Method for manufacturing a film containing silicon and nitrogen

Abstract

To provide methods for making films containing silicon and nitrogen.SOLUTION: A method for forming an optionally carbon-doped silicon nitride film via a plasma ALD process includes introducing a substrate into a reactor, which is heated to about 600°C or less. At least one silicon precursor defined herein and having one or two Si-C-Si linkages is introduced to form a chemisorbed film on the substrate. The reactor is then purged of any unconsumed precursors and / or reaction by-products with a suitable inert gas. Nitrogen-containing plasma is introduced into the reactor to react with the chemisorbed film to form the optionally carbon-doped silicon nitride film. The steps are repeated as necessary so as to grow the deposited optionally carbon-doped silicon nitride film to a predetermined thickness.SELECTED DRAWING: None

Description

Technical Field

[0001] Cross - Reference to Related Applications This application claims priority to U.S. Provisional Patent Application No. 62 / 740,478, filed on October 3, 2018, the entire disclosure of which is incorporated herein by reference.

[0002] The present invention is directed to compositions and methods for the manufacture of electronic devices. More specifically, the present invention is directed to compounds, compositions, and methods for the deposition of silicon - containing films having a low dielectric constant (<6.0) and high oxygen ashing resistance, such as, but not limited to, stoichiometric silicon nitride, carbon - doped silicon nitride films, and carbon - doped silicon oxynitride films.

Background Art

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

[0004] Olsen's "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 gas flow rate by more than 2.3 did not significantly reduce the residual stress, but had a significant adverse effect on the thickness uniformity and deposition rate.

[0005] Taylor et al.'s "Hexachlorodisilane as a Precursor in the LPCVD of Silicon Dioxide and Silicon Oxynitride Films", 136 J.Electrochem.Soc.2382(1989) describes the growth of silicon dioxide and silicon oxynitride films by LPCVD using a gas phase mixture of Si2Cl6, N2 and NH3. The silicon dioxide and silicon oxynitride films were grown by LPCVD using a gas phase mixture of HCDS, N2O, and NH3 in the temperature range of 600 - 850 °C. The deposited silicon dioxide and silicon oxynitride films showed a low chlorine content, typically <1 at% chlorine content.

[0006] M. Tanaka et al.'s "Film Properties of Low-k Silicon Nitride Films Formed by Hexachlorodisilane and Ammonia", 147 J.Electrochem.Soc.2284(2000) describes a low temperature process in combination with good step coverage of silicon nitride (SiN) formed by low pressure chemical vapor deposition (LPCVD) using hexachlorodisilane (HCD).

[0007] Japanese Patent Application Laid-Open No. 2000-100812 describes a method for depositing a film using SiCl4 and NH3 as source gases. The surface of the substrate may be nitrided using NH3 before deposition. An ultrathin film having improved insulating properties is formed. The silicon nitride film is useful as a capacitor insulating film for semiconductor integrated circuits.

[0008] U.S. Patent No. 6355582 discloses a method for forming a silicon nitride film, in which the substrate on which the film is to be formed is heated, and silicon tetrachloride and ammonia gas are supplied to the heated substrate at a predetermined temperature.

[0009] U.S. Patent No. 10049882 describes an atomic layer deposition (ALD) method for manufacturing a semiconductor device, including a step of forming a dielectric layer on a structure having height differences. The method includes a step of forming a structure on a substrate having height differences, and a step of forming a dielectric layer structure on the structure. The step of forming the dielectric layer structure includes a step of forming a first dielectric layer containing silicon nitride on a substrate having height differences. 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 containing the substrate so that the first dielectric layer is formed in situ on the structure having height differences.

[0010] International Publication No. 2018 / 063907 discloses a group including chlorodisilazane, a silicon heteroatom compound synthesized therefrom, a device containing the silicon heteroatom compound, a method for manufacturing chlorodisilazane, the silicon heteroatom compound and the device; and the use of chlorodisilazane, the silicon heteroatom compound, and the device.

[0011] International Publication No. WO 2018 / 057677 discloses a composition comprising trichlorodisilane as a silicon precursor for use in film formation. The composition comprises a silicon precursor compound and at least one of an inert gas, molecular hydrogen, a carbon precursor, a nitrogen precursor, and an oxygen precursor. The publication also discloses a method of forming a silicon-containing film on a substrate using the silicon precursor compound and the silicon-containing film formed thereby.

[0012] U.S. Patent No. 9,984,868 discloses a cyclic method of depositing a silicon nitride film on a substrate. In one embodiment, such a method comprises supplying a halosilane as a silicon precursor into a reactor; supplying a purge gas to the reactor; and supplying an ionized nitrogen precursor into the reactor to react with the substrate to form a silicon nitride film.

[0013] Finally, U.S. Patent Application Publication No. 2009 / 0155606 discloses a cyclic method of depositing a silicon nitride film on a substrate. In one embodiment, the method comprises supplying a chlorosilane to a reactor in which a substrate is being processed; supplying a purge gas to the reactor; and supplying an ammonia plasma to the reactor. The method enables a silicon nitride film to be formed at a low process temperature and a high deposition rate. The resulting silicon nitride film has relatively few impurities and relatively high quality. In addition, a silicon nitride film having good step coverage for shapes having a high aspect ratio and a thin and uniform thickness can be formed.

[0014] In the art, there is a need to provide a composition and a method of using the composition for depositing a doped silicon-containing film having a high carbon content (e.g., a carbon content of about 10 at% or more as measured by X-ray photoelectron spectroscopy (XPS)) for specific applications in the electronics industry.

[0015] Accordingly, there is a need to develop a process for forming high-quality silicon nitride or carbon-doped silicon nitride using a chemical vapor deposition (CVD) or atomic layer deposition (ALD) process or a process similar to ALD, such as, but not limited to, a cyclic chemical vapor deposition process. One particular application, such as an O-N-O stack in 3D NAND flash, requires a silicon nitride film, silicon oxynitride film, or silicon carbonitride film that exhibits low stress and / or a high wet etching rate in phosphoric acid. Further, in a CVD, ALD, or process similar to ALD, it may be desirable to develop a low-temperature deposition (e.g., deposition at one or more temperatures of about 500 °C or less) that improves one or more film properties, such as, but not limited to, purity and / or density.

[0016] The disclosures of the previously identified patents, patent applications, and publications are incorporated herein by reference.

[0017] There is a need in the art to provide a composition for depositing silicon nitride or carbon-doped silicon nitride having the following characteristics: a) a carbon content of about 5 at% or less, about 3 at% or less, about 2 at% or less, about 1 at% or less, or even less, preferably stoichiometric silicon nitride, when measured by X-ray photoelectron spectroscopy (XPS); b) an oxygen content of about 5 at% or less, about 3 at% or less, about 2 at% or less, about 1 at% or less when measured by X-ray photoelectron spectroscopy (XPS); and a step coverage of 90% or more, 95% or more, 99% or more, and a method of using the composition. SUMMARY OF THE INVENTION

[0018] The requirements described above are met, in part, by providing a method for forming a silicon nitride film that may be carbon-doped by a plasma ALD process. According to the method, a substrate having surface features is introduced into a reactor. The reactor is heated to one or more temperatures of about 600 °C or less. The reactor can be maintained at a pressure of 100 torr or less. At least one silicon precursor having one or two Si-C-Si bonds, selected from the group consisting of 1,1,1,3,3-pentachloro-1,3-disilabutane, 1,1,1,3,3-pentachloro-2-methyl-1,3-disilabutane, 1,1,1,3,3,3-hexachloro-2-methyl-1,3-disilapropane, 1,1,1,3,3,3-hexachloro-2,2-dimethyl-1,3-disilapropane, 1,1,1,3,3-pentachloro-2,2-dimethyl-1,3-disilabutane, 1,1,1,3,3-pentachloro-2-ethyl-1,3-disilabutane, 1,1,1,3,3-pentachloro-1,3-disilapentane, 1,1,1,3,3-pentachloro-2-methyl-1,3-disilapentane, 1,1,1,3,3-pentachloro-2,2-dimethyl-1,3-disilapentane, 1,1,1,3,3-pentachloro-2-ethyl-1,3-disilapentane, 1,1,1,3,3,5,5-heptachloro-1,3,5-trisilahexane, 1,1,1,5,5-pentachloro-3,3-dimethyl-1,3,5-trisilahexane, 1,1,1,5,5-pentachloro-1,3,5-trisilahexane, 2,2,4,6,6-pentachloro-4-methyl-2,4,6-trisilaheptane, is introduced into the reactor to form a film chemisorbed on the substrate.

[0019] Next, the reactor is purged with a suitable inert gas of any unconsumed precursor and / or reaction by-products. A plasma containing nitrogen is introduced into the reactor to react with the chemisorbed film to form a silicon nitride film that may be carbon-doped.

[0020] Next, the reactor is again purged with a suitable inert gas to remove any reaction by-products. The steps of introducing at least one precursor, purging if necessary, introducing plasma, and purging again if necessary are repeated as needed to achieve a deposited silicon nitride film, which may be carbon-doped, having a predetermined thickness.

[0021] Requirements such as those described above are further satisfied by a method for forming a silicon nitride film, a carbon-doped silicon nitride film, or a carbon-doped silicon oxynitride film by a plasma ALD process. According to the method, a substrate having surface features is introduced into a reactor. The reactor is heated to one or more temperatures of about 600 °C or less. The reactor can be maintained at a pressure of 100 torr or less. At least one silicon precursor having one or two Si-C-Si bonds, selected from the group consisting of 1,1,1,3,3-pentachloro-1,3-disilabutane, 1,1,1,3,3-pentachloro-2-methyl-1,3-disilabutane, 1,1,1,3,3,3-hexachloro-2-methyl-1,3-disilapropane, 1,1,1,3,3,3-hexachloro-2,2-dimethyl-1,3-disilapropane, 1,1,1,3,3-pentachloro-2,2-dimethyl-1,3-disilabutane, 1,1,1,3,3-pentachloro-2-ethyl-1,3-disilabutane, 1,1,1,3,3-pentachloro-1,3-disilapentane, 1,1,1,3,3-pentachloro-2-methyl-1,3-disilapentane, 1,1,1,3,3-pentachloro-2,2-dimethyl-1,3-disilapentane, 1,1,1,3,3-pentachloro-2-ethyl-1,3-disilapentane, 1,1,1,3,3,5,5-heptachloro-1,3,5-trisilahexane, 1,1,1,5,5-pentachloro-3,3-dimethyl-1,3,5-trisilahexane, 1,1,1,5,5-pentachloro-1,3,5-trisilahexane, and 2,2,4,6,6-pentachloro-4-methyl-2,4,6-trisilaheptane, is introduced into the reactor to form a film chemisorbed on the substrate.

[0022] The reactor is purged with a suitable inert gas of any unconsumed precursors and / or reaction by-products. A plasma containing an ammonia source is introduced into the reactor and reacts with the chemisorbed film to form a silicon nitride film or a carbon-doped silicon nitride film.

[0023] The reactor is then purged again with a suitable inert gas of any reaction by-products. The steps of introducing at least one precursor, purging if necessary, introducing plasma, and purging again if necessary are repeated as needed to achieve a silicon nitride film or a carbon-doped silicon nitride film of a predetermined thickness.

[0024] Optionally, the resulting silicon nitride film or carbon-doped silicon nitride film is then exposed to an oxygen source at one or more temperatures from approximately ambient temperature to 1000 °C, preferably from about 100 °C to 400 °C, to convert the silicon nitride film to a silicon oxynitride film or the carbon-doped silicon nitride film to a carbon-doped silicon oxynitride film.

DETAILED DESCRIPTION OF THE INVENTION

[0025] Throughout this specification, the term "ALD or ALD-like" refers to a process including, but not limited to, the following processes: a) a process in which each reactant containing a silicon precursor and a reactive gas is sequentially introduced into a reactor, such as a single-wafer ALD reactor, a semi-batch ALD reactor, or a batch furnace ALD reactor; b) a process in which each reactant containing a silicon precursor and a reactive gas is exposed to a substrate by moving or rotating the substrate into different compartments of a reactor in which each section is separated by an inert gas curtain, i.e., a spatial ALD reactor or a roll-to-roll ALD reactor.

[0026] Throughout this specification, the term "ammonia-containing plasma" refers to a reactive gas or gas mixture generated in-situ or remotely by a plasma generator. The gas or gas mixture is selected from the group consisting of ammonia, a mixture of ammonia and helium, a mixture of ammonia and neon, a mixture of ammonia and argon, a mixture of ammonia and nitrogen, a mixture of ammonia and hydrogen, and combinations thereof.

[0027] Throughout this specification, the term "inert gas plasma" refers to a reactive inert gas or inert gas mixture generated in-situ or remotely by a plasma generator. The inert gas or gas mixture is selected from the group consisting of helium, neon, argon, and combinations thereof.

[0028] Throughout this specification, the term "ashing" refers to a process of removing a photoresist or a carbon hard mask using a plasma containing an oxygen source, such as an O2 / inert gas plasma, an O2 plasma, a CO2 plasma, a CO plasma, an H2 / O2 plasma, or combinations thereof, in a semiconductor manufacturing process.

[0029] Throughout this specification, the term "damage resistance" refers to the film properties after an oxygen ashing process. Good or high damage resistance is defined as the following film properties after oxygen ashing: having a film dielectric constant less than 6; having a carbon content in the bulk (at a depth deeper than 50 Å in the film) of 5 at% or less, similar to that before ashing; and having less than 50 Å of the film damaged when observed by the difference in etching rate in diluted HF between the film near the surface (shallower than 50 Å) and the film in the bulk (deeper than 50 Å).

[0030] Throughout this specification, the term "alkyl hydrocarbon" refers to a straight-chain or branched-chain C1-C 20 hydrocarbon or a cyclic C6-C 20 hydrocarbon. Exemplary hydrocarbons include, but are not limited to, heptane, octane, nonane, decane, dodecane, cyclooctane, cyclononane, and cyclodecane.

[0031] Throughout this specification, the term "aromatic hydrocarbon" refers to C6 - C 20 aromatic hydrocarbons. Exemplary aromatic hydrocarbons include, but are not limited to, toluene and mesitylene.

[0032] Throughout this specification, the term "step coverage" as used herein is defined as the ratio of the thicknesses of two deposited films in an assembled or characterized substrate having either or both vias or trenches. Bottom step coverage is the ratio (%) of the thickness at the bottom of a feature divided by the thickness at the top of the feature, and intermediate step coverage is the ratio (%) of the thickness at the sidewall of a feature divided by the thickness at the top of the feature. Films deposited using the methods described herein exhibit a step coverage of about 80% or more or about 90% or more, which means the film is conformal.

[0033] Throughout this specification, the term "ammonia - containing plasma" refers to a reactive gas or gas mixture generated in - situ or remotely by a plasma generator. The gas or gas mixture is selected from the group consisting of ammonia, a mixture of ammonia and helium, a mixture of ammonia and neon, a mixture of ammonia and argon, a mixture of ammonia and nitrogen, a mixture of ammonia and hydrogen, nitrogen, a mixture of nitrogen and helium, a mixture of nitrogen and neon, a mixture of nitrogen and argon, and combinations thereof.

[0034] Throughout this specification, the term "nitrogen - containing plasma" refers to a reactive gas or gas mixture generated in - situ or remotely by a plasma generator. The gas or gas mixture is selected from the group consisting of nitrogen, a mixture of nitrogen and helium, a mixture of nitrogen and neon, a mixture of nitrogen and argon, a mixture of ammonia and nitrogen, a mixture of nitrogen and hydrogen, and combinations thereof.

[0035] The following features: a) a carbon content of about 5 at% or less, about 3 at% or less, about 2 at% or less, or about 1 at% or less when measured by X-ray photoelectron spectroscopy (XPS), preferably stoichiometric silicon nitride; b) an oxygen content of about 5 at% or less, about 3 at% or less, about 2 at% or less, about 1 at% or less when measured by X-ray photoelectron spectroscopy (XPS); a step coverage of 90% or more, 95% or more, or 99% or more. A silicon precursor composition for depositing silicon nitride or carbon-doped silicon nitride having such features and a method comprising such a composition are described herein. In one embodiment, the composition for depositing a silicon-containing film comprises: (a) at least one silicon precursor compound having one or two Si-C-Si bonds selected from the group consisting of 1,1,1,3,3-pentachloro-1,3-disilabutane, 1,1,1,3,3-pentachloro-2-methyl-1,3-disilabutane, 1,1,1,3,3,3-hexachloro-2-methyl-1,3-disilapropane, 1,1,1,3,3,3-hexachloro-2,2-dimethyl-1,3-disilapropane, 1,1,1,3,3-pentachloro-2,2-dimethyl-1,3-disilabutane, 1,1,1,3,3-pentachloro-2-ethyl-1,3-disilabutane, 1,1,1,3,3-pentachloro-1,3-disilapentane, 1,1,1,3,3-pentachloro-2-methyl-1,3-disilapentane, 1,1,1,3,3-pentachloro-2,2-dimethyl-1,3-disilapentane, 1,1,1,3,3-pentachloro-2-ethyl-1,3-disilapentane, 1,1,1,3,3,5,5-heptachloro-1,3,5-trisilahexane, 1,1,1,5,5-pentachloro-3,3-dimethyl-1,3,5-trisilahexane, 1,1,1,5,5-pentachloro-1,3,5-trisilahexane, 2,2,4,6,6-pentachloro-4-methyl-2,4,6-trisilaheptane; and (b) at least one solvent.

[0036]

Table 1

Table 2

[0037] In certain embodiments of the compositions described herein, exemplary solvents can include, but are not limited to, ethers, tertiary amines, alkyl hydrocarbons, aromatic hydrocarbons, tertiary amino ethers, siloxanes, and combinations thereof. In certain embodiments, the difference between the boiling point of a compound having one Si-C-Si or two Si-C-Si bonds and the boiling point of the solvent is 40 °C or less. The wt% of the silicon precursor compound in the solvent can vary from 1 to 99 wt%, 10 to 90 wt%, 20 to 80 wt%, 30 to 70 wt%, 40 to 60 wt%, or 50 to 50 wt%. In some embodiments, the compositions can be transported by direct liquid injection into a reactor chamber for a silicon-containing film using conventional direct liquid injection equipment and methods. In one embodiment of the methods described herein, a silicon nitride film or a carbon-doped silicon nitride film has a carbon content of 5 at% or less and is deposited using a plasma-enhanced ALD process. In this embodiment, the method comprises a. placing one or more substrates having surface features in a reactor, heating the reactor to one or more temperatures from ambient temperature to about 600 °C, and optionally maintaining the reactor at a pressure of 100 torr or less; b. Introducing into the reactor at least one silicon precursor having one or two Si-C-Si bonds selected from the group consisting of 1,1,1,3,3-pentachloro-1,3-disilabutane, 1,1,1,3,3-pentachloro-2-methyl-1,3-disilabutane, 1,1,1,3,3,3-hexachloro-2-methyl-1,3-disilapropane, 1,1,1,3,3,3-hexachloro-2,2-dimethyl-1,3-disilapropane, 1,1,1,3,3-pentachloro-2,2-dimethyl-1,3-disilabutane, 1,1,1,3,3-pentachloro-2-ethyl-1,3-disilabutane, 1,1,1,3,3-pentachloro-1,3-disilapentane, 1,1,1,3,3-pentachloro-2-methyl-1,3-disilapentane, 1,1,1,3,3-pentachloro-2,2-dimethyl-1,3-disilapentane, 1,1,1,3,3-pentachloro-2-ethyl-1,3-disilapentane, 1,1,1,3,3,5,5-heptachloro-1,3,5-trisilahexane, 1,1,1,5,5-pentachloro-3,3-dimethyl-1,3,5-trisilahexane, 1,1,1,5,5-pentachloro-1,3,5-trisilahexane, 2,2,4,6,6-pentachloro-4-methyl-2,4,6-trisilaheptane; c. Removing any unreacted silicon precursor by purging with an inert gas; d. Supplying a plasma containing an ammonia source into the reactor to react with the surface to form a silicon nitride film or a carbon-doped silicon nitride film; and e. Purging with an inert gas to remove any reaction by-products including, and steps b - e are repeated until a film of the desired thickness is deposited. In certain embodiments, the methods described herein are f. Optionally, a step of post-treating the silicon nitride film or the carbon-doped silicon nitride film by thermal annealing or spike annealing at a temperature of 400 - 1000 °C, or with a UV light source, and in this or other embodiments, a UV exposure step can be performed either during film deposition or after deposition is complete; g. Optionally, exposing the carbon-doped silicon nitride film to a plasma containing hydrogen, an inert gas, or nitrogen to provide a post-deposition treatment that improves at least one of the physical properties of the film further comprises.

[0038] In another embodiment of the method described herein, the silicon nitride film or the carbon-doped silicon nitride film has a carbon content of 5 at% or less and is deposited using a plasma-enhanced ALD process. In this embodiment, the method comprises a. disposing one or more substrates having surface features in a reactor (e.g., in a conventional ALD reactor), heating the reactor to one or more temperatures in the range of ambient temperature to about 600 °C, and optionally maintaining the reactor at a pressure of 100 torr or less; b. introducing into the reactor at least one silicon precursor having one or two Si-C-Si bonds selected from the group consisting of 1,1,1,3,3-pentachloro-1,3-disilabutane, 1,1,1,3,3-pentachloro-2-methyl-1,3-disilabutane, 1,1,1,3,3,3-hexachloro-2-methyl-1,3-disilapropane, 1,1,1,3,3,3-hexachloro-2,2-dimethyl-1,3-disilapropane, 1,1,1,3,3-pentachloro-2,2-dimethyl-1,3-disilabutane, 1,1,1,3,3-pentachloro-2-ethyl-1,3-disilabutane, 1,1,1,3,3-pentachloro-1,3-disilapentane, 1,1,1,3,3-pentachloro-2-methyl-1,3-disilapentane, 1,1,1,3,3-pentachloro-2,2-dimethyl-1,3-disilapentane, 1,1,1,3,3-pentachloro-2-ethyl-1,3-disilapentane, 1,1,1,3,3,5,5-heptachloro-1,3,5-trisilahexane, 1,1,1,5,5-pentachloro-3,3-dimethyl-1,3,5-trisilahexane, 1,1,1,5,5-pentachloro-1,3,5-trisilahexane, 2,2,4,6,6-pentachloro-4-methyl-2,4,6-trisilaheptane; c. purging with an inert gas; d. Supplying a plasma containing an ammonia source into a reactor to react with the surface to form a silicon nitride film or a carbon-doped silicon nitride film; e. Purging with an inert gas to remove reaction by-products including, and steps b - e are repeated until a film of the desired thickness is deposited. In certain embodiments, the methods described herein are f. Optionally, a spike anneal at a temperature of 400 - 1000 °C, or a UV light source, for post-deposition treatment of the silicon nitride film or the carbon-doped silicon nitride film, and in this or other embodiments, a UV exposure step can be performed either during film deposition or after deposition is complete; g. Optionally, providing a post-deposition treatment to improve at least one of the physical properties of the film by exposing the silicon nitride film or the carbon-doped silicon nitride film to a plasma containing hydrogen, an inert gas, or nitrogen further including.

[0039] In another embodiment of the methods described herein, the carbon-doped silicon oxynitride has a carbon content of 5 at% or less and is deposited using a plasma-enhanced ALD process. In this embodiment, the method is a. Placing one or more substrates having surface features into a reactor (e.g., into a conventional ALD reactor), heating the reactor to one or more temperatures from ambient temperature to about 600 °C, and optionally maintaining the reactor at a pressure of 100 torr or less; b. Introducing into the reactor at least one silicon precursor having one or two Si-C-Si bonds selected from the group consisting of 1,1,1,3,3-pentachloro-1,3-disilabutane, 1,1,1,3,3-pentachloro-2-methyl-1,3-disilabutane, 1,1,1,3,3,3-hexachloro-2-methyl-1,3-disilapropane, 1,1,1,3,3,3-hexachloro-2,2-dimethyl-1,3-disilapropane, 1,1,1,3,3-pentachloro-2,2-dimethyl-1,3-disilabutane, 1,1,1,3,3-pentachloro-2-ethyl-1,3-disilabutane, 1,1,1,3,3-pentachloro-1,3-disilapentane, 1,1,1,3,3-pentachloro-2-methyl-1,3-disilapentane, 1,1,1,3,3-pentachloro-2,2-dimethyl-1,3-disilapentane, 1,1,1,3,3-pentachloro-2-ethyl-1,3-disilapentane, 1,1,1,3,3,5,5-heptachloro-1,3,5-trisilahexane, 1,1,1,5,5-pentachloro-3,3-dimethyl-1,3,5-trisilahexane, 1,1,1,5,5-pentachloro-1,3,5-trisilahexane, 2,2,4,6,6-pentachloro-4-methyl-2,4,6-trisilaheptane; c. Purging with an inert gas; d. Supplying a plasma containing an ammonia source into the reactor to react with the surface to form a silicon nitride film; e. Purging with an inert gas to remove reaction by-products including, and steps b to e are repeated until a film of the desired thickness is deposited. In certain embodiments, the methods described herein are f. Performing a post-deposition treatment of treating the silicon nitride film or the carbon-doped silicon nitride film with an oxygen source at one or more temperatures of approximately ambient temperature to 1000 °C or about 100 °C to 400 °C, either in-situ or in another chamber, to convert the silicon nitride film or the carbon-doped silicon nitride film into a carbon-doped silicon oxynitride film further including.

[0040] In yet another embodiment of the methods described herein, silicon nitride films or carbon-doped silicon nitride films having a carbon content of less than 5 at% are deposited using a plasma-enhanced ALD process. In this embodiment, the method comprises a. placing one or more substrates with surface features in a reactor, heating the reactor to one or more temperatures in the range of ambient temperature to about 600 °C, and optionally maintaining the reactor at a pressure of 100 torr or less; b. introducing into the reactor at least one silicon precursor having one or two Si-C-Si bonds selected from the group consisting of 1,1,1,3,3-pentachloro-1,3-disilabutane, 1,1,1,3,3-pentachloro-2-methyl-1,3-disilabutane, 1,1,1,3,3,3-hexachloro-2-methyl-1,3-disilapropane, 1,1,1,3,3,3-hexachloro-2,2-dimethyl-1,3-disilapropane, 1,1,1,3,3-pentachloro-2,2-dimethyl-1,3-disilabutane, 1,1,1,3,3-pentachloro-2-ethyl-1,3-disilabutane, 1,1,1,3,3-pentachloro-1,3-disilapentane, 1,1,1,3,3-pentachloro-2-methyl-1,3-disilapentane, 1,1,1,3,3-pentachloro-2,2-dimethyl-1,3-disilapentane, 1,1,1,3,3-pentachloro-2-ethyl-1,3-disilapentane, 1,1,1,3,3,5,5-heptachloro-1,3,5-trisilahexane, 1,1,1,5,5-pentachloro-3,3-dimethyl-1,3,5-trisilahexane, 1,1,1,5,5-pentachloro-1,3,5-trisilahexane, 2,2,4,6,6-pentachloro-4-methyl-2,4,6-trisilaheptane; c. removing any unreacted silicon precursor by purging with an inert gas; d. supplying a first plasma containing an ammonia source into the reactor to react with the surface to form a silicon nitride film or a carbon-doped silicon nitride film; e. purging with an inert gas to remove any reaction by-products f. Supplying a second plasma containing a nitrogen source into the reactor to react with the surface to form a silicon nitride film or a carbon-doped silicon nitride film; g. Purging with an inert gas to remove any reaction by-products; comprising, and steps b - g are repeated until a film of the desired thickness is deposited. In certain embodiments, the method described herein further comprises.

[0041] In yet another embodiment of the method described herein, the silicon nitride film or the carbon-doped silicon nitride film has a carbon content of 5 at% or less and is deposited using a plasma-enhanced ALD process. In this embodiment, the method comprises a. Placing one or more substrates having surface features in the reactor, heating the reactor to one or more temperatures from ambient temperature to about 600 °C, and optionally maintaining the reactor at a pressure of 100 torr or less; b. Introducing into the reactor at least one silicon precursor having one or two Si-C-Si bonds, selected from the group consisting of 1,1,1,3,3-pentachloro-1,3-disilabutane, 1,1,1,3,3-pentachloro-2-methyl-1,3-disilabutane, 1,1,1,3,3,3-hexachloro-2-methyl-1,3-disilapropane, 1,1,1,3,3,3-hexachloro-2,2-dimethyl-1,3-disilapropane, 1,1,1,3,3-pentachloro-2,2-dimethyl-1,3-disilabutane, 1,1,1,3,3-pentachloro-2-ethyl-1,3-disilabutane, 1,1,1,3,3-pentachloro-1,3-disilapentane, 1,1,1,3,3-pentachloro-2-methyl-1,3-disilapentane, 1,1,1,3,3-pentachloro-2,2-dimethyl-1,3-disilapentane, 1,1,1,3,3-pentachloro-2-ethyl-1,3-disilapentane, 1,1,1,3,3,5,5-heptachloro-1,3,5-trisilahexane, 1,1,1,5,5-pentachloro-3,3-dimethyl-1,3,5-trisilahexane, 1,1,1,5,5-pentachloro-1,3,5-trisilahexane, 2,2,4,6,6-pentachloro-4-methyl-2,4,6-trisilaheptane; c. Removing any unreacted silicon precursor by purging with an inert gas; d. Supplying a first plasma containing a nitrogen source into the reactor to react with the surface to form a silicon nitride film or a carbon-doped silicon nitride film; e. Purging with an inert gas to remove any reaction by-products f. Supplying a second plasma containing an ammonia source into the reactor to react with the surface to form a silicon nitride film or a carbon-doped silicon nitride film; g. Purging with an inert gas to remove any reaction by-products; including, and steps b to g are repeated until a film of the desired thickness is deposited. In one embodiment, the substrate comprises at least one feature including a patterned trench having an aspect ratio of 1:9 or greater and a gap of 180 nm or less.

[0042] In yet another embodiment, the container for depositing the silicon-containing film contains one or more of the silicon precursor compounds described herein. In one particular embodiment, the container is at least one pressurizable container (preferably, for example, a stainless steel container having the designs disclosed in U.S. Pat. Nos. 7,334,595, 6,077,356, 5,069,244, and 5,465,766, the disclosures of which are incorporated herein by reference). The container is made of glass (borosilicate or fused silica) or a 316, 316L, 304, or 304L series stainless steel alloy (UNS specifications S31600, S31603, S30400, S30403) equipped with suitable valves and adapted to transport one or more precursors to a reactor for a CVD or ALD process. In this or other embodiments, the silicon precursor is supplied in a pressurizable container made of stainless steel, and the purity of the precursor is 98 wt% or more or 99.5% or more and is suitable for semiconductor applications. Preferably, the silicon precursor compound is substantially free of metal ions such as Al 3+ ions, Fe 2+ , Fe 3+ , Ni 2+ , Cr 3+ . As used herein, the term "substantially free of" means, with respect to Al, Fe, Ni, Cr, less than about 5 ppm (by weight), preferably less than about 1 ppm, more preferably less than about 0.1 ppm, and most preferably less than about 0.05 ppm as measured by ICP-MS. In certain embodiments, such a container may further have means for mixing the precursor with one or more additional precursors, if desired. In these or other embodiments, the contents of at least one container may be premixed with additional precursors. Alternatively, the silicon precursor and / or other precursors can be held in separate containers or in a single container having separation means for holding the silicon precursor and other precursors separately during storage.

[0043] The silicon-containing film is deposited on at least the surface of a substrate, for example, on the surface of a semiconductor or display substrate. In the methods described herein, the substrate is made of various materials well-known in the art, including a film of silicon, such as crystalline or amorphous silicon, silicon oxide, silicon nitride, amorphous carbon, silicon oxycarbide, silicon oxynitride, silicon carbide, germanium, germanium-doped silicon, boron-doped silicon, a metal, such as copper, tungsten, aluminum, cobalt, nickel, tantalum, a metal nitride, such as titanium nitride, tantalum nitride, a metal oxide, a group III / V metal or metalloid, such as GaAs, InP, GaP, and GaN, an AMOLED (active matrix organic light-emitting diode) flexible substrate, and combinations thereof, and / or may be coated with such materials. These coatings may completely coat the semiconductor substrate, may be multiple layers of various materials, and may be partially etched to expose underlying layers of the material. The surface may further have a photoresist material deposited thereon that is patterned and developed to partially coat the substrate. In certain embodiments, the semiconductor substrate comprises at least one surface feature selected from the group consisting of pores, vias, trenches, and combinations thereof. Potential uses of the silicon-containing film include, but are not limited to, low-k spacers for FinFETs, nanosheets, or sacrificial hard masks for self-aligned patterning processes (such as SADP, SAQP, or SAOP).

[0044] The deposition method used to form a silicon-containing film or coating is a deposition process. Examples of suitable deposition processes for the methods disclosed herein include, but are not limited to, chemical vapor deposition or atomic layer deposition processes. As used herein, the term "chemical vapor deposition process" refers to any process in which a substrate is exposed to one or more volatile precursors, and the one or more volatile precursors react and / or decompose on the substrate surface to yield the desired deposit. As used herein, the term "atomic layer deposition process" refers to a self-limiting (e.g., the amount of film material deposited in each reaction cycle is constant) sequential surface chemical reaction for depositing a film of material on substrates of various compositions. As used herein, the term "thermal atomic layer deposition process" refers to an atomic layer deposition process at a substrate temperature of room temperature to 600 °C without using in-situ or remote plasma. Precursors, reagents, and sources used herein may sometimes be described as "gaseous," which is understood to mean that the precursor may be either liquid or solid and is transported into the reactor by direct vaporization, bubbling, or sublimation, with or without an inert gas. In some cases, the vaporized precursor may pass through a plasma generator.

[0045] In one embodiment, the silicon-containing film is deposited using an ALD process. In another embodiment, the silicon-containing film is deposited using a CCVD process. In a further embodiment, the silicon-containing film is deposited using a thermal ALD process. As used herein, the term "reactor" includes, but is not limited to, a reaction chamber or a deposition chamber.

[0046] In certain embodiments, the methods disclosed herein avoid pre-reaction of at least one precursor by using an ALD or cyclic CVD process that separates at least one precursor before and / or during introduction into the reactor. Preferably, a deposition technique, such as an ALD or cyclic CVD (CCVD) process, is used to deposit a silicon-containing film. In one embodiment, the film is deposited by exposing a substrate surface to an oxygen source, a nitrogen-containing source, or other precursor or reagent in an ALD process in a typical single-wafer ALD reactor, a semi-batch ALD reactor, or a batch furnace ALD reactor, instead of one or more silicon-containing precursors. Film growth proceeds by self-controlled control of the surface reaction, the pulse length of each precursor or reagent, and the deposition temperature. However, once the surface of the substrate is saturated, film growth stops. In another embodiment, each reactant containing a silicon precursor and a reactive gas is exposed to the substrate by moving or rotating the substrate into different compartments of the reactor, and each compartment is separated by an inert gas curtain, i.e., a spatial ALD reactor or a roll-to-roll ALD reactor.

[0047] In certain embodiments, depending on the deposition method, the silicon precursors described herein, and optionally other silicon-containing precursors, can be introduced into the reactor in a predetermined molar volume, e.g., from about 0.1 to about 100 micromoles. In this or other embodiments, the precursors can be introduced into the reactor over a predetermined time period. In certain embodiments, the time period is from about 0.001 to about 500 s.

[0048] In certain embodiments, a silicon nitride film or a carbon-doped silicon nitride film deposited using the methods described herein is treated with an oxygen source, reagent or precursor containing oxygen, such as water vapor, to convert such a film into a carbon-doped oxynitride. The oxygen source may be introduced into the reactor in the form of at least one oxygen source and / or may additionally be present in other precursors used in the deposition process. Suitable oxygen source gases may include, for example, air, water (H2O) (e.g., deionized water, purified water, distilled water, water vapor, water vapor plasma, hydrogen peroxide, oxygen-saturated water, air, compositions containing water and other organic liquids), oxygen (O2), oxygen plasma, ozone (O3), nitric oxide (NO), nitrogen dioxide (NO2), nitrous oxide (N2O), carbon monoxide (CO), hydrogen peroxide (H2O2), plasma containing water, plasma containing water and argon, hydrogen peroxide, compositions containing hydrogen, compositions containing hydrogen and oxygen, carbon dioxide (CO2), air, and combinations thereof. In certain embodiments, the oxygen source includes an oxygen source gas introduced into the reactor at a flow rate of about 1 to about 10,000 standard cubic centimeters per minute (sccm) or about 1 to about 1000 sccm. The oxygen source can be introduced for a time ranging from about 0.1 to about 100 s. The catalyst is selected from Lewis bases such as pyridine, piperazine, trimethylamine, tert-butylamine, diethylamine, trimethylamine, ethylenediamine, ammonia or other organic amines.

[0049] In embodiments where the film is deposited by ALD or a cyclic CVD process, the precursor pulse may have a pulse duration longer than 0.01 s, the oxygen source may have a pulse duration shorter than 0.01 s, while the water pulse duration may have a pulse duration shorter than 0.01 s.

[0050] In certain embodiments, the oxygen source flows continuously into the reactor, while the precursor pulses and the plasma are introduced sequentially. The precursor pulse may have a pulse duration longer than 0.01 s, while the plasma duration may range from 0.01 s to 100 s.

[0051] In certain embodiments, the silicon-containing film contains silicon and nitrogen. In these embodiments, the silicon-containing film deposited using the methods described herein is formed in the presence of a nitrogen-containing source. The nitrogen-containing source may be introduced into the reactor in the form of at least one nitrogen source gas and / or may additionally be present in other precursors used in the deposition process.

[0052] Suitable ammonia-containing gases may include, for example, ammonia, mixtures of ammonia and inert gases, mixtures of ammonia and nitrogen, mixtures of ammonia and hydrogen, and combinations thereof.

[0053] In certain embodiments, the nitrogen source is introduced into the reactor at a flow rate of about 1 to about 10,000 standard cubic centimeters per minute (sccm) or about 1 to about 1000 sccm. The nitrogen-containing source can be introduced over a time period ranging from about 0.1 to about 100 s. In embodiments where the film is deposited by an ALD or cyclic CVD process using both nitrogen and oxygen sources, the precursor pulse may have a pulse duration longer than 0.01 s, the nitrogen source may have a pulse duration shorter than 0.01 s, while the water pulse duration may have a pulse duration shorter than 0.01 s. In yet another embodiment, the purge duration between pulses can be short, close to 0 s, or there may be no purge between pulses and pulsing is continuous.

[0054] 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 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 (N2), helium (He), neon (Ne), hydrogen (H2), and combinations thereof. In certain embodiments, a purge gas, such as Ar, is supplied into the reactor at a flow rate of about 10 to about 10,000 sccm for a period of about 0.1 to about 1000 s, thereby purging unreacted materials and any by-products that may remain in the reactor.

[0055] Each step of supplying a precursor, an oxygen source, an ammonia-containing source, and / or other precursors, source gases, and / or reagents can be carried out by varying the time for which they are supplied so as to change the stoichiometric composition of the resulting film.

[0056] To initiate the reaction and to form a film or coating on a substrate, energy is applied to at least one of the precursors, an ammonia-containing source, a reducing agent such as a hydrogen plasma, or other precursors, or a combination thereof. Such energy can be supplied by, but is not limited to, heat, plasma, pulsed plasma, helicon plasma, high density plasma, inductively coupled plasma, X-rays, electron beam, photons, remote plasma processes, and combinations thereof.

[0057] In certain embodiments, a secondary RF frequency source can be used to vary the plasma characteristics at the surface of the substrate. In embodiments where the deposition involves a plasma, the plasma generation process can include a direct plasma generation process where the plasma is generated directly in the reactor, or alternatively a remote plasma generation process where the plasma is generated outside the reactor and supplied into the reactor.

[0058] Silicon precursors and / or other silicon-containing precursors can be transported to a reaction chamber, such as a CVD or ALD reactor, in various ways. In one embodiment, a liquid transport system can be utilized. In an alternative embodiment, an apparatus that combines liquid transport and flash evaporation processes, such as a turbo evaporator manufactured by MSP Corporation of Shoreview, MN, can be used to enable the volumetric transport of low volatility materials, which results in reproducible transport and deposition without thermal decomposition of the precursors. In a liquid transport formulation, the precursors described herein can be transported in the form of a stock solution or alternatively used in a solvent formulation or composition containing the precursors. Thus, in certain embodiments, the precursor formulation may include at least one solvent component with suitable characteristics that may be desired and advantageous in a given end use application for forming a film on a substrate.

[0059] In this or other embodiments, the steps of the methods described herein may be performed in various orders, sequentially or simultaneously (e.g., during at least a portion of another step), and it is understood that they may be performed in any combination thereof. Each step of supplying the precursor and the nitrogen-containing source gas can be performed with a varying period for supplying them to vary the stoichiometric composition of the resulting silicon-containing film.

[0060] In further embodiments of the methods described herein, the film or as-deposited film is subjected to a processing step. The processing step can be performed during at least a portion of the deposition step, after the deposition step, and combinations thereof. Exemplary processing steps include, but are not limited to, processing by high temperature thermal annealing that affects one or more properties of the film; plasma processing; ultraviolet (UV) light processing; laser; electron beam processing, and combinations thereof. Films deposited with a silicon precursor having one or two Si-C-Si bonds, as described herein, have improved properties when compared to films deposited with previously disclosed silicon precursors under the same conditions, such as, but not limited to, a wet etching rate that is less than the wet etching rate of the film prior to the processing step, or a density that is higher than the density prior to the processing step. In one particular embodiment, during the deposition process, the as-deposited film is processed intermittently. These intermittent or in-deposition processes can be performed, for example, after each ALD cycle, after a specific number of ALDs, such as, but not limited to, after one (1) ALD cycle, two (2) ALD cycles, five (5) ALD cycles, or after every ten (10) or more ALD cycles.

[0061] In embodiments where the film is processed in a high temperature annealing step, the annealing temperature is at least 100 °C above or higher than the deposition temperature. In this or other embodiments, the annealing temperature is from about 400 °C to about 1000 °C. In this or other embodiments, the annealing process can be performed in a vacuum (<760 Torr), an inert environment, or an oxygen-containing environment (such as ozone, H2O, H2O2, N2O, NO2, or O2).

[0062] In embodiments where the film is processed by UV treatment, the film is exposed to broadband UV having a wavelength of from about 150 nanometers (nm) to about 400 nm or alternatively to a UV source. In one particular embodiment, the as-deposited film is exposed to UV in a chamber different from the deposition chamber after reaching the desired film thickness.

[0063] In an embodiment where the film is treated using plasma, a passivation layer, such as carbon-doped silicon oxide, is deposited to prevent chlorine and nitrogen contaminants from entering the film in the subsequent plasma treatment. The passivation layer can be deposited using atomic layer deposition or cyclic chemical vapor deposition.

[0064] In an embodiment where the film is treated using plasma, the plasma source is selected from the group consisting of a hydrogen plasma, a plasma containing hydrogen and helium, and a plasma containing hydrogen and argon. The hydrogen plasma reduces the film dielectric constant, enhances the damage resistance to the subsequent plasma ashing process, while keeping the carbon content in the bulk almost unchanged.

[0065] The following examples illustrate specific aspects of the present invention and do not limit the scope of the appended claims.

Example

[0066] In the following examples, unless otherwise stated, the properties are obtained from sample films deposited on a silicon wafer having a resistivity of 5 - 20 Ω·cm as a substrate. All film depositions are carried out using a CN-1 reactor having a showerhead design with a 13.56 MHz direct plasma.

[0067] Under typical process conditions, unless otherwise stated, the chamber pressure is fixed at a pressure of about 1 - about 5 Torr. An additional inert gas is used to maintain the chamber pressure.

[0068] Film deposition for plasma-enhanced ALD includes the steps described in Tables 3, 4, and 5. Unless otherwise specifically stated, a total of 100, 200, 300, or 500 deposition cycles are used to obtain the desired film thickness.

Table 3

Table 4

Table 5

[0069] The refractive index (RI) and thickness of the deposited film were measured using an ellipsometer. The film inhomogeneity was calculated using the standard equation: % inhomogeneity = ((maximum thickness - minimum thickness) / (2 × average (avg) thickness)). The film structure and composition were analyzed using Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS). The density of the film was measured by X-ray reflectometry (XRR).

[0070] Example 1: ALD silicon nitride using 1,1,1,3,3-pentachloro-1,3-disilabutane and NH3 / argon plasma A silicon wafer was loaded into a CN-1 reactor with a showerhead design having a chamber pressure of 1 torr and a direct plasma of 13.56 MHz. 1,1,1,3,3-Pentachloro-1,3-disilabutane as a silicon precursor was transported as vapor into the reactor using bubbling or vapor extraction.

[0071] ALD cycles were constructed from the process steps provided in Table 3 with the following process parameters: a. Provide the substrate in the reactor and heat the substrate to about 300 °C b. Introduce the vapor of 1,1,1,3,3-pentachloro-1,3-disilabutane into the reactor Argon flow: 100 sccm through the precursor container Pulse: 2 s Ar flow: 1000 sccm c. Purge Argon flow: 1000 sccm Purge time: 10 s d. Introduce ammonia plasma Argon flow: 1000 sccm Ammonia flow: 300 sccm Plasma power: 300 W Pulse: 15 s e. Purge Argon flow: 1000 sccm Purge time: 5 s was used. Steps b - e were repeated 1000 cycles to provide 32 nm silicon nitride having a composition of 58.66 at% nitrogen, 38.96 at% silicon, and 2.37 at% oxygen. Neither chlorine nor carbon was detected. The refractive index was approximately 1.9.

[0072] Example 2: ALD Silicon Nitride Using 1,1,1,3,3 - Pentachloro - 1,3 - Disilabutane and NH3 / Argon Plasma A silicon wafer was loaded into a CN - 1 reactor equipped with a showerhead design having a chamber pressure of 1 torr and a direct plasma of 13.56 MHz. 1,1,1,3,3 - Pentachloro - 1,3 - disilabutane was transported as a vapor into the reactor using bubbling.

[0073] ALD cycles were constructed from the process steps provided in Table 1 with the following process parameters: a) Provide the substrate in the reactor and heat the substrate to approximately 400 °C b) Introduce the vapor of 1,1,1,3,3 - pentachloro - 1,3 - disilabutane into the reactor Argon flow: 100 sccm through the precursor container Pulse: 2 s Argon: 1000 sccm c) Perform an inert gas purge Argon flow: 1000 sccm Purge time: 15 s d) Introduce ammonia plasma Argon flow: 1000 sccm Ammonia flow: 50 sccm Plasma power: 300 W Pulse: 10 s e) Purge Argon flow: 1000 sccm Purge time: 10 s It was used. Steps b to e were repeated 1000 cycles to provide 26 nm silicon nitride having a composition of 58.30 at% nitrogen, 39.15 at% silicon, and 2.55 at% oxygen. When measured by XPS, neither chlorine nor carbon was detected. The composition of the film obtained in this example was close to stoichiometric silicon nitride. The refractive index was about 1.9.

[0074] Although the foregoing has been illustrated and described with reference to specific particular embodiments and examples, the present invention is not intended to be limited to the details shown. Rather, various modifications may be made in the region and scope of the equivalents of the claims without departing from the spirit of the invention. For example, all ranges broadly discussed herein are expressly intended to include all sub-ranges subsumed within those broad ranges. Embodiments of the present invention include the following embodiments. (Appendix 1) A method for forming silicon nitride or carbon-doped silicon nitride by a plasma-enhanced ALD process, a) providing a substrate having surface features in a reactor, heating the reactor to one or more temperatures of about 600° C. or less, and optionally maintaining the reactor at a pressure of 100 torr or less; b) having one or two Si-C-Si bonds and selected from the group consisting of 1,1,1,3,3,3-hexachloro-2-methyl-1,3-disilapropane, 1,1,1,3,3,3-hexachloro-2,2-dimethyl-1,3-disilapropane, 1,1,1,3,3-pentachloro-1,3-disilabutane, 1,1,1,3,3-pentachloro-2-methyl-1,3-disilabutane, 1,1,1,3,3-pentachloro-2,2-dimethyl-1,3-disilabutane, 1,1,1,3,3-pentachloro-2-ethyl-1,3-disilabutane, 1,1,1,3,3-pentachloro-1,3-disilapentane, 1,1,1,3,3-pentachloro-2-methyl-1,3-disilapentane, 1,1,1,3,3-pentachloro-2,2-dimethyl-1,3-disilapentane, 1,1,1,3,3-pentachloro-2-ethyl-1,3-disilapentane, 1,1,1,3,3,5,5-heptachloro-1,3,5-trisilahexane, 1,1,1,5,5-pentachloro-3,3-dimethyl-1,3,5-trisilahexane, 1,1,1,5,5-pentachloro-1,3,5-trisilahexane, 2,2,4,6,6-pentachloro-4-methyl-2,4,6-trisilaheptane, introducing at least one silicon precursor into the reactor, whereby the silicon precursor reacts with at least a part of the surface features of the substrate to provide a chemisorbed layer; c) purging any unreacted silicon precursor and / or any reaction by-products from the reactor using an inert gas; d) supplying a plasma containing an ammonia source into the reactor to react with the chemisorbed layer to form a silicon nitride film; and e) purging any further reaction by-products from the reactor using an inert gas A method comprising repeating steps b to e until a silicon nitride film of a desired thickness is deposited. (Appendix 2) The method according to Appendix 1, wherein the silicon nitride film is a carbon-doped silicon nitride film. (Supplementary Note 3) The method according to Supplementary Note 1, further comprising a step of treating the silicon nitride film by spike annealing at a temperature of 400 to 1000°C. (Supplementary Note 4) The method according to Supplementary Note 1, further comprising a step of exposing the silicon nitride film to a UV light source either during the deposition of the silicon nitride film or after the deposition of the silicon nitride film. (Supplementary Note 5) The method according to Supplementary Note 1, further comprising a step of exposing the silicon nitride film to a plasma containing one or more gases selected from the group consisting of hydrogen, inert gas, nitrogen, and combinations thereof. (Supplementary Note 6) The method according to Supplementary Note 1, further comprising a treatment step of treating the silicon nitride film with an oxygen source at one or more temperatures from ambient temperature to 1000°C either in-situ or in a chamber separate from the reactor to convert the silicon nitride into a silicon oxynitride film. (Supplementary Note 7) The method according to Supplementary Note 6, wherein the silicon nitride film is a carbon-doped silicon nitride film, and the treatment step of treating the silicon nitride film with an oxygen source converts the carbon-doped silicon nitride into a carbon-doped silicon oxynitride film. (Supplementary Note 8) A film formed by the method according to Supplementary Note 1, having a dielectric constant (k) of about 6 or less and a carbon content of about 5 atomic % or less as measured by X-ray photoelectron spectroscopy. (Supplementary Note 9) The film according to Supplementary Note 8, having a carbon content of about 5 atomic % or less as measured by X-ray photoelectron spectroscopy. (Supplementary Note 10) The film according to Supplementary Note 9, having a carbon content of about 3 atomic % or less as measured by X-ray photoelectron spectroscopy. (Supplementary Note 11) The film according to Supplementary Note 10, having a carbon content of about 2 atomic % or less as measured by X-ray photoelectron spectroscopy. (Supplementary Note 12) The film according to Supplementary Note 11, having a carbon content of about 1 atomic % or less as measured by X-ray photoelectron spectroscopy. (Supplementary Note 13) The method according to Supplementary Note 1, further comprising a step of performing thermal annealing on the silicon nitride film or the carbon-doped silicon nitride film at a temperature of about 300 to about 1000°C. (Supplementary Note 14) The method according to Supplementary Note 1, further comprising a step of performing plasma treatment on the silicon nitride film at a temperature of about 25°C to about 600°C using an inert gas plasma, a hydrogen / inert plasma, or a nitrogen plasma. (Supplementary Note 15) The method according to Supplementary Note 2, further comprising a step of performing plasma treatment on the carbon-doped silicon nitride film at a temperature of about 25°C to about 600°C using an inert gas plasma, a hydrogen / inert plasma, or a nitrogen plasma. (Supplementary Note 16) The method according to Supplementary Note 6, further comprising a step of performing plasma treatment on the silicon oxynitride film at a temperature of about 25°C to about 600°C using an inert gas plasma, a hydrogen / inert plasma, or a nitrogen plasma. (Supplementary Note 17) The method according to Supplementary Note 7, further comprising a step of performing plasma treatment on the carbon-doped silicon oxynitride film at a temperature of about 25°C to about 600°C using an inert gas plasma, a hydrogen / inert plasma, or a nitrogen plasma. (Supplementary Note 18) A method for forming silicon nitride or carbon-doped silicon nitride by a plasma-enhanced ALD process, a) providing a substrate having surface features in a reactor; b) having one or two Si-C-Si bonds and introducing into the reactor at least one silicon precursor selected from the group consisting of 1,1,1,3,3,3-hexachloro-2-methyl-1,3-disilapropane, 1,1,1,3,3,3-hexachloro-2,2-dimethyl-1,3-disilapropane, 1,1,1,3,3-pentachloro-1,3-disilabutane, 1,1,1,3,3-pentachloro-2-methyl-1,3-disilabutane, 1,1,1,3,3-pentachloro-2,2-dimethyl-1,3-disilabutane, 1,1,1,3,3-pentachloro-2-ethyl-1,3-disilabutane, 1,1,1,3,3-pentachloro-1,3-disilapentane, 1,1,1,3,3-pentachloro-2-methyl-1,3-disilapentane, 1,1,1,3,3-pentachloro-2,2-dimethyl-1,3-disilapentane, 1,1,1,3,3-pentachloro-2-ethyl-1,3-disilapentane, 1,1,1,3,3,5,5-heptachloro-1,3,5-trisilahexane, 1,1,1,5,5-pentachloro-3,3-dimethyl-1,3,5-trisilahexane, 1,1,1,5,5-pentachloro-1,3,5-trisilahexane and 2,2,4,6,6-pentachloro-4-methyl-2,4,6-trisilaheptane, whereby the silicon precursor reacts with at least a part of the surface features of the substrate to provide a chemisorbed layer; c) purging any unreacted silicon precursor and / or any reaction by-products from the reactor using an inert gas; d) supplying a first plasma source into the reactor to react with the chemisorbed layer to form an optionally carbon-doped silicon nitride film; e) purging any further reaction by-products from the reactor using an inert gas; f) supplying a second plasma source into the reactor to further react to form an optionally carbon-doped silicon nitride film; g) purging any further reaction by-products from the reactor using an inert gas A method, including, wherein steps b to g are optionally carbon-doped and repeated until the silicon nitride film reaches a desired thickness, and the reactor is maintained at one or more temperatures of about 25°C to about 600°C. (Appendix 19) The method according to Appendix 18, wherein the plasma is a plasma containing an ammonia source, and the second plasma is a plasma containing a nitrogen source. (Appendix 20) The method according to Appendix 18, wherein the first plasma is a plasma containing a nitrogen source, and the second plasma is a plasma containing an ammonia source. (Appendix 21) A stainless steel container containing a composition containing at least one silicon precursor selected from the group consisting of 1,1,1,3,3,3-hexachloro-2-methyl-1,3-disilapropane, 1,1,1,3,3,3-hexachloro-2,2-dimethyl-1,3-disilapropane, 1,1,1,3,3-pentachloro-1,3-disilabutane, 1,1,1,3,3-pentachloro-2-methyl-1,3-disilabutane, 1,1,1,3,3-pentachloro-2,2-dimethyl-1,3-disilabutane, 1,1,1,3,3-pentachloro-2-ethyl-1,3-disilabutane, 1,1,1,3,3-pentachloro-1,3-disilapentane, 1,1,1,3,3-pentachloro-2-methyl-1,3-disilapentane, 1,1,1,3,3-pentachloro-2,2-dimethyl-1,3-disilapentane, 1,1,1,3,3-pentachloro-2-ethyl-1,3-disilapentane, 1,1,1,3,3,5,5-heptachloro-1,3,5-trisilahexane, 1,1,1,5,5-pentachloro-3,3-dimethyl-1,3,5-trisilahexane, 1,1,1,5,5-pentachloro-1,3,5-trisilahexane, and 2,2,4,6,6-pentachloro-4-methyl-2,4,6-trisilaheptane, having one or two Si-C-Si bonds. (Appendix 22) The stainless steel container according to Appendix 21, further containing an inert headspace gas selected from the group consisting of helium, argon, nitrogen, and combinations thereof. (Supplementary Note 23) A silicon nitride film or a carbon-doped silicon nitride film suitable for semiconductor industry or display applications and deposited using the method described in Supplementary Note 1. (Supplementary Note 24) A silicon nitride film or a carbon-doped silicon nitride film suitable for semiconductor industry or display applications and deposited using the method described in Supplementary Note 18.

Claims

1. A method for forming silicon nitride or carbon-doped silicon nitride by a plasma-enhanced ALD process, the method having a carbon content of 5 atomic weight percent or less as measured by X-ray photoelectron spectroscopy, comprising: a) providing a substrate with surface features in a reactor and heating the reactor to one or more temperatures up to 600° C., and optionally maintaining said reactor at a pressure up to 100 torr; b) introducing at least one silicon precursor having one or two Si—C—Si bonds and selected from the group consisting of 1,1,1,3,3,3-hexachloro-2-methyl-1,3-disilapropane, 1,1,1,3,3,3-hexachloro-2,2-dimethyl-1,3-disilapropane, and 2,2,4,6,6-pentachloro-4-methyl-2,4,6-trisilaheptane into the reactor, whereby the silicon precursor reacts with at least a portion of the surface features of the substrate to provide a chemisorbed layer; c) purging the reactor of any unreacted silicon precursor and / or any reaction by-products using an inert gas; d) supplying a plasma containing an ammonia source into the reactor to react with the chemisorbed layer to form a silicon nitride film; and e) purging the reactor of any additional reaction by-products with an inert gas. wherein steps b through e are repeated until a desired thickness of the silicon nitride film is deposited.

2. The method of claim 1 , wherein the silicon nitride film is a carbon-doped silicon nitride film.

3. The method of claim 1, further comprising treating the silicon nitride film with a spike anneal at a temperature between 400 and 1000°C.

4. 10. The method of claim 1, further comprising exposing the silicon nitride film to a UV light source either during deposition of the silicon nitride film or after deposition of the silicon nitride film.

5. 10. The method of claim 1, further comprising exposing the silicon nitride film to a plasma comprising one or more gases selected from the group consisting of hydrogen, an inert gas, nitrogen, and combinations thereof.

6. 10. The method of claim 1, further comprising treating the silicon nitride film with an oxygen source at one or more temperatures between ambient temperature and 1000° C., either in situ or in a chamber separate from the reactor, to convert the silicon nitride to a silicon oxynitride film.

7. 7. The method of claim 6, wherein the silicon nitride film is a carbon-doped silicon nitride film, and the step of treating the silicon nitride film with an oxygen source converts the carbon-doped silicon nitride to a carbon-doped silicon oxynitride film.

8. 10. The method of claim 1, wherein the silicon nitride film has a dielectric constant (k) of 6 or less and a carbon content of 5 atomic percent or less as measured by X-ray photoelectron spectroscopy.

9. 9. The method of claim 8, wherein the silicon nitride film has a carbon content of less than or equal to 3 atomic percent as measured by X-ray photoelectron spectroscopy.

10. 10. The method of claim 9, wherein the silicon nitride film has a carbon content of less than or equal to 2 atomic percent as measured by X-ray photoelectron spectroscopy.

11. 11. The method of claim 10, wherein the silicon nitride film has a carbon content of 1 atomic percent or less as measured by X-ray photoelectron spectroscopy.

12. 2. The method of claim 1, further comprising the step of thermally annealing the silicon nitride film or the carbon-doped silicon nitride film at a temperature between 300 and 1000°C.

13. 10. The method of claim 1, further comprising subjecting the silicon nitride film to a plasma treatment using an inert gas plasma, a hydrogen / inert plasma, or a nitrogen plasma at a temperature between 25°C and 600°C.

14. 3. The method of claim 2, further comprising subjecting the carbon doped silicon nitride film to a plasma treatment using an inert gas plasma, a hydrogen / inert plasma, or a nitrogen plasma at a temperature between 25°C and 600°C.

15. 7. The method of claim 6, further comprising subjecting the silicon oxynitride film to a plasma treatment using an inert gas plasma, a hydrogen / inert plasma, or a nitrogen plasma at a temperature between 25°C and 600°C.

16. 8. The method of claim 7, further comprising subjecting the carbon doped silicon oxynitride film to a plasma treatment using an inert gas plasma, a hydrogen / inert plasma, or a nitrogen plasma at a temperature between 25° C. and 600° C.

17. A method for forming silicon nitride or carbon-doped silicon nitride by a plasma-enhanced ALD process having a carbon content of 5 atomic percent or less as measured by X-ray photoelectron spectroscopy, comprising: a) providing a substrate having surface features in a reactor; b) introducing at least one silicon precursor having one or two Si—C—Si bonds and selected from the group consisting of 1,1,1,3,3,3-hexachloro-2-methyl-1,3-disilapropane, 1,1,1,3,3,3-hexachloro-2,2-dimethyl-1,3-disilapropane, and 2,2,4,6,6-pentachloro-4-methyl-2,4,6-trisilaheptane into the reactor, whereby the silicon precursor reacts with at least a portion of the surface features of the substrate to provide a chemisorbed layer; c) purging the reactor of any unreacted silicon precursor and / or any reaction by-products using an inert gas; d) providing a first plasma source into the reactor to react with the chemisorbed layer to form an optionally carbon-doped silicon nitride film; e) purging the reactor of any additional reaction by-products using an inert gas; f) feeding a second plasma source into the reactor to further react and form a silicon nitride film, optionally doped with carbon; g) purging the reactor of any additional reaction by-products using an inert gas. wherein steps b through g are repeated until the optionally carbon-doped silicon nitride film reaches a desired thickness, and the reactor is held at one or more temperatures between 25° C. and 600° C.

18. 20. The method of claim 17, wherein the first plasma is a plasma comprising an ammonia source and the second plasma is a plasma comprising a nitrogen source.

19. 20. The method of claim 17, wherein the first plasma is a plasma containing a nitrogen source and the second plasma is a plasma containing an ammonia source.

20. 10. The method of claim 1, wherein the silicon nitride film or carbon doped silicon nitride film is suitable for semiconductor industry or display applications.

21. 18. The method of claim 17, wherein the silicon nitride film or carbon doped silicon nitride film is suitable for semiconductor industry or display applications.

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