic layer, i.e., a discontinuous carbon-containing layer, is formed on the silicon-containing layer formed on thewafer 200 in the first step. Accordingly, the second layer including Si and C is formed. The second layer including Si and C may be formed by reacting a portion of the silicon-containing layer with the C3H6 gas and modifying (carbonizing) the silicon-containing layer depending on conditions. - The carbon-containing layer formed on the silicon-containing layer may be a C layer or may be a chemical adsorption layer of a carbon-containing gas (C3H6), that is, a chemical adsorption layer of a material (CxHy) produced by decomposing C3H6. Here, the carbon layer needs to be a discontinuous layer composed of C. In addition, the chemical adsorption layer of CxHy needs to be a discontinuous chemical adsorption layer of CxHy molecules. When the carbon-containing layer formed on the silicon-containing layer is a continuous layer, for example, when a continuous chemical adsorption layer of CxHy is formed on a silicon-containing layer with adsorption of CxHy onto the silicon-containing layer being in a saturated state, a surface of the silicon-containing layer is entirely covered with the chemical adsorption layer of CxHy. In this case, since silicon is not present on a surface of the second layer, nitriding the second layer in the third step to be described below is difficult. This is because N binds to Si but does not bind to C. In order to cause a desired nitridation reaction in the third step to be described below, adsorption of CxHy onto the silicon-containing layer is in an unsaturated state, and thus a surface of the second layer needs to be a state where silicon is exposed.
- In order to make the adsorption of CxHy onto the silicon-containing layer in an unsaturated state, the processing conditions in the second step may preferably be set to the above-described processing conditions. Furthermore, when the processing conditions in the second step are set to the following processing conditions, it becomes easy to make an adsorption state of CxHy onto a silicon-containing layer an unsaturated state.
- Temperature of wafer: 500 to 630° C.
- Pressure in process chamber: 133 to 2,666 Pa
- Partial pressure of C3H6 gas: 67 to 2,820 Pa
- Flow rate of supplied C3H6 gas: 1,000 to 5,000 sccm
- Flow rate of supplied N2 gas: 300 to 1,000 sccm
- Supply time of C3H6 gas: 6 to 100 seconds
- Thereafter, the
valve 243 b of the secondgas supply pipe 232 b is closed to stop supply of the C3H6 gas. In this case, theAPC valve 244 of theexhaust pipe 231 is kept open to vacuum-exhaust the interior of theprocess chamber 201 using thevacuum pump 246, and the residual C3H6 gas in theprocess chamber 201 which has not reacted or has contributed to formation of the carbon-containing layer is removed from theprocess chamber 201. In this case, thevalve 243 f is also kept open to maintain supply of the N2 gas into theprocess chamber 201. Accordingly, the residual C3H6 gas in theprocess chamber 201 which has not reacted or has contributed to formation of the carbon-containing layer can be effectively removed from theprocess chamber 201. - The carbon-containing gas may be acetylene (C2H2) gas or ethylene (C2H4) gas in addition to C3H6 gas.
- [Third Step]
- After the residual gas in the
process chamber 201 is removed, thevalve 243 c of the thirdgas supply pipe 232 c is opened to flow NH3 gas into the thirdgas supply pipe 232 c. A flow rate of the NH3 gas that flows in the thirdgas supply pipe 232 c is regulated by theMFC 241 c. The NH3 gas whose flow rate has been regulated is supplied into theprocess chamber 201 through agas supply hole 250 c of thethird nozzle 249 c and is exhausted through theexhaust pipe 231. The NH3 gas supplied into theprocess chamber 201 is thermally activated. In this case, thevalve 243 g is opened to flow the N2 gas into the inertgas supply pipe 232 g at the same time. The N2 gas is supplied into theprocess chamber 201 together with the NH3 gas and is exhausted through theexhaust pipe 231. - In this case, when the NH3 gas is thermally activated and allowed to flow, a pressure in the
process chamber 201 is regulated, for example, to a range of 50 to 3,000 Pa by properly controlling theAPC valve 244. A flow rate of supplied NH3 gas controlled by theMFC 241 c is set, for example, to a range of 100 to 10,000 sccm. A flow rate of supplied N2 gas controlled by theMFC 241 g is set, for example, to a range of 200 to 2,000 sccm. In this case, a partial pressure of the NH3 gas in theprocess chamber 201 is set to a range of 6 to 2,940 Pa. An exposure time of the NH3 gas to thewafer 200, i.e., a gas supply time (irradiation time), is set, for example, to a range of 1 to 120 seconds. In this case, a temperature of theheater 207 is set such that a temperature of thewafer 200 becomes, for example, 300° C. to 650° C. as in the first step. Since the NH3 gas has a high reaction temperature and is difficult to react at the above-described wafer temperature, the NH3 gas may be thermally activated when the pressure in theprocess chamber 201 is relatively high as described above. Since a soft reaction may be caused by thermally activating and supplying the NH3 gas, a nitridation reaction to be described below may be softly performed. - In this case, the gas flowing in the
process chamber 201 is thermally activated NH3 gas, and neither HCD gas nor C3H6 gas flows in theprocess chamber 201. Thus, the NH3 gas does not cause a vapor phase reaction, and the activated NH3 gas reacts with a portion of a layer including Si and C which is the second layer formed on thewafer 200 in the second step. Accordingly, the second layer is thermally nitrided in a non-plasma environment so that the second layer is changed into the third layer including Si, C, and N, i.e., a silicon carbonitride layer (a SiCN layer). - In this case, the nitridation reaction of the second layer is not allowed to be saturated. For example, when a Si layer of several atomic layers is formed in the first step and a carbon-containing layer of less than one atomic layer is formed in the second step, a portion of the surface layer (one atomic layer of the surface) thereof is nitrided. That is, some or all portion of an area (an area where silicon is exposed) where nitridation may be caused of the surface layer thereof is nitrided. In this case, nitridation is performed under a condition where a nitridation reaction of the second layer is unsaturated so that the entire second layer cannot be nitrided. Although several layers below the surface layer of the second layer may be nitrided depending on conditions, only the surface layer is preferably nitrided to enhance the controllability of the composition ratio of the SiOCN film. For example, when a Si layer of one atomic layer or less than one atomic layer is formed in the first step and a carbon-containing layer of less than one atomic layer is formed in the second step, a portion of the surface layer thereof is nitrided likewise. Even in this case, nitridation is also performed under a condition where a nitridation reaction of the second layer is unsaturated so that the second layer cannot be entirely nitrided.
- In order to make the nitridation reaction of the second layer in an unsaturated state, the processing conditions in the third step preferably may be set to the above-described processing conditions. Furthermore, when processing conditions in the third step are set to the following processing conditions, it becomes easy to make a nitridation reaction of the second layer in an unsaturated state.
- Temperature of wafer: 500 to 630° C.
- Pressure in process chamber: 133 to 2,666 Pa
- Partial pressure of NH3 gas: 67 to 2,820 Pa
- Flow rate of supplied NH3 gas: 1,000 to 5,000 sccm
- Flow rate of supplied N2 gas: 300 to 1,000 sccm
- Supply time of NH3 gas: 6 to 100 seconds
- Thereafter, the
valve 243 c of the thirdgas supply pipe 232 c is closed to stop supply of the NH3 gas. In this case, theAPC valve 244 of theexhaust pipe 231 is kept open to vacuum-exhaust the interior of the process chamber using thevacuum pump 246, and the residual NH3 gas in theprocess chamber 201 which has not reacted or has contributed to the nitridation is removed from theprocess chamber 201. In this case, thevalve 243 g is also kept open to maintain supply of the N2 gas into theprocess chamber 201. Accordingly, the residual NH3 gas in theprocess chamber 201 which has not reacted or has contributed to the nitridation may be effectively removed from theprocess chamber 201. - The nitrogen-containing gas may be diazine (N2H2) gas, hydrazine (N2H4) gas or N3H8 gas in addition to NH3 gas.
- [Fourth Step]
- After the residual gas in the
process chamber 201 is removed, thevalve 243 d of the fourthgas supply pipe 232 d and thevalve 243 h of the fourth inertgas supply pipe 232 h are opened to flow the O2 gas into the fourthgas supply pipe 232 d and flow the N2 gas into the fourth inertgas supply pipe 232 h. A flow rate of the N2 gas that flows in the fourth inertgas supply pipe 232 h is regulated by theMFC 241 h. A flow rate of the O2 gas that flows in the fourth gassupply gas pipe 232 d is regulated by theMFC 241 d. In the fourthgas supply pipe 232 d, the O2 gas whose flow rate has been regulated is mixed with the N2 gas whose flow rate has been regulated and is supplied into thebuffer chamber 237 through thegas supply hole 250 d of thefourth nozzle 249 d. In this case, a high-frequency power is not applied between the first rod-shapedelectrode 269 and the second rod-shapedelectrode 270. Accordingly, after the O2 gas supplied into thebuffer chamber 237 is thermally activated, the O2 gas is directed toward thewafer 200 and supplied into theprocess chamber 201 through thegas supply hole 250 e, and is exhausted through theexhaust chamber 231. In this case, the O2 gas supplied into thebuffer chamber 237 may be activated using plasma by applying high-frequency power between the first rod-shapedelectrode 269 and the second rod-shapedelectrode 270. - When the O2 gas is thermally activated and allowed to flow, a pressure in the
process chamber 201 is set, for example, to a range of 1 to 3,000 Pa by properly regulating theAPC valve 244. A flow rate of supplied O2 gas controlled by theMFC 241 d is set, for example, to a range of 100 to 5,000 sccm (0.1 to 5 slm). A flow rate of supplied N2 gas controlled by theMFC 241 h is set, for example, to a range of 200 to 2,000 sccm (0.2 to 2 slm). In this case, a partial pressure of the O2 gas in theprocess chamber 201 is set to a range of 6 to 2,940 Pa. An exposure time of thewafer 200 to the O2 gas, i.e., a gas supply time (irradiation time), is set, for example, to a range of 1 to 120 seconds. In this case, a temperature of theheater 207 is set such that a temperature of thewafer 200 falls within a range of 300 to 650° C. as in the first through third steps. The O2 gas is thermally activated under the above-described conditions. Since a soft reaction may be caused by thermally activating and supplying the O2 gas, an oxidation reaction to be described below may be softly performed. - In this case, the gas flowing into the
process chamber 201 is thermally activated O2 gas, and none of the HCD gas, the C3H6 gas, and the NH3 gas flows in theprocess chamber 201. Thus, the O2 gas does not cause a vapor phase reaction, and the activated O2 gas reacts with a portion of a SiCN layer serving as the third layer formed on thewafer 200 in the third step. Accordingly, the SiCN layer is thermally oxidized in a non-plasma environment so that the SiCN layer is changed into the fourth layer including Si, C, N, and O, i.e., a SiOCN layer. - In this case, the oxidation reaction of the SiCN layer is not allowed to be saturated. For example, when a SiCN layer of several atomic layers is formed in the first through third steps, at least a portion of the surface layer (one atomic layer of the surface) thereof is oxidized. In this case, oxidation is performed under a condition where the oxidation reaction of the SiCN layer is unsaturated such that the SiCN layer cannot be entirely oxidized. Although several layers below the surface layer of the SiCN layer may be oxidized depending on conditions, only the surface layer is preferably oxidized to enhance controllability of the composition ratio of the SiOCN film. For example, when a SiCN layer of one atomic layer or less than one atomic layer is formed in the first through third steps, a portion of the surface layer thereof is oxidized likewise. Even in this case, oxidation is also performed under a condition where an oxidation reaction of the SiCN layer is unsaturated so that the SiCN layer cannot be entirely oxidized.
- In order to make the oxidation reaction of the SiCN layer (third layer) in an unsaturated state, the processing conditions in the fourth step preferably may be set to the above-described processing conditions. Furthermore, when processing conditions in the fourth step are set to the following processing conditions, it becomes easy to make an oxidation reaction of the second layer in an unsaturated state.
- Temperature of wafer: 500 to 630° C.
- Pressure in process chamber: 133 to 2,666 Pa
- Partial pressure of O2 gas: 67 to 2,820 Pa
- Flow rate of supplied O2 gas: 1,000 to 5,000 sccm
- Flow rate of supplied N2 gas: 300 to 1,000 sccm
- Supply time of O2 gas: 6 to 100 seconds
- Thereafter, the
valve 243 d of the fourthgas supply pipe 232 d is closed to stop supply of the O2 gas. In this case, theAPC valve 244 of theexhaust pipe 231 is kept open to vacuum-exhaust the interior of theprocess chamber 201 using thevacuum pump 246, and the residual O2 gas in theprocess chamber 201 which has not reacted or has contributed to oxidation is removed from theprocess chamber 201. In this case, thevalve 243 h is kept open to maintain supply of the N2 gas into theprocess chamber 201. Accordingly, the residual O2 gas in theprocess chamber 201 which has not reacted or has contributed to oxidation may be effectively removed from theprocess chamber 201 - The oxygen-containing gas may include, vapor (H2O) gas, nitrogen monoxide (NO) gas, nitrous oxide (N2O) gas, nitrogen dioxide (NO2) gas, carbon monoxide (CO) gas, carbon dioxide (CO2) gas, ozone (0.3) gas, a mixture of H2 gas and O2 gas, a mixture of H2 gas and O3 gas, etc., in addition to O2 gas.
- A thin film including Si, C, N, and O, i.e., a SiOCN film, having a predetermined thickness may be formed on the
wafer 200 by performing a cycle including the above-described first through fourth steps once or more. The above-described cycle is preferably repeatedly performed a plurality of times. - In this case, ratios of each of the element components in the SiOCN layer, i.e., a Si component, an O component, a C component and a N component, that is, a Si concentration, an O concentration, a C concentration and a N concentration may be regulated by controlling process conditions such as a pressure in the
process chamber 201 or a gas supply time in the respective steps so that a composition ratio of the SiOCN film may be controlled. - A SiOCN film having a predetermined thickness may be formed on the
wafer 200 by performing, once or more, a cycle including a process of carrying out a set of steps including the above-described first through third steps once or more, and a process of carrying out the fourth step afterwards - That is, a SiOCN film having a predetermined thickness may be formed on a
wafer 200 by performing, a predetermined number of times (n times), a cycle including steps of: - (a) performing a set of steps including (a-1) supplying a silicon-containing gas (HCD gas) into a process vessel accommodating the
wafer 200 under a condition where a CVD reaction is caused to form a silicon-containing layer on the wafer 200 (first step), (a-2) supplying a carbon-containing gas (C3H6 gas) into the process vessel to form a carbon-containing layer on the silicon-containing layer, thereby forming a layer containing Si and C (second step), and (a-3) supplying a nitrogen-containing gas into the process vessel to nitride the layer including Si and C, thereby forming a SiCN layer (third step), the set of steps being performed a predetermined number of times (m times) to form the SiCN layer having a predetermined thickness; and - (b) supplying an oxygen-containing gas (O2 gas) into the process vessel to oxidize the SiCN layer having the predetermined thickness, thereby forming a SiOCN layer (fourth step). In this case as well, the above-described cycle is preferably repeated a plurality of times.
-
FIG. 4 exemplifies formation of a SiOCN film having a predetermined thickness on thewafer 200 by performing, n times, a cycle which includes a process of carrying out a set of the first through third steps twice, and a process of carrying out the fourth step afterwards. - In this way, the ratio of a Si component, a C component, and a N component to an O component of a SiOCN film may be controlled properly (in a rich direction) by performing, a predetermined number of times, a cycle including a process of carrying out a set of the first through third steps a predetermined number of times, and a process of carrying out the fourth step afterwards, and thereby the controllability of a composition ratio of the SiOCN film can be enhanced more. The number of SiCN layers formed per cycle may be increased as the set of steps is increased in number, making it possible to enhance a cycle rate. Accordingly, a film-forming rate may be enhanced.
- When a SiOCN film having a predetermined thickness is formed so as to have a predetermined composition, an inert gas such as N2 gas is supplied into the
process chamber 201 and then is exhausted such that the interior of theprocess chamber 201 is purged by the inert gas (gas purging). Thereafter, an atmosphere in theprocess chamber 201 is substituted with the inert gas (inert gas substitution), and a pressure in theprocess chamber 201 is returned to a normal pressure (returning to atmospheric pressure). - Thereafter, as the
seal cap 219 is lowered by theboat elevator 115 and the lower end of thereaction tube 203 is opened, the processedwafer 200 is unloaded (boat unloading) out of thereaction tube 203 from a lower end of thereaction tube 203 in a state where the processedwafer 200 is supported by theboat 217. Thereafter, the processedwafer 200 is discharged from the boat 217 (wafer discharging). - (Second Sequence)
- Next, a second sequence according to the embodiment of the present invention will be described.
FIG. 5 is a timing diagram illustrating gas supply timing in a second sequence according to the embodiment of the present invention. - In the second sequence according to the embodiment of the present invention, a SiOCN film having a predetermined thickness is formed on the
wafer 200 by performing, a predetermined number of times (n times), a cycle including the steps of: (a) supplying a silicon-containing gas into a process vessel accommodating thewafer 200 under a condition where a CVD reaction is caused to form a silicon-containing layer on thewafer 200; - (b) supplying a carbon-containing gas into the process vessel to form a carbon-containing layer on the silicon-containing layer, thereby forming a first layer including Si and C;
- (c) supplying a silicon-containing gas into the process vessel under a condition where a CVD reaction is caused to form a silicon-containing layer on the first layer including Si and C additionally, thereby forming a second layer including Si and C additionally;
- (d) supplying a nitrogen-containing gas into the process vessel to nitride the second layer including Si and C, thereby forming a SiCN layer; and
- (e) supplying an oxygen-containing gas into the process vessel to oxidize the SiCN layer, thereby forming a SiOCN layer.
- Hereinafter, the second sequence according to the embodiment of the present invention will be described in detail. Here, an example where a SiOCN film serving as an insulating film is formed on a substrate through the sequence of
FIG. 5 , using HCD gas as a silicon-containing gas, C3H6 gas as a carbon-containing gas, NH3 gas as a nitrogen-containing gas, and O2 gas as an oxygen-containing gas will be described. - The second sequence is performed in the same manner as in the first second sequence until the wafer charging, the boat loading, the pressure regulation, the temperature regulation and the wafer rotation are performed. Thereafter, five steps to be described below are sequentially performed.
- [First Step]
- The first step is performed in the same manner as in the first step of the first sequence. That is, processing conditions, a reaction to be caused, a layer to be formed, etc. of the first step are the same as those of the first step of the first sequence. That is, in this step, a silicon-containing layer is formed on a
wafer 200 by supplying HCD gas into theprocess chamber 201. - [Second Step]
- The second step is performed in the same manner as in the second step of the first sequence. That is, processing conditions, a reaction to be caused, a layer to be formed, etc. of the second step are the same as those of the second step of the first sequence. That is, in this step, a first layer including Si and C is formed by supplying C3H6 gas into the
process chamber 201 and forming a carbon-containing layer on a silicon-containing layer. - [Third Step]
- The third step is performed in the same manner as in the first step of the first sequence. That is, processing conditions, a reaction to be caused, a layer to be formed, etc. of the third step are the same as those of the first step of the first sequence. That is, in this step, a second layer including Si and C is formed by supplying HCD gas into the
process chamber 201 and forming a silicon-containing layer on the first layer including Si and C. - [Fourth Step]
- The fourth step is performed in the same manner as in the third step of the first sequence. That is, processing conditions, a reaction to be caused, a layer to be formed, etc. of the fourth step are the same as those of the third step of the first sequence. That is, in this step, a SiCN layer is formed by supplying NH3 gas into the
process chamber 201 and nitriding the second layer including Si and C to form a SiCN layer. - [Fifth Step]
- The fifth step is performed in the same manner as in the fourth step of the first sequence. That is, processing conditions, a reaction to be caused, a layer to be formed, etc. of the fifth step are the same as those of the fourth step of the first sequence. That is, in this step, a SiOCN layer is formed by supplying O2 gas into the
process chamber 201 and oxidizing the SiCN layer. - A SiOCN film having a predetermined thickness may be formed on the
wafer 200 by performing a cycle including the above-described first through fifth steps once or more. The above-described cycle is preferably repeated a plurality of times. - In this case, ratios of each of the element components in the SiOCN layer, i.e., a Si component, an O component, a C component and a N component, that is, a Si concentration, an O concentration, a C concentration and a N concentration, may be regulated by controlling process conditions such as a pressure in the
process chamber 201 or a gas supply time in the respective steps so that a composition ratio of the SiOCN film can be controlled. - A SiOCN film having a predetermined thickness may be formed on the
wafer 200 by performing, once or more, a cycle including a process of carrying out a set of steps including the above-described first through fourth steps once or more, and a process of carrying out the fifth step afterwards. - That is, a SiOCN film having a predetermined thickness may be formed on the
wafer 200 by performing, a predetermined number of times (n times), a cycle including steps of: - (a) performing a set of steps including (a-1) supplying a silicon-containing gas (HCD gas) into a process vessel accommodating the
wafer 200 under a condition where a CVD reaction is caused to form a silicon-containing layer on the wafer 200 (first step), (a-2) supplying a carbon-containing gas (C3H6 gas) into the process vessel to form a carbon-containing layer on the silicon-containing layer, thereby forming a first layer including Si and C (second step), (a-3) supplying a silicon-containing gas (HCD gas) into the process vessel under a condition where a CVD reaction is caused to form a silicon-containing layer on the first layer including Si and C additionally, thereby forming a second layer including Si and C (third step), (a-4) supplying a nitrogen-containing gas into the process vessel to nitride the second layer including Si and C, thereby forming a SiCN layer (fourth step), the set of steps being performed a predetermined number of times (m times) to form a SiCN layer having a predetermined thickness; and - (b) supplying an oxygen-containing gas (O2 gas) into the process vessel to oxidize the SiCN layer having the predetermined thickness, thereby forming a SiOCN layer (fifth step). In this case as well, the above-described cycle is preferably repeated a plurality of times.
-
FIG. 6 exemplifies formation of a SiOCN film having a predetermined thickness on thewafer 200 by performing, n times, a cycle which includes a process of carrying out a set of the first through fourth steps twice, and a process of carrying out the fifth step afterwards. - In this way, the ratio of a Si component, a C component, and a N component to an O component of a SiOCN film may be controlled properly (in a rich direction) by performing, a predetermined number of times, a cycle including a process of carrying out a set of the first through fourth steps a predetermined number of times, and a process of carrying out the fifth step afterwards, and thereby the controllability of a composition ratio of the SiOCN film can be enhanced more. The number of SiCN layers formed per cycle may be increased as the set of steps is increased in number, making it possible to enhance a cycle rate. Accordingly, a film-forming rate may be enhanced.
- In the first sequence, HCD gas is supplied at least once per cycle (first step) to form at least one silicon layer per cycle.
- In this regard, in the second sequence, HCD gas may be supplied at least twice per cycle (first step and third step) to form at least two silicon layers per cycle. That is, according to the second sequence, an amount of Si adsorbed and deposited per cycle may be increased as compared with the first sequence (more than two times), making it possible to enhance a cycle rate.
- In the first sequence, when C, i.e., CxHy is adsorbed onto a Si layer by supplying C3H6 gas in the second step, a Si—C bond is created. Thereafter, when N, i.e., NH3 gas, is supplied in the third step, since C and N are apt to competitively gain Si, a portion of the Si—C bond is substituted with Si—N bond. Thus, C may be separated. As a result, an amount of C introduced into a SiCN film, i.e. a C concentration in the SiCN film, may be reduced in the first sequence.
- In this regard, according to the second sequence, C, i.e., CxHy, is adsorbed onto a Si layer by supplying C3H6 gas in the second step and Si is adsorbed and deposited in the third step, resulting in increased probability of forming a Si—C—Si bond. Thereafter, even when N, i.e. NH3 gas, is supplied in the fourth step, an attack of N is blocked by Si forming the Si—C—Si bond, and thus separation of C may be difficult and C may easily remain. As a result, an amount of C introduced to the SiCN, i.e. a C concentration in the SiCN film, is enhanced.
- In the first sequence, both adsorption of CxHy onto the Si layer in the second step and nitridation of the second layer by NH3 gas in the third step need to be stopped when the adsorption and the nitridation are in an unsaturated state. When nitridation of the second layer by NH3 gas in the third step is saturated, a large amount of C is separated and a C concentration in the SiCN film is severely lowered.
- In this regard, as described above, according to the second sequence, CxHy is adsorbed onto a Si layer in the second step and Si is adsorbed and deposited in the third step, causing a probability of forming a Si—C—Si bond to be increased so that the Si forming the Si—C—Si bond functions as a block layer of C against an attack of N in the fourth step. Accordingly, saturating nitridation of the third layer by NH3 gas in the fourth step is possible. That is, a nitriding force may be increased and more uniform nitridation becomes possible while separation of C is being restrained. As a result, uniformity in a film thickness on a wafer surface of a SiCN film may be enhanced.
- When a SiOCN film having a predetermined composition ratio and a predetermined thickness is formed, the gas purging, the inert gas substitution, the returning to the atmospheric pressure, the boat unloading, and the wafer discharging are performed in the same manner as in the first sequence.
- (3) Effects of the Embodiment of the Present Invention
- The embodiment of the present invention has one or plural effects as follows.
- According to the embodiment of the present invention, in the first sequence, the first through fourth steps are sequentially performed in order, or after a set of steps, i.e., the first through third steps, is performed once or more, the fourth step is performed. Thus, a SiOCN film having a predetermined composition ratio and a predetermined thickness may be formed. Further, in the second sequence, the first through fifth steps are sequentially performed in order, or after a set of steps, i.e., the first through fourth steps, is performed once or more, the fifth step is performed. Thus, a SiOCN film having a predetermined composition ratio and a predetermined thickness may be formed.
- It was confirmed that when the order of the steps in the sequences was changed, for example, the first sequence was performed in the order of the first step, the second step, the fourth step, and the third step, a SiOCN film could not be obtained. It was also confirmed that when the first step, the second step, the third step, the fifth step, and the fourth step were sequentially performed in the second sequence, a SiOCN film could not be obtained. This is because since a binding force of a Si—O bond is stronger than that of a Si—N bond, a layer including Si and C may be oxidized after the layer is nitrided, but the layer including Si and C may not be nitrided after the layer is oxidized. This is because, since a Si—O bond is formed after the layer is oxidized, even when NH3 flows in the state, the Si—O bond may not be broken, and thus a Si—N bond may not be formed. It was also confirmed that after oxidation of the layer including Si and C, the layer may not nitrided even when NH3 gas was activated in a plasma environment by a plasma source in the buffer chamber, and a SiOCN film may not be obtained. Accordingly, it was proved that even when the layer including Si and C is nitrided after the layer is oxidized, a SiOCN film may not be obtained, and the layer including Si and C needs to be oxidized after being nitrided to obtain a SiOCN film.
- According to the embodiment of the present invention, a SiOCN film having an excellent uniformity in film thickness in a wafer surface may be formed in any one of the first sequence and the second sequence. When a SiOCN film formed through the first sequence or the second sequence of the embodiment of the present invention is used as an insulating film, it is possible to provide a uniform performance in a surface of the SiOCN film and to contribute to enhancing a performance of a semiconductor device or enhancing a production rate.
- According to the embodiment of the present invention, ratios of each of the element components in the SiOCN layer, i.e., a Si component, an O component, a C component and a N component, that is, a Si concentration, an O concentration, a C concentration and a N concentration, may be regulated by controlling process conditions such as a pressure in the process chamber or a gas supply time in the respective steps so that a composition ratio of the SiOCN film can be controlled.
- Then, in a conventional CVD method, a plurality of kinds of gases including a plurality of elements constituting a thin film to be formed are simultaneously supplied. In this case, in order to control a composition ratio of a formed thin film, controlling the ratio of flow rates of supplied gases during supply of the gases can be considered for example. In this case, a composition ratio of a thin film cannot be controlled even by controlling supply conditions such as a temperature of a substrate, a pressure in the process chamber, and gas supply times during supply of gases.
- Also, in a conventional ALD method, a plurality of kinds of gases containing a plurality of elements constituting a thin film to be formed are alternately supplied. In this case, for example, controlling flow rates of supplied gases and gas supply times during supply of gases may be considered in order to control a composition ratio of a thin film to be formed. In the ALD method, since a source gas is supplied to be adsorbed and saturated onto a surface of a substrate, there is no need to control a pressure in the process chamber. That is, since adsorption and saturation of a source gas occur at a predetermined pressure or less to which the source gas is adsorbed at a reaction temperature, when a pressure in the process chamber is set to the predetermined pressure or less, the adsorption and saturation of the source gas may be achieved at any pressure. Accordingly, when a film is generally formed through the ALD method, the pressure in the process chamber is set to a pressure according to capability of exhausting a substrate processing apparatus with respect to an amount of supplied gas. When the pressure in the process chamber is varied, chemical adsorption of a source gas onto a surface of a substrate may be hampered or a reaction may be close to the CVD reaction, and thus film formation using the ALD method may not be properly performed. Further, since an ALD reaction (saturated adsorption, and surface reaction) is repeatedly performed in order to form a thin film having a predetermined thickness through the ALD method, unless the ALD reactions are sufficiently performed until the ALD reactions are saturated, deposition may become insufficient and deposition rate may not be sufficient. Thus, in the ALD method, it is difficult to control a composition ratio of a thin film by controlling a pressure in the process chamber.
- In this regard, in the embodiment of the present invention, a composition ratio of a thin film is controlled by controlling a pressure in the process chamber or a gas supply time in respective steps in any of the sequences. Preferably, a composition ratio of a thin film may also be controlled by controlling a pressure in the process chamber or the pressure and a gas supply time.
- When a composition ratio of a thin film is controlled by controlling a pressure in the process chamber in respective steps, effects caused by a difference between other substrate processing apparatuses may be reduced. That is, a composition ratio of a thin film may be controlled under the same control conditions and in the same manner even in the other substrate processing apparatuses. In this case, when a gas supply time is controlled in respective steps, a composition ratio of a thin film may be minutely regulated and a controllability of a composition ratio of the thin film may be enhanced. Also by controlling a pressure in the process chamber in respective steps, a composition ratio of a thin film may be controlled while raising a film-forming rate. That is, a composition ratio of a thin film may be controlled by controlling a pressure in the process chamber, for example, while raising a growth rate of a silicon-containing layer formed in the first steps of the respective sequences. In this way, according to the embodiment of the present invention, the composition ratio of the thin film may be controlled under the same control conditions and in the same manner even in the other substrate processing apparatuses, controllability of the composition ratio of the thin film may be enhanced, and the film formation rate, i.e. productivity may also be enhanced.
- Meanwhile, for example, in forming a film through the ALD method, when a composition ratio of a thin film is controlled by controlling a flow rate of supplied gas and a gas supply time in respective steps, effects caused by a difference between other substrate processing apparatuses is increased. That is, the same control is performed to the other substrate processing apparatuses, a composition ratio of a thin film cannot be controlled in the same manner. For example, even when the flow rates of supplied gases and gas supply times in the other substrate processing apparatuses are set to the same flow rates and gas supply times, the pressures in the process chambers do not become the same value due to the difference between the other substrate processing apparatuses. Thus, in this case, as the pressures in the process chambers are changed in the other substrate processing apparatuses, composition ratios in the substrate processing apparatuses cannot be controlled in a desired manner. When the pressures in the process chambers of the substrate processing apparatuses are varied, chemical adsorption of a source gas onto a surface of a substrate may be hampered or reactions may be close to the CVD reactions, and thus a film cannot be properly formed using the ALD method.
- However, since a SiOCN film of a predetermined composition ratio may be formed according to the embodiment of the present invention, an etching-resistant property, a dielectric constant, and an insulation-resistant property may be controlled. Therefore, a silicon insulating film having a low dielectric constant, an excellent etching-resistant property and a excellent insulation-resistant property may be formed, compared to those of the SiN film.
- The C3H6 gas, the NH3 gas, and the O2 gas supplied into the
process chamber 201 are thermally activated respectively and are supplied to a surface of thewafer 200 in the second through fourth steps of the first sequence of this embodiment and in the second, fourth, and fifth steps of the second sequence. Accordingly, since each of the above-described reactions may be softly caused, formation of the carbon-containing layer, nitridation and oxidation can be easily performed with excellent controllability. - The silicon insulating film formed through the technique of the embodiment of the present invention may be used as a side wall spacer, providing a device forming technology with small leak current and excellent processing.
- Also, the silicon insulating film formed through the technique of the embodiment of the present invention may be used as an etch stopper, providing a device forming technology with excellent processing.
- According to the embodiment of the present invention, a silicon insulating film of an ideal stoichiometric ratio can be formed. Further, since a Si insulating film is formed without using plasma, the silicon insulating film may be applied to a process where plasma damage is concerned, for example, on an SADP film of DPT.
- <Another Embodiment of the Present Invention>
- Although the embodiment of the present invention has been described in detail, the present invention is not limited thereto, but may be often modified without departing from the scope of the invention.
- For example, the
buffer chamber 237 may not be installed inside theprocess chamber 201, but O2 gas may be directly supplied into theprocess chamber 201 through thefourth nozzle 249 d. In this case, the O2 gas may be directly supplied toward thewafer 200 through thefourth nozzle 249 d with thegas supply hole 250 d of thefourth nozzle 249 d facing the center of thereaction tube 203. Also, thefourth nozzle 249 d may not be installed, but only thebuffer chamber 237 may be installed. - For example, the C3H6 gas, NH3 gas, and O2 gas supplied into the
process chamber 201 are not limited to be thermally activated, but, for example, may be activated using plasma. In this case, for example, the gases may be plasma-excited using the plasma source serving as the above-described plasma generator. - For example, a hydrogen-containing gas may be supplied together with an oxygen-containing gas in the fourth step of the first sequence and the fifth step of the second sequence. When an oxygen-containing gas and a hydrogen-containing gas are supplied into the process chamber under an atmosphere less than the atmospheric pressure (reduced pressure), the oxygen-containing gas and the hydrogen-containing gas react with each other in the process vessel to produce an oxidant (atomic oxygen etc.) including oxygen, and then the layers may be oxidized by the oxidant. In this case, oxidation can be performed with a higher oxidizing force than with that of a single oxygen-containing gas. The oxidation is performed in the absence of plasma under a reduced pressure atmosphere. For example, H2 gas may be used as the hydrogen-containing gas. In this case, the above-described hydrogen-containing gas supply system may be used.
- For example, in the above-described embodiment of the present invention, an example of forming a SiOCN film (a semiconductor insulating film) including Si serving as a semiconductor element as an insulating film has been explained. However, the present invention may also be applied to a case of forming a metal oxycarbonitride film (a metal insulating film) including a metal element such as titanium (Ti), zirconium (Zr), hafnium (Hf), tantalum (Ta), aluminum (Al), molybdenum (Mo), gallium (Ga), or germanium (Ge).
- For example, the present invention may also be applied to a titanium oxycarbonitride film (a TiOCN film), a zirconium oxycarbonitride film (a ZrOCN film), a hafnium oxycarbonitride film (a HfOCN film), a tantalum oxycarbonitride film (a TaOCN film), an aluminum oxycarbonitride film (an AlOCN film), a molybdenum oxycarbonitride film (a MoOCN film), a gallium oxycarbonitride film (a GaOCN film), or a germanium oxycarbonitride film (a GeOCN film), or a metal oxycarbonitride film obtained by combination or mixture thereof.
- In this case, a film may be formed though the same sequences (first sequence and second sequence) as in the above-described embodiments using Ti source gas, Zr source gas, Hf source gas. Ta source gas, Al source gas, Mo source gas, Ga source gas, or Ge source gas instead of the Si source gas.
- That is, in this case, a metal oxycarbonitride film having a predetermined thickness is, for example, formed on a wafer in the first sequence by performing, a predetermined number of times (n times), a cycle including the steps of:
- (a) supplying a source gas including a metal element into a process vessel accommodating the wafer under a condition where a CVD reaction is caused to form a layer containing the metal element on the wafer (first step),
- (b) supplying a carbon-containing gas into the process vessel to form a carbon-containing layer on the layer containing the metal element, thereby forming a layer including the metal element and the carbon (second step),
- (c) supplying a nitrogen-containing gas into the process vessel to nitride the layer including the metal element and the carbon, thereby forming a metal carbonitride layer (third step); and
- (d) supplying an oxygen-containing gas into the process vessel to oxidize the metal carbonitride layer, thereby forming a metal oxycarbonitride layer (fourth step).
- In this case as well, as in the above-described embodiment of the present invention, the metal oxycarbonitride film having a predetermined thickness may be formed on the wafer by performing, once or more, a cycle which includes a process of carrying out a set of the first through third steps once or more, and a process of carrying out the fourth step afterwards.
- That is, a metal oxycarbonitride film having a predetermined thickness may be formed on a wafer by performing, a predetermined number of times (n times), a cycle including steps of:
- (a) performing a set of steps including (a-1) supplying a source gas including a metal element into a process vessel accommodating the wafer under a condition where a CVD reaction is caused to form a layer containing the metal element on the wafer (first step), (a-2) supplying a carbon-containing gas into the process vessel to form a carbon-containing layer on the layer containing the metal element, thereby forming a layer including the metal element and the carbon (second step), and (a-3) supplying a nitrogen-containing gas into the process vessel to nitride the layer including the metal element and the carbon, thereby forming a metal carbonitride layer (third step), the set of steps being performed a predetermined number of times (m times) to form the metal carbonitride layer having a predetermined thickness; and
- (b) supplying an oxygen-containing gas into the process vessel to oxidize the metal carbonitride layer having the predetermined thickness, thereby forming a metal oxycarbonitride layer (fourth step).
- Also, in this case, a metal oxycarbonitride film having a predetermined thickness is, for example, formed on a wafer in the second sequence by performing, a predetermined number of times (n times), a cycle including the steps of:
- (a) supplying a source gas including a metal element into a process vessel accommodating the wafer under a condition where a CVD reaction is caused to form a layer containing the metal element on the wafer (first step),
- (b) supplying a carbon-containing gas into the process vessel to form a carbon-containing layer on the layer containing the metal element, thereby forming a first layer including the metal element and the carbon (second step),
- (c) supplying a source gas including the metal element into the process vessel under a condition where a CVD reaction is caused to form a layer containing the metal element on the first layer including the metal element and the carbon additionally, thereby forming a second layer including the metal element and the carbon (third step),
- (d) supplying a nitrogen-containing gas into the process vessel to nitride the second layer including the metal element and the carbon, thereby forming a metal carbonitride layer (fourth step), and
- (e) supplying an oxygen-containing gas into the process vessel to oxidize the metal carbonitride layer, thereby forming a metal oxycarbonitride layer (fifth step).
- In this case as well, as in the above-described embodiment of the present invention, a metal oxycarbonitride film having a predetermined thickness may be formed on a wafer by performing, once or more, a cycle which includes a process of carrying out a set of the first through fourth steps once or more, and a process of carrying out the fifth step afterwards.
- That is, a metal oxycarbonitride film having a predetermined thickness may be formed on a wafer by performing, a predetermined number of times (n times), a cycle including steps of:
- (a) performing a set of steps including (a-1) supplying a source gas including a metal element into a process vessel accommodating the wafer under a condition where a CVD reaction is caused to form a layer containing the metal element on the wafer (first step), (a-2) supplying a carbon-containing gas into the process vessel to form a carbon-containing layer on the layer containing the metal element, thereby forming a first layer including the metal element and the carbon (second step), (a-3) supplying a source gas including the metal element into the process vessel under a condition where a CVD reaction is caused to form a layer containing the metal element on the first layer including the metal element and the carbon, thereby forming a second layer including the metal element and the carbon (third step), and (a-4) supplying a nitrogen-containing gas into the process vessel to nidtride the second layer including the metal element and the carbon, thereby forming a metal carbonitride layer (fourth step), the set of steps being performed a predetermined number of times (m times) to form a metal carbonitride layer having a predetermined thickness; and
- (b) supplying an oxygen-containing gas into the process vessel to oxidize the metal carbonitride layer having the predetermined thickness, thereby forming a metal oxycarbonitride layer (fifth step).
- For example, when a TiOCN film is formed as the metal oxycarbonitride film, a source containing Ti may include an organic source such as tetrakisethylmethylaminotitanium (Ti[N(C2H5)(CH3)]4, TEMAT), tetrakisdimethylaminotitanium (Ti[N(CH3)2]4, TDMAT), and tetrakisdiethylaminotitanium (Ti[N(C2H5)2]4, TDEAT), or an inorganic source such as titanium tetrachloride (TiCl4). The same gases described in the embodiment of the present invention may be used as the carbon-containing gas, the nitrogen-containing gas, or the oxygen-containing gas. In this case, the processing conditions may be, for example, set to the same processing conditions as described in the embodiment of the present invention, but a temperature of the wafer is more preferably, for example, in a range of 100 to 500° C. and a pressure in the process chamber is more preferably in a range of 1 to 1,000 Pa.
- Also, for example, when a ZrOCN film is formed as the metal oxycarbonitride film, a source containing Zr may include an organic source such as tetrakisethylmethylaminozirconium (Zr[N(C2H5)(CH3)]4, TEMAZ), tetrakisdimethylaminozirconium (Zr[N(CH3)2]4, TDMAZ), and tetrakisdiethylaminozirconium (Zr[N(C2H5)2]4, TDEAZ), or an inorganic source such as zirconium tetrachloride (ZrCl4). The same gases described in the embodiment of the present invention may be used as the carbon-containing gas, the nitrogen-containing gas, or the oxygen-containing gas. Also, the processing conditions may be, for example, set to the same processing conditions as described in the embodiment of the present invention, but a temperature of the wafer is more preferably, for example, in a range of 100 to 400° C. and a pressure in the process chamber is more preferably in a range of 1 to 1,000 Pa.
- Also, for example, when a HfOCN film is formed as the metal oxycarbonitride film, a source containing Hf may include an organic source such as tetrakisethylmethylaminohafnium (Hf[N(C2H5)CH3)]4, TEMAH), tetrakisdimethylaminohafnium (Hf[N(CH3)2]4, TDMAH), and tetrakisdiethylaminohafnium (Hf[N(C2H5)2]4, TDEAH), or an inorganic source such as hafnium tetrachloride (HfCl4). The same gas described in the embodiment of the present invention may be used as the carbon-containing gas, the nitrogen-containing gas, or the oxygen-containing gas. Also in this case, the processing conditions may be, for example, set to the same processing conditions as described in the embodiment of the present invention, but a temperature of the wafer is more preferably, for example, in a range of 100 to 400° C. and a pressure in the process chamber is more preferably in a range of 1 to 1,000 Pa.
- Also, for example, when an AlOCN film is formed as the metal oxycarbonitride film, a source containing Al may include an organic source such as trimethylaluminum (Al(CH3)3, TMA), or an inorganic source such as trichloroaluminum (AlCl3). The same gas described in the embodiment of the present invention may be used as the carbon-containing gas, the nitrogen-containing gas, or the oxygen-containing gas. Also in this case, the processing conditions may be, for example, set to the same processing conditions as described in the embodiment of the present invention, but a temperature of the wafer is more preferably, for example, in a range of 100 to 400° C. and a pressure in the process chamber is more preferably in a range of 1 to 1,000 Pa.
- In this way, the present invention may be applied to formation of the metal oxycarbonitride film, in which case the same operations and effects as in the embodiment of the present invention can be obtained.
- As described above, the present invention may be applied to the case of forming a oxycarbonitride film containing a certain element such as a semiconductor element or a metal element.
- SiOCN films were formed while controlling composition ratios through the first sequence according to the above-described embodiment and the composition ratios of the SiOCN films and uniformity in film thicknesses in wafer surfaces were measured. HCD gas was used as the silicon-containing gas, C3H6 gas was used as the carbon-containing gas, NH3 gas was used as the nitrogen-containing gas, and O2 gas was used as the oxygen-containing gas. The composition ratios were controlled by regulating factors for controlling the composition ratios, i.e., a pressure, or a pressure and gas supply time (irradiation time). In controlling the composition ratios, the higher the pressure is and the longer the gas supply time is, the higher the reaction is, and thus layers formed in the corresponding steps become thicker or an adsorption amount is increased. That is, the number of atoms given in the corresponding steps becomes larger. In the meantime, when the adsorption of reaction species or a reaction by the reaction species is saturated, there is a case that a film thickness may not become thicker than one atomic layer.
- First, the pressure in the process chamber and the supply time of C3H6 gas in the second step of the first sequence were regulated, and a SiOCN film having a C concentration of approximately 8 atoms % was formed on the wafer. The processing conditions then were set as follows.
- <First Sequence (Reference Processing Condition)>
- (First Step)
- Temperature in process chamber: 630° C.
- Pressure in process chamber: 133 Pa (1 Torr)
- Flow rate of supplied HCD gas: 0.2 slm
- Irradiation time of HCD gas: 6 seconds
- (Second Step)
- Temperature in process chamber: 630° C.
- Pressure in process chamber: 133 Pa (1 Torr)
- Flow rate of supplied C3H6 gas: 1 slm
- Irradiation time of C3H6 gas: 12 seconds
- (Third Step)
- Temperature in process chamber: 630° C.
- Pressure in process chamber: 866 Pa (6.5 Torr)
- Flow rate of supplied NH3 gas: 4.5 slm
- Irradiation time of NH3 gas: 18 seconds
- (Fourth Step)
- Temperature in process chamber: 630° C.
- Pressure in process chamber: 133 Pa (1 Torr)
- Flow rate of supplied O2 gas: 1 slm
- Irradiation time of O2 gas: 18 seconds
- An attempt was made to form a SiOCN film having a C concentration of approximately 16 atoms % by adjusting each processing condition based on the above-described reference processing condition.
- As a result, a SiOCN film having a C concentration of approximately 16 atoms % was obtained by changing a pressure in the process chamber from 133 Pa (1 Torr) to 2394 Pa (18 Torr) in the second step. In this case, it was confirmed that a SiOCN film having a C ratio higher than that of a SiOCN film formed by the reference processing conditions may be formed. That is, it was confirmed that a SiOCN film having a high C ratio may be formed by setting a pressure in the process chamber in the second step to a higher pressure than a pressure in the process chamber with respect to the reference processing conditions. It was also confirmed that as C concentration increases, N concentration decreases. The processing conditions except for the pressure in the process chamber in the second step were set to the same conditions as in the reference processing conditions. That is, the processing conditions in this case were set as follows.
- <First Sequence (change in pressure during supply of C3H, gas)>
- (First Step)
- Temperature in process chamber: 630° C.
- Pressure in process chamber: 133 Pa (1 Torr)
- Flow rate of supplied HCD gas: 0.2 slm
- Irradiation time of HCD gas: 6 seconds
- (Second Step)
- Temperature in process chamber: 630° C.
- Pressure in process chamber: 2,394 Pa (18 Torr)
- Flow rate of supplied C3H6 gas: 1 slm
- Irradiation time of C3H6 gas: 12 seconds
- (Third Step)
- Temperature in process chamber: 630° C.
- Pressure in process chamber: 866 Pa (6.5 Torr)
- Flow rate of supplied NH3 gas: 4.5 slm
- Irradiation time of NH3 gas: 18 seconds
- (Fourth Step)
- Temperature in process chamber: 630° C.
- Pressure in process chamber: 133 Pa (1 Torr)
- Flow rate of supplied O2 gas: 1 slm
- Irradiation time of O2 gas: 18 seconds
- It was also confirmed that, even when an irradiation time of C3H6 gas is changed from 12 seconds to 96 seconds in the second step, a SiOCN film having a C concentration of approximately 16 atoms % is obtained, which indicates that a SiOCN film having a C ratio higher than that of a SiOCN film formed by the reference processing conditions may be formed. That is, it was confirmed that, even when an irradiation time of C3H6 gas in the second step is longer than that of C3H6 gas with respect to the reference processing conditions, a SiOCN film having a high C ratio may be formed. It was also confirmed that as C concentration increases, N concentration decreases. The processing conditions other than the irradiation time of C3H6 gas in the second step were set to the same conditions as in the reference processing conditions. That is, the processing conditions in this case were set as follows.
- <First Sequence (change in irradiation time during supply of C3H6 gas)>
- (First Step)
- Temperature in process chamber: 630° C.
- Pressure in process chamber: 133 Pa (1 Torr)
- Flow rate of supplied HCD gas: 0.2 slm
- Irradiation time of HCD gas: 6 seconds
- (Second Step)
- Temperature in process chamber: 630° C.
- Pressure in process chamber: 133 Pa (1 Torr)
- Flow rate of supplied C3H6 gas: 1 slm
- Irradiation time of C3H6 gas: 96 seconds
- (Third Step)
- Temperature in process chamber: 630° C.
- Pressure in process chamber: 866 Pa (6.5 Torr)
- Flow rate of supplied NH3 gas: 4.5 slm
- Irradiation time of NH3 gas: 18 seconds
- (Fourth Step)
- Temperature in process chamber: 630° C.
- Pressure in process chamber: 133 Pa (1 Torr)
- Flow rate of supplied O2 gas: 1 slm
- Irradiation time of O2 gas: 18 seconds
- In this case, all the uniformities in film thickness on wafer surfaces of formed SiOCN films were less than ±1.5%, which is an excellent result. The uniformity in film thickness on the wafer surface represents a deviation degree of film thickness distribution on the wafer surface, and as the deviation degree is smaller, the uniformity in film thickness distribution on the wafer surface is excellent.
- According to the embodiment of the present invention, it can be seen that a SiOCN film having an excellent uniformity in film thickness on the wafer surface may be formed. In addition, it can be seen that when a SiOCN film according to the embodiment of the present invention is used as the insulating film, a surface of the SiOCN film may be endowed with uniform performance, thereby contributing to enhanced performance of a semiconductor device or enhanced yield rate
- When the third step and the fourth step of the first sequence according to the above-described embodiment of the present invention were performed in a random order to form a film, a SiOCN film was not formed on the wafer. That is, it was confirmed that when film formation was performed in the order of the first step, the second step, the fourth step, and the third step, a SiOCN film could not be obtained. The processing conditions in each step are set to the same processing conditions as the processing conditions (reference processing conditions) in each step of the embodiment. Accordingly, it was revealed that even when a layer including Si and C formed in the first and second steps is oxidized and then nitrided, a SiOCN film cannot be obtained, and a layer containing Si and C formed in the first and second steps needs to be oxidized after being nitrided in order to obtain a SiOCN film.
- <Preferred Aspects of the Invention>
- Hereinafter, preferred aspects according to the present invention will be additionally stated.
- According to one aspect to the present invention, there is provided a method of manufacturing a semiconductor device including performing a cycle a predetermined number of times to form an oxycarbonitride film having a predetermined thickness on a substrate in a process vessel, wherein the cycle includes steps of:
- (a) performing a set of steps a predetermined number of times to form a carbonitride layer having a predetermined thickness on the substrate; and
- (b) supplying an oxygen-containing gas into the process vessel to oxidize the carbonitride layer having the predetermined thickness, thereby forming an oxycarbonitride layer,
- wherein the set of steps includes:
- (a-1) supplying a gas containing an element into the process vessel accommodating the substrate under a condition where a CVD reaction is caused to form a layer containing the element on the substrate;
- (a-2) supplying a carbon-containing gas into the process vessel to form a carbon-containing layer on the layer containing the element, thereby forming a layer including the element and a carbon; and
- (a-3) supplying a nitrogen-containing gas into the process vessel to nitride the layer including the element and the carbon, thereby forming the carbonitride layer.
- Preferably, in the step (b), the carbonitride layer having the predetermined thickness is thermally oxidized under a condition where an oxidation reaction of the carbonitride layer having the predetermined thickness caused by the oxygen-containing gas is unsaturated.
- Preferably, in the step (a-2), a discontinuous chemical adsorption layer is formed as the carbon-containing layer on the layer containing the element,
- in the step (a-3), the layer including the element and the carbon is thermally nitrided under a condition where a nitridation reaction of the layer including the element and the carbon caused by the nitrogen-containing gas is unsaturated, and
- in the step (b), the carbonitride layer having the predetermined thickness is thermally oxidized under a condition where an oxidation reaction of the carbonitride layer having the predetermined thickness caused by the oxygen-containing gas is unsaturated.
- Preferably, in the step (a-1), a deposition layer of the element is formed as the layer containing the element on the substrate,
- in the step (a-2), a discontinuous chemical adsorption layer is formed as the carbon-containing layer on the layer containing the element,
- in the step (a-3), the layer including the element and the carbon is thermally nitrided under a condition where a nitridation reaction of the layer including the element and the carbon caused by the nitrogen-containing gas is unsaturated, and
- in the step (b), the carbonitride layer having the predetermined thickness is thermally oxidized under a condition where an oxidation reaction of the carbonitride layer having the predetermined thickness caused by the oxygen-containing gas is unsaturated.
- Preferably, a composition of the oxycarbonitride film is adjusted by controlling a pressure in the process vessel, or the pressure and a gas supply time in at least one of the steps.
- Preferably, at least one of concentrations of the element, the carbon, a nitrogen and an oxygen in the oxycarbonitride film is adjusted by controlling a pressure in the process vessel, or the pressure and a gas supply time in at least one of the steps.
- Preferably, the element includes a semiconductor element or a metal element.
- Preferably, the element is a silicon.
- According to another aspect to the present invention, there is provided a method of manufacturing a semiconductor device including performing a cycle a predetermined number of times to form a silicon oxycarbonitride film having a predetermined thickness on a substrate in a process vessel, wherein the cycle includes steps of:
- (a) performing a set of steps a predetermined number of times to form a silicon carbonitride layer having a predetermined thickness on the substrate; and
- (b) supplying an oxygen-containing gas into the process vessel to oxidize the silicon carbonitride layer having the predetermined thickness, thereby forming a silicon oxycarbonitride layer,
- wherein the set of steps includes:
- (a-1) supplying a silicon-containing gas into the process vessel accommodating the substrate under a condition where a CVD reaction is caused to form a silicon-containing layer on the substrate;
- (a-2) supplying a carbon-containing gas into the process vessel to form a carbon-containing layer on the silicon-containing layer, thereby forming a layer including a silicon and a carbon; and
- (a-3) supplying a nitrogen-containing gas into the process vessel to nitride the layer including the silicon and the carbon, thereby forming the silicon carbonitride layer.
- Preferably, in the step (b), the silicon carbonitride layer having the predetermined thickness is thermally oxidized under a condition where an oxidation reaction of the silicon carbonitride layer having the predetermined thickness caused by the oxygen-containing gas is unsaturated.
- Preferably, in the step (a-2), a discontinuous chemical adsorption layer is formed as the carbon-containing layer on the silicon-containing layer,
- in the step (a-3), the layer including the silicon and the carbon is thermally nitrided under a condition where a nitridation reaction of the layer including the silicon and the carbon caused by the nitrogen-containing gas is unsaturated, and
- in the step (b), the silicon carbonitride layer having the predetermined thickness is thermally oxidized under a condition where an oxidation reaction of the silicon carbonitride layer having the predetermined thickness caused by the oxygen-containing gas is unsaturated.
- Preferably, in the step (a-1), a deposition layer of the silicon is formed as the silicon-containing layer on the substrate,
- in the step (a-2), a discontinuous chemical adsorption layer is formed as the carbon-containing layer on the silicon-containing layer,
- in the step (a-3), the layer including the silicon and the carbon is thermally nitrided under a condition where a nitridation reaction of the layer including the silicon and the carbon caused by the nitrogen-containing gas is unsaturated, and
- in the step (b), the silicon carbonitride layer having the predetermined thickness is thermally oxidized under a condition where an oxidation reaction of the silicon carbonitride layer having the predetermined thickness caused by the oxygen-containing gas is unsaturated.
- Preferably, a composition of the silicon oxycarbonitride film is adjusted by controlling a pressure in the process vessel, or the pressure and a gas supply time in at least one of the steps.
- Preferably, at least one of concentrations of the silicon, the carbon, a nitrogen and an oxygen in the silicon oxycarbonitride film is adjusted by controlling a pressure in the process vessel, or the pressure and a gas supply time in at least one of the steps.
- According to still another aspect of the present invention, there is provided a method of manufacturing a semiconductor device including performing a cycle a predetermined number of times to form an oxycarbonitride film having a predetermined thickness on a substrate in a process vessel, wherein the cycle includes steps of:
- (a) supplying a gas containing an element into the process vessel accommodating the substrate under a condition where a CVD reaction is caused to form a layer containing the element on the substrate;
- (b) supplying a carbon-containing gas into the process vessel to form a carbon-containing layer on the layer containing the element, thereby forming a layer including the element and a carbon;
- (c) supplying a nitrogen-containing gas into the process vessel to nitride the layer including the element and the carbon, thereby forming a carbonitride layer; and
- (d) supplying an oxygen-containing gas into the process vessel to oxidize the carbonitride layer having the predetermined thickness, thereby forming an oxycarbonitride layer.
- According to yet another aspect of the present invention, there is provided a method of manufacturing a semiconductor device including performing a cycle a predetermined number of times to form a silicon oxycarbonitride film having a predetermined thickness on a substrate in a process vessel, wherein the cycle includes steps of:
- (a) supplying a silicon-containing gas into the process vessel accommodating the substrate under a condition where a CVD reaction is caused to form a silicon-containing layer on the substrate;
- (b) supplying a carbon-containing gas into the process vessel to form a carbon-containing layer on the silicon-containing layer, thereby forming a layer including the silicon and a carbon;
- (c) supplying a nitrogen-containing gas into the process vessel to nitride the layer including the silicon and the carbon, thereby forming a silicon carbonitride layer; and
- (d) supplying an oxygen-containing gas into the process vessel to oxidize the silicon carbonitride layer having the predetermined thickness, thereby forming a silicon oxycarbonitride layer.
- According to yet another aspect of the present invention, there is provided a method of processing a substrate including performing a cycle a predetermined number of times to form an oxycarbonitride film having a predetermined thickness on a substrate in a process vessel, wherein the cycle includes steps of:
- (a) performing a set of steps a predetermined number of times to form a carbonitride layer having a predetermined thickness on the substrate: and
- (b) supplying an oxygen-containing gas into the process vessel to oxidize the carbonitride layer having the predetermined thickness, thereby forming an oxycarbonitride layer,
- wherein the set of steps includes:
- (a-1) supplying a gas containing an element into the process vessel accommodating the substrate under a condition where a CVD reaction is caused to form a layer containing the element on the substrate;
- (a-2) supplying a carbon-containing gas into the process vessel to form a carbon-containing layer on the layer containing the element, thereby forming a layer including the element and a carbon; and
- (a-3) supplying a nitrogen-containing gas into the process vessel to nitride the layer including the element and the carbon, thereby forming the carbonitride layer.
- According to yet another aspect of the present invention, there is provided a substrate processing apparatus including:
- a process vessel configured to accommodate a substrate;
- a heater configured to heat the substrate in the process vessel;
- an element-containing gas supply system configured to supply a gas containing an element into the process vessel;
- a carbon-containing gas supply system configured to supply a carbon-containing gas into the process vessel;
- a nitrogen-containing gas supply system configured to supply a nitrogen-containing gas into the process vessel;
- an oxygen-containing gas supply system configured to supply an oxygen-containing gas into the process vessel;
- a pressure regulating unit configured to regulate a pressure in the process vessel; and
- a control unit configured to control the heater, the element-containing gas supply system, the carbon-containing gas supply system, the nitrogen-containing gas supply system, the oxygen-containing gas supply system and the pressure regulating unit such that an oxycarbonitride film having a predetermined thickness is formed on the substrate by performing a cycle a predetermined number of times wherein the cycle includes processes of: (a) performing a set of processes a predetermined number of times to form a carbonitride layer having a predetermined thickness on the substrate; and (b) supplying an oxygen-containing gas into the process vessel to oxidize the carbonitride layer having the predetermined thickness, thereby forming an oxycarbonitride layer,
- wherein the set of processes includes: (a-1) supplying a gas containing an element into the process vessel accommodating the substrate under a condition where a CVD reaction is caused to form a layer containing the element on the substrate; (a-2) supplying a carbon-containing gas into the process vessel to form a carbon-containing layer on the layer containing the element, thereby forming a layer including the element and a carbon; and (a-3) supplying a nitrogen-containing gas into the process vessel to nitride the layer including the element and the carbon, thereby forming the carbonitride layer.
- According to yet another aspect of the present invention, there is provided a method of manufacturing a semiconductor device including performing a cycle a predetermined number of times to form an oxycarbonitride film having a predetermined thickness on a substrate in a process vessel, wherein the cycle includes steps of:
- (a) performing a set of steps a predetermined number of times to form a carbonitride layer having a predetermined thickness on the substrate; and
- (b) supplying an oxygen-containing gas into the process vessel to oxidize the carbonitride layer having the predetermined thickness, thereby forming an oxycarbonitride layer,
- wherein the set of steps includes:
- (a-1) supplying a gas containing an element into the process vessel accommodating the substrate under a condition where a CVD reaction is caused to form a layer containing the element on the substrate;
- (a-2) supplying a carbon-containing gas into the process vessel to form a carbon-containing layer on the layer containing the element, thereby forming a first layer including the element and a carbon;
- (a-3) supplying the gas containing the element into the process vessel under a condition where a CVD reaction is caused to form a layer containing the element on the first layer including the element and the carbon, thereby forming a second layer containing the element and the carbon; and
- (a-4) supplying a nitrogen-containing gas into the process vessel to nitride the second layer including the element and the carbon, thereby forming the carbonitride layer.
- According to yet another aspect of the present invention, there is provided a method of manufacturing a semiconductor device including performing a cycle a predetermined number of times to form an oxycarbonitride film having a predetermined thickness on a substrate in a process vessel, wherein the cycle includes steps of:
- (a) supplying a gas containing an element into the process vessel accommodating the substrate under a condition where a CVD reaction is caused to form a layer containing the element on the substrate;
- (b) supplying a carbon-containing gas into the process vessel to form a carbon-containing layer on the layer containing the element, thereby forming a first layer including the element and a carbon;
- (c) supplying the gas containing the element into the process vessel under a condition where a CVD reaction is caused to form a layer containing the element on the first layer including the element and the carbon, thereby forming a second layer containing the element and the carbon;
- (d) supplying a nitrogen-containing gas into the process vessel to nitride the second layer including the element and the carbon, thereby forming the carbonitride layer, and
- (e) supplying an oxygen-containing gas into the process vessel to oxidize the carbonitride layer having the predetermined thickness, thereby forming an oxycarbonitride layer.
- According to yet another aspect of the present invention, there is provided a substrate processing apparatus including:
- a process vessel configured to accommodate a substrate;
- a heater configured to heat the substrate in the process vessel;
- an element-containing gas supply system configured to supply a gas containing an element into the process vessel;
- a carbon-containing gas supply system configured to supply a carbon-containing gas into the process vessel;
- a nitrogen-containing gas supply system configured to supply a nitrogen-containing gas into the process vessel;
- an oxygen-containing gas supply system configured to supply an oxygen-containing gas into the process vessel;
- a pressure regulating unit configured to regulate a pressure in the process vessel; and
- a control unit configured to control the heater, the element-containing gas supply system, the carbon-containing gas supply system, the nitrogen-containing gas supply system, the oxygen-containing gas supply system and the pressure regulating unit such that an oxycarbonitride film having a predetermined thickness is formed on the substrate by performing a cycle a predetermined number of times wherein the cycle includes processes of: (a) performing a set of processes a predetermined number of times to form a carbonitride layer having a predetermined thickness on the substrate; and (b) supplying an oxygen-containing gas into the process vessel to oxidize the carbonitride layer having the predetermined thickness, thereby forming an oxycarbonitride layer,
- wherein the set of processes includes: (a-1) supplying a gas containing an element into the process vessel accommodating the substrate under a condition where a CVD reaction is caused to form a layer containing the element on the substrate; (a-2) supplying a carbon-containing gas into the process vessel to form a carbon-containing layer on the layer containing the element, thereby forming a first layer including the element and a carbon; (a-3) supplying the gas containing the element into the process vessel under a condition where a CVD reaction is caused to form a layer containing the element on the first layer including the element and the carbon, thereby forming a second layer containing the element and the carbon; and (a-4) supplying a nitrogen-containing gas into the process vessel to nitride the second layer including the element and the carbon, thereby forming the carbonitride layer.
Claims (18)
1. A substrate processing apparatus comprising:
a process vessel configured to accommodate a substrate;
an element-containing gas supply system configured to supply a gas containing an element into the process vessel;
a carbon-containing gas supply system configured to supply a carbon-containing gas into the process vessel;
a nitrogen-containing gas supply system configured to supply a nitrogen-containing gas into the process vessel;
an oxygen-containing gas supply system configured to supply an oxygen-containing gas into the process vessel;
a heater configured to heat the substrate in the process vessel; and
a control unit configured to control the element-containing gas supply system, the carbon-containing gas supply system, the nitrogen-containing gas supply system, the oxygen-containing gas supply system and the heater to form an oxycarbonitride film on the substrate by performing a cycle a predetermined number of times, the cycle including:
(a) performing a set a predetermined number of times, the set including: (a-1) supplying the gas containing the element to the substrate; (a-2) supplying the carbon-containing gas to the substrate; and (a-3) supplying the nitrogen-containing gas to the substrate; and
(b) supplying the oxygen-containing gas to the substrate,
wherein the processes (a-1) through (a-3) are non-simultaneously performed, and the processes (a) and (b) are non-simultaneously performed.
2. The apparatus of claim 1 , wherein the control unit is configured to control the element-containing gas supply system and the heater to form a layer containing the element having a thickness ranging from less than one atomic layer to several atomic layers in the process (a-1).
3. The apparatus of claim 1 , wherein the control unit is configured to control the element-containing gas supply system and the heater to form a continuous layer containing the element, a discontinuous layer containing the element or a layer formed by overlaying the continuous layer and the discontinuous layer in the process (a-1).
4. The apparatus of claim 1 , wherein the control unit is configured to control the element-containing gas supply system and the heater to form a deposition layer by depositing the element in the process (a-1), and the deposition layer comprises a continuous deposition layer containing the element, a discontinuous deposition layer containing the element or a layer formed by overlaying the continuous deposition layer and the discontinuous deposition layer.
5. The apparatus of claim 1 , wherein the control unit is configured to control the element-containing gas supply system and the heater to form a continuous chemical adsorption layer of the gas containing the element or a discontinuous chemical adsorption layer of the gas containing the element in the process (a-1).
6. The apparatus of claim 1 , wherein the control unit is configured to control the carbon-containing gas supply system and the heater to form a discontinuous chemical adsorption layer of the carbon-containing gas in the process (a-2).
7. The apparatus of claim 1 , wherein the control unit is configured to control the nitrogen-containing gas supply system and the heater to thermally nitride a layer formed on the substrate under a condition where a nitridation reaction of the layer by the nitrogen-containing gas is unsaturated in the process (a-3).
8. The apparatus of claim 1 , wherein the control unit is configured to control the oxygen-containing gas supply system and the heater to thermally oxidize a layer formed on the substrate under a condition where an oxidation reaction of the layer by the oxygen-containing gas is unsaturated in the process (b).
9. The apparatus of claim 1 , wherein the control unit is configured to control the element-containing gas supply system, the carbon-containing gas supply system, the nitrogen-containing gas supply system, the oxygen-containing gas supply system and the heater to perform the cycle including the set and the process (b) one or more times wherein the set is performed one or more times.
10. The apparatus of claim 1 , wherein the control unit is configured to control the element-containing gas supply system, the carbon-containing gas supply system, the nitrogen-containing gas supply system, the oxygen-containing gas supply system and the heater to alternately perform the set and the process (b) one or more times, wherein the set is performed one or more times.
11. The apparatus of claim 1 , wherein the control unit is configured to control the element-containing gas supply system, the carbon-containing gas supply system, the nitrogen-containing gas supply system, the oxygen-containing gas supply system and the heater to perform each of the processes (a-1), (a-2), (a-3) and (b) under non-plasma atmosphere.
12. The apparatus of claim 1 , wherein the control unit is configured to control the element-containing gas supply system, the carbon-containing gas supply system, the nitrogen-containing gas supply system, the oxygen-containing gas supply system and the heater to supply each gas in thermally activated state to the substrate in the processes (a-1), (a-2), (a-3) and (b).
13. The apparatus of claim 1 , further comprising a pressure regulating unit configured to regulate a pressure in the process vessel,
and the control unit is configured to control the element-containing gas supply system, the carbon-containing gas supply system, the nitrogen-containing gas supply system, the oxygen-containing gas supply system, the heater and the pressure regulating unit to adjust a composition of the oxycarbonitride film by controlling an inner pressure of the process vessel, or by controlling the inner pressure and a gas supply time in at least one of the processes (a-1), (a-2), (a-3) and (b).
14. The apparatus of claim 1 , further comprising a pressure regulating unit configured to regulate a pressure in the process vessel,
and the control unit is configured to control the element-containing gas supply system, the carbon-containing gas supply system, the nitrogen-containing gas supply system, the oxygen-containing gas supply system, the heater and the pressure regulating unit to adjust concentration of at least one of the element, carbon, nitrogen and oxygen in the oxycarbonitride film by controlling an inner pressure of the process vessel, or by controlling the inner pressure and a gas supply time in at least one of the processes (a-1), (a-2), (a-3) and (b).
15. The apparatus of claim 1 , wherein the control unit is configured to control the element-containing gas supply system, the carbon-containing gas supply system, the nitrogen-containing gas supply system, the oxygen-containing gas supply system and the heater to perform the processes (a-1) through (a-3) and (b) separately.
16. The apparatus of claim 1 , wherein the control unit is configured to control the element-containing gas supply system, the carbon-containing gas supply system, the nitrogen-containing gas supply system, the oxygen-containing gas supply system and the heater to perform the processes (a-1) through (a-3) and (b) without mixing the gas containing the element, the carbon-containing gas, the nitrogen-containing gas and the oxygen-containing gas with one another.
17. The apparatus of claim 1 , wherein the control unit is configured to control the element-containing gas supply system, the carbon-containing gas supply system, the nitrogen-containing gas supply system, the oxygen-containing gas supply system and the heater to perform the processes (a-1) through (a-3) and (b) separately by performing gas substitution processes between the processes (a-1) and (a-2), the processes (a-2) and (a-3), the processes (a-3) and (b) and the processes (b) and (a-1)
18. A substrate processing apparatus comprising:
a process vessel configured to accommodate a substrate;
an element-containing gas supply system configured to supply a gas containing an element into the process vessel;
a carbon-containing gas supply system configured to supply a carbon-containing gas into the process vessel;
a nitrogen-containing gas supply system configured to supply a nitrogen-containing gas into the process vessel;
an oxygen-containing gas supply system configured to supply an oxygen-containing gas into the process vessel;
a heater configured to heat the substrate in the process vessel; and
a control unit configured to control the element-containing gas supply system, the carbon-containing gas supply system, the nitrogen-containing gas supply system, the oxygen-containing gas supply system and the heater to form an oxycarbonitride film on the substrate by performing a cycle a predetermined number of times, the cycle including:
(a) performing a set a predetermined number of times, the set including: (a-1) supplying the gas containing the element to the substrate; (a-2) supplying the carbon-containing gas to the substrate; (a-3) supplying the gas containing the element to the substrate; and (a-4) supplying the nitrogen-containing gas to the substrate; and
(b) supplying the oxygen-containing gas to the substrate,
wherein the processes (a-1) through (a-4) are non-simultaneously performed in order, and the processes (a) and (b) are non-simultaneously performed.
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