Polycarbosilazane, composition containing same, and method for producing silicon-containing film using same

Abstract

To provide a polycarbosilazane making it possible to form a silicon-containing film having resistance to acid etching, and a composition comprising the polycarbosilazane.SOLUTION: The present invention provides a polycarbosilazane comprising repeating units of -[R1R2Si-(CH2)n]- and -(R3R4Si-NR5)- (where, R1, R2, R3 and R4 are each independently a single bond, hydrogen or C1-4 alkyl; R5 is independently a single bond or hydrogen; and n is 1-2, and a composition comprising the polycarbosilazane. The present invention also provides a method for forming a silicon-containing film, comprising coating the composition above a substrate and heating.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composition comprising polycarborazane and polycarbosilazane, which can form a silicon-containing film that is resistant to acid etching in a manufacturing process for semiconductor devices, etc. The present invention also relates to a method for forming a silicon-containing film using the composition. [Background technology]

[0002] In the manufacture of electronic devices, particularly semiconductor devices, interlayer insulating films are formed between transistor elements and bit lines, between bit lines and capacitors, between capacitors and metal wiring, between multiple metal wirings, and the like. Furthermore, isolation trenches formed on the surface of a substrate or the like may be filled with insulating material. Furthermore, after semiconductor elements are formed on the surface of a substrate, a covering layer is formed using an encapsulating material, and packaging is performed. Interlayer insulating films and covering layers are often formed from silicon-containing materials.

[0003] To form silicon-containing films such as silicon-based films, silicon nitride films, silicon carbide films, and silicon carbonitride films, chemical vapor deposition (CVD), sol-gel processes, and methods involving applying and heating a composition containing a silicon-containing polymer are used. Among these methods, the method of forming a silicon-containing film using a composition is frequently used because it is a relatively simple method. To form a silicon-containing film, a composition containing a silicon-containing polymer such as polysilazane, polysiloxane, polysiloxazane, polycarbosilane, or polysilane is applied above the surface of a substrate or the like, and the polymer is heated to harden and form the silicon-containing film.

[0004] There is a need for materials that can fill narrow, high aspect ratio trenches in semiconductor devices and that can be converted upon curing into acid-resistant silicon-containing films. Additionally, there is a strong demand for materials that have low residual stress after the curing process.

[0005] U.S. Patent No. 5,011,801 discloses a method for preparing ethylene-bridged chlorosilazane polymers by reacting 1,2-bis(organyldichlorosilyl)ethane with ammonia. The ethylene-bridged chlorosilazane polymers are converted to polysilazanes by reaction with ammonia. The polysilazanes can be converted to silicon nitride-containing ceramic materials by pyrolysis under an inert atmosphere.

[0006] JP 2014-201734 A discloses a composition used for producing a glassy film, and that the use of this composition enables the production of a flexible glassy film by low-temperature curing. The composition used for producing the glassy film contains -[(NR 3 ) n -Si(R 1 3-n )-(CR 4 2) p -Si(R 2 3-m )(-]-) m where R 1 ~R 4 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or a phenyl group which may have a substituent, provided that R 1 and R 2 are not simultaneously hydrogen atoms; p is an integer of 1 to 6; n and m are each independently an integer of 1 to 3;

[0007] U.S. Patent Application Publication No. 2019 / 0040279 discloses a Si-containing film-forming composition for producing films with desirable electrical and physical properties. The composition has the formula [—NR—R 4 R 5 Si-(CH2) t -SiR 2 R 3 ] n wherein t=1 to 4; n=2 to 400; R, R 2 , R 3 , R 4 and R5 are independently H, a hydrocarbon group, or an alkylamino group, with the proviso that R 2 , R 3 , R 4 and R 5 at least one of is H; and R is independently H, a hydrocarbon group, or a silyl group.

[0008] U.S. Patent No. 4,869,854 discloses a method for preparing organosilazanes by ammonolysis of a mixture of 1,2-bis(trichlorosilyl)ethane, methyldichlorosilane, and methyltrichlorosilane. The ammonolysis product is polymerized using a basic catalyst. The organosilazane polymer is sintered to obtain a ceramic material composed of silicon carbide and silicon nitride. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] U.S. Patent No. 5,011,801 [Patent Document 2] Japanese Patent Application Publication No. 2014-201734 [Patent Document 3] US Patent Application Publication No. 2019 / 0040279 [Patent Document 4] U.S. Patent No. 4,869,854 Summary of the Invention

[0010] One aspect of the present invention provides a polycarbosilazane capable of forming a silicon-containing film that is resistant to acid etching during the manufacturing process of semiconductor devices and the like.

[0011] Another aspect of the present invention provides a composition comprising polycarbosilazane and a solvent that is capable of filling narrow, high aspect ratio trenches and producing thick silicon-containing films.

[0012] Yet another aspect of the present invention provides a method for producing a silicon-containing film having excellent electrical properties.

[0013] Yet another aspect of the present invention provides a method for fabricating an electronic device having a silicon-containing film with excellent electrical properties.

[0014] One aspect of the present invention provides a polycarbosilazane comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2): [ka] where R 1 , R 2 , R 3 , and R 4 are each independently a single bond, hydrogen, or C 1-4 alkyl; R 5 are each independently a single bond or hydrogen; and n is 1 to 2.

[0015] Polycarbosilazane is 1 In the H-NMR spectrum, the ratio of the area intensity from 1.7 to 2.2 ppm to the sum of the area intensity from 1.7 to 2.2 ppm (hereinafter sometimes referred to as "CH intensity") and the area intensity from 1.0 to 1.6 ppm (hereinafter sometimes referred to as "NH intensity") is 0.05 to 0.5. 1 The signals at 1.7 to 2.2 ppm in the H-NMR spectrum are due to CH2. 1 The signals at 1.0 to 1.6 ppm in the H-NMR spectrum are thought to be due to NH.

[0016] Polycarbosilazane does not contain Si-Si bonds.

[0017] The polycarbosilazane has a mass average molecular weight of 1,500 to 25,000 in terms of polystyrene as measured by gel permeation chromatography.

[0018] Another aspect of the present invention provides a composition comprising the above-described polycarbosilazane and a solvent.

[0019] Yet another aspect of the present invention provides a method for producing a silicon-containing film, comprising applying the above-described composition over a substrate to form a coating, and curing the coating under a water vapor atmosphere or a non-oxidizing atmosphere.

[0020] Yet another aspect of the present invention provides a method for producing an electronic device having a silicon-containing film produced by a method comprising applying the above-described composition over a substrate to form a coating, and curing the coating in a water vapor atmosphere or a non-oxidizing atmosphere.

[0021] The polycarbosilazane of the present invention can produce a silicon-containing film that is resistant to acid etching during the manufacturing process of semiconductors, etc. A composition containing polycarbosilazane can fill narrow, high-aspect-ratio trenches. Furthermore, the resulting silicon-containing film is characterized by low residual stress after curing and excellent electrical properties. The use of a composition containing polycarbosilazane can improve the yield of electronic devices. [Definition]

[0022] As used herein, unless otherwise stated, the following terms used in the specification and claims shall have the following meanings for purposes of this specification:

[0023] As used herein, unless otherwise stated, the singular includes the plural, and "one" or "the" means "at least one." The term "including," as well as other expressions such as "includes" and "included," is not limiting. Furthermore, terms such as "element" or "component" encompass both elements or components comprising one unit and elements or components comprising more than one unit, unless otherwise specified. As used herein, unless otherwise specified, the conjunction "and" is intended to be inclusive, and the conjunction "or" is not intended to be exclusive. For example, the phrase "or, alternatively" is intended to be exclusive. The term "and / or" includes all combinations of elements and includes singular uses.

[0024] The terms "about" or "approximately," when used in connection with measurable numerical values, mean the indicated value of the variable and all values ​​of the variable within experimental error (e.g., within a 95% confidence limit for the mean) or within ±10 percent of the stated value, whichever is greater.

[0025] As used herein, "C x~y "," "C x ~C y " and "C x " refers to the number of carbons in a molecule or substituent. For example, C 1-6 Alkyl refers to alkyls having from 1 to 6 carbons (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.).

[0026] In this specification, unless otherwise specified, "alkyl" means a straight-chain or branched alkyl, and "cycloalkyl" means an alkyl containing a cyclic structure. A cyclic structure substituted with a straight-chain or branched alkyl is also referred to as cycloalkyl. Furthermore, polycyclic structures such as bicycloalkyl are also included in cycloalkyl. Unless otherwise specified, "heteroalkyl" means an alkyl containing oxygen or nitrogen in the main chain or side chain, for example, alkyl containing oxy, hydroxy, amino, carbonyl, etc. Furthermore, "hydrocarbyl group" means a monovalent, divalent, or higher valent group containing carbon and hydrogen, and optionally oxygen or nitrogen. Furthermore, in this specification, unless otherwise specified, "alkylene" means a divalent group corresponding to the alkyl, for example, a straight-chain alkylene or a branched alkylene having a side chain.

[0027] In this specification, when a numerical range is indicated using "to" or "-", it includes both endpoints and the units are the same. For example, 5 to 25 mol % means 5 mol % or more and 25 mol % or less.

[0028] In this specification, the "area intensity" of -25 to -5 ppm refers to the proton nuclear magnetic resonance ( 1 H-NMR), that is, the area enclosed by the baseline where the intensity is 0 and the curve.

[0029] In the present specification, when a polymer has multiple types of repeating units without any particular definition, these repeating units are copolymerized. The copolymerization may be alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture thereof.

[0030] In this specification, unless otherwise specified, the unit of temperature is Celsius. For example, 20 degrees means 20 degrees Celsius.

[0031] In this specification, unless otherwise specified, "%" means "% by mass" and "parts" means "parts by mass".

[0032] The section headings used herein are for organizational purposes and should not be construed as limiting the subject matter described. All documents or portions of documents cited in this application, including, but not limited to, patents, patent applications, articles, books, and treatises, are expressly incorporated herein in their entirety for any purpose. In the event that one or more of the incorporated documents and similar materials defines a term in a manner that contradicts that term's definition in this application, this application controls. DETAILED DESCRIPTION OF THE INVENTION

[0033] Hereinafter, embodiments of the present invention will be described in detail.

[0034] [Polycarbosilazane] The polycarbosilazane of the present invention comprises a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2).

[0035] [ka] where: R 1 , R 2 , R 3 , and R 4 are each independently a single bond, hydrogen, or C 1-4 is alkyl, R 5 are each independently a single bond or hydrogen, and n is 1 to 2.

[0036] Polycarbosilazane is 1 In the H-NMR spectrum, (CH2 intensity) / [(CH2 intensity)+(NH intensity)] is 0.05 to 0.5. 1Specifically, H-NMR measurements are performed on a sample solution prepared by dissolving 0.4 g of polycarbosilazane in 1.6 g of a deuterated solvent such as deuterated chloroform. To calibrate the chemical shift, tetramethylsilane (TMS) is added to the sample solution as an internal standard. The sample solution is measured 80 times using a nuclear magnetic resonance spectrometer, JNM-ECS400 (JEOL Ltd.). 1 In the present invention, for example, "CH2 intensity" means an integrated intensity in the range of 1.7 to 2.2 ppm, and "NH intensity" means an integrated intensity in the range of 1.0 to 1.6 ppm.

[0037] Polycarbosilazane does not contain Si-Si bonds. The presence of Si-Si bonds in polycarbosilazane is 29 It is evaluated by Si-NMR measurement. 29 Specifically, Si-NMR measurements are performed on a sample solution prepared by dissolving 0.4 g of polycarbosilazane in 1.6 g of a deuterated solvent such as deuterated chloroform. To calibrate the chemical shift, tetramethylsilane (TMS) is added to the sample solution as an internal standard. The sample solution is measured 1,000 times using a nuclear magnetic resonance spectrometer, JNM-ECS400 (JEOL Ltd.). 1 Obtain a H-NMR spectrum. 29 Its presence is confirmed in the Si-NMR spectrum by the peak assigned to the Si-Si bond between -20 and -10 ppm.

[0038] The polycarbosilazane according to the present invention can be obtained by co-ammonolysis of at least one compound selected from the group consisting of silicon compounds represented by the following formula (3) with at least one compound selected from the group consisting of silicon compounds represented by the following formula (4): [ka] where: R 6 , R 7 , R 8 , R9 and R 10 are each independently hydrogen, chlorine, bromine or C 1-4 is alkyl; R 11 is hydrogen or C 1-4 is alkyl; X is chlorine or bromine; and m is 1 to 2.

[0039] The molar ratio of the compound represented by formula (3) to the compound represented by formula (4) is preferably 0.02 to 0.5, more preferably 0.03 to 0.33. If the molar ratio is lower than 0.02, the formed silicon-containing film will not be able to withstand acid etching in processes such as semiconductor device manufacturing. On the other hand, if the molar ratio is higher than 0.5, the polycarbosilazane will melt due to heat, making it difficult to handle in processes such as semiconductor device manufacturing.

[0040] Examples of silicon compounds represented by formula (3) include bis(trichlorosilyl)methane, bis(dichlorosilyl)methane, bis(chlorosilyl)methane, bis(chlorodimethylsilyl)methane, bis(chloroethylmethylsilyl)methane, bis(chlorodiethylsilyl)methane, bis(chlorodiisopropylsilyl)methane, bis(chlorodibutylsilyl)methane, bis(dichloromethylsilyl)methane, bis(dichloroethylsilyl)methane, bis(dichloroisopropylsilyl)methane, bis(butyldichlorosilyl)methane, trichloro[(dichlorosilyl)methyl]silane, chlorosilyl(dichlorosilyl)methane, dichloromethyl[(trichlorosilyl)methyl]silane, chlorodimethyl[(trichlorosilyl)methyl]silane, dichloro[(dichlorosilyl)methyl]methylsilane, chloro[(dichlorosilyl)methyl]dimethylsilane, chloro[(dichlorosilyl)methyl]methyl thylsilane, chloro[(dichloromethylsilyl)methyl]dimethylsilane, dichloroethyl[(trichlorosilyl)methyl]silane, chlorodiethyl[(trichlorosilyl)methyl]silane, dichloro[(dichlorosilyl)methyl]ethylsilane, chloro[(dichlorosilyl)methyl]diethylsilane, chloro[(dichlorosilyl)methyl]ethylsilane, 1,2-bis(trichlorosilyl)ethane, 1,2-bis(dichlorosilyl)ethane, 1,2-bis(chlorosilyl)ethane, 1,2-bis(dichloromethylsilyl)ethane, 1,2-bis(dichloroethylsilyl)ethane, 1,2-bis(dichloropropylsilyl)ethane, 1,2-bis(dichlorobutylsilyl)ethane, 1,2-bis(chlorodimethylsilyl)ethane, 1,2-bis(chloroethylmethylsilyl)ethane, 1,2-bis(chlorodiethylsilyl)ethane, 1,2-bis(chlorodipropylsilyl)ethane, 1,Examples include 2-bis(chlorodibutylsilyl)ethane, trichloro[2-(dichlorosilyl)ethyl]silane, trichloro[2-(chloromethylsilyl)ethyl]silane, dichloromethyl[2-(trichlorosilyl)ethyl]silane, trichloro[2-(chloromethylsilyl)ethyl]silane, chlorodimethyl[2-(trichlorosilyl)ethyl]silane, dichloro[2-(chloromethylsilyl)ethyl]methylsilane, dichloroethyl[2-(trichlorosilyl)ethyl]silane, dichloro[2-(dichlorosilyl)ethyl]ethylsilane, chloro[2-(dichloroethylsilyl)ethyl]diethylsilane, dichloro[2-(dichloroethylsilyl)ethyl]methylsilane, and chloro[2-(chlorodimethylsilyl)ethyl]ethylmethylsilane. These can be used alone or in combination of two or more.

[0041] Examples of the silicon compound represented by formula (4) include trichlorosilane, dichlorosilane, methyldichlorosilane, dimethyldichlorosilane, ethyldichlorosilane, diethyldichlorosilane, ethylmethyldichlorosilane, propyldichlorosilane, dipropyldichlorosilane, methylpropyldichlorosilane, butyldichlorosilane, butylmethyldichlorosilane, dibutyldichlorosilane, di-tert-butyldichlorosilane, and tert-butylmethyldichlorosilane. These can be used alone or in combination of two or more.

[0042] The co-ammonolysis of the silicon compound represented by formula (3) and the silicon compound represented by formula (4) is carried out in a solvent. The silicon compound represented by formula (3) is dissolved in a solvent, and then the silicon compound represented by formula (4) is added to the mixture. Ammonia is added to the mixture. The number of moles of ammonia added is preferably 3 to 6 times the total number of moles of the silicon compound represented by formula (3) and the silicon compound represented by formula (4). The co-ammonolysis is carried out at -10 to 20°C for 1 to 24 hours. After the reaction, by-products from the reaction mixture are removed by filtration to obtain polycarbosilazane in the solvent.

[0043] Many kinds of solvents can be used in the co-ammonolysis. Suitable solvents include, but are not limited to, aromatic compounds (e.g., benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, triethylbenzene); saturated hydrocarbon compounds (e.g., cyclohexane, decahydronaphthalene, dipentene, n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, n-octane, i-octane, n-nonane, i-nonane, n-decane, ethylcyclohexane, methylcyclohexane, cyclohexane, p-menthane); unsaturated hydrocarbons (e.g., cyclohexene); halogenated hydrocarbon compounds (e.g., methylene chloride, chloroform, tetrachloromethane, bromoform, ethylene chloride, chloroform ... ethylidene, trichloroethane, and tetrachloroethane); heterocyclic compounds (e.g., pyrrolidine, pyrrole, imidazolidine, piperidine, pyridine, methylpyridine, dimethylpyridine, pyridazine, azepane, and quinoline); ether compounds (e.g., dipropyl ether, dibutyl ether, anisole); ester compounds (e.g., n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate); ketone compounds (e.g., methyl isobutyl ketone (MIBK)); and tertiary amine compounds (e.g., trimethylamine, dimethylethylamine, diethylmethylamine, and triethylamine). The solvents can be used alone or in combination of two or more.

[0044] When the number of repeating units represented by formula (1) is N1 and the number of repeating units represented by formula (2) is N2, the polycarbosilazane has an N1 / (N1+N2) ratio of 0.02 to 0.33, and more preferably 0.03 to 0.25.

[0045] The polycarbosilazane of the present invention has a specific molecular weight. When a composition containing the polycarbosilazane of the present invention is heated and converted into a silicon-containing film, the polycarbosilazane preferably has a large mass-average molecular weight to prevent vaporization of low-molecular-weight components and to prevent volume reduction in fine trenches. On the other hand, a low viscosity is preferred to ensure good coating properties and to successfully fill trenches with high aspect ratios. The mass-average molecular weight of the polycarbosilazane is preferably 1,500 to 25,000, more preferably 2,000 to 20,000. The mass-average molecular weight here refers to the mass-average molecular weight in terms of polystyrene, and can be measured by gel permeation chromatography (GPC) using polystyrene as the standard.

[0046] R in Equation (1) and Equation (2) 1 , R 2 , R 3 and R 4 is not particularly limited, but examples thereof include a single bond, hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl. The polycarbosilazane of the present invention is preferably a polycarbosilazane represented by the formula (1) and the formula (2) 1 , R 2 , R 3 , R 4 and R 5 is a polyperhydrocarbosilazane in which each of the groups is a single bond or hydrogen. The polyperhydrocarbosilazane can have a -SiH3 end group.

[0047] An example of a polyperhydrocarbosilazane is: [ka]

[0048] [Composition] The composition of the present invention comprises polycarbosilazane and a solvent. Many types of solvents can be used in the composition. Suitable solvents are not particularly limited, but include at least one selected from the group consisting of aromatic compounds, saturated hydrocarbon compounds, unsaturated hydrocarbon compounds, ether compounds, ester compounds, and ketone compounds. Specific examples include the following: Aromatic compounds (e.g., benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, triethylbenzene); saturated hydrocarbon compounds (e.g., cyclohexane, decahydronaphthalene, dipentene, n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, n-octane, i-octane, n-nonane, i-nonane, n-decane, ethylcyclohexane, methylcyclohexane, cyclohexane, p-menthane); unsaturated hydrocarbons (e.g., cyclohexene); ether compounds (e.g., dipropyl ether, dibutyl ether, anisole); ester compounds (e.g., n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate); ketone compounds (e.g., methyl isobutyl ketone (MIBK)). The solvents can be used alone or in combination of two or more. The solubility of polycarbosilazane and the evaporation rate of the solvent can be adjusted by using multiple solvents.

[0049] Considering the workability of the coating method used, the penetration of the composition into fine trenches, and the required film thickness outside the trenches, the amount of solvent in the composition can be appropriately selected depending on the mass-average molecular weight of the polycarbosilazane used. The composition of the present invention contains 1 to 50 mass %, preferably 1 to 30 mass %, of polycarbosilazane based on the total mass of the composition.

[0050] The composition according to the present invention can be combined with optional components (e.g., surfactants, etc.). The use of surfactants is preferred because they can improve application properties. Examples of surfactants that can be used in the composition according to the present invention include nonionic surfactants, anionic surfactants, and amphoteric surfactants.

[0051] Examples of nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, and polyoxyethylene cetyl ether; polyoxyethylene fatty acid diesters, polyoxyethylene fatty acid monoesters, polyoxyethylene polyoxypropylene block polymers; acetylene alcohol derivatives such as acetylene alcohol, acetylene glycol, and polyethoxylates of acetylene alcohol; acetylene glycol derivatives such as polyethoxylates of acetylene glycol; fluorine-containing surfactants such as Fluorad (trade name, manufactured by 3M Limited), Megafac (trade name, manufactured by DIC Corporation), and Sulfuron (trade name, manufactured by Asahi Glass Co., Ltd.); and organic siloxane surfactants such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of the acetylene glycol include 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,6-dimethyl-4-octyne-3,6-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,5-dimethyl-1-hexyn-3-ol, 2,5-dimethyl-3-hexyne-2,5-diol, and 2,5-dimethyl-2,5-hexanediol.

[0052] Examples of anionic surfactants include ammonium salts or organic amine salts of alkyldiphenyletherdisulfonic acids, ammonium salts or organic amine salts of alkyldiphenylethersulfonic acids, ammonium salts or organic amine salts of alkylbenzenesulfonic acids, ammonium salts or organic amine salts of polyoxyethylene alkylethersulfonic acids, and ammonium salts or organic amine salts of alkylsulfuric acids.

[0053] Examples of amphoteric surfactants include 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine and lauric acid amidopropyl hydroxysulfone betaine.

[0054] These surfactants can be used alone or in combination of two or more kinds, and the blending ratio thereof is usually 50 to 10,000 ppm, preferably 100 to 5,000 ppm, based on the total mass of the composition.

[0055] [Method for producing silicon-containing film] The method for producing a silicon-containing film of the present invention comprises applying the above-described composition over a substrate to form a coating, and curing the coating in an oxidizing or non-oxidizing atmosphere.

[0056] The method for applying the composition to such a substrate is not particularly limited, and can be arbitrarily selected from conventionally known methods, such as spin coating, dip coating, spray coating, transfer coating, roll coating, bar coating, doctor coating, brush coating, flow coating, and slit coating. Substrates to which the composition can be applied include, for example, silicon substrates, glass substrates, and resin films. Various semiconductor elements and the like may be formed on these substrates as needed.

[0057] After application of the composition, a pre-baking step is preferably carried out to dry or pre-cure the coating film. The pre-baking step is carried out in an inert gas atmosphere when curing in a non-oxidizing atmosphere, or in air when curing in a non-oxidizing atmosphere, and the process conditions are, for example, 50 to 400°C and 10 seconds to 30 minutes on a hot plate.

[0058] The pre-baked coating film is cured in an oxidizing or non-oxidizing atmosphere.

[0059] The oxidizing atmosphere has an oxygen partial pressure of 20 to 101 kPa, preferably 40 to 101 kPa, and more preferably 1.5 to 80 kPa of water vapor partial pressure when the total pressure is 101 kPa.

[0060] Heating is preferably carried out in an atmosphere containing water vapor. An atmosphere containing water vapor means that the water vapor partial pressure is in the range of 0.5 to 101 kPa, preferably 1 to 90 kPa, and more preferably 1.5 to 80 kPa. Heating is carried out in the temperature range of 200 to 800°C.

[0061] When heating at high temperatures (e.g., temperatures above 600°C) in a water vapor-containing atmosphere, there may be concerns about adverse effects on other elements, such as electronic devices, that are simultaneously exposed to the heat treatment. In such cases, the curing process can be divided into three or more stages. For example, first, heating at a low temperature (e.g., in the range of 200 to 400°C) in a water vapor-containing atmosphere, then heating at a relatively low temperature (e.g., in the range of 300 to 600°C) in a water vapor-containing atmosphere, and finally heating at a higher temperature (e.g., 400 to 800°C) in a water vapor-free atmosphere.

[0062] As a component other than water vapor in the water vapor-containing atmosphere (hereinafter sometimes referred to as a "dilution gas"), any gas can be used, for example, air, oxygen, nitrogen, nitrogen oxide, ozone, helium, and argon. In consideration of the film quality of the silicon-containing film, it is preferable to use oxygen as the dilution gas.

[0063] The non-oxidizing atmosphere refers to an atmosphere with an oxygen concentration of 1 ppm or less and a dew point of −76° C. or less. The atmosphere is preferably N 2 , Ar, He, Ne, H 2 , or a mixed gas of two or more of these. The heating is carried out in a temperature range of 200 to 1000°C.

[0064] The rate of temperature increase and decrease up to the target temperature during heating is not particularly limited, but can generally be in the range of 1 to 100°C / min. The heating retention time after reaching the target temperature is also not particularly limited, but can generally be in the range of 1 minute to 10 hours.

[0065] The silicon-containing film obtained by curing in an oxidizing atmosphere is a siliceous film. In the present invention, the siliceous film refers to a film containing oxygen atoms and silicon atoms, in which the ratio of the number of oxygen atoms to the number of silicon atoms (O / Si) is 1.20 to 2.50, preferably 1.40 to 2.50, and more preferably 1.60 to 2.45. The siliceous film may contain other atoms such as hydrogen, nitrogen, and carbon.

[0066] The silicon-containing film obtained by curing in a non-oxidizing atmosphere is a silicon carbonitrogenous film. In the present invention, a silicon carbonitrogenous film refers to a film containing carbon atoms, nitrogen atoms, and silicon atoms, with a nitrogen to silicon atom ratio (N / Si) of 0.70 to 1.10, preferably 0.75 to 0.98, and a carbon to silicon atom ratio (C / Si) of 0.02 to 12.5, preferably 0.03 to 11.5. The silicon carbonitride film may contain other atoms such as hydrogen and oxygen.

[0067] The thickness of the silicon-containing film is not particularly limited, but is preferably 0.1 to 1.5 μm, and more preferably 0.1 to 1.2 μm.

[0068] The method for producing an electronic device according to the present invention comprises the above-described production method. Preferably, the electronic device according to the present invention is a semiconductor device, a solar cell chip, an organic light-emitting diode, or an inorganic light-emitting diode. A preferred embodiment of the electronic device according to the present invention is a semiconductor device.

[0069] [Example] The present invention will now be described with reference to examples, which are for illustrative purposes only and are not intended to limit the scope of the present invention.

[0070] [Example 1] After flushing the interior of a 1 L reaction vessel equipped with a cooling condenser, mechanical stirrer, and temperature controller with dry nitrogen, 500 ml of dry pyridine was added to the reaction vessel and cooled to -3 °C. 23 g (0.107 mol) of bis(dichlorosilyl)methane was then added to the vessel. 32 g (0.317 mol) of dichlorosilane was then added to the mixture to produce a solid adduct (SiH2Cl2·2C5H5N). After confirming that the reaction mixture had cooled to below -3 °C, 36 g of ammonia was slowly bubbled into the reaction mixture while stirring. After stirring for 12 hours, dry nitrogen was bubbled through the liquid layer for 30 minutes to remove excess ammonia. The resulting reaction product was passed through a 5.0 μm pore size PTFE filter followed by a 0.2 μm pore size PTFE filter to remove by-products. After distilling off the pyridine, a polycarbosilazane composition having a concentration of 20% by mass in xylene was obtained. This polycarbosilazane was analyzed by infrared absorption spectroscopy (FT-IR) using an FTIR6100 (JASCO Corporation). 1 H-NMR and 29 Si-NMR analysis shows that the compound is polyperhydrocarbosilazane. The mass average molecular weight, calculated as polystyrene equivalent by GPC, is 11,450. 1 In the H-NMR spectrum, the (CH intensity) / [(CH intensity)+(NH intensity)] is 0.426. 29 Si-NMR measurements show that it does not have Si-Si bonds.

[0071] The polyperhydrocarbosilazane composition is spin-coated onto a silicon wafer using 1HDX2 (Mikasa Corporation). The coating is pre-baked on a hot plate in air at 150°C for 1 minute. The pre-baked film is cured at 250°C for 30 minutes in an oxygen atmosphere, and then at 400°C for 60 minutes in an atmosphere containing water vapor (40 kPa). The resulting film is annealed at 650°C for 60 minutes. The electrical properties, relative wet etching rate, and residual stress of the cured film are measured. The film thickness is 0.4 μm.

[0072] [Example 2] The polyperhydrocarbosilazane composition of Example 1 is spin-coated onto a silicon wafer using 1HDX2 (Mikasa Corporation). The coating is pre-baked on a hot plate at 150°C for 1 minute under a nitrogen atmosphere. The pre-baked film is cured at 650°C for 60 minutes under a nitrogen atmosphere. The resulting film is annealed at 650°C for 60 minutes. The electrical properties, relative wet etching rate, and residual stress of the cured film are measured. The film thickness is 0.3 μm.

[0073] [Example 3] After flushing the interior of a 1 L reaction vessel equipped with a cooling condenser, mechanical stirrer, and temperature controller with dry nitrogen, 350 ml of dry pyridine was added to the reaction vessel and cooled to -3 °C. 6.6 g (0.031 mol) of bis(dichlorosilyl)methane was then added to the vessel. 25 g (0.248 mol) of dichlorosilane was then added to the mixture to produce a solid adduct (SiH2Cl2·2C5H5N). After confirming that the reaction mixture had cooled to below -3 °C, 24 g of ammonia was slowly bubbled into the reaction mixture while stirring. After stirring for 12 hours, dry nitrogen was bubbled through the liquid layer for 30 minutes to remove excess ammonia. The resulting reaction product was passed through a 5.0 μm pore size PTFE filter followed by a 0.2 μm pore size PTFE filter to remove by-products. After distilling off the pyridine, a polycarbosilazane composition having a concentration of 20% by mass in xylene is obtained. This polycarbosilazane was analyzed by FT-IR, 1 H-NMR and 29 Si-NMR analysis shows that the compound is polyperhydrocarbosilazane. The mass average molecular weight, calculated as polystyrene by GPC, is 4190. 1 In the H-NMR spectrum, the (CH intensity) / [(CH intensity)+(NH intensity)] is 0.276. 29 The silicon-containing film was produced by the same method as in Example 1. Si-NMR measurement showed that it had no Si-Si bond.

[0074] [Example 4] The silicon-containing film is prepared from the polyhydrocarbosilazane composition of Example 3 by the same method as in Example 3.

[0075] [Example 5] After flushing the interior of a 1 L reaction vessel equipped with a cooling condenser, mechanical stirrer, and temperature controller with dry nitrogen, 500 ml of dry pyridine was added to the reaction vessel and cooled to -3 °C. 2.1 g (0.010 mol) of bis(dichlorosilyl)methane was then added to the vessel. 32 g (0.317 mol) of dichlorosilane was then added to the mixture to produce a solid adduct (SiH2Cl2·2C5H5N). After confirming that the reaction mixture had cooled to below -3 °C, 28 g of ammonia was slowly bubbled into the reaction mixture while stirring. After stirring for 12 hours, dry nitrogen was bubbled through the liquid layer for 30 minutes to remove excess ammonia. The resulting reaction product was passed through a 5.0 μm pore size PTFE filter followed by a 0.2 μm pore size PTFE filter to remove by-products. After distilling off the pyridine, a polycarbosilazane composition having a concentration of 20% by mass in xylene is obtained. This polycarbosilazane was analyzed by FT-IR, 1 H-NMR and 29 Si-NMR analysis shows that the compound is polyperhydrocarbosilazane. The mass average molecular weight, calculated as polystyrene equivalent by GPC, is 1958. 1 In the H-NMR spectrum, the (CH intensity) / [(CH intensity)+(NH intensity)] is 0.065. 29 The silicon-containing film was produced by the same method as in Example 1. Si-NMR measurement showed that it had no Si-Si bond.

[0076] [Example 6] A silicon-containing film is prepared from the polyhydrocarbosilazane composition of Example 5 by the same method as in Example 2.

[0077] [Example 7] After flushing the interior of a 1 L reaction vessel equipped with a cooling condenser, mechanical stirrer, and temperature controller with dry nitrogen, 500 ml of dry pyridine was added and cooled to -3 °C. 5.6 g (0.019 mol) of 1,2-bis(trichlorosilyl)ethane was dissolved in 20 g of pyridine and the solution was introduced into the vessel. 30 g (0.297 mol) of dichlorosilane was then added to the mixture to produce a solid adduct (SiH2Cl2·2C5H5N). After confirming that the reaction mixture had cooled to below -3 °C, 27 g of ammonia was slowly bubbled into the reaction mixture while stirring. After stirring for 12 hours, dry nitrogen was bubbled through the liquid layer for 30 minutes to remove excess ammonia. The resulting reaction product was passed through a 5.0 μm pore size PTFE filter followed by a 0.2 μm pore size PTFE filter to remove by-products. After distilling off the pyridine, a polycarbosilazane composition having a concentration of 20% by mass in xylene is obtained. This polycarbosilazane was analyzed by FT-IR, 1 H-NMR and 29 Si-NMR analysis shows that the compound is polyperhydrocarbosilazane. The mass average molecular weight, calculated as polystyrene by GPC, is 5670. 1 In the H-NMR spectrum, the (CH intensity) / [(CH intensity)+(NH intensity)] is 0.131. 29 The silicon-containing film was produced by the same method as in Example 1. Si-NMR measurement showed that it had no Si-Si bond.

[0078] [Example 8] After flushing the interior of a 1 L reaction vessel equipped with a cooling condenser, mechanical stirrer, and temperature controller with dry nitrogen, 500 ml of dry pyridine was added and cooled to -3 °C. 17.2 g (0.08 mol) of 1,2-bis(chlorodimethylsilyl)ethane was dissolved in 100 g of pyridine and the solution was introduced into the vessel. 32 g (0.317 mol) of dichlorosilane was then added to the mixture to produce a solid adduct (SiH2Cl2·2C5H5N). After confirming that the reaction mixture had cooled to below -3 °C, 27 g of ammonia was slowly bubbled into the reaction mixture while stirring. After stirring for 12 hours, dry nitrogen was bubbled through the liquid layer for 30 minutes to remove excess ammonia. The resulting reaction product was passed through a 5.0 μm pore size PTFE filter followed by a 0.2 μm pore size PTFE filter to remove by-products. After distilling off the pyridine, a polycarbosilazane composition having a concentration of 20% by mass in xylene is obtained, and the mass average molecular weight is 2240 as calculated using polystyrene standards by GPC. 1 In the H-NMR spectrum, (CH intensity) / [(CH intensity)+(NH intensity)] is 0.344. Polycarbosilazane teeth, 29 The silicon-containing film was produced by the same method as in Example 1. Si-NMR measurement showed that it had no Si-Si bond.

[0079] [Comparative Example 1] A perhydropolysilazane composition, which is a polymer composed of silicon, nitrogen, and hydrogen and contains a repeating unit of formula (2), and has a weight average molecular weight of 2850, was obtained by the method described in JPH01-138108A. The silicon-containing film was produced by the same method as in Example 1.

[0080] Comparative Example 2 A silicon-containing film is produced from the perhydropolysilazane composition of Comparative Example 1 in the same manner as in Example 2.

[0081] Comparative Example 3 After flushing the interior of a 1 L reaction vessel equipped with a cooling condenser, mechanical stirrer, and temperature controller with dry nitrogen, 500 ml of dry pyridine was added to the reaction vessel and cooled to -3 °C. 1.1 g (0.005 mol) of bis(dichlorosilyl)methane was then added to the vessel. 32 g (0.317 mol) of dichlorosilane was then added to the mixture to produce a solid adduct (SiH2Cl2·2C5H5N). After confirming that the reaction mixture had cooled to below -3 °C, 27 g of ammonia was slowly bubbled into the reaction mixture while stirring. After stirring for 12 hours, dry nitrogen was bubbled through the liquid layer for 30 minutes to remove excess ammonia. The resulting reaction product was passed through a 5.0 μm pore size PTFE filter followed by a 0.2 μm pore size PTFE filter to remove by-products. After distilling off the pyridine, a polycarbosilazane composition having a concentration of 20% by mass in xylene is obtained. This polycarbosilazane was analyzed by FT-IR, 1 H-NMR and 29 Si-NMR analysis shows that the compound is polyperhydrocarbosilazane. The mass average molecular weight, calculated as polystyrene by GPC, is 1848. 1 In the H-NMR spectrum, the (CH intensity) / [(CH intensity)+(NH intensity)] is 0.018. 29 The silicon-containing film is produced by the same method as in Example 1. The silicon-containing film is produced by the same method as in Example 1.

[0082] The results of Examples 1 to 8 and Comparative Examples 1 to 3 are shown in Table 1.

[0083] [Table 1]

[0084] [Mass average molecular weight] Gel permeation chromatography (GPC) was performed using an alliance™ e2695 high-speed GPC system (Nihon Waters, Inc.) and a Super Multipore HZ-N GPC column (Tosoh Corporation). Measurements were performed using monodisperse polystyrene as the standard sample, tetrahydrofuran as the developing solvent, at a flow rate of 0.6 ml / min and a column temperature of 40°C, and the mass-average molecular weight was calculated as the relative molecular weight to the standard sample.

[0085] [NMR measurement] 1 H-NMR measurements were performed using a sample solution prepared by dissolving 0.4 g of polycarbosilazane in 1.6 g of deuterated chloroform. To calibrate the chemical shift, tetramethylsilane was added to the sample solution as an internal standard. Each sample solution was measured 80 times using a JNM-ECS400 nuclear magnetic resonance spectrometer (JEOL Ltd.). 1 Obtain a H-NMR spectrum. Measure the integrated intensity from 1.7 to 2.2 ppm as the CH2 intensity, and the integrated intensity from 1.0 to 1.6 ppm as the NH intensity. Divide the CH2 intensity by the sum of the CH2 intensity and the NH intensity to obtain CH2 intensity / [(CH2 intensity + NH intensity)].

[0086] 29 Si-NMR measurements are performed using a sample solution prepared by dissolving 0.4 g of polycarbosilazane in 1.6 g of deuterated chloroform. To calibrate the chemical shift, tetramethylsilane (TMS) is added to the sample solution as an internal standard. The sample solution is measured 1,000 times using a JNM-ECS400 nuclear magnetic resonance spectrometer (JEOL Ltd.). 29 Obtain a Si-NMR spectrum.

[0087] Residual stress The residual stress of the silicon-containing film is measured using a thin film stress measurement system FLX-3300-T (Toho Technology).

[0088] [Relative Wet Etching Rate (WER)] A silicon-containing film coated on a 4-inch silicon wafer and a silicon thermal oxide film coated on a silicon wafer for comparison were prepared. The film thickness was measured using a spectroscopic ellipsometer M-2000V (JA Woollam). The wafer was immersed in a 1.0 wt% hydrofluoric acid solution at 20°C for 3 minutes, then rinsed with pure water and dried. The film thickness after immersion was measured. This process was repeated. The wet etching rate was calculated by linearly approximating the relationship between etching time and film thickness reduction. The relative WER was calculated by dividing the wet etching rate of the silicon-containing film by the WER of the silicon thermal oxide film.

[0089] [Breakdown electric field (Fbd)] The breakdown field of a silicon-containing film with a thickness of 200 nm is measured using an SSM495 272A-M100 (manufactured by Nippon SSM Co., Ltd.). -6 (A / cm 2 ) is defined as Fbd (MV / cm).

Claims

1. A repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and —SiH ３ a polycarbosilazane which is a polyperhydrocarbosilazane consisting of end groups of 【Chemistry 1】 (where, R １ , R ２ , R ３ , and R ４ are each independently a single bond or hydrogen, R ５ are each independently a single bond or hydrogen, and n is 1 to 2), １ In the H-NMR spectrum, the ratio of the area intensity from 1.7 to 2.2 ppm to the sum of the area intensity from 1.7 to 2.2 ppm and the area intensity from 1.0 to 1.6 ppm is 0.05 to 0.5; The polycarbosilazane does not contain any Si-Si bond.

2. 2. The polycarbosilazane according to claim 1, which has a polystyrene-equivalent weight average molecular weight of 1,500 to 25,000 as measured by gel permeation chromatography.

3. 3. The polycarbosilazane according to claim 1, which has a polystyrene-equivalent weight average molecular weight of 4,190 to 25,000 as measured by gel permeation chromatography.

4. A composition comprising the polycarbosilazane according to any one of claims 1 to 3 and a solvent.

5. The composition according to claim 4, wherein the solvent is at least one selected from the group consisting of aromatic compounds, saturated hydrocarbon compounds, unsaturated hydrocarbon compounds, ether compounds, ester compounds, and ketone compounds.

6. 6. The composition of claim 4, wherein the composition comprises 1 to 50% by weight of polycarbosilazane, based on the total weight of the composition.

7. A method for producing a silicon-containing film, comprising: forming a coating over a substrate using a composition according to any one of claims 4 to 6; and curing the coating film The method comprising:

8. 8. The method for producing a silicon-containing film according to claim 7, wherein the curing is carried out in a water vapor atmosphere.

9. 8. The method for producing a silicon-containing film of claim 7, wherein the curing is performed in a non-oxidizing atmosphere.

10. A method for producing an electronic device, comprising the silicon-containing film produced by the method according to any one of claims 7 to 9.

Images