CN111458979B - Photoresist composition, preparation method and application thereof - Google Patents
Photoresist composition, preparation method and application thereof Download PDFInfo
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- CN111458979B CN111458979B CN202010331849.2A CN202010331849A CN111458979B CN 111458979 B CN111458979 B CN 111458979B CN 202010331849 A CN202010331849 A CN 202010331849A CN 111458979 B CN111458979 B CN 111458979B
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 65
- 239000000203 mixture Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 229920005989 resin Polymers 0.000 claims abstract description 41
- 239000011347 resin Substances 0.000 claims abstract description 41
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 22
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 claims abstract description 22
- -1 tetraphenyl ethylene compound Chemical class 0.000 claims abstract description 21
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 12
- 239000012954 diazonium Substances 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 claims abstract description 6
- 238000006467 substitution reaction Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 18
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 12
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 7
- 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
- 238000002791 soaking Methods 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 238000000206 photolithography Methods 0.000 claims description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical group CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical group CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 229940116333 ethyl lactate Drugs 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 2
- 239000011354 acetal resin Substances 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229920006324 polyoxymethylene Polymers 0.000 claims description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N N-phenyl aniline Natural products C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 4
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 230000000269 nucleophilic effect Effects 0.000 abstract description 2
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 12
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 10
- 238000001259 photo etching Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000004528 spin coating Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical class O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229940126062 Compound A Drugs 0.000 description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- UEJFJTOGXLEPIV-UHFFFAOYSA-M bis(4-tert-butylphenyl)iodanium;4-methylbenzenesulfonate Chemical group CC1=CC=C(S([O-])(=O)=O)C=C1.C1=CC(C(C)(C)C)=CC=C1[I+]C1=CC=C(C(C)(C)C)C=C1 UEJFJTOGXLEPIV-UHFFFAOYSA-M 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BIRLDGKMJJEZRI-UHFFFAOYSA-N 1-bromo-4-[1,2,2-tris(4-bromophenyl)ethenyl]benzene Chemical group C1=CC(Br)=CC=C1C(C=1C=CC(Br)=CC=1)=C(C=1C=CC(Br)=CC=1)C1=CC=C(Br)C=C1 BIRLDGKMJJEZRI-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- VUEDNLCYHKSELL-UHFFFAOYSA-N arsonium Chemical class [AsH4+] VUEDNLCYHKSELL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical group [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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
-
- 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
- G03F7/16—Coating processes; 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
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Materials For Photolithography (AREA)
Abstract
The invention relates to the technical field of photoresist, in particular to a photoresist composition, a preparation method and application thereof. The photoresist composition is mainly prepared from the following components in parts by weight: 20-40 parts of film-forming resin, 5-20 parts of tetraphenyl ethylene derivative, 2-20 parts of cross-linking agent, 0.5-20 parts of photosensitizer and solvent; the tetraphenyl ethylene derivative is a tetraphenyl ethylene compound containing hydroxyl substitution; the crosslinking agent comprises a diazonium resin containing a nitro group. The invention adopts the tetraphenyl ethylene derivative structure with the structure to be matched with a specific cross-linking agent for use, and the tetraphenyl ethylene derivative has certain rigidity, thereby ensuring the high stability of the photoresist product; meanwhile, the electron-withdrawing function of the nitro enables the diazobenzene to generate heterolysis to generate a large amount of diphenylamine cations, and the diphenylamine cations react and crosslink with hydroxyl nucleophilic groups on the tetraphenyl ethylene derivative structure, so that the thermal stability is ensured, the adhesive force between the film layer and the substrate is improved, and the storage time is prolonged.
Description
Technical Field
The invention relates to the technical field of photoresist, in particular to a photoresist composition, a preparation method and application thereof.
Background
Photoresists are used in photolithography for the manufacture of microelectronic devices, such as computer chips, integrated circuits, and the like. The method generally comprises the steps of coating a layer of uniform photoresist on the surface of a substrate material such as a silicon wafer, a sapphire wafer and the like, baking the substrate material to evaporate and remove a solvent in the photoresist, then exposing the substrate material to light to enable main components in the photoresist to react and change component structures and the dissolution speed of the main components in a developing solution, then developing the main components to realize the transfer of a mask pattern on the substrate to form a required photoetching pattern, and finally post-baking and hardening the mask pattern to improve the temperature resistance and the etching resistance of the photoresist in an etching process.
The existing common main raw material resins for the i-line photoresist are phenolic resin, diazo resin and the like, and the conventional main raw material resins have poor heat stability, so that the storage life of the main raw material resins is short, and the application range of the main raw material resins is smaller than that of the main raw material resins at the lower end.
In view of this, the present invention has been made.
Disclosure of Invention
The first object of the present invention is to provide a photoresist composition, which solves the technical problem of poor thermal stability in the prior art.
The second object of the present invention is to provide a method for preparing the above photoresist composition, which is simple to operate, mild in condition, and suitable for mass production.
A third object of the present invention is to provide the use of the photoresist composition described above in the photolithographic manufacture of microelectronic devices.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
the photoresist composition is mainly prepared from the following components in parts by weight:
20-40 parts of film-forming resin, 5-20 parts of tetraphenyl ethylene derivative, 2-20 parts of cross-linking agent, 0.5-20 parts of photosensitizer and solvent;
Wherein the tetraphenyl ethylene derivative is a tetraphenyl ethylene compound containing hydroxyl substitution;
The crosslinking agent comprises a diazonium resin containing a nitro group.
The invention adopts the tetraphenyl ethylene derivative structure with the structure, has certain rigidity, high glass transition temperature and good thermal stability, and ensures the high stability of the photoresist product. And meanwhile, a specific cross-linking agent is matched, when the diazo resin containing nitro is used for exposure, the diazo phenyl group is subjected to heterolysis to generate a large number of diphenylamine cations due to the electron-withdrawing effect of the nitro, and the diphenylamine cations react and crosslink with hydroxyl nucleophilic groups on a tetraphenyl ethylene derivative structure, so that the thermal stability is ensured, the adhesive force between a film layer and a substrate is improved, and the storage time is prolonged.
In a preferred embodiment of the present invention, the hydroxyl-substituted tetraphenyl vinyl compound is selected from one or more of the compounds represented by structural formula (I):
R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11 And R 12 are each independently selected from H, hydroxy or methoxy ,R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11 and R 12 contains at least one hydroxy group.
In a preferred embodiment of the invention ,R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11 and R 12 contain at least two hydroxyl groups, preferably at least three hydroxyl groups, more preferably at least four hydroxyl groups.
In a preferred embodiment of the invention, R 1、R2 and R 3 contain at least one hydroxyl group, R 4、R5 and R 6 contain at least one hydroxyl group, R 7、R8 and R 9 contain at least one hydroxyl group, and R 10、R11 and R 12 contain at least one hydroxyl group.
The tetraphenyl ethylene derivative with the structure can effectively improve the crosslinking degree of the photoresist composition under the action of light, improve the corrosion resistance and the like.
As in the various embodiments, the tetraphenyl ethylene derivative may be used in an amount of 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, etc.; preferably, the tetraphenyl ethylene derivative is used in an amount of 10 to 20 parts.
In a preferred embodiment of the present invention, the nitro group-containing diazo resin has the following structural formula:
Wherein n is an integer between 5 and 100, R 13 is hydrogen, methyl or ethyl, R 14 is hydrogen, methyl or methoxy, and X is hexafluorophosphate or sulfonate.
In a specific embodiment of the present invention, the sulfonate group includes any one of p-toluenesulfonate and dodecylsulfonate.
In a preferred embodiment of the present invention, n is an integer between 6 and 10. As in the various embodiments, n may be 6, 7, 8, 9, 10, etc.
As in the various embodiments, the crosslinking agent may be used in an amount of 2 parts, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, etc.; preferably, the amount of the crosslinking agent is 5 to 15 parts.
In particular embodiments of the present invention, the film-forming resin comprises any one or more of a phenolic resin, a polyvinyl acetal resin.
As in the various embodiments, the film-forming resin may be any one or more of novolac resins, polyvinyl formal phthalate, polyvinyl butyral maleate, and the like, but is not limited thereto. The film-forming resin may be used in an amount of 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, etc.
In specific embodiments of the present invention, the photosensitizer is any one or more of diazonium salt type photosensitizers, ammonium salt type photosensitizers, iodonium salt type photosensitizers, sulfonium salt type photosensitizers, phosphonium salt type photosensitizers, arsonium salt type photosensitizers, oxonium salt type photosensitizers, halogenated organic compound type photosensitizers, quinone diazide compound type photosensitizers, bis (sulfonyl) diazomethane compound type photosensitizers, sulfone compound type photosensitizers, organic acid ester compound type photosensitizers, and organic acid imide compound type photosensitizers.
As in the various embodiments, the photosensitizer may be used in an amount of 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, etc.; preferably, the amount of the photosensitizer is 1 to 6 parts.
In specific embodiments of the present invention, the solvent comprises any one or more of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and diethylene glycol.
The solvent of the invention has wide selection range and good adaptability.
In a preferred embodiment of the present invention, the solvent is used in an amount of 30 to 90 parts.
The photoresist composition of the present invention is a negative photoresist composition. Under the action of light, the crosslinking is carried out to form an insoluble net structure, thereby playing a role in corrosion resistance.
The invention also provides a preparation method of the photoresist composition, which comprises the following steps:
after the components are mixed and dissolved, the photoresist composition is obtained by filtering.
In a specific embodiment of the present invention, filtration is performed using a filter having a pore size of 0.02 μm or less.
Wherein the filter may be a filter membrane.
The invention also provides application of the photoresist composition in the photoetching field.
Specifically, the photoetching process of the photoresist composition comprises the following steps:
and (3) coating the photoresist composition on a pretreated substrate, drying, soaking and developing after ultraviolet light exposure, and baking and hardening after fixation.
The film formed by the photoresist composition has stable structure without collapse under the high temperature condition, and has excellent temperature resistance and etching resistance.
In a specific embodiment of the present invention, the soaking developing liquid is an alkaline aqueous solution. More preferably, the aqueous alkaline solution comprises one or more of an aqueous solution of tetramethylammonium hydroxide, an aqueous solution of potassium hydroxide, an aqueous solution of sodium hydroxide, or an aqueous solution of ammonium hydroxide. More preferably, the aqueous alkaline solution is an aqueous solution of 2.38wt% tetramethylammonium hydroxide.
In a specific embodiment of the present invention, a deionized water fixing process is employed.
In a specific embodiment of the present invention, the drying temperature is 100 to 110 ℃, and the drying time is 60 to 180 seconds.
In a specific embodiment of the present invention, the ultraviolet light is g-line ultraviolet light or i-line ultraviolet light, preferably i-line ultraviolet light. More preferably, the exposure dose is 80-120 mJ/cm 2.
In a specific embodiment of the present invention, the developing temperature is 25±5 ℃, and the developing time is 60 to 90 seconds.
In a specific embodiment of the invention, the temperature of the baked film is 120-130 ℃, and the time for baking the film is 2-3 min.
Compared with the prior art, the invention has the beneficial effects that:
(1) The photoresist composition of the invention is matched with a specific tetraphenyl ethylene derivative structure and a diazo resin containing nitro, so that the heat resistance and corrosion resistance of the photoresist composition can be improved, and the storage time is prolonged;
(2) The preparation method of the photoresist composition is simple, has good repeatability and ensures the high stability of the photoresist composition product;
(3) The photoetching process has high environmental protection performance and is environment-friendly.
Detailed Description
The technical solution of the present invention will be clearly and completely described in conjunction with the specific embodiments, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The general formula of the synthetic route of the hydroxyl-substituted tetraphenyl ethylene compound adopted in the specific embodiment of the invention can be as follows:
Wherein, U 1、U2 and U 3 are independently selected from H, methoxy or hydroxyl, when U 1、U2 and U 3 do not contain hydroxyl, U 1、U2 and U 3 contain at least one methoxy, and the reduction reaction of the boron bromide in the second step is needed; when the hydroxyl groups are contained in U 1、U2 and U 3, the reduction reaction of the boron bromide in the second step may not be performed; when U 1、U2 and U 3 contain hydroxyl groups and methoxy groups, the second reduction of boron bromide may also be performed.
In particular, toFor illustration, the specific synthetic route is as follows:
the method comprises the following specific steps:
(1) Suzuki reaction: mixing tetra (4-bromophenyl) ethylene and phenyl boric acid containing methoxy groups in a molar ratio of 1: (4.5-5) under the protection of high-purity nitrogen or argon, adding 4-6 molar equivalents of sodium carbonate solution with the concentration of 2M and catalytic amount of tetra (triphenylphosphine) palladium into the mixture, and reacting the mixture for 12-24 hours in toluene at the temperature of 50-70 ℃ to obtain a compound A;
(2) And (3) mixing the compound A with BBr 3 in a molar ratio of 1: (10-12), reacting in dry dichloromethane at-50 to-80 ℃ for 4 hours, gradually heating to room temperature, and continuing to react for about 6 hours to obtain the compound B.
And then toFor illustration, the specific synthetic route is as follows:
And then to For illustration, the specific synthetic route is as follows:
the remaining compounds can be synthesized by reference to the general reaction described above.
The general formula of the synthetic route of the nitro-containing diazo resin adopted in the specific embodiment of the invention can be as follows:
Condensing the prepared compound C with paraformaldehyde to prepare diazonium resin, wherein the polymerization method can be referred to a conventional method;
and dissolving the diazonium resin in water, adding a saturated aqueous solution of NaX compound, regulating the pH value, and performing anion exchange to obtain the diazonium resin containing nitro. The specific manner of regulating the pH may be referred to conventional methods.
Wherein HX is sodium hexafluorophosphate, sodium p-toluenesulfonate or sodium dodecyl sulfonate.
Example 1
The photoresist composition of this embodiment comprises the following components:
20g of a film-forming resin,
10G of tetraphenyl ethylene derivative,
5G of a cross-linking agent, wherein,
1G of a photosensitizer, which is used for preparing the dye,
60G of solvent.
Wherein the film-forming resin is a phenolic novolac resin with the following structureR is propyl, n=50;
the structural formula of the tetraphenyl ethylene derivative is
The cross-linking agent is diazo resin, and the structural formula of the diazo resin is
The photosensitizer is triphenylsulfonium hexafluoroantimonate;
the solvent is propylene glycol methyl ether.
The preparation method of the photoresist composition comprises the following steps:
the above components were mixed and sufficiently dissolved, and then filtered through a filter membrane having a pore size of 0.02 μm to obtain a resist composition solution.
The photoetching process of the photoresist composition comprises the following steps:
Spin-coating the photoresist composition solution on a processed substrate such as a silicon wafer, pre-baking the substrate with a hot Plate (PAB) at 100 ℃ for 60s, adjusting the spin-coating rotation speed to enable the film thickness after drying to be 5 mu m, exposing the substrate through a mask by i-line, soaking and developing the substrate with 2.38wt% TMAH for 60s, cleaning the substrate with deionized water, and post-baking the substrate with an oven at 120 ℃ for 120s to complete the photoetching process.
Example 2
The photoresist composition of this embodiment comprises the following components:
30g of a film-forming resin,
10G of tetraphenyl ethylene derivative,
10G of a cross-linking agent, which is a polymer,
2G of a photosensitizer, which is used for preparing the dye,
80G of solvent.
Wherein the film-forming resin is polyvinyl formal phthalate;
the structural formula of the tetraphenyl ethylene derivative is
The cross-linking agent is diazo resin, and the structural formula of the diazo resin isTsO - is p-toluenesulfonate;
the photosensitizer is p-toluenesulfonic acid di (4-tert-butylphenyl) iodonium salt;
The solvent is propylene glycol methyl ether acetate.
The preparation method of the photoresist composition comprises the following steps:
the above components were mixed and sufficiently dissolved, and then filtered through a filter membrane having a pore size of 0.02 μm to obtain a resist composition solution.
The photoetching process of the photoresist composition comprises the following steps:
Spin-coating the photoresist composition solution on a processed substrate such as a silicon wafer, pre-baking (PAB) with a hot plate at 100deg.C for 180s, adjusting spin-coating rotation speed to make the dried film thickness 8 μm, exposing through i-line via mask, soaking and developing with 2.38wt% TMAH for 90s, cleaning with deionized water, and post-baking with an oven at 120deg.C for 120s to complete the photolithography process.
Example 3
The photoresist composition of this embodiment comprises the following components:
40g of a film-forming resin,
18G of a tetraphenyl ethylene derivative,
15G of a cross-linking agent, and the cross-linking agent,
3G of a photosensitizer, which is used for preparing the dye,
90G of solvent.
Wherein the film-forming resin is a phenolic novolac resin with the following structuren＝60；
The structural formula of the tetraphenyl ethylene derivative is
The cross-linking agent is diazo resin, and the structural formula of the diazo resin isX - is dodecyl sulfonate;
The photosensitizer is perfluoro butyl methanesulfonic acid triphenylsulfonium salt;
the solvent is ethyl lactate.
The preparation method of the photoresist composition comprises the following steps:
the above components were mixed and sufficiently dissolved, and then filtered through a filter membrane having a pore size of 0.02 μm to obtain a resist composition solution.
The photoetching process of the photoresist composition comprises the following steps:
Spin-coating the photoresist composition solution on a processed substrate such as a silicon wafer, pre-baking the substrate with a hot Plate (PAB) at 110 ℃ for 120s, adjusting the spin-coating rotation speed to ensure that the dried film thickness is 10 mu m, exposing the substrate through a mask by i-line, soaking and developing the substrate with 2.38wt% TMAH for 90s, cleaning the substrate with deionized water, and post-baking the substrate with an oven at 120 ℃ for 120s to complete the photoetching process.
Comparative example 1
The photoresist composition of comparative example 1 comprises the following components:
40g of a film-forming resin,
10G of a cross-linking agent, which is a polymer,
2G of a photosensitizer, which is used for preparing the dye,
80G of solvent.
Wherein the film-forming resin is polyvinyl formal phthalate;
the cross-linking agent is diazo resin, and the structural formula of the diazo resin is TsO - is p-toluenesulfonate;
the photosensitizer is p-toluenesulfonic acid di (4-tert-butylphenyl) iodonium salt;
The solvent is propylene glycol methyl ether acetate.
The preparation method of the above photoresist composition refers to the preparation method of example 2.
Experimental example
In order to comparatively illustrate the high temperature resistance of the photoresist compositions of the different examples and comparative examples of the present invention, the photoresist composition solutions of examples 1 to 3 and comparative example 1 were subjected to photolithography processes in each example to obtain photoresist patterns, the substrates on which the photoresist patterns were formed were placed in an oven at 200 c for 20 minutes, and after taking out, they were cooled to see whether the photoresist patterns were collapsed, carbonized and discolored, etc., and the test results are shown in table 1.
TABLE 1 test results for different photoresist patterns
| Numbering device | Whether the pattern collapses and deforms | Whether or not the figure is carbonized and discolored |
| Example 1 | Whether or not | Whether or not |
| Example 2 | Whether or not | Whether or not |
| Example 3 | Whether or not | Whether or not |
| Comparative example 1 | Pattern collapse | Blackening by carbonization of surface |
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (11)
1. The negative photoresist composition is characterized by being mainly prepared from the following components in parts by weight:
20-40 parts of film-forming resin, 5-20 parts of tetraphenyl ethylene derivative, 2-20 parts of cross-linking agent, 0.5-20 parts of photosensitizer and solvent;
Wherein the tetraphenyl ethylene derivative is a tetraphenyl ethylene compound containing hydroxyl substitution;
The hydroxyl-containing substituted tetraphenyl ethylene compound is selected from one or more of the compounds shown in the following structural formulas:
the cross-linking agent is selected from diazo resins containing nitro groups;
The structural formula of the nitro-containing diazo resin is as follows:
Wherein n is an integer between 5 and 100, R 13 is hydrogen, methyl or ethyl, R 14 is hydrogen, methyl or methoxy, and X is hexafluorophosphate, p-toluenesulfonate or dodecylsulfonate;
the film-forming resin is selected from any one or more of phenolic resin and polyvinyl acetal resin;
the photosensitizer is selected from any one or more of iodonium salt photosensitizer and sulfonium salt photosensitizer.
2. The photoresist composition according to claim 1, where the tetraphenyl ethylene derivative is used in an amount of 10 to 20 parts.
3. The photoresist composition according to claim 1, wherein n is an integer between 6 and 10 in the diazonium resin containing a nitro group.
4. The photoresist composition according to claim 1, where the cross-linking agent is used in an amount of 5 to 15 parts.
5. The photoresist composition according to claim 1, where the photosensitizer is used in an amount of 1 to 6 parts.
6. The photoresist composition according to claim 1, wherein the solvent is selected from any one or more of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and diethylene glycol.
7. The photoresist composition according to claim 6, where the solvent is used in an amount of 30 to 90 parts.
8. A method of preparing a photoresist composition according to any one of claims 1 to 7, comprising the steps of:
after the components are mixed and dissolved, the photoresist composition is obtained by filtering.
9. The method of producing a photoresist composition according to claim 8, wherein the filtration is performed by using a filter having a pore size of 0.02 μm or less.
10. Use of a photoresist composition according to any of claims 1 to 7 in the field of photolithography.
11. The use according to claim 10, wherein the photolithographic process of the photoresist composition comprises the steps of:
and (3) coating the photoresist composition on a pretreated substrate, drying, soaking and developing after ultraviolet light exposure, and baking and hardening after fixation.
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| CN104530342A (en) * | 2015-01-09 | 2015-04-22 | 京东方科技集团股份有限公司 | Diazoresin, photoresist composition and preparation method of photoresist composition |
| CN104557552A (en) * | 2013-10-22 | 2015-04-29 | 中国科学院理化技术研究所 | Starlike tetraphenylethylene derivative molecular glass, positive photoresist, positive photoresist coating and application thereof |
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| CN104557552A (en) * | 2013-10-22 | 2015-04-29 | 中国科学院理化技术研究所 | Starlike tetraphenylethylene derivative molecular glass, positive photoresist, positive photoresist coating and application thereof |
| CN104530342A (en) * | 2015-01-09 | 2015-04-22 | 京东方科技集团股份有限公司 | Diazoresin, photoresist composition and preparation method of photoresist composition |
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