JP2008032989A - Positive photosensitive composition, pattern film manufacturing method, and semiconductor device - Google Patents

Abstract

A positive photosensitive composition capable of sufficiently dissolving a photosensitive composition in an exposed area in a developer and obtaining a pattern film having an excellent pattern shape, and a method for producing a pattern film using the same And a semiconductor device.
An alkoxysilane condensate (A) having a SiOH group, a thermal acid generator (B), a photocation generator (C), a monofunctional epoxy compound, a monofunctional vinyl ether, and a monofunctional oxetane compound. A positive photosensitive composition containing at least one selected compound (D), a method for producing a patterned film 1C using the same, and a semiconductor element.
[Selection] Figure 1

Description

  The present invention relates to a positive photosensitive composition having photosensitivity, and more specifically, by developing after exposure and heat treatment, the photosensitive composition in an exposed portion can be removed, and a pattern film is formed. The present invention relates to a positive photosensitive composition that can be used, a pattern film manufacturing method 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.

Further, Patent Document 1 discloses a pattern forming method in which the photosensitive resin composition is applied onto a substrate, dried, exposed through a mask, and subsequently developed. In the pattern forming method described in Patent Document 1, specifically, a photosensitive resin composition layer made of a photosensitive resin composition is formed, and the photosensitive resin composition layer is exposed through a mask. In the exposed portion, the crosslinking reaction of the alkoxysilane condensate was advanced to cure the photosensitive resin composition layer.
Japanese Patent Laid-Open No. 06-148895

  Conventionally, a photosensitive resin composition called a negative type as described in Patent Document 1 has been mainly used to form a fine pattern. That is, the photosensitive resin composition described in Patent Document 1, as described above, proceeds with the crosslinking reaction of the siloxane polymer in the exposed portion and is cured to form a pattern, which is not a positive type but a negative type. It was a photosensitive resin composition.

  However, in recent years, in order to form a fine pattern, development of a positive photosensitive resin composition instead of a negative photosensitive resin composition has been strongly demanded.

  When forming a fine pattern using a positive photosensitive resin composition, the photosensitive resin composition is exposed according to the pattern to be formed, as in the case of a negative photosensitive resin composition. Before or after exposure, heat treatment or the like is performed as necessary to cure the photosensitive resin composition in the unexposed area to form a patterned latent image. Next, by developing the photosensitive resin composition with a developer and removing the uncured photosensitive resin composition in the exposed area, a thin film pattern composed of the photosensitive resin composition in the unexposed area can be obtained. it can.

  In the positive photosensitive resin composition, it has been strongly demanded that the photosensitive resin composition in the exposed portion can be surely dissolved in the developer. However, in the conventional positive photosensitive resin composition, when developed, the photosensitive resin composition in the exposed area may not be sufficiently dissolved in the developer, and the photosensitive resin composition remains in the exposed area. Tended to be. As a result, the pattern film formed tends to be inferior in pattern shape.

  In view of the current state of the prior art described above, an object of the present invention is to provide a positive photosensitivity that can sufficiently dissolve a photosensitive composition in an exposed portion in a developer and can obtain a pattern film having an excellent pattern shape. It is in providing the composition, the manufacturing method of a pattern film using the same, and a semiconductor element.

  The positive photosensitive composition according to the present invention includes an alkoxysilane condensate (A) having a SiOH group, a thermal acid generator (B), a photocation generator (C), a monofunctional epoxy compound, It contains at least one compound (D) selected from the group consisting of a functional vinyl ether and a monofunctional oxetane compound.

  In a specific aspect of the positive photosensitive composition according to the present invention, the photocation generator (C) is in a ratio of 0.05 to 15 parts by weight with respect to 100 parts by weight of the alkoxysilane condensate (A). Contained.

  In another specific aspect of the present invention, the equivalent number (a) of SiOH groups of the alkoxysilane condensate (A) in the positive photosensitive composition and the vinyl ether group, epoxy group and oxetanyl of the compound (D) The equivalent ratio (equivalent number (a) / equivalent number (d)) with the total equivalent number (d) of the group is in the range of 0.8 to 1.5.

  In still another specific aspect of the positive photosensitive composition according to the present invention, the thermal acid generator (B) is 0.2 to 15 parts by weight with respect to 100 parts by weight of the alkoxysilane condensate (A). Included as a percentage.

  The method for producing a patterned film according to the present invention comprises a step of forming a photosensitive composition layer comprising a positive photosensitive composition constituted according to the present invention on a substrate, and a photosensitive composition according to the pattern to be formed. The step of selectively exposing the layer and reacting the compound (D) with the SiOH group of the alkoxysilane condensate (A) by the action of the photocation generator (C) in the exposed area, and the compound (D ) Is reacted, and then the photosensitive composition layer is heat-treated, whereby the crosslinking of the alkoxysilane condensate (A) is caused to proceed in the unexposed area by the action of the thermal acid generator (B). A step of making the photosensitive composition layer insoluble in the developer, and making the photosensitive composition layer in the unexposed area insoluble in the developer, and then developing the photosensitive composition layer with the developer to obtain a pattern film Process.

  The semiconductor device according to the present invention comprises 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 a positive photosensitive composition constituted according to the present invention. It is set as the film | membrane formed using.

  The positive photosensitive composition according to the present invention includes an alkoxysilane condensate (A) having a SiOH group, a thermal acid generator (B), a photocation generator (C), a monofunctional epoxy compound, Since it contains at least one compound (D) selected from the group consisting of a functional vinyl ether and a monofunctional oxetane compound, for example, by exposing the photosensitive composition to light or radiation using a photomask, an exposed portion The compound (D) can be reacted with the SiOH group of the alkoxysilane condensate (A) by the action of the photocation generator (C). That is, in the exposed area, the compound (D) reacts with the SiOH group of the alkoxysilane condensate (A), so that even if heat is generated and an acid is generated from the thermal acid generator (B), it becomes an SiOH group. The alkoxysilane condensate reacted with the compound (D) is not crosslinked. Therefore, it is difficult for the photosensitive composition to proceed at the exposed portion.

  In the positive photosensitive composition according to the present invention, the photosensitive composition is subjected to a heat treatment after being exposed to light, so that the thermal acid generator (B) acts to crosslink the alkoxysilane condensate (A) in the unexposed area. The photosensitive composition can be sufficiently cured. Therefore, if it develops after exposure and heat processing, the photosensitive composition of an exposed part can be removed, and the pattern film excellent in the pattern shape which consists of the photosensitive composition of an unexposed part can be obtained.

  When the photocation generator (C) is contained in an amount of 0.05 to 15 parts by weight with respect to 100 parts by weight of the alkoxysilane condensate (A), the SiOH of the alkoxysilane condensate (A) is exposed by exposure. The reaction between the group and the compound (D) can be effectively advanced.

  The number of equivalents (a) of SiOH groups of the condensate (A) of alkoxysilane in the positive photosensitive composition and the total number of equivalents (d) of the vinyl ether group, epoxy group and oxetanyl group of compound (D) When the equivalent ratio (equivalent number (a) / equivalent number (d)) is in the range of 0.8 to 1.5, the compound (D) is sufficiently added to the SiOH group of the alkoxysilane condensate (A). Can be reacted. That is, since the compound (D) can be reacted with many SiOH groups by exposure, it is possible to more effectively suppress the photosensitive composition in the exposed portion from being cured when heat-treated. Therefore, a pattern film having a more excellent pattern shape can be obtained.

  When the thermal acid generator (B) is contained in an amount of 0.2 to 15 parts by weight with respect to 100 parts by weight of the alkoxysilane condensate (A), the curing reaction of the photosensitive composition is further increased by heat treatment. It can proceed efficiently. Further, in the obtained pattern film, a residue due to the thermal acid generator (B) is hardly generated.

  In the method for producing a patterned film according to the present invention, a step of forming a photosensitive composition layer comprising a positive photosensitive composition constituted according to the present invention on a substrate, and a photosensitive composition according to the pattern to be formed. The step of selectively exposing the layer and reacting the compound (D) with the SiOH group of the alkoxysilane condensate (A) by the action of the photocation generator (C) in the exposed area, and the compound (D ) Is reacted, and then the photosensitive composition layer is heat-treated, whereby the crosslinking of the alkoxysilane condensate (A) is caused to proceed in the unexposed area by the action of the thermal acid generator (B). And the step of making the photosensitive composition layer insoluble in a developing solution, the condensate of alkoxysilane in the unexposed area without sufficiently proceeding with the crosslinking reaction of the condensate of alkoxysilane in the exposed area. The crosslinking reaction can be sufficiently advanced, it is possible to form a patterned latent image.

  Furthermore, in the present invention, since the photosensitive composition layer in the unexposed area is insoluble in the developer, the photosensitive composition layer is further developed with the developer to obtain a pattern film. The photosensitive composition layer in the exposed area is removed by development using a developer such as an alkali, and a pattern film having an excellent pattern shape composed of the photosensitive composition layer in the unexposed area can be obtained.

  The semiconductor element 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 the positive photosensitive composition of the present invention. Since it is a formed film, the shape of the film is excellent.

  Details of the present invention will be described below.

  In order to achieve the above-mentioned problems, the inventors of the present invention have made extensive studies on a positive photosensitive composition containing a condensate of alkoxysilane used for pattern formation. As a result, a condensate of alkoxysilane having an SiOH group (A) And at least one compound (D) selected from the group consisting of a thermal acid generator (B), a photocation generator (C), a monofunctional epoxy compound, a monofunctional vinyl ether, and a monofunctional oxetane compound. By containing, after exposing and heat-treating the photosensitive composition, the photosensitive composition in the exposed area can be sufficiently removed by developing, and a pattern film excellent in pattern shape can be obtained. The headline and the present invention were made.

  The positive photosensitive composition according to the present invention includes an alkoxysilane condensate (A) having a SiOH group, a thermal acid generator (B), a photocation generator (C), a monofunctional epoxy compound, And at least one compound (D) selected from the group consisting of a functional vinyl ether and a monofunctional oxetane compound.

  The alkoxysilane condensate (A) having a SiOH group is a condensate obtained by condensing alkoxysilane. At least one kind of alkoxysilane condensate (A) is contained, and therefore, a condensate (A) of two or more kinds of alkoxysilanes may be contained.

  In this invention, it is preferable to contain the condensate of the alkoxysilane obtained by condensing the alkoxysilane represented by following formula (1).

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.

  In addition to the alkoxysilane condensate (A), the positive photosensitive composition according to the present invention further contains a thermal acid generator (B) that generates an acid by the action of heat. The thermal acid generator (B) is blended in order to advance the crosslinking of the alkoxysilane condensate (A) during the heat treatment.

  The thermal acid generator (B) is not particularly limited, and examples thereof include onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, arsonium salts, and sulfonic acid esters. Are preferably used.

Examples of the thermal acid generator (B) include diazonium salts (SI Schlesinger, Photogr. Sci. Eng., 18, 387 (1974), TS Bal et al, Polymer, 21, 423 ( 1980), ammonium salts (specified in US Pat. Nos. 4,0690,05, 4,690,056, Reissue 27992, and JP-A-4-365049), phosphonium salts (DC Necker et al.). al, Macromolecules, 17, 2468 (1984), CS Wen et al, Teh, Proc. Conf. Rad, Curing ASIA, p478 Tokyo, Oct (1988), US Patent Nos. 4069055 and 4069056. ), Iodonium salt (JV Crivello et al, Macromolecules, 10 (6), 1307 (1977), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent No. 104143, US Pat. Nos. 3,390,49, 410201. No. 2, pp. 2-150848 and JP-A-2-296514), sulfonium salts (JV Crivello et al, Polymer J. 17, 73 (1985), J. V. Crivello et al. J. Org. Chem., 43, 3055 (1978), WR Watt et al, J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (1984), J. V. Crivello. et al, Polymer Bull , 14, 279 (1985), JV Crivello et al, Macromolecules, 14 (5), 1141 (1981), JV Crivel. Lo et al, J. Polymer Sci., Polymer Chem. Ed., 17, 2877 (1979), European Patent No. 370693, No. 3902114, No. 233567, No. 293443, No. 297442, U.S. Pat. Nos. 4,933,377, No. 16,1811, No. 410201, No. 339049, No. 4734444, 2833827, German Patent Nos. 2904626, 3604580, 3606041, and the selenonium salt (JV Crivello et al, Macromolecules, 10 6), 1307 (1977), J. V. Crivello et al, J.A. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979)), and arsonium salts (specified in CS Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988)). Examples of the counter anion of the onium salt include BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ and SbF ₆ ⁻ .

  These thermal acid generators (B) may be used alone or in combination of two or more.

  Since an acid is efficiently generated by heat treatment, at least one compound selected from the group consisting of iodonium salts, sulfonium salts and sulfonic acid esters is more preferably used as the thermal acid generator (B).

  The positive photosensitive composition according to the present invention preferably contains 0.2 to 15 parts by weight of the thermal acid generator (B) with respect to 100 parts by weight of the alkoxysilane condensate (A). When the thermal acid generator (B) is less than 0.2 parts by weight, a sufficient amount of acid is not generated by the heat treatment, and the crosslinking of the alkoxysilane condensate (A) may not sufficiently proceed. When the thermal acid generator (B) exceeds 15 parts by weight, it is difficult to uniformly apply the photosensitive composition, and a residue may be generated after development.

  The positive photosensitive composition according to the present invention further contains a photocation generator (C) in addition to the alkoxysilane condensate (A) and the thermal acid generator (B). The photo cation generator (C) is blended for reacting the compound (D) with the SiOH group of the alkoxysilane condensate (A) during exposure.

  The photocation generator (C) is not particularly limited, and examples thereof include onium salts and sulfonic acid esters. These photocation generators (C) may be used alone or in combination of two or more.

  The positive photosensitive composition according to the present invention preferably contains 0.05 to 15 parts by weight of the photocation generator (C) with respect to 100 parts by weight of the alkoxysilane condensate (A). When the photocation generator (C) is less than 0.05 part by weight, the compound (D) may not be sufficiently reacted with the SiOH group of the alkoxysilane condensate (A) by exposure. If the photocation generator (C) exceeds 15 parts by weight, it may be difficult to uniformly apply the photosensitive composition, and a residue may be generated after development.

  The positive photosensitive composition according to the present invention comprises a monofunctional epoxy compound in addition to the alkoxysilane condensate (A), the thermal acid generator (B), and the photocation generator (C). And at least one compound (D) selected from the group consisting of a monofunctional vinyl ether and a monofunctional oxetane compound.

  A feature of the present invention is that it contains a photocation generator (C) and at least one compound (D) selected from the group consisting of a monofunctional epoxy compound, a monofunctional vinyl ether, and a monofunctional oxetane compound. . The composition containing the photo cation generator (C) and the compound (D) will be described in detail later. When the photosensitive composition layer is exposed through a photomask, the alkoxysilane condensate (A) is exposed in the exposed area. The compound (D) can be reacted with the SiOH group. Furthermore, by carrying out heat treatment and developing with a developer, the photosensitive composition in the exposed area is removed, and a pattern film having an excellent pattern shape can be obtained.

  The monofunctional epoxy compound as the compound (D) is not particularly limited, but is methyl glycidyl ether, 2-ethylhexyl glycidyl ether, butyl glycidyl ether, decyl glycidyl ether, phenyl-2-methyl glycidyl ether, cetyl glycidyl ether, stearyl. Glycidyl 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, etc. Can be mentioned.

  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.

  Although it does not specifically limit as monofunctional vinyl ether as said compound (D), Propenyl ether of propylene carbonate, n-dodecyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, 2-chloroethyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, tributyl vinyl ether, And ethylene glycol vinyl ether.

  As a commercial item of the above monofunctional vinyl ether, trade name “PAPI-CURE PEPC” (propenyl ether of propylene carbonate), trade name “PAPI-CURE DDVE” (n-dodecyl vinyl ether), trade name, manufactured by IS Japan Co., Ltd. “PAPI-CURE CVE” (cyclohexyl vinyl ether), trade name “PAPI-CURE EHVE” (2-ethylhexyl vinyl ether) and the like.

  Although it does not specifically limit as a monofunctional oxetane compound as said compound (D), 3 ethyl-3-phenoxymethyl oxetane (molecular weight 192.3), 3-ethyl-3-[(2-ethylhexyloxy) methyl] oxetane (Molecular weight 228.4).

  As a commercial item of the said monofunctional oxetane compound, the brand name "OXT-211" (3-ethyl-3-phenoxymethyl oxetane) by Toa Gosei Co., Ltd., brand name "OXT-212" (3-ethyl-3-[( 2-ethylhexyloxy) methyl] oxetane and the like.

  In the present invention, the SiOH group equivalent number (a) of the alkoxysilane condensate (A) in the positive photosensitive composition and the total equivalent number of the vinyl ether group, epoxy group and oxetanyl group of the compound (D) ( It is preferable that the equivalent ratio with d) (equivalent number (a) / equivalent number (d)) is in the range of 0.8 to 1.5. When the equivalent ratio (number of equivalents (a) / number of equivalents (d)) is less than 0.8, the compound (D) may be excessive and a residue resulting from the excessive compound (D) may be generated. . If the equivalent ratio (equivalent number (a) / equivalent number (d)) exceeds 1.5, the compound (D) may not sufficiently react with the SiOH group of the alkoxysilane condensate (A) after exposure. is there.

  In addition, the equivalent number (a) of the SiOH group in the alkoxysilane condensate can be measured by, for example, pyridine-acetic anhydride acetylation method, and the total of the vinyl ether group, the epoxy group, and the oxetanyl group of the compound (D). The number of equivalents (d) can be measured, for example, by the perchloric acid method.

  In the present invention, an appropriate solvent is further added in addition to the alkoxysilane condensate (A), the thermal acid generator (B), the photocation generator (C), and the compound (D). obtain. By adding a solvent, a positive photosensitive composition that can be easily applied can be provided.

  The solvent is not particularly limited as long as it can dissolve the alkoxysilane condensate, 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, ethylpropyl ether, diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol Ethyl 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 cyclohexa , Methylcyclohexane, 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, Ketones such as cyclohexanone and 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, stearic acid Examples include esters such as butyl. These solvents may be used independently and 2 or more types may be used together.

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

  If necessary, other additives may be further added to the positive photosensitive composition according to the present invention. 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, the positive photosensitive composition is used. For example, as shown in FIG. 1A, a photosensitive composition layer made of a positive photosensitive composition is formed on a substrate. The process of forming 1 is performed. Next, the photosensitive composition layer 1 is selectively exposed using a photomask 3 corresponding to the pattern, and the alkoxysilane condensate (A) is formed by the action of the photocation generator (C) in the exposed portion. By reacting the compound (D) with the SiOH group and then heat-treating the photosensitive composition layer 1A in the exposed area and the photosensitive composition layer 1B in the unexposed area, by the action of the thermal acid generator (B). Then, the step of cross-linking the alkoxysilane condensate (A) in the unexposed area to make the photosensitive composition layer 1B in the unexposed area insoluble in the developer (FIG. 1B) is performed. After making the photosensitive composition layer 1B in the unexposed area insoluble in the developer, the photosensitive composition layers 1A and 1B are developed with the developer to obtain a pattern film 1C (FIG. 1C). Is called.

  Here, the development includes the operation of immersing the photosensitive composition layer 1A in the exposed area and the photosensitive composition layer 1B in the unexposed area 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. The developing solution 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.

  Although the process of forming the said photosensitive composition layer is not specifically limited, For example, the method of providing the said positive photosensitive composition on the board | substrate 2 shown in FIG. 1, and forming the photosensitive composition layer 1 is 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 on which the positive photosensitive composition is applied, a silicon substrate, a glass substrate, a metal plate, a plastics plate, or the like is used depending on the application. The thickness of the photosensitive composition layer varies depending on the use, but 10 nm to 10 μm is a standard. When the photosensitive composition layer coated on the substrate uses a solvent to dissolve the positive photosensitive composition, it is preferably heat-treated to dry the solvent. 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.

  The photosensitive composition layer 1 is formed on the substrate 2, the photosensitive composition layer is covered with a photomask, and light is irradiated in a pattern. Accordingly, the compound (D) can be reacted with the SiOH group of the alkoxysilane condensate (A) by the action of the photocation generator (C) in the exposed portion. In the photosensitive composition layer 1A in the exposed area, the compound (D) reacts with the SiOH group of the alkoxysilane condensate (A), so that it is heat-treated and acid is generated from the thermal acid generator (B). However, the curing of the photosensitive composition layer 1A is difficult to proceed. What is necessary is just to use the common thing marketed as a photomask.

The light source for irradiating light rays such as ultraviolet rays and visible rays, or radiation is not particularly limited, and an ultrahigh pressure mercury lamp, a deep UV lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, an excimer laser, etc. can be used. . These light sources are appropriately selected according to the type and blending amount of the photocation generator (C). The irradiation energy of light is generally in the range of 10 to 1000 mJ / cm ² , although it depends on the type of photocation generator (C) and the type of blending amount. When it is less than 10 mJ / cm ² , the compound (D) may not sufficiently react with the SiOH group of the alkoxysilane condensate (A). Moreover, when larger than 1000 mJ / cm < ² >, there exists a possibility that exposure time may become long and the manufacturing efficiency per time of a pattern film | membrane may fall.

  In the present invention, after reacting the compound (D) with the SiOH group, the photosensitive composition layer is heat-treated, so that the thermal acid generator (B) causes the alkoxysilane condensate (A ) Is allowed to proceed to make the photosensitive composition layer 1B in the unexposed area insoluble in the developer.

  The temperature of the heat treatment can be appropriately selected according to the thermal acid generator (B) to be used, but is preferably in the range of 150 to 350 ° C.

  By developing the photosensitive composition layer after exposure using a developer, the photosensitive composition layer in the exposed portion is dissolved and removed in the developer, and the unexposed portion remains on the substrate. As a result, a pattern is formed. This pattern is called a positive pattern because the exposed portion is removed. In the method for producing a patterned film of the present invention, the photosensitive composition in the exposed area can be sufficiently removed, so that good resolution can be obtained.

  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. After development, the pattern film is preferably washed with distilled water to remove the aqueous alkali solution remaining on the thin film.

  The positive photosensitive composition according to the present invention is suitably used for forming a pattern film in various apparatuses. However, the positive photosensitive composition is preferably used for an insulating protective film of an electronic device. It is done. 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.

  Moreover, the positive 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 cross-sectional view schematically showing a semiconductor device including a passivation film and an interlayer insulating film constituted by using the positive 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 by using the positive photosensitive composition according to the present invention.

  The film | membrane formed using the positive photosensitive composition which concerns on this invention is used for various uses. Here, the “film formed using a positive photosensitive composition” is a film obtained by introducing a cross-linked structure by applying energy such as heat, light or radiation to the positive photosensitive composition. It means that there is.

  The positive 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 of an organic EL element, an interlayer protective film of an IC chip, and an insulating layer of a sensor.

  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.

(Materials used)
[Condensation product of alkoxysilane (A)]
To a 100 ml flask equipped with a condenser, 5 g of phenyltriethoxysilane, 10 g of triethoxysilane, 0.5 g of oxalic acid, 5 ml of water and 50 ml of propylene glycol monomethyl ether acetate were added. The solution was stirred using a semicircular type mechanical stirrer and reacted at 70 ° C. for 6 hours with a mantle heater. Subsequently, 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) having a SiOH group.

[Thermal acid generator (B)]
(B1) Cyclohexyl-p-toluenesulfonate [Photocation generator (C)]
(C1) SP-150 (made by ADEKA)
[Compound (D)]
(D1) 2-ethylhexyl glycidyl ether (manufactured by NOF Corporation, trade name: Epiol EH, monofunctional epoxy compound)
(Preparation of positive photosensitive compositions of Examples and Comparative Examples)
After mixing the alkoxysilane condensate (A), the thermal acid generator (B), the photocation generator (C), and the compound (D) in the blending ratio shown in Table 1 below, A positive photosensitive composition was prepared by dissolving in 500 parts by weight of tetrahydrofuran as a solvent.

(Evaluation of Examples and Comparative Examples)
As a base material, a glass substrate having aluminum deposited on the surface layer was used, and the positive photosensitive compositions of Examples and Comparative Examples were spin-coated on the glass substrate at a rotational speed of 1500 rpm. After coating, it was dried in a hot air oven at 80 ° C. to form a coating film.

Next, ultraviolet rays with 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 1000 mJ / cm ^2. In this way, irradiation was performed for 10 seconds with an ultraviolet illuminance of 100 mW / cm ² .

  Next, the coating film was heat-treated in a hot air oven at 150 ° C. for 5 minutes. Thereafter, the coating film was immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide and developed to form a pattern film.

  The pattern shape of the pattern film obtained as described above was evaluated according to the following evaluation criteria.

[Evaluation criteria for pattern shape]
○: A good pattern is formed. Δ: A pattern is formed only partially. ×: A pattern is not formed. The results are shown in Table 1 below.

また、アルコキシシランの縮合物（Ａ）のＳｉＯＨ基の当量数（ａ）と、化合物（Ｄ）のビニルエーテル基、エポキシ基及びオキセタニル基の合計当量数（ｄ）との当量比（当量数（ａ）／当量数（ｄ））を表１に示す。

Further, the equivalent ratio (equivalent number (a) of the equivalent number (a) of SiOH groups of the condensate (A) of alkoxysilane and the total equivalent number (d) of vinyl ether group, epoxy group and oxetanyl group of compound (D). ) / Number of equivalents (d)) is shown in Table 1.

(A)-(c) is sectional drawing of each process for demonstrating the method of forming a pattern film using the positive photosensitive composition which concerns on this invention. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a front cross-sectional view showing a semiconductor element including a passivation film and an interlayer insulating film configured using a positive photosensitive composition according to the present invention.

Explanation of symbols

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

Claims (6)

  Selected from the group consisting of a condensate (A) of an alkoxysilane having a SiOH group, a thermal acid generator (B), a photocation generator (C), a monofunctional epoxy compound, a monofunctional vinyl ether, and a monofunctional oxetane compound. And a positive photosensitive composition comprising the at least one compound (D).   2. The positive photosensitive composition according to claim 1, comprising 0.05 to 15 parts by weight of the photocation generator (C) with respect to 100 parts by weight of the alkoxysilane condensate (A).   Equivalent number (a) of SiOH group of condensate (A) of alkoxysilane in positive photosensitive composition and total equivalent number (d) of vinyl ether group, epoxy group and oxetanyl group of compound (D) The positive photosensitive composition according to claim 1, wherein the equivalent ratio (number of equivalents (a) / number of equivalents (d)) is in the range of 0.8 to 1.5.   The thermal acid generator (B) is contained in a proportion of 0.2 to 15 parts by weight with respect to 100 parts by weight of the alkoxysilane condensate (A). Positive photosensitive composition. Forming a photosensitive composition layer comprising the positive photosensitive composition according to any one of claims 1 to 4 on a substrate;
The photosensitive composition layer is selectively exposed according to the pattern to be formed, and the compound ((H) of the alkoxysilane condensate (A) is bonded to the compound (A) by the action of the photocation generator (C) in the exposed portion. Reacting D);
After reacting the compound (D) with the SiOH group, the photosensitive composition layer is heat-treated, so that the thermal acid generator (B) acts to condense the alkoxysilane condensate (A) in the unexposed area. A step of making the crosslinking of the photosensitive composition layer in an unexposed part insoluble in a developer,
A process for producing a pattern film, comprising: making a photosensitive composition layer in an unexposed portion insoluble in a developer; and developing the photosensitive composition layer with a developer to obtain a pattern film. .   It comprises 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 the positive photosensitive composition according to any one of claims 1 to 4. A semiconductor element, which is a formed film.

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