Stabilizer for inhibiting silane generation from polysilane compositions and method for inhibiting silane generation

Abstract

The present invention provides a stabilizer for suppressing silane generation from a polysilane composition, a method for suppressing silane generation, a polysilane deactivation treatment method, and a polysilane deactivation treatment composition. The present invention provides a stabilizer for suppressing silane generation from polysilane compositions, the stabilizer being represented by: CH2=CH-R 1 (In the formula, R 1 is C 3~20 linear, branched or cyclic alkyl groups, C 2~15 a linear or branched alkenyl group, or C 7~20 is an aryl group substituted with an alkenyl group of the formula:

Description

[Technical Field]

[0001] The present invention relates to a stabilizer for inhibiting silane generation from a polysilane composition, and a method for inhibiting silane generation.Furthermore, the present invention relates to a polysilane passivation treatment method and a polysilane passivation treatment composition. [Background technology]

[0002] Silicon films have relatively high hardness and airtightness, and are therefore used for a variety of purposes in the field of semiconductor device manufacturing. Specifically, they are used as hard coat films for substrates and circuits, gas barrier films, and films for improving substrate strength. Among these, high-molecular-weight polysilanes are soluble in solvents, allowing thin films to be formed by a simple process of applying a coating solution and heating it without creating a vacuum. Polysilanes can also be used to fill fine grooves in interlayer insulating films of semiconductor devices, etc., by utilizing the capillary phenomenon of the liquid.

[0003] It is known that polysilanes decompose and generate silane gas (SiH4 gas) when stored for a long period of time. SiH4 is a highly volatile gas that can spontaneously combust in air. To ensure safety, such silane gas has traditionally been treated by methods such as hydrolysis using an alkaline solution, adsorption and removal using metal oxides, or combustion. However, all of these treatment methods require equipment. Furthermore, these methods are intended to treat generated silane, but do not suppress the generation of silane, so there is a risk until the treatment is complete.

[0004] When forming a thin film using a coating solution containing polysilane, for example, spin coating can be used. When a solution is applied to a substrate by spin coating, an edge bead is formed around the periphery of the substrate, and the solution spreads around to the backside of the substrate. To prevent this edge bead from causing uneven thickness of the coating film around the periphery of the substrate, an edge bead removal process (hereinafter referred to as EBR process) is usually performed after the coating solution is applied. This process involves applying or spraying a treatment solvent around the periphery of the coating film formed on the front side of the substrate to remove the coating film around the periphery (edge ​​cut). In addition, a back rinse is also performed to remove the polysilane that has spread around to the backside of the substrate and clean the backside. The rinse solution used after this back rinse contains polysilane. In addition, the coating film may need to be peeled off from the substrate depending on the necessity of subsequent processing, and polysilane adhering to a coating device such as a spin coater may need to be washed off and removed. After such processing, the polysilane is contained in the peeling solution, etc. Such a rinse solution or stripper solution containing polysilane may temporarily remain in a waste tank, generating silane gas in the waste tank, which requires the above-described treatment of the silane gas.

[0005] In view of recent demands for more precise quality control and safety assurance, there is a demand for a method that allows polysilanes to be used in a safer and simpler manner. DISCLOSURE OF THE INVENTION [Problem to be solved by the invention]

[0006] The present invention aims to provide a stabilizer for suppressing silane generation from a polysilane composition, a method for suppressing silane generation, a polysilane deactivation method, and a polysilane deactivation composition. [Means for solving the problem]

[0007] The stabilizer for inhibiting silane generation from the polysilane composition of the present invention is represented by the following formula: CH2=CH-R 1 In the formula, R 1 teeth, C 3~20 a linear, branched or cyclic alkyl group, C 2~15 a linear or branched alkenyl group of C 8~20 is an aryl group substituted with an alkenyl group.

[0008] The stabilizer according to the present invention is used to suppress the generation of silane from a polysilane composition by adding the stabilizer to the polysilane composition.

[0009] The method for suppressing silane generation according to the present invention comprises the coexistence of polysilane and the above-mentioned stabilizer.

[0010] The method for inactivating a polysilane-containing waste liquid according to the present invention comprises mixing the above-mentioned stabilizer with the polysilane-containing waste liquid.

[0011] The polysilane deactivation treatment composition according to the present invention comprises the above-mentioned stabilizer and a solvent. [Effects of the Invention]

[0012] According to the present invention, it is possible to suppress the generation of silane from a polysilane composition and maintain the silane concentration at a low level using a simple method. DETAILED DESCRIPTION OF THE INVENTION

[0013] Hereinafter, embodiments of the present invention will be described in detail. In this specification, unless otherwise specified, the symbols, units, abbreviations and terms have the following meanings. In this specification, unless otherwise specified, the singular includes the plural, and "one" and "the" mean "at least one." In this specification, unless otherwise specified, elements of a concept may be expressed by a plurality of species, and when an amount (e.g., mass % or mole %) is described, the amount refers to the sum of the plurality of species. "And / or" includes all combinations of elements and also includes the use of a single element.

[0014] In this specification, 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.

[0015] In this specification, the term "hydrocarbon" refers to a group containing carbon and hydrogen, and optionally oxygen or nitrogen. The term "hydrocarbon group" refers to a monovalent or divalent or higher hydrocarbon group. In this specification, "aliphatic hydrocarbon" refers to a linear, branched, or cyclic aliphatic hydrocarbon, and "aliphatic hydrocarbon group" refers to a monovalent or divalent or higher valent aliphatic hydrocarbon. "Aromatic hydrocarbon" refers to a hydrocarbon containing an aromatic ring, which may optionally have an aliphatic hydrocarbon group as a substituent or may be condensed with an alicyclic ring. "Aromatic hydrocarbon group" refers to a monovalent or divalent or higher valent aromatic hydrocarbon. "Aromatic ring" refers to a hydrocarbon having a conjugated unsaturated ring structure, and "alicyclic ring" refers to a hydrocarbon having a ring structure but not a conjugated unsaturated ring structure.

[0016] In this specification, alkyl refers to a group in which any one hydrogen atom has been removed from a linear or branched saturated hydrocarbon, and includes linear alkyl and branched alkyl. Cycloalkyl refers to a group in which one hydrogen atom has been removed from a saturated hydrocarbon containing a cyclic structure, and the cyclic structure may optionally contain a linear or branched alkyl atom as a side chain.

[0017] As used herein, alkenyl refers to a straight or branched chain hydrocarbon group having one carbon-carbon double bond and having one hydrogen removed from any carbon.

[0018] As used herein, aryl refers to a group obtained by removing one arbitrary hydrogen from an aromatic hydrocarbon. Alkylene refers to a group obtained by removing two arbitrary hydrogens from a linear or branched saturated hydrocarbon. Arylene refers to a hydrocarbon group obtained by removing two arbitrary hydrogens from an aromatic hydrocarbon.

[0019] 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 an alkyl having 1 to 6 carbon atoms (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.). In addition, as used herein, fluoroalkyl refers to an alkyl in which one or more hydrogen atoms have been replaced with fluorine atoms, and fluoroaryl refers to an aryl in which one or more hydrogen atoms have been replaced with fluorine atoms.

[0020] In this specification, when a polymer has multiple types of repeating units, these repeating units are copolymerized, and the copolymerization may be alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture thereof. In this specification, % means mass % and ratio means mass ratio.

[0021] In this specification, the unit of temperature is Celsius. For example, 20 degrees means 20 degrees Celsius.

[0022] <Stabilizer> The stabilizer according to the present invention is used to inhibit silane generation from polysilane compositions and is represented by the following formula: CH2=CH-R 1 In the formula, R 1 teeth, C 3~20 a linear, branched or cyclic alkyl group, C 2~15a linear or branched alkenyl group of C 8~20 is an aryl group substituted with an alkenyl group.

[0023] Preferably, R 1 but, (I C 3~20 a linear or branched alkyl group, (ii) C 5~8 cyclic alkyl groups, (iii)C 3~15 a straight-chain, terminally unsaturated alkenyl group, or (iv) C 8~10 and a phenyl group substituted with an alkenyl group having an unsaturated bond at the terminal.

[0024] R 1 In the case of (i), the stabilizer is Examples include 1-pentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene, 1-heptene, 5-methyl-1-hexene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-octadecene.

[0025] R 1 However, in the case of (ii), the stabilizer preferably has a cyclic alkyl group which is a 5-membered or 6-membered ring, Examples include vinylcyclopentane, vinylcyclohexane, and allylcyclohexane.

[0026] R 1 In the case of (iii), the stabilizer may be: Examples include 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, and 1,11-dodecadiene.

[0027] R 1In the case of (iv), the stabilizer may be: Examples include 1,2-divinylbenzene, 1,3-divinylbenzene, and 1,4-divinylbenzene.

[0028] The stabilizer according to the present invention may be a mixture containing two or more of the above compounds.

[0029] The stabilizer according to the present invention can generally be applied to any polysilane composition. Here, the polysilane composition may consist of only polysilane, or may contain other substances besides polysilane, such as a solvent.

[0030] The polysilane that can be stabilized with the stabilizer of the present invention is not particularly limited as long as it has a main chain consisting only of Si-Si bonds and is a linear, cyclic, or branched compound. Polysilanes with a branched structure are preferred because they have more terminal groups and are therefore more likely to exhibit the silane generation suppression effect of the present invention. When the polysilane is polyperhydrosilane, the effect of the stabilizer according to the present invention is enhanced, and therefore it is preferred. The mass average molecular weight of the polysilane is not particularly limited, but it is believed that the stabilizer of the present invention is most effective when it is 300 to 10,000, and even more effective when it is 500 to 5,000. Here, the mass average molecular weight is the mass average molecular weight converted into polystyrene, and can be measured by gel permeation chromatography using polystyrene as the standard.

[0031] By adding the stabilizer of the present invention to a polysilane composition and allowing the polysilane and the stabilizer of the present invention to coexist, it is possible to suppress the generation of silane from the polysilane composition. Without being bound by theory, this is thought to be due to the following reasons. The stabilizer according to the present invention has a terminal carbon-carbon double bond. Polysilane decomposes to form silylene radicals, which react with other polysilanes to increase the molecular weight of the polysilane. The silylene radicals are likely to bond with compounds having carbon-carbon double bonds to form stable compounds. Therefore, by allowing polysilane and the stabilizer according to the present invention to coexist, the formed silylene radicals react with the stabilizer, preventing further increase in the molecular weight of the polysilane. Since the higher the molecular weight of a polysilane, the more silane gas is generated in a short period of time. Therefore, by using the stabilizer according to the present invention to suppress the polymerization reaction, the amount of silane generated can be reduced.

[0032] The number of moles of the stabilizer according to the present invention based on the number of moles of Si in the polysilane is preferably 10 to 1,000 mol %, more preferably 50 to 300 mol %.

[0033] <Polysilane Deactivation Treatment Composition> The polysilane deactivation treatment composition of the present invention (hereinafter sometimes referred to as the treatment composition) comprises the above-mentioned stabilizer and a solvent. The polysilane deactivation treatment composition of the present invention can be suitably used as an edge bead removal treatment composition or a waste liquid treatment composition. Preferred stabilizers are the same as those described above.

[0034] The solvent is selected from those that can dissolve the stabilizer uniformly. 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); Examples of the hydrocarbon solvent include propylene glycol monoalkyl ethers such as 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. Preferred are cyclooctane, toluene, decalin, and mesitylene. These solvents may be used alone or in combination of two or more.

[0035] The blending ratio of the solvent varies depending on the application, but the ratio of compounds other than the solvent is preferably 1 to 96 mass %, more preferably 2 to 60 mass %.

[0036] The treatment composition of the present invention can be combined with other compounds as needed within the range that does not impair the effects of the present invention. The amount of components other than the stabilizer and solvent in the entire composition is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass.

[0037] 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. In the following description, "parts" are by mass unless otherwise specified.

[0038] In the following synthesis examples and working examples, all steps involving polysilane are carried out in a glove box under a nitrogen atmosphere, with an oxygen concentration of 1.0 ppm or less and a dew point temperature controlled to -76.0°C or less.

[0039] Polysilane synthesis A stirrer tip was placed in a 50 mL screw tube, 30 g (0.166 mol) of cyclohexasilane was added, and the mixture was stirred using a stirrer. A mercury xenon light source was used as the light source, and ultraviolet light with a wavelength of 365 nm was applied at 8.5 J / cm. 2 After ultraviolet irradiation, the polysilane is dissolved in cyclooctane, and cyclooctane is added to adjust the solid content to 19% by mass. The mass average molecular weight of the resulting polysilane is 800.

[0040] Examples 1 to 4 and Comparative Examples 1 to 2 0.2 g of the cyclooctane solution of polysilane obtained in the synthesis example and a stabilizer listed in Table 1 were placed in a 20 ml glass syringe vial (ASLAB2017-V, SCW223: AS ONE Corporation), and diluted with cyclooctane so that the polysilane was 10 mass % of the total solution. Note that no stabilizer was added in Comparative Example 1. Next, the gas phase of the syringe vial is replaced with air and sealed. Three syringe vials are prepared under the same conditions and stored at 23±1°C for 72 hours. After 72 hours, the silane concentration in the gas phase is measured by gas chromatography. The average of the three values ​​is used as the measured value. [Table 1]

[0041] Silane concentration measurement The silane concentration in the gas phase was measured using a gas chromatograph GC-8A (Shimadzu Corporation), carrier gas: N2, column: PoraPak Q80 / 100, detector: TCD. Calibration was performed using 1000 ppm silane standard gas.

Claims

1. A stabilizer for inhibiting silane generation from a polysilane composition, represented by the formula: CH ２ =CH-R １ (In the formula, R １ teeth, C ３～２０ a linear, branched or cyclic alkyl group, C ２～１５ a linear or branched alkenyl group of C8-20 aryl group substituted with an alkenyl group).

2. R １ but, C ３～２０ a linear or branched alkyl group, C ５～８ a cyclic alkyl group, C ３～１５ a straight-chain, terminally unsaturated alkenyl group, or 2. The stabilizer according to claim 1, which is a phenyl group substituted with a C8-10 alkenyl group having an unsaturated bond at the terminal.

3. 3. The stabilizer of claim 1, wherein the stabilizer is selected from the group consisting of 1-pentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene, 1-heptene, 5-methyl-1-hexene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, vinylcyclopentane, vinylcyclohexane, allylcyclohexane, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,2-divinylbenzene, 1,3-divinylbenzene, and 1,4-divinylbenzene.

4. The stabilizer according to any one of claims 1 to 3, wherein the polysilane is polyperhydrosilane.

5. 5. Use of the stabilizer according to claim 1, which is added to a polysilane composition to suppress generation of silane from the polysilane composition.

6. A method for inhibiting silane generation, comprising the coexistence of a polysilane and the stabilizer according to any one of claims 1 to 4.

7. A stabilizer represented by the following formula was added to the polysilane-containing waste liquid: CH ２ =CH-R １ (In the formula, R １ teeth, C ３～２０ a linear, branched or cyclic alkyl group, C ２～１５ a linear or branched alkenyl group of C8-20 aryl group substituted with alkenyl group 1. A method for inactivating a polysilane-containing waste liquid, comprising: mixing the above components.

8. a stabilizer represented by the formula: CH ２ =CH-R １ (In the formula, R １ teeth, C ３～２０ a linear, branched or cyclic alkyl group, C ２～１５ a linear or branched alkenyl group of C8-20 aryl group substituted with alkenyl group Solvent and 1. A polysilane passivation treatment composition comprising:

9. R １ but, C ３～２０ a linear or branched alkyl group, C ５～８ a cyclic alkyl group, C ３～１５ a straight-chain, terminally unsaturated alkenyl group, or The composition according to claim 8, wherein the alkyl group is a phenyl group substituted with a C8-10 alkenyl group having an unsaturated bond at the terminal.

10. 10. The composition of claim 8 or 9, wherein the stabilizer is selected from the group consisting of 1-pentene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene, 1-heptene, 5-methyl-1-hexene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, vinylcyclopentane, vinylcyclohexane, allylcyclohexane, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,2-divinylbenzene, 1,3-divinylbenzene, and 1,4-divinylbenzene.

11. The composition according to any one of claims 8 to 10, which is an edge bead removal treatment composition or a waste liquid treatment composition.

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