Si-containing films deposited at low temperatures from the reaction of chlorosilanes and aminosilanes.

Abstract

A method for depositing silicon and nitrogen containing dielectric films via atomic layer deposition (ALD) or in an ALD-like process. The method includes: a) placing at least one substrate into a reactor and heating the reactor to at least one temperature in the range of about 25°C to about 600°C, and optionally maintaining the reactor at a pressure of about 100 torr or less; b) introducing at least one first precursor into the reactor, the first precursor comprising a halogenated silicon-containing compound that forms a silicon-containing layer; c) purging any unreacted precursor from the reactor using an inert gas; d) introducing at least one second precursor comprising at least two or more primary amino-containing silicon atoms, the second precursor reacting with the silicon-containing layer to form a film comprising silicon and nitrogen; e) purging the reactor using an inert gas; f) introducing a plasma source into the reactor to react with the silicon- and nitrogen-containing film; g) purging any reaction by-products from the reactor using an inert gas; and repeating steps b through g to form a film comprising silicon and nitrogen to a desired thickness.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims the benefit of U.S. Provisional Patent Application No. 63 / 379,433, filed October 13, 2022.

[0002] The present invention relates to compositions and methods for the manufacture of electronic devices. More particularly, the present invention is directed to compounds, compositions, and methods for the deposition of high quality, dense silicon-containing films, such as, but not limited to, stoichiometric silicon nitride, carbon-doped silicon nitride films, and carbon-doped silicon oxynitride films. [Background technology]

[0003] Silicon nitride films are used in semiconductors for a variety of applications. For example, silicon nitride films are commonly used as a final passivation and mechanical protection layer for integrated circuits, a mask layer for selective oxidation of silicon, one of the dielectric materials in stacked oxide-nitride-oxide (ONO) layers in DRAM capacitors or 3D NAND flash memory chips, or as a CMP stop layer in shallow trench isolation applications. In one particular application, the ONO stack in 3D NAND flash requires silicon nitride with low stress and a high wet etch rate in phosphoric acid.

[0004] Olsen, "Analysis of LPCVD Process Conditions for the Deposition of Low Stress Silicon Nitride," 5 Materials Science in Semiconductor Process 51 (2002), describes a wide range of process conditions used to optimize the deposition of low-stress silicon nitride films by low-pressure chemical vapor deposition. The results show that increasing the refractive index beyond 2.3 by increasing gas flow did not appreciably reduce residual stress, but had a significant detrimental effect on thickness uniformity and deposition rate.

[0005] M. Tanaka et al., "Film Properties of Low-k Silicon Nitride Films Formed by Hexachlorodisilane and Ammonia," 147 J. Electrochem. Soc. 2284 (2000), describes a low-temperature process with good step coverage for silicon nitride (SiN) formed by low-pressure chemical vapor deposition (LPCVD) using hexachlorodisilane (HCD).

[0006] JP 2000-100812 A describes a method for depositing a film using SiCl4 and NH3 as source gases. The substrate surface may be nitrided using NH3 prior to deposition. This results in the formation of an ultrathin film with improved insulating properties. Silicon nitride films are useful as capacitor insulating films in semiconductor integrated circuits.

[0007] US Pat. No. 6,355,582 describes a method for forming a silicon nitride film by heating a substrate on which a film is to be formed and supplying silicon tetrachloride and ammonia gas to the substrate heated to a predetermined temperature.

[0008] U.S. Patent No. 10,049,882 describes an atomic layer deposition (ALD) method for manufacturing semiconductor devices, including forming a dielectric layer on a structure having a height difference. The method includes forming a structure having a height difference on a substrate and forming a dielectric layer structure on the structure. The step of forming the dielectric layer structure includes forming a first dielectric layer containing silicon nitride on the structure having a height difference. The step of forming the first dielectric layer includes supplying a first gas containing pentachlorodisilane (PCDS) or diisopropylamine pentachlorodisilane (DPDC) as a silicon precursor and a second gas containing a nitrogen component into a chamber in which the substrate is located, thereby forming the first dielectric layer in situ on the structure having a height difference.

[0009] PCT Publication WO 2018 / 063907 discloses chlorodisilazanes, silicon-heteroatom compounds synthesized therefrom, devices containing the silicon-heteroatom compounds, methods for making the chlorodisilazanes, silicon-heteroatom compounds, and devices, and uses of the chlorodisilazanes, silicon-heteroatom compounds, and devices.

[0010] PCT Publication WO 2018 / 057677 discloses a composition containing trichlorodisilane as a silicon precursor for use in film formation. The composition includes a silicon precursor compound and at least one of an inert gas, molecular hydrogen, a carbon precursor, a nitrogen precursor, and an oxygen precursor. This publication also discloses a method for forming a silicon-containing film on a substrate using the silicon precursor compound, and the silicon-containing film formed thereby.

[0011] U.S. Patent No. 9,984,868 discloses a cyclic method for depositing a silicon nitride film on a substrate. In one embodiment, the method includes the steps of: supplying a halogen silane as a silicon precursor to a reactor; supplying a purge gas to the reactor; and providing an ionized nitrogen precursor to the reactor to react with the substrate to form a silicon nitride film.

[0012] U.S. Patent Application Publication No. 2009 / 0155606 discloses a cyclical method for depositing a silicon nitride film on a substrate. In one embodiment, the method includes supplying a chlorosilane to a reactor in which the substrate is processed, supplying a purge gas to the reactor, and providing an ammonia plasma to the reactor. This method allows for the formation of a silicon nitride film at a low process temperature and at a high deposition rate. The resulting silicon nitride film has relatively few impurities and is of relatively high quality. Furthermore, the silicon nitride film can be formed with good step coverage for features with high aspect ratios and thin, uniform thicknesses.

[0013] Finally, U.S. Patent No. 9,018,104 discloses a method for manufacturing a semiconductor device, which includes a step of forming an insulating film of a predetermined composition and a predetermined thickness on a substrate by alternately repeating a predetermined number of times the following steps: supplying one of a chlorosilane-based raw material and an aminosilane-based raw material to a substrate in a process chamber, and then supplying the other raw material, thereby forming a first layer containing silicon, nitrogen, and carbon on the substrate; and supplying a reactive gas different from each raw material to the substrate in the process chamber, thereby modifying the first layer to form a second layer.

[0014] The disclosures of the above-identified patents, patent applications and publications are incorporated herein by reference.

[0015] There is a need in the art to provide a method for depositing silicon nitride or carbon-doped silicon nitride at temperatures of 600°C or less, preferably 500°C or less, and most preferably 400°C or less, having the following characteristics: a carbon content, preferably stoichiometric silicon nitride, of about 5 atomic % or less, about 3 atomic % or less, about 2 atomic % or less, about 1 atomic % or even less, as measured by X-ray photoelectron spectroscopy (XPS); an oxygen content of about 5 atomic % or less, about 3 atomic % or less, about 2 atomic % or less, about 1 atomic % or less, as measured by X-ray photoelectron spectroscopy (XPS); a step coverage of 90% or greater, 95% or greater, or 99% or greater, and a dielectric constant of 7.0 or less, 6.0 or less, or 5.0 or less. Summary of the Invention

[0016] The above needs are met in part by providing a method for depositing a silicon- and nitrogen-containing dielectric film via an atomic layer deposition (ALD) process, the method comprising the steps of: a) placing at least one substrate in a reactor at a temperature ranging from about 25° C. to about 600° C., and optionally maintaining the reactor at a pressure of about 100 torr or less; b) introducing at least one first silicon precursor comprising at least two halogen atoms into the reactor to form a silicon-containing layer; and c) purging any unreacted precursor from the reactor using an inert gas. d) introducing at least one second silicon precursor comprising at least two primary amino moieties into the reactor, wherein the second silicon precursor reacts with the silicon-containing layer to form a film comprising silicon and nitrogen; e) purging the reactor with an inert gas; f) introducing a plasma source into the reactor to react with the silicon- and nitrogen-containing film; g) purging any reaction by-products from the reactor with an inert gas; and h) repeating steps b through g to form a film comprising silicon and nitrogen to a desired thickness.

[0017] The above needs are further met in part by providing a method for depositing a silicon- and nitrogen-containing dielectric film via an atomic layer deposition (ALD) process, the method comprising the steps of: a) placing at least one substrate in a reactor at a temperature ranging from about 25° C. to about 600° C., and optionally maintaining the reactor at a pressure of about 100 torr or less; b) introducing at least one first silicon precursor comprising at least two primary amino moieties to form a film comprising a silicon-containing layer; and c) using an inert gas to remove any unreacted precursor from the reactor. d) introducing at least one second silicon precursor comprising at least two halogen atoms into the reactor to react with the silicon-containing layer to form a film comprising silicon and nitrogen; e) purging the reactor with an inert gas; f) introducing a plasma source into the reactor to react with the silicon- and nitrogen-containing film; g) purging the reactor of any reaction by-products with an inert gas; and h) repeating steps b through g to form a film comprising silicon and nitrogen to a desired thickness. DETAILED DESCRIPTION OF THE INVENTION

[0018] As used herein, the term "ALD or ALD-like" refers to processes including, but not limited to: a) reactants, including a silicon precursor and a reactive gas, are introduced sequentially into a reactor, such as a single-wafer ALD reactor, a semi-batch ALD reactor, or a batch furnace ALD reactor; and b) reactants, including a silicon precursor and a reactive gas, are exposed to a substrate by moving or rotating the substrate to different sections of the reactor, each section separated by an inert gas curtain, i.e., a spatial ALD reactor or a roll-to-roll ALD reactor.

[0019] Throughout this specification, the term "plasma comprising / containing ammonia" refers to a reactive gas or gas mixture generated in situ or remotely via a plasma generator, the gas or gas mixture being selected from the group consisting of ammonia, ammonia and helium mixtures, ammonia and neon mixtures, ammonia and argon mixtures, ammonia and nitrogen mixtures, ammonia and hydrogen mixtures, and combinations thereof.

[0020] As used herein, the term "plasma containing / comprising hydrogen or deuterium" refers to a reactive gas or gas mixture generated in situ or remotely via a plasma generator. The gas or gas mixture is selected from the group consisting of hydrogen or deuterium, a mixture of hydrogen or deuterium and helium, a mixture of hydrogen or deuterium and neon, a mixture of hydrogen and argon, a mixture of hydrogen or deuterium and nitrogen, and combinations thereof. As used herein, the term "alkyl" refers to a linear or branched C1-C alkyl group. 20 Hydrocarbons, cyclic C6-C 20 Refers to a hydrocarbon. Exemplary hydrocarbons include, but are not limited to, heptane, octane, nonane, decane, dodecane, cyclooctane, cyclononane, and cyclodecane.

[0021] As used herein throughout this specification, the term "step coverage" is defined as the percentage of two thicknesses of a deposited film in a structured or characterized substrate having either vias or trenches, or both. Bottom step coverage is defined as the ratio of the thickness at the bottom of the feature divided by the thickness at the top of the feature. Intermediate step coverage is defined as the ratio (%) of the sidewall thickness of the feature divided by the thickness at the top of the feature. Films deposited using the methods described herein exhibit step coverage of about 80% or greater, or about 90% or greater, indicating that the film is conformal.

[0022] As used herein throughout this specification, the term "silicon precursor" is defined as either a halogenated silicon-containing compound containing at least two halogen atoms or a primary amino-containing silicon compound containing at least two primary amino moieties.

[0023] As used herein throughout this specification, the term "primary amino-containing" refers to a primary organic amine, HNR 1 an organic amino group or moiety HNR derived by removing one hydrogen from 1 Exemplary primary amino-containing groups include ethylamino (-NHEt), n-propylamino (-NHPr n ), and isopropylamino (-NHPr i ), but are not limited to these.

[0024] The new process involves sequentially introducing a silicon halide compound and a precursor containing at least two or more primary amino-containing silicon compounds, followed by either an ammonia- or hydrogen-containing plasma, to induce a reaction between hydrogen and Si-NH and Si-Cl. This new process can produce more Si-N-Si networks in which the nitrogen atom is bonded to three silicon atoms, thus enabling the formation of better silicon nitride films. Existing prior art techniques typically involve one silicon precursor followed by a plasma, such as a silicon halide compound followed by a nitrogen- or ammonia-containing plasma. Importantly, the key innovation of this patent is the deposition of silicon nitride with more nitrogen atoms bonded to three silicon atoms at low temperatures, thereby providing silicon nitride films with lower hydrogen content and a lower wet etch rate than existing techniques that use only one silicon precursor.

[0025] Described herein are methods for depositing silicon and nitrogen-containing dielectric films via atomic layer deposition (ALD) or in an ALD-like process, such as, but not limited to, cyclic chemical vapor deposition (CCVD).

[0026] In one embodiment, the method described in accordance with the exemplary embodiment comprises: a) placing at least one substrate in a reactor at a temperature ranging from about 25° C. to about 600° C., and optionally maintaining the reactor at a pressure of about 100 torr or less; b) introducing at least one first silicon precursor containing at least two halogen atoms into the reactor to form a silicon-containing layer; c) purging the reactor of any unreacted precursor using an inert gas; d) introducing at least one second silicon precursor comprising at least two primary amino moieties into the reactor, wherein the second silicon precursor reacts with the silicon-containing layer to form a film comprising silicon and nitrogen; e) purging the reactor with an inert gas; f) introducing a plasma source into the reactor to react with the silicon and nitrogen containing film; g) purging any reaction by-products from the reactor using an inert gas. Steps bg in this embodiment may be repeated to provide a desired thickness of the silicon and nitrogen containing dielectric.

[0027] In some embodiments of the present invention, steps d-e may be performed before steps b and c. The thickness of the silicon and nitrogen-containing dielectric film ranges from 1 Å to 1000 Å, or 1 Å to 500 Å, or 1 Å to 300 Å, or 1 Å to 200 Å, or 1 Å to 100 Å, or 1 Å to 50 Å. The thickness of the silicon nitride or silicon carbonitride film may also range from 5 Å to 500 Å, or 5 Å to 400 Å, or 5 Å to 300 Å, or 5 Å to 200 Å, or 5 Å to 100 Å, or 5 Å to 50 Å.

[0028] In another embodiment, the method described in accordance with the exemplary embodiment further comprises: a) placing at least one substrate in a reactor at a temperature ranging from about 25° C. to about 600° C., and optionally maintaining the reactor at a pressure of about 100 torr or less; b) introducing at least one first silicon precursor comprising at least two primary amino moieties to form a film comprising a silicon-containing layer; c) purging the reactor of any unreacted precursor using an inert gas; d) introducing at least one second silicon precursor containing at least two halogen atoms into the reactor to react with the silicon-containing layer to form a film containing silicon and nitrogen; e) purging the reactor with an inert gas; f) introducing a plasma source into the reactor to react with the silicon and nitrogen containing film; g) purging any reaction by-products from the reactor using an inert gas. Steps b through i in this embodiment may be repeated to provide a desired thickness of silicon and nitrogen containing dielectric.

[0029] In some embodiments of the present invention, steps d-e may be performed before steps b and c. The thickness of the silicon and nitrogen-containing dielectric film ranges from 1 Å to 1000 Å, or 1 Å to 500 Å, or 1 Å to 300 Å, or 1 Å to 200 Å, or 1 Å to 100 Å, or 1 Å to 50 Å. The thickness of the silicon nitride or silicon carbonitride film may also range from 5 Å to 500 Å, or 5 Å to 400 Å, or 5 Å to 300 Å, or 5 Å to 200 Å, or 5 Å to 100 Å, or 5 Å to 50 Å.

[0030] In yet another embodiment, the method described in accordance with the exemplary embodiment further comprises: a) loading at least one substrate and heating the reactor to at least one temperature in the range of about 25°C to about 600°C, and optionally maintaining the reactor at a pressure of about 100 torr or less; b) introducing into the reactor at least one first precursor comprising a halogenated silicon-containing compound that forms a silicon-containing layer; c) purging the reactor of any unreacted precursor using an inert gas; d) introducing at least one second precursor comprising one or more primary amino-containing silicon compounds that react with the silicon-containing layer to form a film comprising silicon and nitrogen; e) purging the reactor with an inert gas; f) introducing an ammonia-containing plasma source into the reactor to react with the silicon and nitrogen-containing film; g) purging any reaction by-products from the reactor using an inert gas.

[0031] Steps b-g in this embodiment may be repeated to provide a silicon- and nitrogen-containing dielectric of a desired thickness. In some embodiments of the present invention, steps d-e may be performed before steps b and c. The thickness of the silicon- and nitrogen-containing dielectric film ranges from 1 Å to 1000 Å, or from 1 Å to 500 Å, or from 1 Å to 300 Å, or from 1 Å to 200 Å, or from 1 Å to 100 Å, or from 1 Å to 50 Å. The thickness of the silicon nitride or silicon carbonitride film may also range from 5 Å to 500 Å, or from 5 Å to 400 Å, or from 5 Å to 300 Å, or from 5 Å to 200 Å, or from 5 Å to 100 Å, or from 5 Å to 50 Å.

[0032] Furthermore, in another embodiment, the method described in accordance with the exemplary embodiment further comprises: a) loading at least one substrate and heating the reactor to at least one temperature in the range of about 25°C to about 600°C, and optionally maintaining the reactor at a pressure of about 100 torr or less; b) introducing into the reactor at least one first precursor comprising a halogenated silicon-containing compound that forms a silicon-containing layer; c) purging the reactor of any unreacted precursor using an inert gas; d) introducing at least one second precursor comprising one or more primary amino-containing silicon compounds that react with the silicon-containing layer to form a film comprising silicon and nitrogen; e) purging the reactor with an inert gas; f) introducing a nitrogen-free plasma source into the reactor to react with the silicon and nitrogen-containing film; g) purging the reactor with an inert gas.

[0033] Steps b-g in this embodiment may be repeated to provide a silicon- and nitrogen-containing dielectric of a desired thickness. In some embodiments of the present invention, steps d-e may be performed before steps b and c. The thickness of the silicon- and nitrogen-containing dielectric film ranges from 1 Å to 1000 Å, or from 1 Å to 500 Å, or from 1 Å to 300 Å, or from 1 Å to 200 Å, or from 1 Å to 100 Å, or from 1 Å to 50 Å. The thickness of the silicon nitride or silicon carbonitride film may also range from 5 Å to 500 Å, or from 5 Å to 400 Å, or from 5 Å to 300 Å, or from 5 Å to 200 Å, or from 5 Å to 100 Å, or from 5 Å to 50 Å.

[0034] Exemplary halogenated silicon-containing compounds can be selected from the group consisting of i) halogenated silanes, ii) halogenated siloxanes, iii) halogenated silazanes, and iv) halogenated carbosilanes.

[0035] Group i halogenated silanes include, but are not limited to, trichlorosilane, tetrachlorosilane, hexachlorodisilane, pentachlorodisilane, tetrachlorodisilane, octachlorotrisilane, and dichlorosilane.

[0036] Group ii halogenated siloxanes include, but are not limited to, hexachlorodisiloxane, pentachlorodisiloxane, tetrachlorodisiloxane, and octachlorotrisiloxane.

[0037] Group iii halogenated silazanes are selected from the group represented by Formula I: [ka] In the formula, R 1 is hydrogen, straight-chain or branched C1-C 10 Alkyl groups, linear or branched C2-C 10 Alkenyl group, linear or branched C2-C 10 Alkynyl groups, C3-C 10 Cyclic alkyl groups, C2-C6 dialkylamino groups, electron-withdrawing groups, and C6-C 10 aryl groups; R 2 is hydrogen, straight-chain or branched C1-C 10 Alkyl group, linear or branched C2-C6 alkenyl group, linear or branched C2-C6 alkynyl group, C3-C 10 Cyclic alkyl group, C2-C6 dialkylamino group, C6-C 10 is selected from the group consisting of an aryl group, a linear or branched C1-C6 fluorinated alkyl group, an electron-withdrawing group, and a halide selected from the group consisting of Cl, Br, and I; X is a halide selected from the group consisting of Cl, Br, and I.

[0038] Examples of group iii of halogenated silazanes are 1,1,1,3,3,3-hexachloro-disilazane, 1,1,1,3,3-pentachloro-disilazane, 1,1,1,3,3,3-hexachloro-2-methyldisilazane, 1,1,1,3,3,3-hexachloro-2-ethyldisilazane, 1,1,1,3,3,3-hexachloro-2-n-propyldisilazane, 1,1,1,3,3,3-hexachloro-2-isopropyldisilazane, 1,1,1,3,3,3-hexachloro-2-n-butyldisilazane, 1,1,1,3,3,3-hexachloro- 2-Iso-butyldisilazane, 1,1,1,3,3,3-hexachloro-2-sec-butyldisilazane, 1,1,1,3,3,3-hexachloro-2-tert-butyldisilazane, 1,1,1,3,3,3-hexabromo-2-methyldisilazane, 1,1,1,3,3,3-hexabromo-2-ethyldisilazane, 1,1,1,3,3,3-hexabromo-2-n-propyldisilazane, 1,1,1,3,3,3-hexabromo-2-iso-propyldisilazane, 1,1,1,3,3,3-hexabromo-2-n-butyldisilazane, 1,1 ,1,3,3,3-Hexabromo-2-iso-butyldisilazane, 1,1,1,3,3,3-Hexabromo-2-sec-butyldisilazane, 1,1,1,3,3,3-Hexabromo-2-tert-butyldisilazane, 1,1,1,3,3,3-Hexaiodo-2-methyldisilazane, 1,1,1,3,3,3-Hexaiodo-2-ethyldisilazane, 1,1,1,3,3,3-Hexaiodo-2-n-propyldisilazane, 1,1,1,3,3,3-Hexaiodo-2-iso-propyldisilazane, 1,1,1,3,3,3-Hexaiodo -2-n-butyldisilazane, 1,1,1,3,3,3-hexaiodo-2-iso-butyldisilazane, 1,1,1,3,3,3-hexaiodo-2-sec-butyl-disilazane, 1,1,1,3,3,3-hexaiodo-2-tert-butyl-disilazane, 1,1,1,3,3-pentachloro-2-methyldisilazane, 1,1,1,3,3-pentachloro-2-ethyldisilazane, 1,1,1,3,3-pentachloro-2-n-propyldisilazane, 1,1,1,3,3-pentachloro-2-iso-propyldisilazane, 1,1,1,3,3-pentachloro-2-methyl-3-methyl-disilazane, 1,1,1,3,3-pentachloro-2-ethyl-3-methyldisilazane, 1,1,1,3,3-pentachloro-2-n-propyl-3-methyldisilazane, 1,1,1,3,3-pentachloro-2-isopropyl-3-methyldisilazane, 1,1,3,3-tetrachloro-2-methyldisilazane, 1,1,3,3-tetrachloro-2-ethyldisilazane, 1,1,3,3-tetrachloro-2-n-propyldisilazane, 1,1,3,3-tetrachloro-2-isopropyldisilazane, 1,1,3,3-tetrachloro-2-n-butyldisilazane, 1,1,3,3-tetrachloro-2-iso-butyldisilazane, 1,1,3,3-tetrachloro-2-sec-butyldisilazane, 1,1,3,3-tetrachloro-2-tert-butyldisilazane, 1,1,3,3-tetrabromo-2-methyldisilazane, 1,1,3,3-tetrabromo-2-ethyldisilazane, 1,1,3,3-tetrabromo-2-n-propyldisilazane, 1,1,3,3-tetrabromo-2-iso-propyldisilazane, 1,1,3,3-tetrabromo-2-n -butyldisilazane, 1,1,3,3-tetrabromo-2-iso-butyldisilazane, 1,1,3,3-tetrabromo-2-sec-butyldisilazane, 1,1,3,3-tetrachloro-2-tert-butyldisilazane, 1,1,3,3-tetraiodo-2-methyldisilazane, 1,1,3,3-tetraiodo-2-ethyldisilazane, 1,1,3,3-tetraiodo-2-n-propyldisilazane, 1,1,3,3-tetraiodo-2-iso-propyldisilazane, 1,1,3,3-tetraiodo-2-n-butyldisilazane, 1,1,3,3- Tetraiodo-2-iso-butyldisilazane, 1,1,3,3-tetraiodo-2-sec-butyldisilazane, 1,1,3,3-tetraiodo-2-tert-butyldisilazane, 1,1,3,3-tetrachloro-2-cyclopentyldisilazane, 1,1,3,3-tetrachloro-2-cyclohexyldisilazane, 1,1,3,3-tetrachloro-1,3-dimethyl-2-cyclopentyl-2-cyclopentyldisilazane, 1,1,3,3-tetrachloro-1,3-dimethyl-2-cyclohexyldisilazane, 1,1,3,3-tetrachloro-1,It may be selected from the group consisting of 3-dimethyl-2-methyldisilazane, 1,1,3,3-tetrachloro-1,3-dimethyl-tetrachloro-2-ethyldisilazane, 1,1,3,3-tetrachloro-1,3-dimethyl-2-n-propyldisilazane, 1,1,3,3-tetrachloro-1,3-dimethyl-2-isopropyldisilazane, 1,1,3,3-tetrachloro-1,3-dimethyl-2-n-butyldisilazane, 1,1,3,3-tetrachloro-1,3-dimethyl-2-isobutyldisilazane, 1,1,3,3-tetrachloro-1,3-dimethyl-2-sec-butyldisilazane, and 1,1,3,3-tetrachloro-1,3-dimethyl-2-tert-butyldisilazane.

[0039] Examples of halogenated carbosilanes in group iv are 1,1,1,4,4,4-hexachloro-1,4-disilabutane, 1,1,1,4,4,4-hexachloro-2-methyl-1,4-disilabutane, 1,1,1,4,4-pentachloro-1,4-disilapentane, 1,1,1,4,4-pentachloro-2-methyl-1,4-disilapentane, 2,2,5,5-tetrachloro-2,5-disilahexane, 2,2,5,5-tetrachloro-3-methyl-2,5-disilahexane, 1,1,1,5,5,5-hexachloro-1,5-disilapentane, 2,2,6,6 -Tetrachloro-3-methyl-2,6-disilaheptane, 1,1,4,4-tetrachloro-1,4-disilapentane, 1,1,4,4-tetrachloro-2-methyl-1,4-disilapentane, 1,1,4,4,4-pentachloro-1,4-disilabutane, 1,1,4,4,4-pentachloro-2-methyl-1,4-disilabutane, 1,4,4,4-tetrachloro-1,4-disilabutane, 1,4,4,4-tetrachloro-2-methyl-1,4-disilabutane, 1,4,4-trichloro-1,4-disilapentane, 1,4,4-trichloro-2-methyl- 1,4-disilapentane, 1,1,5,5,5-pentachloro-1,5-disilapentane, 1,1,5,5,5-pentachloro-2-methyl-1,5-disilapentane, 1,1,5,5-tetrachloro-1,5-disilahexane, 1,1,5,5-tetrachloro-2-methyl-1,5-disilahexane, 1,5,5,5-tetrachloro-1,5-disilapentane, 1,5,5,5-tetrachloro-2-methyl-1,5-disilapentane, 1,5,5-trichloro-1,5-disilahexane, 1,5,5-trichloro-2-methyl-1,5-disilahexa 1,3-dichloro-1,3-disilacyclobutane, 1,3-dibromo-1,3-disilacyclobutane, 1,1,3-trichloro-1,3-disilacyclobutane, 1,1,3-tribromo-1,3-disilacyclobutane, 1,1,3,3-tetrachloro-1,3-disilacyclobutane, 1,1,3,3-tetrabromo-1,3-disilacyclobutane, 1,3-dichloro-1,3-dimethyl-1,3-disilacyclobutane, 1,3-bromo-1,3-dimethyl-1,3-disilacyclobutane, 1,1,1,3,3,5,5,5-octachloro-1,3,5-Trisilapentane, 1,1,1,3,3,5,5,5-octabromo-1,3,5-trisilapentane, 1,1,3,3,5,5-hexachloro-1,5-dimethyl-1,3,5-trisilapentane, 1,1,1,5,5,5-hexachloro-3,3-dimethyl-1,3,5-trisilapentane, 1,1,3,5,5-pentachloro-1,3,5-trimethyl-1,3,5-trisilapentane, 1,1,1,5,5,5-hexachloro-1,3,5-trisilapentane, 1,1,5,5-tetrachloro-1,3 ,5-trisilapentane, 1,1-diiodo-1,3-disilacyclobutane, 1,3-diiodo-1,3-disilacyclobutane, 1,1,3-triiodo-1,3-disilacyclobutane, 1,1,3,3-tetraiodo-1,3-disilacyclobutane, 1,3-diiodo-1,3-dimethyl-1,3-disilacyclobutane, 1,5-dichloro-1,3,5-trisilapentane, 1,5-dibromo-1,3,5-trisilapentane, and 1,5-diiodo-1,3,5-trisilapentane.

[0040] The primary amino-containing silicon compound can be selected from the group represented by Formula II below: R n Si(HNR 1 ) 4-n Formula II In the formula, R is hydrogen, linear or branched C1-C 10 Alkyl groups, linear or branched C2-C 10 Alkenyl group, linear or branched C2-C 10 Alkynyl groups, C3-C 10 Cyclic alkyl groups, C2-C6 dialkylamino groups, electron-withdrawing groups, and C6-C 10 aryl groups; R 1 is hydrogen, straight-chain or branched C1-C 10 Alkyl group, linear or branched C2-C6 alkenyl group, linear or branched C2-C6 alkynyl group, C3-C 10 Cyclic alkyl group, C2-C6 dialkylamino group, C6-C 10n is selected from the group consisting of aryl groups, linear or branched C1-C6 fluorinated alkyl groups, electron-withdrawing groups, and halides selected from the group consisting of Cl, Br, and I; n=0, 1, and 2. In a preferred embodiment, n=0 and R 1 is methyl, ethyl, n-propyl. In another preferred embodiment, n=1, R is methyl, ethyl, and R 1 is methyl, ethyl, n-propyl, n-butyl, i-propyl. Examples include, but are not limited to, Si(HNEt)4, Si(HNPr-n)4, Si(HNPr-i)4, Si(HNBu-n)4, MeSi(HNEt)3, MeSi(HNPr-n)3, MeSi(HNPr-i)3, and MeSi(HNBu-n)3.

[0041] The primary amino-containing silicon compound can also be selected from the group represented by Formula III: [R n Si(HNR 1 ) 3-n ]2 Formula III In the formula, R is hydrogen, linear or branched C1-C 10 Alkyl groups, linear or branched, C3-C 10 Alkenyl group, linear or branched C3-C 10 Alkynyl groups, C3-C 10 Cyclic alkyl groups, C2-C6 dialkylamino groups, electron-withdrawing groups, and C6-C 10 aryl groups; R 1 is hydrogen, straight-chain or branched C1-C 10 Alkyl group, linear or branched C2-C6 alkenyl group, linear or branched C3-C6 alkynyl group, C3-C 10 Cyclic alkyl group, C2-C6 dialkylamino group, C6-C 10and n=0, 1, and 2. Examples include, but are not limited to, Si2(HNEt)6, Me(EtNH)2SiSi(HNEt)2Me, Me2(EtNH)SiSi(HNEt)Me2, Si2(HNMe)6, Me(MeNH)2SiSi(HNMe)2Me, and Me2(MeNH)SiSi(HNMe)Me2.

[0042] The plasma source can be selected from the group consisting of nitrogen-containing plasma, ammonia-containing plasma, inert gas plasma, and hydrogen-containing plasma. The nitrogen-containing source gas can include, for example, nitrogen / argon plasma and nitrogen / helium plasma. The ammonia-containing plasma can include, for example, ammonia plasma, ammonia / argon plasma, ammonia / helium plasma, ammonia / hydrogen plasma, and ammonia / nitrogen plasma. The inert gas plasma can include, for example, argon plasma, helium plasma, and combinations thereof. The hydrogen plasma can include, for example, hydrogen plasma, hydrogen / helium plasma, hydrogen / argon, and combinations thereof. The nitrogen-free plasma source can be selected from the group consisting of inert gas plasma, hydrogen-containing plasma, and combinations thereof. The inert gas can be selected from the group consisting of argon (Ar), nitrogen (N), helium (He), neon (Ne), and combinations thereof.

[0043] The deposition methods disclosed herein include one or more steps of purging unwanted or unreacted materials from the reactor using a purge gas. The purge gas used to purge away unconsumed reactants and / or reaction by-products is an inert gas that does not react with the precursors. Exemplary purge gases include, but are not limited to, argon (Ar), nitrogen (N), helium (He), neon (Ne), hydrogen (H), and mixtures thereof. In certain embodiments, a purge gas, such as Ar, is fed into the reactor at a flow rate ranging from about 10 to 10,000 sccm for about 0.1 to about 1,000 seconds, thereby purging unreacted materials and any by-products that may remain in the reactor.

[0044] Each step of supplying the precursor, oxygen source, ammonia-containing source, and / or other precursor, source gas, and / or reagent may be performed by varying the time for which they are supplied to vary the stoichiometry of the resulting film.

[0045] In certain embodiments, the reactor temperature in the introducing step is one or more temperatures ranging from about room temperature (e.g., 20° C.) to about 600° C. Alternative ranges of substrate temperatures have one or more of the following endpoints: 20, 25, 50, 75, 100, 125, 150, 175, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475, and 500° C. Exemplary preferred temperature ranges include: 300-450° C., 350-450° C.

[0046] In yet another embodiment, a vessel for depositing silicon-containing films comprises one or more silicon precursor compounds as described herein. In one particular embodiment, the vessel is at least one pressurizable vessel (preferably made of stainless steel, having a design as disclosed in U.S. Patent Nos. 7,334,595, 6,077,356, 5,069,244, and 5,465,766, the disclosures of which are incorporated herein by reference). This vessel can comprise either glass (borosilicate glass or quartz glass) or type 316, 316L, 304, or 304L stainless steel alloy (UNS designations S31600, S31603, S30400, S30403), fitted with appropriate valves and fittings that allow delivery of one or more precursors to a reactor for CVD or ALD processes. In this or other embodiments, the halogenated silane and primary amino-containing silicon compound are provided in a pressurizable vessel containing stainless steel, and the purity of the precursor is 98% by weight or greater, or 99.5% by weight or greater, which is suitable for semiconductor applications. The silicon precursor compound is preferably Al 3+ ion, Fe 2+ , Fe 3+ , Ni 2+ , Cr 3+ As used herein, Al 3+ ion, Fe 2+ , Fe 3+ , Ni 2+ , Cr 3+The term "substantially free" in this context means less than about 5 ppm (by weight), preferably less than about 3 ppm, more preferably less than about 1 ppm, and most preferably about 0.1 ppm. In certain embodiments, such vessels may also have means for mixing the precursor with one or more additional precursors, if desired. In these or other embodiments, the contents of the vessel(s) may be premixed with the additional precursors. Alternatively, the silicon precursor and / or other precursors may be maintained in separate vessels or a single vessel having separation means for keeping the silicon precursor and other precursors separate during storage.

[0047] Energy may be applied to at least one of the precursors, ammonia-containing sources, reducing agents such as hydrogen plasma, other precursors, or combinations thereof to induce a reaction and form a film or coating on the substrate. Such energy may be provided by, but is not limited to, thermal, plasma, pulsed plasma, helicon plasma, high-density plasma, inductively coupled plasma, x-ray, electron beam, photon, remote plasma methods, and combinations thereof.

[0048] In certain embodiments, a secondary RF frequency source can be used to modify the plasma characteristics at the substrate surface. In embodiments where deposition involves a plasma, the plasma generation process may include a direct plasma generation process where the plasma is generated directly within the reactor, or a remote plasma generation process where the plasma is generated outside the reactor and fed into the reactor.

[0049] Silicon precursors and / or other silicon-containing precursors can be delivered to a reaction chamber, such as a CVD or ALD reactor, in a variety of ways. In one embodiment, a liquid delivery system can be utilized. In an alternative embodiment, a combined liquid delivery and flash evaporation process unit, such as a turbo-vaporizer manufactured by MSP Corporation of Shoreview, MN, can be used to enable volumetric delivery of low-volatility materials, resulting in reproducible transport and deposition without precursor thermal decomposition. In liquid delivery formulations, the precursors described herein can be delivered in pure liquid form or can be used in a solvent formulation or a composition including a solvent formulation. Thus, in certain embodiments, the precursor formulation can include solvent component(s) with suitable properties that may be desirable and advantageous in a given end-use application for forming a film on a substrate.

[0050] It is understood that in this or other embodiments, the steps of the methods described herein may be performed in various orders, and may occur sequentially or simultaneously (e.g., between at least a portion of another step), and any combination thereof. Each step of supplying a precursor and a nitrogen-containing source gas may be performed by varying the duration of time for which they are supplied to vary the stoichiometry of the resulting silicon-containing film.

[0051] In yet further embodiments of the methods described herein, the film or deposited film is subjected to a treatment step. The treatment step can be performed during at least a portion of the deposition step, after the deposition step, or a combination thereof. Exemplary treatment steps include, but are not limited to, high-temperature thermal annealing treatment to affect one or more properties of the film; plasma treatment; ultraviolet (UV) radiation treatment; laser treatment; electron beam treatment, and combinations thereof. Films deposited with the silicon precursors described herein have improved properties, such as, but not limited to, a lower wet etch rate than the wet etch rate of the film before the treatment step, or a higher density than the density before the treatment step, when compared to films deposited with previously disclosed silicon precursors under the same conditions. In a particular embodiment, the deposited film is intermittently treated during the deposition process. These intermittent or intermediate deposition treatments can be performed, for example, after each ALD cycle, such as, but not limited to, after every ALD cycle, every two ALD cycles, every five ALD cycles, or every 10 or more ALD cycles.

[0052] In embodiments in which the film is subjected to UV treatment, the film is exposed to broadband UV, or a UV source having a wavelength in the range of about 150 nanometers (nm) to about 400 nm. In one particular embodiment, the deposited film is exposed to UV in a chamber separate from the deposition chamber after reaching a desired film thickness.

[0053] In embodiments where the film is treated with plasma, a passivation layer, such as carbon-doped silicon oxide, is deposited to prevent chlorine and nitrogen contamination from penetrating the film during subsequent plasma treatment. The passivation layer can be deposited using atomic layer deposition or cyclic chemical vapor deposition.

[0054] In embodiments in which the film is treated with a plasma, the plasma source is selected from the group consisting of a hydrogen plasma, a hydrogen and helium-containing plasma, and a hydrogen and argon-containing plasma. The hydrogen plasma lowers the dielectric constant of the film while keeping the carbon content in the bulk substantially unchanged, making it more resistant to damage from subsequent plasma ashing processes.

[0055] The following examples illustrate certain aspects of the present invention and do not limit the scope of the appended claims. [Example]

[0056] In the following examples, unless otherwise stated, the properties are obtained from sample films deposited on silicon wafers with resistivities of 5–20 Ω·cm as substrates.

[0057] In typical process conditions, unless otherwise specified, the chamber pressure is fixed at a pressure in the range of about 1 to about 5 Torr. Additional inert gas is used to maintain the chamber pressure.

[0058] Film deposition processes are for plasma-enhanced ALD. Unless otherwise stated, a total of 100, 200, 300, or 500 deposition cycles were used to obtain the desired film thickness.

[0059] Comparative Example 1

[0060] Silicon nitride films were deposited using SiCl4 and ammonia plasma in PEALD mode at 350° C. The ALD steps listed in Table 1a are as follows: [Table 1] Steps 2-6 were repeated 300 times to obtain a 101 Å film, which translated into a growth per cycle (GPC) of 0.34 Å / cycle. The deposited film had an etch rate of >5.2 vs. a thermal silicon oxide reference in 0.5% diluted HF. The etch rate of a silicon nitride film vs. a thermal silicon oxide reference is defined as the ratio of the etch rate of silicon nitride to the etch rate of thermal silicon oxide measured under the same conditions.

[0061] Comparative Example 2

[0062] As listed in Table 1b, silicon nitride films were deposited using tetrakis(n-propylamino)silane and ammonia plasma in PEALD mode at 350°C. [Table 2]

[0063] The film thickness after 400 cycles was 65 Å, which translated into a GPC of 0.16 Å / cycle. The deposited film had an etch rate of >3.1 against a thermal silicon oxide reference in 0.5% dilute HF.

[0064] Comparative Example 3 As listed in Table 1c, silicon nitride films were deposited using tetrakis(n-propylamino)silane and SiCl4 at 350°C without any plasma. [Table 3] Steps 2 to 5 were repeated 400 times, and the deposited film was 20 Å, which translates to <0.1 Å / cycle.

[0065] Example 1 Silicon nitride films were deposited using a combination of silicon halide precursors and primary amino-containing silicon compounds, followed by an ammonia plasma at 350°C. Tetrachlorosilane (SiCl4) was selected as an example of a silicon halide precursor, and tetrakis(n-propylamino)silane was selected as a primary amino-containing silicon compound. SiCl4 was delivered at room temperature, and tetrakis(n-propylamino)silane was delivered at a canister temperature of 125°C. The deposition process was performed using a 300 mm tool equipped with a remote plasma (2 MHz). Film thickness and refractive index were measured using an ellipsometer. Film quality was characterized by its etch rate relative to a thermal silicon oxide reference, defined as the ratio of the etch rate of the film measured under the same conditions using 0.5% dilute hydrofluoric acid (HF) / H2O at room temperature to the etch rate of thermal silicon oxide. The ALD process shown in Table 2 is as follows: [Table 4] Steps 2–8 were repeated 400 times to deposit a 180 Å film, which was interpreted as a GPC of 0.45 Å / cycle. The deposited film exhibited a higher etch rate resistance in 0.5% diluted HF. The etch rate of the deposited film relative to a thermal silicon oxide reference in 0.5% diluted HF was 1.3, demonstrating much better etch resistance than typical ALD processes, as shown in the comparative example using only one silicon precursor under similar deposition conditions.

[0066] Example 2 Silicon nitride films were deposited using a combination of a silicon halide precursor and a primary amino-containing silicon compound, followed by hydrogen plasma deposition at 350°C. Tetrachlorosilane (SiCl4) was selected as an example of the silicon halide precursor, and tetrakis(n-propylamino)silane was selected as the primary amino-containing silicon compound. The ALD process shown in Table 3 is as follows: [Table 5]

[0067] Steps 2–8 were repeated 200 times to deposit a 40 Å film. This translated into a PEALD growth rate of 0.20 Å / cycle. The film exhibited a higher etch rate resistance with 0.5% diluted HF. The etch rate of the deposited film against a thermal silicon oxide reference was 0.14, demonstrating superior etch resistance compared to typical ALD processes, as shown in the comparative example using only one silicon precursor under similar deposition conditions.

[0068] Although illustrated and described above with reference to certain specific embodiments and examples, the present invention is nevertheless not intended to be limited to the details shown. Rather, various modifications in details may be made, within the scope and range of equivalents of the claims, without departing from the spirit of the invention. For example, all ranges broadly set forth herein are expressly intended to include within their scope all narrower ranges that fall within the broader range.

Claims

1. 1. A method for depositing a silicon and nitrogen containing dielectric film via an atomic layer deposition (ALD) process, comprising: a) placing at least one substrate in a reactor at a temperature ranging from about 25° C. to about 600° C., and optionally maintaining said reactor at a pressure of about 100 torr or less; b) introducing at least one first silicon precursor containing at least two halogen atoms into the reactor to form a silicon-containing layer; c) purging the reactor of any unreacted precursor using an inert gas; d) introducing at least one second silicon precursor comprising at least two primary amino moieties into the reactor, wherein the second silicon precursor reacts with the silicon-containing layer to form a film comprising silicon and nitrogen; e) purging the reactor with an inert gas; f) introducing a plasma source into the reactor to react with the silicon and nitrogen containing film; g) purging the reactor of any reaction by-products using an inert gas; h) repeating steps bg to form the silicon and nitrogen containing film to a desired thickness.

2. 2. The method of claim 1, wherein the first silicon precursor containing at least two halogen atoms is at least one selected from the group consisting of i) halogenated silanes, ii) halogenated siloxanes, iii) halogenated silazanes, and iv) halogenated carbosilanes.

3. 2. The method of claim 1, wherein the first silicon precursor containing at least two halogen atoms is selected from the group consisting of trichlorosilane, tetrachlorosilane, hexachlorodisilane, pentachlorodisilane, tetrachlorodisilane, octachlorotrisilane, and dichlorosilane.

4. 2. The method of claim 1, wherein the first silicon precursor containing at least two halogen atoms is a halogenated siloxane selected from the group consisting of hexachlorodisiloxane, pentachlorodisiloxane, tetrachlorodisiloxane, and octachlorotrisiloxane.

5. The first silicon precursor containing at least two halogen atoms is a halogenated silazane selected from the group represented by the following formula I: 【Chemistry 1】 In the formula, R １ is hydrogen, linear or branched C １ ~C １０ Alkyl group, linear or branched C ２ ~C １０ Alkenyl group, linear or branched C ２ ~C １０ Alkynyl group, C ３ ~C １０ Cyclic alkyl group, C ２ ~C ６ Dialkylamino group, electron-withdrawing group, and C ６ ~C １０ aryl groups; R ２ is hydrogen, linear or branched C １ ~C １０ Alkyl group, linear or branched C ２ ~C ６ Alkenyl group, linear or branched C ３ ~C ６ Alkynyl group, C ３ ~C １０ Cyclic alkyl group, C ２ ~C ６ Dialkylamino group, C ６ ~C １０ Aryl group, linear or branched C １ ~C ６ 2. The method of claim 1, wherein X is selected from the group consisting of fluorinated alkyl groups, electron withdrawing groups, and halides selected from the group consisting of Cl, Br, and I; and X is a halide selected from the group consisting of Cl, Br, and I.

6. the second silicon precursor primary amino-containing silicon compound is selected from the group consisting of compounds represented by Formula II: R ｎ Si(HNR １ ) ４－ｎ Formula II In the formula, R is hydrogen, linear or branched C １ ~C １０ Alkyl group, linear or branched C ２ ~C １０ Alkenyl group, linear or branched C ２ ~C １０ Alkynyl group, C ３ ~C １０ Cyclic alkyl group, C ２ ~C ６ Dialkylamino group, electron-withdrawing group, and C ６ ~C １０ aryl groups; R １ is hydrogen, linear or branched C １ ~C １０ Alkyl group, linear or branched C ２ ~C ６ Alkenyl group, linear or branched C ３ ~C ６ Alkynyl group, C ３ ~C １０ Cyclic alkyl group, C ２ ~C ６ Dialkylamino group, C ６ ~C １０ Aryl group, linear or branched C １ ~C ６ 2. The method of claim 1, wherein n is selected from the group consisting of fluorinated alkyl groups, electron withdrawing groups, and halides selected from the group consisting of Cl, Br, and I; and n=0, 1, and 2.

7. The second silicon precursor primary amino-containing silicon compound is Si(HNEt) ４ and Si(HNPr-n) ４ 7. The method of claim 6, wherein the method is one or both of:

8. The second silicon precursor containing at least two primary amino moieties is selected from the group consisting of compounds according to Formula III: [R ｎ Si(HNR １ ) ３－ｎ ] ２ Formula III In the formula, R is hydrogen, linear or branched C １ ~C １０ Alkyl group, linear or branched C ２ ~C １０ Alkenyl group, linear or branched C ２ ~C １０ Alkynyl group, C ３ ~C １０ Cyclic alkyl group, C ２ ~C ６ Dialkylamino group, electron-withdrawing group, and C ６ ~C １０ aryl groups; R １ is hydrogen, linear or branched C １ ~C １０ Alkyl group, linear or branched C ２ ~C ６ Alkenyl group, linear or branched C ２ ~C ６ Alkynyl group, C ３ ~C １０ Cyclic alkyl group, C ２ ~C ６ Dialkylamino group, C ６ ~C １０ Aryl group, linear or branched C １ ~C ６ 2. The method of claim 1, wherein n is selected from the group consisting of fluorinated alkyl groups, electron withdrawing groups, and halides selected from the group consisting of Cl, Br, and I; and n=0, 1, and 2.

9. The silicon precursor containing at least two primary amino moieties is Si ２ (HNEt) ６ , Me(EtNH) ２ SiSi(HNEt) ２ Me, Me ２ (EtNH)SiSi(HNEt)Me ２ , Si ２ (HNMe) ６ , Me(MeNH) ２ SiSi(HNMe) ２ Me, and Me ２ (MeNHe)SiSi(HNMe)Me ２ 9. The method of claim 8, selected from the group consisting of:

10. 1. A method for depositing a silicon and nitrogen containing dielectric film via an atomic layer deposition (ALD) process, comprising: a) placing at least one substrate in a reactor at a temperature ranging from about 25° C. to about 600° C., and optionally maintaining said reactor at a pressure of about 100 torr or less; b) introducing at least one first silicon precursor comprising at least two primary amino moieties to form a film comprising a silicon-containing layer; c) purging the reactor of any unreacted precursor using an inert gas; d) introducing at least one second silicon precursor containing at least two halogen atoms into the reactor to react with the silicon-containing layer to form a film containing silicon and nitrogen; e) purging the reactor with an inert gas; f) introducing a plasma source into the reactor to react with the silicon and nitrogen containing film; g) purging the reactor of any reaction by-products using an inert gas; h) repeating steps bg to form the silicon and nitrogen containing film to a desired thickness.

11. 11. The method of claim 10, wherein the second silicon precursor comprising at least two halogen atoms is at least one selected from the group consisting of i) halogenated silanes, ii) halogenated siloxanes, iii) halogenated silazanes, and iv) halogenated carbosilanes.

12. 11. The method of claim 10, wherein the second silicon precursor comprising at least two halogen atoms is selected from the group consisting of trichlorosilane, tetrachlorosilane, hexachlorodisilane, pentachlorodisilane, tetrachlorodisilane, octachlorotrisilane, and dichlorosilane.

13. 11. The method of claim 10, wherein the second silicon precursor containing at least two halogen atoms is a halogenated siloxane selected from the group consisting of hexachlorodisiloxane, pentachlorodisiloxane, tetrachlorodisiloxane, and octachlorotrisiloxane.

14. The second silicon precursor containing at least two halogen atoms is a halogenated silazane selected from the group represented by Formula I: 【Chemistry 2】 In the formula, R １ is hydrogen, linear or branched C １ ~C １０ Alkyl group, linear or branched C ２ ~C １０ Alkenyl group, linear or branched C ２ ~C １０ Alkynyl group, C ３ ~C １０ Cyclic alkyl group, C ２ ~C ６ Dialkylamino group, electron-withdrawing group, and C ６ ~C １０ aryl groups; R ２ is hydrogen, linear or branched C １ ~C １０ Alkyl group, linear or branched C ２ ~C ６ Alkenyl group, linear or branched C ３ ~C ６ Alkynyl group, C ３ ~C １０ Cyclic alkyl group, C ２ ~C ６ Dialkylamino group, C ６ ~C １０ Aryl group, linear or branched C １ ~C ６ 11. The method of claim 10, wherein X is selected from the group consisting of fluorinated alkyl groups, electron withdrawing groups, and halides selected from the group consisting of Cl, Br, and I; and X is a halide selected from the group consisting of Cl, Br, and I.

15. the primary amino-containing silicon compound is selected from the group consisting of compounds represented by Formula II: R ｎ Si(HNR １ ) ４－ｎ Formula II In the formula, R is hydrogen, linear or branched C １ ~C １０ Alkyl group, linear or branched C ２ ~C １０ Alkenyl group, linear or branched C ２ ~C １０ Alkynyl group, C ３ ~C １０ Cyclic alkyl group, C ２ ~C ６ Dialkylamino group, electron-withdrawing group, and C ６ ~C １０ aryl groups; R １ is hydrogen, linear or branched C １ ~C １０ Alkyl group, linear or branched C ２ ~C ６ Alkenyl group, linear or branched C ３ ~C ６ Alkynyl group, C ３ ~C １０ Cyclic alkyl group, C ２ ~C ６ Dialkylamino group, C ６ ~C １０ Aryl group, linear or branched C １ ~C ６ 11. The method of claim 10, wherein n is selected from the group consisting of fluorinated alkyl groups, electron withdrawing groups, and halides selected from the group consisting of Cl, Br, and I; and n=0, 1, and 2.

16. The primary amino-containing silicon compound is Si(HNEt) ４ and Si(HNPr-n) ４ 16. The method of claim 15, wherein the method is one or both of:

17. The first silicon precursor containing at least two primary amino moieties is selected from the group consisting of compounds according to Formula III: [R ｎ Si(HNR １ ) ３－ｎ ] ２ Formula III In the formula, R is hydrogen, linear or branched C １ ~C １０ Alkyl group, linear or branched C ２ ~C １０ Alkenyl group, linear or branched C ２ ~C １０ Alkynyl group, C ３ ~C １０ Cyclic alkyl group, C ２ ~C ６ Dialkylamino group, electron-withdrawing group, and C ６ ~C １０ aryl groups; R １ is hydrogen, linear or branched C １ ~C １０ Alkyl group, linear or branched C ２ ~C ６ Alkenyl group, linear or branched C ２ ~C ６ Alkynyl group, C ３ ~C １０ Cyclic alkyl group, C ２ ~C ６ Dialkylamino group, C ６ ~C １０ Aryl group, linear or branched C １ ~C ６ 11. The method of claim 10, wherein n is selected from the group consisting of fluorinated alkyl groups, electron withdrawing groups, and halides selected from the group consisting of Cl, Br, and I; and n=0, 1, and 2.

18. The first silicon precursor containing at least two primary amino moieties is Si ２ (HNEt) ６ , Me(EtNH) ２ SiSi(HNEt) ２ Me, Me ２ (EtNH)SiSi(HNEt)Me ２ , Si ２ (HNMe) ６ , Me(MeNH) ２ SiSi(HNMe) ２ Me, and Me ２ (MeNHe)SiSi(HNMe)Me ２ 18. The method of claim 17, selected from the group consisting of:

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