Method for depositing silicon-containing film

Abstract

[Problem] To provide: a method for effectively depositing a silicon-containing film on a substrate; a substrate having a silicon-containing film deposited thereon by the method; and a product including the substrate. [Solution] Use is made of, for example, a carbon- and nitrogen-source compound represented by formula (1): R1 3E-N=C=N-ER1 3 [wherein the E moieties are independently Si, Ge, or Sn and the R1 moieties are independently a linear or cyclic, C1-C6 alkyl, C2-C6 alkenyl, or C1-C6 alkynyl].

Description

Method for forming silicon-containing film

[0001] The present disclosure relates to methods for depositing silicon-containing films on substrates, and also to substrates having silicon-containing films deposited thereon and articles of manufacture including the substrates.

[0002] Silicon nitride-containing films, such as silicon carbonitride (SiCN) films, are widely used as dielectric materials for various applications in semiconductor device manufacturing. Developing new film deposition methods that improve film properties and process performance is crucial for achieving device downscaling and developing new technologies.

[0003] Non-Patent Document 1 describes that silicon-containing films have excellent physicochemical properties in terms of dielectric properties, engineering and mechanical properties, thermal stability, oxidation resistance, etc. Patent Document 1 describes a method for producing silicon-containing films by using a halosilane compound, an aminosilane compound, and an optional R ２ A method for depositing silicon nitride films using sequential pulses of NH compounds (R is H, C1-C4 alkyl, or combinations thereof) is described.

[0004] E. Ermakova et al., J. Organomet. Chem. 958, 122183 (2022)

[0005] U.S. Patent Publication No. 2023 / 0279545

[0006] The present disclosure provides a method for forming a silicon-containing film, which can effectively form a silicon-containing film having excellent properties on a substrate. It also provides a substrate on which a silicon-containing film having excellent properties has been formed, and a product including the substrate. The method for forming a silicon-containing film according to the present disclosure is, for example, the following method. A method for forming a silicon-containing film on a substrate, comprising: (i) supplying at least one silicon source compound containing at least one silicon halide onto the substrate; and (ii) providing a silicon source compound represented by the formula (1): R １ ３ EN=C=N-ER １ ３ [In formula (1), E is independently Si, Ge, or Sn, and R １are independently C1-C6 alkyl, C2-C6 alkenyl, C4-C6 cycloalkyl, or C4-C6 cycloalkenyl, and the carbon / nitrogen source compound is provided on a substrate.

[0007] Figure 1 shows an example of an implementation scheme of the CVD method in the present disclosure. Figure 2 shows the analysis results of the components of the silicon-containing film of Example 1 by X-ray photoelectron spectroscopy (XPS).

[0008] Hereinafter, embodiments of the present disclosure will be described in detail, but the scope of the present invention is not limited to the embodiments described herein, and various modifications can be made without departing from the spirit of the present invention. The embodiments may be implemented alone or in combination with one another. When a specific description given for one embodiment also applies to other embodiments, that description is omitted in the other embodiments.

[0009] Each numerical range in the present disclosure is intended to include the upper and lower limit values ​​indicated by "to" and "from." For example, the description "A to B" or "A to B" using numerical values ​​A and B means A or more and B or less. Furthermore, the descriptions "A to B," "A to B," or "A or more and B or less" in the numerical ranges described in stages in the present disclosure independently include both "A or more is preferred" and "B or less is preferred," and these lower or upper limit values ​​may be replaced with the upper or lower limit value of another numerical range. Furthermore, the lower or upper limit value of a numerical range described in the present disclosure is a numerical value within that numerical range and may be replaced with a numerical value shown in the examples.

[0010] As used in this disclosure, the singular forms "a," "an," and "the" can include plural referents unless clearly indicated otherwise. As used in this disclosure, "and / or" includes both "and" and "or" relationships. As used in this disclosure, "comprising" includes "consisting essentially of," "consisting essentially of," and "consisting of," and "consisting essentially of" includes "consisting essentially of" and "consisting of," and "consisting essentially of" includes "consisting of."

[0011] [Method for forming a silicon-containing film] In one embodiment, a method for forming a silicon-containing film on a substrate includes: (i) providing at least one silicon source compound containing at least one silicon halide on the substrate; and (ii) providing a silicon source compound represented by the formula (1): R １ ３ EN=C=N-ER １ ３ [In formula (1), E is independently Si, Ge, or Sn, and R １ are independently C1-C6 alkyl, C2-C6 alkenyl, C4-C6 cycloalkyl, or C4-C6 cycloalkenyl, and

[0012] In this embodiment, at least one silicon source compound containing at least one silicon halide is reacted with a carbon / nitrogen source compound represented by formula (1) to form a silicon-containing film containing silicon, carbon, and nitrogen. The by-products of this reaction are generally not salts and are highly volatile. Therefore, they can be easily removed from the reaction system. Conventional methods for producing similar silicon-containing films use, for example, ethylene, methane, acetylene, etc. as the sole carbon source compound, and ammonia, hydrazine, amine, etc. as the nitrogen source compound that reacts directly with the silicon source compound. In this case, salts (e.g., ammonium halides) are generated as by-products of the reaction between the silicon source compound and the nitrogen source compound. Salts generally have low volatility and are difficult to remove from the reaction system. That is, the method of this embodiment can reduce the amount of by-products contaminating the silicon-containing film. Furthermore, the possibility of salts being contaminated into the silicon-containing film can be reduced or eliminated. Therefore, the method of this embodiment makes it possible to deposit a silicon-containing film on a substrate with higher purity and uniformity. Furthermore, the possibility of damage to the structure and function of the substrate due to adhesion of by-products to the substrate can be reduced. In this embodiment, a single compound can be used as the carbon / nitrogen source compound, eliminating the need to separately prepare and use a carbon source compound and a nitrogen source compound, as in conventional methods. Therefore, the method of this embodiment reduces the amount of chemicals and steps required compared to conventional methods, allowing a silicon-containing film to be deposited on a substrate more efficiently. Furthermore, this embodiment reduces or eliminates the possibility of C—H bonds, N—H bonds, and E—H bonds forming in the silicon-containing film, which can adversely affect the sensitivity of the silicon-containing film to humidity, wet etching, and ashing, thereby improving film properties.

[0013] In this embodiment, the silicon-containing film is any film containing silicon nitride, and may be, for example, a silicon carbonitride (SiCN) film, a silicon carbonate nitride (SiOCN) film, a silicon boron carbonitride (SiBCN) film, a silicon boron carbonate nitride (SiBOCN) film, a silicon carbide (SiC) film, or a mixture thereof.

[0014] In this embodiment, in formula (1), E is preferably Si, and R １ is preferably C1-C6 alkyl, more preferably CH ３ Non-limiting examples of compounds of formula (1) include (H ３ C) ３ Si-N=C=N-Si(CH ３ ) ３ , (H ５ C ２ ) ３ Si-N=C=N-Si(C ２ H ５ ) ３ , (H ３ C ２ ) ３ Si-N=C=N-Si(C ２ H ３ ) ３ , (H ７ C ３ ) ３ Si-N=C=N-Si(C ３ H ７ ) ３ , (H ５ C ３ ) ３ Si-N=C=N-Si(C ３ H ５ ) ３ , (H ３ C ３ ) ３ Si-N=C=N-Si(C ３ H ３ ) ３ , (H ９ C ４ ) ３ Si-N=C=N-Si(C ４ H ９ ) ３ , (H ７ C ４ ) ３Si-N=C=N-Si(C ４ H ７ ) ３ ,(H ５ C ４ ) ３ Si-N=C=N-Si(C ４ H ５ ) ３ ,(H １１ C ５ ) ３ Si-N=C=N-Si(C ５ H １１ ) ３ ,(H ９ C ５ ) ３ Si-N=C=N-Si(C ５ H ９ ) ３ ,(H ７ C ５ ) ３ Si-N=C=N-Si(C ５ H ７ ) ３ ,(H １３ C ６ ) ３ Si-N=C=N-Si(C ６ H １３ ) ３ ,(H １１ C ６ ) ３ Si-N=C=N-Si(C ６ H １１ ) ３ ,(H ９ C ６ ) ３ Si-N=C=N-Si(C ６ H ９ ) ３ ,(H ５ C ６ ) ３ Si-N=C=N-Si(C ６ H ５ ) ３ ,(H ３ C) ３ Ge-N=C=N-Ge(CH ３ ) ３ ,(H ５ C ２ ) ３ Ge-N=C=N-Ge(C ２ H ５ )３ 、(H ３ C ２ ) ３ Ge-N=C=N-Ge(C ２ H ３ ) ３ 、(H ７ C ３ ) ３ Ge-N=C=N-Ge(C ３ H ７ ) ３ 、(H ５ C ３ ) ３ Ge-N=C=N-Ge(C ３ H ５ ) ３ 、(H ３ C ３ ) ３ Ge-N=C=N-Ge(C ３ H ３ ) ３ 、(H ９ C ４ ) ３ Ge-N=C=N-Ge(C ４ H ９ ) ３ 、(H ７ C ４ ) ３ Ge-N=C=N-Ge(C ４ H ７ ) ３ 、(H ５ C ４ ) ３ Ge-N=C=N-Ge(C ４ H ５ ) ３ 、(H １１ C ５ ) ３ Ge-N=C=N-Ge(C ５ H １１ ) ３ 、(H ９ C ５ ) ３ Ge-N=C=N-Ge(C ５ H ９ ) ３ 、(H ７ C ５ ) ３ Ge-N=C=N-Ge(C ５ H ７ ) ３ 、(H１３ C ６ ) ３ Ge-N=C=N-Ge(C ６ H １３ ) ３ 、(H １１ C ６ ) ３ Ge-N=C=N-Ge(C ６ H １１ ) ３ 、(H ９ C ６ ) ３ Ge-N=C=N-Ge(C ６ H ９ ) ３ 、(H ５ C ６ ) ３ Ge-N=C=N-Ge(C ６ H ５ ) ３ 、(H ３ C) ３ Sn-N=C=N-Sn(CH ３ ) ３ 、(H ５ C ２ ) ３ Sn-N=C=N-Sn(C ２ H ５ ) ３ 、(H ３ C ２ ) ３ Sn-N=C=N-Sn(C ２ H ３ ) ３ 、(H ７ C ３ ) ３ Sn-N=C=N-Sn(C ３ H ７ ) ３ 、(H ５ C ３ ) ３ Sn-N=C=N-Sn(C ３ H ５ ) ３ 、(H ３ C ３ ) ３ Sn-N=C=N-Sn(C ３ H ３ ) ３ 、(H ９ C ４ ) ３Sn-N=C=N-Sn(C ４ H ９ ) ３ , (H ７ C ４ ) ３ Sn-N=C=N-Sn(C ４ H ７ ) ３ , (H ５ C ４ ) ３ Sn-N=C=N-Sn(C ４ H ５ ) ３ , (H １１ C ５ ) ３ Sn-N=C=N-Sn(C ５ H １１ ) ３ , (H ９ C ５ ) ３ Sn-N=C=N-Sn(C ５ H ９ ) ３ , (H ７ C ５ ) ３ Sn-N=C=N-Sn(C ５ H ７ ) ３ , (H １３ C ６ ) ３ Sn-N=C=N-Sn(C ６ H １３ ) ３ , (H １１ C ６ ) ３ Sn-N=C=N-Sn(C ６ H11) ３ , (H ９ C ６ ) ３ Sn-N=C=N-Sn(C ６ H ９ ) ３ , and (H ５ C ６ ) ３ Sn-N=C=N-Sn(C ６ H ５ ) ３ The compound of formula (1) may be one type or a combination of two or more types.

[0015] In this embodiment, the silicon source compound may be any compound containing at least one silicon halide, but for example, halosilanes, carbo(halo)silanes, halosilanes, organo(halo)siloxanes, and oligohalosilanes are preferably used.

[0016] Halosilanes or carbo(halo)silanes can form films containing silicon carbonitride (SiCN) on a substrate. Non-limiting examples of halosilanes or carbo(halo)silanes include the following: <1> Formula (2): SiX ａ R ４－ａ [wherein a is an integer of 2 to 4; X is Cl, Br, or I; and R is independently H, C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl, or C6-C9 allyl], preferably SiH ２ I ２ , SiI ４ , SiBr ４ , or SiH ３ <2> A compound represented by formula (3): [R １ X ２ Si] ２ [CR ２ R ３ ] ｎ (III) [In formula (3), R １ may independently be Cl, H, C1-C10 alkyl, or C2-C10 alkenyl; R ２ , R ３ may independently be H, C1-C3 alkyl, or C2-C3 alkenyl; n is an integer from 1 to 4; and X is Cl, Br, or I. ３ Si) ２ CH ２ or Cl ３ SiCH ２ CH ２ SiCl ３ A compound represented by the formula (3) (Cl ３ Si) ３ CH.

[0017] The halosilane is preferably selected from the group consisting of chlorosilane, bromosilane, iodosilane, dibromosilane, diiodosilane, tetrabromosilane, tetraiodosilane, pentachlorodisilane, pentabromodisilane, hexachlorodisilane, hexabromodisilane, and octachlorotrisilane.

[0018] Halosiloxane or organo(halo)siloxane can form a film containing silicon carbonate nitride (SiOCN). Furthermore, by using halosiloxane or organo(halo)siloxane, a film containing silicon carbonate nitride (SiOCN) can be formed without an additional oxidation step. Furthermore, by using halosiloxane or organo(halo)siloxane, the oxygen content in the film containing silicon carbonate nitride (SiOCN) can be adjusted. Non-limiting examples of halosiloxanes include those represented by Formula (5): X ３ Si—O(SiX ２ ) ｎ Six ３ [In formula (5), X is Cl, Br, or I; and n is an integer from 0 to 4], and preferably (Cl ３ Si) ２ O or Cl ３ SiOSiCl ２ OSiCl ３ Non-limiting examples of organo(halo)siloxanes include compounds of formula (6): ３－ｎ X ｎ Si—O(SiX ２ ) ｍ Six ｎ R ３－ｎ [In formula (6), X is Cl, Br, or I; n is an integer from 0 to 4; and R is independently H, C1-C4 alkyl, C2-C4 alkenyl, or C2-C4 alkynyl].

[0019] Oligohalosilanes are advantageous in forming thin films at lower temperatures and in increasing the rate at which thin films are formed. Non-limiting examples of oligohalosilanes include those represented by formula (7): Si ｎ H ｍ X（２ｎ＋２）－ｍ [In formula (7), n is an integer of 2 to 6; m is an integer of 0 to 13; and X is Cl, Br, or I], and preferably hexachlorodisilane (Si ２ Cl ６ ), pentachlorodisilane (Si ２ HCl ５ ), hexabromodisilane (Si ２ Br ６ ), 1,2-dichlorodisilane (ClH ２ Si-SiH ２ Cl), 1,2-dibromodisilane (BrH ２ Si-SiH ２ Br), 1,2-diiododisilane (IH ２ Si-SiH ２ I) or octachlorotrisilane (Si ３ Cl ８ )

[0020] In this embodiment, the method for forming a silicon-containing film on a substrate may further include (iii) supplying a catalyst onto the substrate. Supplying a catalyst onto the substrate tends to improve the thin film deposition rate and the properties (e.g., uniformity and conformality) of the formed thin film. The catalyst may be supplied simultaneously with the silicon source compound and the carbon / nitrogen source compound, or simultaneously with the carbon / nitrogen source compound alone. Alternatively, the catalyst may be supplied separately from the silicon source compound and the carbon / nitrogen source compound. The timing of supplying the catalyst onto the substrate is arbitrary as long as it does not impair the effects of the present invention. For example, the catalyst can be supplied onto the substrate before supplying other compounds or reagents onto the substrate, simultaneously with supplying other compounds or reagents onto the substrate, and / or after supplying other compounds or reagents onto the substrate. The catalyst may be supplied onto the substrate once or multiple times. When the catalyst is supplied multiple times, the supplied catalysts may be the same or different.

[0021] Any catalyst can be used as long as it does not impair the effects of the present invention, but typically, an organic amine is preferably used. Non-limiting examples of the organic amine include heterocyclic amines (e.g., pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, dimethylpyridine, N- or C-alkylpiperidine, triethylenediamine, 1,8-diazabicyclo[5.4.0]undec-7-ene), trialkylamines (e.g., triethylamine, dimethylamine), diamines (e.g., N,N'-dialkylethylenediamine), and alkylguanidines.

[0022] In this embodiment, the method for forming a silicon-containing film on a substrate may further include (iv) supplying a nitrogen-containing reagent onto the substrate. By including supplying a nitrogen-containing reagent onto the substrate after the step of supplying the carbon / nitrogen source compound of formula (1), the method of this embodiment may have additional advantageous features (e.g., improved film formation rate, lower film formation temperature). Furthermore, the nitrogen content in the silicon-containing film may be increased. Furthermore, residual halogen in the silicon-containing film may be reduced.

[0023] The nitrogen-containing reagent may be: (a) one or more selected from the group consisting of ammonia, amines, hydrazine, alkylhydrazines, hexamethyldisilazanes, and heptamethyldisilazanes; (b) one or more plasmas selected from the group consisting of ammonia, amines, hydrazine, alkylhydrazines, hexamethyldisilazanes, and heptamethyldisilazanes; (c) nitrogen plasma; or (d) a mixture of (b) one or more plasmas selected from the group consisting of ammonia, amines, hydrazine, alkylhydrazines, hexamethyldisilazanes, and heptamethyldisilazanes, or (c) nitrogen plasma and hydrogen plasma. Here, the mixture (d) may be, for example, a plasma obtained from a mixture of nitrogen gas and hydrogen gas. The plasma may be, for example, direct plasma or remote plasma. Using a nitrogen-containing plasma gas with appropriately adjusted properties is advantageous in appropriately adjusting the nitrogen content in the silicon-containing film. Furthermore, by using a nitrogen-containing plasma, it is possible to reduce or inhibit the formation of C═N or C≡N bonds in the film, which affect the electrical properties and reactivity of the silicon-containing film, and it is possible to effectively reduce the dielectric constant in the silicon-containing film and effectively improve the etching resistance.

[0024] In this embodiment, the method for forming a silicon-containing film on a substrate may further include (v) supplying a silane compound (excluding those containing silicon halides) onto the substrate. By supplying a silane compound (excluding those containing silicon halides) onto the substrate, it is possible to reduce halogen contamination in the thin film and improve the silicon content.

[0025] The silicon-containing reagent is typically represented by the formula (8): Si ｎ R ２ｎ＋２ [In the formula (8), R is independently H or methyl; and n is an integer of 1 to 8.]

[0026] In this embodiment, the method for depositing a silicon-containing film on a substrate may further include (vi) providing a boron-containing reagent on the substrate. By providing a boron-containing reagent on the substrate, a boron-free film (e.g., a silicon carbonitride (SiCN) film or a silicon oxynitride (SiOCN) film) can be converted into a boron-containing film (e.g., a silicon boron carbonitride (SiBCN) film or a silicon boron carboxynitride (SiBOCN) film).

[0027] The boron-containing reagent is typically represented by the formula (9): BR ３ [In formula (9), R is independently Cl, Br, I, H, C1-C9 alkyl, allyl, N(CH ３ ) ２ , or N(C ２ H ５ ) ２ The compound is represented by the formula:

[0028] In this embodiment, the at least one silicon source compound and the carbon / nitrogen source compound may be supplied sequentially onto the substrate, or the at least one silicon source compound and the carbon / nitrogen source compound may be supplied simultaneously onto the substrate.

[0029] In this embodiment, the silicon-containing film may be formed on the substrate by chemical vapor deposition (CVD). CVD is a method in which a gas containing the silicon-containing film raw material is supplied to the substrate surface in a reactor, and a thin film is formed on the substrate through a chemical reaction on the substrate surface or in the gas phase. CVD methods that use heat, plasma, and light to induce chemical reactions are also called thermal CVD, plasma-enhanced CVD (PECVD), and photo-enhanced CVD, respectively. A CVD method in which a gas containing two or more raw materials is sequentially introduced and exhausted repeatedly, reacting the raw material molecules adsorbed on the film surface and depositing them layer by layer at the atomic layer level to form a thin film on the substrate is called atomic phase deposition (ALD).

[0030] In the CVD method of this embodiment, preferably, gases containing reactive raw materials are sequentially supplied onto a substrate, and the supplied raw materials undergo chemical reactions on the substrate surface or in the gas phase, thereby forming a thin film on the substrate. An example of the above-mentioned chemical reaction is a reaction in which a silicon source compound containing a silicon halide or a component in a thin film derived therefrom combines with a carbon / nitrogen source compound or a component in a thin film derived therefrom using an amine as a catalyst. This reaction typically releases volatile by-products containing halogen, and a silicon-containing film is formed on the substrate. The content and ratio of carbon and nitrogen atoms in the silicon-containing film can be appropriately adjusted by adjusting the reagents and reaction conditions used in the reaction. The release of the by-products may be accompanied by the release of nitrogen gas or a nitrogen-containing gas, which can reduce the content and ratio of nitrogen atoms in the silicon-containing film. Furthermore, in this reaction, the silicon source compound can be converted into a more reactive molecular species by reacting with the carbon / nitrogen source compound or a component in a thin film derived therefrom. The conversion of the silicon source compound into a more reactive molecular species can improve the deposition rate of the silicon-containing film.

[0031] In this embodiment, each compound or reagent to be supplied onto the substrate can be supplied onto the substrate by supplying a gas containing the compound or reagent onto the substrate. The gases containing the compounds or reagents can be supplied onto the substrate sequentially or simultaneously.

[0032] An exemplary implementation scheme of the CVD method in this embodiment is shown in Figure 1. In Figure 1, the "silicon source gas" is a gas containing at least one silicon source compound described above, the "carbodiimide (I)" is a carbon / nitrogen source compound represented by the above formula (1), the "catalyst gas" is a gas containing the above catalyst, the nitrogen source gas is a gas containing the above nitrogen-containing reagent, and the "oxidizing gas" is a gas containing the above oxidizing agent. In the scheme of Figure 1, a silicon source gas is supplied to a substrate placed in an apparatus, and then the remaining gas is removed. Subsequently, a gas containing carbodiimide (I) and an optional catalyst gas are supplied, and then the remaining gas is removed. Subsequently, a nitrogen source gas is supplied as needed, and then the remaining gas is removed. Subsequently, an oxidizing gas is supplied as needed, and then the remaining gas is removed. This operation constitutes one cycle, and the cycle is repeated until the thickness of the silicon-containing film reaches a desired value, thereby forming a thin layer on the substrate. 1 is merely an example, and in practice, these gases can be supplied at any timing. For example, a small amount of nitrogen-containing gas can be supplied simultaneously with a gas containing carbodiimide (I). In this case, the amount of carbodiimide (I) reacting can be adjusted by setting conditions such that the carbodiimide (I) is not fed enough.

[0033] Furthermore, the CVD method in this embodiment may involve treatment with hydrogen, helium, or argon plasma, or a mixture thereof. In this case, the plasma may be supplied onto the substrate after the gas containing carbodiimide (I) is supplied or after the nitrogen source gas is supplied. The hydrogen, helium, or argon plasma, or a mixture thereof, may be, for example, direct plasma or remote plasma. Treatment using this plasma can reduce or inhibit the formation of C=N or C≡N, which strongly affect the electrical properties and reactivity of the silicon-containing film. Therefore, by performing this treatment as needed, the dielectric constant of the silicon-containing film can be effectively reduced (e.g., k is 2 or less) or the etching resistance can be improved.

[0034] 1 can be used as a method for depositing a silicon-containing film on a substrate, the method including (i) supplying at least one silicon source compound containing at least one silicon halide onto the substrate, and (ii) supplying a carbon-nitrogen source compound represented by Formula (1) onto the substrate. However, the method is not limited to the CVD method according to the operating sequence shown in FIG. 1. For example, the method may include additional in situ or ex situ treatment after deposition. Examples of such additional treatment include: a) post-heat treatment (annealing) at 400-800°C under reduced pressure or in the presence of nitrogen, ammonia, or hydrogen; (b) post-plasma treatment at low temperature (25-400°C) (treatment with nitrogen, ammonia, amine, or hydrazine plasma, hydrogen plasma, or argon or helium plasma); and / or (c) UV treatment at low temperature (25-400°C). By carrying out these additional processes, it may be easier to form a silicon-containing film with desired physicochemical properties on a substrate.In addition, flowable CVD (FCVD) method can also be used as this method.FCVD can effectively fill gaps, so it is suitable for forming shallow trench isolation (STI), intermetal dielectric layer, passivation layer, etc.In addition, this method can also be used to obtain the composition used for spin-on deposition.

[0035] In this embodiment, the reaction between at least one silicon source compound containing at least one silicon halide and the carbon / nitrogen source compound represented by Formula (1) can be carried out, for example, at 750°C or lower, or 450°C or lower, or 110 to 750°C, or 550 to 650°C. When a silicon-containing film is deposited on a substrate by a CVD method, the CVD method can be carried out at these temperatures. That is, by carrying out the method of this embodiment at these temperatures, silicon-containing films having various compositions and / or good physicochemical properties can be formed on a substrate. As described above, by-products of the reaction between at least one silicon source compound containing at least one silicon halide and the carbon / nitrogen source compound represented by Formula (1) are generally highly volatile. Therefore, the by-products can be easily removed from the reaction system. On the other hand, in conventional methods, as described above, salts (e.g., ammonium halides) are generated as by-products of the reaction, but salts generally have low volatility and are not easily removed from the reaction system.

[0036] In this embodiment, the substrate may be any substrate as long as the effects of the present invention are not impaired. The substrate may have any form, for example, a plate-like form, or may be in the form of a powder, granules, or a three-dimensional structure. The substrate may be made of any material, for example, a substrate formed from a material such as silicon, glass, oxide, ceramic, glass ceramic, or a combination thereof. The substrate may also be used for any purpose, for example, an electronic circuit board or a substrate other than an electronic circuit board. The electronic circuit board may be an optoelectronic circuit board. The substrate in this embodiment may be firmly protected by a highly pure and homogeneous silicon-containing film. Furthermore, the substrate may be a substrate with little contamination by by-products from the film formation process, which may adhere to the substrate and adversely affect its function. Therefore, this substrate may have excellent performance, for example, in terms of reliability and durability.

[0037] [Method for manufacturing a substrate having a film formed thereon and a product including the substrate having a film formed thereon] In one embodiment, a method for manufacturing a substrate having a film formed thereon is provided, including the method for forming a silicon-containing film described above. Further, a method for manufacturing a product including the substrate having a film formed thereon is provided, including the method. The silicon-containing film, the method for forming a silicon-containing film, and the substrate are as described above. The substrate having a film formed thereon has a silicon-containing film provided on at least one surface of the substrate. The product including the substrate having a film formed thereon includes at least one substrate having a silicon-containing film provided on at least one surface.

[0038] The substrate on which the film is formed, manufactured in this embodiment, can be used for any application as long as the effects of the present invention are not impaired. For example, the substrate can be used as a component of a product, including an electronic device. Furthermore, a product including the substrate on which the film is formed, manufactured in this embodiment, can be arbitrarily selected as long as the effects of the present invention are not impaired. The product may be an electronic device. Non-limiting examples of electronic devices include computers and their peripherals, liquid crystal displays, organic EL displays, smartphones (mobile phones), car navigation systems, game consoles, televisions, digital cameras / digital video cameras, electronic dictionaries, calculators, printers, electronic musical instruments, etc.

[0039] The present invention will be described below with reference to examples, but is not limited to these examples. Commercially available reagents and equipment referred to in the examples were used according to the manufacturer's instructions or standard procedures, unless otherwise specified.

[0040] [Example 1] Formation of silicon-containing film by CVD method (550°C) Si was used as a gas containing a silicon source compound. ２ Cl ６ N including ２ The gas is a gas containing a carbon / nitrogen source compound and a catalyst (H ３ C) ３ Si-N=C=N-Si(CH ３ ) ３ (BTMSCDI) and N containing pyridine ２The gases were supplied onto the substrate in this order, with ammonia used as the nitrogen-containing reagent. A silicon-containing film was deposited on the silicon substrate by CVD at 550°C using a tubular horizontal flow-type hot-wall quartz reactor. The CVD conditions are shown in Tables 1 and 2.

[0041]

[0042]

[0043] The thickness and deposition rate (GPC) of the silicon-containing film were analyzed, and the results are shown in Table 3. The thickness of the silicon-containing film was measured by ellipsometry.

[0044]

[0045] As shown in Table 3, the silicon-containing film of Example 1 was deposited to a desired thickness at a good deposition rate.

[0046] The constituent elements of the silicon-containing film of Example 1 were analyzed by X-ray photoelectron spectroscopy (XPS) (FIG. 2). The composition of the silicon-containing film of Example 1 after an etching time of 300 seconds was 53.8% Si2p, 36.2% N1s, 7.5% C1s, 2.0% Cl2p, and 0.4% O1s. That is, the silicon-containing film of Example 1 was rich in Si but had a low O content.

[0047] A non-limiting list of exemplary embodiments and combinations of exemplary embodiments of the present disclosure is disclosed below: [1] A method for depositing a silicon-containing film on a substrate, comprising: (i) providing at least one silicon source compound containing at least one silicon halide on the substrate; and (ii) providing a silicon source compound represented by the formula (1): R １ ３ EN=C=N-ER １ ３ [In formula (1), E is independently Si, Ge, or Sn, and R １[2] The method according to [1], wherein E in formula (1) is Si. [3] A method according to [1], wherein R in formula (1) is １ is CH ３[4] The method according to any one of [1] to [3], wherein the at least one silicon source compound is selected from the group consisting of a halosilane, a carbo(halo)silane, a halosiloxane, an organo(halo)siloxane, and an oligohalosilane. [5] The method according to any one of [1] to [3], wherein the at least one silicon source compound is selected from the group consisting of a chlorosilane, a bromosilane, an iodosilane, a dibromosilane, a diiodosilane, a tetrabromosilane, a tetraiodosilane, a pentachlorodisilane, a pentabromodisilane, a hexachlorodisilane, a hexabromodisilane, and an octachlorotrisilane. [6] The method according to any one of [1] to [5], further comprising: (iii) supplying a catalyst onto the substrate. [7] The method according to [6], wherein the catalyst is an organic amine. [8] The method of any of [1] to [7], further comprising (iv) supplying a nitrogen-containing reagent onto the substrate. [9] The method of [8], wherein the nitrogen-containing reagent is (a) one or more selected from the group consisting of ammonia, amines, hydrazine, alkylhydrazines, hexamethyldisilazane, and heptamethyldisilazane; (b) one or more plasmas selected from the group consisting of ammonia, amines, hydrazine, alkylhydrazines, hexamethyldisilazane, and heptamethyldisilazane; (c) nitrogen plasma; or (d) (b) one or more plasmas selected from the group consisting of ammonia, amines, hydrazine, alkylhydrazines, hexamethyldisilazane, and heptamethyldisilazane, or (c) a mixture of nitrogen plasma and hydrogen plasma.

[10] The method of any of [1] to [9], further comprising (v) supplying a silane compound (excluding those containing silicon halide) onto the substrate.

[11] The method according to any one of [1] to

[10] , further comprising (vi) supplying a boron-containing reagent onto the substrate.

[12] The method according to any one of [1] to

[11] , wherein at least one silicon source compound and a carbon / nitrogen source compound are supplied sequentially onto the substrate.

[13] The method according to any one of [1] to

[12] , wherein at least one silicon source compound and a carbon / nitrogen source compound are supplied simultaneously onto the substrate.

[14] The method according to any one of [1] to

[13] , wherein the silicon-containing film is a silicon carbonitride (SiCN) film.

[15] The method according to any one of [1] to

[13] , wherein the silicon-containing film is a silicon carbonate nitride (SiOCN) film.

[16] The method according to any one of [1] to

[13] , wherein the silicon-containing film is a silicon boron carbonitride (SiBCN) film.

[17] The method according to any one of [1] to

[13] , wherein the silicon-containing film is a silicon boron carbonate nitride (SiBOCN) film.

[18] The method according to any one of [1] to

[13] , wherein the silicon-containing film is a silicon carbide (SiC) film.

[19] The method according to any one of [1] to

[18] , wherein the substrate is an electronic circuit board.

[20] A method for manufacturing a substrate having a film formed thereon, comprising the method according to any one of [1] to

[19] .

[21] A method for manufacturing a product having a substrate having a film formed thereon, comprising the method according to

[20] .

[22] The method according to

[21] , wherein the product having the substrate on which the film is formed is an electronic device.

Claims

1. A method for depositing a silicon-containing film on a substrate, comprising: (i) providing at least one silicon source compound containing at least one silicon halide on the substrate; and (ii) providing a silicon source compound represented by the formula (1): R １ ３ EN=C=N-ER １ ３ [In formula (1), E is independently Si, Ge, or Sn; R １ are independently C1-C6 alkyl, C2-C6 alkenyl, C4-C6 cycloalkyl, or C4-C6 cycloalkenyl, respectively, onto a substrate.

2. The method according to claim 1, wherein in formula (1), E is Si.

3. In formula (1), R １ CH ３ The method of claim 1, wherein 4. The method of claim 1, wherein the at least one silicon source compound is selected from the group consisting of halosilanes, carbo(halo)silanes, halosilanes, organo(halo)siloxanes, and oligohalosilanes.

5. The method of claim 1, wherein the at least one silicon source compound is selected from the group consisting of chlorosilanes, bromosilanes, iodosilanes, dibromosilanes, diiodosilanes, tetrabromosilanes, tetraiodosilanes, pentachlorodisilane, pentabromodisilane, hexachlorodisilane, hexabromodisilane, and octachlorotrisilane.

6. The method of claim 1, further comprising: (iii) providing a catalyst on the substrate.

7. The method of claim 6, wherein the catalyst is an organic amine.

8. The method of claim 1, further comprising: (iv) delivering a nitrogen-containing reagent onto the substrate.

9. The method of claim 8, wherein the nitrogen-containing reagent is: (a) one or more selected from the group consisting of ammonia, amines, hydrazine, alkylhydrazines, hexamethyldisilazane, and heptamethyldisilazane; (b) one or more plasmas selected from the group consisting of ammonia, amines, hydrazine, alkylhydrazines, hexamethyldisilazane, and heptamethyldisilazane; (c) a nitrogen plasma; or (d) a mixture of (b) one or more plasmas selected from the group consisting of ammonia, amines, hydrazine, alkylhydrazines, hexamethyldisilazane, and heptamethyldisilazane, or (c) a nitrogen plasma and a hydrogen plasma.

10. The method of claim 1, further comprising: (v) providing a silane compound (other than one containing a silicon halide) on the substrate.

11. The method of claim 1, further comprising: (vi) providing a boron-containing reagent on the substrate.

12. The method of claim 1, wherein at least one of the silicon source compound and the carbon / nitrogen source compound are supplied sequentially onto the substrate.

13. The method of claim 1, wherein at least one of the silicon source compound and the carbon / nitrogen source compound are supplied simultaneously onto the substrate.

14. The method of claim 1, wherein the silicon-containing film is a silicon carbonitride (SiCN) film.

15. The method of claim 1, wherein the silicon-containing film is a silicon carbonate nitride (SiOCN) film.

16. The method of claim 1, wherein the silicon-containing film is a silicon boron carbonitride (SiBCN) film.

17. The method of claim 1, wherein the silicon-containing film is a silicon boron carbonate nitride (SiBOCN) film.

18. The method of claim 1, wherein the silicon-containing film is a silicon carbide (SiC) film.

19. The method of claim 1, wherein the substrate is an electronic circuit board.

20. A method for producing a deposited substrate comprising the method of any one of claims 1 to 19.

21. A method for manufacturing an article having a deposited substrate comprising the method of claim 20.

22. The method of claim 21, wherein the product having the deposited substrate is an electronic device.

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