Method for forming boron carbonitride-containing film

Abstract

[Problem] To provide: a method for efficiently forming a boron carbonitride-containing film on a substrate; a substrate having a boron carbonitride-containing film formed by the method; and a product having the substrate. [Solution] A carbon and nitrogen source compound represented by formula (1): R1 3E-N=C=N-ER1 3 [in formula (1), E is independently Si, Ge, or Sn, and R1 is independently a linear or cyclic C1-C6 alkyl, C2-C6 alkenyl, or C1-C6 alkynyl] or the like is used.

Description

Method for forming a boron carbonitride-containing film

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

[0002] In order to protect substrates used in various industrial products, including electronic devices, a technique for depositing a boron carbonitride-containing film on the substrate has attracted attention.

[0003] Non-Patent Document 1 describes that a boron carbonitride-containing film has excellent physicochemical properties and is useful for protecting substrates used in various industrial products, including electronic devices.

[0004] S. D. Nahate et al., Mater. Today Adv. 8, 100106 (2020)

[0005] The present disclosure provides a method for forming a boron carbonitride-containing film, which can effectively form a boron carbonitride-containing film having excellent properties on a substrate. It also provides a substrate on which a boron carbonitride-containing film having excellent properties has been formed, and a product including the substrate. The method for forming a boron carbonitride-containing film according to the present disclosure is, for example, the following method. A method for forming a boron carbonitride-containing film on a substrate, comprising: (i) supplying at least one boron source compound containing at least one boron halide onto the substrate; and (ii) providing a boron 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 the carbon / nitrogen source compound is provided on a substrate.

[0006] FIG. 1 shows an example of a reaction cycle of the ALD method according to the present disclosure. FIG. 2 shows an example of an implementation scheme of the ALD method according to the present disclosure. FIG. 3 shows an example of an implementation scheme of the ALD method according to the present disclosure, involving treatment with a hydrogen, helium, or argon plasma, or a mixture thereof. FIG. 4 shows capacitance-voltage (CV) curves of a metal-insulator-semiconductor (MIS) element (metal: Pt, insulator: BCN, semiconductor: Si). FIG. 5 shows the results of X-ray photoelectron spectroscopy (XPS) analysis of the components of the boron carbonitride-containing film of Example 1. FIG. 6 shows the results of X-ray photoelectron spectroscopy (XPS) analysis of the components of the boron carbonitride-containing film of Example 2.

[0007] 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.

[0008] 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.

[0009] 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."

[0010] Method for Depositing a Boron Carbonitride-Containing Film In one embodiment, a method for depositing a boron carbonitride-containing film on a substrate comprises: (i) providing at least one boron source compound containing at least one boron halide on the substrate; and (ii): 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

[0011] In this embodiment, at least one boron source compound containing at least one boron halide is reacted with the carbon / nitrogen source compound represented by formula (1) to form a boron carbonitride-containing film. By-products of this reaction (e.g., BCl as the boron source compound) are ３ As a carbon / nitrogen source compound, １ is CH ３The by-product of this reaction (when a compound where E is Si is used, the by-product is chlorotrimethylsilane) is generally not a salt and is highly volatile. Therefore, the by-product of this reaction can be easily removed from the reaction system. On the other hand, in conventional methods, ethylene, methane, acetylene, etc. are typically used as the carbon source compound and ammonia, hydrazine, amine, alkylhydrazine, etc. are typically used as the nitrogen source compound to produce a boron carbonitride-containing film. In this case, a salt (e.g., ammonium halide) is generated as a by-product of the reaction between the boron source compound and the nitrogen source compound. Salts generally have low volatility and are not easily removed from the reaction system. That is, according to the method of this embodiment, the amount of by-products contaminated in the boron carbonitride-containing film can be reduced. Furthermore, the possibility of salt being contaminated in the boron carbonitride-containing film can be reduced or eliminated. Therefore, according to the method of this embodiment, it is possible to form a boron carbonitride-containing film with higher purity and uniformity on the substrate, and the substrate can be more securely protected. 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, and therefore, unlike conventional methods, it is not necessary to separately prepare and use a carbon source compound and a nitrogen source compound. Therefore, according to the method of this embodiment, a boron carbonitride-containing film can be formed on a substrate more simply and efficiently than conventional methods. Furthermore, this embodiment can reduce or eliminate the possibility of forming C—H bonds, N—H bonds, and E—H bonds in the boron carbonitride-containing film, which can adversely affect the sensitivity of the boron carbonitride-containing film to humidity, wet etching, and ashing.

[0012] In this embodiment, the boron carbonitride-containing film is any film containing boron carbonitride. The boron carbonitride-containing film may be a boron carbonitride film or a boron silicon carbonitride film. The boron carbonitride-containing film may also be a mixture of a boron carbonitride film and a boron silicon carbonitride film.

[0013] In this embodiment, in formula (1), E is preferably Si, and R １is 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 ) ３ Si-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 H１１ ) 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 C３ ) 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 、(H １３ 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 ) ３ Sn-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 H５ ) 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.

[0014] In this embodiment, the at least one boron source compound is BCl ３ , BBr ３ , B.I. ３ , C.H. ３ BCl ２ , C.H. ３ Br ２ , C ６ H ５ BCl ２, borazine, 2,4,6-trichloroborazine, 1,3,5-trimethyl-2,4,6-trichloroborazine, and 1,3,5-triethyl-2,4,6-trichloroborazine.

[0015] Also, at least one boron source compound is represented by the formula (2): X ３ Si-[CR ２ R ３ ] ｎ -BX ２ [In formula (2), X is Cl, Br, or I; R ２ , R ３ are independently H, or C1-C6 alkyl, C2-C6 alkenyl, C4-C6 cycloalkyl, or C4-C6 cycloalkenyl; R ２ and R ３ may be bonded to each other via a C-C bond to form a carbocyclic structure; and n is an integer of 1 to 10. In formula (2), X is preferably Cl or Br. ２ , R ３ are independently preferably H or C1-C6 alkyl, more preferably H or CH ３ n is preferably 1 to 3, and more preferably 1.

[0016] The compound represented by formula (2) is Cl ３ Si—CH ２ -BCl ２ , Cl ３ Si—CH(CH ３ )-BCl ２ , Cl ３ Si—C(CH ３ ) ２ -BCl ２ , Cl ３ Si—C(CH ２ )-BCl ２ , Cl ３ Si—C[C(CH ３ ) ２ ]-BCl ２ ,Br ３ Si—CH ２ -BCl ２ ,Br ３Si—CH ２ -BBr ２ ,Br ３ Si—CH(CH ３ )-BCl ２ ,Br ３ Si—CH(CH ３ )-BBr ２ ,Br ３ Si—C(CH ３ ) ２ -BCl ２ ,Br ３ Si—C(CH ３ ) ２ -BBr ２ ,Br ３ Si—C(CH ２ )-BCl ２ ,Br ３ Si—C(CH ２ )-BBr ２ ,Br ３ Si—C[C(CH ３ ) ２ ]-BCl ２ ,Br ３ Si—C[C(CH ３ ) ２ ]-BBr ２ , Cl ３ Si—CH ２ -BBr ２ , Cl ３ Si—CH(CH ３ )-BBr ２ , Cl ３ Si—C(CH ３ ) ２ -BBr ２ , Cl ３ Si—C(CH ２ )-BBr ２ , and Cl ３ Si—C[C(CH ３ ) ２ ]-BBr ２ The compound may be selected from the group consisting of:

[0017] Also, at least one boron source compound is represented by formula (3): X ２ B-A ｎ -BX ２ [In formula (3), (i) A is CR ２ R ３and n is an integer from 1 to 6, or (ii) A is C═CR ２ R ３ and n is 1; R ２ , R ３ are independently H, or C1-C6 alkyl, C2-C6 alkenyl, C4-C6 cycloalkyl, or C4-C6 cycloalkenyl; R ２ and R ３ may be bonded to each other via a C-C bond to form a carbocyclic structure; and X is F, Cl, Br, or I. In formula (3), X is preferably Cl, Br, or I, more preferably Cl or Br. R ２ , R ３ are independently preferably H or C1-C6 alkyl, more preferably H or CH ３ In formula (3), A is CR ２ R ３ In this case, n is preferably 1 or 2, and more preferably 1.

[0018] The compound represented by formula (3) is Cl ２ B-CH ２ -BCl ２ , Cl ２ B-CH(CH ３ )-BCl ２ , Cl ２ B-C (CH ３ ) ２ -BCl ２ , Cl ２ B-C (CH ２ )-BCl ２ , Cl ２ B-C[C(CH ３ ) ２ ]-BCl ２ ,Br ２ B-CH ２ -BBr ２ ,Br ２ B-CH(CH ３ )-BBr ２ ,Br ２ B-C (CH ３ ) ２ -BBr ２ ,Br ２ B-C (CH２ )-BBr ２ ,Br ２ B-C[C(CH ３ ) ２ ]-BBr ２ , Cl ２ B-CH ２ -BBr ２ , Cl ２ B-CH(CH ３ )-BBr ２ , Cl ２ B-C (CH ３ ) ２ -BBr ２ , Cl ２ B-C (CH ２ )-BBr ２ , and Cl ２ B-C[C(CH ３ ) ２ ]-BBr ２ The compound may be selected from the group consisting of:

[0019] In this embodiment, the method for forming a boron carbonitride-containing film on a substrate may further include (iii) supplying a nitrogen-containing reagent onto the substrate. Here, the nitrogen-containing reagent does not include those used as the carbon / nitrogen source compounds described above. Even in this case, the use of the carbon / nitrogen source compound described above can reduce the amount of by-products contaminating the boron carbonitride-containing film. Furthermore, the possibility of salts being contaminated into the boron carbonitride-containing film can be reduced. By further including supplying a nitrogen-containing reagent onto the substrate, the method of this embodiment can have more advantageous features (e.g., improved film formation rate, lower film formation temperature). Furthermore, the nitrogen content in the boron carbonitride-containing film can be increased, thereby improving the physicochemical properties (e.g., dielectric constant, etching resistance) of the boron carbonitride-containing film. Furthermore, residual halogen in the boron carbonitride-containing film can be reduced. The timing of supplying the nitrogen-containing reagent onto the substrate is not particularly limited as long as the effects of the present invention are not impaired, but typically, the nitrogen-containing reagent is supplied onto the substrate after the carbon / nitrogen source compound is supplied. By supplying the nitrogen-containing reagent onto the substrate after the carbon / nitrogen source compound is supplied, the carbon / nitrogen source compound can be sufficiently reacted before the highly reactive nitrogen-containing reagent is supplied onto the substrate.

[0020] The nitrogen-containing reagent may be: (i) one or more selected from the group consisting of ammonia, amines, hydrazine, alkylhydrazines, hexamethyldisilazanes, and heptamethyldisilazanes; (ii) one or more plasmas selected from the group consisting of ammonia, amines, hydrazine, alkylhydrazines, hexamethyldisilazanes, and heptamethyldisilazanes; (iii) nitrogen plasma; or (iv) a mixture of (ii) one or more plasmas selected from the group consisting of ammonia, amines, hydrazine, alkylhydrazines, hexamethyldisilazanes, and heptamethyldisilazanes, or (iii) nitrogen plasma and hydrogen plasma. Here, the mixture of (iv) may be, for example, a plasma obtained from a mixture of nitrogen gas and hydrogen gas. The plasma may be, for example, a direct plasma or a remote plasma. The use of a nitrogen-containing gas having appropriately adjusted properties, including a highly reactive plasma, is advantageous in terms of appropriately adjusting the nitrogen content in the boron carbonitride-containing film. Furthermore, the use of a nitrogen-containing reagent containing plasma can reduce or inhibit the formation of C═N and C≡N bonds in the film, which strongly affect the electrical properties and reactivity of the boron carbonitride-containing film. Therefore, the use of a nitrogen-containing reagent containing plasma can effectively reduce the dielectric constant (e.g., k=2 or less) and effectively improve the etching resistance of the boron carbonitride-containing film.

[0021] In this embodiment, the at least one boron source compound and the carbon / nitrogen source compound may be supplied sequentially onto the substrate, or the at least one boron source compound and the carbon / nitrogen source compound may be supplied simultaneously onto the substrate.

[0022] In this embodiment, the boron carbonitride-containing film may be formed on a substrate by chemical vapor deposition (CVD). CVD is a method in which a gas containing raw materials for the boron carbonitride-containing film 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 thin films are sequentially formed on a substrate by repeating a cycle of sequentially introducing and exhausting gases containing two or more raw materials, causing reaction of raw material molecules adsorbed on the film surface, and depositing them layer by layer at the atomic layer level is called atomic phase deposition (ALD).

[0023] In this embodiment, any CVD method can be used, but the ALD method is preferably used. An exemplary chemical reaction in the ALD method is shown in Figure 1. Figure 1 shows the reaction of BX as a boron source compound. ３ [X is Cl, Br, or I], and R ３ EN=C=N-ER ３ [E is Si, Ge, or Sn, R is CH ３ An example of a chemical reaction using BX ３ is introduced into the reaction system, and a thin layer containing BX on the surface is deposited on the substrate. ３ EN=C=N-ER ３ is introduced into the reaction system and reacts with BX on the thin layer to produce R as a by-product. ３ EX is generated, and at the same time, -N=C=N-ER is formed on B on the thin layer. ３ Furthermore, BX ３ is introduced into the reaction system, and -N=C=N-ER on the thin layer ３ By chemically reacting with ３ As EX is produced, a new thin layer is formed. This series of chemical reactions constitutes one cycle, and the cycle is repeated until the thickness of the boron carbonitride-containing film reaches the desired value, thereby depositing a thin layer on the substrate.

[0024] In this embodiment, (i) at least one boron source compound containing at least one boron halide, (ii) the carbon / nitrogen source compound represented by formula (1), and / or (iii) the nitrogen-containing reagent can be supplied onto the substrate by supplying, onto the substrate, (i) a gas containing at least one boron source compound containing at least one boron halide, (ii) a gas containing the carbon / nitrogen source compound represented by formula (1), and / or (iii) a gas containing the nitrogen-containing reagent, respectively.

[0025] An exemplary implementation scheme of the ALD method in this embodiment is shown in FIG. 2 . In FIG. 2 , the “boron-containing gas” refers to a gas containing at least one of the boron source compounds described above, the “carbodiimide (III)” refers to a carbon-nitrogen source compound represented by the above formula (1), and the “nitrogen-containing gas” refers to a gas containing the above nitrogen-containing reagent. In the scheme of FIG. 2 , a boron-containing gas is supplied to a substrate placed in an apparatus, and the remaining gas is then removed. Subsequently, a gas containing carbodiimide (III) is supplied, and the remaining gas is then removed. Subsequently, a nitrogen-containing gas is supplied as needed, and the remaining gas is then removed. These operations constitute one cycle, and the cycle is repeated until the thickness of the boron carbonitride-containing film reaches a target value, thereby forming a thin layer on the substrate. Note that the timing of supplying the nitrogen-containing gas in FIG. 2 is merely exemplary, and in practice, the nitrogen-containing gas can be supplied at any timing. For example, a small amount of the nitrogen-containing gas can be supplied simultaneously with the gas containing carbodiimide (III). In this case, the amount of carbodiimide (III) reacting can be adjusted by setting conditions such that the carbodiimide (III) is fed insufficiently.

[0026] The ALD method in this embodiment may involve treatment with a plasma of hydrogen, helium, or argon, or a plasma of a mixture thereof. An exemplary implementation scheme of the ALD method in this case is shown in FIG. 3 . In FIG. 3 , the “boron-containing gas” refers to a gas containing at least one of the boron source compounds described above, the “carbodiimide (III)” refers to a carbon-nitrogen source compound represented by the above formula (1), and the “nitrogen plasma-containing gas” refers to a gas containing a plasma of the nitrogen-containing reagent described above. In the scheme of FIG. 3 , a boron-containing gas is supplied to a substrate placed in an apparatus, and the remaining gas is then removed. Subsequently, a gas containing carbodiimide (III) is supplied, and the remaining gas is then removed. Subsequently, a nitrogen-containing gas is supplied as a plasma supply source, if necessary, and the remaining gas is then removed. Subsequently, a plasma of hydrogen, helium, or argon, or a plasma of a mixture thereof, if necessary, is supplied, and the remaining gas is then removed. These operations constitute one cycle, and the cycle is repeated until the thickness of the boron carbonitride-containing film reaches the desired value, thereby depositing the boron carbonitride-containing film on the substrate. 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 and C≡N, which strongly affect the electrical properties and reactivity of the boron carbonitride-containing film. Therefore, by performing this treatment as needed, the dielectric constant of the boron carbonitride-containing film can be effectively reduced (e.g., k is 2 or less) and the etching resistance can be improved.

[0027] Therefore, the ALD method according to the implementation schemes of Figures 2 and 3 can be used as a method for depositing a boron carbonitride-containing film on a substrate, the method including (i) supplying a gas containing at least one boron source compound containing at least one boron halide, and (ii) supplying a gas containing a carbon-nitrogen source compound represented by Formula (1). However, the method is not limited to the ALD method according to the operational sequence shown in Figures 2 and 3. For example, the method may include additional in situ or ex situ processing after deposition. Examples of such additional processing include: a) post-thermal treatment (annealing) at 400-600°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 boron carbonitride-containing film having desired physicochemical properties on a substrate.Furthermore, 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 layers, passivation layers, etc.Furthermore, this method can also be used to obtain compositions for spin-on deposition.Furthermore, this method can be carried out as a spatial ALD method.

[0028] In this embodiment, the reaction between at least one boron source compound containing at least one boron halide and the carbon / nitrogen source compound represented by Formula (1) can be carried out, for example, at 700°C or less, or 450°C or less, or 20 to 700°C, or 250 to 450°C. When a boron carbonitride-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, a boron carbonitride-containing film having good physicochemical properties can be formed on a substrate. On the other hand, conventional methods generally need to be carried out at higher temperatures in order to form a boron carbonitride-containing film having good physicochemical properties on a substrate. Therefore, the method of this embodiment can produce a substrate on which a boron carbonitride-containing film is formed at a relatively low temperature, thereby reducing the adverse effects on the substrate and the burden on facilities associated with high-temperature conditions. As described above, the by-products of the reaction between at least one boron source compound containing at least one boron 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 even under the above-mentioned relatively low-temperature conditions. On the other hand, in the conventional method, 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 under the above-mentioned relatively low-temperature conditions.

[0029] In this embodiment, the dielectric constant of the boron carbonitride-containing film can be, for example, 6 or less, 5 or less, or 2 or less, or 2 to 6, 2 to 5, or 2 to 4. A boron carbonitride-containing film having a dielectric constant within these ranges has low capacitance and is an excellent insulating material. Therefore, by forming a boron carbonitride-containing film having such a dielectric constant on a substrate, the substrate, such as an electronic circuit board, can be effectively insulated.

[0030] According to the method of this embodiment, the amount of oxygen present in the boron carbonitride-containing film can be reduced to, for example, 10 atomic % or less, preferably 1 atomic % or less, based on the entire boron carbonitride-containing film. Oxygen mixed into the boron carbonitride-containing film may degrade the physicochemical properties of the boron carbonitride-containing film, for example, by oxidizing components of the boron carbonitride-containing film. According to the method of this embodiment, such a possibility is reduced.

[0031] 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 can be robustly protected by a highly pure and homogeneous boron carbonitride-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 can have excellent performance, for example, in terms of reliability and durability.

[0032] [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, comprising the method for forming a boron carbonitride-containing film described above. Further, a method for manufacturing a product including a substrate having a film formed thereon is provided, comprising the method. The boron carbonitride-containing film, the method for forming a boron carbonitride-containing film, and the substrate are as described above. The substrate having a film formed thereon has a boron carbonitride-containing film provided on at least one surface of the substrate. The product including a substrate having a film formed thereon includes at least one substrate having a boron carbonitride-containing film provided on at least one surface.

[0033] 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.

[0034] 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.

[0035] [Example 1] BBr by ALD method (450°C) ３ and (H ３ C) ３ Si-N=C=N-Si(CH ３ ) ３ As a gas containing a boron source compound, BBr ３ N including ２ The gas is a gas containing a carbon / nitrogen source compound, and (H ３ C) ３ Si-N=C=N-Si(CH ３ ) ３ N including (BTMSCDI) ２ A boron carbonitride-containing film was deposited on a silicon substrate by ALD using a tubular horizontal flow-type hot-wall quartz reactor at 450° C. The conditions for the ALD process are shown in Tables 1A and 1B.

[0036]

[0037]

[0038] The thickness, deposition rate (GPC), refractive index (633 nm), dielectric constant (k), wet etching resistance (WER), and step coverage of the boron carbonitride-containing film were analyzed. The results are shown in Table 2. The thickness of the boron carbonitride-containing film was measured by ellipsometry. The dielectric constant (k) of the boron carbonitride-containing film was measured by a standard method based on the CV curve shown in FIG.

[0039]

[0040] As shown in Table 2, high wet etching resistance was demonstrated. ２ The WER of the thermal oxide film was 5.6 nm / min.

[0041] The constituent elements of the boron carbonitride-containing film of Example 1 were analyzed by X-ray photoelectron spectroscopy (XPS) ( FIG. 5 ). The composition of the boron carbonitride-containing film of Example 1 after an etching time of 100 seconds was 41.6% B1s, 29.8% N1s, 26.4% C1s, and 0.1% O1s. That is, the boron carbonitride-containing film of Example 1 was rich in B but had a low O content. O mixed into the boron carbonitride-containing film may oxidize the components of the boron carbonitride-containing film, thereby degrading the physicochemical properties of the boron carbonitride-containing film. This possibility is low for the boron carbonitride-containing film of this example, which has a low O content.

[0042] [Example 2] BBr by ALD method (250°C) ３ and (H ３ C) ３ Si-N=C=N-Si(CH ３ ) ３ As in Example 1, BBr was used as a gas containing a boron source compound. ３ N including ２ The gas is a gas containing a carbon / nitrogen source compound, and (H ３ C) ３ Si-N=C=N-Si(CH ３ ) ３ N including (BTMSCDI) ２The gases used were: ALD, a tubular horizontal flow type hot-wall quartz reactor, and a boron carbonitride-containing film was deposited on a silicon substrate at 250° C. The ALD conditions are shown in Tables 3A and 3B.

[0043]

[0044]

[0045] The measured results of the thickness, deposition rate (GPC), refractive index (633 nm), and wet etching resistance (WER) of the thin layer are shown in Table 4.

[0046]

[0047] As shown in Table 4, the boron carbonitride-containing film of Example 2 had a good thickness and was formed at a good film formation rate. In addition, the boron carbonitride-containing film of Example 2 exhibited high wet etching resistance.

[0048] The constituent elements of the boron carbonitride-containing film of Example 2 were analyzed by X-ray photoelectron spectroscopy (XPS) ( FIG. 6 ). The composition of the boron carbonitride-containing film of Example 2 after an etching time of 100 seconds was 46.1% B1s, 35.4% N1s, 17.4% C1s, and 0.6% O1s. That is, the boron carbonitride-containing film of Example 2, like the boron carbonitride-containing film of Example 1, was rich in B but had a low O content.

[0049] A non-limiting list of exemplary embodiments and combinations of exemplary embodiments of the present disclosure are disclosed below: [1] A method for depositing a boron carbonitride-containing film on a substrate, comprising: (i) providing at least one boron source compound containing at least one boron halide on the substrate; and (ii) providing a 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 [1] or [2], wherein the at least one boron source compound is BCl ３ , BBr ３ , B.I. ３ , C.H. ３ BCl ２ , C.H. ３ BBr ２ , C ６ H ５ BCl ２ [5] The method according to any one of [1] to [3], wherein the at least one boron source compound is selected from the group consisting of borazine, 2,4,6-trichloroborazine, 1,3,5-trimethyl-2,4,6-trichloroborazine, and 1,3,5-triethyl-2,4,6-trichloroborazine. ３ Si-[CR ２ R ３ ] ｎ -BX ２ [In formula (2), X is Cl, Br, or I; R ２ , R ３ are independently H, or C1-C6 alkyl, C2-C6 alkenyl, C4-C6 cycloalkyl, or C4-C6 cycloalkenyl; R ２ and R ３ may be bonded to each other via a C-C bond to form a carbocyclic structure; and n is an integer of 1 to 10. [6] The method according to any one of [1] to [3], wherein the compound represented by formula (2) is a compound represented by the formula: Cl ３ Si—CH ２ -BCl ２ , Cl ３ Si—CH(CH ３ )-BCl ２ , Cl ３ Si—C(CH ３ ) ２ -BCl２ 、Cl ３ Si-C(CHH ２ )-BC, ２ 、Cl ３ Si-C[C(CH ３ ) ２ ]-BCl ２ ,Br ３ Si-Cyclospora ２ -BCl ２ ,Br ３ Si-Cyclospora ２ -BBr ２ ,Br ３ Si-CH3 (CH3) ３ )-BC, ２ ,Br ３ Si-CH3 (CH3) ３ )-BBr ２ ,Br ３ Si-C(CHH ３ ) ２ -BCl ２ ,Br ３ Si-C(CHH ３ ) ２ -BBr ２ ,Br ３ Si-C(CHH ２ )-BC, ２ ,Br ３ Si-C(CHH ２ )-BBr ２ ,Br ３ Si-C[C(CH ３ ) ２ ]-BCl ２ ,Br ３ Si-C[C(CH ３ ) ２ ]-BBr ２ 、Cl ３ Si-Cyclospora ２ -BBr ２ 、Cl ３ Si-CH3 (CH3) ３ )-BBr ２ 、Cl ３ Si-C(CHH ３ ) ２ -BBr ２ 、Cl ３ Si-C(CHH ２ )-BBr ２ 、&&*- ３ Si-C[C(CH ３ )２ ]-BBr ２ [7] The method according to [5], wherein the at least one boron source compound is a compound selected from the group consisting of formula (3): X ２ B-A ｎ -BX ２ [In formula (3), (i) A is CR ２ R ３ and n is an integer from 1 to 6, or (ii) A is C═CR ２ R ３ and n is 1; R ２ , R ３ are independently H, or C1-C6 alkyl, C2-C6 alkenyl, C4-C6 cycloalkyl, or C4-C6 cycloalkenyl; R ２ and R ３ may be bonded to each other via a C-C bond to form a carbocyclic structure; and X is F, Cl, Br, or I. [8] The method according to any one of [1] to [3], wherein the compound represented by formula (3) is a compound represented by the formula: Cl ２ B-CH ２ -BCl ２ , Cl ２ B-CH(CH ３ )-BCl ２ , Cl ２ B-C (CH ３ ) ２ -BCl ２ , Cl ２ B-C (CH ２ )-BCl ２ , Cl ２ B-C[C(CH ３ ) ２ ]-BCl ２ ,Br ２ B-CH ２ -BBr ２ ,Br ２ B-CH(CH ３ )-BBr ２ ,Br ２ B-C (CH ３ ) ２ -BBr ２ ,Br ２ B-C (CH ２ )-BBr ２, Br ２ B - C[C(CH ３ ) ２ - BBr ２ , Cl ２ B - CH ２ - BBr ２ , Cl ２ B - CH(CH ３ ) - BBr ２ , Cl ２ B - C(CH ３ ) ２ - BBr ２ , Cl ２ B - C(CH ２ ) - BBr ２ , and Cl ２ B - C[C(CH ３ ) ２ - BBr ２[9] The method of any one of [1] to [8], further comprising: (iii) supplying a nitrogen-containing reagent onto the substrate.

[10] The method of [9], wherein the nitrogen-containing reagent is: (i) one or more selected from the group consisting of ammonia, amines, hydrazine, alkylhydrazines, hexamethyldisilazanes, and heptamethyldisilazanes; (ii) one or more plasmas selected from the group consisting of ammonia, amines, hydrazine, alkylhydrazines, hexamethyldisilazanes, and heptamethyldisilazanes; (iii) nitrogen plasma; or (iv) (ii) one or more plasmas selected from the group consisting of ammonia, amines, hydrazine, alkylhydrazines, hexamethyldisilazanes, and heptamethyldisilazanes, or (iii) a mixture of nitrogen plasma and hydrogen plasma.

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

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

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

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

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

[12] , wherein a boron carbonitride-containing film is formed on the substrate by chemical vapor deposition.

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

[13] , wherein a boron carbonitride-containing film is formed on the substrate by atomic phase deposition.

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

[14] , wherein the boron carbonitride-containing film is a boron carbonitride film.

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

[14] , wherein the boron carbonitride-containing film is a boron silicon carbonitride film.

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

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

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

[17] .

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

[18] .

[20] The method according to

[19] , wherein the product having a substrate having a film formed thereon is an electronic device.

Claims

1. A method for depositing a boron carbonitride-containing film on a substrate, comprising: (i) providing at least one boron source compound containing at least one boron halide on the substrate; and (ii) providing a boron 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. At least one boron source compound is BCl ３ , BBr ３ , B.I. ３ , C.H. ３ BCl ２ , C.H. ３ BBr ２ , C ６ H ５ BCl ２ 2,4,6-trichloroborazine, 1,3,5-trimethyl-2,4,6-trichloroborazine, and 1,3,5-triethyl-2,4,6-trichloroborazine.

5. At least one boron source compound is represented by the formula (2): X ３ Si-[CR ２ R ３ ] ｎ -BX ２ [In formula (2), X is Cl, Br, or I; R ２ , R ３ is independently H, or C1-C6 alkyl, C2-C6 alkenyl, C4-C6 cycloalkyl, or C4-C6 cycloalkenyl; R ２ and R ３ may be bonded to each other via a C-C bond to form a carbocyclic structure; and n is an integer of 1 to 10.

6. The compound represented by the formula (2) is Cl ３ Si-CH ２ -BCl ２ 、Cl ３ Si-CH(CH ３ )-BCl ２ 、Cl ３ Si-C(CH ３ ) ２ -BCl ２ 、Cl ３ Si-C(CH ２ )-BCl ２ 、Cl ３ Si-C[C(CH ３ ) ２ -BCl ２ 、Br ３ Si-CH ２ -BCl ２ 、Br ３ Si-CH ２ -BBr ２ 、Br ３ Si-CH(CH ３ )-BCl ２ 、Br ３ Si-CH(CH ３ )-BBr ２ 、Br ３ Si-C(CH ３ ) ２ -BCl ２ 、Br ３ Si-C(CH ３ ) ２ -BBr ２ 、Br ３ Si-C(CH ２ )-BCl ２ 、Br ３ Si-C(CH ２ )-BBr ２ 、Br ３ Si-C[C(CH ３ ) ２ -BCl ２ 、Br ３ Si-C[C(CH ３ ) ２ -BBr ２ 、Cl ３ Si-CH ２ -BBr ２ 、Cl ３ Si-CH(CH ３ )-BBr ２ , Cl ３ Si-C(CH ３ ) ２ - BBr ２ , Cl ３ Si-C(CH ２ )-BBr ２ , and Cl ３ Si—C[C(CH ３ ) ２ ]-BBr ２ 6. The method of claim 5, wherein the compound is selected from the group consisting of:

7. At least one boron source compound is represented by the formula (3): X ２ B-A ｎ -BX ２ [In the formula (3), (i) A is CR ２ R ３ and n is an integer from 1 to 6; or (ii) A is C═CR ２ R ３ and n is 1; R ２ , R ３ is independently H, or C1-C6 alkyl, C2-C6 alkenyl, C4-C6 cycloalkyl, or C4-C6 cycloalkenyl; R ２ and R ３ may be bonded to each other via a C-C bond to form a carbocyclic ring structure; and X is F, Cl, Br, or I.

8. The compound represented by formula (3) is Cl ２ B-CH ２ -BCl ２ , Cl ２ B-CH (CH ３ )-BCl ２ , Cl ２ B-C (CH ３ ) ２ -BCl ２ , Cl ２ B-C (CH ２ )-BCl ２ , Cl ２ B-C[C(CH ３ ) ２ ]-BCl ２ , B ２ B-CH ２ - BBr ２ , B ２ B-CH (CH ３ )-BBr ２ , B ２ B-C (CH ３ ) ２ - BBr ２ , B ２ B-C (CH ２ )-BBr ２ , B ２ B-C[C(CH ３ ) ２ ]-BBr ２ , Cl ２ B-CH ２ - BBr ２ , Cl ２ B-CH (CH ３ )-BBr ２ , Cl ２ B-C (CH ３ ) ２ - BBr ２ , Cl ２ B-C (CH ２ )-BBr ２ , and Cl ２ B-C[C(CH ３ ) ２ ]-BBr ２ 8. The method of claim 7, wherein the compound is selected from the group consisting of:

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

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

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

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

13. The method of claim 1, wherein the boron carbonitride-containing film is deposited on the substrate by chemical vapor deposition.

14. The method of claim 1, wherein the boron carbonitride-containing film is deposited on the substrate by atomic phase deposition.

15. The method of claim 1, wherein the boron carbonitride-containing film is a boron carbonitride film.

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

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

18. A method for producing a deposited substrate comprising the method of any one of claims 1 to 17.

19. A method for manufacturing an article having a deposited substrate comprising the method of claim 18.

20. The method of claim 19, wherein the product having the deposited substrate is an electronic device.

Images