High-quality film formation by CVD

Abstract

This application relates to a method for forming high-quality films using a CVD process. Specifically, this application provides a method for depositing a flowable film on a substrate, the method comprising: introducing an organosilicon precursor into a deposition chamber, the deposition chamber containing a substrate; generating at least one nitrogen-containing free radical in a remote plasma; introducing the nitrogen-containing free radical into the deposition chamber; and reacting the nitrogen-containing free radical with the organosilicon precursor to generate polysilazane chains, which deposit on the substrate and become flowable on the surface of the substrate to form the flowable film. This method generates polysilazane chains that become flowable on the surface of the substrate, forming a flowable film. The flowable film quickly fills pores or gaps, avoiding permanent defects caused by the pores or gaps.

Description

[Technical Field]

[0001] The present application relates to the field of semiconductor device manufacturing, and in particular to a method for forming high quality films by CVD. [Background technology]

[0002] During semiconductor device fabrication, devices are typically isolated using shallow trench isolation structures. Shallow trench isolation structures include trenches or gaps in isolation regions of a semiconductor substrate, which can be filled with a dielectric material to prevent electrical coupling between adjacent device structures (e.g., transistors, diodes, etc.). As technology advances, semiconductor device sizes become smaller, but more devices (e.g., transistors, capacitors, diodes, etc.) are required, necessitating ever higher standards of semiconductor manufacturing. With existing manufacturing techniques, it is difficult to fill the trenches or gaps of shallow trench isolation structures without creating holes or gaps. The presence of holes or gaps can adversely affect subsequent semiconductor device fabrication, such as uneven etching, polishing, and annealing. The presence of holes or gaps in semiconductor device products can adversely affect the performance of the semiconductor device, such as dielectric quality, crosstalk, charge leakage, and short circuits.

[0003] There are several techniques to reduce the formation of pores or voids, such as reducing the deposition rate of the dielectric material, but these techniques reduce production efficiency and productivity. Another method to control the formation of pores or voids is to improve the flowability of the deposited dielectric material. A material with greater flowability leads to faster filling of pores or voids, avoiding permanent defects caused by pores or voids. However, commonly used flowable films (e.g., coated silicon dioxide films) have low density and are unstable.

[0004] In view of the above, there is a need to provide an improved method for forming flowable films by CVD, and to form high quality films. Summary of the Invention [Problem to be solved by the invention]

[0005] The present application provides a method for depositing a film on a substrate to solve, in part, at least one of the problems present in the related art.

[0006] According to one aspect of the present application, the present application provides a method of depositing a flowable film on a substrate, the method comprising: introducing an organosilicon precursor into a deposition chamber containing a substrate; generating at least one nitrogen-containing free radical in a remote plasma; introducing the nitrogen-containing free radicals into the deposition chamber; reacting the nitrogen-containing radicals with the organosilicon precursor to generate polysilazane chains, which deposit on the substrate and become flowable on the surface of the substrate to form the flowable film.

[0007] According to an embodiment of the present application, the polysilazane chain contains a Si—N bond. According to an embodiment of the present application, the organosilicon precursor and the nitrogen-containing radical are reacted to form silazane radicals, and the silazane radicals are polymerized to form the polysilazane chains.

[0008] According to an embodiment of the present application, the polysilazane chain is

[0009] [ka]

[0010] It has repeating units, where n is 2-50. According to the examples of the present application, the number average molecular weight of the polysilazane chain is 40-1000 g / mol.

[0011] According to an embodiment of the present application, the organosilicon precursor has at least one of formula I, formula II, formula III, and formula IV,

[0012] [ka]

[0013] [ka]

[0014] [ka]

[0015] [ka]

[0016] where R is independently hydrogen, halogen, or straight-chain C1-C 10 Alkyl group, branched C3-C 10 Alkyl groups, straight or branched C3-C 12 Alkenyl group, straight or branched C3-C 12 Alkynyl group, C4-C 10 Cycloalkyl group or C6-C 10 It is selected from aryl groups.

[0017] According to an embodiment of the present application, when the organosilicon precursor has Formula I, the polysilazane chain has at least one of Formula 1-1, Formula 1-2, and Formula 1-3.

[0018] [ka]

[0019] [ka]

[0020] [ka]

[0021] According to the embodiment of the present application, when the organosilicon precursor has formula II, the polysilazane chain has at least one of formula 2-1 and formula 2-2.

[0022] [ka]

[0023] [ka]

[0024] According to an embodiment of the present application, when the organosilicon precursor has formula III, the polysilazane chain has formula 3:

[0025] [ka]

[0026] According to an embodiment of the present application, when the organosilicon precursor has formula IV, the polysilazane chain has at least one of formula 4-1 and formula 4-2.

[0027] [ka]

[0028] [ka]

[0029] According to an embodiment of the present application, the method further comprises exposing ammonia to the remote plasma to generate the nitrogen-containing free radicals.

[0030] According to an embodiment of the present application, the nitrogen-containing radical has the formula NH x where x is 0, 1 or 2.

[0031] According to another aspect of the present application, there is provided a method of forming a film on a substrate, the method comprising: introducing an organosilicon precursor into a deposition chamber containing a substrate; generating at least one nitrogen-containing free radical in a remote plasma; introducing the nitrogen-containing free radicals into the deposition chamber; reacting the nitrogen-containing radicals with the organosilicon precursor to generate polysilazane chains, which are deposited on the substrate and become flowable on the surface of the substrate to form the flowable film; solidifying the flowable film; and annealing the solidified flowable film to form the film, wherein the film comprises a plurality of Si-O-Si bonds.

[0032] According to an embodiment of the present application, the flowable film is formed by the method of the present application. According to an embodiment of the present application, solidifying the flowable film comprises at least one of the following: (a) exposing the flowable film to ozone and water; (b) exposing the flowable film to ozone and ultraviolet light.

[0033] According to an embodiment of the present application, solidifying the flowable film includes exposing the flowable film to ozone and water at a temperature between 150° C. and 450° C. and a pressure between 400 Torr and 800 Torr.

[0034] According to an embodiment of the present application, solidifying the flowable film includes exposing the flowable film to ozone at a temperature less than 100°C and a pressure between 400 Torr and 800 Torr, followed by exposing the flowable film to ultraviolet light at a pressure less than 150 Torr.

[0035] According to an embodiment of the present disclosure, annealing the solidified flowable film includes performing the annealing in a nitrogen gas atmosphere at a temperature of 1050°C.

[0036] According to an embodiment of the present application, annealing the solidified flowable film includes annealing in a steam atmosphere at a temperature of 200°C to 600°C.

[0037] According to an embodiment of the present application, the vapor includes at least one of water vapor and acid vapor. According to an embodiment of the present application, the method includes performing the annealing in the water vapor ambient to form at least a first portion of the Si—O—Si bonds.

[0038] According to an embodiment of the present application, the method includes performing the annealing in the acidic vapor atmosphere to form at least a second portion of the Si—O—Si bonds.

[0039] According to an embodiment of the present application, the acid vapor comprises hydrochloric acid or acetic acid. According to an embodiment of the present application, the film is a silicon oxide film.

[0040] According to an embodiment of the present application, the density of the film is greater than the density of the flowable film. The method of the present invention generates polysilazane chains through a CVD process, which can flow on the surface of the substrate to form a flowable film. The flowable film can quickly fill pores or gaps and avoid permanent defects caused by pores or gaps. After solidification and annealing, the flowable film can form a high-quality film.

[0041] Additional aspects and advantages of the present application will be set forth in the following description, are illustrated in the following description, or may be learned by practice of the examples of the present application.

[0042] The following briefly describes the drawings necessary for explaining the embodiments of the present application or the prior art, to facilitate the description of the embodiments of the present application. It is clear that the drawings described below are only some of the embodiments of the present application. Those skilled in the art can obtain drawings of other embodiments based on the structures shown in these drawings without any innovative ingenuity. [Brief explanation of the drawings]

[0043] [Figure 1] FIG. 1 shows a simplified flow diagram of a method for depositing a film on a substrate according to an embodiment of the present application. [Figure 2] FIG. 2 shows another simplified flow diagram of a method for depositing a film on a substrate according to an embodiment of the present application. [Figure 3] FIG. 3 shows the chemical reaction mechanism by which a trisilylamine (TSA) precursor according to an embodiment of the present invention and nitrogen-containing free radicals generated by decomposing ammonia in a remote plasma form polysilazane chains. [Figure 4] FIG. 4 shows a reaction flow diagram of a method for depositing a silicon oxide film on a substrate according to an embodiment of the present application. DETAILED DESCRIPTION OF THE INVENTION

[0044] Examples of the present application are specifically described in the following specification. It should be understood that the examples of the present application do not limit the present application.

[0045] In specific embodiments and claims, an item involving the term "at least one of" means any combination of the exemplified items. For example, if items A and B are exemplified, the sentence "at least one of A and B" means A only, B only, or A and B. In another example, if items A, B, and C are exemplified, the sentence "at least one of A, B, and C" means A only, B only, C only, A and B (excluding C), A and C (excluding B), B and C (excluding A), or all of A, B, and C. Item A may include a single element or multiple elements. Item B may include a single element or multiple elements. Item C may include a single element or multiple elements.

[0046] The term "alkyl group" preferably refers to a linear saturated hydrocarbon structure having 1 to 10 carbon atoms. The term "alkyl group" further preferably refers to a branched or cyclic hydrocarbon structure having 3 to 10 carbon atoms. When specifying an alkyl group having a specific number of carbon atoms, it is preferred to include all geometric isomers having that number of carbon atoms. Thus, for example, "butyl group" includes n-butyl group, s-butyl group, isobutyl group, t-butyl group, and cyclobutyl group. "propyl group" includes n-propyl group, isopropyl group, and cyclopropyl group. Illustrative examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, s-butyl, t-butyl, cyclobutyl, n-pentyl, isopentyl, neopentyl, cyclopentyl, methylcyclopentyl, ethylcyclopentyl, n-hexyl, isohexyl, cyclohexyl, n-heptyl, octyl, cyclopropyl, cyclobutyl, norbornyl, and the like.

[0047] The term "alkenyl group" refers to a monovalent unsaturated hydrocarbon functional group having a straight or branched chain and at least one, and typically one, two, or three carbon-carbon double bonds. Unless otherwise specified, such alkenyl groups typically have from 3 to 12 carbon atoms and include (for example) -C 2-4 Alkenyl group, -C 2-6 Alkenyl group, -C 2-10 Representative alkenyl groups include (for example) vinyl, n-propenyl, isopropenyl, n-butyl-2-alkenyl, butyl-3-alkenyl, n-hexyl-3-alkenyl, and the like.

[0048] The term "alkynyl group" refers to a monovalent unsaturated hydrocarbon functional group having a straight or branched chain and at least one, and typically one, two, or three carbon-carbon triple bonds. Unless otherwise specified, such alkynyl groups typically have from 3 to 12 carbon atoms and include (for example) -C 2-4 Alkynyl group, -C 3-6 Alkynyl group, -C 3-10Representative alkynyl groups include (for example) ethynyl, propyl-2-alkynyl (n-propynyl), n-butyl-2-alkynyl, n-hexyl-3-alkynyl, and the like.

[0049] The term "cycloalkyl group" refers to a non-aromatic monocyclic or polycyclic hydrocarbon group composed solely of carbon and hydrogen atoms, including fused or bridged ring systems, having 3 to 15 carbon atoms, preferably 4 to 10 carbon atoms, and may be saturated or unsaturated. Monocyclic functional groups include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like. Polycyclic functional groups include, for example, adamantine, norcamphane, decahydronaphthyl, 7,7-dimethyl-bicyclo[2.2.1]heptyl, and the like.

[0050] The term "aryl group" refers to a monovalent aromatic hydrocarbon having a single ring (e.g., a phenyl group) or fused rings. Fused ring systems include fully unsaturated ring systems (e.g., naphthalene) and partially unsaturated ring systems (e.g., 1,2,3,4-tetrahydronaphthalene). Unless otherwise specified, the aryl group typically contains 6 to 10 ring carbon atoms and (e.g.,) -C 6-10 Representative aryl groups include (for example) phenyl, methylphenyl, propylphenyl, isopropylphenyl, benzyl, naphthalen-1-yl, naphthalen-2-yl, and the like.

[0051] The present application provides a method for depositing a flowable film on a substrate, comprising: introducing an organosilicon precursor into a deposition chamber containing a substrate; generating at least one nitrogen-containing free radical in a remote plasma; introducing the nitrogen-containing free radicals into the deposition chamber; reacting the nitrogen-containing radicals with the organosilicon precursor to generate polysilazane chains, which deposit on the substrate and become flowable on the surface of the substrate to form the flowable film.

[0052] In some embodiments, the polysilazane chain comprises a Si—N bond. In some embodiments, the organosilicon precursor reacts with the nitrogen-containing radical to form a silazane radical, and the silazane radical is polymerized to form the polysilazane chain. The nitrogen-containing radical acts as a chain polymerization initiator to react with the organosilicon precursor to form a silazane small molecule radical, and the silazane small molecule radical reacts with the nitrogen-containing radical to achieve chain polymerization growth, thereby forming a polysilazane chain.

[0053] In some embodiments, the polysilazane chain is

[0054] [ka]

[0055] It has repeating units, and n is 2-50. In some embodiments, n is 5-40. In some embodiments, n is 10-30. In some embodiments, n is 10-20.

[0056] In some embodiments, the polysilazane chain has a number average molecular weight of 40-1000 g / mol, 50-800 g / mol, 100-500 g / mol, or 200-400 g / mol.

[0057] In some embodiments, the organosilicon precursor has at least one of Formula I, Formula II, Formula III, and Formula IV:

[0058] [ka]

[0059] [ka]

[0060] [ka]

[0061] [ka]

[0062] where R is independently hydrogen, halogen, or straight-chain C1-C 10 Alkyl group, branched C3-C 10 Alkyl groups, straight or branched C3-C 12 Alkenyl group, straight or branched C3-C 12 Alkynyl group, C4-C 10 Cycloalkyl group or C6-C 10 It is selected from aryl groups.

[0063] In some embodiments, the organosilicon precursor is trisilylamine (TSA):

[0064] [ka]

[0065] is. In some embodiments, the method further includes exposing ammonia to the remote plasma to generate the nitrogen-containing free radicals. The plasma conditions for decomposing ammonia into nitrogen-containing free radicals include generating the plasma using RF power in the range of 3 kW to 15 kW, at a chamber pressure in the range of 1 Torr to 10 Torr, and at a chamber temperature in the range of room temperature to about 200°C.

[0066] In some embodiments, the nitrogen-containing radical has the formula NH x where x is 0, 1, or 2. In a remote plasma system, ammonia can be decomposed to generate nitrogen-containing free radicals such as N, NH, or NH2.

[0067] In some embodiments, when the organosilicon precursor has Formula I, the polysilazane chain has at least one of Formula 1-1, Formula 1-2, and Formula 1-3.

[0068] [ka]

[0069] [ka]

[0070] [ka]

[0071] In some embodiments, when the organosilicon precursor has Formula II, the polysilazane chain has at least one of Formula 2-1 and Formula 2-2.

[0072] [ka]

[0073] [ka]

[0074] In some embodiments, when the organosilicon precursor has Formula III, the polysilazane chain has Formula 3:

[0075] [ka]

[0076] In some embodiments, when the organosilicon precursor has Formula IV, the polysilazane chain has at least one of Formula 4-1 and Formula 4-2.

[0077] [ka]

[0078] [ka]

[0079] This application utilizes chemical vapor deposition (CVD) to generate polysilazane chains containing Si-N bonds by reacting an organosilicon precursor with at least one nitrogen-containing free radical (e.g., -N, -NH, -NH2) generated in a remote plasma.

[0080] [ka]

[0081] The polymer has repeating units and does not contain carbon or oxygen atoms in its main chain, which leads to improved flowability of the formed film on the substrate, allowing it to quickly and effectively fill trenches or gaps in the substrate.

[0082] The order in which the organosilicon precursor and the nitrogen-containing radicals are introduced into the deposition chamber is not limited. Figure 1 shows a simplified flow diagram of a method for depositing a film on a substrate according to an embodiment of the present application. After providing a substrate in the deposition chamber, the organosilicon precursor is first introduced into the deposition chamber, and then at least one nitrogen-containing radical generated in the remote plasma is introduced into the deposition chamber, where they react to generate polysilazane chains and form a flowable film.

[0083] 2 shows another simplified flow diagram of a method for depositing a film on a substrate according to an embodiment of the present invention. After providing a substrate in a deposition chamber, first, at least one nitrogen-containing free radical generated in a remote plasma is introduced into the deposition chamber, and then an organosilicon precursor is introduced into the deposition chamber, where they react to generate polysilazane chains and form a flowable film.

[0084] 3 illustrates the chemical reaction steps of a trisilylamine (TSA) precursor according to an embodiment of the present invention with nitrogen-containing radicals generated by decomposing ammonia in a remote plasma to form polysilazane chains. As shown in the figure, TSA and the N, NH, and NH2 radicals generated by decomposing ammonia meet in the deposition chamber to form silazane (-Si-N-) radicals, which then undergo a polymerization reaction to generate polysilazane chains and form a flowable film. Other types of silicon-containing precursors react with nitrogen-containing radicals to generate polysilazane chains based on a similar mechanism.

[0085] The CVD method is carried out under the following processing conditions: the precursor flow rate is set to 100-1000 sccm, the deposition chamber is maintained at a pressure in the range of about 1 mTorr to about 600 Torr, and the room temperature is controlled to about 0°C to about 400°C.

[0086] The present application further provides a method of forming a film on a substrate, comprising: introducing an organosilicon precursor into a deposition chamber containing a substrate; generating at least one nitrogen-containing free radical in a remote plasma; introducing the nitrogen-containing free radicals into the deposition chamber; reacting the nitrogen-containing radicals with the organosilicon precursor to generate polysilazane chains, which are deposited on the substrate and become flowable on the surface of the substrate to form the flowable film; solidifying the flowable film; and annealing the solidified flowable film to form the film, wherein the film comprises a plurality of Si-O-Si bonds.

[0087] FIG. 4 shows a reaction flow diagram of a method for depositing a silicon oxide film on a substrate according to an embodiment of the present disclosure. Step 401 represents the formation of polysilazane chains, resulting in highly fluid polysilazane chains. Step 402 represents the solidification process, during which N atoms in the polysilazane chains are replaced with O atoms, increasing the stability of the film and forming a film with a stable structure and no fluidity. Step 403 represents the annealing process, during which H atoms in the film are removed to form a silicon oxide film. The present disclosure can produce high-quality films, including, but not limited to, silicon oxide films, silicon nitride films, silicon oxynitride films, carbon-doped silicon nitride films, and carbon-doped silicon oxide films. Therefore, the present disclosure is widely applicable to the fabrication of various semiconductor devices.

[0088] In some embodiments, the flowable film is formed by the methods of the present application. In some embodiments, solidifying the flowable film comprises at least one of the following: (a) exposing the flowable film to ozone and water; (b) exposing the flowable film to ozone and ultraviolet light.

[0089] In some embodiments, solidifying the flowable film comprises exposing the flowable film to ozone and water at a temperature between 150° C. and 450° C. and a pressure between 400 Torr and 800 Torr.

[0090] In some embodiments, solidifying the flowable film comprises exposing the flowable film to ozone and water at a temperature of 150° C. and a pressure of 600 Torr.

[0091] In some embodiments, solidifying the flowable film comprises exposing the flowable film to ozone at a temperature of less than 100° C. and a pressure of 400 Torr to 800 Torr, followed by exposure to ultraviolet light at a pressure of less than 150 Torr. In some embodiments, solidifying the flowable film comprises exposing the flowable film to ozone at a temperature of 25° C. to 100° C. and a pressure of 600 Torr, followed by exposure to ultraviolet light at a pressure of 50 Torr to 150 Torr.

[0092] In some embodiments, annealing the solidified flowable film includes performing the anneal in a nitrogen gas atmosphere at a temperature of 1050°C.

[0093] In some embodiments, annealing the solidified flowable film includes performing the annealing in a steam ambient at a temperature between 200°C and 600°C.

[0094] In some embodiments, the vapor comprises at least one of water vapor and acid vapor. In some embodiments, the method includes performing the anneal in a water vapor atmosphere to form at least a first portion of the Si—O—Si bonds.

[0095] In some embodiments, the method includes performing the anneal in the acidic vapor atmosphere to form at least a second portion of the Si—O—Si bonds.

[0096] After two annealing steps, H in the solidified flowable film can be almost completely removed, and the film quality can be further improved.

[0097] In some embodiments, the acid vapor comprises hydrochloric acid or acetic acid. In some embodiments, the film is a silicon oxide film.

[0098] In some embodiments, the density of the film is greater than the density of the flowable film. Hereinafter, the formation method of a silicon oxide film will be described with reference to specific examples. It should be understood by those skilled in the art that the methods and films described herein are merely examples, and any other suitable methods and films may be applied. [Example]

[0099] First, a substrate is placed in a deposition chamber and trisilylamine (TSA) is introduced into the chamber. A remote plasma source is then used to generate plasma at a pressure of 1 Torr to 10 Torr and a temperature of room temperature to approximately 200°C, utilizing RF power ranging from 3 kW to 15 kW. Ammonia is decomposed in the plasma to generate H, NH, and NH2 free radicals, which are then introduced into the deposition chamber. In the deposition chamber, the TSA and the free radicals undergo a polymerization reaction, generating polysilazane chains in the gas phase, which then condense into a film on the substrate. The film becomes flowable on the substrate surface, forming a flowable film. The flowable film is then solidified by exposure to ozone and ultraviolet light. Annealing is then performed at a temperature ranging from 20°C to 900°C, yielding a silicon oxide film.

[0100] Throughout the specification, references to "in some embodiments," "in one embodiment," "in another embodiment," "example," "example," "particular example," or "some examples" mean that at least one embodiment or example herein includes the particular feature, structure, material, or characteristic described in that embodiment or example. Thus, appearances of statements such as "in some embodiments," "in an embodiment," "in another embodiment," "in one example," "in a particular example," or "example" in various places throughout the specification are not necessarily all from the same embodiment or example herein. Furthermore, particular features, structures, materials, or characteristics herein may be combined in any suitable manner in one or more embodiments or examples.

[0101] Although illustrative embodiments have been shown and described, it should be understood by those skilled in the art that the above embodiments do not limit the present application, and that changes, substitutions, and modifications of the embodiments can be made without departing from the spirit, principles, and scope of the present application.

Claims

1. 1. A method of depositing a flowable film on a substrate, comprising: introducing an organosilicon precursor into a deposition chamber containing a substrate; generating at least one nitrogen-containing free radical in a remote plasma; introducing the nitrogen-containing free radicals into the deposition chamber; reacting the nitrogen-containing radicals with the organosilicon precursor to generate polysilazane chains, which polysilazane chains deposit on the substrate and become flowable on the surface of the substrate to form the flowable film.

2. 2. The method of claim 1, wherein the polysilazane chain comprises a Si-N bond.

3. 2. The method of claim 1, wherein the organosilicon precursor and the nitrogen-containing radical are reacted to form silazane radicals, and the silazane radicals are polymerized to form the polysilazane chains.

4. 2. The method of claim 1, wherein the polysilazane chain is 【Chemistry 1】 It has repeating units, where n is 2-50.

5. 2. The method according to claim 1, wherein the number average molecular weight of the polysilazane chain is 40-1000 g / mol.

6. 10. The method of claim 1, wherein the organosilicon precursor has at least one of Formula I, Formula II, Formula III, and Formula IV: 【Chemistry 2】 【Transformation 3】 【Chemistry 4】 【Transformation 5】 However, each R is independently hydrogen, halogen, or linear C 1 -C 10 Alkyl group, branched chain C 3 -C 10 Alkyl group, straight or branched C 3 -C 12 Alkenyl group, straight or branched chain C 3 -C 12 Alkynyl group, C 4 -C 10 Cycloalkyl group or C 6 -C 10 It is selected from aryl groups.

7. 7. The method of claim 6, (i) when the organosilicon precursor has Formula I, the polysilazane chain has at least one of Formula 1-1, Formula 1-2, and Formula 1-3; 【Transformation 6】 【Transformation 7】 【Transformation 8】 (ii) when the organosilicon precursor has Formula II, the polysilazane chain has at least one of Formula 2-1 and Formula 2-2; 【Chemistry 9】 【Chemistry 10】 (iii) when the organosilicon precursor has formula III, the polysilazane chain has formula 3, 【Chemistry 11】 (iv) When the organosilicon precursor has formula IV, the polysilazane chain has at least one of formula 4-1 and formula 4-2; 【Chemistry 12】 【Chemistry 13】

8. 10. The method of claim 1, further comprising exposing ammonia to the remote plasma to generate the nitrogen-containing free radicals.

9. 10. The method of claim 1, wherein the nitrogen-containing radical has the formula NH x where x is 0, 1 or 2.

10. 1. A method for forming a film on a substrate, comprising: introducing an organosilicon precursor into a deposition chamber containing a substrate; generating at least one nitrogen-containing free radical in a remote plasma; introducing the nitrogen-containing free radicals into the deposition chamber; reacting the nitrogen-containing radicals with the organosilicon precursor to generate polysilazane chains, which are deposited on the substrate and become flowable on the surface of the substrate to form the flowable film; solidifying the flowable film; and annealing the solidified flowable film to form the film, wherein the film comprises a plurality of Si—O—Si bonds.

11. The method of claim 10, wherein the flowable film is formed by the method of any one of claims 1-9.

12. 11. The method of claim 10, wherein solidifying the flowable film comprises at least one of the following: (a) exposing the flowable film to ozone and water; (b) exposing the flowable film to ozone and ultraviolet light.

13. 13. The method of claim 12, wherein solidifying the flowable film comprises exposing the flowable film to ozone and water at a temperature between 150° C. and 450° C. and a pressure between 400 Torr and 800 Torr.

14. 13. The method of claim 12, wherein solidifying the flowable film comprises exposing the flowable film to ozone at a temperature less than 100° C. and a pressure between 400 Torr and 800 Torr, followed by exposure to ultraviolet light at a pressure less than 150 Torr.

15. 11. The method of claim 10, wherein annealing the solidified flowable film includes annealing the solidified flowable film in a nitrogen gas atmosphere at a temperature of 1050°C.

16. The method of claim 10, wherein annealing the solidified flowable film includes annealing in a steam atmosphere at a temperature of 200°C to 600°C.

17. 17. The method according to claim 16, wherein the vapor comprises at least one of water vapor and acid vapor.

18. 18. The method of claim 17, wherein the method includes performing the annealing in a water vapor atmosphere to form at least a first portion of the Si-O-Si bonds.

19. 20. The method of claim 18, wherein the method includes performing the annealing in the acidic vapor atmosphere to form at least a second portion of the Si-O-Si bonds.

20. 18. The method of claim 17, wherein the acid vapor comprises hydrochloric acid or acetic acid.

21. 11. The method of claim 10, wherein the film is a silicon oxide film.

22. 11. The method of claim 10, wherein the density of the film is greater than the density of the flowable film.

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