Selective deposition of silicon dielectric films

Abstract

A method of selectively depositing a dielectric film containing silicon and oxygen onto a substrate is disclosed. The method includes the step of providing a substrate comprising a dielectric surface and a metal or metal hydride surface to a reactor. A halogenated silicon-containing compound can be introduced into the reactor to form a silicon-containing layer on the dielectric surface in a greater amount than on the metal or metal hydride surface. A nitrogen source can be introduced into the reactor to react with the silicon-containing layer to form a silicon nitride film or a carbon-doped silicon nitride film. An oxygen-containing source can be introduced into the reactor to react with the silicon nitride film or the carbon-doped silicon nitride film to form the dielectric film containing silicon and oxygen.

Description

[0001] Cross-references to related applications

[0002] This application claims priority to U.S. Provisional Patent Application No. 63 / 155,669, filed March 2, 2021. Technical Field

[0003] This document describes a composition and method for manufacturing electronic devices. More specifically, it describes compounds for selectively depositing silicon oxide, silicon oxynitride, carbon-doped silicon oxide, or carbon-doped silicon oxynitride on a dielectric material compared to deposition on a metal or metal hydride material to avoid / minimize oxidation of the metal or metal hydride layer, as well as compositions and methods comprising such compounds. Background of the Invention

[0005] U.S. Patent 9,816,180B discloses a method for selectively depositing material onto a substrate surface relative to a different second surface on which no deposition occurs. An exemplary deposition method includes selectively depositing a material (such as a material comprising nickel, nickel nitride, cobalt, iron, and / or titanium oxide) onto a first substrate surface (such as a silicon oxide surface) relative to a different second surface (such as a hydrogen-sealed surface) of the same substrate. The method includes treating the surface of the substrate prior to deposition to provide hydrogen sealing.

[0006] U.S. Patent Application Publication 20180342388A discloses methods for selectively depositing organic layers and hybrid organic / inorganic layers. More specifically, embodiments of this disclosure relate to methods for selectively depositing molecular layer organic and hybrid organic / inorganic films by modifying hydroxyl-terminated surfaces. Further embodiments of this disclosure relate to the use of cyclic compounds in molecular layer deposition processes.

[0007] U.S. Patent Application Publication 20170037513A discloses a method for selectively depositing a material on a first metal or metal sample surface of a substrate relative to a second dielectric material, or for selectively depositing a metal oxide on a first metal oxide surface of a substrate relative to a second silicon oxide surface. The selectively deposited material can be, for example, a metal, metal oxide, metal nitride, metal silicide, metal carbide, and / or a dielectric material. In some embodiments, the substrate comprising the first metal or metal sample surface and the second dielectric surface is alternately and sequentially contacted with a first gaseous metal halide reactant and a second reactant. In some embodiments, the substrate comprising the first metal oxide surface and the second silicon oxide surface is alternately and sequentially contacted with a first gaseous metal fluoride or chloride reactant and water.

[0008] U.S. Patent 10,460,930B discloses a method and apparatus for selectively depositing silicon oxide on a dielectric surface relative to a metal-containing surface such as copper. The method includes exposing a substrate having a dielectric and a copper surface to a copper-blocking reagent such as an alkylthiol for selective adsorption onto the copper surface; exposing the substrate to a silicon-containing precursor for silicon oxide deposition; exposing the substrate to a weak oxidizing agent gas and igniting plasma to convert the adsorbed silicon-containing precursor to form silicon oxide; and exposing the substrate to a reducing agent to reduce any oxidation of the copper in the weak oxidizing agent gas.

[0009] U.S. Patent Application Publication 20180211833A discloses a processing platform comprising a central transfer station with a robot and an environment containing greater than or equal to about 0.1% by weight of water vapor, a pre-cleaning chamber connected to one side of the transfer station, and a batch processing chamber connected to one side of the transfer station. The processing platform is configured to pre-clean substrates to remove native oxides from a first surface, form a barrier layer using alkylsilanes, and selectively deposit films. Methods for using the processing platform and processing multiple wafers are also described.

[0010] U.S. Patent Application Publication 20190023001A discloses a method for selectively depositing a film on a hydroxide-terminated surface relative to a hydrogen-terminated surface. The hydrogen-terminated surface is exposed to a nitriding agent to form an amine-terminated surface, which is then exposed to blocking molecules to form a blocking layer on the surface. A film can then be selectively deposited on the hydroxide-terminated surface.

[0011] U.S. Patent Application Publication 20180233349A discloses a method and apparatus for selectively depositing silicon oxide on a silicon oxide surface relative to a silicon nitride surface. The method includes pretreating a substrate surface using ammonia and / or nitrogen plasma and selectively depositing silicon oxide on a silicon oxide surface using alternating pulses of an aminosilane silicon precursor and an oxidant in a thermal atomic layer deposition reaction, without depositing silicon oxide on an exposed silicon nitride surface.

[0012] U.S. Patent 10,043,656B discloses a method and apparatus for selectively depositing a silicon-containing dielectric material or a metal-containing dielectric material on a silicon or metal surface selectively reacting with silicon oxide or silicon nitride. The method includes exposing a substrate to an acyl chloride that reacts with the silicon oxide or silicon nitride material, wherein it is undesirable to deposit ketone structures that would prevent deposition on the silicon oxide or silicon nitride material. The exposure to the acyl chloride is performed prior to the deposition of the desired silicon-containing dielectric material or metal-containing dielectric material.

[0013] U.S. Patent Application Publication 20180323055A discloses a method for selectively forming a silicon nitride film on a substrate comprising a first metal surface and a second dielectric surface via a cyclic deposition process. The method may include contacting the substrate with a first reactant comprising a silicon halide source and contacting the substrate with a second reactant comprising a nitrogen source, wherein the incubation period for the first metal surface is shorter than the incubation period for the second dielectric surface. A semiconductor device structure comprising the selective silicon nitride film is also disclosed.

[0014] There is a need in the art to provide a composition and method for selectively depositing a silicon dielectric, such as silicon oxide, silicon oxynitride, carbon-doped silicon oxide, or carbon-doped silicon oxynitride, on top of a dielectric surface, while avoiding deposition of this silicon dielectric material on adjacent or existing metal hydride surfaces during semiconductor processing using thermal atomic layer deposition (TAL) processes. There is also a need in the art to provide this selective deposition without the use of strong oxidants such as ozone or oxygen-containing plasmas. Summary of the Invention

[0015] According to one embodiment, the present invention includes a method for selectively depositing a silicon- and oxygen-containing dielectric film onto a substrate, comprising:

[0016] a) Providing at least one substrate in the reactor comprising at least one dielectric surface and at least one metal or metal hydride surface;

[0017] b) Heating the reactor to at least one temperature in the range of about 25°C to about 600°C, and optionally maintaining the reactor at a pressure of about 100 Torr or less;

[0018] c) Introduce into the reactor at least one precursor comprising a halogenated silicon-containing compound, wherein the halogenated silicon-containing compound forms a silicon-containing layer on the dielectric surface in greater quantity than on the surface of the metal or metal hydride.

[0019] d) Use an inert gas to purge any unreacted precursors from the reactor;

[0020] e) Introduce a nitrogen source to react with the silicon-containing layer to form a silicon nitride film or a carbon-doped silicon nitride film;

[0021] f) Purge the reactor with inert gas;

[0022] g) Introduce an oxygen-containing source into the reactor to react with the silicon nitride film or carbon-doped silicon nitride film to form a dielectric film containing silicon and oxygen.

[0023] h) Purge any unreacted oxygen sources from the reactor using an inert gas; and

[0024] i) Optionally, the substrate is treated with a reducing agent to form a clean metal or metal hydride layer and a clean dielectric layer, and steps c to h or j are repeated in part or in part until the silicon and oxygen-containing dielectric film reaches the desired thickness. Invention Details

[0026] This article describes a method for thermally selectively depositing silicon and oxygen-containing dielectric films on silicon-containing or metal-containing dielectric surfaces without depositing on adjacent or otherwise present metal or metal hydride surfaces in atomic layer deposition (ALD) or ALD-like processes (e.g., but not limited to cyclic chemical vapor deposition (CCVD)).

[0027] Conventional deposition systems use oxidants to form oxygen-containing dielectric films, such as silicon oxide, silicon oxynitride, carbon-doped silicon oxide, or carbon-doped silicon oxynitride, which are not preferred for deposition onto metal surfaces. Oxidants such as ozone and / or oxygen plasma can oxidize metal / metal hydride surfaces to form metal oxide surfaces, thereby preventing the selective deposition of dielectric films onto dielectric surfaces relative to metal / metal hydride surfaces. This invention relates to a process for thermally depositing silicon and oxygen-containing dielectric films. The process steps include thermally depositing silicon nitride or carbon-doped silicon, and then converting it to silicon oxide, silicon oxynitride, carbon-doped silicon oxide, or carbon-doped silicon oxynitride, thereby avoiding or minimizing oxidation of the metal or metal hydride layer during deposition. After the desired silicon oxide, silicon oxynitride, carbon-doped silicon oxide, and / or carbon-doped silicon oxynitride are formed on the dielectric layer, any relatively minimal oxide layer formed on the metal / metal hydride can be removed by using a reducing agent, such as hydrogen, hydrogen-containing plasma, or a forming gas (a mixture of hydrogen and nitrogen), or the reducing properties of silanes, polysilanes, alcohols, or other reducing agents.

[0028] The method described according to an exemplary implementation includes:

[0029] a) Providing in a reactor at least one substrate comprising at least one first surface and at least one second surface, wherein the at least one first surface is a dielectric surface and the at least one second surface is a silicon surface, a metal surface, a metal compound surface or a hydride surface thereof;

[0030] b) Heating the reactor to at least one temperature in the range of about 25°C to about 600°C, and optionally maintaining the reactor at a pressure of about 100 Torr or less;

[0031] c) Introduce into the reactor at least one precursor comprising a halogenated silicon-containing compound, wherein the halogenated silicon-containing compound forms a silicon-containing layer on the at least one first surface in greater quantity than on the at least one second surface;

[0032] d) Purge any unreacted precursors from the reactor using an inert gas;

[0033] e) Introduce a nitrogen source to react with the silicon-containing layer to form a silicon nitride or carbon-doped silicon nitride film;

[0034] f) Purge the reactor with inert gas;

[0035] g) Introduce an oxygen-containing source into the reactor to react with the silicon nitride film or carbon-doped silicon nitride film to form a dielectric film containing silicon and oxygen.

[0036] h) Use an inert gas to purge any unreacted oxygen sources from the reactor;

[0037] i) Optionally, the substrate is treated with a reducing agent to form a clean metal hydride layer and a clean dielectric layer.

[0038] Before introducing steps g to i to form a stable silicon- and oxygen-containing dielectric film, steps c to f in this embodiment may be repeated to provide the desired thickness of silicon nitride or carbon-doped silicon nitride. In some specific embodiments of the invention, steps c to f are repeated to obtain the desired thickness of silicon nitride or silicon carbonitride before introducing the oxygen source in step g. The thickness range of silicon nitride or silicon carbonitride is... to or to or to or to or to or to The thickness range of silicon nitride or silicon carbonitride can also be... to or to or to or to or to or to

[0039] Steps c to h or c to i may be repeated until a silicon- and oxygen-containing dielectric film of the form of silicon oxide of the desired thickness is selectively deposited on the first surface, i.e., on the dielectric surface in a particular embodiment of the method disclosed herein.

[0040] In another embodiment, the deposition process may include the following steps:

[0041] a) Providing in a reactor at least one substrate comprising at least one first surface and at least one second surface, wherein the at least one first surface is a dielectric surface and the at least one second surface is a silicon surface, a metal surface, a metal compound surface or a hydride surface thereof;

[0042] b) Heating the reactor to at least one temperature in the range of about 25°C to about 600°C, and optionally maintaining the reactor at a pressure of about 100 Torr or less;

[0043] c) Introduce into the reactor at least one precursor comprising a halogenated silicon-containing compound, wherein the halogenated silicon-containing compound forms a silicon-containing layer on the at least one surface in greater quantity than on the at least one second surface;

[0044] d) Purge any unreacted precursors from the reactor using an inert gas;

[0045] e) Introduce a nitrogen source to react with the silicon-containing layer to form a silicon nitride film or a carbon-doped silicon nitride film;

[0046] f) Purge the reactor with inert gas;

[0047] g) Optionally, the substrate is treated with a reducing agent to form a clean metal hydride layer and a clean dielectric layer;

[0048] h) An oxygen-containing source is introduced into the reactor to react with the silicon nitride film or carbon-doped silicon nitride film to form a dielectric film containing silicon and oxygen.

[0049] i) Use an inert gas to purge any unreacted oxygen sources from the reactor.

[0050] Before introducing steps g to h or steps g to i to form a stable silicon and oxygen-containing dielectric film, steps c to f in this particular embodiment may be repeated to provide silicon nitride or carbon-doped silicon nitride of the desired thickness. In some embodiments of the invention, steps c to f are repeated before introducing step g or h to obtain silicon nitride or silicon carbonitride of the desired thickness. The thickness range of silicon nitride or silicon carbonitride is... to or to or to or to or to or to The thickness range of silicon nitride or silicon carbonitride can also be... to or to or to or to or to or to

[0051] In this embodiment of the method disclosed herein, steps c to i can be repeated until a silicon- and oxygen-containing dielectric film of the form of silicon oxide of the desired thickness is selectively deposited on the dielectric surface.

[0052] Examples of nitrogen sources can be ammonia, ethylenediamine, methylenediamine, and piperazine.

[0053] The oxygen source is preferably a mild oxidant, which can be selected from air, molecular oxygen, nitrous oxide, water vapor or hydrogen peroxide.

[0054] Oxygen sources can also be selected from ozone, oxygen plasma, nitrous oxide plasma, carbon dioxide plasma, and combinations thereof.

[0055] The at least one second surface may be selected from Si, Co, Cu, Al, Ta, Mo, W, TiN, TiSi, MoN, WN, and their hydrides. The dielectric surface may be selected from metal oxide layers, such as copper oxide, tantalum oxide, aluminum oxide, silicon oxide, carbon-doped silicon oxide, molybdenum oxide, titanium oxide, aluminum nitride, silicon nitride, or combinations thereof, which may include carbon-doped silicon oxynitride and silicon oxynitride.

[0056] The reducing agent can be selected from hydrogen and hydrogen-containing plasma.

[0057] Exemplary silicon-halogenated compounds for selective deposition of silicon oxide or silicon oxynitride are selected from:

[0058] i) silane halogenated, ii) siloxane halogenated, iii) silazane halogenated and iv) carbosilane halogenated.

[0059] The silane halides in group i include, but are not limited to, trichlorosilane, tetrachlorosilane, hexachlorosilane, pentachlorosilane, tetrachlorosilane, octachlorotrisilane, and dichlorosilane.

[0060] Group II halogenated siloxanes include, but are not limited to, hexachlorodisiloxane, pentachlorodisiloxane, tetrachlorodisiloxane, and octachlorotrisiloxane.

[0061] The silazane halides of group iii are selected from the group represented by formula I:

[0062]

[0063] Among them, R 1 Selected from hydrogen, straight-chain or branched C1-C 10Alkyl, straight-chain or branched C3-C 10 Alkenyl, straight-chain or branched C3-C 10 alkynyl group, C3-C 10 Cycloalkyl, C2-C6 dialkylamino, electron-withdrawing groups and C6-C 10 Aryl; R 2 Selected from hydrogen, straight-chain or branched C1-C 10 Alkyl, straight-chain or branched C2-C6 alkenyl, straight-chain or branched C3-C6 alkynyl, C3-C 10 Cycloalkyl, C2-C6 dialkylamino, C6-C 10 Aryl, straight-chain or branched C1-C6 fluorinated alkyl groups, electron-withdrawing groups, C4-C 10 Aryl group and halogens selected from Cl, Br and I; X is a halogen selected from Cl, Br and I.

[0064] Examples of group iii silazane halides can be represented in the following structures.

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071] The halogenated carbosilanes of group IV are selected from silicon compounds having one or two silicon-carbon-silicon bonds. Exemplary carbosilanes of group IV include those represented by formulas II and III:

[0072]

[0073] 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 1 R 2 The amino group, of which R 1 and R 2 Independently selected from hydrogen and C 1-10 Straight-chain alkyl; C 3-10 Branched alkyl; C 3-10 cycloalkyl; C3-10 Alkenyl; C 4-10 Aryl; and C 4-10 Heterocyclic group; in some embodiments of formula II, formula III, or both formula II and III, 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 one embodiment of Formula II, Formula III, or both Formula II and Formula III, the substituent X 1 X 2 X 3 X 4 X 5 and X 6 Any one or more of them are the halogens or amino groups described above. For formulas II and III, X 1 X 2 X 3 X 4 X 5 and X 6 Not all of them can be amino. In some embodiments of formula II or III, formula NR is present. 1 R 2 R in the amino group 1 and R 2 They are connected together to form a loop. In one particular implementation, R 1 and R 2 Selected from straight-chain or branched C3 to C6 alkyl groups, linked to form a ring. In alternative embodiments of Formula II or III, R 1 and R 2 They are not connected together to form a loop. In other implementations, R 1 and R 2 different.

[0074] Examples of group IV halogenated carbosilanes can be represented by the following structures.

[0075]

[0076]

[0077] Example 1 uses 1,1,3,3-tetrachloro-1,3-disilhexacyclobutane to deposit a carbon-doped silicon oxide film on a silicon dielectric (silicon oxide or silicon nitride) instead of on silicon hydride:

[0078] Selective deposition of silicon dielectric films is performed on different types of surfaces, such as silicon dielectrics and silicon hydrogenation. The silicon dielectric surface is selected from commercially available films, such as thermally grown silicon oxide on a silicon wafer. Silicon nitride grown by LPCVD The hydrogenated silicon surface is prepared by removing the native oxide from the silicon wafer. Three samples of each type were used.

[0079] Prior to deposition, all samples were cleaned for 10 minutes at 70°C using a standard semiconductor cleaning (SC-1) process. The SC-1 solution consisted of 30% H₂O₂ : 27% NH₄OH : DI water in a ratio of 1:1:5. After SC-1 cleaning and DI water rinsing, all samples were treated with a 0.5% HF solution at room temperature for 90 seconds to further remove contaminants and native silica from the sample surfaces. Film thickness was measured before and after deposition using an SCI Filmtek 3000 transmission-reflection spectrophotometer.

[0080] The selective growth of silicon-containing films on silicon dielectrics rather than on hydride silicon was demonstrated by using thermal ALD deposition with 1,1,3,3-tetrachloro-1,3-disilheyrobutane and ammonia as reactant gases.

[0081] The deposition process was carried out on a 300 mm PEALD apparatus with inner and outer chambers. The ALD membrane growth steps are listed in Table 1 below:

[0082] Table 1

[0083]

[0084]

[0085] Repeat steps 3 through 6 multiple times to obtain the desired film thickness. Expose the film to air at ambient temperature to convert the deposited carbon-doped silicon nitride into carbon-doped silicon oxide.

[0086] Table 2 shows the thickness of carbon-doped silicon oxide films grown on various surfaces. The reported data only show the thickness growth, i.e., the final film thickness minus the initial film thickness. The standard deviation (std.dev.) is a δ, calculated from three measurements (one measurement per sample).

[0087] Table 2. Comparison of carbon-doped silicon oxide film growth on different surfaces.

[0088]

[0089] Film growth was significantly inhibited on hydride compared to other surfaces (silicon oxide and silicon nitride). Very low film growth was observed on the hydride surface after 25 cycles. The film growth on the surfaces of silicon oxide and silicon nitride are respectively and

Claims

1. A method for selectively depositing a silicon- and oxygen-containing dielectric film onto a substrate, comprising: a) Providing in a reactor at least one substrate comprising at least one first surface and at least one second surface, wherein the at least one first surface is a dielectric surface and the at least one second surface is a silicon surface, a metal surface, a metal compound surface or a hydride surface thereof; b) Heating the reactor to at least one temperature in the range of 25°C to 600°C, and optionally maintaining the reactor at a pressure of 100 Torr or lower; c) Introducing into the reactor at least one precursor comprising a halogenated silicon-containing compound, the halogenated silicon-containing compound forming a silicon-containing layer on the at least one surface in greater quantity than on the at least one second surface, wherein the halogenated silicon-containing compound is selected from halogenated siloxanes, halogenated silazanes, and halogenated carbosilanes; d) Purge any unreacted precursors from the reactor using an inert gas; e) Introduce a nitrogen source to react with the silicon-containing layer to form a silicon nitride or carbon-doped silicon nitride film; f) Purge the reactor with an inert gas; g) Introduce an oxygen-containing source into the reactor to react with the silicon nitride or carbon-doped silicon nitride film to form a silicon- and oxygen-containing dielectric film; h) Purge any unreacted oxygen sources from the reactor using an inert gas; and i) Optionally, the substrate is treated with a reducing agent to form a clean metal hydride layer and a clean dielectric layer.

2. The method of claim 1, wherein the at least one second surface comprises at least one selected from Si, Co, Cu, Al, Ta, Mo, W, TiN, TiSi, MoN, WN and their hydrides.

3. The method according to claim 1, wherein the at least one first surface is selected from copper oxide, tantalum oxide, aluminum oxide, silicon oxide, carbon-doped silicon oxide, carbon-doped molybdenum oxide, carbon-doped titanium oxide, aluminum nitride, silicon nitride, carbon-doped silicon oxynitride, and silicon oxynitride.

4. The method according to claim 1, wherein the silicon- and oxygen-containing dielectric film is selected from silicon oxide, carbon-doped silicon oxide, silicon oxynitride, and carbon-doped silicon oxynitride.

5. The method according to claim 1, wherein the halogenated silicon-containing compound is selected from halogenated carbosilanes.

6. The method of claim 5, wherein the halogenated silicon-containing compound is selected from those represented by formulas II and III: II III 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 1 R 2 The amino group, of which R 1 and R 2 Independently selected from hydrogen and 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.

7. The method according to claim 1, wherein the nitrogen source is selected from ammonia, ethylenediamine, methylenediamine, and piperazine.

8. The method of claim 1, wherein the oxygen source is introduced after the silicon nitride or carbon-doped silicon nitride film has been deposited to a predetermined thickness by repeating steps c to f.

9. The method of claim 1, wherein when some or all of steps c to h are repeated, the oxygen source is always introduced after the nitrogen source is introduced to react with the silicon-containing layer.

10. The method according to claim 8 or 9, wherein the oxygen source is selected from air, molecular oxygen, nitrous oxide, water vapor, and hydrogen peroxide.

11. The method according to claim 8 or 9, wherein the oxygen source is selected from ozone, oxygen plasma, nitrous oxide plasma, carbon dioxide plasma, and combinations thereof.

12. The method of claim 1, further comprising step i, which includes introducing hydrogen or hydrogen plasma as the reducing agent into the reactor to remove some residual film and clean the at least one second surface.

13. A method for selectively depositing a silicon- and oxygen-containing dielectric film onto a substrate, comprising: a) Providing in a reactor at least one substrate comprising at least one first surface and at least one second surface, wherein the at least one first surface is a dielectric surface and the at least one second surface is a silicon surface, a metal surface, a metal compound surface or a hydride surface thereof; b) Heating the reactor to at least one temperature in the range of 25°C to 600°C, and optionally maintaining the reactor at a pressure of 100 Torr or lower; c) Introducing into the reactor at least one precursor comprising a halogenated silicon-containing compound, the halogenated silicon-containing compound forming a silicon-containing layer on the at least one first surface in greater quantity than on the at least one second surface, wherein the halogenated silicon-containing compound is selected from halogenated siloxanes, halogenated silazanes, and halogenated carbosilanes; d) Purge any unreacted precursors from the reactor using an inert gas; e) Introduce a nitrogen source to react with the silicon-containing layer to form a silicon nitride film or a carbon-doped silicon nitride film; f) Purge the reactor with an inert gas; g) Exposing the silicon nitride film or carbon-doped silicon nitride film to an oxygen-containing source to react with the silicon nitride film or carbon-doped silicon nitride film to form a silicon- and oxygen-containing dielectric film; h) Only when the oxygen source is introduced into the reactor, any unreacted oxygen source shall be purged from the reactor using an inert gas; and i) Optionally, the substrate is treated with a reducing agent to form a clean metal or metal hydride layer and a clean dielectric layer, and steps c to h are repeated in some or all until the silicon and oxygen-containing dielectric film reaches the desired thickness.

14. The method of claim 13, wherein the at least one second surface comprises at least one selected from Si, Co, Cu, Al, Ta, Mo, W, TiN, TiSi, MoN, WN, and their hydrides.

15. The method of claim 13, wherein the at least one first surface is selected from copper oxide, tantalum oxide, aluminum oxide, silicon oxide, carbon-doped silicon oxide, carbon-doped molybdenum oxide, carbon-doped titanium oxide, aluminum nitride, silicon nitride, carbon-doped silicon oxynitride, and silicon oxynitride.

16. The method of claim 13, wherein the silicon- and oxygen-containing dielectric film is selected from silicon oxide, carbon-doped silicon oxide, silicon oxynitride, and carbon-doped silicon oxynitride.

17. The method of claim 13, wherein the halogenated silicon-containing compound is selected from halogenated carbosilanes.

18. The method of claim 17, wherein the halogenated silicon-containing compound is selected from those represented by formulas II and III: II III 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 1 R 2 The amino group, of which R 1 and R 2 Independently selected from hydrogen and 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.

19. The method of claim 13, wherein the nitrogen source is selected from ammonia, ethylenediamine, methylenediamine, and piperazine.

20. The method of claim 13, wherein after the silicon nitride film or carbon-doped silicon nitride film is deposited to a predetermined thickness by repeating steps c to f, the silicon nitride film or carbon-doped silicon nitride film is exposed to the oxygen-containing source.

21. The method of claim 13, wherein when some or all of steps c to h are repeated, the silicon nitride film or carbon-doped silicon nitride film is exposed to the oxygen source only after the nitrogen source is introduced to react with the silicon-containing layer.

22. The method according to claim 13, 20 or 21, wherein the silicon nitride film or carbon-doped silicon nitride film is exposed to the oxygen source when in the reactor, and wherein the oxygen source is selected from air, molecular oxygen, nitrous oxide, water vapor and hydrogen peroxide.

23. The method according to claim 13, 20 or 21, wherein the silicon nitride film or carbon-doped silicon nitride film is exposed to the oxygen source when in the reactor, and wherein the oxygen source is selected from ozone, oxygen plasma, nitrous oxide plasma, carbon dioxide plasma and combinations thereof.

24. The method according to claim 13, 20 or 21, wherein the silicon nitride film or carbon-doped silicon nitride film is exposed to the oxygen source when it is outside the reactor, and wherein the oxygen source is air.

25. The method of claim 13, further comprising step i, which includes introducing hydrogen or hydrogen plasma as the reducing agent into the reactor to remove some residual film and clean the at least one second surface.

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