CN1898605A - Radiation-sensitive resin composition, interlayer insulation film, microlens and process for producing them - Google Patents

Radiation-sensitive resin composition, interlayer insulation film, microlens and process for producing them Download PDF

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CN1898605A
CN1898605A CNA200580001422XA CN200580001422A CN1898605A CN 1898605 A CN1898605 A CN 1898605A CN A200580001422X A CNA200580001422X A CN A200580001422XA CN 200580001422 A CN200580001422 A CN 200580001422A CN 1898605 A CN1898605 A CN 1898605A
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radiation
composition
sensitive resin
resin composition
acid
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CN1898605B (en
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梶田彻
蓑轮贵树
志保浩司
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JSR Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides

Abstract

The invention provides a radiation-sensitive resin composition that exhibits high radiation sensitivity, having such a development margin that desirable pattern configuration can be formed even when the optimum development time is exceeded in the development step, that is capable of easily forming a patterned thin film excelling in adherence and reduces the amount of sublimed matter occurring at firing, and that is appropriately usable in production of an interlayer insulation film or microlens. There is provided a radiation-sensitive resin composition comprising carboxylated epoxidized polymer (A) exhibiting a ratio of, as measured by gel permeation chromatography, weight average molecular weight (Mw) in terms of polystyrene to number average molecular weight (Mn) in terms of polystyrene, (Mw/Mn), of 1.7 or below, and 1,2-quinonediazide compound (B).

Description

Radiation-sensitive resin composition, interlayer dielectric and lenticule and their preparation method
Technical field
The present invention relates to radiation-sensitive resin composition, interlayer dielectric and lenticule and their preparation method.
Background technology
Be typically provided with interlayer dielectric in the electronic components such as thin film transistor (TFT) (hereinafter referred to as " TFT ") type liquid crystal display cells or magnetic head element, integrated circuit component, solid-state imager, so that insulate between the wiring of stratiform configuration.As the material that forms interlayer dielectric, owing to preferably make the number of steps that obtains required pattern form few and have the material of abundant planarization, so radiation-sensitive resin composition be used widely (with reference to TOHKEMY 2001-354822 communique and TOHKEMY 2001-343743 communique).
In the above-mentioned electronic component; for example TFT type liquid crystal display cells is through formation ELD on above-mentioned interlayer dielectric; the step that forms liquid crystal orientation film is thereon made again; therefore interlayer dielectric is exposed under the hot conditions in the formation step of ELD; be exposed to again in the stripper of the diaphragm that is used to form electrode pattern, need have enough corrosion stabilitys them.
In recent years, the developments of TFT type liquid crystal display cells is big picture, high brightness, high-resolution, high-speed response, slimming etc., form as employed interlayer dielectric wherein and to use composition, require high sensitivity, for formed interlayer dielectric, increase in the ratio requirement in the past of aspects such as low-k, high-transmission rate, require higher performance.
On the other hand, core as fax, electronic copier, solid-state imager etc. carries the imaging optical system of colored filter or the optical system material of the joints of optical fibre, has used lenticule with the lens diameter about 3-100 μ m or these lenticules has been arranged regularly the microlens array that forms.
Known lenticule or microlens array be formed with following method: form corrosion-resisting pattern, make its fusion by heat treated then, directly as the method for lens corresponding to lens; The lens pattern of fusion as mask, is transferred to lens shape by dry etching method on the base material etc.Be extensive use of radiation-sensitive resin composition (with reference to Japanese kokai publication hei 6-18702 communique and Japanese kokai publication hei 6-136239 communique) in the formation of said lens pattern.
The element that has formed above-mentioned lenticule or microlens array after will be used for following step: in order to remove the various dielectric films on the pad that forms part as wiring; be coated with flatted membrane and etching diaphragm; use required mask to expose, develop; the etching resist of pad portion is removed; then remove flatted membrane or various dielectric film, pad portion is exposed by etching.Therefore, in the film forming step and etching step of flatted membrane and etching protective film, lenticule or microlens array must have solvent resistance or thermotolerance.
Require describedly to be used to form lenticular radiation-sensitive resin composition and to have high sensitivity, and have required radius-of-curvature, and be high-fire resistance, high-transmission rate etc. by the lenticule that it forms.
In interlayer dielectric that obtains like this or the lenticule development step when it forms, if development time is more a little longer than Best Times, then developer solution will penetrate between pattern and the substrate, peel off easily, therefore must strictly control development time, aspect the yield rate of product problem arranged.
Like this, when forming interlayer dielectric or lenticule by radiation-sensitive resin composition, the requirement composition is a high sensitivity, and in the development step that forms step, even peeling off of pattern longly can not take place than the stipulated time in development time yet, show good stickiness, and have high-fire resistance, high solvent resistance, low-k, high-transmission rate etc. by the interlayer dielectric that it forms.When forming lenticule, also require lenticule to have good melt shape (needed radius-of-curvature), high-fire resistance, high solvent resistance, high-transmission rate, but Shang Weijian have the radiation-sensitive resin composition that satisfies above-mentioned requirements.
The sublimate that bakes generation when burning that carries out forming above-mentioned interlayer dielectric or lenticule may pollute production line or device, the radiation-sensitive resin composition that hope has the sublimate of generation to obtain reducing.
Summary of the invention
The present invention is based on above situation and be.Thus, the object of the present invention is to provide a kind of radiation-sensitive resin composition, this radiation-sensitive resin composition has high radiosensitivity; In development step, have the development tolerance,, also can form good pattern even surpass optimum development time; Can easily form the good pattern-like film of stickiness; The sublimate that produces when baking reduces.
Other purpose of the present invention is to provide a kind of radiation-sensitive resin composition, and this radiation-sensitive resin composition can form the interlayer dielectric of high-fire resistance, high solvent resistance, high-transmission rate, low-k when being used to form interlayer dielectric; When being used to form lenticule, can form lenticule, and the sublimate that produces reduces when baking with high-transmission rate and good melt shape.
Another object of the present invention is to provide and use above-mentioned radiation-sensitive resin composition to form interlayer dielectric and lenticular method.
Another purpose of the present invention is to provide interlayer dielectric and the lenticule that is formed by method of the present invention.
Other purpose of the present invention and advantage are as described below.
According to a first aspect of the invention, above-mentioned purpose of the present invention and advantage realize by radiation-sensitive resin composition, it is characterized in that said composition contains: (A) have carboxyl and epoxy radicals and the weight-average molecular weight through polystyrene conversion (Mw) by gel permeation chromatography and ratio (Mw/Mn) through the number-average molecular weight (Mn) of polystyrene conversion and be the polymkeric substance below 1.7; And (B) 1, the 2-quinone di-azido compound.
Second aspect, above-mentioned purpose of the present invention and advantage realize by interlayer dielectric or lenticular formation method, it is characterized in that this method implements following step according to following order:
(1) step of filming of the above-mentioned radiation-sensitive resin composition of formation on substrate;
(2) to the step of this at least a portion of filming irradiation radioactive ray;
(3) development step; And
(4) heating steps.
The third aspect, objects and advantages of the present invention realize by the interlayer dielectric and the lenticule that are formed by said method.
The accompanying drawing summary
Fig. 1 is the mode chart of the lenticular cross sectional shape of expression.
The best mode that carries out an invention
Below radiation-sensitive resin composition of the present invention is described in detail.
Multipolymer (A)
The multipolymer that uses among the present invention (A) can carry out the polymerism potpourri that preferably contains following composition active free radical polymerization and obtain:
(a1) unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides (below can be described as compound (a1)),
(a2) contain epoxy radicals unsaturated compound (below can be described as compound (a2)) and
(a3) (a1) composition and (a2) unsaturated compound beyond the composition (below can be described as compound (a3)).
For example, can in solvent, in the presence of polymerization initiator, carry out active free radical polymerization by the polymerism potpourri that will contain compound (a1), compound (a2) and compound (a3) and prepare multipolymer (A).
Carboxyl that the above-mentioned multipolymer that obtains (A) is had and epoxy radicals are respectively from compound (a1) and compound (a2).
About the initiating agent system of active free radical polymerization, people have proposed various schemes.For example can preferably use the TEMPO system of people's discoveries such as Georges, the initiating agent that the constitutes system that people such as Matyjaszewski propose by copper bromide, brominated ester compounds, the initiating agent that the constitutes system that people such as Higashimura propose by phenixin and ruthenium (II) complex compound, Japanese Unexamined Patent Application Publication 2000-515181 communique, Japanese Unexamined Patent Application Publication 2002-500251 communique and the thiocarbonylthio compound of Japanese Unexamined Patent Application Publication 2004-518773 communique record and the combination of radical initiator etc.
Preferred living polymerization initiating agent is can be according to employed monomeric species in order to obtain polymkeric substance of the present invention (A), suitably select to increase the system of terminal non-inactivation, but from considerations such as polymerization efficiencies, the combination of preferred thiocarbonylthio compound and radical initiator.Here, thiocarbonylthio compound for example has dithioesters class, dithiocarbonates class, trithiocarbonate class, xanthate class etc.
Its object lesson can be a compound shown in the following formula.
Figure A20058000142200081
Figure A20058000142200091
Figure A20058000142200101
Wherein, can exemplify in dithiobenzoic acid cumyl ester, S-cyano methyl-S-dodecyl trithiocarbonate, pyrazoles-1-carbodithioic acid phenyl-methyl ester, the following synthesis example 5 xanthate that uses in the dithioesters that uses and the following synthesis example 6.
Radical initiator can use usually as radical polymerization initiator and compound known for example has: 2,2 '-azoisobutyronitrile, 2,2 '-azo two-(2, the 4-methyl pentane nitrile), 2,2 '-azo two-azo-compounds such as (4-methoxyl-2,4-methyl pentane nitriles); Benzoyl peroxide, lauroyl peroxide, t-butylperoxy pivarate, 1, organic peroxides such as 1 '-two-(t-butylperoxy) cyclohexanes; Hydrogen peroxide; Contain the oxidation-reduction type initiating agent of above-mentioned superoxide and reductive agent etc.
These polymerization initiators can use separately or with mixing more than 2 kinds.
The consumption of above-mentioned thiocarbonyl sulfuration thing is preferably 1-10 with respect to per 100 weight portion polymerization initiators, 000 weight portion, further preferred 10-1,000 weight portion.In addition, contain the monomer mixture of the polymerizable unsaturated compound of epoxy radicals with respect to per 100 weight portions, the consumption of radical polymerization initiator is preferably the 0.01-100 weight portion, further preferred 0.1-10 weight portion.Polymerization temperature during above-mentioned active free radical polymerization is not particularly limited, and preferred 0 ℃-100 ℃, further preferred 10 ℃-85 ℃.
According to the difference of initiating agent system, in order to make the polymerization initiator non-inactivation, can use the ester compounds the carboxyl of compound (a1) protected by the due care group (a1 ') to carry out polymerization, and then by going protection to obtain multipolymer (A).
In the multipolymer used in the present invention (A), preferably the polymerized unit of being derived by compound (a1) accounts for respectively the 5-40% weight by compound (a1), (a2) and the polymerized unit of (a3) deriving or repetitive total amount, preferred especially 10-30% weight.If use this polymerized unit to be lower than the multipolymer of 5% weight, then be difficult to be dissolved in the aqueous alkali during development step, the multipolymer that surpasses 40% weight then has the excessive tendency of dissolubility in aqueous alkali.
Compound (a1) is to have free-radical polymerised unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides, for example has list [(methyl) acryloxyalkyl] ester, two ends of monocarboxylic acid, dicarboxylic acids, dicarboxylic anhydride, polybasic carboxylic acid to have list (methyl) acrylate of the polymkeric substance of carboxyl and hydroxyl, the polycyclic compound with carboxyl and anhydride thereof etc. respectively.
As above-mentioned object lesson, monocarboxylic acid for example has acrylic acid, methacrylic acid, crotonic acid etc.;
Dicarboxylic acids for example has maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid etc.;
Dicarboxylic acid anhydride for example has above-mentioned acid anhydrides as the above-claimed cpd that dicarboxylic acids exemplified etc.;
The list of polybasic carboxylic acid [(methyl) acryloxyalkyl] ester for example has: mono succinate [2-(methyl) acryloxy second] ester, phthalic acid list [2-(methyl) acryloxy second] ester etc.;
List (methyl) acrylate that two ends have the polymkeric substance of carboxyl and hydroxyl respectively for example has: ω-carboxyl polycaprolactone list (methyl) acrylate etc.;
Polycyclic compound and anhydride thereof with carboxyl for example have respectively: 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", 5,6-dicarboxyl dicyclo [2.2.1] hept-2-ene" anhydride etc.
Wherein, preferably use monocarboxylic acid, dicarboxylic acid anhydride, consider, especially preferably use acrylic acid, methacrylic acid, maleic anhydride from copolyreaction, the dissolubility aqueous alkali and the angle of buying easily.They can be used alone or in combination.
The protecting group of carboxyl to protection compound (a1) is not particularly limited, and can use as the protecting group of carboxyl and known group.For example have: trialkylsilkl, 1-alkoxyalkyl, ring-type 1-alkoxyalkyl etc.More specifically, for example have: trimethyl silyl, dimethylbutyl silicyl, 1-ethoxyethyl group, 1-propoxyl group ethyl, tetrahydrofuran base, THP trtrahydropyranyl, trityl group etc.
In the multipolymer used in the present invention (A), preferably the polymerized unit of being derived by compound (a2) accounts for respectively the 10-70% weight by compound (a1), (a2) and the polymerized unit total amount of (a3) deriving, preferred especially 20-60% weight.When this polymerized unit was lower than 10% weight, gained interlayer dielectric or lenticular thermotolerance or skin hardness had the tendency of reduction, and the amount of this polymerized unit is when surpassing 70% weight, and the storage stability of radiation-sensitive resin composition has the tendency of reduction.
Compound (a2) is to have the free-radical polymerised epoxy radicals unsaturated compound that contains.Its example has: glycidyl acrylate, glycidyl methacrylate, 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, a vinyl benzyl glycidol ether, to vinyl benzyl glycidol ether etc.Wherein, consider from copolyreaction and the angle that improves gained interlayer dielectric or lenticular thermotolerance, skin hardness, preferred glycidyl methacrylate, the methacrylic acid-6 of using, 7-epoxy radicals heptyl ester, adjacent vinyl benzyl glycidol ether, a vinyl benzyl glycidol ether, to vinyl benzyl glycidol ether, methacrylic acid 3,4-epoxy radicals cyclohexyl.They can be used alone or in combination.
In the multipolymer used in the present invention (A), preferably the polymerized unit of being derived by compound (a3) accounts for respectively the 5-70% weight by compound (a1), (a2) and the polymerized unit total amount of (a3) deriving, preferred especially 5-50% weight.When this polymerized unit was lower than 5% weight, the storage stability of radiation-sensitive resin composition had the tendency of reduction, and when surpassing 70% weight, in the development step that forms interlayer dielectric or lenticule technology, may be difficult to be dissolved in aqueous alkali.
Compound (a3) is so long as have free-radical polymerised unsaturated compound and get final product, be not particularly limited, for example can be: alkyl methacrylate, alkyl acrylate, methacrylic acid cycloalkyl ester, methacrylate, acrylic acid cycloalkyl ester, aryl methacrylate, acrylic acid aryl ester, unsaturated dicarboxylic diester, dicyclo unsaturated compound, maleimide compound, unsaturated aromatic compounds, conjugated diolefine with hydroxyl.
As above-mentioned object lesson, alkyl methacrylate for example has methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, the secondary butyl ester of methacrylic acid, 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 etc.;
Alkyl acrylate for example has methyl acrylate, isopropyl acrylate etc.;
The methacrylic acid cycloalkyl ester for example has: 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 etc.;
Methacrylate with hydroxyl for example has: 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 etc.;
The acrylic acid cycloalkyl ester for example has 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 etc.;
Aryl methacrylate for example has methacrylic acid phenylester, methacrylic acid benzyl ester etc.;
The acrylic acid aryl ester for example has phenyl acrylate, acrylic acid benzyl ester etc.;
The unsaturated dicarboxylic diester for example has diethyl maleate, DEF, diethyl itaconate etc.;
The dicyclo unsaturated compound for example has: 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" etc.;
Maleimide compound for example has: phenyl maleimide, cyclohexyl maleimide, 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 etc.;
Unsaturated aromatic compounds for example has styrene, α-Jia Jibenyixi, a methyl styrene, p-methylstyrene, vinyltoluene, to methoxy styrene etc.;
Conjugated diolefine for example has 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene etc.;
Other unsaturated compound for example has: vinyl cyanide, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, Methacrylamide, vinyl acetate.
Wherein, preferred alkyl methacrylate, methacrylic acid cycloalkyl ester, dicyclo unsaturated compound, unsaturated aromatic compounds, the conjugated diolefine used, wherein, consider special optimization styrene, metering system tert-butyl acrylate, methacrylic acid three ring [5.2.1.0 from copolyreaction and the deliquescent angle aqueous alkali 2,6] decane-8-base ester, to methoxy styrene, acrylic acid 2-methyl cyclohexane ester, 1,3-butadiene, dicyclo [2.2.1] hept-2-ene".They can be used alone or in combination.
Among the present invention for example there be the preferred object lesson of employed multipolymer (A): methacrylic acid/styrene/methacrylic acid three ring [5.2.1.0 2,6] decane-8-base ester/glycidyl methacrylate/tetrahydrofurfuryl methacrylate multipolymer, methacrylic acid/styrene/methacrylic acid three ring [5.2.1.0 2,6] decane-8-base ester/glycidyl methacrylate/to vinyl benzyl glycidol ether/tetrahydrofurfuryl methacrylate multipolymer, methacrylic acid/styrene/methacrylic acid three ring [5.2.1.0 2,6] decane-8-base ester/glycidyl methacrylate/polyethylene glycol monomethacrylate multipolymer, methacrylic acid/styrene/methacrylic acid three ring [5.2.1.0 2,6] decane-8-base ester/glycidyl methacrylate/polypropylene glycol monomethacrylate multipolymer.
The weight-average molecular weight through polystyrene conversion (hereinafter referred to as " Mw ") of multipolymer used in the present invention (A) by gel permeation chromatography is below 1.7 with ratio (Mw/Mn) through the number-average molecular weight (hereinafter referred to as " Mn ") of polystyrene conversion, and be preferred below 1.5.Mw/Mn surpasses 1.7, then gained interlayer dielectric or lenticular pattern form variation.In addition, Mw is preferably 2 * 10 3-1 * 10 5, more preferably 5 * 10 3-5 * 10 4, Mw is lower than 2 * 10 3, the tolerance deficiency of then may developing, the reductions such as membrane left rate of gained tunicle, or gained interlayer dielectric or lenticular pattern form, thermotolerance equal difference.On the other hand, Mw surpasses 1 * 10 5, then sensitivity reduces, or pattern form is poor.Mn is preferably 1.2 * 10 3-1 * 10 5, more preferably 2.9 * 10 3-5 * 10 4The radiation-sensitive resin composition that contains above-mentioned multipolymer [A] does not produce when developing and develops residually, can easily form the pattern form of regulation.
And multipolymer used in the present invention (A) preferably is lower than 5.0% by the levels of residual monomers of gel permeation chromatography, more preferably less than 3.0%, especially preferably is lower than 2.0%.By using the multipolymer of described residual monomer content, the diaphragm that the sublimate in the time of can obtaining baking reduces.
Among the present invention, multipolymer (A) can use separately or with mixing more than 2 kinds.
In the preparation of multipolymer (A) for example there be employed solvent: alcohol, ether, glycol ethers, ethylene glycol alkyl ether acetic acid esters, diglycol, propylene-glycol monoalky lether, propylene glycol alkyl ether acetic acid ester, propylene glycol alkyl ether propionic ester, aromatic hydrocarbon, ketone, ester etc.
Their object lesson is as follows:
As alcohol, methyl alcohol, ethanol, benzylalcohol, 2-phenylethyl alcohol, 3-phenyl-1-propyl alcohol etc. are for example arranged;
Ethers for example has tetrahydrofuran etc.;
Glycol ethers for example has: glycol monomethyl methyl ether, ethylene glycol monomethyl ether etc.;
Ethylene glycol alkyl ether acetic acid esters for example has methylcellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetic acid esters, ethylene glycol monomethyl ether acetate etc.;
Diglycol for example has diglycol monotertiary methyl ether, carbiphene, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diglycol ethyl-methyl ether etc.;
Propylene-glycol monoalky lether for example has: propylene glycol monomethyl ether, propylene glycol list ethylether etc., propylene glycol list propyl ether, propylene glycol single-butyl ether etc.;
Propylene glycol alkyl ether acetic acid ester for example has methyl proxitol acetate, propylene glycol ethylether acetic acid esters, propylene glycol propyl ether acetic acid esters, propylene glycol butyl ether acetic acid esters etc.;
Propylene glycol alkyl ether propionic ester for example has methyl proxitol propionic ester, propylene glycol ethylether propionic ester, propylene glycol propyl ether propionic ester, propylene glycol butyl ether propionic ester etc.;
Aromatic hydrocarbon for example has toluene, dimethylbenzene etc.;
Ketone for example has methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2 pentanone etc.;
Ester for example has: methyl acetate, ethyl acetate, propyl acetate, butyl acetate, the 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy methyl acetate, hydroxyl ethyl acetate, the glycolic acid butyl ester, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, the 3-hydroxy methyl propionate, 3-hydracrylic acid ethyl ester, 3-hydracrylic acid propyl ester, 3-hydracrylic acid butyl ester, 2-hydroxy-3-methyl methyl butyrate, methoxy menthyl acetate, the methoxyacetic acid ethyl ester, the methoxyacetic acid propyl ester, the methoxyacetic acid butyl ester, ethoxy acetate, ethoxy ethyl acetate, the ethoxyacetic acid propyl ester, the ethoxyacetic acid butyl ester, the propoxyl group methyl acetate, propoxyl group ethyl acetate, the propoxyl group propyl acetate, the propoxyl group butyl acetate, the butoxy acetic acid methyl esters, the butoxy acetic acid ethyl ester, the butoxy acetic acid propyl ester, the butoxy acetic acid butyl ester, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-methoxy propyl acid butyl ester, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-ethoxy-c propyl propionate, 2-ethoxy-c acid butyl ester, 2-butoxy methyl propionate, 2-butoxy ethyl propionate, 2-butoxy propyl propionate, 2-butoxy butyl propionate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, 3-ethoxy-c propyl propionate, 3-ethoxy-c acid butyl ester, 3-propoxyl group methyl propionate, 3-propoxyl group ethyl propionate, 3-propoxyl group propyl propionate, 3-propoxyl group butyl propionate, 3-butoxy methyl propionate, 3-butoxy ethyl propionate, 3-butoxy propyl propionate, esters such as 3-butoxy butyl propionate.
Wherein, preferred ethylene glycol alkyl ether acetic acid esters, diglycol, propylene-glycol monoalky lether, propylene glycol alkyl ether acetic acid ester, wherein preferred especially diethylene glycol dimethyl ether, diglycol ethyl-methyl ether, methyl proxitol, methyl proxitol acetate.
(B) composition
(B) used in the present invention composition is to produce 1 of carboxylic acid through radiation exposure, and the 2-quinone di-azido compound can use phenoloid or alcohol compound (hereinafter referred to as " parent nucleus ") and 1, the condensation product of 2-naphthoquinones diazido sulfonic acid halide.
Above-mentioned parent nucleus for example has trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxy benzophenone, (polyhydroxy phenyl) alkane, other parent nucleus.
Their object lesson is as follows:
Trihydroxybenzophenone for example has: 2,3, and 4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone etc.;
Tetrahydroxybenzophenone for example has: 2,2 ', 4, and 4 '-tetrahydroxybenzophenone, 2,3,4,3 '-tetrahydroxybenzophenone, 2,3,4,4 '-tetrahydroxybenzophenone, 2,3,4,2 '-tetrahydroxy-4 '-methyldiphenyl ketone, 2,3,4,4 '-tetrahydroxy-3 '-methoxy benzophenone etc.;
Pentahydroxybenzophenone for example has: 2,3,4, and 2 ', 6 '-pentahydroxybenzophenone etc.;
The hexahydroxy benzophenone for example has: 2,4,6,3 ', 4 ', and 5 '-hexahydroxy benzophenone, 3,4,5,3 ', 4 ', 5 '-hexahydroxy benzophenone etc.;
(polyhydroxy phenyl) alkane for example has: two (2, the 4-dihydroxy phenyl) methane, two (p-hydroxybenzene) methane, three (p-hydroxybenzene) methane, 1,1,1-three (p-hydroxybenzene) ethane, two (2,3,4-trihydroxy phenyl) methane, 2,2-two (2,3,4-trihydroxy phenyl) propane, 1,1,3-three (2,5-dimethyl-4-hydroxy phenyl)-3-phenyl-propane, 4,4 '-[1-[4-[1-[4-hydroxy phenyl]-1-Methylethyl] phenyl] ethylidene] bis-phenol, two (2,5-dimethyl-4-hydroxy phenyl)-2-hydroxy phenyl methane, 3,3,3 ', 3 '-tetramethyl-1,1 '-spirobindene-5,6,7,5 ', 6 ', 7 '-hexanol, 2,2,4-trimethyl-7,2 ', 4 '-trihydroxy flavane etc.;
Other parent nucleus for example has: 2-methyl-2-(2, the 4-dihydroxy phenyl)-two { (5-isopropyl-4-hydroxy-2-methyl) phenyl } methyl of 4-(4-hydroxy phenyl)-7-hydroxychroman, 2-[], 1-[1-(3-{1-(4-hydroxy phenyl)-1-Methylethyl }-4, the 6-dihydroxy phenyl)-the 1-Methylethyl]-3-(1-(3-{1-(4-hydroxy phenyl)-1-Methylethyl }-4, the 6-dihydroxy phenyl)-and the 1-Methylethyl) benzene, 4, two { 1-(4-hydroxy phenyl)-1-Methylethyl }-1 of 6-, the 3-dihydroxy benzenes.
Also preferred the use changes the ester bond in the above-mentioned parent nucleus that exemplifies 1 of amido link into, 2-naphthoquinones diazido sulfonamides, for example 2,3,4-trihydroxybenzophenone-1,2-naphthoquinones diazido-4-sulfonamide etc.
In these parent nucleus, preferred 2,3,4,4 '-tetrahydroxybenzophenone, 4,4 '-[1-[4-[1-[4-hydroxy phenyl]-1-Methylethyl] phenyl] ethylidene] bis-phenol.
As 1,2-naphthoquinones diazido sulfonic acid halide, preferred 1,2-naphthoquinones diazido sulfonic acid chloride, its object lesson has: 1,2-naphthoquinones diazido-4-sulfonic acid chloride and 1,2-naphthoquinones diazido-5-sulfonic acid chloride wherein preferably uses 1,2-naphthoquinones diazido-5-sulfonic acid chloride.
In the condensation reaction, with respect to the OH base in 1 equivalent phenoloid or the alcohol compound, can preferably use be equivalent to the 30-85% mole, more preferably the 50-70% mole 1,2-naphthoquinones diazido sulfonic acid halide.
Condensation reaction can be implemented by known method.
Above-mentioned (B) composition can separately or will be used in combination more than 2 kinds.
With respect to 100 weight portion multipolymers (A), (B) usage ratio of composition is preferably the 5-100 weight portion, more preferably the 10-50 weight portion.When this ratio is lower than 5 weight portions, radiation exposure part and not illuminated portion be difficult to pattern little, gained interlayer dielectric or lenticular thermotolerance and solvent resistance deficiency in addition as the poor solubility in the aqueous alkali of developer solution.On the other hand, when this ratio surpassed 100 weight portions, the solubleness of radiation exposure part in above-mentioned aqueous alkali was not enough, was difficult to develop.
Other composition
Radiation-sensitive resin composition of the present invention is except that containing above-mentioned multipolymer (A) and (B) the composition, also can contain the acid of (C) thermonasty as required and generate in addition epoxy resin of polymerizable compound that compound, (D) have at least one ethylenic unsaturated double-bond, (E) multipolymer (A), (F) surfactant or (G) gluing auxiliary agent etc.
The acid of above-mentioned (C) thermonasty generates compound and can be used for improving thermotolerance or hardness.Its object lesson has:  salt such as sulfonium salt, benzothiazole  salt, ammonium salt,  salt.
The object lesson of above-mentioned sulfonium salt has: alkyl sulfonium salt, benzyl sulfonium salt, dibenzyl sulfonium salt, substituted benzyl sulfonium salt etc.
Above-mentioned object lesson is as follows:
The alkyl sulfonium salt for example has: hexafluoro-antimonic acid 4-acetyl phenyl dimethyl sulfonium, hexafluoro-antimonic acid 4-acetoxyl group phenyl dimethyl sulfonium, hexafluoro-antimonic acid dimethyl-4-(benzyloxycarbonyloxy) phenyl sulfonium, hexafluoro-antimonic acid dimethyl-4-(benzoyloxy) phenyl sulfonium, hexafluoroarsenate dimethyl-4-(benzoyloxy) phenyl sulfonium, hexafluoro-antimonic acid dimethyl-3-chloro-4-acetoxyl group phenyl sulfonium etc.;
The benzyl sulfonium salt for example has: hexafluoro-antimonic acid benzyl-4-hydroxy phenyl methyl sulfonium, hexafluorophosphoric acid benzyl-4-hydroxy phenyl methyl sulfonium, hexafluoro-antimonic acid 4-acetoxyl group phenyl benzyl methyl sulfonium, hexafluoro-antimonic acid benzyl-4-methoxybenzene ylmethyl sulfonium, hexafluoro-antimonic acid benzyl-2-methyl-4-hydroxy phenyl methyl sulfonium, hexafluoroarsenate benzyl-3-chloro-4-hydroxy phenyl methyl sulfonium, hexafluorophosphoric acid 4-methoxy-benzyl-4-hydroxy phenyl methyl sulfonium etc.;
The dibenzyl sulfonium salt for example has: hexafluoro-antimonic acid dibenzyl-4-hydroxy phenyl sulfonium, hexafluorophosphoric acid dibenzyl-4-hydroxy phenyl sulfonium, hexafluoro-antimonic acid 4-acetoxyl group phenyl dibenzyl sulfonium, hexafluoro-antimonic acid dibenzyl-4-methoxyphenyl sulfonium, hexafluoroarsenate dibenzyl-3-chloro-4-hydroxy phenyl sulfonium, hexafluoro-antimonic acid dibenzyl-3-methyl-4-hydroxyl-5-tert-butyl-phenyl sulfonium, hexafluorophosphoric acid benzyl-4-methoxy-benzyl-4-hydroxy phenyl sulfonium etc.;
The substituted benzyl sulfonium salt for example has: hexafluoro-antimonic acid p-chlorobenzyl-4-hydroxy phenyl methyl sulfonium, hexafluoro-antimonic acid to nitrobenzyl-4-hydroxy phenyl methyl sulfonium, hexafluorophosphoric acid p-chlorobenzyl-4-hydroxy phenyl methyl sulfonium, hexafluoro-antimonic acid to nitrobenzyl-3-methyl-4-hydroxy phenyl methyl sulfonium, hexafluoro-antimonic acid 3,5-dichloro benzyl-4-hydroxy phenyl methyl sulfonium, hexafluoro-antimonic acid o-chlorobenzyl-3-chloro-4-hydroxy phenyl methyl sulfonium etc.
The object lesson of above-mentioned benzothiazole  salt has: hexafluoro-antimonic acid 3-benzyl benzothiazole , hexafluorophosphoric acid 3-benzyl benzothiazole , tetrafluoro boric acid 3-benzyl benzothiazole , hexafluoro-antimonic acid 3-(to methoxy-benzyl) benzothiazole , hexafluoro-antimonic acid 3-benzyl-2-methyl-thio-benzothiazole , hexafluoro-antimonic acid 3-benzyl-benzyl benzothiazole  salt such as 5-chloro benzothiazole .
Wherein preferably use sulfonium salt and benzothiazole  salt, especially preferably use hexafluoroarsenate 4-acetoxyl group phenyl dimethyl sulfonium, hexafluoro-antimonic acid benzyl-4-hydroxy phenyl methyl sulfonium, hexafluoro-antimonic acid 4-acetoxyl group phenyl benzyl methyl sulfonium, hexafluoro-antimonic acid dibenzyl-4-hydroxy phenyl sulfonium, hexafluoro-antimonic acid 4-acetoxyl group phenyl benzyl sulfonium, hexafluoro-antimonic acid 3-benzyl benzothiazole .
Their commercially available product has サ Application エ イ De SI-L85, サ Application エ イ De SI-L110, サ Application エ イ De SI-L145, サ Application エ イ De SI-L150, サ Application エ イ De SI-L160 (manufacturing of three new chemical industry (strain)) etc.
With respect to 100 weight portion multipolymers (A), (C) usage ratio of composition is preferably below 20 weight portions, more preferably below 5 weight portions.When this consumption surpasses 20 weight portions, film to form in the step and will separate out sediment, the formation of filming is produced hinder.
As the polymerizable compound with at least one ethylenic unsaturated double-bond (following can being called " D composition ") of above-mentioned (D) composition, (methyl) acrylate that preference such as simple function (methyl) acrylate, difunctionality (methyl) acrylate or trifunctional are above.
Above-mentioned simple function (methyl) acrylate for example has: (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) carbitol acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid 3-methoxyl butyl ester, phthalic acid 2-(methyl) acryloxy ethyl-2-hydroxy-propyl ester etc.Their commercially available product for example has ア ロ ニ Star Network ス M-101, ア ロ ニ Star Network ス M-111, ア ロ ニ Star Network ス M-114 (above is that (strain) manufacturing is synthesized in East Asia), KAYARAD TC-110S, KAYARAD TC-120S (above is Japanese chemical drug (strain) manufacturing), PVC ス コ-ト 158, PVC ス コ-ト 2311 (above is Osaka organic chemistry industry (strain) manufacturing) etc.
Above-mentioned difunctionality (methyl) acrylate for example has (methyl) acrylic acid glycol ester, two (methyl) acrylic acid 1,6-hexanediol ester, two (methyl) acrylic acid 1,9-nonanediol ester, polypropylene glycol two (methyl) acrylate, two (methyl) acrylic acid butanediol ester, two phenoxetol fluorenes diacrylate, two phenoxetol fluorenes diacrylates etc.Their commercially available product for example has ア ロ ニ Star Network ス M-210, ア ロ ニ Star Network ス M-240, ア ロ ニ Star Network ス M-6200 (above is that (strain) manufacturing is synthesized in East Asia), KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604 (above is Japanese chemical drug (strain) manufacturing), PVC ス コ-ト 260, PVC ス コ-ト 312, PVC ス コ-ト 335HP (above is Osaka organic chemistry industry (strain) manufacturing) etc.
Above (methyl) acrylate of above-mentioned trifunctional for example has: three (methyl) acrylic acid trimethylolpropane, three (methyl) acrylic acid pentaerythritol ester, tricresyl phosphate ((methyl) acryloxy ethyl) ester, four (methyl) acrylic acid pentaerythritol ester, five (methyl) acrylic acid dipentaerythritol ester, six (methyl) acrylic acid dipentaerythritol ester etc.Their commercially available product for example has ア ロ ニ Star Network ス M-309, ア ロ ニ Star Network ス M-400, ア ロ ニ Star Network ス M-405, ア ロ ニ Star Network ス M-450, ア ロ ニ Star Network ス M-7100, ア ロ ニ Star Network ス M-8030, ア ロ ニ Star Network ス M-8060 (above is that (strain) manufacturing is synthesized in East Asia), KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120 (above is Japanese chemical drug (strain) manufacturing), PVC ス コ-ト 295, PVC ス コ-ト 300, PVC ス コ-ト 360, PVC ス コ-ト GPT, PVC ス コ-ト 3PA, PVC ス コ-ト 400 (above is Osaka organic chemistry industry (strain) manufacturing) etc.
Wherein, preferably use above (methyl) acrylate of trifunctional, wherein preferred especially three (methyl) acrylic acid trimethylolpropane, four (methyl) acrylic acid pentaerythritol ester, six (methyl) acrylic acid dipentaerythritol ester.
Above (methyl) acrylate of these simple functions, difunctionality or trifunctional can be used alone or in combination.With respect to 100 weight portion multipolymers (A), (D) below preferred 50 weight portions of the usage ratio of composition, more preferably below 30 weight portions.
By containing (D) composition with aforementioned proportion, can improve interlayer dielectric or lenticular thermotolerance and the skin hardness etc. that obtain by radiation-sensitive resin composition of the present invention.This use amount surpasses 50 weight portions, then may produce the problem of dry film on substrate in the step of filming of formation radiation-sensitive resin composition.
To unqualified as in addition epoxy resin of the multipolymer (A) of above-mentioned (E) composition (below can be described as " E composition "), as long as relative consistency is influence not, the resin that preferred bisphenol A type epoxy resin, solvable fusible phenol aldehyde type epoxy resin, the solvable phenol aldehyde type epoxy resin of cresols, cyclic aliphatic epoxy resin, glycidyl ester type epoxy resin, glycidyl group amine type epoxy resin, hetero ring type epoxy resin, glycidyl methacrylate copolymerization form etc.Wherein, further preferred bisphenol A type epoxy resin, cresols phenolic resin varnish type epoxy resin, glycidyl ester type epoxy resin etc.
With respect to 100 weight portion multipolymers (A), (E) usage ratio of composition is preferably below 30 weight portions.Thermotolerance by having closed (E) composition with aforementioned proportion, can further improve the diaphragm that obtains by radiation-sensitive resin composition of the present invention or dielectric film and skin hardness etc.This ratio surpasses 30 weight portions, and when then forming the filming of radiation-sensitive resin composition on substrate, the film thickness uniformity of filming is not enough.
Multipolymer (A) also can be called " epoxy resin ", but multipolymer (A) has alkali-soluble, and this point is different with (E) composition.
In order further to improve coating, can also use surfactant in the radiation-sensitive resin composition of the present invention as above-mentioned (F) composition.Here, for example can be fit to use fluorine be that surfactant, silicon-type surfactant and nonionic are surfactant to spendable (F) surfactant.
Fluorine is that the object lesson of surfactant has: 1,1,2, and 2-tetrafluoro octyl group (1,1,2,2-tetrafluoro propyl group) ether, 1,1,2,2-tetrafluoro octyl group hexyl ether, eight glycol two (1,1,2,2-tetrafluoro butyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoro amyl group) ether, eight propylene glycol two (1,1,2,2-tetrafluoro butyl) ether, six propylene glycol two (1,1,2,2,3,3-hexafluoro amyl group) ether, perfluor sodium dodecylsulphonate, 1,1,2,2,8,8,9,9,10,10-ten fluorine dodecanes, 1,1,2,2,3, in addition 3-hexafluoro decane etc. also have: the fluoro-alkyl benzene sulfonic acid sodium salt; Fluoroalkyl ethene ethers fluoro-alkyl ammonium iodide, fluoro-alkyl polyoxyethylene ether, perfluoroalkyl poly oxyethanol; The perfluoroalkyl alcoholates; Fluorine is an Arrcostab etc.Their commercially available product for example has BM-1000, BM-1100 (above) by the manufacturing of BMChemie company, メ ガ ア Star Network F142D, メ ガ ア Star Network F172, メ ガ ア Star Network F173, メ ガ ア Star Network F183, メ ガ ア Star Network F178, メ ガ ア Star Network F191, メ ガ ア Star Network F471 (above) by big Japanese ink chemical industry (strain) manufacturing, Off ロ ラ-De FC-170C, FC-171, FC-430, FC-431 (above) by Sumitomo ス リ-エ system (strain) manufacturing, サ-Off ロ Application S-112, サ-Off ロ Application S-113, サ-Off ロ Application S-131, サ-Off ロ Application S-141, サ-Off ロ Application S-145, サ-Off ロ Application S-382, サ-Off ロ Application SC-101, サ-Off ロ Application SC-102, サ-Off ロ Application SC-103, サ-Off ロ Application SC-104, サ-Off ロ Application SC-105, サ-Off ロ Application SC-106 (above) by Asahi Glass (strain) manufacturing, エ Off ト Star プ EF301, エ Off ト Star プ EF303, エ Off ト Star プ EF352 (above change into (strain) make) etc. by new autumn fields.
Above-mentioned silicon-type surfactant has for example with DC3PA, DC7PA, FS-1265, SF-8428, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032 (the Shang You East of Yi レ ダ ウ コ-ニ Application ゲ シ リ コ-Application (strain) is made); The surfactant that TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 trade names such as (above by the シ リ of GE Toshiba コ-Application (strain) manufacturing) are sold.
Above-mentioned nonionic is that surfactant for example can use: polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl base ether, polyoxyethylene oleyl ether; Polyoxyethylene aryl ether such as NONIN HS 240, polyoxyethylene nonylplenyl ether; Polyoxyethylene dialkyls such as polyoxyethylene dilaurate, polyoxyethylene distearate etc.; (methyl) acrylate based copolymer Port リ Off ロ-No.57,59 (common prosperity society chemistry (strain) manufacturings) etc.
These surfactants can separately or will be used in combination more than 2 kinds.
With respect to 100 weight portion multipolymers (A), these (F) surfactants preferably use below 5 weight portions, more preferably use below 2 weight portions.(F) consumption of surfactant surpasses 5 weight portions, then forms when filming on substrate, is easy to generate the dry film of filming.
Be the tackiness of raising with matrix, radiation-sensitive resin composition of the present invention can use the gluing auxiliary agent as (G) composition.Described (G) gluing auxiliary agent for example preferably uses the functional silanes coupling agent.Its example has: have carboxyl, methacryl, isocyanate group, the substituent silane coupling agent of epoxy radicals isoreactivity.More particularly, trimethoxysilyl benzoic acid, γ-methacryloxypropyl trimethoxy silane, vinyltriacetoxy silane, vinyltrimethoxy silane, γ-isocyanate group propyl-triethoxysilicane, γ-glycidol ether propyl trimethoxy silicane, β-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane etc. are arranged.With respect to 100 weight portion multipolymers (A), described (G) gluing auxiliary agent is preferably with below 20 weight portions, more preferably the amount below 10 weight portions is used.The amount of gluing auxiliary agent surpasses 20 weight portions, and it is residual then to be easy to generate development in development step.
Radiation-sensitive resin composition
Radiation-sensitive resin composition of the present invention is by composition and other composition of adding arbitrarily as mentioned above evenly mix and prepare with above-mentioned multipolymer (A) with (B).Radiation-sensitive resin composition of the present invention is preferably dissolved in the appropriate solvent, uses with solution state.For example, by with multipolymer (A) and (B) composition and of the ratio mixing of any other composition that adds, can prepare the radiation-sensitive resin composition of solution state to stipulate.
But other each composition that becomes to grade that the employed solvent of the preparation of radiation-sensitive resin composition of the present invention can use uniform dissolution multipolymer (A) and (B) composition and mix arbitrarily is not with the solvent of each composition reaction.
Described solvent can be and the identical solvent of solvent that can be used for preparing above-mentioned multipolymer (A) that exemplifies.
In the described solvent, from the dissolubility of each composition, with the reactivity of each composition, the easy degree equal angles of filming and forming, preferred for example alcohol, glycol ethers, ethylene glycol alkyl ether acetic acid esters, ester and the diglycol of using.Wherein, for example can especially preferably use benzylalcohol, 2-phenylethanol, 3-phenyl-1-propyl alcohol, ethylene glycol monobutyl ether acetic acid esters, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diglycol ethyl-methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether, methoxypropionic acid methyl esters, ethoxyl ethyl propionate.
In order to improve the inner evenness of thickness, high boiling solvent can also be used in combination with above-mentioned solvent.The high boiling solvent that can be used in combination for example has: N-NMF, N, dinethylformamide, N-methyl formyl aniline, N-methylacetamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), benzylisoeugenol, hexyl ether, acetonyl acetone, isophorone, caproic acid, capric acid, 1-octanol, 1 nonyl alcohol, benzyl acetate, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, gamma-butyrolacton, ethylene carbonate, carbonic allyl ester, ethylene glycol monophenyl ether acetic acid esters etc.Wherein preferred N-Methyl pyrrolidone, gamma-butyrolacton, N,N-dimethylacetamide.
As the solvent of radiation-sensitive resin composition of the present invention, when being used in combination high boiling solvent, its use amount is preferably below 50% weight with respect to the solvent total amount, more preferably below 40% weight, further below preferred 30% weight.The consumption of high boiling solvent surpasses this consumption, and the film thickness uniformity of then filming, sensitivity and membrane left rate may reduce.
When radiation-sensitive resin composition of the present invention is prepared into solution state, composition beyond the solvent in the solution, be multipolymer (A) and (B) the total ratio of composition and other composition of adding arbitrarily can set arbitrarily according to the value of application target, required film thickness etc., for example be 5-50% weight, preferred 10-40% weight, further preferably 15-35% weight.
The composition solution of above-mentioned preparation can be for using after the filtrations of using about the 0.2 μ m of aperture such as millipore filter.
Interlayer dielectric, lenticular formation
Then, to use radiation-sensitive resin composition of the present invention to form interlayer dielectric of the present invention, lenticular method describes.Interlayer dielectric of the present invention and lenticular each formation method all comprise following step, implement according to following order.
(1) step of filming of formation radiation-sensitive resin composition of the present invention on substrate;
(2) to the step of this at least a portion of filming irradiation radioactive ray;
(3) development step; And
(4) heating steps.
(1) step of filming of formation radiation-sensitive resin composition of the present invention on substrate
In the step of above-mentioned (1), composition solution of the present invention is coated on substrate surface, preferably removes and desolvate, form filming of radiation-sensitive resin composition by preceding baking.
The kind of spendable substrate for example has glass substrate, silicon wafer and is formed with the substrate of various metals on above-mentioned surface.
Coating process to composition solution is not particularly limited, and for example can adopt spray-on process, rolling method, method of spin coating (spin-coating method), slit die rubbing method, rod to be coated with suitable methods such as method, ink-jet application method, preferred especially spin-coating method, slit die rubbing method.Before the condition of baking different because of the kind of each composition, usage ratio etc.For example can be to bake about 30 seconds-15 minutes at 60-110 ℃.
Value after the baking is seen in the past, when forming interlayer dielectric, and formed thickness preference of filming such as 3-6 μ m, preference such as 0.5-3 μ m when forming lenticule.
(2) to the step of this at least a portion of filming irradiation radioactive ray
In the step of above-mentioned (2), film via mask irradiation radioactive ray with predetermined pattern to formed.In next step (3), use developer solution to carry out development treatment then, remove the illuminated portion of radioactive ray, form pattern thus.This moment, employed radioactive ray for example had ultraviolet ray, far ultraviolet, X ray, charged particle ray etc.
Above-mentioned ultraviolet ray for example has g ray (wavelength 436nm), i ray (wavelength 365nm) etc.Far ultraviolet for example has KrF excimer laser etc.X ray for example has synchrotron ray etc.The charged particle ray for example has electron ray etc.
Wherein, preferred ultraviolet ray especially preferably contains the radioactive ray of g ray and/or i ray.
About exposure, when forming interlayer dielectric, for example preferred 50-1,500J/m 2, when forming lenticule, for example preferred 50-2,000J/m 2
(3) development step
The employed developer solution of development treatment for example can use NaOH, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethamine, n-propylamine, diethylamine, DEAE diethylaminoethanol, di-n-propylamine, triethylamine, methyl-diethyl-amine, dimethylethanolamine, triethanolamine, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, pyrroles, piperidines, 1,8-diazabicyclo [5.4.0]-7-undecylene, 1, the aqueous solution of 5-diazabicyclo [4.3.0]-alkali (alkali compounds) such as 5-nonane.As developer solution, can also use the aqueous solution of water-miscible organic solvents such as in above-mentioned aqueous alkali, adding methyl alcohol, ethanol in right amount or surfactant, perhaps dissolve the various organic solvents of composition of the present invention.And,, can utilize shop liquid (liquid is contained り) method, infusion process, rock suitable methods such as infusion process, douche as developing method.The development time of this moment is according to the composition of composition and difference, for example can be at 30-120 between second.
For known in the past radiation-sensitive resin composition, if development time surpasses 20-25 about second than optimum development time, then the pattern of Xing Chenging is peeled off, therefore must strictly control development time, but for radiation-sensitive resin composition of the present invention, even the time surpasses more than 30 seconds of optimum development time, also can form good pattern, on product yield, have superiority.
(4) heating steps
After (3) development step of as above implementing, the film that has charted is preferably carried out for example handling by the rinsing of flowing water washing, further preferably by comprehensive irradiation radioactive ray (post-exposure) such as high-pressure sodium lamps, remain in 1 in this film, the resolution process of 2-quinone di-azido compound, then this film is carried out heat treated (the back baking is handled) by heating arrangements such as hot plate, heating furnaces, carry out the cure process of this film thus.Exposure in the above-mentioned post-exposure step is preferred 2,000-5,000J/m 2About.Heating-up temperature in this cure process for example is 120-250 ℃.Heat time heating time, when for example carrying out heat treated on hot plate, for example be 5-30 minute heat time heating time according to the kind of heating machine and difference, and when carrying out heat treated in heating furnace, for example can be 30-90 minute heat time heating time.At this moment, can use the stage of carrying out heating steps more than 2 times to bake method etc.
Like this, can on substrate surface, form corresponding to target interlayer dielectric or lenticular pattern-like film.
From embodiment described later as can be seen, excellence such as the interlayer dielectric of Xing Chenging and lenticular stickiness, thermotolerance, solvent resistance and the transparency as mentioned above.
Interlayer dielectric
The stickiness of interlayer dielectric of the present invention of Xing Chenging and substrate is good as mentioned above, and solvent resistance and excellent heat resistance have high transmissivity, and specific inductive capacity is low, can be preferably used as the interlayer dielectric of electronic component.
Lenticule
The stickiness of lenticule of the present invention of Xing Chenging and substrate is good as mentioned above, solvent resistance and excellent heat resistance, and have high transmissivity and good melt shape, can be preferably used as the lenticule of solid-state imager.
Lenticular shape of the present invention is semi-convex lens shape shown in Fig. 1 (a).
Embodiment
Below provide synthesis example, embodiment, further specify the present invention, but the present invention is not defined as following embodiment.
The molecular weight of＜gel permeation chromatography multipolymer 〉
Device: GPC-101 (clear and electrician's (strain) makes)
Post: GPC-KF-801, GPC-KF-802, GPC-KF-804 and GPC-KF-804 combination
Mobile phase: the tetrahydrofuran that contains 0.5% weight percent phosphoric acid.
The synthesis example of multipolymer (A)
Synthesis example 1
In the flask that possesses condenser pipe, stirrer, add 1 weight portion azoisobutyronitrile, 4 weight portion dithiobenzoic acid cumyl esters and 50 weight portion diglycol ethyl-methyl ethers.Then add 20 parts by weight of styrene, 20 weight portion methacrylic acids, 20 weight portion methacrylic acids, three ring [5.2.1.0 2,6] decane-8-base ester, 40 weight portion glycidyl methacrylate, after the nitrogen displacement, beginning is slowly stirred.Make the temperature of solution rise to 60 ℃, this temperature was kept 24 hours, append 3 weight portion azoisobutyronitriles then, stirred 4 hours at 60 ℃ again, append 200 weight portion diglycol ethyl-methyl ethers, obtain the solution of multipolymer (A-1).The weight-average molecular weight through polystyrene conversion of multipolymer (A-1) (Mw) is 10,000, and molecular weight distribution (Mw/Mn) is 1.4, and residual monomer is 2.0% weight.The solid-state part concentration of polymer solution is 29.8% weight.
Synthesis example 2
In the flask that possesses condenser pipe, stirrer, add 1 weight portion azoisobutyronitrile, 4 weight portion dithiobenzoic acid cumyl esters and 50 weight portion diglycol ethyl-methyl ethers.Then add 16 weight portion methacrylic acids, 18 weight portion glycidyl methacrylate, 6 weight portion methacrylic acids, three ring [5.2.1.0 2,6] decane-8-base ester, 30 weight portions are to vinyl benzyl glycidol ether, 30 weight portion polyglycol (n=2) monomethacrylates, after the nitrogen displacement, beginning is slowly stirred.Make the temperature of solution rise to 60 ℃, this temperature was kept 24 hours, append 3 weight portion azoisobutyronitriles then, stirred 4 hours at 60 ℃ again, append 200 weight portion diglycol ethyl-methyl ethers, obtain the solution of multipolymer (A-2).The weight-average molecular weight through polystyrene conversion of multipolymer (A-2) (Mw) is 11,000, and molecular weight distribution (Mw/Mn) is 13, and residual monomer is 1.2% weight.Here the solid-state part concentration of resulting polymers solution is 30.1% weight.
Synthesis example 3
Use the dithiobenzoic acid cumyl ester in S-cyano methyl-S-dodecyl trithiocarbonate replacement synthesis example 1, obtain the solution of multipolymer (A-3) in addition according to synthesis example 1.The weight-average molecular weight through polystyrene conversion of multipolymer (A-3) (Mw) is 9,500, and molecular weight distribution (Mw/Mn) is 1.3, and residual monomer is 1.5% weight.Here the solid-state part concentration of resulting polymers solution is 29.6% weight.
Synthesis example 4
Use the dithiobenzoic acid cumyl ester in pyrazoles-1-carbodithioic acid phenyl-methyl ester replacement synthesis example 2, obtain containing the polymer solution of multipolymer (A-4) in addition according to synthesis example 2.The weight-average molecular weight through polystyrene conversion of multipolymer (A-4) (Mw) is 12,000, and molecular weight distribution (Mw/Mn) is 1.4, and residual monomer is 1.3% weight.The solid-state part concentration of polymer solution is 29.7% weight.
Synthesis example 5
Use the dithiobenzoic acid cumyl ester in the following dithioesters replacement synthesis example 1, obtain containing the polymer solution of multipolymer (A-5) in addition according to synthesis example 1.The weight-average molecular weight through polystyrene conversion of multipolymer (A-5) (Mw) is 11,000, and molecular weight distribution (Mw/Mn) is 1.3, and residual monomer is 1.4% weight.Here the solid-state part concentration of resulting polymers solution is 29.8% weight.
Figure A20058000142200301
Synthesis example 6
Use the dithiobenzoic acid cumyl ester in the following xanthate replacement synthesis example 2, obtain containing the polymer solution of multipolymer (A-6) in addition according to synthesis example 2.The weight-average molecular weight through polystyrene conversion of multipolymer (A-6) (Mw) is 11,000, and molecular weight distribution (Mw/Mn) is 1.3, and residual monomer is 1.5% weight.The solid-state part concentration of polymer solution is 30.1% weight.
Figure A20058000142200302
Compare synthesis example 1
In the flask that possesses condenser pipe, stirrer, add 8 weight portions 2,2 '-azo two (2, the 4-methyl pentane nitrile) and 220 weight portion diglycol ethyl-methyl ethers.Then add 20 parts by weight of styrene, 20 weight portion methacrylic acids, 40 weight portion glycidyl methacrylate and 20 weight portion phenyl maleimides, after the nitrogen displacement, beginning is slowly stirred.Make the temperature of solution rise to 70 ℃, this temperature was kept 5 hours, obtain containing the polymer solution of multipolymer (a-1).
The weight-average molecular weight through polystyrene conversion of multipolymer (a-1) (Mw) is 7,500, and molecular weight distribution (Mw/Mn) is 2.4, and residual monomer is 5.8% weight.Here the solid-state part concentration of resulting polymer solution is 30.6% weight.
Embodiment 1
The preparation of radiation-sensitive resin composition
With the solution that contains polymkeric substance (A-1) synthetic in the above-mentioned synthesis example 1 as (A) composition, with 4,4 '-[1-[4-[1-[4-hydroxy phenyl]-1-Methylethyl] phenyl] ethylidene] bis-phenol (1.0 moles) and 1, the condensation product (B-1) of 2-naphthoquinones diazido-5-sulfonic acid chloride (2.0 moles) is as composition (B), the composition (A) that will be equivalent to the amount of 100 parts by weight polymer (A-1) (solid-state part) mixes with 30 weight portion compositions (B), and be dissolved in the diglycol ethyl-methyl ether, making solid-state part concentration is 30% weight, membrane filter with aperture 0.2 μ m filters then, makes the solution (S-1) of radiation-sensitive resin composition.
Embodiment 2-9,11-14, comparative example 1
The preparation of radiation-sensitive resin composition
For (A) composition among the embodiment 1 and (B) composition, use kind, amount as table 1 record, in addition operate similarly to Example 1, make the solution (S-2)-(S-9), (S-11)-(S-14) of radiation-sensitive resin composition and (s-1).
In the table 1, the record of (B) composition of embodiment 8 is expression with two kind 1 of B-1 (20 weight portion) and B-2 (15 weight portion), and the 2-quinone di-azido compound is used in combination.
Embodiment 10
Among the embodiment 1, be dissolved in the diglycol ethyl-methyl ether, making solid-state part concentration is 15% weight, in addition prepares composition similarly to Example 1, makes the solution (S-10) of radiation-sensitive resin composition.
In the table 1, following compound represented in the abbreviation of composition.
(B-1): 4,4 '-[1-[4-[1-[4-hydroxy phenyl]-1-Methylethyl] phenyl] ethylidene] bis-phenol (1.0 moles) and 1, the condensation product of 2-naphthoquinones diazido-5-sulfonic acid chloride (2.0 moles)
(B-2): 4,4 '-[1-[4-[1-[4-hydroxy phenyl]-1-Methylethyl] phenyl] ethylidene] bis-phenol (1.0 moles) and 1, the condensation product of 2-naphthoquinones diazido-5-sulfonic acid chloride (1.0 moles)
(B-3): 2,3,4,4 '-tetrahydroxybenzophenone (1.0 moles) and 1,2-naphthoquinones diazido-5-sulphonic acid ester (2.44 moles)
(B-4): 4,4 '-[1-[4-[1-[4-hydroxy phenyl]-1-Methylethyl] phenyl] ethylidene] bis-phenol (1.0 moles) and 1, the condensation product of 2-naphthoquinones diazido-4-sulfonic acid chloride (1.0 moles)
(F): SH-28PA (East レ ダ ウ コ-ニ Application ゲ シ リ コ-Application (strain) is made)
Table 1
The composition kind Copolymer A The B composition Other composition
Kind Weight portion Kind Weight portion Kind Weight portion
Embodiment 1 (S-1) A-1 100 B-1 30 - -
Embodiment 2 (S-2) A-2 100 B-1 25 - -
Embodiment 3 (S-3) A-2 100 B-1 30 - -
Embodiment 4 (S-4) A-1 100 B-1 35 - -
Embodiment 5 (S-5) A-1 100 B-2 40 - -
Embodiment 6 (S-6) A-1 100 B-3 30 - -
Embodiment 7 (S-7) A-1 100 B-4 30 - -
Embodiment 8 (S-8) A-1 100 B-1+B-2 20+15 - -
Embodiment 9 (S-9) A-1 100 B-1 30 F 0.01
Embodiment 10 (S-10) A-1 100 B-1 30 - -
Embodiment 11 (S-11) A-3 100 B-1 30 - -
Embodiment 12 (S-12) A-4 100 B-1 30 - -
Embodiment 13 (S-13) A-5 100 B-1 30 - -
Embodiment 14 (S-14) A-6 100 B-1 30 - -
Comparative example 1 (s-1) a-1 100 B-3 30 - -
Embodiment 15-28, comparative example 2-4
Performance evaluation during as interlayer dielectric
Use the radiation-sensitive resin composition of preparation as mentioned above, the various characteristics of following evaluation during as interlayer dielectric.The composition that in comparative example 3 and 4, uses all be between/paracresol bakelite and 1, the commercially available product of the composition of 2-naphthoquinones diazido-5-sulphonic acid ester (Tokyo should be changed (strain) and make).
The evaluation of sensitivity
Use the spin coating instrument for embodiment 15-27, comparative example 2-4, use slit dies coating instrument for embodiment 28, the composition of coating table 2 on silicon substrate, then 90 ℃, went forward to dry by the fire 2 minutes at hot plate, form filming of thickness 3.0 μ m.PLA-501F exposure machine (ultrahigh pressure mercury lamp) by キ ャ ノ Application (strain) manufacturing, change the time shutter, via mask gained is filmed and expose, then with predetermined pattern, with the tetramethyl ammonium hydroxide aqueous solution of the solution level of table 2, by shop liquid Faxian shadow 90 seconds.With ultrapure water flowing water washing 1 minute, make its drying, on silicon wafer, form pattern.Measure the line of 3.0 μ m and the gap pattern of gap (10 to 1) and dissolve required exposure fully., be illustrated in the table 2 as sensitivity with this value.This value is 1,000J/m 2When following, we can say that sensitivity is good.
The evaluation of development tolerance
Use the spin coating instrument for embodiment 15-27, comparative example 2-4, use slit dies coating instrument for embodiment 28, the composition of coating table 2 on silicon substrate, then 90 ℃, went forward to dry by the fire 2 minutes at hot plate, form filming of thickness 3.0 μ m.The PLA-501F exposure machine (ultrahigh pressure mercury lamp) that uses Canon Co., Ltd. to make, mask via the pattern of the line with 3.0 μ m and gap (10 to 1), the exposure of the sensitivity value of measuring in above-mentioned with being equivalent to " sensitivity evaluation " is filmed to gained and is exposed, tetramethyl ammonium hydroxide aqueous solution with the solution level of table 2, at 25 ℃, by spreading liquid Faxian shadow 90 seconds.With ultrapure water flowing water washing 1 minute, make its drying, on silicon wafer, form pattern.Reach 3 μ ms required development time with live width this moment is optimum development time, is illustrated in the table 2.Continue to develop, mensuration,, is illustrated in the table 2 as the development tolerance to the time that the line pattern of 3.0 μ m is peeled off by optimum development time.This value is more than 30 seconds the time, we can say that the development tolerance is good.
The evaluation of solvent resistance
Use the spin coating instrument for embodiment 15-27, comparative example 2-4, use slit dies coating instrument for embodiment 28, the composition of coating table 2 on silicon substrate, then 90 ℃, went forward to dry by the fire 2 minutes at hot plate, form filming of thickness 3.0 μ m.The PLA-501F exposure machine made from Canon Co., Ltd. (ultrahigh pressure mercury lamp) is filmed to gained and is exposed, and making cumulative exposure is 3,000J/m 2, this silicon substrate in cleaning oven, 220 ℃ of heating 1 hour, is obtained cured film.Measure the thickness (T1) of gained cured film.The silicon substrate that formed this cured film was soaked 20 minutes in temperature is controlled at 70 ℃ dimethyl sulfoxide (DMSO), measures the thickness (t1) of this cured film then, calculate the Thickness Variation rate that causes by immersion | t1-T1|/T1} * 100[%].The result is as shown in table 2.This value is 5% when following, we can say that solvent resistance is good.
In the evaluation of solvent resistance, need not pattern on formed film, therefore omit radiation exposure step and development step, only form step, back baking step and the heating steps of filming and be used for estimating.
Stable on heating evaluation
Operate equally with the evaluation of above-mentioned solvent resistance, form cured film, measure the thickness (T2) of gained cured film.Then, this cured film substrate appended in cleaning oven, at 240 ℃ bakes 1 hour, measure the thickness (t2) of this cured film then, calculate by append the Thickness Variation rate that causes of baking | t2-T2|/T2} * 100[%].The result is as shown in table 2.This value is 5% when following, we can say that thermotolerance is good.
The transparency is estimated
In above-mentioned solvent resistance is estimated, use glass substrate " コ-ニ Application ゲ 7059 (コ-ニ Application グ company makes) " to replace silicon substrate, in addition similarly on glass substrate, form cured film.With spectrophotometer " manufacturing of 150-20 type Double Beam (strain) Hitachi ", measure the light transmittance of glass substrate with the wavelength of 400-800nm scope with this cured film.The value representation of the minimum light transmittance of this moment is in table 2.This value is 90% when above, we can say that the transparency is good.
The evaluation of relative dielectric constant
Use the spin coating instrument for embodiment 15-27, comparative example 2-4, use slit dies coating instrument for embodiment 28, the composition of coating table 2 on the system of the SUS304 through grinding substrate, then 90 ℃, went forward to dry by the fire 2 minutes at hot plate, form filming of thickness 3.0 μ m.The PLA-501F exposure machine made from Canon Co., Ltd. (ultrahigh pressure mercury lamp) is filmed to gained and is exposed, and making cumulative exposure is 3,000J/m 2, this substrate in cleaning oven, baked 1 hour at 220 ℃, is obtained cured film.
On this cured film, form the Pt/Pd electrode pattern by vapour deposition method, make the sample that is used to measure specific inductive capacity.The HP16451B electrode and the accurate LCR instrument of HP4284A that use Co., Ltd. of Yokogawa Hewlett-Packard to make with the frequency of 10kHz, are measured the relative dielectric constant of this substrate by the CV method.The result is as shown in table 2.This value is 3.6 when following, we can say that relative dielectric constant is good.
In the evaluation of relative dielectric constant, need not pattern on formed film, therefore omit radiation exposure step and development step, only form step, back baking step and the heating steps of filming and be used for estimating.
The evaluation of sublimate
Use the spin coating instrument for embodiment 15-27, comparative example 2-4, use slit dies coating instrument for embodiment 28, the composition of coating table 2 on silicon substrate, then 90 ℃, went forward to dry by the fire 2 minutes at hot plate, form filming of thickness 3.0 μ m.The PLA-501F exposure machine made from Canon Co., Ltd. (ultrahigh pressure mercury lamp) is filmed to gained and is exposed, and makes cumulative exposure reach 3,000J/m 2, this silicon substrate in cleaning oven, 220 ℃ of heating 1 hour, is obtained cured film.Above the gained cured film, vacate 1 centimetre of interval, the naked silicon wafer that is used to cool off is installed, on hot plate, 230 ℃ of processing of heating of carrying out 1 hour.Do not change the naked silicon wafer of cooling, 20 silicon substrates that form above-mentioned cured film are in addition handled continuously, whether visual then checking has sublimate to be attached on the naked silicon wafer.Do not see when sublimate is arranged, we can say that sublimate is evaluated as well.
Table 2
The composition kind Sensitivity is estimated The development tolerance Solvent resistance Thermotolerance The transparency (%) Relative dielectric constant Sublimate
Solution level (% weight) Sensitivity (J/m 2) Optimum development time (second) Development tolerance (second) Sclerosis after-hardening film (μ m) Thickness Variation (%) Sclerosis after-hardening film (μ m) Thickness Variation (%)
Embodiment 15 (S-1) 0.5 550 60 30 2.3 1 2.3 1 92 3.5 Do not have
Embodiment 16 (S-2) 0.5 550 60 30 2.4 1 2.4 1 93 3.4 Do not have
Embodiment 17 (S-3) 0.4 600 60 35 2.5 1 2.5 1 93 3.3 Do not have
Embodiment 18 (S-4) 0.4 500 60 30 2.5 1 2.5 1 93 3.3 Do not have
Embodiment 19 (S-5) 0.4 600 70 30 2.5 1 2.5 1 93 3.4 Do not have
Embodiment 20 (S-6) 0.4 500 60 30 2.3 1 2.3 1 92 3.4 Do not have
Embodiment 21 (S-7) 2.38 600 60 35 2.3 1 2.3 1 91 3.5 Do not have
Embodiment 22 (S-8) 0.4 550 60 30 2.3 1 2.3 1 93 3.4 Do not have
Embodiment 23 (S-9) 0.4 500 60 35 2.4 1 2.4 1 93 3.3 Do not have
Embodiment 24 (S-10) 0.5 600 60 30 2.3 1 2.3 1 92 3.4 Do not have
Embodiment 25 (S-11) 0.5 550 60 30 2.3 1 2.3 1 92 3.5 Do not have
Embodiment 26 (S-12) 0.5 500 60 30 2.4 1 2.4 1 93 3.4 Do not have
Embodiment 27 (S-13) 0.5 550 60 30 2.3 1 2.3 1 92 3.3 Do not have
Embodiment 28 (S-14) 0.5 500 60 30 2.4 1 2.4 1 93 3.3 Do not have
Comparative example 2 (s-1) 0.4 700 60 15 2.4 3 2.4 3 94 3.3 Have
Comparative example 3 OFPR-800 2.38 2200 60 25 2 10 2 15 83 3.7 Have
Comparative example 4 OFPR-5000 2.38 2200 60 20 1.9 12 1.9 14 82 3.7 Have
Embodiment 29-42, comparative example 5-7
＜performance evaluation when the lenticule 〉
Use the radiation-sensitive resin composition of preparation as mentioned above, the following evaluation of carrying out lenticular various characteristics.Thermotolerance is estimated, transparent evaluation can be with reference to result's (table 2) of above-mentioned performance evaluation during as interlayer dielectric.
In the comparative example 6 and 7 employed composition all be between/paracresol bakelite and 1, the commercially available product of the composition of 2-naphthoquinones diazido-5-sulphonic acid ester (Tokyo should change (strain) make).The evaluation of sensitivity
Use the spin coating instrument for embodiment 29-38,40-42, comparative example 5-7, use slit dies coating instrument for embodiment 39, the composition of coating table 3 on silicon substrate, then 90 ℃, went forward to dry by the fire 2 minutes at hot plate, form filming of thickness 3.0 μ m.The NSR1755i7A reduced projection exposure machine of making by ニ コ Application (strain) (NA=0.50, λ=365nm), change the time shutter, via mask gained is filmed and to expose with predetermined pattern, then, with the tetramethyl ammonium hydroxide aqueous solution of the solution level of table 3, at 25 ℃ by shop liquid Faxian shadow 1 minute.Use water wash, drying forms pattern on silicon wafer.Measure the line of 0.8 μ m and the gap live width of gap pattern (1 to 1) and reach the required time shutter of 0.8 μ m., be illustrated in the table 3 as sensitivity with this value.This value is 2,500J/m 2When following, we can say that sensitivity is good.The evaluation of development tolerance
Use the spin coating instrument for embodiment 29-38,40-42, comparative example 5-7, use slit dies coating instrument for embodiment 39, the composition of coating table 3 on silicon substrate, then 90 ℃, went forward to dry by the fire 2 minutes at hot plate, form filming of thickness 3.0 μ m.The NSR1755i7A reduced projection exposure machine of making by ニ コ Application (strain) (NA=0.50, λ=365nm), via mask with predetermined pattern, the exposure of the sensitivity value of measuring in above-mentioned with being equivalent to " sensitivity evaluation " is filmed to gained and is exposed, tetramethyl ammonium hydroxide aqueous solution with the solution level of table 3, at 25 ℃, by spreading liquid Faxian shadow 1 minute.Use water wash, drying forms pattern on silicon wafer.Reaching the required development time of 0.8 μ m with the gap live width of the line of 0.8 μ m and gap pattern (1 to 1) is optimum development time, is illustrated in the table 3.Continue to develop, mensuration, as the development tolerance, is illustrated in the table 3 with this to the time (development tolerance) that the pattern of wide 0.8 μ m is peeled off by optimum development time.This value is more than 30 seconds the time, we can say that the development tolerance is good.
The evaluation of solvent resistance
Use the spin coating instrument for embodiment 29-38,40-42, comparative example 5-7, use slit dies coating instrument for embodiment 39, the composition of coating table 3 on silicon substrate, then 90 ℃, went forward to dry by the fire 2 minutes at hot plate, form filming of thickness 3.0 μ m.The PLA-501F exposure machine made from Canon Co., Ltd. (ultrahigh pressure mercury lamp) exposes, and making cumulative exposure is 3,000J/m 2, this silicon substrate in cleaning oven, 220 ℃ of heating 1 hour, is obtained cured film.Measure the thickness (T3) of gained cured film.The silicon substrate that forms this cured film was soaked 10 minutes in temperature is controlled at 50 ℃ isopropyl alcohol, measures the thickness (t3) of this cured film then, calculate the Thickness Variation rate that causes by immersion | t3-T3|/T3} * 100[%].The result is as shown in table 3.This value is 5% when following, we can say that solvent resistance is good.
In the evaluation of solvent resistance, need not on formation film, to chart, therefore omit radiation exposure step and development step, only form step, back baking step and the heating steps of filming and be used for estimating.
Lenticular formation
Use the spin coating instrument for embodiment 29-38,40-42, comparative example 5-7, use slit dies coating instrument for embodiment 39, the composition of coating table 3 on silicon substrate, then 90 ℃, went forward to dry by the fire 2 minutes at hot plate, form filming of thickness 3.0 μ m.The NSR1755i7A reduced projection exposure machine of making by ニ コ Application (strain) (NA=0.50, λ=365nm), via mask with 4.0 μ m points and 2.0 μ m gap patterns, the exposure of the sensitivity value of measuring in above-mentioned with being equivalent to " sensitivity evaluation " is filmed to gained and is exposed, with in the table 3 as sensitivity estimate the tetramethyl ammonium hydroxide aqueous solution of concentration of solution level record, at 25 ℃, by spreading liquid Faxian shadow 1 minute.Use water wash, drying forms pattern on silicon wafer.The PLA-501F exposure machine made from Canon Co., Ltd. (ultrahigh pressure mercury lamp) exposes then, and making cumulative exposure is 3,000J/m 2Heated 10 minutes at 160 ℃ with hot plate afterwards, 230 ℃ of heating 10 minutes, make the pattern fusion again, form lenticule.
The size (diameter) and the cross sectional shape of the lenticular bottom (with the contacted face of substrate) that forms are as shown in table 3.The size of lenticule bottom surpasses 4.0 μ m but when being lower than 5.0 μ m, we can say good.If this is of a size of more than the 5.0 μ m, then be state of contact between the adjacent lenses, not preferred.Cross sectional shape is in the mode chart shown in Figure 1 during (a) such semi-convex lens shape in addition, and is then good, if be (b) the such slightly side of being platform shape, then bad.
Table 3
The composition kind Sensitivity is estimated The development tolerance Solvent resistance Microlens shape
Solution level (% weight) Sensitivity (J/m 2) Optimum development time (second) Development tolerance (second) Sclerosis after-hardening film (μ m) Thickness Variation (%) Bottom size (mm) Cross sectional shape
Embodiment 29 (S-1) 0.5 620 60 30 2.3 1 4.2 On the semi-convex lens
Embodiment 30 (S-2) 0.5 690 60 30 2.4 1 4.3 On the semi-convex lens
Embodiment 31 (S-3) 0.4 670 60 35 2.5 1 4.3 On the semi-convex lens
Embodiment 32 (S-4) 0.4 730 60 30 2.5 1 4.3 On the semi-convex lens
Embodiment 33 (S-5) 0.4 620 70 30 2.5 1 4.3 On the semi-convex lens
Embodiment 34 (S-6) 0.4 690 60 30 2.3 1 4.6 On the semi-convex lens
Embodiment 35 (S-7) 2.38 720 60 35 2.3 1 4.5 On the semi-convex lens
Embodiment 36 (S-8) 0.4 680 60 30 2.3 1 4.6 On the semi-convex lens
Embodiment 37 (S-9) 0.4 620 60 35 2.4 1 4.2 On the semi-convex lens
Embodiment 38 (S-10) 0.5 620 60 35 2.3 1 4.2 On the semi-convex lens
Embodiment 39 (S-11) 0.5 620 60 30 2.3 1 4.2 On the semi-convex lens
Embodiment 40 (S-12) 0.5 680 60 30 2.4 1 4.3 On the semi-convex lens
Embodiment 41 (S-13) 0.5 660 60 30 2.3 1 4.2 On the semi-convex lens
Embodiment 42 (S-14) 0.5 700 60 30 2.4 1 4.3 On the semi-convex lens
Comparative example 5 (s-1) 0.4 840 60 15 2.4 3 4.4 On the semi-convex lens
Comparative example 6 OFPR-800 2.38 2800 60 25 2 8 ＞5.0 The adjacent lens contact can't be observed shape
Comparative example 7 OFPR-5000 2.38 3000 60 20 1.9 10 ＞5.0 The adjacent lens contact can't be observed shape
Radiation-sensitive resin composition of the present invention has high radiosensitivity, in development step, have the development tolerance,, also can form good pattern form even surpass optimum development time, can easily form stickiness excellent pattern shape film, the sublimate that produces when baking reduces.
The interlayer dielectric of the present invention that is formed by above-mentioned composition and the stickiness of substrate are good, and solvent resistance and excellent heat resistance have high-transmission rate, and specific inductive capacity is low, is suitable as the interlayer dielectric of electronic component.
The lenticule of the present invention that is formed by above-mentioned composition and the stickiness of substrate are good, solvent resistance and excellent heat resistance, and have high-transmission rate and good melt shape, be suitable as the lenticule of solid-state imager.
Claims
(according to the modification of the 19th of treaty)
1. radiation-sensitive resin composition, it is characterized in that: said composition contains (A), and to have carboxyl and epoxy radicals and the weight-average molecular weight through polystyrene conversion (Mw) by gel permeation chromatography and ratio (Mw/Mn) through the number-average molecular weight (Mn) of polystyrene conversion be polymkeric substance below 1.5, and (B) 1, the 2-quinone di-azido compound.
2. radiation-sensitive resin composition, it is characterized in that: said composition contains (A) and (B) 1, the 2-quinone di-azido compound, wherein (A) thus be that the polymerism potpourri that will contain following composition carries out active free radical polymerization to have carboxyl and epoxy radicals and the weight-average molecular weight through polystyrene conversion (Mw) by gel permeation chromatography and ratio (Mw/Mn) through the number-average molecular weight (Mn) of polystyrene conversion be polymkeric substance below 1.7:
(a1) unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides,
(a2) contain epoxy radicals unsaturated compound and
(a3) (a1) composition and (a2) composition unsaturated compound in addition.
3. the radiation-sensitive resin composition of claim 2, wherein multipolymer (A) is (being total to) polymkeric substance that obtains as the active free radical polymerization of controlling agent by with thiocarbonylthio compound.
4. claim 1 or 2 radiation-sensitive resin composition, said composition is used to form interlayer dielectric.
5. the formation method of interlayer dielectric is characterized in that implementing following step according to following order:
(1) on substrate, forms the step of filming of the radiation-sensitive resin composition of claim 1 or 2;
(2) to the step of this at least a portion of filming irradiation radioactive ray;
(3) development step; And
(4) heating steps.
6. the interlayer dielectric that forms by the method for claim 5.
7. claim 1 or 2 radiation-sensitive resin composition, said composition is used to form lenticule.
8. lenticular formation method is characterized in that this method comprises the following steps of implementing according to following order:
(1) on substrate, forms the step of filming of the radiation-sensitive resin composition of claim 1 or 2;
(2) to the step of this at least a portion of filming irradiation radioactive ray;
(3) development step; And
(4) heating steps.
9. the lenticule that forms by the method for claim 8.

Claims (9)

1. radiation-sensitive resin composition, it is characterized in that: said composition contains (A), and to have carboxyl and epoxy radicals and the weight-average molecular weight through polystyrene conversion (Mw) by gel permeation chromatography and ratio (Mw/Mn) through the number-average molecular weight (Mn) of polystyrene conversion be polymkeric substance below 1.7, and (B) 1, the 2-quinone di-azido compound.
2. the radiation-sensitive resin composition of claim 1, wherein said multipolymer (A) carries out active free radical polymerization by the polymerism potpourri that will contain following composition and obtains:
(a1) unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydrides,
(a2) contain epoxy radicals unsaturated compound and
(a3) (a1) composition and (a2) composition unsaturated compound in addition.
3. claim 1 or 2 radiation-sensitive resin composition, wherein said multipolymer (A) are (being total to) polymkeric substance that obtains as the active free radical polymerization of controlling agent by with thiocarbonylthio compound.
4. the radiation-sensitive resin composition of claim 1, said composition is used to form interlayer dielectric.
5. 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.
6. the interlayer dielectric that forms by the method for claim 5.
7. the radiation-sensitive resin composition of claim 1, said composition is used to form lenticule.
8. 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.
9. the lenticule that forms by the method for claim 8.
CN200580001422XA 2004-04-08 2005-02-18 Radiation-sensitive resin composition, interlayer insulation film, microlens and process for producing them Expired - Fee Related CN1898605B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP114525/2004 2004-04-08
JP2004114525 2004-04-08
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CN101359174B (en) * 2007-07-30 2012-11-28 Jsr株式会社 Radiation-sensitive resin composition, layer insulation film and microlens and manufacture method thereof
CN102955358A (en) * 2011-08-09 2013-03-06 Jsr株式会社 Photosensitive composition, micro lens array and stereoscopic image display device

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US7696292B2 (en) 2003-09-22 2010-04-13 Commonwealth Scientific And Industrial Research Organisation Low-polydispersity photoimageable acrylic polymers, photoresists and processes for microlithography
KR101250733B1 (en) * 2005-03-15 2013-04-03 제이에스알 가부시끼가이샤 Radiation Sensitive Resin Composition, Protrusion and Spacer Made Therefrom, and Liquid Crystal Display Device Comprising Them
JP4654867B2 (en) * 2005-10-07 2011-03-23 Ｊｓｒ株式会社 Radiation-sensitive resin composition, interlayer insulating film and microlens, and production method thereof
JP4656316B2 (en) * 2005-12-22 2011-03-23 Ｊｓｒ株式会社 Interlayer insulating film, microlens, and manufacturing method thereof

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JP2000327877A (en) * 1999-05-17 2000-11-28 Jsr Corp Radiation-sensitive resin composition, use thereof for interlayer insulation film and microlens, and interlayer insulation film and microlens
JP2000347397A (en) * 1999-06-04 2000-12-15 Jsr Corp Radiation sensitive resin composition and its use for interlayer dielectric
JP3467488B2 (en) * 2001-03-31 2003-11-17 アダムス テクノロジー カンパニー リミテッド Resist composition for column spacer of liquid crystal display device
JP2003041224A (en) * 2001-07-31 2003-02-13 Kanegafuchi Chem Ind Co Ltd Adhesive composition
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Cited By (3)

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Publication number Priority date Publication date Assignee Title
CN101359174B (en) * 2007-07-30 2012-11-28 Jsr株式会社 Radiation-sensitive resin composition, layer insulation film and microlens and manufacture method thereof
CN102803318A (en) * 2009-06-30 2012-11-28 氰特表面技术有限公司 Process for the preparation of radiation curable compositions
CN102955358A (en) * 2011-08-09 2013-03-06 Jsr株式会社 Photosensitive composition, micro lens array and stereoscopic image display device

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TW200602806A (en) 2006-01-16
WO2005101124A1 (en) 2005-10-27

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