Silicon-containing films having surfaces modified from halogenated silicon-containing compounds

Abstract

A method for depositing a high-quality, smooth, and continuous silicon-containing film includes a) providing at least one substrate in a reactor, b) heating the reactor to at least one temperature in the range from ambient temperature to about 750°C, and selectively maintaining the reactor at a pressure of about 100 Torr or less, c) introducing at least one first silicon precursor into the reactor, the first silicon precursor comprising at least one organic amine group and at least one halogenated group having the formula: SiHmXn(NR 1R2)4-mn where m = 0, 1, 2; n = 1, 2, 3, and m + n ≤ 3; X is selected from the group consisting of Cl, Br, and I; R1 and R2 are each independently selected from the group consisting of straight-chain or branched C1 to C10 alkyl, straight-chain or branched C3 to C10 alkenyl, straight-chain or branched C3 to C10 alkynyl, C3 to C10 cyclic alkyl, C2 to C6 dialkylamino, electron-withdrawing group, and C6 to C10 aryl, to form a first silicon-containing layer; d) flushing any unreacted precursors in the reactor with an inert gas; e) introducing a nitrogen source to react with the first silicon-containing layer to form a seed layer containing at least one of the group consisting of silicon nitride and carbon-doped silicon nitride; f) flushing the reactor with an inert gas; g) The reactor is introduced with at least one second silicon precursor comprising a halogenated silicon compound, which reacts with the seed layer to form a second silicon-containing layer comprising at least one group selected from silicon nitride, carbon-doped silicon nitride, silicon oxynitride, and carbon-doped silicon oxynitride; h) the reactor is flushed with an inert gas; i) a nitrogen source is introduced to react with the second silicon-containing layer to form silicon nitride or carbon-doped silicon nitride; and j) the reactor is flushed with an inert gas.

Description

Silicon-containing film having a surface modified by a halogenated silicon-containing compound The present invention relates to compositions and methods for fabricating electronic devices. More specifically, the present invention relates to compounds, compositions, and methods for depositing high-quality silicon-containing films, such as, but not limited to, silicon nitride, carbon-doped silicon nitride, silicon oxynitride, and carbon-doped silicon oxynitride. Silicon nitride films are used in a variety of semiconductor applications. For example, they are often used as a final passivation and mechanical protection layer for integrated circuits, a mask layer for selective oxidation of silicon, as one of the dielectric materials in a dynamic random access memory (DRAM) capacitor or in a stacked oxide-nitride-oxide (ONO) layer in 3D NAND flash memory chips, or as a chemical mechanical polishing (CMP) stop layer in shallow trench isolation applications. There is a need to form a conformal and continuous thin film of high-quality silicon-containing films <200 angstroms or less, <150 angstroms or less, <100 angstroms or less, <50 angstroms or less, <30 angstroms or less, <20 angstroms or less, <15 angstroms or less, <10 angstroms or less, such as silicon nitride, carbon-doped silicon oxide, silicon oxynitride, or carbon-doped silicon oxynitride on an oxide surface such as silicon oxide or other metal oxide. Chlorosilanes or chlorodisilanes, such as dichlorosilane and hexachlorodisilane, and ammonia-based processes are commonly used to deposit high-quality silicon nitride. However, chlorine coordination has a relatively high activation energy to react with the oxide surface, resulting in so-called island growth. For chlorosilane-based films, the silicon-containing films need to have a certain critical thickness to obtain a smooth and continuous film. Furthermore, with each generation of semiconductor devices, the pitch width shrinks, which in turn causes the films to shrink. In some applications, a thin silicon nitride layer is deposited on top of silicon monoxide or other types of metal oxides using an atomic layer deposition (ALD) process comprising chlorosilane / chlorodisilane and ammonia. At the beginning of the deposition process, the films have uneven and discontinuous island growth. After reaching a certain critical thickness, the island growth becomes a smooth and continuous silicon nitride layer. Therefore, there is a need to develop a process for forming a smooth and continuous high-quality silicon-containing film, such as silicon nitride or carbon-doped silicon nitride, using a chemical vapor deposition (CVD) or atomic layer deposition (ALD) process or an ALD process, such as an unlimited-cycle CVD process. Olsen, “Analysis of LPCVD Process Conditions for the Deposition of Low Stress Silicon Nitride,” 5 Materials Science in Semiconductor Process 51 (2002), describes various process conditions used to optimize the deposition of low-stress silicon nitride films using low-stress chemical vapor deposition. The results show that increasing the refractive index above 2.3 by increasing the gas flow does not significantly reduce residual stress, but does have a significant negative impact on thickness uniformity and deposition rate. M. Tanaka et al., “Film Properties of Low-k Silicon Nitride Films Formed by Hexachlorodisilane and Ammonia,” 147 J. Electrochem. Soc. 2284 (2000), describe a low-temperature process for forming silicon nitride (SiN) with good step coverage by low-pressure chemical vapor deposition (LPCVD) using hexachlorodisilane (HCDS). JP2000100812 describes the use of SiCl 4 and NH 3 as a source gas to deposit a film. NH 3. Nitriding the substrate surface to form a very thin film with improved insulating properties. The silicon nitride film can be used as a capacitor insulating film in a semiconductor integrated circuit. US Patent No. 6,355,582 describes a method for forming a silicon nitride film, wherein the substrate on which the film is to be formed is heated, and silicon tetrachloride and ammonia gas are supplied to the substrate heated to a predetermined temperature. U.S. Patent No. 10,049,882 describes an atomic layer deposition (ALD) method for manufacturing a semiconductor device, including the step of 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. Forming the dielectric layer structure includes forming a first dielectric layer comprising silicon nitride on the structure having the height difference. Forming the first dielectric layer includes supplying a first gas comprising pentachlorodisilane (PCDS) or diisopropylamine pentachlorodisilane (DPDC) as a silicon precursor and a second gas comprising a nitrogen component into a chamber containing the substrate, such that the first dielectric layer is formed in situ on the structure having the height difference. U.S. Patent Publication No. 2022119947 A discloses a class of chlorodisilazanes, silicon heteroatom compounds synthesized therefrom, devices containing the silicon heteroatom compounds, methods for preparing the chlorodisilazanes, the silicon heteroatom compounds, and the devices; and uses of the chlorodisilazanes, the silicon heteroatom compounds, and the devices. U.S. Patent No. 11,142,462 discloses a composition comprising trichlorodisilane as a silicon precursor for film formation. The composition comprises the silicon precursor compound and at least one of an inert gas, molecular hydrogen, a carbon precursor, a nitrogen precursor, and an oxygen precursor. The disclosure 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. 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 supplying a halogenated silane as a silicon precursor into a reactor; supplying a purge gas into the reactor; and providing an ionized nitrogen precursor into the reactor to react with the substrate and form the silicon nitride film. U.S. Patent Publication No. 2009 / 0155606 discloses a cyclic method for depositing a silicon nitride film on a substrate. In one embodiment, the method includes supplying monochlorosilane to a reactor in which a substrate is processed; supplying a purge gas to the reactor; and providing an ammonia plasma to the reactor. The method allows for the formation of a silicon nitride film at a low process temperature and a high deposition rate. The resulting silicon nitride film has relatively low impurities and a relatively high quality. In addition, a silicon nitride film can be formed with good step coverage and a thin, uniform thickness on features with high aspect ratios. The disclosures of these previously identified patents, patent applications, and publications are incorporated herein by reference. The above needs are met, in one aspect, by providing a novel deposition method comprising an ALD thinner seed layer followed by an ALD thicker layer to achieve a conformal and continuous high-quality silicon-containing film (e.g., silicon nitride) to meet the requirements of future semiconductor devices. The above and other needs are met by a method for depositing a high-quality, smooth, and continuous silicon-containing film comprising a) providing at least one substrate in a reactor, b) heating the reactor to at least one temperature in a range from ambient temperature to about 750° C. and optionally maintaining the reactor at a pressure of about 100 Torr or less, c) introducing into the reactor at least one first silicon precursor comprising at least one organic amine group and at least one halide group having a formula: SiH m X n (NR 1 R 2 ) 4-m-n wherein m = 0, 1, 2; n = 1, 2, 3, and m + n ≤ 3; X is selected from the group consisting of Cl, Br, and I; R 1 and R 2 Each independently selected from a straight chain or branched chain C 1 to C 10 Alkyl, straight chain or branched chain C 3 to C 10 Alkenyl, straight chain or branched C 3 to C 10 Alkynyl, one C 3 to C 10 Cyclic alkyl, -C 2 to C 6 dialkylamine, an electron withdrawing group and a C 6 to C 10and an aromatic group to form a first silicon-containing layer, d) purging any unreacted precursor in the reactor with an inert gas, e) introducing a nitrogen source to react with the first silicon-containing layer to form a seed layer comprising at least one selected from the group consisting of silicon nitride and carbon-doped silicon nitride, f) purging the reactor with an inert gas, g) introducing at least one second silicon precursor comprising a halogenated silicon-containing compound into the reactor to react with the seed layer and form a second silicon-containing layer comprising at least one selected from the group consisting of silicon nitride, carbon-doped silicon nitride, silicon oxynitride, and carbon-doped silicon oxynitride, h) purging the reactor with an inert gas, i) introducing a nitrogen source to react with the second silicon-containing layer to form silicon nitride or carbon-doped silicon nitride, and j) purging the reactor with an inert gas. Throughout this specification, the term "ALD or ALD-like" refers to a process including but not limited to the following processes: a) each reactant including a silicon precursor and a reaction 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) each reactant including a silicon precursor and a reaction gas is exposed to a substrate by moving or rotating the substrate to different parts of the reactor, and each part is separated by an inert gas curtain, i.e., a spatial ALD reactor or a roll-to-roll ALD reactor. Throughout this specification, the term "plasma comprising / containing ammonia" refers to a reactive gas or gas mixture generated locally 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. Throughout the specification, the term "plasma comprising hydrogen or deuterium" refers to a reactive gas or gas mixture generated locally or remotely by 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. Throughout the specification, the term "alkyl" refers to a linear or branched C 1 to C 20 Hydrocarbons, cyclic C 6 to C 20 Hydrocarbons. Exemplary hydrocarbons include, but are not limited to, methyl, ethyl, isopropyl, n-propyl, sec-butyl, isobutyl, n-butyl, tert-butyl. In one embodiment, a method according to an exemplary embodiment comprises: a) providing at least one substrate in a reactor; b) heating the reactor to at least one temperature in a range from ambient temperature to about 750° C., and optionally maintaining the reactor at a pressure of about 100 Torr or less; c) introducing at least one first silicon precursor into the reactor, the first silicon precursor comprising at least one organic amino group and at least one halide group having a formula: SiH m X n (NR 1 R 2 ) 4-m-n , wherein m = 0, 1, 2; n = 1, 2, 3, and m + n ≤ 3; X is selected from the group consisting of Cl, Br and I; R 1 and R 2 Each independently selected from a straight chain or branched chain C 1 to C 10 Alkyl, straight chain or branched chain C 3 to C 10 Alkenyl, straight chain or branched C 3 to C 10 Alkynyl, one C 3 to C 10 Cyclic alkyl, -C 2 to C 6 dialkylamine, an electron withdrawing group and a C 6 to C 10 a group of silicon precursors comprising a halogenated silicon-containing compound to react with the silicon nitride or carbon-doped silicon nitride film to form a silicon nitride or carbon-doped silicon nitride or silicon oxynitride or carbon-doped silicon oxynitride; h) flushing the reactor with an inert gas; i) introducing a nitrogen source to react with the silicon-containing layer to form a silicon nitride or carbon-doped silicon nitride seed layer, and j) flushing the reactor with an inert gas. In some embodiments, steps g to j are repeated to provide a smooth and continuous thickness of silicon nitride or carbon-doped silicon nitride or silicon oxynitride or carbon-doped silicon oxynitride after step f. In other embodiments of the present invention, steps c to f are repeated to achieve a desired thickness of a silicon nitride or silicon carbonitride seed layer ranging from about 0.2 angstroms to about 1 angstrom or less, 0.2 angstroms to about 2 angstroms or less, or about 0.2 angstroms to about 3 angstroms or less, or about 0.2 angstroms to about 5 angstroms or less, or about 0.2 angstroms to about 8 angstroms or less, or about 0.2 angstroms to about 10 angstroms or less, and steps g to j are then repeated to provide a smooth and continuous silicon nitride or carbon-doped silicon nitride or silicon oxynitride or carbon-doped silicon oxynitride of a desired thickness ranging from about 5 angstroms to about 2000 angstroms or greater, or about 5 angstroms to about 1000 angstroms or greater, or about 5 angstroms to about 800 angstroms or greater, or about 5 angstroms to about 500 angstroms or greater, or about 5 angstroms to about 400 angstroms or greater, or about 5 angstroms to about 100 angstroms or greater, or about 5 angstroms to about 500 angstroms or greater. angstroms or greater, or in the range of about 5 angstroms to about 20 angstroms or greater. According to an exemplary embodiment, steps c to f are performed in one reactor chamber, and steps g to j are performed in the same reactor chamber or another reactor chamber at the same or different substrate temperatures. The nitrogen source is selected from, for example, ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, nitrogen, nitrogen / hydrogen, nitrogen / argon plasma, nitrogen / helium plasma, ammonia plasma, nitrogen plasma, nitrogen / hydrogen plasma, organic amines such as tert-butylamine, dimethylamine, diethylamine, isopropylamine, diethylamine plasma, dimethylamine plasma, trimethylamine plasma, trimethylamine plasma, ethylenediamine plasma, and monoalkoxyamines such as ethanolamine plasma, and mixtures thereof. In yet other embodiments, the nitrogen-containing source comprises an ammonia plasma, a plasma comprising nitrogen and argon, a plasma comprising nitrogen and helium, or a plasma comprising hydrogen and a nitrogen source gas. Some exemplary first silicon precursors are selected from the group consisting of (di-isopropylamino)chlorosilane, (di-isopropylamino)dichlorosilane, (di-isopropylamino)trichlorosilane, (di-di-butylamino)chlorosilane, (di-di-butylamino)dichlorosilane, (di-di-butylamino)trichlorosilane, (di-isopropylamino)bromosilane, (di-isopropylamino)dibromosilane, (di-isopropylamino)tribromosilane, (di-di-butylamino)bromosilane, (di-di-butylamino)dibromosilane, (di-di-butylamino)tribromosilane, (di-isopropylamino)iodosilane, and (di-isopropylamino)diiodosilane. It is believed that the organoamine groups react with hydroxyl groups on the substrate surface to provide a conformal silicon halide-containing monolayer that will react with ammonia to produce a smooth and continuous silicon nitride seed layer. Exemplary silicon halide compounds may be selected from the group consisting of i) silane halides, ii) siloxane halides, iii) silazane halides, and iv) carbosilane halides. The silane halides of group i include, but are not limited to, monochlorosilane, dichlorosilane, trichlorosilane, tetrachlorosilane, hexachlorodisilane, pentachlorodisilane, tetrachlorodisilane, octachlorotrisilane, dichlorosilane, monochlorosilane, monobromosilane, dibromosilane, tribromosilane, tetrabromosilane, monoiodosilane, diiodosilane, triiodosilane, and tetraiodosilane. The halogenated siloxanes of Group II include, but are not limited to, hexachlorodisiloxane, pentachlorodisiloxane, tetrachlorodisiloxane, and octachlorotrisiloxane. The halogenated silazanes of group iii are selected from the group represented by the following formula I: where R 3 Selected from hydrogen, straight chain or branched chain C 1 to C 10 Alkyl, straight chain or branched chain C 3 to C 10 Alkenyl, straight chain or branched C 3 to C 10 Alkynyl, one C 3 to C 10 Cyclic alkyl, -C 2 to C 6 dialkylamine, an electron withdrawing group and a C 6 to C 10 A group consisting of aromatic groups; R 4 Selected from hydrogen, straight chain or branched chain C 1 to C 10 Alkyl, straight chain or branched chain C 2 to C 6 alkenyl, straight chain or branched C 3 to C 6-alkynyl, one C 3 to C 10 Cyclic alkyl, -C 2 to C 6-dialkylamino, C 6 to C 10 Aryl, straight chain or branched chain C 1 to C 6-fluorinated alkyl, an electron-withdrawing group, a C 4 to C 10 aryl, and a halide 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. Examples of halogenated silazanes of group iii can be represented by the following structures: The halogenated carbosilanes of group iv are selected from the group consisting of silicon compounds having one or two Si-C-Si bonds. Exemplary carbosilanes of group iv include those represented by formula II and III: II III where X 1 、X 2 、X 3 、X 4 、X 5 and X 6 Each independently selected from a H atom; a halide atom selected from F, Cl, Br and I; an isocyanate; a compound having the formula NR 5 R 6 The amino group, where R 5 and R 6 independently selected from hydrogen, 1- 10 Straight chain alkyl; 3-10 Branched alkyl; 3-10 Cyclic alkyl; 3-10 Alkenyl; -C 4-10 Aryl; and -C 4-10Heterocyclyl; In some embodiments of Formula I, II, or both I and II, the substituent X 1 、X 2 、X 3 、X 4 、X 5 and X 6 One or more of the following are connected to form a substituted or unsubstituted, saturated or unsaturated cyclic group. In a specific embodiment of formula II, III or both II and III, the substituent X 1 、X 2 、X 3 、X 4 、X 5 and X 6 Any one or more of which are the above-mentioned halides or amino groups. 1 、X 2 、X 3 、X 4 、X 5 and X 6 In certain embodiments of formula II or III, the 5 R 6 The R in the amino group 5 and R 6 are connected together to form a ring. In a specific embodiment, R 5 and R 2 Selected from a straight chain or branched chain C 3 to C 6 alkyl groups and are connected to form a cyclic ring. In alternative embodiments of formula II or III, R 5 and R 6 are not connected together to form a ring. In other embodiments, R 5 and R 6 different. Examples of silazane halides of group iv can be represented by the following structures: Working Example 1. Use of (di-isopropylamino)dichlorosilane in a silicon nitride seed layer (Di-isopropylamino)dichlorosilane was used to form a nitride seed layer on the silicon native oxide surface. The subsequent silicon nitride was grown using monochlorosilane and ammonia. The deposition process was performed using a Picosun screening ALD tool equipped with a JA Woollam in-situ ellipsometer. The silicon nitride seed layer was achieved by exposing the wafer surface to (di-isopropylamino)dichlorosilane and confirmed using JA Woollam in situ ellipsometer. The process steps for depositing silicon nitride are as follows: a. Introducing a silicon wafer with native oxide into the reactor b. Heating the reactor to 300°C c. Introducing (di-isopropylamino)dichlorosilane into the reactor for 40 seconds d. Purge the reaction byproducts in the reactor with 500 sccm of argon for 10 seconds e. Introducing NH 3 plasma for 10 seconds Ø NH 3. Flow rate = 30 sccm. Ø Ar flow rate = 150 sccm. Ø Plasma power = 2500 W; plasma frequency = 2 GHz. f. Purge the reaction byproducts in the reactor with 500 sccm of Ar for 10 seconds. g. Introduce monochlorosilane (MCS) into the reactor for 1 second. Ø MCS flow rate = 80 sccm. h. Purge the reaction byproducts in the reactor with 500 sccm of Ar for 10 seconds. i. Introduce NH 3* up to 10 seconds Ø NH 3. Flow rate = 30 sccm Ø Ar flow rate = 150 sccm Ø Plasma power = 2500W; Plasma frequency = 2 GHz j. Purge the reaction byproducts in the reactor with 500 sccm of Ar for 10 seconds. Repeat step gj 100 times to obtain the desired thickness of silicon nitride. Remove the sample from the reactor. For comparison, use monochlorosilane and NH 3 plasma growth of silicon nitride on a silicon native oxide surface without a seed layer. The process uses the following steps: a. Introducing a silicon wafer with native oxide into the reactor b. Heating the reactor to 300 °C c. Introducing NH 3 plasma for 10 seconds Ø NH 3. Flow rate = 30 sccm. Ø Ar flow rate = 150 sccm. Ø Plasma power = 2500 W; plasma frequency = 2 GHz. d. Purge the reaction byproducts in the reactor with 500 sccm of Ar for 10 seconds. e. Introduce monochlorosilane (MCS) into the reactor for 1 second. Ø MCS flow rate = 80 sccm. f. Purge the reaction byproducts in the reactor with 500 sccm of Ar for 10 seconds. g. Introduce NH 3 plasma up to 10 sec Ø NH 3. Flow rate = 30 sccm; Ar flow rate = 150 sccm; Plasma power = 2500 W; Plasma frequency = 2 GHz. h. Purge the reaction byproducts from the reactor with 500 sccm of Ar for 10 seconds. Repeat steps e through h 100 times to obtain the desired silicon nitride thickness. Remove the sample from the reactor. In situ ellipsometry was used to determine the film thickness and calculate the film growth. Figure 1 shows the film thickness at 600 °C using monochlorosilane and NH Plasma growth per cycle (GPC) of as-deposited silicon nitride on a silicon oxide surface. Error bars represent five replicate runs (circles) for deposition on a silicon oxide surface without a seed layer; (crosses) for deposition on a silicon oxide surface with a seed layer using (di-isopropylamino)dichlorosilane, performed once using steps c through f. Starting from the first deposition cycle, films deposited on the treated surface exhibited a GPC of ~0.4 Å / cycle. This GPC was consistent throughout the 10-cycle deposition process. On the other hand, the films deposited on the untreated surface exhibited greater variability. Furthermore, the films deposited with a seed layer exhibited improved smoothness compared to those without a seed layer. The smoother films and reduced GPC variability on the films grown on the silicon oxide surface with the silicon nitride seed layer indicate more consistent, higher-quality film deposition. Atomic force microscopy (AFM) was used to measure the film roughness. Table 1 shows the surface roughness of the deposited films, indicating that the treated surface provides a smoother silicon nitride film, i.e., 0.12 nm (nanometer) versus 0.15 nm. Table 1. Roughness of deposited films Although the present invention is shown and described above with reference to certain specific embodiments and working examples, it is not intended that the invention be limited to the details shown. Rather, various modifications may be made to the details without departing from the spirit of the invention and within the scope and range of equivalents of the claims. For example, it is expressly intended that all categories recited broadly in this document include within their scope all narrower categories that fall within such broader categories. FIG1 shows a GPC for depositing silicon nitride on silicon oxide with or without a silicon nitride seed layer according to Working Example 1 below.

Claims

1. A method for depositing high-quality, smooth, and continuous silicon-containing films, comprising: a) providing at least one substrate in a reactor; b) heating the reactor to at least one temperature in the range from ambient temperature to about 750°C, and selectively maintaining the reactor at a pressure of about 100 Torr or less; c) introducing at least one first silicon precursor into the reactor, comprising at least one organic amine group and at least one halogen group, having the formula: SiHmXn(NR1R2)4-mn where m = 0, 1, 2; n = 1, 2, 3, and m + n ≤ 3; X is selected from the group consisting of Cl, Br, and I; R1 and R2 are each independently selected from straight-chain C1 to C10 alkyl, branched C3 to C10 alkyl, straight-chain or branched C3 to C10 alkenyl, straight-chain or branched C3 to C10 alkynyl, -C3 to C10 cyclic alkyl, -C2 to C6 d) The reactor is flushed with an inert gas to form a first silicon-containing layer; e) A nitrogen source is introduced to react with the first silicon-containing layer to form a seed layer comprising at least one of the group consisting of silicon nitride and carbon-doped silicon nitride; f) The reactor is flushed with an inert gas; g) At least one second silicon precursor comprising a halide silicon-containing compound is introduced into the reactor to react with the seed layer and form a second silicon-containing layer comprising at least one of the group consisting of silicon nitride, carbon-doped silicon nitride, silicon oxynitride, and carbon-doped silicon oxynitride; h) The reactor is flushed with an inert gas; i) A nitrogen source is introduced to react with the second silicon-containing layer to form silicon nitride or carbon-doped silicon nitride; and j) The reactor is flushed with an inert gas. The at least one second silica precursor is at least one selected from the group consisting of i) silane halides, ii) siloxane halides, iii) silazane halides and iv) carbosilane halides, wherein the silane halide is selected from the group consisting of monochlorosilane, dichlorosilane, trichlorosilane, tetrachlorosilane, hexachlorodisilane, pentachlorodisilane, tetrachlorodisilane, octachlorotrisilane, monobromosilane, dibromosilane, tribromosilane, tetrabromosilane, monoiodosilane, diiodosilane, triiodosilane, and tetraiodosilane.

2. The method of claim 1, wherein steps c to f are repeated to provide the seed layer of a certain thickness, and steps g to j are repeated to achieve a smooth and continuous second silicon-containing layer.

3. The method of claim 2, wherein steps c to f are repeated to achieve a thickness of the seed layer ranging from about 0.2 angstroms to about 20 angstroms.

4. The method of claim 2, wherein steps g to j are repeated to achieve a thickness of the second silicon-containing layer in the range of about 5 angstroms to about 2000 angstroms.

5. The method of claim 1, wherein steps c to f are carried out in one reactor, and steps g to j are carried out at the same or different substrate temperatures in the same reactor or another reactor.

6. The method of claim 1, wherein the at least one first silicon precursor is one or more selected from the group consisting of (di-isopropylamino)chlorosilane, (di-isopropylamino)dichlorosilane, (di-isopropylamino)trichlorosilane, (di-di-dibutylamino)chlorosilane, (di-di-di-di-di-dichlorosilane), (di-di-di-di-di-di-dichlorosilane), (di-di-di-di-di-dichlorosilane), (di-isopropylamino)bromosilane, (di-isopropylamino)dibromosilane, (di-isopropylamino)iodosilane, and (di-isopropylamino)diiodosilane.

7. The method of claim 1, wherein the halosiloxane is selected from the group consisting of hexachlorodisiloxane, pentachlorodisiloxane, tetrachlorodisiloxane and octachlorotrisiloxane.

8. The method of claim 1, wherein the silazane halide has a structure according to formula I: Formula I wherein R3 is selected from the group consisting of hydrogen, straight-chain C1 to C10 alkyl, branched C3 to C10 alkyl, straight-chain or branched C3 to C10 alkenyl, straight-chain or branched C3 to C10 ynyl, -C3 to C10 cyclic alkyl, -C2 to C6 dialkylamino, -electron-withdrawing group and -C6 to C10 aryl; R4 is selected from the group consisting of hydrogen, straight-chain C1 to C10 alkyl, branched C3 to C10 alkyl, straight-chain C2 to C6 alkenyl, branched C3 to C6 alkenyl, straight-chain or branched C3 to C6 ynyl, -C3 to C10 cyclic alkyl, -C2 to C6 dialkylamino, -C6 to C10 aryl, straight-chain or branched C1 The group consisting of C6 fluorinated alkyl groups, electron-withdrawing groups, C4 to C10 aryl groups, and groups selected from Cl, Br, and I; and X is a group selected from Cl, Br, and I.

9. The method of claim 1, wherein the halogenated carbon silane has a structure of formula II or III: Formula II Formula III wherein X1, X2, X3, X4, X5 and X6 are each independently selected from hydrogen, a halogen selected from F, Cl, Br and I, an isocyanate, and an amino group having formula NR5R6, wherein R5 and R6 are independently selected from the group consisting of hydrogen, a C1-10 straight-chain alkyl; a C3-10 branched alkyl; a C3-10 cyclic alkyl; a C3-10 alkenyl; a C4-10 aryl; and a C4-10 heterocyclic group, and optionally R5 and R6 are a ring formed by straight-chain or branched C3 to C6 alkyl groups linked together, and at least one of X1, X2, X3, X4, X5 and X6 is the halogen.

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