CN1898605B - Radiation-sensitive resin composition, interlayer insulating film, and microlens, and their production methods - Google Patents

Abstract

The invention provides a radiation-sensitive resin composition suitable for forming an interlayer insulating film or a microlens, which has high radiation sensitivity, has development latitude in a development step, can form a good pattern shape even if an optimum development time is exceeded, can easily form a pattern-like thin film excellent in adhesion, and generates less sublimate during baking. The radiation-sensitive resin composition contains a polymer which has a carboxyl group and an epoxy group and has a ratio (Mw/Mn) of a polystyrene-equivalent weight average molecular weight (Mw) to a polystyrene-equivalent number average molecular weight (Mn) as measured by gel permeation chromatography of 1.7 or less, and (B) a 1, 2-quinonediazide compound.

Description

Radiation-sensitive resin composition, interlayer insulating film, and microlens, and their production methods

technical field

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

Background technique

Electronic devices such as thin-film transistor (hereinafter referred to as "TFT") liquid crystal display elements, magnetic head elements, integrated circuit elements, and solid-state imaging elements are generally provided with an interlayer insulating film to insulate interconnections arranged in layers. As a material for forming an interlayer insulating film, since it is preferable to obtain a desired pattern shape with a small number of steps and a material with sufficient flatness, radiation-sensitive resin compositions are widely used (refer to Japanese Patent Laid-Open No. 2001-354822 and Japanese Patent Application Laid-Open No. 2001-343743).

Among the above-mentioned electronic components, for example, TFT liquid crystal display elements are manufactured through the steps of forming a transparent electrode film on the above-mentioned interlayer insulating film, and then forming a liquid crystal alignment film thereon, so the interlayer insulating film is placed on the transparent electrode film. It is necessary to have sufficient corrosion resistance against exposure to high temperature conditions in the forming step and exposure to a stripping liquid for forming a protective film of an electrode pattern.

In recent years, the development trend of TFT-type liquid crystal display elements is large screen, high brightness, high definition, high-speed response, and thinning. Interlayer insulating films are required to have higher performance than before in terms of low dielectric constant and high transmittance.

On the other hand, as optical system materials for imaging optical systems of on-core color filters in facsimiles, electronic copiers, solid-state imaging devices, etc., or optical fiber connectors, microlenses with a lens diameter of about 3 to 100 μm, or These microlenses are regularly arranged into a microlens array.

It is known that microlenses or microlens arrays are formed by the following methods: forming a resist pattern corresponding to the lens, then melting it by heat treatment, and directly using it as a lens; using the fused lens pattern as a mask, drying A method of transferring the shape of a lens to a substrate by etching, etc. Radiation-sensitive resin compositions are widely used for forming the above-mentioned lens patterns (see JP-A-6-18702 and JP-A-6-136239).

The element on which the above-mentioned microlens or microlens array is formed will be used in the following steps: in order to remove various insulating films on the pads as the wiring formation part, apply a flattening film and a protective film for etching, use the required The mask is exposed and developed to remove the etching resist on the pad portion, and then the planarization film or various insulating films are removed by etching to expose the pad portion. Therefore, the microlens or the microlens array must have solvent resistance or heat resistance in the film-forming step of the planarization film and the etching protective film and the etching step.

The radiation-sensitive resin composition for forming a microlens is required to have high sensitivity, and the microlens formed therefrom has a desired radius of curvature, and is high heat resistance, high transmittance, and the like.

In the development step of the interlayer insulating film or microlens obtained in this way, if the development time is slightly longer than the optimum time, the developer will penetrate between the pattern and the substrate, and peeling will easily occur, so it must be strictly controlled. The development time has a problem in the yield of the product.

In this way, when an interlayer insulating film or a microlens is formed from a radiation-sensitive resin composition, the composition is required to be highly sensitive, and in the developing step of the forming step, even if the developing time is longer than the specified time, the pattern will not be peeled off. , showing good adhesion, and the interlayer insulating film formed by it has high heat resistance, high solvent resistance, low dielectric constant, high transmittance, etc. When forming a microlens, it is also required that the microlens has a good melt shape (required radius of curvature), high heat resistance, high solvent resistance, and high transmittance, but there is no radiation-sensitive resin combination that meets the above requirements. things.

Sublimates generated during baking for forming the above-mentioned interlayer insulating film or microlenses may contaminate production lines or devices, and a radiation-sensitive resin composition in which generated sublimates are reduced is desired.

Contents of the invention

The present invention is based on the above circumstances. Therefore, the object of the present invention is to provide a radiation-sensitive resin composition which has high radiation sensitivity; has a developing latitude in the developing step, and can form Good pattern; can easily form a patterned film with good adhesion; the sublimation produced during baking is reduced.

Another object of the present invention is to provide a radiation-sensitive resin composition which can form high heat resistance, high solvent resistance, high transmittance, low Interlayer insulating film with high dielectric constant; when used to form microlenses, microlenses with high transmittance and good melt shape can be formed, and the sublimation produced during baking is reduced.

Another object of the present invention is to provide a method of forming an interlayer insulating film and a microlens using the above radiation-sensitive resin composition.

Still another object of the present invention is to provide an interlayer insulating film and a microlens formed by the method of the present invention.

Other objects and advantages of the present invention are as described below.

According to the first aspect of the present invention, the above objects and advantages of the present invention are achieved by a radiation-sensitive resin composition, characterized in that the composition contains: (A) has carboxyl and epoxy groups, and is determined by gel permeation chromatography A polymer having a ratio (Mw/Mn) of polystyrene-equivalent weight average molecular weight (Mw) to polystyrene-equivalent number average molecular weight (Mn) of 1.7 or less; and (B) 1,2-quinonedi Azides.

In a second aspect, the above-mentioned purpose and advantages of the present invention are realized by a method for forming an interlayer insulating film or a microlens, which is characterized in that the method implements the following steps in the following order:

(1) a step of forming a coating film of the above-mentioned radiation-sensitive resin composition on the substrate;

(2) a step of irradiating at least a part of the coating film;

(3) a developing step; and

(4) Heating step.

In the third aspect, the objects and advantages of the present invention are achieved by the interlayer insulating film and the microlens formed by the above method.

Brief description of the drawings

FIG. 1 is a schematic diagram showing a cross-sectional shape of a microlens.

The best way to practice the invention

The radiation-sensitive resin composition of the present invention will be described in detail below.

Copolymer (A)

The copolymer (A) used in the present invention can be obtained by living radical polymerization of a polymerizable mixture preferably containing the following components:

(a1) unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride (hereinafter may be referred to as compound (a1)),

(a2) an epoxy group-containing unsaturated compound (hereinafter may be referred to as compound (a2)), and

(a3) Unsaturated compounds other than (a1) component and (a2) component (it may be called a compound (a3) hereafter).

For example, the copolymer (A) can be produced by living radical polymerization of a polymerizable mixture containing compound (a1), compound (a2) and compound (a3) in a solvent in the presence of a polymerization initiator.

The carboxyl group and epoxy group which the copolymer (A) obtained above has are derived from compound (a1) and compound (a2), respectively.

Various proposals have been made regarding the initiator system for living radical polymerization. For example, the TEMPO system discovered by Georges et al., the initiator system composed of copper bromide and bromine-containing ester compounds proposed by Matyjaszewski et al., the carbon tetrachloride and ruthenium (II) complex proposed by Higashimura et al. Initiator system composed of a combination of compounds, combination of thiocarbonylsulfide compound and free radical initiator described in JP 2000-515181, JP 2002-500251 and JP 2004-518773 wait.

In order to obtain the polymer (A) of the present invention, the preferred living polymerization initiator system can be appropriately selected according to the type of monomer used, and the system that does not deactivate the extended end, but from the viewpoint of polymerization efficiency, etc., thiocarbonylsulfide compounds are preferred. and free radical initiators. Here, the thiocarbonylsulfide compound includes, for example, dithioesters, dithiocarbonates, trithiocarbonates, xanthates, and the like.

Specific examples thereof may be compounds represented by the following formulae.

Among them, cumyl dithiobenzoate, S-cyanomethyl-S-dodecyl trithiocarbonate, phenyl-methyl pyrazole-1-dithiocarboxylate, Dithioester used in Synthesis Example 5 below and xanthate used in Synthesis Example 6 below.

As the radical initiator, a compound generally known as a radical polymerization initiator can be used, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis-(2,4-dimethyl valeronitrile), 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile) and other azo compounds; benzoyl peroxide, lauroyl peroxide, neopentyl peroxide Organic peroxides such as tert-butyl acid, 1,1'-di-(tert-butylperoxy)cyclohexane; hydrogen peroxide; redox-type initiators containing the above-mentioned peroxides and reducing agents, etc.

These polymerization initiators can be used individually or in mixture of 2 or more types.

The above-mentioned thiocarbonyl sulfide is used in an amount of preferably 1 to 10,000 parts by weight, more preferably 10 to 1,000 parts by weight, per 100 parts by weight of the polymerization initiator. In addition, the radical polymerization initiator is used in an amount of preferably 0.01-100 parts by weight, more preferably 0.1-10 parts by weight per 100 parts by weight of the monomer mixture containing the epoxy group-containing polymerizable unsaturated compound. The polymerization temperature in the above-mentioned living radical polymerization is not particularly limited, but is preferably 0°C to 100°C, more preferably 10°C to 85°C.

Depending on the initiator system, in order not to deactivate the polymerization initiator, an ester compound (a1') that protects the carboxyl group of the compound (a1) with an appropriate protecting group can be used for polymerization, and then the copolymer can be obtained by deprotection (A).

In the copolymer (A) used in the present invention, it is preferred that the polymerized units derived from the compound (a1) account for 5-40 of the total amount of polymerized units or repeating units derived from the compounds (a1), (a2) and (a3) respectively % by weight, particularly preferably 10-30% by weight. If the copolymer is used with less than 5% by weight of the polymerized units, it is difficult to dissolve in an aqueous alkali solution during the developing step, and if it exceeds 40% by weight, the copolymer tends to be too soluble in an aqueous alkali solution.

Compound (a1) is unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride having radical polymerizability, such as mono [(meth)acryloyl group of monocarboxylic acid, dicarboxylic acid, dicarboxylic acid anhydride, polycarboxylic acid Oxyalkyl] esters, mono(meth)acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, polycyclic compounds having carboxyl groups and their anhydrates, and the like.

As the above specific examples, monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, etc.;

Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, etc.;

Dibasic carboxylic acid anhydrides include, for example, acid anhydrides of the above-mentioned compounds listed as dibasic carboxylic acids;

Mono [(meth)acryloyloxyalkyl] esters of polycarboxylic acids are, for example: succinic acid mono[2-(meth)acryloyloxyethyl] ester, phthalic acid mono[2-(methyl) ) acryloyloxyethyl] ester, etc.;

Examples of mono(meth)acrylates of polymers having carboxyl and hydroxyl groups at both ends include: ω-carboxy polycaprolactone mono(meth)acrylate, etc.;

Polycyclic compounds with carboxyl groups and their anhydrates are, for example: 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxybicyclo[2.2.1]hept-2-ene, -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]hept-2-ene anhydrous, etc. .

Among them, monocarboxylic acids and dicarboxylic anhydrides are preferably used, and acrylic acid, methacrylic acid, and maleic anhydride are particularly preferably used from the viewpoints of copolymerization reactivity, solubility in aqueous alkali solutions, and ease of availability. They can be used alone or in combination.

The protecting group for protecting the carboxyl group of the compound (a1) is not particularly limited, and known carboxyl protecting groups can be used. For example, there are trialkylsilyl group, 1-alkoxyalkyl group, cyclic 1-alkoxyalkyl group and the like. More specifically, there are, for example: trimethylsilyl, dimethylbutylsilyl, 1-ethoxyethyl, 1-propoxyethyl, tetrahydrofuryl, tetrahydropyranyl, triphenyl methyl etc.

In the copolymer (A) used in the present invention, it is preferred that the polymerized units derived from compound (a2) account for 10-70% by weight of the total amount of polymerized units derived from compounds (a1), (a2) and (a3), Particular preference is given to 20-60% by weight. When the polymerized unit is less than 10% by weight, the heat resistance or surface hardness of the resulting interlayer insulating film or microlens tends to decrease, and when the amount of the polymerized unit exceeds 70% by weight, the preservation of the radiation-sensitive resin composition Stability tends to decrease.

Compound (a2) is an epoxy group-containing unsaturated compound having radical polymerizability. Examples are: glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethacrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, acrylic acid-3,4 -epoxybutyl methacrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl 6,7-epoxyheptyl acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, etc. Among them, glycidyl methacrylate, 6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate. They can be used alone or in combination.

In the copolymer (A) used in the present invention, it is preferred that the polymerized units derived from the compound (a3) account for 5-70% by weight of the total amount of polymerized units derived from the compounds (a1), (a2) and (a3), Particular preference is given to 5-50% by weight. When the polymerized unit is less than 5% by weight, the preservation stability of the radiation-sensitive resin composition tends to decrease, and when it exceeds 70% by weight, it may be difficult to dissolve in the developing step of the process of forming an interlayer insulating film or a microlens. In alkaline aqueous solution.

The compound (a3) is not particularly limited as long as it is an unsaturated compound having radical polymerizability, for example, alkyl methacrylate, alkyl acrylate, cycloalkyl methacrylate, methacrylate having a hydroxyl group Acrylic acid esters, cycloalkyl acrylates, aryl methacrylates, aryl acrylates, unsaturated dicarboxylic acid diesters, bicyclic unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated Diene.

As specific examples of the above, alkyl methacrylates include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, methacrylic acid 2-ethylhexyl ester, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate, etc.;

Alkyl acrylates include methyl acrylate, isopropyl acrylate, etc.;

Cycloalkyl methacrylates include, for example, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl methacrylate, methyl Tricyclo[5.2.1.0 ^2,6 ]decane-8-yloxyethyl acrylate, isobornyl methacrylate, etc.;

Examples of methacrylates with hydroxyl groups include: hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diglycol methacrylate Alcohol esters, 2,3-dihydroxypropyl methacrylate, 2-methacryloyl ethyl glucoside, 4-hydroxyphenyl methacrylate, etc.;

Cycloalkyl acrylates include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate, tricyclo[5.2.1.0 ^2,6 acrylate ]decane-8-yloxyethyl ester, isobornyl acrylate, etc.;

Aryl methacrylates include, for example, phenyl methacrylate, benzyl methacrylate, etc.;

Aryl acrylates include, for example, phenyl acrylate, benzyl acrylate, etc.;

Unsaturated dicarboxylic acid diesters include diethyl maleate, diethyl fumarate, diethyl itaconate, etc.;

Examples of bicyclic unsaturated compounds are: bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene , 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene -2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxy Carbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]heptene -2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene , 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'- Hydroxyethyl)bicyclo[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-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, etc.;

Examples of maleimide compounds include: phenylmaleimide, cyclohexylmaleimide, benzylmaleimide, N-succinimidyl-3-maleimide benzoic acid Ester, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N-succinimidyl-3-maleimide Iminopropionate, N-(9-acridyl)maleimide, etc.;

Unsaturated aromatic compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, etc.;

Conjugated dienes include, for example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.;

Other unsaturated compounds are, for example: acrylonitrile, methacrylonitrile, vinyl chloride, 1,1-dichloroethylene, acrylamide, methacrylamide, vinyl acetate.

Among them, alkyl methacrylates, cycloalkyl methacrylates, bicyclic unsaturated compounds, unsaturated aromatic compounds, and conjugated dienes are preferably used. From the point of view, styrene, tert-butyl methacrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl methacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate are particularly preferred Esters, 1,3-butadiene, bicyclo[2.2.1]hept-2-ene. They can be used alone or in combination.

Preferred specific examples of the copolymer (A) used in the present invention are, for example: methacrylic acid/styrene/methacrylic acid tricyclo[5.2.1.0 ^2,6 ]decane-8-yl ester/methacrylic acid shrink Glycerides/tetrahydrofurfuryl methacrylate copolymer, methacrylic acid/styrene/tricyclo[5.2.1.0 ^2,6 ]decane-8-yl methacrylate/glycidyl methacrylate/p-ethylene Benzyl glycidyl ether/tetrahydrofurfuryl methacrylate copolymer, methacrylic acid/styrene/tricyclo[5.2.1.0 ^2,6 ]decane-8-yl methacrylate/glycidyl methacrylate Ester/polyethylene glycol monomethacrylate copolymer, methacrylic acid/styrene/tricyclo[5.2.1.0 ^2,6 ]decane-8-yl methacrylate/glycidyl methacrylate/poly Propylene Glycol Monomethacrylate Copolymer.

The copolymer (A) used in the present invention has a polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") and a polystyrene-equivalent number average molecular weight (hereinafter referred to as "Mn") measured by gel permeation chromatography. ") ratio (Mw/Mn) is 1.7 or less, preferably 1.5 or less. When Mw/Mn exceeds 1.7, the pattern shape of the obtained interlayer insulating film or microlens will deteriorate. In addition, Mw is preferably 2×10 ³ to 1×10 ⁵ , more preferably 5×10 ³ to 5×10 ⁴ . If Mw is lower than 2×10 ³ , the development latitude may be insufficient, and the film retention rate of the resulting film may decrease. , or the pattern shape, heat resistance, etc. of the resulting interlayer insulating film or microlens are poor. On the other hand, when Mw exceeds 1×10 ⁵ , the sensitivity decreases or the pattern shape is poor. Mn is preferably 1.2×10 ³ to 1×10 ⁵ , more preferably 2.9×10 ³ to 5×10 ⁴ . The radiation-sensitive resin composition containing the above-mentioned copolymer [A] does not generate development residue during development, and can easily form a predetermined pattern shape.

Furthermore, the amount of residual monomers of the copolymer (A) used in the present invention measured by gel permeation chromatography is preferably less than 5.0%, more preferably less than 3.0%, particularly preferably less than 2.0%. By using a copolymer having such a residual monomer content, a protective film with reduced sublimation during baking can be obtained.

In this invention, a copolymer (A) can be used individually or in mixture of 2 or more types.

The solvent used in the preparation of copolymer (A) is for example: alcohol, ether, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate , propylene glycol alkyl ether propionate, aromatic hydrocarbons, ketones, esters, etc.

Their specific examples are as follows:

Examples of alcohols include methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol, etc.;

Ethers such as tetrahydrofuran, etc.;

Glycol ethers include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.;

Ethylene glycol alkyl ether acetate, such as methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate wait;

Diethylene glycol, for example, includes diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc.;

Propylene glycol monoalkyl ethers include, for example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, etc., propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc.;

Propylene glycol alkyl ether acetate, for example, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, etc.;

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.;

Aromatic hydrocarbons include toluene, xylene, etc.;

Ketones include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, etc.;

Examples of esters are: methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methylpropionate Ethyl glycolate, methyl glycolate, ethyl glycolate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate , 3-hydroxypropionate, 3-hydroxypropionate, 3-hydroxypropionate, 2-hydroxy-3-methylbutyrate, methoxymethyl acetate, methoxyethyl acetate, methoxypropyl acetate , butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, propyl ethoxy acetate, butyl ethoxy acetate, methyl propoxy acetate, ethyl propoxy acetate, Propyl Propyl Acetate, Butyl Propoxy Acetate, Methyl Butoxy Acetate, Ethyl Butoxy Acetate, Propyl Butoxy Acetate, Butyl Butyl Acetate, Methyl 2-Methoxy Propionate ester, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate Esters, Propyl 2-Ethoxypropionate, Butyl 2-Ethoxypropionate, Methyl 2-Butoxypropionate, Ethyl 2-Butoxypropionate, Propyl 2-Butoxypropionate Esters, Butyl 2-Butoxypropionate, Methyl 3-Methoxypropionate, Ethyl 3-Methoxypropionate, Propyl 3-Methoxypropionate, Butyl 3-Methoxypropionate ester, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate ester, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate ester, 3-butoxypropyl propionate, 3-butoxy butyl propionate and other esters.

Among them, ethylene glycol alkyl ether acetate, diethylene glycol, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate are preferred, and diethylene glycol dimethyl ether and diethylene glycol ethyl methyl ether are particularly preferred. , Propylene Glycol Methyl Ether, Propylene Glycol Methyl Ether Acetate.

(B) Ingredients

The (B) component used in the present invention is a 1,2-quinone diazide compound that generates a carboxylic acid by irradiation with radiation, and a phenolic compound or an alcoholic compound (hereinafter referred to as a "mother core") and a 1,2-quinone diazide compound can be used. - Condensates of naphthoquinonediazidosulfonyl halides.

The above-mentioned core includes, for example, trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl)alkane, and other cores.

Their specific examples are as follows:

Trihydroxybenzophenones include, for example: 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, etc.;

Tetrahydroxybenzophenones include, for example: 2,2',4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4' -Tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxydiphenyl Methanone, etc.;

Pentahydroxybenzophenone, for example: 2,3,4,2',6'-pentahydroxybenzophenone, etc.;

Hexahydroxybenzophenone, for example: 2,4,6,3',4',5'-hexahydroxybenzophenone, 3,4,5,3',4',5'-hexahydroxydiphenyl Methanone, etc.;

(Polyhydroxyphenyl)alkanes include, for example, bis(2,4-dihydroxyphenyl)methane, bis(p-hydroxyphenyl)methane, tris(p-hydroxyphenyl)methane, 1,1,1-tri(p-hydroxyphenyl)methane, Hydroxyphenyl) ethane, bis(2,3,4-trihydroxyphenyl)methane, 2,2-bis(2,3,4-trihydroxyphenyl)propane, 1,1,3-tri(2 , 5-Dimethyl-4-hydroxyphenyl)-3-phenylpropane, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]benzene base] ethylene] bisphenol, bis(2,5-dimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, 3,3,3',3'-tetramethyl-], 1 '-spirobiindene-5,6,7,5',6',7'-hexanol, 2,2,4-trimethyl-7,2',4'-trihydroxyflavan, etc.;

Other nuclei include, 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-dihydroxy phenyl)-1-methylethyl)benzene, 4,6-bis{1-(4-hydroxyphenyl)-1-methylethyl}-1,3-dihydroxybenzene.

It is also preferred to use 1,2-naphthoquinonediazidosulfonamides that change the ester bond in the above-mentioned exemplified core to an amide bond, such as 2,3,4-trihydroxybenzophenone-1,2 -Naphthoquinonediazido-4-sulfonamide and the like.

Among these cores, 2,3,4,4'-tetrahydroxybenzophenone, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl ]phenyl]ethylene]bisphenol.

As 1,2-naphthoquinonediazidosulfonyl halide, preferably 1,2-naphthoquinonediazidosulfonyl chloride, its specific examples are: 1,2-naphthoquinonediazido-4-sulfonyl chloride and 1,2-Naphthoquinonediazido-5-sulfonyl chloride, among which 1,2-naphthoquinonediazido-5-sulfonyl chloride is preferably used.

In the condensation reaction, relative to the OH group in 1 equivalent of phenolic compound or alcoholic compound, it is preferable to use 1,2-naphthoquinonediazide sulfonic acid corresponding to 30-85% mole, more preferably 50-70% mole Acyl halide.

The condensation reaction can be carried out by a known method.

The said (B) component can be used individually or in combination of 2 or more types.

The usage ratio of (B) component is preferably 5-100 weight part with respect to 100 weight part of copolymer (A), More preferably, it is 10-50 weight part. When the ratio is less than 5 parts by weight, the difference in solubility between the radiation-irradiated part and the non-irradiated part in the alkaline aqueous solution as the developing solution is small, and it is difficult to make a pattern. In addition, the heat resistance and solvent resistance of the obtained interlayer insulating film or microlens will insufficient. On the other hand, when the ratio exceeds 100 parts by weight, the solubility of the radiation-irradiated portion in the aqueous alkali solution is insufficient, making it difficult to develop.

other ingredients

The radiation-sensitive resin composition of the present invention may contain (C) a thermosensitive acid generating compound, (D) having at least one ethylenic non- Polymerizable compounds with saturated double bonds, (E) epoxy resins other than the copolymer (A), (F) surfactants, (G) adhesion aids, and the like.

The above-mentioned (C) thermosensitive acid generating compound can be used to improve heat resistance or hardness. Specific examples thereof include onium salts such as sulfonium salts, benzothiazolium salts, ammonium salts, and phosphonium salts.

Specific examples of the aforementioned sulfonium salts include alkylsulfonium salts, benzylsulfonium salts, dibenzylsulfonium salts, substituted benzylsulfonium salts and the like.

Specific examples of the above are as follows:

Alkylsulfonium salts include, for example: 4-acetylphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, dimethyl-4-(benzyl Oxycarbonyloxy)phenylsulfonium, dimethyl-4-(benzoyloxy)phenylsulfonium hexafluoroantimonate, dimethyl-4-(benzoyloxy)phenyl hexafluoroarsenate Sulfonium, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate, etc.;

Benzylsulfonium salts are, for example: benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzyl hexafluoroantimonate methylsulfonium hexafluoroantimonate, benzyl-4-methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl hexafluoroarsenate -3-Chloro-4-hydroxyphenylmethylsulfonium, 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, etc.;

Dibenzylsulfonium salts include, for example: dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyldibenzyl hexafluoroantimonate Dibenzyl-4-methoxyphenylsulfonium hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methoxyhexafluoroantimonate Base-4-hydroxy-5-tert-butylphenylsulfonium, benzyl-4-methoxybenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, etc.;

Substituted benzylsulfonium salts include: p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-chlorobenzyl hexafluoroantimonate, Benzyl-4-hydroxyphenylmethylsulfonium, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4 hexafluoroantimonate -Hydroxyphenylmethylsulfonium, o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, etc.

Specific examples of the aforementioned benzothiazolium salts include: 3-benzylbenzothiazolium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluorophosphate, 3-benzylbenzothiazolium tetrafluoroborate, 3-(p-methoxybenzyl)benzothiazolium antimonate, 3-benzyl-2-methylthiobenzothiazolium hexafluoroantimonate, 3-benzyl-5-chlorobenzene hexafluoroantimonate Benzylbenzothiazolium salts such as thiazolium.

Among them, sulfonium salts and benzothiazolium salts are preferably used, and 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, antimony hexafluoro Acid 4-acetoxyphenylbenzylmethylsulfonium, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate, 3-hexafluoroantimonate Benzylbenzothiazolium.

These commercially available products include Suned SI-L85, Suned SI-L110, Suned SI-L145, Suned SI-L150, Suned SI-L160 (manufactured by Sanshin Chemical Industry Co., Ltd.) and the like.

The proportion of component (C) used is preferably 20 parts by weight or less, more preferably 5 parts by weight or less, based on 100 parts by weight of the copolymer (A). When the amount exceeds 20 parts by weight, deposits are deposited in the coating film forming step, which hinders the formation of the coating film.

As the above-mentioned (D) component, a polymerizable compound having at least one ethylenically unsaturated double bond (hereinafter may be referred to as "D component") is preferably, for example, a monofunctional (meth)acrylate, a difunctional (meth)acrylic acid ester or trifunctional or more (meth)acrylate.

The above-mentioned monofunctional (meth)acrylates include, for example: 2-hydroxyethyl (meth)acrylate, carbitol (meth)acrylate, isobornyl (meth)acrylate, 3-methyl (meth)acrylate Oxybutyl ester, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, etc. These commercially available items include, for example, ARONIX M-101, ARONIX M-111, ARONIX M-114 (the above are manufactured by Toagosei Co., Ltd.), KAYARAD TC-110S, KAYARAD TC-120S (the above are Nippon Kayaku Co., Ltd. Manufactured), BISUCO-TO 158, BISUCO-TO 2311 (the above are manufactured by Osaka Organic Chemical Industry Co., Ltd.), etc.

The above-mentioned bifunctional (meth)acrylates include, for example, ethylene glycol (meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate , polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, bisphenoxyethanol fluorene diacrylate, bisphenoxyethanol fluorene diacrylate, etc. Their commercially available products include, for example, Aronicus M-210, Aronicus M-240, Aronicus M-6200 (the above are manufactured by Toagosei Co., Ltd.), KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604 (the above are Nippon Kayaku (manufactured by Co., Ltd.), BISUCO-TO 260, BISUCO-TO 312, BISUCO-TO 335HP (the above are manufactured by Osaka Organic Chemical Industry Co., Ltd.), etc.

Examples of (meth)acrylates with more than three functions include: trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris((meth)acryloyloxyethyl)phosphate , Pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. These commercially available items include, for example, Aronics M-309, Aronics M-400, Aronics M-405, Aronics M-450, Aronics M-7100, Aronics M-8030, Aronics M-8060 (the above are manufactured by Toagosei Co., Ltd. ), KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.), ビスコ-ト295, ビスコ-ト300, ビスコ- 360, BISUCO-TO GPT, BISUCO-TO 3PA, BISUCO-TO 400 (the above are manufactured by Osaka Organic Chemical Industry Co., Ltd.), etc.

Among them, it is preferable to use trifunctional or higher (meth)acrylates, among which trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate are particularly preferable.

These monofunctional, difunctional or trifunctional or more functional (meth)acrylates can be used alone or in combination. The proportion of component (D) used is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, based on 100 parts by weight of the copolymer (A).

By containing (D)component in the said ratio, the heat resistance of the interlayer insulating film obtained from the radiation-sensitive resin composition of this invention, a microlens, surface hardness, etc. can be improved. If the amount exceeds 50 parts by weight, a dry film problem may arise in the step of forming a coating film of the radiation-sensitive resin composition on the substrate.

Epoxy resins other than the copolymer (A) as the above-mentioned (E) component (hereinafter may be referred to as "E component") are not limited as long as they do not affect compatibility, and bisphenol A type epoxy resins, Novolac epoxy resins, cresol novolac epoxy resins, cycloaliphatic epoxy resins, glycidyl ester epoxy resins, glycidylamine epoxy resins, heterocyclic epoxy resins Resin, resin obtained by copolymerization of glycidyl methacrylate, etc. Among them, bisphenol A-type epoxy resins, cresol novolac-type epoxy resins, glycidyl ester-type epoxy resins, and the like are more preferable.

It is preferable that the usage ratio of (E) component is 30 weight part or less with respect to 100 weight part of copolymers (A). By containing (E) component in the said ratio, the heat resistance, surface hardness, etc. of the protective film or insulating film obtained from the radiation-sensitive resin composition of this invention can be improved further. If this ratio exceeds 30 parts by weight, when a coating film of the radiation-sensitive resin composition is formed on a substrate, the film thickness uniformity of the coating film will be insufficient.

Copolymer (A) can also be called "epoxy resin", but copolymer (A) is alkali-soluble, and it differs from (E) component.

In order to further improve applicability, the radiation-sensitive resin composition of the present invention may also use a surfactant as the above-mentioned (F) component. Here, as the (F) surfactant that can be used, for example, a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant can be suitably used.

Specific examples of fluorosurfactants include: 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl Hexyl 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 perfluorododecylsulfonate, 1, 1, 2, 2, 8, 8, 9, 9, 10, 10-decafluorododecane, 1, 1, 2, 2, 3, 3-hexafluorodecane, etc., in addition to: fluorine Sodium substituted alkylbenzene sulfonate; fluoroalkyl ammonium iodide, fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethanol; perfluoroalkyl alcoholate; fluorine series Alkyl esters, etc. Their commercially available products include, for example, BM-1000, BM-1100 (the above are manufactured by BM Chemie Co., Ltd.), Mega-Arch F142D, Mega-Arch F172, Mega-Arch F173, Mega-Arch F183, Mega-Arch F178, Mega-Arch F191, Mega-Arch F471 (above are manufactured by Dainippon Ink Chemical Industry Co., Ltd. (manufactured by Sumitomo Corporation), Flora-do FC-170C, FC-171, FC-430, FC-431 (manufactured by Sumitomo Suli-Em Co., Ltd.), Surflon S-112, Surflon S-113 , Surfron S-131, Surfron S-141, Surfron S-145, Surfron S-382, Surfron SC-101, Surfron SC-102, Surfron SC-103, Surfron SC-104, Surfron SC-105, Surfron SC-106 (the above are manufactured by Asahi Glass Co., Ltd.), Efttop EF301, Efttop EF303, Efttop EF352 (the above are manufactured by Shin Akita Chemical Co., Ltd.) wait.

The above-mentioned organosilicon-based surfactants include, for example, DC3PA, DC7PA, FS-1265, SF-8428, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032 (above by レ·ダウコ— Ning Sirikon Co., Ltd.); TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (manufactured by GE Toshiba Sirikon Co., Ltd.), etc. Surfactants marketed under the name.

The above-mentioned nonionic surfactant can be used, for example: polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene Polyoxyethylene aryl ethers such as oxyethylene nonylphenyl ether; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; (meth)acrylate copolymers Polyflo-No. 57, 59 (manufactured by Kyoeisha Chemical Co., Ltd.), etc.

These surfactants can be used alone or in combination of two or more.

These (F) surfactants are preferably used in an amount of 5 parts by weight or less, more preferably in an amount of 2 parts by weight or less, based on 100 parts by weight of the copolymer (A). (F) When the amount of the surfactant exceeds 5 parts by weight, when a coating film is formed on a substrate, a dry film of the coating film is likely to occur.

The radiation-sensitive resin composition of the present invention may use an adhesion aid as the component (G) in order to improve the adhesiveness with the substrate. As the (G) adhesion aid, for example, a functional silane coupling agent is preferably used. Examples thereof include silane coupling agents having reactive substituents such as carboxyl groups, methacryloyl groups, isocyanate groups, and epoxy groups. More specifically, there are trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyl Triethoxysilane, γ-glycidyl ether propyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc. The (G) adhesion aid is preferably used in an amount of 20 parts by weight or less, more preferably 10 parts by weight or less, relative to 100 parts by weight of the copolymer (A). When the amount of the adhesion aid exceeds 20 parts by weight, development residue is likely to occur in the development step.

Radiation Sensitive Resin Composition

The radiation-sensitive resin composition of the present invention is prepared by uniformly mixing the above-mentioned copolymer (A) and (B) components and other components arbitrarily added as described above. The radiation-sensitive resin composition of the present invention is preferably dissolved in an appropriate solvent and used in a solution state. For example, a radiation-sensitive resin composition in a solution state can be prepared by mixing the components of the copolymers (A) and (B) and optionally added other components in a predetermined ratio.

The solvent used for the preparation of the radiation-sensitive resin composition of the present invention can uniformly dissolve each component such as the components (A) and (B) of the copolymer and other components mixed arbitrarily, and does not react with each component.

The solvent may be the same solvent as exemplified as the solvent usable for the preparation of the above-mentioned copolymer (A).

Among the solvents, alcohols, glycol ethers, glycol alkyl ether acetates, esters, and Diethylene glycol. Among them, for example, benzyl alcohol, 2-phenylethanol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, Alcohol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl methoxypropionate, ethoxypropyl ethyl acetate.

In order to improve the in-plane uniformity of the film thickness, a high boiling point solvent may also be used in combination with the above solvents. High boiling point solvents that can be used in combination are, for example: N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide Amide, N-Methylpyrrolidone, Dimethylsulfoxide, Benzylethyl Ether, Dihexyl Ether, Acetonylacetone, Isophorone, Caproic Acid, Capric Acid, 1-Octanol, 1-Nonanol, Acetic Acid Benzyl ester, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. Among them, N-methylpyrrolidone, γ-butyrolactone, and N,N-dimethylacetamide are preferable.

As the solvent of the radiation-sensitive resin composition of the present invention, when a high boiling point solvent is used in combination, the usage amount thereof is preferably 50% by weight or less, more preferably 40% by weight or less, further preferably 30% by weight or less, based on the total amount of solvents. If the amount of the high-boiling point solvent exceeds this amount, the film thickness uniformity, sensitivity, and film retention rate of the coating film may decrease.

When the radiation-sensitive resin composition of the present invention is prepared in a solution state, the total ratio of the components other than the solvent in the solution, that is, the components of the copolymers (A) and (B) and other components optionally added can be adjusted according to the purpose of use, the desired The value of the required film thickness etc. is set arbitrarily, for example, it is 5-50 weight%, Preferably it is 10-40 weight%, More preferably, it is 15-35 weight%.

The composition solution prepared above can be used after being filtered through a microporous filter having a pore size of about 0.2 μm or the like.

Formation of interlayer insulating film and microlens

Next, a method of forming the interlayer insulating film and the microlens of the present invention using the radiation-sensitive resin composition of the present invention will be described. Each method for forming an interlayer insulating film and a microlens according to the present invention includes the following steps and is implemented in the following order.

(1) a step of forming a coating film of the radiation-sensitive resin composition of the present invention on a substrate;

(2) a step of irradiating at least a part of the coating film;

(3) a developing step; and

(4) Heating step.

(1) Step of forming a coating film of the radiation-sensitive resin composition of the present invention on a substrate

In the step (1) above, the composition solution of the present invention is coated on the surface of the substrate, and the solvent is preferably removed by pre-baking to form a coating film of the radiation-sensitive resin composition.

The types of substrates that can be used include, for example, glass substrates, silicon wafers, and substrates on which various metals are formed on the above surfaces.

The coating method of the composition solution is not particularly limited, and for example, appropriate methods such as spray coating, roll coating, spin coating (spin coating), slot die coating, bar coating, and inkjet coating can be used. methods, spin coating and slot die coating are particularly preferred. The pre-baking conditions vary depending on the type and usage ratio of each component. For example, it can be baked at 60-110° C. for about 30 seconds to 15 minutes.

From the value after prebaking, the thickness of the formed coating film is preferably, for example, 3-6 μm when forming an interlayer insulating film, and preferably, for example, 0.5-3 μm when forming a microlens.

(2) Step of irradiating at least a part of the coating film with radiation

In the step of (2) above, the formed coating film is irradiated with radiation through a mask having a predetermined pattern. Then, in the next step (3), a developing treatment is performed using a developing solution to remove radiation-irradiated portions, thereby forming a pattern. The radiation used at this time includes, for example, ultraviolet rays, extreme ultraviolet rays, X-rays, charged particle rays, and the like.

The above-mentioned ultraviolet rays include, for example, g-rays (wavelength: 436 nm), i-rays (wavelength: 365 nm) and the like. Far-ultraviolet rays include, for example, KrF excimer lasers and the like. X-rays include, for example, synchrotron rays and the like. Charged particle beams include, for example, electron beams and the like.

Among them, ultraviolet rays are preferable, and radiation containing g-rays and/or i-rays is particularly preferable.

The amount of exposure is preferably 50-1,500 J/m ² when forming an interlayer insulating film, and preferably 50-2,000 J/m ² when forming a microlens.

(3) Development step

The developer used for the development process can be used, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-normal Propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5.4. Aqueous solutions of bases (basic compounds) such as 0]-7-undecene and 1,5-diazabicyclo[4.3.0]-5-nonane. As a developing solution, 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 in which the composition of the present invention is dissolved can also be used. In addition, as a developing method, appropriate methods such as a liquid spreading method, a dipping method, a shaking dipping method, and a flushing method can be utilized. The developing time at this time varies depending on the composition of the composition, and may be, for example, between 30 and 120 seconds.

For known radiation-sensitive resin compositions in the past, if the developing time exceeds about 20-25 seconds than the optimal developing time, the pattern formed will peel off, so the developing time must be strictly controlled, but for the radiation-sensitive resin of the present invention The composition can form a good pattern even if the time exceeds the optimal development time of 30 seconds or more, and has an advantage in product yield.

(4) Heating step

After the (3) development step carried out as above, it is preferable to perform a rinsing treatment such as washing with running water on the film that has been drawn, and it is more preferable to irradiate the entire surface with radiation (post-exposure) by a high-pressure mercury lamp or the like to perform 1 remaining in the film. After the decomposition treatment of the 2-quinonediazide compound, the film is then subjected to heat treatment (post-baking treatment) by a heating device such as a hot plate or a heating furnace, whereby hardening treatment of the film is performed. The exposure amount in the above-mentioned post-exposure step is preferably around 2,000-5,000 J/m ² . The heating temperature in this hardening process is 120-250 degreeC, for example. The heating time varies depending on the type of heating equipment. For example, when heating on a hot plate, the heating time is 5-30 minutes, and when heating in a furnace, the heating time is 30-90 minutes. At this time, a step-baking method in which heating steps are performed two or more times or the like can 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.

As can be seen from Examples described later, the interlayer insulating film and microlenses formed as described above are excellent in adhesion, heat resistance, solvent resistance, transparency, and the like.

interlayer insulating film

The interlayer insulating film of the present invention formed as described above has good adhesion to the substrate, is excellent in solvent resistance and heat resistance, has high transmittance, and has a low dielectric constant, and can be preferably used as an interlayer insulation of electronic components. membrane.

micro lens

The microlens of the present invention formed as described above has good adhesion to the substrate, excellent solvent resistance and heat resistance, high transmittance and good melt shape, and can be preferably 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. 1( a ).

Example

Synthesis examples and examples are given below to further describe the present invention in detail, but the present invention is not limited to the following examples.

<Determination of Molecular Weight of Copolymer by Gel Permeation Chromatography>

Device: GPC-101 (manufactured by Showa Denko Co., Ltd.)

Column: GPC-KF-801, GPC-KF-802, GPC-KF-804 and GPC-KF-804 combined

Mobile phase: tetrahydrofuran containing 0.5% by weight phosphoric acid.

Synthesis example of copolymer (A)

Synthesis Example 1

1 part by weight of azobisisobutyronitrile, 4 parts by weight of cumyl dithiobenzoate and 50 parts by weight of diethylene glycol ethyl methyl ether were added to a flask equipped with a condenser tube and a stirrer. Then add 20 parts by weight of styrene, 20 parts by weight of methacrylic acid, 20 parts by weight of tricyclo[ ^5.2.1.02,6 ]decane-8-yl ester, 40 parts by weight of glycidyl methacrylate, After nitrogen replacement, slow stirring was started. The temperature of the solution was raised to 60°C, and the temperature was maintained for 24 hours, then 3 parts by weight of azobisisobutyronitrile was added, and stirred at 60°C for 4 hours, and 200 parts by weight of diethylene glycol ethyl methyl ether was added to obtain Solution of Copolymer (A-1). The polystyrene-equivalent weight average molecular weight (Mw) of the copolymer (A-1) was 10,000, the molecular weight distribution (Mw/Mn) was 14, and the residual monomer was 2.0% by weight. The solid fraction concentration of the polymer solution was 29.8% by weight.

Synthesis example 2

1 part by weight of azobisisobutyronitrile, 4 parts by weight of cumyl dithiobenzoate and 50 parts by weight of diethylene glycol ethyl methyl ether were added to a flask equipped with a condenser tube and a stirrer. Then add 16 parts by weight of methacrylic acid, 18 parts by weight of glycidyl methacrylate, 6 parts by weight of tricyclo[5.2.1.0 ^2,6 ]decane-8-yl ester, 30 parts by weight of p-vinylbenzyl Base glycidyl ether, 30 parts by weight of polyethylene glycol (n=2) monomethacrylate, after replacing with nitrogen, start to stir slowly. The temperature of the solution was raised to 60°C, and the temperature was maintained for 24 hours, then 3 parts by weight of azobisisobutyronitrile was added, and stirred at 60°C for 4 hours, and 200 parts by weight of diethylene glycol ethyl methyl ether was added to obtain Solution of Copolymer (A-2). The polystyrene-equivalent weight average molecular weight (Mw) of the copolymer (A-2) was 11,000, the molecular weight distribution (Mw/Mn) was 1.3, and the residual monomer was 1.2% by weight. The solid fraction concentration of the polymer solution obtained here was 30.1% by weight.

Synthesis example 3

Use S-cyanomethyl-S-dodecyl trithiocarbonate instead of cumyl dithiobenzoate in Synthesis Example 1, obtain copolymer (A-3) according to Synthesis Example 1 except that solution. The polystyrene-equivalent weight average molecular weight (Mw) of the copolymer (A-3) was 9,500, the molecular weight distribution (Mw/Mn) was 1.3, and the residual monomer was 1.5% by weight. The solid fraction concentration of the polymer solution obtained here was 29.6% by weight.

Synthesis Example 4

Using pyrazole-1-dithiocarboxylate phenyl-methyl ester instead of cumyl dithiobenzoate in Synthesis Example 2, obtain a polymer containing copolymer (A-4) according to Synthesis Example 2 except that substance solution. The polystyrene-equivalent weight average molecular weight (Mw) of the copolymer (A-4) was 12,000, the molecular weight distribution (Mw/Mn) was 1.4, and the residual monomer was 1.3% by weight. The solid fraction concentration of the polymer solution was 29.7% by weight.

Synthesis Example 5

A polymer solution containing a copolymer (A-5) was obtained in accordance with Synthesis Example 1 except that the following dithioester was used instead of cumyl dithiobenzoate in Synthesis Example 1. The polystyrene-equivalent weight average molecular weight (Mw) of the copolymer (A-5) was 11,000, the molecular weight distribution (Mw/Mn) was 1.3, and the residual monomer was 1.4% by weight. The solid fraction concentration of the polymer solution obtained here was 29.8% by weight.

Synthesis Example 6

A polymer solution containing a copolymer (A-6) was obtained in accordance with Synthesis Example 2 except that the following xanthate was used instead of cumyl dithiobenzoate in Synthesis Example 2. The polystyrene-equivalent weight average molecular weight (Mw) of the copolymer (A-6) was 11,000, the molecular weight distribution (Mw/Mn) was 1.3, and the residual monomer was 1.5% by weight. The solid fraction concentration of the polymer solution was 30.1% by weight.

Comparative Synthesis Example 1

8 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethyl methyl ether were added to a flask equipped with a condenser and a stirrer. Next, 20 parts by weight of styrene, 20 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate and 20 parts by weight of phenylmaleimide were added, replaced with nitrogen, and then slowly stirred. The temperature of the solution was raised to 70°C, and the temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (a-1).

The polystyrene-equivalent weight average molecular weight (Mw) of the copolymer (a-1) was 7,500, the molecular weight distribution (Mw/Mn) was 2.4, and the residual monomer was 5.8% by weight. The polymer solution obtained here had a solid fraction concentration of 30.6% by weight.

Example 1

Preparation of Radiation Sensitive Resin Composition

With the solution containing the polymer (A-1) synthesized in the above synthesis example 1 as the (A) component, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methyl Condensate (B-1) of ethyl ethyl] phenyl] ethylene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazido-5-sulfonyl chloride (2.0 mol) as component (B) , the composition (A) of the amount equivalent to 100 parts by weight of the polymer (A-1) (solid part) is mixed with 30 parts by weight of the composition (B), and dissolved in diethylene glycol ethyl methyl ether to make the solid The partial concentration was 30% by weight, and then filtered through a membrane filter with a pore size of 0.2 μm to prepare a solution (S-1) of the radiation-sensitive resin composition.

Embodiment 2-9, 11-14, comparative example 1

Preparation of Radiation Sensitive Resin Composition

For the (A) component and (B) component in Example 1, use the type and amount described in Table 1, except that it is performed in the same manner as in Example 1 to obtain a solution of the radiation-sensitive resin composition ( S-2)-(S-9), (S-11)-(S-14) and (s-1).

In Table 1, the description of the (B) component of Example 8 means that two 1,2-quinonediazide compounds of B-1 (20 parts by weight) and B-2 (15 parts by weight) were used in combination.

Example 10

In Example 1, the composition was prepared in the same manner as in Example 1 except that it was dissolved in diethylene glycol ethyl methyl ether so that the solid content concentration was 15% by weight, and a solution of the radiation-sensitive resin composition was obtained. (S-10).

In Table 1, the abbreviations of components represent the following compounds.

(B-1): 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylene]bisphenol (1.0 mol) with 1 , Condensate of 2-naphthoquinonediazido-5-sulfonyl chloride (2.0 moles)

(B-2): 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylene]bisphenol (1.0 mol) with 1 , Condensate of 2-naphthoquinonediazido-5-sulfonyl chloride (1.0 mol)

(B-3): 2,3,4,4'-tetrahydroxybenzophenone (1.0 mol) and 1,2-naphthoquinonediazido-5-sulfonate (2.44 mol)

(B-4): 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylene]bisphenol (1.0 mol) with 1 , Condensate of 2-naphthoquinonediazido-4-sulfonyl chloride (1.0 mol)

(F): SH-28PA (manufactured by Toray Dow-ning Siricon Co., Ltd.)

Table 1

Embodiment 15-28, comparative example 2-4

Performance evaluation as an interlayer insulating film

Using the radiation-sensitive resin composition prepared as described above, various properties as an interlayer insulating film were evaluated as follows. The compositions used in Comparative Examples 3 and 4 are all commercially available compositions of m/p-cresol novolak resin and 1,2-naphthoquinonediazido-5-sulfonate (Tokyo Ohka (strain) manufacturing).

Evaluation of Sensitivity

Use a spin coater for Examples 15-27 and Comparative Examples 2-4, and use a slot die coater for Example 28 to coat the composition in Table 2 on a silicon substrate, and then place it on a hot plate at 90°C. Bake for 2 minutes to form a coating film with a film thickness of 3.0 μm. Using the PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Cannon Co., Ltd., the exposure time was changed, and the obtained coating film was exposed through a mask with a predetermined pattern, and then, tetrahydroxide with the concentration of the developer in Table 2 was used. Methylammonium aqueous solution, developed by spreading for 90 seconds. It was washed with running ultrapure water for 1 minute and dried to form a pattern on a silicon wafer. The amount of exposure required to completely dissolve a 3.0 μm line and space (10 to 1) space pattern was determined. Take this value as the sensitivity and show it in Table 2. When this value is 1,000 J/m ² or less, it can be said that the sensitivity is good.

Evaluation of developing latitude

Use a spin coater for Examples 15-27 and Comparative Examples 2-4, and use a slot die coater for Example 28 to coat the composition in Table 2 on a silicon substrate, and then place it on a hot plate at 90°C. Bake for 2 minutes to form a coating film with a film thickness of 3.0 μm. Using a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon Corporation, through a mask having a pattern of lines and spaces (10 to 1) of 3.0 μm, with a sensitivity value equivalent to that measured in the above "sensitivity evaluation" Exposure amount of the obtained coating film was exposed, and the tetramethylammonium hydroxide aqueous solution with the concentration of the developer in Table 2 was used for developing at 25° C. for 90 seconds by the spreading method. It was washed with running ultrapure water for 1 minute and dried to form a pattern on a silicon wafer. At this time, the developing time required for the line width to reach 3 μm is regarded as the optimal developing time, which is shown in Table 2. The development was continued, and the time from the optimal development time to the peeling of the line pattern of 3.0 μm was measured, and it was shown in Table 2 as the development latitude. When this value is 30 seconds or more, it can be said that the development latitude is good.

Evaluation of Solvent Resistance

Use a spin coater for Examples 15-27 and Comparative Examples 2-4, and use a slot die coater for Example 28 to coat the composition in Table 2 on a silicon substrate, and then place it on a hot plate at 90°C. Bake for 2 minutes to form a coating film with a film thickness of 3.0 μm. The obtained coating film was exposed with a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon Co., Ltd. so that the cumulative irradiation dose was 3,000 J/m ² , and the silicon substrate was heated at 220° C. for 1 hour in a clean oven. , to obtain a hardened film. The film thickness (T1) of the obtained cured film was measured. Soak the silicon substrate with the hardened film in dimethyl sulfoxide at a temperature controlled at 70°C for 20 minutes, then measure the film thickness (t1) of the hardened film, and calculate the film thickness change rate {|t1 caused by immersion -T1|/T1}×100[%]. The results are shown in Table 2. When this value is 5% or less, it can be said that the solvent resistance is good.

In the evaluation of solvent resistance, since it is not necessary to pattern the formed film, the radiation irradiation step and the development step are omitted, and only the step of forming a coating film, the post-baking step, and the heating step are performed for evaluation.

Evaluation of heat resistance

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

Transparency evaluation

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

Evaluation of Relative Permittivity

For Examples 15-27 and Comparative Examples 2-4, a spin coater was used, and a slot die coater was used for Example 28. The composition in Table 2 was coated on a ground SUS304 substrate, and then at 90° C. Front-bake on a hot plate for 2 minutes to form a coating film with a film thickness of 3.0 μm. The obtained coating film was exposed with a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon Co., Ltd., so that the cumulative irradiation dose was 3,000J/m ² , and the substrate was baked at 220°C for 1 hour in a clean oven. , to obtain a hardened film.

A Pt/Pd electrode pattern was formed on this cured film by a vapor deposition method, and a sample for measuring a dielectric constant was produced. The relative permittivity of this substrate was measured by the CV method at a frequency of 10 kHz using a HP16451B electrode manufactured by Yokogawa Hewlett-Packard Co., Ltd. and a HP4284A precision LCR instrument. The results are shown in Table 2. When this value is 3.6 or less, it can be said that the relative permittivity is good.

In the evaluation of the relative permittivity, it is not necessary to pattern the formed film, so the radiation irradiation step and the development step are omitted, and only the step of forming a coating film, the post-baking step, and the heating step are performed for evaluation.

Evaluation of sublimates

Use a spin coater for Examples 15-27 and Comparative Examples 2-4, and use a slot die coater for Example 28 to coat the composition in Table 2 on a silicon substrate, and then place it on a hot plate at 90°C. Bake for 2 minutes to form a coating film with a film thickness of 3.0 μm. The obtained coating film was exposed with a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon Co., Ltd. so that the cumulative irradiation dose became 3,000J/m ² , and the silicon substrate was heated at 220°C for 1 hour in a clean oven. , to obtain a hardened film. A bare silicon wafer for cooling was mounted with a space of 1 cm above the obtained cured film, and a heating treatment was performed on a hot plate at 230° C. for 1 hour. Without replacing the bare silicon wafer for cooling, 20 silicon substrates on which the above-mentioned cured film was separately formed were continuously processed, and then it was visually checked whether or not sublimation was attached to the bare silicon wafer. When no sublimation is observed, it can be said that the evaluation of the sublimation is good.

Embodiment 29-42, comparative example 5-7

<Performance evaluation when used as a microlens>

Using the radiation-sensitive resin composition prepared as described above, evaluation of various characteristics of the microlens was performed as follows. For heat resistance evaluation and transparency evaluation, refer to the above-mentioned performance evaluation results when used as an interlayer insulating film (Table 2).

The compositions used in Comparative Examples 6 and 7 are all commercial products of the composition of m/p-cresol resole phenolic resin and 1,2-theophylquinonediazido-5-sulfonate (Tokyo Ohka (strain) manufacturing).

Evaluation of Sensitivity

Use a spin coater for Examples 29-38, 40-42, and Comparative Examples 5-7, and use a slot die coater for Example 39 to coat the composition of Table 3 on a silicon substrate, and then at 90 ° C, in Front-bake on a hot plate for 2 minutes to form a coating film with a film thickness of 3.0 μm. Using NSR1755i7A reduction projection exposure machine (NA=0.50, λ=365nm) manufactured by Nicon Co., Ltd., changing the exposure time, exposing the obtained coating film through a mask with a predetermined pattern, and then using the concentration of the developer in Table 3 An aqueous solution of tetramethylammonium hydroxide was developed at 25°C for 1 minute by the spreading method. Rinse with water, dry, and form a pattern on a silicon wafer. The exposure time required to achieve a line width of 0.8 μm for a line and space pattern (1:1) of 0.8 μm was measured. Take this value as the sensitivity and show it in Table 3. When this value is 2,500 J/m ² or less, it can be said that the sensitivity is good.

Evaluation of developing latitude

Use a spin coater for Examples 29-38, 40-42, and Comparative Examples 5-7, and use a slot die coater for Example 39 to coat the composition of Table 3 on a silicon substrate, and then at 90 ° C, in Front-bake on a hot plate for 2 minutes to form a coating film with a film thickness of 3.0 μm. Using NSR1755i7A reduction projection exposure machine (NA=0.50, λ=365nm) manufactured by Nicon Co., Ltd., through a mask with a predetermined pattern, the obtained coating film was exposed to the exposure amount corresponding to the sensitivity value measured in the above "sensitivity evaluation". Exposure was performed, and development was carried out at 25° C. for 1 minute by a flooding method using an aqueous solution of tetramethylammonium hydroxide having the concentration of the developer in Table 3. Rinse with water, dry, and form a pattern on a silicon wafer. The optimal developing time is the developing time required for the line-and-space pattern (1:1) with a gap line width of 0.8 μm to reach 0.8 μm, which is shown in Table 3. The development was continued, and the time (development latitude) from the optimal development time to the peeling of the pattern with a width of 0.8 μm was measured, which was shown in Table 3 as the development latitude. When this value is 30 seconds or more, it can be said that the development latitude is favorable.

Evaluation of Solvent Resistance

Use a spin coater for Examples 29-38, 40-42, and Comparative Examples 5-7, and use a slot die coater for Example 39 to coat the composition of Table 3 on a silicon substrate, and then at 90 ° C, in Front-bake on a hot plate for 2 minutes to form a coating film with a film thickness of 3.0 μm. Exposure was performed with a PLA-501F exposure machine (ultra-high pressure mercury lamp) manufactured by Canon Co., Ltd., so that the cumulative irradiation dose was 3,000J/m ² , and the silicon substrate was heated in a clean oven at 220°C for 1 hour to obtain a cured film . The film thickness (T3) of the obtained cured film was measured. Soak the silicon substrate forming the cured film in isopropanol at a temperature of 50°C for 10 minutes, then measure the film thickness (t3) of the cured film, and calculate the film thickness change rate {|t3-T3| /T3}×100[%]. The results are shown in Table 3. When this value is 5% or less, it can be said that the solvent resistance is good.

In the evaluation of solvent resistance, it is not necessary to draw a pattern on the formed film, so the radiation irradiation step and the development step are omitted, and only the step of forming a coating film, the post-baking step, and the heating step are performed for evaluation.

Microlens Formation

Use a spin coater for Examples 29-38, 40-42, and Comparative Examples 5-7, and use a slot die coater for Example 39 to coat the composition of Table 3 on a silicon substrate, and then at 90 ° C, in Front-bake on a hot plate for 2 minutes to form a coating film with a film thickness of 3.0 μm. Using NSR1755i7A reduction projection exposure machine (NA=0.50, λ=365nm) manufactured by Nicon Co., Ltd., through a mask having a pattern of 4.0 μm dots and 2.0 μm gaps, the sensitivity value corresponding to the sensitivity value measured in the above-mentioned "sensitivity evaluation" was measured. Exposure Amount The obtained coating film was exposed, and was developed at 25° C. for 1 minute by the flooding method with an aqueous tetramethylammonium hydroxide solution having a concentration described in Table 3 as the developer solution concentration for sensitivity evaluation. Rinse with water, dry, and form a pattern on a silicon wafer. Then, exposure was performed using a PLA-501F exposure machine (ultrahigh pressure mercury lamp) manufactured by Canon Corporation so that the cumulative irradiation amount became 3,000 J/m ² . Thereafter, the pattern was melted by heating at 160° C. for 10 minutes and further at 230° C. for 10 minutes with a hot plate to form microlenses.

Table 3 shows the size (diameter) and cross-sectional shape of the bottom (surface in contact with the substrate) of the formed microlens. When the size of the bottom of the microlens exceeds 4.0 μm but is less than 5.0 μm, it can be said to be good. When the size is 5.0 μm or more, adjacent lenses will be in contact with each other, which is not preferable. In addition, when the cross-sectional shape is a semi-convex lens shape like (a) in the schematic diagram shown in FIG. 1, it is good, and if it is a substantially square trapezoid shape like (b), it is unfavorable.

The radiation-sensitive resin composition of the present invention has high radiation sensitivity, has a development latitude in the development step, can form a good pattern shape even if the optimum development time is exceeded, and can easily form a pattern shape with excellent adhesion Thin film, the sublimation produced during baking is reduced.

The interlayer insulating film of the present invention formed by the above composition has good adhesion to the substrate, excellent solvent resistance and heat resistance, high transmittance, low dielectric constant, and is suitable for use as an interlayer insulating film for electronic components .

The microlens of the present invention formed from the above composition has good adhesion to a substrate, excellent solvent resistance and heat resistance, high transmittance and good melt shape, and is suitable for use as a microlens for a solid-state imaging device.

Claims (7)

1. radiation-sensitive resin composition; It is characterized in that: said composition contains (A) and (B) 1; The 2-quinone di-azido compound; Wherein (A) will contain that following composition (a1), (a2) and polymerism mixture (a3) carry out active free radical polymerization with thiocarbonylthio compound as controlling agent and the copolymer that obtains; It is that Mw/Mn be 1.5 below through the weight average molecular weight Mw of polystyrene conversion with ratio through the number-average molecular weight Mn of polystyrene conversion by gel permeation chromatography

(a1) for being selected from following at least a unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides: acrylic acid, methacrylic acid, crotonic acid, maleic acid, citraconic acid, mesaconic acid, itaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, mono succinate [2-(methyl) acryloxy second] ester, phthalic acid list [2-(methyl) acryloxy second] ester, ω-carboxyl polycaprolactone list (methyl) acrylate, 5-carboxyl dicyclo [2.2.1] hept-2-ene", 5,6-dicarboxyl dicyclo [2.2.1] hept-2-ene", 5-carboxyl-5-methyl bicycle [2.2.1] hept-2-ene", 5-carboxyl-5-ethyl dicyclo [2.2.1] hept-2-ene", 5-carboxyl-6-methyl bicycle [2.2.1] hept-2-ene", 5-carboxyl-6-ethyl dicyclo [2.2.1] hept-2-ene" and 5,6-dicarboxyl dicyclo [2.2.1] hept-2-ene" anhydride;

(a2) for being selected from the following at least a unsaturated compound that contains epoxy radicals: glycidyl acrylate, glycidyl methacrylate, the α-Yi Jibingxisuan ethylene oxidic ester, α-n-pro-pyl glycidyl acrylate, α-normal-butyl glycidyl acrylate, acrylic acid-3,4-epoxy radicals butyl ester, methacrylic acid-3,4-epoxy radicals butyl ester, acrylic acid-6,7-epoxy radicals heptyl ester, methacrylic acid-6,7-epoxy radicals heptyl ester, α-Yi Jibingxisuan-6,7-epoxy radicals heptyl ester, adjacent vinyl benzyl glycidol ether, between the vinyl benzyl glycidol ether, to vinyl benzyl glycidol ether and methacrylic acid 3,4-epoxy radicals cyclohexyl;

(a3) be at least a following unsaturated compound that is selected from: methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, the secondary butyl ester of methacrylic acid, the metering system tert-butyl acrylate, methacrylic acid 2-ethylhexyl, isodecyl methacrylate, the positive Lauryl Ester of methacrylic acid, methacrylic acid tridecyl ester, the positive stearyl of methacrylic acid, methyl acrylate, isopropyl acrylate, the methacrylic acid cyclohexyl ester, methacrylic acid 2-methylcyclohexyl ester, methacrylic acid three ring [5.2.1.0 ^2,6] decane-8-base ester, methacrylic acid three ring [5.2.1.0 ^2,6] decane-8-base oxygen base ethyl ester, isobornyl methacrylate, methacrylic acid hydroxyl methyl esters, 2-hydroxyethyl methacrylate, methacrylic acid 3-hydroxy propyl ester, methacrylic acid 4-hydroxyl butyl ester, monomethyl acrylic acid diglycol ester, methacrylic acid 2,3-dihydroxy propyl ester, 2-methacryl ethyl glucoside, methacrylic acid 4-hydroxy phenyl ester, acrylic acid cyclohexyl ester, acrylic acid 2-methylcyclohexyl ester, acrylic acid three ring [5.2.1.0 ^2,6] decane-8-base ester, acrylic acid three ring [5.2.1.0 ^2,6] decane-8-base oxygen base ethyl ester, isobornyl acrylate, the methacrylic acid phenylester, the methacrylic acid benzyl ester, phenyl acrylate, the acrylic acid benzyl ester, diethyl maleate, DEF, diethyl itaconate, dicyclo [2.2.1] hept-2-ene", 5-methyl bicycle [2.2.1] hept-2-ene", 5-ethyl dicyclo [2.2.1] hept-2-ene", 5-methoxyl dicyclo [2.2.1] hept-2-ene", 5-ethoxy dicyclo [2.2.1] hept-2-ene", 5,6-dimethoxy dicyclo [2.2.1] hept-2-ene", 5,6-diethoxy dicyclo [2.2.1] hept-2-ene", 5-tert-butoxycarbonyl dicyclo [2.2.1] hept-2-ene", 5-cyclohexyloxy carbonyl dicyclo [2.2.1] hept-2-ene", 5-phenyloxycarbonyl dicyclo [2.2.1] hept-2-ene", 5,6-two (tert-butoxycarbonyl) dicyclo [2.2.1] hept-2-ene", 5,6-two (cyclohexyl oxygen base carbonyl) dicyclo [2.2.1] hept-2-ene", 5-(2 '-hydroxyethyl) dicyclo [2.2.1] hept-2-ene", 5,6-dihydroxy dicyclo [2.2.1] hept-2-ene", 5,6-two (hydroxymethyl) dicyclo [2.2.1] hept-2-ene", 5,6-two (2 '-hydroxyethyl) dicyclo [2.2.1] hept-2-ene", 5-hydroxy-5-methyl base dicyclo [2.2.1] hept-2-ene", 5-hydroxyl-5-ethyl dicyclo [2.2.1] hept-2-ene", 5-hydroxymethyl-5-methyl bicycle [2.2.1] hept-2-ene", phenyl maleimide, the cyclohexyl maleimide, the benzyl maleimide, N-succinimide base-3-maleimide benzoic ether, N-succinimide base-4-maleimide butyric ester, N-succinimide base-6-maleimide capronate, N-succinimide base-3-maleimide propionic ester, N-(9-acridinyl) maleimide, styrene, α-Jia Jibenyixi, between methyl styrene, p-methylstyrene, vinyltoluene, to methoxy styrene, 1, the 3-butadiene, isoprene, 2,3-dimethyl-1, the 3-butadiene, vinyl cyanide, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, Methacrylamide and vinyl acetate;

Wherein, in the described multipolymer, based on respectively by the total amount of above-claimed cpd (a1), (a2) and the polymerized unit of (a3) deriving, polymerized unit 5～70 weight % that polymerized unit 10～70 weight % that contain polymerized unit 5～40 weight % that derived by above-claimed cpd (a1), derived by above-claimed cpd (a2) and above-claimed cpd (a3) are derived.

2. the radiation-sensitive resin composition of claim 1, said composition is used to form interlayer dielectric.

3. the radiation-sensitive resin composition of claim 1, said composition is used to form lenticule.

4. the formation method of interlayer dielectric is characterized in that implementing following step according to following order:

(1) step of filming of the radiation-sensitive resin composition of formation claim 1 on substrate;

(2) to the step of this at least a portion of filming irradiation radioactive ray;

(3) development step; And

(4) heating steps.

5. the interlayer dielectric that forms by the method for claim 4.

6. lenticular formation method is characterized in that this method comprises the following steps of implementing according to following order:

(1) step of filming of the radiation-sensitive resin composition of formation claim 1 on substrate;

(2) to the step of this at least a portion of filming irradiation radioactive ray;

(3) development step; And

(4) heating steps.

7. the lenticule that forms by the method for claim 6.

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