CN116661241A - Monodisperse part protected molecule, preparation method thereof and application thereof in lithography - Google Patents
Monodisperse part protected molecule, preparation method thereof and application thereof in lithography Download PDFInfo
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- CN116661241A CN116661241A CN202210147449.5A CN202210147449A CN116661241A CN 116661241 A CN116661241 A CN 116661241A CN 202210147449 A CN202210147449 A CN 202210147449A CN 116661241 A CN116661241 A CN 116661241A
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- Prior art keywords
- compound
- formula
- lithography
- photoresist
- positive photoresist
- Prior art date
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000001459 lithography Methods 0.000 title claims description 17
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 67
- 150000001875 compounds Chemical class 0.000 claims abstract description 62
- 239000000463 material Substances 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 17
- 239000002253 acid Substances 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 238000001900 extreme ultraviolet lithography Methods 0.000 claims description 9
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 9
- 238000000609 electron-beam lithography Methods 0.000 claims description 8
- 239000012953 triphenylsulfonium Substances 0.000 claims description 6
- 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 claims description 5
- 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 5
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 238000010511 deprotection reaction 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
- 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
- 230000008569 process Effects 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
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 claims description 2
- 125000005571 adamantylene group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 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
- 150000002148 esters Chemical class 0.000 claims description 2
- 229940116333 ethyl lactate Drugs 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 238000001127 nanoimprint lithography Methods 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 150000002367 halogens Chemical group 0.000 claims 1
- 238000000206 photolithography Methods 0.000 claims 1
- 239000011521 glass Substances 0.000 abstract description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 9
- 230000035945 sensitivity Effects 0.000 abstract description 8
- 230000001965 increasing effect Effects 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000004090 dissolution Methods 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 93
- 238000006243 chemical reaction Methods 0.000 description 42
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 38
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 33
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 27
- 239000010408 film Substances 0.000 description 26
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 24
- 239000000243 solution Substances 0.000 description 22
- -1 (4-hydroxy-3, 5-di (4-hydroxy) phenyl) adamantane derivative Chemical class 0.000 description 20
- 239000007787 solid Substances 0.000 description 15
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000001259 photo etching Methods 0.000 description 12
- 239000001294 propane Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 11
- 230000009477 glass transition Effects 0.000 description 10
- 150000003462 sulfoxides Chemical class 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 235000013824 polyphenols Nutrition 0.000 description 8
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 description 7
- 238000004528 spin coating Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 3
- KKLCYBZPQDOFQK-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-phenyl-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=CC=C1 KKLCYBZPQDOFQK-UHFFFAOYSA-N 0.000 description 3
- 229940126062 Compound A Drugs 0.000 description 3
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- DFFDSQBEGQFJJU-UHFFFAOYSA-M butyl carbonate Chemical group CCCCOC([O-])=O DFFDSQBEGQFJJU-UHFFFAOYSA-M 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- GWLNEIMIWYJPNU-UHFFFAOYSA-N tert-butyl 2-(4-bromophenoxy)acetate Chemical compound CC(C)(C)OC(=O)COC1=CC=C(Br)C=C1 GWLNEIMIWYJPNU-UHFFFAOYSA-N 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- BMQDAIUNAGXSKR-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid Chemical compound CC(C)(O)C(C)(C)OB(O)O BMQDAIUNAGXSKR-UHFFFAOYSA-N 0.000 description 1
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 1
- RIVSTXVFMIBRJD-UHFFFAOYSA-N 1,2-diphenyladamantane Chemical compound C1C(C2)CC3CC1CC2(C=1C=CC=CC=1)C3C1=CC=CC=C1 RIVSTXVFMIBRJD-UHFFFAOYSA-N 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
- 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
- 125000005916 2-methylpentyl group Chemical group 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
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- JJHHIJFTHRNPIK-UHFFFAOYSA-N Diphenyl sulfoxide Chemical compound C=1C=CC=CC=1S(=O)C1=CC=CC=C1 JJHHIJFTHRNPIK-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000007664 blowing Methods 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
- 238000004364 calculation method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012141 concentrate Substances 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
- 238000010586 diagram Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 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
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000010354 integration Effects 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
- 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
- 230000000670 limiting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 230000036961 partial effect Effects 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
- 239000012466 permeate Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 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
- 239000007858 starting material Substances 0.000 description 1
- IWOKCMBOJXYDEE-UHFFFAOYSA-N sulfinylmethane Chemical compound C=S=O IWOKCMBOJXYDEE-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000005469 synchrotron radiation Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- KUYMVWXKHQSIAS-UHFFFAOYSA-N tert-butyl 2-chloroacetate Chemical compound CC(C)(C)OC(=O)CCl KUYMVWXKHQSIAS-UHFFFAOYSA-N 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Abstract
The application discloses a compound with a monodispersed part protection function shown in a formula (I), and a preparation method and application thereof. Compared with the molecular glass photoresist protected by the polydisperse part, the compound used as the molecular glass photoresist has high synthesis repeatability and uniform components. The dissolution rate of the exposure area in the developing solution is consistent, which is beneficial to improving the line edge and the line width roughness; compared with the full-protection molecular glass photoresist, the exposed hydroxyl is increased, the solubility difference between an exposure area and a non-exposure area can be realized by smaller exposure dose, and the sensitivity of the photoresist is further improved.
Description
Technical Field
The application belongs to the technical field of materials, and particularly relates to a monodisperse part-protected molecule, a preparation method thereof and application thereof in lithography.
Background
Photoresists are a class of photon or electron sensitive thin film materials that after irradiation, have significant solubility differences between exposed and non-exposed areas, and are further developed to provide lithographic patterns. The photoresist film acts as a barrier layer, and its properties determine the quality of the lithographic pattern, which in turn affects the quality of the subsequent etching process and the substrate pattern.
The performance of a photoresist is generally evaluated in terms of Resolution (Resolution), sensitivity (Sensitivity), line edge roughness (Line Edge Roughness, LER)/line width roughness (Line Width Roughness, LWR), contrast (Contrast), etch resistance (Etching Durability), and gas production (outlay). In order to meet the increasing demands of the semiconductor industry for chip integration, excellent photoresist must have the characteristics of high resolution, high sensitivity, low line edge roughness, high etching resistance, low gas yield, and the like. Therefore, the development of high-performance photoresist is of great significance.
The traditional chemical amplification photoresist main body material generally adopts polymer resin with molecular weight of 5000-15000 daltons, the photoetching resolution is limited by molecular size and acid distribution non-uniformity, and meanwhile, the main body material is not suitable for the next generation extreme ultraviolet photoetching because of factors such as large polymer molecular volume, polydisperse molecular weight, molecular chain winding and the like, which easily cause larger line edge roughness. At present, research hot spots of extreme ultraviolet photoresist concentrate on molecular glass, and the small molecular compound has a definite molecular structure, stable amorphous state and high glass transition temperature, and simultaneously has the thermal stability and film forming property of a polymer, thereby being suitable for being used as a main material of high-resolution photoresist. According to the report of the related literature, a very good result is obtained by taking molecular glass as a main material of the photoresist, and the resolution of the photoetching stripes can reach below 20nm by means of extreme ultraviolet photoetching technology (Performance of EUV molecular resists based on fullerene derivatives-Proc. SPIE 7972 (2011) 797209). However, the main material of the molecular glass photoresist is basically a part of protection structure with polydisperse acid sensitive groups. The polydisperse partially protected structure is a mixture of which the synthesized molecular structure is not identical and the position and number of protecting groups is indeterminate. In finer lithography, fine differences in molecular structure can also have a significant impact on the lithographic results.
Disclosure of Invention
In order to overcome the defects of the prior art, the application provides a molecular glass compound with a monodispersed part for protection, and a preparation method and application thereof. The monodisperse partially-protected molecular glass has a definite structure, and is obtained by precisely synthesizing and regulating the proportion of partial protection. Higher resolution can be realized, and the photoetching effect with better performance can be obtained.
The application firstly provides a compound shown as a formula I:
wherein A is selected from the group consisting of-S-, -S (O) 2 -、-C(CH 3 ) 2 -or adamantylene;
R 1 identical, R 2 Identical, R 3 Identical, R 1 、R 2 And R is R 3 Identical or different, independently of one another, from H, OR a Or C 1-12 Alkyl, said R a Is an acid-sensitive group; and R is 1 、R 2 And R is R 3 One of them is OR a 。
According to an embodiment of the present application, the value of the number of acid-sensitive groups/(the number of acid-sensitive groups+OH number) in the compound of formula (I) is expressed as a protection ratio, which is about 67%, and the fraction is expressed as two thirds.
According to an embodiment of the present application, the acid-sensitive group refers to a group that can be detached from the host material under acid-catalyzed conditions.
According to an embodiment of the application, the R a Selected from the following groups:
wherein ,representing a connection key.
According to an embodiment of the present application, the compound represented by formula (I) has a structure represented by the following formula (IA):
wherein ,R2 Selected from OR a ，A、R a As defined above.
According to an embodiment of the present application, the compound of formula (I) is selected from the following structures:
wherein ,R1 、R 2 、R 3 Independently of each other, have the definition described above.
According to an embodiment of the present application, the compound of formula (I) has the following structure:
the application also provides a preparation method of the compound shown in the formula (I), which comprises the following steps:
wherein A、R1 、R 2 、R 3 R is as defined above b Is oxygen-protectedRadicals, e.g. unsubstituted or substituted by C 1-6 Alkyl, C 1-6 Alkoxy substituted benzyl;
a1 (I-3) reacting a compound of formula (I-3) with R b -X to give a compound of formula (I-2) wherein X is halogen;
a2 Reacting the compound of formula (I-2) with a compound of formula (I-4) or an ester thereof (e.g., pinacol ester) to give a compound of formula (I-1),
wherein ,R1 、R 2 、R 3 As defined above in the description of the application,
a3 And then carrying out deprotection reaction on the compound of the formula (I-1) to obtain the compound of the formula (I).
The application also provides application of the compound as a photoresist main body material.
The application further provides a positive photoresist composition comprising the above compound.
According to the present application, the photoresist composition includes the above-described compound, a photoacid generator, and a photoresist solvent.
According to the application, in the photoresist composition, the compound accounts for 1-10wt% of the total mass of the positive photoresist composition, the photoacid generator accounts for 0.01-1wt% of the total mass of the positive photoresist composition, and the balance is photoresist solvent.
According to the application, the photoacid generator is selected from ionic or nonionic photoacid generators, and comprises one or more of triphenylsulfonium triflate, triphenylsulfonium perfluorobutylsulfonate, di (4-tert-butylphenyl) iodonium tosylate or N-hydroxynaphthalimide triflate.
According to the application, the photoresist solvent is selected from one or more of propylene glycol monomethyl ether acetate, ethyl lactate, ethylene glycol monomethyl ether or cyclohexanone.
The application also provides a positive photoresist film comprising the compound.
The application also provides a preparation method of the positive photoresist film, which comprises the step of applying the positive photoresist composition to a substrate to form a film so as to obtain the positive photoresist film.
In one embodiment, the application is spin coating.
In one embodiment, the substrate may be a silicon wafer.
The application also provides a positive photoresist composition and application of the positive photoresist film in lithography.
In one embodiment, the positive photoresist composition, positive photoresist film is used in lithography techniques such as 248nm lithography, 193nm lithography, extreme ultraviolet lithography (EUV), nanoimprint lithography, or electron beam lithography; is especially suitable for electron beam lithography and extreme ultraviolet lithography.
Advantageous effects
1. The application provides a compound shown in a formula I, the protection proportion is about 67%, and the compound is a partially-protected monodisperse molecular glass photoresist when being used as a photoresist main body material, and has high synthesis repeatability and uniform components compared with a polydisperse partially-protected molecular glass photoresist. The dissolution rate of the exposure area in the developing solution is consistent, which is beneficial to improving the line edge and the line width roughness;
2. compared with the full-protection molecular glass photoresist, the partially-protected monodisperse molecular glass photoresist has the advantages that the exposed hydroxyl is increased, the solubility difference between an exposure area and a non-exposure area can be realized by smaller exposure dose, and the sensitivity of the photoresist is further improved.
3. The microelectronic device usually adopts a high-purity silicon wafer as a substrate, has stronger hydrophilicity, and generally needs to be subjected to hydrophobic treatment before film coating. The molecular glass protected by the monodisperse part has phenolic hydroxyl groups, so that the adhesion to a substrate is improved. Meanwhile, hydrogen bonding exists between molecules, so that acting force between the molecules is increased, the film is harder, the glass transition temperature of the film is improved, and the exposure pattern is not easy to collapse;
4. the molecular glass photoresist with the monodispersed part protection has higher sensitivity compared with the molecular glass photoresist with the whole protection because the molecule itself contains part of phenolic hydroxyl groups. In addition, the proportion of acid sensitive groups is reduced, and the proportion of hydrocarbon of partially protected molecular glass is increased, so that the etching resistance of the photoresist is improved;
5. the selected core skeleton is halogenated polyphenols, and after palladium catalytic coupling, a branched polyphenyl structure is formed, so that a stable amorphous state is easy to form, and spin coating film formation is facilitated;
6. the molecular glass protected by the monodisperse part enables the accumulation between molecules to be more compact, can enhance the etching resistance of the film, reduces the proportion of acid sensitive groups in the whole molecule, and is also beneficial to enhancing the etching resistance of the molecules. The molecular glass photoresist of the monodisperse part contains naked phenolic hydroxyl groups and can be modified again according to requirements. For example, introducing silicon-containing units, increasing etch resistance, introducing sulfur-containing units, increasing refractive index, etc.
Drawings
FIG. 1 is a thermogram and differential scanning calorimeter of bis- ((4-hydroxy-3, 5-bis (4-t-butylcarbonate) phenyl) sulfine of example 5
FIG. 2 is a photograph of a resist pattern obtained by electron beam exposure using bis- ((4-hydroxy-3, 5-bis (4-t-butylcarbonate) phenyl) sulfoxide as a resist host material in example 6
FIG. 3 lithography patterns obtained by electron beam lithography with a monodisperse partially protected compound di- ((4-hydroxy-3, 5-di (4-t-butylcarbonate) phenyl) adamantane, a fully protected compound di- ((4-t-butylcarbonate-3, 5-di (4-t-butylcarbonate) phenyl) adamantane and a polydispersity di- ((4-hydroxy-3, 5-di (4-hydroxy) phenyl) adamantane derivative with a protection ratio of 67% as the resist host material, respectively
FIG. 4 differential scanning calorimetry of a monodisperse partially protected compound di- ((4-hydroxy-3, 5-di (4-t-butylcarbonate) phenyl) propane, a fully protected compound di- ((4-t-butylcarbonate-3, 5-di (4-t-butylcarbonate) phenyl) propane and a polydispersity di- ((4-hydroxy-3, 5-di (4-hydroxy) phenyl) propane derivative with a protection ratio of 67%
FIG. 5 extreme ultraviolet lithography patterns obtained with monodisperse partially protected compound di- ((4-hydroxy-3, 5-di (4-t-butylcarbonate) phenyl) propane, fully protected compound di- ((4-t-butylcarbonate-3, 5-di (4-t-butylcarbonate) phenyl) propane, and polydispersion di- ((4-hydroxy-3, 5-di (4-hydroxy) phenyl) propane derivative with a protection ratio of 67% as the resist host material, respectively
Definition and description of terms
Unless otherwise indicated, the radical and term definitions recited in the specification and claims of the present application, including as examples, exemplary definitions, preferred definitions, definitions recited in tables, definitions of specific compounds in the examples, and the like, may be arbitrarily combined and coupled with each other. Such combinations and combinations of radical definitions and structures should be understood to be within the scope of the present description and/or claims.
The numerical ranges recited in the specification and claims are equivalent to at least each specific integer number recited therein unless otherwise stated. For example, a numerical range "1-12" corresponds to each of the integer numbers recited in the numerical range "1-12," i.e., 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12. Furthermore, when certain numerical ranges are defined as "numbers," it is to be understood that both endpoints of the range, each integer within the range, and each fraction within the range are delineated. For example, a "number of 0 to 10" should be understood to describe not only each integer of 0, 1,2, 3, 4, 5, 6, 7, 8, 9 and 10, but also at least the sum of each integer with 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, respectively.
The term "C 1-12 Alkyl "is understood to mean a straight-chain or branched saturated monovalent hydrocarbon radical having from 1 to 12 carbon atoms. For example, "C 1-10 Alkyl "means straight-chain and branched alkyl having 1,2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms," C 1-8 Alkyl "means having 1,2Straight and branched alkyl groups of 3, 4, 5, 6, 7, or 8 carbon atoms, "C 1-6 Alkyl "means straight and branched alkyl groups having 1,2, 3, 4, 5 or 6 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-ethylpropyl, 1, 2-dimethylpropyl, neopentyl, 1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3-dimethylbutyl, 2-dimethylbutyl, 1-dimethylbutyl, 2, 3-dimethylbutyl, 1, 3-dimethylbutyl, or 1, 2-dimethylbutyl, or the like, or an isomer thereof.
Detailed Description
The technical scheme of the application will be further described in detail below with reference to specific embodiments. It should be understood that the following examples are illustrative of and illustrate the present application and should not be construed as limiting the scope of the application. All techniques implemented based on the above description of the application are intended to be included within the scope of the application.
Unless otherwise indicated, the starting materials and reagents used in the following examples are commercially available or may be prepared by known methods.
Example 1
In the first step, preparation of tert-butyl 2- (4-bromophenoxy) acetate:
the specific operation steps are as follows: in a 100mL single port reaction flask, p-bromophenol (1.73 g,10.0mmol,1.0 eq), t-butyl chloroacetate (1.65 g,11mmol,1.1 eq), potassium carbonate (1.65 g,12mmol, 1.2 eq), tetra-N-butylammonium bromide (128 mg,0.4mmol,0.04 eq) as a catalyst, and 30mL of N-methylpyrrolidone as a solvent were added, and the reaction system was warmed to 80℃and reacted for 6 hours. The reaction system was cooled to room temperature, the reaction was terminated by pouring the reaction solution into 100ml of water, extracting the aqueous phase with methylene chloride multiple times, combining the organic phases,washed once with water and saturated brine, respectively, and dried over anhydrous sodium sulfate. Spin-drying the solvent gave 2.64g of a colorless transparent oil in 92% yield. 1 H NMR(400MHz,CDCl 3 ):δ(ppm)7.48(d，2H，benzene)，6.98(d， 2H，benzene)，4.88(s，2H，-CH 2 )，1.52(s，9H，-CH 3 ). MS (MALDI-TOF) m/z=287.1, calculated (C 12 H 15 BrO 3 )m/z＝287.2(M+)。
Second, preparation of tert-butyl 2- (4- (pinacol borate) phenoxy) acetate:
the specific operation steps are as follows: tert-butyl 2- (4-bromophenoxy) acetate (2.87 g,10.0mmol,1.0 eq), pinacol biborate (2.79 g,11mmol,1.1 eq), catalyst [1,1' -bis (diphenylphosphino) ferrocene]2. Palladium chloride (73 mg,0.1mmol,0.01 eq) and 30ml of dry dioxane were placed in a 100ml schlenk reaction flask, the vacuum-nitrogen was repeated three times, and the reaction apparatus was placed in an oil bath at 100℃and reacted under reflux for 7 hours. After the completion of the reaction, the reaction mixture was poured into 100ml of water, the aqueous phase was extracted with methylene chloride several times, the organic phases were combined, washed once with water and saturated brine, and dried over anhydrous sodium sulfate. Spin-drying the solvent gave 3.2g of a pale yellow oil in 96% yield. 1 H NMR(400MHz,CDCl 3 ):δ(ppm)7.48(d，2H， benzene)，6.98(d，2H，benzene)，4.88(s，2H，-CH 2 )，1.52(s，9H，-CH 3 )， 1.21(s，12H，-CH 3 ). MS (MALDI-TOF) m/z=334.2, calculated (C 18 H 27 BO 5 ) m/z＝334.3(M+)。
Example 2
The core skeleton is diphenyl sulfoxide, the acid sensitive group is tert-butoxycarbonyl, the protection ratio is about 67%, and the fraction is expressed as two thirds;
in the first step, preparation of di- ((4-benzyloxy-3, 5-dibromo) phenyl) sulfoxide:
the specific operation steps are as follows: at 250mL single portTo the reaction flask were added di- ((4-hydroxy-3, 5-dibromo) phenyl) sulfoxide (5.49 g,10mmol,1.0 eq), benzyl bromide (3.59 g,21mmol,2.1 eq), potassium carbonate (3.3 g,24mmol,2.4 eq), 18-crown-6 (528 mg,2mmol,0.2 eq) and dry acetone 100mL, and the reaction system was warmed to 70℃for 6h. The reaction system was cooled to room temperature, the reaction solution was dried by spinning, the solid was dissolved in 200ml of methylene chloride, washed twice with water, washed once with saturated brine, and dried over anhydrous sodium sulfate. Spin-drying the solvent gave a white solid, 7g, 95.8% yield. 1 H NMR(400MHz,CDCl 3 ):δ(ppm)7.74(s， 4H，benzene)，7.32-7.48(m，10H，benzene)5.26(s，4H，-CH 2 ). MS (MALDI-TOF) m/z=729.7, calculated (C 26 H 18 Br 4 O 3 S)m/z＝729.9(M+)。
Second step, preparation of di- ((4-benzyloxy-3, 5-bis (4-tert-butylcarbonate) phenyl) sulfoxide:
the specific operation steps are as follows: in a 50mL Schlenk reaction flask were charged di- ((3, 5-dibromo-4-benzyloxy) phenyl) sulfoxide (0.73 g,1.0mmol,1.0 eq), 4-tert-butylcarbonate-based phenylboronic acid pinacol ester (1.92 g,6.0mmol,6.0 eq), potassium carbonate (0.828 g,6.0mmol,6.0 eq) and tetrakis triphenylphosphine palladium (11.6 mg, 0.01mmol,0.01 eq). A mixed solvent of 8ml of dioxane and 8ml of water was added to the reaction flask by a syringe under a nitrogen atmosphere. The reaction device is placed in an oil bath pot at 100 ℃ for reflux reaction for 8 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature, 100ml of methylene chloride was added thereto, the mixture was washed twice with water, and once with saturated brine, and dried over anhydrous sodium sulfate. The solvent was removed to give a yellow oil. The solid was dissolved in 5ml of methylene chloride, and was added dropwise to 100ml of ethanol to precipitate a white solid (1.1 g, yield 93.2%). 1 H NMR(400MHz,CDCl 3 ):δ(ppm)7.74(s，4H，benzene)，7.68(d，8H，benzene)， 7.32-7.48(m，10H，benzene)7.12(d，8H，benzene)，5.26(s，4H，-CH 2 )， 1.34(s，36H，-CH 3 ). MS (MALDI-TOF) m/z= 1182.3, calculated (C 70 H 70 O 15 S) m/z＝1182.9(M+)。
Third step, preparation of di- ((4-hydroxy-3, 5-di (4-t-butylcarbonate) phenyl) sulfoxide:
the specific operation steps are as follows: bis- ((4-benzyloxy-3, 5-bis (4-t-butylcarbonate) phenyl) sulfoxide (1.18 g,1mmol,1.0 eq) was dissolved in ethyl acetate, and Pd/C (60 mg,0.05mmol, 0.05 eq) was weighed as a catalyst and reacted under a hydrogen atmosphere at a reaction temperature set to 60 ℃. After the reaction is finished for about 48 hours, the catalyst is removed by filtration, and the filtrate is dried by spin to obtain the target product, thus obtaining 0.9g of white solid with the yield of 90 percent. 1 H NMR(400MHz,CDCl 3 ):δ(ppm)10.2(s，2H，-OH)，7.74(s，4H， benzene)，7.68(d，8H，benzene)，7.12(d，8H，benzene)，1.34(s，36H， -CH 3 ). MS (MALDI-TOF) m/z= 1002.3, calculated (C 56 H 58 O 15 S)m/z＝1002.6(M+)。
Example 3
The core skeleton is diphenyl adamantane, the acid sensitive group is tert-butoxycarbonyl, the protection ratio is 67%, and the fraction is expressed as two thirds;
first step, preparation of di- ((4-benzyloxy-3, 5-dibromo) phenyl) adamantane:
the specific operation steps are as follows: in a 250mL single port reaction flask was added di- ((4-hydroxy-3, 5-dibromo) phenyl) adamantane (6.51 g,10mmol,1.0 eq), benzyl bromide (3.59 g,21mmol,2.1 eq), potassium carbonate (3.3 g,24mmol,2.4 eq), 18-crown-6 (528 mg,2mmol,0.2 eq) and dry acetone 120mL, and the reaction system was warmed to 70℃for 8h. The reaction system was cooled to room temperature, the reaction solution was dried by spinning, the solid was dissolved in 250ml of methylene chloride, washed twice with water, washed once with saturated brine, and dried over anhydrous sodium sulfate. Spin-drying the solvent gave a white solid, 7.6g, 93.3% yield. 1 H NMR(400MHz,CDCl 3 ):δ(ppm) 7.73(s，4H，benzene)7.31-7.45(m，10H，benzene)5.26(s，4H，-CH 2 ) 2.33 (s, 2H, adamantane), 1.91-1.84 (m, 10H, adamantane), 1.76 (s, 2H, adamantane). MS (MALDI-TOF) m/z= 815.9, calculationValue (C) 36 H 32 Br 4 O 2 )m/z＝815.9(M+)。
Second step, preparation of di- ((4-benzyloxy-3, 5-bis (4-tert-butylcarbonate) phenyl) adamantane:
the specific operation steps are as follows: in a 50mL Schlenk reaction flask was charged di- ((3, 5-dibromo-4-benzyloxy) phenyl) adamantane (0.81 g,1.0mmol,1.0 eq), 4-tert-butylcarbonate-based phenylboronic acid pinacol ester (1.92 g,6.0mmol,6.0 eq), potassium carbonate (0.828 g,6.0mmol,6.0 eq) and tetrakis triphenylphosphine palladium (11.6 mg, 0.01mmol,0.01 eq). A mixed solvent of 10ml of dioxane and 10ml of water was added to the reaction flask by a syringe under a nitrogen atmosphere. The reaction device is placed in an oil bath pot at 100 ℃ for reflux reaction for 8 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature, 100ml of methylene chloride was added, the mixture was washed twice with water, and once with saturated brine, and dried over anhydrous sodium sulfate. The solvent was removed to give a yellow oil. The solid was dissolved in 5ml of methylene chloride, and was added dropwise to 100ml of ethanol to precipitate a white solid (1.1 g, yield: 87.3%). 1 H NMR(400MHz,CDCl 3 ):δ(ppm)7.74(s，4H，benzene)，7.67(d，8H，benzene)， 7.33-7.47(m，10H，benzene)7.13(d，8H，benzene)，5.24(s，4H，-CH 2 )， 2.34(s,2H,adamantane),1.92–1.83(m,10H,adamantane),1.76(s,2H, adamantane)，1.34(s，36H，-CH 3 ). MS (MALDI-TOF) m/z= 1268.6, calculated (C 80 H 84 O 14 )m/z＝1268.6(M+)。
Third step, preparation of di- ((4-hydroxy-3, 5-di (4-t-butylcarbonate) phenyl) adamantane:
the specific operation steps are as follows: di- ((4-benzyloxy-3, 5-bis (4-tert-butylcarbonate) phenyl) adamantane (1.27 g,1mmol,1.0 eq) was dissolved in ethyl acetate, and Pd/C (60 mg,0.05mmol, 0.05 eq) was weighed as a catalyst, and the reaction was carried out under a hydrogen atmosphere at a reaction temperature set to 60 ℃. After the reaction is completed for about 48 hours, the catalyst is removed by filtration, and the filtrate is dried by spin to obtain the target product, 1.0g of white solid is obtained, and the yield is 91.8%. 1 H NMR(400MHz,CDCl 3 ):δ(ppm)10.0(s，2H，-OH)， 7.74(s，4H，benzene)，7.68(d，8H，benzene)，7.12(d，8H，benzene)， 2.34(s,2H,adamantane),1.92–1.83(m,10H,adamantane),1.75(s,2H, adamantane)，1.34(s，36H，-CH 3 ). MS (MALDI-TOF) m/z= 1088.5, calculated (C 66 H 72 O 14 )m/z＝1088.5(M+)。
Example 4
The core skeleton is bisphenol A, the acid sensitive group is tert-butoxycarbonyl, the protection ratio is 67%, and the fraction is two thirds;
first, preparation of di- ((4-benzyloxy-3, 5-dibromo) phenyl) propane:
the specific operation steps are as follows: in a 250mL single port reaction flask were added di- ((4-hydroxy-3, 5-dibromo) phenyl) propane (5.4 g,10mmol,1.0 eq), benzyl bromide (3.59 g,21mmol,2.1 eq), potassium carbonate (3.3 g,24mmol,2.4 eq), 18-crown-6 (528 mg,2mmol,0.2 eq) and dry acetone 80mL, and the reaction was warmed to 70℃for 6h. The reaction system was cooled to room temperature, the reaction solution was dried by spinning, the solid was dissolved in 150ml of methylene chloride, washed twice with water, washed once with saturated brine, and dried over anhydrous sodium sulfate. Spin-drying the solvent gave a white solid, 6.9g, 95.4% yield. 1 H NMR(400MHz,CDCl 3 ):δ(ppm)7.72 (s，4H，benzene)，7.32-7.46(m，10H，benzene)5.24(s，4H，-CH 2 ),1.56(s， 6H，-CH 3 ). MS (MALDI-TOF) m/z= 723.8, calculated (C 29 H 24 Br 4 O 2 )m/z＝723.8(M+)。
Second step, preparation of di- ((4-benzyloxy-3, 5-bis (4-tert-butylcarbonate) phenyl) propane:
the specific operation steps are as follows: in a 50mL Schlenk reaction flask were charged di- ((3, 5-dibromo-4-benzyloxy) phenyl) propane (0.72 g,1.0mmol,1.0 eq), 4-tert-butylcarbonate-based phenylboronic acid pinacol ester (1.92 g,6.0mmol,6.0 eq), potassium carbonate (0.828 g,6.0mmol,6.0 eq) and tetrakis triphenylphosphine palladium (11.6 mg, 0.01mmol, 0)01 eq). A mixed solvent of 10ml of dioxane and 10ml of water was added to the reaction flask by a syringe under a nitrogen atmosphere. The reaction device is placed in an oil bath pot at 100 ℃ for reflux reaction for 8 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature, 100ml of methylene chloride was added, the mixture was washed twice with water, and once with saturated brine, and dried over anhydrous sodium sulfate. The solvent was removed to give a yellow oil. The solid was dissolved in 5ml of methylene chloride, and was added dropwise to 100ml of ethanol to precipitate a white solid (1.0 g, yield: 85.5%). 1 H NMR(400MHz,CDCl 3 ):δ(ppm)7.73(s，4H，benzene)，7.67(d，8H，benzene)， 7.32-7.45(m，10H，benzene)7.11(d，8H，benzene)，5.26(s，4H，-CH 2 )， 1.58(s，6H，-CH 3 )，1.34(s，36H，-CH 3 ). MS (MALDI-TOF) m/z= 1176.5, calculated value (C 73 H 76 O 14 )m/z＝1176.5(M+)。
Third step, preparation of di- ((4-hydroxy-3, 5-di (4-t-butylcarbonate) phenyl) propane:
the specific operation steps are as follows: bis- ((4-benzyloxy-3, 5-bis (4-t-butylcarbonate) phenyl) propane (1.18 g,1mmol,1.0 eq) was dissolved in ethyl acetate and Pd/C (60 mg,0.05mmol, 0.05 eq) was weighed as a catalyst and reacted under a hydrogen atmosphere at a reaction temperature set to 60 ℃. After the reaction is finished for about 48 hours, the catalyst is removed by filtration, and the filtrate is dried by spin to obtain the target product, thus obtaining 0.9g of white solid with the yield of 90 percent. 1 H NMR(400MHz,CDCl 3 ):δ(ppm)10.4(s，2H，-OH)，7.78(s，4H， benzene)，7.68(d，8H，benzene)，7.14(d，8H，benzene)，1.56(s，6H， -CH 3 )，1.34(s，36H，-CH 3 ). MS (MALDI-TOF) m/z= 996.4, calculated (C 59 H 64 O 14 ) m/z＝996.4(M+)。
Example 5
The thermal stability and glass transition temperature of the molecular glass di- ((4-hydroxy-3, 5-di (4-tertiary butyl carbonate) phenyl) sulfoxide in the example 2 are measured by a thermogravimetric analyzer and a differential scanning calorimeter, and the thermal decomposition temperature is higher than 150 ℃ and the glass transition temperature is higher than 100 ℃ according to the thermal weight curve and the differential scanning calorimeter curve (shown in figure 1) of the compound, so that the requirement of a photoetching process on the heat treatment temperature is met.
Example 6
A positive photoresist composition comprising the bis- ((4-hydroxy-3, 5-bis (4-t-butylcarbonate) phenyl) sulfoxide, propylene glycol monomethyl ether acetate, and triphenylsulfonium perfluoro-butylsulfonate salt obtained in example 2. The specific method comprises the following steps: the compound di- ((4-hydroxy-3, 5-di (4-tertiary butyl carbonate) phenyl) sulfoxide prepared in example 2 was dissolved in Propylene Glycol Monomethyl Ether Acetate (PGMEA) to prepare a solution with a mass concentration of 5%, 0.5wt% of triphenylsulfonium perfluoro-butylsulfonate as photoacid generator was added, and the solution was filtered with a microporous filter with a pore size of 0.1 μm to obtain a spin-coating solution, spin-coated on a silicon wafer substrate, baked at 100 ℃ for 2 minutes, and the prepared film was subjected to electron beam lithography experiments in a national center of nano-meter, an exposure period of 80nm, to obtain very uniform lithography stripes with a line width of 30nm, and lithography results were shown in fig. 2.
Example 7
Substances A, B and C are each a monodisperse partially protected compound di- ((4-hydroxy-3, 5-bis (4-tert-butylcarbonate) phenyl) adamantane, a fully protected compound di- ((4-tert-butylcarbonate-3, 5-bis (4-tert-butylcarbonate) phenyl) adamantane and a polydispersity di- ((4-hydroxy-3, 5-bis (4-hydroxy) phenyl) adamantane derivative with a protection ratio of 67%, wherein compound A is derived from the synthesis of examples 3, B and C by the prior patent (patent application number: CN 201710578509.8). The substances A, B and C are respectively used as a main material of the photoresist, and the positive photoresist is composed of triphenylsulfonium perfluoro-butyl sulfonate and propylene glycol monomethyl ether acetate. The specific method comprises the following steps: taking a substance A as an example, dissolving the substance A in propylene glycol monomethyl ether acetate to prepare a solution with a mass concentration of 5%, adding 0.5wt% of triphenylsulfonium perfluoro-butylsulfonate as a photoacid generator, and filtering by a microporous filter with a pore diameter of 0.1 mu m to obtain a spin-on solution. And (3) dripping a proper amount of spin coating liquid onto a silicon wafer substrate, spin coating to form a film, baking at 100 ℃ for 2 minutes, and removing the photoresist solvent. And carrying out an electron beam lithography experiment on the prepared photoresist film in the national center of nanometer, wherein the electron beam lithography layout is 30nm L/S. The substances B and C are prepared in the same manner to obtain a photoresist film, and electron beam lithography is performed. After the exposure was completed, development was performed with 2.38wt% TMAH lye, rinsed with ultrapure water for 60s and dried by blowing nitrogen gas. FIGS. 3 (a), (b) and (C) are lithographic patterns obtained by electron beam exposure using substances A, B and C, respectively, as host materials. From the point of view of the quality and contrast of the lithographic pattern, FIG. 3 (a) is significantly better than (b) and (c). The groove part in fig. 3 (b) cannot be completely cleaned, and obvious bridging exists between the photoetching stripes, because the surface of the fully-protected main body material is too hydrophobic, hydrophilic developing solution is difficult to permeate into the groove part, so that the development is incomplete, more defects appear in the photoetching pattern, and the resolution ratio of the photoetching pattern is affected. FIG. 3 (c) is a graph showing that not only the contrast is poor, but also the photoresist stripe is broken because the main material of the exposure area is multi-dispersible, the deprotection ratio of the acid-sensitive group is not uniform, the dissolution rate in the developing solution is not uniform, and the developing condition of each part is not uniform, so that the stripe is broken. Compared with the main materials B and C, the molecular structure of the compound A is determined, the deprotection proportion of the exposed area tends to be consistent, the dissolution rate in the developing solution tends to be consistent, and the conditions of breaking and blurring of the photoetching pattern are avoided. Meanwhile, the phenolic hydroxyl exposed by the compound A is beneficial to adjusting the hydrophilicity and hydrophobicity of the surface of the film, so that the developing solution can be spread on the surface of the film, the developing solution can enter the groove, and the cleaning area is cleaner. In addition, the compound protected by the monodisperse part is used as a main body material, and the photoetching sensitivity is highest, because the main body material contains part of naked phenolic hydroxyl groups, and can be dissolved in a developing solution only by small dose exposure.
Example 8
Substances E, F and G are, respectively, monodisperse partially protected compound di- ((4-hydroxy-3, 5-bis (4-tert-butylcarbonate) phenyl) propane, fully protected compound di- ((4-tert-butylcarbonate-3, 5-bis (4-tert-butylcarbonate) phenyl) propane and polydispersity di- ((4-hydroxy-3, 5-bis (4-hydroxy) phenyl) propane derivatives with a protection ratio of 67%, wherein compound E is derived from the synthetic reference existing patents of examples 4,F and G (patent application number: CN 201210156675.6). Their glass transition temperatures were measured by a differential scanning calorimeter and the results are shown in FIG. 4. By analysis and calculation, the glass transition temperature was E (143 ℃) to F (127 ℃) to G (102 ℃) in this order from high to low. G is a polydisperse mixture, resulting in a minimum glass transition temperature. E is a monodisperse part protecting compound, and the exposed hydroxyl enhances the acting force between molecules through hydrogen bonding, so that the glass transition temperature is the highest. According to the report of related literature (DOI: 10.1016/j.mee.2007.01.052), strong intermolecular force and high glass transition temperature are beneficial to inhibiting collapse of the lithography pattern and enhancing resolution and contrast of the lithography pattern.
Example 9
The materials E, F and G in example 8 were used as a resist host material, respectively, and triphenylsulfonium triflate and propylene glycol monomethyl ether acetate were used to make up a positive resist. The specific method comprises the following steps: taking a substance E as an example, dissolving the substance E in propylene glycol monomethyl ether acetate to prepare a solution with a mass concentration of 5%, adding 0.5wt% of triphenylsulfonium triflate as a photoacid generator, and filtering by a microporous filter with a pore diameter of 0.1 mu m to obtain a spin-on solution. And (3) dripping a proper amount of spin coating liquid onto a silicon wafer substrate, spin coating to form a film, baking at 100 ℃ for 2 minutes, and removing the photoresist solvent. And (3) carrying out extreme ultraviolet lithography on the prepared photoresist film at a soft X-ray station of the Shanghai synchrotron radiation light source, wherein the period of the grating is 100nm. The substances F and G are prepared in exactly the same way to obtain a photoresist film, and extreme ultraviolet lithography is performed. After the exposure was completed, the film was developed with 2.38wt% TMAH lye, rinsed with ultra pure water for 60s and dried with nitrogen. FIGS. 5 (e), (f) and (G) are lithographic patterns obtained by EUV exposure using substances E, F and G, respectively, as host materials. From the point of view of the quality and contrast of the lithographic pattern, FIG. 5 (e) is significantly better than FIGS. (f) and (g). The groove portion of fig. 5 (f) is not completely cleaned because the surface of the fully protected main material is too hydrophobic, and the hydrophilic developing solution is difficult to penetrate into the groove portion, so that the development is not thorough, and the resolution of the lithography pattern is affected. FIG. 5 (G) is a diagram showing not only poor pattern contrast but also collapse of the photolithographic stripe due to the polydispersion of the material G, relatively low glass transition temperature, weak mechanical strength of the photolithographic stripe, and easy collapse of the pattern when the aspect ratio is too large. Compared with the main materials F, G and E, the compound has definite molecular structure and contains naked phenolic hydroxyl groups, the acting force between molecules is enhanced by means of hydrogen bond action, and the mechanical strength of the photoresist film is improved, so that the photoresist film is not easy to collapse. Meanwhile, the phenolic hydroxyl group exposed out of the compound E can reduce the hydrophobicity of the film surface, so that the developing solution can be conveniently spread on the film surface, the developing solution can enter the groove, the cleaning place is cleaner, and the resolution of the photoetching pattern is improved. Similar to example 7, the compound protected by the monodisperse moiety was used as the host material, and the lithography sensitivity was the highest, as in example 7.
The embodiments of the technical solution of the present application have been described above by way of example. It should be understood that the protection scope of the present application is not limited to the above embodiments. Any modification, equivalent replacement, improvement, etc. made by those skilled in the art within the spirit and principles of the present application should be included in the scope of the present application as defined in the appended claims.
Claims (10)
1. A compound of formula I:
wherein A is selected from the group consisting of-S-, -S (O) 2 -、-C(CH 3 ) 2 -or adamantylene;
R 1 identical, R 2 Identical, R 3 Identical, R 1 、R 2 And R is R 3 Identical or different, independently of one another, from H, OR a Or C 1-12 Alkyl, said R a Is an acid-sensitive group; and R is 1 、R 2 And R is R 3 One of them is OR a 。
2. The compound of claim 1, wherein R a Selected from the following groups:
wherein ,representing a connection key.
3. The compound according to claim 1 or 2, wherein the compound of formula (I) has a structure represented by formula (II):
R 2 selected from OR a ，A、R a Having the definition of claim 1 or 2.
4. A compound according to any one of claims 1 to 3, wherein the compound of formula (I) is selected from the following structures:
wherein ,R1 、R 2 、R 3 Independent of each other, have the definition as claimed in any one of claims 1 to 3.
5. A compound according to any one of claims 1 to 4, wherein the compound of formula (I) is selected from the following structures:
6. a process for the preparation of a compound according to any one of claims 1 to 5, comprising the steps of:
wherein A、R1 、R 2 、R 3 Having the definition as claimed in any one of claims 1 to 5, R b For oxygen protecting groups, e.g. unsubstituted or C 1-6 Alkyl, C 1-6 Alkoxy substituted benzyl; the method comprises the steps of carrying out a first treatment on the surface of the
A1 (I-3) reacting a compound of formula (I-3) with R b -X to give a compound of formula (I-2) wherein X is halogen;
a2 Reacting the compound of formula (I-2) with a compound of formula (I-4) or an ester thereof (e.g., pinacol ester) to give a compound of formula (I-1),
wherein ,R1 、R 2 、R 3 Independent of each other having the definition according to any one of claims 1 to 5,
a3 And then carrying out deprotection reaction on the compound of the formula (I-1) to obtain the compound of the formula (I).
7. Use of a compound according to any one of claims 1-5 as a photoresist host material.
8. A positive photoresist composition comprising a compound of any one of claims 1-5;
preferably, the photoresist composition comprises the above compound, a photoacid generator, and a photoresist solvent;
preferably, in the photoresist composition, the compound accounts for 1 to 10 weight percent of the total mass of the positive photoresist composition, the photoacid generator accounts for 0.01 to 1 weight percent of the total mass of the positive photoresist composition, and the balance is photoresist solvent;
preferably, the photoacid generator is selected from ionic or nonionic photoacid generators, and comprises one or more of triphenylsulfonium triflate, triphenylsulfonium perfluorobutylsulfonate, di (4-tert-butylphenyl) iodonium tosylate or N-hydroxynaphthalimide triflate;
preferably, the photoresist solvent is selected from one or more of propylene glycol monomethyl ether acetate, ethyl lactate, ethylene glycol monomethyl ether or cyclohexanone.
9. A positive photoresist film comprising the compound of any one of claims 1-5.
10. Use of the positive photoresist composition of claim 8 and/or the positive photoresist film of claim 9 in photolithography;
preferably, the positive photoresist composition, positive photoresist film is used in 248nm lithography, 193nm lithography, extreme ultraviolet lithography, nanoimprint lithography or electron beam lithography.
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| CN202210147449.5A CN116661241A (en) | 2022-02-17 | 2022-02-17 | Monodisperse part protected molecule, preparation method thereof and application thereof in lithography |
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| CN202210147449.5A CN116661241A (en) | 2022-02-17 | 2022-02-17 | Monodisperse part protected molecule, preparation method thereof and application thereof in lithography |
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