Method for forming carbon boron nitride-containing film

Abstract

[Problem] To provide a method for efficiently forming a carbon boron nitride-containing film on a substrate; a substrate on which a carbon boron nitride-containing film has been formed by the method; and a product comprising the substrate. [Solution] For example, a carbon-nitrogen source compound represented by formula (1) is used: R13E-N = C = N-ER13 [in formula (1), E is independently Si, Ge, or Sn, and R1 is independently a linear or cyclic C1-C6 alkyl group, C2-C6 alkenyl group, or C1-C6 alkynyl group].

Description

Technical Field

[0001] This disclosure relates to a method for forming a boron carbonitride-containing film on a substrate. Furthermore, this disclosure relates to a substrate on which a boron carbonitride-containing film has been formed, and to a product comprising the substrate. Background Technology

[0002] Attention has been focused on the technology used to form boron carbonitride films on substrates used in various industrial products, including electronic devices, to protect the substrates.

[0003] Non-patent document 1 shows that boron carbonitride-containing films have excellent physical and chemical properties and can be used to protect substrates used in various industrial products, including electronic devices.

[0004] Existing technical documents Non-patent literature

[0005] Non-patent literature 1: SD Nahate et al., Mater. Today Adv. Vol. 8, 100106 (2020) Summary of the Invention

[0006] This disclosure provides a method for forming a boron carbonitride-containing film, which allows for the efficient formation of a boron carbonitride-containing film with excellent properties on a substrate. Furthermore, this disclosure provides a substrate on which a boron carbonitride-containing film with excellent properties has been formed, and a product comprising such a substrate.

[0007] For example, the method for forming a boron carbonitride-containing film according to this disclosure is as follows.

[0008] A method for forming a boron carbonitride-containing film on a substrate, the method comprising: (i) supplying at least one boron source compound containing at least one boron halide onto the substrate; and (ii) The carbon-nitrogen source compound represented by formula (1) is supplied to the substrate: R 1 3E-N=C=N-ER 1 3 In equation (1), E is independently Si, Ge, or Sn, and R 1 Independently, it is C1-C6 alkyl, C2-C6 alkenyl, C4-C6 cycloalkyl, or C4-C6 cycloalkenyl. Attached Figure Description

[0009] [ Figure 1 ] Figure 1An example of the reaction cycle in the ALD process of this disclosure is shown.

[0010] [ Figure 2 ] Figure 2 An example of a scheme for implementing the ALD process in this disclosure is shown.

[0011] [ Figure 3 ] Figure 3 Examples of schemes for implementing the ALD process as disclosed herein are shown, which involve processing with hydrogen, helium, or argon plasma or a mixture thereof.

[0012] [ Figure 4 ] Figure 4 It is the capacitance-voltage (CV) curve of a metal-insulator-semiconductor (MIS) element (metal: Pt, insulator: BCN, semiconductor: Si).

[0013] [ Figure 5 ] Figure 5 The analytical results of the compositional composition of the boron carbonitride-containing membrane according to Example 1, obtained by X-ray photoelectron spectroscopy (XPS), are shown.

[0014] [ Figure 6 ] Figure 6 The results of the compositional analysis of the boron carbonitride-containing membrane according to Example 2, obtained by X-ray photoelectron spectroscopy (XPS), are shown. Detailed Implementation

[0015] The embodiments of this disclosure are described in detail below; however, the scope of the invention is not limited to the embodiments described herein, and various changes can be made without departing from the spirit of the invention. Embodiments may be implemented individually or in combination of more than one. Specific descriptions of one embodiment applicable to other embodiments will not be repeated for those other embodiments.

[0016] The numerical ranges in this disclosure include upper and lower limits indicated by "-" and "from". For example, the statement "AB" or "A to B" using the values ​​A and B means A or greater to B or less. The expressions "AB", "A to B", or "A or greater to B or less" used to indicate stepwise numerical ranges in this disclosure also independently include both "preferably A or greater" and "preferably B or less", where the lower and upper limits can be replaced by other upper and lower limits of numerical ranges. The lower or upper limits of the numerical ranges given in this disclosure are values ​​within the numerical range and can be replaced by the values ​​given in the examples.

[0017] Unless otherwise expressly stated, the singular forms “a / an” and “the” as used in this disclosure may include more than one referent. As used in this disclosure, “and / or” includes both the relationship expressed by “and” and the relationship expressed by “or”. In this disclosure, “comprises” covers “consistent with…”, “substantially composed of…” and “composed of…”, while “consistent with…” covers “substantially composed of…” and “composed of…”, and “substantially composed of…” covers “composed of…”.

[0018] [Method for forming boron carbonitride-containing films] One embodiment provides: A method for forming a boron carbonitride-containing film on a substrate, the method comprising: (i) supplying at least one boron source compound containing at least one boron halide onto the substrate; and (ii): The carbon-nitrogen source compound represented below will be supplied to the substrate: R 1 3E-N=C=N-ER 1 3 In equation (1), E is independently Si, Ge, or Sn, and R 1 Independently, it is C1-C6 alkyl, C2-C6 alkenyl, C4-C6 cycloalkyl, or C4-C6 cycloalkenyl.

[0019] In this embodiment, at least one boron source compound containing at least one boron halide reacts with a carbon-nitrogen source compound represented by formula (1) to result in the formation of a boron carbonitride-containing film. Reaction byproducts (e.g., when BCl3 is used as the boron source compound and when R in formula (1) is used) 1 When a compound containing CH3 and E is Si is used as a carbon-nitrogen source, the reaction byproduct is trichlorosilane. This byproduct is typically not a salt and is highly volatile. Therefore, the reaction byproduct can be readily removed from the reaction system.

[0020] On the other hand, in conventional methods for producing boron carbonitride-containing membranes, ethylene, methane, and acetylene are typically used as carbon source compounds, while ammonia, hydrazine, amines, and alkylhydrazines are used as nitrogen source compounds. In these cases, salts (e.g., ammonium halides) appear as byproducts of the reaction between the boron and nitrogen source compounds. Salts are typically low in volatility and difficult to remove from the reaction system.

[0021] Specifically, the method of this embodiment allows for a reduction in the amount of byproducts that contaminate boron carbonitride (BCN) films. Therefore, potential salt contamination of BCN films can be reduced or eliminated. Consequently, the method of this embodiment also allows for the formation of more uniform, higher-purity BCN films on the substrate, thereby providing stronger substrate protection. Potential structural and functional substrate damage due to byproduct adhesion to the substrate can also be mitigated.

[0022] In this embodiment, a single compound can be used as the carbon-nitrogen source compound, thereby eliminating the need to prepare and use the carbon and nitrogen source compounds separately, unlike conventional methods. Therefore, the method of this embodiment allows for the formation of boron carbonitride films on substrates more easily and efficiently than in conventional methods.

[0023] This embodiment can also reduce or eliminate the potential formation of CH, NH, and EH bonds in boron carbonitride films (which may adversely affect the sensitivity of boron carbonitride films to humidity, wet etching, and ashing).

[0024] In this embodiment, the boron carbonitride-containing film is any film containing boron carbonitride. The boron carbonitride-containing film can be a boron carbonitride film or a silicon boron carbonitride film. Furthermore, the boron carbonitride-containing film can be a mixture of boron carbonitride and silicon boron carbonitride films.

[0025] In this embodiment, E in equation (1) is preferably Si, and R 1 Preferably, it is a C1-C6 alkyl group, and more preferably CH3.

[0026] Non-limiting examples of compounds having formula (1) that may be cited include: (H3C)3Si-N=C=N-Si(CH3)3, (H5C2)3Si-N=C=N-Si(C2H5)3, (H3C2)3Si-N=C=N-Si(C2H3)3, (H7C3)3Si-N=C=N-Si(C3H7)3, (H5C3)3Si-N=C=N-Si(C3H5)3, (H3C3)3Si-N=C=N-Si(C3H3)3, (H9C4)3Si-N=C=N-Si(C4H9)3, (H7C4)3Si-N=C=N-Si(C4H7)3, (H5C4)3Si-N=C=N-Si(C4H5)3, (H 11 C5)3Si-N=C=N-Si(C5H 11 )3, (H9C5)3Si-N=C=N-Si(C5H9)3, (H7C5)3Si-N=C=N-Si(C5H7)3, (H 13 C6)3Si-N=C=N-Si(C6H 13 3. (H)11 C6)3Si-N=C=N-Si(C6H 11 )3、(H9C6)3Si-N=C=N-Si(C6H9)3、(H5C6)3Si-N=C=N-Si(C6H5)3、(H3C)3Ge-N=C=N-Ge(CH3)3、(H5C2)3Ge-N=C=N-Ge(C2H5)3、(H3C2)3Ge-N=C=N-Ge(C2H3)3、(H7C3)3Ge-N=C=N-Ge(C3H7)3、(H5C3)3Ge-N=C=N-Ge(C3H5)3、(H3C3)3Ge-N=C=N-Ge(C3H3)3、(H9C4)3Ge-N=C=N-Ge(C4H9)3、(H7C4)3Ge-N=C=N-Ge(C4H7)3、(H5C4)3Ge-N=C=N-Ge(C4H5)3、(H 11 C5)3Ge-N=C=N-Ge(C5H 11 )3、(H9C5)3Ge-N=C=N-Ge(C5H9)3、(H7C5)3Ge-N=C=N-Ge(C5H7)3、(H 13 C6)3Ge-N=C=N-Ge(C6H 13 )3、(H 11 C6)3Ge-N=C=N-Ge(C6H 11 )3、(H9C6)3Ge-N=C=N-Ge(C6H9)3、(H5C6)3Ge-N=C=N-Ge(C6H5)3、(H3C)3Sn-N=C=N-Sn(CH3)3、(H5C2)3Sn-N=C=N-Sn(C2H5)3、(H3C2)3Sn-N=C=N-Sn(C2H3)3、(H7C3)3Sn-N=C=N-Sn(C3H7)3、(H5C3)3Sn-N=C=N-Sn(C3H5)3、(H3C3)3Sn-N=C=N-Sn(C3H3)3、(H9C4)3Sn-N=C=N-Sn(C4H9)3、(H7C4)3Sn-N=C=N-Sn(C4H7)3、(H5C4)3Sn-N=C=N-Sn(C4H5)3、(H 11 C5)3Sn-N=C=N-Sn(C5H 11 )3、(H9C5)3Sn-N=C=N-Sn(C5H9)3、(H7C5)3Sn-N=C=N-Sn(C5H7)3、(H 13 C6)3Sn-N=C=N-Sn(C6H 13 )3、(H 11C6)3Sn-N=C=N-Sn(C6H11)3, (H9C6)3Sn-N=C=N-Sn(C6H9)3, and (H5C6)3Sn-N=C=N-Sn(C6H5)3. Compounds having formula (1) can be used alone or in combination of two or more.

[0027] In this embodiment, at least one boron source compound may be at least one compound selected from the group consisting of: BCl3, BBr3, BI3, CH3BCl2, CH3Br2, C6H5BCl2, borazine, 2,4,6-trichloroborazine, 1,3,5-trimethyl-2,4,6-trichloroborazine, and 1,3,5-triethyl-2,4,6-trichloroborazine.

[0028] Furthermore, at least one boron source compound can be a compound represented by formula (2): X3Si-[CR 2 R 3 ] n -BX2 In equation (2), X is Cl, Br, or I; R 2 and R 3 Independently, it is H or C1-C6 alkyl, C2-C6 alkenyl, C4-C6 cycloalkyl, or C4-C6 cycloalkenyl; R 2 and R 3 They can bond to each other via C-C bonds to form carbon ring structures; and n is an integer from 1 to 10.

[0029] In equation (2), X is preferably Cl or Br. 2 and R 3 It is preferably H or C1-C6 alkyl, and more preferably H or CH3. n is preferably 1-3, and more preferably 1.

[0030] The compound represented by formula (2) can be a compound selected from the group consisting of: Cl3Si-CH2-BCl2, Cl3Si-CH(CH3)-BCl2, Cl3Si-C(CH3)2-BCl2, Cl3Si-C(CH2)-BCl2, Cl3Si-C[C(CH3)2]-BCl2, Br3Si-CH2-BCl2, Br3Si-CH2-BBr2, Br3Si-CH(CH3)-BCl2, Br3Si-CH(CH3)-BBr2, Br3Si-C(CH3)2- BCl2, Br3Si-C(CH3)2-BBr2, Br3Si-C(CH2)-BCl2, Br3Si-C(CH2)-BBr2, Br3Si-C[C(CH3)2]-BCl2, Br3Si-C[C(CH3)2]- BBr2, Cl3Si-CH2-BBr2, Cl3Si-CH(CH3)-BBr2, Cl3Si-C(CH3)2-BBr2, Cl3Si-C(CH2)-BBr2, and Cl3Si-C[C(CH3)2]-BBr2.

[0031] In addition, at least one boron source compound can be a compound represented by formula (3): X2B-A n -BX2 In equation (3): (i) A is CR 2 R 3 n is an integer from 1 to 6, or (ii) A is C=CR 2 R 3 And n is 1; R 2 and R 3 It is independently H or C1-C6 alkyl, C2-C6 alkenyl, C4-C6 cycloalkyl, or C4-C6 cycloalkenyl; R 2 and R 3 They can bond together via C-C bonds to form a carbon ring structure; and X is F, Cl, Br, or I.

[0032] In formula (3), X is preferably Cl, Br, or I, and more preferably Cl or Br. 2 and R 3 Independently preferably, it is H or a C1-C6 alkyl group, and more preferably H or CH3. In formula (3), when A is CR 2 R 3 When n is used, n is preferably 1 or 2, and more preferably 1.

[0033] The compound represented by formula (3) can be a compound selected from the group consisting of: Cl2B-CH2-BCl2, Cl2B-CH(CH3)-BCl2, Cl2B-C(CH3)2-BCl2, Cl2B-C(CH2)-BCl2, Cl2B-C[C(CH3)2]-BCl2, Br2B-CH2-BBr2, Br2B-CH(CH3)-BBr2, Br2B-C(CH3)2-BBr2, Br2B-C(CH2)-BBr2, Br2B-C[C(CH3)2]-BBr2, Cl2B-CH2-BBr2, Cl2B-CH(CH3)-BBr2, Cl2B-C(CH3)2-BBr2, Cl2B-C(CH2)-BBr2, and Cl2B-C[C(CH3)2]-BBr2.

[0034] In this embodiment, the method for forming a boron carbonitride-containing film on a substrate may further include: (iii) Supply a nitrogen-containing reagent onto the substrate.

[0035] Here, compounds used as the aforementioned carbon-nitrogen source compounds are excluded from the list of nitrogen-containing reagents.

[0036] In this context, using the aforementioned carbon-nitrogen source compounds will also allow for a reduction in the amount of byproducts that contaminate boron carbonitride membranes. Furthermore, potential salt fouling of boron carbonitride membranes can be reduced.

[0037] In this embodiment, further supplying a nitrogen-containing reagent to the substrate can produce more advantageous characteristics, such as a better film formation rate and lower temperatures during film formation. Increasing the nitrogen content in the boron carbonitride-containing film can improve its physical and chemical properties (such as dielectric constant and etch resistance). It can also reduce halogen residues in the boron carbonitride-containing film.

[0038] There is no particular limitation on the timing of supplying the nitrogen-containing reagent to the substrate, as long as it does not impair the effects of the invention; however, typically the nitrogen-containing reagent is supplied to the substrate after the carbon-nitrogen source compound has been supplied. Supplying the nitrogen-containing reagent to the substrate after the carbon-nitrogen source compound allows the carbon-nitrogen source compound to react sufficiently before the highly reactive nitrogen-containing reagent is supplied to the substrate.

[0039] Nitrogen-containing reagents can be: (i) Selected from one or more of the following groups: ammonia, amine, hydrazine, alkylhydrazine, hexamethyldisilazane, and heptamethyldisilazane; (ii) One or more plasmas selected from the group consisting of: ammonia, amine, hydrazine, alkylhydrazine, hexamethyldisilazane, and heptamethyldisilazane; (iii) Nitrogen plasma; or (iv) a mixture of hydrogen plasma and (ii) one or more plasmas selected from the group consisting of ammonia, amine, hydrazine, alkylhydrazine, hexamethyldisilazane, and heptamethyldisilazane, or (iii) nitrogen plasma.

[0040] The mixture (iv) can here be, for example, a plasma obtained from a mixture of nitrogen and hydrogen.

[0041] The plasma can be, for example, direct plasma or remote plasma. Using a nitrogen-containing gas containing highly reactive plasma and with appropriately tuned properties is advantageous in terms of properly adjusting the nitrogen content in boron carbonitride films. Using a nitrogen-containing reagent containing plasma can also reduce or suppress the formation of C=N and C≡N bonds in the film that strongly influence the electrical properties and reactivity of boron carbonitride films. Therefore, using a nitrogen-containing reagent containing plasma will allow for an effective reduction in the dielectric constant of boron carbonitride films (e.g., to no greater than 2 k) and effectively enhance etch resistance.

[0042] In this embodiment, at least one boron source compound and a carbon-nitrogen source compound may be sequentially supplied to the substrate. Alternatively, at least one boron source compound and a carbon-nitrogen source compound may be supplied to the substrate simultaneously.

[0043] In this embodiment, a boron carbonitride-containing film can be formed on a substrate using chemical vapor deposition (CVD). CVD is a process in which a gas containing a boron carbonitride-containing film raw material is supplied to the surface of a substrate in a reactor to form a thin film on the substrate via a chemical reaction on the substrate surface or in the gas phase. CVD processes that use heat, plasma, or light to induce the chemical reaction are respectively called thermal CVD, plasma-enhanced CVD (PECVD), and light-assisted CVD. Atomic layer deposition (ALD) is a CVD process in which a thin film is formed on a substrate via repeated cycles (in which gases containing two or more raw materials are successively introduced and exhausted), and the raw material molecules adsorbed on the film formation surface react, resulting in the sequential deposition of atomic layers.

[0044] In this embodiment, any CVD process can be used, but ALD is preferred. Figure 1 An exemplary chemical reaction in the ALD process is shown.

[0045] Figure 1An example of a chemical reaction is illustrated when BX3 [X is Cl, Br, or I] is used as the boron source compound and R3E-N=C=N-ER3 [E is Si, Ge, or Sn, and R is CH3] is used as the carbon-nitrogen source compound. Specifically, BX3 is introduced into the reaction system, and a thin layer containing BX is deposited on the substrate surface. Next, R3E-N=C=N-ER3 is introduced into the reaction system and reacts chemically with the BX on the thin layer, thereby forming R3EX as a byproduct, and -N=C=N-ER3 bonds to B on the thin layer. BX3 is further introduced into the reaction system and reacts chemically with -N=C=N-ER3 on the thin layer, thereby forming R3EX as a byproduct and forming a new thin layer. This series of chemical reactions constitutes a cycle, which is repeated until the boron carbon nitride film reaches the desired thickness, resulting in the formation of a thin layer on the substrate.

[0046] In this embodiment, (i) at least one boron source compound containing at least one boron halide, (ii) a carbon-nitrogen source compound represented by formula (1), and / or (iii) a nitrogen-containing reagent can be supplied to the substrate by supplying the following to the substrate respectively: (i) a gas containing at least one boron source compound containing at least one boron halide, (ii) a gas containing a carbon-nitrogen source compound represented by formula (1), and / or (iii) a gas containing a nitrogen-containing reagent.

[0047] Figure 2 An exemplary scheme for implementing the ALD process in this embodiment is shown. Figure 2 In this context, “boron-containing gas” is a gas containing at least one boron source compound, “carbodiimide (III)” is a carbon-nitrogen source compound represented by formula (1), and “nitrogen-containing gas” is a gas containing a nitrogen-containing reagent.

[0048] exist Figure 2 In the illustrated scheme, a boron-containing gas is supplied to a substrate already disposed in the apparatus, and then the residual gas is removed. A gas containing carbodiimide(III) is then supplied, and then the residual gas is removed. A nitrogen-containing gas is then supplied as needed, and then the residual gas is removed. These operations constitute a cycle, which is repeated until the boron carbonitride film reaches the desired thickness, resulting in the formation of a thin layer on the substrate.

[0049] Figure 2 The timing of the nitrogen-containing gas supply is merely an example, and in reality, nitrogen-containing gas can be supplied at any time. For instance, nitrogen-containing gas can be supplied in small quantities simultaneously with a gas containing carbodiimide(III). In such cases, the amount of carbodiimide(III) to be reacted can also be adjusted by setting the conditions to a carbodiimide(III) lean feed.

[0050] The ALD process in this embodiment may involve processing with hydrogen, helium, or argon plasma, or a mixture thereof. Figure 3 An exemplary scheme for implementing the ALD process in this case is shown. Figure 3 In this context, “boron-containing gas” is a gas containing at least one boron source compound, “carbodiimide (III)” is a carbon-nitrogen source compound represented by formula (1), and “nitrogen-containing plasma gas” is a gas containing a nitrogen-containing reagent.

[0051] exist Figure 3 In the illustrated scheme, a boron-containing gas is supplied to a substrate already positioned in the apparatus, and then the residual gas is removed. A gas containing carbodiimide (III) is then supplied, and then the residual gas is removed. A nitrogen-containing gas, which serves as a plasma supply source, is then supplied as needed, and then the residual gas is removed. Hydrogen, helium, or argon plasma, or a plasma mixture thereof, is then supplied as needed, followed by the removal of the residual gas. These operations constitute a cycle, which is repeated until the boron carbonitride film reaches the desired thickness, resulting in the formation of a boron carbonitride film on the substrate.

[0052] For example, hydrogen, helium, or argon plasma, or mixtures thereof, can be direct or remote plasma. Such plasma treatment can reduce or suppress the formation of C=N and C≡N bonds that strongly influence the electrical properties and reactivity of boron carbonitride films. Therefore, performing this treatment as needed will allow for an effective reduction in the dielectric constant of boron carbonitride films (e.g., to no greater than 2 k) and enhanced etch resistance.

[0053] Therefore, based on Figure 2 and Figure 3 The ALD process of the embodiment shown can be used as a method for forming a boron carbonitride film on a substrate, the method comprising: (i) supplying a gas comprising at least one boron source compound containing at least one boron halide; and (ii) supplying a gas comprising a carbon-nitrogen source compound represented by formula (1).

[0054] However, this method is not limited to... Figure 2 and Figure 3 The ALD process is shown in the operating procedure.

[0055] For example, the method may include additional in-situ or ex-situ post-deposition treatments. Examples of additional treatments include: (a) post-heat treatment (annealing) at 400°C–600°C under reduced pressure or in the presence of nitrogen, ammonia, or hydrogen; (b) plasma post-treatment at low temperatures (25°C–400°C) (using nitrogen, ammonia, amine, or hydrazine plasma, hydrogen plasma, or argon or helium plasma); and / or (c) UV treatment at low temperatures (25°C–400°C). These additional treatments can facilitate the formation of boron carbonitride films with the desired physical and chemical properties on the substrate.

[0056] Flowable CVD (FCVD) can also be used as a method. FCVD can ensure effective gap filling and is therefore suitable for use during shallow trench isolation (STI) and the formation of intermetallic dielectric or passivation layers.

[0057] This method can also be used to obtain compositions for use in spin coating deposition.

[0058] Furthermore, this method can be performed as a spatial ALD process.

[0059] 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 below, or 450°C or below, or 20°C to 700°C, or 250°C to 450°C. If a boron carbonitride-containing film is deposited on a substrate via a CVD process, the CVD process can be carried out at these temperatures.

[0060] Specifically, the method of this embodiment can be performed at these temperatures to allow the formation of a boron carbonitride film with good physical and chemical properties on a substrate. Conventional methods typically require higher temperatures to form a boron carbonitride film with good physical and chemical properties on a substrate. Therefore, the method of this embodiment enables the production of substrates with a boron carbonitride film formed thereon at relatively low temperatures, which thus mitigates the adverse effects on the substrate and equipment-related requirements associated with high temperatures.

[0061] The byproducts of the reaction between at least one boron source compound containing at least one boron halide and a carbon-nitrogen source compound represented by formula (1) are typically highly volatile, as described above. Therefore, these byproducts can also be readily removed from the reaction system under the relatively low temperature conditions described above. On the other hand, in conventional methods, salts (e.g., ammonium halides) are generated as byproducts of the reaction, as described above; however, salts are typically low in volatility and are not easily removed from the reaction system under the relatively low temperature conditions described above.

[0062] In this embodiment, the relative permittivity of the boron carbonitride-containing film can be, for example, 6 or less, 5 or less, or 2 or less, or 2-6, 2-5, or 2-4.

[0063] Boron carbonitride films with relative permittivity in these ranges exhibit low capacitance and are excellent insulators. Therefore, forming boron carbonitride films with such relative permittivity on a substrate allows for effective insulation of the substrate (e.g., electronic circuit boards).

[0064] According to the method of this embodiment, the amount of oxygen present in the boron carbonitride membrane can be reduced to, for example, 10 at% or less, and preferably 1 at% or less, relative to the entire boron carbonitride membrane.

[0065] Oxygen contaminating boron carbonitride membranes can oxidize the membrane's components, potentially leading to deterioration of the membrane's physical and chemical properties. The method described in this embodiment reduces this possibility.

[0066] In this embodiment, the substrate can be any substrate, provided that the effects of the invention are not compromised. The substrate can be in any form, such as a plate, powder, granules, or a three-dimensional structure. The substrate can be any material and can be formed from materials such as silicon, glass, oxides, ceramics, glass-ceramics, or combinations thereof. The substrate can be used for any application and can be, for example, an electronic circuit board or a board other than an electronic circuit board. The electronic circuit board can be an optoelectronic circuit board.

[0067] The substrate in this embodiment can be more effectively protected by a high-purity, uniform boron carbonitride film. There is also less substrate contamination due to byproducts during the film formation process, which could adhere to the substrate and adversely affect its function. Therefore, the substrate can exhibit better performance, such as in terms of reliability and durability.

[0068] [A method for producing a substrate on which a film has been formed, and a product comprising a substrate on which a film has been formed] One embodiment provides a method for producing a substrate on which a film has been formed, the method comprising the above-described method for forming a boron carbonitride-containing film. A method for producing a product comprising a substrate on which a film has been formed, the method comprising the above-described method. The boron carbonitride-containing film, the method for forming the boron carbonitride-containing film, and the substrate are as described above. The substrate on which a film has been formed has a boron carbonitride-containing film disposed on at least one surface of the substrate. The product comprising a substrate on which a film has been formed includes at least one substrate having a boron carbonitride-containing film disposed on at least one surface thereon.

[0069] The substrate on which the film has been formed, produced in this embodiment, can be used in any application, provided that the effects of the invention are not compromised. For example, the substrate can be used as a component of a product including an electronic device. Any product including the substrate on which the film has been formed, produced in this embodiment, can be selected, provided that the effects of the invention are not compromised. The product can 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, gaming devices, televisions, digital cameras / digital camcorders, electronic dictionaries, calculators, printers, and electronic musical instruments.

[0070] Example

[0071] The invention is illustrated by the following examples, but these examples are not intended to limit the invention. It should be noted that, unless otherwise stated, commercially available reagents and equipment mentioned in the examples should be used according to the manufacturer's instructions or standard methods.

[0072] [Example 1] Boron carbonitride films were formed by ALD (450°C) using BBr3 and (H3C)3Si-N=C=N-Si(CH3)3. N2 gas containing BBr3 was used as the gas containing the boron source compound, and N2 gas containing (H3C)3Si-N=C=N-Si(CH3)3 (BTMSCDI) was used as the gas containing the carbon-nitrogen source compound.

[0073] Boron carbonitride films were formed on silicon substrates using a tubular horizontal flow hot-wall quartz reactor at 450°C via ALD. The conditions in the ALD are shown in Tables 1A and 1B.

[0074] [Table 1A]

[0075] [Table 1B]

[0076] The thickness, deposition rate (GPC), refractive index (633 nm), dielectric constant (k), wet etch resistance (WER), and step coverage of the boron carbonitride-containing film were analyzed. The results are shown in Table 2.

[0077] The thickness of the boron carbonitride-containing film was determined by elliptic polarization.

[0078] based on Figure 4 The CV curves shown are obtained by measuring the dielectric constant (k) of the boron carbonitride-containing film using standard methods.

[0079] [Table 2]

[0080] High resistance to wet etching was demonstrated, as shown in Table 2. It should be noted that the WER of the SiO2 thermal oxide film, measured under the same conditions, was 5.6 nm / min.

[0081] Furthermore, the elemental composition of the boron carbonitride-containing film in Example 1 was analyzed by X-ray photoelectron spectroscopy (XPS). Figure 5 The boron carbonitride film of Example 1 (etching time: 100 seconds) comprises 41.6% B1s, 29.8% N1s, 26.4% C1s, and 0.1% O1s. Specifically, the boron carbonitride film of Example 1 has a rich B content but a low O content.

[0082] O2 contamination of boron carbonitride membranes can oxidize the membrane's components, potentially leading to deterioration of the membrane's physical and chemical properties. However, the likelihood of this occurring in the boron carbonitride membrane with low oxygen content in this example is very small.

[0083] [Example 2] Boron carbonitride films were formed by ALD (250°C) using BBr3 and (H3C)3Si-N=C=N-Si(CH3)3. In the same manner as in Example 1, N2 gas containing BBr3 was used as the gas containing the boron source compound, and N2 gas containing (H3C)3Si-N=C=N-Si(CH3)3 (BTMSCDI) was used as the gas containing the carbon-nitrogen source compound.

[0084] Boron carbonitride films were formed on silicon substrates using a tubular horizontal flow hot-wall quartz reactor at 250°C via ALD. The conditions in the ALD are shown in Tables 3A and 3B.

[0085] [Table 3A]

[0086] [Table 3B]

[0087] The results of measuring the film thickness, film formation rate (GPC), refractive index (633 nm), and wet etch resistance (WER) are shown in Table 4.

[0088] [Table 4]

[0089] As shown in Table 4, the boron carbonitride-containing film of Example 2 has a good thickness and is formed at a good film-forming rate.

[0090] Furthermore, the boron carbonitride-containing film in Example 2 exhibits high resistance to wet etching.

[0091] Furthermore, the elemental composition of the boron carbonitride-containing film in Example 2 was analyzed by X-ray photoelectron spectroscopy (XPS). Figure 6 Example 2 (etching time: 100 seconds) shows a boron carbonitride film composition comprising 46.1% B1s, 35.4% N1s, 17.4% C1s, and 0.6% O1s. Specifically, in the same manner as the boron carbonitride film of Example 1, the boron carbonitride film of Example 2 has a high B content but a low O content.

[0092] The following discloses a non-limiting list of exemplary embodiments and combinations of exemplary embodiments.

[0093] [1] A method for forming a boron carbonitride-containing film on a substrate, the method comprising: (i) supplying at least one boron source compound containing at least one boron halide onto the substrate; and (ii) The carbon-nitrogen source compound represented by formula (1) is supplied to the substrate: R 1 3E-N=C=N-ER 1 3 In equation (1), E is independently Si, Ge, or Sn, and R 1 Independently, it is C1-C6 alkyl, C2-C6 alkenyl, C4-C6 cycloalkyl, or C4-C6 cycloalkenyl.

[0094] [2] According to the method described in [1], E in equation (1) is Si.

[0095] [3] According to the method described in [1] or [2], wherein R in equation (1) 1 It is CH3.

[0096] [4] 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: BCl3, BBr3, BI3, CH3BCl2, CH3BBr2, C6H5BCl2, borazine, 2,4,6-trichloroborazine, 1,3,5-trimethyl-2,4,6-trichloroborazine, and 1,3,5-triethyl-2,4,6-trichloroborazine.

[0097] [5] The method according to any one of [1] to [3], wherein the at least one boron source compound is a compound represented by formula (2): X3Si-[CR 2 R 3 ] n -BX2 In equation (2), X is Cl, Br, or I; R 2 and R 3 Independently, it is H or C1-C6 alkyl, C2-C6 alkenyl, C4-C6 cycloalkyl, or C4-C6 cycloalkenyl; R 2 and R 3 They can bond to each other via C-C bonds to form carbon ring structures; and n is an integer from 1 to 10.

[0098] [6] According to the method described in [5], wherein the compound represented by formula (2) is a compound selected from the group consisting of: Cl3Si-CH2-BCl2, Cl3Si-CH(CH3)-BCl2, Cl3Si-C(CH3)2-BCl2, Cl3Si-C(CH2)-BCl2, Cl3Si-C[C(CH3)2]-BCl2, Br3Si-CH2-BCl2, Br3Si-CH2-BBr2, Br3Si-CH(CH3)-BCl2, Br3Si-CH(CH3)-BBr2, Br3Si-C(CH3)2-B Cl2, Br3Si-C(CH3)2-BBr2, Br3Si-C(CH2)-BCl2, Br3Si-C(CH2)-BBr2, Br3Si-C[C(CH3)2]-BCl2, Br3Si-C[C(CH3)2]- BBr2, Cl3Si-CH2-BBr2, Cl3Si-CH(CH3)-BBr2, Cl3Si-C(CH3)2-BBr2, Cl3Si-C(CH2)-BBr2, and Cl3Si-C[C(CH3)2]-BBr2.

[0099] [7] The method according to any one of [1] to [3], wherein the at least one boron source compound is a compound represented by formula (3): X2B-A n -BX2 In equation (3): (i) A is CR 2 R 3 n is an integer from 1 to 6, or (ii) A is C=CR 2 R 3 And n is 1; R 2 and R 3 It is independently H or C1-C6 alkyl, C2-C6 alkenyl, C4-C6 cycloalkyl, or C4-C6 cycloalkenyl; R 2 and R 3 They can bond together via C-C bonds to form a carbon ring structure; and X is F, Cl, Br, or I.

[0100] [8] According to the method described in [7], wherein the expression is derived from equation (3). The compounds represented are those selected from the group consisting of: Cl2B-CH2-BCl2, Cl2B-CH(CH3)-BCl2, Cl2B-C(CH3)2-BCl2, Cl2B-C(CH2)-BCl2, Cl2B-C[C(CH3)2]-BCl2, Br2B-CH2-BBr2, Br2B-CH(CH3)-BBr2, Br2B-C(CH3)2-BBr2, Br2B-C(CH2)-BBr2, Br2B-C[C(CH3)2]-BBr2, Cl2B-CH2-BBr2, Cl2B-CH(CH3)-BBr2, Cl2B-C(CH3)2-BBr2, Cl2B-C(CH2)-BBr2, and Cl2B-C[C(CH3)2]-BBr2.

[0101] [9] The method according to any one of [1] to [8], the method further comprising: (iii) A nitrogen-containing reagent is supplied to the substrate.

[0102]

[10] According to the method described in [9], wherein the nitrogen-containing reagent is: (i) Selected from one or more of the following groups: ammonia, amine, hydrazine, alkylhydrazine, hexamethyldisilazane, and heptamethyldisilazane; (ii) One or more plasmas selected from the group consisting of: ammonia, amine, hydrazine, alkylhydrazine, hexamethyldisilazane, and heptamethyldisilazane; (iii) Nitrogen plasma; or (iv) a mixture of hydrogen plasma and (ii) one or more plasmas selected from the group consisting of ammonia, amine, hydrazine, alkylhydrazine, hexamethyldisilazane, and heptamethyldisilazane, or (iii) nitrogen plasma.

[0103]

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

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

[0104]

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

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

[0105]

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

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

[0106]

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

[13] , wherein the boron carbonitride film is formed on the substrate by an atomic layer deposition process.

[0107]

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

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

[0108]

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

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

[0109]

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

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

[0110]

[18] A method for producing a substrate on which a film has been formed, the method comprising the method according to any one of [1] to

[17] .

[0111]

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

[18] .

[0112]

[20] According to the method of

[19] , the product comprising a substrate on which a film has been formed is an electronic device. Claims (as amended under Article 19 of the Treaty) 1. A method for forming a boron carbonitride film on a substrate by chemical vapor deposition or atomic layer deposition, the method comprising: (i) supplying at least one boron source compound containing at least one boron halide onto the substrate; and (ii) The carbon-nitrogen source compound represented by formula (1) is supplied to the substrate: R 1 3E-N=C=N-ER 1 3 In equation (1), E is independently Si, Ge, or Sn, and R 1 Independently, it is C1-C6 alkyl, C2-C6 alkenyl, C4-C6 cycloalkyl, or C4-C6 cycloalkenyl. 2. The method according to claim 1, wherein E in formula (1) is Si. 3. The method according to claim 1, wherein R in formula (1)1 It is CH3. 4. The method according to claim 1, wherein the at least one boron source compound is selected from the group consisting of: BCl3, BBr3, BI3, CH3BCl2, CH3BBr2, C6H5BCl2, borazine, 2,4,6-trichloroborazine, 1,3,5-trimethyl-2,4,6-trichloroborazine, and 1,3,5-triethyl-2,4,6-trichloroborazine. 5. The method according to claim 1, wherein the at least one boron source compound is a compound represented by formula (2): X3Si-[CR 2 R 3 ] n -BX2 In equation (2), X is Cl, Br, or I; R 2 and R 3 Independently, it is H or C1-C6 alkyl, C2-C6 alkenyl, C4-C6 cycloalkyl, or C4-C6 cycloalkenyl; R 2 and R 3 They can bond to each other via C-C bonds to form carbon ring structures; and n is an integer from 1 to 10. 6. The method according to claim 5, wherein the compound represented by formula (2) is a compound selected from the group consisting of: Cl3Si-CH2-BCl2, Cl3Si-CH(CH3)-BCl2, Cl3Si-C(CH3)2-BCl2, Cl3Si-C(CH2)-BCl2, Cl3Si-C[C(CH3)2]-BCl2, Br3Si-CH2-BCl2, Br3Si-CH2-BBr2, Br3Si-CH(CH3)-BCl2, Br3Si-CH(CH3)-BBr2, Br3Si-C(CH3)2-B Cl2, Br3Si-C(CH3)2-BBr2, Br3Si-C(CH2)-BCl2, Br3Si-C(CH2)-BBr2, Br3Si-C[C(CH3)2]-BCl2, Br3Si-C[C(CH3)2]- BBr2, Cl3Si-CH2-BBr2, Cl3Si-CH(CH3)-BBr2, Cl3Si-C(CH3)2-BBr2, Cl3Si-C(CH2)-BBr2, and Cl3Si-C[C(CH3)2]-BBr2. 7. The method according to claim 1, wherein the at least one boron source compound is a compound represented by formula (3): X2B-A n -BX2 In Equation 3: (i) A is CR 2 R 3 n is an integer from 1 to 6, or (ii) A is C=CR 2 R 3 And n is 1; R 2 and R 3 It is independently H or C1-C6 alkyl, C2-C6 alkenyl, C4-C6 cycloalkyl, or C4-C6 cycloalkenyl; R 2 and R 3 They can bond together via C-C bonds to form a carbon ring structure; and X is F, Cl, Br, or I. 8. The method according to claim 7, wherein the compound represented by formula (3) is a compound selected from the group consisting of: Cl2B-CH2-BCl2, Cl2B-CH(CH3)-BCl2, Cl2B-C(CH3)2-BCl2, Cl2B-C(CH2)-BCl2, Cl2B-C[C(CH3)2]-BCl2, Br2B-CH2-BBr2, Br2B-CH(CH3)-BBr2, Br2B-C(CH3)2-BBr2, Br2B-C(CH2)-BBr2, Br2B-C[C(CH3)2]-BBr2, Cl2B-CH2-BBr2, Cl2B-CH(CH3)-BBr2, Cl2B-C(CH3)2-BBr2, Cl2B-C(CH2)-BBr2, and Cl2B-C[C(CH3)2]-BBr2. 9. The method according to claim 1, further comprising: (iii) Supply a nitrogen-containing reagent onto the substrate. 10. The method according to claim 9, wherein the nitrogen-containing reagent is: (i) Selected from one or more of the following groups: ammonia, amine, hydrazine, alkylhydrazine, hexamethyldisilazane, and heptamethyldisilazane; (ii) One or more plasmas selected from the group consisting of: ammonia, amine, hydrazine, alkylhydrazine, hexamethyldisilazane, and heptamethyldisilazane; (iii) Nitrogen plasma; or (iv) a mixture of hydrogen plasma and (ii) one or more plasmas selected from the group consisting of ammonia, amine, hydrazine, alkylhydrazine, hexamethyldisilazane, and heptamethyldisilazane, or (iii) nitrogen plasma. 11. The method according to claim 1, wherein the at least one boron source compound and the carbon-nitrogen source compound are sequentially supplied to the substrate. 12. The method according to claim 1, wherein the at least one boron source compound and the carbon-nitrogen source compound are simultaneously supplied to the substrate. 13. Delete 14. Delete 15. The method according to claim 1, wherein the boron carbonitride-containing membrane is a boron carbonitride membrane. 16. The method according to 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 substrate on which a film has been formed, the method comprising the method according to any one of claims 1 to 17. 19. A method for producing a product comprising a substrate having a film formed thereon, the method comprising the method according to claim 18. 20. The method of claim 19, wherein the product comprising a substrate on which a film has been formed is an electronic device.

Claims

1. A method for forming a boron carbonitride-containing film on a substrate, the method comprising: (i) Supplying at least one boron source compound containing at least one boron halide onto the substrate; as well as (ii) The carbon-nitrogen source compound represented by formula (1) is supplied to the substrate: R 1 3E-N=C=N-ER 1 3 In equation (1), E is independently Si, Ge, or Sn, and R 1 Independently, it is C1-C6 alkyl, C2-C6 alkenyl, C4-C6 cycloalkyl, or C4-C6 cycloalkenyl.

2. The method according to claim 1, wherein, In equation (1), E is Si.

3. The method according to claim 1, wherein, R in equation (1) 1 It is CH3.

4. The method according to claim 1, wherein, The at least one boron source compound is selected from the group consisting of: BCl3, BBr3, BI3, CH3BCl2, CH3BBr2, C6H5BCl2, borazine, 2,4,6-trichloroborazine, 1,3,5-trimethyl-2,4,6-trichloroborazine, and 1,3,5-triethyl-2,4,6-trichloroborazine.

5. The method according to claim 1, wherein, The at least one boron source compound is a compound represented by formula (2): X3Si-[CR 2 R 3 ] n -BX2 In equation (2), X is Cl, Br, or I; R 2 and R 3 Independently, it is H or C1-C6 alkyl, C2-C6 alkenyl, C4-C6 cycloalkyl, or C4-C6 cycloalkenyl; R 2 and R 3 They can bond to each other via C-C bonds to form carbon ring structures; and n is an integer from 1 to 10.

6. The method according to claim 5, wherein, The compound represented by formula (2) is a compound selected from the group consisting of: Cl3Si-CH2-BCl2, Cl3Si-CH(CH3)-BCl2, Cl3Si-C(CH3)2-BCl2, Cl3Si-C(CH2)-BCl2, Cl3Si-C[C(CH3)2]-BCl2, Br3Si-CH2-BCl2, Br3Si-CH2-BBr2, Br3Si-CH(CH3)-BCl2, Br3Si-CH(CH3)-BBr2, Br3Si-C(CH3)2-B Cl2, Br3Si-C(CH3)2-BBr2, Br3Si-C(CH2)-BCl2, Br3Si-C(CH2)-BBr2, Br3Si-C[C(CH3)2]-BCl2, Br3Si-C[C(CH3)2]- BBr2, Cl3Si-CH2-BBr2, Cl3Si-CH(CH3)-BBr2, Cl3Si-C(CH3)2-BBr2, Cl3Si-C(CH2)-BBr2, and Cl3Si-C[C(CH3)2]-BBr2.

7. The method according to claim 1, wherein, The at least one boron source compound is a compound represented by formula (3): X2B-A n -BX2 In Equation 3: (i) A is CR 2 R 3 n is an integer from 1 to 6, or (ii) A is C=CR 2 R 3 And n is 1; R 2 and R 3 It is independently H or C1-C6 alkyl, C2-C6 alkenyl, C4-C6 cycloalkyl, or C4-C6 cycloalkenyl; R 2 and R 3 They can bond together via C-C bonds to form a carbon ring structure; and X is F, Cl, Br, or I.

8. The method according to claim 7, wherein, The compound represented by formula (3) is a compound selected from the group consisting of: Cl2B-CH2-BCl2, Cl2B-CH(CH3)-BCl2, Cl2B-C(CH3)2-BCl2, Cl2B-C(CH2)-BCl2, Cl2B-C[C(CH3)2]-BCl2, Br2B-CH2-BBr2, Br2B-CH(CH3)-BBr2, Br2B-C(CH3)2-BBr2, Br2B-C(CH2)-BBr2, Br2B-C[C(CH3)2]-BBr2, Cl2B-CH2-BBr2, Cl2B-CH(CH3)-BBr2, Cl2B-C(CH3)2-BBr2, Cl2B-C(CH2)-BBr2, and Cl2B-C[C(CH3)2]-BBr2.

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

10. The method according to claim 9, wherein, The nitrogen-containing reagent is: (i) Selected from one or more of the following groups: ammonia, amine, hydrazine, alkylhydrazine, hexamethyldisilazane, and heptamethyldisilazane; (ii) One or more plasmas selected from the group consisting of: ammonia, amine, hydrazine, alkylhydrazine, hexamethyldisilazane, and heptamethyldisilazane; (iii) Nitrogen plasma; or (iv) a mixture of hydrogen plasma and (ii) one or more plasmas selected from the group consisting of ammonia, amine, hydrazine, alkylhydrazine, hexamethyldisilazane, and heptamethyldisilazane, or (iii) nitrogen plasma.

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

12. The method according to claim 1, wherein, The at least one boron source compound and the carbon-nitrogen source compound are simultaneously supplied to the substrate.

13. The method according to claim 1, wherein, The boron carbon nitride film was formed on the substrate using a chemical vapor deposition process.

14. The method according to claim 1, wherein, The boron carbon nitride film was formed on the substrate using an atomic layer deposition process.

15. The method according to claim 1, wherein, The boron carbonitride-containing membrane is a boron carbonitride membrane.

16. The method according to claim 1, wherein, The boron carbonitride-containing membrane is a boron silicon carbonitride membrane.

17. The method according to claim 1, wherein, The substrate is an electronic circuit board.

18. A method for producing a substrate on which a film has been formed, the method comprising the method according to any one of claims 1 to 17.

19. A method for producing a product comprising a substrate having a film formed thereon, the method comprising the method according to claim 18.

20. The method according to claim 19, wherein, The product, including the substrate on which a film has been formed, is an electronic device.

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