JP5105073B2 - Radiation-sensitive resin composition, and method for producing interlayer insulating film and microlens - Google Patents

Description

  The present invention relates to a radiation-sensitive resin composition, and a method for producing an interlayer insulating film and a microlens.

  In an electronic component such as a thin film transistor (hereinafter referred to as “TFT”) type liquid crystal display element, magnetic head element, integrated circuit element, solid-state imaging element, etc., an interlayer insulation is generally used to insulate between wirings arranged in layers. A membrane is provided. As a material for forming an interlayer insulating film, a material having a small number of steps for obtaining a required pattern shape and having sufficient flatness is preferable, and thus a radiation sensitive resin composition is widely used (patents) Reference 1 and Patent Document 2).

  On the other hand, a microlens having a lens diameter of about 3 to 100 μm or an optical system material for an on-chip color filter such as a facsimile, an electronic copying machine, a solid-state image sensor, or the like is defined as an optical system material. An array of microlenses is used. To form a microlens or microlens array, a resist pattern corresponding to the lens is formed and then melt-flowed by heat treatment and used as it is as a lens, or by using the melt-flowed lens pattern as a mask and drying. A method of transferring a lens shape to a base by etching is known. For the formation of the lens pattern, a radiation sensitive resin composition is widely used (see Patent Document 3 and Patent Document 4).

These interlayer insulating films and microlenses or microlens arrays are required to have various performances such as high heat resistance, high solvent resistance, high transparency, and adhesion to the substrate. In recent years, TFT-type liquid crystal display devices have been in the trend of larger screens, higher response speeds, thinner thicknesses, etc., and as a composition for forming an interlayer insulating film used therefor, they have high sensitivity, and the interlayer insulation to be formed. The film is required to have higher performance than the conventional one because of its low dielectric constant. Furthermore, when manufacturing an interlayer insulating film or a microlens, if the development time is slightly longer than the optimum time in the development process, the developer tends to penetrate between the pattern and the substrate, and peeling is likely to occur. Since it was necessary to strictly control the development time, development of a radiation sensitive resin composition having a sufficient development margin is required.
JP 2001-354822 A JP 2001-343743 A JP-A-6-18702 JP-A-6-136239

  The present invention has been made based on the above situation. Therefore, an object of the present invention is to provide a radiation-sensitive composition that can easily form a patterned thin film having high radiation sensitivity, excellent development margin, and excellent adhesion to a base. There is.

  Another object of the present invention is to form an interlayer insulating film having high heat resistance, high solvent resistance, high transmittance and low dielectric constant when used for forming an interlayer insulating film, and for forming a microlens. When using, it is providing the radiation sensitive resin composition which can form the micro lens which has a high transmittance | permeability and a favorable melt shape.

  Still another object of the present invention is to provide a method for forming an interlayer insulating film and a microlens using the radiation sensitive resin composition.

  Still other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the above objects and advantages of the present invention are as follows.
[A] (a1) at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and (a2) selected from the group consisting of an oxiranyl group-containing unsaturated compound and an oxetanyl group-containing unsaturated compound A copolymer of an unsaturated mixture containing at least one (hereinafter sometimes referred to as "copolymer [A]"),
[B] 1,2-quinonediazide compound (hereinafter sometimes referred to as “[B] component”), and [C] a silsesquioxane having an aryl group having 6 to 15 carbon atoms (hereinafter referred to as “[C] Sometimes referred to as “component”.)
It achieves by the radiation sensitive resin composition characterized by containing.

According to the present invention, the objects and advantages of the present invention are secondly:
This is achieved by a method for forming an interlayer insulating film or a microlens, which includes the following steps in the order described below.
(1) The process of forming the coating film of said radiation sensitive resin composition on a board | substrate,
(2) A step of irradiating at least a part of the coating film with radiation,
(3) a step of developing the irradiated coating film, and (4) a step of heating the developed coating film.

The radiation-sensitive resin composition of the present invention has a high radiation sensitivity and an excellent development margin, and furthermore, by using the radiation-sensitive resin composition, a patterned thin film having excellent adhesion to the ground is obtained. It can be formed easily.
The interlayer insulating film of the present invention formed from the above composition is excellent in solvent resistance and heat resistance, has high transmittance and low dielectric constant, and can be suitably used as an interlayer insulating film for electronic parts.
The microlens of the present invention formed from the above composition is excellent in solvent resistance and heat resistance, has high transmittance and good melt shape, and is suitably used as a microlens for a solid-state imaging device. it can.

  Hereinafter, the radiation sensitive resin composition of this invention is explained in full detail.

Copolymer [A]
The copolymer [A] used in the present invention may be referred to as (a1) at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter referred to as “compound (a1)”). ), And (a2) at least one selected from the group consisting of an oxiranyl group-containing unsaturated compound and an oxetanyl group-containing unsaturated compound (hereinafter sometimes referred to as “compound (a2)”). The mixture can be produced by radical copolymerization in a solvent in the presence of a polymerization initiator.
The compound (a1) is an unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride having radical polymerizability, such as monocarboxylic acid, dicarboxylic acid, dicarboxylic acid anhydride, polyvalent carboxylic acid mono [(meth)]. Acryloyloxyalkyl] ester, mono (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both ends, a polycyclic compound having a carboxyl group, and anhydrides thereof.

Specific examples thereof include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid;
Examples of dicarboxylic acids include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like;
As anhydrides of dicarboxylic acids, for example, anhydrides of the compounds exemplified as the above dicarboxylic acids;
Examples of mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl];
Examples of the mono (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate;
Examples of the polycyclic compound having a carboxyl group and anhydrides thereof include 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2- Ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6- Methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] And hept-2-ene anhydride.

  Of these, monocarboxylic acid and dicarboxylic acid anhydrides are preferably used. In particular, acrylic acid, methacrylic acid, and maleic anhydride are preferably used from the viewpoint of copolymerization reactivity, solubility in an alkali developer, and availability. It is done. These compounds (a1) are used alone or in combination of two or more.

  The compound (a2) is an unsaturated compound having an oxiranyl group and / or an unsaturated compound having an oxetanyl group. Examples of the unsaturated compound having an oxiranyl group include glycidyl acrylate, glycidyl methacrylate, and glycidyl α-ethyl acrylate. Glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, -6,7-epoxyheptyl acrylate, methacryl Acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, acrylic acid-3,4-epoxycyclohexyl, methacrylic acid-3,4-epoxycyclohexyl, acrylic acid-3,4-epoxy Cyclohexylmethyl, methacrylic acid-3,4 Epoxycyclohexylmethyl, o- vinylbenzyl glycidyl ether, m- vinylbenzyl glycidyl ether, p- vinylbenzyl glycidyl ether. Among these, glycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, methacrylic acid-3,4-epoxycyclohexyl, methacryl Acid-3,4-epoxycyclohexylmethyl is preferably used from the viewpoint of increasing the copolymerization reactivity and the heat resistance and surface hardness of the resulting interlayer insulating film or microlens.

Examples of the unsaturated compound having an oxetanyl group include 3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, and 3- (acryloyl). Oxymethyl) -2-trifluoromethyloxetane, 3- (acryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (acryloyloxymethyl) -2-phenyloxetane, 3- (acryloyloxymethyl) -2,2 -Difluorooxetane, 3- (acryloyloxymethyl) -2,2,4-trifluorooxetane, 3- (acryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (2-acryloyloxyethyl) ) Oxetane, 3- ( -Acryloyloxyethyl) -2-ethyloxetane, 3- (2-acryloyloxyethyl) -3-ethyloxetane, 3- (2-acryloyloxyethyl) -2-trifluoromethyloxetane, 3- (2-acryloyloxy) Ethyl) -2-pentafluoroethyloxetane, 3- (2-acryloyloxyethyl) -2-phenyloxetane, 3- (2-acryloyloxyethyl) -2,2-difluorooxetane, 3- (2-acryloyloxyethyl) ) Acrylic acid esters such as -2,2,4-trifluorooxetane and 3- (2-acryloyloxyethyl) -2,2,4,4-tetrafluorooxetane;
3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- (methacryloyloxymethyl) -2,2-difluorooxetane, 3- (methacryloyloxymethyl) -2,2,4-trifluorooxetane, 3- (methacryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) 2-ethyloxetane, 3- (2-methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) -2-tolylolomethyloxetane, 3- (2-methacryloyloxyethyl) -2- Pentafluoroethyloxetane, 3- (2-methacryloyloxyethyl) -2-phenyloxetane, 3- (2-methacryloyloxyethyl) -2,2-difluorooxetane, 3- (2-methacryloyloxyethyl) -2,2 , 4-trifluorooxetane, methacrylic acid esters such as 3- (2-methacryloyloxyethyl) -2,2,4,4-tetrafluorooxetane, and the like.

Of these, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -3-Ethyloxetane or the like is preferably used from the viewpoint of copolymerization reactivity.
These compounds (a2) are used alone or in combination.

  The copolymer [A] used in the present invention may be referred to as the above-mentioned compounds (a1) and (a2) and other unsaturated compounds copolymerizable with these (hereinafter referred to as “compound (a3)”). And a copolymer thereof. Such a compound (a3) is not particularly limited as long as it is an unsaturated compound having radical polymerizability. For example, methacrylic acid alkyl ester, methacrylic acid cyclic alkyl ester, acrylic acid alkyl ester, acrylic acid Cyclic alkyl ester, methacrylic acid aryl ester, acrylic acid aryl ester, unsaturated dicarboxylic acid diester, methacrylic acid ester having a hydroxyl group, bicyclounsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene, tetrahydrofuran skeleton, furan skeleton, Mention may be made of unsaturated compounds having a tetrahydropyran skeleton, a pyran skeleton or a (poly) alkylene glycol skeleton, unsaturated compounds having a phenolic hydroxyl group and other unsaturated compounds.

Specific examples thereof include methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, Tridecyl methacrylate, n-stearyl methacrylate and the like; Examples of methacrylic acid cyclic ester include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate (hereinafter, “ Dicyclopentanyl methacrylate ”), tricyclo [5.2.1.0 ^2,6 ] decan-8-yloxyethyl methacrylate, isobornyl methacrylate. Tacrylate, etc .; As acrylic acid alkyl ester, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, etc .; As acrylic acid cyclic ester, for example , Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate (hereinafter referred to as “dicyclopentanyl acrylate”), tricyclo [5.2.1. acrylic acid aryl esters such as phenyl acrylate, benzyl acrylate; .0 ^2,6] decan-8-yl oxy ethyl acrylate, isobornyl acrylate and methacrylic acid ants For example, phenyl methacrylate, benzyl methacrylate and the like; unsaturated dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate; methacrylic acid esters having a hydroxyl group such as hydroxymethyl methacrylate, 2- Hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol monomethacrylate, 2,3-dihydroxypropyl methacrylate, 2-methacryloxyethylglycoside and the like;
Examples of the bicyclo unsaturated compound include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1]. Hept-2-ene, 5-hydroxybicyclo [2.2.1] Hept-2-ene, 5-carboxybicyclo [2.2.1] Hept-2-ene, 5-hydroxymethylbicyclo [2.2. 1] Hept-2-ene, 5- (2-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] Hept-2-ene, 5-ethoxy Bicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2 -Ene, 5,6-di (hydroxymethyl) bicyclo [2.2 .1] Hept-2-ene, 5,6-di (2-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] Hept-2 -Ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5 Ethylbicyclo [2.2.1] Hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] Hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] ] Hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride), 5-t-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5- Cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-di (t-butoxycarbonyl) bicyclo [2. 2.1] hept-2-ene, 5,6-di (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene and the like;
Examples of maleimide compounds include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) maleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like;
As unsaturated aromatic compounds, for example, styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, etc .; as conjugated dienes, for example, 1,3-butadiene, isoprene, 2 As unsaturated compounds containing a tetrahydrofuran skeleton, for example, tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyl As unsaturated compounds containing a furan skeleton, for example, 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, 1-furan- 2-butyl-3-en-2-one, 1 Furan-2-butyl-3-methoxy-3-en-2-one, 6- (2-furyl) -2-methyl-1-hexen-3-one, 6-furan-2-yl-hex-1- En-3-one, acrylic acid 2-furan-2-yl-1-methyl-ethyl ester, 6- (2-furyl) -6-methyl-1-hepten-3-one, etc .; containing tetrahydropyran skeleton Examples of unsaturated compounds include (tetrahydropyran-2-yl) methyl methacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) -oct-1-en-3-one, and tetrahydropyran 2-methacrylate. 2-yl ester, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one, etc .; unsaturated compounds containing a pyran skeleton include, for example, 4- (1, 4-dioxa-5-oxo-6-heptenyl) -6-methyl-2-pyrone, 4- (1,5-dioxa-6-oxo-7-octenyl) -6-methyl-2-pyrone, etc .;
Examples of unsaturated compounds having a (poly) alkylene glycol skeleton include polyethylene glycol (n = 2 to 10) mono (meth) acrylate and polypropylene glycol (n = 2 to 10) mono (meth) acrylate;
Examples of unsaturated compounds having a phenolic hydroxyl group include 4-hydroxybenzyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, o-hydroxystyrene, p-hydroxystyrene, α-methyl-p-hydroxystyrene, N- (4-hydroxybenzyl) (meth) acrylamide, N- (3,5-dimethyl-4-hydroxybenzyl) (meth) acrylamide, N- (4-hydroxyphenyl) (meth) acrylamide and the like;
Examples of other unsaturated compounds include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate.

Among these, methacrylic acid alkyl ester, methacrylic acid cyclic alkyl ester, acrylic acid cyclic alkyl ester, maleimide compound, unsaturated aromatic compound, conjugated diene, tetrahydrofuran skeleton, furan skeleton, tetrahydropyran skeleton, pyran skeleton, (poly) alkylene An unsaturated compound having a glycol skeleton and an unsaturated compound having a phenolic hydroxyl group are preferably used, and particularly styrene, t-butyl methacrylate, n-lauryl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8. -Yl methacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, 1,3-butadiene, tetrahydrofurfuryl (meth) acrylate, polyethylene Glycol (n = 2 to 10) mono (meth) acrylate, 3- (meth) acryloyloxytetrahydrofuran-2-one, 4-hydroxybenzyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, o-hydroxystyrene N- (4-hydroxyphenyl) (meth) acrylamide, p-hydroxystyrene, and α-methyl-p-hydroxystyrene are preferable from the viewpoints of copolymerization reactivity and solubility in an aqueous alkali solution.
These compounds (a3) are used alone or in combination of two or more.

Preferable specific examples of the copolymer [A] used in the present invention include, for example, methacrylic acid / tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate / 2-methylcyclohexyl acrylate / methacrylic acid. Glycidyl acid / styrene, methacrylic acid / tetrahydrofurfuryl methacrylate / glycidyl methacrylate / N-cyclohexylmaleimide / lauryl methacrylate / α-methyl-p-hydroxystyrene, styrene / methacrylic acid / glycidyl methacrylate / (3-ethyloxetane-3 -Yl) methacrylate / tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, styrene / methacrylic acid / glycidyl methacrylate / N- (4-hydroxyphenyl) methacrylamide.

The copolymer [A] used in the present invention preferably has repeating units derived from the compound (a1) based on the total number of repeating units derived from the compounds (a1), (a2) and (a3). 5 to 40% by weight, particularly preferably 5 to 25% by weight. When a copolymer having a repeating unit of less than 5% by weight is used, it is difficult to dissolve in an alkaline aqueous solution during the development step, whereas a copolymer exceeding 40% by weight tends to be too soluble in an alkaline aqueous solution. .
In addition, the copolymer [A] used in the present invention has a repeating unit derived from the compound (a2) based on the total number of repeating units derived from the compounds (a1), (a2) and (a3). , Preferably 10 to 80% by weight, particularly preferably 30 to 80% by weight. When this repeating unit is less than 10% by weight, the heat resistance, surface hardness and stripping solution resistance of the resulting interlayer insulating film and microlens tend to decrease, while when the amount of this repeating unit exceeds 80% by weight. The storage stability of the radiation sensitive resin composition tends to decrease.

The copolymer [A] used in the present invention has a polystyrene-equivalent weight average molecular weight (hereinafter referred to as “Mw”), preferably 2 × 10 ³ to 1 × 10 ⁵ , more preferably 5 × 10 ^{3 to} 5 × 10. ⁴ . If the Mw is less than 2 × 10 ³ , the development margin may not be sufficient, the remaining film ratio of the resulting film may decrease, the pattern shape of the resulting interlayer insulating film or microlens, heat resistance, etc. On the other hand, if it exceeds 1 × 10 ⁵ , the sensitivity may be lowered or the pattern shape may be inferior. The molecular weight distribution (hereinafter referred to as “Mw / Mn”) is preferably 5.0 or less, more preferably 3.0 or less. When Mw / Mn exceeds 5.0, the pattern shape of the obtained interlayer insulating film or microlens may be inferior. The radiation-sensitive resin composition containing the copolymer [A] can easily form a predetermined pattern shape without causing a development residue during development.

Copolymer [A] can be synthesized, for example, by polymerizing compound (a1), compound (a2) and compound (a3) in the presence of a radical polymerization initiator in an appropriate solvent.
Examples of the solvent used for the production of the copolymer [A] include alcohol, ether, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol alkyl ether propio Nates, aromatic hydrocarbons, ketones, esters and the like.

Specific examples thereof include alcohols such as methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, and 3-phenyl-1-propanol;
Tetrahydrofuran as ether;
Examples of glycol ethers include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether;
Examples of ethylene glycol alkyl ether acetate include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate;
Examples of diethylene glycol include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether;
Examples of propylene glycol monoalkyl ethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
As propylene glycol alkyl ether propionate, for example, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, etc .;
Examples of propylene glycol alkyl ether acetates include propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate;
Aromatic hydrocarbons such as toluene, xylene, etc .;
Examples of ketones include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, etc .;
Examples of esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, hydroxy Ethyl acetate, hydroxybutyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy -3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, propoxy Methyl acetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionic acid Propyl, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate Propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropyl Butyl pionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxypropion Examples thereof include esters such as propyl acid, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate.

  Of these, ethylene glycol alkyl ether acetate, diethylene glycol, propylene glycol monoalkyl ether, and propylene glycol alkyl ether acetate are preferable. Particularly, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol methyl ether. Acetate and methyl 3-methoxypropionate are preferred.

As the polymerization initiator used for the production of the copolymer [A], those known as radical polymerization initiators can be used. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile) Azo compounds such as; benzoyl peroxide, lauroyl peroxide, t-butyl peroxypivalate, organic peroxides such as 1,1′-bis- (t-butylperoxy) cyclohexane; and hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, the peroxide may be used together with a reducing agent to form a redox initiator.
In the production of the copolymer [A], a molecular weight modifier can be used to adjust the molecular weight. Specific examples thereof include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, thioglycolic acid; dimethylxanthogen sulfide, Xanthogens such as diisopropylxanthogen disulfide; terpinolene, α-methylstyrene dimer and the like.

[B] Component The [B] component used in the present invention is a 1,2-quinonediazide compound that generates a carboxylic acid upon irradiation with radiation, and is a phenolic compound or an alcoholic compound (hereinafter referred to as “mother nucleus”). And a condensate of 1,2-naphthoquinonediazide sulfonic acid halide can be used.
Examples of the mother nucleus include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, and other mother nuclei.

Specific examples thereof include trihydroxybenzophenone such as 2,3,4-trihydroxybenzophenone and 2,4,6-trihydroxybenzophenone;
As tetrahydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,3′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,3,4 2,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone, etc .;
Examples of pentahydroxybenzophenone include 2,3,4,2 ′, 6′-pentahydroxybenzophenone and the like;
Examples of hexahydroxybenzophenone include 2,4,6,3 ′, 4 ′, 5′-hexahydroxybenzophenone, 3,4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone and the like;
Examples of (polyhydroxyphenyl) alkanes include bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tri (p-hydroxyphenyl) methane, and 1,1,1-tri (p-hydroxyphenyl). ) Ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-dimethyl-4) -Hydroxyphenyl) -3-phenylpropane, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, bis (2,5-dimethyl- 4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindene-5 6,7,5 ′, 6 ′, 7′-hexanol, 2,2,4-trimethyl-7,2 ′, 4′-trihydroxyflavan and the like;
As other mother nucleus, for example, 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 2- [bis {(5-isopropyl-4-hydroxy- 2-methyl) phenyl} methyl], 1- [1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl] -3- ( 1- (3- {1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl) benzene, 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene.

Further, 1,2-naphthoquinone diazide sulfonic acid amides in which the ester bond of the mother nucleus exemplified above is changed to an amide bond, such as 2,3,4-trihydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonic acid amide, etc. Are also preferably used.
Among these mother nuclei, 2,3,4,4′-tetrahydroxybenzophenone, 4,4 ′-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] Bisphenol is preferred.
The 1,2-naphthoquinone diazide sulfonic acid halide is preferably 1,2-naphthoquinone diazide sulfonic acid chloride, and specific examples thereof include 1,2-naphthoquinone diazide-4-sulfonic acid chloride and 1,2-naphtho. Examples thereof include quinonediazide-5-sulfonic acid chloride, and among these, 1,2-naphthoquinonediazide-5-sulfonic acid chloride is preferably used.

In the condensation reaction, 1,2-naphthoquinonediazide sulfonic acid halide corresponding to 30 to 85 mol%, more preferably 50 to 70 mol% is used with respect to the number of OH groups in the phenolic compound or alcoholic compound. be able to.
The condensation reaction can be carried out by a known method.
These [B] components can be used alone or in combination of two or more.

  [B] The usage-amount of a component becomes like this. Preferably it is 5-100 weight part with respect to 100 weight part of copolymers [A], More preferably, it is 10-50 weight part. When this ratio is less than 5 parts by weight, the difference in solubility between the irradiated portion and the unirradiated portion in the alkaline aqueous solution that is the developer is small, and patterning may be difficult. Alternatively, the heat resistance and solvent resistance of the microlens may be insufficient. On the other hand, when this ratio exceeds 100 parts by weight, the solubility in the alkaline aqueous solution may be insufficient in the radiation irradiated portion, and development may be difficult.

[C] Component The [C] component used in the present invention is silsesquioxane having an aryl group having 6 to 15 carbon atoms. By incorporating such a component in the radiation sensitive resin composition, a radiation sensitive resin composition having high radiation sensitivity and an excellent development margin can be obtained, and an interlayer insulating film having a low dielectric constant can be formed. At the same time, an interlayer insulating film or a microlens having excellent adhesion to the base can be formed.
[C] component, the silane compound represented by the following following formula (1) (hereinafter may. Be referred to as "compound (c1)) can be produced by hydrolyzing.
Si (R ¹ ) (OR ² ) (OR ³ ) (OR ⁴ ) (1)
(In the formula, R ¹ represents an aryl group having 6 to 15 carbon atoms, and R ^{2 to} R ⁴ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or an acyl group. .)
It is understood that the hydrolyzate includes those in which all the hydrolyzable parts in the raw material are hydrolyzed, and those in which some of them are hydrolyzed and part of them remain without being hydrolyzed. Should.
In the above formula (1), examples of the aryl group having 6 to 15 carbon atoms of R ¹ include a naphthyl group, a phenyl group, an anthracenyl group, a phenanthryl group, and a benzyl group, and a phenyl group or a benzyl group is preferable. A phenyl group is particularly preferred.

Specific examples of the compound (c1) include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propyloxysilane, phenyltri-i-propyloxysilane, phenyltriacetoxysilane, and phenyltri (methoxyethoxy) silane. And so on.
Of these, phenyltrimethoxysilane and phenyltriethoxysilane are preferred from the viewpoints of reactivity and storage stability. A compound (c1) can be used individually or in combination of 2 or more types.

[C] component used by this invention is a silane compound (henceforth "compound (c2)") represented by the compound (c1) and the following formula (2) from the point of image development margin and the adhesiveness of the cured film obtained. it is.) and but it may also I hydrolyzed condensate der.
Si (R ⁵ ) (OR ⁶ ) (OR ⁷ ) (OR ⁸ ) (2)
(In the formula, R ⁵ is an alkyl group having 1 to 15 carbon atoms, and R ^{6 to} R ⁸ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or an acyl group. )
In the above formula (2), the alkyl group having 1 to 15 carbon atoms is preferably a linear or branched alkyl group having 1 to 6 carbon atoms or a cyclic alkyl group having 5 to 10 carbon atoms. For example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a tert-butyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, an isobornyl group, a tricyclodecynyl group, and the like are more preferable. The group is particularly preferred.

  Specific examples of the compound (c2) include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propyloxysilane, methyltri-i-propyloxysilane, methyltriacetoxysilane, methyltri (methoxyethoxy) silane, ethyltri Methoxysilane, ethyltriethoxysilane, ethyltri-n-propyloxysilane, ethyltri-i-propyloxysilane, ethyltriacetoxysilane, ethyltri (methoxyethoxy) silane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propyloxysilane, n-propyltri-i-propyloxysilane, n-propyltriacetoxysilane, n-propyltri (methoxyethoxy) silane, cyclohexyl Silane, cyclohexyl triethoxysilane, cyclohexyltrimethoxysilane -n- propyl silane, cyclohexyl-tri -i- propyl silane, cyclohexyl triacetoxy silane, and a cyclohexyl tri (methoxyethoxy) silane.

  Of these, methyltrimethoxysilane and methyltriethoxysilane are preferred from the viewpoints of reactivity and storage stability. A compound (c2) can be used individually or in combination of 2 or more types.

The component [C] used in the present invention preferably contains 50% by weight or more of repeating units derived from the compound (c1) based on the total repeating units derived from the compounds (c1) and (c2). More preferably, it contains 50 to 95% by weight, particularly preferably 60 to 90% by weight. If this repeating unit is less than 50% by weight, phase separation may occur with the copolymer [A] in the radiation-sensitive resin composition, and the coating film formation may be hindered.
The hydrolysis reaction for producing the component [C] is preferably carried out in a suitable solvent. Examples of such solvents include methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, t-butyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, Examples thereof include water-soluble solvents such as tetrahydrofuran, dioxane and acetonitrile, and aqueous solutions thereof.

Since these water-soluble solvents are removed in a later step, those having a relatively low boiling point such as methanol, ethanol, n-propanol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, and tetrahydrofuran are suitable. In terms of solubility, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone are more preferable, and methyl isobutyl ketone is particularly preferable.
The hydrolysis reaction is preferably an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, acidic ion exchange resin, various Lewis acids, or a base catalyst such as , Ammonia, primary amines, secondary amines, tertiary amines, nitrogen-containing aromatic compounds such as pyridine, basic ion exchange resins, hydroxides such as sodium hydroxide, carbonates such as potassium carbonate, acetic acid It is carried out in the presence of a carboxylate such as sodium and various Lewis bases. The amount of the catalyst to be used is preferably 0.2 mol or less, more preferably 0.00001 to 0.1 mol, relative to 1 mol of the monomer.
Water content, reaction temperature, and reaction time are appropriately set. For example, the following conditions can be adopted.
The water content is 1.5 mol or less, preferably 1 mol or less, more preferably 0.9 mol or less with respect to 1 mol of the total amount of hydrolyzable groups in the silane compound used for production. is there.
The reaction temperature is preferably 40 to 200 ° C, more preferably 50 to 150 ° C.
The reaction time is preferably 30 minutes to 24 hours, more preferably 1 to 12 hours.

The weight average molecular weight in terms of polystyrene of the [C] component used in the present invention is preferably 5 × 10 ^{2 to} 5 × 10 ³ , more preferably 1 × 10 ^{3 to} 4.5 × 10 ³ . If the weight average molecular weight of the component [C] is less than 5 × 10 ² , the development margin may not be sufficient. On the other hand, if it exceeds 5 × 10 ³ , the copolymer [A ] May cause phase separation and hinder coating formation.
The ratio of the component [C] used is preferably 10 to 100 parts by weight or less, more preferably 15 to 50 parts by weight or less with respect to 100 parts by weight of the copolymer [A]. If the use ratio is less than 10 parts by weight, the desired effect may not be obtained. On the other hand, if it exceeds 100 parts by weight, phase separation occurs with the copolymer [A] and the coating film formation is hindered. There is a risk of causing.

Other Components The radiation-sensitive resin composition of the present invention contains the above-mentioned copolymers [A], [B] and [C] as essential components, but [D] a heat-sensitive acid as necessary. Product compound, [E] polymerizable compound having at least one ethylenically unsaturated double bond, epoxy resin other than [F] copolymer [A], [G] surfactant, or [H] adhesion aid An agent can be contained.
[D] The heat-sensitive acid generating compound can be used to improve heat resistance and hardness. Specific examples thereof include known onium salts such as sulfonium salts, benzothiazonium salts, ammonium salts, and phosphonium salts.
The proportion of the component [D] used is preferably 20 parts by weight or less, more preferably 5 parts by weight or less with respect to 100 parts by weight of the copolymer [A]. When the amount used exceeds 20 parts by weight, precipitates may be deposited in the coating film forming step, which may hinder the coating film formation.

Examples of the polymerizable compound having at least one ethylenically unsaturated double bond as the component [E] include a known monofunctional (meth) acrylate, bifunctional (meth) acrylate, or trifunctional or higher (meth). An acrylate can be mentioned preferably. Of these, trifunctional or higher functional (meth) acrylates are preferably used, and trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa (meth) acrylate are particularly preferable.
[E] The use ratio of the component is preferably 50 parts by weight or less, more preferably 30 parts by weight or less with respect to 100 parts by weight of the copolymer [A].
By including the [E] component at such a ratio, the heat resistance, surface hardness, etc. of the interlayer insulating film or microlens obtained from the radiation-sensitive resin composition of the present invention can be improved. If the amount used exceeds 50 parts by weight, film roughening may occur in the step of forming a coating film of the radiation-sensitive resin composition on the substrate.

The epoxy resin other than the copolymer [A] as the [F] component is not limited as long as the compatibility is not affected. Preferably, bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, cyclic aliphatic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, heterocyclic epoxy resin, glycidyl methacrylate ) Polymerized resins and the like can be mentioned. Of these, bisphenol A type epoxy resins, cresol novolac type epoxy resins, glycidyl ester type epoxy resins and the like are particularly preferable.
The proportion of the component [F] used is preferably 30 parts by weight or less with respect to 100 parts by weight of the copolymer [A]. By containing the component [F] at such a ratio, the heat resistance and surface hardness of the protective film or insulating film obtained from the radiation-sensitive resin composition of the present invention can be further improved. When this ratio exceeds 30 parts by weight, the film thickness uniformity of the coating film may be insufficient when a coating film of the radiation sensitive resin composition is formed on the substrate.
The copolymer [A] can also be referred to as an “epoxy resin”, but differs from the [F] component in that it has alkali solubility. [F] component is alkali-insoluble.

  In the radiation sensitive resin composition of the present invention, a surfactant which is the above [G] component can be used in order to further improve the coating property. [G] As the surfactant, for example, a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant can be suitably used.

  Specific examples of the fluorosurfactant include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether. , Octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1 , 2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecyl sulfonate, 1,1,2,2,8 , 8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, etc. Sodium Zensuruhon acid; fluoroalkyl polyoxyethylene ethers; fluoroalkyl ammonium iodide, fluoroalkyl polyoxyethylene ethers, perfluoroalkyl polyoxyethylene ethanol; can be exemplified fluorine-based alkyl esters; perfluoroalkyl alkoxylates. These commercial products include BM-1000, BM-1100 (manufactured by BM Chemie), MegaFuck F142D, F172, F173, F183, F178, F191, F191 (and above, Dainippon Ink). Chemical Industries, Ltd.), Fluorad FC-170C, FC-171, FC-430, FC-431 (above, manufactured by Sumitomo 3M), Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.) ), F-top EF301, 303, and 352 (manufactured by Shin-Akita Kasei Co., Ltd.).

  Examples of the silicone surfactant include DC3PA, DC7PA, FS-1265, SF-8428, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032 (above, Toray Dow Corning) -Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 (above, GE Toshiba Silicone Co., Ltd.) are commercially available. You can list what you have.

  Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and the like. Polyoxyethylene aryl ethers; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; (meth) acrylic acid copolymer polyflow Nos. 57 and 95 (manufactured by Kyoeisha Chemical Co., Ltd.) Etc. can be used.

These surfactants can be used alone or in combination of two or more.
These [G] surfactants are preferably used in an amount of 5 parts by weight or less, more preferably 2 parts by weight or less based on 100 parts by weight of the copolymer [A]. [G] If the amount of the surfactant used exceeds 5 parts by weight, the coating film may be easily formed when the coating film is formed on the substrate.

  In the radiation sensitive resin composition of the present invention, an adhesion assistant as the [H] component can also be used in order to improve the adhesion to the substrate. As such [H] adhesion assistant, a functional silane coupling agent is preferably used, and examples thereof include a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group. . Specifically, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like. Such [H] adhesion assistant is preferably used in an amount of 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the copolymer [A]. In the case where the amount of the adhesion assistant exceeds 20 parts by weight, there may be a case where a development residue is likely to occur in the development process.

Radiation-sensitive resin composition The radiation-sensitive resin composition of the present invention is a uniform mixture of the above-mentioned copolymer [A], [B] and [C] components and other components optionally added as described above. To be prepared. The radiation-sensitive resin composition of the present invention is preferably used in a solution state after being dissolved in an appropriate solvent. For example, preparing a radiation-sensitive resin composition in a solution state by mixing the copolymer [A], [B] and [C] components and other optionally added components in a predetermined ratio. Can do.

As the solvent used for the preparation of the radiation sensitive resin composition of the present invention, the respective components of the copolymer [A], [B] and [C] components and other components optionally blended are uniformly dissolved. And what does not react with each component is used.
As such a solvent, the thing similar to what was illustrated as a solvent which can be used in order to manufacture copolymer [A] mentioned above can be mentioned.

  Among such solvents, alcohol, glycol ether, ethylene glycol alkyl ether acetate, ester and diethylene glycol are preferably used from the viewpoints of solubility of each component, reactivity with each component, ease of film formation, and the like. . Among these, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, Purpylene glycol monomethyl ether acetate, methyl methoxypropionate, and ethyl ethoxypropionate can be particularly preferably used.

  Furthermore, in order to improve the in-plane uniformity of the film thickness together with the solvent, a high boiling point solvent can be used in combination. Examples of the high boiling point solvent that can be used in combination include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzylethyl ether. , Dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl Examples include cellosolve acetate. Of these, N-methylpyrrolidone, γ-butyrolactone, and N, N-dimethylacetamide are preferable.

  When a high boiling point solvent is used in combination as the solvent of the radiation sensitive resin composition of the present invention, the amount used is 50% by weight or less, preferably 40% by weight or less, more preferably 30% by weight or less, based on the total amount of the solvent. can do. If the amount of the high-boiling solvent used exceeds this amount, the coating film thickness uniformity, sensitivity, and residual film rate may decrease.

When preparing the radiation-sensitive resin composition of the present invention in a solution state, components other than the solvent in the solution, that is, the copolymer [A], [B] and [C] components and other optionally added components The ratio of the total amount of the components can be arbitrarily set according to the purpose of use, the desired film thickness value, and the like. Still, it is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, and further preferably 15 to 35% by weight.
The composition solution thus prepared can be used after being filtered using a Millipore filter having a pore size of about 0.2 μm.

Formation of Interlayer Insulating Film and Microlens Next, a method for forming the interlayer insulating film and microlens of the present invention using the radiation sensitive resin composition of the present invention will be described. The method for forming an interlayer insulating film or microlens of the present invention includes the following steps in the order described below.
(1) The process of forming the coating film of the radiation sensitive composition of this invention on a board | substrate,
(2) A step of irradiating at least a part of the coating film with radiation,
(3) a step of developing the irradiated coating film, and (4) a step of heating the developed coating film.

(1) Step of forming a coating film of the radiation-sensitive composition of the present invention on a substrate In the step (1), the composition solution of the present invention is applied to the substrate surface, preferably by pre-baking. The solvent is removed to form a coating film of the radiation sensitive resin composition.
Examples of the types of substrates that can be used include glass substrates, silicon wafers, and substrates on which various metals are formed.
The method of applying the composition solution is not particularly limited, and an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, an ink jet method, or the like is employed. In particular, spin coating and slit die coating are preferred. Prebaking conditions vary depending on the type of each component, the proportion of use, and the like. For example, it can be set at 60 to 110 ° C. for about 30 seconds to 15 minutes.
The thickness of the coating film to be formed is, for example, 3 to 6 μm when the interlayer insulating film is formed, and 0.5 to 3 μm, for example, when the microlens is formed, as the value after pre-baking preferable.

(2) Step of irradiating at least a part of the coating film In the step (2), the developer is irradiated with radiation through a mask having a predetermined pattern on the formed coating film. The patterning is performed by removing the irradiated portion using the development process. Examples of the radiation used at this time include ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.
Examples of the ultraviolet rays include g-line (wavelength 436 nm), i-line (wavelength 365 nm), and the like. Examples of the far ultraviolet rays include KrF excimer laser. Examples of X-rays include synchrotron radiation. Examples of the charged particle beam include an electron beam.
Among these, ultraviolet rays are preferable, and radiation containing g-line and / or i-line is particularly preferable.
The exposure amount, 50~1,500J / ^{m 2} In the case of forming an interlayer insulating film, in the case of forming a micro-lens is preferably set to 50~2,000J / ^{m 2.}

(3) Development process Examples of the developer used in the development process include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-acid. -N-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene An aqueous solution of an alkali (basic compound) such as 1,5-diazabicyclo [4.3.0] -5-nonane can be used. In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the above aqueous alkali solution, or various organic solvents that dissolve the composition of the present invention can be used as a developing solution. Furthermore, as a developing method, for example, an appropriate method such as a liquid piling method, a dipping method, a rocking dipping method, a shower method, or the like can be used. The development time at this time varies depending on the composition of the composition, but can be, for example, 30 to 120 seconds.
In addition, the conventionally known radiation-sensitive resin composition has been required to strictly control the development time because the formed pattern peels when the development time exceeds about 20 to 25 seconds from the optimum value. In the case of the radiation-sensitive resin composition of the invention, good pattern formation is possible even when the excess time from the optimum development time is 30 seconds or more, and there is an advantage in product yield.

(4) Heating step (3) Performed as described above (3) After the development step, the patterned thin film is preferably rinsed, for example, by washing with running water, and more preferably irradiated with radiation from a high-pressure mercury lamp or the like. (After post-exposure), the 1,2-quinonediazite compound remaining in the thin film is decomposed, and then the thin film is heated (post-baked) by a heating device such as a hot plate or an oven. The thin film is cured. The exposure amount in the post-exposure step is preferably about 2,000 to 5,000 J / m ² . Moreover, the baking temperature in this hardening process is 120-250 degreeC, for example. Although heating time changes with kinds of heating apparatus, for example, when performing heat processing on a hotplate, it can be set to 30 to 90 minutes when performing heat processing in oven, for example. At this time, a step baking method or the like in which a heating process is performed twice or more can also be used.
In this way, a patterned thin film corresponding to the target interlayer insulating film or microlens can be formed on the surface of the substrate.
The interlayer insulating film and the microlens formed as described above are excellent in dielectric constant, adhesion, heat resistance, solvent resistance, transparency, etc., as will be clarified from examples described later. .

The interlayer insulating film of the present invention formed as described above has a low dielectric constant, good adhesion to the substrate, excellent solvent resistance and heat resistance, and high transmittance. Yes, it can be suitably used as an interlayer insulating film of electronic parts.

The microlens of the present invention formed as described above has good adhesion to the substrate, excellent solvent resistance and heat resistance, and has high transmittance and a good melt shape. It can be suitably used as a microlens for a solid-state imaging device.
The shape of the microlens of the present invention is a semi-convex lens shape as shown in FIG.

  The present invention will be described more specifically with reference to synthesis examples and examples. However, the present invention is not limited to the following examples.

Synthesis example of copolymer [A] Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethyl methyl ether. Subsequently, 16 parts by weight of methacrylic acid, 14 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 20 parts by weight of 2-methylcyclohexyl acrylate, 40 parts by weight of glycidyl methacrylate, 10 parts by weight of styrene Then, 3 parts by weight of α-methylstyrene dimer was charged and purged with nitrogen, and then gently stirred. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 4 hours to obtain a polymer solution containing the copolymer [A-1].
The copolymer [A-1] had a polystyrene equivalent weight average molecular weight (Mw) of 8,000 and a molecular weight distribution (Mw / Mn) of 2.3. The solid content concentration of the polymer solution obtained here was 34.4% by weight.

Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 8 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethyl methyl ether. Subsequently, 13 parts by weight of methacrylic acid, 12 parts by weight of tetrahydrofurfuryl methacrylate, 40 parts by weight of glycidyl methacrylate, 15 parts by weight of N-cyclohexylmaleimide, 10 parts by weight of lauryl methacrylate, 10 parts by weight of α-methyl-p-hydroxystyrene and α- After 3 parts by weight of methylstyrene dimer was charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer [A-2].
The copolymer [A-2] had a polystyrene equivalent weight average molecular weight (Mw) of 8,000 and a molecular weight distribution (Mw / Mn) of 2.3. Moreover, the solid content concentration of the polymer solution obtained here was 31.9% by weight.

Synthesis example 3
A flask equipped with a condenser and a stirrer was charged with 8 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethyl methyl ether. Subsequently, 10 parts by weight of styrene, 20 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, 10 parts by weight of (3-ethyloxetane-3-yl) methacrylate and tricyclo [5.2.1.0 ^2,6 ] decane-8. -After 20 parts by weight of yl methacrylate was charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer [A-3].
The copolymer [A-3] had a polystyrene equivalent weight average molecular weight (Mw) of 7,900 and a molecular weight distribution (Mw / Mn) of 2.4. The solid content concentration of the polymer solution obtained here was 31.6% by weight.

Synthesis example 4
A flask equipped with a condenser and a stirrer was charged with 8 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethyl methyl ether. Subsequently, 15 parts by weight of styrene, 15 parts by weight of methacrylic acid, 45 parts by weight of glycidyl methacrylate and 20 parts by weight of N- (4-hydroxyphenyl) methacrylamide were charged, and after nitrogen substitution, 5 parts by weight of 1,3-butadiene was added. Then, the stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer [A-4].
The copolymer [A-4] had a polystyrene equivalent weight average molecular weight (Mw) of 7,900 and a molecular weight distribution (Mw / Mn) of 2.4. Further, the solid content concentration of the polymer solution obtained here was 31.5% by weight.

Synthesis example of component [C] Synthesis example 5
100 g of phenyltrimethoxysilane was collected in a 500 mL three-necked flask, 100 g of methyl isobutyl ketone was added and dissolved, and the mixture was heated to 60 ° C. while stirring with a magnetic stirrer. To this solution, 8.6 g of ion-exchanged water in which 1% by weight of oxalic acid was dissolved was continuously added over 1 hour. After the temperature of the solution was maintained at 60 ° C. and reacted for 4 hours, the resulting reaction solution was cooled to room temperature. Thereafter, the alcohol as a reaction by-product was distilled off from the reaction solution under reduced pressure. The weight average molecular weight of the silsesquioxane [C-1] thus obtained was 1,600.

Synthesis Example 6
Collect 79.8 g of phenyltrimethoxysilane and 21.2 g of methyltrimethoxysilane in a 500 mL three-necked flask, add 100 g of propylene glycol methyl ether acetate to dissolve, and heat to 60 ° C. while stirring with a magnetic stirrer. did. To this solution, 8.6 g of ion-exchanged water in which 1% by weight of oxalic acid was dissolved was continuously added over 1 hour. After the temperature of the solution was maintained at 60 ° C. and reacted for 4 hours, the resulting reaction solution was cooled to room temperature. Thereafter, the alcohol as a reaction by-product was distilled off from the reaction solution under reduced pressure. The weight average molecular weight of the silsesquioxane [C-2] thus obtained was 2,000.

Example 1
[Preparation of radiation-sensitive resin composition]
100 parts by weight (in terms of solid content) of the copolymer [A-1] synthesized in Synthesis Example 1 as the [A] component and 4,4 ′-[1- [4- [1- [ 4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) (B-1) 30 Part by weight and 30 parts by weight of silsesquioxane [C-1] (in terms of solid content) were mixed and dissolved in diethylene glycol ethyl methyl ether so that the solid content concentration was 30% by weight, The solution was filtered through a 2 μm membrane filter to prepare a radiation sensitive resin composition solution (S-1).

Examples 2 to 8 and Comparative Example 1
[Preparation of radiation-sensitive resin composition]
In Example 1, it carried out like Example 1 except having used the kind and quantity as shown in Table 1 as [A]-[C] component, and carried out similarly to the solution of a radiation sensitive resin composition ( S-2) to (S-8) and (s-1) were prepared.
In Examples 2, 4, 6, and 8, the description of the component [B] represents that two types of 1,2-quinonediazide compounds were used in combination.

Example 9
In Example 1, it was dissolved in diethylene glycol ethyl methyl ether / propylene glycol monomethyl ether acetate = 6/4 so that the solid content concentration was 20% by weight, and a silicone surfactant SH-28PA (Toray Dow Corning A composition was prepared in the same manner as in Example 1 except that Silicone Co., Ltd. was added, and a radiation-sensitive resin composition solution (S-9) was prepared.
In Table 1, the abbreviations of the components indicate the following compounds.

B-1: 4,4 ′-[1- [4- [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5 -Condensation product of sulfonic acid chloride (2.0 mol) B-2: 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1 0.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (1.0 mol) F: silicone surfactant (trade name SH-28PA, manufactured by Toray Dow Corning Silicone Co., Ltd.) )

Examples 10 to 18 and Comparative Example 2
<Performance evaluation as interlayer insulation film>
Using the radiation-sensitive resin composition prepared as described above, various characteristics as an interlayer insulating film were evaluated as follows.

[Evaluation of sensitivity]
On Examples 10 to 17 and Comparative Example 2 on a silicon substrate, the composition described in Table 2 was applied using a spinner, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to obtain a film thickness of 3. A 0 μm coating film was formed. Example 18 was coated with a slit die coater, vacuum dried at 0.5 Torr, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. The obtained coating film was exposed through a pattern mask having a predetermined pattern with a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc., and the exposure time was changed. When using a developer with a concentration of tetramethylammonium hydroxide at 25 ° C. and a concentration of 0.4%, 80 seconds when using a developer with a concentration of 0.4%, 50 seconds when using a developer with a concentration of 2.38% Developed with. The substrate was washed with ultrapure water for 1 minute and dried to form a pattern on the wafer. The amount of exposure required to completely dissolve the 3.0 μm line-and-space (10 to 1) space pattern was measured. This value is shown in Table 2 as sensitivity. It can be said that the sensitivity is good when this value is 1,000 J / m ² or less.

[Evaluation of development margin]
On Examples 10 to 17 and Comparative Example 2 on a silicon substrate, the composition described in Table 2 was applied using a spinner, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to obtain a film thickness of 3. A 0 μm coating film was formed. Example 18 was coated with a slit die coater, vacuum dried at 0.5 Torr, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. Using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. through a mask having a 3.0 μm line and space (10 to 1) pattern on the obtained coating film, Exposure is carried out with an exposure amount corresponding to the sensitivity value measured in [Evaluation of Sensitivity], and a liquid piling method is performed by changing the development time with an aqueous tetramethylammonium hydroxide solution having the concentration shown in Table 2 at 25 ° C. Developed with. Subsequently, the substrate was washed with ultrapure water for 1 minute and dried to form a pattern on the wafer. At this time, the development time necessary for the line width to be 3.0 μm is shown in Table 2 as the optimum development time. Further, when the development was further continued from the optimum development time, the time until the 3.0 μm line pattern was peeled off was measured and shown in Table 2 as a development margin. When this value is 30 seconds or more, it can be said that the development margin is good.

[Evaluation of solvent resistance]
On the silicon substrate, for Examples 10 to 17 and Comparative Example 2, the composition shown in Table 2 was applied using a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film. did. Example 18 was coated with a slit die coater, vacuum dried at 0.5 Torr, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film. The obtained coating film was exposed to a cumulative irradiation amount of 3,000 J / m ² with a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc., and this silicon substrate was exposed to 220 in a clean oven. Heated at 0 ° C. for 1 hour to obtain a cured film having a thickness of 3.0 μm. The film thickness (T1) of the obtained cured film was measured. And after immersing the silicon substrate in which this cured film was formed in dimethyl sulfoxide temperature-controlled at 70 degreeC for 20 minutes, the film thickness (t1) of the said cured film was measured, and the film thickness change rate by immersion { | T1-T1 | / T1} × 100 [%] was calculated. The results are shown in Table 2. When this value is 5% or less, the solvent resistance is good.
In the evaluation of solvent resistance, patterning of the film to be formed is unnecessary, so the development process was omitted, and only the coating film forming process, the radiation irradiation process, and the heating process were performed for evaluation.

[Evaluation of heat resistance]
A cured film was formed in the same manner as the evaluation of the solvent resistance, and the film thickness (T2) of the obtained cured film was measured. Next, this cured film substrate was additionally baked in a clean oven at 240 ° C. for 1 hour, and then the film thickness (t2) of the cured film was measured, and the film thickness change rate {| t2-T2 | / T2 due to the additional baking. } × 100 [%] was calculated. The results are shown in Table 2. When this value is 5% or less, the heat resistance is good.

[Evaluation of cured film adhesion]
A cured film is formed in the same manner as the evaluation of the solvent resistance, and an aluminum stat pin (manufactured by QUAD) having a circular adhesive surface with a diameter of 0.27 cm, to which an epoxy resin is applied in advance, is attached to the substrate. The pin was adhered onto the cured film so as to be vertical, and baked at 150 ° C. for 1 hour in a clean oven to cure the epoxy resin. Then, the force at the time of peeling a board | substrate and a cured film was measured by pulling a stat pin using the tensile tester "Motorized Standard SDMS-0201-100SL (made by Imada Manufacturing Co., Ltd.)". Table 2 shows the force values at that time. When this value is 150 N or more, it can be said that the adhesion to the substrate is good.

[Evaluation of transparency]
In the evaluation of the solvent resistance, a cured film was formed on the glass substrate in the same manner except that a glass substrate “Corning 7059 (manufactured by Corning)” was used instead of the silicon substrate. The light transmittance of the glass substrate having this cured film was measured at a wavelength in the range of 400 to 800 nm using a spectrophotometer “150-20 type double beam (manufactured by Hitachi, Ltd.)”. Table 2 shows the values of the minimum light transmittance at that time. When this value is 90% or more, it can be said that the transparency is good.

[Evaluation of relative permittivity]
After applying the compositions shown in Table 2 on a polished SUS304 substrate using Examples 10-17 and Comparative Example 2 using a spinner, the film was prebaked on a hot plate at 90 ° C. for 2 minutes. A coating film having a thickness of 3.0 μm was formed. Example 18 was coated with a slit die coater, vacuum dried at 0.5 Torr, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. The obtained coating film was exposed with a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Co., Ltd. so that the integrated irradiation amount was 3,000 J / m ^2, and this substrate was 220 ° C. in a clean oven. The cured film was obtained by baking for 1 hour. About this cured film, the Pt / Pd electrode pattern was formed by the vapor deposition method, and the sample for dielectric constant measurement was created. The relative dielectric constant of the substrate was measured at a frequency of 10 kHz by a CV method using an HP16451B electrode and an HP4284A precision LCR meter manufactured by Yokogawa-Hewlett-Packard Co., Ltd. The results are shown in Table 2. When this value is 3.9 or less, the dielectric constant is good.
In the evaluation of the dielectric constant, since the patterning of the film to be formed is unnecessary, the development process was omitted, and only the coating film forming process, the radiation irradiation process, and the heating process were performed for evaluation.

Examples 19 to 26 and Comparative Example 3
<Performance evaluation as a micro lens>
Using the radiation-sensitive resin composition prepared as described above, various characteristics as a microlens were evaluated as follows. For the evaluation of solvent resistance, evaluation of heat resistance, and evaluation of transparency, refer to the results in the performance evaluation as the interlayer insulating film.

[Evaluation of sensitivity]
A composition shown in Table 3 was applied to a silicon substrate using Examples 19 to 26 and Comparative Example 3 using a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes to obtain a film thickness of 2.0 μm. The coating film was formed. The obtained coating film was exposed with a NSR1755i7A reduction projection exposure machine (NA = 0.50, λ = 365 nm) manufactured by Nikon Corporation through a pattern mask having a predetermined pattern, and exposure was performed in Table 3. Development was carried out by a puddle method at 25 ° C. for 1 minute in an aqueous tetramethylammonium hydroxide solution having the concentration described. It was rinsed with water and dried to form a pattern on the wafer. The exposure time required for the space line width of the 0.8 μm line and space pattern (one to one) to be 0.8 μm was measured. This value is shown in Table 3 as sensitivity. It can be said that the sensitivity is good when this value is 2,000 J / m ² or less.

[Evaluation of development margin]
A composition shown in Table 3 was applied to a silicon substrate using Examples 19 to 26 and Comparative Example 3 using a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes to obtain a film thickness of 2.0 μm. The coating film was formed. The obtained coating film was measured by the above-mentioned “[Evaluation of sensitivity]” with a NSR1755i7A reduction projection exposure machine (NA = 0.50, λ = 365 nm) manufactured by Nikon Corporation through a pattern mask having a predetermined pattern. Exposure was carried out with an exposure amount corresponding to the sensitivity value, and development was carried out with a tetramethylammonium hydroxide aqueous solution having a concentration shown in Table 3 at 25 ° C. for 1 minute. It was rinsed with water and dried to form a pattern on the wafer. Table 3 shows the development time required for the space line width of 0.8 μm line and space pattern (one to one) to be 0.8 μm as the optimum development time. Further, the time (development margin) until the pattern having a width of 0.8 μm was peeled off when the development was further continued from the optimum development time was shown in Table 3 as the development margin. When this value is 30 seconds or more, it can be said that the development margin is good.

[Formation of microlenses]
A composition shown in Table 3 was applied on a silicon substrate using Examples 19 to 26 and Comparative Example 3 using a spinner, and then prebaked on a hot plate at 90 ° C. for 2 minutes to have a film thickness of 2.0 μm. A coating film was formed. The obtained coating film was passed through a pattern mask having 4.0 [mu] m dots and 2.0 [mu] m space pattern with the NSR1755i7A reduction projection exposure machine (NA = 0.50, [lambda] = 365 nm) manufactured by Nikon Corporation. Exposure is performed with an exposure amount corresponding to the sensitivity value measured in [Evaluation of Sensitivity], and 25 ° C. is applied in a tetramethylammonium hydroxide aqueous solution having a concentration described as the developer concentration in the sensitivity evaluation in Table 3. Development was carried out by a puddle method for 1 minute. It was rinsed with water and dried to form a pattern on the wafer. Then, it exposed so that the integrated irradiation amount might be set to 3,000 J / m < ² > with the PLA-501F exposure machine (extra-high pressure mercury lamp) by Canon. Thereafter, the pattern was melt-flowed by heating at 160 ° C. for 10 minutes on a hot plate and further at 230 ° C. for 10 minutes to form a microlens.

  Table 3 shows the size (diameter) and cross-sectional shape of the bottom (surface contacting the substrate) of the formed microlens. It can be said that the microlens bottom portion is good when it is larger than 4.0 μm and smaller than 5.0 μm. In addition, when this dimension is 5.0 μm or more, the adjacent lenses are in contact with each other, which is not preferable. Further, the cross-sectional shape is good when it is a semi-convex lens shape as shown in (a) in the schematic diagram shown in FIG. 1, and it is bad when it is on a substantially trapezoidal shape as shown in (b).

It is a schematic diagram of the cross-sectional shape of a micro lens.

Claims (6)

[A] (a1) at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and (a2) selected from the group consisting of an oxiranyl group-containing unsaturated compound and an oxetanyl group-containing unsaturated compound A copolymer of an unsaturated mixture comprising at least one species,
[B] 1,2-quinonediazide compound, and [C] silsesquioxane is a hydrolyzed condensate of the silane compound represented by lower following formula (1)
A radiation-sensitive resin composition comprising:
Si (R ¹ ) (OR ² ) (OR ³ ) (OR ⁴ ) (1)
(Wherein R ¹ is an aryl group having 6 to 15 carbon atoms, and R ^{2 to} R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or an acyl group. ) [A] (a1) at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and (a2) selected from the group consisting of an oxiranyl group-containing unsaturated compound and an oxetanyl group-containing unsaturated compound A copolymer of an unsaturated mixture comprising at least one species,
[B] Hydrolysis of 1,2-quinonediazide compound and [C] 50 to 95% by weight of a silane compound represented by the following formula (1) and 5 to 50% by weight of a silane compound represented by the following formula (2) Silsesquioxane , a decomposition condensate
A radiation-sensitive resin composition comprising:
Si (R ¹ ) (OR ² ) (OR ³ ) (OR ⁴ ) (1)
(Wherein R ¹ is an aryl group having 6 to 15 carbon atoms, and R ^{2 to} R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or an acyl group. )
Si (R ⁵ ) (OR ⁶ ) (OR ⁷ ) (OR ⁸ ) (2)
(In the formula, R ⁵ is an alkyl group having 1 to 15 carbon atoms, and R ^{6 to} R ⁸ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or an acyl group. ) The radiation-sensitive resin composition according to claim 1 or 2 which is for forming an interlayer insulating film. The manufacturing method of the interlayer insulation film characterized by including the following processes in order of description below.
(1) The process of forming the coating film of the radiation sensitive resin composition of Claim 3 on a board | substrate,
(2) A step of irradiating at least a part of the coating film with radiation,
(3) a step of developing the irradiated coating film, and (4) a step of heating the developed coating film. The radiation-sensitive resin composition according to claim 1 or 2 , which is used for forming a microlens. The manufacturing method of the micro lens characterized by including the following processes in order of description below.
(1) The process of forming the coating film of the radiation sensitive resin composition of Claim 5 on a board | substrate,
(2) A step of irradiating at least a part of the coating film with radiation,
(3) a step of developing the irradiated coating film, and (4) a step of heating the developed coating film.

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