JP2005091407A - Method for evaluating radiation-sensitive resin and radiation-sensitive resin composition - Google Patents
Method for evaluating radiation-sensitive resin and radiation-sensitive resin composition Download PDFInfo
- Publication number
- JP2005091407A JP2005091407A JP2003320589A JP2003320589A JP2005091407A JP 2005091407 A JP2005091407 A JP 2005091407A JP 2003320589 A JP2003320589 A JP 2003320589A JP 2003320589 A JP2003320589 A JP 2003320589A JP 2005091407 A JP2005091407 A JP 2005091407A
- Authority
- JP
- Japan
- Prior art keywords
- group
- radiation
- resin
- sensitive resin
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011347 resin Substances 0.000 title claims abstract description 140
- 229920005989 resin Polymers 0.000 title claims abstract description 140
- 230000005855 radiation Effects 0.000 title claims abstract description 79
- 239000011342 resin composition Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims description 28
- 239000002904 solvent Substances 0.000 claims abstract description 44
- 238000009792 diffusion process Methods 0.000 claims abstract description 39
- 238000011161 development Methods 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims description 32
- 230000008859 change Effects 0.000 claims description 23
- 238000002296 dynamic light scattering Methods 0.000 claims description 14
- 238000005259 measurement Methods 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 10
- 230000009471 action Effects 0.000 claims description 6
- 230000007547 defect Effects 0.000 abstract description 25
- 238000011156 evaluation Methods 0.000 abstract description 17
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- -1 alicyclic ester Chemical class 0.000 description 88
- 239000000243 solution Substances 0.000 description 65
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 46
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 39
- 239000000178 monomer Substances 0.000 description 32
- 238000006116 polymerization reaction Methods 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 25
- 229910052757 nitrogen Inorganic materials 0.000 description 22
- 230000018109 developmental process Effects 0.000 description 20
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- 125000000217 alkyl group Chemical group 0.000 description 13
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- JJMQLQLMPJLIPZ-UHFFFAOYSA-N (5-oxo-4-oxatricyclo[4.2.1.03,7]nonan-2-yl) 2-methylprop-2-enoate Chemical compound O1C(=O)C2CC3C(OC(=O)C(=C)C)C1C2C3 JJMQLQLMPJLIPZ-UHFFFAOYSA-N 0.000 description 12
- KCAMXZBMXVIIQN-UHFFFAOYSA-N octan-3-yl 2-methylprop-2-enoate Chemical compound CCCCCC(CC)OC(=O)C(C)=C KCAMXZBMXVIIQN-UHFFFAOYSA-N 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 10
- 230000035945 sensitivity Effects 0.000 description 10
- 125000002723 alicyclic group Chemical group 0.000 description 9
- 230000007423 decrease Effects 0.000 description 9
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- CEIPQQODRKXDSB-UHFFFAOYSA-N ethyl 3-(6-hydroxynaphthalen-2-yl)-1H-indazole-5-carboximidate dihydrochloride Chemical compound Cl.Cl.C1=C(O)C=CC2=CC(C3=NNC4=CC=C(C=C43)C(=N)OCC)=CC=C21 CEIPQQODRKXDSB-UHFFFAOYSA-N 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 7
- SMEROWZSTRWXGI-UHFFFAOYSA-N Lithocholsaeure Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)CC2 SMEROWZSTRWXGI-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 6
- 238000007689 inspection Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000010926 purge Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- 229940009976 deoxycholate Drugs 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CEZIJESLKIMKNL-UHFFFAOYSA-N 1-(4-butoxynaphthalen-1-yl)thiolan-1-ium Chemical compound C12=CC=CC=C2C(OCCCC)=CC=C1[S+]1CCCC1 CEZIJESLKIMKNL-UHFFFAOYSA-N 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- XNUYPROIFFCXAE-UHFFFAOYSA-N (4-cyclohexylphenyl)-diphenylsulfanium Chemical compound C1CCCCC1C1=CC=C([S+](C=2C=CC=CC=2)C=2C=CC=CC=2)C=C1 XNUYPROIFFCXAE-UHFFFAOYSA-N 0.000 description 3
- WFQNMENFJSZTGD-UHFFFAOYSA-O 2,6-dimethyl-4-(thiolan-1-ium-1-yl)phenol Chemical compound CC1=C(O)C(C)=CC([S+]2CCCC2)=C1 WFQNMENFJSZTGD-UHFFFAOYSA-O 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- DNFSNYQTQMVTOK-UHFFFAOYSA-N bis(4-tert-butylphenyl)iodanium Chemical compound C1=CC(C(C)(C)C)=CC=C1[I+]C1=CC=C(C(C)(C)C)C=C1 DNFSNYQTQMVTOK-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 3
- JFCFIXGDCBSLRW-UHFFFAOYSA-N heptan-2-yl 1,1,2,2-tetrafluoroethanesulfonate Chemical compound CC(CCCCC)OS(=O)(=O)C(C(F)F)(F)F JFCFIXGDCBSLRW-UHFFFAOYSA-N 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical compound C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 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 description 3
- 239000012953 triphenylsulfonium Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- JYVXNLLUYHCIIH-UHFFFAOYSA-N (+/-)-mevalonolactone Natural products CC1(O)CCOC(=O)C1 JYVXNLLUYHCIIH-UHFFFAOYSA-N 0.000 description 2
- VNYGZQZFJDADCT-UHFFFAOYSA-N (3-methyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2C(C)(OC(=O)C=C)CC1C2 VNYGZQZFJDADCT-UHFFFAOYSA-N 0.000 description 2
- MFNBODQBPMDPPQ-UHFFFAOYSA-N (4-tert-butylphenyl)-diphenylsulfanium Chemical compound C1=CC(C(C)(C)C)=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 MFNBODQBPMDPPQ-UHFFFAOYSA-N 0.000 description 2
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 2
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical compound CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 2
- DWYHDSLIWMUSOO-UHFFFAOYSA-N 2-phenyl-1h-benzimidazole Chemical compound C1=CC=CC=C1C1=NC2=CC=CC=C2N1 DWYHDSLIWMUSOO-UHFFFAOYSA-N 0.000 description 2
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 2
- JVZRCNQLWOELDU-UHFFFAOYSA-N 4-Phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=NC=C1 JVZRCNQLWOELDU-UHFFFAOYSA-N 0.000 description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 229960003964 deoxycholic acid Drugs 0.000 description 2
- KXGVEGMKQFWNSR-UHFFFAOYSA-N deoxycholic acid Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)C(O)C2 KXGVEGMKQFWNSR-UHFFFAOYSA-N 0.000 description 2
- OZLBDYMWFAHSOQ-UHFFFAOYSA-N diphenyliodanium Chemical compound C=1C=CC=CC=1[I+]C1=CC=CC=C1 OZLBDYMWFAHSOQ-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001312 dry etching Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- BHXIWUJLHYHGSJ-UHFFFAOYSA-N ethyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OCC BHXIWUJLHYHGSJ-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N isobutyl acetate Chemical compound CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- CKFGINPQOCXMAZ-UHFFFAOYSA-N methanediol Chemical compound OCO CKFGINPQOCXMAZ-UHFFFAOYSA-N 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- LPEKGGXMPWTOCB-UHFFFAOYSA-N methyl 2-hydroxypropionate Chemical compound COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 229940057061 mevalonolactone Drugs 0.000 description 2
- 125000006606 n-butoxy group Chemical group 0.000 description 2
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 238000001226 reprecipitation Methods 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229960002317 succinimide Drugs 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 230000005469 synchrotron radiation Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- ZMOJTPABCOWEOS-UHFFFAOYSA-N tris(4-tert-butylphenyl)sulfanium Chemical compound C1=CC(C(C)(C)C)=CC=C1[S+](C=1C=CC(=CC=1)C(C)(C)C)C1=CC=C(C(C)(C)C)C=C1 ZMOJTPABCOWEOS-UHFFFAOYSA-N 0.000 description 2
- SNICXCGAKADSCV-JTQLQIEISA-N (-)-Nicotine Chemical compound CN1CCC[C@H]1C1=CC=CN=C1 SNICXCGAKADSCV-JTQLQIEISA-N 0.000 description 1
- YUOCJTKDRNYTFJ-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)S(=O)(=O)ON1C(=O)CCC1=O YUOCJTKDRNYTFJ-UHFFFAOYSA-N 0.000 description 1
- IFAMWFCILVCFKD-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)S(=O)(=O)ON1C(=O)CCC1=O IFAMWFCILVCFKD-UHFFFAOYSA-N 0.000 description 1
- XSSDZVAXPMVGEC-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) 2-(3-bicyclo[2.2.1]heptanyl)-1,1,2,2-tetrafluoroethanesulfonate Chemical compound C1C(C2)CCC2C1C(F)(F)C(F)(F)S(=O)(=O)ON1C(=O)CCC1=O XSSDZVAXPMVGEC-UHFFFAOYSA-N 0.000 description 1
- OKRLWHAZMUFONP-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) trifluoromethanesulfonate Chemical compound FC(F)(F)S(=O)(=O)ON1C(=O)CCC1=O OKRLWHAZMUFONP-UHFFFAOYSA-N 0.000 description 1
- DUVDEQGMXBXFEV-UHFFFAOYSA-N (2-oxooxan-4-yl) prop-2-enoate Chemical compound C=CC(=O)OC1CCOC(=O)C1 DUVDEQGMXBXFEV-UHFFFAOYSA-N 0.000 description 1
- MWMWRSCIFDZZGW-UHFFFAOYSA-N (2-oxooxolan-3-yl) prop-2-enoate Chemical compound C=CC(=O)OC1CCOC1=O MWMWRSCIFDZZGW-UHFFFAOYSA-N 0.000 description 1
- SPGPUDJMXMJNCU-FHWLQOOXSA-N (2S,3S,4S)-4-methyl-5-oxo-2-(14-oxopentadecyl)oxolane-3-carboxylic acid Chemical compound C[C@H]1[C@H](C(O)=O)[C@H](CCCCCCCCCCCCCC(C)=O)OC1=O SPGPUDJMXMJNCU-FHWLQOOXSA-N 0.000 description 1
- OFHHPVYGGQKWQL-UHFFFAOYSA-N (3,3-dimethyl-5-oxooxolan-2-yl)methyl prop-2-enoate Chemical compound CC1(C)CC(=O)OC1COC(=O)C=C OFHHPVYGGQKWQL-UHFFFAOYSA-N 0.000 description 1
- PNXSDOXXIOPXPY-UHFFFAOYSA-N (3,5-dioxo-4-azatricyclo[5.2.1.02,6]dec-8-en-4-yl) 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound C1=CC2CC1C1C2C(=O)N(OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C1=O PNXSDOXXIOPXPY-UHFFFAOYSA-N 0.000 description 1
- RNWQNJSIQVREPH-UHFFFAOYSA-N (3-ethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2C(CC)(OC(=O)C=C)CC1C2 RNWQNJSIQVREPH-UHFFFAOYSA-N 0.000 description 1
- UFADEYDBOXASBQ-UHFFFAOYSA-M (4-cyclohexylphenyl)-diphenylsulfanium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F.C1CCCCC1C1=CC=C([S+](C=2C=CC=CC=2)C=2C=CC=CC=2)C=C1 UFADEYDBOXASBQ-UHFFFAOYSA-M 0.000 description 1
- QEYKXSMQZGHJSX-UHFFFAOYSA-M (4-cyclohexylphenyl)-diphenylsulfanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1CCCCC1C1=CC=C([S+](C=2C=CC=CC=2)C=2C=CC=CC=2)C=C1 QEYKXSMQZGHJSX-UHFFFAOYSA-M 0.000 description 1
- NYJFKKATAUTNIQ-UHFFFAOYSA-N (4-methyl-2-oxooxan-4-yl) prop-2-enoate Chemical compound C=CC(=O)OC1(C)CCOC(=O)C1 NYJFKKATAUTNIQ-UHFFFAOYSA-N 0.000 description 1
- GXZZZWUTJCPYHC-UHFFFAOYSA-M (4-tert-butylphenyl)-diphenylsulfanium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F.C1=CC(C(C)(C)C)=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 GXZZZWUTJCPYHC-UHFFFAOYSA-M 0.000 description 1
- RLAWXWSZTKMPQQ-UHFFFAOYSA-M (4-tert-butylphenyl)-diphenylsulfanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC(C(C)(C)C)=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 RLAWXWSZTKMPQQ-UHFFFAOYSA-M 0.000 description 1
- GKMCOMBDUTZHID-UHFFFAOYSA-N (5-oxooxolan-2-yl)methyl prop-2-enoate Chemical compound C=CC(=O)OCC1CCC(=O)O1 GKMCOMBDUTZHID-UHFFFAOYSA-N 0.000 description 1
- NLFBWKWLKNHTDC-UHFFFAOYSA-N (5-oxooxolan-3-yl) prop-2-enoate Chemical compound C=CC(=O)OC1COC(=O)C1 NLFBWKWLKNHTDC-UHFFFAOYSA-N 0.000 description 1
- PQONLZARMHVIPW-UHFFFAOYSA-N (7,7-dimethyl-3-oxo-4-bicyclo[2.2.1]heptanyl)methanesulfonate;2,6-dimethyl-4-(thiolan-1-ium-1-yl)phenol Chemical compound CC1=C(O)C(C)=CC([S+]2CCCC2)=C1.C1CC2(CS([O-])(=O)=O)C(=O)CC1C2(C)C PQONLZARMHVIPW-UHFFFAOYSA-N 0.000 description 1
- HHYVKZVPYXHHCG-UHFFFAOYSA-M (7,7-dimethyl-3-oxo-4-bicyclo[2.2.1]heptanyl)methanesulfonate;diphenyliodanium Chemical compound C=1C=CC=CC=1[I+]C1=CC=CC=C1.C1CC2(CS([O-])(=O)=O)C(=O)CC1C2(C)C HHYVKZVPYXHHCG-UHFFFAOYSA-M 0.000 description 1
- FJALTVCJBKZXKY-UHFFFAOYSA-M (7,7-dimethyl-3-oxo-4-bicyclo[2.2.1]heptanyl)methanesulfonate;triphenylsulfanium Chemical compound C1CC2(CS([O-])(=O)=O)C(=O)CC1C2(C)C.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 FJALTVCJBKZXKY-UHFFFAOYSA-M 0.000 description 1
- OEPCINZNIXWOPJ-UHFFFAOYSA-N (7-oxo-6-oxabicyclo[3.2.1]octan-4-yl) prop-2-enoate Chemical compound C=CC(=O)OC1CCC2C(=O)OC1C2 OEPCINZNIXWOPJ-UHFFFAOYSA-N 0.000 description 1
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 1
- GWENLLRIMBJBRA-IHWYPQMZSA-N (z)-4-amino-3-methyl-4-oxobut-2-enoic acid Chemical compound NC(=O)C(/C)=C\C(O)=O GWENLLRIMBJBRA-IHWYPQMZSA-N 0.000 description 1
- BSSNZUFKXJJCBG-UPHRSURJSA-N (z)-but-2-enediamide Chemical compound NC(=O)\C=C/C(N)=O BSSNZUFKXJJCBG-UPHRSURJSA-N 0.000 description 1
- VLLPVDKADBYKLM-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate;triphenylsulfanium Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 VLLPVDKADBYKLM-UHFFFAOYSA-M 0.000 description 1
- HWZAQSLOKICOMP-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate;tris(4-tert-butylphenyl)sulfanium Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F.C1=CC(C(C)(C)C)=CC=C1[S+](C=1C=CC(=CC=1)C(C)(C)C)C1=CC=C(C(C)(C)C)C=C1 HWZAQSLOKICOMP-UHFFFAOYSA-M 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical class CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- AJGQZZMDEXEZKB-UHFFFAOYSA-M 1,1-difluoro-2-(4-tetracyclo[6.2.1.13,6.02,7]dodecanyl)ethanesulfonate tris(4-tert-butylphenyl)sulfanium Chemical compound C12C3C(CC(C2C2CCC1C2)C3)CC(S(=O)(=O)[O-])(F)F.C(C)(C)(C)C3=CC=C(C=C3)[S+](C3=CC=C(C=C3)C(C)(C)C)C3=CC=C(C=C3)C(C)(C)C AJGQZZMDEXEZKB-UHFFFAOYSA-M 0.000 description 1
- BXGYVRIBHDBIJQ-UHFFFAOYSA-M 1-(4-butoxynaphthalen-1-yl)thiolan-1-ium;(7,7-dimethyl-3-oxo-4-bicyclo[2.2.1]heptanyl)methanesulfonate Chemical compound C1CC2(CS([O-])(=O)=O)C(=O)CC1C2(C)C.C12=CC=CC=C2C(OCCCC)=CC=C1[S+]1CCCC1 BXGYVRIBHDBIJQ-UHFFFAOYSA-M 0.000 description 1
- WNDABSCBNOUSTE-UHFFFAOYSA-M 1-(4-butoxynaphthalen-1-yl)thiolan-1-ium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F.C12=CC=CC=C2C(OCCCC)=CC=C1[S+]1CCCC1 WNDABSCBNOUSTE-UHFFFAOYSA-M 0.000 description 1
- JQIQJUCEFIYYOJ-UHFFFAOYSA-M 1-(4-butoxynaphthalen-1-yl)thiolan-1-ium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C12=CC=CC=C2C(OCCCC)=CC=C1[S+]1CCCC1 JQIQJUCEFIYYOJ-UHFFFAOYSA-M 0.000 description 1
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 1
- LCFXRSKBJWQHON-UHFFFAOYSA-N 1-benzyl-2-phenylbenzimidazole Chemical compound C=1C=CC=CC=1C1=NC2=CC=CC=C2N1CC1=CC=CC=C1 LCFXRSKBJWQHON-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- 125000004066 1-hydroxyethyl group Chemical group [H]OC([H])([*])C([H])([H])[H] 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- ZWNMRZQYWRLGMM-UHFFFAOYSA-N 2,5-dimethylhexane-2,5-diol Chemical compound CC(C)(O)CCC(C)(C)O ZWNMRZQYWRLGMM-UHFFFAOYSA-N 0.000 description 1
- GNZYDSUXCMLOMM-UHFFFAOYSA-N 2,6-dimethyl-4-(thiolan-1-ium-1-yl)phenol;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound CC1=C(O)C(C)=CC([S+]2CCCC2)=C1.[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F GNZYDSUXCMLOMM-UHFFFAOYSA-N 0.000 description 1
- VAOHUAFTTHSCRT-UHFFFAOYSA-N 2,6-dimethyl-4-(thiolan-1-ium-1-yl)phenol;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CC1=C(O)C(C)=CC([S+]2CCCC2)=C1 VAOHUAFTTHSCRT-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- VRUJBNLUYHMBBN-UHFFFAOYSA-M 2-(3-bicyclo[2.2.1]heptanyl)-1,1,2,2-tetrafluoroethanesulfonate;(4-tert-butylphenyl)-diphenylsulfanium Chemical compound C1CC2C(C(F)(F)C(F)(F)S(=O)(=O)[O-])CC1C2.C1=CC(C(C)(C)C)=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 VRUJBNLUYHMBBN-UHFFFAOYSA-M 0.000 description 1
- NIKOMHHZILSBRS-UHFFFAOYSA-M 2-(3-bicyclo[2.2.1]heptanyl)-1,1,2,2-tetrafluoroethanesulfonate;bis(4-tert-butylphenyl)iodanium Chemical compound C1CC2C(C(F)(F)C(F)(F)S(=O)(=O)[O-])CC1C2.C1=CC(C(C)(C)C)=CC=C1[I+]C1=CC=C(C(C)(C)C)C=C1 NIKOMHHZILSBRS-UHFFFAOYSA-M 0.000 description 1
- FUARBSGJOAXCCL-UHFFFAOYSA-M 2-(3-bicyclo[2.2.1]heptanyl)-1,1,2,2-tetrafluoroethanesulfonate;diphenyliodanium Chemical compound C=1C=CC=CC=1[I+]C1=CC=CC=C1.C1CC2C(C(F)(F)C(F)(F)S(=O)(=O)[O-])CC1C2 FUARBSGJOAXCCL-UHFFFAOYSA-M 0.000 description 1
- SPBNQWDOUKTPIC-UHFFFAOYSA-M 2-(3-bicyclo[2.2.1]heptanyl)-1,1,2,2-tetrafluoroethanesulfonate;triphenylsulfanium Chemical compound C1CC2C(C(F)(F)C(F)(F)S(=O)(=O)[O-])CC1C2.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 SPBNQWDOUKTPIC-UHFFFAOYSA-M 0.000 description 1
- BHJJROUQCIMVFG-UHFFFAOYSA-M 2-(3-bicyclo[2.2.1]heptanyl)-1,1,2,2-tetrafluoroethanesulfonate;tris(4-tert-butylphenyl)sulfanium Chemical compound C1CC2C(C(F)(F)C(F)(F)S(=O)(=O)[O-])CC1C2.C1=CC(C(C)(C)C)=CC=C1[S+](C=1C=CC(=CC=1)C(C)(C)C)C1=CC=C(C(C)(C)C)C=C1 BHJJROUQCIMVFG-UHFFFAOYSA-M 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 1
- UTENGZNBNPABQE-UHFFFAOYSA-N 2-[3-(carboxymethyl)-1-adamantyl]acetic acid Chemical compound C1C(C2)CC3CC1(CC(=O)O)CC2(CC(O)=O)C3 UTENGZNBNPABQE-UHFFFAOYSA-N 0.000 description 1
- OJPDDQSCZGTACX-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)anilino]ethanol Chemical compound OCCN(CCO)C1=CC=CC=C1 OJPDDQSCZGTACX-UHFFFAOYSA-N 0.000 description 1
- ZVUNTIMPQCQCAQ-UHFFFAOYSA-N 2-dodecanoyloxyethyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCCOC(=O)CCCCCCCCCCC ZVUNTIMPQCQCAQ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- NRGGMCIBEHEAIL-UHFFFAOYSA-N 2-ethylpyridine Chemical compound CCC1=CC=CC=N1 NRGGMCIBEHEAIL-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- SFAMKDPMPDEXGH-UHFFFAOYSA-N 2-hydroxyethyl propanoate Chemical compound CCC(=O)OCCO SFAMKDPMPDEXGH-UHFFFAOYSA-N 0.000 description 1
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 1
- JGBOVFKUKBGAJQ-UHFFFAOYSA-N 2-methylidenebutanediamide Chemical compound NC(=O)CC(=C)C(N)=O JGBOVFKUKBGAJQ-UHFFFAOYSA-N 0.000 description 1
- WFCSWCVEJLETKA-UHFFFAOYSA-N 2-piperazin-1-ylethanol Chemical compound OCCN1CCNCC1 WFCSWCVEJLETKA-UHFFFAOYSA-N 0.000 description 1
- GBMGBQZYDVQBCQ-UHFFFAOYSA-N 3-(2-phenylbenzimidazol-1-yl)propan-1-ol Chemical compound N=1C2=CC=CC=C2N(CCCO)C=1C1=CC=CC=C1 GBMGBQZYDVQBCQ-UHFFFAOYSA-N 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- GPIUUMROPXDNRH-UHFFFAOYSA-N 3647-74-3 Chemical compound C1C2C3C(=O)NC(=O)C3C1C=C2 GPIUUMROPXDNRH-UHFFFAOYSA-N 0.000 description 1
- ISRILTSNFOSMRA-UHFFFAOYSA-O 4-(2,2-difluoroethyl)tetracyclo[6.2.1.13,6.02,7]dodecane 2,6-dimethyl-4-(thiolan-1-ium-1-yl)phenol Chemical compound C12C3C(CC(C2C2CCC1C2)C3)CC(F)F.CC=3C=C(C=C(C3O)C)[S+]3CCCC3 ISRILTSNFOSMRA-UHFFFAOYSA-O 0.000 description 1
- VJXRKZJMGVSXPX-UHFFFAOYSA-N 4-ethylpyridine Chemical compound CCC1=CC=NC=C1 VJXRKZJMGVSXPX-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 101100434207 Arabidopsis thaliana ACT8 gene Proteins 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 230000005653 Brownian motion process Effects 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- TWJCCJIDMMQRBC-UHFFFAOYSA-N C(=O)=C1C2(CC3CC(CC1C3)C2)NC Chemical compound C(=O)=C1C2(CC3CC(CC1C3)C2)NC TWJCCJIDMMQRBC-UHFFFAOYSA-N 0.000 description 1
- SBKFKXOWSGKTAE-UHFFFAOYSA-L C([O-])([O-])=O.C(C)(C)(C)C1=CC=C(C=C1)[S+](C1=CC=C(C=C1)C(C)(C)C)C1=CC=C(C=C1)C(C)(C)C.C(C)(C)(C)C1=CC=C(C=C1)[S+](C1=CC=C(C=C1)C(C)(C)C)C1=CC=C(C=C1)C(C)(C)C Chemical compound C([O-])([O-])=O.C(C)(C)(C)C1=CC=C(C=C1)[S+](C1=CC=C(C=C1)C(C)(C)C)C1=CC=C(C=C1)C(C)(C)C.C(C)(C)(C)C1=CC=C(C=C1)[S+](C1=CC=C(C=C1)C(C)(C)C)C1=CC=C(C=C1)C(C)(C)C SBKFKXOWSGKTAE-UHFFFAOYSA-L 0.000 description 1
- JFSVPXZKPLRNDS-UHFFFAOYSA-N C12(C(=O)CC(CC1)C2(C)C)CS(=O)(=O)OC2=C(C=CC=C2)CCCCCC Chemical compound C12(C(=O)CC(CC1)C2(C)C)CS(=O)(=O)OC2=C(C=CC=C2)CCCCCC JFSVPXZKPLRNDS-UHFFFAOYSA-N 0.000 description 1
- ZYGHCOCJAGHCLT-UHFFFAOYSA-N C12(C(=O)CC(CC1)C2(C)C)CS(=O)(=O)OS(=O)(=O)O Chemical compound C12(C(=O)CC(CC1)C2(C)C)CS(=O)(=O)OS(=O)(=O)O ZYGHCOCJAGHCLT-UHFFFAOYSA-N 0.000 description 1
- MPWDUPVIMTXFTO-UHFFFAOYSA-M C12=CC=CC=C2C(OCCCC)=CC=C1[S+]1CCCC1.C12C(C3)CCC3C2C2CC(CC(F)(F)S(=O)(=O)[O-])C1C2 Chemical compound C12=CC=CC=C2C(OCCCC)=CC=C1[S+]1CCCC1.C12C(C3)CCC3C2C2CC(CC(F)(F)S(=O)(=O)[O-])C1C2 MPWDUPVIMTXFTO-UHFFFAOYSA-M 0.000 description 1
- GMMMYGMYYKUVOG-UHFFFAOYSA-M C12C(C3)CCC3C2C2CC(CC(F)(F)S(=O)(=O)[O-])C1C2.C1=CC(C(C)(C)C)=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 Chemical compound C12C(C3)CCC3C2C2CC(CC(F)(F)S(=O)(=O)[O-])C1C2.C1=CC(C(C)(C)C)=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 GMMMYGMYYKUVOG-UHFFFAOYSA-M 0.000 description 1
- GOLGCYSYKQTBST-UHFFFAOYSA-M C12C3C(CC(C2C2CCC1C2)C3)CC(S(=O)(=O)[O-])(F)F.C3(CCCCC3)C3=CC=C(C=C3)[S+](C3=CC=CC=C3)C3=CC=CC=C3 Chemical compound C12C3C(CC(C2C2CCC1C2)C3)CC(S(=O)(=O)[O-])(F)F.C3(CCCCC3)C3=CC=C(C=C3)[S+](C3=CC=CC=C3)C3=CC=CC=C3 GOLGCYSYKQTBST-UHFFFAOYSA-M 0.000 description 1
- KLCAYRSCMGIQGL-UHFFFAOYSA-M C=1C=CC=CC=1[I+]C1=CC=CC=C1.C12C(C3)CCC3C2C2CC(CC(F)(F)S(=O)(=O)[O-])C1C2 Chemical compound C=1C=CC=CC=1[I+]C1=CC=CC=C1.C12C(C3)CCC3C2C2CC(CC(F)(F)S(=O)(=O)[O-])C1C2 KLCAYRSCMGIQGL-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XTJFFFGAUHQWII-UHFFFAOYSA-N Dibutyl adipate Chemical compound CCCCOC(=O)CCCCC(=O)OCCCC XTJFFFGAUHQWII-UHFFFAOYSA-N 0.000 description 1
- VIZORQUEIQEFRT-UHFFFAOYSA-N Diethyl adipate Chemical compound CCOC(=O)CCCCC(=O)OCC VIZORQUEIQEFRT-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical class COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 1
- XXRCUYVCPSWGCC-UHFFFAOYSA-N Ethyl pyruvate Chemical compound CCOC(=O)C(C)=O XXRCUYVCPSWGCC-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- FLRQOWAOMJMSTP-JJTRIOAGSA-N [(2s)-2-[(2r)-3,4-dihydroxy-5-oxo-2h-furan-2-yl]-2-hydroxyethyl] (6z,9z,12z)-octadeca-6,9,12-trienoate Chemical compound CCCCC\C=C/C\C=C/C\C=C/CCCCC(=O)OC[C@H](O)[C@H]1OC(=O)C(O)=C1O FLRQOWAOMJMSTP-JJTRIOAGSA-N 0.000 description 1
- DFPAKSUCGFBDDF-ZQBYOMGUSA-N [14c]-nicotinamide Chemical compound N[14C](=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-ZQBYOMGUSA-N 0.000 description 1
- NVJPBZCLWGTJKD-UHFFFAOYSA-N [bis(4-tert-butylphenyl)-lambda3-iodanyl] trifluoromethanesulfonate Chemical compound CC(C)(C)c1ccc(cc1)[I](OS(=O)(=O)C(F)(F)F)c1ccc(cc1)C(C)(C)C NVJPBZCLWGTJKD-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- RVIZJROSQMQZCG-UHFFFAOYSA-N adamantane-1,2-diol Chemical compound C1C(C2)CC3CC1C(O)C2(O)C3 RVIZJROSQMQZCG-UHFFFAOYSA-N 0.000 description 1
- MOLCWHCSXCKHAP-UHFFFAOYSA-N adamantane-1,3-diol Chemical compound C1C(C2)CC3CC1(O)CC2(O)C3 MOLCWHCSXCKHAP-UHFFFAOYSA-N 0.000 description 1
- AUKWRHADVIQZRJ-UHFFFAOYSA-N adamantane-1,4-diol Chemical compound C1C(C2)CC3C(O)C1CC2(O)C3 AUKWRHADVIQZRJ-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- RGWHHWWMFUXNAX-UHFFFAOYSA-N bis(1-adamantyl)methanone Chemical class C1C(C2)CC(C3)CC2CC13C(=O)C1(C2)CC(C3)CC2CC3C1 RGWHHWWMFUXNAX-UHFFFAOYSA-N 0.000 description 1
- UESKLPHTGBBMEL-UHFFFAOYSA-M bis(4-tert-butylphenyl)iodanium 1,1-difluoro-2-(4-tetracyclo[6.2.1.13,6.02,7]dodecanyl)ethanesulfonate Chemical compound C12C(C3)CCC3C2C2CC(CC(F)(F)S(=O)(=O)[O-])C1C2.C1=CC(C(C)(C)C)=CC=C1[I+]C1=CC=C(C(C)(C)C)C=C1 UESKLPHTGBBMEL-UHFFFAOYSA-M 0.000 description 1
- DJBAOXYQCAKLPH-UHFFFAOYSA-M bis(4-tert-butylphenyl)iodanium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F.C1=CC(C(C)(C)C)=CC=C1[I+]C1=CC=C(C(C)(C)C)C=C1 DJBAOXYQCAKLPH-UHFFFAOYSA-M 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005537 brownian motion Methods 0.000 description 1
- 150000001716 carbazoles Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- KXGVEGMKQFWNSR-LLQZFEROSA-N deoxycholic acid Chemical class C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)[C@@H](O)C1 KXGVEGMKQFWNSR-LLQZFEROSA-N 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- QVQGTNFYPJQJNM-UHFFFAOYSA-N dicyclohexylmethanamine Chemical compound C1CCCCC1C(N)C1CCCCC1 QVQGTNFYPJQJNM-UHFFFAOYSA-N 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- JCCAVOLDXDEODY-UHFFFAOYSA-N dimethyldiazene Chemical group CN=NC JCCAVOLDXDEODY-UHFFFAOYSA-N 0.000 description 1
- ORPDKMPYOLFUBA-UHFFFAOYSA-M diphenyliodanium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound C=1C=CC=CC=1[I+]C1=CC=CC=C1.[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ORPDKMPYOLFUBA-UHFFFAOYSA-M 0.000 description 1
- SBQIJPBUMNWUKN-UHFFFAOYSA-M diphenyliodanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C=1C=CC=CC=1[I+]C1=CC=CC=C1 SBQIJPBUMNWUKN-UHFFFAOYSA-M 0.000 description 1
- QSVAYRBPFFOQMK-UHFFFAOYSA-N ditert-butyl hexanedioate Chemical compound CC(C)(C)OC(=O)CCCCC(=O)OC(C)(C)C QSVAYRBPFFOQMK-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000012156 elution solvent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- IJUHLFUALMUWOM-UHFFFAOYSA-N ethyl 3-methoxypropanoate Chemical compound CCOC(=O)CCOC IJUHLFUALMUWOM-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 229940117360 ethyl pyruvate Drugs 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- HSDFKDZBJMDHFF-UHFFFAOYSA-N methyl 3-ethoxypropanoate Chemical compound CCOCCC(=O)OC HSDFKDZBJMDHFF-UHFFFAOYSA-N 0.000 description 1
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- CWKLZLBVOJRSOM-UHFFFAOYSA-N methyl pyruvate Chemical compound COC(=O)C(C)=O CWKLZLBVOJRSOM-UHFFFAOYSA-N 0.000 description 1
- HEPOEAALKWFVLE-UHFFFAOYSA-N n -((perfluorooctanesulfonyl)oxy)-5-norbornene-2,3-dicarboximide Chemical compound C1=CC2CC1C1C2C(=O)N(OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C1=O HEPOEAALKWFVLE-UHFFFAOYSA-N 0.000 description 1
- YCMDNBGUNDHOOD-UHFFFAOYSA-N n -((trifluoromethylsulfonyl)oxy)-5-norbornene-2,3-dicarboximide Chemical compound C1=CC2CC1C1C2C(=O)N(OS(=O)(=O)C(F)(F)F)C1=O YCMDNBGUNDHOOD-UHFFFAOYSA-N 0.000 description 1
- FRQONEWDWWHIPM-UHFFFAOYSA-N n,n-dicyclohexylcyclohexanamine Chemical compound C1CCCCC1N(C1CCCCC1)C1CCCCC1 FRQONEWDWWHIPM-UHFFFAOYSA-N 0.000 description 1
- COFKFSSWMQHKMD-UHFFFAOYSA-N n,n-didecyldecan-1-amine Chemical compound CCCCCCCCCCN(CCCCCCCCCC)CCCCCCCCCC COFKFSSWMQHKMD-UHFFFAOYSA-N 0.000 description 1
- CLZGJKHEVKJLLS-UHFFFAOYSA-N n,n-diheptylheptan-1-amine Chemical compound CCCCCCCN(CCCCCCC)CCCCCCC CLZGJKHEVKJLLS-UHFFFAOYSA-N 0.000 description 1
- DIAIBWNEUYXDNL-UHFFFAOYSA-N n,n-dihexylhexan-1-amine Chemical compound CCCCCCN(CCCCCC)CCCCCC DIAIBWNEUYXDNL-UHFFFAOYSA-N 0.000 description 1
- OOHAUGDGCWURIT-UHFFFAOYSA-N n,n-dipentylpentan-1-amine Chemical compound CCCCCN(CCCCC)CCCCC OOHAUGDGCWURIT-UHFFFAOYSA-N 0.000 description 1
- 229960002715 nicotine Drugs 0.000 description 1
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Natural products CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 229960003512 nicotinic acid Drugs 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000004043 oxo group Chemical group O=* 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 150000004885 piperazines Chemical class 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- PMZDQRJGMBOQBF-UHFFFAOYSA-N quinolin-4-ol Chemical compound C1=CC=C2C(O)=CC=NC2=C1 PMZDQRJGMBOQBF-UHFFFAOYSA-N 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 229930187593 rose bengal Natural products 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000001370 static light scattering Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 238000005307 time correlation function Methods 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- HHMQUQRJNPTPAJ-UHFFFAOYSA-M trifluoromethanesulfonate;tris(4-tert-butylphenyl)sulfanium Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC(C(C)(C)C)=CC=C1[S+](C=1C=CC(=CC=1)C(C)(C)C)C1=CC=C(C(C)(C)C)C=C1 HHMQUQRJNPTPAJ-UHFFFAOYSA-M 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 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 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Materials For Photolithography (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
Description
本発明は、感放射線性樹脂の評価方法およびこの評価方法を用いた感放射線性樹脂組成物、特にＫｒＦエキシマレーザーあるいはＡｒＦエキシマレーザー等の遠紫外線、シンクロトロン放射線等のＸ線、電子線等の荷電粒子線の如き各種の放射線を使用する微細加工に有用な化学増幅型レジストとして好適に使用できる感放射線性樹脂組成物に関する。 The present invention relates to a method for evaluating a radiation sensitive resin and a radiation sensitive resin composition using this evaluation method, in particular, far ultraviolet rays such as KrF excimer laser or ArF excimer laser, X-rays such as synchrotron radiation, electron beams, etc. The present invention relates to a radiation sensitive resin composition that can be suitably used as a chemically amplified resist useful for microfabrication using various types of radiation such as charged particle beams.
集積回路素子の製造に代表される微細加工の分野においては、より高い集積度を得るために、最近ではＡｒＦエキシマレーザー（波長１９３ｎｍ）、Ｆ2エキシマレーザー（波長１５７ｎｍ）等を用いた１００ｎｍ以下のレベルでの微細加工が可能なリソグラフィー技術が必要とされている。このようなエキシマレーザーによる照射に適した感放射線性樹脂組成物として、酸解離性官能基を有する成分と放射線の照射により酸を発生する成分である酸発生剤とによる化学増幅効果を利用した化学増幅型感放射線性樹脂組成物が数多く提案されている。
例えば、感放射線性樹脂組成物として、２−アルキル−２−アダマンチル基、または１−アダマンチル−１−アルキルアダマンチル基で保護されたアルカリ可溶性を有し、それ自身ではアルカリに不溶または難溶であるが、酸の作用でアルカリに可溶となる樹脂と特定のスルホニウム塩系酸発生剤を含有する化学増幅型ポジ型レジスト組成物（特許文献１参照）。特定の基板密着性脂環式エステルと特定の脂環式骨格を有する酸脱離性のエステルに、第３成分として上記２成分の中間の極性を持つ特定の脂環式エステルを加えて３元共重合させたフォトレジスト用高分子化合物（特許文献２参照）、同じく脂環式骨格を有する特定構造の３種の単量体ユニットを特定の割合で含む樹脂（特許文献３参照）等が知られている。
また、これらの感放射線性樹脂組成物に用いられる樹脂は、感放射線性樹脂組成物としたときの解像度や透過率により、あるいは樹脂と溶媒との溶解度パラメーターにより、それぞれ評価されてきた。
In the field of microfabrication represented by the manufacture of integrated circuit elements, in order to obtain a higher degree of integration, recently, an ArF excimer laser (wavelength 193 nm), an F 2 excimer laser (wavelength 157 nm) or the like is used. There is a need for a lithography technique that enables fine processing at a level. As a radiation-sensitive resin composition suitable for irradiation with such an excimer laser, a chemical utilizing the chemical amplification effect by the component having an acid-dissociable functional group and the acid generator which is a component generating an acid by irradiation with radiation. Many amplification type radiation sensitive resin compositions have been proposed.
For example, the radiation-sensitive resin composition has alkali solubility protected with a 2-alkyl-2-adamantyl group or 1-adamantyl-1-alkyladamantyl group, and is itself insoluble or hardly soluble in alkali. However, a chemically amplified positive resist composition containing a resin that is soluble in alkali by the action of an acid and a specific sulfonium salt-based acid generator (see Patent Document 1). Three-component by adding a specific alicyclic ester having an intermediate polarity between the above two components as a third component to an acid-eliminating ester having a specific substrate adhesion alicyclic ester and a specific alicyclic skeleton. Known are polymer compounds for photoresist (see Patent Document 2), resins containing three types of monomer units having a specific structure having an alicyclic skeleton in a specific ratio (see Patent Document 3), and the like. It has been.
Moreover, the resin used for these radiation sensitive resin compositions has been evaluated by the resolution and transmittance when the radiation sensitive resin composition is used, or by the solubility parameter of the resin and the solvent, respectively.
しかしながら、半導体分野において、より高い集積度が求められるようになると、レジストである感放射線性樹脂組成物はより優れた解像度が必要とされるようになってきた。次世代の半導体素子等は現世代以上に微細なパターンを必要とするため、今まで以上にウエハー内でのパターン寸法の均一性、および、パターン解像欠損の発生し易さの改善が求められるようになってきた。これらの課題を克服するためには、感放射線性樹脂組成物としての解像性能等の向上もさることながら、樹脂としての解像性や溶解性能の均一性を従来以上に厳格に判断する必要が出てきたが、従来の解像性や溶解性能の均一性に対する評価方法では十分でないという問題がある。
解決しようとする課題は、感放射線性樹脂の微小な解像性や溶解性の僅かな相違点を評価する評価方法がないことである。
また、評価方法がないため、従来のレジスト性能を維持したまま、現像欠陥を発生することがなく、またＬＥＲ特性に優れた感放射線性樹脂組成物が得られないことである。
The problem to be solved is that there is no evaluation method for evaluating slight differences in minute resolution and solubility of the radiation-sensitive resin.
Further, since there is no evaluation method, development defects are not generated while maintaining conventional resist performance, and a radiation-sensitive resin composition having excellent LER characteristics cannot be obtained.
本発明の評価方法は、感放射線性樹脂のレジスト溶剤溶液の動的光散乱を測定し、該溶液の濃度変化に伴う感放射線性樹脂の溶液中の拡散係数変化を表す係数（ｋD）により感放射線性樹脂の現像特性を評価することを特徴とする。ここで、現像特性とは現像欠陥およびラインエッジラフネス（ＬＥＲ）をいう。
上記係数（ｋD）は溶液の濃度変化に伴う拡散係数変化を表す。また、溶液の濃度変化時の濃度とはレジストがウエハー上にスピン塗布されるときの濃度変化を想定することができるので、係数（ｋD）は塗布後の膜中に生成する樹脂成分の拡散係数から求められる流体力学半径の平均値を間接的に表す指標となる。
この係数（ｋD）は、その値が正の値であった場合、高濃度でも樹脂同士の接触・絡まりが見られず結果として塗布後に樹脂成分の凝集を形成し難いが、負の値であった場合、高濃度で樹脂同士の接触・絡まりが見られ、この係数（ｋD）の微小な変化で生成する樹脂成分の凝集体（クラスター）分布の大小に大きく影響することが分かった。このため、係数（ｋD）は非常に重要な値であると考えられる。特に、未露光部の現像液に対する溶解性が乏しいＡｒＦ用途のポリアクリル酸エステルベースの樹脂を用いる場合、その樹脂成分の凝集体の流体力学半径の分布ばらつきが現像液に対する溶解性のばらつきに反映され、現像欠陥やＬＥＲのロット間差へと結びつく可能性があることが見出された。このため、係数（ｋD）を測定することにより、レジストをその原料段階で評価・選別できることが分かった。本発明はこのような知見に基づくものである。
The evaluation method of the present invention measures dynamic light scattering of a resist solvent solution of a radiation sensitive resin, and uses a coefficient (k D ) representing a change in diffusion coefficient of the radiation sensitive resin in the solution accompanying a change in concentration of the solution. It is characterized by evaluating the development characteristics of a radiation sensitive resin. Here, the development characteristics refer to development defects and line edge roughness (LER).
The coefficient (k D ) represents a change in diffusion coefficient accompanying a change in solution concentration. Further, since the concentration at the time of changing the concentration of the solution can be assumed to be a concentration change when the resist is spin-coated on the wafer, the coefficient (k D ) is a diffusion of the resin component generated in the coated film. This is an index that indirectly represents the average value of the hydrodynamic radius obtained from the coefficient.
If this coefficient (k D ) is a positive value, contact and entanglement between the resins are not seen even at high concentrations, and as a result, it is difficult to form agglomeration of resin components after coating, but a negative value In such a case, the contact / entanglement between the resins was observed at a high concentration, and it was found that the size of the aggregate (cluster) distribution of the resin component produced by a minute change in this coefficient (k D ) was greatly affected. For this reason, the coefficient (k D ) is considered to be a very important value. In particular, when using a polyacrylate ester-based resin for ArF, which has poor solubility in the developer in the unexposed area, the dispersion in the hydrodynamic radius of the aggregate of the resin component is reflected in the dispersion in the solubility in the developer. It has been found that this may lead to development defects and LER lot-to-lot differences. For this reason, it was found that the resist can be evaluated and selected at the raw material stage by measuring the coefficient (k D ). The present invention is based on such knowledge.
本発明の感放射線性樹脂組成物は、アルカリ不溶性またはアルカリ難溶性であって酸の作用によりアルカリ易溶性となる酸解離性基含有樹脂（Ａ）を単独または２種以上と、レジスト溶剤（Ｂ）と、感放射線性酸発生剤（Ｃ）とを含有し、上記酸解離性基含有樹脂（Ａ）の少なくとも１種は、該樹脂（Ａ）のレジスト溶剤（Ｂ）溶液の動的光散乱測定により、該溶液の濃度変化に伴う感放射線性樹脂の溶液中の拡散係数変化を表す係数（ｋD）が−２．２０ｇ／ｇ以上であることを特徴とする。すなわち、酸解離性基含有樹脂（Ａ）を複数含有する場合には、それらのうち少なくとも１つの樹脂（Ａ）のｋD値が−２．２０ｇ／ｇ以上であることを特徴とする。 The radiation-sensitive resin composition of the present invention comprises an acid-dissociable group-containing resin (A) which is alkali-insoluble or hardly soluble in alkali and easily soluble in alkali by the action of an acid, or a resist solvent (B ) And a radiation sensitive acid generator (C), and at least one of the acid dissociable group-containing resins (A) is a dynamic light scattering of a resist solvent (B) solution of the resin (A). According to the measurement, a coefficient (k D ) representing a change in diffusion coefficient of the radiation-sensitive resin in the solution accompanying a change in the concentration of the solution is −2.20 g / g or more. That is, when a plurality of acid dissociable group-containing resins (A) are contained, at least one of the resins (A) has a k D value of −2.20 g / g or more.
本発明の評価方法は、樹脂溶液の動的光散乱を測定し、その濃度変化に伴う感放射線性樹脂の溶液中の拡散係数変化を表す係数（ｋD）により感放射線性樹脂の現像欠陥を評価するので、第一に、現像欠陥の発生を抑えることができ、第二に、樹脂が形成するクラスターのサイズ分布に起因するＬＥＲを改善できる感放射線性樹脂の評価・選別が容易になる。
また、酸解離性基含有樹脂（Ａ）と、レジスト溶剤（Ｂ）と、感放射線性酸発生剤（Ｃ）とを含有し、上記酸解離性基含有樹脂（Ａ）は、該樹脂（Ａ）のレジスト溶剤（Ｂ）溶液の動的光散乱測定により、該溶液の濃度変化に伴う感放射線性樹脂の溶液中の拡散係数変化を表す係数（ｋD）が−２．２０ｇ／ｇ以上であり、酸解離性基含有樹脂（Ａ）を複数含有する場合には、それらのうち少なくとも１つの樹脂（Ａ）のｋD値が−２．２０ｇ／ｇ以上であるので、活性放射線、特に、ＡｒＦエキシマレーザー（波長１９３ｎｍ）に代表される遠紫外線に感応する化学増幅型レジストとして、放射線に対する透明性が高く、感度、解像度、ドライエッチング耐性、パターン形状も良好であるレジストとしての基本的性能を有しているだけでなく、第一に、現像欠陥の発生を抑えることができ、第二に、樹脂の粒経分布に起因するＬＥＲを改善することができ、今後さらに微細化が進むと予想される半導体デバイスの製造に極めて好適に使用することができる。
The evaluation method of the present invention measures the dynamic light scattering of a resin solution, and develops development defects of the radiation-sensitive resin by a coefficient (k D ) representing a change in diffusion coefficient in the solution of the radiation-sensitive resin accompanying the concentration change. Since evaluation is performed, firstly, the occurrence of development defects can be suppressed, and secondly, evaluation and selection of a radiation-sensitive resin that can improve LER caused by the size distribution of clusters formed by the resin is facilitated.
Further, it contains an acid-dissociable group-containing resin (A), a resist solvent (B), and a radiation-sensitive acid generator (C), and the acid-dissociable group-containing resin (A) is a resin (A). ) Of the resist solvent (B) solution, the coefficient (k D ) representing the diffusion coefficient change in the solution of the radiation sensitive resin accompanying the change in the concentration of the solution is −2.20 g / g or more. Yes, when a plurality of acid-dissociable group-containing resins (A) are contained, the k D value of at least one of the resins (A) is −2.20 g / g or more, so actinic radiation, in particular, As a chemically amplified resist sensitive to far-ultraviolet rays typified by an ArF excimer laser (wavelength 193 nm), it has basic performance as a resist with high transparency to radiation, sensitivity, resolution, dry etching resistance, and good pattern shape. I just have it First, it is possible to suppress development defects, and second, it is possible to improve the LER caused by the particle size distribution of the resin, and for the production of semiconductor devices that are expected to be further miniaturized in the future. It can be used very suitably.
樹脂溶液の動的光散乱を測定するための動的光散乱測定装置は、ドイツＡＬＶ社製光散乱装置を用いた。この装置の仕様は、ゴニオメータとしてＡＬＶ／ＤＬＳ／ＳＬＳ−５０２２Ｆ(Ａｔｔｅｎｕａｔｏｒ付き）、レーザー光源として波長６３２．８ｎｍ、２２ｍＷ Ｈｅ−Ｎｅレーザー、散乱光検出部としてデュアル式アバランシェフォトダイオ−ド（ＡＬＶ−Ｈｉｇｈ ＱＥ ＡＰＤ×２）＋ビームスプリッター、相関計としてＡＬＶ−５０００／ＥＰＰ＋Ｆａｓｔモード測定用ＡＬＶ−６０１０／１６０である。また、制御・解析プログラムはＡＬＶ−５０００Ｅ／ＷＩＮ（ｖｅｒ．３）を使用した。
なお、レーザー光源としては、Ａｒレーザー（波長４８８ｎｍ）、固体半導体レーザー（ＹＡＧ２倍波、５３２ｎｍ）等を、散乱光検出部には、例えば光電子倍増管（フォトマルチプライヤー）、フォトダイオ−ド等を使用できる。
As a dynamic light scattering measuring apparatus for measuring the dynamic light scattering of the resin solution, a light scattering apparatus manufactured by ALV Germany was used. The specifications of this apparatus are as follows: ALV / DLS / SLS-5022F (with Attenuator) as a goniometer, wavelength 632.8 nm, 22 mW He-Ne laser as a laser light source, and dual avalanche photodiode (ALV-High) as a scattered light detector. QE APD × 2) + beam splitter, ALV-5000 / EPP + Fast mode measurement ALV-6010 / 160 as a correlator. The control / analysis program used was ALV-5000E / WIN (ver. 3).
As a laser light source, an Ar laser (wavelength 488 nm), a solid-state semiconductor laser (YAG double wave, 532 nm), etc. are used, and for example, a photomultiplier tube (photomultiplier), a photodiode, etc. are used as the scattered light detector. Can be used.
動的光散乱の測定原理について以下に説明する。
溶液中に溶解している物質はブラウン運動による濃度揺らぎを生じる。動的光散乱法では、溶液に干渉性の高いレーザー光などを当てて、濃度揺らぎに起因する散乱光強度の時間変化を制御コンピューターメモリー上に記憶させ、散乱光強度の時間相関関数を計算した指数型減衰曲線から、各濃度おける拡散係数を測定することができる。
一方、線状高分子一本鎖の挙動を調べるためには、希薄とされる有限濃度域の測定値の濃度ゼロ外挿から得られる無限希釈状態での拡散係数Ｄ0を用いる必要がある。
また、下の（イ)式で定義されるアインシュタイン−ストークスの関係より得られる無限希釈状態における流体力学半径ＲHは線状高分子一本鎖あたりの広がりを表すパラメーターとして使用される。
（イ)：Ｄ0＝ｋBＴ／６πηＲH
ここで、Ｄ0は無限希釈状態での拡散係数、ｋBはボルツマン定数、Ｔは絶対温度、ηは溶媒粘度、ＲHは無限希釈状態での流体力学半径をそれぞれ表す。
The measurement principle of dynamic light scattering will be described below.
Substances dissolved in the solution cause concentration fluctuations due to Brownian motion. In the dynamic light scattering method, a laser beam with high coherence is applied to the solution, and the temporal change of the scattered light intensity caused by concentration fluctuation is stored in the control computer memory, and the time correlation function of the scattered light intensity is calculated. From the exponential decay curve, the diffusion coefficient at each concentration can be measured.
On the other hand, in order to examine the behavior of the linear polymer single chain, it is necessary to use the diffusion coefficient D 0 in the infinite dilution state obtained from the concentration zero extrapolation of the measured value in the finite concentration region that is diluted.
In addition, the hydrodynamic radius R H in the infinite dilution state obtained from the Einstein-Stokes relationship defined by the following equation (A) is used as a parameter representing the spread per linear polymer chain.
(A): D 0 = k B T / 6πηR H
Here, D 0 is the diffusion coefficient in the infinite dilution state, k B is the Boltzmann constant, T is the absolute temperature, η is the solvent viscosity, and R H is the hydrodynamic radius in the infinite dilution state.
有限濃度での拡散係数Ｄは、溶媒中に存在する高分子間の引力、斥力の相互作用を含んでいるため、上記Ｄ0とは異なる値をとる場合が多く、正式には「見かけ上の拡散係数」と呼ばれる。同様に、有限濃度における流体力学半径Ｒも正式には「見かけ上の流体力学半径」とされる。また、高分子に分子量分布がある場合には、解析法としてＣＯＮＴＩＮ法（逆ラプラス変換法）を用いることにより、ｚ平均のＤの分布を求めることができる。
なお、感放射線性樹脂組成物中の樹脂成分の分子量程度では、一般的に測定されるすべての散乱角度、例えば１２〜１５５度の散乱角度、において質点として観測される。このため、内部運動・回転運動などに起因する拡散係数の散乱角度、すなわちｑ＝４ｎπ／λ×ｓｉｎ（θ／２）［ｎは溶媒の屈折率、λはレーザービームの波長、θは散乱角度］で定義される散乱ベクトルｑ依存性は認められず、樹脂成分の並進拡散運動が測定される。従って、各散乱角度における拡散係数の平均値を、その濃度における「見かけ上の拡散係数」の実測値とできる。
Since the diffusion coefficient D at a finite concentration includes the interaction of attractive force and repulsive force between polymers present in the solvent, it often takes a value different from the above D 0 . It is called "diffusion coefficient". Similarly, the hydrodynamic radius R at a finite concentration is formally designated as an “apparent hydrodynamic radius”. When the polymer has a molecular weight distribution, the z-average D distribution can be obtained by using the CONTIN method (inverse Laplace transform method) as an analysis method.
In addition, the molecular weight of the resin component in the radiation-sensitive resin composition is observed as a mass point at all generally measured scattering angles, for example, a scattering angle of 12 to 155 degrees. Therefore, the scattering angle of the diffusion coefficient due to internal motion / rotational motion, ie, q = 4nπ / λ × sin (θ / 2) [n is the refractive index of the solvent, λ is the wavelength of the laser beam, and θ is the scattering angle. ], The translational diffusion motion of the resin component is measured. Therefore, the average value of the diffusion coefficient at each scattering angle can be an actual measurement value of the “apparent diffusion coefficient” at the concentration.
拡散係数Ｄ0は上述したように、動的光散乱法を用いて測定される有限濃度域の見かけ上の拡散係数Ｄ値を濃度ゼロに外挿することで得られる。拡散係数Ｄ値と濃度ｃとの関係を図１に示す。図１は見かけ上の拡散係数Ｄを縦軸に、濃度ｃ（重量％）を横軸にして、希薄な順に、濃度ｃ1、ｃ2、ｃ3に対する見かけ上の拡散係数Ｄ1、Ｄ2、Ｄ3、をプロットした図である。測定すべき濃度ｃ（重量％）の範囲は、Ｄとｃとの間に直線関係が成立する範囲が好ましい。Ｄとｃとの間に成立する直線をｃ→０に外挿することで一義的にそのプロット図の切片の値が拡散係数Ｄ0になる。本発明において、測定すべき濃度ｃ（重量％）の範囲は、約１０重量％以下の濃度域が好ましい。約１０重量％以下の濃度で直線関係が成立する。なお、樹脂成分と溶媒成分との組み合わせによっては明確な直線とならない場合があるが、その場合には直線性が良好な低濃度側でのデータを用いて直線とすることができる。
理論的な扱いでは通常濃度ｃの単位はｇ／ｍｌを用いるのが一般的ではあるが、本発明では感放射線性樹脂組成物の調製が重量測定で行なわれているので重量％を使用した。従って、後述するｋDの単位はｇ／ｇとなる。
As described above, the diffusion coefficient D 0 can be obtained by extrapolating the apparent diffusion coefficient D value in the finite concentration range measured using the dynamic light scattering method to zero concentration. The relationship between the diffusion coefficient D value and the concentration c is shown in FIG. FIG. 1 shows the apparent diffusion coefficients D 1 and D 2 for the concentrations c 1 , c 2 , and c 3 in the order of dilution, with the apparent diffusion coefficient D on the vertical axis and the concentration c (wt%) on the horizontal axis. , D 3 are plotted. The range of concentration c (% by weight) to be measured is preferably a range in which a linear relationship is established between D and c. By extrapolating a straight line formed between D and c to c → 0, the value of the intercept in the plot is uniquely the diffusion coefficient D 0 . In the present invention, the range of concentration c (wt%) to be measured is preferably a concentration range of about 10 wt% or less. A linear relationship is established at a concentration of about 10% by weight or less. In addition, although it may not become a clear straight line depending on the combination of a resin component and a solvent component, in that case, it can be made a straight line using data on the low concentration side with good linearity.
Theoretically, the unit of the concentration c is generally g / ml, but in the present invention, the radiation sensitive resin composition is prepared by weight measurement, so the weight% is used. Therefore, the unit of k D described later is g / g.
上記直線関係式は、下記（ロ）式で表される。
（ロ)：Ｄ＝Ｄ0（１＋ｋDｃ）
本発明においては、（ロ）式における拡散係数の濃度勾配ｋDを用いて感放射線性樹脂の現像欠陥を評価する。
動的光散乱法を用いて測定される濃度勾配ｋDは、静的光散乱法により測定される第２ビリアル係数Ａ2と密接な関係にあるとされている。第２ビリアル係数Ａ2は高分子鎖と溶媒の相互作用を表すパラメーターとして高分子溶液物性において一般的に用いられている。具体的にはＡ2＝０を非摂動状態であるθ状態として、溶媒和によりポリマーの広がりが理論よりも大きくなり排除体積効果が現れるＡ2＞０を良溶媒系、逆にポリマーセグメント間に引力が働き広がりが小さくなるとされているＡ2＜０を貧溶媒系として定義している。Ａ2の符号が負で値が小さいほどポリマーと溶媒の相性は悪くなり、場合によっては析出、沈殿してしまう。
The linear relational expression is represented by the following (b) expression.
(B): D = D 0 (1 + k D c)
In the present invention, the development defect of the radiation sensitive resin is evaluated using the concentration gradient k D of the diffusion coefficient in the equation (b).
The concentration gradient k D measured using the dynamic light scattering method is said to be closely related to the second virial coefficient A 2 measured by the static light scattering method. The second virial coefficient A 2 is generally used in polymer solution properties as a parameter representing the interaction between the polymer chain and the solvent. Specifically, assuming that A 2 = 0 is a non-perturbed θ state, the solvation causes the polymer spread to be larger than the theoretical value, and an excluded volume effect appears. A 2 > 0 is a good solvent system, and conversely between polymer segments A 2 <0, which is considered to be that the attractive force acts and the spread becomes small, is defined as a poor solvent system. The smaller the sign of A 2 and the smaller the value, the worse the compatibility between the polymer and the solvent, and in some cases, precipitation and precipitation occur.
濃度勾配ｋD値は、対象物質の分子量にも依存するが、一般的にはＡ2＞０である良溶媒系と言われている樹脂成分／溶媒の組み合わせにおいて正の値をとる。樹脂成分の溶解状態が良好であるものほどｋDの値は大きくなる傾向にある。一方、ｋD値の値が負の値をとる場合には、濃度上昇とともに拡散係数は小さくなる。ｋD値が小さいほど（負の勾配が急であるほど）溶媒が貧である、即ち、ポリマーのセグメント間には引力が働き、分子内では収縮方向（粒経が小さくなる方向）に、分子間では引力が働くことにより凝集しやすい傾向にある。
以上のことから、濃度勾配ｋDは樹脂溶液の濃度変化に伴う感放射線性樹脂の溶液中の拡散係数変化を表す係数（ｋD）といえる。また、このｋD値が感放射線性樹脂の微小な溶解性の僅かな相違点を表しているので、この値により感放射線性樹脂の現像欠陥およびＬＥＲを評価できる。
The concentration gradient k D value depends on the molecular weight of the target substance, but generally takes a positive value in a resin component / solvent combination that is said to be a good solvent system with A 2 > 0. The better the dissolved state of the resin component, the larger the value of k D tends to be. On the other hand, when the k D value takes a negative value, the diffusion coefficient decreases as the concentration increases. The smaller the k D value (the steeper negative slope), the poorer the solvent, that is, the attractive force acts between the polymer segments, and the molecules in the shrinking direction (the direction in which the particle size decreases) In between, there is a tendency to aggregate due to the attraction.
From the above, it can be said that the concentration gradient k D is a coefficient (k D ) representing a change in diffusion coefficient in the solution of the radiation-sensitive resin accompanying a change in the concentration of the resin solution. Further, since this k D value represents a slight difference in the minute solubility of the radiation sensitive resin, the development defect and LER of the radiation sensitive resin can be evaluated by this value.
本発明方法は、ネガ型感放射線性樹脂、ポジ型感放射線性樹脂のいずれの感放射線性樹脂であっても、その現像特性を評価できる。
特に樹脂と溶媒との組み合わせにおいて、ｋD値が負の値をとる樹脂と溶媒との組み合わせに適用することが好ましい。
また、ｋD値は評価の対象となる感放射線性樹脂および溶媒の組み合わせによって異なるが、ポリアクリル酸エステルベースの樹脂とそのレジスト溶媒の場合、−２．２０ｇ／ｇ以上、好ましくは−２．１０ｇ／ｇ以上である。
The method of the present invention can evaluate the development characteristics of any radiation sensitive resin of negative type radiation sensitive resin and positive type radiation sensitive resin.
In particular, the combination of a resin and a solvent is preferably applied to a combination of a resin and a solvent having a negative k D value.
The k D value varies depending on the combination of the radiation-sensitive resin and the solvent to be evaluated, but in the case of a polyacrylate ester-based resin and its resist solvent, it is −2.20 g / g or more, preferably −2. It is 10 g / g or more.
以下、本発明に係る感放射線性樹脂組成物について説明する。
アルカリ不溶性またはアルカリ難溶性であって酸の作用によりアルカリ易溶性となる酸解離性基含有樹脂（Ａ）は、下記式（１−１）で表される繰り返し単位（１−１）と式（１−２）で表される繰り返し単位（１−２）とを含有することが好ましい。
The acid-dissociable group-containing resin (A) that is insoluble in alkali or hardly soluble in alkali and easily soluble in alkali by the action of an acid has a repeating unit (1-1) represented by the following formula (1-1) and a formula ( It is preferable to contain the repeating unit (1-2) represented by 1-2).
ここで、以下で用いる多環型の脂環式骨格の名称に関して命名根拠を下式（命名）に示す。
上記式（１−２）中のＲ2としては、例えばビシクロ［２．２．１］ヘプタン、トリシクロ［５．２．１．０2,6］デカン、テトラシクロ［６．２．１．１3,6．０2,7］ドデカン、アダマンタン、シクロペンタン、シクロヘキサン等のシクロアルカン類等に由来する脂環族環からなる基；これら脂環族環からなる基を例えば、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、２−メチルプロピル基、１−メチルプロピル基、ｔ−ブチル基等の炭素数１〜４の直鎖状、分岐状または環状のアルキル基の１種以上あるいは１個以上で置換した基等が挙げられる。 The R 2 in the above formula (1-2), for example, bicyclo [2.2.1] heptane, tricyclo [5.2.1.0 2,6] decane, tetracyclo [6.2.1.1 3 , 6 . 0 2,7 ] a group consisting of an alicyclic ring derived from cycloalkanes such as dodecane, adamantane, cyclopentane, cyclohexane, etc .; a group consisting of these alicyclic rings is, for example, methyl group, ethyl group, n-propyl A linear, branched or cyclic alkyl group having 1 to 4 carbon atoms such as a group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, etc. The above or a group substituted with one or more may be mentioned.
また、Ｒ2の１価または２価の脂環式炭化水素基の誘導体としては、例えば、ヒドロキシル基；カルボキシル基；オキソ基（即ち、＝Ｏ基）；ヒドロキシメチル基、１−ヒドロキシエチル基、２−ヒドロキシエチル基、１−ヒドロキシプロピル基、２−ヒドロキシプロピル基、３−ヒドロキシプロピル基、２−ヒドロキシブチル基、３−ヒドロキシブチル基、４−ヒドロキシブチル基等の炭素数１〜４のヒドロキシアルキル基；メトキシ基、エトキシ基、ｎ−プロポキシ基、ｉ−プロポキシ基、ｎ−ブトキシ基、２−メチルプロポキシ基、１−メチルプロポキシ基、ｔ−ブトキシ基等の炭素数１〜４のアルコキシル基；シアノ基；シアノメチル基、２−シアノメチル基、３−シアノプロピル基、４−シアノブチル基等の炭素数２〜５のシアノアルキル基等の置換基を１種以上あるいは１個以上有する基が挙げられる。
これらの置換基のうち、ヒドロキシル基、カルボキシル基、ヒドロキシメチル基、シアノ基、シアノメチル基等が好ましい。
Examples of the derivative of R 2 monovalent or divalent alicyclic hydrocarbon group include, for example, hydroxyl group; carboxyl group; oxo group (ie, ═O group); hydroxymethyl group, 1-hydroxyethyl group, C1-C4 hydroxy such as 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, etc. Alkyl group; alkoxy group having 1 to 4 carbon atoms such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group Cyano group; C 2-5 cyano such as cyanomethyl group, 2-cyanomethyl group, 3-cyanopropyl group, 4-cyanobutyl group, etc. A group having a substituent such as alkyl group one or more or one or more.
Of these substituents, a hydroxyl group, a carboxyl group, a hydroxymethyl group, a cyano group, a cyanomethyl group, and the like are preferable.
また、Ｒ2の炭素数１〜４の直鎖状もしくは分岐状のアルキル基としては、例えば、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、２−メチルプロピル基、１−メチルプロピル基、ｔ−ブチル基等が挙げられる。
これらのアルキル基のうち、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基が好ましい。
式（１−２）中の−Ｃ（Ｒ2）3を形成する官能基側鎖として好ましいものを挙げると、１−メチル−１−シクロペンチル基、１−エチル−１−シクロペンチル基、１−メチル−１−シクロヘキシル基、１−エチル−１−シクロヘキシル基、２−メチルアダマンタン−２−イル基、２−メチル−３−ヒドロキシアダマンタン−２−イル基、２−エチルチルアダマンタン−２−イル基、２−エチル−３−ヒドロキシアダマンタン−２−イル基、２−ｎ−プロピルアダマンタン−２−イル基、２−ｎ−プロピル−３−ヒドロキシアダマンタン−２−イル基、２−イソプロピルアダマンタン−２−イル基、２−イソプロピル−３−ヒドロキシアダマンタン−２−イル基、２−メチルビシクロ［２．２．１］ヘプト−２−イル基、２−エチルビシクロ［２．２．１］ヘプト−２−イル基、８−メチルトリシクロ［５．２．１．０2,6］デカ−８−イル基、８−エチルトリシクロ［５．２．１．０2,6］デカ−８−イル基、４−メチル−テトラシクロ［６．２．１．１3,6．０2,7］ドデカ−４−イル基、４−エチル−テトラシクロ［６．２．１．１3,6．０2,7］ドデカ−４−イル基、１−（ビシクロ［２．２．１］ヘプト−２−イル）−１−メチルエチル基、１−（トリシクロ［５．２．１．０2,6］デカ−８−イル）−１−メチルエチル基、１−（テトラシクロ［６．２．１．１3,6．０2,7］デカ−４−イル）−１−メチルエチル基、１−（アダマンタン−１−イル）−１−メチルエチル基、１−（３−ヒドロキシアダマンタン−１−イル）−１−メチルエチル基、１，１−ジシクロヘキシルエチル基、１，１−ジ（ビシクロ［２．２．１］ヘプト−２−イル）エチル基、１，１−ジ（トリシクロ［５．２．１．０2,6］デカ−８−イル）エチル基、１，１−ジ（テトラシクロ［６．２．１．１3,6．０2,7］ドデカ−４−イル）エチル基、１，１−ジ（アダマンタン−１−イル）エチル基等が挙げられる。
Examples of the linear or branched alkyl group having 1 to 4 carbon atoms of R 2 include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and 2-methylpropyl. Group, 1-methylpropyl group, t-butyl group and the like.
Of these alkyl groups, a methyl group, an ethyl group, an n-propyl group, and an i-propyl group are preferable.
Preferred examples of the functional group side chain forming -C (R 2 ) 3 in formula (1-2) include 1-methyl-1-cyclopentyl group, 1-ethyl-1-cyclopentyl group, 1-methyl -1-cyclohexyl group, 1-ethyl-1-cyclohexyl group, 2-methyladamantan-2-yl group, 2-methyl-3-hydroxyadamantan-2-yl group, 2-ethyltyladamantan-2-yl group, 2-ethyl-3-hydroxyadamantan-2-yl group, 2-n-propyladamantan-2-yl group, 2-n-propyl-3-hydroxyadamantan-2-yl group, 2-isopropyladamantan-2-yl group Group, 2-isopropyl-3-hydroxyadamantan-2-yl group, 2-methylbicyclo [2.2.1] hept-2-yl group, 2-ethylbicyclo 2.2.1] hept-2-yl group, 8-methyltricyclo [5.2.1.0 2, 6] dec-8-yl group, 8-ethyl-tricyclo [5.2.1.0 2,6 ] dec-8-yl group, 4-methyl-tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-yl group, 4-ethyl-tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodec-4-yl group, 1- (bicyclo [2.2.1] hept-2-yl) -1-methylethyl group, 1- (tricyclo [5.2.1.0 2, 6 ] dec-8-yl) -1-methylethyl group, 1- (tetracyclo [6.2.1.1 3,6 .0 2,7 ] dec-4-yl) -1-methylethyl group, 1 -(Adamantan-1-yl) -1-methylethyl group, 1- (3-hydroxyadamantan-1-yl) -1-methylethyl group, 1,1-dicyclohexylethyl group, 1,1-di (bicyclo [ 2.2.1] Hept-2-yl) ethyl group, 1,1-di (tricyclo [5.2.1.0 2,6 ] dec-8-yl) ethyl group, 1,1-di (tetracyclo) [6.2.1.1 3,6 .0 2,7] dodeca-4-yl) ethyl group, 1,1-di (adamantan-1-yl) ethyl group, And the like.
式（２−１）中のＸ1およびＸ2のうちアルキル基としては、メチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基等が挙げられる。フッ素化アルキル基としては、モノフルオロメチル基、ジフルオロメチル基、トリフルオロメチル基等が挙げられる。
式（２−２）におけるＲ3、式（２−３）におけるＲ4、式（２−４）におけるＲ5において、炭素数１〜４の直鎖状もしくは分岐状アルキル基としては、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、ｔ−ブチル基等が挙げられる。また、炭素数１〜４の直鎖状もしくは分岐状アルコキシル基としては、メトキシ基、エトキシ基、ｎ−プロポキシ基、ｉ−プロポキシ基、ｎ−ブトキシ基、ｔ−ブトキシ基等が挙げられる。
Of X 1 and X 2 in formula (2-1), examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group. Examples of the fluorinated alkyl group include a monofluoromethyl group, a difluoromethyl group, and a trifluoromethyl group.
In R 3 in Formula (2-2), R 4 in Formula (2-3), and R 5 in Formula (2-4), the linear or branched alkyl group having 1 to 4 carbon atoms is a methyl group. , Ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group and the like. Examples of the linear or branched alkoxyl group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, and a t-butoxy group.
繰り返し単位（１−１）を与える単量体の中で好ましいものとしては、（メタ）アクリル酸（１，１，１−トリフルオロ−２−トリフルオロメチル−２−ヒドロキシ−３−プロピル）エステル、（メタ）アクリル酸（１，１，１−トリフルオロ−２−トリフルオロメチル−２−ヒドロキシ−４−ブチル）エステル、（メタ）アクリル酸（１，１，１−トリフルオロ−２−トリフルオロメチル−２−ヒドロキシ−５−ペンチル）エステル、（メタ）アクリル酸（１，１，１−トリフルオロ−２−トリフルオロメチル−２−ヒドロキシ−４−ペンチル）エステル、（メタ）アクリル酸２−｛[５−（1'，1'，1'−トリフルオロ−２'−トリフルオロメチル−２'−ヒドロキシ）プロピル]ビシクロ［２．２．１］ヘプチル｝エステル、（メタ）アクリル酸３−｛[８−（1'，1'，1'−トリフルオロ−２'−トリフルオロメチル−２'−ヒドロキシ）プロピル] テトラシクロ［６．２．１．１3,6．０2,7］ドデシル｝エステル、（メタ）アクリル酸−５−オキソー４−オキサートリシクロ［４．２．１．０3,7］ノナー２−イルエステル、（メタ）アクリル酸−７−オキソー６−オキサービシクロ［３．２．１］オクター４−イルエステル、（メタ）アクリル酸−２−オキソテトラヒドロピラン−４−イルエステル、（メタ）アクリル酸−４−メチルー２−オキソテトラヒドロピラン−４−イルエステル、（メタ）アクリル酸−５−オキソテトラヒドロフラン−３−イルエステル、（メタ）アクリル酸−２−オキソテトラヒドロフランー３−イルエステル、（メタ）アクリル酸−５−オキソテトラヒドロフラン−２−イルメチルエステル、（メタ）アクリル酸−３，３−ジメチル−５−オキソテトラヒドロフラン−２−イルメチルエステル等が挙げられる。 Among the monomers that give the repeating unit (1-1), (meth) acrylic acid (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-3-propyl) ester is preferable. , (Meth) acrylic acid (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-4-butyl) ester, (meth) acrylic acid (1,1,1-trifluoro-2-tri Fluoromethyl-2-hydroxy-5-pentyl) ester, (meth) acrylic acid (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-4-pentyl) ester, (meth) acrylic acid 2 -{[5- (1 ', 1', 1'-trifluoro-2'-trifluoromethyl-2'-hydroxy) propyl] bicyclo [2.2.1] heptyl} ester, (meth) acrylic acid 3-{[8- (1 ′, 1 ′, 1′-trifluoro-2′-trifluoromethyl-2′-hydroxy) propyl] tetracyclo [6.2.1.1 3,6 . 0 2,7 ] dodecyl} ester, (meth) acrylic acid-5-oxo-4-oxatricyclo [4.2.1.0 3,7 ] noner 2-yl ester, (meth) acrylic acid-7- Oxo-6-oxabicyclo [3.2.1] oct-4-yl ester, (meth) acrylic acid-2-oxotetrahydropyran-4-yl ester, (meth) acrylic acid-4-methyl-2-oxotetrahydropyran -4-yl ester, (meth) acrylic acid-5-oxotetrahydrofuran-3-yl ester, (meth) acrylic acid-2-oxotetrahydrofuran-3-yl ester, (meth) acrylic acid-5-oxotetrahydrofuran-2 -Ylmethyl ester, (meth) acrylic acid-3,3-dimethyl-5-oxotetrahydrofuran-2-ylmethyl ester Etc.
繰り返し単位（１−２）を与える単量体の中で好ましいものとしては、（メタ）アクリル酸２−メチルアダマンチル−２−イルエステル、（メタ）アクリル酸２−メチル−３−ヒドロキシアダマンタン−２−イルエステル、（メタ）アクリル酸２−エチルアダマンタン−２−イルエステル、（メタ）アクリル酸２−エチル−３−ヒドロキシアダマンタン−２−イルエステル、（メタ）アクリル酸２−ｎ−プロピルアダマンタン−２−イルエステル、（メタ）アクリル酸２−イソプロピルアダマンタン−２−イルエステル、（メタ）アクリル酸−２−メチルビシクロ［２．２．１］ヘプト−２−イルエステル、（メタ）アクリル酸−２−エチルビシクロ［２．２．１］ヘプト−２−イルエステル、（メタ）アクリル酸−８−メチルトリシクロ［５．２．１．０2,6］デカン−８−イルエステル、（メタ）アクリル酸−８−エチルトリシクロ［５．２．１．０2,6］デカン−８−イルエステル、（メタ）アクリル酸−４−メチルテトラシクロ［６．２．１3,6．０2,7］ドデカン−４−イルエステル、（メタ）アクリル酸−４−エチルテトラシクロ［６．２．１3,6．０2,7］ドデカン−４−イルエステル、（メタ）アクリル酸１−（ビシクロ［２．２．１］ヘプト−２−イル）−１−メチルエチルエステル、（メタ）アクリル酸１−（トリシクロ［５．２．１．０２，６］デカン−８−イル）−１−メチルエチルエステル、（メタ）アクリル酸１−（テトラシクロ［６．２．１3,6．０2,7］ドデカン−４−イル）−１−メチルエチルエステル、（メタ）アクリル酸１−（アダマンタン−１−イル）−１−メチルエチルエステル、（メタ）アクリル酸１−（３−ヒドロキシアダマンタン−１−イル）−１−メチルエチルエステル、（メタ）アクリル酸１，１−ジシクロヘキシルエチルエステイル、（メタ）アクリル酸１，１−ジ（ビシクロ［２．２．１］ヘプト−２−イル）エチルエステル、（メタ）アクリル酸１，１−ジ（トリシクロ［５．２．１．０2,6］デカン−８−イル）エチルエステル、（メタ）アクリル酸１，１−ジ（テトラシクロ［６．２．１3,6．０2,7］ドデカン−４−イル）エチルエステル、（メタ）アクリル酸１，１−ジ（アダマンタン−１−イル）エチルエステル、（メタ）アクリル酸１−メチル−１−シクロペンチルエステル、（メタ）アクリル酸１−エチル−１−シクロペンチルエステル、（メタ）アクリル酸１−メチル−１−シクロヘキシルエステル、（メタ）アクリル酸１−エチル−１−シクロヘキシルエステル等が挙げられる。 Among the monomers that give the repeating unit (1-2), (meth) acrylic acid 2-methyladamantyl-2-yl ester, (meth) acrylic acid 2-methyl-3-hydroxyadamantane-2 are preferable. -Yl ester, (meth) acrylic acid 2-ethyladamantan-2-yl ester, (meth) acrylic acid 2-ethyl-3-hydroxyadamantan-2-yl ester, (meth) acrylic acid 2-n-propyladamantane- 2-yl ester, (meth) acrylic acid 2-isopropyladamantan-2-yl ester, (meth) acrylic acid-2-methylbicyclo [2.2.1] hept-2-yl ester, (meth) acrylic acid- 2-Ethylbicyclo [2.2.1] hept-2-yl ester, (meth) acrylic acid-8-methyltricyclo [ .2.1.0 2,6] decan-8-yl ester, (meth) ethyl-8-acrylic acid tricyclo [5.2.1.0 2,6] decan-8-yl ester, (meth) 4-methyltetracycloacrylic acid [6.2.1 3,6 . 0 2,7 ] dodecan-4-yl ester, (meth) acrylic acid-4-ethyltetracyclo [6.2.1 3,6 . 0 2,7 ] dodecan-4-yl ester, (meth) acrylic acid 1- (bicyclo [2.2.1] hept-2-yl) -1-methylethyl ester, (meth) acrylic acid 1- (tricyclo [5.2.1.02,6] decan-8-yl) -1-methylethyl ester, (meth) acrylic acid 1- (tetracyclo [6.2.1 3,6 .0 2,7 ] dodecane- 4-yl) -1-methylethyl ester, (meth) acrylic acid 1- (adamantan-1-yl) -1-methylethyl ester, (meth) acrylic acid 1- (3-hydroxyadamantan-1-yl)- 1-methylethyl ester, (meth) acrylic acid 1,1-dicyclohexylethyl ester, (meth) acrylic acid 1,1-di (bicyclo [2.2.1] hept-2-yl) ethyl ester, (meth Acry 1,1-di (tricyclo [5.2.1.0 2,6] decan-8-yl) ethyl ester, (meth) acrylic acid 1,1-di (tetracyclo [6.2.1 3,6 .0 2,7] dodecane-4-yl) ethyl ester, (meth) acrylic acid 1,1-di (adamantan-1-yl) ethyl ester, (meth) acrylic acid 1-methyl-1-cyclopentyl ester, ( Examples include (meth) acrylic acid 1-ethyl-1-cyclopentyl ester, (meth) acrylic acid 1-methyl-1-cyclohexyl ester, (meth) acrylic acid 1-ethyl-1-cyclohexyl ester, and the like.
繰り返し単位（１−２）を与える単量体の中で、特に好適な単量体としては、（メタ）アクリル酸２−メチルアダマンタン−２−イルエステル、（メタ）アクリル酸２−エチルアダマンタン−２−イルエステル、（メタ）アクリル酸−２−メチルビシクロ［２．２．１］ヘプト−２−イルエステル、（メタ）アクリル酸−２−エチルビシクロ［２．２．１］ヘプト−２−イルエステル、（メタ）アクリル酸１−（ビシクロ［２．２．１］ヘプト−２−イル）−１−メチルエチルエステル、（メタ）アクリル酸１−（アダマンタン−１−イル）−１−メチルエチルエステル、（メタ）アクリル酸１−メチル−１−シクロペンチルエステル、（メタ）アクリル酸１−エチル−１−シクロペンチルエステル、（メタ）アクリル酸１−メチル−１−シクロヘキシルエステル、（メタ）アクリル酸１−エチル−１−シクロヘキシルエステル等が挙げられる。 Among the monomers giving the repeating unit (1-2), particularly preferred monomers are (meth) acrylic acid 2-methyladamantan-2-yl ester, (meth) acrylic acid 2-ethyladamantane- 2-yl ester, (meth) acrylic acid-2-methylbicyclo [2.2.1] hept-2-yl ester, (meth) acrylic acid-2-ethylbicyclo [2.2.1] hept-2-yl Yl ester, (meth) acrylic acid 1- (bicyclo [2.2.1] hept-2-yl) -1-methylethyl ester, (meth) acrylic acid 1- (adamantan-1-yl) -1-methyl Ethyl ester, (meth) acrylic acid 1-methyl-1-cyclopentyl ester, (meth) acrylic acid 1-ethyl-1-cyclopentyl ester, (meth) acrylic acid 1-methyl-1-silane B hexyl ester, and (meth) acrylic acid 1-ethyl-1-cyclohexyl ester.
樹脂（Ａ）は、上記繰り返し単位（１−１）、（１−２）以外にさらに他の繰り返し単位を含むことができる。他の繰り返し単位を与える単量体としては、例えば（メタ）アクリル酸３−ヒドロキシアダマンタン−１−イルエステル、（メタ）アクリル酸３、５−ジヒドロキシアダマンタン−１−イルエステル、（メタ）アクリル酸３−シアノアダマンタン−１−イルエステル、（メタ）アクリル酸３−カルボキシルアダマンタン−１−イルエステル、（メタ）アクリル酸３、５−ジカルボキシルアダマンタン−１−イルエステル、（メタ）アクリル酸３−カルボキシル−５−ヒドロキシアダマンタン−１−イルエステル、（メタ）アクリル酸３−メトキシカルボニル−５−ヒドロキシアダマンタン−１−イルエステル、（メタ）アクリル酸、（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、クロトンアミド、マレインアミド、フマルアミド、メサコンアミド、シトラコンアミド、イタコンアミド等の不飽和アミド化合物；メチレングリコールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、２，５−ジメチル−２，５−ヘキサンジオールジ（メタ）アクリレート、１，２−アダマンタンジオールジ（メタ）アクリレート、１，３−アダマンタンジオールジ（メタ）アクリレート、１，４−アダマンタンジオールジ（メタ）アクリレート、トリシクロデカニルジメチロールジ（メタ）アクリレート等の多官能性単量体等が挙げられる。 Resin (A) can contain another repeating unit in addition to the repeating units (1-1) and (1-2). Examples of monomers that give other repeating units include (meth) acrylic acid 3-hydroxyadamantan-1-yl ester, (meth) acrylic acid 3, 5-dihydroxyadamantan-1-yl ester, and (meth) acrylic acid. 3-cyanoadamantan-1-yl ester, (meth) acrylic acid 3-carboxyladamantan-1-yl ester, (meth) acrylic acid 3, 5-dicarboxyladamantan-1-yl ester, (meth) acrylic acid 3- Carboxyl-5-hydroxyadamantan-1-yl ester, (meth) acrylic acid 3-methoxycarbonyl-5-hydroxyadamantan-1-yl ester, (meth) acrylic acid, (meth) acrylamide, N, N-dimethyl (meth) ) Acrylamide, crotonamide, maleamide, fu Unsaturated amide compounds such as luamide, mesaconamide, citraconic amide, itaconic amide; methylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, 2,5-dimethyl-2,5-hexanediol di (meth) acrylate, 1,2-adamantanediol di (meth) acrylate, 1,3-adamantanediol di (meth) acrylate, 1,4-adamantanediol di (meth) acrylate, tricyclodecanyl dimethylol di (meth) acrylate, etc. A functional monomer etc. are mentioned.
樹脂（Ａ）は、上記繰り返し単位（１−１）、繰り返し単位（１−２）で構成することが好ましい。、繰り返し単位（１−１）および繰り返し単位（１−２）の配合割合は、全繰り返し単位に対して、繰り返し単位（１−１）が２０〜７０モル％、好ましくは３０〜６０モル％；繰り返し単位（１−２）が１０〜６０モル％、好ましくは１０〜５０モル％である。
繰り返し単位（１−１）の含有率が、２０モル％未満では、レジストとしての現像性および解像性が低下する傾向にあり、その含有率が７０モル％をこえるとレジスト溶媒への溶解性が低下する傾向にある。繰り返し単位（１−２）の含有率が、１０モル％未満では、レジストとしての解像性が劣化する傾向にあり、含有率が６０モル％をこえるとレジストとしての現像性が低下する傾向にある。また、その他の繰り返し単位を含有でき、含有量は通常５０モル％以下、好ましくは３０モル％以下である。
The resin (A) is preferably composed of the repeating unit (1-1) and the repeating unit (1-2). The blending ratio of the repeating unit (1-1) and the repeating unit (1-2) is 20 to 70 mol%, preferably 30 to 60 mol% of the repeating unit (1-1) with respect to all repeating units; The repeating unit (1-2) is 10 to 60 mol%, preferably 10 to 50 mol%.
When the content of the repeating unit (1-1) is less than 20 mol%, the developability and resolution as a resist tend to be lowered. When the content exceeds 70 mol%, the solubility in a resist solvent is increased. Tend to decrease. When the content of the repeating unit (1-2) is less than 10 mol%, the resolution as a resist tends to deteriorate, and when the content exceeds 60 mol%, the developability as a resist tends to decrease. is there. Moreover, another repeating unit can be contained and content is 50 mol% or less normally, Preferably it is 30 mol% or less.
樹脂（Ａ）は、例えば、各繰り返し単位に対応する単量体の混合物を、ヒドロパーオキシド類、ジアルキルパーオキシド類、ジアシルパーオキシド類、アゾ化合物等のラジカル重合開始剤を使用し、必要に応じて連鎖移動剤の存在下、適当な溶媒中で重合することにより製造することができる。
上記重合に使用される溶媒としては、例えば、シクロヘキサン、シクロヘプタン、シクロオクタン、デカリン、ノルボルナン等のシクロアルカン類；酢酸エチル、酢酸ｎ−ブチル、酢酸ｉ−ブチル、プロピオン酸メチル、プロピレングリコールモノメチルエーテルアセテート等の飽和カルボン酸エステル類；γ−ブチロラクトン等のアルキルラクトン類；テトラヒドロフラン、ジメトキシエタン類、ジエトキシエタン類等のエーテル類；２−ブタノン、２−ヘプタノン、メチルイソブチルケトン等のアルキルケトン類；シクロヘキサノン等のシクロアルキルケトン類；２−プロパノール、プロピレングリコールモノメチルエーテル等のアルコール類等を挙げることができる。
これらの溶媒は、単独でまたは２種以上を混合して使用することができる。また、重合における反応温度は、通常、４０〜１２０℃、好ましくは５０〜１００℃であり、反応時間は、通常、１〜４８時間、好ましくは１〜２４時間である。
Resin (A) is, for example, a mixture of monomers corresponding to each repeating unit, using a radical polymerization initiator such as hydroperoxides, dialkyl peroxides, diacyl peroxides, azo compounds, etc. Accordingly, it can be produced by polymerization in an appropriate solvent in the presence of a chain transfer agent.
Examples of the solvent used for the polymerization include cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; ethyl acetate, n-butyl acetate, i-butyl acetate, methyl propionate, propylene glycol monomethyl ether. Saturated carboxylic acid esters such as acetate; alkyl lactones such as γ-butyrolactone; ethers such as tetrahydrofuran, dimethoxyethanes and diethoxyethanes; alkyl ketones such as 2-butanone, 2-heptanone and methyl isobutyl ketone; Examples thereof include cycloalkyl ketones such as cyclohexanone; alcohols such as 2-propanol and propylene glycol monomethyl ether.
These solvents can be used alone or in admixture of two or more. Moreover, the reaction temperature in superposition | polymerization is 40-120 degreeC normally, Preferably it is 50-100 degreeC, and reaction time is 1-48 hours normally, Preferably it is 1-24 hours.
本発明における樹脂（Ａ）は、ハロゲン、金属等の不純物が少ないのは当然のことながら、残留単量体やオリゴマー成分が既定値以下、例えばＨＰＬＣで０．１重量％等、であることが好ましく、それにより、レジストとしての感度、解像度、プロセス安定性、パターン形状等をさらに改善することができるだけでなく、液中異物や感度等の経時変化がないレジストを提供できる。
樹脂（Ａ）の精製法としては、例えば、以下の方法が挙げられる。金属等の不純物を除去する方法としては、ゼータ電位フィルターを用いて樹脂溶液中の金属を吸着させる方法や蓚酸やスルホン酸等の酸性水溶液で樹脂溶液を洗浄することで金属をキレート状態にして除去する方法等が挙げられる。また、残留単量体やオリゴマー成分を規定値以下に除去する方法としては、水洗や適切な溶媒を組み合わせることにより残留単量体やオリゴマー成分を除去する液々抽出法、特定の分子量以下のもののみを抽出除去する限外濾過等の溶液状態での精製方法や、樹脂溶液を貧溶媒へ滴下することで樹脂を貧溶媒中に凝固させることにより残留単量体等を除去する再沈澱法や濾別した樹脂スラリー貧溶媒で洗浄する等の固体状態での精製方法が有る。また、これらの方法を組み合わせることもできる。
上記再沈澱法に用いられる貧溶媒としては、精製する樹脂の物性等に左右され一概には例示することはできない。適宜、貧溶媒は選定されるものである。
The resin (A) in the present invention is naturally low in impurities such as halogen and metal, and the residual monomer and oligomer components are not more than predetermined values, for example, 0.1% by weight by HPLC. Preferably, this not only can further improve the sensitivity, resolution, process stability, pattern shape, and the like as a resist, but also can provide a resist that does not change with time such as foreign matter in liquid or sensitivity.
Examples of the purification method of the resin (A) include the following methods. As a method of removing impurities such as metals, the metal is chelated and removed by adsorbing the metal in the resin solution using a zeta potential filter or by washing the resin solution with an acidic aqueous solution such as oxalic acid or sulfonic acid. And the like. In addition, as a method of removing residual monomer and oligomer components below the specified value, a liquid-liquid extraction method that removes residual monomers and oligomer components by combining water washing and an appropriate solvent, those having a specific molecular weight or less A purification method in a solution state such as ultrafiltration that only extracts and removes, and a reprecipitation method that removes residual monomers by coagulating the resin in the poor solvent by dropping the resin solution into the poor solvent, There is a purification method in a solid state such as washing with a resin slurry poor solvent separated by filtration. Moreover, these methods can also be combined.
The poor solvent used in the reprecipitation method depends on the physical properties of the resin to be purified and cannot be generally exemplified. As appropriate, the poor solvent is selected.
樹脂（Ａ）のゲルパーミエーションクロマトグラフィー（ＧＰＣ）によるポリスチレン換算重量平均分子量（以下、「Ｍｗ」という。）は、通常、１，０００〜３００，０００、好ましくは２，０００〜２００，０００、さらに好ましくは３，０００〜１００，０００である。この場合、樹脂（Ａ）のＭｗが１，０００未満では、レジストとしての耐熱性が低下する傾向があり、一方３００，０００をこえると、レジストとしての現像性が低下する傾向がある。
また、樹脂（Ａ）のＭｗとゲルパーミエーションクロマトグラフィー（ＧＰＣ）によるポリスチレン換算数平均分子量（以下、「Ｍｎ」という。）との比（Ｍｗ／Ｍｎ）は、通常、１〜５、好ましくは１〜３である。本発明において、樹脂（Ａ）は、単独でまたは２種以上を混合して使用できる。
The weight average molecular weight (hereinafter referred to as “Mw”) in terms of polystyrene by gel permeation chromatography (GPC) of the resin (A) is usually 1,000 to 300,000, preferably 2,000 to 200,000, More preferably, it is 3,000-100,000. In this case, if the Mw of the resin (A) is less than 1,000, the heat resistance as a resist tends to decrease, while if it exceeds 300,000, the developability as a resist tends to decrease.
The ratio (Mw / Mn) of Mw of the resin (A) to polystyrene-reduced number average molecular weight (hereinafter referred to as “Mn”) by gel permeation chromatography (GPC) is usually 1 to 5, preferably 1-3. In this invention, resin (A) can be used individually or in mixture of 2 or more types.
樹脂（Ａ）は、上記特性に加えて上述した動的光散乱法による測定の結果、後述するレジスト溶剤（Ｃ）溶液の樹脂濃度変化に伴う係数（ｋD）が−２．２０ｇ／ｇ以上、好ましくは−２．１０ｇ／ｇ以上あることが必要であり、樹脂（Ａ）を２種以上混合して使用する場合は、少なくとも１種が上記範囲になることが必要である。動的光散乱法を用いることにより、感放射線性樹脂（Ａ）の微小な解像性や溶解性の僅かな相違点が評価でき、係数（ｋD）が−２．２０ｇ／ｇ以上あることにより、従来のレジスト性能を維持したまま、現像欠陥を発生することがない優れた感放射線性樹脂組成物が得られる。また、樹脂（Ａ）を２種以上混合して使用する場合は、上記特性を有する樹脂が少なくとも１重量％以上、好ましくは５重量％以上含有することが好ましい。 Resin (A) has a coefficient (k D ) of −2.20 g / g or more as a result of measurement by the above-described dynamic light scattering method in addition to the above characteristics, as a result of a resin concentration change in a resist solvent (C) solution described later. In addition, it is necessary to be −2.10 g / g or more, and when two or more kinds of resins (A) are mixed and used, it is necessary that at least one kind falls within the above range. By using the dynamic light scattering method, slight differences in the resolution and solubility of the radiation-sensitive resin (A) can be evaluated, and the coefficient (k D ) is −2.20 g / g or more. Thus, an excellent radiation-sensitive resin composition that does not generate development defects while maintaining the conventional resist performance can be obtained. Moreover, when using 2 or more types of resin (A) in mixture, it is preferable that the resin which has the said characteristic contains at least 1 weight% or more, Preferably it contains 5 weight% or more.
レジスト溶剤（Ｂ）
本発明で使用できるレジスト溶剤（Ｂ）は特に限定されるものではないが、上記樹脂（Ａ）を溶解させること、沸点が約１５０℃以上あること、および樹脂溶液塗布時にハレーションを発生させないことの３つの条件を満たすレジスト溶剤であることが好ましい。
好ましいレジスト溶剤（Ｂ）としては、２−ヘキサノン、２−ヘプタノン、２−オクタノン、シクロペンタノン、シクロヘキサノン、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、２−ヒドロキシプロピオン酸メチル、２−ヒドロキシプロピオン酸エチル、３−メトキシプロピオン酸メチル、３−メトキシプロピオン酸エチル、３−エトキシプロピオン酸メチル、３−エトキシプロピオン酸エチル、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、酢酸ｎ−ブチル、ピルビン酸メチル、ピルビン酸エチル、Ｎ−メチルピロリドン、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、γ−ブチロラクトン等が挙げられる。
これらの溶剤は、単独でまたは２種以上を混合して使用できるが、例中、２−ヘプタノン、シクロヘキサノン、プロピレングリコールモノメチルエーテルアセテート、２−ヒドロキシプロピオン酸エチル、３−エトキシプロピオン酸エチル、プロピレングリコールモノメチルエーテル、γ−ブチロラクトン等が好ましい。
Resist solvent (B)
The resist solvent (B) that can be used in the present invention is not particularly limited, but it is possible to dissolve the resin (A), to have a boiling point of about 150 ° C. or higher, and not to generate halation when the resin solution is applied. A resist solvent that satisfies the three conditions is preferred.
Preferred resist solvents (B) include 2-hexanone, 2-heptanone, 2-octanone, cyclopentanone, cyclohexanone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 2-hydroxypropionate, 2-hydroxy Ethyl propionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Propylene glycol monomethyl ether, propylene glycol monoethyl ether acetate n- butyl, methyl pyruvate, ethyl pyruvate, N- methylpyrrolidone, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, .gamma.-butyrolactone.
These solvents can be used alone or in admixture of two or more. In the examples, 2-heptanone, cyclohexanone, propylene glycol monomethyl ether acetate, ethyl 2-hydroxypropionate, ethyl 3-ethoxypropionate, propylene glycol Monomethyl ether, γ-butyrolactone and the like are preferable.
感放射線性樹脂組成物は、上記樹脂（Ａ）を酸解離性基含有樹脂として用い、放射線の照射により酸を発生する成分である酸発生剤（Ｃ）と組み合わせることにより得られる。
感放射線性酸発生剤（Ｃ）として好ましいものとしては、
トリフェニルスルホニウムトリフルオロメタンスルホネート、トリフェニルスルホニウムノナフルオロ−ｎ−ブタンスルホネート、トリフェニルスルホニウムパーフルオロ−ｎ−オクタンスルホネート、トリフェニルスルホニウム２−ビシクロ［２．２．１］ヘプト−２−イル−１，１，２，２−テトラフルオロエタンスルホネート、トリフェニルスルホニウム２−（３−テトラシクロ［４．４．０．１2,5．１7,10］ドデカニル）−１，１−ジフルオロエタンスルホネート、トリフェニルスルホニウムＮ，Ｎ−ビス（ノナフルオロ−ｎ−ブタンスルホニル）イミデート、トリフェニルスルホニウムカンファースルホネート、
The radiation-sensitive resin composition is obtained by using the resin (A) as an acid-dissociable group-containing resin and combining with an acid generator (C) that is a component that generates an acid upon irradiation with radiation.
As a preferred radiation sensitive acid generator (C),
Triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium 2-bicyclo [2.2.1] hept-2-yl-1, 1,2,2-tetrafluoroethane sulfonate, triphenylsulfonium 2- (3-tetracyclo [4.4.0.1 2,5 .1, 7,10 ] dodecanyl) -1,1-difluoroethane sulfonate, triphenylsulfonium N, N-bis (nonafluoro-n-butanesulfonyl) imidate, triphenylsulfonium camphorsulfonate,
４−シクロヘキシルフェニルジフェニルスルホニウムトリフルオロメタンスルホネート、４−シクロヘキシルフェニルジフェニルスルホニウムノナフルオロ−ｎ−ブタンスルホネート、４−シクロヘキシルフェニルジフェニルスルホニウムパーフルオロ−ｎ−オクタンスルホネート、４−シクロヘキシルフェニルジフェニルスルホニウム２−ビシクロ［２．２．１］ヘプト−２−イル−１，１，２，２−テトラフルオロエタンスルホネート、４−シクロヘキシルフェニルジフェニルスルホニウム２−（３−テトラシクロ［４．４．０．１2,5．１7,10］ドデカニル）−１，１−ジフルオロエタンスルホネート、４−シクロヘキシルフェニルジフェニルスルホニウムＮ，Ｎ−ビス（ノナフルオロ−ｎ−ブタンスルホニル）イミデート、４−シクロヘキシルフェニルジフェニルスルホニウムカンファースルホネート、 4-cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-cyclohexylphenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-cyclohexylphenyldiphenylsulfonium 2-bicyclo [2. 2.1] Hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium 2- (3-tetracyclo [4.4.0.1 2,5 .1 7, 10] dodecanyl) -1,1-difluoroethanesulfonate, 4-cyclohexyl-phenyl diphenyl sulfonium N, N-bis (nonafluoro -n- butanesulfonyl) imidate, 4-sik Hexylphenyl camphorsulfonate,
４−ｔ−ブチルフェニルジフェニルスルホニウムトリフルオロメタンスルホネート、４−ｔ−ブチルフェニルジフェニルスルホニウムノナフルオロ−ｎ−ブタンスルホネート、４−ｔ−ブチルフェニルジフェニルスルホニウムパーフルオロ−ｎ−オクタンスルホネート、４−ｔ−ブチルフェニルジフェニルスルホニウム２−ビシクロ［２．２．１］ヘプト−２−イル−１，１，２，２−テトラフルオロエタンスルホネート、４−ｔ−ブチルフェニルジフェニルスルホニウム２−（３−テトラシクロ［４．４．０．１2,5．１7,10］ドデカニル）−１，１−ジフルオロエタンスルホネート、４−ｔ−ブチルフェニルジフェニルスルホニウムＮ，Ｎ−ビス（ノナフルオロ−ｎ−ブタンスルホニル）イミデート、４−ｔ−ブチルフェニルジフェニルスルホニウムカンファースルホネート、
トリ（４−ｔ−ブチルフェニル）スルホニウムトリフルオロメタンスルホネート、トリ（４−ｔ−ブチルフェニル）スルホニウムノナフルオロ−ｎ−ブタンスルホネート、トリ（４−ｔ−ブチルフェニル）スルホニウムパーフルオロ−ｎ−オクタンスルホネート、トリ（４−ｔ−ブチルフェニル）スルホニウム２−ビシクロ［２．２．１］ヘプト−２−イル−１，１，２，２−テトラフルオロエタンスルホネート、トリ（４−ｔ−ブチルフェニル）スルホニウム２−（３−テトラシクロ［４．４．０．１2,5．１7,10］ドデカニル）−１，１−ジフルオロエタンスルホネート、トリ（４−ｔ−ブチルフェニル）スルホニウムＮ，Ｎ−ビス（ノナフルオロ−ｎ−ブタンスルホニル）イミデート、トリ（４−ｔ−ブチルフェニル）スルホニウムカンファースルホネート、
4-t-butylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-t-butylphenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-t-butylphenyl Diphenylsulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-t-butylphenyldiphenylsulfonium 2- (3-tetracyclo [4.4. 0.1 2,5 .1 7,10 ] dodecanyl) -1,1-difluoroethanesulfonate, 4-t-butylphenyldiphenylsulfonium N, N-bis (nonafluoro-n-butanesulfonyl) imidate, 4-t-butyl Phenyldiphenyl Sulfo camphorsulfonate,
Tri (4-t-butylphenyl) sulfonium trifluoromethanesulfonate, tri (4-t-butylphenyl) sulfonium nonafluoro-n-butanesulfonate, tri (4-t-butylphenyl) sulfonium perfluoro-n-octanesulfonate, Tri (4-t-butylphenyl) sulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, tri (4-t-butylphenyl) sulfonium 2 - (3-tetracyclo [4.4.0.1 2,5 .1 7,10] dodecanyl) -1,1-difluoroethanesulfonate, tri (4-t- butylphenyl) sulfonium N, N-bis (nonafluoro - n-butanesulfonyl) imidate, tri (4-t-butylphenyl) sulfonium carbonate Far sulfonate,
ジフェニルヨードニウムトリフルオロメタンスルホネート、ジフェニルヨードニウムノナフルオロ−ｎ−ブタンスルホネート、ジフェニルヨードニウムパーフルオロ−ｎ−オクタンスルホネート、ジフェニルヨードニウム２−ビシクロ［２．２．１］ヘプト−２−イル−１，１，２，２−テトラフルオロエタンスルホネート、ジフェニルヨードニウム２−（３−テトラシクロ［４．４．０．１2,5．１7,10］ドデカニル）−１，１−ジフルオロエタンスルホネート、ジフェニルヨードニウムＮ，Ｎ−ビス（ノナフルオロ−ｎ−ブタンスルホニル）イミデート、ジフェニルヨードニウムカンファースルホネート、
ビス（４−ｔ−ブチルフェニル）ヨードニウムトリフルオロメタンスルホネート、ビス（４−ｔ−ブチルフェニル）ヨードニウムノナフルオロ−ｎ−ブタンスルホネート、ビス（４−ｔ−ブチルフェニル）ヨードニウムパーフルオロ−ｎ−オクタンスルホネート、ビス（４−ｔ−ブチルフェニル）ヨードニウム２−ビシクロ［２．２．１］ヘプト−２−イル−１，１，２，２−テトラフルオロエタンスルホネート、ビス（４−ｔ−ブチルフェニル）ヨードニウム２−（３−テトラシクロ［４．４．０．１2,5．１7,10］ドデカニル）−１，１−ジフルオロエタンスルホネート、ビス（４−ｔ−ブチルフェニル）ヨードニウムＮ，Ｎ−ビス（ノナフルオロ−ｎ−ブタンスルホニル）イミデート、ビス（４−ｔ−ブチルフェニル）ヨードニウムカンファースルホネート、
Diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2, 2-tetrafluoroethane sulfonate, diphenyliodonium 2- (3-tetracyclo [4.4.0.1 2,5 .1 7,10] dodecanyl) -1,1-difluoroethanesulfonate, diphenyliodonium N, N-bis ( Nonafluoro-n-butanesulfonyl) imidate, diphenyliodonium camphorsulfonate,
Bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, Bis (4-t-butylphenyl) iodonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, bis (4-t-butylphenyl) iodonium 2 - (3-tetracyclo [4.4.0.1 2,5 .1 7,10] dodecanyl) -1,1-difluoroethanesulfonate, bis (4-t- butylphenyl) iodonium N, N-bis (nonafluoro - n-butanesulfonyl) imidate, bis (4-t-butylphenyl) iodonium Far sulfonate,
１−（４−ｎ−ブトキシナフタレンー１−イル）テトラヒドロチオフェニウムトリフルオロメタンスルホネート、１−（４−ｎ−ブトキシナフタレンー１−イル）テトラヒドロチオフェニウムノナフルオロ−ｎ−ブタンスルホネート、１−（４−ｎ−ブトキシナフタレンー１−イル）テトラヒドロチオフェニウムパーフルオロ−ｎ−オクタンスルホネート、１−（４−ｎ−ブトキシナフタレンー１−イル）テトラヒドロチオフェニウム２−ビシクロ［２．２．１］ヘプト−２−イル−１，１，２，２−テトラフルオロエタンスルホネート、１−（４−ｎ−ブトキシナフタレンー１−イル）テトラヒドロチオフェニウム２−（３−テトラシクロ［４．４．０．１2,5．１7,10］ドデカニル）−１，１−ジフルオロエタンスルホネート、１−（４−ｎ−ブトキシナフタレンー１−イル）テトラヒドロチオフェニウムＮ，Ｎ−ビス（ノナフルオロ−ｎ−ブタンスルホニル）イミデート、１−（４−ｎ−ブトキシナフタレンー１−イル）テトラヒドロチオフェニウムカンファースルホネート、 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, (4-n-Butoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium 2-bicyclo [2.2. 1] Hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium 2- (3-tetracyclo [4.4. 0.1 2,5 .1 7,10] dodecanyl) -1,1-difluoroethanesulfonate, 1- (4 n- butoxy naphthalen-1-yl) tetrahydrothiophenium N, N-bis (nonafluoro -n- butanesulfonyl) imidate, 1- (4-n- butoxy-naphthalene-1-yl) tetrahydrothiophenium camphorsulfonate,
１−（３，５−ジメチル−４−ヒドロキシフェニル）テトラヒドロチオフェニウムトリフルオロメタンスルホネート、１−（３，５−ジメチル−４−ヒドロキシフェニル）テトラヒドロチオフェニウムノナフルオロ−ｎ−ブタンスルホネート、１−（３，５−ジメチル−４−ヒドロキシフェニル）テトラヒドロチオフェニウムパーフルオロ−ｎ−オクタンスルホネート、１−（３，５−ジメチル−４−ヒドロキシフェニル）テトラヒドロチオフェニウム２−ビシクロ［２．２．１］ヘプト−２−イル−１，１，２，２−テトラフルオロエタンスルホネート、１−（３，５−ジメチル−４−ヒドロキシフェニル）テトラヒドロチオフェニウム２−（３−テトラシクロ［４．４．０．１2,5．１7,10］ドデカニル）−１，１−ジフルオロエタンスルホネート、１−（３，５−ジメチル−４−ヒドロキシフェニル）テトラヒドロチオフェニウムＮ，Ｎ−ビス（ノナフルオロ−ｎ−ブタンスルホニル）イミデート、１−（３，５−ジメチル−４−ヒドロキシフェニル）テトラヒドロチオフェニウムカンファースルホネート、 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, (3,5-Dimethyl-4-hydroxyphenyl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium 2-bicyclo [2.2. 1] Hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium 2- (3-tetracyclo [4.4. 0.1 2,5 .1 7,10] dodecanyl) -1,1-difluoroethane scan Phonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium N, N-bis (nonafluoro-n-butanesulfonyl) imidate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydro Thiophenium camphorsulfonate,
Ｎ−（トリフルオロメタンスルホニルオキシ）スクシンイミド、Ｎ−（ノナフルオロ−ｎ−ブタンスルホニルオキシ）スクシンイミド、Ｎ−（パーフルオロ−ｎ−オクタンスルホニルオキシ）スクシンイミド、Ｎ−（２−ビシクロ［２．２．１］ヘプト−２−イル−１，１，２，２−テトラフルオロエタンスルホニルオキシ）スクシンイミド、Ｎ−（２−（３−テトラシクロ［４．４．０．１2,5．１7,10］ドデカニル）−１，１−ジフルオロエタンスルホニルオキシ）スクシンイミド、Ｎ−（カンファースルホニルオキシ）スクシンイミド、 N- (trifluoromethanesulfonyloxy) succinimide, N- (nonafluoro-n-butanesulfonyloxy) succinimide, N- (perfluoro-n-octanesulfonyloxy) succinimide, N- (2-bicyclo [2.2.1] Hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy) succinimide, N- (2- (3-tetracyclo [4.4.0.1 2,5 .1, 7,10 ] dodecanyl) -1,1-difluoroethanesulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide,
Ｎ−（トリフルオロメタンスルホニルオキシ）ビシクロ［２．２．１］ヘプト−５−エン−２，３−ジカルボキシイミド、Ｎ−（ノナフルオロ−ｎ−ブタンスルホニルオキシ）ビシクロ［２．２．１］ヘプト−５−エン−２，３−ジカルボキシイミド、Ｎ−（パーフルオロ−ｎ−オクタンスルホニルオキシ）ビシクロ［２．２．１］ヘプト−５−エン−２，３−ジカルボキシイミド、Ｎ−（２−ビシクロ［２．２．１］ヘプト−２−イル−１，１，２，２−テトラフルオロエタンスルホニルオキシ）ビシクロ［２．２．１］ヘプト−５−エン−２，３−ジカルボキシイミド、Ｎ−（２−（３−テトラシクロ［４．４．０．１2,5．１7,10］ドデカニル）−１，１−ジフルオロエタンスルホニルオキシ）ビシクロ［２．２．１］ヘプト−５−エン−２，３−ジカルボキシイミド、Ｎ−（カンファースルホニルオキシ）ビシクロ［２．２．１］ヘプト−５−エン−２，３−ジカルボキシイミド、等が挙げられる。 N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hept -5-ene-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- ( 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy imide, N- (2- (3- tetracyclo [4.4.0.1 2,5 .1 7,10] dodecanyl) -1,1-difluoroethane-sulfonyloxy) bicyclo [2.2.1] hept -5 -D 2,3-dicarboximide, N- (camphorsulfonyloxy oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, and the like.
本発明において、感放射線性酸発生剤（Ｃ）は、単独でまたは２種以上を混合して使用できる。感放射線性酸発生剤（Ｃ）の使用量は、レジストとしての感度および現像性を確保する観点から、樹脂（Ａ）１００重量部に対して、通常、０．１〜２０重量部、好ましくは０．１〜７重量部である。この場合、感放射線性酸発生剤（Ｃ）の使用量が０．１重量部未満では、感度および現像性が低下する傾向があり、一方１０重量部をこえると、放射線に対する透明性が低下して、矩形のレジストパターンを得られ難くなる傾向がある。 In this invention, a radiation sensitive acid generator (C) can be used individually or in mixture of 2 or more types. The amount of the radiation sensitive acid generator (C) used is usually 0.1 to 20 parts by weight, preferably 100 parts by weight with respect to 100 parts by weight of the resin (A), from the viewpoint of securing the sensitivity and developability as a resist. 0.1 to 7 parts by weight. In this case, if the amount of the radiation-sensitive acid generator (C) used is less than 0.1 parts by weight, the sensitivity and developability tend to decrease. On the other hand, if it exceeds 10 parts by weight, the transparency to radiation decreases. Therefore, it tends to be difficult to obtain a rectangular resist pattern.
本発明の感放射線性樹脂組成物には、露光により感放射線性酸発生剤（Ｃ）から生じる酸のレジスト被膜中における拡散現象を制御し、非露光領域における好ましくない化学反応を抑制する作用を有する酸拡散制御剤（Ｆ）を配合することが好ましい。酸拡散制御剤（Ｆ）を配合することにで、感放射線性樹脂組成物の貯蔵安定性やレジストとしての解像度がさらに向上するとともに、露光から現像処理までの引き置き時間（ＰＥＤ）の変動によるレジストパターンの線幅変化を抑えることができ、プロセス安定性に極めて優れた組成物が得られる。
酸拡散制御剤（Ｆ）としては、レジストパターンの形成工程中の露光や加熱処理により塩基性が変化しない含窒素有機化合物が好ましい。このような含窒素有機化合物としては、「３級アミン化合物」、「アミド基含有化合物」、「４級アンモニウムヒドロキシド化合物」、「含窒素複素環化合物」等が挙げられる。
The radiation-sensitive resin composition of the present invention has the effect of controlling the diffusion phenomenon in the resist film of the acid generated from the radiation-sensitive acid generator (C) by exposure and suppressing undesirable chemical reactions in the non-exposed areas. It is preferable to mix the acid diffusion controlling agent (F) having. By blending the acid diffusion control agent (F), the storage stability of the radiation-sensitive resin composition and the resolution as a resist are further improved, and due to fluctuations in the holding time (PED) from exposure to development processing. A change in the line width of the resist pattern can be suppressed, and a composition having excellent process stability can be obtained.
The acid diffusion controller (F) is preferably a nitrogen-containing organic compound whose basicity does not change by exposure or heat treatment during the resist pattern formation step. Examples of such nitrogen-containing organic compounds include “tertiary amine compounds”, “amide group-containing compounds”, “quaternary ammonium hydroxide compounds”, “nitrogen-containing heterocyclic compounds”, and the like.
「３級アミン化合物」としては、例えば、トリエチルアミン、トリ−ｎ−プロピルアミン、トリ−ｎ−ブチルアミン、トリ−ｎ−ペンチルアミン、トリ−ｎ−ヘキシルアミン、トリ−ｎ−ヘプチルアミン、トリ−ｎ−オクチルアミン、トリ−ｎ−デシルアミン、シクロヘキシルジメチルアミン、ジシクロヘキシルメチルアミン、トリシクロヘキシルアミン等のトリ（シクロ）アルキルアミン類；Ｎ，Ｎ−ジメチルアニリン、２，６−ジメチルアニリン、２，６−ジイソプロピルアニリン等の芳香族アミン類；トリエタノールアミン、ジエタノールアニリンなどのアルカノールアミン類；Ｎ，Ｎ，Ｎ'，Ｎ'−テトラキス（２−ヒドロキシプロピル）エチレンジアミン、ビス（２−ジメチルアミノエチル）エーテル、ビス（２−ジエチルアミノエチル）エーテル等が挙げられる。 Examples of the “tertiary amine compound” include triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n. -Tri (cyclo) alkylamines such as octylamine, tri-n-decylamine, cyclohexyldimethylamine, dicyclohexylmethylamine, tricyclohexylamine; N, N-dimethylaniline, 2,6-dimethylaniline, 2,6-diisopropyl Aromatic amines such as aniline; alkanolamines such as triethanolamine and diethanolaniline; N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, bis (2-dimethylaminoethyl) ether, bis (2-Diethylaminoe Le) ether and the like.
「アミド基含有化合物」としては、例えば、Ｎ−ｔ−ブトキシカルボニルジ−ｎ−オクチルアミン、Ｎ−ｔ−ブトキシカルボニルジシクロヘキシルアミン、Ｎ−ｔ−ブトキシカルボニル−１−アダマンチルアミン、Ｎ−ｔ−ブトキシカルボニル−Ｎ−メチル−１−アダマンチルアミン、Ｎ−ｔ−ブトキシカルボニル−４，４'−ジアミノジフェニルメタン、Ｎ−ｔ−ブトキシカルボニルピロリジン、Ｎ−ｔ−ブトキシカルボニル−４−ヒペリジン、Ｎ−ｔ−ブトキシカルボニルアミノ−１−アダマンタン、Ｎ−ｔ−ブトキシカルボニルアミノ−２−アダマンタン、Ｎ−ｔ−ブトキシカルボニルベンズイミダゾール、Ｎ−ｔ−ブトキシカルボニル−２−メチルベンズイミダゾール、Ｎ−ｔ−ブトキシカルボニル−２−フェニルベンズイミダゾール等のＮ−ｔ−ブトキシカルボニル基含有アミノ化合物；ホルムアミド、Ｎ−メチルホルムアミド、Ｎ，Ｎ−ジメチルホルムアミド、アセトアミド、Ｎ−メチルアセトアミド、Ｎ，Ｎ−ジメチルアセトアミド、プロピオンアミド、ベンズアミド、ピロリドン、Ｎ−メチルピロリドン等が挙げられる。 Examples of the “amide group-containing compound” include Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxy. Carbonyl-N-methyl-1-adamantylamine, Nt-butoxycarbonyl-4,4′-diaminodiphenylmethane, Nt-butoxycarbonylpyrrolidine, Nt-butoxycarbonyl-4-hyperidine, Nt-butoxy Carbonylamino-1-adamantane, Nt-butoxycarbonylamino-2-adamantane, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, Nt-butoxycarbonyl-2- Phenylbenzimidazole Nt-butoxycarbonyl group-containing amino compounds such as formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N- And methyl pyrrolidone.
「４級アンモニウムヒドロキシド化合物」としては、例えば、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラ−ｎ−プロピルアンモニウムヒドロキシド、テトラ−ｎ−ブチルアンモニウムヒドロキシド等が挙げられる。
「含窒素複素環化合物」としては、例えば、イミダゾール、４−メチルイミダゾール、１−ベンジル−２−メチルイミダゾール、４−メチル−２−フェニルイミダゾール、ベンズイミダゾール、２−フェニルベンズイミダゾール、Ｎ−メチル２−フェニルベンズイミダゾール、Ｎ−ベンジル２−フェニルベンズイミダゾール、Ｎ−（３−ヒドロキシプロピル）２−フェニルベンズイミダゾール、等のイミダゾール類；ピリジン、２−メチルピリジン、４−メチルピリジン、２−エチルピリジン、４−エチルピリジン、２−フェニルピリジン、４−フェニルピリジン、２−メチル−４−フェニルピリジン、ニコチン、ニコチン酸、ニコチン酸アミド、キノリン、４−ヒドロキシキノリン、８−オキシキノリン、アクリジン等のピリジン類；ピペラジン、１−（２−ヒドロキシエチル）ピペラジン等のピペラジン類のほか、ピラジン、ピラゾール、ピリダジン、キノザリン、プリン、ピロリジン、ピペリジン、３−ピペリジノ−１，２−プロパンジオール、モルホリン、４−メチルモルホリン、１，４−ジメチルピペラジン、１，４−ジアザビシクロ [２．２．２] オクタン等が挙げられる。
Examples of the “quaternary ammonium hydroxide compound” include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetra-n-butylammonium hydroxide, and the like.
Examples of the “nitrogen-containing heterocyclic compound” include imidazole, 4-methylimidazole, 1-benzyl-2-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, N-methyl-2. -Imidazoles such as phenylbenzimidazole, N-benzyl 2-phenylbenzimidazole, N- (3-hydroxypropyl) 2-phenylbenzimidazole; pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, Pyridines such as 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 4-hydroxyquinoline, 8-oxyquinoline and acridine Pipette In addition to piperazines such as gin and 1- (2-hydroxyethyl) piperazine, pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, 3-piperidino-1,2-propanediol, morpholine, 4-methylmorpholine, Examples include 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane.
これらの含窒素有機化合物のうち、３級アミン化合物、アミド基含有化合物、含窒素複素環化合物等が好ましく、またアミド基含有化合物の中ではＮ−ｔ−ブトキシカルボニル基含有アミノ化合物が好ましく、含窒素複素環化合物の中ではイミダゾール類が好ましい。これら酸拡散制御剤（Ｆ）は、単独でまたは２種以上を混合して使用できる。
酸拡散制御剤（Ｆ）の配合量は、樹脂（Ａ）１００重量部に対して、通常、５重量部以下、好ましくは３重量部以下、さらに好ましくは２重量部以下である。この場合、酸拡散制御剤の配合量が５重量部を超えると、レジストとしての感度や露光部の現像性が低下する傾向がある。なお、酸拡散制御剤の配合量が０．０１重量部未満であると、プロセス条件によっては、レジストとしてのパターン形状や寸法忠実度が低下するおそれがある。
Of these nitrogen-containing organic compounds, tertiary amine compounds, amide group-containing compounds, nitrogen-containing heterocyclic compounds and the like are preferable, and among the amide group-containing compounds, Nt-butoxycarbonyl group-containing amino compounds are preferable. Among the nitrogen heterocyclic compounds, imidazoles are preferable. These acid diffusion control agents (F) can be used alone or in admixture of two or more.
The compounding amount of the acid diffusion controller (F) is usually 5 parts by weight or less, preferably 3 parts by weight or less, more preferably 2 parts by weight or less with respect to 100 parts by weight of the resin (A). In this case, when the compounding amount of the acid diffusion controller exceeds 5 parts by weight, the sensitivity as a resist and the developability of the exposed part tend to be lowered. If the blending amount of the acid diffusion controller is less than 0.01 parts by weight, the pattern shape and dimensional fidelity as a resist may be lowered depending on the process conditions.
また、本発明の感放射線性樹脂組成物には、ドライエッチング耐性、パターン形状、基板との接着性等をさらに改善する作用を示す他の添加剤を配合できる。他の添加剤は酸解離性有機基を含有していても、あるいは酸解離性有機基を含有していなくてもよい。
このような他の添加剤としては、例えば、１−アダマンタンカルボン酸ｔ−ブチル、１−アダマンタンカルボン酸ｔ−ブトキシカルボニルメチル、１−アダマンタンカルボン酸α−ブチロラクトンエステル、１，３−アダマンタンジカルボン酸ジ−ｔ−ブチル、１−アダマンタン酢酸ｔ−ブチル、１−アダマンタン酢酸ｔ−ブトキシカルボニルメチル、１，３−アダマンタンジ酢酸ジ−ｔ−ブチル、２，５−ジメチル−２，５−ジ（アダマンチルカルボニルオキシ）ヘキサン等のアダマンタン誘導体類；デオキシコール酸ｔ−ブチル、デオキシコール酸ｔ−ブトキシカルボニルメチル、デオキシコール酸２−エトキシエチル、デオキシコール酸２−シクロヘキシルオキシエチル、デオキシコール酸３−オキソシクロヘキシル、デオキシコール酸テトラヒドロピラニル、デオキシコール酸メバロノラクトンエステル等のデオキシコール酸エステル類；リトコール酸ｔ−ブチル、リトコール酸ｔ−ブトキシカルボニルメチル、リトコール酸２−エトキシエチル、リトコール酸２−シクロヘキシルオキシエチル、リトコール酸３−オキソシクロヘキシル、リトコール酸テトラヒドロピラニル、リトコール酸メバロノラクトンエステル等のリトコール酸エステル類：アジピン酸ジメチル、アジピン酸ジエチル、アジピン酸時プロピル、アジピン酸ジｎ−ブチル、アジピン酸ジｔ−ブチル等のアルキルカルボン酸エステル類；等が挙げられる。
これらの他の添加剤は、単独でまたは２種以上を混合して使用することができる。他の添加剤の配合量は、樹脂（Ａ）１００重量部に対して、通常、５０重量部以下、好ましくは３０重量部以下である。この場合、添加剤の配合量が５０重量部をこえると、レジストとしての耐熱性が低下する傾向がある。
In addition, the radiation-sensitive resin composition of the present invention can be blended with other additives exhibiting the action of further improving dry etching resistance, pattern shape, adhesion to the substrate, and the like. Other additives may contain an acid dissociable organic group or may not contain an acid dissociable organic group.
Examples of such other additives include 1-adamantanecarboxylic acid t-butyl, 1-adamantanecarboxylic acid t-butoxycarbonylmethyl, 1-adamantanecarboxylic acid α-butyrolactone ester, and 1,3-adamantane dicarboxylic acid diester. -T-butyl, 1-adamantane acetate t-butyl, 1-adamantane acetate t-butoxycarbonylmethyl, 1,3-adamantanediacetate di-t-butyl, 2,5-dimethyl-2,5-di (adamantylcarbonyl) Adamantane derivatives such as oxy) hexane; deoxycholate t-butyl, deoxycholate t-butoxycarbonylmethyl, deoxycholate 2-ethoxyethyl, deoxycholate 2-cyclohexyloxyethyl, deoxycholate 3-oxocyclohexyl, Deoxychol Deoxycholic acid esters such as tetrahydropyranyl, deoxycholic acid mevalonolactone ester; lithocholic acid t-butyl, lithocholic acid t-butoxycarbonylmethyl, lithocholic acid 2-ethoxyethyl, lithocholic acid 2-cyclohexyloxyethyl, lithocholic acid Lithocholic acid esters such as 3-oxocyclohexyl, lithocholic acid tetrahydropyranyl, lithocholic acid mevalonolactone ester: dimethyl adipate, diethyl adipate, propyl at the time of adipic acid, di-n-butyl adipate, di-t-butyl adipate And the like, and the like.
These other additives can be used alone or in admixture of two or more. The amount of other additives is usually 50 parts by weight or less, preferably 30 parts by weight or less with respect to 100 parts by weight of the resin (A). In this case, when the compounding amount of the additive exceeds 50 parts by weight, the heat resistance as a resist tends to decrease.
また、本発明の感放射線性樹脂組成物には、塗布性、現像性等を改良する作用を示す界面活性剤を配合できる。
界面活性剤としては、例えば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンｎ−オクチルフェニルエーテル、ポリオキシエチレンｎ−ノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート等のノニオン系界面活性剤のほか、以下商品名で、ＫＰ３４１（信越化学工業（株）製）、ポリフローＮｏ．７５、同Ｎｏ．９５（共栄社化学（株）製）、エフトップＥＦ３０１、同ＥＦ３０３、同ＥＦ３５２（トーケムプロダクツ（株）製）、メガファックスＦ１７１、同Ｆ１７３（大日本インキ化学工業（株）製）、フロラードＦＣ４３０、同ＦＣ４３１（住友スリーエム（株）製）、アサヒガードＡＧ７１０、サーフロンＳ−３８２、同ＳＣ−１０１、同ＳＣ−１０２、同ＳＣ−１０３、同ＳＣ−１０４、同ＳＣ−１０５、同ＳＣ−１０６（旭硝子（株）製）等が挙げられる。
これらの界面活性剤は、単独でまたは２種以上を混合して使用できる。界面活性剤の配合量は、樹脂（Ａ）１００重量部に対して、通常、２重量部以下である。
In addition, the radiation-sensitive resin composition of the present invention can be blended with a surfactant exhibiting an effect of improving coatability, developability and the like.
Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol In addition to nonionic surfactants such as distearate, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), Ftop EF301, EF303, EF352 (manufactured by Tochem Products), Megafax F171, F173 (manufactured by Dainippon Ink and Chemicals), Florard FC430, FC431 (Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 ( Asahi Glass Co., Ltd.).
These surfactants can be used alone or in admixture of two or more. The compounding quantity of surfactant is 2 parts weight or less normally with respect to 100 weight part of resin (A).
また、本発明の感放射線性樹脂組成物には、感度等を改良する作用を示す増感剤を配合できる。好ましい増感剤としては、例えば、カルバゾール類、ベンゾフェノン類、ローズベンガル類、アントラセン類、フェノール類等が挙げられる。
これらの増感剤は、単独でまたは２種以上を混合して使用できる。増感剤の配合量は、樹脂（Ａ）１００重量部に対して、好ましくは５０重量部以下である。
さらに、上記以外の添加剤としては、ハレーション防止剤、接着助剤、保存安定化剤、消泡剤等が挙げられる。
Moreover, the radiation sensitive resin composition of this invention can be mix | blended with the sensitizer which shows the effect | action which improves a sensitivity. Preferred sensitizers include, for example, carbazoles, benzophenones, rose bengals, anthracenes, phenols and the like.
These sensitizers can be used alone or in admixture of two or more. The blending amount of the sensitizer is preferably 50 parts by weight or less with respect to 100 parts by weight of the resin (A).
Furthermore, examples of additives other than those mentioned above include antihalation agents, adhesion assistants, storage stabilizers, antifoaming agents, and the like.
以下、実施例を挙げて、本発明の実施の形態をさらに具体的に説明する。ここで、部は、特記しない限り重量基準である。
合成例、実施例および比較例における各測定・評価は、下記の要領で行なった。
（１）ＭｗおよびＭｎ
東ソー（株）製ＧＰＣカラム（Ｇ２０００ＨＸＬ ２本、Ｇ３０００ＨＸＬ １本、Ｇ４０００ＨＸＬ １本）を用い、流量１．０ミリリットル／分、溶出溶媒テトラヒドロフラン、カラム温度４０℃の分析条件で、単分散ポリスチレンを標準とするゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定した。
（２）ｋD値
合成例３〜６で得られる樹脂（Ａ−３）〜（Ａ−６）に関して、規定濃度の樹脂溶液を調製後充分にローター攪拌を行ない均一溶液を得た。このとき用いた溶剤（Ｂ）の混合比は、プロピレングリコールモノメチルエーテルアセテート／シクロヘキサノン／γ−ブチロラクトン＝５３．４６／４３．８５／２．６９（重量％）を用いた。この樹脂溶液を上記混合比の溶剤（Ｂ）を用いて規定濃度に希釈したサンプルを孔径０．２ミクロンのフィルター（有機溶媒用）で濾過し、メタノール還流洗浄器にて２時間以上洗浄を行なった直径２０ｍｍの石英ガラスセルに注入した。溶液粘度は温度に依存するため、２３．００±０．０２℃で精密に制御して動的光散乱測定を行なった。各散乱角度における拡散係数の平均値を、その濃度における見かけ上の拡散係数Ｄとする。このＤを濃度ｃ（単位重量％）に対してプロットした図において切片はＤ0、勾配はＤ0×ｋDを表すので、両者よりそれぞれの樹脂溶液のｋD値を得ることができる。
（３）放射線透過率
組成物溶液を石英ガラス上に塗布し、表２に示した温度条件に保持したホットプレート上で表２に示した条件の間ＰＢを行って形成した膜厚０．３４μｍのレジスト被膜について、波長１９３ｎｍにおける吸光度から、放射線透過率を算出して、遠紫外線領域における透明性の尺度とした。
（４）感度
ＡｒＦ光源にて露光を行なう場合、ウエハー表面に膜厚７７ｎｍのＡＲＣ２９Ａ（（Ｂｒｅｗｅｒ Ｓｃｉｅｎｃｅ社製）膜を形成したシリコーンウエハー（ＡＲＣ２９Ａ））を用い、各組成物溶液を、基板上にスピンコートにより塗布し、ホットプレート上にて、表２に示す条件でＰＢを行なって形成した膜厚２１５ｎｍのレジスト被膜に、ニコン製ＡｒＦエキシマレーザー露光装置（Ｓ３０６Ｃ 開口数０．７８）を用い、マスクパターンを介して露光した。その後、表２に示す条件でＰＥＢを行なったのち、２．３８重量％のテトラメチルアンモニウムヒドロキシド水溶液により、２５℃で４０秒間現像し、水洗し、乾燥して、ポジ型のレジストパターンを形成した。このとき、マスクにおいて線幅１００ｎｍでピッチ１１００ｎｍ（１Ｌ１０Ｓ）が線幅７０ｎｍになるような露光量（マスクバイアス：＋３０ｎｍ）を最適露光量とし、この最適露光量を感度とした。
（５）バイアス
上記最適露光量におけるマスクにおいて線幅１００ｎｍでピッチ２２０ｎｍ（１Ｌ１．２Ｓ）の線幅と上記７０ｎｍとの差をバイアスとする。
Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. Here, the part is based on weight unless otherwise specified.
Measurements and evaluations in the synthesis examples, examples, and comparative examples were performed in the following manner.
(1) Mw and Mn
Using a GPC column (2 G2000HXL, 1 G3000HXL, 1 G4000HXL) manufactured by Tosoh Corporation, monodisperse polystyrene was used as the standard under the analysis conditions of a flow rate of 1.0 ml / min, elution solvent tetrahydrofuran, and column temperature of 40 ° C. Measured by gel permeation chromatography (GPC).
(2) k D value With respect to the resins (A-3) to (A-6) obtained in Synthesis Examples 3 to 6, a rotor solution was sufficiently stirred after preparing a resin solution having a specified concentration to obtain a uniform solution. As a mixing ratio of the solvent (B) used at this time, propylene glycol monomethyl ether acetate / cyclohexanone / γ-butyrolactone = 53.46 / 43.85 / 2.69 (% by weight) was used. A sample obtained by diluting the resin solution to a specified concentration with the solvent (B) having the above mixing ratio is filtered through a filter (for organic solvent) having a pore diameter of 0.2 microns and washed with a methanol reflux washer for 2 hours or more. It was poured into a quartz glass cell having a diameter of 20 mm. Since the solution viscosity depends on the temperature, dynamic light scattering measurement was performed with precise control at 23.00 ± 0.02 ° C. The average value of the diffusion coefficient at each scattering angle is defined as an apparent diffusion coefficient D at that concentration. In the graph in which D is plotted against the concentration c (unit weight%), the intercept represents D 0 and the gradient represents D 0 × k D , so that the k D value of each resin solution can be obtained from both.
(3) Radiation transmittance A film thickness of 0.34 μm formed by applying the composition solution on quartz glass and performing PB on the hot plate kept at the temperature condition shown in Table 2 during the conditions shown in Table 2. With respect to the resist film, the radiation transmittance was calculated from the absorbance at a wavelength of 193 nm and used as a measure of transparency in the far ultraviolet region.
(4) Sensitivity When performing exposure using an ArF light source, a 77 nm-thick ARC29A film (made by Brewer Science) (silicon wafer (ARC29A)) is used on the wafer surface, and each composition solution is applied onto the substrate. Using a Nikon ArF excimer laser exposure apparatus (S306C numerical aperture 0.78) on a resist film having a film thickness of 215 nm formed by spin coating and performing PB on a hot plate under the conditions shown in Table 2. Exposure was through a mask pattern. Thereafter, PEB is performed under the conditions shown in Table 2, and then developed with a 2.38 wt% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 40 seconds, washed with water, and dried to form a positive resist pattern. did. At this time, the exposure amount (mask bias: +30 nm) at which the line width is 100 nm and the pitch is 1100 nm (1L10S) is 70 nm in the mask is set as the optimal exposure amount, and this optimal exposure amount is set as the sensitivity.
(5) Bias The difference between the line width of 100 nm and the pitch of 220 nm (1L1.2S) in the mask at the above optimum exposure amount and the above 70 nm is defined as the bias.
（６）現像欠陥
現像欠陥はケー・エル・エー・テンコール（株）社製の欠陥検査装置（ＫＬＡ２３５１）を用いる方法により評価した。欠陥検査用ウエハーは、次のように作製した。ＡＲＣ２９Ａ（日産化学社製）７７ｎｍをウエハー基板に作成した基板上に、評価用レジストを２１０ｎｍの膜厚で塗布後１２６℃／９０秒の条件でＰＢし、Ｎｉｋｏｎ社製ＡｒＦ露光装置（Ｓ３０６Ｃ）により１８０ｎｍのアクティブパターンが全面にあるマスクを介してその最適露光量にて露光した。露光後、１２６℃／９０秒の条件でＰＥＢを行なった後、２．３８重量％のテトラメチルアンモニウムヒドロキシド水溶液により２３℃で４０秒間現像し、水洗、乾燥して、欠陥検査用ウエハーを作製した。上記の塗布、焼成および現像は東京エレクトロン社製のＡＣＴ８を使用し、すべてインラインで実施した。
上述の方法により作成した欠陥検査用ウエハーを、ケー・エル・エー・テンコール（株）社製の欠陥検査装置（ＫＬＡ２３５１）を使用することにより露光部の現像欠陥を検査した。欠陥総数の検査は、アレイモードで観察して、比較イメージとピクセル単位の重ね合わせによって生じる差異から抽出される欠陥総数を検出することにより行なった。欠陥総数の検出は、０．１５μｍ以上の欠陥を検出できるように、この装置の感度を設定して行なった。
（７）ＬＥＲ
上記最適露光量で形成された７０ｎｍのラインパターンにおいて、日立ハイテクノロジーズ社製Ｓ９２２０を用いて、その線幅を別のＹ軸上で１０点以上線幅を測定したときの線幅ばらつき（３σ）を計測した。そのばらつき（３σ）が１５ｎｍ以上の場合「不良」とし、１５ｎｍ未満の場合「良好」とした。
(6) Development defect The development defect was evaluated by a method using a defect inspection apparatus (KLA2351) manufactured by KLA-Tencor Corporation. The wafer for defect inspection was produced as follows. An ARC29A (manufactured by Nissan Chemical Industries, Ltd.) 77 nm on a wafer substrate was coated with a resist for evaluation with a film thickness of 210 nm and then subjected to PB under conditions of 126 ° C./90 seconds, and then Nikon ArF exposure apparatus (S306C). The exposure was performed at the optimum exposure amount through a mask having an active pattern of 180 nm on the entire surface. After exposure, PEB was performed at 126 ° C./90 seconds, developed with 2.38 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 40 seconds, washed with water and dried to produce a wafer for defect inspection. did. The above coating, baking and development were all performed inline using ACT8 manufactured by Tokyo Electron.
The defect inspection wafer produced by the above-described method was inspected for development defects in the exposed portion by using a defect inspection apparatus (KLA2351) manufactured by KLA-Tencor Corporation. The inspection of the total number of defects was performed by observing in the array mode and detecting the total number of defects extracted from the difference caused by the comparison image and the pixel unit. The total number of defects was detected by setting the sensitivity of this apparatus so that defects of 0.15 μm or more could be detected.
(7) LER
Line width variation (3σ) when the line width is measured at 10 points or more on another Y-axis using S9220 manufactured by Hitachi High-Technologies Corporation in the 70 nm line pattern formed at the optimum exposure amount. Was measured. When the variation (3σ) was 15 nm or more, it was judged as “bad”, and when it was less than 15 nm, it was judged as “good”.
合成例１
合成例２
合成例３
合成例４
合成例５
合成例６
下記表１に、樹脂（Ａ−３）〜（Ａ−６）について測定された係数（ｋD）を示す。
実施例１
樹脂（Ａ−１）、樹脂（Ａ−２）および樹脂（Ａ−３）を表１に示す割合で混合した混合物を表２に示す他の成分を配合した感放射線性樹脂組成物溶液について、表３の条件で評価し、評価結果を表４に示す。なお、樹脂（Ａ−１）および樹脂（Ａ−２）の係数（ｋD）はそれぞれ−２．４ｇ／ｇおよび−２．９ｇ／ｇであった。
表２における重合体（Ａ−１）〜（Ａ−６）以外の成分は以下の通りである。
レジスト溶剤（Ｂ）
Ｂ−１：プロピレングリコールモノメチルエーテルアセテート
Ｂ−２：シクロヘキサノン
Ｂ−３：γ−ブチロラクトン
酸発生剤（Ｃ）
Ｃ−１： １−（４−ｎ−ブトキシナフタレンー１−イル）テトラヒドロチオフェニウム パーフルオロ−ｎ−オクタンスルホネート
酸拡散制御剤（Ｆ）
Ｄ−１：Ｎ−ｔ−ブトキシカルボニル−２−フェニルベンズイミダゾール
添加剤（Ｅ）
Ｅ−１：デオキシコール酸ｔ−ブトキシカルボニルメチル
Example 1
About the radiation sensitive resin composition solution which mix | blended the other component which shows the mixture which mixed resin (A-1), resin (A-2), and resin (A-3) in the ratio shown in Table 1 in Table 2, Evaluation was performed under the conditions shown in Table 3, and the evaluation results are shown in Table 4. The coefficients (k D ) of Resin (A-1) and Resin (A-2) were −2.4 g / g and −2.9 g / g, respectively.
Components other than the polymers (A-1) to (A-6) in Table 2 are as follows.
Resist solvent (B)
B-1: Propylene glycol monomethyl ether acetate B-2: Cyclohexanone B-3: γ-Butyrolactone Acid generator (C)
C-1: 1- (4-n-Butoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate Acid diffusion controller (F)
D-1: Nt-butoxycarbonyl-2-phenylbenzimidazole additive (E)
E-1: Deoxycholic acid t-butoxycarbonylmethyl
実施例２
樹脂（Ａ−３）を樹脂（Ａ−４）に代える以外は実施例１と同様にして係数（ｋD）の測定、および感放射線性樹脂組成物溶液を作製して、表３の条件で評価し、評価結果を表４に示す。
Example 2
Except that the resin (A-3) is replaced with the resin (A-4), the measurement of the coefficient (k D ) and the radiation-sensitive resin composition solution are made in the same manner as in Example 1, and the conditions in Table 3 are used. The evaluation results are shown in Table 4.
実施例３
樹脂（Ａ−３）を樹脂（Ａ−５）に代える以外は実施例１と同様にして係数（ｋD）の測定、および感放射線性樹脂組成物溶液を作製して、表３の条件で評価し、評価結果を表４に示す。
Example 3
The coefficient (k D ) was measured in the same manner as in Example 1 except that the resin (A-3) was replaced with the resin (A-5), and a radiation-sensitive resin composition solution was prepared. The evaluation results are shown in Table 4.
実施例４
樹脂（Ａ−３）を樹脂（Ａ−６）に代える以外は実施例１と同様にして係数（ｋD）の測定、および感放射線性樹脂組成物溶液を作製して、表３の条件で評価し、評価結果を表４に示す。
Except that the resin (A-3) is replaced with the resin (A-6), the measurement of the coefficient (k D ) and the radiation-sensitive resin composition solution are made in the same manner as in Example 1, and the conditions in Table 3 are used. The evaluation results are shown in Table 4.
表４に示すように、感放射線性樹脂の係数（ｋD）値により、現像欠陥やＬＥＲの性能を予測できる。すなわち、複数配合される少なくとも１つの樹脂のｋD値が−２．２０ｇ／ｇ以上あれば現像欠陥やＬＥＲ特性に優れた感放射線性樹脂組成物が得られる。 As shown in Table 4, development defect and LER performance can be predicted from the coefficient (k D ) value of the radiation sensitive resin. That is, if the k D value of at least one resin to be blended is −2.20 g / g or more, a radiation-sensitive resin composition excellent in development defects and LER characteristics can be obtained.
感放射線性樹脂の現像特性が係数（ｋD）により評価・選別できるので、より高い集積度が求められ半導体分野に適用できる。
また、この評価方法を用いることで、ＫｒＦエキシマレーザーあるいはＡｒＦエキシマレーザー等の遠紫外線、シンクロトロン放射線等のＸ線、電子線等の荷電粒子線の如き各種の放射線を使用する微細加工に有用な化学増幅型レジストとして好適に使用できる感放射線性樹脂組成物の製造に適用できる。
Since the development characteristics of the radiation-sensitive resin can be evaluated and selected by the coefficient (k D ), a higher degree of integration is required and can be applied to the semiconductor field.
Moreover, by using this evaluation method, it is useful for microfabrication using various types of radiation such as deep ultraviolet rays such as KrF excimer laser or ArF excimer laser, X-rays such as synchrotron radiation, and charged particle beams such as electron beams. The present invention can be applied to the production of a radiation sensitive resin composition that can be suitably used as a chemically amplified resist.
Claims (2)
前記酸解離性基含有樹脂（Ａ）の少なくとも１種は、該樹脂（Ａ）のレジスト溶剤（Ｂ）溶液の動的光散乱測定により、該溶液の濃度変化に伴う感放射線性樹脂の溶液中の拡散係数変化を表す係数（ｋD）が−２．２０ｇ／ｇ以上であることを特徴とする感放射線性樹脂組成物。 An acid-dissociable group-containing resin (A) that is insoluble or hardly soluble in alkali and easily soluble in alkali by the action of an acid, alone or in combination, a resist solvent (B), and a radiation-sensitive acid generator (C And a radiation sensitive resin composition comprising:
At least one of the acid dissociable group-containing resin (A) is contained in a solution of a radiation sensitive resin accompanying a change in the concentration of the solution by dynamic light scattering measurement of a resist solvent (B) solution of the resin (A). A radiation-sensitive resin composition having a coefficient (k D ) representing a change in diffusion coefficient of -2.20 g / g or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003320589A JP4356407B2 (en) | 2003-09-12 | 2003-09-12 | Evaluation method of radiation sensitive resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003320589A JP4356407B2 (en) | 2003-09-12 | 2003-09-12 | Evaluation method of radiation sensitive resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005091407A true JP2005091407A (en) | 2005-04-07 |
| JP4356407B2 JP4356407B2 (en) | 2009-11-04 |
Family
ID=34452506
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003320589A Expired - Lifetime JP4356407B2 (en) | 2003-09-12 | 2003-09-12 | Evaluation method of radiation sensitive resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4356407B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008096373A (en) * | 2006-10-16 | 2008-04-24 | Shimadzu Corp | Method and device for measuring nanoparticles |
| JP2009037184A (en) * | 2007-07-09 | 2009-02-19 | Jsr Corp | Method for evaluating resin, and radiation-sensitive resin composition |
| JP2009211044A (en) * | 2008-02-07 | 2009-09-17 | Jsr Corp | Evaluation method and radiation-sensitive resin composition |
| WO2011004787A1 (en) * | 2009-07-07 | 2011-01-13 | 三菱レイヨン株式会社 | Copolymer for lithography and method for evaluating same |
| JP2011048354A (en) * | 2009-07-28 | 2011-03-10 | Mitsubishi Rayon Co Ltd | Evaluation method of copolymer for lithography |
| JP2013214032A (en) * | 2012-03-07 | 2013-10-17 | Mitsubishi Rayon Co Ltd | Evaluation method of polymer for semiconductor lithography, and manufacturing method of polymer for semiconductor lithography including the evaluation method |
| US9109060B2 (en) | 2009-07-07 | 2015-08-18 | Mitsubishi Rayon, Co., Ltd. | Method for producing polymer, polymer for lithography, resist composition, and method for producing substrate |
| WO2022210319A1 (en) | 2021-03-31 | 2022-10-06 | 丸善石油化学株式会社 | Evaluation method for resist polymer |
-
2003
- 2003-09-12 JP JP2003320589A patent/JP4356407B2/en not_active Expired - Lifetime
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008096373A (en) * | 2006-10-16 | 2008-04-24 | Shimadzu Corp | Method and device for measuring nanoparticles |
| JP2009037184A (en) * | 2007-07-09 | 2009-02-19 | Jsr Corp | Method for evaluating resin, and radiation-sensitive resin composition |
| JP2009211044A (en) * | 2008-02-07 | 2009-09-17 | Jsr Corp | Evaluation method and radiation-sensitive resin composition |
| US9109060B2 (en) | 2009-07-07 | 2015-08-18 | Mitsubishi Rayon, Co., Ltd. | Method for producing polymer, polymer for lithography, resist composition, and method for producing substrate |
| CN102472982A (en) * | 2009-07-07 | 2012-05-23 | 三菱丽阳株式会社 | Copolymer for lithography and method for evaluating the same |
| KR20140099504A (en) | 2009-07-07 | 2014-08-12 | 미츠비시 레이온 가부시키가이샤 | Copolymer for lithography and method for evaluating same |
| US9023578B2 (en) | 2009-07-07 | 2015-05-05 | Mitsubishi Rayon Co., Ltd. | Copolymer for lithography and method for evaluating the same |
| WO2011004787A1 (en) * | 2009-07-07 | 2011-01-13 | 三菱レイヨン株式会社 | Copolymer for lithography and method for evaluating same |
| JP5845578B2 (en) * | 2009-07-07 | 2016-01-20 | 三菱レイヨン株式会社 | Method for evaluating a copolymer for lithography |
| US9296842B2 (en) | 2009-07-07 | 2016-03-29 | Mitsubishi Rayon Co., Ltd. | Polymer for lithography |
| JP2011048354A (en) * | 2009-07-28 | 2011-03-10 | Mitsubishi Rayon Co Ltd | Evaluation method of copolymer for lithography |
| JP2013214032A (en) * | 2012-03-07 | 2013-10-17 | Mitsubishi Rayon Co Ltd | Evaluation method of polymer for semiconductor lithography, and manufacturing method of polymer for semiconductor lithography including the evaluation method |
| WO2022210319A1 (en) | 2021-03-31 | 2022-10-06 | 丸善石油化学株式会社 | Evaluation method for resist polymer |
| KR20230164650A (en) | 2021-03-31 | 2023-12-04 | 마루젠 세끼유가가꾸 가부시키가이샤 | Method for evaluating polymers for resists |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4356407B2 (en) | 2009-11-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5141459B2 (en) | Radiation sensitive resin composition | |
| WO2010029965A1 (en) | Radiation-sensitive resin composition | |
| JP2010282189A (en) | Radiation-sensitive resin composition | |
| JP2009134088A (en) | Radiation-sensitive resin composition | |
| JP5565443B2 (en) | Acrylic copolymer and radiation-sensitive resin composition | |
| JP2010254960A (en) | Polymer and positive-tone radiation-sensitive resin composition | |
| JP2004210917A (en) | (meth)acrylic polymer and radiation-sensitive resin composition | |
| JP2005255742A (en) | (meth)acrylic acid polymer and radiation-sensitive resin composition | |
| JP4356407B2 (en) | Evaluation method of radiation sensitive resin | |
| JP5311089B2 (en) | Method for evaluating resist solvent solution and radiation-sensitive resin composition | |
| JP5333227B2 (en) | Radiation-sensitive composition and method for forming photoresist pattern | |
| JP5304204B2 (en) | Polymer and radiation-sensitive resin composition | |
| JP5051232B2 (en) | Radiation sensitive resin composition and pattern forming method | |
| JP2005023234A (en) | Acrylic polymer and radiation-sensitive resin composition | |
| JP5176909B2 (en) | Polymer and radiation-sensitive resin composition | |
| JP4765625B2 (en) | Acrylic polymer and radiation-sensitive resin composition | |
| JP2004176049A (en) | Acrylic copolymer and radiation-sensitive resin composition | |
| JP2005068418A (en) | Acrylic polymer and radiation-sensitive resin composition | |
| JP2010152349A (en) | Polymer and radiation sensitive resin composition | |
| JP5510086B2 (en) | (Meth) acrylic acid polymer and radiation sensitive resin composition | |
| JP2010160348A (en) | Radiation-sensitive resin composition and polymer | |
| JP5077354B2 (en) | Radiation sensitive composition | |
| JP2009211044A (en) | Evaluation method and radiation-sensitive resin composition | |
| JP2004157199A (en) | Radiation-sensitive resin composition | |
| JPWO2008133270A1 (en) | Radiation sensitive resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20051020 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20051104 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20081021 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20081126 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090317 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090401 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20090714 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20090727 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120814 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4356407 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120814 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120814 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130814 Year of fee payment: 4 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |