CN114106325B - Photosensitive resin, photoresist, preparation method and application thereof - Google Patents
Photosensitive resin, photoresist, preparation method and application thereof Download PDFInfo
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- CN114106325B CN114106325B CN202111488453.XA CN202111488453A CN114106325B CN 114106325 B CN114106325 B CN 114106325B CN 202111488453 A CN202111488453 A CN 202111488453A CN 114106325 B CN114106325 B CN 114106325B
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- 239000011347 resin Substances 0.000 title claims abstract description 69
- 229920005989 resin Polymers 0.000 title claims abstract description 69
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title description 19
- 239000000178 monomer Substances 0.000 claims abstract description 75
- 239000007864 aqueous solution Substances 0.000 claims abstract description 28
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 27
- 150000004985 diamines Chemical class 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 48
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical group CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 30
- JUSLPJHNRDQHBJ-UHFFFAOYSA-N NC(C=C1)=CC(C(F)(F)F)=C1OC(C=CC(C(C=C1)=CC(C(O)=O)=C1OC(C=C1)=C(C(F)(F)F)C=C1N)=C1)=C1C(O)=O Chemical group NC(C=C1)=CC(C(F)(F)F)=C1OC(C=CC(C(C=C1)=CC(C(O)=O)=C1OC(C=C1)=C(C(F)(F)F)C=C1N)=C1)=C1C(O)=O JUSLPJHNRDQHBJ-UHFFFAOYSA-N 0.000 claims description 22
- 238000011161 development Methods 0.000 claims description 21
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 17
- ARMLDFCODOKMKS-UHFFFAOYSA-N [O-][N+](C(C=C1)=CC(C(F)(F)F)=C1OC(C=CC(C(C=C1)=CC(C(O)=O)=C1OC(C=C1)=C(C(F)(F)F)C=C1[N+]([O-])=O)=C1)=C1C(O)=O)=O Chemical group [O-][N+](C(C=C1)=CC(C(F)(F)F)=C1OC(C=CC(C(C=C1)=CC(C(O)=O)=C1OC(C=C1)=C(C(F)(F)F)C=C1[N+]([O-])=O)=C1)=C1C(O)=O)=O ARMLDFCODOKMKS-UHFFFAOYSA-N 0.000 claims description 15
- 229920005575 poly(amic acid) Polymers 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- DNTHMWUMRGOJRY-UHFFFAOYSA-N 1-fluoro-4-nitro-2-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC=C(F)C(C(F)(F)F)=C1 DNTHMWUMRGOJRY-UHFFFAOYSA-N 0.000 claims description 11
- 239000004952 Polyamide Substances 0.000 claims description 10
- 239000003504 photosensitizing agent Substances 0.000 claims description 10
- 229920002647 polyamide Polymers 0.000 claims description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000006555 catalytic reaction Methods 0.000 claims description 8
- 238000006482 condensation reaction Methods 0.000 claims description 7
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 7
- UISWLBIMLGAHMF-UHFFFAOYSA-N 5-(3-carboxy-4-hydroxyphenyl)-2-hydroxybenzoic acid Chemical compound C1=C(O)C(C(=O)O)=CC(C=2C=C(C(O)=CC=2)C(O)=O)=C1 UISWLBIMLGAHMF-UHFFFAOYSA-N 0.000 claims description 6
- 239000012024 dehydrating agents Substances 0.000 claims description 6
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- URQUNWYOBNUYJQ-UHFFFAOYSA-N diazonaphthoquinone Chemical compound C1=CC=C2C(=O)C(=[N]=[N])C=CC2=C1 URQUNWYOBNUYJQ-UHFFFAOYSA-N 0.000 claims description 3
- 150000002632 lipids Chemical class 0.000 claims description 3
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical group OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 claims description 2
- 238000000059 patterning Methods 0.000 claims description 2
- 238000001259 photo etching Methods 0.000 abstract description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 abstract description 3
- 239000004973 liquid crystal related substance Substances 0.000 abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 20
- 229920001721 polyimide Polymers 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 238000000944 Soxhlet extraction Methods 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 239000004642 Polyimide Substances 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 5
- 239000009719 polyimide resin Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- -1 4-aminophenoxyphenyl Chemical group 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 2
- ZPSUIVIDQHHIFH-UHFFFAOYSA-N 3-(trifluoromethyl)-4-[2-(trifluoromethyl)phenyl]benzene-1,2-diamine Chemical group FC(F)(F)C1=C(N)C(N)=CC=C1C1=CC=CC=C1C(F)(F)F ZPSUIVIDQHHIFH-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000003949 imides Chemical group 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- 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
-
- 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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention provides a photosensitive resin, which has the following chemical structural formula:wherein, the liquid crystal display device comprises a liquid crystal display device,is the residue of a dianhydride monomer,is a diamine monomer residue, m=0.2 to 1, n=5 to 200. The molecular structure of the photosensitive resin provided by the invention contains carboxyl and trifluoromethyl, and the photosensitive resin can be developed in an alkaline aqueous solution after being further prepared into photoresist, so that the photosensitive resin is environment-friendly, the main chain is of a high-rigidity structure, and the photoetching resolution is high.
Description
Technical Field
The invention relates to the field of functional polymer materials, in particular to photosensitive resin, photoresist, a preparation method and application thereof.
Background
In chip design, a specific pattern is needed for packaging and passivating an insulating layer, but the traditional insulating material Polyimide (PI) has no photosensitive function and is mostly indissolvable, and an etching process is needed for pattern transfer to obtain a required pattern. For example: electrochem. Soc.,1991,138 (4), 1080-1084 describes a positive photosensitive polyimide resin (PSPI) with an ortho-nitrophenyl structure in the prepolymer PAA, and U.S. Pat. No. 5, 5518864 describes a PSPI with a phenolic hydroxyl structure in the prepolymer PAA, which, although they all have a developability, all require pattern transfer by an etching process to obtain the desired pattern.
Conventional positive tone lithography processes are developed based on the dissolution of a pre-polymerized polyamic acid (PAA) in the exposed areas and the insolubility in an alkaline solution in the non-exposed areas, followed by removal of the photoresist. The traditional positive photoetching process is complex in procedure, the solubility difference of the PAA precursor in an exposure area and a non-exposure area is small, the contrast is low, and the subsequent amination with high Wen Xianya is needed, so that the pattern can be damaged. For example: macromol. Res. 2021,29 (2), 164-171 describes a synthesis of directly developable PSPI, but the process is complex and does not overcome the technical drawbacks of the conventional positive photolithography process.
If the polyimide is endowed with a photosensitive function, the processing procedure is greatly simplified by direct exposure and development. However, the traditional positive photosensitive polyimide resin has complex preparation process, the development process is difficult to control accurately, the resolution of the photoetching pattern is low, and organic solvents such as cyclohexanone and N-methylpyrrolidone are mainly adopted as developing solutions, so that the positive photosensitive polyimide resin is not environment-friendly, has large smell and can pollute the working environment. An alkaline aqueous solution such as a tetramethyl ammonium hydroxide aqueous solution (THAM aq) is an environment-friendly developing solution, and if the photosensitive polyimide resin can be dissolved in the alkaline aqueous solution, the popularization and application of the photosensitive polyimide resin are greatly facilitated, but general PI is difficult to dissolve in the alkaline aqueous solution such as the THAM aq.
Disclosure of Invention
Accordingly, it is necessary to provide a photosensitive resin and a photoresist which can use an alkaline aqueous solution as a developer, and which have a simple processing step and a high photolithography resolution, and a method for producing the same, and applications thereof.
The invention provides a photosensitive resin, which has the following chemical structural formula:
wherein,is a dianhydride monomer residue->Is a diamine monomer residue, m=0.2 to 1, n=5 to 200.
In one embodiment, theEach occurrence is divided intoAnd is independently selected from one of the following groups:
in one embodiment, theEach occurrence is independently selected from one of the following groups:
the invention also provides a preparation method of the photosensitive resin, which comprises the following steps:
mixing dianhydride monomer, diamine monomer and 3,3 '-dicarboxyl-4, 4' -bis (4-amino-2-trifluoromethyl phenoxy) biphenyl monomer in a first organic solvent, dissolving, and performing condensation reaction to prepare polyamide acid prepolymer;
dehydrating the polyamic acid prepolymer to imidize the polyamic acid prepolymer to prepare the photosensitive resin;
wherein the structural formula of the dianhydride monomer is as follows:
the structural formula of the diamine monomer is as follows:
the structural formula of the 3,3 '-dicarboxy-4, 4' -bis (4-amino-2-trifluoromethyl phenoxy) biphenyl monomer is as follows:
the structural formula of the polyamic acid prepolymer is as follows:
in one embodiment, the ratio of the amounts of the dianhydride monomer, the diamine monomer, and the 3,3 '-dicarboxy-4, 4' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl monomer is 1 (0.1-0.3): 0.7-0.9.
In one embodiment, the preparation method of the 3,3 '-dicarboxy-4, 4' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl monomer comprises the following steps:
mixing 4,4 '-dihydroxy-3, 3' -biphenyl with 2-fluoro-5-nitrobenzotrifluoride to perform nucleophilic substitution reaction to prepare 3,3 '-dicarboxyl-4, 4' -bis (4-nitro-2-trifluoromethylphenoxy) biphenyl;
reducing the nitro group of the 3,3 '-dicarboxy-4, 4' -bis (4-nitro-2-trifluoromethylphenoxy) biphenyl to an amino group;
wherein the structural formula of the 4,4 '-dihydroxy-3, 3' -biphenyl dicarboxylic acid is as follows:
the structural formula of the 2-fluoro-5-nitro benzotrifluoride is as follows:
the structural formula of the 3,3 '-dicarboxy-4, 4' -bis (4-nitro-2-trifluoromethyl phenoxy) biphenyl is as follows:
in one embodiment, the ratio of the amount of the 4,4 '-dihydroxy-3, 3' -biphenyl dicarboxylic acid to the amount of the 2-fluoro-5-nitrobenzotrifluoride material is 1 (2.1-2.5).
In one embodiment, the conditions for nucleophilic substitution reaction include: under the catalysis condition, reacting for 12-24 h; and/or
The reaction conditions for the nitro reduction of the 3,3 '-dicarboxy-4, 4' -bis (4-nitro-2-trifluoromethylphenoxy) biphenyl include: under the catalysis condition, hydrogen is introduced to lead the pressure to be 3 bar-7 bar, and the reaction is carried out for 4 h-8 h.
In one embodiment, the condensation reaction is carried out under the following conditions: reacting for 8-24 h in ice bath environment; and/or
The step of dehydrating and imidizing the polyamide acid prepolymer is to add a dehydrating agent and a catalyst into a reaction system of the polyamide acid prepolymer at a temperature of 25-50 ℃ for 8-24 hours.
In one embodiment, the dehydrating agent is acetic anhydride; and/or
The catalyst is one or a mixture of more of pyridine, isoquinoline and triethylamine.
The invention also provides an application of the photosensitive resin in positive development, wherein the photosensitive resin is the photosensitive resin in any embodiment.
The invention also provides a photoresist comprising a photosensitive resin as described in any of the embodiments above, a photosensitizer, and a second organic solvent.
In one embodiment, the mass ratio of the photosensitive resin, the photosensitive agent and the second organic solvent is (20-40): 5-30): 35-100.
In one embodiment, the photosensitizer is one or a mixture of a diazonaphthoquinone, a diazonaphthoquinone-type lipid, and a trifluoromethylsulfonyloxy-1, 8-naphthalimide.
The invention also provides a preparation method of the photoresist, which comprises the steps of dissolving the photosensitive resin in any embodiment in a second organic solvent and adding a photosensitizer.
The invention also provides a positive developing method, wherein the photoresist in any embodiment is coated on a substrate, prebaked, exposed and developed, and the photoresist is dissolved in an exposure area and remains in a non-exposure area to form a pattern layer.
In one embodiment, the developer for development is an aqueous alkaline solution.
In one embodiment, the alkaline aqueous solution is one or a mixture of a plurality of tetramethyl ammonium hydroxide aqueous solution, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution and triethylamine aqueous solution; and/or
The concentration of the alkaline aqueous solution is 2% -5%.
In one embodiment, the patterning layer has a lithographic resolution of 3 μm to 10 μm.
The molecular structure of the photosensitive resin contains carboxyl and trifluoromethyl, the photosensitive resin can be developed in an alkaline aqueous solution after being further prepared into photoresist, the photosensitive resin is environment-friendly, the main chain is of a high-rigidity structure, the photosensitive resin has less swelling during photoetching, the contrast ratio is high, and the photoetching resolution of a pattern layer can be greatly improved. The photosensitive resin can be further prepared into photoresist which can be directly subjected to positive development after exposure, and compared with the prior art, the development process is greatly simplified. Further, the photosensitive resin is prepared from key monomers 3,3 '-dicarboxyl-4, 4' -bis (4-amino-2-trifluoromethyl phenoxy) biphenyl monomer, dianhydride monomer and diamine monomer by means of homopolymerization or copolymerization, and the key monomers have simple synthesis process and high yield and are suitable for popularization.
Drawings
FIG. 1 is an infrared spectrum of a photosensitive resin of example 1;
FIG. 2 is a SEM scan pattern after positive development of example 4;
FIG. 3 is an SEM scan pattern after positive development of example 3;
fig. 4 is an SEM scan pattern after positive development of comparative example 1.
Detailed Description
In order to facilitate understanding of the present invention, the photosensitive resin, the photoresist, and the preparation methods and applications thereof will be more fully described with reference to examples. This invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
In the invention, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics.
An embodiment of the present invention provides a photosensitive resin, which has the following chemical structural formula:
wherein,is a dianhydride monomer residue->Is a diamine monomer residue, m=0.2 to 1, n=5 to 200.
In a specific example, theEach occurrence is independently selected from one of the following groups:
further, the saidEach occurrence is independently selected from one of the following groups:
in a specific example, theEach occurrence is independently selected from one of the following groups:
further, the saidEach occurrence is independently selected from one of the following groups:
an embodiment of the present invention also provides a method for preparing a photosensitive resin, including the following steps S10 to S20.
Step S10: dianhydride monomer, diamine monomer and 3,3 '-dicarboxyl-4, 4' -bis (4-amino-2-trifluoromethyl phenoxy) biphenyl monomer are mixed and dissolved in a first organic solvent, and condensation reaction is carried out to prepare the polyamic acid prepolymer.
Further, the conditions of the condensation reaction are: and reacting for 8-24 h in an ice bath environment.
Further, the condensation reaction is carried out under anhydrous and anaerobic conditions.
Wherein, the structural formula of the dianhydride monomer is:
the structural formula of the diamine monomer is as follows:
the structural formula of the 3,3 '-dicarboxy-4, 4' -bis (4-amino-2-trifluoromethyl phenoxy) biphenyl monomer is as follows:
the structural formula of the polyamic acid prepolymer is as follows:
in a specific example, the ratio of the amounts of the dianhydride monomer, diamine monomer, and 3,3 '-dicarboxy-4, 4' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl monomer is 1 (0.1 to 0.3): 0.7 to 0.9.
Alternatively, the first organic solvent includes, but is not limited to, one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, γ -butyrolactone, cyclohexanone, chloroform, tetrahydrofuran, and m-cresol.
In a specific example, the preparation method of the 3,3 '-dicarboxy-4, 4' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl monomer includes the following steps S11 to S12. The monomer synthesis method is simple and the yield is high.
Step S11:4,4 '-dihydroxy-3, 3' -biphenyl is mixed with 2-fluoro-5-nitrobenzotrifluoride to carry out nucleophilic substitution reaction to prepare 3,3 '-dicarboxyl-4, 4' -bis (4-nitro-2-trifluoromethylphenoxy) biphenyl.
Wherein, the structure of the 4,4 '-dihydroxy-3, 3' -biphenyl dicarboxylic acid is as follows:
the structural formula of the 2-fluoro-5-nitro benzotrifluoride is as follows:
the structural formula of the 3,3 '-dicarboxy-4, 4' -bis (4-nitro-2-trifluoromethyl phenoxy) biphenyl is as follows:
further, the conditions for nucleophilic substitution reaction include: under the catalysis condition, the reaction is carried out for 12 to 24 hours.
Alternatively, the catalyst used for catalysis may be, but is not limited to, potassium carbonate.
Further, the nucleophilic substitution reaction is performed under nitrogen protection.
Further, 4 '-dihydroxy-3, 3' -biphthalic acid and 2-fluoro-5-nitrobenzotrifluoride may be dissolved and mixed in an organic solvent such as N, N-dimethylformamide.
Furthermore, toluene can be added into the reaction, and the toluene can be used as an azeotrope of water generated in the reaction process, so that the water generated in the reaction process can be removed.
In a specific example, the ratio of the amounts of 4,4 '-dihydroxy-3, 3' -biphthalic acid and 2-fluoro-5-nitrobenzotrifluoride is 1 (2.1 to 2.5).
Step S12: reducing the nitro group in 3,3 '-dicarboxy-4, 4' -bis (4-nitro-2-trifluoromethylphenoxy) biphenyl to an amino group.
Further, the reaction conditions in step S12 are: under the catalysis condition, hydrogen is introduced to lead the pressure to be 3 bar-7 bar, and the reaction is carried out for 4 h-8 h.
Further, the reaction conditions require anhydrous and anaerobic.
Further, the catalyst used for catalysis may be, but is not limited to, palladium on charcoal.
Further, this step may be performed in an organic solvent such as tetrahydrofuran.
In the preparation of the 3,3 '-dicarboxyl-4, 4' -di (4-amino-2-trifluoromethylphenoxy) biphenyl monomer, the yield of the 3,3 '-dicarboxyl-4, 4' -di (4-nitro-2-trifluoromethylphenoxy) biphenyl synthesized by the step S11 reaches more than 80 percent, and the yield of the monomer obtained after the reduction by the step S12 reaches more than 97 percent, so that the yield is very high.
Step S20: the polyamic acid prepolymer is dehydrated to imidize, so as to prepare the photosensitive resin.
Further, the step of dehydrating and imidizing the polyamide acid is to add a dehydrating agent and a catalyst into a reaction system of the polyamide acid prepolymer at a temperature of 25-50 ℃ for 8-24 hours.
Alternatively, the dehydrating agent may be, but is not limited to, acetic anhydride.
Alternatively, the catalyst may be, but is not limited to, one or a mixture of several of pyridine, isoquinoline and triethylamine.
It will be appreciated that the photosensitive resin prepared in step S20 may be further purified by precipitation, filtration, extraction, and the like.
An embodiment of the present invention also provides an application of the photosensitive resin in positive development, where the photosensitive resin is a photosensitive resin in any of the specific examples above.
An embodiment of the present invention also provides a photoresist including the photosensitive resin, the photosensitizer, and the second organic solvent as in any of the specific examples above.
In a specific example, the mass ratio of the photosensitive resin, the photosensitizer and the second organic solvent is (20-40): 5-30): 35-100.
Alternatively, the photosensitizer may be, but not limited to, one or a mixture of a diazonaphthoquinone, a diazonaphthoquinone-type lipid, and a trifluoromethylsulfonyloxy-1, 8-naphthalimide.
Alternatively, the second organic solvent may be, but not limited to, one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, γ -butyrolactone, cyclohexanone, chloroform, tetrahydrofuran, and m-cresol.
An embodiment of the present invention further provides a method for preparing a photoresist, in which the photosensitive resin in any of the specific examples above is dissolved in a second organic solvent, and a photosensitizer is added.
An embodiment of the present invention further provides a positive-working method, in which a photoresist as described in any of the above specific examples is coated on a substrate, prebaked, exposed, developed, and the photoresist is dissolved in an exposed area and remains in a non-exposed area to form a patterned layer.
Alternatively, the substrate may be, but is not limited to, a silicon wafer.
In a specific example, the pre-baking temperature is 70-120 ℃ and the time is 3-240 min.
In a specific example, the energy of the exposure is 250mJ/cm 2 ～350mJ/cm 2 ；
In a specific example, the developing solution for development is an alkaline aqueous solution;
further, the alkaline aqueous solution is one or a mixture of a plurality of tetramethyl ammonium hydroxide aqueous solution, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution and triethylamine aqueous solution.
Further, the concentration of the alkaline aqueous solution is 2% -5%.
In one specific example, the development time is 30s to 60s.
In a specific example, the method further comprises the steps of:
and exposing and developing the product to be developed coated with the photoresist to form a pattern, cleaning, and heating for curing.
Further, the temperature of heating and curing is 200-250 ℃ and the time is 15-30 min.
In a specific example, the lithographic resolution of the patterned layer is 3 μm to 10 μm.
In a specific example, the pattern layer has a film thickness of 12 μm to 15 μm.
In one specific example, the graphic layer has a coefficient of thermal expansion of 20×10 -6 K -1 ～36×10 -6 K -1 。
In one specific example, the patterned layer has a light transmittance of greater than 80% for 550nm light.
The molecular structure of the photosensitive resin contains carboxyl and trifluoromethyl, the photosensitive resin can be developed in an alkaline aqueous solution after being further prepared into photoresist, the photosensitive resin is environment-friendly, the main chain is of a high-rigidity structure, the photosensitive resin has less swelling during photoetching, the contrast ratio is high, and the photoetching resolution of a pattern layer can be greatly improved. The photosensitive resin can be further prepared into photoresist which can be directly subjected to positive development after exposure, compared with the traditional technology of forming patterns at the stage of pre-polymer polyamide acid, removing the photoresist, and forming polyimide patterns by high-temperature treatment, the development process is greatly simplified, the photosensitive resin has stable property and long service life, and the defect of difficult storage of polyamide acid is overcome. Further, the photosensitive resin is prepared from key monomers 3,3 '-dicarboxyl-4, 4' -bis (4-amino-2-trifluoromethyl phenoxy) biphenyl monomer, dianhydride monomer and diamine monomer by means of homopolymerization or copolymerization, and the key monomers have simple synthesis process and high yield and are suitable for popularization.
The following are examples, in which all raw materials are commercially available unless otherwise specified.
The general chemical reaction formula of the following specific examples is as follows:
example 1:
step 1, preparation of 3,3 '-dicarboxy-4, 4' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl monomer:
(1) After 5.48g (20 mmol) of 4,4 '-dihydroxy-3, 3' -biphenyl dicarboxylic acid and 9.20g (44 mmol) of 2-fluoro-5-nitrobenzotrifluoride were dissolved in 160ml of N, N-Dimethylformamide (DMF), 6.08g (44 mmol) of potassium carbonate (K) 2 CO 3 ) Toluene was used as a catalyst, and was refluxed under nitrogen for 20 hours as an azeotrope with water produced during the reaction to give 10.42g of 3,3 '-dicarboxy-4, 4' -bis (4-nitro-2-trifluoromethylphenoxy) biphenyl. The chemical reaction formula is as follows:
(2) 6.52g (10 mmol) of 3,3 '-dicarboxy-4, 4' -bis (4-nitro-2-trifluoromethylphenoxy) biphenyl prepared in step (1) was dissolved in 100ml of Tetrahydrofuran (THF) under anhydrous and anaerobic conditions, a catalytic amount of palladium on charcoal (Pd/C), hydrogen (H 2 ) As a reducing agent and maintaining a pressure of 5bar for 4 hours, 3 is produced5.74g of 3 '-dicarboxy-4, 4' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl. The chemical reaction formula is as follows:
step 2, preparation of photosensitive resin:
(1) To a 250ml three-necked flask with a magnetic stirrer, 4.74g (8 mmol) of the 3,3' -dicarboxy-4, 4' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl monomer prepared in step 1, 0.82g (2 mmol) of 2,2' -bis [4- (4-aminophenoxyphenyl) ] propane (BAPP, diamine monomer) and 50ml of DMF were sequentially added under anhydrous and anaerobic conditions. After the materials in the system were completely dissolved, 2.94g (10 mmol) of 3,3', 4' -biphenyltetracarboxylic dianhydride (BPDA, dianhydride monomer) was added and stirred under ice bath for 8 hours.
(2) After the reaction of the step (1) is finished and the reaction system is restored to 25 ℃, 5.4ml of acetic anhydride and 1ml of pyridine are added for continuous reaction for 24 hours, and the purification is carried out through methanol precipitation, filtration and Soxhlet extraction.
The chemical reaction formula of step 2 is as follows:
step 3, preparation of photoresist:
and (3) dissolving the photosensitive resin prepared in the step (2) in gamma-butyrolactone, adding DNQ, and stirring for dissolving, wherein the mass ratio of the photosensitive agent to polyimide to gamma-butyrolactone is 1:5:20.
Step 4, positive development:
spin-coating the photoresist solution prepared in the step 3 on the surface of a silicon wafer, pre-baking for 3 minutes at 90 ℃, and then placing the silicon wafer on an i-line exposure machine for photoetching, wherein the exposure energy is 300mJ/cm 2 And then placing the silicon wafer into a tetramethyl ammonium hydroxide aqueous solution with the mass concentration of 2.38% for development treatment for 40 seconds, cleaning the silicon wafer with ultrapure water, and finally curing the silicon wafer at 200 ℃ for 15 minutes.
Example 2:
step 1 is the same as step 1 of example 1.
Step 2, preparation of photosensitive resin:
(1) To a 250ml three-necked flask with a magnetic stirrer were successively added 4.15g (7 mmol) of the 3,3' -dicarboxy-4, 4' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl monomer prepared in step 1, 0.60g (3 mmol) of 4,4' -diaminodiphenyl ether (ODA, diamine monomer) and 50ml of DMF under anhydrous and anaerobic conditions. After the materials in the system were completely dissolved, 3.22g (10 mmol) of 3,3', 4' -benzophenone tetracarboxylic dianhydride (BTDA, dianhydride monomer) was added and stirred for 8 hours in an ice bath environment.
(2) After the reaction of the step (1) is finished and the reaction system is restored to 25 ℃, 5.4ml of acetic anhydride and 1ml of pyridine are added for continuous reaction for 24 hours, and the purification is carried out through methanol precipitation, filtration and Soxhlet extraction.
The chemical reaction formula of step 2 is as follows:
step 3 is the same as step 3 of example 1.
Step 4 is the same as step 4 of example 1.
Example 3:
step 1 is the same as step 1 of example 1.
Step 2, preparation of photosensitive resin:
(1) 5.33g (9 mmol) of the 3,3 '-dicarboxy-4, 4' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl monomer prepared in step 1, 0.30g (1 mmol) of 1, 3-bis (4-aminophenoxy) benzene (diamine monomer) and 50ml of DMF were sequentially added to a 250ml three-necked flask with a magnetic stirrer under anhydrous and anaerobic conditions. After the materials in the system were completely dissolved, 4.44g (10 mmol) of hexafluorodianhydride (6 FDA, dianhydride monomer) was added and stirred for 8 hours in an ice bath environment.
(2) After the reaction of the step (1) is finished and the reaction system is restored to 25 ℃, 5.4ml of acetic anhydride and 1ml of pyridine are added for continuous reaction for 24 hours, and the purification is carried out through methanol precipitation, filtration and Soxhlet extraction.
The chemical reaction formula of step 2 is as follows:
step 3 is the same as step 3 of example 1.
Step 4 is the same as step 4 of example 1.
Example 4:
step 1 is the same as step 1 of example 1.
Step 2, preparation of photosensitive resin:
(1) 5.33g (9 mmol) of the 3,3 '-dicarboxy-4, 4' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl monomer prepared in step 1, 0.30g (1 mmol) of 1, 3-bis (4-aminophenoxy) benzene (diamine monomer) and 50ml of DMF were sequentially added to a 250ml three-necked flask with a magnetic stirrer under anhydrous and anaerobic conditions. After the materials in the system were completely dissolved, 2.94g (10 mmol) of 3,3', 4' -biphenyltetracarboxylic dianhydride (BPDA, dianhydride monomer) was added and stirred under ice bath for 8 hours.
(2) After the reaction of the step (1) is finished and the reaction system is restored to 25 ℃, 5.4ml of acetic anhydride and 1ml of pyridine are added for continuous reaction for 24 hours, and the purification is carried out through methanol precipitation, filtration and Soxhlet extraction.
The chemical reaction formula of step 2 is as follows:
step 3 is the same as step 3 of example 1.
Step 4 is the same as step 4 of example 1.
Example 5:
step 1 is the same as step 1 of example 1.
Step 2, preparation of photosensitive resin:
(1) 5.33g (9 mmol) of the 3,3' -dicarboxy-4, 4' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl monomer prepared in step 1, 0.20g (1 mmol) of 4,4' -diaminodiphenyl ether (ODA, diamine monomer) and 50ml of DMF were sequentially added into a 250ml three-necked flask with a magnetic stirrer under anhydrous and anaerobic conditions. After the materials in the system were completely dissolved, 2.94g (10 mmol) of 3,3', 4' -biphenyltetracarboxylic dianhydride (BPDA, dianhydride monomer) was added and stirred under ice bath for 8 hours.
(2) After the reaction of the step (1) is finished and the reaction system is restored to 25 ℃, 5.4ml of acetic anhydride and 1ml of pyridine are added for continuous reaction for 24 hours, and the purification is carried out through methanol precipitation, filtration and Soxhlet extraction.
The chemical reaction formula of step 2 is as follows:
step 3 is the same as step 3 of example 1.
Step 4 is the same as step 4 of example 1.
Comparative example 1:
step 1, preparation of photosensitive resin:
(1) To a 250ml three-necked flask with a magnetic stirrer, 2.88g (9 mmol) of 2,2 '-bis (trifluoromethyl) diaminobiphenyl, 0.41g (1 mmol) of 2,2' -bis [4- (4-aminophenoxyphenyl) ] propane (BAPP, diamine monomer) and 50ml of DMF were successively added under anhydrous and anaerobic conditions. After the materials in the system were completely dissolved, 2.94g (10 mmol) of 3,3', 4' -biphenyltetracarboxylic dianhydride (BPDA, dianhydride monomer) was added and stirred under ice bath for 8 hours.
(2) After the reaction of the step (1) is finished and the reaction system is restored to 25 ℃, 5.4ml of acetic anhydride and 1ml of pyridine are added for continuous reaction for 24 hours, and the purification is carried out through methanol precipitation, filtration and Soxhlet extraction.
The chemical reaction formula of step 1 is as follows:
step 2 is the same as step 3 of example 1.
Step 3, step 4 of example 1.
Comparative example 2:
step 1, preparation of photosensitive resin:
(1) To a 250ml three-necked flask with a magnetic stirrer, 4.10g (10 mmol) of 2,2' -bis [4- (4-aminophenoxyphenyl) ] propane (BAPP, diamine monomer) and 50ml of DMF were successively added under anhydrous and anaerobic conditions. After the materials in the system were completely dissolved, 2.94g (10 mmol) of 3,3', 4' -biphenyltetracarboxylic dianhydride (BPDA, dianhydride monomer) was added and stirred under ice bath for 8 hours.
(2) After the reaction of the step (1) is finished and the reaction system is restored to 25 ℃, 5.4ml of acetic anhydride and 1ml of pyridine are added for continuous reaction for 24 hours, and the purification is carried out through methanol precipitation, filtration and Soxhlet extraction.
The chemical reaction formula of step 1 is as follows:
step 2 is the same as step 3 of example 1.
Step 3, step 4 of example 1.
In example 1,3 '-dicarboxy-4, 4' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl monomer was prepared, the yield of the synthesized 3,3 '-dicarboxy-4, 4' -bis (4-nitro-2-trifluoromethylphenoxy) biphenyl was 80%, and the yield of the key monomer obtained after reduction was 97%.
As shown in FIG. 1, the infrared signature was performed on the synthetic photosensitive resin of example 1, which was found to be at 1775, 1714cm -1 Has the characteristic absorption peak of symmetrical and asymmetrical extension vibration of carbonyl group on imide ring; 1597cm -1 Having a stretching vibration peak belonging to c=o on the carboxyl group; 1167cm -1 Has an absorption peak belonging to C-O stretching vibration characteristics; 1229cm -1 Has absorption peak of C-F stretching vibration characteristic of 2168-1954cm -1 Has characteristic absorption peaks belonging to benzene rings. 1680cm -1 Characteristic absorption peak belonging to dianhydride monomer c=o and 3400cm -1 The characteristic absorption peak belonging to diamine monomer N-H disappeared, indicating that the reaction was complete. Similarly, the infrared spectrum analysis of examples 2 to 5 also matches the corresponding structural characteristic peaks of the photosensitive resinAnd the reaction was complete.
As shown in fig. 2 to 4, the pattern layers after positive development of example 4, example 3 and comparative example 1 were scanned by a Scanning Electron Microscope (SEM), and it was found that the pattern layers of example 4 and example 3 were clearer than the pattern layer of comparative example 1.
Further, the thermal expansion coefficients, 550nm transmittance, film thickness, and lithography resolution of the patterned layers formed after positive development of examples 1 to 5 and comparative examples 1 to 2 were tested, and the test results are shown in table 1 below.
The test method of the thermal expansion coefficient comprises the following steps: the measurement was performed using a thermo-mechanical analysis (TMA) method, the instrument was a TA-400 thermo-mechanical analyzer from TA company, america, under the test condition of N 2 Atmosphere, heating rate 10 ℃/min.
The 550nm light transmittance test method comprises the following steps: the measurement was performed by using a violet spectrum, and the instrument was an ultraviolet-visible spectrophotometer by Shimadzu corporation.
The film thickness testing method comprises the following steps: the measurement was performed using a three-way screw micrometer in japan.
The method for testing the photoetching resolution comprises the following steps: the measurement was performed using a scanning electron microscope, and the apparatus was a field emission scanning electron microscope of JEOL corporation, japan, and was subjected to gold plating before the test.
TABLE 1 Performance test results of formed graphic layer after positive development
As can be seen from Table 1, comparing examples 1 to 5 with comparative examples 1 to 2, the patterned layers formed after positive development of examples 1 to 5 each had a suitable thermal expansion coefficient and film thickness, and the light transmittance was high. The photolithographic resolution of examples 1 to 5 is significantly higher than that of comparative examples 1 to 2, and it can be seen that the photolithographic resolution can be greatly improved after the photosensitive resin of the present invention is made into photoresist.
The technical features of the above embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The foregoing examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (19)
1. A photosensitive resin is characterized by having the following chemical structural formula:
，
wherein the saidEach occurrence is independently selected from one of the following groups:
；
the saidEach occurrence is independently selected from one of the following groups:
；
m=0.2~1，n=5~200，m:(1-m)=（0.7~0.9）:（0.1~0.3）。
2. the photosensitive resin of claim 1, wherein saidEach occurrence is independently selected from one of the following groups:
。
3. the photosensitive resin of claim 1, wherein saidEach occurrence is independently selected from one of the following groups:
。
4. a method for preparing a photosensitive resin, comprising the steps of:
mixing dianhydride monomer, diamine monomer and 3,3 '-dicarboxyl-4, 4' -bis (4-amino-2-trifluoromethyl phenoxy) biphenyl monomer in a first organic solvent, dissolving, and performing condensation reaction to prepare polyamide acid prepolymer;
dehydrating the polyamic acid prepolymer to imidize the polyamic acid prepolymer to prepare the photosensitive resin;
wherein the structural formula of the dianhydride monomer is as follows:；
the structural formula of the diamine monomer is as follows:；
the structural formula of the 3,3 '-dicarboxy-4, 4' -bis (4-amino-2-trifluoromethyl phenoxy) biphenyl monomer is as follows:
；
the structural formula of the polyamic acid prepolymer is as follows:
；
m=0.2~1，n=5~200；
wherein the saidEach occurrence is independently selected from one of the following groups:
；
the saidEach occurrence is independently selected from one of the following groups:
；
the ratio of the amount of the 3,3 '-dicarboxy-4, 4' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl monomer to the amount of the diamine monomer is (0.7-0.9): 0.1-0.3.
5. The method of producing a photosensitive resin according to claim 4, wherein the ratio of the amounts of the dianhydride monomer, the diamine monomer, and the 3,3 '-dicarboxy-4, 4' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl monomer is 1 (0.1 to 0.3): 0.7 to 0.9.
6. The method for preparing a photosensitive resin according to claim 4, wherein the method for preparing 3,3 '-dicarboxy-4, 4' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl monomer comprises the steps of:
mixing 4,4 '-dihydroxy-3, 3' -biphenyl with 2-fluoro-5-nitrobenzotrifluoride to perform nucleophilic substitution reaction to prepare 3,3 '-dicarboxyl-4, 4' -bis (4-nitro-2-trifluoromethylphenoxy) biphenyl;
reducing the nitro group of the 3,3 '-dicarboxy-4, 4' -bis (4-nitro-2-trifluoromethylphenoxy) biphenyl to an amino group;
wherein the structural formula of the 4,4 '-dihydroxy-3, 3' -biphenyl dicarboxylic acid is as follows:；
the structural formula of the 2-fluoro-5-nitro benzotrifluoride is as follows:；
the structural formula of the 3,3 '-dicarboxy-4, 4' -bis (4-nitro-2-trifluoromethyl phenoxy) biphenyl is as follows:
。
7. the method of producing a photosensitive resin according to claim 6, wherein the ratio of the amount of the 4,4 '-dihydroxy-3, 3' -biphenyl dicarboxylic acid to the amount of the 2-fluoro-5-nitrobenzotrifluoride is 1 (2.1 to 2.5).
8. The method for producing a photosensitive resin according to claim 6, wherein the conditions for nucleophilic substitution reaction include: under the catalysis condition, reacting for 12-24 hours; and/or
The reaction conditions for the nitro reduction of the 3,3 '-dicarboxy-4, 4' -bis (4-nitro-2-trifluoromethylphenoxy) biphenyl include: under the catalysis condition, hydrogen is introduced to enable the pressure to be 3 bar-7 bar, and the reaction is carried out for 4-8 h.
9. The method for producing a photosensitive resin according to any one of claims 4 to 8, wherein the conditions for performing the condensation reaction are: reacting for 8-24 hours in an ice bath environment; and/or
The step of dehydrating and imidizing the polyamide acid prepolymer is to add a dehydrating agent and a catalyst into a reaction system of the polyamide acid prepolymer at the temperature of 25-50 ℃ for 8-24 hours.
10. The method for producing a photosensitive resin according to claim 9, wherein the dehydrating agent is acetic anhydride; and/or
The catalyst is one or a mixture of more of pyridine, isoquinoline and triethylamine.
11. Use of a photosensitive resin in positive working, characterized in that the photosensitive resin is the photosensitive resin according to any one of claims 1 to 3.
12. A photoresist comprising the photosensitive resin according to any one of claims 1 to 3, a photosensitizer, and a second organic solvent.
13. The photoresist of claim 12, wherein the mass ratio of the photosensitive resin, the photosensitive agent and the second organic solvent is (20-40): 5-30): 35-100.
14. The resist according to claim 12, wherein the photosensitizer is one or a mixture of a diazonaphthoquinone, a diazonaphthoquinone-type lipid, and a trifluoromethanesulfonyl-1, 8-naphthalimide.
15. A method for preparing a photoresist, wherein the photosensitive resin according to any one of claims 1 to 3 is dissolved in a second organic solvent, and a photosensitizer is added.
16. A positive-working method, characterized in that the photoresist according to any one of claims 12 to 14 is coated on a substrate, prebaked, exposed, developed, and the photoresist is dissolved in the exposed areas and remains in the non-exposed areas to form a pattern layer.
17. The method of positive working according to claim 16, wherein the developing solution for development is an aqueous alkaline solution.
18. The method of positive developing according to claim 17, wherein the basic aqueous solution is one or a mixture of a tetramethylammonium hydroxide aqueous solution, a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, and a triethylamine aqueous solution; and/or
The concentration of the alkaline aqueous solution is 2% -5%.
19. The positive-working method according to any one of claims 16 to 18, wherein the patterning layer has a lithographic resolution of 3 μm to 10 μm.
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Citations (4)
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|---|---|---|---|---|
| US4477648A (en) * | 1983-04-07 | 1984-10-16 | Trw Inc. | High-temperature polyimides prepared from 2,2-bis-[(2-halo-4-aminophenoxy)-phenyl]hexafluoropropane |
| CN110183637A (en) * | 2019-04-30 | 2019-08-30 | 珠海派锐尔新材料有限公司 | A kind of thermatropic ciquid crystal polymer and preparation method thereof |
| CN111303421A (en) * | 2019-11-20 | 2020-06-19 | 上海极紫科技有限公司 | Polyimide resin capable of being used as positive photoresist and preparation method thereof |
| CN111303422A (en) * | 2019-11-21 | 2020-06-19 | 上海极紫科技有限公司 | Polyimide resin for positive photoresist and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4477648A (en) * | 1983-04-07 | 1984-10-16 | Trw Inc. | High-temperature polyimides prepared from 2,2-bis-[(2-halo-4-aminophenoxy)-phenyl]hexafluoropropane |
| CN110183637A (en) * | 2019-04-30 | 2019-08-30 | 珠海派锐尔新材料有限公司 | A kind of thermatropic ciquid crystal polymer and preparation method thereof |
| CN111303421A (en) * | 2019-11-20 | 2020-06-19 | 上海极紫科技有限公司 | Polyimide resin capable of being used as positive photoresist and preparation method thereof |
| CN111303422A (en) * | 2019-11-21 | 2020-06-19 | 上海极紫科技有限公司 | Polyimide resin for positive photoresist and preparation method thereof |
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