WO2010141668A2 - Methods of forming strontium titanate films - Google Patents

Methods of forming strontium titanate films Download PDF

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WO2010141668A2
WO2010141668A2 PCT/US2010/037184 US2010037184W WO2010141668A2 WO 2010141668 A2 WO2010141668 A2 WO 2010141668A2 US 2010037184 W US2010037184 W US 2010037184W WO 2010141668 A2 WO2010141668 A2 WO 2010141668A2
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film
tio
sro
forming
films
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PCT/US2010/037184
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French (fr)
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WO2010141668A3 (en
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Laura Matz
Xiangxin Rui
Xinjian Lei
Sunil Shanker
Moo-Sung Kim
Nobi Fuchigami
Iain Buchanan
Anh Duong
Sandra Malhotra
Imran Hashim
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Intermolecular, Inc.
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Publication of WO2010141668A2 publication Critical patent/WO2010141668A2/en
Publication of WO2010141668A3 publication Critical patent/WO2010141668A3/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
    • C23C16/45531—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations specially adapted for making ternary or higher compositions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/409—Oxides of the type ABO3 with A representing alkali, alkaline earth metal or lead and B representing a refractory metal, nickel, scandium or a lanthanide
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
    • H01L21/02197—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides the material having a perovskite structure, e.g. BaTiO3
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H01L21/0228—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
    • H01L21/02356—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment to change the morphology of the insulating layer, e.g. transformation of an amorphous layer into a crystalline layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/314—Inorganic layers
    • H01L21/3141—Deposition using atomic layer deposition techniques [ALD]
    • H01L21/3142—Deposition using atomic layer deposition techniques [ALD] of nano-laminates, e.g. alternating layers of Al203-Hf02
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/314—Inorganic layers
    • H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
    • H01L21/31691—Inorganic layers composed of oxides or glassy oxides or oxide based glass with perovskite structure
    • 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
    • H01L28/55—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

Definitions

  • the present invention relates generally to semiconductor processing. More specifically, methods of forming high dielectric constant films using atomic layer deposition are described.
  • Figure 1 is a flowchart describing a method of forming a capacitive device including forming a strontium titanate film
  • Figure 2 is a flowchart describing a method of forming a strontium titanate layer, according to one embodiment
  • Figure 3 is a flowchart describing a method of forming layers by atomic layer deposition, according to one embodiment of the current invention
  • Figures 4A-4D illustrate the formation of a strontium titanate film by atomic layer deposition
  • Figures 5A-5B illustrate the chemical structures of precursors that may be used in the atomic layer deposition of a strontium titanate layer, according to various embodiments of the current invention
  • Figures 6A and 6B are data from an x-ray photoelectron spectroscopy (XPS) analysis of the carbon content of two strontium titanate films; [0015]
  • Figure 7 is a chart showing the results of a study of strontium titanate film compositions having various ALD supercycle thicknesses and ratios;
  • Figure 8A is a graph showing the relationship between the ALD supercycle thicknesses and the dielectric constant values in strontium titanate films
  • Figure 8B is a comparison of x-ray crystallography data of strontium titanate films having varied supercycle thicknesses but the same composition
  • Figure 8C is a chart showing the data for multiple strontium titanate films having varied strontium oxide to titanium oxide ratios of supercycle thicknesses and the related leakage density, dielectric constant (k), and effective oxide thickness (EOT) values for each film; [0023]
  • Figure 9 is a graph showing the impact of composition of various strontium titanate films on dielectric constant value
  • Figure 1OA is a graph showing the relationship between the strontium titanate film composition, leakage density (J), and dielectric constant (k);
  • Figure 1OB is a graph showing the relation ship between the strontium titanate film composition, leakage density (J), and effective oxide thickness (EOT); [0029]
  • Figure 11 is a contour plot of dielectric constant values for strontium titanate films having varied supercycle thicknesses and varied compositions
  • Figure 12 is a graph comparing the leakage density of strontium titanate films (approx. 0.52 Sr/(Sr+Ti)) where strontium is deposited first to strontium titanate films where titanium is deposited first; this graph also compares strontium titanate films annealed at different temperatures and for different times; [0033]
  • Figure 13 is a chart comparing a strontium titanate film that was deposited by a method where 50 strontium presaturation pulses were used to a strontium titanate film that was deposited by a method where 100 strontium presaturation pulses were used.
  • Embodiments of the current invention include methods of forming a strontium titanate (SrTiO 3 ) film using atomic layer deposition (ALD). More particularly, the method includes forming a plurality of strontium oxide (SrO) unit films using ALD and forming a plurality of titanium oxide (TiO 2 ) unit films using ALD. The combined thickness of the SrO and TiO 2 unit films is less than approximately 5 angstroms. The SrO and TiO 2 units films are then annealed to form a strontium titanate layer. This anneal may occur before the deposition of any other material over the SrO and TiO 2 unit films.
  • ALD atomic layer deposition
  • FIG. 1 illustrates a flowchart describing an embodiment of forming a capacitive device that includes a strontium titanate dielectric film.
  • a first conductive layer 405 is formed over a substrate 403, as illustrated in Figure 4.
  • the first conductive layer 405 may be a material such as titanium nitride (TiN), platinum, iridium, iridium oxide, tungsten, tungsten oxide, molybdenum, molybdenum oxide, ruthenium and ruthenium oxide that are often used as the electrode materials of dynamic random access memory (DRAM) cells.
  • TiN titanium nitride
  • platinum platinum, iridium, iridium oxide, tungsten, tungsten oxide, molybdenum, molybdenum oxide, ruthenium and ruthenium oxide that are often used as the electrode materials of dynamic random access memory (DRAM) cells.
  • DRAM dynamic random access memory
  • a strontium oxide (SrO) film 410 may then be deposited over the first conductive layer 405 at block 102.
  • SrO is deposited on the first conductive layer before the deposition of titanium oxide because experimental data have shown that depositing SrO first may lower the leakage density of the ultimately formed strontium titanate film, as will be shown later in the experimental results section.
  • the SrO film 410 may be deposited by a vapor deposition method such as atomic layer deposition (ALD) or chemical vapor deposition (CVD).
  • ALD atomic layer deposition
  • CVD chemical vapor deposition
  • a plurality of SrO unit films are deposited using atomic layer deposition (ALD) or CVD.
  • the strontium oxide unit films are formed as described in blocks 301 and 302 of the flowchart of Figure 3 by forming at block 301 a strontium-containing monolayer on a substrate by pulsing a strontium precursor over a substrate and at block 302 by oxidizing said strontium containing monlayer by pulsing an oxygen containing source over the substrate.
  • the oxygen containing source may be selected from the list including ozone, oxygen, plasma activated oxygen, and water.
  • a strontium (Sr)-containing monolayer is formed by pulsing a Sr precursor over the substrate.
  • the strontium- containing precursors may be polydentate ⁇ -ketoiminates which are found, for example, in co-pending application US20070248754A1, US Serial No. 11/945678 filed on November 27, 2007, co-pending application U.S. Serial No. 12/266,806 which was filed on November 11, 2008, and co-pending application or U.S. Serial No. 12/245,196 which was filed on October 3, 2008.
  • the polydentate ⁇ -ketoiminates may incorporate an alkoxy group in the imino group.
  • the polydentate ⁇ -ketoiminates are selected from the group represented by the following Structure A. [0040] Structure A is defined as
  • M is Strontium;
  • R 1 is selected from the group consisting of alkyl, fluoroalkyl, cycloaliphatic, having from 1 to 10 carbon atoms, preferably a group containing 1 to 6 carbon atoms, and an aryl group having from 6 to 12 carbon atoms;
  • R 2 is selected from the group consisting of hydrogen, alkyl, alkoxy, cycloaliphatic, having from 1 to 10 carbon atoms, preferably a group containing 1 to 6 carbon atoms, and an aryl group having from 6 to 12 carbon atoms;
  • R 3 is selected from the group consisting of alkyl, fluoroalkyl, cycloaliphatic, having from 1 to 10 carbon atoms, preferably a group containing 1 to 6 carbon atoms, and an aryl group having from 6 to 12 carbon atoms;
  • R 4 is a C 2 - 3 linear or branched alkylene bridge with or without chiral carbon atom, thus making a five
  • the temperature of the substrate during deposition of the strontium precursor may be in the approximate range of 290 0 C and 310 0 C, and more particularly approximately 300 0 C. This temperature range is selected because it is the temperature window within which the deposition of the strontium precursor is optimal.
  • the Sr- precursor can be delivered to the deposition chamber using vapor draw (with or without charging up), bubbling, or direct liquid injection. A carrier gas may be used to deliver the Sr-precursor. The choice of delivery system typically depends on the particular ALD deposition tool.
  • the Sr-precursor is pulsed into the ALD reaction chamber for a time sufficient to form a monolayer or less of the Sr-precursor material on the substrate.
  • the pulse time for the Sr- precursor to form one monolayer on the substrate may vary from tool to tool, precursor delivery method, substrate temperature, and similar factors.
  • the pulse time may be approximately one second on a Cambridge NanoTech atomic layer deposition tool (Savannah) with 20 SCCM Argon carrier gas at 300 0 C.
  • the pulsing of the Ti- precursor may be followed by a purge by an inert gas such as Argon.
  • the purge may be a five second argon purge.
  • This class of strontium precursors have been found not to incorporate detectable amounts of carbon in the films. Without being bound by theory, it is postulated that with these precursors the Sr ligand bonds are completely oxidized during exposure to an oxygen containing source such as ozone or oxygen.
  • the oxidation in the flow occurs at block 302 of the flowchart of Figure 3.
  • a strontium oxide (SrO) unit film is formed by reacting the Sr-containing monolayer with ozone as the oxidizer.
  • ozone is practical and cost-effective because an exotic oxidizer is not needed.
  • the forming of the SrO film is then repeated to form multiple layers of the SrO film during the ALD supercycle.
  • An ALD supercycle is when more than one unit film is layered to obtain a particular thickness of material.
  • the multiple layers of the SrO unit films 411, 412, 413, 414, 415, and 416 may be in the form of a film stack 410.
  • the deposition of the strontium monolayer may include multiple pre- saturation pulses.
  • the pre-saturation pulses may be performed during only the first Sr-precursor deposition of SrO film 411 over the first conductive layer 405.
  • the number of pre-saturation pulses may be in the approximate range of 50 - 200 pulses in a Cambridge NanoTech atomic layer deposition tool (Savannah). Experimental results of embodiments of the current invention support this claim.
  • TiO 2 titanium oxide
  • the TiO 2 may also be deposited by the method described in the flowchart of Figure 2 at block 202 by forming a plurality of TiO 2 films using ALD. More specifically, the ALD deposition may occur as described in Figure 3 at blocks 304 and 305.
  • a Ti-containing monolayer is formed on the substrate by pulsing a Ti precursor over the substrate.
  • the Ti precursor may be chosen from the family of liquid group 4 precursors are represented by the following formula I:
  • M comprises Ti;
  • R 1 is an alkyl group comprising from 1 to 10 carbon atoms;
  • R 2 is an alkyl group comprising from 1 to 10 carbon atoms;
  • R 3 is chosen from hydrogen or an alkyl group comprising from 1 to 3 carbon atoms;
  • R 4 is an alkyl group comprising from 1 to 6 carbon atoms.
  • the titanium precursor may be described as Ti-I, a precursor in which the titanium atom is coordinated with 2 tert- butoxy groups and 2 unsymmetrical beta-diketonato resulting in a preferred coordination number of 6 for Ti atom.
  • Ti-precursor a precursor in which the titanium atom is coordinated with 2 tert- butoxy groups and 2 unsymmetrical beta-diketonato resulting in a preferred coordination number of 6 for Ti atom.
  • An example of this class of Ti-I precursors is illustrated in Figure 5B.
  • the substrate may be a conductive layer such as an electrode described above in relation to the SrO deposition or the substrate may be one or more layers of the previously deposited SrO films.
  • the temperature of the substrate may be in the approximate range of 250 0 C and 400 0 C, and more particularly in the approximate range of 290 0 C and 310 0 C, and even more particularly approximately 300 0 C. This temperature range is selected because it is the temperature within which the deposition of this class titanium precursor, and in particular Ti-I, is optimal.
  • the Ti-precursor can be delivered to the deposition chamber using vapor draw (with or without charging up), bubbling, or direct liquid injection. A carrier gas may be used to deliver the Ti-precursor.
  • the choice of delivery system typically depends on the particular ALD deposition tool.
  • the Ti- precursor is pulsed into the ALD reaction chamber for a time sufficient to form a monolayer or less of the Ti-precursor material on the substrate.
  • the absorption of the precursor on the substrate is self -limiting, so under optimized process conditions the absorption should stop once the monolayer or less of the precursor material has formed on the surface.
  • the pulse time for the Ti-precursor to form one monolayer on the substrate may vary from tool to tool, precursor delivery method, substrate temperature, and similar factors.
  • the pulse time may be approximately one second on a Cambridge NanoTech atomic layer deposition tool (Savannah) with 20 SCCM Argon carrier gas at 300 0 C.
  • the pulsing of the Ti-precursor may be followed by a purge of an inert gas such as Argon.
  • the purge may be a five second argon purge on the Cambridge NanoTech ALD tool described above.
  • a TiO 2 unit film is formed by reacting the titanium containing monolayer with ozone (O 3 ) as the oxidizer.
  • the temperature of the substrate is maintained at the same temperature as the deposition of the Ti-precursor monolayer.
  • Ozone is pulsed into the ALD deposition chamber for a time sufficient to oxidize all of the titanium atoms in the Ti-containing monolayer.
  • the oxidation reaction is self-limiting and therefore under the optimized conditions will not continue reacting once all of the titanium precursor molecules have been oxidized.
  • the ozone is flowed into the deposition chamber for a pulse time of approximately 1 second followed an approximately 5 second argon purge.
  • the Ti-I precursor and ozone may be selected to form the TiO 2 film because they are compatible and ozone is a practical and cost effective oxidizer.
  • TiO 2 unit films are formed by repeating the forming of the TiO 2 film during an ALD supercycle at block 306 of the flowchart in Figure 3.
  • An ALD supercycle is when more than one unit film is layered to obtain a particular thickness of material.
  • the plurality of TiO 2 unit films is illustrated in Figure 4A as the film stack 420 that is made up of the individual TiO 2 unit films 421, 422, 423, and 424.
  • Figure 4A illustrates the TiO 2 film stack 420 formed over the SrO film stack 410.
  • the number of unit films depends on the ultimate ratio of titanium to strontium desired in the final STO film. For purposes of example four unit films of TiO 2 are illustrated in Figure 4A, but any number of unit films may be deposited.
  • the total thickness of the combination of ALD supercycle to form the multiple depositions of the TiO 2 unit films illustrated as film stack 420 and the ALD supercycle to form multiple depositions of the SrO unit films illustrated as film stack 410 has a thickness in the approximate range of 2 angstroms to 10 angstroms, and in some embodiments of less than approximately 5 angstroms and in a more particular embodiment the total thickness is in the approximate range of 3 angstroms and 4 angstroms.
  • the total thickness of both film stacks 410 and 420 of the SrO and TiO 2 unit films was determined experimentally as those film stacks providing improved dielectric constant and leakage data, as will be described in more detail later.
  • Deposition of the plurality of SrO and the plurality of TiO 2 unit films in multiple ALD supercycles may be repeated to ultimately form a strontium titanate film having any predetermined thickness.
  • Figure 4B illustrates one embodiment where only one SrO film stack and one TiO 2 film stack are formed, but this is not meant to be limiting. Further ALD supercycle depositions may be performed above the TiO 2 film stack 420, depositing SrO alternating with TiO 2 to build any predetermined thickness for the ultimate strontium titanate film.
  • the predetermined thickness of the strontium titanate film may be in the range of 10 nm - 20 nm and more particularly approximately 15 nm. These thicknesses of the strontium titanate film were determined by the optimization of the strontium titanate film to have a high dielectric constant (k) of greater than 45 and more particularly a dielectric constant of greater than 50 and may also provide lower leakage density values, as will be shown in the Experimental Results. Additionally, in one particular embodiment, the ratio of the plurality of SrO films in film stack 410 to the plurality of TiO 2 films in the film stack 420 for a capacitive device may be 3:2, or any multiple of the 3:2 ratio, for example 6:4 (as illustrated in Figure 4B) or 12:8.
  • both the plurality of SrO unit films (film stack 410) and the plurality of TiO 2 unit films (film stack 420) are annealed to form a strontium titanate (STO) layer 440 as illustrated in Figure 4C.
  • the annealing may be at a temperature in the approximate range of 550 0 C and 700 0 C, and more particularly at a temperature of approximately 600 0 C and 650 0 C.
  • the annealing of the SrO film stack 410 (or film stacks) and the TiO 2 film stack 420 (or film stacks) may occur before forming a second conductive layer over the STO film.
  • annealing the SrO and TiO 2 film stacks may provide lower leakage density (J) and a higher dielectric constant (k) for strontium titanate films formed by this method.
  • the annealing may occur after forming the second conductive layer.
  • the ambient atmosphere in which the annealing is performed may be nitrogen gas, oxygen gas, or an inert gas.
  • the composition of the strontium titanate layer depends on the ratio of the number of TiO 2 unit films to the number of SrO unit films deposited.
  • the forming of the TiO 2 unit film is repeated a first number of times and the forming of the SrO unit film is repeated a second number of times, and the ratio of the first number to the second number is selected to form a strontium titanate film having a predetermined stoiciometry.
  • the predetermined stoiciometry may be in the approximate range of 0.48 Sr/(Sr+Ti) to 0.56 Sr/(Sr+Ti), and more particularly in the range of 0.50 Sr/(Sr+Ti) to 0.52 Sr/(Sr+Ti).
  • FIGS 6A and 6B show that the selection of the Ti-I and the Sr-precursor in combination with ozone may lead to less incorporation of carbon in the final strontium titanate film. It is theorized that the TiO 2 unit film incorporates little to no carbon because the Ti-precursor makes a clean break between the Ti-C bonds during the reaction with ozone so that the oxygen from the ozone may react only with the Ti atoms. It was unexpected that ozone would be the best oxidizer for the formation of the TiO 2 films using the Ti-precursor.
  • Figures 6A and 6B show x-ray photoelectron spectroscopy (XPS) data of the atomic percent of carbon in two strontium titanate films formed by ALD using the Ti-AP-I and Sr-C+ precursors.
  • FIG. 7 shows a chart 700 having data of the predicted atomic percent of strontium (column 701) vs. actual measured atomic percent of strontium (column 702) for multiple strontium titanate films varied by the number of TiO 2 unit films (Ti cycles, column 703) and SrO unit films (Sr cycles, column 704) deposited in an ALD supercycle. These experiments were conducted to not only determine the actual stoiciometry of each strontium titanate film, but also to provide strontium titanate films from which physical and electrical data could be collected.
  • the STO films represented by Figure 7 were deposited on both SiO 2 and platinum (Pt) substrates.
  • the Pt samples were used to identify the optimal supercycle thickness and the optimal supercycle ratio of TiO 2 to SrO unit films within the supercycle to obtain a particular atomic percent of strontium in the strontium titanate film.
  • the study of the strontium titanate films represented by the data in chart 700 of Figure 7 compares different variations in the ratio of the number of TiO 2 unit films to the number of SrO unit films within an ALD supercycle.
  • set # Ia in row 705 the composition of the resulting strontium titanate film after annealing the film stack is the same for each experiment, but the thicknesses of the individual unit films within the ALD supercycle are varied.
  • set # Ib in row 706 the composition of the resulting strontium titanate film is varied along with variation of the thicknesses of the unit films within the ALD supercycle.
  • set # 2 in row 707 and set # 3 in row 708 represent extreme variations of both the unit film thicknesses in a single ALD supercycle as well as extreme variations in strontium titanate compositions.
  • Figure 8A shows experimental data of the impact of the supercycle thickness on the dielectric constant of the final strontium titanate film.
  • the supercycle thickness is plotted against the dielectric constant (k) of the strontium titanate film.
  • the optimal thickness was found to be in the approximate range of 2 angstroms and 10 angstroms because the dielectric constant (k) values are the highest. Obtaining a high k value while minimizing the thickness of the strontium titanate film may be valuable in the use of strontium titanate films of the current invention as the insulator in memory devices (such as DRAM.)
  • the impact of the ALD supercycle thickness on the dielectric constant was studied.
  • the ALD supercycle thickness is the combination of both the TiO 2 and SrO unit films.
  • Figure 8A plots the ALD supercycle thickness in angstroms (A) on the x-axis and the dielectric constant (k) on the y-axis of the data from set # Ia in row 605 of Figure 6. The graph shows that the highest dielectric constants (k) having values of approximately 40 and higher are provided by ALD supercycle film stacks having an ALD supercycle thickness of less than approximately 6 angstroms.
  • FIG. 8B shows that the variation in the ALD supercycle film stack thickness does not impact the composition of the final resulting strontium titanate films after annealing.
  • Figure 8B shows x-ray crystallography data for strontium titanate films having the same ratios of TiO 2 unit films to SrO unit films but where the thicknesses of those unit films was varied.
  • the strontium titanate (110) peak position did not change for any of the STO films analyzed. This result suggests that the ALD supercycle thickness does not have a significant impact on the final resulting composition of the STO films formed after annealing the ALD supercycle film stack.
  • Figure 8C is a chart showing the relationship between SrO/TiO 2 ratio, film stack thickness, leakage density (J), effective oxide thickness (EOT), and dielectric constant (K).
  • Figure 9 shows the impact of the variation of composition of the strontium titanate films on the dielectric constant (k) of the STO film. A sampling of the strontium titanate films formed according to the data provided in Figure 7 are shown on the graph of Figure 9.
  • Figure 9 plots the composition of the strontium titanate film (Sr/((Sr+Ti)) against the dielectric constant (k) of the films.
  • the films having a composition of approximately 0.50 Sr/((Sr+Ti) have the highest dielectric constants of above approximately 40. More specifically, the compositions of approximately 0.52 + 0.1 Sr/((Sr+Ti) yield a dielectric constant (k) of above 50 and more particularly a k of 54.
  • Figure 1OA shows data of how the composition of the strontium titanate film effects the leakage density (J) of the strontium titanate film.
  • Figure 1OB shows data of how the composition of the strontium titanate film affects the effective oxide thickness (EOT) of the strontium titanate film.
  • Figure 11 provides another way to look at the optimal range of supercycle film stack thicknesses and the optimal range of strontium titanate compositions.
  • the strontium titanate composition (Sr/(Sr+Ti)) is plotted on the x-axis and the supercycle film stack thickness (angstroms) is plotted on the y-axis to form a contour plot showing an area where the dielectric constant values are optimized to be greater than 45.
  • Figure 12 Leakage density was improved in this embodiment by depositing SrO first.
  • Figure 13 Prepulsing before first deposition on the first conductive layer (electrode) improves leakage density of strontium titanate film.
  • the ALD process is optimized to form a strontium titanate film having no carbon in the bulk portion of the film, where the detectable limit of carbon is an atomic ratio of less than approximately 0.2.
  • Figures 1OA and 1OB show x-ray photoelectron spectroscopy (XPS) data of the atomic percent of carbon in two strontium titanate films formed by ALD using the Ti-AP-I and Sr-C+ precursors.
  • Figure 1OA is an XPS analysis graph of counts per second (CPS) (x 10 3 ) vs.
  • Binding Energy (eV) of a strontium titanate film formed by the annealing of an ALD supercycle nanolaminate where the number of titanium oxide layers is 10 and the number of SrO layers is 20 (Ti:Sr 10:20).
  • eV Binding Energy
  • Figure 1OB is an XPS analysis graph of CPS (x 10 3 ) vs.
  • Binding Energy (eV) of a strontium titanate film formed by the annealing of an ALD supercycle nanolaminate where the number of titanium oxide layers is 11 and the number of SrO layers is 20 (Ti:Sr 11:20).
  • this film having an atomic percent of strontium of 0.57 (Sr/(Sr+Ti)) there is no detectable carbon in the bulk strontium titanate film and also no detectable carbon at the surface of the film. Therefore, it has been experimentally shown that a strontium titanate film formed by the annealing of an ALD nanolaminate can be formed with an atomic percent of carbon of 0.2 or less.
  • the optimization of the strontium titanate film to obtain a film having an atomic percent of carbon of 0.2 or less may be accomplished through the selection of the precursors and the selection of the process conditions. Minimizing the amount of carbon in the film increases the dielectric constant of the strontium titanate film. Less carbon is theorized to improve the crystallization of the strontium titanate film into the cubic phase that maximizes the value of the dielectric constant (k).
  • an optimized strontium titanate film having a dielectric constant value (k) of greater than 50 may be obtained using methodologies disclosed herein.
  • a strontium titanate film having a dielectric constant of greater than 50 may be formed by the annealing of an ALD supercycle nanolaminate structure having an overall thickness of approximately 15 nm.
  • This ALD supercycle nanolaminate structure is formed by repeating the deposition of a plurality of TiO 2 unit films and a plurality of SrO unit films where the thickness of the TiO 2 and SrO unit films in a single supercycle are in the approximate range of 3 angstroms and 4 angstroms.
  • Multiple ALD supercycles may be performed to obtain the overall thickness of an approximately 15 nm nanolaminate structure.
  • the ratio of TiO 2 to SrO unit films within each of the ALD supercycles is selected to provide a strontium titanate film having approximately 52 atomic percent strontium.
  • the combination of the supercycle thicknesses, the thickness of the ALD supercycle nanolaminate structure, and the composition of the strontium titanate film were experimentally determined, as shown by the results described earlier, to provide an optimized strontium titanate film having a k value of greater than 50.

Abstract

Embodiments of the current invention include methods of forming a strontium titanate (SrTiO3) film using atomic layer deposition (ALD). More particularly, the method includes forming a plurality of titanium oxide (TiO2) unit films using ALD and forming a plurality of strontium oxide (SrO) unit films using ALD. The combined thickness of the TiO2 and SrO unit films is less than approximately 5 angstroms. The TiO2 and SrO units films are then annealed to form a strontium titanate layer.

Description

Method of Forming Strontium Titanate Films
FIELD OF THE INVENTION
[0001] The present invention relates generally to semiconductor processing. More specifically, methods of forming high dielectric constant films using atomic layer deposition are described.
BACKGROUND OF THE INVENTION
[0002] Industry continues to search for new semiconductor materials that exhibit a high dielectric constant and low leakage to enable further miniaturization of electronic technologies. Such materials for example may be used as the dielectric layer in electronic components such as capacitors, memory cell structures, and other types of electronic components. But, most materials investigated to date exhibit either high dielectric constant and high leakage, or low dielectric constant and low leakage. Therefore, industry has turned to investigating combinations of these materials in order to develop materials with the requisite properties. Strontium titanate (SrTiO3) is one such material that is being investigated for having a high dielectric constant and low leakage.
BRIEF DESCRIPTION OF THE DRAWINGS
[0003] Various embodiments of the invention are disclosed in the following detailed description and the accompanying drawings:
[0004] Figure 1 is a flowchart describing a method of forming a capacitive device including forming a strontium titanate film;
[0005]
[0006] Figure 2 is a flowchart describing a method of forming a strontium titanate layer, according to one embodiment; [0007]
[0008] Figure 3 is a flowchart describing a method of forming layers by atomic layer deposition, according to one embodiment of the current invention;
[0009]
[0010] Figures 4A-4D illustrate the formation of a strontium titanate film by atomic layer deposition;
[0011]
[0012] Figures 5A-5B illustrate the chemical structures of precursors that may be used in the atomic layer deposition of a strontium titanate layer, according to various embodiments of the current invention; [0013]
[0014] Figures 6A and 6B are data from an x-ray photoelectron spectroscopy (XPS) analysis of the carbon content of two strontium titanate films; [0015]
[0016] Figure 7 is a chart showing the results of a study of strontium titanate film compositions having various ALD supercycle thicknesses and ratios;
[0017] [0018] Figure 8A is a graph showing the relationship between the ALD supercycle thicknesses and the dielectric constant values in strontium titanate films;
[0019]
[0020] Figure 8B is a comparison of x-ray crystallography data of strontium titanate films having varied supercycle thicknesses but the same composition; [0021]
[0022] Figure 8C is a chart showing the data for multiple strontium titanate films having varied strontium oxide to titanium oxide ratios of supercycle thicknesses and the related leakage density, dielectric constant (k), and effective oxide thickness (EOT) values for each film; [0023]
[0024] Figure 9 is a graph showing the impact of composition of various strontium titanate films on dielectric constant value;
[0025]
[0026] Figure 1OA is a graph showing the relationship between the strontium titanate film composition, leakage density (J), and dielectric constant (k);
[0027] [0028] Figure 1OB is a graph showing the relation ship between the strontium titanate film composition, leakage density (J), and effective oxide thickness (EOT); [0029]
[0030] Figure 11 is a contour plot of dielectric constant values for strontium titanate films having varied supercycle thicknesses and varied compositions; [0031]
[0032] Figure 12 is a graph comparing the leakage density of strontium titanate films (approx. 0.52 Sr/(Sr+Ti)) where strontium is deposited first to strontium titanate films where titanium is deposited first; this graph also compares strontium titanate films annealed at different temperatures and for different times; [0033]
[0034] Figure 13 is a chart comparing a strontium titanate film that was deposited by a method where 50 strontium presaturation pulses were used to a strontium titanate film that was deposited by a method where 100 strontium presaturation pulses were used.
DETAILED DESCRIPTION
[0035] A detailed description of one or more embodiments is provided below along with accompanying figures. The detailed description is provided in connection with such embodiments, but is not limited to any particular example. The scope is limited only by the claims and numerous alternatives, modifications, and equivalents are encompassed. Numerous specific details are set forth in the following description in order to provide a thorough understanding. These details are provided for the purpose of example and the described techniques may be practiced according to the claims without some or all of these specific details. For the purpose of clarity, technical material that is known in the technical fields related to the embodiments has not been described in detail to avoid unnecessarily obscuring the description.
[0036] Embodiments of the current invention include methods of forming a strontium titanate (SrTiO3) film using atomic layer deposition (ALD). More particularly, the method includes forming a plurality of strontium oxide (SrO) unit films using ALD and forming a plurality of titanium oxide (TiO2) unit films using ALD. The combined thickness of the SrO and TiO2 unit films is less than approximately 5 angstroms. The SrO and TiO2 units films are then annealed to form a strontium titanate layer. This anneal may occur before the deposition of any other material over the SrO and TiO2 unit films. The strontium titanate layer formed by these methods and others described herein may have an increased dielectric constant and an improved electrical leakage value (J). In embodiments, the strontium titanate film may be the dielectric layer of a capacitive device. [0037] Figure 1 illustrates a flowchart describing an embodiment of forming a capacitive device that includes a strontium titanate dielectric film. At block 101 of Figure 1 a first conductive layer 405 is formed over a substrate 403, as illustrated in Figure 4. The first conductive layer 405 may be a material such as titanium nitride (TiN), platinum, iridium, iridium oxide, tungsten, tungsten oxide, molybdenum, molybdenum oxide, ruthenium and ruthenium oxide that are often used as the electrode materials of dynamic random access memory (DRAM) cells.
[0038] In an embodiment, a strontium oxide (SrO) film 410 may then be deposited over the first conductive layer 405 at block 102. In this particular embodiment, SrO is deposited on the first conductive layer before the deposition of titanium oxide because experimental data have shown that depositing SrO first may lower the leakage density of the ultimately formed strontium titanate film, as will be shown later in the experimental results section. The SrO film 410 may be deposited by a vapor deposition method such as atomic layer deposition (ALD) or chemical vapor deposition (CVD). The flowchart of Figure 2 describes forming a plurality of SrO unit films using ALD or CVD. At block 201 of Figure 2 a plurality of SrO unit films are deposited using atomic layer deposition (ALD) or CVD. The strontium oxide unit films are formed as described in blocks 301 and 302 of the flowchart of Figure 3 by forming at block 301 a strontium-containing monolayer on a substrate by pulsing a strontium precursor over a substrate and at block 302 by oxidizing said strontium containing monlayer by pulsing an oxygen containing source over the substrate. The oxygen containing source may be selected from the list including ozone, oxygen, plasma activated oxygen, and water. [0039] At block 301 a strontium (Sr)-containing monolayer is formed by pulsing a Sr precursor over the substrate. In embodiments of the current invention, the strontium- containing precursors may be polydentate β-ketoiminates which are found, for example, in co-pending application US20070248754A1, US Serial No. 11/945678 filed on November 27, 2007, co-pending application U.S. Serial No. 12/266,806 which was filed on November 11, 2008, and co-pending application or U.S. Serial No. 12/245,196 which was filed on October 3, 2008. In certain embodiments, the polydentate β-ketoiminates may incorporate an alkoxy group in the imino group. The polydentate β-ketoiminates are selected from the group represented by the following Structure A. [0040] Structure A is defined as
Figure imgf000009_0001
[0041] wherein M is Strontium; R1 is selected from the group consisting of alkyl, fluoroalkyl, cycloaliphatic, having from 1 to 10 carbon atoms, preferably a group containing 1 to 6 carbon atoms, and an aryl group having from 6 to 12 carbon atoms; R2 is selected from the group consisting of hydrogen, alkyl, alkoxy, cycloaliphatic, having from 1 to 10 carbon atoms, preferably a group containing 1 to 6 carbon atoms, and an aryl group having from 6 to 12 carbon atoms; R3 is selected from the group consisting of alkyl, fluoroalkyl, cycloaliphatic, having from 1 to 10 carbon atoms, preferably a group containing 1 to 6 carbon atoms, and an aryl group having from 6 to 12 carbon atoms; R4 is a C2-3 linear or branched alkylene bridge with or without chiral carbon atom, thus making a five- or six-membered coordinating ring to the metal center; R5"6 are individually selected from the group consisting of alkyl, fluoroalkyl, cycloaliphatic, having from 1 to 10 carbon atoms, preferably a group containing 1 to 6 carbon atoms, and an aryl group having from 6 to 12 carbon atoms, and they can be connected to form a ring containing carbon, oxygen, or nitrogen atoms. Figure 5 illustrates one particular embodiment of the strontium precursor selected from the class of polydentate β- ketoiminates.
[0042] The temperature of the substrate during deposition of the strontium precursor may be in the approximate range of 2900C and 310 0C, and more particularly approximately 300 0C. This temperature range is selected because it is the temperature window within which the deposition of the strontium precursor is optimal. The Sr- precursor can be delivered to the deposition chamber using vapor draw (with or without charging up), bubbling, or direct liquid injection. A carrier gas may be used to deliver the Sr-precursor. The choice of delivery system typically depends on the particular ALD deposition tool. The Sr-precursor is pulsed into the ALD reaction chamber for a time sufficient to form a monolayer or less of the Sr-precursor material on the substrate. The absorption of the precursor on the substrate is self-limiting, so under ALD process mode conditions the absorption should stop once the monolayer or less of the precursor material has formed on the surface. In an embodiment, the pulse time for the Sr- precursor to form one monolayer on the substrate may vary from tool to tool, precursor delivery method, substrate temperature, and similar factors. For example, the pulse time may be approximately one second on a Cambridge NanoTech atomic layer deposition tool (Savannah) with 20 SCCM Argon carrier gas at 3000C. The pulsing of the Ti- precursor may be followed by a purge by an inert gas such as Argon. In one particular embodiment, using the Cambridge NanoTech ALD tool described above, the purge may be a five second argon purge. [0043] This class of strontium precursors have been found not to incorporate detectable amounts of carbon in the films. Without being bound by theory, it is postulated that with these precursors the Sr ligand bonds are completely oxidized during exposure to an oxygen containing source such as ozone or oxygen. The oxidation in the flow occurs at block 302 of the flowchart of Figure 3. At block 302 a strontium oxide (SrO) unit film is formed by reacting the Sr-containing monolayer with ozone as the oxidizer. The use of ozone is practical and cost-effective because an exotic oxidizer is not needed. The forming of the SrO film is then repeated to form multiple layers of the SrO film during the ALD supercycle. An ALD supercycle is when more than one unit film is layered to obtain a particular thickness of material. For example, in Figure 4A the multiple layers of the SrO unit films 411, 412, 413, 414, 415, and 416 may be in the form of a film stack 410.
[0044] In an embodiment, the deposition of the strontium monolayer may include multiple pre- saturation pulses. The pre-saturation pulses may be performed during only the first Sr-precursor deposition of SrO film 411 over the first conductive layer 405. The number of pre-saturation pulses may be in the approximate range of 50 - 200 pulses in a Cambridge NanoTech atomic layer deposition tool (Savannah). Experimental results of embodiments of the current invention support this claim.
[0045] At block 103 of the flowchart in Figure 1 a titanium oxide (TiO2) film is also deposited over the conductive layer. The TiO2 may also be deposited by the method described in the flowchart of Figure 2 at block 202 by forming a plurality of TiO2 films using ALD. More specifically, the ALD deposition may occur as described in Figure 3 at blocks 304 and 305. At block 304 a Ti-containing monolayer is formed on the substrate by pulsing a Ti precursor over the substrate. The Ti precursor may be chosen from the family of liquid group 4 precursors are represented by the following formula I:
Figure imgf000012_0001
In formula I above, M comprises Ti; R1 is an alkyl group comprising from 1 to 10 carbon atoms; R2 is an alkyl group comprising from 1 to 10 carbon atoms; R3 is chosen from hydrogen or an alkyl group comprising from 1 to 3 carbon atoms; R4 is an alkyl group comprising from 1 to 6 carbon atoms.
[0046] In a particular embodiment, the titanium precursor (Ti-precursor) may be described as Ti-I, a precursor in which the titanium atom is coordinated with 2 tert- butoxy groups and 2 unsymmetrical beta-diketonato resulting in a preferred coordination number of 6 for Ti atom. An example of this class of Ti-I precursors is illustrated in Figure 5B.
[0047] The substrate may be a conductive layer such as an electrode described above in relation to the SrO deposition or the substrate may be one or more layers of the previously deposited SrO films. The temperature of the substrate may be in the approximate range of 2500C and 4000C, and more particularly in the approximate range of 2900C and 3100C, and even more particularly approximately 3000C. This temperature range is selected because it is the temperature within which the deposition of this class titanium precursor, and in particular Ti-I, is optimal. The Ti-precursor can be delivered to the deposition chamber using vapor draw (with or without charging up), bubbling, or direct liquid injection. A carrier gas may be used to deliver the Ti-precursor. The choice of delivery system typically depends on the particular ALD deposition tool. The Ti- precursor is pulsed into the ALD reaction chamber for a time sufficient to form a monolayer or less of the Ti-precursor material on the substrate. The absorption of the precursor on the substrate is self -limiting, so under optimized process conditions the absorption should stop once the monolayer or less of the precursor material has formed on the surface. In an embodiment, the pulse time for the Ti-precursor to form one monolayer on the substrate may vary from tool to tool, precursor delivery method, substrate temperature, and similar factors. For example, the pulse time may be approximately one second on a Cambridge NanoTech atomic layer deposition tool (Savannah) with 20 SCCM Argon carrier gas at 3000C. The pulsing of the Ti-precursor may be followed by a purge of an inert gas such as Argon. In one particular embodiment the purge may be a five second argon purge on the Cambridge NanoTech ALD tool described above.
[0048] In an embodiment, there may be multiple pre- saturation pulses of the Ti-I precursor before the deposition of the first TiO2 unit film, particularly in the instance where the Ti-I precursor is deposited directly on an electrode. This may have an effect on the formation of the intermediate layer between the electrode and the TiO2 film which may reduce the overall leakage of the strontium titanate film that is ultimately formed. Experimental results of embodiments of the current invention support this claim. [0049] At block 305 of Figure 3 a TiO2 unit film is formed by reacting the titanium containing monolayer with ozone (O3) as the oxidizer. In an embodiment, the temperature of the substrate is maintained at the same temperature as the deposition of the Ti-precursor monolayer. Ozone is pulsed into the ALD deposition chamber for a time sufficient to oxidize all of the titanium atoms in the Ti-containing monolayer. As described above for the formation of the Ti-precursor monolayer, the oxidation reaction is self-limiting and therefore under the optimized conditions will not continue reacting once all of the titanium precursor molecules have been oxidized. In one particular embodiment, the ozone is flowed into the deposition chamber for a pulse time of approximately 1 second followed an approximately 5 second argon purge. The Ti-I precursor and ozone may be selected to form the TiO2 film because they are compatible and ozone is a practical and cost effective oxidizer. Additionally, as will be in the Experimental Results section, the combination of the Ti-I precursor and ozone may also lower the carbon content of the ultimately formed strontium titanate film. [0050] Multiple TiO2 unit films are formed by repeating the forming of the TiO2 film during an ALD supercycle at block 306 of the flowchart in Figure 3. An ALD supercycle is when more than one unit film is layered to obtain a particular thickness of material. The plurality of TiO2 unit films is illustrated in Figure 4A as the film stack 420 that is made up of the individual TiO2 unit films 421, 422, 423, and 424. Figure 4A illustrates the TiO2 film stack 420 formed over the SrO film stack 410. The number of unit films depends on the ultimate ratio of titanium to strontium desired in the final STO film. For purposes of example four unit films of TiO2 are illustrated in Figure 4A, but any number of unit films may be deposited.
[0051] In this embodiment, the total thickness of the combination of ALD supercycle to form the multiple depositions of the TiO2 unit films illustrated as film stack 420 and the ALD supercycle to form multiple depositions of the SrO unit films illustrated as film stack 410. The total thickness of the SrO and TiO2 layers of unit films deposited by the ALD supercycles has a thickness in the approximate range of 2 angstroms to 10 angstroms, and in some embodiments of less than approximately 5 angstroms and in a more particular embodiment the total thickness is in the approximate range of 3 angstroms and 4 angstroms. The total thickness of both film stacks 410 and 420 of the SrO and TiO2 unit films was determined experimentally as those film stacks providing improved dielectric constant and leakage data, as will be described in more detail later. [0052] Deposition of the plurality of SrO and the plurality of TiO2 unit films in multiple ALD supercycles may be repeated to ultimately form a strontium titanate film having any predetermined thickness. Figure 4B illustrates one embodiment where only one SrO film stack and one TiO2 film stack are formed, but this is not meant to be limiting. Further ALD supercycle depositions may be performed above the TiO2 film stack 420, depositing SrO alternating with TiO2 to build any predetermined thickness for the ultimate strontium titanate film. In an embodiment, the predetermined thickness of the strontium titanate film may be in the range of 10 nm - 20 nm and more particularly approximately 15 nm. These thicknesses of the strontium titanate film were determined by the optimization of the strontium titanate film to have a high dielectric constant (k) of greater than 45 and more particularly a dielectric constant of greater than 50 and may also provide lower leakage density values, as will be shown in the Experimental Results. Additionally, in one particular embodiment, the ratio of the plurality of SrO films in film stack 410 to the plurality of TiO2 films in the film stack 420 for a capacitive device may be 3:2, or any multiple of the 3:2 ratio, for example 6:4 (as illustrated in Figure 4B) or 12:8. These ratios were experimentally determined to provide lower leakage density as measured on a completed strontium titanate film as will be shown in the Experimental Results section. The flowcharts and figures describe a strontium titanate film formed by first depositing SrO films before depositing TiO2 films. This embodiment is not meant to be limiting because in an alternate embodiment a titanium oxide (TiO2) film may be deposited first over the first conductive layer 405 followed by the deposition of the SrO film.
[0053] At block 203 of the flowchart in Figure 2, both the plurality of SrO unit films (film stack 410) and the plurality of TiO2 unit films (film stack 420) are annealed to form a strontium titanate (STO) layer 440 as illustrated in Figure 4C. The annealing may be at a temperature in the approximate range of 550 0C and 7000C, and more particularly at a temperature of approximately 600 0C and 650 0C. In one embodiment, represented by block 105 of Figure 1, the annealing of the SrO film stack 410 (or film stacks) and the TiO2 film stack 420 (or film stacks) may occur before forming a second conductive layer over the STO film. Experimental results show that in some embodiments annealing the SrO and TiO2 film stacks may provide lower leakage density (J) and a higher dielectric constant (k) for strontium titanate films formed by this method. In an alternate embodiment, the annealing may occur after forming the second conductive layer. The ambient atmosphere in which the annealing is performed may be nitrogen gas, oxygen gas, or an inert gas. The composition of the strontium titanate layer depends on the ratio of the number of TiO2 unit films to the number of SrO unit films deposited. During the ALD supercycle described above and in blocks 101 and 102 of the flowchart of Figure 1, the forming of the TiO2 unit film is repeated a first number of times and the forming of the SrO unit film is repeated a second number of times, and the ratio of the first number to the second number is selected to form a strontium titanate film having a predetermined stoiciometry. In an embodiment of the current invention, the predetermined stoiciometry may be in the approximate range of 0.48 Sr/(Sr+Ti) to 0.56 Sr/(Sr+Ti), and more particularly in the range of 0.50 Sr/(Sr+Ti) to 0.52 Sr/(Sr+Ti). In one particular embodiment, the composition is formed to have a stoiciometry of approximately 0.52 atomic % strontium in the strontium titanate film (Sr/(Sr + Ti) = 0.52+0.2). [0054] Experimental Results:
[0055] Figures 6A and 6B show that the selection of the Ti-I and the Sr-precursor in combination with ozone may lead to less incorporation of carbon in the final strontium titanate film. It is theorized that the TiO2 unit film incorporates little to no carbon because the Ti-precursor makes a clean break between the Ti-C bonds during the reaction with ozone so that the oxygen from the ozone may react only with the Ti atoms. It was unexpected that ozone would be the best oxidizer for the formation of the TiO2 films using the Ti-precursor. This is because ozone is often not compatible with many Ti- precursors and, in embodiments of this invention, ozone is not only compatible with Ti-I but also ultimately provides low carbon strontium titanate films. Experimental results shown in Figures 6A and 6B show no detectable carbon within bulk strontium titanate films formed using ozone as the oxidizer, a strontium precursor selected from the class of polydentate β-ketoiminates, and Ti-I using the processing conditions described above. The ALD process is optimized to form a strontium titanate film having no carbon in the bulk portion of the film, where the detectable limit of carbon is an atomic ratio of less than approximately 0.2. Figures 6A and 6B show x-ray photoelectron spectroscopy (XPS) data of the atomic percent of carbon in two strontium titanate films formed by ALD using the Ti-AP-I and Sr-C+ precursors. Figure 6A is an XPS analysis graph of counts per second (CPS) (x 103) vs. Binding Energy (eV) of a strontium titanate film formed by the annealing of an ALD supercycle nanolaminate where the number of titanium oxide layers is 10 and the number of SrO layers is 20 (Ti:Sr = 10:20). For this film having an atomic percent of strontium of 0.60 (Sr/(Sr+Ti)) there is no detectable carbon in the bulk strontium titanate film and a small amount of detectable carbon at the surface of the film. Figure 6B is an XPS analysis graph of CPS (x 10 ) vs. Binding Energy (eV) of a strontium titanate film formed by the annealing of an ALD supercycle nanolaminate where the number of titanium oxide layers is 11 and the number of SrO layers is 20 (Ti:Sr = 11 :20). For this film having an atomic percent of strontium of 0.57 (Sr/(Sr+Ti)) there is no detectable carbon in the bulk strontium titanate film and also no detectable carbon at the surface of the film. Therefore, it has been experimentally shown that a strontium titanate film formed by the annealing of an ALD nanolaminate can be formed with an atomic percent of carbon of 0.2 or less. The optimization of the strontium titanate film to obtain a film having an atomic percent of carbon of 0.2 or less may be accomplished through the selection of the precursors and the selection of the process conditions. Minimizing the amount of carbon in the film increases the dielectric constant of the strontium titanate film. Less carbon is theorized to improve the crystallization of the strontium titanate film into the cubic phase that maximizes the value of the dielectric constant (k). [0056] Figure 7 shows a chart 700 having data of the predicted atomic percent of strontium (column 701) vs. actual measured atomic percent of strontium (column 702) for multiple strontium titanate films varied by the number of TiO2 unit films (Ti cycles, column 703) and SrO unit films (Sr cycles, column 704) deposited in an ALD supercycle. These experiments were conducted to not only determine the actual stoiciometry of each strontium titanate film, but also to provide strontium titanate films from which physical and electrical data could be collected. As such, the STO films represented by Figure 7 were deposited on both SiO2 and platinum (Pt) substrates. The Pt samples were used to identify the optimal supercycle thickness and the optimal supercycle ratio of TiO2 to SrO unit films within the supercycle to obtain a particular atomic percent of strontium in the strontium titanate film. The study of the strontium titanate films represented by the data in chart 700 of Figure 7 compares different variations in the ratio of the number of TiO2 unit films to the number of SrO unit films within an ALD supercycle. In the first set of experiments, set # Ia in row 705, the composition of the resulting strontium titanate film after annealing the film stack is the same for each experiment, but the thicknesses of the individual unit films within the ALD supercycle are varied. In the second set of experiments, set # Ib in row 706, the composition of the resulting strontium titanate film is varied along with variation of the thicknesses of the unit films within the ALD supercycle. The last two sets of experiments, set # 2 in row 707 and set # 3 in row 708, represent extreme variations of both the unit film thicknesses in a single ALD supercycle as well as extreme variations in strontium titanate compositions. [0057] Figure 8A shows experimental data of the impact of the supercycle thickness on the dielectric constant of the final strontium titanate film. On the x-axis the supercycle thickness is plotted against the dielectric constant (k) of the strontium titanate film. The optimal thickness was found to be in the approximate range of 2 angstroms and 10 angstroms because the dielectric constant (k) values are the highest. Obtaining a high k value while minimizing the thickness of the strontium titanate film may be valuable in the use of strontium titanate films of the current invention as the insulator in memory devices (such as DRAM.) In Figure 8A the impact of the ALD supercycle thickness on the dielectric constant was studied. The ALD supercycle thickness is the combination of both the TiO2 and SrO unit films. Figure 8A plots the ALD supercycle thickness in angstroms (A) on the x-axis and the dielectric constant (k) on the y-axis of the data from set # Ia in row 605 of Figure 6. The graph shows that the highest dielectric constants (k) having values of approximately 40 and higher are provided by ALD supercycle film stacks having an ALD supercycle thickness of less than approximately 6 angstroms. These data suggest that an increase in ALD supercycle film stack thickness may cause a decrease in dielectric constant of the strontium titanate films. This graph also shows the difference in dielectric constant values for strontium titanate films having compositions of approximately 0.532 atomic percent strontium and approximately 0.56 atomic percent strontium. [0058] Figure 8B shows that the variation in the ALD supercycle film stack thickness does not impact the composition of the final resulting strontium titanate films after annealing. Figure 8B shows x-ray crystallography data for strontium titanate films having the same ratios of TiO2 unit films to SrO unit films but where the thicknesses of those unit films was varied. The strontium titanate (110) peak position did not change for any of the STO films analyzed. This result suggests that the ALD supercycle thickness does not have a significant impact on the final resulting composition of the STO films formed after annealing the ALD supercycle film stack.
[0059] Figure 8C is a chart showing the relationship between SrO/TiO2 ratio, film stack thickness, leakage density (J), effective oxide thickness (EOT), and dielectric constant (K). [0060] Figure 9 shows the impact of the variation of composition of the strontium titanate films on the dielectric constant (k) of the STO film. A sampling of the strontium titanate films formed according to the data provided in Figure 7 are shown on the graph of Figure 9. Figure 9 plots the composition of the strontium titanate film (Sr/((Sr+Ti)) against the dielectric constant (k) of the films. These data suggest that higher amounts of strontium (Sr/(Sr+Ti)) in the strontium titanate films increases the dielectric constant. The films having a composition of approximately 0.50 Sr/((Sr+Ti) have the highest dielectric constants of above approximately 40. More specifically, the compositions of approximately 0.52 + 0.1 Sr/((Sr+Ti) yield a dielectric constant (k) of above 50 and more particularly a k of 54. [0061] Figure 1OA shows data of how the composition of the strontium titanate film effects the leakage density (J) of the strontium titanate film.
[0062] Figure 1OB shows data of how the composition of the strontium titanate film affects the effective oxide thickness (EOT) of the strontium titanate film. [0063] Figure 11 provides another way to look at the optimal range of supercycle film stack thicknesses and the optimal range of strontium titanate compositions. The strontium titanate composition (Sr/(Sr+Ti)) is plotted on the x-axis and the supercycle film stack thickness (angstroms) is plotted on the y-axis to form a contour plot showing an area where the dielectric constant values are optimized to be greater than 45.
[0064] Figure 12: Leakage density was improved in this embodiment by depositing SrO first.
[0065] Figure 13: Prepulsing before first deposition on the first conductive layer (electrode) improves leakage density of strontium titanate film. [0066] Additionally, the ALD process is optimized to form a strontium titanate film having no carbon in the bulk portion of the film, where the detectable limit of carbon is an atomic ratio of less than approximately 0.2. Figures 1OA and 1OB show x-ray photoelectron spectroscopy (XPS) data of the atomic percent of carbon in two strontium titanate films formed by ALD using the Ti-AP-I and Sr-C+ precursors. Figure 1OA is an XPS analysis graph of counts per second (CPS) (x 103) vs. Binding Energy (eV) of a strontium titanate film formed by the annealing of an ALD supercycle nanolaminate where the number of titanium oxide layers is 10 and the number of SrO layers is 20 (Ti:Sr = 10:20). For this film having an atomic percent of strontium of 0.60 (Sr/(Sr+Ti)) there is no detectable carbon in the bulk strontium titanate film and a small amount of detectable carbon at the surface of the film. Figure 1OB is an XPS analysis graph of CPS (x 103) vs. Binding Energy (eV) of a strontium titanate film formed by the annealing of an ALD supercycle nanolaminate where the number of titanium oxide layers is 11 and the number of SrO layers is 20 (Ti:Sr = 11:20). For this film having an atomic percent of strontium of 0.57 (Sr/(Sr+Ti)) there is no detectable carbon in the bulk strontium titanate film and also no detectable carbon at the surface of the film. Therefore, it has been experimentally shown that a strontium titanate film formed by the annealing of an ALD nanolaminate can be formed with an atomic percent of carbon of 0.2 or less. The optimization of the strontium titanate film to obtain a film having an atomic percent of carbon of 0.2 or less may be accomplished through the selection of the precursors and the selection of the process conditions. Minimizing the amount of carbon in the film increases the dielectric constant of the strontium titanate film. Less carbon is theorized to improve the crystallization of the strontium titanate film into the cubic phase that maximizes the value of the dielectric constant (k).
[0067] Therefore, in an embodiment of the current invention based on experimental results, an optimized strontium titanate film having a dielectric constant value (k) of greater than 50 may be obtained using methodologies disclosed herein. In one particular embodiment, a strontium titanate film having a dielectric constant of greater than 50 may be formed by the annealing of an ALD supercycle nanolaminate structure having an overall thickness of approximately 15 nm. This ALD supercycle nanolaminate structure is formed by repeating the deposition of a plurality of TiO2 unit films and a plurality of SrO unit films where the thickness of the TiO2 and SrO unit films in a single supercycle are in the approximate range of 3 angstroms and 4 angstroms. Multiple ALD supercycles may be performed to obtain the overall thickness of an approximately 15 nm nanolaminate structure. The ratio of TiO2 to SrO unit films within each of the ALD supercycles is selected to provide a strontium titanate film having approximately 52 atomic percent strontium. The combination of the supercycle thicknesses, the thickness of the ALD supercycle nanolaminate structure, and the composition of the strontium titanate film were experimentally determined, as shown by the results described earlier, to provide an optimized strontium titanate film having a k value of greater than 50. [0068] Although the foregoing examples have been described in some detail for purposes of clarity of understanding, the invention is not limited to the details provided. There are many alternative ways of implementing the invention. The disclosed examples are illustrative and not restrictive.

Claims

What is claimed:
1. A method of forming a strontium titanate layer, comprising: forming a plurality of TiO2 unit films using atomic layer deposition (ALD); forming a plurality of SrO unit films using ALD, wherein the plurality of TiO2 unit films and the plurality of SrO unit films have a combined thickness of less than approximately 5 angstroms; and annealing both the plurality of TiO2 unit films and the plurality of SrO unit films to form the strontium titanate layer.
2. The method of claim 1, wherein the plurality of TiO2 unit films are formed using a Ti precursor comprising Ti-I and an oxidizer comprising ozone.
3. The method of claim 1, wherein the plurality of SrO unit films are formed using a Sr precursor comprising Sr-I and ozone.
4. The method of claim 1, wherein forming the plurality of TiO2 unit films and forming the plurality of SrO unit films comprises an ALD supercycle that is repeated to form a strontium titanate layer having a thickness of less than 15 nanometers.
5. The method of claim 1, wherein the method of forming the strontium titanate layer further comprises selecting process conditions to form the strontium titanate layer with a dielectric constant of greater than approximately 50.
6. The method of claim 1, wherein the method of forming the strontium titanate layer further comprises selecting process conditions to form the strontium titanate layer with an atomic percent of strontium of approximately 52.
7. A method of forming a film by atomic layer deposition, comprising: forming a Ti-containing monolayer over a substrate by pulsing a Ti precursor comprising Ti-I over the substrate; forming a TiO2 unit film by reacting the Ti-containing monolayer with ozone; repeating the forming of the TiO2 unit film to form a plurality of TiO2 unit films; forming a Sr-containing monolayer on the substrate by pulsing a Sr precursor comprising Sr-I over the substrate; forming a SrO unit film by reacting the Sr-containing monolayer with ozone; repeating the forming of the SrO unit film to form a plurality of SrO unit films, wherein a total thickness of the plurality of TiO2 unit films and the plurality of TiO2 unit films is in the approximate range of 2 angstroms and 10 angstroms.
8. The method of claim 7, further comprising annealing the plurality of TiO2 unit films and the plurality of SrO unit films to form a strontium titanate film.
9. The method of claim 7, wherein the substrate temperature is in the approximate range of 2900C and 3100C.
10. The method of claim 7, wherein the substrate temperature is approximately 3000C.
11. The method of claim 7, wherein the repeating of the forming of the TiO2 unit film is performed a first number of times and the repeating of the forming of the SrO film is performed a second number of times, wherein the ratio of the first number to the second number is selected to form the strontium titanate film having a stoiciometry of approximately 0.5 Sr/(Sr+Ti).
12. The method of claim 7, wherein the ALD process is optimized to form a strontium titanate film having an atomic ratio of carbon of less than approximately 0.2.
13. The method of claim 7, wherein the Ti precursor comprising Ti-I is pulsed over the substrate for approximately 1 second followed by a purge by an inert gas for approximately 5 seconds.
14. The method of claim 7, wherein the Sr precursor comprising Sr-I is pulsed over the substrate for approximately 1 second followed by a purge by an inert gas for approximately 5 seconds.
15. The method of claim 7, wherein an oxidizer comprising ozone is pulsed over the substrate for approximately 1 second followed by a purge by an inert gas for approximately 5 seconds.
16. The method of claim 7, wherein the total thickness of the TiO2 and SrO layers is in the approximate range of 3 angstroms and 4 angstroms
17. A method of forming a capacitive device, comprising: forming a first conductive layer over a substrate; depositing a SrO film over the first conductive layer; depositing a TiO2 film over the first conductive layer; annealing the TiO2 film and the SrO film to form a strontium titanate (STO) dielectric film; and forming a second conductive layer over the STO dielectric film after annealing the STO dielectric film.
18. The method of claim 17, wherein depositing the SrO film comprises depositing the SrO film over the first conductive layer before depositing the TiO2 film.
19. The method of claim 17, wherein depositing the SrO film comprises depositing a plurality of SrO unit films.
20. The method of claim 17, wherein depositing the TiO2 film comprises depositing a
plurality of TiO2 unit films.
21. The method of claim 17, wherein annealing the TiO2 film and the SrO film to form the STO dielectric film is performed in a nitrogen ambient and at an annealing temperature in the approximate range of 5500C to 7000C and at an annealing time in the approximate range of 2 - 10 minutes.
22. The method of claim 21, wherein the TiO2 film and the SrO film have a total thickness of 120 angstroms or less, the annealing temperature is approximately 6000C, and the annealing time is approximately 5 minutes.
23. The method of claim 17, wherein forming at least one of the first conductive layer or forming the second conductive layer comprises forming an electrode having a material selected from the group of titanium nitride (TiN), platinum, iridium, iridium oxide, tungsten, tungsten oxide, molybdenum, molybdenum oxide, ruthenium and ruthenium oxide
24. The method of claim 17, further comprising fabricating a dynamic random access memory cell that includes the capacitive device.
25. The method of claim 24, further comprising fabricating a dynamic random access memory device, having an array of dynamic random access memory cells, each cell including the capacitive device.
26. An intermediate film for a capacitive device, comprising: a first capacitive layer formed over a substrate; a plurality of SrO unit films formed over the first capacitive layer; a plurality of TiO2 unit films formed over the SrO film, wherein the ratio of the plurality of SrO films to the plurality of TiO2 films is 3:4.
27. The film of claim 26, further comprising a second capacitive layer formed over the plurality of TiO2 films.
28. The film of claim 27, wherein at least one of the first capacitive layer and the second capacitive layer comprise an electrode having a material selected from the group of titanium nitride (TiN), platinum, iridium, iridium oxide, tungsten, tungsten oxide, molybdenum, molybdenum oxide, ruthenium and ruthenium oxide.
29. The film of claim 26, wherein the plurality of SrO unit films comprise a multiple of three monolayers.
30. The film of claim 26, wherein the plurality of TiO2 films comprises a multiple of four monolayers.
PCT/US2010/037184 2009-06-03 2010-06-03 Methods of forming strontium titanate films WO2010141668A2 (en)

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