JP2008107409A - Photosensitive composition, method for producing patterned film using the same and semiconductor device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition capable of obtaining a patterned film excellent in insulation performance without carrying out heat treatment at such a relatively high temperature as ≥500°C, a method for producing a patterned film using the same and a semiconductor device. <P>SOLUTION: The photosensitive composition comprises: a component (X) obtained by reacting a condensation product (A) of an alkoxysilane with at least one compound (B) selected from the group consisting of monofunctional alkoxysilane compounds, monofunctional silanol compounds, monofunctional epoxy compounds and monofunctional isocyanate compounds; and an acid or base generator (Y) which generates an acid or base upon exposure to light. The method for producing a patterned film using the same and a semiconductor device are also provided. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a photosensitive composition having photosensitivity, capable of forming a pattern film by developing after selective exposure, a method for producing a pattern film using the same, and a semiconductor element.

  In manufacturing electronic devices such as semiconductors, a passivation film, a gate insulating film, and the like are formed by a fine pattern forming method. For forming these films, for example, a photosensitive resin composition containing an alkoxysilane condensate or the like is used.

  In Patent Document 1 below, as an example of a photosensitive resin composition used for pattern formation, (1) an alkali-soluble siloxane polymer, (2) a compound that generates a reaction accelerator by light, and (3) a solvent are mainly used. A photosensitive resin composition as a component is disclosed. In Patent Document 1, (1) an alkali-soluble siloxane polymer obtained by removing water and a catalyst from a reaction solution obtained by hydrolyzing and condensing alkoxysilane with water and a catalyst is used as the alkali-soluble siloxane polymer. Yes.

Patent Document 1 discloses a pattern film forming method in which the photosensitive resin composition is applied onto a substrate, dried, exposed through a mask, and subsequently developed. In this pattern film forming method, it is described that after exposure through a mask, heating may be performed before development. By heating before development, polymerization in the exposed area proceeds due to the action of the reaction accelerator generated by exposure, and the difference in developer solubility from the unexposed area is widened, resulting in improved resolution contrast. It is said that.
Japanese Patent Laid-Open No. 06-148895

  However, in patent document 1, after hardening the photosensitive resin composition layer, the crosslinking reaction of the condensate of alkoxysilane might not fully advance. That is, the uncrosslinked component of the alkoxysilane condensate may remain in the photosensitive resin composition layer after the photosensitive resin composition layer is cured. There are many SiOH groups in the uncrosslinked component of the alkoxysilane condensate. Therefore, the obtained pattern film tends to be inferior in insulation performance.

  For example, a very high insulating performance is required for a passivation film, a gate insulating film, and the like of a semiconductor element. However, the pattern film comprised using the photosensitive resin composition of patent document 1 has low insulation performance, and insulation performance was not enough for using for such a use.

  Patent Document 1 describes that the polymerization in the exposed portion can be advanced by the action of a reaction accelerator generated by exposure by heating after exposure and before development. However, since most of the reaction accelerators generated by light are consumed by exposure, it is difficult to sufficiently progress the polymerization in the exposed area with only the reaction accelerator remaining after exposure.

  In order to sufficiently advance the crosslinking reaction of the alkoxysilane condensate, it is necessary to heat-treat the photosensitive resin composition layer at a high temperature of, for example, 500 ° C. or higher after the exposure. When performing heat treatment at such a very high temperature of 500 ° C. or higher, it is necessary to use special heating equipment. Furthermore, when heat treatment is performed at 500 ° C. or higher, not only the substrate and the pattern film but also portions other than the pattern film on the substrate tend to deteriorate.

  An object of the present invention is to provide a photosensitive composition capable of obtaining a patterned film having excellent insulating performance without performing heat treatment at a relatively high temperature of, for example, 500 ° C. It is an object to provide a method for manufacturing a patterned film and a semiconductor element using the above-described method.

  The photosensitive composition according to the present invention is selected from the group consisting of an alkoxysilane condensate (A), a monofunctional alkoxysilane compound, a monofunctional silanol compound, a monofunctional epoxy compound, and a monofunctional isocyanate compound. And a component (X) obtained by reacting at least one compound (B), and an acid or base generator (Y) that generates an acid or a base when exposed to light.

  The method for producing a patterned film according to the present invention includes a step of forming a photosensitive composition layer comprising the photosensitive composition of the present invention on a substrate, and selectively forming the photosensitive composition layer according to the pattern to be formed. The photosensitive composition layer in the exposed area is cured by exposing and curing the photosensitive composition layer by crosslinking the component (X) in the exposed area by the action of the acid or base generated from the acid or base generator (Y). After making the photosensitive composition layer insoluble in the developing solution and the photosensitive composition layer in the exposed portion insoluble in the developing solution, the photosensitive composition layer is developed with the developing solution, and the photosensitive composition layer in the unexposed portion is removed. And a step of obtaining a pattern film.

  The semiconductor device according to the present invention includes at least one film selected from the group consisting of a gate insulating film, a passivation film, and an interlayer insulating film, and the film uses a photosensitive composition configured according to the present invention. The film is formed.

  In the photosensitive composition according to the present invention, the alkoxysilane condensate (A) is selected from the group consisting of a monofunctional alkoxysilane compound, a monofunctional silanol compound, a monofunctional epoxy compound, and a monofunctional isocyanate compound. Since it contains the component (X) obtained by reacting at least one compound (B) and an acid or base generator (Y) that generates an acid or base when exposed to light, for example, a pattern to be formed Accordingly, a pattern film with a reduced proportion of SiOH groups can be obtained by developing after selectively exposing the photosensitive composition. Therefore, since the proportion of SiOH groups can be reduced, the insulating performance of the pattern film can be improved.

  In the conventional photosensitive resin composition, since a relatively large amount of SiOH groups remain in the pattern film obtained by crosslinking an alkoxysilane condensate, the insulating performance tends to be inferior. In the case of using a conventional photosensitive resin composition, it is necessary to perform heat treatment at a very high temperature of, for example, 500 ° C. or higher in order to reduce the existence ratio of SiOH groups in the pattern film and improve the insulation performance. When performing heat treatment at such a very high temperature of 500 ° C. or higher, it is necessary to use special heating equipment. Furthermore, when heat treatment is performed at 500 ° C. or higher, not only the substrate and the pattern film but also portions other than the pattern film on the substrate tend to deteriorate.

  On the other hand, in the present invention, the alkoxysilane condensate (A) is at least selected from the group consisting of a monofunctional alkoxysilane compound, a monofunctional silanol compound, a monofunctional epoxy compound, and a monofunctional isocyanate compound. Since the component (X) obtained by reacting one kind of compound (B) is used, the presence ratio of SiOH groups is reduced in the pattern film obtained by crosslinking the component (X). Therefore, a pattern film having excellent insulating performance can be provided without heat treatment at a relatively high temperature of, for example, 500 ° C. or higher.

  In the method for producing a patterned film according to the present invention, a step of forming a photosensitive composition layer comprising the photosensitive composition of the present invention on a substrate, and the photosensitive composition layer selectively according to the pattern to be formed. The photosensitive composition layer in the exposed area is cured by exposing and curing the photosensitive composition layer by crosslinking the component (X) in the exposed area by the action of the acid or base generated from the acid or base generator (Y). After making the photosensitive composition layer insoluble in the developing solution and the photosensitive composition layer in the exposed portion insoluble in the developing solution, the photosensitive composition layer is developed with the developing solution, and the photosensitive composition layer in the unexposed portion is removed. And the step of obtaining the pattern film, the existence ratio of SiOH groups is reduced, and a pattern film having excellent insulating performance can be obtained.

  The semiconductor device according to the present invention includes at least one film selected from the group consisting of a gate insulating film, a passivation film, and an interlayer insulating film, and the film is formed using the photosensitive composition of the present invention. Therefore, it has excellent electrical characteristics.

  Details of the present invention will be described below.

  In order to achieve the above-mentioned problems, the inventors of the present application have made extensive studies on the photosensitive composition used for forming the pattern film. As a result, the alkoxysilane condensate (A) has a monofunctional alkoxysilane compound and a monofunctional compound. A component (X) obtained by reacting at least one compound (B) selected from the group consisting of a silanol compound, a monofunctional epoxy compound and a monofunctional isocyanate compound, and an acid or base upon exposure When using a photosensitive composition containing an acid or base generator (Y) that generates acid, it was found that when the pattern film was formed, the insulating performance of the pattern film was improved, and the present invention was made. .

  The photosensitive composition according to the present invention is selected from the group consisting of an alkoxysilane condensate (A), a monofunctional alkoxysilane compound, a monofunctional silanol compound, a monofunctional epoxy compound, and a monofunctional isocyanate compound. The component (X) obtained by reacting at least one compound (B) and an acid or base generator (Y) that generates an acid or a base when exposed to light are contained.

  As the alkoxysilane condensate (A), a condensate obtained by condensing alkoxysilane is used. Preferably, an alkoxysilane condensate (A) obtained by condensing alkoxysilane with an acid catalyst is used. At least one kind of alkoxysilane condensate is contained, and therefore, a condensate of two or more kinds of alkoxysilanes may be contained.

  An alkoxysilane condensate (A) represented by the following formula (1) is more preferably used.

Si (R ₁ ) _p (R ₂ ) _q (R ₃ ) _4-pq Formula (1)
In the above formula (1), R ₁ represents hydrogen or a non-hydrolyzable organic group having 1 to 30 carbon atoms, R ₂ represents an alkoxy group, and R ₃ represents a hydrolyzable group other than the alkoxy group. , P represents an integer of 0 to 3, q represents an integer of 1 to 4, and p + q ≦ 4. When p is 2 or 3, the plurality of R ₁ may be the same or different. When q is 2 to 4, a plurality of R ₂ may be the same or different. When p + q ≦ 2, the plurality of R ₃ may be the same or different.

The alkoxy group R ₂ and the hydrolyzable group R ₃ other than the alkoxy group are usually hydrolyzed by heating in the temperature range of room temperature (25 ° C.) to 100 ° C. in the presence of excess water without catalyst. It is a group that can be decomposed to form a silanol group, or a group that can be further condensed to form a siloxane bond.

Examples of the alkoxy group R _2, is not particularly limited, specifically, methoxy group, an ethoxy group, an alkoxy group having 1 to 6 carbon atoms such as a propoxy group.

The hydrolyzable group R ₃ other than the alkoxy group is not particularly limited, specifically, chlorine, halogeno group such as bromine, an amino group, and a hydroxyl group or a carboxyl group.

The non-hydrolyzable organic group R ₁ is not particularly limited, and examples thereof include an organic group having 1 to 30 carbon atoms that hardly causes hydrolysis and is a stable hydrophobic group. As the organic group having 1 to 30 carbon atoms which is a stable hydrophobic group, methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, octyl group, pentyl group, decyl group, dodecyl group, tetradecyl group, Alkyl groups having 1 to 30 carbon atoms such as hexadecyl group, octadecyl group and eicosyl group, and alkyl halide groups such as fluorinated, chlorinated and brominated alkyl groups (for example, 3-chloropropyl group, 6-chloropropyl group) , 6-chlorohexyl group, 6,6,6-trifluorohexyl group, etc.), aromatic substituted alkyl groups such as halogen-substituted benzyl groups (for example, benzyl group, 4-chlorobenzyl group, 4-bromobenzyl group, etc.) ), Aryl groups (eg phenyl group, tolyl group, mesityl group, naphthyl group, etc.), vinyl groups and epoxy groups Group, an organic group containing an amino group, and the like organic group containing a thiol group.

  Specific examples of the alkoxysilane include, for example, triphenylethoxysilane, trimethylethoxysilane, triethylethoxysilane, triphenylmethoxysilane, triethylmethoxysilane, ethyldimethylmethoxysilane, methyldiethylmethoxysilane, ethyldimethylethoxysilane, methyldiethyl. Ethoxysilane, phenyldimethylmethoxysilane, phenyldiethylmethoxysilane, phenyldimethylethoxysilane, phenyldiethylethoxysilane, methyldiphenylmethoxysilane, ethyldiphenylmethoxysilane, methyldiphenylethoxysilane, ethyldiphenylethoxysilane, tert-butoxytrimethylsilane, butoxy Trimethylsilane, dimethylethoxysilane, methoxydimethylvinylsilane , Ethoxydimethylvinylsilane, diphenyldiethoxysilane, phenyldiethoxysilane, dimethyldimethoxysilane, diacetoxymethylsilane, diethoxymethylsilane, 3-chloropropyldimethoxymethylsilane, chloromethyldiethoxymethylsilane, diethoxydimethylsilane Diacetoxymethylvinylsilane, diethoxymethylvinylsilane, diethoxydiethylsilane, dimethyldipropoxysilane, dimethoxymethylphenylsilane, methyltrimethoxysilane, methyltriethoxysilane, methyl-tri-n-propoxysilane, ethyltrimethoxysilane, Ethyltriethoxysilane, ethyl-tri-n-propoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyl-tri-n Propoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltripropoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, isobutyltripropoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexyl Tripropoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexyltripropoxysilane, octyltrimethoxysilane, octyltriethoxysilane, octyltripropoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, dodecyltripropoxysilane, tetra Decyltrimethoxysilane, tetradecyltriethoxysilane, tetradecyltripropoxysilane, hex Sadecyltrimethoxysilane, hexadecyltriethoxysilane, hexadecyltripropoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, octadecyltripropoxysilane, eicosyldecyltrimethoxysilane, eicosyltriethoxysilane, eicosyltripropoxy Silane, 6-chlorohexyltrimethoxysilane, 6,6,6-trifluorohexyltrimethoxysilane, benzyltrimethoxysilane, 4-chlorobenzyltrimethoxysilane, 4-bromobenzyltri-n-propoxysilane, phenyltrimethoxy Silane, phenyltriethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- Glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, γ-amino Propyltrimethoxysilane, γ-aminopropyltriethoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, N-β-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltri Methoxysilane, triethoxysilane, trimethoxysilane, triisopropoxysilane, tri-n-propoxysilane, triacetoxysilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraiso Examples include propoxysilane and tetraacetoxysilane. An alkoxysilane condensate obtained by condensing these alkoxysilanes is more preferably used. In constituting the alkoxysilane condensate (A), it is sufficient that at least one alkoxysilane is used, and therefore two or more alkoxysilanes may be used.

  Although the photosensitive composition contains component (X), component (X) is a monofunctional alkoxysilane compound, monofunctional silanol compound, monofunctional epoxy compound, and the alkoxysilane condensate (A). It can be obtained by reacting at least one compound (B) selected from the group consisting of monofunctional isocyanate compounds.

  The feature of the present invention is that at least one selected from the group consisting of a monofunctional alkoxysilane compound, a monofunctional silanol compound, a monofunctional epoxy compound, and a monofunctional isocyanate compound is added to the alkoxysilane condensate (A). The component (X) obtained by reacting the compound (B) is used. By reacting the alkoxysilane condensate (A) with the compound (B), more specifically, reacting the compound (B) as a cap agent on the SiOH group of the alkoxysilane condensate (A), In the obtained component (X), the abundance ratio of SiOH groups can be reduced. As a result, when the pattern film is formed using the photosensitive composition, the proportion of SiOH groups present in the pattern film can be reduced, and the insulating performance of the pattern film can be improved.

  The monofunctional alkoxysilane compound is not particularly limited, but trimethylmethoxysilane, trimethylethoxysilane, trimethylpropoxysilane, triethylmethoxysilane, triethylethoxysilane, triethylpropoxysilane, dimethylethoxysilane, diethylethoxysilane, dimethylmethoxysilane. , Dimethylethoxysilane, methylmethoxysilane, methylethoxysilane, ethylmethoxysilane, ethylethoxysilane, diisopropylethoxysilane, dimethylaminomethylethoxysilane, diphenylmethylethoxysilane, diphenylmethylmethoxysilane, diphenylethylmethoxysilane, diphenylethylethoxysilane , Triphenylmethoxysilane, triphenylethoxysilane, n-oct Decyl dimethyl silane, octyl dimethyl silane, phenyl dimethyl methoxysilane, phenyl dimethyl ethoxy silane, trimethyl acetoxy silane, and tri propyl methoxy silane. Among them, since the proportion of SiOH groups in the component (X) can be further reduced, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, dimethylethoxysilane, diethylethoxysilane, dimethylmethoxysilane Dimethylethoxysilane, methylmethoxysilane, methylethoxysilane, ethylmethoxysilane, and ethylethoxysilane are preferably used.

  The monofunctional silanol compound is not particularly limited, and examples thereof include trimethylsilanol, triethylsilanol, triphenylsilanol, and t-butyldimethylsilanol. Of these, trimethylsilanol and triethylsilanol are preferably used because the proportion of SiOH groups present in component (X) can be further reduced.

  The monofunctional epoxy compound is not particularly limited, but is methyl glycidyl ether, ethyl glycidyl ether, 2-ethylhexyl glycidyl ether, butyl glycidyl ether, decyl glycidyl ether, phenyl-2-methyl glycidyl ether, cetyl glycidyl ether, stearyl glycidyl ether. Ether, p-sec-butylphenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, phenyl glycidyl ether, orthocresyl glycidyl ether, metapatacridyl glycidyl ether, glycidyl methacrylate, isopropyl glycidyl ether, allyl glycidyl ether be able to. As a commercial item of the said monofunctional epoxy compound, the brand name "Epiol M" (methyl glycidyl ether) by Nippon Oil & Fats Co., Ltd., brand name "Epiol EH" (2-ethylhexyl glycidyl ether), etc. are mentioned. Of these, methyl glycidyl ether and ethyl glycidyl ether are preferably used because the proportion of SiOH groups present in component (X) can be further reduced.

  Although it does not specifically limit as said monofunctional isocyanate compound, Trimethylsilyl isocyanate, a triethylsilyl isocyanate, etc. can be mentioned. Of these, trimethylsilyl isocyanate is preferably used because the proportion of SiOH groups present in component (X) can be further reduced.

  The method of reacting the alkoxysilane condensate (A) with the compound (B) is not particularly limited. For example, the compound (B) is added immediately after the alkoxysilane condensate (A) is produced, There is a method of reacting by heating to a temperature. At that time, for example, an acid or a basic compound may be used as a reaction catalyst, if necessary.

  The blending ratio when the alkoxysilane condensate (A) and the compound (B) are reacted can be appropriately set depending on the proportion of SiOH groups remaining in the alkoxysilane condensate (A), Although not particularly limited, the compound (B) is preferably blended at a ratio of 1.0 to 150 parts by weight with respect to 100 parts by weight of the alkoxysilane condensate (A). When the compound (B) is less than 1.0 part by weight, the existing ratio of SiOH groups may not be sufficiently reduced. When the compound (B) exceeds 150 parts by weight, the compound (B) becomes excessive, resulting in an insulating performance of the pattern film. May have adverse effects.

  In addition to the component (X), the photosensitive composition further contains an acid or base generator (Y) that generates an acid or a base when exposed to light.

The acid or base generator (Y) that generates an acid or a base when exposed to light is not particularly limited, and examples thereof include onium salts. More specifically, diazonium, phosphonium, and iodonium salts such as BF ₄ ⁻ , PF ₆ ⁻ , SBF ₆ ⁻ , and ClO ₄ ^— , and other organic halogen compounds, organic metals, and organic halides can be used. .

  The acid generator (Y) that generates an acid when exposed to light is not particularly limited, but triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethaneantimonate, triphenylsulfonium benzosulfonate, cyclohexylmethyl (2 -Oxocyclohexyl) sulfonium trifluoromethanesulfonate, dicyclohexyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, dicyclohexylsulfonylcyclohexanone, dimethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, and other sulfonium salt compounds, diphenyliodonium trifluoromethanesulfone Iodonium salts such as nato, N-hydroxysuccinimide triflu B methanesulfonate, and the like. An acid generator (Y) may be used independently and 2 or more types may be used together.

  The acid generator (A) is not particularly limited, but preferably, at least one compound selected from the group consisting of a more reactive onium salt, diazonium salt, and sulfonic acid ester is used.

  In addition to these photosensitizers acid or base generator (Y), a sensitizer may be further added in order to further increase sensitivity.

  The sensitizer is not particularly limited. Specifically, benzophenone, p, p′-tetramethyldiaminobenzophenone, p, p′-tetraethylaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, Anthracene, pyrene, perylene, phenothiazine, benzyl, acridine orange, benzoflavin, cetoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2- Chloro-4-nitroaniline, N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone, 2-ethylanthraquinone, 2-t rt-butylanthraquinone, 1,2-benzanthraquinone, 3-methyl-1,3-diaza-1,9-benzanthrone, dibenzalacetone, 1,2-naphthoquinone, 3,3′-carbonyl-bis ( 5,7-dimethoxycarbonylcoumarin) and coronene, and the like are preferable.

  The base generator (Y) that generates a base when exposed to light is not particularly limited, and examples thereof include cobaltamine complexes, o-acyloximes, carbamic acid derivatives, formamide derivatives, quaternary ammonium salts, tosylamines, carbamates, An amine imide compound etc. can be mentioned. Specific examples include 2-nitrobenzyl carbamate, 2,5-dinitrobenzyl cyclohexyl carbamate, N-cyclohexyl-4-methylphenylsulfonamide, 1,1-dimethyl-2-phenylethyl-N-isopropylcarbamate, and the like. . A base generator (Y) may be used independently and 2 or more types may be used together.

  As the base generator (Y), an amine imide compound that generates a base upon irradiation with light or radiation is preferably used. Such an amine imide compound is not particularly limited as long as it generates a base when irradiated with light or radiation. Examples of such amine imide compounds include compounds represented by the following general formula (2) or (3).

In the above formulas (2) and (3), R ¹ , R ² and R ³ are independently hydrogen, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and an alkylidene having 1 to 8 carbon atoms. Group, a cycloalkyl group having 4 to 8 carbon atoms, a cycloalkenyl group having 4 to 8 carbon atoms, a phenoxyalkyl group having 7 to 12 carbon atoms, a phenyl group, an electron donating group and / or an electron withdrawing group And a benzyl group substituted with a group, a benzyl group, an electron donating group and / or an electron withdrawing group. As a C1-C8 alkyl group, the alkyl group which has a substituent other than a linear alkyl group, for example, an isopropyl group, an isobutyl group, t-butyl group etc. are included. Among these substituents, from the viewpoint of ease of synthesis, solubility of amine imide, etc., an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 6 to 8 carbon atoms, and a phenoxyalkyl group having 7 to 12 carbon atoms. Is preferred. R ⁴ independently represents an alkyl group having 1 to 5 carbon atoms, a hydroxyl group, a cycloalkyl group having 4 to 8 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a phenyl group. Ar ¹ in the general formula (2) is an aromatic group, and such an amine imide compound is known prior to the filing of the present application as disclosed in, for example, Japanese Patent Application Laid-Open No. 2003-35949. Are available. In the general formula (3), Ar ² is an aromatic group.

  The amine imide compound has a higher base generation efficiency than a compound that generates a primary or secondary amine when irradiated with light or radiation. Therefore, it is desirable to include an amine imide compound because the exposure time can be shortened and the manufacturing process can be shortened.

  The content ratio of the acid or base generator (Y) is preferably in the range of 0.05 to 50 parts by weight with respect to 100 parts by weight of the component (X). When the acid or base generator (Y) is less than 0.05 parts by weight, the sensitivity may not be sufficient, and it may be difficult to form a pattern film. When the acid or base generator (Y) exceeds 50 parts by weight, it is difficult to uniformly apply the photosensitive composition, and a residue may be generated after development.

  In addition, in order to obtain an optimal resist shape, the acid generator (A) for generating the acid and the base generator (A) for generating the base may be used in combination of two or more.

  In addition to the components described above, an appropriate solvent can be added to the photosensitive composition. By adding a solvent, a photosensitive composition that can be easily applied can be provided.

  By the way, when forming the pattern film using the photosensitive composition, when the uncured photosensitive composition not cured is dissolved in the developer, the unexposed photosensitive composition is not cured. May not dissolve easily in the developer. This is because the proportion of SiOH groups present in component (X) is reduced. Since the photosensitive composition can be easily dissolved in the developer, that is, the developability is improved, the photosensitive composition preferably contains a surfactant.

  Although it does not specifically limit as said surfactant, Polyethylene glycol octyl phenyl ether, polyoxyethylene lauryl alcohol ether, sorbitan monooleate, sorbitan sesquioleate, etc. are mentioned, It uses preferably.

  An appropriate solvent may be further added to the photosensitive composition. By adding a solvent, a photosensitive composition that can be easily applied can be provided.

  The solvent is not particularly limited as long as it can dissolve component (X), but is an aromatic hydrocarbon compound such as benzene, xylene, toluene, ethylbenzene, styrene, trimethylbenzene, diethylbenzene; cyclohexane, cyclohexene, dipentene, n- Saturated or unsaturated hydrocarbon compounds such as pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, n-octane, isooctane, n-nonane, isononane, n-decane, isodecane, tetrahydronaphthalene, squalane; diethyl ether , Di-n-propyl ether, di-isopropyl ether, dibutyl ether, ethyl propyl ether, diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether , Diethylene glycol dibutyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, dipropylene glycol methyl ethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene Glycol methyl ethyl ether, tetrahydrofuran, 1,4-dioxane, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl cyclohexane, methyl Hexane, p-menthane, o-menthane, m-menthane; ethers such as dipropyl ether and dibutyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, methyl amyl ketone, cyclopentanone, cyclohexanone, Ketones such as cycloheptanone; ethyl acetate, methyl acetate, butyl acetate, propyl acetate, cyclohexyl acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethyl lactate, propyl lactate, butyl lactate, isoamyl lactate, butyl stearate, etc. And the like. These solvents may be used independently and 2 or more types may be used together.

  What is necessary is just to select suitably the mixture ratio of the said solvent so that it may apply uniformly, for example, when a photosensitive composition is applied on a board | substrate and a photosensitive composition layer is formed. Preferably, the concentration of the photosensitive composition is 0.5 to 60% by weight, more preferably about 2 to 40% by weight in terms of solid content.

  If necessary, other additives may be further added to the photosensitive composition. Such additives include fillers, pigments, dyes, leveling agents, antifoaming agents, antistatic agents, UV absorbers, pH adjusters, dispersants, dispersion aids, surface modifiers, plasticizers, plasticizers. Examples include accelerators and sagging inhibitors.

  In the method for producing a patterned film according to the present invention, a step of forming a photosensitive composition layer on a substrate, a step of exposing the photosensitive composition, and a step of developing the photosensitive composition layer to obtain a patterned film include: Done in order. Specifically, a step of forming a photosensitive composition layer composed of the photosensitive composition of the present invention on a substrate, and selectively exposing the photosensitive composition layer according to the pattern to be formed, acid or base By the action of the acid or base generated from the generator (Y), the photosensitive composition layer is cured by crosslinking the component (X) in the exposed area, and the photosensitive composition layer in the exposed area is insoluble in the developer. After the step and the photosensitive composition layer in the exposed area are insoluble in the developer, the photosensitive composition layer is developed with the developer, and the unexposed area of the photosensitive composition layer is removed to obtain a pattern film. The steps are performed in this order.

  In the method for producing a patterned film according to the present invention, first, as shown in FIG. 1A, for example, a step of forming a photosensitive composition layer 1 made of the photosensitive composition of the present invention on a substrate is performed. .

  The step of forming the photosensitive composition layer 1 is not particularly limited. For example, a method of forming the photosensitive composition layer 1 by applying the photosensitive composition according to the present invention on the substrate 2 shown in FIG. Can be mentioned. As a specific method in this case, a general coating method can be used, for example, dip coating, roll coating, bar coating, brush coating, spray coating, spin coating, extrusion coating. Work, gravure coating, etc. can be used. As the substrate 2 to which the photosensitive composition is applied, a silicon substrate, a glass substrate, a metal plate, a plastic plate, or the like is used depending on the application. Although the thickness of the photosensitive composition layer 1 changes with uses, 10 nm-10 micrometers become a standard.

  The photosensitive composition layer 1 coated on the substrate 2 is preferably heat-treated in order to dry the solvent when a solvent is used to dissolve the component (X). The heat treatment temperature is generally 40 ° C. to 200 ° C., and is appropriately selected according to the boiling point and vapor pressure of the solvent.

  Next, as shown in FIG.1 (b), the process of exposing the photosensitive composition layer 1 is performed. The photosensitive composition layer 1 is selectively exposed using a photomask 3 or the like corresponding to the pattern shape. In the exposed photosensitive composition layer 1A, an acid or base is generated from the acid or base generator (Y). On the other hand, in the photosensitive composition layer 1B that is not exposed, no acid or base is generated from the acid or base generator (Y).

  In the exposed photosensitive composition layer 1A, the component (X) is crosslinked by the action of the acid or base generated from the acid or base generator (Y). When the component (X) is crosslinked, the photosensitive composition layer 1A is cured. As a result, the photosensitive composition layer 1A in the exposed area becomes insoluble in the developer.

The light source for irradiating active energy rays such as ultraviolet rays and visible light during exposure is not particularly limited, but an ultrahigh pressure mercury lamp, deep UV lamp, high pressure mercury lamp, low pressure mercury lamp, metal halide lamp, excimer laser, etc. are used. can do. These light sources are appropriately selected according to the photosensitive wavelength of the constituent components of the photosensitive composition. The irradiation energy of light is generally in the range of 10 to 3000 mJ / cm ² , although depending on the desired film thickness and the constituent components of the photosensitive composition. If less than 10 mJ / cm ^2, it may be impossible to sufficiently remove the photosensitive composition layer 1B of the unexposed portion with a developing solution, may 3000 mJ / cm ² greater than the exposure time is too long, There is a possibility that the production efficiency per hour of the pattern film may be lowered.

  Next, the process of developing the photosensitive composition layers 1A and 1B with a developer to obtain the pattern film 1C is performed. By developing with the developer, the photosensitive composition layer 1B in the unexposed area is dissolved and removed in the developer, and the pattern film 1C is obtained.

  After selectively exposing the photosensitive composition layer 1, the photosensitive composition layers 1 </ b> A and 1 </ b> B are developed with a developer so that the unexposed photosensitive composition layer 1 </ b> B is dissolved and removed in the developer. The photosensitive composition layer 1 </ b> A in the exposed area remains on the substrate 2. As a result, a pattern film 1C is obtained. This pattern is called a negative pattern because the photosensitive composition layer 1B in the unexposed area is removed.

  Here, the development includes the operation of immersing the photosensitive composition layer 1A in the exposed portion and the photosensitive composition layer 1B in the unexposed portion in a developer such as an alkaline aqueous solution, as well as the photosensitive composition layer 1A, Various operations for treating the photosensitive composition layers 1A and 1B with a developing solution, such as an operation of washing the surface of 1B with a developing solution or an operation of spraying the developing solution onto the surface of the photosensitive composition layers 1A and 1B, are included. Shall be.

  In addition, a developing solution is a liquid which melt | dissolves the photosensitive composition 1B of an unexposed part, after exposing the photosensitive composition layer 1 selectively. Since the photosensitive composition layer 1A in the exposed portion is cured, it does not dissolve in the developer. The developer is not limited to an alkaline aqueous solution, and an acidic aqueous solution or various solvents may be used. Examples of the solvent include the various solvents described above. Examples of the acidic aqueous solution include oxalic acid, formic acid, acetic acid and the like.

  As the developer, an explosion-proof facility is unnecessary, and the burden on the facility due to corrosion or the like is small, so an alkaline aqueous solution is preferably used. For example, alkaline aqueous solutions, such as tetramethylammonium hydroxide aqueous solution, sodium silicate aqueous solution, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, are mentioned. The time required for development depends on the thickness of the photosensitive composition layer and the type of solvent, but is preferably in the range of 10 seconds to 5 minutes because development can be efficiently performed and production efficiency is increased. It is preferable to wash the pattern film with distilled water after development to remove a developer such as an aqueous alkali solution remaining on the film.

  In addition, although the photosensitive composition concerning this invention is used suitably for forming a pattern film | membrane in various apparatuses, the said photosensitive composition is used suitably for the insulation protective film of an electronic device. By using a pattern film composed of the photosensitive composition as an insulating protective film of an electronic device, the shape stability of the obtained insulating protective film can be effectively increased. Examples of such an insulating protective film for an electronic device include a TFT protective film for protecting a thin film transistor (TFT) in a liquid crystal display element, and a protective film for protecting a filter in a color filter.

  The photosensitive composition according to the present invention is more preferably used to constitute an interlayer insulating film or a passivation film of a semiconductor element.

  FIG. 2 is a front sectional view schematically showing a semiconductor element provided with a passivation film and an interlayer insulating film made of the photosensitive composition according to the present invention.

  In the semiconductor element 11 shown in FIG. 2, a gate electrode 13 is provided at the center of the upper surface of the substrate 12. A gate insulating film 14 is formed on the upper surface of the substrate 12 so as to cover the gate electrode 13. A source electrode 15 and a drain electrode 16 are provided on the gate insulating film 14. A semiconductor layer 17 is formed on the gate insulating film 14 so as to cover part of the source electrode 15 and part of the drain electrode 16. Further, a passivation film 18 is formed so as to cover the portion of the source electrode 15 and the drain electrode 16 that are not covered with the semiconductor layer 17 and the semiconductor layer 17. In the semiconductor element 11, the gate insulating film 14 and the passivation film 18 are films formed using the photosensitive composition according to the present invention.

  The film | membrane formed using the photosensitive composition is used for various uses. Here, the “film formed using the photosensitive composition” means a film obtained by introducing energy such as heat or light to the photosensitive composition to introduce a crosslinked structure.

  The photosensitive composition according to the present invention can be widely used as an insulating protective film for various electronic devices such as a TFT protective film for organic EL elements, an interlayer protective film for IC chips, and an insulating layer for sensors.

  In recent years, a film made of polyphenylene oxide, polyethylene terephthalate, or the like has been used as a substrate on which the pattern film is formed, instead of a glass substrate or the like. As described above, the pattern film formed using the photosensitive composition of the present invention has excellent insulating performance even if it is not heat-treated at a high temperature of 500 ° C. or higher. Therefore, the photosensitive composition of the present invention is preferably used for forming a pattern film on a substrate that cannot be subjected to such heat treatment at 500 ° C. or higher. Moreover, when using the photosensitive composition of this invention for a flexible display use, it may be unable to heat-process, for example, 220 degreeC or more, and the photosensitive composition of this invention is preferably used also for such a use. Can do.

  Hereinafter, the present invention will be clarified by giving examples and comparative examples of the present invention. In addition, this invention is not limited to a following example.

(Example 1)
To a 100 ml flask equipped with a condenser, 15 g of phenyltriethoxysilane, 10 g of triethoxysilane, 0.5 g of oxalic acid, 7 ml of water and 60 ml of propylene glycol monomethyl ether acetate were added. The solution was stirred using a semicircular type mechanical stirrer and reacted with a mantle heater at 70 ° C. for 3 hours to obtain a solution containing an alkoxysilane condensate (A1).

  Subsequently, 5 g of triethylsilanol which is a monofunctional silanol compound was added and further reacted at 70 ° C. for 2 hours. Thereafter, ethanol and residual water produced by the condensation reaction with water were removed using an evaporator. After completion of the reaction, the flask was left to reach room temperature to prepare component (X1). The weight average molecular weight in terms of polystyrene of the component (X1) was 1100.

  100 parts by weight of the component (X1) and 2 parts by weight of naphthalimide camphorsulfonate (sulfonium salt photoacid generator, CAS No. 83697-56-7) as an acid generator (Y1) are mixed, A photosensitive composition was obtained.

(Example 2)
Component (X2) was prepared in the same manner as in Example 1 except that 6 g of dimethylethoxysilane, which is a monofunctional alkoxysilane compound, was used instead of 5 g of triethylsilanol. The weight average molecular weight in terms of polystyrene of the component (X2) was 1000.

  A photosensitive composition was obtained in the same manner as in Example 1 except that 100 parts by weight of the obtained component (X2) was used instead of 100 parts by weight of the component (X1).

(Example 3)
Component (X3) was prepared in the same manner as in Example 1 except that 5 g of trifunctional silanol compound, trimethylsilanol, was used instead of 5 g of triethylsilanol. The weight average molecular weight of the component (X3) in terms of polystyrene was 950.

  A photosensitive composition was obtained in the same manner as in Example 1 except that 100 parts by weight of the obtained component (X3) was used instead of 100 parts by weight of the component (X1).

Example 4
Component (X4) was prepared in the same manner as in Example 1 except that 5 g of trifunctional ethoxysilane, which is a monofunctional alkoxysilane compound, was used instead of 5 g of triethylsilanol. The weight average molecular weight in terms of polystyrene of the component (X4) was 1250.

  A photosensitive composition was obtained in the same manner as in Example 1 except that 100 parts by weight of the obtained component (X4) was used instead of 100 parts by weight of the component (X1).

(Example 5)
Component (X5) was prepared in the same manner as in Example 1 except that 5 g of methyl glycidyl ether, which is a monofunctional epoxy compound, was used instead of 5 g of triethylsilanol. The weight average molecular weight of the component (X5) in terms of polystyrene was 1050.

  A photosensitive composition was obtained in the same manner as in Example 1 except that 100 parts by weight of the obtained component (X5) was used instead of 100 parts by weight of the component (X1).

(Example 6)
Component (X6) was prepared in the same manner except that 5 g of trifunctional silyl isocyanate, which is a monofunctional isocyanate compound, was used instead of 5 g of triethylsilanol. The weight average molecular weight of the component (X6) in terms of polystyrene was 980.

  A photosensitive composition was obtained in the same manner as in Example 1 except that 100 parts by weight of the obtained component (X6) was used instead of 100 parts by weight of the component (X1).

(Example 7)
To a 100 ml flask equipped with a condenser, 15 g of phenyltriethoxysilane, 10 g of methyltriethoxysilane, 0.5 g of oxalic acid, 7 ml of water and 60 ml of propylene glycol monomethyl ether acetate were added. The solution was stirred using a semicircular type mechanical stirrer and reacted with a mantle heater at 70 ° C. for 3 hours to obtain a solution containing an alkoxysilane condensate (A2).

  Subsequently, 5 g of triethylsilanol which is a monofunctional silanol compound was added and further reacted at 70 ° C. for 2 hours. Thereafter, ethanol and residual water produced by the condensation reaction with water were removed using an evaporator. After completion of the reaction, the flask was left to reach room temperature to prepare component (X7). The weight average molecular weight in terms of polystyrene of the component (X7) was 1100.

  A photosensitive composition was obtained in the same manner as in Example 1 except that 100 parts by weight of the obtained component (X7) was used instead of 100 parts by weight of the component (X1).

(Comparative Example 1)
To a 100 ml flask equipped with a condenser, 15 g of phenyltriethoxysilane, 10 g of triethoxysilane, 0.5 g of oxalic acid, 7 ml of water and 60 ml of propylene glycol monomethyl ether acetate were added. The solution was stirred using a semicircular type mechanical stirrer and reacted with a mantle heater at 70 ° C. for 3 hours to obtain a solution containing an alkoxysilane condensate (A1).

  Thereafter, ethanol and residual water produced by the condensation reaction with water were removed using an evaporator. After completion of the reaction, the flask was left to reach room temperature to prepare an alkoxysilane condensate (A1). The weight average molecular weight of the alkoxysilane condensate (A1) in terms of polystyrene was 950.

  A photosensitive composition was obtained in the same manner as in Example 1 except that 100 parts by weight of the resulting alkoxysilane condensate (A1) was used instead of 100 parts by weight of the component (X1).

(Evaluation of volume resistance)
A glass substrate on which aluminum was deposited as a surface layer was used, and each photosensitive composition was spin-coated on the glass substrate at a rotation speed of 1500 rpm. After coating, it was dried in a hot air oven at 80 ° C. to form a coating film having a thickness of 1 μm.

Next, ultraviolet rays having a wavelength of 365 nm are applied to the coating film through a photomask having a predetermined pattern (USHIO Inc., Spot Cure SP-5), and the irradiation energy is 500 mJ / cm ² . It was irradiated for 5 seconds with an ultraviolet illuminance of 100 mW / cm ² . Thereafter, the coating film was dried in a hot air oven at 100 ° C. for 5 minutes.

  Next, the coating film was immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide and developed to form a pattern film.

  The obtained pattern film was heat-treated in a hot air oven at 200 ° C. for 30 minutes or in a hot air oven at 500 ° C. for 1 hour.

  For the patterned film after the heat treatment, volume resistance was determined according to JIS K 6911 using R8252 (electrometer) and R12704 (module) (manufactured by Advantest).

  The results are shown in Table 1 below.

(Example 8)
100 parts by weight of component (X1) obtained in Example 1 and 2 parts by weight of naphthalimide camphorsulfonate (sulfonium salt photoacid generator, CAS No. 83697-56-7) as acid generator (Y1) Part and 5 parts by weight of polyethylene glycol octyl phenyl ether (CAS No. 9002-93-1) as a surfactant were mixed to obtain a photosensitive composition.

(Evaluation of developability)
The developability of the photosensitive composition of Example 1 in which no surfactant was blended and the photosensitive composition of Example 8 in which a surfactant was blended were evaluated.

  Similarly to the evaluation of the volume resistance, a 1 μm-thick coating film was formed on the substrate, irradiated with ultraviolet rays, and the coating film was dried in a hot air oven at 100 ° C. for 5 minutes. The film was immersed in a 38% aqueous solution and developed. The developability at this time, that is, the solubility of the photosensitive composition layer in the unexposed area was evaluated according to the following evaluation criteria.

A: A good pattern is formed. B: A pattern is formed only partially. X: The photosensitive composition layer in the unexposed area is not dissolved and a pattern film is not formed.

(A)-(c) is sectional drawing of each process for demonstrating the method to manufacture a pattern film using the photosensitive composition concerning this invention. BRIEF DESCRIPTION OF THE DRAWINGS Front sectional drawing which shows a semiconductor element provided with the passivation film and interlayer insulation film which consist of a photosensitive composition concerning this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Photosensitive composition layer 1A ... Photosensitive composition layer of exposed part 1B ... Photosensitive composition layer of unexposed part 1C ... Pattern film 2 ... Substrate 3 ... Photomask 11 ... Semiconductor element 12 ... Substrate 13 ... Gate electrode DESCRIPTION OF SYMBOLS 14 ... Gate insulating film 15 ... Source electrode 16 ... Drain electrode 17 ... Semiconductor layer 18 ... Passivation film

Claims (3)

  At least one compound (B) selected from the group consisting of a monofunctional alkoxysilane compound, a monofunctional silanol compound, a monofunctional epoxy compound and a monofunctional isocyanate compound is added to the alkoxysilane condensate (A). A photosensitive composition comprising a component (X) obtained by reaction and an acid or base generator (Y) that generates an acid or a base when exposed to light. Forming a photosensitive composition layer comprising the photosensitive composition according to claim 1 on a substrate;
The photosensitive composition layer is selectively exposed according to the pattern to be formed, and the component (X) is crosslinked in the exposed portion by the action of the acid or base generated from the acid or base generator (Y). Curing the photosensitive composition layer and making the photosensitive composition layer in an exposed portion insoluble in a developer; and
The step of making the photosensitive composition layer in the exposed area insoluble in a developer, developing the photosensitive composition layer with a developer, removing the photosensitive composition layer in the unexposed area, and obtaining a pattern film A method for producing a patterned film, comprising:   A film comprising at least one film selected from the group consisting of a gate insulating film, a passivation film, and an interlayer insulating film, wherein the film is formed using the photosensitive composition according to claim 1. A semiconductor element.

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