CN103012227A - Sulfonium salt photo-acid generator having high photo-acid generation quantum yield, and preparation method and application thereof - Google Patents
Sulfonium salt photo-acid generator having high photo-acid generation quantum yield, and preparation method and application thereof Download PDFInfo
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- 239000002253 acid Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000006862 quantum yield reaction Methods 0.000 title claims abstract description 18
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract 7
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 34
- -1 hexafluorophosphate Chemical group 0.000 claims abstract description 22
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 125000006505 p-cyanobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C#N)C([H])([H])* 0.000 claims abstract 2
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims abstract 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 26
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 229920006395 saturated elastomer Polymers 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000004440 column chromatography Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- RBHJBMIOOPYDBQ-UHFFFAOYSA-N carbon dioxide;propan-2-one Chemical compound O=C=O.CC(C)=O RBHJBMIOOPYDBQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 4
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 239000003480 eluent Substances 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims 3
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims 2
- PLDWAJLZAAHOGG-UHFFFAOYSA-N 1-bromo-3-methoxybenzene Chemical compound COC1=CC=CC(Br)=C1 PLDWAJLZAAHOGG-UHFFFAOYSA-N 0.000 claims 1
- UMLFTCYAQPPZER-UHFFFAOYSA-N 4-(bromomethyl)benzonitrile Chemical compound BrCC1=CC=C(C#N)C=C1 UMLFTCYAQPPZER-UHFFFAOYSA-N 0.000 claims 1
- 238000004458 analytical method Methods 0.000 claims 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims 1
- 239000012267 brine Substances 0.000 claims 1
- 239000012141 concentrate Substances 0.000 claims 1
- 125000003963 dichloro group Chemical group Cl* 0.000 claims 1
- 238000002523 gelfiltration Methods 0.000 claims 1
- 230000001678 irradiating effect Effects 0.000 claims 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims 1
- LSEFCHWGJNHZNT-UHFFFAOYSA-M methyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 LSEFCHWGJNHZNT-UHFFFAOYSA-M 0.000 claims 1
- XDEPVFFKOVDUNO-UHFFFAOYSA-N pentafluorobenzyl bromide Chemical compound FC1=C(F)C(F)=C(CBr)C(F)=C1F XDEPVFFKOVDUNO-UHFFFAOYSA-N 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 claims 1
- 239000004332 silver Substances 0.000 claims 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims 1
- 125000005504 styryl group Chemical group 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000003384 imaging method Methods 0.000 abstract 1
- 230000001443 photoexcitation Effects 0.000 abstract 1
- 125000002827 triflate group Chemical group FC(S(=O)(=O)O*)(F)F 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 42
- 239000000463 material Substances 0.000 description 23
- 238000000034 method Methods 0.000 description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 238000001259 photo etching Methods 0.000 description 7
- 230000003321 amplification Effects 0.000 description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000003199 nucleic acid amplification method Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000003292 glue Substances 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- CFNMGCBIEOFTFD-UHFFFAOYSA-N bromobenzene methylsulfanylmethane Chemical compound CSC.BrC1=CC=CC=C1 CFNMGCBIEOFTFD-UHFFFAOYSA-N 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- NTKVWOTYTNWGRK-UHFFFAOYSA-N P.Br.Br.Br Chemical compound P.Br.Br.Br NTKVWOTYTNWGRK-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000001459 lithography Methods 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- WCGIGOVLOFXAMG-UHFFFAOYSA-N silver;trifluoromethanesulfonic acid Chemical compound [Ag].OS(=O)(=O)C(F)(F)F WCGIGOVLOFXAMG-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000009966 trimming Methods 0.000 description 3
- 229960004418 trolamine Drugs 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 230000000640 hydroxylating effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910000474 mercury oxide Inorganic materials 0.000 description 2
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- HNKJADCVZUBCPG-UHFFFAOYSA-N thioanisole Chemical compound CSC1=CC=CC=C1 HNKJADCVZUBCPG-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 235000009161 Espostoa lanata Nutrition 0.000 description 1
- 240000001624 Espostoa lanata Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000007239 Wittig reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一种高光生酸量子产率硫鎓盐类光生酸剂、制备方法及其应用。本发明提出的光生酸剂化合物，其中：R1为甲基、苄基、五氟代苯基或4-氰基苄基；R2为三氟甲烷磺酸根、六氟磷酸根、六氟锑酸根或四氟硼酸根。本发明的PAG适用于诸如365nm、385nm、405nm，425nm的紫外区到近可见光区成像的光刻胶光活性成分。此类光生酸剂合成步骤简单，易于提纯，产率高，在365nm～425nm区域内，此类光生酸剂用于光刻胶体系能制备出性能优良的光刻胶，体现出0.3～0.6的光生酸量子产率，光激发效率高，催化活性高。
The invention relates to a sulfonium salt photoacid generator with high photoacid quantum yield, a preparation method and application thereof. The photoacid generator compound proposed by the present invention, wherein: R is methyl, benzyl, pentafluorophenyl or 4-cyanobenzyl; R is trifluoromethanesulfonate, hexafluorophosphate, hexafluoroantimony acid or tetrafluoroborate. The PAG of the present invention is suitable for the photoresist photoactive components for imaging from the ultraviolet region to the near-visible region such as 365nm, 385nm, 405nm and 425nm. This kind of photoacid generator has simple synthesis steps, is easy to purify, and has a high yield. In the region of 365nm to 425nm, this kind of photoacid generator can be used in photoresist systems to prepare photoresists with excellent performance, reflecting the 0.3~0.6 Photogenerated acid quantum yield, high photoexcitation efficiency, high catalytic activity.
Description
Technical field
The present invention relates to a kind of high photogenerated acid quantum yield sulfosalt class photo-acid agent, preparation method and application thereof.
Background technology
Photoresist material is to suprabasil photosensitive film with image transfer.They form the negative or positive image.After being coated in photoresist material in the substrate, seeing through figuratum mask or light shield coating is exposed to such as UV-light, under the activation energy of near visible, in photoetching agent pattern, form sub-image.For activating radiation, light shield has opaque zone and transparent zone, has determined to transfer to the image of following substrate.By with the sub-image pattern development in the photoresist coating, obtained three-dimensional image.
Photo-acid agent is the important component in the photoresist material system, and photo-acid agent is a kind of efficient chemical amplification agent that is developed the eighties in 20th century.It can be by absorbing the photon energy generation proton that dissociates, thereby cause the variation of exposure area physicochemical property.Because the sour mechanism of this product is extraneous controlled, and this chemical amplification effect can improve photochemically reactive speed greatly, so photo-acid agent has been widely used in photoresist material in recent years, Computer To Plate is in the numerous areas such as acid polymerization and lucifuge indicator as [201010625168.3] etc.A sulfosalt type photo-acid agent conduct large class is wherein used widely by people, and various method of modifying also emerge in an endless stream.After the photoresist coating exposure that will contain photo-acid agent, select the cracking blocking group, polar functional group is provided, for example carboxyl, phenol or imines, this causes in photoresist coating exposure and the different solvability of unexposed zone formation.
Summary of the invention
The object of the invention is to a kind of high photogenerated acid quantum yield sulfosalt class photo-acid agent, preparation method and application thereof.
The isomers that contains the para-orientation in this class photo-acid agent and 201010284441 of the present invention is compared, and can provide preferably lithographic results after being made into photoresist material.Referring to following embodiment 6 for example, 7 result.
A kind of high photogenerated acid quantum yield sulfosalt class photo-acid agent that the present invention proposes, the structural formula of described photo-acid agent is as follows:
R wherein
1For in methyl, benzyl, phenyl-pentafluoride base or the 4-cyano group benzyl any; R
2 -Be gegenion.
Among the present invention, described R
2 -For in trifluoromethayl sulfonic acid root, hexafluoro-phosphate radical, hexafluoroantimonic anion or the tetrafluoroborate any.
The preparation method of the high photogenerated acid quantum yield sulfosalt class photo-acid agent that the present invention proposes, concrete steps are as follows:
(1) under protection of inert gas, with 2.67g, 10mmol N, N-pentanoic benzaldehyde is dissolved in the anhydrous tetrahydro furan, and adds 5.36g, 15mmol methyltriphenylphospbromide bromide phosphorus, 0
oDrip the 3.6g that is dissolved in tetrahydrofuran (THF) under the C, the 30mmol potassium tert.-butoxide, keeping system temperature is 0
oC ~ 10
oC; Be warming up to room temperature after dripping, stirring reaction 3 ~ 6 hours, reaction soln is poured into water, dichloromethane extraction, salt water washing, organic phase anhydrous sodium sulfate drying, column chromatography obtains liquid, after desolventizing, vacuum obtains white powder product (2.168g, 8mmol) N, N-hexichol amido vinylbenzene;
(2) under the protection of inert gas, with step (1) product 2.71g, 10mmol N; N-hexichol amido vinylbenzene adds in the 33mL trolamine, adds 2.03g, 10mmol 3-bromobenzene dimethyl sulfide and 40mg again; 0.18mmol palladium is heated with stirring to 100 ~ 120
oC, lucifuge stirs, and reacts after 10 ~ 12 hours, is poured into water to produce blackish green solid, filter, the solid that filtration is obtained is dissolved in the methylene dichloride, removes palladium through filtered through silica gel, and filtrate desolventizes rear acquisition thick liquid, purify through column chromatography, obtain faint yellow solid product 2.87g, 7mmol 3-(N, N-hexichol amido styryl) thioanisole; Wherein: the eluent that adopts in the column chromatography is the mixed solution of cyclohexane and ethyl acetate, and the volume ratio of hexanaphthene and ethyl acetate is 10/1 ~ 5/1;
(3) with step (2) product 3-(N, N-hexichol amido styryl) thioanisole is dissolved in the anhydrous methylene chloride, in dry ice acetone bath, add the trifluoro-methane sulfonic acid silver of 1.5 times of amounts and halogenated alkane or the halogenated aryl hydrocarbon of 1.5 times of amounts, lucifuge stirs after 0.5 ~ 1 hour and removes freezing plant, the desolventizing after 20 ~ 24 hours of lucifuge stirring at room, add the acetonitrile dissolving, the filtering undissolved solid, concentrated solution is added dropwise in the anhydrous diethyl ether, produce yellow mercury oxide, filter to such an extent that be dissolved in acetone after the precipitation, be added dropwise in the saturated aqueous solution of inorganic salt, produce yellow mercury oxide, obtain yellow powder after filtering, be required product.
Among the present invention, rare gas element is nitrogen described in step (1) and the step (2).
Among the present invention, halogenated alkane described in the step (3) adopts methyl iodide; Halogenated aryl hydrocarbon can adopt in benzyl bromine, 4-cyano group benzyl bromine or five fluorobenzyl bromides etc. any.
Among the present invention, the saturated aqueous solution of inorganic salt described in the step (3) be in phosphofluoric acid potassium solution, hexafluoro-antimonic acid sodium solution or the Tetrafluoroboric acid sodium solution any.
Among the present invention, the ratio of anhydrous diethyl ether and acetonitrile solution is the ether volume in the step (3): the acetonitrile solution volume is 10:1.
Among the present invention, the saturated aqueous solution of inorganic salt and the ratio of acetone soln are the saturated aqueous solution volume in the step (3): the acetone soln volume is 25:1.
The application of high photogenerated acid quantum yield sulfosalt class photo-acid agent of the present invention in photoresist material.
Among the present invention, described high photogenerated acid quantum yield sulfosalt class photo-acid agent is applied to form the photoresist material camegraph, and step is as follows:
(1) at slide glass or silicon chip coating photoetching compositions film;
(2) heating, drying is removed solvent on hot platform;
(3) with the photographic developer flash trimming;
(4) with the light source irradiation photoresist film, described optical source wavelength is 365nm～425nm;
(5) baking photoresist material after;
The film that (6) will shine with developing solution develops;
(7) cleaning and dry.
Photoresist material of the present invention is in accordance with known methods preparation generally, and except replacing existing Photoactive compounds of filling a prescription for this class photoresist material with PAG of the present invention, and PAG photogenerated acid ability of the present invention is stronger, sees embodiment 5.
Beneficial effect of the present invention is: this type of photo-acid agent synthesis step is simple, be easy to purify, productive rate is high, in 365nm～425nm zone, this type of photo-acid agent is used for the photoresist material that the photoresist material system can be prepared excellent property, embody 0.3～0.6 photogenerated acid quantum yield, optical excitation efficient is high, and catalytic activity is high.
Description of drawings
Fig. 1 SU-8 2005 rotating speeds-thickness relationship figure.
The photo-acid agent of Fig. 2 difference amount of mixing in photoresist material relative hydrogen ion content and the relation between the exposure dose.
The pattern that Fig. 3 mask plate obtains at microscopically, (a) and (b) are the image under the different amplification.
The pattern that Fig. 4 photoengraving pattern obtains under scanning electron microscope, (a) and (b), (c), (d) they are respectively the patterns under the different amplification, wherein, (a) and (b), (c) they are vertical views, (d) are sectional views.
The pattern that Fig. 5 mask plate obtains at microscopically, (a) and (b) are the image under the different amplification.
The pattern that Fig. 6 photoengraving pattern obtains under scanning electron microscope, (a) and (b), (c), (d) they are respectively the patterns under the different amplification, wherein, (a) and (b) are vertical views, (c), (d) be sectional view.
Embodiment
The preferred photo-acid agent compound of the present invention comprises following 1-4 compound.
Among these compounds 1-4, R
2 -Be trifluoromethayl sulfonic acid root, hexafluoro-phosphate radical, hexafluoroantimonic anion or tetrafluoroborate.
The concrete preparation method of photo-acid agent in the photoetching compositions of the present invention (following with specific examples as to further instruction of the present invention, but should not regard limitation of the invention as).
In the invention, parent material is N, and N-pentanoic benzaldehyde obtains intermediate N, N-hexichol amido vinylbenzene by the Wittig reaction; React intermediate N by Heck, N-hexichol amido vinylbenzene and 3-bromobenzene dimethyl sulfide carry out coupling again, and then obtain the photo-acid agent of triphen amine; Described R
1Be 4-cyano group benzyl, R
2For hexafluoro-phosphate radical is example, the used synthetic route of this preparation method is expressed as follows:
In the formula:
I: methyltriphenylphospbromide bromide phosphorus, potassium tert.-butoxide, tetrahydrofuran (THF), room temperature was reacted 4 hours;
Ii: palladium, trolamine, 3-bromobenzene dimethyl sulfide, reacted 12 hours by 120 ℃;
Iii: trifluoro-methane sulfonic acid silver, 4-cyano group benzyl bromine, methylene dichloride, room temperature, Potassium Hexafluorophosphate reacted 24 hours.
1. prepare N, N-hexichol amido vinylbenzene
Under nitrogen protection, with 10gN, N-pentanoic benzaldehyde dissolves in the anhydrous tetrahydro furan of 250mL, and drops into 17.5g methyltriphenylphospbromide bromide phosphorus, places ice bath to stir.When being cooled to 0 ℃ of left and right sides, system drips at a slow speed the tetrahydrofuran (THF) that 40mL is dissolved with 4.6 gram potassium tert.-butoxides.System maintains below 10 ℃.After dripping system is warming up to room temperature, stirred 4 hours, thin plate chromatography detection reaction finishes.Afterwards mixing solutions is toppled in the entry, use dichloromethane extraction, and use the salt water washing, column chromatography for separation obtains colourless liquid after the anhydrous sodium sulfate drying organic phase.Obtain the white powder product after the solvent removed in vacuo and be N, N-diphenyl benzene ethene, productive rate: 70%.Nuclear magnetic data is consistent with report.
2. prepare target photo-acid agent precursor
With 1.2g N, N-diphenyl benzene ethene, 1.0g 3-bromobenzene dimethyl sulfide, the 20mg palladium adds in the 25mL trolamine, and system vacuumizes logical nitrogen totally three times.Under nitrogen atmosphere, be heated to 100 ℃, lucifuge stirred 12 hours.Thin plate chromatography detection reaction finishes, system is poured into water, produce blackish green solid, collect solid and it is dissolved in the methylene dichloride, remove the insoluble substances such as palladium by filtered through silica gel, obtain the glassy yellow clear liquid, obtain yellow thick liquid after the desolventizing, remove unreacted impurity (eluent: cyclohexane/ethyl acetate=9/1), obtain faint yellow solid through column chromatography, be target photo-acid agent precursor, productive rate: 69.3%.
1H?NMR?(CDCl
3,?δ
ppm):?2.515?(s,?3H,?CH
3);?6.960?(d,?1H,?C
2H
2);?7.032~7.190?(m,?6H,?PhH)?;?7.101?(m,?6H,?PhH)?;?7.240~7.280?(m,?4H,?PhH)?;?7.365~7.86?(m,?3H,?PhH).
3. prepare the target photo-acid agent
284 mg photo-acid agent precursors are dissolved in the 15mL anhydrous methylene chloride, will be cooled to-78 ℃ in system placement and the dry ice acetone bath, add afterwards equimolar trifluoro-methane sulfonic acid silver and 4-cyano group benzyl bromine under the lucifuge condition, low temperature stirred 1 hour.Remove afterwards dry ice acetone bath, stirred 24 hours under the room temperature lucifuge condition.Thin plate chromatography detection reaction finishes, and with the methylene dichloride evaporate to dryness, with acetonitrile dissolving, elimination solid impurity, concentrated solution, the ether sedimentation with 10 times of volumes gets product, is the photo-acid agent that trifluoro-methanyl sulfonate is negatively charged ion.If directly carry out salt exchange (twice), the crude product sulfosalt is dissolved in a small amount of acetone, it is slowly splashed in the saturated phosphofluoric acid aqueous solutions of potassium of 25 times of volumes of stirring.Precipitation is arranged, filter, drying gets yellow powder 329mg, is the target product that hexafluorophosphate is negatively charged ion.Overall yield is: 69.8%.
1H?NMR(CDCl
3,?δ
ppm):?3.2462?(s,?3H,?CH
3);?4.7812?(q,?2H,?CH
2);?7.0106(q,?2H,?CH=CH);?7.0547~7.8770(m,?22H,?PhH)。
Embodiment 2
Identical with embodiment 1 preparation method, just at preparation N, in the cinnamic process of N-hexichol amido, under nitrogen protection, divide to add solid potassium tert-butoxide to system three times, and should fully stir after adding at every turn, so that system temperature is not higher than 10 ℃.
Embodiment 3
Identical with embodiment 1 preparation method, just when the preparation precursor, change solvent into DMF and triethylamine, all the other steps are constant, then synthesize identical precursor after processing.
Embodiment 4
Identical with embodiment 1 preparation method, just at the preparation target product be, 4-cyano group benzyl bromine is replaced to methyl iodide or the cylite of equivalent, all the other steps are constant, then synthesize the target photo-acid agent that methyl or benzyl replace after processing.
Embodiment 5
The various photo-acid agents of preparing are dissolved in the dry acetonitrile, be that light source adds narrow ripple pass filter and excites various photo-acid agent solution with low pressure mercury lamp, with the light intensity of light intensity instrumentation amount by spectral filter, with rhodamine B as sour indicator, as calculated, various compounds all show very high photogenerated acid quantum yield.Be that photogenerated acid quantum yield under exciting is 0.56 with the substituent target product of 4-cyano group benzyl at the 404nm visible light wherein.
Embodiment 6
Identical with embodiment 1 preparation method, just at the preparation target product be, 4-cyano group benzyl bromine is replaced to methyl iodide or the cylite of equivalent, all the other steps are constant, then synthesize the target photo-acid agent that methyl or benzyl replace after processing.
Embodiment 7 lithography process flow processs
(1) pre-treatment of substrate generally is with silicon chip or the sheet glass H at 85 ℃
2SO
4: H
2O
2Soaked one hour in the=7:3 solution, then immerse volume ratio and be that 5min removes the substrate surface zone of oxidation in 80 ℃ of aqueous solution of water 37% hydrochloric acid of 5:1:1 and hydrogen peroxide, immerse again that 5min carries out hydroxylating in 80 ℃ of aqueous solution of the water ammoniacal liquor of volume ratio 6:1:1 and hydrogen peroxide.The substrate of hydroxylating is put into silane coupling agent process, assemble 12h under the room temperature, dry after the ultrasonic cleaning, can obtain being deposited on suprabasil siloxanes organic monolayer.
(2) film.With the photoresist material for preparing, can use sol evenning machine to carry out film forming.Concerning SU-8 2005 glue, the rotating speed corresponding relation between thickness and the sol evenning machine rotating speed can be with reference to table 1.
(3) flash trimming.In the spin-coating process, photoresist material may be piled up at the edge of substrate, for better with the contacting of mask, can use cotton balls to dip a small amount of photographic developer or CH
3Cl
3The place is piled up at the edge wipe, reach the purpose of flash trimming.
(4) front oven dry.The main purpose of front oven dry is in order to remove the solvent in the SU-8 glue, and the front drying time of respective thickness can be with reference to table 1.
(5) exposure.What we adopted is that wavelength is the light source of 405nm, and exposure energy corresponding to respective thickness is referring to table 2.Long when the time shutter, may cause excessively crosslinkedly, so that the SU-8 glue of part can't be removed is clean, when exposure energy is not enough, may cause the crosslinked not thorough of film in the process of developing, be easy to cause coming off of film in the process of development.And it is also different that different photo-acid agents produces protogenic ability, the ratio of mixing of photo-acid agent has a great impact producing the acid amount too, we have studied the sour ability of life of the photo-acid agent that mixes different types of photo-acid agent and different percentage compositions in photoresist material, referring to Fig. 2, can the ratio of mixing of exposure dose and photo-acid agent be changed by Fig. 2, obtain preferably photoengraving pattern.
(6) exposure post-drying.Should immediately film be carried out heatable catalytic after the exposure, the thermocatalysis time of different thickness sees Table 3.
(7) develop.Behind the film cool to room temperature behind the thermocatalysis, be immersed in the developing solution, soak 1min, can be aided with suitable ultrasonic.
(8) cleaning-drying.Film after developing is cleaned in Virahol, remove residual photographic developer, then dry.
The corresponding front drying time of table 1 different thickness
The exposure energy that table 2 different thickness is corresponding
The thermocatalysis time of different thickness after table 3 exposure
The preparation of embodiment 8 photo-resists and lithography process
Photoresist material of the present invention is by mixing following component preparation, each amounts of components based on the photoetching compositions gross weight by weight percentage ratio represent:
Photoresist material amounts of components (wt%)
Resin binder 99%
Photo-acid agent 1%
Resin binder is that the SU-8 that does not add photo-acid agent 2005 glue that excellent company buys are thought in Nanjing hundred, and the structure of photo-acid agent compound is shown in 9.
The photoresist material for preparing is used after sol evenning machine films, heat 3min at hot platform, temperature is controlled at about 95 ± 2 ℃, is covered with after the mask, uses wavelength to be about as the light source of the 405nm 25s(light intensity of exposing: 8.7 ± 0.3mwcm
-2), heat 3min at 95 ± 2 ℃ hot platform again, then in developing solution, develop, obtain photoengraving pattern, and then it is cleaned with Virahol, drying.Lower Fig. 3 is the mask pattern of examining under a microscope, and Fig. 4 is the image of observing under the SEM Electronic Speculum after the photoetching.
The preparation of embodiment 9 photo-resists and lithography process
Photoresist material of the present invention is by mixing following component preparation, each amounts of components based on the photoetching compositions gross weight by weight percentage ratio represent:
Photoresist material amounts of components (wt%)
Resin binder 99%
Photo-acid agent 1%
Resin binder is that the SU-8 that does not add photo-acid agent 2005 glue that excellent company buys are thought in Nanjing hundred, and the structure of photo-acid agent compound is shown in 9.
The photoresist material for preparing is used after sol evenning machine films, heat 3min at hot platform, temperature is controlled at about 95 ± 2 ℃, is covered with after the mask, uses wavelength to be about as the light source of the 405nm 25s(light intensity of exposing: 8.7 ± 0.3mwcm
-2), heat 3min at 95 ± 2 ℃ hot platform again, then in developing solution, develop, obtain photoengraving pattern, and then it is cleaned with Virahol, drying.Fig. 5 is the mask pattern of examining under a microscope, and Fig. 6 is the image of observing under the SEM Electronic Speculum after the photoetching.
Claims (10)
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104181772A (en) * | 2014-08-15 | 2014-12-03 | 同济大学 | Two-photon active photoacid generators taking biphenyl as conjugated structure and preparation method and application of two-photon active photoacid generators |
| CN104238268A (en) * | 2014-08-15 | 2014-12-24 | 同济大学 | Sulfonium salt photoacid generator adopting triphenylethylene as main body, preparation method of sulfonium salt photoacid generator and application of sulfonium salt photoacid generator |
| WO2015174471A1 (en) * | 2014-05-13 | 2015-11-19 | 東洋合成工業株式会社 | Onium salt, photoacid generator, photosensitive resin composition, and method for producing device |
| CN107129487A (en) * | 2017-04-10 | 2017-09-05 | 同济大学 | LED of one class using thioxanthone as conjugated structure can excite the preparation method and applications of sulfosalt |
| CN110105256A (en) * | 2019-04-30 | 2019-08-09 | 同济大学 | α-amido ketone-talan sulphur salt compounds and its preparation method and application |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5633409A (en) * | 1994-01-28 | 1997-05-27 | Shin-Etsu Chemical Co., Ltd. | Tristertbutoxyphenyl sulfonium tosylate compound |
| WO1999028295A1 (en) * | 1997-12-04 | 1999-06-10 | Asahi Denka Kogyo Kabushiki Kaisha | Novel aromatic sulfonium compounds, photoacid generators comprising the same, photopolymerizable compositions containing the same, stereolithographic resin compositions, and stereolithographic process |
| CN1408077A (en) * | 1999-12-07 | 2003-04-02 | 科莱恩金融(Bvi)有限公司 | Photoresist composition for deep UV radiation |
| CN1659477A (en) * | 2002-06-13 | 2005-08-24 | Az电子材料日本株式会社 | Photoresist composition for deep ultraviolet lithography comprising a mixture of photoactive compounds |
| CN101930174A (en) * | 2010-09-17 | 2010-12-29 | 同济大学 | A kind of two-photon photoacid generator containing triphenylamine as an electron-pushing group and its preparation method |
| CN102141731A (en) * | 2011-02-23 | 2011-08-03 | 同济大学 | Toluylene-containing meta-substituted sulfonium salt photoproduction acid agent and preparation method thereof |
-
2013
- 2013-01-04 CN CN2013100004900A patent/CN103012227A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5633409A (en) * | 1994-01-28 | 1997-05-27 | Shin-Etsu Chemical Co., Ltd. | Tristertbutoxyphenyl sulfonium tosylate compound |
| WO1999028295A1 (en) * | 1997-12-04 | 1999-06-10 | Asahi Denka Kogyo Kabushiki Kaisha | Novel aromatic sulfonium compounds, photoacid generators comprising the same, photopolymerizable compositions containing the same, stereolithographic resin compositions, and stereolithographic process |
| CN1408077A (en) * | 1999-12-07 | 2003-04-02 | 科莱恩金融(Bvi)有限公司 | Photoresist composition for deep UV radiation |
| CN1659477A (en) * | 2002-06-13 | 2005-08-24 | Az电子材料日本株式会社 | Photoresist composition for deep ultraviolet lithography comprising a mixture of photoactive compounds |
| CN101930174A (en) * | 2010-09-17 | 2010-12-29 | 同济大学 | A kind of two-photon photoacid generator containing triphenylamine as an electron-pushing group and its preparation method |
| CN102141731A (en) * | 2011-02-23 | 2011-08-03 | 同济大学 | Toluylene-containing meta-substituted sulfonium salt photoproduction acid agent and preparation method thereof |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015174471A1 (en) * | 2014-05-13 | 2015-11-19 | 東洋合成工業株式会社 | Onium salt, photoacid generator, photosensitive resin composition, and method for producing device |
| CN106458879A (en) * | 2014-05-13 | 2017-02-22 | 东洋合成工业株式会社 | Onium salt, photoacid generator, photosensitive resin composition, and method for producing device |
| JPWO2015174471A1 (en) * | 2014-05-13 | 2017-04-20 | 東洋合成工業株式会社 | Onium salt, photoacid generator, photosensitive resin composition and device manufacturing method |
| CN104181772A (en) * | 2014-08-15 | 2014-12-03 | 同济大学 | Two-photon active photoacid generators taking biphenyl as conjugated structure and preparation method and application of two-photon active photoacid generators |
| CN104238268A (en) * | 2014-08-15 | 2014-12-24 | 同济大学 | Sulfonium salt photoacid generator adopting triphenylethylene as main body, preparation method of sulfonium salt photoacid generator and application of sulfonium salt photoacid generator |
| CN104238268B (en) * | 2014-08-15 | 2017-12-26 | 同济大学 | Sulfosalt class photo-acid agent based on triphenylethylene, preparation method and applications |
| CN104181772B (en) * | 2014-08-15 | 2018-07-03 | 同济大学 | Two-photon activity photo-acid agent of the one kind using biphenyl as conjugated structure, preparation method and applications |
| CN107129487A (en) * | 2017-04-10 | 2017-09-05 | 同济大学 | LED of one class using thioxanthone as conjugated structure can excite the preparation method and applications of sulfosalt |
| CN107129487B (en) * | 2017-04-10 | 2019-12-03 | 同济大学 | One kind can excite the preparation method and applications of sulfosalt using thioxanthone as the LED of conjugated structure |
| CN110824836A (en) * | 2018-08-13 | 2020-02-21 | 常州强力先端电子材料有限公司 | Cationic photocurable composition and application thereof |
| CN110105256A (en) * | 2019-04-30 | 2019-08-09 | 同济大学 | α-amido ketone-talan sulphur salt compounds and its preparation method and application |
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