CN113200858A - Synthesis based on triptycene derivative monomolecular resin, positive photoresist and application of positive photoresist in photoetching - Google Patents
Synthesis based on triptycene derivative monomolecular resin, positive photoresist and application of positive photoresist in photoetching Download PDFInfo
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- CN113200858A CN113200858A CN202010049066.5A CN202010049066A CN113200858A CN 113200858 A CN113200858 A CN 113200858A CN 202010049066 A CN202010049066 A CN 202010049066A CN 113200858 A CN113200858 A CN 113200858A
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- NGDCLPXRKSWRPY-UHFFFAOYSA-N Triptycene Chemical class C12=CC=CC=C2C2C3=CC=CC=C3C1C1=CC=CC=C12 NGDCLPXRKSWRPY-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 47
- 238000001259 photo etching Methods 0.000 title claims abstract description 16
- 229920005989 resin Polymers 0.000 title abstract description 12
- 239000011347 resin Substances 0.000 title abstract description 12
- 230000015572 biosynthetic process Effects 0.000 title description 6
- 238000003786 synthesis reaction Methods 0.000 title description 4
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 238000001900 extreme ultraviolet lithography Methods 0.000 claims abstract description 8
- 238000000609 electron-beam lithography Methods 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 63
- 150000001875 compounds Chemical class 0.000 claims description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims description 28
- 239000001257 hydrogen Substances 0.000 claims description 28
- -1 arylboronic acid esters Chemical class 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 22
- 125000001424 substituent group Chemical group 0.000 claims description 20
- 125000001072 heteroaryl group Chemical group 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 11
- 150000003254 radicals Chemical class 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 9
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 8
- DYHSDKLCOJIUFX-UHFFFAOYSA-N tert-butoxycarbonyl anhydride Chemical compound CC(C)(C)OC(=O)OC(=O)OC(C)(C)C DYHSDKLCOJIUFX-UHFFFAOYSA-N 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 7
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000005840 aryl radicals Chemical class 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 238000010894 electron beam technology Methods 0.000 claims description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical compound C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 claims description 4
- 239000012953 triphenylsulfonium Substances 0.000 claims description 4
- FAYMLNNRGCYLSR-UHFFFAOYSA-M triphenylsulfonium triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 FAYMLNNRGCYLSR-UHFFFAOYSA-M 0.000 claims description 4
- RCVDPBFUMYUKPB-UHFFFAOYSA-N (3,4-dimethoxyphenyl)boronic acid Chemical compound COC1=CC=C(B(O)O)C=C1OC RCVDPBFUMYUKPB-UHFFFAOYSA-N 0.000 claims description 3
- XUIURRYWQBBCCK-UHFFFAOYSA-N (3,5-dimethoxyphenyl)boronic acid Chemical compound COC1=CC(OC)=CC(B(O)O)=C1 XUIURRYWQBBCCK-UHFFFAOYSA-N 0.000 claims description 3
- VOAAEKKFGLPLLU-UHFFFAOYSA-N (4-methoxyphenyl)boronic acid Chemical compound COC1=CC=C(B(O)O)C=C1 VOAAEKKFGLPLLU-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229940089960 chloroacetate Drugs 0.000 claims description 3
- 238000004528 spin coating Methods 0.000 claims description 3
- LWHOMMCIJIJIGV-UHFFFAOYSA-N (1,3-dioxobenzo[de]isoquinolin-2-yl) trifluoromethanesulfonate Chemical compound C1=CC(C(N(OS(=O)(=O)C(F)(F)F)C2=O)=O)=C3C2=CC=CC3=C1 LWHOMMCIJIJIGV-UHFFFAOYSA-N 0.000 claims description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 150000001543 aryl boronic acids Chemical class 0.000 claims description 2
- UEJFJTOGXLEPIV-UHFFFAOYSA-M bis(4-tert-butylphenyl)iodanium;4-methylbenzenesulfonate Chemical compound 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 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229940116333 ethyl lactate Drugs 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims description 2
- YPJUNDFVDDCYIH-UHFFFAOYSA-M 2,2,3,3,4,4,4-heptafluorobutanoate Chemical compound [O-]C(=O)C(F)(F)C(F)(F)C(F)(F)F YPJUNDFVDDCYIH-UHFFFAOYSA-M 0.000 claims 1
- 238000000206 photolithography Methods 0.000 claims 1
- 230000009477 glass transition Effects 0.000 abstract description 5
- 239000007806 chemical reaction intermediate Substances 0.000 abstract description 2
- 239000012467 final product Substances 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 126
- 239000000243 solution Substances 0.000 description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 33
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 32
- 239000007787 solid Substances 0.000 description 25
- 238000005160 1H NMR spectroscopy Methods 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 239000010408 film Substances 0.000 description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 9
- 239000012044 organic layer Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 125000002619 bicyclic group Chemical group 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 238000001459 lithography Methods 0.000 description 5
- 125000006413 ring segment Chemical group 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- ARCROJYJJMBGNU-UHFFFAOYSA-N [4-(1-adamantyl)phenyl] acetate Chemical compound C1=CC(OC(=O)C)=CC=C1C1(C2)CC(C3)CC2CC3C1 ARCROJYJJMBGNU-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000005605 benzo group Chemical group 0.000 description 3
- 230000031709 bromination Effects 0.000 description 3
- 238000005893 bromination reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000002950 monocyclic group Chemical group 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- JGTNAGYHADQMCM-UHFFFAOYSA-N perfluorobutanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-N 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 125000006708 (C5-C14) heteroaryl group Chemical group 0.000 description 2
- 125000003762 3,4-dimethoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C(OC([H])([H])[H])C([H])=C1* 0.000 description 2
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 2
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- USLKCMBGQFYUFI-UHFFFAOYSA-N dichloromethane;tribromoborane Chemical compound ClCCl.BrB(Br)Br USLKCMBGQFYUFI-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 1
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 125000004931 azocinyl group Chemical group N1=C(C=CC=CC=C1)* 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000004603 benzisoxazolyl group Chemical group O1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 1
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 125000000259 cinnolinyl group Chemical group N1=NC(=CC2=CC=CC=C12)* 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000004855 decalinyl group Chemical group C1(CCCC2CCCCC12)* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007416 differential thermogravimetric analysis Methods 0.000 description 1
- 125000005046 dihydronaphthyl group Chemical group 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000003392 indanyl group Chemical group C1(CCC2=CC=CC=C12)* 0.000 description 1
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000003406 indolizinyl group Chemical group C=1(C=CN2C=CC=CC12)* 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000001127 nanoimprint lithography Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004593 naphthyridinyl group Chemical group N1=C(C=CC2=CC=CN=C12)* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical compound C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000001715 oxadiazolyl group Chemical group 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001791 phenazinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3N=C12)* 0.000 description 1
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 1
- 125000004592 phthalazinyl group Chemical group C1(=NN=CC2=CC=CC=C12)* 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001042 pteridinyl group Chemical group N1=C(N=CC2=NC=CN=C12)* 0.000 description 1
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical class [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005329 tetralinyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Images
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- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
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- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
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- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
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- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
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- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
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- 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
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- G03F7/004—Photosensitive materials
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Abstract
The invention provides a novel monomolecular resin based on triptycene derivatives, and a preparation method and application thereof. The resin has the characteristics of high glass transition temperature, good stability, small and single molecular size and the like, and can be widely applied to the field of photoetching, in particular to application in positive photoresist. The positive photoetching film or the positive photoresist composition prepared by the invention has better advantages in electron beam lithography and extreme ultraviolet lithography. The triptycene derivative disclosed by the invention is simple in synthetic process, convenient in separation and purification of a reaction intermediate and a final product, suitable for industrial production and wide in application prospect.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a triptycene derivative monomolecular resin-based synthesis and positive photoresist and application thereof in photoetching.
Background
Photoresists, also known as photoresists, are etch-resistant thin film materials whose solubility changes upon irradiation or radiation by light sources such as ultraviolet light, excimer laser, electron beam, ion beam, or x-ray, and are widely used in microfabrication of integrated circuits and semiconductor discrete devices. The photoresist is used as an etching barrier layer, and a required fine pattern can be transferred to a substrate to be processed from the mask plate, so that the pattern transfer is realized. To achieve higher precision pattern transfer, the exposure wavelength of the photoresist is shifted from the broad spectrum ultraviolet in the direction of g-line (436nm) → i-line (365 nm) → KrF (248nm) → ArF (193nm) → EUV (13.5 nm). The current research focus is the extreme ultraviolet lithography technology, the exposure wavelength used by the technology is 13.5nm, the high-resolution lithography below 10nm can be achieved, and the corresponding photoresist has more rigorous requirements. The traditional photoresist main body material usually adopts polymer resin with the molecular weight of 5000-15000 daltons, and the polymer material has great influence on the edge roughness or line width roughness of an exposure pattern due to large molecular size, wide molecular weight distribution, molecular chain winding and the like, and cannot meet the requirement of more fine lithography.
The monomolecular resin is a small molecular compound with relatively low molecular mass, presents a stable amorphous state and has a glass transition temperature. Compared with the traditional polymer photoresist, the molecule has monodispersity and small gyration radius, simultaneously has the thermal stability and film forming property of the polymer, and is a novel photoresist main body material. The monomolecular resin designed by taking triptycene as the core can fully utilize the advantages of the structure, such as high glass transition temperature, good thermal stability and the like. Meanwhile, the spatial solid geometrical skeleton of the rigid structure can effectively inhibit the crystallinity of compound molecules and better form a film. The monomolecular resin is used as a main material of a positive photoresist, can be applied to photoetching, and is particularly suitable for high-resolution extreme ultraviolet and electron beam photoetching.
Disclosure of Invention
In order to improve the problems, the invention provides a triptycene derivative shown as a formula (A):
wherein R is1、R2、R3、R4、R5、R6Identical or different, independently of one another, from hydrogen or from 1 to 5RaSubstituted aryl, heteroaryl; r1And R2Group R3And R4Group R5And R6In three groups of substituents, each group has at least one substituent of 1-5RaSubstituted aryl, heteroaryl; each RaIdentical OR different, independently of one another, from hydrogen, OR-ORbSaid R isbIs an acid-sensitive group, R in the molecule of the formula (A)aAt least one is-ORb。
The acid-sensitive group refers to a group which can react under acidic conditions, thereby being removed from the main body.
In one embodiment of the invention, the acid-sensitive group Rbis-CR1-O-R1、-CO-O-R1、 -CH2-CO-O-R1、
Wherein R is1Identical or different, independently of one another, from the group unsubstituted or optionally substituted by one, two or more Rs2Substituted with the following groups: c1-15Alkyl radical, C3-20A cycloalkyl group;
m is any integer of 1 to 4,
represents a bond of the group to the host structure;
Rs2identical or different, independently of one another, from the following groups: NO2Halogen, C1-15Alkyl radical, C1-15Alkoxy radical, C3-20A cycloalkyl group.
In one embodiment, said R is1Is a quilt C1-6Alkyl substituted or unsubstituted the following groups: c1-6Alkyl radical, C3-8Monocyclic cycloalkyl, C7-12Bridged cycloalkyl.
According to an embodiment of the invention, R1、R2、R3、R4、R5、R6The same or different, independently from each other, are selected from hydrogen or substituted by 1,2 or 3RaSubstituted C6-10Aryl, heteroaryl; r1And R2Group R3And R4Group R5And R6In three groups of substituents, each group has at least one substituent substituted by 1,2, or 3RaSubstituted C6-10Aryl, heteroaryl; each RaIdentical OR different, independently of one another, from hydrogen, OR-ORbR in each molecule of formula (A)aAt least one is-ORb；
According to an embodiment of the invention, R1、R2、R3、R4、R5、R6Identical or different, independently of one another, from hydrogen or substituted by 1,2 or 3RaSubstituted phenyl; r1And R2Group R3And R4Group R5And R6In three groups of substituents, each group has at least one substituent being substituted by 1,2 or 3RaSubstituted phenyl; each RaIdentical OR different, independently of one another, from hydrogen OR-ORbR in each molecule of formula (A)aAt least one is-ORb；
According to an embodiment of the invention, R1、R2、R3、R4、R5、R6Identical or different, independently of one another, from hydrogen or
And R is1And R2Group R3And R4Group R5And R6In three groups of substituents, each group has at least one substituent of
Each RaIdentical OR different, independently of one another, from hydrogen OR-ORbR in each molecule of formula (A)aAt least one is-ORb；
Preferably, the group RbSelected from the group consisting of:
wherein,
represents a connecting bond;
preferably, the present invention also provides compounds represented by formula (I), formula (II) and formula (III):
wherein: ra1、Ra2、Ra3And the above-mentioned RaThe definitions are the same;
according to an embodiment of the invention, the triptycene derivative is selected from the following structures:
wherein Boc represents
Substituent, AD represents
BH represents
And (4) a substituent.
The invention also provides a preparation method of the triptycene derivative shown in the formula (A), which comprises the following steps:
1) carrying out Suzuki coupling reaction on the compound a and a compound b to obtain a compound c, wherein the compound b is selected from 1-5Ra' substituted arylboronic acids, arylboronic acid esters, heteroarylboronic acids or heteroarylboronic acid esters, such as: 3, 4-dimethoxyphenylboronic acid, 4-methoxyphenylboronic acid, 3, 5-dimethoxyphenylboronic acid; ra' selected from C1-12Alkoxy or aryl radicals C1-6Alkoxy, such as methoxy, ethoxy, benzyloxy;
wherein R is1'、R2'、R3'、R4'、R5'、R6' same or different, independently from each other, are selected from hydrogen, fluorine, chlorine, bromine or iodine and are not simultaneously hydrogen;
R1”、R2”、R3”、R4”、R5”、R6"identical or different, independently of one another, from hydrogen or substituted by 1 to 5Ra' substituted aryl or heteroaryl, and not both hydrogen; ra' selected from C1-12Alkoxy or aryl radicals C1-6Alkoxy, such as methoxy, ethoxy, benzyloxy;
2) reacting the compound c with a reducing agent to obtain a compound d;
wherein R is1”'、R2”'、R3”'、R4”'、R5”'、R6"' are the same or different and are independently selected from hydrogen or aryl or heteroaryl substituted with 1,2 or 3 OH, and are not simultaneously hydrogen;
3) reacting compound d with compound RbReacting L to obtain the triptycene derivative shown as the formula (A), wherein L is a leaving group or L and RbForm a group containing RbAcid anhydride of RbAs has been described above, in the above-mentioned,
wherein R is1、R2、R3、R4、R5、R6As defined above.
According to the invention, the compound RbL is, for example, di-tert-butyl dicarbonate, adamantane- α -chloroacetate, norbornyl chloroacetate.
The reducing agent is selected, for example, from boron tribromide or boron trichloride.
The invention also provides the use of the compound (A) for a host material of a photoresist.
The invention also provides a positive photoresist composition, which comprises the triptycene derivative shown as the formula (A), a photoacid generator and a photoresist solvent;
in the invention, the weight of the triptycene derivative shown in the formula (A) is 1-10 wt% of the total weight of the positive photoresist composition, the weight of the photoacid generator is 0.01-1 wt%, and the balance is a photoresist solvent.
In the invention, the photoacid generator is selected from ionic or non-ionic photoacid generators, and comprises one or more of triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium perfluorobutylsulfonate, bis (4-tert-butylphenyl) iodonium p-toluenesulfonate and N-hydroxynaphthalimide trifluoromethanesulfonate.
In the invention, the photoresist solvent is selected from one or more of propylene glycol monomethyl ether acetate, ethyl lactate, ethylene glycol monomethyl ether or cyclohexanone.
The invention also provides a positive photoresist film comprising the compound represented by the formula (A).
The invention also provides a preparation method of the positive photoresist film, which comprises the step of applying the positive photoresist composition on a substrate to form a film. The application method is a spin coating method.
In one embodiment, the substrate may be a silicon wafer.
The invention also provides the positive photoresist composition and the application of the positive photoresist film in photoetching.
According to the present invention, the lithography is 248nm lithography, 193nm lithography, extreme ultraviolet lithography (EUV), nanoimprint lithography, or electron beam lithography, and particularly, the positive photoresist composition, the positive photoresist coating, is used for electron beam lithography and extreme ultraviolet lithography.
Advantageous effects
The invention provides a series of novel monomolecular resins based on triptycene derivatives represented by formula (A). It has the characteristics of high glass transition temperature (more than 100 ℃) and good thermal stability. The monomolecular resin has a determined molecular structure, is small and single in molecular size, and well meets the requirement of photoetching.
The invention fully utilizes the characteristic that the triptycene has a spatial solid geometric framework, and can effectively inhibit the crystallization of molecules, so that the photoresist taking the monomolecular resin as a main material is easy to form a film.
The synthesis process of the monomolecular resin is simple, the reaction intermediate and the final product can be separated from the system through recrystallization or precipitation, and the method is suitable for industrial production.
Definition and description of terms
Unless defined otherwise, all technical and scientific terms herein have the same meaning as commonly understood by one of ordinary skill in the art to which the claimed subject matter belongs.
The term "alkyl" is understood to mean having from 1 to 12A straight or branched chain saturated monovalent hydrocarbon group of carbon atoms. For example, "C1-6Alkyl "denotes straight and branched chain alkyl groups having 1,2, 3,4, 5, or 6 carbon atoms. The alkyl group is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a 2-methylbutyl group, a 1-ethylpropyl group, a 1, 2-dimethylpropyl group, a neopentyl group, a 1, 1-dimethylpropyl group, a 4-methylpentyl group, a 3-methylpentyl group, a 2-ethylbutyl group, a 1-ethylbutyl group, a 3, 3-dimethylbutyl group, a 2, 2-dimethylbutyl group, a 1, 1-dimethylbutyl group, a 2, 3-dimethylbutyl group, a 1, 3-dimethylbutyl group or a 1, 2-dimethylbutyl group, or the like, or isomers thereof.
The term "alkoxy" is to be understood as meaning-O-C1-12Alkyl radical, wherein C1-12Alkyl groups have the above definitions.
The term "cycloalkyl" is understood to mean a saturated monovalent monocyclic, bicyclic or polycyclic hydrocarbon ring (also referred to as fused ring hydrocarbon ring) having 3 to 20, preferably 3 to 10, carbon atoms. Bicyclic or polycyclic cycloalkyl groups include fused cycloalkyl, bridged cycloalkyl, spirocycloalkyl; the fused ring refers to a fused ring structure formed by two or more ring structures sharing two adjacent ring atoms with each other (i.e., sharing one bond). The bridged ring refers to a condensed ring structure formed by two or more than two ring structures sharing two non-adjacent ring atoms. The spiro ring refers to a fused ring structure formed by two or more cyclic structures sharing one ring atom with each other. For example, the cycloalkyl group may be C3-8Monocyclic cycloalkyl, e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, or is C7-12And cyclic cycloalkyl groups such as decalin ring; or may be C7-12Bridged cycloalkyl radicals, e.g. norbornane, adamantane, bicyclo [2,2 ]]Octane.
The term "aryl" is to be understood as meaning a mono-, bi-or tricyclic hydrocarbon ring of monovalent or partial aromaticity having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, preferably "C6-8Aryl ". The term "C6-8Aryl "is understood to mean preferably having 6,7 or 8Monocyclic, bicyclic or tricyclic hydrocarbon rings of monovalent or partially aromatic character by carbon atoms ('C')6-14Aryl group "), in particular a ring having 6 carbon atoms (" C6Aryl "), such as phenyl; or biphenyl, or is a ring having 9 carbon atoms ("C9Aryl), such as indanyl or indenyl, or a ring having 10 carbon atoms ("C10Aryl radicals), such as tetralinyl, dihydronaphthyl or naphthyl, or rings having 13 carbon atoms ("C13Aryl radicals), such as the fluorenyl radical, or a ring having 14 carbon atoms ("C)14Aryl), such as anthracenyl. When said C is6-10When the aryl group is substituted, it may be mono-or polysubstituted. And, the substitution site thereof is not limited, and may be, for example, ortho-, para-or meta-substitution.
The term "heteroaryl" is understood to include such monovalent monocyclic, bicyclic or tricyclic aromatic ring systems: having 5 to 20 ring atoms and comprising 1 to 5 heteroatoms independently selected from N, O and S, such as "5-14 membered heteroaryl". The term "5-14 membered heteroaryl" is understood to include such monovalent monocyclic, bicyclic or tricyclic aromatic ring systems: which has 5, 6,7, 8, 9, 10, 11, 12, 13 or 14 ring atoms, in particular 5 or 6 or 9 or 10 carbon atoms, and which contains 1 to 5, preferably 1 to 3 heteroatoms independently selected from N, O and S and, in addition, can be benzo-fused in each case. In particular, heteroaryl is selected from thienyl, furyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl and the like and their benzo derivatives, such as benzofuranyl, benzothienyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl, benzotriazolyl, indazolyl, indolyl, isoindolyl and the like; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and the like, and benzo derivatives thereof, such as quinolyl, quinazolinyl, isoquinolyl, and the like; or azocinyl, indolizinyl, purinyl and the like and benzo derivatives thereof; or cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, pteridinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, and the like.
Drawings
FIG. 1 is a differential scanning calorimetry trace and a thermogram of example 3(2,7, 14-tris- (3, 4-di-tert-butylcarbonatylphenyl) triptycene) according to the present invention.
FIG. 2 is a differential scanning calorimetry graph and a thermogravimetry graph of example 4(2,3,6,7,14, 15-hexa- (4-adamantylphenyl acetate) triptycene) of the present invention.
FIG. 3 is a Scanning Electron Microscope (SEM) image of EUV lithography fringes of positive photoresist film formation of the bulk material of example 3(2,7, 14-tris- (3, 4-di-tert-butylcarbonate phenyl) triptycene) of the present invention.
FIG. 4 is a Scanning Electron Microscope (SEM) image of electron beam lithography stripes of positive photoresist film formation of example 4(2,3,6,7,14, 15-hexa- (4-adamantylphenyl acetate) triptycene) host material of the present invention.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
The 2,3,6,7,14, 15-hexabromotriptycene, 2,7, 14-tribromotriptycene and 2,6, 14-tribromotriptycene of the present invention can be prepared by referring to the prior documents of Nature chemistry, 2014,6, 774-. (such bromo compounds are commercially available, some methods for their preparation are also provided below)
Example 1
Preparation of 2,3,6,7,14, 15-hexabromotriptycene
The method comprises the following specific steps: at 500Into a mL reaction flask were added triptycene (3.0g, 11.80mmol), iron powder (0.085g, 1.52mmol) and 200mL chloroform, and the reaction was stirred at room temperature. Bromine (3.8mL, 11.80g, 73.84mmol) was added to the reaction, stirred vigorously and refluxed. After 4h of reaction, the reaction was completed, the reaction solution was cooled to room temperature, and then washed with saturated sodium sulfite solution and water, and the organic layer was spin-dried to obtain a yellow solid. Recrystallization of the yellow solid from acetone gave 5g of pure colorless crystals in 60% yield.1H NMR(400MHz,CDCl3):δ(ppm)7.62(s,6H),5.23(s,2H)。
Example 2
Preparation of 2,6, 14-tribromotriptycene and 2,7, 14-tribromotriptycene (involving nitration, reduction and bromination of triptycene)
1) Nitration of triptycenes
The method comprises the following specific steps: triptycene (2.5g, 10mmol) and 100mL concentrated nitric acid were added to a 250mL reaction flask, and the reaction was warmed to 75 ℃ and stirred for 24 h. When the reaction is finished, the reaction solution is cooled to room temperature, the reaction solution is dripped into 1000mL of water, and the precipitate is collected. The precipitate was separated by column chromatography to give 2,6, 14-trinitrotriptycene (2.5g, 65%) and 2,7, 14-trinitrotriptycene (0.82g, 21%) as white solids.
2,6, 14-trinitrotriptycene1H NMR(300MHz,CDCl3):δ5.82(s,1H),5.84(s,1H), 7.62-7.67(m,3H),8.03-8.07(m,3H),8.32-8.34(m,3H)；
2,7, 14-trinitrotriptycene1H NMR(300MHz,CDCl3):δ5.80(s,1H),5.84(s,1H), 7.62(d,J＝8.2Hz,3H),8.05(dd,J＝8.2,2.2Hz,3H),8.34(d,J＝2.2Hz,3H)。
2) Reduction of 2,6, 14-trinitrotriptycene
The method comprises the following specific steps: in a 100mL reaction flask2,6, 14-trinitrotriptycene (1.0g, 2.6mmol), 1.5mL hydrazine hydrate, Raney Ni (1.0g) and 20mL tetrahydrofuran were added and the reaction was warmed to 60 ℃ and stirred for 3 h. At the end of the reaction, the reaction mixture was cooled to room temperature, filtered, and the solvent was distilled off under reduced pressure to obtain a white solid (760mg, 99%).1H NMR(300MHz,CDCl3):δ3.47(s,6H),5.01(s,1H), 5.04(s,1H),6.21-6.26(m,3H),6.69-6.73(m,3H),7.04-7.07(m,3H)。
The reduction of the 2,7, 14-trinitrotriptycene is the same as the above, the yield is 99 percent,1H NMR(300MHz,CDCl3):δ 3.40(s,6H),4.97(s,1H),5.05(s,1H),6.23(dd,J＝7.7,2.1Hz,3H),6.70(d,J＝7.7 Hz,3H),7.03(d,J＝2.1Hz,3H)。
3) bromination of 2,6, 14-triaminotriptycene
The method comprises the following specific steps: 2,6, 14-triaminotriptycene (1.0g, 3.6mmol), 3mL of concentrated bromic acid and 10mL of water were added to a 100mL reaction flask, the reaction was placed in an ice-water bath, and an aqueous solution of sodium nitrite (0.8g, 12.6 mmol) was added dropwise. After the reaction was stirred for 20min, the reaction mixture was slowly added to a refluxing solution of cuprous bromide (2.2g, 15.0mmol) and hydrobromic acid (5 mL). The reaction system is stirred and refluxed for 2 hours, and is extracted by dichloromethane after being cooled, washed by water and dried by anhydrous sodium sulfate. The solvent was removed by distillation under reduced pressure, and the crude product was recrystallized from ethanol to give 1.1g of a white solid in 67% yield.1H NMR(300MHz,CDCl3):δ5.26(s, 1H),5.29(s,1H),7.12(dd,J＝7.8,1.8Hz,3H),7.20(d,J＝7.8Hz,3H),7.49(d,J＝1.8 Hz,3H)。
The bromination of 2,7, 14-triaminotriptycene is as above, the yield is 63 percent,1H NMR(300MHz,CDCl3):δ 5.25(s,1H),5.31(s,1H),7.13(dd,J)7.8,1.8Hz,3H),7.21(d,J＝7.8Hz,3H),7.49 (d,J＝1.8Hz,3H)。
example 3
A process for the preparation of 2,7, 14-tris- (3, 4-di-tert-butylcarbonate ylphenyl) triptycene, the process comprising the steps of:
1) the preparation of 2,7, 14-tri- (3, 4-dimethoxyphenyl) triptycene has the following synthetic route:
the method comprises the following specific steps: under the protection of high-purity nitrogen, 2,7, 14-tribromotriptycene (975.6mg,2mmol,1.0eq), tetratriphenylphosphine palladium (230mg,0.2mmol,0.1eq), 3, 4-dimethoxyphenylboronic acid (1.64g,9mmol,4.5eq) and 30mL of redistilled toluene are added into a 100mL Schlenk reaction bottle, and after stirring and dissolving, 6mL of ethanol solution and 2M Na are added into the reaction bottle2CO33mL of aqueous solution, heating the reaction solution to 60-100 ℃, refluxing for 12h, cooling to room temperature, extracting with dichloromethane/water, combining organic layers, washing the organic layers once with saturated saline solution, and drying with anhydrous sodium sulfate. And (4) carrying out suction filtration, and distilling the filtrate under reduced pressure to obtain a gray solid. The solid was dissolved with 5mL of dichloromethane, precipitated into 100mL of ethanol, filtered, and oven dried in vacuo to give 1.2g of a white solid in 91% yield.1H NMR(400MHz,CDCl3):δ(ppm)6.97-6.99(d,3H， benzene),6.80-6.82(d,3H，benzene),7.08(s,3H，benzene),7.32-7.36(d,3H， benzene),7.41-7.45(d,3H，benzene),7.50(s,3H，benzene),5.82(s,2H，-CH), 3.93-3.94(d,18H,-OCH3). MS (MALDI-TOF) m/z 662.3, calculated value (C)44H38O6) m/z＝662.4(M+)。
2) The preparation of 2,7, 14-tri- (3, 4-dihydroxyphenyl) triptycene has the following synthetic route:
the method comprises the following specific steps: adding 2,7, 14-tris- (3, 4-dimethoxyphenyl) triptycene (662mg, 1mmol,1.0eq) and 30mL of dichloromethane into a 100mL reaction bottle, dissolving in nitrogen atmosphere, dropwise adding a boron tribromide dichloromethane solution (1.0mL, 10.0mmol, 10.0eq) into the reaction solution at a low temperature of-78 ℃ by using a syringe, reacting the reaction system at-78 ℃ for 1h, gradually raising the temperature to room temperature, and continuing to reactThe reaction was continued for 12h, and 10mL of ice water was slowly added to the reaction system to quench the reaction. The reaction solution was washed with water to neutrality, washed with saturated brine once and dried over anhydrous sodium sulfate. Suction filtration and reduced pressure distillation of the filtrate gave 540mg of a white solid in 93% yield.1H NMR(400MHz,CDCl3) δ (ppm)6.95 to 6.99(d,3H, benzene),6.83 to 6.87 (d,3H, benzene),7.21(s,3H, benzene),7.32 to 7.36(d,3H, benzene),7.41 to 7.45(d,3H, benzene),7.50(s,3H, benzene),5.86(s,2H, -CH),5.42(s,6H, -OH). MS (MALDI-TOF) m/z 578.1, calculated value (C)38H26O6)m/z＝578.0(M+)。
3) The preparation of 2,7, 14-tri- (3, 4-di-tert-butylcarbonate phenyl) triptycene (compound (1)) has the following synthetic route:
in the reaction scheme, Boc represents
The substituent, DMAP, is known under the Chinese name 4-dimethylaminopyridine.
The method comprises the following specific steps: 2,7, 14-tris- (3, 4-dihydroxyphenyl) triptycene (578.1mg, 1mmol,1.0eq), Boc anhydride (di-tert-butyl dicarbonate) (2.0g, 9mmol,9.0eq) and 20mL of dry tetrahydrofuran were charged in a 100mL reaction flask, stirred to dissolve completely under nitrogen, a catalytic amount of DMAP (12.2mg, 0.1mmol,0.1eq) was added to the solution to initiate the reaction, and stirred at room temperature for 24 h. The reaction solution was extracted with dichloromethane/water, and the organic phase was washed twice with water and once with saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure to obtain a semisolid substance. The semi-solid was dissolved in 4mL of tetrahydrofuran and precipitated dropwise into 100mL of ethanol to give 0.95g of a white solid in 80% yield.1H NMR(400MHz, CDCl3):δ(ppm)6.97-6.99(d,3H，benzene),6.80-6.82(d,3H，benzene),7.08(s,3H， benzene),7.32-7.36(d,3H，benzene),7.41-7.45(d,3H，benzene),7.50(s,3H， benzene),5.82(s,2H，-CH),1.55(d,54H,-O(CH3)3). MS (MALDI-TOF) m/z 1179.3, calculated value (C)68H74O18)m/z＝1179.2(M+)。
Example 4
Preparation of Compound (2)
The preparation method comprises the following steps:
1) the preparation of 2,3,6,7,14, 15-hexa- (4-methoxyphenyl) triptycene has the following synthetic route:
the method comprises the following specific steps: under the protection of high-purity nitrogen, 2,3,6,7,14, 15-hexabromotriptycene (728mg,1mmol,1.0eq), palladium tetratriphenylphosphine (115mg,0.1mmol,0.1eq), 4-methoxyphenylboronic acid (1.4g,9mmol,9.0eq) and 20mL of redistilled toluene are added into a 100mL Schlenk reaction flask, 5mL of ethanol solution and 2M Na are added into the reaction flask after stirring and dissolving2CO32mL of aqueous solution, heating the reaction solution to 60-100 ℃, refluxing for 12h, cooling to room temperature, extracting with dichloromethane/water, combining organic layers, washing the organic layers once with saturated saline solution, and drying with anhydrous sodium sulfate. And (4) carrying out suction filtration, and distilling the filtrate under reduced pressure to obtain a gray solid. The solid was dissolved with 4mL dichloromethane, precipitated in 100mL ethanol, filtered and oven dried in vacuo to afford 803mg of a white solid in 90% yield.1H NMR(400MHz，CDCl3):δ(ppm)7.48(s,6H， benzene),7.01-7.03(d,12H，benzene),6.74-6.76(d,12H，benzene),5.59(s,2H， -CH),3.77(s,18H,-OCH3). MS (MALDI-TOF) m/z 891.1, calculated value (C)62H50O6) m/z＝891.2(M+)。
2) The preparation of 2,3,6,7,14, 15-hexa- (4-hydroxyphenyl) triptycene has the following synthetic route:
the method comprises the following specific steps: adding 2,3,6,7,14, 15-hexa- (4-methoxyphenyl) triptycene (890mg, 1mmol,1.0eq) and 40mL of dichloromethane into a 100mL reaction bottle, dissolving under nitrogen atmosphere, dropwise adding a dichloromethane solution (2.0mL, 10.0mmol, 10.0eq) of boron tribromide into the reaction liquid at low temperature of-78 ℃ by using an injector, placing the reaction system at-78 ℃ for reaction for 1h, gradually raising the temperature to room temperature, continuing the reaction for 12h, slowly adding 15mL of ice water into the reaction system, and quenching the reaction, wherein white solids are separated out. Filtering to obtain white solid, dissolving in ethyl acetate, washing with water to neutrality, washing with saturated saline solution once, and drying with anhydrous sodium sulfate. Suction filtration and reduced pressure distillation of the filtrate gave 750mg of a white solid in 93% yield.1H NMR(400MHz，CDCl3) Delta (. delta.,. sup.49 (s,6H, benzene),7.05-7.08(d,12H, benzene),6.79-6.78(d,12H, benzene),5.61(s,2H, -CH),5.46(s,6H, -OH). MS (MALDI-TOF) m/z 806.3, calculated value (C)56H38O6)m/z＝806.5(M+)。
3) The preparation of 2,3,6,7,14, 15-hexa- (4-adamantylphenyl acetate) triptycene has the following synthetic route:
in the reaction formula, AD represents
The method comprises the following specific steps: a100 mL reaction flask was charged with 2,3,6,7,14, 15-hexa- (4-hydroxyphenyl) triptycene (806mg, 1mmol,1.0eq), tetrabutylammonium bromide (800mg, 2.4mmol, 2.4eq), potassium carbonate (5.6g, 40mmol) and N-methylpyrrolidone (NMP, 50mL), stirred at room temperature for 2h, and the reaction mixture was slowly dropped with adamantane α -chloroacetate (2.9g, 12mmol, 12eq) in NMP(20mL) the solution was heated to 60 ℃ and reacted for 48 h. After the reaction was completed, the reaction solution was cooled to room temperature, the reaction solution was extracted with ethyl acetate/water, the organic phase was washed once with 3 wt% oxalic acid solution and water, respectively, the organic layers were combined, dried over anhydrous sodium sulfate, the solvent was removed under reduced pressure, and recrystallization was performed with ethyl acetate/n-hexane mixed solvent to obtain 1.6g of a white solid with a yield of 78%.1H NMR(400MHz，CDCl3) Delta (. delta.) (ppm)7.48(s,6H, benzene), 7.01-7.03(d,12H, benzene),6.74-6.76(d,12H, benzene),5.59(s,2H, -CH), 1.67-1.70(m, 114H). MS (MALDI-TOF) m/z 2044.1, calculated value (C)134H146O18) m/z＝2044.3(M+)。
Example 5
Preparation of Compound (3)
The preparation method comprises the following steps:
1) the preparation of 2,6, 14-tri- (3, 5-dimethoxyphenyl) triptycene has the following synthetic route:
the method comprises the following specific steps: under the protection of high-purity nitrogen, 2,6, 14-tribromotriptycene (975.6mg,2mmol,1.0eq), palladium tetratriphenylphosphine (230mg,0.2mmol,0.1eq), 3, 5-dimethoxyphenylboronic acid (1.64g,9mmol,4.5eq) and 30mL of redistilled toluene are added into a 100mL Schlenk reaction bottle, and after stirring and dissolving, 6mL of ethanol solution and 2MNa are added into the reaction bottle2CO33mL of aqueous solution, heating the reaction solution to 60-100 ℃, refluxing for 12h, cooling to room temperature, extracting with dichloromethane/water, combining organic layers, washing the organic layers once with saturated saline solution, and drying with anhydrous sodium sulfate. And (4) carrying out suction filtration, and distilling the filtrate under reduced pressure to obtain a gray solid. Dissolve the solid with 4mL of dichloromethaneAfter decomposition, precipitation in 100mL of ethanol, filtration and drying in a vacuum oven gave 1.3g of a white solid with a yield of 98%.1H NMR(400MHz,CDCl3):δ(ppm)6.96(s,3H， benzene),7.14(s,6H，benzene),7.20(s,3H，benzene),7.32-7.36(d,3H，benzene), 7.45(d,3H，benzene),5.82(s,2H，-CH),3.93-3.94(s,18H,-OCH3). MS (MALDI-TOF) m/z 662.3, calculated value (C)44H38O6)m/z＝662.4(M+)。
2) The preparation of 2,6, 14-tri- (3, 5-dihydroxyphenyl) triptycene has the following synthetic route:
the method comprises the following specific steps: adding 2,6, 14-tris- (3, 5-dimethoxyphenyl) triptycene (662mg, 1mmol,1.0eq) and 30mL of dichloromethane into a 100mL reaction bottle, dissolving in nitrogen atmosphere, dropwise adding a boron tribromide dichloromethane solution (1.0mL, 10.0mmol, 10.0eq) into the reaction solution at a low temperature of-78 ℃ by using a syringe, reacting the reaction system at-78 ℃ for 1h, gradually raising the temperature to room temperature, continuing to react for 12h, and slowly adding 10mL of ice water into the reaction system to quench the reaction. The reaction solution was washed with water to neutrality, washed with saturated brine once and dried over anhydrous sodium sulfate. Suction filtration and reduced pressure distillation of the filtrate gave 540mg of a white solid in 93% yield.1H NMR(400MHz,CDCl3) δ (ppm)6.97(s,3H, benzene),7.16(s,6H, benzene),7.22(s,3H, benzene),7.34-7.35(d,3H, benzene),7.45(d,3H, benzene), 5.85(s,2H, -CH),3.93-3.94(s,6H, -OH). MS (MALDI-TOF) m/z 578.1, calculated value (C)38H26O6)m/z＝578.0(M+)。
3) The preparation of 2,6, 14-tri- (3, 5-norbornanyl phenyl diacetate) triptycene has the following synthetic route formula:
in the reaction formula, BH represents
And (4) a substituent.
The method comprises the following specific steps: 2,6, 14-tris- (3, 5-dihydroxyphenyl) triptycene (578.1mg, 1mmol,1.0eq), tetrabutylammonium bromide (800mg, 2.4mmol, 2.4eq), potassium carbonate (5.6g, 40mmol) and N-methylpyrrolidone (NMP, 50mL) were added to a 100mL reaction flask, stirred at room temperature for 2h, a solution of norbornyl chloroacetate (2.9g, 12mmol, 12eq) in NMP (20mL) was slowly dropped into the reaction solution, and the temperature was raised to 60 ℃ for reaction for 48 h. After the reaction was completed, the reaction solution was cooled to room temperature, the reaction solution was extracted with ethyl acetate/water, the organic phase was washed once with 3 wt% oxalic acid solution and water, respectively, the organic layers were combined, dried over anhydrous sodium sulfate, the solvent was removed under reduced pressure, and recrystallization was carried out with ethyl acetate/n-hexane mixed solvent to obtain 1.1g of a white solid with a yield of 70%.1H NMR(400MHz，CDCl3):δ(ppm)6.95(s,3H，benzene),7.12(s,6H， benzene),7.21(s,3H，benzene),7.32-7.36(d,3H，benzene),7.45(d,3H，benzene), 5.83(s,2H，-CH),1.63-1.70(m,90H,-OCH3). MS (MALDI-TOF) m/z 1576.2, calculated value (C)98H110O18)m/z＝1576.4(M+)。
Example 6
The thermal properties of 2,7, 14-tris- (3, 4-di-tert-butylcarbonate-ylphenyl) triptycene (compound (1)) prepared in example 3 are shown in FIG. 1 by differential scanning calorimetry and thermogravimetric analysis, and the glass transition temperature reaches 150 ℃ or higher, which shows good thermal stability.
Example 7
A positive photoresist composition comprising 2,7, 14-tris- (3, 4-di-tert-butylcarbonatophenyl) triptycene prepared in example 3, Propylene Glycol Monomethyl Ether Acetate (PGMEA), and triphenylsulfonium triflate. The specific method comprises the following steps: the 2,7, 14-tris- (3, 4-di-tert-butylcarbonate phenyl) triptycene prepared in example 3 was dissolved in Propylene Glycol Monomethyl Ether Acetate (PGMEA) to prepare a solution with a mass concentration of 5%, 0.1 wt% of triphenylsulfonium trifluoromethanesulfonate was added as a photoacid generator, the solution was filtered through a microporous filter with a pore size of 0.22 μm to obtain a spin-on solution, a spin-on film was formed on an acid-base treated silicon substrate, the film was baked at 100 ℃ for 3 minutes, and the prepared film was subjected to an extreme ultraviolet exposure experiment at an upper sea light source interference light reticle station (BL08U1B) with an exposure period of 140nm to obtain very uniform photo-etched stripes, which had a resolution of 44.1nm as shown in fig. 2.
Example 8
A positive photoresist composition comprising the compound (2) prepared in example 4, cyclohexanone and triphenylsulfonium perfluorobutylsulfonate. The specific method comprises the following steps: the compound (2) prepared in example 4 was dissolved in cyclohexanone to prepare a solution with a mass concentration of 10%, 0.1 wt% of triphenylsulfonium perfluorobutylsulfonate as a photoacid generator was added, and the solution was filtered through a microporous filter with a pore size of 0.22 μm to obtain a spin-on solution, and a film was formed on an acid-base treated silicon substrate by spin coating, and was baked at 100 ℃ for 3 minutes, and the film obtained was subjected to an electron beam exposure experiment with an exposure period of 150nm to obtain a very uniform photo-etching fringe, the resolution of which was 59.5nm as shown in fig. 4.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A triptycene derivative represented by the formula (A):
wherein R is1、R2、R3、R4、R5、R6Identical or different, independently of one another, from hydrogen or from 1 to 5RaSubstituted aryl, heteroaryl; r1And R2Group R3And R4Group R5And R6In three groups of substituents, each group has at least one substituent of 1-5RaSubstituted aryl, heteroaryl; each RaIdentical OR different, independently of one another, from hydrogen, OR-ORbSaid R isbIs an acid-sensitive group, R in the molecule of the formula (A)aAt least one is-ORb；
The acid-sensitive group refers to a group which can react under an acidic condition so as to be removed from the main body;
preferably, the acid-sensitive group Rbis-CR1-O-R1、-CO-O-R1、-CH2-CO-O-R1、
Wherein R is1Identical or different, independently from each other, from the following groups unsubstituted or optionally substituted by one, two or more Rs 2: c1-15Alkyl radical, C3-20A cycloalkyl group;
m is any integer of 1 to 4,
represents a bond of the group to the host structure;
rs2, which are identical or different, are independently selected from the following groups: NO2Halogen, C1-15Alkyl radical, C1-15Alkoxy radical, C3-20A cycloalkyl group;
preferably, said R is1Is a quilt C1-6Alkyl substituted or unsubstituted the following groups: c1-6Alkyl radical, C3-8Monocyclic cycloalkyl, C7-12Bridged cycloalkyl.
2. The triptycene derivative of claim 1, wherein R is1、R2、R3、R4、R5、R6The same or different, independently from each other, are selected from hydrogen or substituted by 1,2 or 3RaSubstituted C6-10Aryl, heteroaryl; r1And R2Group R3And R4Group R5And R6In three groups of substituents, each group has at least one substituent substituted by 1,2, or 3RaSubstituted C6-10Aryl, heteroaryl; each RaIdentical OR different, independently of one another, from hydrogen, OR-ORbR in each molecule of formula (A)aAt least one is-ORb(ii) a The R isbHaving the definition set forth in claim 1.
3. The triptycene derivative of claim 1, wherein R is1、R2、R3、R4、R5、R6Identical or different, independently of one another, from hydrogen or substituted by 1,2 or 3RaSubstituted phenyl; r1And R2Group R3And R4Group R5And R6In three groups of substituents, each group has at least one substituent being substituted by 1,2 or 3RaSubstituted phenyl; each RaIdentical OR different, independently of one another, from hydrogen OR-ORbR in each molecule of formula (A)aAt least one is-ORb(ii) a The R isbHaving the definition set forth in claim 1.
4. The triptycene derivative of claim 1, wherein R is1、R2、R3、R4、R5、R6Identical or different, independently of one another, from hydrogen or
And R is1And R2Group R3And R4Group R5And R6In three groups of substituents, each group has at least one substituent of
Each RaIdentical OR different, independently of one another, from hydrogen OR-ORbR in each molecule of formula (A)aAt least one is-ORb；
The group RbSelected from the group consisting of:
wherein,
represents a connecting bond;
preferably, the present invention also provides compounds represented by formula (I), formula (II) and formula (III):
wherein: ra1、Ra2、Ra3And RaThe definitions are the same;
preferably, the triptycene derivative is selected from the following structures:
wherein Boc represents
Substituent, AD represents
BH represents
And (4) a substituent.
5. A process for the preparation of a triptycene derivative according to any one of claims 1 to 4, comprising the steps of:
1) carrying out Suzuki coupling reaction on the compound a and a compound b to obtain a compound c, wherein the compound b is selected from 1-5Ra' substituted arylboronic acids, arylboronic acid esters, heteroarylboronic acids or heteroarylboronic acid esters, such as: 3, 4-dimethoxyphenylboronic acid, 4-methoxyphenylboronic acid, 3, 5-dimethoxyphenylboronic acid; ra' selected from C1-12Alkoxy or aryl radicals C1-6Alkoxy, such as methoxy, ethoxy, benzyloxy;
wherein R is1'、R2'、R3'、R4'、R5'、R6' same or different, independently from each other, are selected from hydrogen, fluorine, chlorine, bromine or iodine and are not simultaneously hydrogen;
R1”、R2”、R3”、R4”、R5”、R6"identical or different, independently of one another, from hydrogen or substituted by 1 to 5Ra' substituted aryl or heteroaryl, and not both hydrogen; ra' selected from C1-12Alkoxy or aryl radicals C1-6Alkoxy, such as methoxy, ethoxy, benzyloxy;
2) reacting the compound c with a reducing agent to obtain a compound d;
wherein R is1”'、R2”'、R3”'、R4”'、R5”'、R6"' are the same or different and are independently selected from hydrogen or aryl or heteroaryl substituted with 1,2 or 3 OH, and are not simultaneously hydrogen;
3) reacting compound d with compound Rb-L-reaction of the compound (I),obtaining the triptycene derivative shown as the formula (A), wherein L is a leaving group or L and RbForm a group containing RbAcid anhydride of RbHaving the definition as claimed in claim 1 or 4,
wherein R is1、R2、R3、R4、R5、R6Having the definition of any one of claims 1 to 4;
preferably, said compound RbL is, for example, di-tert-butyl dicarbonate, adamantane- α -chloroacetate, norbornyl chloroacetate;
preferably, the reducing agent is selected, for example, from boron tribromide or boron trichloride.
6. Use of a triptycene derivative of any one of claims 1-4 as a host material for a photoresist.
7. A positive-working photoresist composition comprising the triptycene derivative of any one of claims 1-4, a photoacid generator, and a photoresist solvent;
preferably, the mass of the triptycene derivative shown in the formula (A) is 1-10 wt% of the total mass of the positive photoresist composition, the mass of the photoacid generator is 0.01-1 wt%, and the balance is a photoresist solvent;
preferably, the photoacid generator is selected from ionic or non-ionic photoacid generators, including one or more of triphenylsulfonium triflate, triphenylsulfonium perfluorobutyrate, bis (4-tert-butylphenyl) iodonium p-toluenesulfonate, or N-hydroxynaphthalimide trifluoromethanesulfonate;
preferably, the photoresist solvent is selected from one or more of propylene glycol monomethyl ether acetate, ethyl lactate, ethylene glycol monomethyl ether, or cyclohexanone.
8. A positive-working photoresist film comprising the triptycene derivative of any of claims 1-4.
9. The method of producing a positive-working photoresist film according to claim 8, which comprises applying the positive-working photoresist composition according to claim 7 on a substrate to form a film;
preferably, the application mode is a spin coating method;
preferably, the substrate may be a silicon wafer.
10. Use of a positive-working photoresist composition according to claim 7 and/or a positive-working photoresist film according to claim 8 in photolithography;
the photoetching is 248nm photoetching, 193nm photoetching, extreme ultraviolet photoetching (EUV), nano-imprint photoetching or electron beam photoetching;
preferably, the positive photoresist composition, positive photoresist coating are used for electron beam lithography and extreme ultraviolet lithography.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2023282114A1 (en) * | 2021-07-09 | 2023-01-12 | 東京エレクトロン株式会社 | Pattern forming method and plasma processing method |
| CN117865866A (en) * | 2024-01-18 | 2024-04-12 | 中国科学院理化技术研究所 | Polythienium salt single-molecule resin photoresist based on triptycene and preparation method thereof |
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| JP2008308433A (en) * | 2007-06-14 | 2008-12-25 | Idemitsu Kosan Co Ltd | Compound having triptycene structure, photoresist base material and photoresist composition |
| US20190361342A1 (en) * | 2018-05-28 | 2019-11-28 | Tokyo Ohka Kogyo Co., Ltd. | Resist composition and method of forming resist pattern |
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| JP2008308433A (en) * | 2007-06-14 | 2008-12-25 | Idemitsu Kosan Co Ltd | Compound having triptycene structure, photoresist base material and photoresist composition |
| US20190361342A1 (en) * | 2018-05-28 | 2019-11-28 | Tokyo Ohka Kogyo Co., Ltd. | Resist composition and method of forming resist pattern |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023282114A1 (en) * | 2021-07-09 | 2023-01-12 | 東京エレクトロン株式会社 | Pattern forming method and plasma processing method |
| CN117865866A (en) * | 2024-01-18 | 2024-04-12 | 中国科学院理化技术研究所 | Polythienium salt single-molecule resin photoresist based on triptycene and preparation method thereof |
| CN117865866B (en) * | 2024-01-18 | 2024-05-24 | 中国科学院理化技术研究所 | Polythienium salt single-molecule resin photoresist based on triptycene and preparation method thereof |
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