CN104597712A - Negative photo sensitive resin composition, interlayer insulating film and forming method thereof - Google Patents

Negative photo sensitive resin composition, interlayer insulating film and forming method thereof Download PDF

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Publication number
CN104597712A
CN104597712A CN201510087880.5A CN201510087880A CN104597712A CN 104597712 A CN104597712 A CN 104597712A CN 201510087880 A CN201510087880 A CN 201510087880A CN 104597712 A CN104597712 A CN 104597712A
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group
sensitive resin
negative light
carbon number
cyclic olefin
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福山雄大
增田克之
平田知广
小林雄二
安克彦
二宫智
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Showa Denko Materials Co ltd
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Hitachi Chemical Co Ltd
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F277/00—Macromolecular compounds obtained by polymerising monomers on to polymers of carbocyclic or heterocyclic monomers as defined respectively in group C08F32/00 or in group C08F34/00
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • G03F7/405—Treatment with inorganic or organometallic reagents after imagewise removal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02118—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • H01L21/0274—Photolithographic processes

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  • Polymerisation Methods In General (AREA)
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  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
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Abstract

The invention relates to a negative photo sensitive resin composition, an interlayer insulating film and a forming method thereof. Disclosed is a negative photosensitive resin composition comprised of (A) an annual olefin resin containing repeating units represented by a general formula (1) (where R1, R2, R3 and R4 each represent an independent substituent group chosen from: a hydrogen atom, an alkyl group having 1-15 carbon atoms, an alkenyl group with 2-20 carbon atoms, a cycloalkyl group with 5-15 carbon atoms, an aryl group with 6-20 carbon atoms or an alkoxy group with 1-20 carbon atoms; or a hydrolysable silyl group, an alkoxycarbonyl group with 2-20 carbon atoms, a trialkylsiloxy carbonyl group with 4-20 carbon atoms, an alkyl carbonyl oxy group with 2-20 carbon atoms, an alkenyl carbonyl oxy group with 3-20 carbon atoms and an oxetanyl group; attached directly or via and jointly with an oxygen atom, a nitrogen atom or a sulphur atom), (B) a polyfunctional acrylic monomer and (C) a photoinitiator.

Description

Negative light-sensitive resin combination, interlayer dielectric and forming method thereof
The application is the applying date is on February 23rd, 2011, and application number is 201180010940.3, and denomination of invention is the divisional application of the Chinese patent application of " negative light-sensitive resin combination, interlayer dielectric and forming method thereof ".
Technical field
The present invention relates to a kind of negative light-sensitive resin combination, interlayer dielectric and forming method thereof.
Background technology
(following at thin film transistor (TFT), be denoted as " TFT ") in the electronic unit such as type liquid crystal display cells, magnetic head element, integrated circuit component and solid-state image pickup tube elements, the wiring closet insulation configured to make stratiform, arranges interlayer dielectric (see patent documentation 1) usually.As its material, because the process number being preferred for obtaining required pattern form is few and have the material of abundant flatness, therefore widely use negative light-sensitive resin combination (see patent documentation 2).
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2000-10089 publication
Patent documentation 2: Jap.P. No. 3650985 publication
Summary of the invention
The problem that invention will solve
In above-mentioned electronic unit, TFT type liquid crystal display cells is through and forms ELD on interlayer dielectric, then the operation forming liquid crystal orientation film thereon manufactures.At this moment, because this interlayer dielectric is exposed under the high temperature conditions in the formation process of ELD, therefore need, to it, there is sufficient patience.
In addition, in recent years, for TFT type liquid crystal display cells, have the multiple technologies trends such as large screen, high briliancy, high-precision refinement and high-speed response, the structure of liquid crystal display cells also becomes complicated thereupon.Therefore, for interlayer dielectric used, at low-k, high transmission rate (>80%, λ=400nm) etc. aspect also require the high-performance that improves than ever, simultaneously, in the structure of liquid crystal display cells, also start requirement and can realize to particular/special requirements such as the thick-films of about 50 μm.
But, be generally used for the negative light-sensitive resin combination of the formation of existing interlayer dielectric, realize thick-film and high permeability and high resolving power aspect at the same time extremely difficult, be strongly required a kind of negative light-sensitive resin combination that can form interlayer dielectric with such characteristic of exploitation.
The present invention carries out in view of the foregoing, even if its object is to provide a kind of thick-film, the negative light-sensitive resin combination of all very excellent interlayer dielectric of the various characteristics such as resolution, the transparency, thermotolerance, resistance to thermochromism and solvent resistance also can be formed.In addition, the object of the invention is also to provide a kind of interlayer dielectric formed by this negative light-sensitive resin combination and forming method thereof.
The method of dealing with problems
The invention provides a kind of negative light-sensitive resin combination, it contains: comprise (A) cyclic olefin resin of the repetitive represented by following general formula (1), (B) multi-functional acrylic's monomer and (C) Photoepolymerizationinitiater initiater.In formula (1), R 1, R 2, R 3and R 4represent independently of one another and be selected from hydrogen atom, carbon number is the alkyl of 1 ~ 15, carbon number is the thiazolinyl of 2 ~ 20, carbon number is the naphthenic base of 5 ~ 15, carbon number be 6 ~ 20 aryl or carbon number be the alkoxy of 1 ~ 20, or hydrolyzable silyl group, carbon number is the alkoxy carbonyl of 2 ~ 20, carbon number is the trialkylsiloxy carbonyl of 4 ~ 20, carbon number is the alkyl carbonyl oxy of 2 ~ 20, carbon number is the thiazolinyl carbonyl oxygen base of 3 ~ 20 and the substituting group of oxetanylmethoxy, and also directly or oxygen atom can be passed through, nitrogen-atoms or sulphur atom and be connected to each other.
[changing 1]
Even if having the negative light-sensitive resin combination thick-film of above-mentioned formation, the interlayer dielectric that the various characteristics such as resolution, the transparency, thermotolerance, resistance to thermochromism and solvent resistance are all very excellent also can be formed.
(A) cyclic olefin resin preferably comprises represented by above-mentioned general formula (1), R 1, R 2, R 3and R 4for the structural unit of hydrogen atom.
In addition, (A) cyclic olefin resin preferably comprises represented by above-mentioned general formula (1), R 1, R 2, R 3and R 4any one be the structural unit of the alkyl carbonyl oxy of 2 ~ 20 for carbon number.
The invention provides a kind of negative light-sensitive resin combination, it may be used for the formation method of interlayer dielectric, and it is the ultraviolet operation of below 400nm that described method has the illumination wavelength at least partially of the film formed by this negative light-sensitive resin combination.
Negative light-sensitive resin combination of the present invention is also preferably further containing (D) alkali soluble resin.
The invention provides a kind of interlayer dielectric formed by above-mentioned negative light-sensitive resin combination.
The invention provides a kind of formation method of interlayer dielectric, it has the operation of irradiating light at least partially, the operation of postradiation for light aforementioned films being developed to the film formed by above-mentioned negative light-sensitive resin combination and burns till the above-mentioned film after development, forms the operation of interlayer dielectric.
Invention effect
According to the present invention, even if a kind of thick-film can be provided, the negative light-sensitive resin combination of all very excellent interlayer dielectric of the various characteristics such as resolution, the transparency, thermotolerance, resistance to thermochromism and solvent resistance also can be formed.
Embodiment
Below, the preferred embodiment of the present invention is described in detail.
Negative light-sensitive resin combination in present embodiment contains: (A) cyclic olefin resin, (B) multi-functional acrylic's monomer and (C) Photoepolymerizationinitiater initiater.Below, each composition is described in detail.
-(A) cyclic olefin resin-
(A) cyclic olefin resin of present embodiment is the polymkeric substance of the repetitive had represented by following general formula (1).
[changing 2]
Above-mentioned R 1, R 2, R 3and R 4represent independently of one another and be selected from hydrogen atom, carbon number is the alkyl of 1 ~ 15, carbon number is the thiazolinyl of 2 ~ 20, carbon number is the naphthenic base of 5 ~ 15, carbon number be 6 ~ 20 aryl or carbon number be the alkoxy of 1 ~ 20, or hydrolyzable silyl group, carbon number is the alkoxy carbonyl of 2 ~ 20, carbon number is the trialkylsiloxy carbonyl of 4 ~ 20, carbon number is the alkyl carbonyl oxy of 2 ~ 20, carbon number is the thiazolinyl carbonyl oxygen base of 3 ~ 20 and the substituting group of oxetanylmethoxy, and also directly or oxygen atom can be passed through, nitrogen-atoms or sulphur atom and be connected to each other.
More preferably, R 1, R 2, R 3and R 4independently of one another for being selected from hydrogen atom, the carbon number alkyl that is 1 ~ 15, the carbon number thiazolinyl that is 2 ~ 20, carbon number be 6 ~ 15 aryl or carbon number be 6 ~ 20 alkoxy and carbon number be the substituting group of the alkyl carbonyl oxy of 2 ~ 20.By being formed as such formation, can obtain improving such effect to the dissolubility of various solvent.
Herein, as hydrolyzable silyl group, trimethoxysilyl, methyl dimethoxy oxygen base silicyl specifically can be enumerated.
Be the alkoxy carbonyl of 2 ~ 20 as carbon number, specifically can enumerate methyl ester group, tert-butyl group ester group, 2-ethylhexyl ester group, benzyl ester group, cyclopentyl ester group, cyclohexyl ester group and allyl ester group.Wherein, from the viewpoint of thermotolerance, particularly preferably use methyl ester group and benzyl ester group etc.
(A) cyclic olefin resin used in present embodiment, with the total amount of formula (1) structural unit in cyclic olefin for benchmark, preferably containing the R represented by more than 1 % by mole above-mentioned general formula (1) 1, R 2, R 3and R 4for the structural unit of hydrogen atom, and more preferably containing more than 10 % by mole.When this ratio is more than 1 % by mole, the tendency that the thermotolerance that there is rewarding negative light-sensitive resin combination improves.In addition, aforementioned proportion is preferably less than 60 % by mole, and is more preferably less than 50 % by mole.When aforementioned proportion is below 60 % by mole, have the tendency that the solubility of the solvent for modulating negative light-sensitive resin combination is improved.
(A) cyclic olefin resin used in present embodiment, with the total amount of formula (1) structural unit in cyclic olefin for benchmark, preferably containing the R represented by more than 1 % by mole above-mentioned general formula (1) 1, R 2, R 3and R 4any one be the structural unit of the alkyl carbonyl oxy of 2 ~ 20 for carbon number, and more preferably containing more than 10 % by mole.When this ratio is more than 1 % by mole, have the tendency that can obtain the solubility of the solvent for modulating negative light-sensitive resin combination being improved to such effect.Aforementioned proportion is preferably less than 60 % by mole, and is more preferably less than 50 % by mole.When aforementioned proportion is below 60 % by mole, the thermotolerance having the negative light-sensitive resin combination that can obtain gained improves the tendency of such effect.
Above-mentioned (A) cyclic olefin resin, can, by a solvent, under the existence of metallic catalyst, make the monomer represented by following general formula (2) carry out addition copolymerization (pay and add common coincidence) and manufacture.
[changing 3]
As the solvent for the manufacture of (A) cyclic olefin resin, such as, the nitrogenous system hydrocarbon such as the halogenated hydrocarbons such as the aromatic hydrocarbons such as the clicyclic hydrocarbon such as aliphatic hydrocarbon, cyclohexane, benzene, toluene and dimethylbenzene, methylene chloride, chloroform and chlorobenzene, nitromethane, nitrobenzene and acetonitrile such as pentane, hexane and heptane and the ethers such as Anaesthetie Ether, diox and tetrahydrofuran can be enumerated.These solvents can be used alone a kind, or can be used in combination by two or more.
As the catalyzer (E) be polymerized for (A) cyclic olefin resin, preferably at least cyclopentadiene base system part and a kind of complex compound of transition-metal coordination gained being selected from periodic table the 8th race's element, the 9th race's element and the 10th race's element.As object lesson, iron (Fe), cobalt (Co), nickel (Ni), ruthenium (Ru), rhodium (Rh), palladium (Pd) and platinum (Pt) can be enumerated.Wherein, from the viewpoint of raising polymerization catalyst activity, preferred element is cobalt, nickel, palladium and platinum, and particularly preferably uses palladium.
As the promotor (F) be polymerized for (A) cyclic olefin resin, preferably promote the material dissociated of the part of the complex compound forming catalyzer (E).Such as, the ionic compound of non-coordinated negative ion by following citing and cation combination can be enumerated.
As non-coordinated negative ion, such as, four (phenyl) borate (ボ レ ー ト can be enumerated), four (difluorophenyl) borate, four (difluorophenyl) borate, four (trifluorophenyl) borate, four (tetrafluoro phenyl) borate, four (pentafluorophenyl group) borate, four (trifluoromethyl phenyl) borate, four (toluyl (ト リ イ Le)) borate, four (xylyl) borate, (triphenyl, pentafluorophenyl group) borate, [three (pentafluorophenyl groups), phenyl] borate and 13 hydrogen-7, two carbon 11-borate root (the ト リ デ カ Ha イ De ラ イ De-7 of 8-, 8-ジ カ Le バ ウ Application デ カ ボ レ ー ト).
As above-mentioned kation, carbocation, oxygen kation, ammonium cation, phosphonium cation, cycloheptatriene kation (シ Network ロ ヘ プ チ Le ト リ エ ニ Le カ チ オ Application) can be enumerated and there is the ferrocene cation (Off ェ ロ セ ニ ウ system カ チ オ Application) etc. of transition metal.
As the object lesson of carbocation, triphenylcarbenium cation and tri-substituted phenyl carbocation etc. three can be enumerated and replace carbocation.As the object lesson of tri-substituted phenyl carbocation, three (aminomethyl phenyl) carbocations and three (3,5-dimethylphenyl) carbocation can be enumerated.
As the object lesson of ammonium cation, trialkylammonium cation, the N such as trimethyl ammonium cation, triethyl ammonium kation, tripropyl ammonium cation, tributyl ammonium kation and three (normal-butyl) ammonium cation can be enumerated, N-diethylaniline (ア ニ リ ニ ウ system) kation and N, N-2,4, the N such as 6-pentamethylaminobenzene kation, N-dialkylanilinium cations, and the dialkyl ammonium cations such as two (isopropyl) ammonium cations and dicyclohexyl ammonium cation.
The object lesson of Zuo Wei phosphonium cation, can enumerate triphenyl phosphonium kation, three (aminomethyl phenyl) phosphonium cation and three (the San Fang Ji phosphonium cations such as 3,5-dimethylphenyl) phosphonium cation.
As above-mentioned ionic compound, be such as trityl four (pentafluorophenyl group) borate, triphenylcarbenium four (difluorophenyl) borate, N, accelerine four (pentafluorophenyl group) borate and 1,1 '-dimethyl ferrocene four (pentafluorophenyl group) borate.
In the present embodiment, the ratio of catalyzer (E) and promotor (F) is different along with the change of various condition, therefore can not determine without exception, but be usually preferably 1/0.1 ~ 1/10000 in E/F (mol ratio), be more preferably 1/0.5 ~ 1/5000, and more preferably 1/1 ~ 1/2000.
In present embodiment, the polystyrene conversion weight-average molecular weight (hereinafter referred to as " Mw ") of (A) cyclic olefin resin is preferably 2 × 10 3to 2 × 10 5, and be more preferably 2 × 10 4to 1.8 × 10 5.If Mw is less than 2 × 10 3, then the tendency that the thermotolerance of gained tunicle and skin hardness decline is had.On the other hand, if Mw is more than 2 × 10 5, then developability, tendency to the decreased solubility of photosensitive polymer combination modulation solvent is had.
-(B) multi-functional acrylic monomer-
As (B) multi-functional acrylic monomer of present embodiment, can use 2 officials can above multifunctional (methyl) acrylate.Specifically, dipentaerythritol acrylate can be enumerated, dipentaerythritol hexamethacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol pentamethacrylates, tetramethylol methane tetraacrylate, pentaerythritol tetramethylacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, pentaerythritol diacrylate, dimethyl pentaerythritol acrylate, tetra methylol tetraacrylate, tetra methylol propane tetramethyl acrylate, tetramethylol methane tetraacrylate, tetramethylol methane tetramethyl acrylate, trimethylolpropane triacrylate, trimethylol-propane trimethacrylate, 1,3,5-triacryl six hydrogen-S-triazine, 1,3,5-trimethacrylate acyl group six hydrogen-S-triazine, three (hydroxylethyl acyl group) isocyanuric acid ester, three (hydroxyethyl methyl acryloyl group) isocyanuric acid ester, triacryl dimethoxym ethane, trimethacrylate acyl group dimethoxym ethane, 1,6-hexanediol acrylate, 1,6-hexanediol methacrylate, neopentylglycol diacrylate, neopentylglycol dimethacrylate, glycol diacrylate, ethylene glycol dimethacrylate, 2-hydroxyl propylene glycol diacrylate, 2-hydroxyl dimethacrylate, diethylene glycol diacrylate, dimethacrylate, Isopropanediol diacrylate, Isopropanediol dimethylacrylate, triethylene glycol diacrylate, TEGDMA, N, N '-two (acryloyl group) halfcystine, N, N '-two (methacryl) halfcystine, sulphur support diethanol diacrylate, sulphur support diethanol dimethylacrylate, bisphenol a diacrylate, bisphenol a dimethacrylate, Bisphenol F diacrylate, Bisphenol F dimethylacrylate, bisphenol S diacrylate, bisphenol S dimethylacrylate, two phenoxetol fluorenes diacrylates, two phenoxetol fluorenes dimethylacrylates, diallyl ether bisphenol-A, adjacent diallyl bisphenol, diallyl maleate and triallyl trimellitate.By using 2 officials can above multifunctional (methyl) acrylate, physical strength can be obtained and strengthen such effect.
Above-mentioned multi-functional acrylic's monomer, can be easy to as commodity obtain, such as, can enumerate KYARAD T-1420, KYARAD DPHA, KYARAD DPHA-2C, KYARAD D-310, KYARAD D-330, KYARAD DPCA-20, KYARAD DPCA-30, KYARADDPCA-60, KYARAD DPCA-120, KYARAD DN-0075, KYARAD DN-2475, KYARAD R-526, KYARAD NPGDA, KYARAD PEG400DA, KYARADMANDA, KYARAD R-167, KYARAD HX-220, KYARAD HX620, KYARADR-551, KYARAD R-712, KYARAD R-604, KYARAD R-684, KYARADGPO-303, KYARAD TMPTA, KYARAD THE-330, KYARAD TPA-320, KYARAD TPA-330, KYARAD PET-30, KYARAD RP-1040 (being Japanese chemical drug (strain) manufacture above), Aronix (ア ロ ニ ッ Network ス) M-210, Aronix M-240, AronixM-6200, Aronix M-305, Aronix M-309, Aronix M-400, Aronix M-402, Aronix M-405, Aronix M-450, Aronix M-7100, Aronix M-8030, AronixM-8060, Aronix M-1310, Aronix M-1600, Aronix M-1960, Aronix M-8100, Aronix M-8530, Aronix M-8560, Aronix M-9050 (above for East Asia synthesis (strain) manufactures), Viscoat (PVC ス コ ー ト) 295, Viscoat 300, Viscoat 360, Viscoat GPT, Viscoat 3PA, Viscoat 400, Viscoat 260, Viscoat 312 and Viscoat 335HP (being Osaka Organic Chemical Industry (strain) manufacture above).In addition, these multi-functional acrylic's monomers can be used alone a kind, or can be used in combination by two or more.
In these multi-functional acrylic's monomers, from to the dissolubility of developer solution and the transparency, particularly preferably dipentaerythritol acrylate, dipentaerythritol hexamethacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol pentamethacrylates, tetramethylol methane tetraacrylate, pentaerythritol tetramethylacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, pentaerythritol diacrylate and dimethyl pentaerythritol acrylate.
-(C) Photoepolymerizationinitiater initiater-
As (C) Photoepolymerizationinitiater initiater in present embodiment, photonasty radical polymerization initiator can be enumerated.As photonasty radical polymerization initiator, such as, the α-diones such as benzil and diacetyl can be enumerated, the acyloin classes such as benzoin, benzoin methyl ether, the acyloin ethers such as benzoin ethyl ether and benzoin isopropyl ether, thioxanthones, 2,4-diethyl thioxanthone, thioxanthones-4-sulfonic acid, benzophenone, the benzophenones such as 4,4 '-two (dimethylamino) benzophenone and 4,4 '-two (diethylamino) benzophenone, acetophenone, p-dimethylamino benzoylformaldoxime, α, α '-dimethoxy acetoxyl group benzophenone, 2,2 '-dimethoxy-2-phenyl acetophenone, p-methoxyacetophenone, 2-methyl (4-(methyl mercapto) phenyl)-2-morpholino (the モ Le Off ォ リ ノ) acetophenones such as-1-acetone and 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-butane-1-ketone, the quinones such as anthraquinone and 1,4-naphthoquinone, phenacyl chloride, the halogen compounds such as trisbromomethyl phenyl sulfone and three (trichloromethyl)-s-triazine, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, two (2,6-dimethoxybenzoyl)-2,4,4-acylphosphine oxide such as trimethyl-pentyl phosphine oxide and two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide, and the superoxide etc. such as di-tert-butyl peroxide.By use sense photosensitiveness radical polymerization initiator, the susceptibility of negative light-sensitive resin combination to light can be obtained and improve such effect.
As the commercially available product of these photonasty radical polymerization initiators, such as, IRGACURE-184 can be enumerated, IRGACURE-369, IRGACURE-500, IRGACURE-651, IRGACURE-907, IRGACURE-1700, IRGACURE-819, IRGACURE-124, IRGACURE-1000, IRGACURE-2959, IRGACURE-149, IRGACURE-1800, IRGACURE-1850, IRGACURE-OXE-01, Darocur-1173, Darocur-1116, Darocur-2959, Darocur-1664, Darocur-4043 (above for Ciba Specialty Chemicals manufactures), KAYACURE-DETX, KAYACURE-MBP, KAYACURE-DMBI, KAYACURE-EPA, KAYACURE-OA (being Japanese chemical drug (strain) manufacture above), LUCIRINTPO (BASFCo.LTD manufacture), VICURE-10, VICURE-55 (above for STAUFFER Co.LTD manufactures), TRIGONALP1 (AKZO Co.LTD manufactures), SANDORAY1000 (SANDOZCo.LTD manufacture), DEAP (APJOHN Co.LTD manufactures), QUANTACURE-PDO, QUANTACURE-ITX and QUANTACURE-EPD (above for WARDBLEKINSOPCo.LTD manufactures).In addition, by and with these photonasty radical polymerization initiators and photosensitive sensitizer, the negative light-sensitive resin combination of the high sensitivity that the inactivation that can also obtain causing because of oxygen is less.
In above-mentioned photonasty radical polymerization initiator, the transparency after the dissolubility to photosensitive polymer combination modulating liquid, exposure, be particularly preferably α, α '-dimethoxy acetoxyl group benzophenone, 2-methyl (4-(methyl mercapto) phenyl)-2-morpholino-1-acetone and 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-butane-1-ketone.
-(D) alkali soluble resin-
As the alkali soluble resin of present embodiment, can promote suitably to select in the alkali soluble resin of the group (such as, carboxyl, phosphate and sulfonic group etc.) of alkali-soluble from for there is at least one wire organic high molecular polymer, molecule (being preferably the molecule being main chain with acrylic acid series copolymer, styrene based copolymer).Wherein, be more preferably and dissolve in organic solvent and can carry out by weak base aqueous solution the material that develops.
In the manufacture of alkali soluble resin, such as, the method adopting known radical polymerization can be suitable for.In radical polymerization, the kind of temperature during manufacture alkali soluble resin, pressure, radical polymerization initiator and amount, and the polymerizing condition such as the kind of solvent, can set easily to those skilled in the art, and experimentally determination condition can be formed as.
As above-mentioned wire organic high molecular polymer, preferably there is on side chain the polymkeric substance of carboxylic acid.Such as, No. 59-44615, Japanese Laid-Open Patent Publication can be enumerated, No. 54-34327, Japanese Patent Publication, No. 58-12577, Japanese Patent Publication, No. 54-25957, Japanese Patent Publication, such methacrylic acid copolymer described in each publication of No. 59-53836, Japanese Laid-Open Patent Publication and No. 59-71048, Japanese Laid-Open Patent Publication, acrylic copolymer, itaconic acid copolymer, crotonic acid copolymers, maleic acid, the maleic acid of partial esterification, the acid cellulose derivant that side chain has carboxylic acid and the high molecular polymer etc. making acid anhydrides carry out addition with the polymkeric substance with hydroxyl and obtain, in addition, as preferred high molecular polymer, the high molecular polymer with (methyl) acryloyl group can also be set forth on side chain.
Among these, (methyl) benzyl acrylate/(methyl) acrylic copolymer and the multiple copolymer comprising (methyl) benzyl acrylate/(methyl) acrylic acid/other monomer are particularly suitable.In addition, as useful material, the polymkeric substance of copolymerization HEMA can also be enumerated.This polymkeric substance can be used in combination to measure arbitrarily.
In addition to the foregoing, (methyl) acrylic acid 2-hydroxypropyl acrylate/Group-capped Polystyrene Macromer/benzyl methacrylate/methacrylic acid copolymer described in Japanese Unexamined Patent Publication 7-140654 publication can also be enumerated, 2-hydroxyl-3-phenoxypropylacrylate/polymethylmethacrylate macromonomer/benzyl methacrylate/methacrylic acid copolymer, HEMA/Group-capped Polystyrene Macromer/methyl methacrylate/methacrylic acid copolymer and HEMA/Group-capped Polystyrene Macromer/benzyl methacrylate/methacrylic acid copolymer etc.
For the concrete structural unit of (D) alkali soluble resin, (methyl) acrylic acid and can be particularly suitable with the multipolymer of other monomer of its copolymerization.As can with other monomer of above-mentioned (methyl) acrylic acid copolymer, (methyl) alkyl acrylate, (methyl) benzyl acrylate and vinyl compound etc. can be enumerated.Herein, the hydrogen atom of alkyl and aryl, also can be substituted with a substituent.
As the object lesson of above-mentioned (methyl) alkyl acrylate with (methyl) benzyl acrylate, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) 2-ethyl hexyl acrylate, (methyl) phenyl acrylate, benzyl acrylate, CA, acrylic acid naphthalene ester and cyclohexyl acrylate can be enumerated.
In addition, as above-mentioned vinyl compound, such as, styrene, α-methyl styrene, vinyltoluene, glycidyl methacrylate, vinyl cyanide, vinyl acetate, NVP, tetrahydrofurfuryl methacrylate, Group-capped Polystyrene Macromer, polymethylmethacrylate macromonomer, CH can be enumerated 2=CR 5r 6[herein, R 5represent that hydrogen atom or carbon number are the alkyl of 1 ~ 5, R 6represent that carbon number is the aromatic hydrocarbon ring of 6 ~ 10.] and CH 2=C (R 5) (COOR 7) [herein, R 5represent that hydrogen atom or carbon number are the alkyl of 1 ~ 5, R 7represent carbon number be 1 ~ 8 alkyl or carbon number be the aralkyl of 6 ~ 12.]。These can other monomer of copolymerization, can be used alone a kind, or two or more can be combinationally used.
Preferably can other monomer of copolymerization, be selected from CH 2=CR 5r 6, CH 2=C (R 5) (COOR 7), (methyl) phenyl acrylate, (methyl) benzyl acrylate and cinnamic at least one, and be particularly preferably CH 2=CR 5r 6and/or CH 2=C (R 5) (COOR 7).
-modulation of negative light-sensitive resin combination-
Negative light-sensitive resin combination in present embodiment is modulated by each composition mixing by above-mentioned (A) cyclic olefin resin, (B) multi-functional acrylic monomer and (C) Photoepolymerizationinitiater initiater.Above-mentioned negative light-sensitive resin combination to be dissolved in aptly in suitable solvent and to use with solution state.Such as, can pass through by (A) cyclic olefin resin, (B) multi-functional acrylic monomer, (C) Photoepolymerizationinitiater initiater and other compounding ingredient as required to specify that ratio mixes, and modulate the negative light-sensitive resin combination of solution state.
For the negative light-sensitive resin combination in present embodiment, relative to (A) cyclic olefin resin 10 weight portion, preferably with 10 ~ 150 weight portions and more preferably the ratio of 40 ~ 120 weight portions contains (B) multi-functional acrylic monomer.When (B) multi-functional acrylic monomer is less than 10 weight portion, has and cannot fully obtain photosensitive tendency.On the other hand, when more than 150 weight portion, then there is the tendency that fracture strength declines.In addition, (C) Photoepolymerizationinitiater initiater preferably with 1 ~ 40 weight portion and more preferably the ratio of 3 ~ 35 weight portions contain.When (C) Photoepolymerizationinitiater initiater is less than 1 weight portion, have the tendency that cannot obtain thermotolerance, skin hardness and resistance to chemical reagents.On the other hand, when more than 40 weight portion, then there is the tendency that the transparency declines.
As the solvent of the negative light-sensitive resin combination for modulating present embodiment, dissolving (A) cyclic olefin resin, (B) multi-functional acrylic monomer and each composition of (C) Photoepolymerizationinitiater initiater can be used, and the solvent do not reacted with each composition.Specifically, the alcohols such as methyl alcohol and ethanol can be enumerated, the ethers such as tetrahydrofuran, the glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monomethyl ether, the ethylene glycol such as methylcellosolve acetate and ethyl cellosolve acetate alkylether acetates class, diethylene glycol monomethyl ether, TC, diethylene glycol dimethyl ether, the diethylene glycol classes such as diethylene glycol ethyl methyl ether and diethylene glycol diethyl ether, methyl proxitol, propylene glycol ethyl ether, the propylene-glycol monoalky lether such as propylene glycol propyl ether and propylene glycol butyl ether class, methyl proxitol acetate, propylene glycol ethyl ether acetic acid esters, the propylene glycol alkyl ether acetic acid ester classes such as propylene glycol propyl ether acetic acid esters and propylene glycol butyl ether acetic acid esters, methyl proxitol propionic ester, propylene glycol ethyl ether propionic ester, the propylene glycol alkyl ether propionic acid esters such as propylene glycol propyl ether propionic ester and propylene glycol butyl ether propionic ester, toluene and dimethylbenzene etc. are aromatic hydrocarbon based, MEK, the ketones such as cyclohexanone and 4-hydroxy-4-methyl-2-pentanone, and methyl acetate, ethyl acetate, propyl acetate, butyl acetate, 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxy methyl acetate, hydroxyl ethyl acetate, Butyl Glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxy methyl propionate, 3-hydroxypropionate, 3-hydracrylic acid propyl ester, 3-hydroxy methyl propionate, 3-butoxy ethyl propionate, the ester classes such as 3-butoxy propyl propionate and 3-butoxy butyl propionate.
In these solvents, from dissolubility, the easy degree that formed with the reactivity of each composition and film, propylene glycol alkyl ether acetic acid ester class, propylene glycol alkyl ether propionic acid ester and aromatic hydrocarbon based preferably can be used.
Further, above-mentioned solvent and high boiling solvent can also be used.As the high boiling solvent that can be used together, such as, N-METHYLFORMAMIDE, N can be enumerated, dinethylformamide, N-methyl N-formailide, N-methylacetamide, DMA, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), benzylisoeugenol, hexyl ether, acetonyl acetone, isophorone, caproic acid, sad, 1-octanol, 1 nonyl alcohol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, gamma-butyrolacton, ethylene carbonate, carbonic allyl ester and ethylene glycol monophenyl ether acetic acid esters.The negative light-sensitive resin combination of present embodiment within the scope without prejudice to the object of the present invention, can also contain other composition other than the above as required.
The negative light-sensitive resin combination of modulation described above can also use aperture be reoffer use after the millipore filter etc. of about 0.2 ~ 0.5 μm filters.
-the formation method of interlayer dielectric-
The formation method of the interlayer dielectric of present embodiment comprises at least following operation.(1) on substrate, the operation of the film of above-mentioned negative light-sensitive resin combination, (2) are formed to the light of irradiation at least partially of above-mentioned film (hereinafter sometimes referred to " exposure ".) operation, (3) operation of above-mentioned film development after exposure, (4) are burnt till the above-mentioned film after development (hereinafter sometimes referred to " cure (ベ ー Network) ".), form the operation of interlayer dielectric.
Herein, so-called in present embodiment " light " refers to and comprises ultraviolet, far ultraviolet, X ray, electron beam, molecular beam, gamma-rays, synchrotron light (シ Application Network ロ ト ロ Application light) and proton beam etc.
Below, these operations are described in detail.
-(1) operation-
In (1) operation, using negative light-sensitive resin combination preferably as liquid composition, form film on the surface of the substrate, and carry out prebake except desolventizing, form the film of negative light-sensitive resin combination.
As the kind of operable substrate, glass substrate, silicon wafer can be enumerated and form the substrate etc. of various metal over their surface.As the method for the film of formation composition solution, be not particularly limited, be preferably the method adopting coating.As coating process, the proper methods such as spray-on process, rolling method, spin-coating method, slit die rubbing method, stick coating method and ink-jet method can be adopted.
The condition of prebake is different according to the kind of the constituent of negative light-sensitive resin combination and usage ratio etc., such as, can carry out at 60 ~ 130 DEG C 30 second ~ 15 minutes.As the thickness of the above-mentioned film formed, be preferably 5 ~ 20 μm as the value after prebake.
-(2) operation-
In (2) operation, to exposing at least partially of the above-mentioned film formed.At this moment, when only exposing a part for above-mentioned film, the photomask usually by having regulation character pattern exposes.
As exposure light used, such as, the X ray such as far ultraviolet, synchrotron light such as ultraviolet, KrF excimer laser and ArF excimer laser such as i line (wavelength is 365nm) can be enumerated, and the charged particle beam such as electron beam.In these light, preferred ultraviolet, more preferably wavelength is the ultraviolet of below 400nm, and preferably comprises the ultraviolet of i line further.Exposure is preferably set to 50 ~ 10000J/m 2left and right.
-(3) operation-
In (3) operation, developed by the above-mentioned film after exposure, removing unexposed portion, forms the pattern of regulation shape thus.
As developer solution used in development, be preferably NaOH, potassium hydroxide, sodium carbonate, sodium silicate (ケ イ acid Na ト リ ウ system), sodium silicate (メ タ ケ イ acid Na ト リ ウ system), ammonia, ethamine, n-propylamine, diethylamine, DEAE diethylaminoethanol, di-n-propylamine, triethylamine, methyl-diethyl-amine, dimethylethanolamine, triethanolamine, Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, pyrroles, piperidines, 1, 8-diazabicyclo [5, 4, 0]-7-undecylene and 1, 5-diazabicyclo [4, 3, 0] aqueous solution of the alkali compounds such as-5-nonene.In the aqueous solution of above-mentioned alkali compounds, water-miscible organic solvent and the surfactants such as appropriate methyl alcohol and ethanol can be added.
In addition, in the present embodiment, when negative light-sensitive resin combination is not containing the insoluble composition such as filler, pigment, as developer solution, the various organic solvents dissolving constituent can also be used.
As developing method, the proper methods such as fluid containing method (liquid contains り method), infusion process, shake infusion process and shower method (シ ャ ワ ー method) can be adopted.
Development time is different according to the cooperation composition of negative light-sensitive resin combination, such as, and can for establishing for 30 ~ 300 seconds.In addition, all the time for the formation of the negative light-sensitive resin combination of interlayer dielectric, if development time from top condition more than more than 20 seconds, the pattern then formed can produce defects such as peeling off, therefore need strictly to control development time, and when negative light-sensitive resin combination of the present invention, even if be more than 30 seconds from the overtime of optimum development time, also can form good pattern, and the yield rate of product improves.
-(4) operation-
In (4) operation, after carrying out post-exposure as required, the above-mentioned film after development is cured by the heating arrangement such as hot plate and baking oven, thus above-mentioned film is solidified, form interlayer dielectric.As the light for post-exposure, such as, the X ray such as far ultraviolet, synchrotron light such as ultraviolet, KrF excimer laser and ArF excimer laser such as i line (wavelength is 365nm) can be enumerated, and the charged particle beam such as electron beam.
In these light, preferred ultraviolet, more preferably wavelength is the ultraviolet of below 400nm, and more preferably comprises the ultraviolet of i line further.The exposure of post-exposure is preferably set to 50 ~ 10000J/m 2.Baking conditions is different according to the kind of the constituent of negative light-sensitive resin combination and usage ratio, desired pattern form and heating arrangement used etc., and when hot plate, such as, at being 150 ~ 240 DEG C 10 ~ 30 minutes, when baking oven, such as, at being 150 ~ 240 DEG C 30 ~ 90 minutes.In addition, when curing, the substep baking process etc. carrying out heating for more than 2 times can also be adopted.
In this wise, target interlayer dielectric can be formed on substrate.Even if the interlayer dielectric thick-film of gained, the various characteristics such as its resolution, the transparency, thermotolerance, resistance to thermochromism and solvent resistance are also all excellent, such as, can extremely suitable ground for comprising the electronic units etc. such as the various liquid crystal display cells of TFT type liquid crystal display cells, magnetic head element, integrated circuit component and solid-state imager.In addition, the formation method of interlayer dielectric according to the present embodiment, can form the interlayer dielectric with excellent specific property easily with high finished product rate.
Embodiment
Below, display embodiment makes more specific description to the present invention, but the present invention is not limited thereto.
(embodiment 1)
-modulation of negative light-sensitive resin combination-
Using Aronix M-305 (East Asia synthesis (strain) manufacture of 10g as (B) multi-functional acrylic monomer, trade name) be dissolved in 36.4g toluene, in the solution of gained, adding 1g (A) cyclic olefin resin and 0.6g, (Ciba Specialty Chemicals manufactures as 2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholino propane-1-ketone of (C) Photoepolymerizationinitiater initiater, trade name: IRGACURE-907), wherein said (A) cyclic olefin resin is R 1, R 2and R 4for hydrogen atom, R 3for monomer and the R of methyl ester group 1, R 2, R 3and R 4for the monomer of hydrogen atom to carry out the material of copolymerization gained with 1:1 (mol ratio), then filter with the film filter that aperture is 0.5 μm, modulate the negative light-sensitive resin combination (S-1) that overall solid component concentration is the such solution state of 30 quality %.
-formation of interlayer dielectric-
To use on table coating machine by negative light-sensitive resin combination (S-1) coating on the glass substrate, then prebake 10 minutes in the explosion-proof dryer of 80 DEG C, forms film.Then, by the photomask with regulation character pattern with cumulative exposure amount for 100mJ/cm 2mode be the ultraviolet of 365nm to this film exposure wavelength.Then, use the tetramethylammonium hydroxide aqueous solution of 2.38 quality %, at 25 DEG C, immersion development is after 5 minutes, with pure water 1 minute, removes unwanted part, obtains pattern-like film.
Then, the pattern-like film of gained is cured 30 minutes in the baking oven of 200 DEG C, makes it solidify, thus the thickness obtaining having predetermined pattern shape is the interlayer dielectric of 50 μm.
-evaluate-
Then, evaluate according to following main points.The thickness of evaluation result and interlayer dielectric is shown in table 1 (lower same) in the lump.
-evaluation of resolution-
For the interlayer dielectric of gained, use diameter is that resolution evaluated by the mask pattern of 50 μm.Be evaluated as good (A) when 50 μm of square sectional hole patterns can be differentiated, be evaluated as bad (B) when 50 μm of square sectional hole patterns cannot be differentiated.
-transparency evaluation-
For the continuous film part of the interlayer dielectric of gained, use double beam spectrophotometer U-2900 ((strain) Hitachi manufactures, trade name) measures transmitance during wavelength 400nm, and evaluates.When this transmitance is more than 90%, the transparency good (A) can be said.
-evaluation of thermotolerance-
Heated 60 minutes in the baking oven of 220 DEG C by the interlayer dielectric of gained, the digital display scale (digimatic indicator) using (strain) mitsutoyo to manufacture measures the Thickness Variation rate (%) [thickness before the heating of=(thickness after the thickness-heating before heating) × 100/] before and after heating and evaluates.When this rate of change is within 5%, thermotolerance good (A) can be said.
-evaluation of Nai thermochromism-
Remove with the baking oven of nitrogen to 250 DEG C, the interlayer dielectric of gained is heated 60 minutes wherein, and the continuous film part to interlayer dielectric, ((strain) Hitachi manufactures to use double beam spectrophotometer U-2900, trade name) transmitance when measuring wavelength 400nm, and evaluated by the rate of change (%) [transmitance before the heating of=(transmitance after the transmitance-heating before heating) × 100/] of transmitance before and after heating.When this rate of change is within 5%, resistance to thermochromism good (A).
-evaluation of solvent resistance-
Flooded 15 minutes in the 1-METHYLPYRROLIDONE of 50 DEG C by the glass substrate defining interlayer dielectric, the digital display scale using (strain) mitsutoyo to manufacture measures the Thickness Variation rate (%) [thickness before the dipping of=(thickness before the thickness-dipping after dipping) × 100/] of interlayer dielectric before and after dipping and evaluates.When this rate of change is within ± 10%, solvent resistance good (A) can be said.
(embodiment 2)
Except in embodiment 1, (East Asia synthesis (strain) manufactures to use 10g Aronix M-402, trade name) replace beyond 10g Aronix M-305, similarly modulate the negative light-sensitive resin combination (S-2) of solution state with embodiment 1, the thickness obtaining the pattern form with regulation is the interlayer dielectric of 40 μm.Evaluation result is shown in table 1.
[table 1]
Thickness (μm) Resolution The transparency Thermotolerance Resistance to thermochromism Solvent resistance
Embodiment 1 50 A A A A A
Embodiment 2 40 A A A A A
Can confirm any one interlayer dielectric of embodiment 1 and 2, even if thick-film, its resolution, the transparency, thermotolerance, resistance to thermochromism and solvent resistance are also all excellent.

Claims (34)

1. a negative light-sensitive resin combination, it contains:
Comprise (A) cyclic olefin resin of the repetitive represented by following general formula (1),
(B) multi-functional acrylic's monomer and
(C) Photoepolymerizationinitiater initiater,
In formula, R 1, R 2, R 3and R 4represent independently of one another and be selected from hydrogen atom, carbon number is the alkyl of 1 ~ 15, carbon number is the thiazolinyl of 2 ~ 20, carbon number is the naphthenic base of 5 ~ 15, carbon number be 6 ~ 20 aryl or carbon number be the alkoxy of 1 ~ 20, or hydrolyzable silyl group, carbon number is the alkoxy carbonyl of 2 ~ 20, carbon number is the trialkylsiloxy carbonyl of 4 ~ 20, carbon number is the alkyl carbonyl oxy of 2 ~ 20, carbon number is the thiazolinyl carbonyl oxygen base of 3 ~ 20 and the substituting group of oxetanylmethoxy, and also directly or oxygen atom can be passed through, nitrogen-atoms or sulphur atom and be connected to each other.
2. negative light-sensitive resin combination as claimed in claim 1, wherein (A) cyclic olefin resin comprises the R represented by described general formula (1) 1, R 2, R 3and R 4for the structural unit of hydrogen atom.
3. negative light-sensitive resin combination as claimed in claim 1 or 2, wherein (A) cyclic olefin resin comprises the R represented by described general formula (1) 1, R 2, R 3and R 4any one for carbon number be 2 ~ 20 alkoxy carbonyl or carbon number be the structural unit of the alkyl carbonyl oxy of 2 ~ 20.
4. negative light-sensitive resin combination, wherein R as claimed in claim 1 1, R 2, R 3and R 4the alkoxy, the carbon number that are 6 ~ 20 for alkyl, carbon number that to be selected from by hydrogen atom, carbon number be 1 ~ 15 thiazolinyl that is 2 ~ 20, the carbon number aryl that is 6 ~ 15, carbon number be independently of one another 2 ~ 20 alkoxy carbonyl and carbon number be substituting group in the group that forms of alkyl carbonyl oxy of 2 ~ 20.
5. negative light-sensitive resin combination as claimed in claim 1, wherein said hydrolyzable silyl group is be selected from least one in the group that is made up of trimethoxysilyl and methyl dimethoxy oxygen base silicyl.
6. negative light-sensitive resin combination as claimed in claim 1, wherein said carbon number be 2 ~ 20 alkoxy carbonyl be selected from least one in the group that is made up of methyl ester group, tert-butyl group ester group, 2-ethylhexyl ester group, benzyl ester group, cyclopentyl ester group, cyclohexyl ester group and allyl ester group.
7. negative light-sensitive resin combination as claimed in claim 1, wherein said carbon number be 2 ~ 20 alkoxy carbonyl be selected from least one in the group that is made up of methyl ester group, 2-ethylhexyl ester group, benzyl ester group, cyclopentyl ester group, cyclohexyl ester group and allyl ester group.
8. negative light-sensitive resin combination as claimed in claim 2, wherein (A) cyclic olefin resin with the total amount of formula (1) structural unit in cyclic olefin for benchmark, containing the R represented by 1 % by mole of the above general formula (1) 1, R 2, R 3and R 4for the structural unit of hydrogen atom.
9. negative light-sensitive resin combination as claimed in claim 2, wherein (A) cyclic olefin resin with the total amount of formula (1) structural unit in cyclic olefin for benchmark, containing the R represented by 10 % by mole of the above general formulas (1) 1, R 2, R 3and R 4for the structural unit of hydrogen atom.
10. negative light-sensitive resin combination as claimed in claim 2, wherein (A) cyclic olefin resin is with the total amount of formula (1) structural unit in cyclic olefin for benchmark, contains the R represented by described general formula (1) with the ratio of less than 60 % by mole 1, R 2, R 3and R 4for the structural unit of hydrogen atom.
11. negative light-sensitive resin combinations as claimed in claim 2, wherein (A) cyclic olefin resin is with the total amount of formula (1) structural unit in cyclic olefin for benchmark, contains the R represented by described general formula (1) with the ratio of less than 50 % by mole 1, R 2, R 3and R 4for the structural unit of hydrogen atom.
12. negative light-sensitive resin combinations as claimed in claim 3, wherein (A) cyclic olefin resin with the total amount of formula (1) structural unit in cyclic olefin for benchmark, containing the R represented by 1 % by mole of the above general formula (1) 1, R 2, R 3and R 4any one for carbon number be 2 ~ 20 alkoxy carbonyl or carbon number be the structural unit of the alkyl carbonyl oxy of 2 ~ 20.
13. negative light-sensitive resin combinations as claimed in claim 3, wherein (A) cyclic olefin resin with the total amount of formula (1) structural unit in cyclic olefin for benchmark, containing the R represented by 10 % by mole of the above general formulas (1) 1, R 2, R 3and R 4any one for carbon number be 2 ~ 20 alkoxy carbonyl or carbon number be the structural unit of the alkyl carbonyl oxy of 2 ~ 20.
14. negative light-sensitive resin combinations as claimed in claim 3, wherein (A) cyclic olefin resin is with the total amount of formula (1) structural unit in cyclic olefin for benchmark, contains the R represented by described general formula (1) with the ratio of less than 60 % by mole 1, R 2, R 3and R 4any one for carbon number be 2 ~ 20 alkoxy carbonyl or carbon number be the structural unit of the alkyl carbonyl oxy of 2 ~ 20.
15. negative light-sensitive resin combinations as claimed in claim 3, wherein (A) cyclic olefin resin is with the total amount of formula (1) structural unit in cyclic olefin for benchmark, contains the R represented by described general formula (1) with the ratio of less than 50 % by mole 1, R 2, R 3and R 4any one for carbon number be 2 ~ 20 alkoxy carbonyl or carbon number be the structural unit of the alkyl carbonyl oxy of 2 ~ 20.
16. negative light-sensitive resin combinations according to any one of claim 1 ~ 15, wherein the polystyrene conversion weight-average molecular weight of (A) cyclic olefin resin is 2 × 10 3to 2 × 10 5.
17. negative light-sensitive resin combinations according to any one of claim 1 ~ 15, wherein the polystyrene conversion weight-average molecular weight of (A) cyclic olefin resin is 2 × 10 4to 1.8 × 10 5.
18. negative light-sensitive resin combinations according to any one of claim 1 ~ 17, wherein (B) multi-functional acrylic monomer comprises and is selected from by dipentaerythritol acrylate, dipentaerythritol hexamethacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol pentamethacrylates, tetramethylol methane tetraacrylate, pentaerythritol tetramethylacrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, pentaerythritol diacrylate, dimethyl pentaerythritol acrylate, tetra methylol tetraacrylate, tetra methylol propane tetramethyl acrylate, tetramethylol methane tetraacrylate, tetramethylol methane tetramethyl acrylate, trimethylolpropane triacrylate, trimethylol-propane trimethacrylate, 1,3,5-triacryl six hydrogen-S-triazine, 1,3,5-trimethacrylate acyl group six hydrogen-S-triazine, three (hydroxylethyl acyl group) isocyanuric acid ester, three (hydroxyethyl methyl acryloyl group) isocyanuric acid ester, triacryl dimethoxym ethane, trimethacrylate acyl group dimethoxym ethane, 1,6-hexanediol acrylate, 1,6-hexanediol methacrylate, neopentylglycol diacrylate, neopentylglycol dimethacrylate, glycol diacrylate, ethylene glycol dimethacrylate, 2-hydroxyl propylene glycol diacrylate, 2-hydroxyl dimethacrylate, diethylene glycol diacrylate, dimethacrylate, Isopropanediol diacrylate, Isopropanediol dimethylacrylate, triethylene glycol diacrylate, TEGDMA, N, N '-two (acryloyl group) halfcystine, N, N '-two (methacryl) halfcystine, sulphur support diethanol diacrylate, sulphur support diethanol dimethylacrylate, bisphenol a diacrylate, bisphenol a dimethacrylate, Bisphenol F diacrylate, Bisphenol F dimethylacrylate, bisphenol S diacrylate, bisphenol S dimethylacrylate, two phenoxetol fluorenes diacrylates, two phenoxetol fluorenes dimethylacrylates, diallyl ether bisphenol-A, adjacent diallyl bisphenol, at least one in the group of diallyl maleate and triallyl trimellitate composition.
19. negative light-sensitive resin combinations according to any one of claim 1 ~ 18, wherein (C) Photoepolymerizationinitiater initiater comprises at least one in the group being selected from and being made up of α-diones, acyloin class, acyloin ethers, benzophenone, acetophenones, quinones, halogen compounds, acylphosphine oxide and superoxide.
20. negative light-sensitive resin combinations according to any one of claim 1 ~ 19, wherein (C) Photoepolymerizationinitiater initiater comprise be selected from by α, α ' at least one in the group of-dimethoxy acetoxyl group benzophenone, 2-methyl (4-(methyl mercapto) phenyl)-2-morpholino-1-acetone and 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-butane-1-ketone composition.
21. negative light-sensitive resin combinations according to any one of claim 1 ~ 20, wherein relative to (A) cyclic olefin resin 10 weight portion, contain (B) multi-functional acrylic monomer with the ratio of 10 ~ 150 weight portions.
22. negative light-sensitive resin combinations according to any one of claim 1 ~ 20, wherein relative to (A) cyclic olefin resin 10 weight portion, contain (B) multi-functional acrylic monomer with the ratio of 40 ~ 120 weight portions.
23. negative light-sensitive resin combinations according to any one of claim 1 ~ 22, wherein relative to (A) cyclic olefin resin 10 weight portion, contain (C) Photoepolymerizationinitiater initiater with the ratio of 1 ~ 40 weight portion.
24. negative light-sensitive resin combinations according to any one of claim 1 ~ 22, wherein relative to (A) cyclic olefin resin 10 weight portion, contain (C) Photoepolymerizationinitiater initiater with the ratio of 3 ~ 35 weight portions.
25. negative light-sensitive resin combinations according to any one of claim 1 ~ 24, wherein use to comprise and are selected from by the solvent of at least one in propylene glycol alkyl ether acetic acid ester class, propylene glycol alkyl ether propionic acid ester and the aromatic hydrocarbon based group formed and modulate.
26. negative light-sensitive resin combinations as described in any one of claim 1 ~ 25, it may be used for the formation method of interlayer dielectric, and it is the ultraviolet operation of below 400nm that described method has the illumination wavelength at least partially of the film formed by this negative light-sensitive resin combination.
27. negative light-sensitive resin combinations as described in any one of claim 1 ~ 26, it is further containing (D) alkali soluble resin.
28. negative light-sensitive resin combinations as claimed in claim 27, wherein (D) alkali soluble resin comprises wire organic high molecular polymer, and described wire organic high molecular polymer has the group that at least one promotes alkali-soluble.
29. negative light-sensitive resin combinations as claimed in claim 28, the molecule that it is main chain that wherein said wire organic high molecular polymer comprises with acrylic acid series copolymer or styrene based copolymer.
30. negative light-sensitive resin combinations as described in claim 28 or 29, the group of wherein said promotion alkali-soluble is at least one in the group selecting free carboxyl group, phosphate and sulfonic group to form.
31. negative light-sensitive resin combinations according to any one of claim 28 ~ 30, wherein said wire organic high molecular polymer comprises at least one multipolymer in the group being selected from and being made up of (methyl) benzyl acrylate/(methyl) acrylic copolymer and the multiple copolymer that comprises (methyl) benzyl acrylate/(methyl) acrylic acid/other monomer.
32. negative light-sensitive resin combinations according to any one of claim 27 ~ 31, wherein (D) alkali soluble resin comprise (methyl) acrylic acid and can with the multipolymer of other monomer of (methyl) acrylic acid copolymer.
33. interlayer dielectrics formed by the negative light-sensitive resin combination described in any one of claim of right1~32.
The formation method of 34. 1 kinds of interlayer dielectrics, its have the operation of irradiating light at least partially to the film formed by the negative light-sensitive resin combination described in any one of claim of right1~32,
Postradiation for light described film is carried out the operation of developing and
Burn till the described film after development, form the operation of interlayer dielectric.
CN201510087880.5A 2010-02-25 2011-02-23 Negative photo sensitive resin composition, interlayer insulating film and forming method thereof Pending CN104597712A (en)

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