US20060231028A1 - Method for depositing metallic nitride series thin film - Google Patents

Method for depositing metallic nitride series thin film Download PDF

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US20060231028A1
US20060231028A1 US11/446,395 US44639506A US2006231028A1 US 20060231028 A1 US20060231028 A1 US 20060231028A1 US 44639506 A US44639506 A US 44639506A US 2006231028 A1 US2006231028 A1 US 2006231028A1
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gas
thin film
tin
process vessel
vessel
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Hayashi Otsuki
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    • H01L28/40—Capacitors
    • H01L28/55—Capacitors with a dielectric comprising a perovskite structure material
    • H01L28/56—Capacitors with a dielectric comprising a perovskite structure material the dielectric comprising two or more layers, e.g. comprising buffer layers, seed layers, gradient layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L28/00—Passive two-terminal components without a potential-jump or surface barrier for integrated circuits; Details thereof; Multistep manufacturing processes therefor
    • H01L28/40—Capacitors
    • H01L28/60—Electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L28/00—Passive two-terminal components without a potential-jump or surface barrier for integrated circuits; Details thereof; Multistep manufacturing processes therefor
    • H01L28/40—Capacitors
    • H01L28/60—Electrodes
    • H01L28/75—Electrodes comprising two or more layers, e.g. comprising a barrier layer and a metal layer

Definitions

  • the present invention relates generally to a method for depositing a metallic nitride series thin film, typically a Tin-series thin film, which is used as, e.g., a barrier layer, a capacitor top electrode, a gate electrode or a contact part, in a semiconductor device.
  • Al aluminum
  • W tungsten
  • an alloy mainly containing Al or W is generally used. If such a metal or alloy directly contacts an underlying Si (silicon) substrate or Al wiring, there is the possibility that an alloy of both metals is formed due to the Si-suction effect of Al (counter diffusion) in the boundary portion between the metals.
  • the alloy thus formed has a large value of resistance, so that the formation of such an alloy is not preferred from the point of view of the decrease of power consumption and high speed operation which are recently required for devices.
  • WF 6 gas used for forming the embedded layer tends to react with silicon of the substrate to deteriorate electrical characteristics to obtain undesired results.
  • a barrier layer is formed on the inner walls thereof, and the embedded layer is formed thereon.
  • the barrier layer a double layer structure of a Ti (titanium) film and a TiN (titanium nitride) film is generally used.
  • PVD physical vapor deposition
  • the Ti film and TiN film constituting the barrier layer are deposited by a chemical vapor deposition (CVD) capable of expecting to form a better quality of film.
  • CVD chemical vapor deposition
  • TiCl 4 titanium tetrachloride
  • H 2 hydrogen
  • TiCl 4 and NH 3 ammonia
  • MMA monomethyl hydrazine
  • a high dielectric material such as Ta 2 O 5
  • a capacitor gate material in order to obtain a high capacitance without changing scale.
  • a high dielectric material is not more stable than SiO 2 which has been conventionally used as a capacitor gate material. Therefore, when a polysilicon, which has been conventionally used as a top electrode, is used, it is oxidized by heat history after the preparation of a capacitor, so that it is impossible to form a stable device. Therefore, TiN or the like, which is more difficult to be oxidized, is required as a top electrode.
  • the TiN film or the like has been conventionally deposited by the above described PVD.
  • a recent highly integrated capacitor type which requires a high coverage, e.g., a crown type, a fin type, or a RUG polysilicon, which has irregularities formed on a polysilicon layer in order to increase the capacity of a capacitor when the crown type or fin type is formed, can not be deposited as a top electrode.
  • a TiN film constituting a capacitor top electrode is also deposited by a CVD which is expected to be capable of forming a better quality of film at a high coverage. Also in this case, TiCl 4 and NH 3 or MMH are used as reaction gases for depositing the TiN film.
  • the TiN film which is a columnar crystal, has a low barrier characteristic since intergranular diffusion is easy to occur therein.
  • the low barrier characteristic causes problems when the TiN film is used as a barrier layer for a Cu (copper) wiring or when the TiN film is used as an oxygen diffusion barrier, on the occasion of forming a Ta 2 O 5 capacitor top electrode. That is, the corrosion of the Cu wiring due to the remaining chlorine and the decrease of the capacity of Ta 2 O 5 due to the diffusion of O (oxygen), which increases the thickness of the Ta 2 O 5 film, cause problems.
  • the inventor has found that a TiN-series thin film, which is deposited by a CVD and which contains Ti, O and N (nitride), has a higher barrier characteristic than that of a conventional TiN film, and is suitable for a barrier layer.
  • a TiN-series thin film, which is deposited by a CVD and which contains Ti, N and P (phosphorus) has a lower resistance than that of a conventional.
  • TiN film and is suitable for a barrier layer and a capacitor top electrode.
  • the TiN-series thin film simultaneously containing O and P having the above described functions has both of a high barrier characteristic and a low resistance characteristic.
  • the present invention also relates to a method for producing a film structure including such a metallic nitride series thin film.
  • a method for depositing a TiN-series thin film comprising the steps of: arranging a substrate in a process vessel; evacuating said process vessel, while heating said substrate; pre-heating said substrate while introducing a N 2 gas and a NH 3 gas into said process vessel; pre-flowing a TiCl 4 gas and an O-containing gas, without introducing same into said process vessel; and introducing said TiCl 4 gas, said N 2 gas, said NH 3 gas and said O-containing gas into said process vessel to form a thin film containing Ti, O and N on said substrate by a CVD, wherein flow rates of said gases in said pre-flowing step are equal to those in said introducing step.
  • a method for depositing a TiN-series thin film comprising the steps of: arranging a substrate in a process vessel; evacuating said process vessel, while heating said substrate; pre-heating said substrate while introducing a N 2 gas and a NH 3 gas into said process vessel; pre-flowing a TiCl 4 gas, an O-containing gas and a PH 3 gas, without introducing same into said process vessel; and introducing said TiCl 4 gas, said N 2 gas, said NH 3 gas, said O-containing gas and said PH 3 gas into said process vessel to form a thin film containing Ti, O, N and P on said substrate by a CVD.
  • a method for depositing a TiN-series thin film comprising the steps of: arranging a substrate in a process vessel; evacuating said process vessel, while heating said substrate; pre-heating said substrate while introducing a N 2 gas and a NH 3 , gas into said process vessel; pre-flowing a TiCl 4 gas and an O-containing gas, without introducing same into said process vessel; introducing said TiCl 4 gas, said N 2 gas, said NH 3 gas and said. O-containing gas into a process vessel to form a first thin film containing.
  • Ti, O and N by a CVD; pre-flowing TiCl 4 gas and PH 3 gas, without introducing same into said-process vessel; and introducing said TiCl 4 gas, said N 2 gas, said NH 3 gas and said PH 3 gas into said process vessel to form a second thin film containing Ti, N and P on said first thin film by a CVD.
  • a method for depositing a TiN-series thin film comprising the steps of: arranging a substrate in a process vessel; evacuating said process vessel, while heating said substrate; pre-heating said substrate while introducing a N 2 gas and a NH 3 gas into said process vessel; pre-flowing a TiCl 4 gas and a first O-containing gas, without introducing same into said process vessel; introducing said TiCl 4 gas, said N 2 gas, said NH 3 gas and said first O-containing gas into a process vessel to form a first thin film containing Ti, O and N by a CVD; pre-flowing a TiCl 4 gas and a PH 3 gas, without introducing same into said process vessel; introducing said TiCl 4 gas, said N 2 gas, said NH 3 gas and said PH 3 gas into said process vessel to form a second thin film containing Ti, N and P on said first thin film by a CVD; pre-flowing a TiCl 4 gas and a second
  • a method for depositing a TiN-series thin film comprising the steps of: arranging a substrate in a process vessel; evacuating said process vessel, while heating said substrate; pre-heating said substrate while introducing a N 2 gas and a NH 3 gas into said process vessel; pre-flowing a TiCl 4 gas and a PH 3 gas, without introducing same into said process vessel; and introducing said TiCl 4 gas, said N 3 gas, said NH 3 gas and said PH 3 gas into said process vessel to form a thin film containing Ti, N and P on said substrate by a CVD.
  • a method for producing a film structure comprising the steps of: forming a first conductive layer on a substrate; forming a TiN-series thin film on said first conductive layer; and forming a second conductive layer on said TiN-series thin film, wherein said step of forming a TiN-series thin film includes the sub-steps of: arranging said substrate in a process vessel; evacuating said process vessel, while heating said substrate; pre-heating said substrate while introducing a N 2 gas and a NH 3 gas into said process vessel; pre-flowing a TiCl 4 gas and at least one of an O-containing gas and a PH 3 gas, without introducing same into said process vessel; and introducing said TiCl 4 gas, said N 2 gas, said NH 3 gas, and said at least one of said O-containing gas and said PH 3 gas into said process vessel to form a thin film containing Ti, N, and at least one of O and P on said first conductive layer by a CV
  • the TiN-series thin film formed by the method according to the present invention contains Ti, O and N to have a higher barrier characteristic than those of conventional TiN films, so that the, TiN-series thin film is suitable for a barrier layer.
  • the TiN-series thin film according to the present invention is formed by a CVD and contains Ti, N and P to have a lower resistance than those of conventional TiN films, so that the TiN-series thin film is suitable for a barrier layer or a capacitor top electrode.
  • the TiN-series thin film which is formed by a CVD and which contains Ti, O, N and P, can have both of a high barrier characteristic and a low resistance characteristic.
  • the TiN-series thin film has a stacked structure of a first thin film which is formed by a CVD and which contains Ti, O and N, and a second thin film which is formed by a CVD and which contains Ti, N and P, the high barrier characteristic of the first layer and the low resistance characteristic of the second layer can provide obtain characteristics which are the same as or superior to conventional barrier layers even if the thickness is smaller than the conventional barrier layers.
  • the TiN-series thin film has a stacked structure of a first thin film which is formed by a CVD and which contains Ti, O and N, a second thin film which is formed by a CVD and which contains Ti, N and P, and a third thin film which is formed by a CVD and which contains Ti, O and N, it is possible to obtain the barrier characteristic against layers on both sides.
  • these TiN-series thin films are used as (1) a barrier layer or an embedded wiring portion in a contact part between a wiring layer and a semiconductor substrate or a conductive layer arranged thereon, (2) a top electrode layer, barrier layer or bottom electrode of a capacitor portion having, an insulating layer of Ta 2 O 5 , RuO and so forth, (3) at least a part of a gate electrode, and (4) a contact structure on a major surface of a semiconductor substrate, so that it is possible to obtain excellent characteristics.
  • the present invention it is possible to deposit such TiN-series thin films of high-quality by carrying out the pre-heating step and/or the pre-flowing step.
  • the pre-heating step it is possible to stabilize the temperature of the substrate before the later step of forming a thin film.
  • the pre-flowing step it is possible to stabilize the flows of the TiCl 4 gas, the O-containing gas and/or the PH 3 gas before the next step of introducing those gases into the process vessel, i.e. the step of forming a thin film.
  • the pre-flowing step it is possible to precisely control the flow rates of those gases in the next step of forming a thin film, even if the flow rates are very small. It is more effective to equalize the flow rates in the pre-flowing step with those in the next step of forming a thin film.
  • a method for depositing a metallic nitride series thin film comprising the steps of: arranging a substrate in a process vessel; evacuating said process vessel, while heating said substrate; pre-heating said substrate while introducing an inert gas and a reducing gas into said process vessel; pre-flowing a metallic-element containing gas and at least one of an O-containing gas, a PH 3 gas and a B 2 H 6 gas, without introducing same into said process vessel; and introducing said metallic-element containing gas, said inert gas, said reducing gas, and at least one of said O-containing gas, a PH 3 gas and a B 2 H 6 gas into said process vessel to form a metallic nitride thin film containing at least one of O, P and B on said substrate by a CVD, wherein flow rates of said gases in said pre-flowing step are equal to those in said introducing step.
  • a method for producing a film structure comprising the steps of: forming a dielectric layer on a first conductive layer; forming a metallic nitride series thin film on said dielectric layer; and forming a second conductive layer on said metallic nitride series thin film, wherein said step of forming a metallic nitride series thin film includes the sub-steps of: pre-flowing a metallic-element containing gas without introducing same into a process vessel; and introducing said metallic-element containing gas, a N 2 gas, a NH 3 gas, and at least one of an O-containing gas, a PH 3 gas and a B 2 H 6 gas into a process vessel to form said metallic nitride series thin film comprising at least one of a thin film containing said metallic-element, O and N, a thin film containing said metallic-element, N and P, a thin film containing said metallic-element, N and B, a thin film containing said metallic
  • a method for depositing a metallic nitride series thin film comprising the steps of: arranging a substrate in a process vessel; evacuating said process vessel, while heating said substrate; pre-heating said substrate while introducing a N-containing gas into said process vessel; pre-flowing a metallic-element containing gas without introducing said metallic-element containing gas into said process vessel; and introducing said metallic-element containing gas, an inert gas and a reducing gas into said process vessel to form a metallic nitride series thin film on said substrate by a CVD, wherein flow rate of said metallic-element containing gas in said pre-flowing step is equal to that in said introducing step.
  • FIG. 1 is a sectional view of a deposition system for depositing a TiN-series thin film according to the present invention
  • FIG. 2 is a graph showing the relationship between flow ratios O 2 /NH 3 and the specific resistance values of a TiON thin film
  • FIG. 3 is a graph showing the relationship between flow ratios PH 3 and the specific resistance values of a TiN-series thin film
  • FIG. 4 is a graph showing the relationships between deposition temperatures and the specific resistance values of a TiN-series thin film when PH 3 is used and is not used;
  • FIG. 5 is a graph showing the relationships between flow ratios O 2 /NH 3 and the specific resistance values of a TiN-series thin film when PH3 is use and is not used;
  • FIG. 6 is a sectional view showing examples (a) and (b) of a stacked structure of a TiN-series thin film according to the present invention.
  • FIG. 7 is a sectional view of a film structure using a TiN-series thin film according to the present invention.
  • FIG. 8 is a sectional view showing examples (a) through (c) of a TiN-series thin film according to the present invention which is used for a contact part of a metal wiring layer;
  • FIG. 9 is a sectional view showing examples (a) through (c) of a TiN-series thin film according to the present invention which is used for a capacitor structure of a DRAM or the like;
  • FIG. 10 is a schematic view showing an example of a deposition system capable of continuously depositing a TiN-series thin film and other films according to the present invention.
  • FIG. 11 is a sectional view showing examples (a) and (b) of a TiN-series thin film according to the present invention which is used for a gate electrode;
  • FIG. 12 is a sectional view showing examples (a) and (b) of a TiN-series thin film according to the present invention which is used for a gate electrode;
  • FIG. 13 is a sectional view showing an example of a TiN-series thin film according to the present invention which is used for a contact structure when a wiring is formed in a diffusion region formed in a major surface of a semiconductor substrate.
  • FIG. 1 is a sectional view of a deposition system for depositing a TiN-series thin film according to the present invention.
  • This deposition system has a substantially cylindrical airtight process vessel 11 , in which a susceptor 12 for horizontally supporting a semiconductor wafer W serving as an object to be processed is arranged while being supported on a cylindrical supporting member 13 .
  • a guide ring 14 for guiding the semiconductor wafer W is provided on the outer edge portion of the susceptor 12 .
  • a heater 15 is embedded in the susceptor 12 .
  • the power supply 16 is connected to a controller 17 which controls the output of the heater 15 in accordance with a signal from a temperature sensor (not shown).
  • the ceiling wall 11 a of the process vessel 11 is provided with a shower head 20 .
  • a large number of gas discharging holes 20 a and 20 b for discharging a gas toward the susceptor 12 are alternately formed.
  • the piping of a gas supply mechanism 30 is connected to the shower head 20 .
  • main flow lines 45 for supplying TiCl 4 are connected to the gas discharging holes 20 a
  • main flow lines 46 for supplying NH 3 gas are connected to the gas discharging holes 20 b , so that predetermined gases are introduced into the process vessel 11 via the shower head 20 .
  • the shower head 20 is a matrix type shower head, and adopts a post mix system wherein TiCl 4 and NH 3 gases serving as reaction gases are mixed after being discharged from the discharging holes 20 a and 20 b which are alternately formed.
  • the gas supply mechanism 30 has a ClF 3 supply source 31 for supplying ClF 3 which is a cleaning gas, an N 2 supply source 32 for supplying N 2 , a TiCl 4 supply source 33 for supplying TiCl 4 which is a reaction gas, a PH 3 supply source 34 for supplying PH 3 serving as a P containing gas, an NH 3 supply source 35 for supplying NH 3 which is a reaction gas and which contains N and H, and an O 2 gas supply source 36 for supplying O 2 serving as an O-containing gas.
  • a gas line 39 is connected to the ClF 3 supply source 31
  • a gas line 40 is connected to the N 2 supply source 32
  • a gas line 41 is connected to the TiCl 4 supply source 33
  • a gas line 42 is connected to the PH 3 supply source 34
  • a gas line 43 is connected to the NH 3 supply source 35
  • a gas line 44 is connected to the O 2 gas supply source 36 .
  • Each of the lines 39 through 44 is provided with amass flow controller 48 and first and second valves 47 , 38 at the upstream side and the downstream side with respect to the mass flow controller 48 , respectively.
  • the gas line 40 extending from the N 2 supply source 32 meets the gas line 41 extending from the TiCl 4 supply source 33 , so that TiCl 4 gas carried on N 2 gas flowing through the gas line 40 and the pipe 45 is introduced into the process vessel 11 via the gas discharging holes 20 a of the shower head 20 .
  • the gas line 39 extending from the ClF 3 supply source 31 meets the gas line 40 , so that ClF 3 serving as a cleaning gas is introduced into the process vessel 11 from the gas discharging holes 20 a via the gas lines 39 and 40 and the main flow lines 45 by opening the valve provided in the gas line 39 .
  • the gas lines 42 , 43 and 44 extending from the PH 3 , NH 3 and O 2 supply sources 34 , 35 and 36 are connected to the main flow lines 46 , so that those gases are introduced into the process vessel 11 from the gas discharging holes 20 b of the shower head 20 .
  • this deposition system has pre-flow lines 22 , 23 for pre-flowing the gases from the gas supply sources 33 , 34 and/or 36 , and exhausting those gases before the main flow lines 45 and 46 , i.e. before the process vessel 11 .
  • the pre-flow lines 22 , 23 are connected, via third valves 37 , to the corresponding gas lines 41 , 42 and 44 between the mass flow controllers 48 and the second valves 38 .
  • N-containing gas and the H containing gas monomethyl hydrazine (MMH) may be used in place of NH 3 , or an N-containing gas and an H containing gas may be introduced as separate gases.
  • N-containing gas NO gas or N 2 O gas may be used in place of O 2 gas.
  • Ar may be substituted for N 2 .
  • an exhaust pipe 18 is connected to the bottom wall 11 b of the process vessel 11 .
  • an exhaust system 19 including a vacuum pump is connected to this exhaust pipe 18 .
  • the downstream ends of the pre-flow lines 22 , 23 are connected to the exhaust line 21 so that the pre-flown gases are exhausted by the exhaust system 19 .
  • the semiconductor wafer W is mounted on the susceptor 12 in the process vessel 11 . Then, while the wafer W is heated by the heater 15 , the process vessel 11 is evacuated to a high vacuum state by the exhaust system 19 . Subsequently, N 2 gas and NH 3 gas are introduced into the process vessel 11 at a predetermined flow ratio so that the pressure in the process vessel 11 is 133 to 1333 Pa, while pre-heating the semiconductor wafer W at a temperature of about 400 to 700° C.
  • the pressure in the process vessel 11 is changed to 13.3 to 1.33 Pa, and while the flow rates of N 2 gas and NH 3 gas are maintained, TiCl 4 gas and at least one of O 2 gas and PH 3 gas are pre-flown thorough the pre-flow lines 22 , 23 , without introducing those gases into the process vessel 11 , at predetermined flow rates for about 5 to 20 seconds.
  • the deposition of a predetermined TiN-series thin film is carried out by introducing TiCl 4 gas and at least one of O 2 gas and PH 3 gas thorough the main flow lines 45 , 46 on the same conditions (flow rates of the gases, pressure in the process vessel 11 , and so forth) as those in the pre-flowing step. At this time, the deposition of the TiN-series thin film is carried out at substantially the same temperature as that in the pre-heating step.
  • the pre-heating step By carrying out the pre-heating step, it is possible to stabilize the temperature of the semiconductor wafer W before the later step of forming a thin film.
  • the pre-flowing step By carrying out the pre-flowing step, it is possible to stabilize the flows of the TiCl 4 gas, the O-containing gas and/or the PH 3 gas before the next step of introducing those gases into the process vessel, i.e. the step of forming a thin film.
  • the pre-flowing step it is possible to precisely control the flow rates of those gases in the next step of forming a thin film, even if the flow rates are very small. It is more effective to equalize the flow rates in the pre-flowing step with those in the next step of forming a thin film.
  • the semiconductor wafer is carried out from the process vessel 11 .
  • ClF 3 gas serving as a cleaning gas is introduced into the process vessel 11 to clean the interior of the process vessel 11 .
  • TiN-series film which contains Ti, N and O and which has a high barrier characteristic while maintaining a relatively low resistance value. That is, since the crystal of the TiN film is a columnar crystal, the intergranular diffusion, whereby metal or O may diffuse via the grain boundary of TiN crystal, is easy to occur therein. Therefor, if the TiN film is formed by the thermal CVD with the O-containing gas, the barrier characteristic of the grain boundary of TiN crystal can be improved.
  • the volume ratio of O 2 to NH 3 is preferably in the range of from 0.0001 to 0.001. Thus, the value of resistance can be in a desired range.
  • FIG. 2 shows the relationship between the flow rates O 2 /NH 3 and the specific resistance values of the TiON film.
  • the flow rate of TiCl 4 gas was 0.02 L/min
  • the flow rate of NH 3 gas was 0.5 L/min
  • the flow rate of N 2 was 0.15 L/min
  • the flow rate of O 2 was changed in the range of from 5 ⁇ 10 ⁇ 5 to 4 ⁇ 10 ⁇ 3 L/min (the flow ratio O 2 /NH 3 was in the range of from 0.00001 to 0.008).
  • the substrate temperature was 550° C.
  • the pressure in the process vessel was 300 mTorr
  • the thickness of the film was 50 nm.
  • the specific resistance (resistivity) value of the TiON film is in the range of from 360 to 7500 ⁇ cm which is an allowable range.
  • the value of resistance can be in a suitable range by converting it into the above described range of O 2 .
  • the barrier characteristic is good if the specific resistance value is about 700 ⁇ cm or higher. Therefore, it can be seen from FIG. 2 that the flow ratio O 2 /NH 3 is 0.0006 or higher in order to obtain a good barrier characteristic.
  • TiN-series film which contains Ti, N and P, will be described below.
  • TiN-series film which contains Ti, N and P and which has a low value of resistance while maintaining a relatively good barrier characteristic.
  • PH 3 gas By using PH 3 gas, it is possible to remove the remaining chlorine by the reducing function of PH 3 gas, so that it is possible to reduce the value of resistance of the TiN-series film.
  • the flow rate of PH 3 is preferably in the range of from 0.04 to 0.5 L/min. If it is less than 0.04 L/min, it does not have so great effect.
  • the flow rate of PH 3 is 0.1 L/min or higher, the formed thin film is amorphous and compact, so that the resistance can be decreased and the barrier characteristic can be good.
  • FIG. 3 shows the relationship between the flow rates of PH 3 and the specific resistance values of the TiN-series film.
  • the flow rate of TiCl 4 gas was 0.02 L/min
  • the flow rate of NH 3 gas was 0.5 L/min
  • the flow rate of N 2 was 0.15 L/min
  • the flow rate of PH 3 was changed in the range of from 0 to 0.2 L/min.
  • the substrate temperature was 430° C. and 550° C.
  • the pressure in the process vessel was 40 Pa
  • the thickness of the film was 50 nm.
  • the value of resistance clearly decreases.
  • the deposition temperature 550° C. when the deposition temperature 550° C., the value of resistance tends to be lower. In the case of the deposition at 550° C., when the flow rate of PH 3 is 0.2 L/min, it is possible to obtain 70 ⁇ cm which is a very low value.
  • the relationship between deposition temperatures and the specific resistance values of the TiN-series film is shown in FIG. 4 .
  • the flow rate of TiCl 4 gas was 0.02 L/min
  • the flow rate of NH 3 gas was 0.5 L/min
  • the flow rate of N 2 was 0.15 L/min
  • the flow rate of PH 3 was 0.2 L/min.
  • the pressure in the process vessel was 40 Pa
  • the thickness of the film was 50 nm.
  • TiN-series film which contains Ti, N, O and P, will be described below.
  • TiN-series film which contains Ti, N, O and P and which has both of a high barrier characteristic and a low resistance characteristic. That is, although the barrier characteristic is improved by supplying O 2 gas during the deposition, the value of resistance increases as the amount of O 2 (the flow ratio O 2 /NH 3 ) increases, as shown in FIG. 5 . However, by introducing P by supplying PH 3 gas, the value of resistance can be lower than that when P is not introduced, so that it is possible to obtain a TiN-series film which has both of a high barrier characteristic and a low resistance characteristic.
  • the flow rate of TiCl 4 gas was 0.02 L/min
  • the flow rate of NH 3 gas was 0.5 L/min
  • the flow rate of N 2 was 0.15 L/min
  • the flow rate of PH 3 was 0.2 L/min and 0 L/min
  • the flow rate of O 2 was changed in the range of from 5 ⁇ 10 ⁇ 5 to 1 ⁇ 10 ⁇ 3 L/min (the flow ratio O 2 /NH 3 was in the range of from 0.0001 to 0.001).
  • the pressure in the process vessel was 40 Pa
  • the thickness of the film was 50 nm.
  • TiCl 4 gas, NH 3 gas and O 2 gas are first introduced into the process vessel 11 to form a first thin film 51 containing Ti, O and N on an underlying layer 50 . Thereafter, the O 2 line 44 is closed and the PH 3 gas line is open to introduce TiCl 4 gas, NH 3 gas and PH 3 gas into the process vessel 11 to form a second thin film 52 containing Ti, N and P on the first thin film 51 .
  • the thickness of the first thin film 51 is preferably in the range of from 1 to 10 nm
  • the thickness of the second thin film 52 is preferably in the range of from 3 to 50 nm.
  • the thickness of a conventional TiN film when a film is used as a barrier layer for a Cu wiring layer, the thickness of a conventional TiN film must be 50 nm or more in order to obtain good barrier effects.
  • the thickness of the first thin film 51 which is a high barrier TiON film
  • the thickness of the second thin film 52 which is a low resistance TiN-series film containing P
  • the barrier layer can have the same barrier characteristic and resistance values as those of conventional TiN films.
  • the first thin film and the second thin film may be deposited in reverse order.
  • a TiN film may have a triple layer structure.
  • TiCl 4 gas, NH 3 gas and O 2 gas are first introduced into the process vessel 11 to form a first thin film 51 containing Ti, O and N on an underlying layer 50 .
  • the O 2 line 44 is closed and the PH 3 gas line is open to introduce TiCl 4 gas, NH 3 gas and PH 3 gas into the process vessel 11 to form a second thin film 52 containing Ti, N and P on the first thin film 51 .
  • the PH 3 gas line 42 is closed and the O 2 line 44 is open again to introduce TiCl 4 gas, NH 3 gas and O 2 gas into the process vessel 11 to form a third film containing Ti, O and N on the second thin film 52 .
  • the thickness of the first thin film 51 and third thin film 53 is preferably in the range of from 1 to 10 nm, and the thickness of the second thin film 52 is preferably in the range of from 3 to 50 nm.
  • Such a triple layer structure can be effectively used as, e.g., a top electrode of a capacitor portion having an insulating layer of Ta 2 O 5 or RuO.
  • a P containing gas may be introduced into the process vessel when the first thin film 51 and/or the third thin film 53 is formed.
  • a thin film containing Ti, O, N and P is formed or when the second thin film 52 is formed, if an O-containing gas is introduced into the process vessel, a thin film containing Ti, O, N and P can be formed.
  • an O-containing gas is introduced into the process vessel, a thin film containing Ti, O, N and P can be formed.
  • the TiN-series thin film obtained according to the present invention has at least one of a high barrier characteristic and a low resistance characteristic to be suitable for a barrier layer for a metal wiring layer and for a top electrode of a capacitor even if it has a single layer structure or a stacked structure.
  • the TiN-series thin film according to the present invention is actually used as a film structure which is stacked on another layer. Specifically, as shown in, e.g., FIG. 7 , a TiN thin film 55 of any one of a thin film containing Ti, O and N, a thin film containing Ti, N and P, and a thin film containing Ti, O, N and P is provided between the other first layer 54 and the second layer 56 .
  • Such a film structure can be applied to various portions of semiconductor devices.
  • a contact layer such as a Ti thin film, a TiSi thin film or a CoSi thin film
  • the TiN thin film 55 according to the present invention is formed thereon.
  • a metal layer e.g., W, Al or Cu layer, which is applied as a wiring layer or an embedded wiring portion, is formed thereon as the second layer.
  • a CoSi thin film serving as the first layer 54 may be used as a gate electrode, and a metal layer serving as a wiring layer may be formed via a TiN-series thin film electrode according to the present invention serving as a barrier layer.
  • such a film structure can be applied to a capacitor portion or metal gate electrode portion of a DRAM as will be described later.
  • the TiN-series thin film thus used according to the present invention is formed by the CVD
  • the TiN-series film is formed by the above described system shown in FIG. 1 (i.e., before NH 3 gas, TiCl 4 gas, and O 2 gas and/or PH 3 gas are introduced)
  • an O-containing gas O 2 gas in the above described system shown in FIG.1
  • a first layer of, e.g., a Ti thin film, a TiSi thin film and a CoSi thin film is first formed by the PVD or CVD (the plasma CVD or thermal CVD).
  • O 2 gas is introduced into a CVD process vessel, and after the TiN-series thin film is formed, O 2 gas is introduced again. Thereafter, a second layer of a metal of, e.g., Al, W or Cu, is formed by the PVD or CVD (the plasma CVD or thermal CVD). Furthermore, any one of the introductions of O 2 gas may be omitted.
  • a thin oxide film is formed on the underlying first layer and/or the TiN-series thin film, so that it is possible to enhance the barrier characteristic against the adjacent first layer and/or second layer. Therefore, when the thin film containing Ti, O and N and the thin film containing Ti, O, N and P are formed, it is possible to reduce the amount of O to maintain a good barrier characteristic. Furthermore, even if the TiN-series thin film is the above described stacked film, such effects can be obtained by introducing an O-containing gas before and/or after the thin films are continuously deposited in the process vessel 11 .
  • FIGS. 8 ( a ) through 8 ( c ) examples of a TiN-series thin film according to the present invention, which is used as a contact part of a metal wiring layer, will be described below.
  • an interlayer dielectric film 61 is formed on a silicon substrate 60 , and a contact hole 62 extending downwardly to an impurity diffusion region 60 a of the silicon substrate 60 is formed in the interlayer dielectric layer 61 .
  • an Ti thin film 63 and a TiN-series thin film 64 according to the, present invention are formed on thee surface of the interlayer dielectric film 61 and contact hole 62 .
  • the TiN-series thin film 64 has a higher barrier characteristic than those of conventional TiN thin film, the presence of the TiN-series thin film 64 can very effectively prevent the formation of a compound by a reaction of Cu or W with Si. In addition, since the TiN-series thin film 64 has such a high barrier characteristic, it is possible to very effectively prevent the diffusion of Cl 2 .
  • the TiN-series thin film 64 is preferably a TiON film or a TiONP film in order to obtain a high barrier characteristic.
  • a TiNP film may be used since it has a relatively high barrier characteristic if it is amorphous. In this case, it is not always required to provide the Ti thin film 63 .
  • an interlayer dielectric film 61 is formed on a silicon substrate 60 , and a contact hole 62 extending downwardly to an impurity diffusion region 60 a of the silicon substrate 60 is formed in the interlayer dielectric layer 61 .
  • an Ti containing film 69 having a double stacked structure of a TiNP film 67 and a TiON film 68 is provided on the surface of the interlayer dielectric film 61 and contact hole 62 .
  • This metal wiring layer 66 is also filled in the contact hole 62 , so that the conducting state between the impurity diffusion region 60 a of the silicon substrate, 60 and the metal wiring layer 66 is established.
  • the TiNP film 67 functions as a contact layer
  • the TiON film 68 functions as a barrier layer, so that it is possible to obtain better characteristics than those of conventional Ti/TiN films.
  • an interlayer dielectric film 61 is formed on a silicon substrate 60 , and a contact hole 62 extending downwardly to an impurity diffusion region 60 a of the silicon substrate 60 is formed in the interlayer dielectric layer 61 .
  • an embedded wiring layer (plug) 70 of a TiNP thin film is formed, and a metal wiring layer 72 of Cu or W is formed thereon via a TiON barrier layer 71 .
  • the TiNP thin film has a low resistance, it can be thus used as the embedded wiring layer.
  • the metal wiring layers 66 and 72 may be made of any one of metals other than Cu and W, or an alloy.
  • the metal wiring layers 66 and 72 may be applied to via hole portions conducting to other conductive layers, in addition to the contact hole portion.
  • FIGS. 9 ( a ) through 9 ( c ) examples of a TiN-series thin film according to the present invention, which is applied to a capacitor structure of a DRAM or the like, will be described below.
  • a bottom electrode layer 81 of amorphous silicon is connected to an impurity diffusion region 80 a of a silicon substrate 80 .
  • an insulating layer 83 of TA 2 O 5 or RuO is formed via an SiN barrier layer 82 which is formed by the rapid thermal nitrization (RTN) process of silicon.
  • a top electrode layer 84 of a TiN-series thin, film according to the present invention is formed.
  • a metal wiring layer (not shown) is formed.
  • the top electrode layer 84 Conventionally, a TiN film is used as the top electrode layer 84 .
  • the heat treatment in a post-process causes O of Ta 2 O 5 to diffuse into the TiN film to change to TiO, so that the thickness of the TiN film decreases to increase the thickness of Ta 2 O 5 to reduce the capacity.
  • the TiN-series film constituting the top electrode 84 is preferably a TiON film or a TiONP film in order to hold a high barrier characteristic.
  • the stacked structure of the TiN-series film and a TiNP film is provided, it is possible to obtain a good barrier characteristic while maintaining a usual specific resistance even if the thickness of the stacked structure is small.
  • the triple stacked structure of TiON film or TiONP film/TiNP film/TiON film or TiONP film is provided, it is possible to effectively prevent the diffusion of oxygen and metals on both sides of the top electrode layer 84 .
  • the basic structure of the example shown in FIG. 9 ( b ) is the same as that of the example shown in FIG. 9 ( a ).
  • a barrier layer 85 of a TiN-series thin film according to the present invention is formed in place of the SiN barrier layer 82 on the bottom electrode layer 81 .
  • the TiN-series thin film constituting the barrier layer 85 is preferably a TiON film or a TiONP film in order to hold a high barrier characteristic.
  • the stacked structure of the TiN-series thin film and a TiNP film may be also used.
  • the TiN-series thin film according to the present invention may be applied to a metal isolation metal (MIM) structure which uses a metal, such as ruthenium, in place of amorphous silicon for a bottom electrode.
  • MIM metal isolation metal
  • a TiN-series thin film according to the present invention may be used as a bottom electrode having the MIM structure.
  • FIG. 9 ( c ) a bottom electrode 86 of a TiNP film is provided in place of the bottom electrode 81 of amorphous silicon.
  • a barrier layer 87 of a TiON film or a TiONP film is provided on the bottom electrode 86 .
  • an insulating layer 83 and a top electrode layer 84 have the same structures as those in the examples shown in FIGS. 9 ( a ) and 9 ( b ).
  • the TiN-series thin film according to the present invention, and the metal wiring or the insulating Layer of Ta 2 O 5 , RuO or HfO 2 can be continuously deposited using a cluster tool type process system shown in FIG. 10 .
  • This system comprises: a transfer chamber 90 which is arranged at the center; and two cassette vessels 91 and 92 , a degassing vessel 93 , a deposition unit 94 , a pre-cleaning unit 95 , a deposition unit 96 , a deposition unit 97 and a cooling vessel 98 , which are arranged around the transfer chamber 90 .
  • a semiconductor wafer W is introduced into and carried out from each of the vessels by means of a transfer arm 99 which is provided in the transfer chamber 90 .
  • one of the deposition units 94 , 96 and 97 is provided for forming a TiN-series thin film according to the present invention, and other units are provided for forming a metal wiring or an insulating layer of Ta 2 O 5 or RuO.
  • the formation of the capacitor structure shown in FIG. 9 ( b ) will be described below.
  • a semiconductor wafer W is taken out of the cassette vessel 91 by means of the transfer arm 99 , and introduced into the pre-cleaning unit 95 utilizing the inductively coupled plasma (ICP) or remote plasma.
  • ICP inductively coupled plasma
  • the pre-cleaning unit 95 oxides and so forth on the surface of the wafer W are removed by using at least one of Ar, H 2 and BrCl 3 .
  • the semiconductor wafer W is introduced into the degassing vessel 93 by means of the ram 99 to degas the wafer.
  • a barrier layer of a TiN-series thin film according to the present invention is deposited on the semiconductor wafer W by means of any one of the deposition units 94 , 96 and 97 .
  • the wafer W is introduced into another deposition unit by means of the arm 99 while maintaining the vacuum state, to form an insulating layer of Ta 2 O 5 .
  • the wafer W is introduced into the first deposition unit again to deposit a top electrode layer of a TiN-series thin film according to the present invention.
  • the wafer W is introduced into another deposition unit to form a metal wiring layer on the top electrode layer.
  • a predetermined deposition process is completed, and then, the semiconductor wafer W is cooled by means of the cooling vessel 98 to be housed in the cassette vessel 92 .
  • FIGS. 11 ( a ), 11 ( b ) and 12 examples of a TiN-series thin film according to the present invention, which is applied to a gate electrode, will be described below.
  • a gate electrode 104 A is provided on a silicon substrate 100 via an insulating film 101 .
  • the gate electrode 104 A comprises a gate oxide film 115 , a TiNP thin film 103 and a polysilicon film 102 between those films 115 and 103 on the TiNP thin film 103 , a W wiring layer 106 is formed. That is, WSi of the gate electrode of the conventional double layer structure of a polysilicon and tungsten silicide (WSi) is replaced with TiNP. Furthermore, reference number 105 denotes a spacer of SiN. Since TiNP used for the gate electrode has a low resistance and an excellent barrier characteristic and is thermally stable, the structure of FIG.
  • the barrier characteristic can be further enhanced, so that it is possible to obtain more excellent characteristics. Specifically, it is possible to achieve a higher speed, and it is possible to reduce the thickness of the film.
  • each of the polysilicon and tungsten silicide (WSi) of the 25 gate electrode of the conventional double layer structure of the polysilicon and tungsten silicide is 100 nm, so that the total thickness is 200 nm on the other hand, the thickness of the TiNP layer on the polysilicon may be in the range of from 10 to 50 nm, so that the total thickness may be in the range of from 110 to 150 nm which is far thinner than that of the gate electrode of the conventional double layer structure.
  • the thickness can be particularly small.
  • a gate electrode 104 B comprising a gate oxide film 115 and a TiNP thin film 107 directly formed on the film 115 is provided in place of the gate electrode 104 of FIG. 11 ( a ).
  • the TiNP thin film has allow resistance, a high heat resistance and an excellent barrier characteristic. Therefore, the TiNP thin film alone can also obtain excellent characteristics as a gate electrode similar to the double layer structure of polysilicon/TiNP.
  • the thickness of the TiNP gate electrode 107 is sufficient to be in the range of from about 20 nm to about 50 nm, so that it is possible to realize a very thin gate electrode.
  • a TiON thin film may be formed between the gate oxide film 115 and the TiNP thin film 107 .
  • a gate electrode 104 C is used in place of the gate electrodes 104 A and 104 B of FIG. 11 .
  • the gate electrode 104 C comprises a gate oxide film 115 , a polysilicon film 116 , a CoSi thin film 108 and a barrier layer 109 .
  • the barrier layer 109 is a TiN-series thin film formed by the CVD according to the present invention.
  • the CoSi thin film 108 is formed for obtaining a contact resistance.
  • the CoSi thin film 108 and the polysilicon film 116 have low resistance and can provide excellent characteristics to the gate electrode 104 C, so that it is possible to reduce the thickness of the gate electrode itself.
  • the barrier layer 109 of the TiN-series thin film according to the present invention it is possible to obtain an excellent barrier characteristic.
  • an insulating layer 110 of high dielectric material is formed on a silicon substrate 100 .
  • the insulating layer 110 is made of at least one of SiO 2 , HfO 2 , Ta 2 O 5 , RuO, BST, PZT (Pb(Zr, Ti)O 3 : lead zirconate titanate).
  • a barrier layer 111 of a CVD-TiN-series thin film according to the present invention is formed thereon, and a metal gate electrode 112 of Al, W or Cu is formed thereon.
  • reference numbers 113 and 114 denote a source and a drain, respectively.
  • a metal gate structure 118 capable of responding to accelerating is constructed.
  • the barrier layer 11 of the CVD-TiN-series thin film according to the present invention can effectively prevent the relative diffusion between the gate electrode 112 and an insulating layer 110 of a high dielectric material.
  • a contact layer 122 of a TiSi thin film or a CoSi thin film is formed on a diffusion region (source or drain) 121 which is formed in the major surface of a silicon substrate 120 .
  • a barrier layer 123 of a TiN-series thin film according to the present intention is formed thereon, and a wiring layer 124 of Al, W or Cu is formed thereon.
  • reference number 125 denotes a gate electrode.
  • the present invention should not be limited to the above described preferred embodiments, but the invention can be modified in various ways.
  • the conditions in each process are merely described as an example, so that the conditions may be suitably set in accordance with processes.
  • the substrate to be used should not be limited to the semiconductor wafer, but it may be another substrate.
  • another layer may be formed on the surface of the substrate.
  • the TiN-series thin film has been deposited by the thermal CVD in the above described preferred embodiments, the present invention should not be limited thereto, but other CVDs may be used. However, if the thermal CVD is used for the deposition, the TiN-series thin film can be relatively easily formed without the need of any complicated processes, so that the thermal CVD is preferably used for the deposition.
  • the present invention is not limited to the deposition of the TiN-series thin films. That is to say, the present invention can be applied to metallic nitride series thin films other than the TiN-series thin films.
  • metallic nitride series thin films include Al, W, Zr, Hf, Ru, Ta, and La nitride series thin films.
  • corresponding metallic element containing gas and N-containing gas are used as the process gases.
  • O-containing gas can be used as an additional process gas.
  • Al-containing gas is at least one of Al(OC 2 H 5 ) 3 gas, Al(OCH 3 ) 3 gas and AlC 3 gas.
  • W-containing gas is at least one of WF 6 gas and W(CO) 6 gas.
  • Zr-containing gas is at least one of ZrCl 4 gas and Zr[N(OC 2 H 5 ) 2 ] 4 gas.
  • Hf-containing gas is at least one of HfCl 4 gas and Hf[N(OC 2 H 5 ) 2 ] 4 gas.
  • Ru-containing gas is at least one of Ru(CO) 5 gas and RuCl 3 gas.
  • Ta-containing gas is at least one of TaCl 5 gas, Ta(OC 2 H 5 ) 3 gas and Ta(OCH 3 ) 3 gas.
  • La-containing gas is at least one of LaCl 3 gas, La(OC 2 H 5 ) 3 gas and La(OCH 3 ) 3 gas.
  • the N-containing gas is NH 3 gas and the O-containing gas is at least one of O 2 gas, NO gas and N 2 O gas.
  • TiN-series thin films When depositing the TiN-series thin films, as Ti-containing gases, TiI 4 gas, Ti(OC 2 H 5 ) 3 gas and/or Ti(OCH 3 ) 3 gas can be used in addition to/in place of the TiCl 4 gas. Furthermore, TiN-series thin films can contain B (boron) in place of P (phosphorus). In this case, at least one of BH 3 gas and B 2 H 6 gas is used in place of PH 3 gas.
  • the metallic nitride: series thin film can be generally used as an intermediate layer between first and second conductive layers and/or an intermediate layer between a dielectric layer on the first conductive layer and the second conductive layer.
  • the first conductive layer may be one of a TiSi layer, a CoSi layer and a Si layer
  • the second conductive layer may be one of an Al layer, a W layer and a Cu layer.
  • a polysilicon layer can be used as the first conductive layer.
  • the dielectric layer may comprise at least one of SiO 2 , SiON, HfO 2 , ZrO, Ta 2 O 5 , RuO, PZT and BST.

Abstract

The present invention generally relates to a method for depositing a metallic nitride series thin film, typically a TiN-series thin film. The TiN-series thin film according to the present invention is formed by a CVD, and contains Ti, O and N to have a higher barrier characteristic than those of conventional TiN thin films, so that TiN-series thin film can suitably used as a barrier layer. In addition, a TiN-series thin film according to the present invention is formed by a CVD, and contains Ti, N and P to have a lower resistance than those of conventional TiN films, so that TiN-series thin film can suitably used as a barrier layer or a capacitor top electrode. Moreover, if a TiN-series thin film containing Ti, O, N and P is formed by a CVD, the TiN-series thin film can have both of a high barrier characteristic and a low resistance characteristic.

Description

    CROSS REFERENCE TO RELATED APPLICATION
  • This is a continuation-in-part application of patent application Ser. No. 09/660,546 filed on Sep. 12, 2000, now abandoned.
    • BACKGROUND OF THE INVENTION
  • 1. Field of the Invention
  • The present invention relates generally to a method for depositing a metallic nitride series thin film, typically a Tin-series thin film, which is used as, e.g., a barrier layer, a capacitor top electrode, a gate electrode or a contact part, in a semiconductor device.
  • 2. Description of the Related Art
  • In the production of semiconductor devices, the construction of circuits tends to have a multilayer metallization structure on a recent demand for higher density and higher density integration. Therefore, an embedding technique for electrical connections between layers, such as a contact hole which is a connecting part between a bottom semiconductor device layer and a top wiring layer, and a via hole which is a connecting part between top and bottom wiring layers, is important. In addition, with the high-density integration, a technique four depositing a top electrode of capacitor gate material of a DRAM memory part, at a high coverage is important. Recently, a high dielectric material, such as Ta2O5, is used as a capacitor gate material.
  • In the embedding of the contact hole and via hole of the above described techniques, Al (aluminum), W (tungsten) or an alloy mainly containing Al or W is generally used. If such a metal or alloy directly contacts an underlying Si (silicon) substrate or Al wiring, there is the possibility that an alloy of both metals is formed due to the Si-suction effect of Al (counter diffusion) in the boundary portion between the metals. The alloy thus formed has a large value of resistance, so that the formation of such an alloy is not preferred from the point of view of the decrease of power consumption and high speed operation which are recently required for devices.
  • In addition, when W or a W alloy is used as an embedded layer for a contact hole, WF6 gas used for forming the embedded layer tends to react with silicon of the substrate to deteriorate electrical characteristics to obtain undesired results.
  • Therefore, in order to prevent these disadvantages, before an embedded layer is formed in a contact hole or a via hole, a barrier layer is formed on the inner walls thereof, and the embedded layer is formed thereon. In this case, as the barrier layer, a double layer structure of a Ti (titanium) film and a TiN (titanium nitride) film is generally used.
  • Conventionally, such a barrier layer is deposited using a physical vapor deposition (PVD). Recently, the scale down and high density integration of devices are particularly required, and the design rule is particularly severe. In accordance therewith, the line width and the diameter of holes further decrease and the aspect ratio increases. As a result, the embedding performance of the PVD film is bad, so that it is not possible to ensure a sufficient contact resistance.
  • Therefore, the Ti film and TiN film constituting the barrier layer are deposited by a chemical vapor deposition (CVD) capable of expecting to form a better quality of film. When the Ti film is deposited by the CVD, TiCl4 (titanium tetrachloride) and H2 (hydrogen) are used as reaction gases to be activated as plasma to deposit the film. When the TiN film is deposited, TiCl4 and NH3 (ammonia) or MMA (monomethyl hydrazine) are used as reaction gases.
  • On the other hand, as described above, with the high density integration, a high dielectric material, such as Ta2O5, is used as a capacitor gate material in order to obtain a high capacitance without changing scale. However, such a high dielectric material is not more stable than SiO2 which has been conventionally used as a capacitor gate material. Therefore, when a polysilicon, which has been conventionally used as a top electrode, is used, it is oxidized by heat history after the preparation of a capacitor, so that it is impossible to form a stable device. Therefore, TiN or the like, which is more difficult to be oxidized, is required as a top electrode.
  • Also in the case of this technique, the TiN film or the like has been conventionally deposited by the above described PVD. However, a recent highly integrated capacitor type, which requires a high coverage, e.g., a crown type, a fin type, or a RUG polysilicon, which has irregularities formed on a polysilicon layer in order to increase the capacity of a capacitor when the crown type or fin type is formed, can not be deposited as a top electrode.
  • Therefore, a TiN film constituting a capacitor top electrode is also deposited by a CVD which is expected to be capable of forming a better quality of film at a high coverage. Also in this case, TiCl4 and NH3 or MMH are used as reaction gases for depositing the TiN film.
  • By the way, when a Tin film is thus deposited by the CVD, Cl (chlorine) remains in the film, so that the deposited film has a high specific resistance. If the specific resistance is so high, it is not possible to obtain sufficient characteristics when it is applied to a capacitor top electrode. In addition, the formed film is a high stress film. Moreover, the TiN film, which is a columnar crystal, has a low barrier characteristic since intergranular diffusion is easy to occur therein. In particular, the low barrier characteristic causes problems when the TiN film is used as a barrier layer for a Cu (copper) wiring or when the TiN film is used as an oxygen diffusion barrier, on the occasion of forming a Ta2O5 capacitor top electrode. That is, the corrosion of the Cu wiring due to the remaining chlorine and the decrease of the capacity of Ta2O5 due to the diffusion of O (oxygen), which increases the thickness of the Ta2O5 film, cause problems.
    • SUMMARY OF THE INVENTION
  • The inventor has found that a TiN-series thin film, which is deposited by a CVD and which contains Ti, O and N (nitride), has a higher barrier characteristic than that of a conventional TiN film, and is suitable for a barrier layer. In addition, the inventor has found that a TiN-series thin film, which is deposited by a CVD and which contains Ti, N and P (phosphorus), has a lower resistance than that of a conventional. TiN film, and is suitable for a barrier layer and a capacitor top electrode. Moreover, the inventor has found that the TiN-series thin film simultaneously containing O and P having the above described functions has both of a high barrier characteristic and a low resistance characteristic.
  • It is therefore an object of the present invention to provide a method for depositing a high-quality metallic nitride series, typically TiN-series, thin film having a higher barrier characteristic and/or a lower resistance than those of a conventional TiN film formed by a CVD.
  • The present invention also relates to a method for producing a film structure including such a metallic nitride series thin film.
  • Therefore, there is provided a method for depositing a TiN-series thin film, said method comprising the steps of: arranging a substrate in a process vessel; evacuating said process vessel, while heating said substrate; pre-heating said substrate while introducing a N2 gas and a NH3 gas into said process vessel; pre-flowing a TiCl4 gas and an O-containing gas, without introducing same into said process vessel; and introducing said TiCl4 gas, said N2 gas, said NH3 gas and said O-containing gas into said process vessel to form a thin film containing Ti, O and N on said substrate by a CVD, wherein flow rates of said gases in said pre-flowing step are equal to those in said introducing step.
  • There is also provided a method for depositing a TiN-series thin film, said method comprising the steps of: arranging a substrate in a process vessel; evacuating said process vessel, while heating said substrate; pre-heating said substrate while introducing a N2 gas and a NH3 gas into said process vessel; pre-flowing a TiCl4 gas, an O-containing gas and a PH3 gas, without introducing same into said process vessel; and introducing said TiCl4 gas, said N2 gas, said NH3 gas, said O-containing gas and said PH3 gas into said process vessel to form a thin film containing Ti, O, N and P on said substrate by a CVD.
  • There is also provided a method for depositing a TiN-series thin film, said method comprising the steps of: arranging a substrate in a process vessel; evacuating said process vessel, while heating said substrate; pre-heating said substrate while introducing a N2 gas and a NH3, gas into said process vessel; pre-flowing a TiCl4 gas and an O-containing gas, without introducing same into said process vessel; introducing said TiCl4 gas, said N2 gas, said NH3 gas and said. O-containing gas into a process vessel to form a first thin film containing. Ti, O and N by a CVD; pre-flowing TiCl4 gas and PH3 gas, without introducing same into said-process vessel; and introducing said TiCl4 gas, said N2 gas, said NH3 gas and said PH3 gas into said process vessel to form a second thin film containing Ti, N and P on said first thin film by a CVD.
  • There is also provided a method for depositing a TiN-series thin film, said method comprising the steps of: arranging a substrate in a process vessel; evacuating said process vessel, while heating said substrate; pre-heating said substrate while introducing a N2 gas and a NH3 gas into said process vessel; pre-flowing a TiCl4 gas and a first O-containing gas, without introducing same into said process vessel; introducing said TiCl4 gas, said N2 gas, said NH3 gas and said first O-containing gas into a process vessel to form a first thin film containing Ti, O and N by a CVD; pre-flowing a TiCl4 gas and a PH3 gas, without introducing same into said process vessel; introducing said TiCl4 gas, said N2 gas, said NH3 gas and said PH3 gas into said process vessel to form a second thin film containing Ti, N and P on said first thin film by a CVD; pre-flowing a TiCl4 gas and a second O-containing gas, without introducing same into said process vessel; and introducing said TiCl4 gas, said N2 gas, said NH3 gas and said second O-containing gas into said process vessel to form a third thin film containing Ti, O and N on said second thin film by a CVD.
  • There is also provided a method for depositing a TiN-series thin film, said method comprising the steps of: arranging a substrate in a process vessel; evacuating said process vessel, while heating said substrate; pre-heating said substrate while introducing a N2 gas and a NH3 gas into said process vessel; pre-flowing a TiCl4 gas and a PH3 gas, without introducing same into said process vessel; and introducing said TiCl4 gas, said N3 gas, said NH3 gas and said PH3 gas into said process vessel to form a thin film containing Ti, N and P on said substrate by a CVD.
  • There is also provided a method for producing a film structure, said method comprising the steps of: forming a first conductive layer on a substrate; forming a TiN-series thin film on said first conductive layer; and forming a second conductive layer on said TiN-series thin film, wherein said step of forming a TiN-series thin film includes the sub-steps of: arranging said substrate in a process vessel; evacuating said process vessel, while heating said substrate; pre-heating said substrate while introducing a N2 gas and a NH3 gas into said process vessel; pre-flowing a TiCl4 gas and at least one of an O-containing gas and a PH3 gas, without introducing same into said process vessel; and introducing said TiCl4 gas, said N2 gas, said NH3 gas, and said at least one of said O-containing gas and said PH3 gas into said process vessel to form a thin film containing Ti, N, and at least one of O and P on said first conductive layer by a CVD, wherein flow rates of said gases in said pre-flowing step are equal to those in said introducing step.
  • As described above, the TiN-series thin film formed by the method according to the present invention contains Ti, O and N to have a higher barrier characteristic than those of conventional TiN films, so that the, TiN-series thin film is suitable for a barrier layer. In addition, the TiN-series thin film according to the present invention is formed by a CVD and contains Ti, N and P to have a lower resistance than those of conventional TiN films, so that the TiN-series thin film is suitable for a barrier layer or a capacitor top electrode.
  • In addition, the TiN-series thin film, which is formed by a CVD and which contains Ti, O, N and P, can have both of a high barrier characteristic and a low resistance characteristic.
  • Moreover, if the TiN-series thin film has a stacked structure of a first thin film which is formed by a CVD and which contains Ti, O and N, and a second thin film which is formed by a CVD and which contains Ti, N and P, the high barrier characteristic of the first layer and the low resistance characteristic of the second layer can provide obtain characteristics which are the same as or superior to conventional barrier layers even if the thickness is smaller than the conventional barrier layers.
  • In addition, if the TiN-series thin film has a stacked structure of a first thin film which is formed by a CVD and which contains Ti, O and N, a second thin film which is formed by a CVD and which contains Ti, N and P, and a third thin film which is formed by a CVD and which contains Ti, O and N, it is possible to obtain the barrier characteristic against layers on both sides.
  • Moreover, in a semiconductor device, these TiN-series thin films are used as (1) a barrier layer or an embedded wiring portion in a contact part between a wiring layer and a semiconductor substrate or a conductive layer arranged thereon, (2) a top electrode layer, barrier layer or bottom electrode of a capacitor portion having, an insulating layer of Ta2O5, RuO and so forth, (3) at least a part of a gate electrode, and (4) a contact structure on a major surface of a semiconductor substrate, so that it is possible to obtain excellent characteristics.
  • According to the present invention, it is possible to deposit such TiN-series thin films of high-quality by carrying out the pre-heating step and/or the pre-flowing step. Specifically, by carrying out the pre-heating step, it is possible to stabilize the temperature of the substrate before the later step of forming a thin film. By carrying out the pre-flowing step, it is possible to stabilize the flows of the TiCl4 gas, the O-containing gas and/or the PH3 gas before the next step of introducing those gases into the process vessel, i.e. the step of forming a thin film. In addition, by carrying out the pre-flowing step, it is possible to precisely control the flow rates of those gases in the next step of forming a thin film, even if the flow rates are very small. It is more effective to equalize the flow rates in the pre-flowing step with those in the next step of forming a thin film.
  • According to the present invention, there is also provided a method for depositing a metallic nitride series thin film, said method comprising the steps of: arranging a substrate in a process vessel; evacuating said process vessel, while heating said substrate; pre-heating said substrate while introducing an inert gas and a reducing gas into said process vessel; pre-flowing a metallic-element containing gas and at least one of an O-containing gas, a PH3gas and a B2H6 gas, without introducing same into said process vessel; and introducing said metallic-element containing gas, said inert gas, said reducing gas, and at least one of said O-containing gas, a PH3 gas and a B2H6 gas into said process vessel to form a metallic nitride thin film containing at least one of O, P and B on said substrate by a CVD, wherein flow rates of said gases in said pre-flowing step are equal to those in said introducing step.
  • There is also provided a method for producing a film structure, said method comprising the steps of: forming a dielectric layer on a first conductive layer; forming a metallic nitride series thin film on said dielectric layer; and forming a second conductive layer on said metallic nitride series thin film, wherein said step of forming a metallic nitride series thin film includes the sub-steps of: pre-flowing a metallic-element containing gas without introducing same into a process vessel; and introducing said metallic-element containing gas, a N2 gas, a NH3 gas, and at least one of an O-containing gas, a PH3 gas and a B2H6 gas into a process vessel to form said metallic nitride series thin film comprising at least one of a thin film containing said metallic-element, O and N, a thin film containing said metallic-element, N and P, a thin film containing said metallic-element, N and B, a thin film containing said metallic-element, O, N and P and a thin film containing said metallic-element, O, N and B, by a CVD.
  • There is also provided a method for depositing a metallic nitride series thin film, said method comprising the steps of: arranging a substrate in a process vessel; evacuating said process vessel, while heating said substrate; pre-heating said substrate while introducing a N-containing gas into said process vessel; pre-flowing a metallic-element containing gas without introducing said metallic-element containing gas into said process vessel; and introducing said metallic-element containing gas, an inert gas and a reducing gas into said process vessel to form a metallic nitride series thin film on said substrate by a CVD, wherein flow rate of said metallic-element containing gas in said pre-flowing step is equal to that in said introducing step.
  • Thus, according to the present invention, it is possible to deposit such metallic nitride series thin films of high-quality by carrying out the pre-heating step and/or the pre-flowing step.
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • The present invention will be understood more fully from the detailed description given herebelow and from the accompanying drawings of the preferred embodiments of the invention. However, the drawings are not intended to imply limitation of the invention to a specific embodiment, but are for explanation and understanding only.
  • In the drawings:
  • FIG. 1 is a sectional view of a deposition system for depositing a TiN-series thin film according to the present invention;
  • FIG. 2 is a graph showing the relationship between flow ratios O2/NH3 and the specific resistance values of a TiON thin film;
  • FIG. 3 is a graph showing the relationship between flow ratios PH3 and the specific resistance values of a TiN-series thin film;
  • FIG. 4 is a graph showing the relationships between deposition temperatures and the specific resistance values of a TiN-series thin film when PH3 is used and is not used;
  • FIG. 5 is a graph showing the relationships between flow ratios O2/NH3 and the specific resistance values of a TiN-series thin film when PH3 is use and is not used;
  • FIG. 6 is a sectional view showing examples (a) and (b) of a stacked structure of a TiN-series thin film according to the present invention;
  • FIG. 7 is a sectional view of a film structure using a TiN-series thin film according to the present invention;
  • FIG. 8 is a sectional view showing examples (a) through (c) of a TiN-series thin film according to the present invention which is used for a contact part of a metal wiring layer;
  • FIG. 9 is a sectional view showing examples (a) through (c) of a TiN-series thin film according to the present invention which is used for a capacitor structure of a DRAM or the like;
  • FIG. 10 is a schematic view showing an example of a deposition system capable of continuously depositing a TiN-series thin film and other films according to the present invention;
  • FIG. 11 is a sectional view showing examples (a) and (b) of a TiN-series thin film according to the present invention which is used for a gate electrode;
  • FIG. 12 is a sectional view showing examples (a) and (b) of a TiN-series thin film according to the present invention which is used for a gate electrode; and
  • FIG. 13 is a sectional view showing an example of a TiN-series thin film according to the present invention which is used for a contact structure when a wiring is formed in a diffusion region formed in a major surface of a semiconductor substrate.
    • DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • Referring now to the accompanying drawings, the preferred embodiments of the present invention will be described in detail below.
  • FIG. 1 is a sectional view of a deposition system for depositing a TiN-series thin film according to the present invention. This deposition system has a substantially cylindrical airtight process vessel 11, in which a susceptor 12 for horizontally supporting a semiconductor wafer W serving as an object to be processed is arranged while being supported on a cylindrical supporting member 13. On the outer edge portion of the susceptor 12, a guide ring 14 for guiding the semiconductor wafer W is provided. In addition, a heater 15 is embedded in the susceptor 12. When an electrical power is fed to the heater 15 from a power supply 16, the heater 15 heats the semiconductor waver W, which is an object to be processed, to a predetermined temperature. The power supply 16 is connected to a controller 17 which controls the output of the heater 15 in accordance with a signal from a temperature sensor (not shown).
  • The ceiling wall 11 a of the process vessel 11 is provided with a shower head 20. In the shower head 20, a large number of gas discharging holes 20 a and 20 b for discharging a gas toward the susceptor 12 are alternately formed. To the shower head 20, the piping of a gas supply mechanism 30 is connected. As will be described later, main flow lines 45 for supplying TiCl4 are connected to the gas discharging holes 20 a, and main flow lines 46 for supplying NH3 gas are connected to the gas discharging holes 20 b, so that predetermined gases are introduced into the process vessel 11 via the shower head 20. Thus, the shower head 20 is a matrix type shower head, and adopts a post mix system wherein TiCl4 and NH3 gases serving as reaction gases are mixed after being discharged from the discharging holes 20 a and 20 b which are alternately formed.
  • The gas supply mechanism 30 has a ClF3 supply source 31 for supplying ClF3 which is a cleaning gas, an N2 supply source 32 for supplying N2, a TiCl4 supply source 33 for supplying TiCl4 which is a reaction gas, a PH3 supply source 34 for supplying PH3 serving as a P containing gas, an NH3 supply source 35 for supplying NH3 which is a reaction gas and which contains N and H, and an O2 gas supply source 36 for supplying O2 serving as an O-containing gas. In addition, a gas line 39 is connected to the ClF3 supply source 31, a gas line 40 is connected to the N2 supply source 32, a gas line 41 is connected to the TiCl4 supply source 33, a gas line 42 is connected to the PH3 supply source 34, a gas line 43 is connected to the NH3 supply source 35, and a gas line 44 is connected to the O2 gas supply source 36. Each of the lines 39 through 44 is provided with amass flow controller 48 and first and second valves 47, 38 at the upstream side and the downstream side with respect to the mass flow controller 48, respectively.
  • The gas line 40 extending from the N2 supply source 32 meets the gas line 41 extending from the TiCl4 supply source 33, so that TiCl4 gas carried on N2 gas flowing through the gas line 40 and the pipe 45 is introduced into the process vessel 11 via the gas discharging holes 20 a of the shower head 20. The gas line 39 extending from the ClF3 supply source 31 meets the gas line 40, so that ClF3 serving as a cleaning gas is introduced into the process vessel 11 from the gas discharging holes 20 a via the gas lines 39 and 40 and the main flow lines 45 by opening the valve provided in the gas line 39. The gas lines 42, 43 and 44 extending from the PH3, NH3 and O2 supply sources 34, 35 and 36 are connected to the main flow lines 46, so that those gases are introduced into the process vessel 11 from the gas discharging holes 20 b of the shower head 20.
  • In addition, this deposition system has pre-flow lines 22, 23 for pre-flowing the gases from the gas supply sources 33, 34 and/or 36, and exhausting those gases before the main flow lines 45 and 46, i.e. before the process vessel 11. The pre-flow lines 22, 23 are connected, via third valves 37, to the corresponding gas lines 41, 42 and 44 between the mass flow controllers 48 and the second valves 38.
  • As the N-containing gas and the H containing gas, monomethyl hydrazine (MMH) may be used in place of NH3, or an N-containing gas and an H containing gas may be introduced as separate gases. In addition, as the O-containing gas, NO gas or N2O gas may be used in place of O2 gas. Moreover, Ar may be substituted for N2.
  • To the bottom wall 11 b of the process vessel 11, an exhaust pipe 18 is connected. To this exhaust pipe 18, an exhaust system 19 including a vacuum pump is connected via an exhaust line 21. By operating the exhaust system 19, the pressure in the process vessel 11 can reduced to a predetermined degree of vacuum. The downstream ends of the pre-flow lines 22, 23 are connected to the exhaust line 21 so that the pre-flown gases are exhausted by the exhaust system 19.
  • A method for depositing a TiN-series thin film on a semiconductor wafer W using such a system will be described below.
  • First, the semiconductor wafer W is mounted on the susceptor 12 in the process vessel 11. Then, while the wafer W is heated by the heater 15, the process vessel 11 is evacuated to a high vacuum state by the exhaust system 19. Subsequently, N2 gas and NH3 gas are introduced into the process vessel 11 at a predetermined flow ratio so that the pressure in the process vessel 11 is 133 to 1333 Pa, while pre-heating the semiconductor wafer W at a temperature of about 400 to 700° C.
  • Then, the pressure in the process vessel 11 is changed to 13.3 to 1.33 Pa, and while the flow rates of N2 gas and NH3 gas are maintained, TiCl4 gas and at least one of O2 gas and PH3 gas are pre-flown thorough the pre-flow lines 22, 23, without introducing those gases into the process vessel 11, at predetermined flow rates for about 5 to 20 seconds. Subsequently, the deposition of a predetermined TiN-series thin film is carried out by introducing TiCl4 gas and at least one of O2 gas and PH3 gas thorough the main flow lines 45, 46 on the same conditions (flow rates of the gases, pressure in the process vessel 11, and so forth) as those in the pre-flowing step. At this time, the deposition of the TiN-series thin film is carried out at substantially the same temperature as that in the pre-heating step.
  • By carrying out the pre-heating step, it is possible to stabilize the temperature of the semiconductor wafer W before the later step of forming a thin film. By carrying out the pre-flowing step, it is possible to stabilize the flows of the TiCl4 gas, the O-containing gas and/or the PH3 gas before the next step of introducing those gases into the process vessel, i.e. the step of forming a thin film. In addition, by carrying out the pre-flowing step, it is possible to precisely control the flow rates of those gases in the next step of forming a thin film, even if the flow rates are very small. It is more effective to equalize the flow rates in the pre-flowing step with those in the next step of forming a thin film.
  • After the deposition, the semiconductor wafer is carried out from the process vessel 11. Then, ClF3 gas serving as a cleaning gas is introduced into the process vessel 11 to clean the interior of the process vessel 11.
  • When NH3 gas, TiCl4 gas and O2 gas are used as process gasses in the above described deposition, a TiN-series film (TiON film), which contains Ti, N and O and which has a high barrier characteristic while maintaining a relatively low resistance value, is formed. That is, since the crystal of the TiN film is a columnar crystal, the intergranular diffusion, whereby metal or O may diffuse via the grain boundary of TiN crystal, is easy to occur therein. Therefor, if the TiN film is formed by the thermal CVD with the O-containing gas, the barrier characteristic of the grain boundary of TiN crystal can be improved. In this case, the volume ratio of O2 to NH3 is preferably in the range of from 0.0001 to 0.001. Thus, the value of resistance can be in a desired range.
  • FIG. 2 shows the relationship between the flow rates O2/NH3 and the specific resistance values of the TiON film. In this case, the flow rate of TiCl4 gas was 0.02 L/min, the flow rate of NH3 gas was 0.5 L/min, the flow rate of N2 was 0.15 L/min, and the flow rate of O2 was changed in the range of from 5×10−5 to 4×10−3 L/min (the flow ratio O2/NH3 was in the range of from 0.00001 to 0.008). In addition, during the deposition, the substrate temperature was 550° C., the pressure in the process vessel was 300 mTorr, and the thickness of the film was 50 nm. As shown in FIG. 2, when the flow ratio O2/NH3 in the above described range, the specific resistance (resistivity) value of the TiON film is in the range of from 360 to 7500 μΩ·cm which is an allowable range.
  • Furthermore, even if another gas, such as NO or N2O, is used as the O-containing gas, the value of resistance can be in a suitable range by converting it into the above described range of O2.
  • In addition, the barrier characteristic is good if the specific resistance value is about 700 μΩ·cm or higher. Therefore, it can be seen from FIG. 2 that the flow ratio O2/NH3 is 0.0006 or higher in order to obtain a good barrier characteristic.
  • Next, the process for forming a TiN-series film (TiNP film), which contains Ti, N and P, will be described below.
  • When NH3 gas, TiCl4 gas and PH3 gas are used as process gases, a TiN-series film (TiNP film), which contains Ti, N and P and which has a low value of resistance while maintaining a relatively good barrier characteristic, is formed. By using PH3 gas, it is possible to remove the remaining chlorine by the reducing function of PH3 gas, so that it is possible to reduce the value of resistance of the TiN-series film. In this case, the flow rate of PH3 is preferably in the range of from 0.04 to 0.5 L/min. If it is less than 0.04 L/min, it does not have so great effect. In addition, if the flow rate of PH3 is 0.1 L/min or higher, the formed thin film is amorphous and compact, so that the resistance can be decreased and the barrier characteristic can be good.
  • FIG. 3 shows the relationship between the flow rates of PH3 and the specific resistance values of the TiN-series film. In this case, the flow rate of TiCl4 gas was 0.02 L/min, the flow rate of NH3 gas was 0.5 L/min, the flow rate of N2 was 0.15 L/min, and the flow rate of PH3 was changed in the range of from 0 to 0.2 L/min. In addition, during the deposition, the substrate temperature was 430° C. and 550° C., the pressure in the process vessel was 40 Pa, and the thickness of the film was 50 nm. As shown in FIG. 3, when the flow rate of PH3 is 0.04 L/min, the value of resistance clearly decreases. In addition, when the deposition temperature 550° C., the value of resistance tends to be lower. In the case of the deposition at 550° C., when the flow rate of PH3 is 0.2 L/min, it is possible to obtain 70 μΩ·cm which is a very low value.
  • In this case, the relationship between deposition temperatures and the specific resistance values of the TiN-series film is shown in FIG. 4. As shown in FIG. 4, when PH3 is added, the dependence of the specific resistance value on temperature is smaller than when PH3 is not added, so that the value of resistance is stably low. Furthermore, in FIG. 4, the flow rate of TiCl4 gas was 0.02 L/min, the flow rate of NH3 gas was 0.5 L/min, the flow rate of N2 was 0.15 L/min, and the flow rate of PH3 was 0.2 L/min. In addition, the pressure in the process vessel was 40 Pa, and the thickness of the film was 50 nm.
  • Next, the process for forming a TiN-series film (TiONP film), which contains Ti, N, O and P, will be described below.
  • When NH3 gas, TiCl4 gas, O2 gas and PH3 gas are used as process gasses in the deposition, it is possible to obtain a TiN-series film (TiONP film) which contains Ti, N, O and P and which has both of a high barrier characteristic and a low resistance characteristic. That is, although the barrier characteristic is improved by supplying O2 gas during the deposition, the value of resistance increases as the amount of O2 (the flow ratio O2/NH3) increases, as shown in FIG. 5. However, by introducing P by supplying PH3 gas, the value of resistance can be lower than that when P is not introduced, so that it is possible to obtain a TiN-series film which has both of a high barrier characteristic and a low resistance characteristic. Furthermore, in FIG. 5, the flow rate of TiCl4 gas was 0.02 L/min, the flow rate of NH3 gas was 0.5 L/min, the flow rate of N2 was 0.15 L/min, the flow rate of PH3 was 0.2 L/min and 0 L/min, and the flow rate of O2 was changed in the range of from 5×10−5 to 1×10−3 L/min (the flow ratio O2/NH3 was in the range of from 0.0001 to 0.001). In addition, the pressure in the process vessel was 40 Pa, and the thickness of the film was 50 nm.
  • During the above described deposition, a single TiN-series film was formed without changing gas. On other hand, if a stacked film comprising a plurality of TIN-series films is formed as follows, it is possible to obtain a higher barrier characteristic by a smaller thickness. Specifically, as shown in FIG. 6(a), TiCl4 gas, NH3 gas and O2 gas are first introduced into the process vessel 11 to form a first thin film 51 containing Ti, O and N on an underlying layer 50. Thereafter, the O2 line 44 is closed and the PH3 gas line is open to introduce TiCl4 gas, NH3 gas and PH3 gas into the process vessel 11 to form a second thin film 52 containing Ti, N and P on the first thin film 51.
  • By forming such a double layer structure, it is possible to improve the barrier characteristic while maintaining the same specific resistance as conventional specific resistance values if the thickness of the film is smaller than those of conventional films. In this case, the thickness of the first thin film 51 is preferably in the range of from 1 to 10 nm, and the thickness of the second thin film 52 is preferably in the range of from 3 to 50 nm.
  • In particular, when a film is used as a barrier layer for a Cu wiring layer, the thickness of a conventional TiN film must be 50 nm or more in order to obtain good barrier effects. However, if such a stacked structure is formed, even if the thickness of the first thin film 51, which is a high barrier TiON film, is in the range of from 1 to 5, nm and the thickness of the second thin film 52, which is a low resistance TiN-series film containing P, is in the range of from 5 to 20 nm so that the total thickness is decreased to 25 nm or less which is smaller than the conventional thickness, the barrier layer can have the same barrier characteristic and resistance values as those of conventional TiN films. Furthermore, the first thin film and the second thin film may be deposited in reverse order.
  • In addition, as shown in FIG. 6(b), a TiN film may have a triple layer structure. In this case, TiCl4 gas, NH3 gas and O2 gas are first introduced into the process vessel 11 to form a first thin film 51 containing Ti, O and N on an underlying layer 50. Thereafter, the O2 line 44 is closed and the PH3 gas line is open to introduce TiCl4 gas, NH3 gas and PH3 gas into the process vessel 11 to form a second thin film 52 containing Ti, N and P on the first thin film 51. Thereafter, the PH3 gas line 42 is closed and the O2 line 44 is open again to introduce TiCl4 gas, NH3 gas and O2 gas into the process vessel 11 to form a third film containing Ti, O and N on the second thin film 52.
  • By forming such a triple layer structure, it is possible to improve the barrier characteristic against the films on both sides while maintaining the same specific resistance and the thickness of the film is smaller than those of conventional films. In this case, the thickness of the first thin film 51 and third thin film 53 is preferably in the range of from 1 to 10 nm, and the thickness of the second thin film 52 is preferably in the range of from 3 to 50 nm. Such a triple layer structure can be effectively used as, e.g., a top electrode of a capacitor portion having an insulating layer of Ta2O5 or RuO.
  • The above described double layer and triple layer structures can be formed in a short time without any difficulty since each layer can be continuously formed only by switching gases in the same system.
  • Furthermore, in either case of the above described double layer and triple layer structures, a P containing gas may be introduced into the process vessel when the first thin film 51 and/or the third thin film 53 is formed. When a thin film containing Ti, O, N and P is formed or when the second thin film 52 is formed, if an O-containing gas is introduced into the process vessel, a thin film containing Ti, O, N and P can be formed. Thus, it is possible to further improve characteristics in accordance with a film to be obtained.
  • As described above, the TiN-series thin film obtained according to the present invention has at least one of a high barrier characteristic and a low resistance characteristic to be suitable for a barrier layer for a metal wiring layer and for a top electrode of a capacitor even if it has a single layer structure or a stacked structure.
  • The TiN-series thin film according to the present invention is actually used as a film structure which is stacked on another layer. Specifically, as shown in, e.g., FIG. 7, a TiN thin film 55 of any one of a thin film containing Ti, O and N, a thin film containing Ti, N and P, and a thin film containing Ti, O, N and P is provided between the other first layer 54 and the second layer 56.
  • Such a film structure can be applied to various portions of semiconductor devices. For example, a contact layer, such as a Ti thin film, a TiSi thin film or a CoSi thin film, is formed as the first layer 54, and the TiN thin film 55 according to the present invention is formed thereon. Then, a metal layer, e.g., W, Al or Cu layer, which is applied as a wiring layer or an embedded wiring portion, is formed thereon as the second layer. In addition, a CoSi thin film serving as the first layer 54 may be used as a gate electrode, and a metal layer serving as a wiring layer may be formed via a TiN-series thin film electrode according to the present invention serving as a barrier layer. Moreover, such a film structure can be applied to a capacitor portion or metal gate electrode portion of a DRAM as will be described later.
  • When the TiN-series thin film thus used according to the present invention is formed by the CVD, before the TiN-series film is formed by the above described system shown in FIG. 1 (i.e., before NH3 gas, TiCl4 gas, and O2 gas and/or PH3 gas are introduced), or after the supply of NH3 gas and PH3 gas is stopped to complete the formation of the thin film, or at both times, an O-containing gas (O2 gas in the above described system shown in FIG.1) is introduced into the process vessel 11. Specifically, a first layer of, e.g., a Ti thin film, a TiSi thin film and a CoSi thin film, is first formed by the PVD or CVD (the plasma CVD or thermal CVD). Thereafter, before the TiN-series thin film is formed by the CVD, O2 gas is introduced into a CVD process vessel, and after the TiN-series thin film is formed, O2 gas is introduced again. Thereafter, a second layer of a metal of, e.g., Al, W or Cu, is formed by the PVD or CVD (the plasma CVD or thermal CVD). Furthermore, any one of the introductions of O2 gas may be omitted.
  • By the introduction of oxygen at this time, a thin oxide film is formed on the underlying first layer and/or the TiN-series thin film, so that it is possible to enhance the barrier characteristic against the adjacent first layer and/or second layer. Therefore, when the thin film containing Ti, O and N and the thin film containing Ti, O, N and P are formed, it is possible to reduce the amount of O to maintain a good barrier characteristic. Furthermore, even if the TiN-series thin film is the above described stacked film, such effects can be obtained by introducing an O-containing gas before and/or after the thin films are continuously deposited in the process vessel 11.
  • Referring to FIGS. 8(a) through 8(c), examples of a TiN-series thin film according to the present invention, which is used as a contact part of a metal wiring layer, will be described below.
  • In the example shown in FIG. 8(a) an interlayer dielectric film 61 is formed on a silicon substrate 60, and a contact hole 62 extending downwardly to an impurity diffusion region 60 a of the silicon substrate 60 is formed in the interlayer dielectric layer 61. On thee surface of the interlayer dielectric film 61 and contact hole 62, an Ti thin film 63 and a TiN-series thin film 64 according to the, present invention are formed. On the TiN-series thin film 64, a metal wiring layer 66 of, e.g., Cu or W, is formed. This metal wiring layer 66 is also filled in the contact hole 62, so that the conducting state between the impurity diffusion region 60 a of the silicon substrate 60 and the metal wiring layer 66 is established.
  • Since the TiN-series thin film 64 has a higher barrier characteristic than those of conventional TiN thin film, the presence of the TiN-series thin film 64 can very effectively prevent the formation of a compound by a reaction of Cu or W with Si. In addition, since the TiN-series thin film 64 has such a high barrier characteristic, it is possible to very effectively prevent the diffusion of Cl2. The TiN-series thin film 64 is preferably a TiON film or a TiONP film in order to obtain a high barrier characteristic. In addition, a TiNP film may be used since it has a relatively high barrier characteristic if it is amorphous. In this case, it is not always required to provide the Ti thin film 63.
  • In the example shown in FIG. 8(b), similar to the example shown in FIG. 8(a), an interlayer dielectric film 61 is formed on a silicon substrate 60, and a contact hole 62 extending downwardly to an impurity diffusion region 60 a of the silicon substrate 60 is formed in the interlayer dielectric layer 61. On the surface of the interlayer dielectric film 61 and contact hole 62, an Ti containing film 69 having a double stacked structure of a TiNP film 67 and a TiON film 68 is provided. On the TiN-series thin film 69, a metal wiring layer 66 of, e.g., Cu or W, is formed. This metal wiring layer 66 is also filled in the contact hole 62, so that the conducting state between the impurity diffusion region 60 a of the silicon substrate, 60 and the metal wiring layer 66 is established. Thus, the TiNP film 67 functions as a contact layer, and the TiON film 68 functions as a barrier layer, so that it is possible to obtain better characteristics than those of conventional Ti/TiN films.
  • In the example shown in FIG. 8(c), similar to the example shown in FIG. 8(a), an interlayer dielectric film 61 is formed on a silicon substrate 60, and a contact hole 62 extending downwardly to an impurity diffusion region 60 a of the silicon substrate 60 is formed in the interlayer dielectric layer 61. In the contact hole 62, an embedded wiring layer (plug) 70 of a TiNP thin film is formed, and a metal wiring layer 72 of Cu or W is formed thereon via a TiON barrier layer 71. As described above, the TiNP thin film has a low resistance, it can be thus used as the embedded wiring layer.
  • Furthermore, the metal wiring layers 66 and 72 may be made of any one of metals other than Cu and W, or an alloy. In addition, the metal wiring layers 66 and 72 may be applied to via hole portions conducting to other conductive layers, in addition to the contact hole portion.
  • Referring to FIGS. 9(a) through 9(c), examples of a TiN-series thin film according to the present invention, which is applied to a capacitor structure of a DRAM or the like, will be described below.
  • In the example shown in FIG. 9(a), a bottom electrode layer 81 of amorphous silicon is connected to an impurity diffusion region 80 a of a silicon substrate 80. On the bottom electrode layer 81, an insulating layer 83 of TA2O5 or RuO is formed via an SiN barrier layer 82 which is formed by the rapid thermal nitrization (RTN) process of silicon. On the insulating layer 83, a top electrode layer 84 of a TiN-series thin, film according to the present invention is formed. On the top electrode layer 84, a metal wiring layer (not shown) is formed.
  • Conventionally, a TiN film is used as the top electrode layer 84. However, there is a problem in that the heat treatment in a post-process causes O of Ta2O5to diffuse into the TiN film to change to TiO, so that the thickness of the TiN film decreases to increase the thickness of Ta2O5 to reduce the capacity. Such a problem can be solved by using the top electrode 84 of the TiN-series thin film according to the present invention. In this case, the TiN-series film constituting the top electrode 84 is preferably a TiON film or a TiONP film in order to hold a high barrier characteristic. In addition, if the stacked structure of the TiN-series film and a TiNP film is provided, it is possible to obtain a good barrier characteristic while maintaining a usual specific resistance even if the thickness of the stacked structure is small. Moreover, the triple stacked structure of TiON film or TiONP film/TiNP film/TiON film or TiONP film is provided, it is possible to effectively prevent the diffusion of oxygen and metals on both sides of the top electrode layer 84.
  • The basic structure of the example shown in FIG. 9(b) is the same as that of the example shown in FIG. 9(a). However, in the example shown in FIG. 9(b), a barrier layer 85 of a TiN-series thin film according to the present invention is formed in place of the SiN barrier layer 82 on the bottom electrode layer 81. The TiN-series thin film constituting the barrier layer 85 is preferably a TiON film or a TiONP film in order to hold a high barrier characteristic. In addition, the stacked structure of the TiN-series thin film and a TiNP film may be also used.
  • While the TiN-series thin film according to the present invention has been applied to the metal isolation silicon (MIS) structure, the TiN-series thin film according to the present invention may be applied to a metal isolation metal (MIM) structure which uses a metal, such as ruthenium, in place of amorphous silicon for a bottom electrode. In addition, a TiN-series thin film according to the present invention may be used as a bottom electrode having the MIM structure. This example is shown in FIG. 9(c). In this example, a bottom electrode 86 of a TiNP film is provided in place of the bottom electrode 81 of amorphous silicon. On the bottom electrode 86, a barrier layer 87 of a TiON film or a TiONP film is provided. Furthermore, an insulating layer 83 and a top electrode layer 84 have the same structures as those in the examples shown in FIGS. 9(a) and 9(b).
  • In the examples shown in FIGS. 8(a) through 8(c) and 9(a) through 9(c), the TiN-series thin film according to the present invention, and the metal wiring or the insulating Layer of Ta2O5, RuO or HfO2 can be continuously deposited using a cluster tool type process system shown in FIG. 10. This system comprises: a transfer chamber 90 which is arranged at the center; and two cassette vessels 91 and 92, a degassing vessel 93, a deposition unit 94, a pre-cleaning unit 95, a deposition unit 96, a deposition unit 97 and a cooling vessel 98, which are arranged around the transfer chamber 90. In addition, a semiconductor wafer W is introduced into and carried out from each of the vessels by means of a transfer arm 99 which is provided in the transfer chamber 90.
  • In such a deposition system, one of the deposition units 94, 96 and 97 is provided for forming a TiN-series thin film according to the present invention, and other units are provided for forming a metal wiring or an insulating layer of Ta2O5 or RuO. As an example of the operation of a deposition process, the formation of the capacitor structure shown in FIG. 9(b) will be described below.
  • First, a semiconductor wafer W is taken out of the cassette vessel 91 by means of the transfer arm 99, and introduced into the pre-cleaning unit 95 utilizing the inductively coupled plasma (ICP) or remote plasma. In the pre-cleaning unit 95, oxides and so forth on the surface of the wafer W are removed by using at least one of Ar, H2 and BrCl3. Then, the semiconductor wafer W is introduced into the degassing vessel 93 by means of the ram 99 to degas the wafer. Thereafter, a barrier layer of a TiN-series thin film according to the present invention is deposited on the semiconductor wafer W by means of any one of the deposition units 94, 96 and 97. Thereafter, the wafer W is introduced into another deposition unit by means of the arm 99 while maintaining the vacuum state, to form an insulating layer of Ta2O5. Thereafter, the wafer W is introduced into the first deposition unit again to deposit a top electrode layer of a TiN-series thin film according to the present invention. According to circumstances, the wafer W is introduced into another deposition unit to form a metal wiring layer on the top electrode layer. Thus, a predetermined deposition process is completed, and then, the semiconductor wafer W is cooled by means of the cooling vessel 98 to be housed in the cassette vessel 92.
  • Referring to FIGS. 11(a), 11(b) and 12, examples of a TiN-series thin film according to the present invention, which is applied to a gate electrode, will be described below.
  • In the example of FIG. 11(a), a gate electrode 104A is provided on a silicon substrate 100 via an insulating film 101. The gate electrode 104A comprises a gate oxide film 115, a TiNP thin film 103 and a polysilicon film 102 between those films 115 and 103 on the TiNP thin film 103, a W wiring layer 106 is formed. That is, WSi of the gate electrode of the conventional double layer structure of a polysilicon and tungsten silicide (WSi) is replaced with TiNP. Furthermore, reference number 105 denotes a spacer of SiN. Since TiNP used for the gate electrode has a low resistance and an excellent barrier characteristic and is thermally stable, the structure of FIG. 11(a) has superior characteristics to those of the gate electrode of the conventional double structure of a polysilicon and WSi. Moreover, if it is amorphous, the barrier characteristic can be further enhanced, so that it is possible to obtain more excellent characteristics. Specifically, it is possible to achieve a higher speed, and it is possible to reduce the thickness of the film. The thickness of each of the polysilicon and tungsten silicide (WSi) of the 25 gate electrode of the conventional double layer structure of the polysilicon and tungsten silicide is 100 nm, so that the total thickness is 200 nm on the other hand, the thickness of the TiNP layer on the polysilicon may be in the range of from 10 to 50 nm, so that the total thickness may be in the range of from 110 to 150 nm which is far thinner than that of the gate electrode of the conventional double layer structure. When TiNP is amorphous to improve the barrier characteristic, the thickness can be particularly small.
  • In the example of FIG. 11(b), a gate electrode 104B comprising a gate oxide film 115 and a TiNP thin film 107 directly formed on the film 115 is provided in place of the gate electrode 104 of FIG. 11(a). As described above, the TiNP thin film has allow resistance, a high heat resistance and an excellent barrier characteristic. Therefore, the TiNP thin film alone can also obtain excellent characteristics as a gate electrode similar to the double layer structure of polysilicon/TiNP. In this case, the thickness of the TiNP gate electrode 107 is sufficient to be in the range of from about 20 nm to about 50 nm, so that it is possible to realize a very thin gate electrode. Thus, also in the case of the TiNP layer alone, it is possible to particularly reduce the thickness by causing the TiNP layer to be amorphous to improve the barrier characteristic. Incidentally a TiON thin film may be formed between the gate oxide film 115 and the TiNP thin film 107.
  • In the example of FIG. 12(a), a gate electrode 104C is used in place of the gate electrodes 104A and 104B of FIG. 11. The gate electrode 104C comprises a gate oxide film 115, a polysilicon film 116, a CoSi thin film 108 and a barrier layer 109. The barrier layer 109 is a TiN-series thin film formed by the CVD according to the present invention. The CoSi thin film 108 is formed for obtaining a contact resistance. The CoSi thin film 108 and the polysilicon film 116 have low resistance and can provide excellent characteristics to the gate electrode 104C, so that it is possible to reduce the thickness of the gate electrode itself. In addition, by the barrier layer 109 of the TiN-series thin film according to the present invention, it is possible to obtain an excellent barrier characteristic.
  • In the example of FIG. 12(b), an insulating layer 110 of high dielectric material is formed on a silicon substrate 100. The insulating layer 110 is made of at least one of SiO2, HfO2, Ta2O5, RuO, BST, PZT (Pb(Zr, Ti)O3: lead zirconate titanate). Then, a barrier layer 111 of a CVD-TiN-series thin film according to the present invention is formed thereon, and a metal gate electrode 112 of Al, W or Cu is formed thereon. In FIG. 12(b), reference numbers 113 and 114 denote a source and a drain, respectively. Thus, a metal gate structure 118 capable of responding to accelerating is constructed. The barrier layer 11 of the CVD-TiN-series thin film according to the present invention can effectively prevent the relative diffusion between the gate electrode 112 and an insulating layer 110 of a high dielectric material.
  • An example of a TiN-series thin film according to the present invention, which is applied to a contact structure for forming a wiring in a diffusion region formed in the major surface of a semiconductor substrate, will be described below. In an example of FIG. 13, a contact layer 122 of a TiSi thin film or a CoSi thin film is formed on a diffusion region (source or drain) 121 which is formed in the major surface of a silicon substrate 120. Then, a barrier layer 123 of a TiN-series thin film according to the present intention is formed thereon, and a wiring layer 124 of Al, W or Cu is formed thereon. In this case, since the TiSi thin film and the CoSi thin film have a low resistance, these thin films can have good characteristics as a contact layer, and it is possible to obtain a good barrier characteristic by the TiN-series thin film according to the present invention, so that it is possible to obtain a contact structure having very good characteristics. Furthermore, reference number 125 denotes a gate electrode.
  • Furthermore, the present invention should not be limited to the above described preferred embodiments, but the invention can be modified in various ways. For example, the conditions in each process are merely described as an example, so that the conditions may be suitably set in accordance with processes. In addition, the substrate to be used should not be limited to the semiconductor wafer, but it may be another substrate. Moreover, another layer may be formed on the surface of the substrate. In addition, while the TiN-series thin film has been deposited by the thermal CVD in the above described preferred embodiments, the present invention should not be limited thereto, but other CVDs may be used. However, if the thermal CVD is used for the deposition, the TiN-series thin film can be relatively easily formed without the need of any complicated processes, so that the thermal CVD is preferably used for the deposition.
  • Although the preferred embodiments have been represented by the TiN-series thin films, the present invention is not limited to the deposition of the TiN-series thin films. That is to say, the present invention can be applied to metallic nitride series thin films other than the TiN-series thin films. Such metallic nitride series thin films include Al, W, Zr, Hf, Ru, Ta, and La nitride series thin films. To deposit each metallic nitride series thin film, corresponding metallic element containing gas and N-containing gas are used as the process gases. O-containing gas can be used as an additional process gas.
  • For example, Al-containing gas is at least one of Al(OC2H5)3 gas, Al(OCH3)3 gas and AlC3 gas. W-containing gas is at least one of WF6 gas and W(CO)6 gas. Zr-containing gas is at least one of ZrCl4 gas and Zr[N(OC2H5)2]4 gas. Hf-containing gas is at least one of HfCl4 gas and Hf[N(OC2H5)2]4 gas. Ru-containing gas is at least one of Ru(CO)5 gas and RuCl3 gas. Ta-containing gas is at least one of TaCl5 gas, Ta(OC2H5)3 gas and Ta(OCH3)3 gas. La-containing gas is at least one of LaCl3 gas, La(OC2H5)3 gas and La(OCH3)3 gas. The N-containing gas is NH3 gas and the O-containing gas is at least one of O2 gas, NO gas and N2O gas.
  • When depositing the TiN-series thin films, as Ti-containing gases, TiI4gas, Ti(OC2H5)3 gas and/or Ti(OCH3)3 gas can be used in addition to/in place of the TiCl4 gas. Furthermore, TiN-series thin films can contain B (boron) in place of P (phosphorus). In this case, at least one of BH3 gas and B2H6 gas is used in place of PH3 gas.
  • The metallic nitride: series thin film can be generally used as an intermediate layer between first and second conductive layers and/or an intermediate layer between a dielectric layer on the first conductive layer and the second conductive layer. In this case, the first conductive layer may be one of a TiSi layer, a CoSi layer and a Si layer, and the second conductive layer may be one of an Al layer, a W layer and a Cu layer. In addition, a polysilicon layer can be used as the first conductive layer. The dielectric layer may comprise at least one of SiO2, SiON, HfO2, ZrO, Ta2O5, RuO, PZT and BST.
  • While the present invention has been disclosed in terms of the preferred embodiment in order to facilitate better understanding thereof, it should be appreciated that the invention can be embodied in various ways without departing from the principle of the invention. Therefore, the invention should be understood to include all possible embodiments and modification to the shown embodiments which can be embodied without departing from the principle of the invention as set forth in the appended claims.

Claims (14)

1-38. (canceled)
39. A gas processing apparatus for processing an object with a gas, said apparatus comprising:
a process vessel for containing therein said object;
an exhaust system for exhausting an atmosphere in said process vessel;
a gas supply source for supplying said gas;
a gas flow line connected between said process vessel and said gas supply source;
a mass flow controller provided in said gas flow line;
a first on-off valve provided in said gas flow line between said gas supply source and said mass flow controller;
a second on-off valve provided in said gas flow line between said mass flow controller and said process vessel; and
a pre-flow line connected to said gas flow line between said mass flow controller and said second on-off valve, for exhausting said gas without introducing same into said process vessel; and
a third on-off valve provided in said pre-flow line.
40. The apparatus as set forth in claim 39, wherein a shower head is provided in a top of said process vessel for discharging said gas supplied through said gas flow line into said process vessel.
41. The apparatus as set forth in claim 39, wherein said exhaust system includes an exhaust line connected to a bottom of said process vessel.
42. The apparatus as set forth in claim 41, wherein a downstream-end of said pre-flow line is connected to said exhaust line.
43. The apparatus as set forth in claim 39, wherein said object is a substrate and said gas is a material gas for depositing a thin film on said substrate.
44. A cluster tool type process system comprising:
a cassette vessel for housing a plurality of objects;
a plurality of gas processing units for processing an object with a gas; and
a transfer vessel connected to said cassette vessel and said gas processing units, said transfer vessel being provided with a transfer arm therein,
at least one of said gas processing units comprising:
a process vessel for containing therein said object;
an exhaust system for exhausting an atmosphere in said process vessel;
a gas supply source for supplying said gas;
a gas flow line connected between said process vessel and said gas supply source;
a mass flow controller provided in said gas flow line;
a first on-off valve provided in said gas flow line between said gas supply source and said mass flow controller;
a second on-off valve provided in said gas flow line between said mass flow controller and said process vessel;
a pre-flow line connected to said gas flow line between said mass flow controller and said second on-off valve, for exhausting said gas without introducing same into said process vessel; and
a third on-off valve provided in said pre-flow line.
45. The system as set forth in claim 44, wherein said at least one of said gas processing units is a deposition unit for depositing a thin film on a substrate as said object with a material gas.
46. The system as set forth in claim 45, further comprising a pre-cleaning unit connected to said transfer vessel.
47. The system as set forth in claim 46, wherein said pre-cleaning unit is arranged for a pre-cleaning of said substrate utilizing an inductively coupled plasma or a remote plasma.
48. The system as set forth in claim 45, further comprising a degassing vessel connected to said transfer vessel.
49. The system as set forth in claim 45, further comprising a cooling vessel connected to said transfer vessel.
50. A method for processing an object with a gas, said method comprising the steps of:
arranging said object in a process vessel;
evacuating said process vessel; and
introducing said gas into said process vessel through a gas flow line provided with a mass flow controller to process said object with said gas,
said method further comprising, between said evacuating step and said introducing step, the step of pre-flowing said gas through a pre-flow line connected to said gas flow line between said mass flow controller and said process vessel to exhaust said gas, without introducing said gas into said process vessel.
51. The method as set forth in claim 50, wherein said object is a substrate and said gas is a material gas for depositing a thin film on said substrate.
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US20050089634A1 (en) 2005-04-28
US20030129309A1 (en) 2003-07-10
US6824825B2 (en) 2004-11-30

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