Silicon-containing film-forming composition and method for producing silicon-containing film using the same

Abstract

To provide a silicon-containing film-forming composition having high affinity with a substrate. The present invention relates to a silicon-containing film-forming composition comprising: (I) a polymer having a polysilane skeleton containing specific repeating units; (II) a silicon compound having an unsaturated hydrocarbon bond; and (III) a solvent.

Description

[Technical field]

[0001] The present invention relates to a silicon-containing film-forming composition and a method for producing a silicon-containing film using the same. [Background technology]

[0002] Electronic devices, particularly semiconductor devices, are composed of thin films such as semiconductor films, insulating films, conductive films, etc. Silicon-containing films are used as semiconductor films, as etching masks in insulating film processing, and as sacrificial films in the manufacture of metal gates, etc.

[0003] Chemical vapor deposition (CVD), deposition, sputtering, and other methods are used to form amorphous silicon films and polycrystalline silicon films. At advanced nodes, using a gas-phase process such as CVD can cause excessive growth in narrow trenches, making it necessary to repeat etching and CVD. Therefore, a method of forming a film by applying and baking a liquid composition containing a silicon-containing polymer is being considered. Polysilanes such as hydrogenated polysilanes are known as silicon-containing polymers, but liquid compositions containing these have low affinity with substrates, and the cases in which they can be used to form films are very limited.

[0004] In order to impart functionality to polysilane, the introduction of specific functional groups has been investigated. For example, Patent Document 1 discloses a method for producing a polysilane copolymer by polymerizing a halosilane compound and a vinyl compound. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2002-128897 A Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention has been made based on the above-mentioned background art, and provides a silicon-containing film-forming composition having high affinity with a substrate. [Means for solving the problem]

[0007] The silicon-containing film-forming composition according to the present invention comprises: (I) A polymer having a polysilane skeleton comprising a repeating unit represented by formula (ia): [ka] (where: R a1 and R a2 are each independently a single bond, hydrogen, halogen, or C 1-6 Alkyl, C 6-10 Aryl, or -SiR A 3 (where R A are each independently hydrogen or C 1-8 alkyl), and p is an integer greater than or equal to 5); (II) silicon compounds having unsaturated hydrocarbon bonds; and (III) Solvent The present invention relates to a method for producing a semiconductor device comprising the steps of:

[0008] The method for producing a silicon-containing film according to the present invention includes the steps of: Applying the silicon-containing film-forming composition to a substrate to form a coating film; and Heating the coating The present invention relates to a method for producing a semiconductor device comprising the steps of:

[0009] The method for producing an electronic device according to the present invention comprises the method for producing a silicon-containing film described above. Effect of the Invention

[0010] The silicon-containing film-forming composition according to the present invention has high affinity with a substrate and has good coatability and adhesion to the substrate. The silicon-containing film formed using the silicon-containing film-forming composition according to the present invention has low residual stress. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] [Definition] In this specification, unless otherwise specifically stated, the definitions and examples set forth in this paragraph shall be followed. The singular includes the plural, and "a" or "the" means "at least one." An element of a concept may be expressed by a plurality of species, and when an amount thereof (e.g., mass % or mole %) is stated, the amount refers to the sum of the plurality of species. "And / or" includes all combinations of the elements as well as its use alone. When a numerical range is indicated using "~" 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. Alkyl means a group obtained by removing one arbitrary hydrogen from a linear, branched or cyclic saturated hydrocarbon, and includes linear alkyl, branched alkyl and cyclic alkyl, and optionally includes a linear or branched alkyl as a side chain in a cyclic structure. Aryl means a group obtained by removing one arbitrary hydrogen from an aromatic hydrocarbon. "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 an alkyl chain having from 1 to 6 carbons (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.). When a polymer has multiple types of repeating units, these repeating units are copolymerized. These copolymerizations may be alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture of these. When polymers or resins are shown by structural formulas, the n or m in parentheses indicates the number of repeats. Temperature is measured in degrees Celsius. For example, 20 degrees means 20 degrees Celsius. The additive refers to a compound having that function (for example, in the case of a base generator, it is a compound that generates a base). The compound may be dissolved or dispersed in a solvent and added to the composition. In one embodiment of the present invention, such a solvent is preferably contained in the composition of the present invention as the solvent (III) or another component.

[0012] Hereinafter, an embodiment of the present invention will be described in detail.

[0013] <Silicon-containing film-forming composition> The silicon-containing film-forming composition of the present invention (hereinafter, sometimes referred to as the composition) comprises (I) a polymer having a polysilane skeleton having a specific structure, (II) a silicon compound having an unsaturated hydrocarbon bond, and (III) a solvent.

[0014] (I) Polymers with polysilane skeletons The composition according to the present invention comprises a polymer having a polysilane skeleton comprising a repeating unit represented by formula (ia) (hereinafter, may be referred to as a polymer having a polysilane skeleton, a polymer, or a component (I)).

[0015] Equation (ia) is as follows: [ka] Where: R a1 and R a2 are each independently a single bond, hydrogen, halogen, or C 1-6 Alkyl, C 6-10 Aryl, or -SiR A 3, preferably a single bond, hydrogen, or -SiR A 3, more preferably hydrogen. a1 or R a2 When R is a single bond, it bonds to a single bond in another repeating unit represented by formula (ia) or a repeating unit represented by formula (ib) in the polymer, and directly bonds the silicon atoms to which they are bonded. a1may be the same or different, and each R a2 may be the same or different. a1 and R a2 In a preferred embodiment of the present invention, R a1 and R a2 An embodiment different from the above is also another embodiment of the present invention. R A are each independently hydrogen or C 1-8 It is alkyl, preferably hydrogen or methyl, more preferably hydrogen. p is an integer of 5 or more, preferably 5-20, and more preferably 6-10.

[0016] The polymer having a polysilane skeleton used in the present invention preferably further contains a repeating unit represented by formula (ib). Formula (ib) is as follows: [ka] Where: R b1 and R b2 are each independently a single bond, hydrogen, halogen, or C 1-6 Alkyl, C 6-10 Aryl, or -SiR B 3, preferably a single bond, hydrogen, or -SiR B 3, more preferably hydrogen or a single bond, with the proviso that R b1 and R b2 At least one of R is a single bond. b1 or R b2 When is a single bond, it bonds to a single bond in another repeating unit represented by formula (ib) or a repeating unit represented by formula (ia) in the polymer, directly bonding the silicon atoms to which they are bonded. R B are each independently hydrogen or C 1-8 It is alkyl, preferably hydrogen or methyl, more preferably hydrogen. q is an integer of 5 or more, preferably 5 to 12, and more preferably 6.

[0017] Specific examples of polymers having a polysilane skeleton include the following. [ka]

[0018] In a preferred embodiment of the present invention, the polymer having a polysilane skeleton does not have a Si-C bond. The absence of a Si-C bond makes it easier to etch the polymer in an alkaline solution after film formation, and improves processability.

[0019] The mass average molecular weight of the polymer having a polysilane skeleton is preferably 500 to 20,000, more preferably 1,000 to 15,000, from the viewpoints of solubility in a solvent, flatness of the film formed, and adhesion to a substrate. Here, the mass average molecular weight is a polystyrene-equivalent mass average molecular weight, and can be measured by gel permeation chromatography using polystyrene as a standard.

[0020] The polymer having a polysilane skeleton is preferably a polymer obtained by polymerizing a polysilane compound containing 5 or more silicon atoms (hereinafter, sometimes referred to as a polysilane compound). In a preferred embodiment, the polymer having a polysilane skeleton is formed by polymerizing the polysilane compound by light irradiation and / or heating. The number of silicon atoms contained in the polysilane compound is preferably 5 to 8, and more preferably 5 or 6. The polysilane compound may be an inorganic compound or an organic compound, and may be linear, branched, or partially have a cyclic structure.

[0021] The polysilane compound may be one type or a mixture of two or more types, and preferably comprises a cyclic polysilane, and more preferably consists of a cyclic polysilane. The cyclic polysilane is preferably represented by the following formula (ib'): [ka] Where: R b1 ' and R b2 ' are each independently hydrogen, halogen, or C 1-6 Alkyl, C 6-10 Aryl, or -SiR B’ 3, preferably hydrogen or silyl, more preferably hydrogen. R B’ are each independently hydrogen or C 1-8 It is alkyl, preferably hydrogen or methyl, preferably hydrogen. q' is an integer of 5 or more, preferably 5 to 8, and more preferably 5 or 6.

[0022] The cyclic polysilane is preferably at least one selected from the group consisting of silylcyclopentasilane, silylcyclohexasilane, disilylcyclohexasilane, cyclopentasilane, and cyclohexasilane, and more preferably cyclohexasilane or cyclopentasilane.

[0023] The polysilane compound may contain a linear or branched polysilane. Examples of the linear or branched polysilane include neopentasilane, hexasilane, 3-silylpentasilane, 2,2-disilyltetrasilane, heptasilane, tetrasilyltetrasilane, and hexasilylpentasilane. The inclusion of at least one of these is also a preferred embodiment of the present invention.

[0024] The polysilane compound is preferably polymerized by light irradiation and / or heating, and more preferably polymerized by light irradiation. In the case of light irradiation, the peak wavelength is preferably 248 to 436 nm, more preferably 282 to 405 nm. The irradiation intensity is preferably 10 to 250 mW / cm. 2 and more preferably 50 to 150 mW / cm 2The irradiation time is preferably 30 to 300 seconds, and more preferably 50 to 200 seconds. In the case of heating, it is preferable to carry out the heating at 40 to 200° C. for 3 to 300 minutes. It is also preferable to combine the above-mentioned light irradiation and heating. When the polysilane compound contains cyclic polysilane, it is considered that the light irradiation and / or heating in this process causes a part or all of the cyclic polysilane to be ring-opened. The polymer having a polysilane skeleton may contain a cyclic polysilane structure that is not ring-opened.

[0025] Component (I) may be one type or a mixture of two or more types. The content of the component (I) is preferably 2.0 to 30.0 mass %, and more preferably 5.0 to 25.0 mass %, based on the total mass of the composition.

[0026] (II) Silicon compounds having unsaturated hydrocarbon bonds The composition according to the present invention comprises a silicon compound having an unsaturated hydrocarbon bond (hereinafter sometimes referred to as component (II), the same applies to the other components). The composition according to the present invention contains component (II), which increases the affinity with the substrate, improving the coatability and adhesion. As a result, a uniform coating film can be formed on the substrate. Without being bound by theory, this is believed to be due to the fact that the silicon compound having an unsaturated hydrocarbon bond forms a bond with the polymer having a polysilane skeleton, and the silicon compound having the unsaturated hydrocarbon bond forms a bond with the hydroxyl group or the like on the substrate surface. Furthermore, the residual stress of the silicon-containing film formed can be reduced, which is believed to be because, without being bound by theory, the hydrocarbon of the silicon compound having unsaturated hydrocarbon bonds partially inhibits the formation of a three-dimensional silicon-containing network. It is also possible to lower the refractive index of the silicon-containing film that is formed. Without being bound by theory, it is believed that silicon carbide or graphite is formed locally in the silicon-containing film by the carbon of the silicon compound having an unsaturated hydrocarbon bond.

[0027] Component (II) has at least one carbon-carbon double bond or carbon-carbon triple bond, and preferably has two or more carbon-carbon double bonds. The unsaturated bond is preferably at a terminal, and therefore component (II) more preferably has two or more vinyl groups, and more preferably has 2 to 4 vinyl groups.

[0028] In a preferred embodiment, component (II) is represented by formula (ii). [ka] Where: L ii are each independently a single bond or C 1-5 It is alkylene, preferably a single bond, methylene, or ethylene, more preferably a single bond. R ii are each independently hydrogen or C 1-5 It is alkyl, preferably hydrogen, methyl or ethyl, more preferably methyl. n is 1, 2, 3, or 4, preferably 2, 3, or 4, and more preferably 4.

[0029] Preferably, component (II) is at least one selected from the group consisting of divinylsilane, trivinylsilane, tetravinylsilane, methyldivinylsilane, dimethyldivinylsilane, methyltrivinylsilane, diallylsilane, triallylsilane, diallylmethylsilane, diallyldimethylsilane, triallylmethylsilane, and tetraallylsilane.

[0030] The molecular weight of the component (II) is preferably 50-300, and more preferably 80-200. The component (II) may be one type or a mixture of two or more types. The content of component (II) is preferably 0.20 to 10.0 mass %, and more preferably 0.40 to 7.0 mass %, based on the total mass of the composition.

[0031] (III) Solvent The composition according to the present invention comprises a solvent. The solvent is selected from those that uniformly dissolve or disperse each component contained in the composition. Specific examples of the solvent include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether, diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ... Examples of the propylene glycol monoalkyl ethers include propylene glycol monoethyl ether, propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate, aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene, ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone, alcohols such as isopropanol and propanediol, and alicyclic hydrocarbons such as cyclooctane and decalin. Cyclooctane, toluene, decalin, and mesitylene are preferred. These solvents may be used alone or in combination of two or more.

[0032] In order to dissolve the polysilane homogeneously, the relative dielectric constant of the solvent is preferably 3.0 or less, more preferably 2.5 or less, as described in Solvent Handbook, 1st Edition, Kodansha Scientific.

[0033] The blending ratio of the solvent varies depending on the coating method and the required film thickness after coating, but the ratio of compounds other than the solvent (solid content ratio) is 1 to 96 mass %, preferably 2 to 60 mass %.

[0034] (IV) Polysilazane The composition according to the present invention may further include (IV) polysilazane. By further including polysilazane, the coating property may be improved. In addition, the smoothness of the silicon-containing film formed may be improved. The polysilazane can be selected arbitrarily as long as it does not impair the effects of the present invention. It may be either an inorganic compound or an organic compound, and may be linear, branched, or have a cyclic structure in part.

[0035] The polysilazane used in the present invention preferably contains 20 or more, preferably 20 to 350, more preferably 20 to 130 repeating units selected from the group consisting of the following formulas (iv-1) to (iv-6). In this case, it is preferable that each repeating unit is directly bonded to the others without being connected via a repeating unit other than (iv-1) to (iv-6). [ka] Here, R 1 ~R 9 are each independently hydrogen or C 1-4 It is an alkyl.

[0036] More preferably, the polysilazane used in the present invention is perhydropolysilazane (hereinafter referred to as PHPS). PHPS is a silicon-containing polymer that contains Si-N bonds as repeating units and is composed only of Si, N, and H. In this PHPS, all elements bonded to Si and N, except for the Si-N bonds, are H, and other elements such as carbon and oxygen are not substantially included. The simplest structure of perhydropolysilazane is a chain structure having the following repeating units.

[0037] [ka]

[0038] In the present invention, a PHPS having a chain structure and a cyclic structure in the molecule may be used, for example, a PHPS composed of repeating units represented by the following formulas (iv-a) to (iv-f) in the molecule and a terminal group represented by the following formula (iv-g).

[0039] [ka]

[0040] Such a PHPS has a branched or cyclic structure in the molecule, and a specific example of the partial structure of such a PHPS is shown in the following general formula.

[0041] [ka]

[0042] In addition, it may have a structure represented by the following formula, that is, a structure in which a plurality of Si-N molecular chains are crosslinked. [ka]

[0043] The PHPS used in the present invention is not limited in structure, as long as it is a silicon-containing polymer that contains Si-N bonds as repeating units and is composed only of Si, N, and H, and can have various structures other than those exemplified above. For example, it may have a structure that combines the linear structure, cyclic structure, and crosslinked structure as described above. The PHPS used in the present invention is preferably one that has a cyclic structure or a crosslinked structure, particularly a crosslinked structure.

[0044] From the viewpoints of solubility in a solvent and reactivity, the mass average molecular weight of the polysilazane used in the production method according to the present invention is preferably 900 to 15,000, and more preferably 900 to 10,000. The mass average molecular weight here is a weight average molecular weight in terms of polystyrene, and can be measured by gel permeation chromatography using polystyrene as the standard.

[0045] The content of the component (IV) is preferably 0 to 5.0 mass %, and more preferably 0.50 to 3.0 mass %, based on the total mass of the composition.

[0046] The composition used in the present invention can be combined with further compounds as necessary. Materials that can be combined with these are described below. The components other than (I) to (IV) in the entire composition are preferably 10% or less, more preferably 5% or less, based on the total mass.

[0047] A surfactant can be used to improve the coating property. Examples of the surfactant include a nonionic surfactant, an anionic surfactant, and an amphoteric surfactant.

[0048] Examples of the nonionic surfactant 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, acetylene glycol, acetylene alcohol derivatives such as polyethoxylate of acetylene alcohol, acetylene glycol derivatives such as polyethoxylate 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-hexyne-3-ol, 2,5-dimethyl-3-hexyne-2,5-diol, and 2,5-dimethyl-2,5-hexanediol.

[0049] Examples of the anionic surfactant include ammonium salts or organic amine salts of alkyldiphenyl ether disulfonic acids, ammonium salts or organic amine salts of alkyldiphenyl ether sulfonic acids, ammonium salts or organic amine salts of alkylbenzene sulfonic acids, ammonium salts or organic amine salts of polyoxyethylene alkyl ether sulfates, and ammonium salts or organic amine salts of alkyl sulfates.

[0050] Examples of amphoteric surfactants include 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine and lauric acid amidopropyl hydroxysulfone betaine.

[0051] 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.

[0052] <Method for preparing silicon-containing film-forming composition> The method for preparing the silicon-containing film-forming composition according to the present invention is not particularly limited. When the polymer having a polysilane skeleton is a polymer of a cyclic polysilane containing 5 or more silicon atoms, for example, (A) a step of irradiating a cyclic polysilane containing 5 or more silicon atoms with light; (B) preparing a mixture containing the silicon compound having an unsaturated hydrocarbon bond used in the present invention; (C) irradiating the mixture with light; It is produced by a method comprising: An example of the manufacturing method will be described below step by step.

[0053] The wavelength in step (A) preferably includes a peak wavelength of at least 172 to 405 nm, more preferably 282 to 405 nm. The irradiation intensity is preferably 10 to 250 mW / cm. 2 and more preferably 50 to 150 mW / cm 2 The irradiation time is preferably 30 to 300 seconds, and more preferably 50 to 200 seconds. Since cyclopentasilane or cyclohexasilane is a liquid at room temperature, the liquid cyclic polysilane can be irradiated with light while stirring. If the cyclic polysilane is a solid, it can be dissolved in a suitable solvent and irradiated with light while stirring. It is believed that the light irradiation in this step opens some or all of the cyclic polysilane rings.

[0054] (B) A step of preparing a mixture containing a silicon compound having an unsaturated hydrocarbon bond to be used in the present invention. When the irradiated cyclic polysilane is in a liquid state at room temperature, the silicon compound having the unsaturated hydrocarbon bond described above is added and stirred to prepare a mixture. When the irradiated cyclic polysilane is in a solid state, it can be dissolved in a suitable solvent. It is also possible to dissolve the silicon compound having the unsaturated hydrocarbon bond in a suitable solvent, add it to the irradiated cyclic polysilane, and stir to prepare a mixture.

[0055] (C) A step of irradiating the mixture with light It is believed that the light irradiation in this process causes condensation between polysilanes to form a polymer having a polysilane skeleton. In this case, the exposure wavelength preferably includes a peak wavelength of at least 172 to 405 nm, and more preferably 282 to 405 nm. The irradiation intensity is preferably 10 to 250 mW / cm. 2 and more preferably 50 to 150 mW / cm 2 The irradiation time is preferably 5 to 100 minutes, more preferably 5 to 60 minutes. The irradiation energy is preferably 3 to 1,500 J, more preferably 25 to 500 J. The order of steps (B) and (C) may be reversed, that is, the light irradiation described in step (C) may be carried out after step (A), and then the silicon compound having an unsaturated hydrocarbon bond may be added to prepare a mixture. The above steps (A), (B), and (C) are preferably carried out in a non-oxidizing atmosphere. The solvent may be added in steps (A) and (B) as described above, or may be added after step (C). The optional components described above are preferably added after step (C).

[0056] <Method for producing silicon-containing film> The method for producing a silicon-containing film according to the present invention includes the steps of: Applying the silicon-containing film-forming composition to a substrate to form a coating film; and Heating the coating The present invention relates to a method for producing a semiconductor device comprising the steps of: In the present invention, the term "on a substrate" includes cases where the composition is applied directly to the substrate, and cases where the composition is applied to the substrate via one or more intermediate layers.

[0057] The coating method can be selected from conventionally known methods such as spin coating, dipping, spraying, transfer, inkjet, roll coating, bar coating, brush coating, doctor coating, flow coating, and slit coating. As the substrate to which the composition is applied, a suitable substrate such as a silicon substrate, a glass substrate, or a resin film can be used. Various semiconductor elements may be formed on these substrates as necessary. When the substrate is a film, gravure coating can also be used. If desired, a drying step can be separately provided after the coating. If necessary, the coating step can be repeated once or twice or more to form the coating film having the desired thickness.

[0058] After forming a coating film using the composition of the present invention, the coating film may be prebaked (heat treated) in order to dry the coating film and reduce the amount of remaining solvent. The pre-baking step can be carried out in an oxidizing or non-oxidizing atmosphere, preferably at a temperature of 50 to 400° C., for 10 seconds to 60 minutes when using a hot plate, or for 1 to 120 minutes when using a clean oven.

[0059] After forming a coating film using the composition according to the present invention, the coating film can be irradiated with an electron beam or light before heating for curing, and is preferably irradiated with an electron beam. In the case of electron beam irradiation, the acceleration voltage is preferably 20 to 200 kV, and the exposure dose is preferably 5,000 to 50,000 kGy. In the case of light irradiation, light having a peak wavelength of preferably 248 to 436 nm, more preferably 248 to 405 nm, is irradiated. The irradiation intensity is preferably 10 to 800 mW / cm. 2 and more preferably 40 to 600 mW / cm 2 The irradiation time is preferably 30 to 3,500 seconds, and more preferably 50 to 3,000 seconds.

[0060] Thereafter, the coating film, which has been prebaked as necessary, irradiated with electron beams and / or light, is heated in a non-oxidizing atmosphere, an oxidizing atmosphere, and / or an ammonia atmosphere to harden and form a silicon-containing film. The heating temperature is preferably 200 to 1000°C, more preferably 300°C or higher. The heating time is not particularly limited, and is preferably 0.001 seconds to 24 hours. The heating may be performed by flash annealing. Usually, it takes several seconds to several hours for the pattern film to reach a desired temperature from the temperature before heating.

[0061] 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 an atmosphere of N2, Ar, He, Ne, H2, or a mixed gas of two or more of these.

[0062] The oxidizing atmosphere has an oxygen partial pressure of 20 to 101 kPa, preferably 40 to 101 kPa, and more preferably contains a water vapor partial pressure of 1.5 to 80 kPa when the total pressure is 101 kPa. In addition, when heating at a high temperature (for example, a temperature exceeding 600°C) in an atmosphere containing water vapor, there may be a concern that other elements such as electronic devices exposed to the heat treatment at the same time may be adversely affected. In such a case, the heating process can be divided into two or more stages (more preferably, three or more stages). For example, the material can be first heated at a low temperature (for example, in the temperature range of 200 to 400°C) in an atmosphere containing water vapor, then heated at a relatively low temperature (for example, in the temperature range of 300 to 600°C) in an atmosphere containing water vapor, and finally heated at a higher temperature (for example, in the temperature range of 400 to 800°C) in an atmosphere not containing water vapor.

[0063] As the component other than water vapor in the water vapor-containing atmosphere (hereinafter, sometimes referred to as dilution gas), any gas can be used, for example, air, oxygen, nitrogen, nitrogen oxide, ozone, helium, and argon. Considering the film quality of the silicon-containing film, it is preferable to use oxygen as the dilution gas.

[0064] The ammonia atmosphere means that the ammonia partial pressure is 20 to 101 kPa when the total pressure is 101 kPa, and preferably 25 to 80 kPa.

[0065] The silicon-containing film according to the present invention can be made into an amorphous silicon film by curing it by heating in a non-oxidizing atmosphere. After curing, the film is confirmed to be an amorphous silicon film by observing no diffraction peak of crystalline Si by X-ray diffraction (XRD).

[0066] The silicon-containing film according to the present invention can be made into a siliceous film by curing it by heating in an oxidizing atmosphere. 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 can contain other atoms such as hydrogen, nitrogen, and carbon.

[0067] The silicon-containing film according to the present invention can be made into a silicon nitride film by curing it by heating in an ammonia atmosphere. In the present invention, the silicon nitride film refers to a film in which the ratio of the number of nitrogen atoms to the number of silicon atoms (N / Si) is 0.2 to 2.0, preferably 0.4 to 1.6. The silicon nitride film can contain other atoms such as hydrogen and oxygen.

[0068] The thickness of the formed silicon-containing film is not particularly limited, but is preferably 20 to 500 nm, and more preferably 20 to 300 nm. By using the composition according to the present invention, a silicon-containing film having high flatness can be formed. The formed silicon-containing film has low residual stress.

[0069] The method for producing an electronic device according to the present invention includes the above-mentioned production method. The electronic device according to the present invention is preferably 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.

[0070] 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.

[0071] All of the polysilane synthesis and composition preparation steps in the following Examples and Comparative Examples are carried out in a glove box under a nitrogen atmosphere with an oxygen concentration of 0.1 ppm or less and a dew point temperature of -76.0°C or less.

[0072] [Example 1] A stirrer tip was placed in a 9 mL screw tube, 246.4 mg of cyclohexasilane was added, and while stirring using a stirrer, 0.7 J / cm of ultraviolet light with a wavelength of 365 nm from an LED lamp was applied. 2 After the ultraviolet irradiation, 68.1 mg of tetravinylsilane and 31.4 mg of perhydropolysilazane are added, and the mixture is stirred at room temperature for 12 hours using a stirrer. After stirring, 2957 mg of cyclooctane is added, stirred for 3 minutes, and filtered using a 0.2 μm PTFE filter (Advantec, DISMIC-13JP) to obtain the composition of Example 1. The weight average molecular weight of the polymer having a polysilane skeleton is 4,800. The weight average molecular weight (Mw) is measured by gel permeation chromatography (GPC) using polystyrene as the standard. GPC is performed using an allianceTM e2695 high-speed GPC system (Nihon Waters K.K.) and an organic solvent GPC column Shodex KF-805L (Showa Denko K.K.). The measurement is performed using monodisperse polystyrene as the standard sample and cyclohexene as the developing solvent under the measurement conditions of a flow rate of 0.6 milliliters / minute and a column temperature of 40°C, and then Mw is calculated as the molecular weight relative to the standard sample.

[0073] [Examples 2 to 8, Comparative Example 1] The compositions of Examples 2 to 8 and Comparative Example 1 were prepared in the same manner as in Example 1, except that the components and conditions shown in Table 1 were used. The Mw of the resulting polymer having a polysilane skeleton was measured in the same manner as above, and the results are shown in Table 1. [Table 1]

[0074] [Formation of silicon-containing films] The composition of Example 1 prepared above is applied to a Si substrate in a nitrogen atmosphere using a spin coater to form a coating film. The resulting coating film is heated on a hot plate in a nitrogen atmosphere at 400°C for 15 minutes to obtain a silicon-containing film. The compositions of Examples 2 to 8 and Comparative Example 1 prepared above are heated in the same manner as above, except that the heating conditions are changed to those shown in Table 2. The FT-IR spectrum of the silicon-containing film formed using the compositions of Examples 1 to 6 and Comparative Example 1 was measured at room temperature using an FTIR-6100 (JASCO Corporation), and it was confirmed that the obtained silicon-containing film was an amorphous silicon film. In the case where the composition of Example 7 is used, the FT-IR spectrum measurement confirms that the resulting silicon-containing film is a siliceous film. In the case where the composition of Example 8 is used, the FT-IR spectrum measurement confirms that the resulting silicon-containing film is a silicon nitride film. When the compositions of Examples 1 to 8 and Comparative Example 1 were used, the coating properties were good, a uniform coating film could be formed on a substrate, and a uniform silicon-containing film could be formed without peeling off from the substrate even when heated. In the heating conditions of Example 5, the coating film of Example 5 on the Si substrate was irradiated with 32,000 kGy of electron beams at room temperature in a nitrogen atmosphere, at an acceleration voltage of 70 kV, and at a tube current of 7.6 mA using a line irradiation type low energy electron beam irradiation apparatus EES-30L-MPM01 (Hamamatsu Photonics K.K.), and heated on a hot plate in a nitrogen atmosphere at 400°C for 15 minutes to obtain a silicon-containing film.

[0075] [Film thickness] The thickness of the silicon-containing film obtained is measured using a spectroscopic ellipsometer M-2000V (JA Woollam). The thickness is measured at eight points on the wafer excluding the center, and the average value is used. The results are shown in Table 2.

[0076] [Refractive index] The refractive index of the obtained silicon-containing film is measured at a wavelength of 633 nm using a spectroscopic ellipsometer M-2000V (JA Woollam). The obtained results are shown in Table 2.

[0077] Residual stress Residual stress was measured using a thin film stress measurement device, FLX-3300-T (Toho Technology). The measurements are shown in Table 2. [Table 2]

Claims

1. (I) A polymer having a polysilane skeleton comprising a repeating unit represented by formula (ia): 【Chemistry 1】 (where, R ａ１ and R ａ２ are each independently a single bond, hydrogen, halogen, or C １－６ Alkyl, C ６－１０ Aryl, or —SiR Ａ ３ (where R Ａ are each independently hydrogen or C １－８ alkyl), and p is an integer of 5 or greater; (II) a silicon compound having an unsaturated hydrocarbon bond; and (III) Solvent A silicon-containing film-forming composition comprising:

2. 2. The composition according to claim 1, wherein (I) the polymer having a polysilane skeleton further comprises a repeating unit represented by formula (ib): 【Chemistry 2】 (where, R ｂ１ and R ｂ２ are each independently a single bond, hydrogen, halogen, or C １－６ Alkyl, C ６－１０ Aryl, or —SiR Ｂ ３ (where R Ｂ are each independently hydrogen or C １－８ alkyl), where R ｂ１ and R ｂ２ At least one of is a single bond, and q is an integer of 5 or more.

3. The composition of claim 1 further comprising (IV) a polysilazane.

4. 2. The composition according to claim 1, wherein (II) the silicon compound having an unsaturated hydrocarbon bond is represented by formula (ii): 【Transformation 3】 (where, L ｉｉ are each independently a single bond or C １－５ is alkylene, R ｉｉ are each independently hydrogen or C １－５ is alkyl, and n is 1, 2, 3, or 4.

5. (II) The composition according to claim 1, wherein the silicon compound having an unsaturated hydrocarbon bond is at least one selected from the group consisting of divinylsilane, trivinylsilane, tetravinylsilane, methyldivinylsilane, dimethyldivinylsilane, methyltrivinylsilane, diallylsilane, triallylsilane, diallylmethylsilane, diallyldimethylsilane, triallylmethylsilane, and tetraallylsilane.

6. (III) The composition according to claim 1, wherein the solvent has a relative dielectric constant of 3.0 or less.

7. 2. The composition according to claim 1, wherein (I) the polymer having a polysilane skeleton is a polymer obtained by polymerizing a polysilane compound containing 5 or more silicon atoms.

8. The composition of claim 7 , wherein the polysilane compound comprises a cyclic polysilane.

9. 9. The composition of claim 8, wherein the cyclic polysilane is represented by formula (ib'). 【Chemistry 4】 (where, R ｂ１ ' and R ｂ２ ' are each independently hydrogen, halogen, C １－６ Alkyl, C ６－１０ Aryl, or —SiR Ｂ’ ３ (where R Ｂ’ are each independently hydrogen, C １－８ alkyl), and q' is an integer of 5 or greater.

10. 9. The composition of claim 8, wherein the cyclic polysilane is at least one selected from the group consisting of silylcyclopentasilane, silylcyclohexasilane, disilylcyclohexasilane, cyclopentasilane, and cyclohexasilane.

11. 8. The composition according to claim 7, wherein the polysilane compound is at least one selected from the group consisting of neopentasilane, hexasilane, 3-silylpentasilane, 2,2-disilyltetrasilane, heptasilane, tetrasilyltetrasilane, and hexasilylpentasilane.

12. Applying the composition according to any one of claims 1 to 11 to a substrate to form a coating; and Heating the coating film A method for producing a silicon-containing film, comprising:

13. 13. The method of claim 12, comprising heating the coating in a non-oxidizing atmosphere.

14. 13. The method of claim 12, comprising heating the coating in an oxidizing atmosphere.

15. 13. The method of claim 12, comprising heating the coating under an ammonia atmosphere.

16. The method according to claim 12, wherein after forming the coating film, the coating film is further irradiated with light having a peak wavelength of 248 to 436 nm.

17. The method according to claim 12, wherein the coating film is irradiated with an electron beam after being formed and before being heated.

18. The method of claim 12, wherein the heating is carried out at 200 to 1000°C.

19. A method for producing an electronic device, comprising the method of claim 12.

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