CN111123649A - Negative photoresist composition containing high-heat-resistance carboxyl phenolic resin - Google Patents
Negative photoresist composition containing high-heat-resistance carboxyl phenolic resin Download PDFInfo
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- CN111123649A CN111123649A CN202010009705.5A CN202010009705A CN111123649A CN 111123649 A CN111123649 A CN 111123649A CN 202010009705 A CN202010009705 A CN 202010009705A CN 111123649 A CN111123649 A CN 111123649A
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- negative photoresist
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 46
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 28
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 22
- 239000000203 mixture Substances 0.000 title claims abstract description 21
- -1 carboxyl phenolic resin Chemical compound 0.000 title claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- 239000000654 additive Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 230000000996 additive effect Effects 0.000 claims abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 claims description 12
- 238000010791 quenching Methods 0.000 claims description 11
- 230000000171 quenching effect Effects 0.000 claims description 11
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 6
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 3
- MLIWQXBKMZNZNF-UHFFFAOYSA-N 2,6-bis[(4-azidophenyl)methylidene]-4-methylcyclohexan-1-one Chemical compound O=C1C(=CC=2C=CC(=CC=2)N=[N+]=[N-])CC(C)CC1=CC1=CC=C(N=[N+]=[N-])C=C1 MLIWQXBKMZNZNF-UHFFFAOYSA-N 0.000 claims description 3
- VQMBXLGTPLWJOJ-UHFFFAOYSA-N 2-amino-1,1,2-triethoxyethanol Chemical compound CCOC(N)C(O)(OCC)OCC VQMBXLGTPLWJOJ-UHFFFAOYSA-N 0.000 claims description 3
- PPPFYBPQAPISCT-UHFFFAOYSA-N 2-hydroxypropyl acetate Chemical compound CC(O)COC(C)=O PPPFYBPQAPISCT-UHFFFAOYSA-N 0.000 claims description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 3
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 3
- GOIOEVOIKOUGQA-UHFFFAOYSA-N 9-(2-methoxyethoxymethyl)anthracene Chemical compound C1=CC=C2C(COCCOC)=C(C=CC=C3)C3=CC2=C1 GOIOEVOIKOUGQA-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- BFEHYQIEGSRACK-UHFFFAOYSA-N anthracen-9-ylmethyl acetate Chemical compound C1=CC=C2C(COC(=O)C)=C(C=CC=C3)C3=CC2=C1 BFEHYQIEGSRACK-UHFFFAOYSA-N 0.000 claims description 3
- 229940116333 ethyl lactate Drugs 0.000 claims description 3
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 3
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 3
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 3
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 3
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 claims description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- QLNYTCSELYEEPV-UHFFFAOYSA-N 2,2-dimethylpropyl acetate Chemical compound CC(=O)OCC(C)(C)C QLNYTCSELYEEPV-UHFFFAOYSA-N 0.000 claims description 2
- UJXBFCQRJCHTQC-UHFFFAOYSA-N 2-(2,2,2-trimethoxyethoxymethoxy)ethanamine Chemical compound COC(OC)(OC)COCOCCN UJXBFCQRJCHTQC-UHFFFAOYSA-N 0.000 claims description 2
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002250 absorbent Substances 0.000 claims description 2
- 230000002745 absorbent Effects 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 230000009477 glass transition Effects 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 229960001124 trientine Drugs 0.000 claims description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims 8
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims 1
- KLWRBJMBBMGLMC-UHFFFAOYSA-N CC(CC1CC=CC(C=C2)=CC=C2N=[N+]=[N-])CC(CC=CC(C=C2)=CC=C2N=[N+]=[N-])C1=O Chemical compound CC(CC1CC=CC(C=C2)=CC=C2N=[N+]=[N-])CC(CC=CC(C=C2)=CC=C2N=[N+]=[N-])C1=O KLWRBJMBBMGLMC-UHFFFAOYSA-N 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 15
- 239000011347 resin Substances 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 238000012360 testing method Methods 0.000 abstract description 4
- CQKOEPBDZWNFFC-UHFFFAOYSA-N 2,6-bis[3-(4-azidophenyl)prop-2-enylidene]-4-methylcyclohexan-1-one Chemical compound O=C1C(=CC=CC=2C=CC(=CC=2)N=[N+]=[N-])CC(C)CC1=CC=CC1=CC=C(N=[N+]=[N-])C=C1 CQKOEPBDZWNFFC-UHFFFAOYSA-N 0.000 description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 4
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- XPKFJIVNCKUXOI-UHFFFAOYSA-N formaldehyde;2-hydroxybenzoic acid Chemical compound O=C.OC(=O)C1=CC=CC=C1O XPKFJIVNCKUXOI-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000001259 photo etching Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 229920000289 Polyquaternium Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Images
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
- G03F7/038—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
Abstract
The invention discloses a negative photoresist composition containing high-heat-resistance carboxyl phenolic resin. The high heat resistance carboxyl phenolic resin has a structural general formula of
Wherein x is 0-4, the ratio of m to n is 0.05-0.75:1, R is H, phenyl or C1-C9 alkyl, and the weight average molecular weight of the resin is 8000-35000 g/mol. The film-forming resin is mixed with components such as a photoacid generator, a curing agent, an additive, a solvent and the like to obtain the negative photoresist composition. Tests show that the negative photoresist composition has high resolution and good heat resistance, and is suitable for lift-off metal stripping process under high-temperature operation conditions.
Description
Technical Field
The invention relates to the technical field of functional polymer materials, in particular to a negative photoresist composition prepared by taking high-heat-resistance carboxyl phenolic resin as film-forming resin.
Background
The photoresist is widely applied to the field of microelectronic manufacturing of discrete devices, LEDs, integrated circuits, TFT-LCDs and the like, influences important fields of information engineering, energy environmental protection, national defense and public affairs and the like, and plays an important role in the development of high-tech industry and national economy. The photoresist is divided into a positive photoresist and a negative photoresist according to a developing mechanism, and after exposure, the negative photoresist is partially crosslinked by illumination so that the negative photoresist cannot be washed away during development, and conversely, the positive photoresist is used.
lift-off metal lift-off process is a delicate photolithographic etching process. After the substrate is coated with photoresist, exposed and developed, the photoresist film with a certain pattern is used as a mask, the required metal is evaporated with the photoresist, then the metal on the photoresist film is stripped off completely while the photoresist is removed, and only the metal with the original pattern is left on the substrate. The metal lift-off process has the advantages of submicron patterns, steep edges and precise pattern size, and can be generally applied to the manufacture of semiconductor devices requiring fine photoetching patterns. As the process improves, the evaporation temperature has reached 140 ℃ under special requirements, which is a challenge for conventional negative photoresist. How to improve the heat resistance of the photoresist has become an important development direction in the photoresist industry.
The photoresist mainly comprises film-forming resin, a photoacid generator, an additive, a solvent and the like, wherein the film-forming resin plays a role of a framework and determines the thermal property and the film-forming property of the photoresist. The traditional film-forming resin, namely the linear phenolic resin, has insufficient heat resistance because phenolic hydroxyl and methylene are easy to oxidize, so that the protection of the hydroxyl and the methylene becomes an important way for improving the heat resistance of the phenolic resin.
Disclosure of Invention
The invention aims to adopt high heat-resistant carboxyl phenolic resin as film-forming resin of a negative photoresist, and compared with the traditional novolac phenolic resin for the negative photoresist, the resin has more benzene ring structures, lower methylene proportion and higher molecular weight, so that the resin has excellent heat resistance, and carboxyl groups can ensure the alkali solubility of the resin. When the photo-etching solution is applied to the negative photoresist, the heat resistance of an imaging graph can be improved, the sensitivity of the negative photoresist is increased, and the dosage of a photo-acid generator and a curing agent is reduced.
The technical scheme of the invention is as follows:
the invention provides a negative photoresist composition containing high-heat-resistance carboxyl phenolic resin, which comprises the following components in parts by weight:
wherein the structural general formula of the high heat-resistant carboxyl phenolic resin is
Wherein x is 0-4, the ratio of m to n is 0.05-0.75:1, and R is H, phenyl or C1-C9 alkyl.
Further, the weight average molecular weight of the high heat-resistant carboxyl phenolic resin is 8000-35000g/mol, the glass transition temperature is 123-153 ℃, and the dissolution rate in a 2.38% tetramethylammonium hydroxide aqueous solution is 500-4500 angstroms/second.
Further, the photoacid generator is one or more of the following structural formulas (I), (II), (III), (IV), (V), (VI) and (VII):
(I)
(II)
x is 0 to 12
(III)
y is 0 to 12
(IV)
R1is-C3F7、C8H17、
(V)
R2is-C3F7、C4F9Or
(VI)
R3is-CF3、C6F5Or
(VII)
R4Is composed of
Further, the curing agent is one or more of the following compounds of the structures (VII), (IX), (X), (XI), (XII) and (XIII):
wherein in each compound at least two of R are-CH2OCH3。
Further, the additive comprises one or more of a leveling control agent, an ultraviolet absorber and a quencher.
Further, the leveling control agent is one or more selected from BYK 310, BYK 315, BYK 320, BYK 325, BYK 331, BYK 358N, BYK 3550 and BYK 3560 which are produced by Bick of Germany.
Further, the ultraviolet absorbent is selected from one or more of 9- (2-methoxyethoxy) methylanthracene, 9-anthrylmethylacetate, diazomethane sulfonyl, 2, 6-bis (4 '-azidobenzylidene) -4-methylcyclohexanone and 2, 6-bis (4' -azidocinnamylidene) -4-methylcyclohexanone.
Further, the quenching agent is selected from one or more of ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylene tetramine, triethanolamine, tripropylamine, triethoxy ethanolamine, trioctylamine, tributylamine, trimethoxyethoxymethoxyethylamine, tetramethylammonium hydroxide, polyquaternium, diaminodiphenyl sulfone, diaminodiphenylmethane, m-phenylenediamine, dicyandiamide, imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole.
Further, the solvent is one or more of propylene glycol methyl ether acetate, propylene glycol monoacetate, ethylene glycol methyl ether acetate, diethylene glycol, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, diethylene glycol methyl ether, diethylene glycol ethyl ether, butyl acetate, neopentyl acetate, ethyl lactate, methyl ethyl ketone and methyl isobutyl ketone.
The invention has the beneficial effects that:
1. the invention selects the high molecular weight linear phenolic resin containing carboxyl and triphenyl structures as the film-forming resin to improve the thermal property of the photoresist, the selected resin has high molecular weight and long molecular chain segment, can increase the entanglement among the chain segments, increase the chain group shape, reduce the free moving capability of each molecule, simultaneously ensure that a larger proportion of phenolic hydroxyl groups are embedded in the chain group, slow down the oxidation speed of the phenolic hydroxyl groups, but the proportion of peripheral hydroxyl groups reduced by the method can greatly reduce the alkali solubility of the resin, and introduce carboxyl with stronger alkali solubility in order to make up the lost alkali solubility. The improvement of the molecular weight of the resin can also increase the sensitivity of the photoresist, reduce the use amount of the photo-acid generator and the curing agent and save the cost.
2. The film-forming resin selected by the invention has a triphenyl structure in a certain proportion, and has good heat resistance.
3. The triphenyl structure is increased, so that the proportion of methylene on the main chain is reduced, the oxidation resistance is enhanced, and the heat resistance is increased.
Drawings
FIG. 1 is a heat resistant profile of a lithographic pattern of a negative photoresist composition of example 6 containing a high heat resistant carboxy phenolic resin;
FIG. 2 is a graph of heat resistant topography for a lithographic pattern of a negative photoresist composition of example 8 containing a highly heat resistant carboxy phenolic resin.
Detailed Description
The present invention will be described in detail with reference to examples.
The high heat resistant carboxy phenol-formaldehyde resins used in the examples were of the following structure:
TABLE 1 high Heat resistant carboxy phenol-formaldehyde resins used in examples 1-9
The photoacid generators used in the examples were the following compounds:
example 1:
example 2:
example 3:
example 4:
example 5:
example 6:
example 7:
example 8:
example 9:
the curing agents used in the examples were the following compounds:
example 1:
example 2:
example 3:
example 4:
example 5:
example 6:
example 7:
example 8:
example 9:
the additives used in the examples were the following compounds:
example 1
Leveling control agent: BYK 310; ultraviolet absorber: 9- (2-methoxyethoxy) methylanthracene; quenching agent: ethylene diamine.
Example 2:
leveling control agent: BYK 315; ultraviolet absorber: 9-anthracenylmethyl acetate; quenching agent: hexamethylenediamine.
Example 3:
leveling control agent: BYK 320; ultraviolet absorber: diazomethane sulfonyl; quenching agent: tripropylamine.
Example 4:
leveling control agent: BYK 325; ultraviolet absorber: 2, 6-bis (4' -azidobenzylidene) -4-methylcyclohexanone; quenching agent: m-phenylenediamine.
Example 5:
leveling control agent: BYK 331; ultraviolet absorber: 2, 6-bis (4' -azidocinnamylidene) -4-methylcyclohexanone; quenching agent: trioctylamine.
Example 6:
leveling control agent: BYK 358N; ultraviolet absorber: 2, 6-bis (4' -azidocinnamylidene) -4-methylcyclohexanone; quenching agent: tributylamine.
Example 7
Leveling control agent: BYK 3550; ultraviolet absorber: 2, 6-bis (4' -azidocinnamylidene) -4-methylcyclohexanone; quenching agent: triethoxyethanolamine.
Example 8:
leveling control agent: BYK 3560; ultraviolet absorber: 2, 6-bis (4' -azidocinnamylidene) -4-methylcyclohexanone; quenching agent: 2-methylimidazole.
Example 9:
leveling control agent: BYK 3560; ultraviolet absorber: 2, 6-bis (4' -azidocinnamylidene) -4-methylcyclohexanone; quenching agent: 2-phenylimidazole.
The solvents used in the examples were the following compounds:
example 1: propylene glycol methyl ether acetate.
Example 2: propylene glycol monoacetate.
Example 3: ethylene glycol methyl ether acetate.
Example 4: and (3) ethyl lactate.
Example 5: methyl ethyl ketone.
Example 6: propylene glycol methyl ether acetate.
Example 7: ethylene glycol methyl ether acetate.
Example 8: ethylene glycol methyl ether acetate.
Example 9: ethylene glycol methyl ether acetate.
The above compounds, prepared in parts by mass as in the following table examples, were shaken on an oscillator for 24 hours to be sufficiently dissolved in each other, filtered once with a 0.5 μm pore size filter, and filtered once with a 0.2 μm pore size filter to obtain a negative photoresist composition containing a high heat-resistant carboxyl group phenolic resin.
TABLE 2 Components of the Compounds of examples 1-9
Photolithography experimental methods and results: the negative photoresist composition containing the high heat-resistant carboxyl phenolic resin is prepared on a 6-inch silicon wafer at the speed of 1000-Spin-coating at a speed of/min, baking at 90 deg.C for 90 s, and exposing with Nikon I12I-line stepper exposure machine (NA 0.63) at an exposure intensity of 25-300mj/cm2After exposure, the substrate was baked on a hot plate at 110 ℃ for 110 seconds, finally developed in a 2.38% TMAH developer for 90 seconds, and then baked and examined for the lithography result by an electron microscope. The obtained patterns are baked on hot plates at 130,140,150,160 ℃ and 170 ℃ for 180 seconds respectively to verify the heat resistance degree of the photoresist, and the appearance of the preferred embodiment is shown in the attached figure.
The test results are shown in the following table:
table 3 examples 1-9 test results
Tests show that the negative photoresist composition has high resolution and good heat resistance, reaches over 140 ℃, can be applied to a high-temperature process at 160 ℃ at the highest, and has wide application prospect in the field of high-performance photoresist.
The above description is only a preferred embodiment of the present invention, and the present invention is not limited to the content of the embodiment. It will be apparent to those skilled in the art that various changes and modifications can be made within the technical scope of the present invention, and any changes and modifications made are within the protective scope of the present invention.
Claims (9)
1. A negative photoresist composition containing high heat-resistant carboxyl phenolic resin is characterized in that: comprises the following components in parts by weight:
wherein the structural general formula of the high heat-resistant carboxyl phenolic resin is
Wherein x is 0-4, the ratio of m to n is 0.05-0.75:1, and R is H, phenyl or C1-C9 alkyl.
2. The negative photoresist composition containing high heat-resistant carboxyl phenol resin according to claim 1, wherein: the weight average molecular weight of the high-heat-resistance carboxyl phenolic resin is 8000-35000g/mol, the glass transition temperature is 123-153 ℃, and the dissolution rate in 2.38% tetramethyl ammonium hydroxide aqueous solution is 500-4500 angstroms/second.
3. The negative photoresist composition containing high heat-resistant carboxyl phenol resin according to claim 1, wherein: the photoacid generator is one or more of the following structural formulas (I), (II), (III), (IV), (V), (VI) and (VII):
(I)
(II)
x is 0 to 12
(III)
y is 0 to 12
(IV)
R1is-C3F7、C8H17、
(V)
R2is-C3F7、C4F9Or
(VI)
R3is-CF3、C6F5Or
(VII)
R4Is composed of
4. The negative photoresist composition containing high heat-resistant carboxyl phenol resin according to claim 1, wherein: the curing agent is one or more of the following compounds with structures (VII), (IX), (X), (XI), (XII) and (XIII):
wherein in each compound at least two of R are-CH2OCH3。
5. The negative photoresist composition containing high heat-resistant carboxyl phenol resin according to claim 1, wherein: the additive comprises one or more of a leveling control agent, an ultraviolet absorber and a quencher.
6. The negative photoresist composition containing high heat-resistant carboxyl phenol resin according to claim 5, wherein: the leveling control agent is selected from one or more of BYK 310, BYK 315, BYK 320, BYK 325, BYK 331, BYK 358N, BYK 3550 and BYK 3560 which are produced by Bick of Germany.
7. The negative photoresist composition containing high heat-resistant carboxyl phenol resin according to claim 5, wherein: the ultraviolet absorbent is one or more selected from 9- (2-methoxyethoxy) methylanthracene, 9-anthryl methylacetate, diazomethane sulfonyl, 2, 6-bis (4 '-azidobenzylidene) -4-methylcyclohexanone and 2, 6-bis (4' -azidocinnamyl) -4-methylcyclohexanone.
8. The negative photoresist composition containing high heat-resistant carboxyl phenol resin according to claim 5, wherein: the quenching agent is selected from one or more of ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylene tetramine, triethanolamine, tripropylamine, triethoxy ethanolamine, trioctylamine, tributylamine, trimethoxyethoxymethoxyethylamine, tetramethyl ammonium hydroxide, polyquaternary ammonium base, diamino diphenyl sulfone, diamino diphenyl methane, m-phenylenediamine, dicyandiamide, imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole.
9. The negative photoresist composition containing high heat-resistant carboxyl phenol resin according to claim 1, wherein: the solvent is one or more of propylene glycol methyl ether acetate, propylene glycol monoacetate, ethylene glycol methyl ether acetate, diethylene glycol, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, diethylene glycol methyl ether, diethylene glycol diethyl ether, butyl acetate, neopentyl acetate, ethyl lactate, methyl ethyl ketone and methyl isobutyl ketone.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04122940A (en) * | 1990-09-13 | 1992-04-23 | Konica Corp | Photosensitive composition |
| CN102050908A (en) * | 2010-11-22 | 2011-05-11 | 昆山西迪光电材料有限公司 | Chemical amplitude-increasing type silicon-containing I-line ultraviolet negative photoresist and forming resin thereof |
| CN103304521A (en) * | 2012-03-16 | 2013-09-18 | 中国科学院化学研究所 | Molecular glass photoresist of taking tetraphenyl furan, tetraphenyl pyrrole, tetraphenylthiophene and quinary phenylpyridine as cores |
| CN103809378A (en) * | 2014-01-26 | 2014-05-21 | 京东方科技集团股份有限公司 | Negative photoresist as well as preparation method and application method thereof |
| CN104614941A (en) * | 2015-01-08 | 2015-05-13 | 苏州瑞红电子化学品有限公司 | High-heat resistance chemically-amplified photoresist resin and photoresist combination using same |
| CN110032040A (en) * | 2018-01-12 | 2019-07-19 | 中国科学院化学研究所 | Chemically amplified resists composition and its application in ultraviolet photolithographic |
| WO2019239784A1 (en) * | 2018-06-13 | 2019-12-19 | Dic株式会社 | Phenolic novolac resin, method for manufacturing same, photosensitive composition, resist material, and resist film |
-
2020
- 2020-01-06 CN CN202010009705.5A patent/CN111123649B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04122940A (en) * | 1990-09-13 | 1992-04-23 | Konica Corp | Photosensitive composition |
| CN102050908A (en) * | 2010-11-22 | 2011-05-11 | 昆山西迪光电材料有限公司 | Chemical amplitude-increasing type silicon-containing I-line ultraviolet negative photoresist and forming resin thereof |
| CN103304521A (en) * | 2012-03-16 | 2013-09-18 | 中国科学院化学研究所 | Molecular glass photoresist of taking tetraphenyl furan, tetraphenyl pyrrole, tetraphenylthiophene and quinary phenylpyridine as cores |
| CN103809378A (en) * | 2014-01-26 | 2014-05-21 | 京东方科技集团股份有限公司 | Negative photoresist as well as preparation method and application method thereof |
| CN104614941A (en) * | 2015-01-08 | 2015-05-13 | 苏州瑞红电子化学品有限公司 | High-heat resistance chemically-amplified photoresist resin and photoresist combination using same |
| CN110032040A (en) * | 2018-01-12 | 2019-07-19 | 中国科学院化学研究所 | Chemically amplified resists composition and its application in ultraviolet photolithographic |
| WO2019239784A1 (en) * | 2018-06-13 | 2019-12-19 | Dic株式会社 | Phenolic novolac resin, method for manufacturing same, photosensitive composition, resist material, and resist film |
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