Silicon-containing films having surfaces modified with

Abstract

A process 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 the range of ambient temperature to about 750 DEG 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 amino group and at least one halide group and having the formula: SiHmXn (NR1R2) 4-m-n wherein m-0, 1, 2; m is 1, n-1, 2, 3, and m + n is less than 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 a linear or branched C1 to C10 alkyl group, a linear or branched C3 to C10 alkenyl group, a linear or branched C3 to C10 alkynyl group, a C3 to C10 cycloalkyl group, a C2 to C6 dialkylamino group, an electron withdrawing group, and a C6 to C10 aryl group, to form a first silicon-containing layer, d) purging any unreacted precursor from 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 into the reactor at least one second silicon precursor comprising a halogenated silicon-containing compound, the first silicon-containing layer comprises 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 d) introducing a nitrogen source to react with the silicon nitride or carbon-doped silicon nitride to form a second silicon-containing layer comprising at least one selected from the group consisting of silicon nitride, carbon-doped silicon nitride and carbon-doped silicon oxynitride. And j) purging the reactor with an inert gas.

Description

[0001] Cross-references to related applications

[0002] This application claims priority to U.S. Provisional Patent Application No. 63 / 588,994, filed October 9, 2023, the entire contents of which are incorporated herein by reference.

[0003] Invention Field

[0004] This invention relates to compositions and methods for manufacturing electronic devices. More specifically, this 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 films, silicon oxynitride, and carbon-doped silicon oxynitride films. Background of the Invention

[0006] Silicon nitride films are used in a variety of applications in semiconductors. For example, silicon nitride films are commonly used as a final passivation and mechanical protection layer for integrated circuits, a mask layer for silicon selective oxidation, one of the dielectric materials in the stacked oxide-nitride-oxide (ONO) layers in DRAM capacitors or 3D NAND flash memory chips, or as a CMP stop layer in shallow trench isolation applications.

[0007] There is a need to form conformal and continuous thin films (< 200 Å or less, < 150 Å or less, < 100 Å or less, < 50 Å or less, < 30 Å or less, < 20 Å or less, < 15 Å or less, < 10 Å or less) of high-quality silicon-containing films (such as silicon nitride, carbon-doped silicon oxide, silicon oxynitride, or carbon-doped silicon oxynitride) on oxide surfaces (such as silicon oxide or other metal oxides). High-quality silicon nitride is typically deposited using chlorosilanes or disilasans (such as dichlorosilane and hexachlorodisilasan) and ammonia-based processes. However, chlorine ligands have relatively high activation energies for reacting with oxide surfaces, leading to so-called island growth. For chlorosilane-based films, the silicon-containing film needs to be at a certain critical thickness to achieve a smooth and continuous film.

[0008] Furthermore, the pitch width shrinks with each generation of semiconductor devices, which in turn leads to a shrinkage of the film. In some applications, atomic layer deposition (ALD) processes involving chlorosilanes / disilazanes and ammonia are used to deposit thin silicon nitride layers on top of silicon oxide or other types of metal oxides. At the start of the deposition process, the film has a non-uniform and discontinuous island-like growth. After reaching a certain critical thickness, the island-like growths become a smooth and continuous Si nitride layer. Therefore, there is a need to develop processes that use chemical vapor deposition (CVD) or atomic layer deposition (ALD) processes or similar ALD processes (e.g., but not limited to cyclic CVD processes) to form smooth and continuous high-quality silicon-containing films (such as silicon nitride or carbon-doped silicon nitride).

[0009] 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 for optimizing the deposition of low-stress silicon nitride films via low-pressure chemical vapor deposition. The results show that increasing the refractive index to over 2.3 by increasing the gas flow rate did not significantly reduce residual stress, but had a significant adverse effect on thickness uniformity and deposition rate.

[0010] 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).

[0011] JP2000100812 describes a method for depositing films using SiCl4 and NH3 as source gases. Prior to deposition, the substrate surface can be nitrided using NH3. This forms an electrode film with improved insulating properties. Silicon nitride films can be used as capacitor insulating films in semiconductor integrated circuits.

[0012] US Patent No. 6,355,582 describes a method for forming a silicon nitride film, wherein a substrate to be subjected to film formation is heated, and silicon tetrachloride and ammonia are supplied to the substrate heated to a predetermined temperature.

[0013] US Patent No. 10,049,882 describes an atomic layer deposition (ALD) method for manufacturing semiconductor devices, which includes 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 a height difference. Forming the first dielectric layer includes supplying a first gas and a second gas into a chamber including the substrate, thereby forming the first dielectric layer in situ on the structure having a height difference, wherein the first gas comprises pentachlorodisilazane (PCDS) or diisopropylaminepentachlorodisilazane (DPDC) as a silicon precursor, and the second gas comprises a nitrogen component.

[0014] US Publication No. 2022119947 A discloses a class of chlorodisilazanes, silicon-heteroatom compounds synthesized therefrom, devices comprising said silicon-heteroatom compounds, methods for preparing said chlorodisilazanes, said silicon-heteroatom compounds and said devices; and uses of said chlorodisilazanes, silicon-heteroatom compounds and devices.

[0015] US 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 the following: 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 therefrom.

[0016] US Patent No. 9,984,868 discloses a cyclic method for depositing a silicon nitride film on a substrate. In one embodiment, such a method includes supplying a halosilane as a silicon precursor to a reactor; supplying a purge gas to the reactor; and providing an ionized nitrogen precursor to the reactor to react with the substrate and form the silicon nitride film.

[0017] US Publication No. 2009 / 0155606 discloses a cyclic method for depositing silicon nitride films on a substrate. In one embodiment, the method includes supplying a chlorosilane to a reactor in which a substrate is processed; supplying a purge gas to the reactor; and providing an ammonia plasma to the reactor. This method allows for the formation of silicon nitride films at low process temperatures and high deposition rates. The resulting silicon nitride films have relatively few impurities and relatively high quality. Furthermore, silicon nitride films with good stepped coverage on features with high aspect ratios and thin, uniform thickness can be formed.

[0018] The contents of previously confirmed patents, patent applications and published materials are incorporated herein by reference. Invention Overview

[0020] In one aspect, the above-mentioned needs are met by providing a novel deposition method that includes a thin seed layer of ALD followed by a thicker layer of ALD to achieve conformal and continuous high-quality silicon-containing films (such as silicon nitride) to meet the requirements of future semiconductor devices.

[0021] The above and other requirements are met by depositing high-quality, smooth, and continuous silicon-containing films, the method comprising: a) providing at least one substrate in a reactor; b) heating the reactor to at least one temperature in the range of 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, comprising at least one organic amino group and at least one halogen group, and having the formula:

[0022] SiH m X n (NR 1 R 2 ) 4-m-n

[0023] 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; R 1 and R 2 Each is independently selected from the following groups: straight chain or branched chain C1 to C2. 10 Alkyl, straight-chain or branched C3 to C4 10 Alkenyl, straight-chain or branched C3 to C 10 alkynyl group, C3 to C 10 Cycloalkyl, C2 to C6 dialkylamino, electron-withdrawing groups and C6 to C 10 d) purging any unreacted precursor from the reactor using 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 using an inert gas; g) introducing at least one second silicon precursor comprising a silicon halide 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 using 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 using an inert gas. Brief description of the attached diagram

[0025] Figure 1The image shows a GPC depositing silicon nitride on silicon oxide with or without a silicon nitride seed layer, according to Working Example 1 below. Invention Details

[0027] Throughout this specification, the term "ALD or similar ALD" refers to methods including, but not limited to, the following processes: a) sequentially introducing each reactant containing a silicon precursor and a reactive gas into a reactor, such as a single-wafer ALD reactor, a semi-batch ALD reactor, or a batch furnace ALD reactor; b) exposing each reactant containing a silicon precursor and a reactive gas to a substrate by moving or rotating the substrate to different sections of the reactor, with each section separated by an inert gas curtain, i.e., a space ALD reactor or a roll-to-roll ALD reactor.

[0028] Throughout this specification, the term "plasma comprising / containing ammonia" 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, mixtures of ammonia and helium, mixtures of ammonia and neon, mixtures of ammonia and argon, mixtures of ammonia and nitrogen, mixtures of ammonia and hydrogen, and combinations thereof.

[0029] Throughout this specification, the term "plasma comprising / containing hydrogen or deuterium" 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: hydrogen or deuterium, mixtures of hydrogen or deuterium and helium, mixtures of hydrogen or deuterium and neon, mixtures of hydrogen and argon, mixtures of hydrogen or deuterium and nitrogen, and combinations thereof. Throughout this specification, the term "alkyl" refers to a straight-chain or branched C1 to C2 chain. 20 Hydrocarbons, cyclic C6 to C 20 Hydrocarbons. Exemplary hydrocarbons include, but are not limited to, methyl, ethyl, isopropyl, n-propyl, sec-butyl, isobutyl, n-butyl, and tert-butyl.

[0030] In one embodiment, the method described according to an exemplary embodiment includes:

[0031] a) Provide at least one substrate in the reactor.

[0032] b) Heating the reactor to at least one temperature in the range of ambient temperature to about 750°C, and optionally maintaining the reactor at a pressure of about 100 Torr or less;

[0033] c) Introducing at least one first silicon precursor into the reactor, which comprises at least one organic amino group and at least one halogen group, and which has the formula SiH m X n (NR 1 R 2 )4-m-n 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; R 1 and R 2 Each is independently selected from the following groups: straight chain or branched chain C1 to C2. 10 Alkyl, straight-chain or branched C3 to C4 10 Alkenyl, straight-chain or branched C3 to C 10 alkynyl group, C3 to C 10 Cycloalkyl, C2 to C6 dialkylamino, electron-withdrawing groups and C6 to C 10 Aryl groups form silicon-containing layers;

[0034] d) Purge any unreacted precursors from the reactor using an inert gas;

[0035] e) Introduce a nitrogen source to react with the silicon-containing layer to form a silicon nitride or carbon-doped silicon nitride seed layer;

[0036] f) Purge the reactor with an inert gas;

[0037] g) Introduce a second silicon precursor, comprising a silicon halide compound, into the reactor to react with the silicon nitride or carbon-doped silicon nitride film to form silicon nitride or carbon-doped silicon nitride or silicon oxynitride or carbon-doped silicon oxynitride.

[0038] h) Purge the reactor with an inert gas;

[0039] 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

[0040] j) Purge the reactor with an inert gas.

[0041] In some implementations, steps g to j are repeated after step f to provide a smooth and continuous silicon nitride or carbon-doped silicon nitride or silicon oxynitride or carbon-doped silicon oxynitride of a certain thickness. In other embodiments of the invention, steps c to f are repeated to achieve the desired thickness of the silicon nitride or silicon carbonitride seed layer, ranging from about 0.2 Å to about 1 Å or less, 0.2 Å to about 2 Å or less, or about 0.2 Å to about 3 Å or less, or about 0.2 Å to about 5 Å or less, or about 0.2 Å to about 8 Å or less, or about 0.2 Å to about 10 Å or less. Steps g to j are then repeated to provide a smooth and continuous desired thickness of silicon nitride or carbon-doped silicon nitride or silicon oxynitride or carbon-doped silicon oxynitride, ranging from about 5 Å to about 2000 Å or greater, or about 5 Å to about 1000 Å or greater, or about 5 Å to about 800 Å or greater, or about 5 Å to about 500 Å or greater, or about 5 Å to about 400 Å or greater, or about 5 Å to about 100 Å or greater, or about 5 Å to about 500 Å. Å or ​​greater, or about 5 Å to about 20 Å or greater.

[0042] According to an exemplary embodiment, steps c to f are performed in one reactor chamber, while steps g to j are performed in the same reactor chamber or another reactor chamber at the same or different substrate temperatures.

[0043] The nitrogen source is selected from the group consisting of, 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 alkoxyamines (such as ethanolamine plasma) and mixtures thereof. In other embodiments, the nitrogen source includes, for example, ammonia plasma, plasma containing nitrogen and argon, plasma containing nitrogen and helium, or plasma containing hydrogen and a nitrogen source gas.

[0044] Some exemplary first silicon precursors are selected from the group consisting of: (diisopropylamino)chlorosilane, (diisopropylamino)dichlorosilane, (diisopropylamino)trichlorosilane, (di-sec-butylamino)chlorosilane, (di-sec-butylamino)dichlorosilane, (di-sec-butylamino)trichlorosilane, (diisopropylamino)bromosilane, (diisopropylamino)dibromosilane, (diisopropylamino)tribromosilane, (di-sec-butylamino)bromosilane, (di-sec-butylamino)dibromosilane, (di-sec-butylamino)tribromosilane, (diisopropylamino)iodosilane, and (diisopropylamino)diiodosilane. It is believed that the organic amino groups react with hydroxyl groups on the surface of the substrate to provide a conformal monolayer of halo-containing silicon, which will react with ammonia to produce a smooth and continuous silicon nitride seed layer.

[0045] Exemplary silicon halide compounds may be selected from the group consisting of: i) silane halide, ii) siloxane halide, iii) silazane halide, and iv) carbosilane halide.

[0046] The silane halides in 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.

[0047] The halogenated siloxanes in Group ii include, but are not limited to: hexachlorodisiloxane, pentachlorodisiloxane, tetrachlorodisiloxane, and octachlorotrisiloxane.

[0048] The silazane halides in Group iii are selected from the group represented by the following formula I:

[0049]

[0050] Where R 3 Choose from the group consisting of: hydrogen, straight-chain or branched C1 to C2. 10 Alkyl, straight-chain or branched C3 to C4 10 Alkenyl, straight-chain or branched C3 to C 10 alkynyl group, C3 to C 10 Cycloalkyl, C2 to C6 dialkylamino, electron-withdrawing groups and C6 to C 10 Aryl; R 4 Selected from hydrogen, straight-chain or branched C1 to C2. 10 Alkyl, straight-chain or branched C2 to C6 alkenyl, straight-chain or branched C3 to C6 ynyl, C3 to C 10 Cycloalkyl, C2 to C6 dialkylamino, C6 to C 10 Aryl, straight-chain or branched C1 to C6 fluoroalkyl, electron-withdrawing group, C4 to C 10The aryl group and the halogen group selected from the group consisting of Cl, Br and I; and X is a halogen group selected from the group consisting of Cl, Br and I.

[0051] Examples of group iii silazane halogens can be represented by the following structures:

[0052]

[0053]

[0054]

[0055]

[0056]

[0057] The carbosilanes in Group IV are selected from the group consisting of silicon compounds having one or two Si-C-Si bonds. Exemplary carbosilanes in Group IV include those represented by formulas II and III:

[0058]

[0059] Where X 1 X 2 X 3 X 4 X 5 and X 6 Each is independently selected from: H atoms; halogen atoms selected from F, Cl, Br, and I; isocyanates; having the formula NR 5 R 6 The amino group, of which R 5 and R 6 Choose independently from the following groups: hydrogen, C 1-10 Straight-chain alkyl; C 3-10 Branched alkyl; C 3-10 cycloalkyl; C 3-10 alkenyl; C 4-10 Aryl; and C 4-10 Heterocyclic group. In some embodiments of formula I, II, or both I and II, substituent X 1 X 2 X 3 X 4 X 5 and X 6 One or more of them are linked to form substituted or unsubstituted, saturated or unsaturated cyclic groups. In a particular embodiment of formula II, III, or both II and III, substituent X 1 X 2 X 3 X 4 X5 and X 6 One or more of them are the aforementioned halogen or amino groups. For II, X 1 X 2 X 3 X 4 X 5 and X 6 It cannot be entirely amino. In some embodiments of formula II or III, it has formula NR. 5 R 6 In the amino group, R 5 and R 6 They are connected together to form a loop. In one particular implementation, R 5 and R 2 Selected from straight-chain or branched C3 to C6 alkyl groups, and linked to form a cyclic ring. In alternative embodiments of formula II or III, R 5 and R 6 They are not connected together to form a loop. In other embodiments, R 5 and R 6 They are different.

[0060] Examples of Group IV halosilanes can be represented by the following structures:

[0061]

[0062]

[0063]

[0064] Working Example 1. Use of (diisopropylamino)dichlorosilane in silicon nitride seed layers

[0065] A nitride seed layer was formed on the native oxide surface of silicon using (diisopropylamino)dichlorosilane. Subsequent silicon nitride growth was performed using monochlorosilane and ammonia. The deposition process was carried out using a Picosun ALD screening tool equipped with a JAWoollam in-situ ellipsometry.

[0066] The silicon nitride seed layer was achieved by exposing (diisopropylamino)dichlorosilane to the wafer surface and confirmed using the JAWoollam in-situ ellipticometer.

[0067] The steps for depositing silicon nitride are as follows:

[0068] a. Introduce a Si wafer with native oxide into the reactor.

[0069] b. Heat the reactor to 300 °C

[0070] c. Introduce (diisopropylamino)dichlorosilane into the reactor for 40 seconds.

[0071] d. Purge the reaction byproducts from the reactor using 500 sccm of Ar for 10 seconds.

[0072] e. Introduce NH3 plasma for 10 seconds.

[0073] NH3 flow rate = 30 sccm

[0074] Ar flow rate = 150 sccm

[0075] Plasma power = 2500 W; Plasma frequency = 2 GHz

[0076] f. Purge the reaction byproducts from the reactor using 500 sccm of Ar for 10 seconds.

[0077] g. Introduce monochlorosilane (MCS) into the reactor for 1 second.

[0078] MCS flow rate = 80 sccm.

[0079] h. Purge the reaction byproducts from the reactor using 500 sccm of Ar for 10 seconds.

[0080] i. Introducing NH3 Lasting 10 seconds

[0081] NH3 flow rate = 30 sccm

[0082] Ar flow rate = 150 sccm

[0083] Plasma power = 2500 W; Plasma frequency = 2 GHz

[0084] j. Purge the reaction byproducts from the reactor using 500 sccm of Ar for 10 seconds.

[0085] Repeat step gj 100 times to obtain the desired thickness of silicon nitride. Remove the sample from the reactor.

[0086] In contrast, silicon nitride was grown on a silicon native oxide surface without a seed layer using monochlorosilane and NH3 plasma. The method utilizes the following steps:

[0087] a. Introduce a Si wafer with native oxide into the reactor.

[0088] b. Heat the reactor to 300 °C

[0089] c. Introduce NH3 plasma for 10 seconds

[0090] NH3 flow rate = 30 sccm

[0091] Ar flow rate = 150 sccm

[0092] Plasma power = 2500 W; Plasma frequency = 2 GHz

[0093] d. Purge the reaction byproducts from the reactor using 500 sccm of Ar for 10 seconds.

[0094] e. Introduce monochlorosilane (MCS) into the reactor for 1 second.

[0095] MCS flow rate = 80 sccm.

[0096] f. Purge the reaction byproducts from the reactor using 500 sccm Ar for 10 seconds.

[0097] g. Introduce NH3 plasma for 10 seconds.

[0098] NH3 flow rate = 30 sccm

[0099] Ar flow rate = 150 sccm

[0100] Plasma power = 2500 W; Plasma frequency = 2 GHz

[0101] h. Purge the reaction byproducts from the reactor using 500 sccm of Ar for 10 seconds.

[0102] Repeat steps e through h 100 times to obtain the desired thickness of silicon nitride. Remove the sample from the reactor.

[0103] The in-situ ellipsometry is used to measure the thickness of the membrane and calculate the membrane growth. Figure 1This illustrates each cycle of GPC growth of silicon nitride on a silicon oxide surface using monochlorosilane and NH3 plasma at 600 °C. Error bars represent 5 repeated runs: (circle) corresponds to deposition on a silicon oxide surface without a seed layer; (cross) corresponds to deposition on a silicon oxide surface with a seed layer using (diisopropylamino)dichlorosilane, where steps c to f are performed once.

[0104] Films deposited on treated surfaces exhibit a glycemic index (GPC) of ~0.4 Å / cycle starting from the first deposition cycle. This GPC remains consistent throughout 10 deposition cycles. Conversely, films deposited on untreated surfaces show greater variation. Furthermore, films deposited using a seed layer exhibit better smoothness than those deposited without a seed layer. On silicon oxide surfaces with a silicon nitride seed layer, both the smoother film and the lower GPC variation during film growth indicate more consistent and higher-quality film deposition.

[0105] The roughness of the film was determined using atomic force microscopy (AFM). Table 1 shows the surface roughness of the deposited film, indicating that the treated surface provides a much smoother silicon nitride film, i.e., 0.12 nm vs. 0.15 nm.

[0106] Table 1. Roughness of the deposited film

[0107]

[0108] Although the invention has been described and illustrated above with reference to certain specific embodiments and working examples, it is by no means intended to be limited to the details shown. Rather, various modifications may be made to the details within the scope and region of the equivalents of the claims, without departing from the spirit of the invention. For example, it is expressly intended that all scopes broadly referenced herein include all narrower scopes falling within the broader scope.

Claims

1. A method for depositing a high-quality, smooth, and continuous silicon-containing film, comprising: a) Provide at least one substrate in the reactor; b) Heating the reactor to at least one temperature in the range of 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, which comprises at least one organic amino group and at least one halogen group, and has the formula: SiH m X n (NR 1 R 2 ) 4-m-n 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; R 1 and R 2 Each is independently selected from the following groups: straight chain or branched chain C1 to C2. 10 Alkyl, straight-chain or branched C3 to C4 10 Alkenyl, straight-chain or branched C3 to C 10 alkynyl group, C3 to C 10 Cycloalkyl, C2 to C6 dialkylamino, electron-withdrawing groups and C6 to C 10 Aryl groups are used to form the first silicon-containing layer; d) Purge any unreacted precursors from the reactor using an inert gas; e) Introducing a nitrogen source to react with the first silicon-containing layer to form a seed layer, which comprises at least one selected from the group consisting of silicon nitride and carbon-doped silicon nitride; f) Purge the reactor with an inert gas; g) Introduce at least one second silicon precursor comprising a silicon halide 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) Purge 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) Purge the reactor with an inert gas.

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 according to claim 2, wherein steps c to f are repeated to achieve a seed layer thickness ranging from about 0.2 Å to about 20 Å, preferably from 0.2 Å to about 10 Å, and most preferably from 0.2 Å to about 5 Å.

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

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

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

7. The method of claim 1, wherein the at least one second silicon precursor is selected from at least one of the following: i) silane haloside, ii) siloxane haloside, iii) silazane haloside, and iv) carbosilane haloside.

8. The method according to claim 7, wherein the silane halide is selected from the group consisting of: monochlorosilane, dichlorosilane, trichlorosilane, tetrachlorosilane, hexachlorodisilane, pentachlorodisilane, tetrachlorodisilane, octachlorotrisilane, dichlorosilane, monochlorosilane, monobromosilane, dibromosilane, tribromosilane, tetrabromosilane, monoiodosilane, diiodosilane, triiodosilane, and tetraiodosilane.

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

10. The method according to claim 7, wherein the halosilazane has a structure according to formula I: Where R 3 Choose from the group consisting of: hydrogen, straight-chain or branched C1 to C2. 10 Alkyl, straight-chain or branched C3 to C4 10 Alkenyl, straight-chain or branched C3 to C 10 alkynyl group, C3 to C 10 Cycloalkyl, C2 to C6 dialkylamino, electron-withdrawing groups and C6 to C 10 Aryl; R 4 Choose from the group consisting of: hydrogen, straight-chain or branched C1 to C2. 10 Alkyl, straight-chain or branched C2 to C6 alkenyl, straight-chain or branched C3 to C6 ynyl, C3 to C 10 Cycloalkyl, C2 to C6 dialkylamino, C6 to C 10 Aryl, straight-chain or branched C1 to C6 fluoroalkyl, electron-withdrawing group, C4 to C 10 The aryl group and the halogen group selected from the group consisting of Cl, Br and I; and X is a halogen group selected from the group consisting of Cl, Br and I.

11. The method of claim 7, wherein the halosilane has a structure according to formula II or III: Where X 1 X 2 X 3 X 4 X 5 and X 6 Each independently selected from hydrogen, halogen atoms selected from F, Cl, Br and I, isocyanates, having the formula NR 5 R 6 The amino group, of which R 5 and R 6 Choose independently from the following groups: hydrogen, C 1-10 Straight-chain alkyl; C 3-10 Branched alkyl, C 3-10 cycloalkyl, C 3-10 alkenyl, C 4-10 Aryl and C 4-10 Heterocyclic groups, and optionally linked together to form a ring, And for formula II or formula III, the substituent X 1 X 2 X 3 X 4 X 5 and X 6 One or more of them are optionally linked to form substituted or unsubstituted, saturated or unsaturated cyclic groups, or optionally are the halogen or amino groups described above, provided that X 1 X 2 X 3 X 4 X 5 and X 6 It cannot be entirely amino, and optionally, in formula II or III, it has formula NR. 5 R 6 In the amino group, R 5 and R 6 They are connected together to form a loop.

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