CN114573641A - Iridium complex derivative, preparation method and application thereof - Google Patents
Iridium complex derivative, preparation method and application thereof Download PDFInfo
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- CN114573641A CN114573641A CN202210263819.1A CN202210263819A CN114573641A CN 114573641 A CN114573641 A CN 114573641A CN 202210263819 A CN202210263819 A CN 202210263819A CN 114573641 A CN114573641 A CN 114573641A
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- iridium complex
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- coumarin
- complex derivative
- photoresist
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- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 43
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- -1 cyclodecyl Chemical group 0.000 claims description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 14
- WEIGQBHMLRHDGX-UHFFFAOYSA-N chromen-2-one;iridium Chemical compound [Ir].C1=CC=C2OC(=O)C=CC2=C1 WEIGQBHMLRHDGX-UHFFFAOYSA-N 0.000 claims description 12
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims description 12
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 239000003504 photosensitizing agent Substances 0.000 claims description 8
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 6
- LTHJXDSHSVNJKG-UHFFFAOYSA-N 2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOC(=O)C(C)=C LTHJXDSHSVNJKG-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 claims description 4
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 claims description 4
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 claims description 4
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- UYAAVKFHBMJOJZ-UHFFFAOYSA-N diimidazo[1,3-b:1',3'-e]pyrazine-5,10-dione Chemical compound O=C1C2=CN=CN2C(=O)C2=CN=CN12 UYAAVKFHBMJOJZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 125000000962 organic group Chemical group 0.000 claims description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 229940116423 propylene glycol diacetate Drugs 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 4
- GJEZBVHHZQAEDB-SYDPRGILSA-N (1s,5r)-6-oxabicyclo[3.1.0]hexane Chemical compound C1CC[C@H]2O[C@H]21 GJEZBVHHZQAEDB-SYDPRGILSA-N 0.000 claims description 3
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 3
- SAPGBCWOQLHKKZ-UHFFFAOYSA-N 6-(2-methylprop-2-enoyloxy)hexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCOC(=O)C(C)=C SAPGBCWOQLHKKZ-UHFFFAOYSA-N 0.000 claims description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 claims description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 2
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 claims description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 2
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- MJRFDVWKTFJAPF-UHFFFAOYSA-K trichloroiridium;hydrate Chemical group O.Cl[Ir](Cl)Cl MJRFDVWKTFJAPF-UHFFFAOYSA-K 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims 1
- 230000035945 sensitivity Effects 0.000 abstract description 6
- CFNMUZCFSDMZPQ-GHXNOFRVSA-N 7-[(z)-3-methyl-4-(4-methyl-5-oxo-2h-furan-2-yl)but-2-enoxy]chromen-2-one Chemical compound C=1C=C2C=CC(=O)OC2=CC=1OC/C=C(/C)CC1OC(=O)C(C)=C1 CFNMUZCFSDMZPQ-GHXNOFRVSA-N 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 3
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 3
- 206010034972 Photosensitivity reaction Diseases 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract description 2
- 230000005284 excitation Effects 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 230000036211 photosensitivity Effects 0.000 abstract description 2
- 239000003999 initiator Substances 0.000 abstract 1
- 238000001259 photo etching Methods 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000000206 photolithography Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 125000000332 coumarinyl group Chemical group O1C(=O)C(=CC2=CC=CC=C12)* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000005281 excited state Effects 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
- 238000010884 ion-beam technique Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- FKRCODPIKNYEAC-UHFFFAOYSA-N propionic acid ethyl ester Natural products CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
- C07F15/004—Iridium compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
-
- 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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials For Photolithography (AREA)
Abstract
The invention relates to the technical field of photoresist, and relates to an iridium complex derivative, a preparation method and application thereof. According to the invention, by virtue of the property of high molar absorption coefficient of a coumarin derivative, a metal heavy atom iridium atom is introduced to enhance intermolecular cross-over, and through excitation of a triplet state, electron transfer is further initiated and effectively generated by a co-initiator, so that the sensitive wavelength of the photoresist is changed, the yield of photoacid is improved, the photosensitivity of the photoresist composition is improved, and the sensitivity of the photoresist, the crosslinking capability of a monomer, the line width roughness of the photoresist, the resolution and the film forming capability are further enhanced.
Description
Technical Field
The invention relates to the technical field of photoresist, in particular to an iridium complex derivative, a preparation method and application thereof.
Background
The photoresist, also called as photoresist, refers to a resist film material whose solubility changes by irradiation or radiation of light sources such as ultraviolet light, excimer laser, electron beam, ion beam, and X-ray. The method is mainly used for the micro-processing of integrated circuits and semiconductor discrete devices, and also has wide application in the manufacturing processes of flat panel displays, LEDs, magnetic heads with inverted buckle packages, precision sensors and the like. According to the difference of photochemical reaction mechanism, the photoresist is divided into a positive photoresist and a negative photoresist: after exposure, the solubility of the photoresist in a developing solution is increased, and the photoresist with the same pattern as the mask is obtained and is called as a positive photoresist; after exposure, the solubility of the photoresist in a developing solution is reduced, even the photoresist is insoluble, and the negative photoresist with a pattern opposite to that of the mask is obtained. Three important parameters of the photoresist include resolution, sensitivity and line width roughness, which determine the process window of the photoresist during chip fabrication.
In photoresist compositions, poor sensitivity can render the monomer insufficiently crosslinked, requiring the addition of a photosensitizer to further adjust its sensitivity. However, excessive amounts of photosensitizer can cause overexposure, and it is important to add the photosensitizer in an appropriate ratio. As the size of the lithographic pattern is required to be smaller and higher, the resolution and edge roughness of the lithographic pattern are required to be higher and higher, and therefore, it is necessary to develop a new photosensitive system to improve the performance of the photoresist.
Disclosure of Invention
In order to solve the problems, the invention provides an iridium complex derivative, a preparation method and application thereof in photoresist, wherein by means of the property of high molar absorption coefficient of a coumarin derivative, a metal heavy atom iridium atom is introduced to strengthen intersystem crossing of the coumarin derivative, and through excitation of a triplet state, electron transfer is further initiated to effectively generate with a coinitiator, so that the sensitive wavelength of the photoresist is changed, the yield of photoacid is improved, the photosensitivity of the photoresist composition is improved, and the sensitivity of the photoresist, the crosslinking capability of a monomer, the line width roughness of the photoresist, the resolution, the film forming capability and the like are further enhanced.
To achieve the purpose, the method is realized by the following technical scheme:
an iridium complex derivative, the structure of which is one of the following formulas:
wherein:
R1and R2Selected from hydrogen atoms, C1～C20Alkyl of (C)3～C20Cycloalkyl or a monovalent organic radical having a carbon-carbon unsaturated double bond, R1And R2The same or different; r3、R4、R5And R6Selected from hydrogen atom, methoxy group, phenoxy group, nitro group, cyano group, trifluoromethyl group, carboxyl group, mercapto group, halogen atom or alkyl group, R3、R4、R5And R6The same or different; r7、R8、R9、R10、R11And R12Selected from carbon atoms or nitrogen atoms, R7、R8、R9、R10、R11And R12The same or different.
The alkyl can be methyl, ethyl or propyl, and can also be substituted methyl, ethyl or propyl; c1～C20The alkyl group of (a) may be methyl, ethyl, n-propyl, isopropyl, n-pentyl, dodecyl, octadecyl or eicosyl; c3～C20The cycloalkyl group of (a) may be cyclopropyl, cyclopentyl, cyclodecyl, cyclododecyl or cycloeicosyl; the monovalent organic group having a carbon-carbon unsaturated double bond may be a group in which a hydrogen atom in a vinyl group is partially substituted.
The preparation method of the iridium complex derivative comprises the following specific steps:
the iridium complex derivative with the structure of formula (I) is prepared by mixing coumarin phenanthroline and an iridium complex in a solvent for reaction;
the iridium complex derivative with the structure of formula (II) is prepared by mixing and reacting coumarin iridium complex and 2,2' -bipyridine in a solvent;
the iridium complex derivative with the structure of formula (III) is prepared by mixing coumarin phenanthroline and coumarin iridium complex in a solvent for reaction;
wherein:
the iridium complex is iridium trichloride monohydrate or di-mu-chloro-tetra [2- (2-pyridyl-kN) phenyl-kC ] diidium (III) or di-mu-chloro-tetra [2- (2-pyridyl-kN) pyridyl-kC ] diidium (III);
preferably, the structure of the coumarin phenanthroline is
The coumarin iridium complex has a structure of
Wherein R1 and R2 are independently selected from hydrogen, C1～C20Alkyl of (C)3～C20A cycloalkyl group or a monovalent organic group having a carbon-carbon unsaturated double bond; r3, R4, R5 and R6 are independently selected from any one of a hydrogen atom, a methoxy group, a phenoxy group, a nitro group, a cyano group, a trifluoromethyl group, a carboxyl group, a mercapto group, a halogen atom or an alkyl group.
Preferably, the solvent is a mixed solvent of dichloromethane and methanol, wherein the volume ratio of dichloromethane to methanol is 2: (0.8 to 1).
Preferably, the molar ratio of the coumarin phenanthroline to the iridium complex, the 2,2' bipyridine or the coumarin iridium complex is 2: (0.8-1).
Preferably, the temperature of the mixing reaction is 40-70 ℃.
Preferably, the mixing reaction time is 5-10 h.
The iridium complex derivative is used as a photosensitizer as a photoresist component, and the photoresist component comprises, by mass, 0.1-5% of the photosensitizer, 3-5% of a photoacid generator, 30-50% of an acidic active resin and 50-70% of an organic solvent.
Preferably, the formula of the photoacid generator is
Preferably, the acidic active resin is tetraethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane triacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol dimethacrylate, pentaerythritol tetramethacrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl methacrylate, 4-vinylpyridine, 1, 6-hexanediol dimethacrylate, and the like, One or more than two of SU-8 resin, 2-hydroxyethyl acrylate, 1, 2-epoxycyclopentane and 3, 4-epoxycyclohexyl formic acid-3 ',4' -epoxycyclohexyl methyl ester; further preferred is SU-8 resin.
Preferably, the organic solvent is one or a mixture of more than two of propylene glycol methyl ether acetate, propylene glycol diacetate, 3-ethoxy-3-imine ethyl propionate, N-methyl pyrrolidone, 2-heptane, 3-heptane, cyclopentanone and cyclohexanone; more preferably, propylene glycol methyl ether acetate and propylene glycol diacetate are mixed, and cyclopentanone and cyclohexanone are mixed.
The invention has the beneficial effects that:
(1) the coumarin group is introduced, has higher molar extinction coefficient in near ultraviolet and visible light regions, has strong absorption characteristic, and can be widely applied to g-line and i-line photoetching. The iridium atoms are introduced to effectively promote the crossing of excited state energy generation systems, so that more energy is distributed on a triplet state, and efficient electron transfer is generated between the iridium atoms and a photoacid generator, thereby promoting the generation of photoacid.
(2) The invention introduces iridium complex derivatives, effectively improves the sensitivity of the photoresist, prepares the photoresist composition with lower photosensitizer dosage, photoacid generator and acid resin, has simple preparation and is easy to obtain micrometer resolution ratio photoetching samples.
Drawings
FIG. 1 is a photograph of an electron scanning lens obtained by photolithography using a photoresist composition of an iridium complex derivative prepared in example 2 of the present invention.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way.
Example 1
In a clean 50ml round bottom flask, 87mg coumarin phenanthroline, 208mg coumarin iridium complex are added, and the volume ratio is 2: 1 and a methanol solvent at the reaction temperature of 40 ℃ for 5 hours to obtain the iridium complex derivative shown in the formula (III).
In a new clean 10mL glass bottle, 0.8g trimethylolpropane triacrylate, 1mg iridium complex derivative of formula (III), 100mg iodonium salt, 1.0g propylene glycol methyl ether acetate solvent were added. The mixture was shaken in a glass bottle for 24 hours at room temperature to dissolve it sufficiently. The photoresist solution was then filtered through 0.22 micron and 0.02 micron filters, respectively. After completion, photolithography experiments were performed.
The photoetching experimental method comprises the following steps: the prepared photoresist composition is coated on a quartz silicon wafer at 500 rpm/s; spin-coating at 3000rpm/s to form a film, baking at 95 deg.C on a hot plate for 60 s, and exposing to i-line (365nm) exposure machine for 14 s at a dose of 140mJ/cm2. After exposure, the plate was baked on a hot plate at 95 ℃ for 120 seconds, finally developed in SU-8 developer for 55 seconds and rinsed in isopropanol for 10 seconds.
The structure of the coumarin phenanthroline compound described in this embodiment is:
the structure of the coumarin iridium complex compound described in this embodiment is:
example 2
In a clean 50ml round bottom flask, 30.2mg of 2,2' -bipyridine, 208mg of coumarin iridium complex were added, and a solution of 2: 0.8 of dichloromethane and methanol solvent, the reaction temperature is 70 ℃, and the reaction time is 10 hours, so as to obtain the iridium complex derivative shown in the formula (II).
In a new clean 10mL glass vial, 1.0g of 1, 2-epoxycyclopentane, 100mg of the iridium complex derivative of formula (II), 100mg of the iodonium salt, 2.0g of equal volume ratio solvents for cyclopentanone and cyclohexanone were added. The mixture was shaken in a glass bottle for 24 hours at room temperature to dissolve it sufficiently. The photoresist solution was then filtered through 0.22 micron and 0.02 micron filters, respectively. After completion, photolithography experiments were performed.
The photoetching experimental method comprises the following steps: the prepared photoresist composition is coated on a quartz silicon wafer at 500 rpm/s; spin-coating at 3000rpm/s to form a film, baking at 105 deg.C on a hot plate for 60 s, and exposing to an i-line (365nm) exposure machine for 15 s at a dose of 150mJ/cm2. After exposure, the plate was baked on a hot plate at 105 ℃ for 120 seconds, finally developed in SU-8 developer for 55 seconds and rinsed in isopropanol for 10 seconds.
The coumarin iridium complex compound described in this embodiment has a structure:
example 3
In a clean 50ml round bottom flask, 87mg coumarin phenanthroline, 107mg iridium complex are added, and the volume ratio is 2: 0.8 of dichloromethane and methanol solvent, the reaction temperature is 55 ℃, and the reaction time is 6 hours, so as to obtain the iridium complex derivative shown in the formula (I).
In a new clean 10mL glass vial, 0.7g SU-8 resin, 7.9mg iridium complex derivative of formula (I), 83mg iodonium salt, 1.2g cyclopentanone solvent are added. The mixture was shaken in a glass bottle for 24 hours at room temperature to dissolve it sufficiently. The photoresist solution was then filtered through 0.22 micron and 0.02 micron filters, respectively. After completion, photolithography experiments were performed.
The photoetching experimental method comprises the following steps: the prepared photoresist composition is arranged on a quartz silicon wafer at the speed of 500 rpm/s; spin-coating at 3000rpm/s to form a film, baking at 110 deg.C on a hot plate for 60 s, and exposing to i-line (365nm) exposure machine for 17 s at a dose of 170mJ/cm2. After exposure, baking the substrate on a hot plate at 110 ℃ for 120 seconds, finally developing the substrate in SU-8 developer for 60 seconds, cleaning the substrate in isopropanol for 10 seconds, drying the substrate, carrying out gold spraying treatment on the photoetching sample, and detecting the photoetching result in a scanning electron microscope, wherein the experimental result is shown in figure 1.
The structure of the coumarin phenanthroline compound described in this embodiment is:
the iridium complex compound described in this embodiment has the structure:
Claims (10)
1. an iridium complex derivative, wherein the structure of the iridium complex derivative is one of the following formulas:
wherein:
R1and R2Selected from hydrogen atoms, C1～C20Alkyl of (C)3～C20Cycloalkyl or a monovalent organic radical having a carbon-carbon unsaturated double bond, R1And R2The same or different; r3、R4、R5And R6Selected from hydrogen atom, methoxy group, phenoxy group, nitro group, cyano group, trifluoromethyl group, carboxyl group, mercapto group, halogen atom or alkyl group, R3、R4、R5And R6The same or different; r7、R8、R9、R10、R11And R12Selected from carbon atoms or nitrogen atoms, R7、R8、R9、R10、R11And R12The same or different.
2. An iridium complex derivative according to claim 1, wherein the alkyl group is a methyl, ethyl or propyl group, or a substituted methyl, ethyl or propyl group; c1～C20Alkyl of (a) is methyl, ethyl, n-propyl, isopropyl, n-pentyl, dodecyl, octadecyl or eicosyl; c3～C20Cycloalkyl of (a) is cyclopropyl, cyclopentyl, cyclodecyl, cyclododecyl or cycloeicosyl; the monovalent organic group having a carbon-carbon unsaturated double bond is a case where a hydrogen atom in a vinyl group is partially substituted.
3. The method for producing an iridium complex derivative according to claim 1 or 2, which is characterized by comprising:
the iridium complex derivative with the structure of formula (I) is prepared by mixing coumarin phenanthroline and an iridium complex in a solvent for reaction;
the iridium complex derivative with the structure of formula (II) is prepared by mixing and reacting coumarin iridium complex and 2,2' bipyridine in a solvent;
the iridium complex derivative with the structure of formula (III) is prepared by mixing coumarin phenanthroline and coumarin iridium complex in a solvent for reaction;
wherein:
the iridium complex is iridium trichloride monohydrate or di-mu-chloro-tetra [2- (2-pyridyl-kN) phenyl-kC ] diidium (III) or di-mu-chloro-tetra [2- (2-pyridyl-kN) pyridyl-kC ] diidium (III);
the structure of the coumarin phenanthroline is
The coumarin iridium complex has a structure of
Wherein R1 and R2 are independently selected from hydrogen, C1～C20Alkyl of (C)3～C20A cycloalkyl group or a monovalent organic group having a carbon-carbon unsaturated double bond; r3, R4, R5 and R6 are independently selected from any one of a hydrogen atom, a methoxy group, a phenoxy group, a nitro group, a cyano group, a trifluoromethyl group, a carboxyl group, a mercapto group, a halogen atom or an alkyl group;
the solvent is a mixed solvent of dichloromethane and methanol.
4. The process for producing an iridium complex derivative according to claim 3,
the volume ratio of the dichloromethane to the methanol is 2: (0.8 to 1);
the molar ratio of the coumarin phenanthroline to the iridium complex to the 2,2' -bipyridine or coumarin iridium complex is 2: (0.8-1).
5. The process for producing an iridium complex derivative according to claim 3 or 4,
the temperature of the mixing reaction is 40-70 ℃;
the mixing reaction time is 5-10 h.
6. The iridium complex derivative as claimed in claim 1 or 2, which is used as a photosensitizer as a photoresist component, wherein the photoresist component comprises, by mass, 0.1% to 5% of the photosensitizer, 3% to 5% of the photoacid generator, 30% to 50% of the acidic reactive resin, and 50% to 70% of an organic solvent.
7. The use of the iridium complex derivative as claimed in claim 6, wherein the photoacid generator has the structural formula
8. The use of the iridium complex derivative according to claim 7, wherein the acidic reactive resin is tetraethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane triacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol dimethacrylate, pentaerythritol tetramethacrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, pentaerythritol, styrene, divinylbenzene, and mixtures thereof, One or more of N-vinyl pyrrolidone, 2-hydroxyethyl methacrylate, SU-8 resin, 2-hydroxyethyl acrylate, 1, 2-epoxycyclopentane, and 3, 4-epoxycyclohexylcarboxylic acid-3 ',4' -epoxycyclohexylmethyl ester.
9. The use of the iridium complex derivative according to claim 7 or 8, wherein the organic solvent is one or more selected from propylene glycol methyl ether acetate, propylene glycol diacetate, ethyl 3-ethoxy-3-imine propionate, N-methylpyrrolidone, 2-heptane, 3-heptane, cyclopentanone, and cyclohexanone.
10. The use of the iridium complex derivative according to claim 9, wherein the organic solvent is a mixture of propylene glycol methyl ether acetate and propylene glycol diacetate, or a mixture of cyclopentanone and cyclohexanone.
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Non-Patent Citations (4)
| Title |
|---|
| JIFU SUN等: "Visible-light harvesting iridium complexes as singlet oxygen sensitizers for photooxidation of 1,5-dihydroxynaphthalene", 《CHEM. COMMUN.》 * |
| JIFU SUN等: "Visible-Light Harvesting with Cyclometalated Iridium(III) Complexes Having Long-Lived 3IL Excited States and Their Application in Triplet-Triplet-Annihilation Based Upconversion", 《EUR. J. INORG. CHEM.》 * |
| KEJING XU等: "Switching of the Triplet−Triplet-Annihilation Upconversion with Photoresponsive Triplet Energy Acceptor: Photocontrollable Singlet/Triplet Energy Transfer and Electron Transfer", 《J. PHYS. CHEM. A》 * |
| MOHAMAD-ALI TEHFE等: "Iridium complexes incorporating coumarin moiety as catalyst photoinitiators: Towards household green LED bulb and halogen lamp irradiation", 《POLYMER》 * |
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