CN103069339B - Photoresist resin combination - Google Patents
Photoresist resin combination Download PDFInfo
- Publication number
- CN103069339B CN103069339B CN201180040734.7A CN201180040734A CN103069339B CN 103069339 B CN103069339 B CN 103069339B CN 201180040734 A CN201180040734 A CN 201180040734A CN 103069339 B CN103069339 B CN 103069339B
- Authority
- CN
- China
- Prior art keywords
- cyclic olefin
- resin
- group
- photoresist
- olefin resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such 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
-
- 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
- G03F7/0381—Macromolecular compounds which are rendered insoluble or differentially wettable using a combination of a phenolic resin and a polyoxyethylene resin
-
- 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
- G03F7/0385—Macromolecular compounds which are rendered insoluble or differentially wettable using epoxidised novolak resin
-
- 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
- G03F7/20—Exposure; Apparatus 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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
- G03F7/201—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by an oblique exposure; characterised by the use of plural sources; characterised by the rotation of the optical device; characterised by a relative movement of the optical device, the light source, the sensitive system or the mask
-
- 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
-
- 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
- G03F7/0236—Condensation products of carbonyl compounds and phenolic compounds, e.g. novolak resins
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials For Photolithography (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a kind of photoresist resin combination, it has high-fire resistance especially and has the residual film of good light sensitivity, resolution and height, and other characteristic is not inferior to general photoresist resin combination yet.Described photoresist resin combination contains phenolics, cyclic olefin resin and the compound containing naphthoquinones diazido, preferred cyclic olefin resin is norbornene resin, this norbornene resin preferably has acidic-group, particularly phenolic group, molecular weight is 1000 ~ 500000 dalton.
Description
Technical field
The present invention relates to a kind of photoresist resin combination.
The application at the Patent 2010-190880 CLAIM OF PRIORITY of Japanese publication, here cites its content based on August 27th, 2010.
Background technology
As liquid crystal indicator circuit or SIC (semiconductor integrated circuit), fine circuit pattern makes the pattern of target shape in the following manner, namely, the dielectric film be formed on substrate or conductive metal film apply or painting photoresist composition equably, under the mask of regulation shape exists, coated photo-corrosion-resisting agent composition is exposed, develops.Thereafter, make for after removing metal film or dielectric film using figuratum for formation photoresist film as mask, the photoresist film that removing is residual, substrate forms fine circuits.Such photo-corrosion-resisting agent composition is solvable or insoluble according to the part exposed, photoresist film, is categorized as minus and eurymeric.
Usually in positive light anti-etching agent composition, use naphthoquinones diazido compound etc. to have photosensitizer and the alkali soluble resin (such as, novolak phenolics) of quinone diazido.Demonstrate high resolving power by the development utilizing aqueous slkali to carry out after exposure by such positive light anti-etching agent composition formed that forms, be used to the manufactures of the liquid crystal display picture such as semiconductor manufacturing, LCD equipment such as IC, LSI and the manufacture etc. of printing original edition plate.In addition, novolak phenolics is for plasma dry etch, also because having the structure of aromatic rings in a large number, there is high-fire resistance, up to now, the positive light anti-etching agent of the One's name is legion containing novolak phenolics and naphthoquinones diazido system photosensitizer is developed out and practical, obtains very large achievement.
Liquid crystal indicator circuit photo-corrosion-resisting agent composition practical in key property be the light sensitivity of etchant resist, development contrast, resolution, bonding force, residual film ratio, thermotolerance and the circuit line width uniformity coefficient (CDuniformity) with substrate that are formed.The long time shutter at production line particularly caused due to the large area of the substrate of the feature as thin-film transistor LCD device, so requirement must improve light sensitivity.In addition, light sensitivity and residual film ratio are inverse relation, the trend that the high then residual film ratio display of light sensitivity reduces.
Between making under being generally used in the existence of acid catalyst in liquid crystal indicator circuit positive light anti-etching agent/paracresol and formaldehyde reaction and the novolak phenolics obtained.And, in order to adjust or improve the characteristic of photoresist, to carry out being used as between raw material phenols the research of/ratio of paracresol, the molecular weight, molecular weight distribution etc. of phenolics.In addition, Patent Document 1 discloses to use and carry out to novolac resin the method that fractionation (Fractionation) processes in order to improve photoresist characteristic, foregoing is widely known in those skilled in the art to be known.
Usually, the raising of the light sensitivity of photoresist is realized by the molecular weight reducing novolac resin.But when adopting the method, the residual film ratio reduction etc. in thermotolerance variation or unexposed portion, it is poor fully to obtain with the dissolution velocity in exposure portion, causes the reduction of the development contrast in exposure portion and unexposed portion.Further, its result generation resolution reduces such problem.On the other hand, if increase the molecular weight of novolac resin, then thermotolerance and resolution improve, but the light sensitivity that etchant resist occurs reduces.That is, if want improvement one side, then can produce the opposing party and be deteriorated so extremely serious unsuitable.
Up to now, unsuitable for this, attempt various improvement.But, when not yet developing any one characteristic in the excellent specific property of not sacrificing light sensitivity, residual film ratio, development contrast, resolution, the liquid crystal indicator circuit photo-corrosion-resisting agent composition such with the bonding force, circuit line width uniformity coefficient etc. of substrate, above-mentioned characteristic can be improved and the diversified liquid crystal indicator circuit photo-corrosion-resisting agent composition of various industrial processes can be applicable to.Therefore, this requirement is being continued.
Patent documentation 1: Japanese Unexamined Patent Application Publication 2002-508415 publication
Summary of the invention
The object of the present invention is to provide a kind of photoresist resin combination, it has high-fire resistance especially and has good light sensitivity resolution and the residual film of height, and other characteristic is not inferior to general photoresist resin combination yet.
The photoresist resin combination of a mode of the present invention is containing novolak phenolics, cyclic olefin resin and the photoresist resin combination by the photosensitizer formed containing the compound of naphthoquinones diazido.
In above-mentioned photoresist resin combination, above-mentioned cyclic olefin resin can be norbornene resin.
In above-mentioned photoresist resin combination, above-mentioned cyclic olefin resin also can for the cyclic olefin resin containing the repetitive represented by following general formula (1).
At this, in above-mentioned formula (1), X is O, CH
2, CH
2cH
2in any one, n is the integer of 0 ~ 5, R
1~ R
4be selected from hydrogen or can the monovalent organic group of carbon number 1 ~ 30 containing O and/or F in its structure, R independently of one another
1~ R
4can be different in the repetition of monomer, but at the R of whole repetitive
1~ R
4in, at least one has acidic-group.
In above-mentioned photoresist resin combination, above-mentioned acidic-group can for being selected from the group of more than 1 in carboxyl, phenolic group, fluoro alcohol radical and sulfoamido.
In above-mentioned photoresist resin combination, the weight-average molecular weight of above-mentioned cyclic olefin resin can be 1000 ~ 500000 dalton.
In above-mentioned photoresist resin combination, above-mentioned cyclic olefin resin can be 1 ~ 90 % by weight relative to the mixture ratio of above-mentioned phenolics.
By the present invention, can provide a kind of photoresist resin combination, it has high-fire resistance and has good light sensitivity, resolution, high residual film, and other characteristic is not inferior to general photoresist resin combination yet.
Embodiment
Below, the present invention is described in detail.
The present invention relates to a kind of photoresist resin combination.
The novolak phenolics used in the manufacture of photo-corrosion-resisting agent composition of the present invention is according to conventional methods, carries out condensation reaction in the presence of acid catalyst synthesize by making phenols and aldehydes.
As the phenols used in above-mentioned reaction, be not particularly limited, such as phenol can be enumerated, orthoresol, metacresol, the cresols classes such as paracresol, 2, 3-xylenol, 2, 4-xylenol, 2, 5-xylenol, 2, 6-xylenol, 3, 4-xylenol, 3, the diformazan phenols such as 5-xylenol, o-ethyl phenol, m-ethylphenol, the ethylbenzene phenols such as paraethyl phenol, isopropyl-phenol, butylphenol, the alkyl benzene phenols such as p-t-butyl phenol, in addition, also resorcinol can be enumerated, catechol, p-dihydroxy-benzene, 1,2,3,-thrihydroxy-benzene, the polyatomic phenols such as phloroglucin, alkyl-resorcin, alkyl catechol, the alkyl polyatomic phenols (carbon number of any alkyl is 1 ~ 4) such as alkyl p-dihydroxy-benzene.They can be used alone or in combination of two kinds or more.
In above-mentioned phenols, particularly preferably use metacresol and paracresol.By using these phenols and the compounding ratio of both adjustments, thus the various characteristic such as light sensitivity, thermotolerance as photoresist can be regulated.Now, the ratio of metacresol and paracresol is not particularly limited, preferred weight ratio (metacresol/paracresol)=9/1 ~ 1/9.More preferably 8/2 ~ 2/8.If the ratio of metacresol is less than above-mentioned lower limit, then light sensitivity reduces sometimes, if be greater than above-mentioned higher limit, then thermotolerance reduces sometimes.
As the aldehydes used in above-mentioned reaction, be not particularly limited, such as can enumerate formaldehyde, paraformaldehyde, trioxymethylene, acetaldehyde, propionic aldehyde, polyoxymethylene, trichloroacetaldehyde, hexamethylene tetramine, furfural, glyoxal, hutanal, hexanal, allyl aldehyde, benzaldehyde, crotonaldehyde, acryl aldehyde, four formaldehyde (tetraoxymethylene), phenylacetaldehyde, o-tolualdehyde, salicylide etc.Wherein, characteristically formaldehyde, paraformaldehyde is preferably used.
Above-mentioned phenols (P) is not particularly limited with the reaction mol ratio (F/P) of aldehydes (F), and a mode of the present invention can be implemented by reaction mol ratio known in the manufacture of novolak phenolics.
Particularly make the novolak phenolics obtained be applicable to the photoresist used time, preferred reaction mol ratio is 0.5 ~ 1.0.Thus, can obtain that there is the suitable resin combination as the molecular weight of photoresist.If above-mentioned reaction mol ratio is greater than above-mentioned higher limit, then can there is the macromolecule quantification of superfluous ground as the photoresist used time or because of reaction conditions, gelation etc. occur in resin combination sometimes.In addition, if be less than above-mentioned lower limit, then the content of low aromatic ring composition becomes many relatively sometimes, and efficiency when being therefore removed reduces.
Usually acid catalyst is used in the reaction of above-mentioned phenols and aldehydes.As acid catalyst, be not particularly limited, such as, the organic carboxyl acid such as oxalic acid, acetic acid etc. can be enumerated.Separately or can be mixed two or more use from these.The use amount of acid catalyst is not particularly limited, and is preferably 0.01 ~ 5 % by weight relative to above-mentioned phenols.In addition, when photoresist resin is used for photo-corrosion-resisting agent composition, in order to prevent the interference to photoresist characteristic, preferably residual in resin catalyzer is a small amount of.Certainly, common removing method (neutralization, washing, metre filter etc.) can be utilized in the process of synthetic resin to remove catalyzer.
In addition, as the reaction dissolvent that manufacture photoresist resin combination of the present invention uses, preferred appropriate nonpolar solvent, such as, can enumerate hexane, benzene, dimethylbenzene etc.
As the phenolics that manufacture photoresist resin combination of the present invention uses, preferably by GPC(GelPermeationChromatography) weight-average molecular weight that measures is 1000 ~ 20000 daltonian phenolics, further preferable weight-average molecular weight is 3000 ~ 10000 dalton.By the weight-average molecular weight of the phenolics of use in above-mentioned scope, thus the light sensitivity of photoresist resin combination, thermotolerance, residual film ratio can be made to be best.
Above-mentioned weight-average molecular weight calculates based on the calibration curve using polystyrene standards matter to make.It can be eluting solvent with tetrahydrofuran that GPC measures, under the condition of flow 1.0ml/min, column temperature 40 DEG C, differential refractometer is used as detecting device implements.The device that can use, such as, can use respectively
1) main body: TOSOH Inc. " HLC-8020 "
2) detecting device: the TOSOH Inc. " UV-8011 " being set to wavelength 280nm
3) analysis post: Showa electrician Inc. " SHODEXKF-802, KF-803, KF-805 ".
Manufacturing the cyclic olefin resin that photoresist resin combination of the present invention uses is the resin in its main chain with cyclic olefin structure, owing to having the upright and outspoken structure directly linked at the chain length direction of polymkeric substance from the ring structure of cyclic olefin, so have high glass-transition temperature.In such resin, from the view point of the performance of the photo-corrosion-resisting agent composition obtained, preferred norbornene resin.As the structure of norbornene resin, such as, can enumerate the structure represented by general formula (1).As the functional group on norbornene resin, suitably can select according to the application target of the photo-corrosion-resisting agent composition obtained, can use without particular limitation.
At this, in formula (1), X is O, CH
2, CH
2cH
2in any one, n is the integer of 0 ~ 5, R
1~ R
4be selected from hydrogen or can the monovalent organic group of carbon number 1 ~ 30 containing O and/or F in its structure, R independently of one another
1~ R
4can be different in the repetition of monomer, but at the R of whole repetitive
1~ R
4in, at least one has acidic-group.
Give the acidic-group of alkali-soluble as to resin, can enumerate carboxyl, phenolic group, fluoro alcohol radical, sulfoamido etc., what can import in these groups is one kind or two or more.Wherein, the phenolic group presenting high-contrast and high residual film ratio can particularly preferably be expected by the interaction with photosensitizer.
Usually used as the example of the synthetic method of these resins, can enumerate the cyclic olefin represented with general formula (2) is that monomer is polymerized.
At this, in formula (2), X is O, CH
2, CH
2cH
2in any one, n is the integer of 0 ~ 5, R
1~ R
4be selected from hydrogen or can the monovalent organic group of carbon number 1 ~ 30 containing O and/or F in its structure, R independently of one another
1~ R
4can be different in the repetition of monomer, but at the R of whole repetitive
1~ R
4in, at least one has acidic-group.As acidic-group, can enumerate carboxyl, phenolic group, fluoro alcohol radical, sulfoamido, what can import in these groups is one kind or two or more.
As the concrete example of the cyclic olefin monomers used in the present invention, such as, can enumerate dicyclo [2.2.1] hept-2-ene"-5-carboxylic acid, Fourth Ring [4.4.0.1
2,5.1
7,10] 12-3-alkene-8-carboxylic acids, 8-methyl Fourth Ring [4.4.0.1
2,5.1
7,10] 12-3-alkene-8-carboxylic acids, (dicyclo [2.2.1] hept-2-ene"-5-base) acetic acid, 2-(dicyclo [2.2.1] hept-2-ene"-5-base) propionic acid, 3-(dicyclo [2.2.1] hept-2-ene"-5-base) butyric acid, 3-(dicyclo [2.2.1] hept-2-ene"-5-base) valeric acid, 3-(dicyclo [2.2.1] hept-2-ene"-5-base) caproic acid, mono succinate-(2-(dicyclo [2.2.1] hept-2-ene"-5-base) ketonic oxygen ethyl) ester, mono succinate-(2-(dicyclo [2.2.1] hept-2-ene"-5-base) ketonic oxygen propyl group) ester, mono succinate-(2-(dicyclo [2.2.1] hept-2-ene"-5-base) ketonic oxygen butyl) ester, phthalic acid list-(2-(dicyclo [2.2.1] hept-2-ene"-5-base) ketonic oxygen ethyl) ester, caproic acid list-(2-(dicyclo [2.2.1] hept-2-ene"-5-base) ketonic oxygen butyl) ester, (dicyclo [2.2.1] hept-2-ene"-5-base) ketonic oxygen acetic acid, 2-(dicyclo [2.2.1] hept-2-ene"-5-base) methylphenol, 3-(dicyclo [2.2.1] hept-2-ene"-5-base) methylphenol, 4-(dicyclo [2.2.1] hept-2-ene"-5-base) methylphenol, 4-(dicyclo [2.2.1] hept-2-ene"-5-base) phenol, 4-(dicyclo [2.2.1] hept-2-ene"-5-base) methyl pyrocatechol, 3-methoxyl-4-(dicyclo [2.2.1] hept-2-ene"-5-base) methylphenol, 3-methoxyl-2-(dicyclo [2.2.1] hept-2-ene"-5-base) methylphenol, 2-(dicyclo [2.2.1] hept-2-ene"-5-base) methylresorcinol, two (trifluoromethyl)-2-(dicyclo [2.2.1] hept-2-ene"-5-base of 1,1-) ethanol, two (trifluoromethyl)-3-(dicyclo [2.2.1] hept-2-ene"-5-base of 1,1-) propyl alcohol, two (trifluoromethyl)-4-(dicyclo [2.2.1] hept-2-ene"-5-base of 1,1-) butanols, two (trifluoromethyl)-5-(dicyclo [2.2.1] hept-2-ene"-5-base of 1,1-) amylalcohol, two (trifluoromethyl)-6-(dicyclo [2.2.1] hept-2-ene"-5-base of 1,1-) hexanol etc., be not limited to these structures.
Or, after the cyclic olefin monomers without acidic-group also can be used to replace the cyclic olefin monomers represented by general formula (2) to carry out same polymerization, in its residue, import acidic-group by high molecular weight reactive and obtain.Or, also can use ionogenic hydrogen atom in the acidic-group that to be instead of by other structure in the cyclic olefin monomers represented by general formula (2) and the monomer obtained, after its addition polymerization, import original hydrogen atom by carrying out deprotection and obtain.The recovery of the acidic-group utilizing deprotection to carry out can utilize conventional method to carry out.
The acidic-group equivalent at side chain with the cyclic olefin resin of acidic-group that manufacture as photoresist resin combination of the present invention uses, different according to its molecular structure, therefore be not particularly limited at this, be preferably less than 600g/ mole, be more preferably less than 400g/ mole.If acidic-group equivalent is below afore mentioned rules value, then dissolve in the inorganic base such as NaOH, potassium hydroxide, ammoniacal liquor used when developing, the aqueous solution of organic bases such as Tetramethylammonium hydroxide, ethamine, triethylamine, triethanolamine class.If acidic-group equivalent is greater than above-mentioned higher limit, be then difficult to be presented on the dissolubility in above-mentioned alkaline aqueous solution, be difficult to carry out pattern processing.The amount of the acidic-group in resin can be measured by the titration etc. of the resin solution using standard alkali solution.
The acidic-group equivalent of the resin obtained can by the molecular structure with the monomer of acidic-group of choice for use or change the monomer with acidic-group with do not have acidic-group monomer existence ratio and carry out copolymerization etc. and control.
As the method manufacturing cyclic olefin resin, known method can be suitable for.Such as, the nickel compound of coordination polymerization catalysts or palladium compound etc. can be used as to carry out addition polymerization.As the example of nickel compound, such as, can enumerate by chemical formula: E
nni(C
6f
5)
2the such catalyzer represented, in this chemical formula, n represents 1 or 2, and E represents neutral ligand.When n is 1, π-arene ligand that the preferred toluene of E, benzene and sym-trimethyl benzene are such.When n is 2, E is preferably selected from ether, THF(tetrahydrofuran), ethyl acetate and two
alkane.Such as can enumerate (toluene) two (perfluorophenyl) nickel, (sym-trimethyl benzene) two (perfluorophenyl) nickel, (benzene) two (perfluorophenyl) nickel, two (tetrahydrofuran) two (perfluorophenyl) nickel, two (ethyl acetate) two (perfluorophenyl) nickel and two (two
alkane) two (perfluorophenyl) nickel etc.Detailed content describes in PCTWO97/33198, PCTWO00/20472, Japanese Unexamined Patent Application Publication 2010-523766 publication, Japanese Kohyo 11-505880 publication etc.
As the preferred polymer solvent used in these polymerizations, comprise hydrocarbon, aromatic solvent.As the example of hydrocarbon solvent, pentane, hexane, heptane etc. can be enumerated, but be not limited to these.In addition, as the example of aromatic solvent, be toluene, dimethylbenzene, sym-trimethyl benzene etc., be also not limited to these.In addition, also tetrahydrofuran, ether, ethyl acetate, lactone, ketone etc. can be used.These solvents can be used alone one, in addition, also can mix more than two kinds and be used as polymer solvent use.
For the polymerization of the monomer contained in photoresist resin combination of the present invention, such as, can by changing the ratio of catalyzer and monomer or polymerization temperature, the molecular weight of resin that obtains in controlling to be polymerized of the polarity etc. of polymer solvent.In addition, can by adding suitable chain-transferring agent to control the molecular weight of the resin obtained in polymerization.
The weight-average molecular weight of the cyclic olefin resin used in the manufacture of photoresist resin combination of the present invention is 1000 ~ 500000 dalton.If weight-average molecular weight is greater than above-mentioned scope, then add man-hour at its light, resin combination reduces the dissolubility of alkaline aqueous solution, possibly cannot obtain good light processability.On the other hand, if weight-average molecular weight is less than above-mentioned lower limit, then possibly fully cannot obtain the performance enhancing effects produced because of interpolation.
As the use level of cyclic olefin resin relative to phenolics, be preferably 1 ~ 90 % by weight, be more preferably 5 ~ 50 % by weight.Addition can improve the degree of effect according to desired thermotolerance and at random set, if but addition is too much, then may reduce the character such as the light sensitivity that phenolics has.On the other hand, if addition is very few, then the raising effect of thermotolerance is insufficient sometimes.
The photosensitizer used in the manufacture of photo-corrosion-resisting agent composition of the present invention is the compound containing naphthoquinones diazido.As the compound containing naphthoquinones diazido, such as, can enumerate
(1) 2, 3, 4-trihydroxybenzophenone, 2, 4, 4 '-trihydroxybenzophenone, 2, 4, 6-trihydroxybenzophenone, 2, 3, 6-trihydroxybenzophenone, 2, 3, 4-trihydroxy-2 '-methyl benzophenone, 2, 3, 4, 4 '-tetrahydroxybenzophenone, 2, 2 ', 4, 4 '-tetrahydroxybenzophenone, 2, 3 ', 4, 4 ', 6-pentahydroxybenzophenone, 2, 2 ', 3, 4, 4 '-pentahydroxybenzophenone, 2, 2 ', 3, 4, 5-pentahydroxybenzophenone, 2, 3 ', 4, 4 ', 5 ', 6-hexahydroxy benzophenone, 2, 3, 3 ', 4, 4 ', the polyhydroxy benzophenone classes such as 5 '-hexahydroxy benzophenone,
(2) two (2, 4-dihydroxy phenyl) methane, two (2, 3, 4-trihydroxy phenyl) methane, 2-(4-hydroxy phenyl)-2-(4 '-hydroxy phenyl) propane, 2-(2, 4-dihydroxy phenyl)-2-(2 ', 4 '-dihydroxy phenyl) propane, 2-(2, 3, 4-trihydroxy phenyl)-2-(2 ', 3 ', 4 '-trihydroxy phenyl) propane, 4, 4 '-1-4-(2-(4-hydroxy phenyl)-2-propyl group) and phenyl ］ ethylidene } bis-phenol, 3, two ［ (many) hydroxy phenyls ］ alkanes such as 3 '-dimethyl-{ 1-［ 4-(2-(3-methyl-4-hydroxy phenyl)-2-propyl group) phenyl ］ ethylidene } bis-phenol,
(3) three (4-hydroxy phenyl) methane, two (4-hydroxyl-3,5-3,5-dimethylphenyl)-4-hydroxy phenyl methane, two (4-hydroxyl-2,5-3,5-dimethylphenyl)-4-hydroxy phenyl methane, two (4-hydroxyl-3,5-3,5-dimethylphenyl)-2-hydroxy phenyl methane, two (4-hydroxyl-2,5-3,5-dimethylphenyl)-2-hydroxy phenyl methane, two (4-hydroxyl-2,5-3,5-dimethylphenyl)-3,4-dihydroxy benzenes methylmethane, two (4-hydroxyl-3,5-3,5-dimethylphenyl)-3, three (hydroxy phenyl) methane class or its methyl substituted bodies such as 4-dihydroxy benzenes methylmethane
(4) two (3-cyclohexyl-4-hydroxy phenyl)-3-hydroxy phenyl methane, two (3-cyclohexyl-4-hydroxy phenyl)-2-hydroxy phenyl methane, two (3-cyclohexyl-4-hydroxy phenyl)-4-hydroxy phenyl methane, two (5-cyclohexyl-4-hydroxy-2-methyl phenyl)-2-hydroxy phenyl methane, two (5-cyclohexyl-4-hydroxy-2-methyl phenyl)-3-hydroxy phenyl methane, two (5-cyclohexyl-4-hydroxy-2-methyl phenyl)-4-hydroxy phenyl methane, two (3-cyclohexyl-2-hydroxy phenyl)-3-hydroxy phenyl methane, two (5-cyclohexyl-4-hydroxy-3-methyl phenyl)-4-hydroxy phenyl methane, two (5-cyclohexyl-4-hydroxy-3-methyl phenyl)-3-hydroxy phenyl methane, two (5-cyclohexyl-4-hydroxy-3-methyl phenyl)-2-hydroxy phenyl methane, two (3-cyclohexyl-2-hydroxy phenyl)-4-hydroxy phenyl methane, two (3-cyclohexyl-2-hydroxy phenyl)-2-hydroxy phenyl methane, two (5-cyclohexyl-2-hydroxy-4-methyl phenyl)-2-hydroxy phenyl methane, two (cyclohexyl hydroxy phenyl) (hydroxy phenyl) methane class or its methyl substituted body etc. such as two (5-cyclohexyl-2-hydroxy-4-methyl phenyl)-4-hydroxy phenyl methane and naphthoquinones-1, the complete ester compounds of the sulfonic acid containing quinone diazido such as 2-diazido-5-sulfonic acid or naphthoquinones-1,2-diazido-4-sulfonic acid, partial esterification compound, amidate or partial amides compound etc.
At this, as the above-mentioned chemical composition containing naphthoquinones diazido, separately containing a kind of, also can be contained two or more.
In resin combination of the present invention, as the use level of photosensitizer, be not particularly limited, relative to phenolics 100 weight portion, usually at 5 ~ 100 weight portions, preferably can coordinate in the scope of 10 ~ 50 weight portions.If the use level of photosensitizer is less than above-mentioned lower limit, be then sometimes difficult to the image obtaining faithful to pattern, transferability reduces.On the other hand, if be greater than above-mentioned higher limit, then sometimes can find out that light sensitivity reduces as photoresist.
The solvent coordinated in composition of the present invention, is just not particularly limited as long as can dissolve above-mentioned phenolics, cyclic olefin resin and the compound containing naphthoquinones diazido.In the present invention, these component dissolves are used in solvent.The solvent used in manufacture as photo-corrosion-resisting agent composition of the present invention, following solvents can be used alone or as a mixture: METHYLPYRROLIDONE, gamma-butyrolacton, N, N-dimethyl acetamide, dimethyl sulfoxide (DMSO), diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dibutyl ethylene glycol ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol methyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl isophthalic acid, 3-butylene glycol acetic acid esters, 1, 3-butylene glycol 20-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, 3-methoxy methyl propionate etc.
Should illustrate, in composition of the present invention, except composition described above, the various adjuvants such as the stabilizing agents such as antioxidant, plastifier, surfactant, adaptation improving agent, dissolution accelerator can also be used as required.
As the preparation method of composition of the present invention, be not particularly limited, when not adding packing material, pigment in composition, can be only with usual way mix and blend mentioned component, when adding packing material, pigment, such as, the diverting devices such as dissolver, homogenizer, three-roll grinder can be used to carry out disperseing, mixing.In addition, as required, can granular membrane, membrane filter etc. be used further to filter.
For the composition of the present invention obtained like this, by exposing via mask, thus in the change of exposure portion composition recurring structure, the dissolubility in alkaline developer can be promoted.On the other hand, owing to remaining on the low-solubility in alkaline developer in non-exposed portion, so function against corrosion can be given by the difference of consequent dissolubility.
When composition of the present invention is used as photoresist, the compound generation chemical change containing naphthoquinones diazido by the irradiation of light in composition, in follow-up developing procedure, together alkaline-based developer is dissolved in novolac resin, between unexposed part, produce clear and definite dissolution velocity poor, target pattern can be obtained by development thus.
Below, by synthesis example and embodiment, the present invention is described.But, the invention is not restricted to these synthesis examples and embodiment.In addition, " part " and " % " of recording in synthesis example, embodiment and comparative example all represents " weight portion " and " % by weight ".But, except the concentration (%) of formlinata aquae concentratac.
Embodiment
1. the synthesis of phenolics
(synthesis example 1)
Possess stirring apparatus, thermometer, heat exchanger 3L four-hole boiling flask in load 600g metacresol, 400g paracresol, 37% formalin 527g, oxalic acid 5g, under reflux conditions react 4 hours.Thereafter, dehydration is to interior temperature 170 DEG C at ambient pressure, further 9.3 × 10
3carry out dehydration demonomerization to 200 DEG C under the decompression of Pa, obtain the daltonian phenolics of 950g weight-average molecular weight 4200.
2. the synthesis of cyclic olefin resin
(synthesis example 2)
Load in the reaction vessel possessing stirring apparatus [4-(2-dicyclo [2.2.1]-5-in heptan alkene) phenyl] acetic acid esters (11.4g, 50mmol), toluene (17.6g) and methyl ethyl ketone (27.4g), inner with drying nitrogen displacement.Heating content, adds (η when interior temperature reaches 50 DEG C
6-toluene) Ni(C
6f
5)
2(0.97g, 2.00mmol) is dissolved in the solution of 10g toluene.React after 3 hours at 50 DEG C, be cooled to room temperature.Add THF(50g) and 10% potassium hydroxide aqueous solution (80g), back flow reaction 5 hours.Thereafter, add acetic acid and neutralize, then implement the washing operation utilizing ion exchange water for 3 times.After evaporator concentration of organic layers, precipitate again with hexane.By late with the vacuum drier dry of 60 DEG C for the solid obtained, obtain 8.2g pale yellow powder.Utilize GPC to measure, the molecular weight of the polymkeric substance obtained is Mw=11000, Mn=5300.
(synthesis example 3)
By 3-methoxyl-4-(dicyclo [2.2.1] hept-2-ene"-5-base) methylphenol (5.0g, 18.4mmol), 3-(3-dicyclo [2.2.1]-5-in heptan alkene) ethyl propionate (0.89g, 4.59mmol), toluene (28g) and methyl ethyl ketone (10g) loading possess in the reaction vessel of stirring apparatus, with drying nitrogen displacement inside.Heating content, adds (η when interior temperature reaches 60 DEG C
6-toluene) Ni(C
6f
5)
2(0.22g, 0.46mmol) is dissolved in the solution of 5g toluene.React after 3 hours at 60 DEG C, be cooled to room temperature.Add THF(50g) and 10% potassium hydroxide aqueous solution (50g), back flow reaction 5 hours.Thereafter, add acetic acid and neutralize, then implement the washing operation utilizing ion exchange water for 3 times.After evaporator concentration of organic layers, precipitate again with hexane.By late with the vacuum drier dry of 60 DEG C for the solid obtained, obtain 8.2g pale yellow powder.Utilize GPC to measure, the molecular weight of the polymkeric substance obtained is Mw=16000, Mn=9000.
(synthesis example 4)
By 3-(3-dicyclo [2.2.1]-5-in heptan alkene) ethyl propionate (37.3g, 0.19mol), 1, two (trifluoromethyl)-2-(dicyclo [2.2.1] hept-2-ene"-5-base of 1-) ethanol (13.2g, 0.05mol), toluene (55g), triethyl silicane (1.4g), ethyl acetate (13g), dimethyl puratized agricultural spray four (pentafluorophenyl group) borate (0.06g, 0.07mmol) loading possesses in the reaction vessel of stirring apparatus, inner with drying nitrogen displacement.Heating content, when interior temperature reaches 100 DEG C, adds ethyl acetate (6g) solution that (acetonitrile) two (tri isopropyl phosphine) closes palladium (acetic acid esters) (pentafluorophenylboronic acid ester) (0.03g, 0.02mmol).Be cooled to room temperature 100 DEG C of reactions after 16 hours, add THF and 10% potassium hydroxide aqueous solution (300g), back flow reaction 5 hours.Thereafter, add acetic acid and neutralize, then implement the washing operation utilizing ion exchange water for 3 times.After evaporator concentration of organic layers, precipitate again with hexane.By late with the vacuum drier dry of 60 DEG C for the solid obtained, obtain 27g white powder.Utilize GPC to measure, the molecular weight of the polymkeric substance obtained is Mw=8200, Mn=4200.
(synthesis example 5)
By 1, two (trifluoromethyl)-2-(dicyclo [2.2.1] hept-2-ene"-5-base of 1-) ethanol (9.9g, 0.036mol), dicyclo [2.2.1] hept-2-ene"-5-carboxylic acid trimethyl silyl ester (2.2g, 0.012mol), the loading of ethyl acetate (100g), cyclohexane (100g) possesses in the reaction vessel of stirring apparatus, with drying nitrogen displacement inside.Heating content, adds (allyl) when interior temperature reaches 100 DEG C and closes methylene chloride (2g) solution of palladium (tricyclohexyl phosphine) trifluoro-acetate (0.006g, 0.008mmol) and toluene (2g) solution of 0.034g tetra-(pentafluorophenyl group) lithium borate.Further interpolation 1-hexene (2.6g, 0.03mol), reacts after 5 hours and is cooled to room temperature at 20 DEG C.The polymkeric substance obtained is fed in methyl alcohol, sediment is condensed, after fully cleaning with water, dry under vacuo, obtain 7.8g white powder.Utilize GPC to measure, the molecular weight of the polymkeric substance obtained is Mw=12200, Mn=6100.
(synthesis example 6)
5-butyl dicyclo [2.2.1] hept-2-ene" (13.0g, 0.087mol), toluene (18g) and methyl ethyl ketone (11g) being loaded possesses in the reaction vessel of stirring apparatus, inner with drying nitrogen displacement.Content is heated, when interior temperature arrives 60 DEG C, adds (η
6-toluene) Ni(C
6f
5)
2(0.42g, 0.87mmol) is dissolved in the solution of 10g toluene.React after 3 hours at 60 DEG C, be cooled to room temperature.By reacted solubilize in 300g hexane, implement the washing operation utilizing ion exchange water for 3 times.After evaporator concentration of organic layers, precipitate again with methyl alcohol, obtain white solid.By late with the vacuum drier dry of 60 DEG C for the solid obtained, obtain 7.5g white powder.Utilize GPC to measure, the molecular weight of the polymkeric substance obtained is Mw=31000, Mn=14000.
4. the preparation of photoresist composition
(embodiment 1)
By obtain in the novolak phenolics obtained in 30 parts of synthesis examples 1 and 6 parts of synthesis examples 2 cyclic olefin resin, 6 part 2,3,4,4 '-tetrahydroxybenzophenone and 6-diazo-5, after the ester of 6-dihydro-5-oxo-naphthalene-1-sulfonic acid is dissolved in 150 parts of propylene glycol methyl ether acetates, the membrane filter in 1.0 μm, aperture is used to prepare photo-corrosion-resisting agent composition.
(embodiment 2)
By obtain in the novolak phenolics obtained in 30 parts of synthesis examples 1 and 15 parts of synthesis examples 2 cyclic olefin resin, 6 part 2,3,4,4 '-tetrahydroxybenzophenone and 6-diazo-5, after the ester of 6-dihydro-5-oxo-naphthalene-1-sulfonic acid is dissolved in 150 parts of propylene glycol methyl ether acetates, the membrane filter in 1.0 μm, aperture is used to prepare photo-corrosion-resisting agent composition.
(embodiment 3)
By obtain in the novolak phenolics obtained in 30 parts of synthesis examples 1 and 3 parts of synthesis examples 3 cyclic olefin resin, 6 part 2,3,4,4 '-tetrahydroxybenzophenone and 6-diazo-5, after the ester of 6-dihydro-5-oxo-naphthalene-1-sulfonic acid is dissolved in 150 parts of propylene glycol methyl ether acetates, the membrane filter in 1.0 μm, aperture is used to prepare photo-corrosion-resisting agent composition.
(embodiment 4)
By obtain in the novolak phenolics obtained in 30 parts of synthesis examples 1 and 6 parts of synthesis examples 4 cyclic olefin resin, 6 part 2,3,4,4 '-tetrahydroxybenzophenone and 6-diazo-5, after the ester of 6-dihydro-5-oxo-naphthalene-1-sulfonic acid is dissolved in 150 parts of propylene glycol methyl ether acetates, the membrane filter in 1.0 μm, aperture is used to prepare photo-corrosion-resisting agent composition.
(embodiment 5)
By obtain in the novolak phenolics obtained in 30 parts of synthesis examples 1 and 6 parts of synthesis examples 5 cyclic olefin resin, 6 part 2,3,4,4 '-tetrahydroxybenzophenone and 6-diazo-5, after the ester of 6-dihydro-5-oxo-naphthalene-1-sulfonic acid is dissolved in 150 parts of propylene glycol methyl ether acetates, the membrane filter in 1.0 μm, aperture is used to prepare photo-corrosion-resisting agent composition.
(embodiment 6)
By obtain in the novolak phenolics obtained in 30 parts of synthesis examples 1 and 3 parts of synthesis examples 6 cyclic olefin resin, 6 part 2,3,4,4 '-tetrahydroxybenzophenone and 6-diazo-5, after the ester of 6-dihydro-5-oxo-naphthalene-1-sulfonic acid is dissolved in 150 parts of propylene glycol methyl ether acetates, the membrane filter in 1.0 μm, aperture is used to prepare photo-corrosion-resisting agent composition.
(comparative example 1)
By obtain in 30 parts of synthesis examples 1 novolak phenolics, 6 part 2,3,4,4 '-tetrahydroxybenzophenone and 6-diazo-5, after the ester of 6-dihydro-5-oxo-naphthalene-1-sulfonic acid is dissolved in 150 parts of propylene glycol methyl ether acetates, the membrane filter in 1.0 μm, aperture is used to prepare photo-corrosion-resisting agent composition.
Evaluating characteristics shown in have used the photo-corrosion-resisting agent composition obtained in embodiment 1 ~ 5 and comparative example 1 ~ 2 to carry out following.Show the result in table 1.
Table 1
5. the evaluation method of characteristic
(1) evaluation method of thermotolerance
Be coated on the silicon wafer of hexamethyldisilazane process with the mode spin coating instrument that thickness during drying is 1.5 μm, at 110 DEG C, dry 90 seconds on hot plate.Thereafter, use reduced projection exposure device, expose via test pattern mask, use developer solution (tetramethylammonium hydroxide aqueous solution of 2.38%) to develop for 60 seconds.The silicon wafer obtained is placed on hot plate upper 3 minute changing temperature, observes the shape of the corrosion-resisting pattern on silicon wafer with scanning electron microscope, temperature when cannot obtain normal corrosion-resisting pattern is as heat resisting temperature.
(2) residual film ratio assay method
With spin coating instrument, photo-corrosion-resisting agent composition is coated on 3 inch silicon wafer in the mode of the thickness becoming about 1 μm, dry 100 seconds on the hot plate of 110 DEG C.This water immersion after 60 seconds, is cleaned with water, dry 100 seconds on the hot plate of 110 DEG C in developer solution (tetramethylammonium hydroxide aqueous solution of 2.38%).The ratio of thickness before thickness after development and development is represented with percent, as residual film ratio.Thus, the known degree as the residual film (patience) when photosensitizer and photoresist, numerical value higher expression residual film ratio is higher.
(3) assay method of light sensitivity
With spin coating instrument, photo-corrosion-resisting agent composition is coated on 3 inch silicon wafer in the mode of the thickness becoming about 1 μm, dry 100 seconds on the hot plate of 110 DEG C.Then, on this silicon wafer, overlap test figure mask, irradiates 20mJ/cm respectively
2, 40mJ/cm
2, 60mJ/cm
2ultraviolet, use developer solution (tetramethylammonium hydroxide aqueous solution of 2.38%) developed for 90 seconds.By observing pattern form to the pattern scanning electron microscope obtained, evaluate with following benchmark.
A:20mJ/cm
2below image can be formed.
B: be greater than 20mJ/cm
2and 40mJ/cm
2below image can be formed.
C: be greater than 40mJ/cm
2and 60mJ/cm
2below image can be formed.
(4) mensuration of resolution
Use spin coating instrument by the coating of the photo-corrosion-resisting agent composition of above-mentioned preparation on silicon, in prebake 100 second at 110 DEG C, define the etchant resist of thickness 1.5 μm.Via the pattern mask being carved with 100 ~ 1 μm of line widths, ultraviolet is used to expose it.After exposure, utilize the tetramethylammonium hydroxide aqueous solution of 2.38wt% to develop for 60 seconds at 23 DEG C immediately, carry out washing, dry, obtain eurymeric pattern.Now, using the size of the minimum photoresist pattern with constant exposure amount exploring as resolution.
Can be proved by the result of table 1, embodiment 1 ~ 5 is photoresist resin combinations of the present invention, compared with not being the comparative example 1 ~ 2 of resin combination of the present invention, having excellent residual film ratio, light sensitivity and has thermotolerance especially.
Utilizability in industry
Due to photoresist resin combination of the present invention, there is good thermal stability and there is ISO high resolving power and the residual film of height, so the manufacture of fine circuits of liquid crystal indicator circuit, SIC (semiconductor integrated circuit) can be applicable to.
Claims (10)
1. a photoresist resin combination, is characterized in that, containing novolak phenolics, cyclic olefin resin and by the photosensitizer formed containing the compound of naphthoquinones diazido, wherein, described cyclic olefin resin is norbornene resin.
2. photoresist resin combination according to claim 1, wherein, described cyclic olefin resin is the cyclic olefin resin containing the repetitive represented by following general formula (1),
In formula (1), X is O, CH
2, CH
2cH
2in any one, n is the integer of 0 ~ 5, R
1~ R
4be selected from hydrogen independently of one another or can the monovalent organic group of carbon number 1 ~ 30 containing O and/or F in its structure, R
1~ R
4can be different in the repetition of monomer, but at the R of whole repetitive
1~ R
4in, at least one has acidic-group.
3. photoresist resin combination according to claim 2, wherein, described acidic-group is the group of more than 1 be selected from carboxyl, phenolic group, fluoro alcohol radical and sulfoamido.
4. the photoresist resin combination according to Claims 2 or 3, wherein, described acidic-group has phenolic group.
5. the etch-resist resin composition according to any one of claims 1 to 3, wherein, the weight-average molecular weight of described cyclic olefin resin is 1000 ~ 500000 dalton.
6. etch-resist resin composition according to claim 4, wherein, the weight-average molecular weight of described cyclic olefin resin is 1000 ~ 500000 dalton.
7. the etch-resist resin composition according to any one of claims 1 to 3, wherein, described cyclic olefin resin is 1 ~ 90 % by weight relative to the mixture ratio of described phenolics.
8. etch-resist resin composition according to claim 4, wherein, described cyclic olefin resin is 1 ~ 90 % by weight relative to the mixture ratio of described phenolics.
9. etch-resist resin composition according to claim 5, wherein, described cyclic olefin resin is 1 ~ 90 % by weight relative to the mixture ratio of described phenolics.
10. etch-resist resin composition according to claim 6, wherein, described cyclic olefin resin is 1 ~ 90 % by weight relative to the mixture ratio of described phenolics.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-190880 | 2010-08-27 | ||
| JP2010190880 | 2010-08-27 | ||
| PCT/JP2011/068975 WO2012026465A1 (en) | 2010-08-27 | 2011-08-23 | Resin composition for photoresist |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103069339A CN103069339A (en) | 2013-04-24 |
| CN103069339B true CN103069339B (en) | 2015-11-25 |
Family
ID=45723459
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180040734.7A Expired - Fee Related CN103069339B (en) | 2010-08-27 | 2011-08-23 | Photoresist resin combination |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5692232B2 (en) |
| KR (1) | KR101830459B1 (en) |
| CN (1) | CN103069339B (en) |
| TW (1) | TWI505022B (en) |
| WO (1) | WO2012026465A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150102132A (en) | 2014-02-27 | 2015-09-07 | 삼성디스플레이 주식회사 | Complex substrate for display apparatus, display apparatus having the same and method of manufacturing the same |
| JP2015184325A (en) * | 2014-03-20 | 2015-10-22 | 住友ベークライト株式会社 | Photosensitive resin composition and electronic device |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1237719A (en) * | 1998-06-02 | 1999-12-08 | 住友化学工业株式会社 | Positive resist composition |
| CN1292002A (en) * | 1998-02-23 | 2001-04-18 | B.F.谷德里奇公司 | Polycyclic resist composition with increased etch resistance |
| JP2002508415A (en) * | 1997-12-15 | 2002-03-19 | クラリアント・インターナシヨナル・リミテッド | Separated novolak resin and photoresist composition obtained therefrom |
| WO2006129875A1 (en) * | 2005-06-01 | 2006-12-07 | Zeon Corporation | Radiation-sensitive resin composition, layered product, and process for producing the same |
| CN101427382A (en) * | 2006-06-07 | 2009-05-06 | 住友电木株式会社 | Method for manufacturing light receiving apparatus |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE602005011017D1 (en) * | 2004-07-07 | 2008-12-24 | Promerus Llc | LENS-SENSITIVE DIELECTRIC RESIN COMPOSITIONS AND ITS USES |
| JP4748324B2 (en) * | 2007-03-22 | 2011-08-17 | Ｊｓｒ株式会社 | Radiation-sensitive resin composition, interlayer insulating film, microlens and manufacturing method thereof |
-
2011
- 2011-08-23 WO PCT/JP2011/068975 patent/WO2012026465A1/en active Application Filing
- 2011-08-23 KR KR1020137004083A patent/KR101830459B1/en active IP Right Grant
- 2011-08-23 CN CN201180040734.7A patent/CN103069339B/en not_active Expired - Fee Related
- 2011-08-23 JP JP2012530677A patent/JP5692232B2/en not_active Expired - Fee Related
- 2011-08-26 TW TW100130624A patent/TWI505022B/en active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002508415A (en) * | 1997-12-15 | 2002-03-19 | クラリアント・インターナシヨナル・リミテッド | Separated novolak resin and photoresist composition obtained therefrom |
| CN1292002A (en) * | 1998-02-23 | 2001-04-18 | B.F.谷德里奇公司 | Polycyclic resist composition with increased etch resistance |
| CN1237719A (en) * | 1998-06-02 | 1999-12-08 | 住友化学工业株式会社 | Positive resist composition |
| WO2006129875A1 (en) * | 2005-06-01 | 2006-12-07 | Zeon Corporation | Radiation-sensitive resin composition, layered product, and process for producing the same |
| CN101427382A (en) * | 2006-06-07 | 2009-05-06 | 住友电木株式会社 | Method for manufacturing light receiving apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012026465A1 (en) | 2012-03-01 |
| JP5692232B2 (en) | 2015-04-01 |
| CN103069339A (en) | 2013-04-24 |
| KR20130100989A (en) | 2013-09-12 |
| TW201211690A (en) | 2012-03-16 |
| JPWO2012026465A1 (en) | 2013-10-28 |
| TWI505022B (en) | 2015-10-21 |
| KR101830459B1 (en) | 2018-02-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI694098B (en) | Resin composition, photosensitive resin composition, resin film, and electronic device | |
| CN102365268B (en) | The the offending and disobeying with rude remarks reflection coating composition and utilize photoresist agent composition and the formation method of said composition of self-forming | |
| TWI711655B (en) | Resin and resist film containing phenolic hydroxyl group | |
| TWI591432B (en) | Photoresist composition, photoresist and manufacturing of liquid crystal device | |
| CN107797384B (en) | Photosensitive resin, positive photoresist and application | |
| CN103329042B (en) | Photoresist resin combination | |
| JP2013189531A (en) | Method for producing novolac-type phenolic resin, novolac-type phenolic resin, and photoresist composition | |
| CN103069339B (en) | Photoresist resin combination | |
| EP0677068B1 (en) | Using a lewis base to control molecular weight of novolak resins | |
| JP4101670B2 (en) | Positive photoresist composition for LCD production and method for forming resist pattern | |
| KR20200051748A (en) | Phenolic resin composition for photoresist and photoresist composition | |
| EP0873368B1 (en) | Acidic ion exchange resin as a catalyst to synthesize a novolak resin and photoresist composition therefrom | |
| EP1042381A1 (en) | Fractionated novolak resin and photoresist composition therefrom | |
| JP2010230850A (en) | Resin composition for photoresist | |
| KR102012053B1 (en) | Photoresist resin composition | |
| JP6031905B2 (en) | Method for producing novolac type phenol resin, method for producing resin composition for photoresist, and method for producing liquid crystal device | |
| JP2009075436A (en) | Photoresist resin composition | |
| EP0865455B1 (en) | Isolation of novolak resin without high temperature distillation and photoresist composition therefrom | |
| JP4929733B2 (en) | Method for producing novolac type phenolic resin | |
| EP0948552B1 (en) | Method for producing a water insoluble, aqueous alkali soluble novolak resin | |
| CN117751327A (en) | Positive photosensitive resin composition containing specific copolymer | |
| KR101253351B1 (en) | Process for preparing of novolak type phenolic resin, novolak type phenolic resin and phenolic resin composition for photo resist | |
| JP2020055955A (en) | Novolak type phenolic resin, photosensitive resin composition and manufacturing method of novolak type phenolic resin | |
| JP2013186233A (en) | Photoresist resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151125 Termination date: 20200823 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |