Silicon-containing film forming composition and method for manufacturing silicon-containing films using the same.

Abstract

The objective of this invention is to provide a silicon-containing film-forming composition with high affinity for a substrate. The solution is a silicon-containing film-forming composition comprising: (I) a polymer having a polysilane backbone comprising specific repeating units, (II) a silicon compound having unsaturated hydrocarbon bonds, and (III) a solvent.

Description

Technical Field

[0001] This invention relates to a silicon-containing film forming composition and a method for manufacturing a silicon-containing film using the same. Prior Technology

[0002] Electronic devices, especially semiconductor devices, are made of thin films such as semiconductor films, insulating films, and conductive films. Silicon-containing films can be used as semiconductor films, as etching masks during the processing of insulating films, and as sacrificial films during the manufacture of metal gates.

[0003] Methods for forming amorphous and polycrystalline silicon films include chemical vapor deposition (CVD), evaporation, and sputtering. At more advanced stages, when using vapor phase processes such as CVD, overgrowth can occur in narrow trenches, necessitating repeated etching and CVD. Therefore, an investigation is underway into coating and sintering a liquid composition containing a silicon-containing polymer to form the film. Polysilanes such as hydrogenated polysilanes are known as silicon-containing polymers, but liquid compositions containing these have low affinity for the substrate, which greatly limits their use in film formation.

[0004] To impart functionality to polysilanes, investigations are underway into introducing specific functional groups. For example, Patent Document 1 discloses a method for producing polysilane copolymers by polymerizing a halosilane compound with a vinyl compound. [Previous Technical Documents] [Patent Literature]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2002-128897 Summary of the Invention

[0006] [The problem that the invention aims to solve]

[0007] The present invention was made based on the prior art as described above, and provides a silicon-containing film forming composition with high affinity for the substrate. [Methods used to solve problems]

[0008] The silicon-containing film forming composition of the present invention comprises the following components: (I) A polymer having a polysilane backbone comprising repeating units as shown in formula (ia): (in, Ra1 and Ra2 are independent entities, each being a single bond, hydrogen, halogen, C1-6 alkyl, C6-10 aryl, or -SiRA3 (here, RA is independent, being either hydrogen or C1-8 alkyl), and p is an integer greater than or equal to 5); (II) Silicon compounds having unsaturated hydrocarbon bonds; and (III) Solvent.

[0009] The method for manufacturing the silicon-containing film of the present invention comprises the following steps: The aforementioned silicon-containing film-forming composition is coated onto a substrate to form a coating film; and The aforementioned coating was heated.

[0010] The manufacturing method of the electronic component of the present invention includes the above-mentioned manufacturing method of silicon-containing film. [Invention Effects]

[0011] The silicon-containing film forming composition of this invention has high affinity with the substrate and good coating and adhesion properties. The silicon-containing film system formed using the silicon-containing film forming composition of this invention has low residual stress. Simple Explanation of the Diagram

[0012] none. Implementation

[0013] [definition] In this specification, unless otherwise specified and mentioned, the definitions and examples set forth in this paragraph shall prevail. The singular form includes the plural form, and "a" and "its" mean "at least one". The elements of a concept can be expressed in plural forms, and when their quantity is stated (e.g., mass %, moles %), their quantity means the sum of such plural forms. "And / or" includes all combinations of elements, as well as uses in single-unit form. When using "~" or "-" to represent a numerical range, both endpoints are included, and the units are common. For example, 5~25 mol% means more than 5 mol% and less than 25 mol%. The term "alkyl group" refers to a group formed by removing any one hydrogen atom from a straight-chain, branched, or cyclic saturated hydrocarbon. It includes straight-chain alkyl, branched alkyl, and cyclic alkyl groups. Depending on the need, straight-chain or branched alkyl groups can also be included as side chains in the cyclic structure. The term "aryl group" refers to a group formed by removing any one hydrogen atom from an aromatic hydrocarbon. The notations "C x -y", "C x~C y", and "C x" refer to the number of carbons in a molecule or substituent. For example, C 1-6 alkyl refers to an alkyl chain with one to six carbons (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.). When a polymer has a plurality of repeating units, these repeating units are copolymerized. These copolymerization systems can be any of cross-polymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture thereof. When polymers or resins are represented by structural formulas, the numbers n, m, etc., written together with parentheses indicate the number of repeating units. Temperature is measured in Celsius. For example, 20 degrees means 20 degrees Celsius. Additives refer to the compound itself that has the function (for example, if it is a base-generating agent, it is the compound itself that generates base). It may also be the form in which the compound is dissolved or dispersed in a solvent and added to the composition. As one aspect of the present invention, such a solvent is preferably contained in the composition of the present invention in the form of solvent (III) or other components.

[0014] The following is a detailed description of embodiments of the present invention.

[0015] <Silicone-containing film-forming components> The silicon-containing film-forming composition of the present invention (hereinafter referred to as the composition) comprises (I) a polymer having a polysilane backbone having a specific structure, (II) a silicon compound having unsaturated hydrocarbon bonds, and (III) a solvent.

[0016] (I) Polymers with a polysilane backbone The composition of the present invention comprises: a polymer having a polysilane backbone consisting of repeating units represented by formula (ia) (hereinafter referred to as a polymer having a polysilane backbone, a polymer or component (I)).

[0017] The formula (ia) is as follows. in, Ra1 and Ra2 are independent and are single bonds, hydrogen, halogens, C1-6 alkyl, C6-10 aryl, or -SiRA3, preferably single bonds, hydrogen, or -SiRA3, and more preferably hydrogen. When Ra1 or Ra2 is a single bond, it is bonded to a single bond in a repeating unit of formula (ia) or formula (ib) in the polymer, directly bonding the silicon components of these bonds together. The respective Ra1 systems can be the same or different, and the respective Ra2 systems can be the same or different. While having the same Ra1 and Ra2 is a preferred embodiment of the invention, having different Ra1 and Ra2 is also another embodiment of the invention. RA is independent and is either hydrogen or C1-8 alkyl, preferably hydrogen or methyl, and even more preferably hydrogen. p is an integer greater than or equal to 5, preferably 5 to 20, and even more preferably 6 to 10.

[0018] The polymer system with a polysilane backbone used in this invention is preferably further comprising repeating units represented by formula (ib). The formula (ib) is as follows. in, Rb1 and Rb2 are each independent and are single bonds, hydrogen, halogens, C1-6 alkyl, C6-10 aryl, or -SiRB3, preferably single bonds, hydrogen, or -SiRB3, more preferably hydrogen or single bonds, wherein at least one of Rb1 and Rb2 is a single bond. When Rb1 or Rb2 is a single bond, it is bonded to a single bond in another repeating unit of formula (ib) or formula (ia) in the polymer, directly bonding the silicon of these bonds together. RB are independent and are either hydrogen or C1-8 alkyl, preferably hydrogen or methyl, and even more preferably hydrogen. q is an integer greater than or equal to 5, preferably 5 to 12, and even more preferably 6.

[0019] Specific examples of polymers having a polysilane backbone are listed below.

[0020] Polymers with a polysilane backbone that do not have Si-C bonds are also a preferred form of the present invention. By lacking Si-C bonds, etching in alkaline solutions becomes easier after film formation, thus improving processability.

[0021] The mass-average molecular weight of polymers with a polysilane backbone is preferably 500 to 20,000, more preferably 1,000 to 15,000, based on considerations of solubility in the solvent, flatness of the formed film, and adhesion to the substrate. Here, the mass-average molecular weight refers to the converted mass-average molecular weight of polystyrene, which can be determined using gel permeation chromatography based on polystyrene.

[0022] The polymer having a polysilane backbone is preferably a polymer formed by polymerizing a polysilane compound containing five or more silicon atoms (hereinafter referred to as a polysilane compound). In a preferred embodiment, the polymer having a polysilane backbone is formed by polymerizing the polysilane compound by irradiation and / or heating. The number of silicon atoms contained in polysilane compounds is preferably 5 to 8, with 5 or 6 being more preferred. Polysilane compounds can be inorganic or organic compounds, and can be linear, branched, or partially cyclic.

[0023] The polysilane compound system may be one or a mixture of two or more, preferably comprising cyclic polysilanes, and more preferably composed of cyclic polysilanes. Cyclic polysilane systems are preferably represented by the following formula (ib'). Here, Rb1' and Rb2' are independent and are hydrogen, halogen, C1-6 alkyl, C6-10 aryl or -SiRB'3, preferably hydrogen or silicon, and more preferably hydrogen. R and B' are independent and are either hydrogen or C1-8 alkyl, preferably hydrogen or methyl, and even more preferably hydrogen. q' is an integer greater than or equal to 5, preferably 5 to 8, and even more preferably 5 or 6.

[0024] The cyclic polysilane is preferably at least one selected from the group consisting of silylcyclopentane, silylcyclohexane, disylosilylcyclohexane, cyclopentane and cyclohexane, more preferably cyclohexane or cyclopentane.

[0025] The polysilane compound system may also include chain-like or branched polysilanes. Examples of chain-like or branched polysilanes include neopentyl silane, hexane, 3-silylpentyl silane, 2,2-dicylosyltetrasilane, heptyl silane, tetrasilyltetrasilane, and hexasilylpentyl silane. It is also a preferred embodiment of the present invention to include at least one of these.

[0026] The aforementioned polysilane compounds are preferably polymerized by light and / or heating, and more preferably by light. Under illumination, the wavelength of the peak is preferably 248~436nm, more preferably 282~405nm. The illumination intensity is preferably 10~250mW / cm², more preferably 50~150mW / cm², and the illumination time is preferably 30~300 seconds, more preferably 50~200 seconds. When heating, it is preferable to perform the process at 40~200℃ for 3~300 minutes. Combining the above-mentioned light exposure and heating is also preferable. It is speculated that through this step of light exposure and / or heating, when the polysilane compound contains cyclic polysilane, some or all of the cyclic polysilane is ring-opened. Polymers having a polysilane backbone may also contain cyclic polysilane structures that are not ring-opened.

[0027] (I) The components may be one or a mixture of two or more. (I) The content of the component is based on the total mass of the composition, preferably 2.0 to 30.0% by mass, more preferably 5.0 to 25.0% by mass.

[0028] (II) Silicon compounds containing unsaturated hydrocarbon bonds The composition of the present invention comprises a silicon compound having unsaturated hydrocarbon bonds (hereinafter referred to as component (II), and the same applies to other components). The composition of this invention contains component (II), thereby increasing its affinity with the substrate and improving its coatability and adhesion. As a result, a uniform coating film can be formed on the substrate. While not theoretically limited, this is presumably because: the silicon compound with unsaturated hydrocarbon bonds forms bonds with the polymer having a polysilane backbone, and the bonded silicon compound with unsaturated hydrocarbon bonds forms bonds with hydroxyl groups on the substrate surface. Furthermore, it can reduce the residual stress of the formed silicon-containing film. Although this is not limited by theory, it is speculated that this is because the hydrocarbon locality of silicon compounds with unsaturated hydrocarbon bonds hinders the formation of a three-dimensional silicon-containing network. Furthermore, it can also reduce the refractive index of the formed silicon-containing film. Although not limited by theory, it is speculated that this is achieved through the carbon in silicon compounds with unsaturated hydrocarbon bonds, and that silicon carbide and graphite are locally formed in the silicon-containing film.

[0029] (II) The component has at least one carbon-carbon double bond or carbon-carbon triple bond, preferably having more than two carbon-carbon double bonds. The unsaturated bonds are preferably present at the ends, therefore, (II) the component preferably has more than two vinyl groups, and more preferably has two to four vinyl groups.

[0030] In the preferred form, component (II) is represented by formula (ii). Li and ii are independent of each other, and are single bonds or C1-5 alkyl groups, preferably single bonds, methylene, or ethyl groups, and more preferably single bonds. Rii are independent and are hydrogen or C1-5 alkyl, preferably hydrogen, methyl or ethyl, and more preferably methyl. n can be 1, 2, 3 or 4, preferably 2, 3 or 4, and even better is 4.

[0031] Preferably, (II) is composed of at least one selected from the group consisting of divinylsilane, trivinylsilane, tetravinylsilane, methyl divinylsilane, dimethyl divinylsilane, methyl trivinylsilane, diallylsilane, triallylsilane, diallyl methylsilane, diallyl dimethylsilane, triallyl methylsilane and tetravinylsilane.

[0032] (II) The molecular weight of the component is preferably 50~300, more preferably 80~200. (II) The components may be a mixture of one or more. (II) The content of the component is based on the total mass of the composition, preferably 0.20 to 10.0% by mass, more preferably 0.40 to 7.0% by mass.

[0033] (III) Solvent The composition of this invention comprises a solvent. This solvent can be selected from those that uniformly dissolve or disperse the various components contained in the composition. Specifically, examples of solvents 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 ceroxythionate and ethyl ceroxythionate; propylene glycol monomethyl ether (PGME); and propylene glycol. Propylene glycol monoalkyl ethers such as monoethyl ether, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. (propylene glycol alkyl ether acetates), 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 propylene glycol, and alicyclic hydrocarbons such as cyclooctane and decahydronaphthalene. Cyclooctane, toluene, decahydronaphthalene, and mesitylene are preferred. These solvent systems can be used individually or in combination of two or more.

[0034] The relative permittivity of the solvent is determined to ensure uniform dissolution of polysilane. According to the values ​​recorded in the first edition of the Solvent Handbook, Kodansha Science Journal, it is preferably 3.0 or less, and more preferably 2.5 or less.

[0035] The ratio of solvent varies depending on the coating method and the required film thickness after coating, but the ratio of compounds other than solvent (solid content ratio) is 1 to 96% by mass, preferably 2 to 60% by mass.

[0036] (IV) Polysilazane The composition of this invention can further include (IV) polysilazane. By further including polysilazane, coatability can be improved. Furthermore, the smoothness of the formed silicon-containing film can be improved. The polysilazane system can be arbitrarily selected without impairing the effectiveness of the invention. It can be any inorganic or organic compound, and can also be linear, branched, or partially cyclic.

[0037] Preferably, the polysilazane used in this invention comprises 20 or more, more preferably 20 to 350, and even more preferably 20 to 130 repeating units selected from the group consisting of formulas (iv-1) to (iv-6). In this case, each repeating unit is preferably directly bonded without passing through repeating units other than (iv-1) to (iv-6). Here, R1 to R9 are independent and are either hydrogen or C1-4 alkyl.

[0038] Even more preferably, the polysilazane used in this invention is a perhydropolysilazane (hereinafter referred to as PHPS). PHPS is a silicon-containing polymer containing only Si, N, and H, with Si-N bonds as repeating units. In addition to the Si-N bonds, all elements bonded to Si and N in this PHPS system are H, and it substantially does not contain other elements such as carbon or oxygen. The simplest structure of perhydropolysilazane is a chain structure with the following repeating units.

[0039]

[0040] In this invention, PHPS with intramolecular chain and ring structures can be used. For example, PHPS composed of repeating units represented by formulas (iv-a) to (iv-f) and terminal groups represented by formula (iv-g) can be used.

[0041]

[0042] These types of PHPS have branched or ring structures within their molecules. Examples of specific local structures of these PHPS are shown in the following general formula.

[0043]

[0044] Alternatively, it can have the structure shown in the following formula, that is, a structure formed by cross-linking of multiple Si-N molecular chains.

[0045] The PHPS used in this invention is not limited in structure as long as it is a silicon-containing polymer containing only Si, N, and H, with Si-N bonds as repeating units. Various other structures as exemplified above can be used. For example, it can also have a structure combining the linear, cyclic, and cross-linked structures described above. Furthermore, the PHPS used in this invention preferably has a cyclic or cross-linked structure, especially a cross-linked structure.

[0046] The mass-average molecular weight of the polysilazane used in the manufacturing method of this invention is preferably 900-15,000, more preferably 900-10,000, based on its solubility and reactivity with the solvent. Here, the mass-average molecular weight refers to the weight-average molecular weight converted from polystyrene, which can be determined using gel permeation chromatography based on polystyrene.

[0047] (IV) The content of the component is based on the total mass of the composition, preferably 0 to 5.0% by mass, more preferably 0.50 to 3.0% by mass.

[0048] The components used in this invention can be further combined with compounds as needed. The materials that can be combined with these compounds are explained below. Furthermore, the components other than (I) to (IV) in the total composition are preferably 10% or less, more preferably 5% or less, relative to the total mass.

[0049] Surfactants are used to improve coatability. Examples of surfactants include nonionic surfactants, anionic surfactants, and amphoteric surfactants.

[0050] Examples of nonionic surfactants include: polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene oil-based ether, and polyoxyethylene cetyl ether; polyoxyethylene fatty acid diesters, polyoxyethylene fatty acid monoesters, and polyoxyethylene polyoxypropylene block polymers; ethynyl alcohol derivatives such as ethynyl alcohol, ethynyl glycol, and polyethynyl alcohol polyethoxylates; ethynyl glycol derivatives such as ethynyl glycol polyethoxylates; fluorinated surfactants such as Florard (trade name, manufactured by 3M Corporation), Megafac (trade name, manufactured by DIC Corporation), and Sulfuron (trade name, manufactured by Asahi Glass Corporation); or organosiloxane surfactants such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of acetylene glycols mentioned above include: 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,6-dimethyl-4-octyyn-3,6-diol, 2,4,7,9-tetramethyl-5-decyn-4,7-diol, 3,5-dimethyl-1-hexyn-3-ol, 2,5-dimethyl-3-hexyn-2,5-diol, and 2,5-dimethyl-2,5-hexanediol.

[0051] Examples of anionic surfactants include ammonium salts or organic amine salts of alkyl diphenyl ether disulfonic acid, ammonium salts or organic amine salts of alkyl diphenyl ether sulfonic acid, ammonium salts or organic amine salts of alkylbenzene sulfonic acid, ammonium salts or organic amine salts of polyoxyethylene alkyl ether sulfuric acid, and ammonium salts or organic amine salts of alkyl sulfuric acid.

[0052] Examples of amphoteric surfactants include 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine and laurate aminopropyl hydroxybenzene.

[0053] These surfactants can be used alone or in combination of two or more, with the mixing ratio based on the total mass of the composition, typically 50 to 10,000 ppm, preferably 100 to 5,000 ppm.

[0054] <Preparation Method of Silicon-Containing Film Forming Constituents> The preparation method of the silicon-containing film-forming composition of the present invention is not particularly limited. When the polymer having a polysilane backbone is a cyclic polysilane containing five or more silicon atoms, it can be manufactured, for example, by a method comprising the following steps: (A) The step of irradiating cyclic polysilanes containing five or more silicon atoms. (B) The step of preparing the mixture comprising a silicon compound having unsaturated hydrocarbon bonds used in this invention. (C) Step of irradiating the mixture. The following is an example of a manufacturing method, explained step by step.

[0055] The wavelength in step (A) is preferably composed of a peak wavelength of at least 172-405 nm, more preferably 282-405 nm. The irradiation intensity is preferably 10-250 mW / cm², more preferably 50-150 mW / cm², and the irradiation time is preferably 30-300 seconds, more preferably 50-200 seconds. Since cyclopentane or cyclohexane are liquids at room temperature, cyclic polysilanes in their liquid state can be stirred and exposed to light simultaneously. Alternatively, when the cyclic polysilane is a solid, it can be dissolved in a suitable solvent and stirred while being exposed to light. It is speculated that the ring-opening of one or all of the cyclic polysilane is achieved through the illumination in this step.

[0056] (B) Steps for preparing the mixture comprising a silicon compound having unsaturated hydrocarbon bonds used in this invention When the irradiated cyclic polysilane is in a liquid state at room temperature, the aforementioned silicon compound with unsaturated hydrocarbon bonds is added, and the mixture is stirred to prepare a mixture. Alternatively, if the irradiated cyclic polysilane is in a solid state, it can be dissolved in a suitable solvent. The mixture can also be prepared by dissolving the silicon compound with unsaturated hydrocarbon bonds in a suitable solvent, then adding it to the irradiated cyclic polysilane, and stirring.

[0057] (C) Step of irradiating the mixture It is hypothesized that the light exposure during this step causes the polysilanes to condense together, forming a polymer with a polysilane backbone. The exposure wavelength is preferably composed of a peak wavelength of at least 172-405 nm, more preferably 282-405 nm. The irradiation intensity is preferably 10-250 mW / cm², more preferably 50-150 mW / cm², and the irradiation time is preferably 5-100 minutes, more preferably 5-60 minutes. The irradiation energy is preferably 3-1,500 J, more preferably 25-500 J. Alternatively, the order of steps (B) and (C) can be reversed. That is, step (C) can be performed after step (A), followed by the addition of a silicon compound with unsaturated hydrocarbon bonds to prepare a mixture. Steps (A), (B) and (C) above should preferably be carried out in a non-oxidizing environment. The solvent system, as described above, can be added during steps (A) and (B), or after step (C). It is preferable that any of the above components be added after step (C).

[0058] <Manufacturing Method of Silicon-Containing Films> The method for manufacturing the silicon-containing film of the present invention comprises the following steps: The aforementioned silicon-containing film-forming composition is coated onto a substrate to form a coating film; and The coating is heated. In this invention, "on a substrate" may also include cases where the composition is directly coated on the substrate, or cases where the composition is coated on the substrate through one or more intermediate layers.

[0059] As for the coating method, any previously known method can be selected, such as spin coating, dip coating, spray coating, transfer coating, inkjet coating, roller coating, bar coating, brush coating, doctor blade coating, blow coating, and slot coating. Furthermore, as the substrate for the coating composition, suitable substrates such as silicon substrates, glass substrates, and resin films can be used. Various semiconductor devices can be formed on these substrates as needed. When the substrate is a thin film, gravure coating can also be used. A drying step can also be added separately after coating, depending on the desired result. Furthermore, the coating step can be repeated once or more as needed to achieve the desired film thickness.

[0060] Alternatively, after forming a coating film using the composition of the present invention, the coating film may be pre-baked (heat-treated) in order to dry the coating film and reduce the amount of solvent residue. The pre-baking step can be carried out in an oxidizing or non-oxidizing environment, preferably at a temperature of 50~400℃, for 10 seconds to 60 minutes when using a heating plate, and for 1~120 minutes when using a clean oven.

[0061] After forming a coating film using the composition of the present invention, the coating film can be subjected to electron beam irradiation or light irradiation before heating for curing, preferably electron beam irradiation. The accelerating voltage of the electron beam irradiation system is preferably 20-200 kV, and the irradiation linearity is preferably 5,000-50,000 kGy. The light irradiation system preferably uses light with a peak wavelength of 248-436 nm, more preferably 248-405 nm. The irradiation intensity is preferably 10-800 mW / cm², more preferably 40-600 mW / cm², and the irradiation time is preferably 30-3,500 seconds, more preferably 50-3,000 seconds.

[0062] Subsequently, the pre-baked, electron-beam-irradiated, and / or light-treated coating is heated in a non-oxidizing environment, an oxidizing environment, and / or an ammonia environment to harden it, thereby forming a silicon-containing film. The heating temperature is preferably 200~1000℃, more preferably above 300℃. The heating time is not particularly limited, but should be set from 0.001 seconds to 24 hours. Flash annealing can also be used. Generally, it takes from a few seconds to several hours for the patterned film to reach the desired temperature from the initial temperature.

[0063] The so-called non-oxidizing environment refers to an environment with an oxygen concentration of less than 1 ppm and a dew point of less than -76°C. Preferably, it is an environment of N2, Ar, He, Ne, H2, or a mixture of two or more of these gases.

[0064] An oxidizing environment refers to an oxygen partial pressure of 20~101kPa, preferably 40~101kPa, and more preferably including a water vapor partial pressure of 1.5~80kPa at a total pressure of 101kPa. Furthermore, in environments containing water vapor, when heating at high temperatures (e.g., exceeding 600°C), there are concerns about potential adverse effects on other elements, such as electronic devices, exposed to the heat treatment. In such cases, the heating process can be divided into two or more stages (preferably three or more stages). For example, heating can be performed initially in an environment containing water vapor at a low temperature (e.g., a temperature range of 200–400°C), followed by heating in an environment containing water vapor at a relatively low temperature (e.g., a temperature range of 300–600°C), and then heating in an environment without water vapor at a higher temperature (e.g., 400–800°C).

[0065] As a component other than water vapor in an environment containing water vapor (hereinafter referred to as a diluent gas), any gas can be used, such as air, oxygen, nitrogen, nitric oxide, ozone, helium, and argon. When considering the membrane material of a silicon-containing membrane, it is preferable to use oxygen as the diluent gas.

[0066] The so-called ammonia environment refers to an ammonia partial pressure of 20~101kPa, preferably 25~80kPa, when the total pressure is 101kPa.

[0067] By heating and hardening in a non-oxidizing environment, the silicon-containing film of the present invention can be made into an amorphous silicon film. After hardening, no diffraction peak of crystalline Si was observed by X-ray diffraction (XRD), thus confirming that it is an amorphous silicon film.

[0068] By hardening it through heating in an oxidizing environment, the silicon-containing film of the present invention can be made into a silicon dioxide film. In the present invention, the so-called silicon dioxide film refers to a film containing both oxygen and silicon atoms, where the ratio of oxygen atoms to silicon atoms (O / Si) is 1.20~2.50, more preferably 1.40~2.50, and even more preferably 1.60~2.45. The silicon dioxide film can contain other atoms such as hydrogen, nitrogen, and carbon.

[0069] The silicon-containing film of the present invention can be made into a silicon nitride film by hardening it through heating in an ammonia environment. In the present invention, the so-called silicon nitride film refers to a film in which the ratio of nitrogen atoms to 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.

[0070] The thickness of the silicon-containing film formed is not particularly limited, but is preferably 20~500nm, and more preferably 20~300nm. By using the components of this invention, silicon-containing films with high flatness can be formed. The formed silicon-containing films have low residual stress.

[0071] Furthermore, the manufacturing method of the electronic component of the present invention comprises the manufacturing method described above. The electronic component of the present invention is preferably a semiconductor element, a solar cell chip, an organic light-emitting diode, or an inorganic light-emitting diode. A preferred form of the electronic component of the present invention is a semiconductor element.

[0072] The present invention will now be described by way of examples. These examples are illustrative and are not intended to limit the scope of the invention.

[0073] The synthesis of polysilane and the preparation of its components in the following examples and comparative examples were all carried out in a glove box under a controlled nitrogen atmosphere, with an oxygen concentration of less than 0.1 ppm and a dew point temperature of less than -76°C.

[0074] [Example 1] A stir bar was placed in a 9 mL spiral tube, and 246.4 mg of cyclohexylsilane was added. While stirring with a stir bar, the tube was irradiated with 0.7 J / cm² ultraviolet light at a wavelength of 365 nm using an LED lamp as the light source. After UV irradiation, 68.1 mg of tetravinylsilane and 31.4 mg of perhydropolysilazane were added, and the mixture was stirred with a stir bar at room temperature for 12 hours. After stirring, 2957 mg of cyclooctane was added, and the mixture was stirred for 3 minutes. The mixture was then filtered using a 0.2 μm PTFE filter (Advantec, DISMIC-13JP) to obtain the composition of Example 1. Furthermore, the polymer with a polysilane backbone has a mass-average molecular weight of 4,800. The mass-average molecular weight (Mw) was determined using gel permeation chromatography (GPC) with polystyrene as a reference. GPC was performed using an Alliance™ e2695 high-speed GPC system (Japan Waters Co., Ltd.) and an organic solvent-based GPC column, Shodex KF-805L (Showa Denko Co., Ltd.). The determination was conducted under the following conditions: monodisperse polystyrene as the standard sample, cyclohexene as the developing solvent, a flow rate of 0.6 mL / min, and a column temperature of 40°C. Mw was then calculated as the relative molecular weight relative to the standard sample.

[0075] [Examples 2-8, Comparative Example 1] Except for the ingredients and composition listed in Table 1, the same procedures were performed as in Example 1 to prepare the compositions of Examples 2-8 and Comparative Example 1. The Mw system of the obtained polymers with polysilane backbones was measured in the same manner as described above, and the results are recorded in Table 1. [Table 1] (I) Polymers with a polysilane backbone (II) Possesses unsaturated hydrocarbon bonds Silicon compounds (III) Solvent (IV) Polysilazane Polysilane compounds Ultraviolet radiation Mw Example 1 Cyclohexane 246.4 mg 365nm (LED) 0.7 J / cm 2 4,800 Tetravinylsilane 68.1 mg Cyclooctane 2957 mg perhydropolysilazane 31.4 mg Example 2 Cyclohexane 246.4 mg 365nm (LED) 0.7 J / cm 2 5,350 Tetravinylsilane 38.4 mg Cyclooctane 1879 mg perhydropolysilazane 15.5 mg Example 3 Cyclohexane 246.4 mg 365nm (LED) 0.7 J / cm 2 5,630 Tetravinylsilane 117.9 mg Cyclooctane 1813 mg perhydropolysilazane 31.4 mg Example 4 Cyclohexane 246.4 mg 365nm (LED) 0.7 J / cm 2 5,180 Tetravinylsilane 13.6 mg Cyclooctane 2096 mg perhydropolysilazane 41.7 mg Example 5 Cyclohexane 246.4 mg 365nm (LED) 0.7 J / cm 2 5,200 Tetravinylsilane 39.3 mg Cyclooctane 2999 mg perhydropolysilazane 31.4 mg Example 6 Cyclohexane 246.4 mg 365nm (LED) 0.5 J / cm 2 4,620 dimethyldivinylsilane 21.0 mg Cyclooctane 2136 mg - - Example 7 Cyclohexane 246.4 mg 365nm (LED) 0.7 J / cm 2 4,800 Tetravinylsilane 68.1 mg Cyclooctane 2957 mg perhydropolysilazane 31.4 mg Example 8 Cyclohexane 246.4 mg 365nm (LED) 0.7 J / cm 2 4,800 Tetravinylsilane 68.1 mg Cyclooctane 2957 mg perhydropolysilazane 31.4 mg Comparative Example 1 Cyclohexane 268.7 mg 365nm (LED) 8.4 J / cm 2 8,650 - - Cyclooctane 1226 mg perhydropolysilazane 17.3 mg

[0076] [Formation of silicon-containing films] In a nitrogen atmosphere, a spin coater was used to coat the composition of Example 1 prepared as described above onto a Si substrate to form a coating film. In a nitrogen atmosphere, the obtained coating film was heated at 400°C for 15 minutes on a hot plate to obtain a silicon-containing film. Except for using the compositions prepared according to Examples 2-8 and Comparative Example 1 as described above, and changing the heating conditions to those described in Table 2, the heating was performed in the same manner. Using the compositions of Examples 1-6 and Comparative Example 1, the FT-IR spectra of the formed silicon-containing films were performed at room temperature using an FTIR-6100 (JASCO) to confirm that the obtained silicon-containing films were amorphous silicon films. In the case of using the composition of Example 7, the obtained silicon-containing film was confirmed to be a silicon dioxide film by FT-IR spectroscopy. In the case of using the composition of Example 8, the obtained silicon-containing film was confirmed to be a silicon nitride film by FT-IR spectroscopy. When using the compositions of Examples 1-8 and Comparative Example 1, the coating properties are good, a coating film can be uniformly formed on the substrate, and it will not peel off from the substrate when heated, thus forming a uniform silicon-containing film. Regarding the heating conditions of Example 5, a linear irradiation type low-energy electron beam irradiation device EES-30L-MPM01 (Hamamatsu Photonics Co., Ltd.) was used to irradiate the coating film of Example 5 on the Si substrate with an electron beam of 32,000 kGy at room temperature and in a nitrogen atmosphere, with an accelerating voltage of 70 kV and a tube current of 7.6 mA. The film was heated at 400°C for 15 minutes on a hot plate in a nitrogen atmosphere to obtain a silicon-containing film.

[0077] [film thickness] The thickness of the silicon-containing film was determined using a spectroradiometer M-2000V (JA Woollam). The film thickness was measured at eight points on the wafer, excluding the center, and the average value was used. The results are recorded in Table 2.

[0078] [Refractive Index] The refractive index of the obtained silicon-containing film was measured using a spectroradiometer M-2000V (JA Woollam) at a wavelength of 633 nm. The results are recorded in Table 2.

[0079] [Residual Stress] Residual stress was measured using a thin-film stress measuring device FLX-3300-T (Dongpeng Technology). The results are recorded in Table 2. [Table 2] Film thickness (nm) Refractive index @ 633nm Residual stress (MPa) Heating conditions Example 1 176 2.02 7. Stretching Nitrogen atmosphere, 400℃, 15 minutes Example 2 155 2.05 56 Stretching Nitrogen atmosphere, 400℃, 15 minutes Example 3 170 1.99 -21 compression Nitrogen atmosphere, 400℃, 15 minutes Example 4 160 2.41 98 stretch Nitrogen atmosphere, 400℃, 15 minutes Example 5 149 2.01 70 stretch After electron beam irradiation Nitrogen atmosphere, 400℃, 15 minutes Example 6 208 2.88 44 Stretching Nitrogen atmosphere, 400℃, 15 minutes Example 7 193 1.46 32 stretching Water vapor environment 400℃ for 15 minutes Example 8 152 1.79 156 stretch Ammonia environment, 400℃, for 15 minutes Comparative Example 1 202 3.18 320 stretch Nitrogen atmosphere, 400℃, 15 minutes

[0080] none

Claims

1. A silicon-containing film-forming composition comprising the following components: (I) a polymer having a polysilane backbone comprising repeating units of formula (ia): (wherein Ra1 and Ra2 are each independently a single bond, hydrogen, halogen, C1-6 alkyl, C6-10 aryl or -SiRA3 (here, RA are each independently hydrogen or C1-8 alkyl), and p is an integer of 5 or more); (II) a silicon compound having unsaturated hydrocarbon bonds; and (III) a solvent.

2. The composition of claim 1, wherein (I) the polymer having a polysilane backbone further comprises repeating units of formula (ib): (wherein, Rb1 and Rb2 are each independent and can be a single bond, hydrogen, halogen, C1-6 alkyl, C6-10 aryl, or -SiRB3 (where Rb1 and Rb2 are each independent and can be hydrogen or C1-8 alkyl), wherein at least one of Rb1 and Rb2 is a single bond, and q is an integer greater than or equal to 5.

3. The composition of claim 1 or 2 further comprising (IV) polysilazane.

4. A composition as claimed in claim 1 or 2, wherein (II) is a silicon compound having unsaturated hydrocarbon bonds represented by formula (ii): (wherein, Lii is independent and is a single bond or a C1-5 alkyl group; Rii is independent and is hydrogen or a C1-5 alkyl group; n is 1, 2, 3 or 4.

5. A composition of claim 1 or 2, wherein (II) the silicon compound having an unsaturated hydrocarbon bond is at least one selected from the group consisting of diallyl silane, trivinyl silane, tetravinyl silane, methyl diallyl silane, dimethyl diallyl silane, methyl trivinyl silane, diallyl silane, triallyl silane, diallyl methyl silane, diallyl dimethyl silane, triallyl methyl silane and tetravinyl silane.

6. The composition of claim 1 or 2, wherein the relative permittivity of the solvent in (III) is 3.0 or less.

7. The composition of claim 1, wherein (I) the polymer having a polysilane backbone is a polymer formed by polymerizing a polysilane compound comprising 5 or more silicon atoms.

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

9. The composition of claim 8, wherein the cyclic polysilane is of formula (ib'): (wherein, Rb1' and Rb2' are each independent and can be hydrogen, halogen, C1-6 alkyl, C6-10 aryl, or -SiRB'3 (where RB' is independent and can be hydrogen or C1-8 alkyl), and q' is an integer of 5 or more.

10. The composition of claim 8 or 9, wherein the cyclic polysilane is at least one selected from the group consisting of silylcyclopentane, silylcyclohexane, disylosilylcyclohexane, cyclopentane, and cyclohexane.

11. A composition of any one of claims 7 to 9, wherein the polysilane compound is at least one selected from the group consisting of neopentyl silane, hexyl silane, 3-silylpentyl silane, 2,2-dicylosilane, heptyl silane, tetrasilyltetrasilane, and hexasilylpentyl silane.

12. A method for manufacturing a silicon-containing film, comprising the steps of: coating a composition of any one of claims 1 to 11 onto a substrate to form a coating film; and heating the coating film.

13. The method of claim 12, wherein the coating is formed by heating it in a non-oxidizing environment.

14. The method of claim 12, which involves heating the coating in an oxidizing environment.

15. The method of claim 12 or 13, which involves heating the coating in an ammonia environment.

16. The method of claim 12 or 13, wherein after the coating is formed, light with a peak wavelength of 248 to 436 nm is further irradiated.

17. The method of claim 12 or 13, wherein an electron beam is irradiated after the coating is formed and before the coating is heated.

18. The method of claim 12 or 13, wherein the heating is performed at 200 to 1000°C.

19. A method for manufacturing an electronic component, comprising the method of any one of claims 12 to 18.