WO2023017702A1 - 感活性光線性又は感放射線性樹脂組成物、感活性光線性又は感放射線性膜、パターン形成方法及び電子デバイスの製造方法 - Google Patents
感活性光線性又は感放射線性樹脂組成物、感活性光線性又は感放射線性膜、パターン形成方法及び電子デバイスの製造方法 Download PDFInfo
- Publication number
- WO2023017702A1 WO2023017702A1 PCT/JP2022/027517 JP2022027517W WO2023017702A1 WO 2023017702 A1 WO2023017702 A1 WO 2023017702A1 JP 2022027517 W JP2022027517 W JP 2022027517W WO 2023017702 A1 WO2023017702 A1 WO 2023017702A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- atom
- sensitive
- groups
- general formula
- Prior art date
Links
- 230000005855 radiation Effects 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000011342 resin composition Substances 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 230000007261 regionalization Effects 0.000 title abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 183
- 239000002253 acid Substances 0.000 claims abstract description 179
- 239000011347 resin Substances 0.000 claims abstract description 57
- 229920005989 resin Polymers 0.000 claims abstract description 57
- 230000009471 action Effects 0.000 claims abstract description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 233
- 125000003118 aryl group Chemical group 0.000 claims description 179
- 125000004432 carbon atom Chemical group C* 0.000 claims description 161
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 153
- 125000001424 substituent group Chemical group 0.000 claims description 138
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 92
- 125000000962 organic group Chemical group 0.000 claims description 90
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 84
- 125000005647 linker group Chemical group 0.000 claims description 69
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 60
- 125000003342 alkenyl group Chemical group 0.000 claims description 43
- 229910052757 nitrogen Inorganic materials 0.000 claims description 43
- 125000005843 halogen group Chemical group 0.000 claims description 41
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 39
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 34
- 125000004434 sulfur atom Chemical group 0.000 claims description 34
- 125000002947 alkylene group Chemical group 0.000 claims description 31
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 29
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 28
- 229910052717 sulfur Inorganic materials 0.000 claims description 26
- 125000004429 atom Chemical group 0.000 claims description 22
- 101000836268 Homo sapiens U4/U6.U5 tri-snRNP-associated protein 1 Proteins 0.000 claims description 4
- 102100027244 U4/U6.U5 tri-snRNP-associated protein 1 Human genes 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 3
- 239000000203 mixture Substances 0.000 abstract description 63
- 238000011161 development Methods 0.000 abstract description 23
- 230000018109 developmental process Effects 0.000 abstract description 23
- 230000007547 defect Effects 0.000 abstract description 14
- -1 nitrogen-containing compound Chemical class 0.000 description 86
- 238000010494 dissociation reaction Methods 0.000 description 85
- 230000005593 dissociations Effects 0.000 description 85
- 125000001153 fluoro group Chemical group F* 0.000 description 84
- 229910052731 fluorine Inorganic materials 0.000 description 75
- 125000000524 functional group Chemical group 0.000 description 54
- 150000001768 cations Chemical class 0.000 description 49
- 125000000129 anionic group Chemical group 0.000 description 45
- 150000002430 hydrocarbons Chemical group 0.000 description 41
- 150000001450 anions Chemical class 0.000 description 37
- 230000002378 acidificating effect Effects 0.000 description 36
- 239000010408 film Substances 0.000 description 31
- 125000002950 monocyclic group Chemical group 0.000 description 31
- 125000000623 heterocyclic group Chemical group 0.000 description 30
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 28
- 125000005842 heteroatom Chemical group 0.000 description 27
- 150000002892 organic cations Chemical class 0.000 description 26
- 229910052799 carbon Inorganic materials 0.000 description 25
- 125000003367 polycyclic group Chemical group 0.000 description 25
- 239000002904 solvent Substances 0.000 description 24
- 125000004122 cyclic group Chemical group 0.000 description 23
- 125000003545 alkoxy group Chemical group 0.000 description 22
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 21
- 150000001721 carbon Chemical group 0.000 description 21
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 21
- 238000009792 diffusion process Methods 0.000 description 19
- 229910052740 iodine Inorganic materials 0.000 description 19
- 125000003277 amino group Chemical group 0.000 description 18
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 17
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 17
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical class OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 16
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 16
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 16
- 239000007787 solid Substances 0.000 description 16
- 150000008053 sultones Chemical group 0.000 description 16
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 15
- 150000003839 salts Chemical class 0.000 description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 14
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 13
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 13
- 125000001624 naphthyl group Chemical group 0.000 description 13
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 12
- 150000007514 bases Chemical class 0.000 description 12
- 125000002993 cycloalkylene group Chemical group 0.000 description 12
- 238000010894 electron beam technology Methods 0.000 description 12
- 150000002596 lactones Chemical group 0.000 description 12
- 150000003384 small molecules Chemical class 0.000 description 12
- 239000004094 surface-active agent Substances 0.000 description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 11
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- 230000035945 sensitivity Effects 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- 125000004450 alkenylene group Chemical group 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 230000000269 nucleophilic effect Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 125000001931 aliphatic group Chemical group 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 7
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 125000000732 arylene group Chemical group 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 7
- 125000000686 lactone group Chemical group 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 7
- 125000006574 non-aromatic ring group Chemical group 0.000 description 7
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000007983 Tris buffer Substances 0.000 description 6
- 125000002723 alicyclic group Chemical group 0.000 description 6
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 6
- 125000003368 amide group Chemical group 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 6
- 150000002891 organic anions Chemical class 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical group C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 5
- 238000003775 Density Functional Theory Methods 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 125000004414 alkyl thio group Chemical group 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 125000004185 ester group Chemical group 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 4
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 4
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 4
- 229940077388 benzenesulfonate Drugs 0.000 description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 4
- 125000005587 carbonate group Chemical group 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 150000001924 cycloalkanes Chemical class 0.000 description 4
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 4
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 4
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 125000002883 imidazolyl group Chemical group 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 125000000542 sulfonic acid group Chemical group 0.000 description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 4
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical group FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- 125000004423 acyloxy group Chemical group 0.000 description 3
- 125000003158 alcohol group Chemical group 0.000 description 3
- 125000004104 aryloxy group Chemical group 0.000 description 3
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 3
- 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 3
- 125000006575 electron-withdrawing group Chemical group 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 125000003709 fluoroalkyl group Chemical group 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 125000005462 imide group Chemical group 0.000 description 3
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 3
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000004043 oxo group Chemical group O=* 0.000 description 3
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 3
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- 229910052711 selenium Chemical group 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 125000000547 substituted alkyl group Chemical group 0.000 description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 3
- 150000003512 tertiary amines Chemical group 0.000 description 3
- 125000000101 thioether group Chemical group 0.000 description 3
- NENLYAQPNATJSU-UHFFFAOYSA-N 1,2,3,4,4a,5,6,7,8,8a-decahydroisoquinoline Chemical group C1NCCC2CCCCC21 NENLYAQPNATJSU-UHFFFAOYSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical group C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-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
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 125000005142 aryl oxy sulfonyl group Chemical group 0.000 description 2
- RFRXIWQYSOIBDI-UHFFFAOYSA-N benzarone Chemical compound CCC=1OC2=CC=CC=C2C=1C(=O)C1=CC=C(O)C=C1 RFRXIWQYSOIBDI-UHFFFAOYSA-N 0.000 description 2
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 150000003983 crown ethers Chemical group 0.000 description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000004210 ether based solvent Substances 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
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000026045 iodination Effects 0.000 description 2
- 238000006192 iodination reaction Methods 0.000 description 2
- 239000011630 iodine Substances 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
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- LGRLWUINFJPLSH-UHFFFAOYSA-N methanide Chemical compound [CH3-] LGRLWUINFJPLSH-UHFFFAOYSA-N 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 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 2
- 239000000178 monomer Substances 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004957 naphthylene group Chemical group 0.000 description 2
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 125000006239 protecting group Chemical group 0.000 description 2
- 125000003373 pyrazinyl group Chemical group 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 125000003003 spiro group Chemical group 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 2
- 125000000565 sulfonamide group Chemical group 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 1
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 1
- UGUHFDPGDQDVGX-UHFFFAOYSA-N 1,2,3-thiadiazole Chemical group C1=CSN=N1 UGUHFDPGDQDVGX-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- DOVZUKKPYKRVIK-UHFFFAOYSA-N 1-methoxypropan-2-yl propanoate Chemical compound CCC(=O)OC(C)COC DOVZUKKPYKRVIK-UHFFFAOYSA-N 0.000 description 1
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- ZMZGFLUUZLELNE-UHFFFAOYSA-N 2,3,5-triiodobenzoic acid Chemical compound OC(=O)C1=CC(I)=CC(I)=C1I ZMZGFLUUZLELNE-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical group OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 description 1
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 description 1
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- AGIJRRREJXSQJR-UHFFFAOYSA-N 2h-thiazine Chemical compound N1SC=CC=C1 AGIJRRREJXSQJR-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical class CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 229910018286 SbF 6 Inorganic materials 0.000 description 1
- LINDOXZENKYESA-UHFFFAOYSA-N TMG Natural products CNC(N)=NC LINDOXZENKYESA-UHFFFAOYSA-N 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical group C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- 239000007877 V-601 Substances 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 125000004036 acetal group Chemical group 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical group C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 1
- 125000005078 alkoxycarbonylalkyl group Chemical group 0.000 description 1
- 125000005194 alkoxycarbonyloxy group Chemical group 0.000 description 1
- 125000004457 alkyl amino carbonyl group Chemical group 0.000 description 1
- 125000005196 alkyl carbonyloxy group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 125000004653 anthracenylene group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- GUNJVIDCYZYFGV-UHFFFAOYSA-K antimony trifluoride Chemical class F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 125000005100 aryl amino carbonyl group Chemical group 0.000 description 1
- 125000001769 aryl amino group Chemical group 0.000 description 1
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 1
- 125000005163 aryl sulfanyl group Chemical group 0.000 description 1
- 125000005110 aryl thio group Chemical group 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 125000001231 benzoyloxy group Chemical group C(C1=CC=CC=C1)(=O)O* 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical class FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000004744 butyloxycarbonyl group Chemical group 0.000 description 1
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004966 cyanoalkyl group Chemical group 0.000 description 1
- 150000005676 cyclic carbonates Chemical group 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 125000006310 cycloalkyl amino group Chemical group 0.000 description 1
- 125000005112 cycloalkylalkoxy group Chemical group 0.000 description 1
- 125000005201 cycloalkylcarbonyloxy group Chemical group 0.000 description 1
- 125000005170 cycloalkyloxycarbonyl group Chemical group 0.000 description 1
- 125000005144 cycloalkylsulfonyl group Chemical group 0.000 description 1
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000000298 cyclopropenyl group Chemical group [H]C1=C([H])C1([H])* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- CSCPPACGZOOCGX-WFGJKAKNSA-N deuterated acetone Substances [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical group C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 1
- IYYZUPMFVPLQIF-ALWQSETLSA-N dibenzothiophene Chemical group C1=CC=CC=2[34S]C3=C(C=21)C=CC=C3 IYYZUPMFVPLQIF-ALWQSETLSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000609 electron-beam lithography Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002497 iodine compounds Chemical class 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 1
- 150000002540 isothiocyanates Chemical class 0.000 description 1
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 238000001393 microlithography Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000004776 molecular orbital Methods 0.000 description 1
- MKQLBNJQQZRQJU-UHFFFAOYSA-N morpholin-4-amine Chemical compound NN1CCOCC1 MKQLBNJQQZRQJU-UHFFFAOYSA-N 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 125000004998 naphthylethyl group Chemical group C1(=CC=CC2=CC=CC=C12)CC* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- 238000007344 nucleophilic reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 125000006551 perfluoro alkylene group Chemical group 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000006678 phenoxycarbonyl group Chemical group 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- WKFBZNUBXWCCHG-UHFFFAOYSA-N phosphorus trifluoride Chemical class FP(F)F WKFBZNUBXWCCHG-UHFFFAOYSA-N 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 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
- SBMSLRMNBSMKQC-UHFFFAOYSA-N pyrrolidin-1-amine Chemical compound NN1CCCC1 SBMSLRMNBSMKQC-UHFFFAOYSA-N 0.000 description 1
- 125000002112 pyrrolidino group Chemical group [*]N1C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N pyrroline Natural products C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229940081974 saccharin Drugs 0.000 description 1
- 235000019204 saccharin Nutrition 0.000 description 1
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- QPILZZVXGUNELN-UHFFFAOYSA-M sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonate;hydron Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S([O-])(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-M 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000005156 substituted alkylene group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 125000005717 substituted cycloalkylene group Chemical group 0.000 description 1
- 125000005650 substituted phenylene group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 1
- 125000005463 sulfonylimide group Chemical group 0.000 description 1
- 125000003375 sulfoxide group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000008027 tertiary esters Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 125000005628 tolylene group Chemical group 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
Definitions
- the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and an electronic device manufacturing method. More specifically, the present invention provides an ultra-microlithography process applicable to ultra LSI (Large Scale Integration) and high-capacity microchip manufacturing processes, nanoimprint mold manufacturing processes, high-density information recording medium manufacturing processes, and the like.
- the present invention relates to an actinic ray- or radiation-sensitive resin composition, an actinic ray- or radiation-sensitive film, a pattern forming method, and an electronic device manufacturing method which are preferably used in other photofabrication processes.
- immersion liquid a liquid with a high refractive index
- Patent Documents 1 and 2 describe a resist composition containing a nitrogen-containing compound having an iodine atom as a quencher.
- LWR performance refers to performance that can reduce the LWR of a pattern.
- An actinic ray- or radiation-sensitive resin composition comprising a resin (A) whose polarity increases under the action of an acid and a compound represented by the following general formula (DA1).
- X1 represents a sulfur atom or NQ3 .
- Q3 represents a hydrogen atom, an organic group, -OH or -NH2 .
- Q1 represents a hydrogen atom or a substituent.
- X2 represents a linking group Xz or a single bond.
- the linking group Xz is a divalent linking group consisting of at least one atom selected from the group consisting of carbon atoms, oxygen atoms, nitrogen atoms and sulfur atoms.
- the nitrogen atom may be bonded to a hydrogen atom, an alkyl group, an aryl group or an aromatic heterocyclic group
- the sulfur atom may be bonded to a hydrocarbon group.
- Ar a1 represents an aromatic group.
- Q2 represents a hydrogen atom or an alkyl group.
- Q 1 and Q 2 may combine to form a ring.
- At least one selected from the group consisting of Q 1 and Q 2 and Q 3 may combine to form a ring.
- k represents an integer of 1 to 5;
- m represents an integer of 1 to 3;
- X 1 , X 2 , Q 1 , Q 2 , Q 3 and Ar a1 may be the same or different when there are a plurality of them. However, when n represents 0, the following condition (i) or (ii) is satisfied.
- X2 represents the above linking group Xz.
- X 2 in the general formula (DA1) represents a divalent linking group or a single bond represented by any of the following formulas (X2-1) to (X2-11). Actinic ray or radiation sensitive resin composition.
- Q4 and Q5 each independently represent a hydrogen atom, an alkyl group, an aryl group or an aromatic heterocyclic group.
- X3 and X4 each independently represent a single bond, a hydrocarbon group, an oxygen atom or NQ6 .
- Q6 represents a hydrogen atom, an alkyl group, an aryl group or an aromatic heterocyclic group.
- X5 represents an oxygen atom, a sulfur atom or NG1 .
- X 6 represents -SG 2 or -NG 3 G 4 .
- G 1 , G 3 and G 4 each independently represent a hydrogen atom, an alkyl group, an aryl group or an aromatic heterocyclic group.
- G2 represents a hydrocarbon group.
- the resin (A) is selected from the group consisting of repeating units represented by the following general formula (3), repeating units represented by the following general formula (6), and repeating units represented by the following general formula (7).
- Each of R 5 to R 7 independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
- L2 represents a divalent linking group.
- Each of R 8 to R 10 independently represents an alkyl group, cycloalkyl group, aryl group, aralkyl group or alkenyl group. Two of R 8 to R 10 may combine to form a ring.
- R 22 to R 24 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
- L4 represents a single bond or a divalent linking group.
- Ar 1 represents an aromatic group.
- R 25 to R 27 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
- R 26 and R 27 may combine to form a ring.
- R24 or R25 may be linked to Ar1 .
- R 28 to R 30 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
- L5 represents a single bond or a divalent linking group.
- R 31 and R 32 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
- R33 represents an alkyl group, cycloalkyl group, aryl group, aralkyl group or alkenyl group.
- R 32 and R 33 may combine to form a ring.
- R 101 , R 102 and R 103 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
- LA represents a single bond or a divalent linking group.
- Ar A represents an aromatic group.
- k represents an integer of 1 to 5; However, R 102 may be bonded to Ar 2 A , and when R 102 and Ar 2 are bonded, R 102 represents a single bond or an alkylene group.
- DA1 represents 1 or 2.
- a pattern forming method comprising: [12] A method for manufacturing an electronic device, including the pattern forming method according to [11].
- the present invention it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition that is excellent in EL performance and LWR performance and capable of reducing development defects. Further, the present invention can provide an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and an electronic device manufacturing method using the actinic ray-sensitive or radiation-sensitive resin composition.
- FIG. 1 is an NMR chart of compound (D-1) obtained in Synthesis Example 2.
- actinic ray or “radiation” refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV: Extreme Ultraviolet), X-rays, soft X-rays, and electron It means a line (EB: Electron Beam) or the like.
- light means actinic rays or radiation.
- exposure means, unless otherwise specified, not only the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, X-rays, and EUV exposure, but also electron beams and ion beams. It also includes drawing with particle beams such as beams.
- the bonding direction of the divalent groups described in this specification is not limited unless otherwise specified.
- Y when Y is -COO-, Y may be -CO-O- or -O-CO- may Further, the above compound may be "X--CO--O--Z" or "X--O--CO--Z.”
- (meth)acrylate represents at least one of acrylate and methacrylate.
- (Meth)acrylic acid represents at least one of acrylic acid and methacrylic acid.
- the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (also referred to as molecular weight distribution) (Mw/Mn) of the resin are measured by GPC (Gel Permeation Chromatography) equipment (HLC manufactured by Tosoh Corporation). -8120 GPC) by GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 ⁇ L, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40 ° C., flow rate: 1.0 mL / min, detector: It is defined as a polystyrene conversion value by a differential refractive index detector (Refractive Index Detector).
- GPC Gel Permeation Chromatography
- an "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
- organic group refers to a group containing at least one carbon atom.
- substituents in this specification, the type of substituents, the position of the substituents, and the number of substituents when "may have a substituent" are not particularly limited.
- the number of substituents can be, for example, one, two, three, or more.
- substituents include monovalent nonmetallic atomic groups excluding hydrogen atoms, and can be selected from the following substituents T, for example.
- the substituent T includes halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; alkoxy groups such as a methoxy group, an ethoxy group and a tert-butoxy group; an aryloxy group such as a phenoxy group and a p-tolyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group; acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and methoxalyl group, etc.
- halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom
- alkoxy groups such as a me
- an acyl group an alkylsulfanyl group such as a methylsulfanyl group and a tert-butylsulfanyl group; an arylsulfanyl group such as a phenylsulfanyl group and a p-tolylsulfanyl group; aryl group (e.g., 6 to 20 carbon atoms); heteroaryl group; hydroxyl group; carboxy group; formyl group; sulfo group; silyl groups; amino groups; monoalkylamino groups; dialkylamino groups; arylamino groups, nitro groups;
- the acid dissociation constant (pKa) represents the pKa in an aqueous solution. , is a calculated value. All pKa values described herein are calculated using this software package.
- Software Package 1 Advanced Chemistry Development (ACD/Labs) Software V8.14 for Solaris (1994-2007 ACD/Labs).
- pKa can also be obtained by molecular orbital calculation.
- a specific method for this is a method of calculating the H 2 + dissociation free energy in the solvent based on the thermodynamic cycle.
- water is usually used as the solvent, and DMSO (dimethylsulfoxide) is used when the pKa cannot be obtained with water.
- the H + dissociation free energy can be calculated by, for example, DFT (density functional theory), but various other methods have been reported in literature and the like, and the method is not limited to this. Note that there are a plurality of software that can implement DFT, and Gaussian16 is an example.
- the pKa in the present specification refers to a value obtained by calculating a value based on a database of Hammett's substituent constants and known literature values using Software Package 1, as described above. If it cannot be calculated, a value obtained by Gaussian 16 based on DFT (density functional theory) is adopted.
- the actinic ray-sensitive or radiation-sensitive resin composition of the present invention (also referred to as “the composition of the present invention”) comprises a resin (A) whose polarity increases under the action of an acid, and a resin represented by the following general formula (DA1). It is an actinic ray-sensitive or radiation-sensitive resin composition containing the compound.
- X1 represents a sulfur atom or NQ3 .
- Q3 represents a hydrogen atom, an organic group, -OH or -NH2 .
- Q1 represents a hydrogen atom or a substituent.
- X2 represents a linking group Xz or a single bond.
- the linking group Xz is a divalent linking group consisting of at least one atom selected from the group consisting of carbon atoms, oxygen atoms, nitrogen atoms and sulfur atoms.
- the nitrogen atom may be bonded to a hydrogen atom, an alkyl group, an aryl group or an aromatic heterocyclic group
- the sulfur atom may be bonded to a hydrocarbon group.
- Ar a1 represents an aromatic group.
- Q2 represents a hydrogen atom or an alkyl group.
- Q 1 and Q 2 may combine to form a ring.
- At least one selected from the group consisting of Q 1 and Q 2 and Q 3 may combine to form a ring.
- k represents an integer of 1 to 5;
- m represents an integer of 1 to 3;
- X 1 , X 2 , Q 1 , Q 2 , Q 3 and Ar a1 may be the same or different when there are a plurality of them. However, when n represents 0, the following condition (i) or (ii) is satisfied.
- Condition (i): X2 represents a single bond and Ar a1 represents an aromatic heterocyclic group.
- X2 represents the above linking group Xz.
- the composition of the present invention is preferably a resist composition, and may be a positive resist composition or a negative resist composition. Moreover, it may be a resist composition for alkali development or a resist composition for organic solvent development.
- the composition of the present invention is preferably a positive resist composition.
- the composition of the present invention is preferably a resist composition for alkali development.
- the composition of the present invention is preferably a chemically amplified resist composition, more preferably a chemically amplified positive resist composition.
- the composition of the present invention contains a compound represented by general formula (DA1).
- the compound represented by the general formula (DA1) is a nitrogen-containing compound having an aromatic group substituted with an iodine atom, and has a polar group around the nitrogen atom that does not reduce the basicity of the nitrogen atom. Due to such a structure, the compound represented by the general formula (DA1) is highly basic and has sufficiently high ability to quench the generated acid, so it is considered to have good LWR performance.
- a polar group has a high effect of suppressing acid diffusion due to hydrogen bonding, resulting in good EL performance. Furthermore, it is believed that the hydrophilicity of the polar group improves the solubility in an aqueous developer such as an alkaline developer, which is a typical developer, so that development defects can be suppressed.
- X1 represents a sulfur atom or NQ3 .
- X 1 preferably represents NQ 3 .
- Q3 represents a hydrogen atom, an organic group, -OH or -NH2 .
- the organic group is not particularly limited, but an organic group having 1 to 20 carbon atoms is preferable, and an organic group having 1 to 10 carbon atoms is more preferable.
- the organic group is preferably an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, -OQ 3a or -NQ 3b Q 3c .
- Q 3a represents an organic group.
- Q3b represents an organic group.
- Q3c represents a hydrogen atom or an organic group.
- the alkyl group may be linear or branched. Moreover, the said alkyl group may have a substituent.
- the above alkyl group is preferably an alkyl group having 1 to 10 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group, and 1 to 6 carbon atoms. is more preferred.
- the cycloalkyl group when Q3 represents a cycloalkyl group may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group.
- the cycloalkyl group preferably has 3 to 20 carbon atoms, more preferably 4 to 15 carbon atoms, and still more preferably 5 to 10 carbon atoms.
- the cycloalkyl group may have a substituent.
- the cycloalkyl group is preferably a monocyclic cycloalkyl group such as cyclopentyl group or cyclohexyl group, or a polycyclic cycloalkyl group such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group or adamantyl group.
- the aryl group when Q3 represents an aryl group may be a monocyclic aryl group or a polycyclic aryl group. Moreover, the aryl group may have a substituent. As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 10 carbon atoms is more preferable, and examples thereof include a phenyl group, a naphthyl group and an anthryl group.
- the alkenyl group may be linear or branched. Moreover, the said alkenyl group may have a substituent.
- the alkenyl group an alkenyl group having 2 to 10 carbon atoms such as a vinyl group is preferable, and an alkenyl group having 2 to 6 carbon atoms is more preferable.
- the heterocyclic group is preferably an aromatic heterocyclic group or a non-aromatic heterocyclic group.
- the aromatic heterocyclic group is an aromatic heterocyclic group containing at least one heteroatom selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom.
- a cyclic group is preferred, and an aromatic heterocyclic group containing one or more nitrogen atoms is more preferred.
- the aromatic heterocyclic group includes, for example, five-membered ring aromatic heterocyclic compounds containing one or more nitrogen atoms such as pyrrole, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, triazole, etc.
- Removed groups, and groups obtained by removing one hydrogen atom from six-membered aromatic heterocyclic compounds containing one or more nitrogen atoms such as pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiazine, and oxazine.
- the aromatic heterocyclic group is such that the five-membered aromatic heterocyclic compound or the six-membered aromatic heterocyclic compound is the five-membered aromatic heterocyclic compound, the six-membered aromatic heterocyclic compound, Aromatic hydrocarbons (e.g., benzene, naphthalene, etc.), cycloalkanes (e.g., cyclopentane, cyclohexane, etc.), and non-aromatic heterocyclic compounds (e.g., five-membered non-aromatic heterocyclic compounds described later, six-membered rings It may be a group obtained by removing one hydrogen atom from a compound condensed with at least one member selected from the group consisting of non-aromatic heterocyclic compounds (eg, indole, quinoline, isoquinoline, etc.).
- the aromatic heterocyclic group may have a substituent.
- a carbon atom contained as a ring member in the aromatic heterocyclic group may be substitute
- the non-aromatic heterocyclic group includes at least one heteroatom selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom. are preferred, and non-aromatic heterocyclic groups containing one or more nitrogen atoms are more preferred.
- Non-aromatic heterocyclic groups include, for example, groups obtained by removing one hydrogen atom from five-membered ring non-aromatic heterocyclic compounds containing one or more nitrogen atoms such as pyrrolidine, pyrroline, 2-oxazolidone, and morpholine, A group obtained by removing one hydrogen atom from a six-membered ring non-aromatic heterocyclic compound containing one or more nitrogen atoms, such as piperidine and piperazine.
- the five-membered non-aromatic heterocyclic compound or the six-membered non-aromatic heterocyclic compound is the five-membered non-aromatic heterocyclic compound or the six-membered non-aromatic It may be a group obtained by removing one hydrogen atom from a compound condensed with at least one member selected from the group consisting of group heterocyclic compounds and cycloalkanes (eg, cyclopentane, cyclohexane, etc.).
- the non-aromatic heterocyclic group may have a substituent.
- Q3 preferably represents a hydrogen atom or an organic group, more preferably a hydrogen atom, an alkyl group, an alkenyl group or an aryl group.
- Q1 represents a hydrogen atom or a substituent.
- the substituent is not particularly limited, but is preferably an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group or an amino group.
- Q 1 represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group
- the description, specific examples and preferred ranges of each group are as follows: or the same as those described for each group when representing a heterocyclic group.
- the amino group when Q 1 represents an amino group may have a substituent.
- the amino group is preferably represented by -NQ 1a Q 1b .
- Q 1a and Q 1b each independently represent a hydrogen atom or a substituent, and Q 1a and Q 1b may combine to form a ring.
- the substituent is not particularly limited, but an organic group is preferred. Examples of the organic group include alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, heterocyclic groups, and groups represented by the following general formula (na1).
- alkyl group, cycloalkyl group, alkenyl group, aryl group, and heterocyclic group described above are for the case where Q3 represents an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or a heterocyclic group. It is the same as described for each group.
- * represents the bonding position with the nitrogen atom of the amino group represented by Q1 .
- Xq represents O, S or NQ7 .
- Q7 , Q8 and Q9 each independently represent a hydrogen atom, an amino group, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group. At least two selected from the group consisting of Q 7 , Q 8 and Q 9 may combine to form a ring.
- Xq preferably represents NQ7 .
- Q 7 , Q 8 and Q 9 represent an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group
- the description, specific examples and preferred ranges of each group are as follows:
- Q 3 is an alkyl group, a cycloalkyl group , an alkenyl group, an aryl group or a heterocyclic group are the same as those described for each group.
- the ring formed may be an aromatic ring or a non-aromatic ring.
- the rings may be monocyclic (eg, five- or six-membered rings) or polycyclic.
- the ring may contain at least one member selected from the group consisting of an oxygen atom and a sulfur atom.
- the ring may have a substituent.
- Q 7 , Q 8 and Q 9 preferably represent a hydrogen atom or an alkyl group.
- the description of the ring when Q 1a and Q 1b combine to form a ring is the one described when at least two selected from the group consisting of Q 7 , Q 8 and Q 9 combine to form a ring. is similar to
- Q 1 preferably represents a substituent containing a nitrogen atom.
- X2 represents a linking group Xz or a single bond.
- the linking group Xz is a divalent linking group consisting of at least one atom selected from the group consisting of carbon atoms, oxygen atoms, nitrogen atoms and sulfur atoms.
- the nitrogen atom may be bonded to a hydrogen atom, an alkyl group, an aryl group or an aromatic heterocyclic group
- the sulfur atom may be bonded to a hydrocarbon group.
- X2 does not consist only of divalent hydrocarbon groups. Also, X2 does not consist of a divalent hydrocarbon group and at least one selected from an ester bond and an ether bond.
- X 2 preferably represents a divalent linking group or a single bond represented by any one of formulas (X2-1) to (X2-11) below.
- Q4 and Q5 each independently represent a hydrogen atom, an alkyl group, an aryl group or an aromatic heterocyclic group.
- X3 and X4 each independently represent a single bond, a hydrocarbon group, an oxygen atom or NQ6 .
- Q6 represents a hydrogen atom, an alkyl group, an aryl group or an aromatic heterocyclic group.
- X5 represents an oxygen atom, a sulfur atom or NG1 .
- X 6 represents -SG 2 or -NG 3 G 4 .
- G 1 , G 3 and G 4 each independently represent a hydrogen atom, an alkyl group, an aryl group or an aromatic heterocyclic group.
- G2 represents a hydrocarbon group.
- *1 represents the bonding position with the nitrogen atom in general formula (DA1)
- *2 represents the bonding position with Ara1 in general formula (DA1).
- Q 4 and Q 5 each independently represent a hydrogen atom, an alkyl group, an aryl group or an aromatic heterocyclic group.
- Q4 and Q5 represent an alkyl group, an aryl group, or an aromatic heterocyclic group
- the description, specific examples, and preferred ranges of each group are those when Q3 represents an alkyl group, an aryl group, or an aromatic heterocyclic group. are the same as those described for each group.
- X3 and X4 each independently represent a single bond, hydrocarbon group, oxygen atom or NQ6 .
- the hydrocarbon group is preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrocarbon group having 1 to 10 carbon atoms.
- the hydrocarbon group is preferably an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group.
- the description, specific examples and preferred range of the above alkyl group, cycloalkyl group, alkenyl group or aryl group are the same as those described for each group when Q3 represents an alkyl group, cycloalkyl group, alkenyl group or aryl group. is.
- Q6 represents a hydrogen atom, an alkyl group, an aryl group or an aromatic heterocyclic group.
- the description, specific examples and preferred ranges of each group when Q6 represents an alkyl group, an aryl group or an aromatic heterocyclic group are the respective groups when Q3 represents an alkyl group, an aryl group or an aromatic heterocyclic group. is the same as described for
- X5 represents an oxygen atom, a sulfur atom or NG1 .
- G1 represents a hydrogen atom, an alkyl group, an aryl group or an aromatic heterocyclic group. Description, specific examples and preferred ranges of each group when G 1 represents an alkyl group, an aryl group or an aromatic heterocyclic group refer to each group when Q 3 represents an alkyl group, an aryl group or an aromatic heterocyclic group is the same as described for X5 preferably represents an oxygen atom.
- X 6 represents -SG 2 or -NG 3 G 4 .
- G2 represents a hydrocarbon group.
- G3 and G4 each independently represent a hydrogen atom, an alkyl group, an aryl group or an aromatic heterocyclic group.
- the description, specific examples and preferred range of the hydrocarbon group represented by G 2 are the same as those described when X 3 and X 4 represent the hydrocarbon group.
- the description, specific examples and preferred ranges of each group when G3 and G4 represent an alkyl group, an aryl group or an aromatic heterocyclic group are those when Q3 represents an alkyl group, an aryl group or an aromatic heterocyclic group. are the same as those described for each group.
- X 6 preferably represents -NG 3 G 4 .
- X 2 is a divalent linking group or a single bond represented by any one selected from the group consisting of the above formulas (X2-1), (X2-3), (X2-4) and (X2-11) It is more preferable to express
- Ar a1 represents an aromatic group.
- the aromatic group represented by Ar a1 is preferably an aryl group or an aromatic heterocyclic group. Specific examples and preferred ranges when Ar a1 represents an aryl group or an aromatic heterocyclic group are the same as those described for each group when Q3 represents an aryl group or an aromatic heterocyclic group.
- the aromatic group represented by Ara1 has k iodine atoms as substituents.
- the aromatic group represented by Ar a1 may have a substituent in addition to k iodine atoms. Examples of the substituent include the substituent T described above.
- Ar a1 preferably represents an aromatic heterocyclic group containing a nitrogen atom.
- n in the general formula (DA1) represents 0 and satisfies the above condition (ii)
- the description, specific examples and preferred range of the linking group Xz represented by X 2 are as described above, but X 2 is the above formula It is particularly preferred to represent a divalent linking group represented by (X2-11).
- Q2 represents a hydrogen atom or an alkyl group. Specific examples and preferred ranges when Q 2 represents an alkyl group are the same as those described when Q 3 represents an alkyl group.
- Q 1 and Q 2 may combine to form a ring.
- a ring in which Q 1 and Q 2 combine to form a ring is also referred to as “ring Qr”.
- Ring Qr may be monocyclic or polycyclic. In the case of a monocyclic ring, a 5- or 6-membered ring is preferred.
- the ring Qr contains at least one nitrogen atom as a ring member, and may further contain at least one ring member selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom.
- Ring Qr may be an aromatic ring or a non-aromatic ring.
- the aromatic ring includes, for example, the five-membered aromatic heterocyclic compound containing one or more nitrogen atoms described in the case where Q3 represents an aromatic heterocyclic group, A six-membered aromatic heterocyclic compound containing one or more, the five-membered aromatic heterocyclic compound, or the six-membered aromatic heterocyclic compound is the five-membered aromatic heterocyclic compound, the six-membered aromatic heterocyclic compound A ring structure possessed by a compound condensed with at least one selected from the group consisting of ring compounds, aromatic hydrocarbons, cycloalkanes, and non-aromatic heterocyclic compounds.
- the non-aromatic ring when the ring Qr is a non-aromatic ring includes, for example, the five-membered ring non-aromatic heterocyclic compounds containing one or more nitrogen atoms described when Q 3 represents a non-aromatic heterocyclic group,
- a six-membered non-aromatic heterocyclic compound containing one or more nitrogen atoms, the five-membered non-aromatic heterocyclic compound, or the six-membered non-aromatic heterocyclic compound is the five-membered non-aromatic heterocyclic compound , the above-mentioned six-membered non-aromatic heterocyclic compounds, and compounds condensed with at least one selected from the group consisting of cycloalkanes.
- Ring Qr may have a substituent.
- At least one selected from the group consisting of Q 1 and Q 2 and Q 3 may combine to form a ring.
- Q1 and Q3 may combine to form a ring, or Q2 and Q3 may combine to form a ring.
- a ring in which at least one selected from the group consisting of Q 1 and Q 2 and Q 3 combine to form a ring is also referred to as “ring Qs”.
- the description, specific examples and preferred range of the ring Qs are the same as those described for the ring Qr.
- k represents an integer of 1 to 5, preferably an integer of 1 to 3.
- I in Ik in general formula (DA1) is an iodine atom.
- m represents an integer of 1 to 3, preferably 1 or 2.
- n and p each independently represent an integer of 0 to 2.
- n represents 1 or 2
- n represents 0, the above condition (ii) is satisfied
- X 2 is represented by the above formula (X2-11) It preferably represents a divalent linking group.
- the pKa of the conjugate acid of the compound represented by the general formula (DA1) is preferably 0.1 or more, more preferably 2 or more from the viewpoint of quenching the acid, and further preferably 3 to 15. 3.5 to 12 is particularly preferred. It is particularly preferred that n in the general formula (DA1) represents 1 or 2 and the pKa of the conjugate acid of the compound represented by the general formula (DA1) is 2 or more.
- the molecular weight of the compound represented by the general formula (DA1) is not particularly limited, it is preferably 2000 or less, more preferably 1500 or less, and particularly preferably 1000 or less.
- the compound represented by general formula (DA1) is preferably a nonionic compound.
- the compounds represented by general formula (DA1) may be used singly or in combination of two or more.
- the content of the compound represented by the general formula (DA1) (the total if multiple types exist) is based on the total solid content of the composition of the present invention, 0.001 to 40 % by mass is preferable, 0.01 to 30% by mass is more preferable, and 0.1 to 20% by mass is even more preferable.
- solid content intends the component except the solvent in a composition, and if it is a component other than a solvent, even if it is a liquid component, it will be considered as solid content.
- the method for synthesizing the compound represented by the general formula (DA1) is not particularly limited, but for example, it may be synthesized by condensing an iodine-containing aromatic carboxylic acid derivative, a sulfonic acid derivative, an isocyanate, an isothiocyanate, or the like with a corresponding nitrogen-containing compound. (Examples of synthetic routes are shown below.
- X 1 , Q 1 , n, Q 2 , p, Ar a1 and k are respectively X 1 , Q 1 , n, Q 2 , has the same meaning as p, Ar a1 and k, Y represents a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, a sulfooxy group or a halogen atom, and Z represents an oxygen atom or a sulfur atom). It can also be synthesized by iodination of the corresponding aromatic compound. With regard to iodination, for example, reference can be made to "Suzuki Futomi Supervised, Manac Co., Ltd. Research Institute, Organic Synthetic Reagents and Synthetic Methods of Bromine and Iodine Compounds (2017). Maruzen Publishing" and the like.
- Resin (A) is a resin that is decomposed by the action of an acid to increase its polarity.
- the resin (A) preferably contains a group that is decomposed by the action of an acid to increase its polarity (also referred to as an "acid-decomposable group"), and more preferably contains a repeating unit having an acid-decomposable group.
- the resin (A) becomes more polar under the action of an acid, increases its solubility in an alkaline developer, and decreases its solubility in an organic solvent.
- a positive pattern is typically formed when an alkaline developer is employed as the developer, and an organic developer is typically used as the developer. When employed, a negative pattern is formed.
- the acid-decomposable group is preferably a group that is decomposed by the action of an acid to form a polar group.
- the acid-decomposable group preferably has a structure in which the polar group is protected with a leaving group that leaves under the action of an acid. That is, the resin (A) preferably has a repeating unit having a group that is decomposed by the action of an acid to form a polar group.
- the polar group is preferably an alkali-soluble group such as a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphoric acid group, a sulfonamide group, a sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl)(alkylcarbonyl)imide group, bis(alkylcarbonyl)methylene group, bis(alkylcarbonyl)imide group, bis(alkylsulfonyl)methylene group, bis(alkylsulfonyl)imide group, tris(alkylcarbonyl) ) methylene group, acidic groups such as tris(alkylsulfonyl)methylene group, alcoholic hydroxyl group, and the like.
- alkali-soluble group such as a carboxy group, a
- the polar group is preferably a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group, more preferably a carboxy group or a phenolic hydroxyl group.
- the acid-decomposable group is preferably a group that is decomposed by the action of an acid to form a carboxyl group or a group that is decomposed by the action of an acid to form a phenolic hydroxyl group.
- the resin (A) contains a repeating unit having at least one acid-decomposable group selected from the group consisting of a group that decomposes under the action of an acid to yield a carboxyl group and a group that decomposes under the action of an acid to yield a phenolic hydroxyl group. It is preferable to have
- Examples of the leaving group that leaves by the action of an acid include groups represented by formulas (Y1) to (Y4).
- Formula (Y1) -C(Rx 1 )(Rx 2 )(Rx 3 )
- Formula (Y3) —C(R 36 )(R 37 )(OR 38 )
- Rx 1 to Rx 3 each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an aryl group (monocyclic or polycyclic), an aralkyl group (linear or branched), or an alkenyl group (linear or branched).
- Rx 1 to Rx 3 are alkyl groups (linear or branched)
- at least two of Rx 1 to Rx 3 are preferably methyl groups.
- Rx 1 to Rx 3 preferably each independently represent a linear or branched alkyl group, and Rx 1 to Rx 3 each independently represent a linear alkyl group. is more preferred.
- Two of Rx 1 to Rx 3 may combine with each other to form a ring (either monocyclic or polycyclic).
- the alkyl group of Rx 1 to Rx 3 is preferably an alkyl group having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group.
- the cycloalkyl groups represented by Rx 1 to Rx 3 include monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, and polycyclic groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl and adamantyl groups. is preferred.
- the aryl group represented by Rx 1 to Rx 3 is preferably an aryl group having 6 to 10 carbon atoms, such as phenyl group, naphthyl group and anthryl group.
- the aralkyl group represented by Rx 1 to Rx 3 is preferably a group in which one hydrogen atom in the alkyl group represented by Rx 1 to Rx 3 is substituted with an aryl group having 6 to 10 carbon atoms (preferably a phenyl group), For example, a benzyl group and the like can be mentioned.
- a vinyl group is preferable as the alkenyl group for Rx 1 to Rx 3 .
- the ring formed by combining two of Rx 1 to Rx 3 is preferably a cycloalkyl group.
- the cycloalkyl group formed by combining two of Rx 1 to Rx 3 includes a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, and a tetracyclododecanyl group. or a polycyclic cycloalkyl group such as an adamantyl group, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms.
- the cycloalkyl group formed by combining two of Rx 1 to Rx 3 is, for example, a group in which one of the methylene groups constituting the ring has a heteroatom such as an oxygen atom, a heteroatom such as a carbonyl group, or a vinylidene group may be substituted.
- these cycloalkyl groups one or more ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.
- Rx 1 is a methyl group or an ethyl group
- Rx 2 and Rx 3 combine to form the above-described cycloalkyl group. is preferred.
- R 36 to R 38 each independently represent a hydrogen atom or a monovalent organic group.
- R 37 and R 38 may combine with each other to form a ring.
- Monovalent organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkenyl groups, and the like. It is also preferred that R 36 is a hydrogen atom.
- the alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a heteroatom such as an oxygen atom and/or a group having a heteroatom such as a carbonyl group.
- one or more methylene groups are replaced with a heteroatom such as an oxygen atom and/or a group having a heteroatom such as a carbonyl group.
- R 38 may combine with another substituent of the main chain of the repeating unit to form a ring.
- the group formed by bonding R 38 and another substituent of the main chain of the repeating unit to each other is preferably an alkylene group such as a methylene group.
- L 1 and L 2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining these (for example, a group combining an alkyl group and an aryl group).
- M represents a single bond or a divalent linking group.
- Q is an alkyl group optionally containing a heteroatom, a cycloalkyl group optionally containing a heteroatom, an aryl group optionally containing a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group in which these are combined (for example, a group in which an alkyl group and a cycloalkyl group are combined).
- Alkyl and cycloalkyl groups may, for example, have one of the methylene groups replaced by a heteroatom such as an oxygen atom or a heteroatom-bearing group such as a carbonyl group.
- L 1 and L 2 is preferably a hydrogen atom, and the other is preferably an alkyl group, a cycloalkyl group, an aryl group, or a combination of an alkylene group and an aryl group. At least two of Q, M, and L1 may combine to form a ring (preferably a 5- or 6-membered ring).
- L2 is preferably a secondary or tertiary alkyl group, more preferably a tertiary alkyl group.
- Secondary alkyl groups include isopropyl, cyclohexyl and norbornyl groups, and tertiary alkyl groups include tert-butyl and adamantane groups.
- the Tg (glass transition temperature) and the activation energy are increased, so that the film strength can be ensured and fogging can be suppressed.
- Ar represents an aromatic ring group.
- Rn represents an alkyl group, a cycloalkyl group, or an aryl group.
- Rn and Ar may combine with each other to form a non-aromatic ring.
- Ar is more preferably an aryl group.
- the ring member atoms adjacent to the ring member atoms directly bonded to the polar group (or residue thereof) do not have halogen atoms such as fluorine atoms as substituents.
- the leaving group that leaves by the action of an acid also includes a 2-cyclopentenyl group having a substituent (such as an alkyl group) such as a 3-methyl-2-cyclopentenyl group, and a 1,1,4 , 4-tetramethylcyclohexyl group having a substituent (such as an alkyl group) may also be used.
- a 2-cyclopentenyl group having a substituent such as an alkyl group
- a 1,1,4 , 4-tetramethylcyclohexyl group having a substituent such as an alkyl group
- the resin (A) is selected from the group consisting of repeating units represented by the following general formula (3), repeating units represented by the following general formula (6), and repeating units represented by the following general formula (7). It is preferred to have at least one
- Each of R 5 to R 7 independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
- L2 represents a divalent linking group.
- Each of R 8 to R 10 independently represents an alkyl group, cycloalkyl group, aryl group, aralkyl group or alkenyl group. Two of R 8 to R 10 may combine to form a ring.
- R 22 to R 24 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
- L4 represents a single bond or a divalent linking group.
- Ar 1 represents an aromatic group.
- R 25 to R 27 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
- R 26 and R 27 may combine to form a ring.
- R24 or R25 may be linked to Ar1 .
- R 28 to R 30 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
- L5 represents a single bond or a divalent linking group.
- R 31 and R 32 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
- R33 represents an alkyl group, cycloalkyl group, aryl group, aralkyl group or alkenyl group.
- R 32 and R 33 may combine to form a ring.
- the repeating unit represented by formula (3) is described below.
- the repeating unit represented by formula (3) is a repeating unit having an acid-decomposable group.
- the alkyl group represented by R 5 , R 6 and R 7 may be linear or branched. Although the number of carbon atoms in the alkyl group is not particularly limited, it is preferably 1-5, more preferably 1-3.
- Cycloalkyl groups represented by R 5 , R 6 and R 7 include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and polycyclic cycloalkyl groups such as adamantyl groups are preferred.
- Halogen atoms represented by R 5 , R 6 and R 7 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom or an iodine atom.
- the alkyl group contained in the alkoxycarbonyl group represented by R 5 , R 6 and R 7 may be linear or branched. Although the number of carbon atoms in the alkyl group contained in the alkoxycarbonyl group is not particularly limited, it is preferably 1-5, more preferably 1-3.
- Divalent linking groups represented by L 2 include -CO-, -O-, -S-, -SO-, -SO 2 -, hydrocarbon groups (e.g., alkylene groups, cycloalkylene groups, alkenylene groups , an arylene group, etc.), and a linking group in which a plurality of these are linked.
- hydrocarbon groups e.g., alkylene groups, cycloalkylene groups, alkenylene groups , an arylene group, etc.
- the alkyl groups represented by R 8 to R 10 may be linear or branched. Although the number of carbon atoms in the alkyl group is not particularly limited, it is preferably 1-5, more preferably 1-3. In the alkyl group represented by R 8 to R 10 , the methylene group may be substituted with at least one of -CO- and -O-. Cycloalkyl groups represented by R 8 to R 10 include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. is preferred.
- a phenyl group is preferable as the aryl group represented by R 8 to R 10 .
- the aralkyl group represented by R 8 to R 10 one hydrogen atom in the alkyl group represented by R 8 to R 10 is replaced by an aryl group having 6 to 10 carbon atoms (preferably a phenyl group). Substituted groups are preferred, and examples thereof include benzyl groups and the like.
- a vinyl group is preferred as the alkenyl group represented by R 8 to R 10 .
- a cycloalkyl group is preferable as the ring formed by combining two of R 8 to R 10 .
- the cycloalkyl group formed by combining two of R 8 to R 10 includes a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, and a tetracyclododecanyl group. or a polycyclic cycloalkyl group such as an adamantyl group, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms.
- a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, and a tetracyclododecanyl group.
- a polycyclic cycloalkyl group such as an adamantyl group, and more preferably a monocyclic
- a cycloalkyl group formed by bonding two of R 8 to R 10 is, for example, a group in which one of the methylene groups constituting the ring has a heteroatom such as an oxygen atom, a heteroatom such as a carbonyl group, or a vinylidene group may be substituted.
- one or more ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.
- Each group in the general formula (3) may have a substituent, and examples of the substituent include the substituent T described above.
- the repeating unit represented by formula (6) is described below.
- the repeating unit represented by formula (6) is a repeating unit having an acid-decomposable group.
- R 22 , R 23 and R 24 have the same meanings as R 5 , R 6 and R 7 in general formula (3), and the preferred embodiments are also the same.
- L 4 represents a divalent linking group
- examples of the divalent linking group include —CO—, —O—, —S—, —SO—, —SO 2 —, hydrocarbon groups (e.g., alkylene groups, a cycloalkylene group, an alkenylene group, an arylene group, etc.), and a linking group in which a plurality of these are linked.
- the aromatic group represented by Ar 1 is not particularly limited, but includes, for example, a phenylene group and a naphthylene group, preferably a phenylene group.
- Examples of the alkyl group, cycloalkyl group, aryl group, aralkyl group and alkenyl group represented by R 25 to R 27 include the alkyl group represented by R 8 to R 10 in the above general formula (3), cyclo Examples include groups similar to alkyl groups, aryl groups, aralkyl groups, and alkenyl groups.
- the alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group represented by R 25 to R 27 may have a substituent. mentioned.
- the rings formed by combining R 26 and R 27 , Ar 1 and R 24 , and R 25 and Ar 1 are preferably cycloalkyl groups.
- the cycloalkyl group formed by combining R 26 and R 27 , Ar 1 and R 24 , and R 25 and Ar 1 is a cyclopentyl group, a monocyclic cycloalkyl group such as a cyclohexyl group, or a norbornyl group. , a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group are preferable, and monocyclic cycloalkyl groups having 5 to 6 carbon atoms are more preferable.
- one of the methylene groups constituting the ring is a hetero atom such as an oxygen atom, a carbonyl It may be substituted with a group having a heteroatom such as a group, or a vinylidene group.
- one or more ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.
- the repeating unit represented by formula (7) is described below.
- the repeating unit represented by formula (7) is a repeating unit having an acid-decomposable group.
- R 28 , R 29 , R 30 and L 5 are synonymous with R 22 , R 23 , R 24 and L 4 in formula (6), and the preferred embodiments are also the same.
- the alkyl group, cycloalkyl group, aryl group, aralkyl group and alkenyl group represented by R 31 , R 32 and R 33 are represented by R 8 to R 10 in general formula (3) above. Examples include groups similar to alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups.
- the alkyl group, cycloalkyl group, aryl group, aralkyl group and alkenyl group represented by R 31 , R 32 and R 33 may have a substituent.
- the ring formed by combining R32 and R33 is preferably a cycloalkyl group.
- the cycloalkyl group formed by combining R 32 and R 33 includes a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, Alternatively, a polycyclic cycloalkyl group such as an adamantyl group is preferable, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
- one of the methylene groups constituting the ring is a group having a heteroatom such as an oxygen atom, a heteroatom such as a carbonyl group, or a vinylidene group. may be replaced.
- one or more ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.
- the repeating unit having an acid-decomposable group may or may not contain a halogen atom, but preferably does not contain a halogen atom.
- the content of repeating units having an acid-decomposable group is preferably 5 mol% or more, more preferably 10 mol% or more, and 15 mol% or more, relative to all repeating units in the resin (A). is more preferable.
- the content of repeating units having an acid-decomposable group is preferably 95 mol% or less, more preferably 90 mol% or less, and 85 mol% of all repeating units in the resin (A). % or less is particularly preferred.
- repeating units having an acid-decomposable group are shown below, but are not limited thereto.
- Xa 1 represents any one of H, CH 3 , CF 3 and CH 2 OH
- Rxa and Rxb each independently represents a linear or branched alkyl group having 1 to 5 carbon atoms. show.
- Resin (A) preferably has a repeating unit represented by the following general formula (A2).
- R 101 , R 102 and R 103 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
- LA represents a single bond or a divalent linking group.
- Ar A represents an aromatic group.
- k represents an integer of 1 to 5; However, R 102 may be bonded to Ar 2 A , and when R 102 and Ar 2 are bonded, R 102 represents a single bond or an alkylene group.
- R 101 , R 102 and R 103 in general formula (A2) represent an alkyl group
- the alkyl group is not particularly limited, but is preferably an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 8 carbon atoms. is more preferred, and an alkyl group having 1 to 3 carbon atoms is even more preferred.
- Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group.
- R 101 , R 102 and R 103 in general formula (A2) represent a cycloalkyl group
- the cycloalkyl group may be monocyclic or polycyclic.
- monocyclic cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group and cyclohexyl group are preferable.
- R 101 , R 102 and R 103 in general formula (A2) represent a halogen atom
- examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, with a fluorine atom being preferred.
- alkyl group contained in the alkoxycarbonyl group when R 101 , R 102 and R 103 in general formula (A2) represent an alkoxycarbonyl group are R 1 , R 2 and R It is the same as the alkyl group when 3 represents an alkyl group.
- each group described above can further have one or more substituents, it may have one or more additional substituents.
- substituents include, but are not limited to, alkyl groups, cycloalkyl groups, aryl groups, amino groups, amido groups, ureido groups, urethane groups, hydroxyl groups, carboxy groups, halogen atoms, alkoxy groups, thioether groups, Examples include acyl groups, acyloxy groups, alkoxycarbonyl groups, cyano groups, and nitro groups.
- Further substituents preferably have 8 or less carbon atoms.
- R 101 and R 102 in general formula (A2) are preferably hydrogen atoms.
- R 103 in general formula (A2) is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.
- Ar 2 A in general formula (A2) represents an aromatic group, and more specifically represents a (k+1)-valent aromatic group.
- the divalent aromatic group when k is 1 is, for example, a phenylene group, a tolylene group, a naphthylene group, an arylene group having 6 to 18 carbon atoms such as an anthracenylene group, or a thiophene ring, a furan ring, a pyrrole ring, A divalent aromatic group containing a hetero ring such as a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring and a thiazole ring is preferred.
- the said aromatic group may have a substituent.
- Specific examples of the (k+1)-valent aromatic group when k is an integer of 2 or more include the above specific examples of the divalent aromatic group, excluding any (k-1) hydrogen atoms.
- a group formed by The (k+1)-valent aromatic group may further have a substituent.
- Substituents that the (k+1)-valent aromatic group may have are not particularly limited, but examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2 - alkyl groups such as ethylhexyl group, octyl group and dodecyl group; alkoxy groups such as methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group and butoxy group; aryl groups such as phenyl group;
- Ar 2 A preferably represents an aromatic group having 6 to 18 carbon atoms, more preferably a benzene ring group, a naphthalene ring group or a biphenylene ring group.
- LA in general formula (A2) represents a single bond or a divalent linking group.
- L A represents a divalent linking group
- the divalent linking group is not particularly limited. group.
- R64 above represents a hydrogen atom or an alkyl group.
- the alkylene group is not particularly limited, but is preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, ethylene group, propylene group, butylene group, hexylene group and octylene group.
- R 64 represents an alkyl group
- examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl and dodecyl.
- Alkyl groups having 20 or less carbon atoms, such as groups, are preferred, and alkyl groups having 8 or less carbon atoms are preferred.
- the repeating unit represented by formula (A2) preferably has a hydroxystyrene structure. That is, Ar A preferably represents a benzene ring group. k preferably represents an integer of 1 to 3, more preferably 1 or 2.
- repeating unit represented by formula (A2) Specific examples of the repeating unit represented by formula (A2) are shown below. In the structural formulas of the following specific examples, a represents 1, 2 or 3. Further, as specific examples of the repeating unit represented by the general formula (A2), the descriptions in paragraphs [0068] to [0072] of WO 2018/193954 can be referred to, and the contents thereof are incorporated herein.
- the content of the repeating unit represented by the general formula (A2) is not particularly limited, but all repeating units in the resin (A) It is preferably 5 mol % or more, more preferably 10 mol % or more, and even more preferably 20 mol % or more.
- the content of the repeating unit represented by the general formula (A2) is preferably 90 mol% or less, more preferably 85 mol% or less, relative to all repeating units in the resin (A). , 80 mol % or less.
- the resin (A) may contain repeating units other than the repeating units described above.
- the content of the other repeating units is not particularly limited, but is 1 mol% or more and 60% of the total repeating units in the resin (A). It is preferably mol % or less, more preferably 3 mol % or more and 50 mol % or less, and even more preferably 5 mol % or more and 40 mol % or less.
- Resin (A) may further have a repeating unit having an acid group in addition to the repeating units described above.
- the acid group for example, a carboxy group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, an isopropanol group and the like are preferable.
- a fluorinated alcohol group preferably a hexafluoroisopropanol group
- a sulfonic acid group preferably sulfonic acid group
- a sulfonamide group an isopropanol group and the like are preferable.
- an isopropanol group and the like are preferable.
- the hexafluoroisopropanol group one or more (preferably 1 to 2) fluorine atoms may be substituted with groups other than fluorine atoms (eg, alkyloxycarbonyl group, etc.).
- —C(CF 3 )(OH)—CF 2 — thus formed is also preferred as an acid group.
- one or more of the fluorine atoms may be substituted with a group other than a fluorine atom to form a ring containing -C(CF 3 )(OH)-CF 2 -.
- the repeating unit having an acid group the description in paragraph [0205] of WO 2019/054282 can be referred to, the contents of which are incorporated herein.
- the repeating unit having an acid group is not limited to these.
- the resin (A) may further have a repeating unit that has a fluorine atom or an iodine atom and does not exhibit acid decomposability.
- repeating units that have a fluorine atom or an iodine atom and do not exhibit acid decomposability are shown below, but are not limited to these.
- Resin (A) may further have a repeating unit having a lactone group, a sultone group, or a carbonate group, in addition to the repeating units described above.
- the lactone group or sultone group may have a lactone structure or sultone structure.
- the lactone structure or sultone structure is preferably a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure.
- the resin (A) has a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-21), or a lactone structure represented by any of the following general formulas (SL1-1) to (SL1-3). It is preferable to have a repeating unit having a lactone group or a sultone group obtained by extracting one or more hydrogen atoms from the ring member atoms of the sultone structure. Also, a lactone group or a sultone group may be directly bonded to the main chain. For example, ring member atoms of a lactone group or a sultone group may constitute the main chain of resin (A).
- the lactone structure or sultone structure portion may have a substituent (Rb 2 ).
- Preferred substituents (Rb 2 ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, and a carboxy group. , a halogen atom, a hydroxyl group, a cyano group, an acid-decomposable group, and the like.
- n2 represents an integer from 0 to 4; When n2 is 2 or more, multiple Rb2 may be different, and multiple Rb2 may combine to form a ring.
- repeating unit having a lactone structure for example, the description in paragraph [0088] of WO 2018/193954 can be considered, and the contents thereof are incorporated herein.
- repeating units having a lactone structure are not limited to these.
- a cyclic carbonate group is preferable as the carbonate group.
- Resin (A) may have a repeating unit having a photoacid-generating group.
- the repeating unit having a photoacid-generating group descriptions in paragraphs [0090] to [0096] of International Publication No. 2018/193954 can be referred to, and the contents thereof are incorporated herein.
- the resin (A) has various repeating units for the purpose of adjusting, for example, dry etching resistance, suitability for standard developer, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, and the like. may be Other repeating units other than those described above can be referred to in paragraphs [0097] to [0100] and [0102] to [0133] of International Publication No. WO 2018/193954, the contents of which are incorporated herein. .
- Resin (A) can be synthesized according to a conventional method (for example, radical polymerization).
- the weight average molecular weight of resin (A) is not particularly limited, but is preferably 1,000 to 200,000, more preferably 2,000 to 30,000, even more preferably 3,000 to 20,000.
- the dispersity (molecular weight distribution) of the resin (A) is usually 1.0 to 5.0, preferably 1.0 to 3.0, more preferably 1.0 to 2.5. , 1.0 to 2.0.
- the content of the resin (A) in the composition of the present invention is not particularly limited, but is preferably 50 to 99.9% by mass, preferably 60 to 99.0%, based on the total solid content of the composition of the present invention. % by mass is more preferred.
- solid content intends the component except the solvent in a composition, and if it is a component other than a solvent, even if it is a liquid component, it will be considered as solid content.
- the resin (A) contained in the composition of the present invention may be of only one type, or may be of two or more types.
- the actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a compound (photoacid generator) that generates an acid upon exposure to actinic rays or radiation.
- a compound that generates an acid upon exposure to actinic rays or radiation is also referred to as "compound (B)” or "photoacid generator (B)".
- Compound (B) may be in the form of a low-molecular-weight compound, or may be in the form of being incorporated into a part of a polymer (for example, resin (A)). Moreover, the form of a low-molecular-weight compound and the form incorporated into a part of a polymer (for example, resin (A)) may be used together.
- the molecular weight of compound (B) is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less. Although the lower limit is not particularly limited, 100 or more is preferable.
- compound (B) When the compound (B) is in the form of being incorporated into a part of the polymer, it may be incorporated into a part of the resin (A) or into a resin different from the resin (A).
- Compound (B) is preferably a low-molecular-weight compound.
- Examples of the compound (B) include compounds (onium salts) represented by “M + X ⁇ ”, and compounds that generate an organic acid upon exposure are preferred.
- Examples of the organic acid include sulfonic acid (aliphatic sulfonic acid, aromatic sulfonic acid, camphorsulfonic acid, etc.), carboxylic acid (aliphatic carboxylic acid, aromatic carboxylic acid, aralkyl carboxylic acid, etc.), carbonyl Sulfonylimidic acids, bis(alkylsulfonyl)imidic acids, and tris(alkylsulfonyl)methide acids.
- sulfonic acid aliphatic sulfonic acid, aromatic sulfonic acid, camphorsulfonic acid, etc.
- carboxylic acid aliphatic carboxylic acid, aromatic carboxylic acid, aralkyl carboxylic acid, etc.
- carbonyl Sulfonylimidic acids bis(alkylsulf
- the molecular weight of the generated acid of compound (B) is preferably 240 or more, more preferably 250 or more, still more preferably 260 or more, particularly preferably 270 or more, and 280 or more. is most preferred.
- M + represents an organic cation.
- the structure of the organic cation is not particularly limited. Also, the valence of the organic cation may be 1 or 2 or more.
- a cation represented by the following general formula (ZaI) hereinafter also referred to as “cation (ZaI)”
- cation (ZaII) a cation represented by the following general formula (ZaII)
- ZaII cation (ZaII)
- R 201 , R 202 and R 203 each independently represent an organic group.
- R 204 and R 205 each independently represent an organic group.
- the general formulas (ZaI) and (ZaII) are described in detail below.
- At least one of R 201 , R 202 and R 203 in the general formula (ZaI) is an aryl group, or
- At least one of R 204 and R 205 in formula (ZaII) is preferably an aryl group.
- the aryl group may have a substituent, and the substituent is preferably a halogen atom (preferably a fluorine atom or an iodine atom) or an organic group.
- At least one of R 201 , R 202 and R 203 in general formula (ZaI) has an acid-decomposable group, or at least one of R 204 and R 205 in general formula (ZaII) is It is also preferred to have an acid-decomposable group.
- the acid-decomposable group is the same as in resin (A).
- at least one of R 201 , R 202 and R 203 in general formula (ZaI) has an acid-decomposable group
- at least one of R 201 , R 202 and R 203 contains an acid-decomposable group.
- An aryl group substituted with an organic group is preferred.
- At least one of R 204 and R 205 in general formula (ZaII) has an acid-decomposable group
- at least one of R 204 and R 205 is an aryl group substituted with an organic group containing an acid-decomposable group. is preferably
- the number of carbon atoms in the organic groups as R 201 , R 202 and R 203 is generally 1-30, preferably 1-20. Also, two of R 201 to R 203 may combine to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. Examples of the group formed by combining two of R 201 to R 203 include an alkylene group (eg, a butylene group and a pentylene group) and —CH 2 —CH 2 —O—CH 2 —CH 2 —. mentioned.
- alkylene group eg, a butylene group and a pentylene group
- Preferred embodiments of the organic cation in formula (ZaI) include cation (ZaI-1), cation (ZaI-2), and organic cations represented by formula (ZaI-3b) (cation (ZaI-3b) ), and an organic cation represented by the formula (ZaI-4b) (cation (ZaI-4b)).
- Cation (ZaI-1) is an arylsulfonium cation in which at least one of R 201 to R 203 in formula (ZaI) above is an aryl group.
- R 201 to R 203 may be aryl groups, or part of R 201 to R 203 may be aryl groups and the rest may be alkyl groups or cycloalkyl groups.
- one of R 201 to R 203 may be an aryl group, and the remaining two of R 201 to R 203 may combine to form a ring structure, in which an oxygen atom, a sulfur atom, It may contain an ester group, an amide group, or a carbonyl group.
- the group formed by bonding two of R 201 to R 203 includes, for example, one or more methylene groups substituted with an oxygen atom, a sulfur atom, an ester group, an amide group and/or a carbonyl group. alkylene groups (eg, butylene group, pentylene group, and —CH 2 —CH 2 —O—CH 2 —CH 2 —).
- Arylsulfonium cations include, for example, triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.
- the aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
- the aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Heterocyclic structures include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene residues.
- the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different.
- the alkyl group or cycloalkyl group optionally possessed by the arylsulfonium cation is a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or 3 to 15 carbon atoms. is preferred, and a methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group or cyclohexyl group is more preferred.
- the substituents that the aryl group, alkyl group and cycloalkyl group of R 201 to R 203 may have are each independently an alkyl group (eg, 1 to 15 carbon atoms), a cycloalkyl group (eg, carbon 3 to 15), aryl groups (eg, 6 to 14 carbon atoms), alkoxy groups (eg, 1 to 15 carbon atoms), cycloalkylalkoxy groups (eg, 1 to 15 carbon atoms), halogen atoms (eg, fluorine and iodine), hydroxyl, carboxy, ester, sulfinyl, sulfonyl, alkylthio and phenylthio groups are preferred.
- alkyl group eg, 1 to 15 carbon atoms
- a cycloalkyl group eg, carbon 3 to 15
- aryl groups eg, 6 to 14 carbon atoms
- alkoxy groups eg, 1 to 15 carbon
- the substituent may further have a substituent, and the alkyl group preferably has a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group.
- the above substituents form an acid-decomposable group by any combination.
- the acid-decomposable group is intended to be a group that is decomposed by the action of an acid to generate a polar group, and preferably has a structure in which the polar group is protected by a leaving group that is eliminated by the action of an acid.
- the polar group and leaving group are as described above.
- Cation (ZaI-2) is a cation in which R 201 to R 203 in formula (ZaI) each independently represents an organic group having no aromatic ring.
- Aromatic rings also include aromatic rings containing heteroatoms.
- the organic group having no aromatic ring as R 201 to R 203 generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
- R 201 to R 203 are each independently preferably an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, and a linear or branched 2-oxoalkyl group, 2-oxocycloalkyl group or alkoxy
- a carbonylmethyl group is more preferred, and a linear or branched 2-oxoalkyl group is even more preferred.
- the alkyl groups and cycloalkyl groups of R 201 to R 203 are, for example, linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, , butyl group, and pentyl group), and cycloalkyl groups having 3 to 10 carbon atoms (eg, cyclopentyl group, cyclohexyl group, and norbornyl group).
- R 201 to R 203 may be further substituted with a halogen atom, an alkoxy group (eg, 1-5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group. It is also preferred that the substituents of R 201 to R 203 each independently form an acid-decomposable group by any combination of substituents.
- the cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).
- R 1c to R 5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, or a hydroxyl group , represents a nitro group, an alkylthio group, or an arylthio group.
- R 6c and R 7c each independently represent a hydrogen atom, an alkyl group (eg, t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group.
- R x and R y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group. It is also preferred that the substituents of R 1c to R 7c , R x and R y independently form an acid-decomposable group by any combination of substituents.
- R 1c to R 5c , R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y may combine with each other to form a ring.
- the rings may each independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
- Examples of the ring include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic hetero rings, and polycyclic condensed rings in which two or more of these rings are combined.
- the ring includes a 3- to 10-membered ring, preferably a 4- to 8-membered ring, more preferably a 5- or 6-membered ring.
- Examples of groups formed by bonding two or more of R 1c to R 5c , R 6c and R 7c , and R x and R y include alkylene groups such as a butylene group and a pentylene group. A methylene group in this alkylene group may be substituted with a heteroatom such as an oxygen atom.
- the group formed by combining R 5c and R 6c and R 5c and R x is preferably a single bond or an alkylene group.
- Alkylene groups include methylene and ethylene groups.
- R 1c to R 5c , R 6c , R 7c , R x , R y , and two or more of R 1c to R 5c , R 5c and R 6c , R 6c and R 7c , R 5c and R x , and the ring formed by combining each other with R x and R y may have a substituent.
- the cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).
- a halogen atom e.g., fluorine atom, iodine atom, etc.
- R 14 is a hydroxyl group, a halogen atom (e.g., fluorine atom, iodine atom, etc.), an alkyl group, a halogenated alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl represents a group containing a group (either a cycloalkyl group itself or a group partially containing a cycloalkyl group). These groups may have a substituent. When two or more R 14 are present, each independently represents the above group such as a hydroxyl group.
- a halogen atom e.g., fluorine atom, iodine atom, etc.
- Each R 15 independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. Two R 15 may be joined together to form a ring. When two R 15 are combined to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom. In one aspect, two R 15 are alkylene groups, preferably joined together to form a ring structure. The ring formed by combining the alkyl group, the cycloalkyl group, the naphthyl group, and the two R 15 groups may have a substituent.
- the alkyl groups of R 13 , R 14 and R 15 may be linear or branched.
- the number of carbon atoms in the alkyl group is preferably 1-10.
- the alkyl group is more preferably a methyl group, an ethyl group, an n-butyl group, a t-butyl group, or the like. It is also preferred that the substituents of R 13 to R 15 , R x and R y each independently form an acid-decomposable group by any combination of substituents.
- R 204 and R 205 each independently represent an organic group, preferably an aryl group, an alkyl group or a cycloalkyl group.
- the aryl group for R 204 and R 205 is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
- the aryl group for R 204 and R 205 may be an aryl group having a heterocyclic ring having an oxygen atom, a nitrogen atom, a sulfur atom, or the like.
- Skeletons of heterocyclic aryl groups include, for example, pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
- the alkyl group and cycloalkyl group of R 204 and R 205 are linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl or a pentyl group), or a cycloalkyl group having 3 to 10 carbon atoms (eg, a cyclopentyl group, a cyclohexyl group, or a norbornyl group).
- the aryl group, alkyl group and cycloalkyl group of R 204 and R 205 may each independently have a substituent.
- substituents that the aryl group, alkyl group and cycloalkyl group of R 204 and R 205 may have include an alkyl group (eg, 1 to 15 carbon atoms) and a cycloalkyl group (eg, 3 to 15), aryl groups (eg, 6 to 15 carbon atoms), alkoxy groups (eg, 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups. It is also preferred that the substituents of R 204 and R 205 each independently form an acid-decomposable group by any combination of substituents.
- X ⁇ represents an organic anion.
- the organic anion is not particularly limited, and includes organic anions having a valence of 1, 2 or more.
- an anion having a significantly low ability to cause a nucleophilic reaction is preferred, and a non-nucleophilic anion is more preferred.
- non-nucleophilic anions examples include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, , and aralkylcarboxylate anions), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methide anions.
- the aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be a linear or branched alkyl group or a cycloalkyl group, and may be a straight chain having 1 to 30 carbon atoms. Alternatively, a branched alkyl group or a cycloalkyl group having 3 to 30 carbon atoms is preferred.
- the alkyl group may be, for example, a fluoroalkyl group (which may have a substituent other than a fluorine atom, or may be a perfluoroalkyl group).
- the aryl group in the aromatic sulfonate anion and the aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group.
- the alkyl group, cycloalkyl group, and aryl group listed above may have a substituent.
- the substituent is not particularly limited, but specifically includes a nitro group, a halogen atom such as a fluorine atom or a chlorine atom, a carboxy group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), Acyl group (preferably with 2 to 12 carbon atoms), alkoxycarbonyloxy group (preferably with 2 to 7 carbon atoms), alkylthio group (preferably with 1 to 15 carbon atoms), alkylsulfonyl group (preferably with 1 to 15 carbon atoms)
- aralkyl group in the aralkylcarboxylate anion an aralkyl group having 7 to 14 carbon atoms is preferable.
- Aralkyl groups having 7 to 14 carbon atoms include, for example, benzyl, phenethyl, naphthylmethyl, naphthylethyl and naphthylbutyl groups.
- Sulfonylimide anions include, for example, saccharin anions.
- alkyl group in the bis(alkylsulfonyl)imide anion and the tris(alkylsulfonyl)methide anion an alkyl group having 1 to 5 carbon atoms is preferable.
- substituents of these alkyl groups include halogen atoms, halogen-substituted alkyl groups, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryloxysulfonyl groups.
- a fluorine atom or an alkyl group substituted with a fluorine atom is preferred.
- the alkyl groups in the bis(alkylsulfonyl)imide anion may combine with each other to form a ring structure. This increases the acid strength.
- non-nucleophilic anions include, for example, phosphorous fluorides (eg, PF 6 ⁇ ), boron fluorides (eg, BF 4 ⁇ ), and antimony fluorides (eg, SbF 6 ⁇ ).
- non-nucleophilic anions examples include aliphatic sulfonate anions in which at least the ⁇ -position of sulfonic acid is substituted with fluorine atoms, aromatic sulfonate anions in which fluorine atoms or groups having fluorine atoms are substituted, and alkyl groups in which fluorine atoms are present.
- a bis(alkylsulfonyl)imide anion substituted with or a tris(alkylsulfonyl)methide anion in which an alkyl group is substituted with a fluorine atom is preferred.
- perfluoroaliphatic sulfonate anions preferably having 4 to 8 carbon atoms
- benzenesulfonate anions having a fluorine atom are more preferable, nonafluorobutanesulfonate anions, perfluorooctanesulfonate anions, pentafluoro A benzenesulfonate anion or a 3,5-bis(trifluoromethyl)benzenesulfonate anion is more preferred.
- non-nucleophilic anions include anions represented by the following formula (AN4).
- R 1 to R 3 each independently represent an organic group or a hydrogen atom.
- L represents a divalent linking group.
- L represents a divalent linking group.
- divalent linking groups include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO 2 -, alkylene groups ( preferably 1 to 6 carbon atoms), a cycloalkylene group (preferably 3 to 15 carbon atoms), an alkenylene group (preferably 2 to 6 carbon atoms), and a divalent linking group combining a plurality of these.
- the divalent linking group includes -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -SO 2 -, and -O-CO-O-alkylene group- , -COO-alkylene group-, or -CONH-alkylene group- is preferred, and -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, -SO 2 - , or -COO-alkylene group- is more preferred.
- L is preferably, for example, a group represented by the following formula (AN4-2). * a - (CR 2a 2 ) X - Q- (CR 2b 2 ) Y - * b (AN4-2)
- * a represents the bonding position with R3 in formula (AN4).
- * b represents the bonding position with —C(R 1 )(R 2 )— in formula (AN4).
- X and Y each independently represent an integer of 0-10, preferably an integer of 0-3.
- R 2a and R 2b each independently represent a hydrogen atom or a substituent. When multiple R 2a and R 2b are present, the multiple R 2a and R 2b may be the same or different. However, when Y is 1 or more, R 2b in CR 2b 2 directly bonded to —C(R 1 )(R 2 )— in formula (AN4) is other than a fluorine atom.
- Q is * A -O-CO-O-* B , * A -CO-* B , * A -CO-O-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B or * A - SO2- * B .
- Q is * A -O-CO- O-* B , * A -CO-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B , or * A - SO2- * B show.
- * A represents the bonding position on the R 3 side in formula (AN4)
- * B represents the bonding position on the —SO 3 — side in formula (AN4).
- R 1 to R 3 each independently represent an organic group.
- the above organic group is not limited as long as it has 1 or more carbon atoms. It may be a branched chain alkyl group) or a cyclic group.
- the organic group may or may not have a substituent.
- the organic group may or may not have a heteroatom (oxygen atom, sulfur atom, and/or nitrogen atom, etc.). Examples of the above organic groups also include substituents that are not electron-withdrawing groups.
- substituents that are not electron-withdrawing groups include hydrocarbon groups, hydroxyl groups, oxyhydrocarbon groups, oxycarbonyl hydrocarbon groups, amino groups, hydrocarbon-substituted amino groups, and hydrocarbon-substituted amide groups. be done.
- substituents that are not electron-withdrawing groups independently include -R', -OH, -OR', -OCOR', -NH 2 , -NR' 2 , -NHR', or -NHCOR ' is preferred.
- R' is a monovalent hydrocarbon group.
- Examples of the monovalent hydrocarbon group represented by R' include alkyl groups such as methyl, ethyl, propyl, and butyl; alkenyl groups such as ethenyl, propenyl, and butenyl; ethynyl monovalent linear or branched hydrocarbon groups such as alkynyl groups such as groups, propynyl groups, and butynyl groups; cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, cyclohexyl groups, norbornyl groups, and adamantyl groups Cycloalkyl group; monovalent alicyclic hydrocarbon group such as cycloalkenyl group such as cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, and norbornenyl group; phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, methyl aryl groups such as
- R 3 is preferably an organic group having a cyclic structure.
- the cyclic structure may be monocyclic or polycyclic, and may have a substituent.
- the ring in the organic group containing a cyclic structure is preferably directly bonded to L in formula (AN4).
- the organic group having a cyclic structure may or may not have a heteroatom (oxygen atom, sulfur atom, and/or nitrogen atom, etc.), for example. Heteroatoms may replace one or more of the carbon atoms that form the ring structure.
- the organic group having a cyclic structure is preferably, for example, a hydrocarbon group having a cyclic structure, a lactone ring group, or a sultone ring group.
- the organic group having a cyclic structure is preferably a hydrocarbon group having a cyclic structure.
- the above hydrocarbon group having a cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may have a substituent.
- the cycloalkyl group may be monocyclic (such as cyclohexyl group) or polycyclic (such as adamantyl group), and preferably has 5 to 12 carbon atoms.
- Examples of the lactone group and sultone group include structures represented by the above formulas (LC1-1) to (LC1-21) and structures represented by formulas (SL1-1) to (SL1-3). , preferably a group obtained by removing one hydrogen atom from a ring member atom constituting a lactone structure or a sultone structure.
- an anion represented by the following formula (AN1) is also preferable.
- o represents an integer of 1-3.
- p represents an integer from 0 to 10;
- q represents an integer from 0 to 10;
- Xf represents a fluorine atom or an organic group.
- the organic group may be an organic group substituted with at least one fluorine atom, or may be an organic group having no fluorine atom.
- the number of carbon atoms in the organic group (preferably alkyl group) is preferably 1-10, more preferably 1-4.
- As the organic group (preferably alkyl group) substituted with at least one fluorine atom a perfluoroalkyl group is preferred.
- At least one Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF 3 , and even more preferably both Xf's are fluorine atoms.
- R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When multiple R 4 and R 5 are present, each of R 4 and R 5 may be the same or different.
- the alkyl groups represented by R 4 and R 5 preferably have 1 to 4 carbon atoms. The above alkyl group may have a substituent. Hydrogen atoms are preferred as R 4 and R 5 .
- Specific examples and preferred aspects of the alkyl group substituted with at least one fluorine atom are the same as the specific examples and preferred aspects of Xf in formula (AN1).
- L represents a divalent linking group.
- divalent linking groups include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO 2 -, alkylene groups ( preferably 1 to 6 carbon atoms), a cycloalkylene group (preferably 3 to 15 carbon atoms), an alkenylene group (preferably 2 to 6 carbon atoms), and a divalent linking group combining a plurality of these.
- the divalent linking group includes -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -SO 2 -, and -O-CO-O-alkylene group- , -COO-alkylene group-, or -CONH-alkylene group- is preferred, and -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, -SO 2 - , or -COO-alkylene group- is more preferred.
- W represents an organic group containing a cyclic structure.
- a cyclic organic group is preferable.
- Cyclic organic groups include, for example, alicyclic groups, aryl groups, and heterocyclic groups.
- the alicyclic group may be monocyclic or polycyclic.
- Monocyclic alicyclic groups include, for example, monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
- the polycyclic alicyclic group includes, for example, a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and a polycyclic cycloalkyl group such as an adamantyl group.
- alicyclic groups having a bulky structure with 7 or more carbon atoms such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups, are preferred.
- Aryl groups may be monocyclic or polycyclic.
- the aryl group include phenyl group, naphthyl group, phenanthryl group, and anthryl group.
- a heterocyclic group may be monocyclic or polycyclic. Especially, when it is a polycyclic heterocyclic group, diffusion of acid can be further suppressed. Moreover, the heterocyclic group may or may not have aromaticity. Heterocyclic rings having aromaticity include, for example, furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, and pyridine ring.
- Non-aromatic heterocycles include, for example, a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring.
- the heterocyclic ring in the heterocyclic group is preferably a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring.
- the cyclic organic group may have a substituent.
- substituents include alkyl groups (either linear or branched, preferably having 1 to 12 carbon atoms), cycloalkyl groups (monocyclic, polycyclic, and spirocyclic). any group, preferably having 3 to 20 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), hydroxyl group, alkoxy group, ester group, amide group, urethane group, ureido group, thioether group, sulfonamide and sulfonate ester groups.
- carbonyl carbon may be sufficient as carbon (carbon which contributes to ring formation) which comprises a cyclic
- two or more substituents may bond together to form a ring.
- two alkoxy groups, or a hydroxyl group and an alkoxy group may combine to form a ring having a cyclic acetal structure.
- This ring may have a substituent.
- substituents include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms).
- Examples of anions represented by formula (AN1) include SO 3 ⁇ —CF 2 —CH 2 —OCO-(L) q′ —W, SO 3 ⁇ —CF 2 —CHF—CH 2 —OCO-(L) q ' -W, SO 3 - -CF 2 -COO-(L) q' -W, SO 3 - -CF 2 -CF 2 -CH 2 -CH 2 -(L) q -W, or SO 3 - - CF 2 —CH(CF 3 )—OCO—(L) q′ —W is preferred.
- L, q and W are the same as in formula (AN1).
- q' represents an integer from 0 to 10;
- AN1 As the anion represented by the formula (AN1), the following aspects (AN2) and (AN3) are also preferred.
- Preferred aspects of q, L, and W are the same as described above.
- Two Xf's bonded to the carbon atom Z1 are preferably hydrogen atoms. At least one of the two Xf's bonded to the carbon atom Z2 is preferably a fluorine atom or a fluorine atom-containing organic group, more preferably both are a fluorine atom or a fluorine atom-containing organic group, and both are fluorine An alkyl group substituted with is more preferred.
- one of the two Xf's each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom; It represents a hydrogen atom or an organic group having no fluorine atom.
- Preferred embodiments of o, p, q, R 4 , R 5 , L and W are the same as those described above.
- the non-nucleophilic anion may be a benzenesulfonate anion, preferably a benzenesulfonate anion substituted with a branched alkyl group or cycloalkyl group.
- an aromatic sulfonate anion represented by the following formula (AN5) is also preferable.
- Ar represents an aryl group (such as a phenyl group), and may further have a substituent other than the sulfonate anion and -(D-B) group.
- substituents which may be further included include, for example, a fluorine atom and a hydroxyl group.
- n represents an integer of 0 or more. n is preferably 1 to 4, more preferably 2 to 3, and still more preferably 3.
- D represents a single bond or a divalent linking group.
- Divalent linking groups include ether groups, thioether groups, carbonyl groups, sulfoxide groups, sulfone groups, sulfonate ester groups, ester groups, and groups consisting of combinations of two or more thereof.
- B represents a hydrocarbon group
- B is an aliphatic hydrocarbon structure.
- B is more preferably an isopropyl group, a cyclohexyl group, or an optionally substituted aryl group (such as a tricyclohexylphenyl group).
- B may further have a substituent represented by "-(L) q -W".
- L, q and W have the same meanings as L, q and W in formula (AN1) above, and specific examples and preferred ranges are also the same.
- Disulfonamide anions are also preferred as non-nucleophilic anions.
- a disulfonamide anion is, for example, an anion represented by N ⁇ (SO 2 —R q ) 2 .
- R q represents an optionally substituted alkyl group, preferably a fluoroalkyl group, more preferably a perfluoroalkyl group.
- Two R q may combine with each other to form a ring.
- the group formed by bonding two R q together is preferably an optionally substituted alkylene group, preferably a fluoroalkylene group, more preferably a perfluoroalkylene group.
- the alkylene group preferably has 2 to 4 carbon atoms.
- Non-nucleophilic anions also include anions represented by the following formulas (d1-1) to (d1-4).
- R 51 represents a hydrocarbon group (eg, an aryl group such as a phenyl group) optionally having a substituent (eg, hydroxyl group).
- Z 2c represents an optionally substituted hydrocarbon group having 1 to 30 carbon atoms (provided that the carbon atom adjacent to S is not substituted with a fluorine atom).
- the above hydrocarbon group for Z 2c may be linear or branched, and may have a cyclic structure.
- the carbon atom in the hydrocarbon group (preferably the carbon atom that is a ring member atom when the hydrocarbon group has a cyclic structure) may be carbonyl carbon (--CO-).
- Examples of the hydrocarbon group include a group having an optionally substituted norbornyl group.
- a carbon atom forming the norbornyl group may be a carbonyl carbon.
- Z 2c —SO 3 ⁇ in formula (d1-2) is preferably different from the anion represented by formula (AN4), (AN1) or (AN5) above.
- Z 2c is preferably other than an aryl group.
- atoms at the ⁇ - and ⁇ -positions with respect to —SO 3 — in Z 2c are preferably atoms other than carbon atoms having a fluorine atom as a substituent.
- the ⁇ -position atom and/or the ⁇ -position atom with respect to —SO 3 — is preferably a ring member atom in a cyclic group.
- R 52 represents an organic group (preferably a hydrocarbon group having a fluorine atom)
- Y 3 represents a linear, branched or cyclic alkylene group, an arylene group, or represents a carbonyl group
- Rf represents a hydrocarbon group
- R 53 to R 54 each represent an organic group (preferably a hydrocarbon group having a fluorine atom). R 53 to R 54 may combine with each other to form a ring.
- the organic anions may be used singly or in combination of two or more.
- the resist composition contains two or more compounds (B), or that the compound (B) is at least one selected from the group consisting of the following compound (I) and the following compound (II). .
- Compound (B) is also preferably at least one selected from the group consisting of compound (I) and compound (II) below.
- Compound (I) is a compound having one or more structural moieties X shown below and one or more structural moieties Y shown below, wherein the first acidic It is a compound that generates an acid containing a site and a second acidic site described below derived from the structural site Y described below.
- Structural site X Structural site consisting of an anionic site A 1 ⁇ and a cation site M 1 + and forming a first acidic site represented by HA 1 upon exposure to actinic rays or radiation
- Structural site Y anionic site A structural moiety consisting of A 2 ⁇ and a cation site M 2 + and forming a second acidic site represented by HA 2 upon exposure to actinic rays or radiation: a cation site M 1 + and a cation site M 2 + each independently represents an organic cation, and specific examples and preferred ranges are the same as those of the organic cation represented by M + above.
- the compound (I) satisfies the following condition I.
- Condition I A compound PI obtained by replacing the cation site M 1 + in the structural site X and the cation site M 2 + in the structural site Y in the compound (I) with H + in the structural site X and the acid dissociation constant a1 derived from the acidic site represented by HA 1 obtained by replacing the cation site M 1 + with H + , and replacing the cation site M 2 + in the structural site Y with H + It has an acid dissociation constant a2 derived from the acidic site represented by HA2 , and the acid dissociation constant a2 is greater than the acid dissociation constant a1.
- compound PI corresponds to "a compound having HA 1 and HA 2 ".
- the acid dissociation constant a1 and the acid dissociation constant a2 of the compound PI are such that when the acid dissociation constant of the compound PI is determined, the compound PI has "A 1 - and HA 2 is the acid dissociation constant a1, and the pKa when the above "compound having A 1 - and HA 2 " becomes "the compound having A 1 - and A 2 - " is the acid dissociation constant. constant a2.
- compound (I) is, for example, a compound that generates an acid having two first acidic sites derived from the structural site X and one second acidic site derived from the structural site Y.
- compound PI is a "compound with two HA 1 and one HA 2 ".
- the acid dissociation constant when the "compound having A 1 - , one HA 1 and one HA 2 " becomes “the compound having two A 1 - and one HA 2 " is the acid dissociation constant a1 correspond to Also, the acid dissociation constant when "a compound having two A 1 - and one HA 2 -" becomes "a compound having two A 1 - and A 2 - " corresponds to the acid dissociation constant a2.
- the acid dissociation constant when the compound PI becomes "a compound having one A 1 - , one HA 1 and one HA 2 " is aa, and "one A 1 - and one HA 1 and 1
- the relationship between aa and ab satisfies aa ⁇ ab, where ab is the acid dissociation constant when a compound having two HA2 's becomes a compound having two A1- and one HA2 . .
- the acid dissociation constant a1 and the acid dissociation constant a2 are determined by the method for measuring the acid dissociation constant described above.
- the above compound PI corresponds to an acid generated when compound (I) is irradiated with actinic rays or radiation.
- the structural moieties X may be the same or different.
- Two or more of A 1 ⁇ and two or more of M 1 + may be the same or different.
- a 1 ⁇ and A 2 ⁇ , and M 1 + and M 2 + may be the same or different, but A 1 ⁇ and A 2 ⁇ may be the same or different.
- Each A 2 - is preferably different.
- the difference (absolute value) between the acid dissociation constant a1 (the maximum value when there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is preferably 0.1 or more, and preferably 0.5 or more. More preferably, 1.0 or more is even more preferable.
- the upper limit of the difference (absolute value) between the acid dissociation constant a1 (the maximum value if there are a plurality of acid dissociation constants a1) and the acid dissociation constant a2 is not particularly limited, but is, for example, 16 or less.
- the acid dissociation constant a2 is, for example, 20 or less, preferably 15 or less.
- the lower limit of the acid dissociation constant a2 is preferably -4.0 or more.
- the acid dissociation constant a1 is preferably 2.0 or less, more preferably 0 or less.
- the lower limit of the acid dissociation constant a1 is preferably ⁇ 20.0 or more.
- the anion site A 1 - and the anion site A 2 - are structural sites containing negatively charged atoms or atomic groups, for example, formulas (AA-1) to (AA-3) and formula (BB -1) to (BB-6).
- the anion site A 1 - is preferably one capable of forming an acidic site with a small acid dissociation constant, and more preferably one of the formulas (AA-1) to (AA-3). AA-1) and (AA-3) are more preferred.
- the anion site A 2 - is preferably one capable of forming an acidic site having a larger acid dissociation constant than the anion site A 1 - , and is represented by any one of formulas (BB-1) to (BB-6). is more preferred, and either formula (BB-1) or (BB-4) is even more preferred.
- * represents a bonding position.
- compound (I) is not particularly limited, but includes, for example, compounds represented by formulas (Ia-1) to (Ia-5) described below.
- the compound represented by formula (Ia-1) generates an acid represented by HA 11 -L 1 -A 12 H upon exposure to actinic rays or radiation.
- M 11 + and M 12 + each independently represent an organic cation.
- a 11 - and A 12 - each independently represent a monovalent anionic functional group.
- L 1 represents a divalent linking group.
- M 11 + and M 12 + may be the same or different.
- a 11 - and A 12 - may be the same or different, but are preferably different.
- the acid dissociation constant a2 derived from the acidic site represented by HA11 is greater than the acid dissociation constant a1 derived from the acidic site represented by HA11 .
- the preferred values of the acid dissociation constant a1 and the acid dissociation constant a2 are as described above. Also, the acid generated from compound PIa and the compound represented by formula (Ia-1) upon exposure to actinic rays or radiation is the same. At least one of M 11 + , M 12 + , A 11 ⁇ , A 12 ⁇ , and L 1 may have an acid-decomposable group as a substituent.
- the monovalent anionic functional group represented by A 11 - intends a monovalent group containing the above-described anion site A 1 - .
- the monovalent anionic functional group represented by A 12 - intends a monovalent group containing the above-mentioned anion site A 2 - .
- the monovalent anionic functional groups represented by A 11 - and A 12 - include any of the above formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6). It is preferably a monovalent anionic functional group containing an anion site, selected from the group consisting of formulas (AX-1) to (AX-3) and formulas (BX-1) to (BX-7) is more preferably a monovalent anionic functional group.
- monovalent anionic functional groups represented by A 11 - monovalent anionic functional groups represented by any one of formulas (AX-1) to (AX-3) are preferred. preferable.
- monovalent anionic functional group represented by A 12 - a monovalent anionic functional group represented by any one of formulas (BX-1) to (BX-7) is preferable.
- a monovalent anionic functional group represented by any one of the formulas (BX-1) to (BX-6) is more preferable.
- R A1 and R A2 each independently represent a monovalent organic group. * represents a binding position.
- Monovalent organic groups represented by R A1 include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.
- the monovalent organic group represented by RA2 is preferably a linear, branched or cyclic alkyl group or aryl group.
- the number of carbon atoms in the alkyl group is preferably 1-15, more preferably 1-10, even more preferably 1-6.
- the above alkyl group may have a substituent.
- the substituent is preferably a fluorine atom or a cyano group, more preferably a fluorine atom.
- the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group.
- the aryl group is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
- the aryl group may have a substituent.
- the substituent is preferably a fluorine atom, an iodine atom, a perfluoroalkyl group (for example, preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), or a cyano group, a fluorine atom, an iodine atom, a perfluoroalkyl group, or a cyano group.
- Fluoroalkyl groups are more preferred.
- R 2 B represents a monovalent organic group.
- * represents a binding position.
- the monovalent organic group represented by RB is preferably a linear, branched or cyclic alkyl group or aryl group.
- the number of carbon atoms in the alkyl group is preferably 1-15, more preferably 1-10, even more preferably 1-6.
- the above alkyl group may have a substituent. Although the substituent is not particularly limited, the substituent is preferably a fluorine atom or a cyano group, more preferably a fluorine atom. When the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group.
- the carbon atom that is the bonding position in the alkyl group (for example, in the case of formulas (BX-1) and (BX-4), the carbon atom directly bonded to -CO- indicated in the formula in the alkyl group is applicable.
- the carbon atom directly bonded to -SO 2 - specified in the formula in the alkyl group corresponds, and in the case of formula (BX-6),
- the carbon atom directly bonded to N-- in the formula. has a substituent, it is preferably a substituent other than a fluorine atom or a cyano group.
- the carbon atom of the alkyl group may be substituted with carbonyl carbon.
- the aryl group is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
- the aryl group may have a substituent.
- substituents include a fluorine atom, an iodine atom, a perfluoroalkyl group (eg, preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), a cyano group, an alkyl group (eg, 1 to 10 carbon atoms).
- an alkoxy group eg, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.
- an alkoxycarbonyl group eg, 2 to 10 carbon atoms are preferred, and those having 2 to 6 carbon atoms are more preferred.
- the divalent linking group represented by L 1 is not particularly limited, and includes -CO-, -NR-, -CO-, -O-, -S-, -SO-, —SO 2 —, an alkylene group (preferably having 1 to 6 carbon atoms, which may be linear or branched), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), ), a divalent aliphatic heterocyclic group (preferably a 5- to 10-membered ring having at least one N atom, O atom, S atom, or Se atom in the ring structure, more preferably a 5- to 7-membered ring, 5 ⁇ 6-membered ring is more preferable.), a divalent aromatic heterocyclic group (at least one N atom, O atom, S atom, or Se atom in the ring structure is preferably a 5- to 10-membered ring, 5- A 7
- the above R includes a hydrogen atom or a monovalent organic group.
- the monovalent organic group is not particularly limited, for example, an alkyl group (preferably having 1 to 6 carbon atoms) is preferable.
- the alkylene group, the cycloalkylene group, the alkenylene group, the divalent aliphatic heterocyclic group, the divalent aromatic heterocyclic group, and the divalent aromatic hydrocarbon ring group have a substituent. You may have Substituents include, for example, halogen atoms (preferably fluorine atoms).
- the divalent linking group represented by L1 is preferably a divalent linking group represented by formula (L1).
- L 111 represents a single bond or a divalent linking group.
- the divalent linking group represented by L 111 is not particularly limited, and may be, for example, —CO—, —NH—, —O—, —SO—, —SO 2 —, or have a substituent.
- Alkylene group preferably having 1 to 6 carbon atoms, which may be linear or branched
- optionally substituted cycloalkylene group preferably having 3 to 15 carbon atoms
- substituted An aryl group preferably having 6 to 10 carbon atoms
- a divalent linking group combining a plurality of these groups may be mentioned.
- the substituent is not particularly limited, and examples thereof include halogen atoms.
- Each Xf 1 independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
- the number of carbon atoms in this alkyl group is preferably 1-10, more preferably 1-4.
- a perfluoroalkyl group is preferable as the alkyl group substituted with at least one fluorine atom.
- Each Xf2 independently represents a hydrogen atom, an alkyl group optionally having a fluorine atom as a substituent, or a fluorine atom.
- the number of carbon atoms in this alkyl group is preferably 1-10, more preferably 1-4.
- Xf2 preferably represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, more preferably a fluorine atom or a perfluoroalkyl group.
- Xf 1 and Xf 2 are each independently preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF 3 .
- both Xf 1 and Xf 2 are more preferably fluorine atoms.
- * represents a binding position.
- a 21a - and A 21b - each independently represent a monovalent anionic functional group.
- the monovalent anionic functional groups represented by A 21a - and A 21b - are meant to be monovalent groups containing the above-described anionic site A 1 - .
- the monovalent anionic functional groups represented by A 21a - and A 21b - are not particularly limited.
- Anionic functional groups are included.
- a 22 - represents a divalent anionic functional group.
- the divalent anionic functional group represented by A 22 - intends a divalent group containing the above-described anion site A 2 - .
- Examples of the divalent anionic functional group represented by A 22 - include divalent anionic functional groups represented by formulas (BX-8) to (BX-11) shown below.
- M 21a + , M 21b + , and M 22 + each independently represent an organic cation.
- the organic cations represented by M 21a + , M 21b + , and M 22 + are synonymous with M 1 + described above, and the preferred embodiments are also the same.
- L21 and L22 each independently represent a divalent organic group.
- the site-derived acid dissociation constant a2 is greater than the acid dissociation constant a1-1 derived from A 21a H and the acid dissociation constant a1-2 derived from the acidic site represented by A 21b H.
- the acid dissociation constant a1-1 and the acid dissociation constant a1-2 correspond to the acid dissociation constant a1 described above.
- a 21a - and A 21b - may be the same or different.
- M 21a + , M 21b + , and M 22 + may be the same or different.
- At least one of M 21a + , M 21b + , M 22 + , A 21a ⁇ , A 21b ⁇ , L 21 and L 22 may have an acid-decomposable group as a substituent.
- a 31a - and A 32 - each independently represent a monovalent anionic functional group.
- the definition of the monovalent anionic functional group represented by A 31a - is synonymous with A 21a - and A 21b - in formula (Ia-2) described above, and the preferred embodiments are also the same.
- the monovalent anionic functional group represented by A 32 - intends a monovalent group containing the above-mentioned anion site A 2 - .
- the monovalent anionic functional group represented by A 32 - is not particularly limited, and is, for example, a monovalent anionic functional group selected from the group consisting of the above formulas (BX-1) to (BX-7). is mentioned.
- a 31b - represents a divalent anionic functional group.
- the divalent anionic functional group represented by A 31b - intends a divalent group containing the above-mentioned anionic site A 1 - .
- Examples of the divalent anionic functional group represented by A 31b - include a divalent anionic functional group represented by formula (AX-4) shown below.
- M 31a + , M 31b + , and M 32 + each independently represent a monovalent organic cation.
- the organic cations represented by M 31a + , M 31b + , and M 32 + are synonymous with M 1 + described above, and the preferred embodiments are also the same.
- L 31 and L 32 each independently represent a divalent organic group.
- an acidic compound represented by A 32 H The acid dissociation constant a2 derived from the site is greater than the acid dissociation constant a1-3 derived from the acidic site represented by A 31a H and the acid dissociation constant a1-4 derived from the acidic site represented by A 31b H. .
- the acid dissociation constant a1-3 and the acid dissociation constant a1-4 correspond to the acid dissociation constant a1 described above.
- a 31a - and A 32 - may be the same or different.
- M 31a + , M 31b + , and M 32 + may be the same or different. At least one of M 31a + , M 31b + , M 32 + , A 31a ⁇ , A 32 ⁇ , L 31 and L 32 may have an acid-decomposable group as a substituent.
- a 41a ⁇ , A 41b ⁇ , and A 42 ⁇ each independently represent a monovalent anionic functional group.
- the definitions of the monovalent anionic functional groups represented by A 41a - and A 41b - are the same as those of A 21a - and A 21b - in formula (Ia-2) described above.
- the definition of the monovalent anionic functional group represented by A 42 - is the same as that of A 32 - in formula (Ia-3) described above, and the preferred embodiments are also the same.
- M 41a + , M 41b + , and M 42 + each independently represent an organic cation.
- L41 represents a trivalent organic group.
- an acidic compound represented by A 42 H The acid dissociation constant a2 derived from the site is greater than the acid dissociation constant a1-5 derived from the acidic site represented by A 41a H and the acid dissociation constant a1-6 derived from the acidic site represented by A 41b H. .
- the acid dissociation constant a1-5 and the acid dissociation constant a1-6 correspond to the acid dissociation constant a1 described above.
- a 41a ⁇ , A 41b ⁇ , and A 42 ⁇ may be the same or different.
- M 41a + , M 41b + , and M 42 + may be the same or different. At least one of M 41a + , M 41b + , M 42 + , A 41a ⁇ , A 41b ⁇ , A 42 ⁇ , and L 41 may have an acid-decomposable group as a substituent.
- the divalent organic groups represented by L 21 and L 22 in formula (Ia-2) and L 31 and L 32 in formula (Ia-3) are not particularly limited, for example, —CO— , —NR—, —O—, —S—, —SO—, —SO 2 —, an alkylene group (preferably having 1 to 6 carbon atoms, which may be linear or branched), a cycloalkylene group (preferably 3 to 15 carbon atoms), alkenylene groups (preferably 2 to 6 carbon atoms), divalent aliphatic heterocyclic groups (at least one N atom, O atom, S atom, or Se atom in the ring structure 5 A to 10-membered ring is preferred, a 5- to 7-membered ring is more preferred, and a 5- to 6-membered ring is even more preferred.), a divalent aromatic heterocyclic group (at least one N atom, O atom, S atom, or Se A 5- to 10-membered ring having an atom in the
- the above R includes a hydrogen atom or a monovalent organic group.
- the monovalent organic group is not particularly limited, for example, an alkyl group (preferably having 1 to 6 carbon atoms) is preferable.
- the alkylene group, the cycloalkylene group, the alkenylene group, the divalent aliphatic heterocyclic group, the divalent aromatic heterocyclic group, and the divalent aromatic hydrocarbon ring group have a substituent. You may have Substituents include, for example, halogen atoms (preferably fluorine atoms).
- Examples of divalent organic groups represented by L 21 and L 22 in formula (Ia-2) and L 31 and L 32 in formula (Ia-3) are represented by the following formula (L2): It is also preferred that it is a divalent organic group that
- q represents an integer of 1-3. * represents a binding position.
- Each Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
- the number of carbon atoms in this alkyl group is preferably 1-10, more preferably 1-4.
- a perfluoroalkyl group is preferable as the alkyl group substituted with at least one fluorine atom.
- Xf is preferably a fluorine atom or a C 1-4 perfluoroalkyl group, more preferably a fluorine atom or CF 3 . In particular, it is more preferable that both Xf are fluorine atoms.
- LA represents a single bond or a divalent linking group.
- the divalent linking group represented by L A is not particularly limited, and examples thereof include -CO-, -O-, -SO-, -SO 2 -, alkylene groups (preferably having 1 to 6 carbon atoms, straight-chain may be in the form of a branched chain), a cycloalkylene group (preferably having 3 to 15 carbon atoms), a divalent aromatic hydrocarbon ring group (preferably a 6- to 10-membered ring, more preferably a 6-membered ring), and Divalent linking groups in which a plurality of these are combined are included.
- the alkylene group, the cycloalkylene group, and the divalent aromatic hydrocarbon ring group may have a substituent. Substituents include, for example, halogen atoms (preferably fluorine atoms).
- Examples of the divalent organic group represented by formula (L2) include *-CF 2 -*, *-CF 2 -CF 2 -*, *-CF 2 -CF 2 -CF 2 -*, *- Ph-O- SO2 - CF2- *, *-Ph-O- SO2 - CF2 - CF2- *, *-Ph-O- SO2 - CF2 - CF2 - CF2- *, and , *—Ph—OCO—CF 2 —*.
- Ph is an optionally substituted phenylene group, preferably a 1,4-phenylene group.
- an alkyl group eg, preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms
- an alkoxy group eg, preferably having 1 to 10 carbon atoms, 1 to 1 carbon atoms, 6 is more preferable
- an alkoxycarbonyl group eg, preferably having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms.
- L 31 and L 32 in formula (Ia-3) represent a divalent organic group represented by formula (L2)
- the bond (*) on the L A side in formula (L2) is Bonding with A 31a - and A 32 - in formula (Ia-3) is preferred.
- a 51a ⁇ , A 51b ⁇ , and A 51c ⁇ each independently represent a monovalent anionic functional group.
- the monovalent anionic functional groups represented by A 51a ⁇ , A 51b ⁇ , and A 51c ⁇ are intended to be monovalent groups containing the above-described anion site A 1 ⁇ .
- the monovalent anionic functional groups represented by A 51a ⁇ , A 51b ⁇ , and A 51c ⁇ are not particularly limited, but are, for example, the group consisting of the above formulas (AX-1) to (AX-3) A selected monovalent anionic functional group can be mentioned.
- a 52a - and A 52b - represent divalent anionic functional groups.
- the divalent anionic functional groups represented by A 52a - and A 52b - are intended to be divalent groups containing the above-described anionic site A 2 - .
- the divalent anionic functional group represented by A 22 - includes, for example, divalent anionic functional groups selected from the group consisting of the above formulas (BX-8) to (BX-11).
- M 51a + , M 51b + , M 51c + , M 52a + , and M 52b + each independently represent an organic cation.
- the organic cations represented by M 51a + , M 51b + , M 51c + , M 52a + , and M 52b + are synonymous with M 1 + described above, and preferred embodiments are also the same.
- L51 and L53 each independently represent a divalent organic group.
- the divalent organic groups represented by L 51 and L 53 have the same meanings as L 21 and L 22 in formula (Ia-2) above, and the preferred embodiments are also the same.
- L52 represents a trivalent organic group.
- the trivalent organic group represented by L 52 has the same definition as L 41 in formula (Ia-4) above, and the preferred embodiments are also the same.
- the acid dissociation constant a2-1 derived from the acidic site represented by A 52a H and the acid dissociation constant a2-2 derived from the acidic site represented by A 52b H are the acid dissociation constant a1- derived from A 51a H. 1, greater than the acid dissociation constant a1-2 derived from the acidic site represented by A 51b H and the acid dissociation constant a1-3 derived from the acidic site represented by A 51c H.
- the acid dissociation constants a1-1 to a1-3 correspond to the acid dissociation constant a1 described above, and the acid dissociation constants a2-1 and a2-2 correspond to the acid dissociation constant a2 described above.
- a 51a ⁇ , A 51b ⁇ , and A 51c ⁇ may be the same or different.
- a 52a - and A 52b - may be the same or different.
- M 51a + , M 51b + , M 51c + , M 52a + , and M 52b + may be the same or different.
- At least one of M 51b + , M 51c + , M 52a + , M 52b + , A 51a ⁇ , A 51b ⁇ , A 51c ⁇ , L 51 , L 52 and L 53 is an acid-decomposable group as a substituent. may have a sexual group.
- Compound (II) is a compound having two or more of the above structural moieties X and one or more of the following structural moieties Z, wherein the first acidic It is an acid-generating compound containing two or more sites and an acid-generating compound containing the structural site Z described above.
- Structural site Z nonionic site capable of neutralizing acid
- the preferred range of the acid dissociation constant a1 derived from the acidic site represented by is the same as the acid dissociation constant a1 in the above compound PI.
- the compound (II) is a compound that generates an acid having two of the first acidic sites derived from the structural site X and the structural site Z
- the compound PII is "two HA 1 It corresponds to "a compound having When the acid dissociation constant of this compound PII is determined, the acid dissociation constant when the compound PII is "a compound having one A 1 - and one HA 1 " and "one A 1 - and one HA
- the acid dissociation constant when the "compound having 1 " becomes "the compound having two A 1 - " corresponds to the acid dissociation constant a1.
- the acid dissociation constant a1 is obtained by the method for measuring the acid dissociation constant described above.
- the above compound PII corresponds to an acid generated when compound (II) is irradiated with actinic rays or radiation.
- the two or more structural sites X may be the same or different.
- Two or more of A 1 ⁇ and two or more of M 1 + may be the same or different.
- the nonionic site capable of neutralizing the acid in the structural site Z is not particularly limited.
- a site containing a group capable of electrostatically interacting with protons or a functional group having electrons is preferred.
- a group capable of electrostatically interacting with protons or a functional group having electrons is a functional group having a macrocyclic structure such as a cyclic polyether, or a lone pair of electrons that does not contribute to ⁇ conjugation.
- a functional group having a nitrogen atom is included.
- a nitrogen atom having a lone pair of electrons that does not contribute to ⁇ -conjugation is, for example, a nitrogen atom having a partial structure represented by the following formula.
- Partial structures of functional groups having electrons or groups capable of electrostatically interacting with protons include, for example, a crown ether structure, an azacrown ether structure, a primary to tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure. Among them, primary to tertiary amine structures are preferred.
- the compound (II) is not particularly limited, but includes, for example, compounds represented by the following formulas (IIa-1) and (IIa-2).
- a 61a - and A 61b - have the same meanings as A 11 - in formula (Ia-1) above, and preferred embodiments are also the same.
- M 61a + and M 61b + have the same meanings as M 11 + in formula (Ia-1) described above, and the preferred embodiments are also the same.
- L 61 and L 62 have the same definitions as L 1 in formula (Ia-1) above, and the preferred embodiments are also the same.
- R 2X represents a monovalent organic group.
- the monovalent organic group represented by R 2X is not particularly limited . - may be substituted with one or a combination of two or more selected from the group consisting of an alkyl group (preferably having 1 to 10 carbon atoms, may be linear or branched), a cycloalkyl group (preferably has 3 to 15 carbon atoms), or an alkenyl group (preferably 2 to 6 carbon atoms).
- the alkylene group, the cycloalkylene group, and the alkenylene group may have a substituent. Examples of substituents include, but are not particularly limited to, halogen atoms (preferably fluorine atoms).
- the acid derived from the acidic site represented by A 61a H The dissociation constant a1-7 and the acid dissociation constant a1-8 derived from the acidic site represented by A 61b H correspond to the acid dissociation constant a1 described above.
- the compound PIIa-1 obtained by replacing the cation sites M 61a + and M 61b + in the structural site X in the structural site X in the compound (IIa-1) with H + is HA 61a -L 61 -N(R 2X ) -L 62 -A 61b H.
- compound PIIa-1 is the same as the acid generated from the compound represented by formula (IIa-1) upon exposure to actinic rays or radiation.
- At least one of M 61a + , M 61b + , A 61a ⁇ , A 61b ⁇ , L 61 , L 62 and R 2X may have an acid-decomposable group as a substituent.
- a 71a ⁇ , A 71b ⁇ , and A 71c ⁇ have the same meanings as A 11 ⁇ in formula (Ia-1) above, and preferred embodiments are also the same.
- M 71a + , M 71b + , and M 71c + have the same meanings as M 11 + in formula (Ia-1) above, and preferred embodiments are also the same.
- L 71 , L 72 , and L 73 have the same meanings as L 1 in formula (Ia-1) above, and preferred embodiments are also the same.
- a compound PIIa-2 obtained by replacing the cation sites M 71a + , M 71b + , and M 71c + in the structural site X of the compound (IIa-1) with H + is HA 71a -L 71 -N(L 73 -A 71c H) -L 72 -A 71b H.
- compound PIIa-2 is the same as the acid generated from the compound represented by formula (IIa-2) upon exposure to actinic rays or radiation.
- At least one of M 71a + , M 71b + , M 71c + , A 71a ⁇ , A 71b ⁇ , A 71c ⁇ , L 71 , L 72 and L 73 has an acid-decomposable group as a substituent. You may have
- Examples of the compound (B) include, for example, paragraphs [0135] to [0171] of WO2018/193954, paragraphs [0077] to [0116] of WO2020/066824, and WO2017/154345. It is also preferred to use the photoacid generators disclosed in paragraphs [0018] to [0075] and [0334] to [0335] of .
- the content of compound (B) in the composition of the present invention is not particularly limited, but is preferably 0.1% by mass or more, more preferably 1% by mass or more, based on the total solid content of the composition of the present invention. 5% by mass or more is more preferable. Moreover, the content of the compound (B) is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less, relative to the total solid content of the composition of the present invention. Compound (B) may be used alone or in combination of two or more.
- composition of the present invention can further contain other acid diffusion control agents in addition to the compound represented by general formula (DA1).
- the acid diffusion control agent traps the acid generated from the photoacid generator or the like during exposure, and acts as a quencher that suppresses the reaction of the resin (A) in the unexposed area due to excess generated acid.
- the acid diffusion control agent include basic compounds (DA), basic compounds (DB) whose basicity is reduced or lost by irradiation with actinic rays or radiation, and acid generated from the photoacid generator (B).
- R 200 , R 201 and R 202 may be the same or different and each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl represents a group (6 to 20 carbon atoms).
- R 201 and R 202 may combine with each other to form a ring.
- R 203 , R 204 , R 205 and R 206 may be the same or different and each independently represent an alkyl group having 1 to 20 carbon atoms.
- the alkyl groups in general formulas (A) and (E) may be substituted or unsubstituted.
- the substituted alkyl group is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms. More preferably, the alkyl groups in formulas (A) and (E) are unsubstituted.
- the basic compound (DA) is preferably thiazole, benzothiazole, oxazole, benzoxazole, guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine, or compounds having these structures.
- a basic compound (DB) whose basicity is reduced or lost by irradiation with actinic rays or radiation (hereinafter also referred to as "compound (DB)”) has a proton acceptor functional group, and actinic rays or It is a compound whose proton acceptor property is reduced or lost, or whose proton acceptor property is changed to acidic by being decomposed by irradiation with radiation.
- the proton-accepting functional group is a functional group having electrons or a group capable of electrostatically interacting with protons, for example, a functional group having a macrocyclic structure such as cyclic polyether, or a ⁇ -conjugated means a functional group having a nitrogen atom with a lone pair of electrons that does not contribute to A nitrogen atom having a lone pair of electrons that does not contribute to ⁇ -conjugation is, for example, a nitrogen atom having a partial structure represented by the following formula.
- Preferable partial structures of proton acceptor functional groups include, for example, a crown ether structure, an azacrown ether structure, a primary to tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure.
- the compound (DB) is decomposed by exposure to actinic rays or radiation to reduce or eliminate its proton acceptor property, or to generate a compound whose proton acceptor property is changed to an acidic one.
- the reduction or disappearance of proton acceptor property, or the change from proton acceptor property to acidity is a change in proton acceptor property due to the addition of protons to the proton acceptor functional group.
- the acid dissociation constant pKa of the compound generated by decomposition of the compound (DB) by irradiation with actinic rays or radiation preferably satisfies pKa ⁇ 1, more preferably satisfies ⁇ 13 ⁇ pKa ⁇ 1, and ⁇ More preferably, 13 ⁇ pKa ⁇ -3 is satisfied.
- onium salt (DC) compounds represented by the following general formulas (d1-1) to (d1-3) are preferable.
- R 51 is an optionally substituted hydrocarbon group
- Z 2c is an optionally substituted hydrocarbon group having 1 to 30 carbon atoms (provided that the carbon adjacent to S is not substituted with a fluorine atom)
- R 52 is an organic group
- Y 3 is a linear, branched or cyclic alkylene group or arylene group
- Rf is a fluorine atom and each M + is independently an ammonium cation, a sulfonium cation, or an iodonium cation.
- Preferred examples of the sulfonium cation or iodonium cation represented by M + include the sulfonium cations exemplified by general formula (ZI) and the iodonium cations exemplified by general formula (ZII).
- DC onium salt
- C-1 a compound represented by any one of the following general formulas (C-1) to (C-3) are preferable.
- R 1 , R 2 and R 3 each independently represent a substituent having 1 or more carbon atoms.
- L 1 represents a divalent linking group or a single bond that links the cation site and the anion site.
- —X — represents an anionic moiety selected from —COO ⁇ , —SO 3 ⁇ , —SO 2 ⁇ , and —N ⁇ —R 4 .
- R 1 to R 3 together represent one divalent substituent, which may be bonded to the N atom via a double bond.
- substituents having 1 or more carbon atoms for R 1 to R 3 include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a cycloalkylamino
- An alkyl group, a cycloalkyl group, or an aryl group is preferred.
- L 1 as a divalent linking group is a linear or branched alkylene group, a cycloalkylene group, an arylene group, a carbonyl group, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, and two of these A group formed by combining more than one species and the like can be mentioned.
- L 1 is preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of these.
- a low-molecular-weight compound (DD) having a nitrogen atom and a group that leaves under the action of an acid has a group that leaves under the action of an acid on the nitrogen atom. It is preferably an amine derivative having The group that leaves by the action of an acid is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group, more preferably a carbamate group or a hemiaminal ether group.
- the molecular weight of the compound (DD) is preferably 100-1000, more preferably 100-700, even more preferably 100-500.
- Compound (DD) may have a carbamate group with a protecting group on the nitrogen atom.
- a protecting group constituting a carbamate group is represented by the following general formula (d-1).
- Rb each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 30 carbon atoms), an aryl group (preferably having 3 to 30 carbon atoms), an aralkyl group ( preferably 1 to 10 carbon atoms) or an alkoxyalkyl group (preferably 1 to 10 carbon atoms).
- Rb's may combine with each other to form a ring.
- the alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by Rb are each independently a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, a functional group such as an oxo group, an alkoxy group, or It may be substituted with a halogen atom.
- Rb The same applies to the alkoxyalkyl group represented by Rb.
- Rb is preferably a linear or branched alkyl group, cycloalkyl group or aryl group, more preferably a linear or branched alkyl group or cycloalkyl group.
- Examples of the ring formed by connecting two Rb's to each other include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons and derivatives thereof.
- Specific structures of the group represented by formula (d-1) include, but are not limited to, structures disclosed in paragraph [0466] of US Patent Publication No. US2012/0135348A1.
- the compound (DD) preferably has a structure represented by the following general formula (6).
- l represents an integer of 0 to 2
- m represents an integer of 1 to 3
- Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
- the two Ra's may be the same or different, and the two Ra's may be linked together to form a heterocyclic ring together with the nitrogen atom in the formula.
- This heterocyclic ring may contain a heteroatom other than the nitrogen atom in the formula.
- Rb has the same definition as Rb in formula (d-1) above, and preferred examples are also the same.
- the alkyl group, cycloalkyl group, aryl group, and aralkyl group as Ra are each independently substituted with an alkyl group, cycloalkyl group, aryl group, and aralkyl group as Rb. It may be substituted with the same groups as the groups described above as good groups.
- alkyl group, cycloalkyl group, aryl group, and aralkyl group (these groups may be substituted with the above groups) for Ra include the same groups as the specific examples described above for Rb. be done.
- Specific examples of particularly preferred compounds (DD) in the present invention include, but are not limited to, compounds disclosed in paragraph [0475] of US Patent Application Publication No. 2012/0135348A1.
- the onium salt compound (DE) having a nitrogen atom in the cation moiety is preferably a compound having a basic site containing a nitrogen atom in the cation moiety.
- the basic moiety is preferably an amino group, more preferably an aliphatic amino group. More preferably all of the atoms adjacent to the nitrogen atom in the basic moiety are hydrogen atoms or carbon atoms.
- an electron-withdrawing functional group a carbonyl group, a sulfonyl group, a cyano group, a halogen atom, etc.
- Preferred specific examples of the compound (DE) include, but are not limited to, compounds disclosed in paragraph [0203] of US Patent Application Publication No. 2015/0309408A1.
- the acid diffusion controller may be used singly or in combination of two or more.
- the content of the other acid diffusion controller in the composition of the invention (Total if multiple types are present) is preferably 0.001 to 20% by mass, more preferably 0.01 to 15% by mass, based on the total solid content of the composition of the present invention.
- the composition of the invention preferably contains a solvent.
- a known resist solvent can be appropriately used as a solvent in the composition of the present invention.
- the solvent include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate, alkyl alkoxypropionate, cyclic lactone (preferably having 4 to 10 carbon atoms), monoketone compound which may have a ring. (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates, and alkyl pyruvates.
- the description in paragraphs [0187] to [0197] of International Publication No. 2019/058890 can be referred to, and the contents thereof are incorporated herein.
- the solid content concentration of the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is generally 1.0 to 30% by mass, preferably 1.5 to 10% by mass. By setting the solid content concentration within the above range, the resist solution can be uniformly applied onto the substrate.
- the solid content concentration is the mass percentage of the mass of other components excluding the solvent with respect to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition.
- the composition of the invention may further contain a surfactant.
- a surfactant By containing a surfactant, when an exposure light source with a wavelength of 250 nm or less, particularly 220 nm or less is used, it is possible to form a pattern with good adhesion and less development defects with good sensitivity and resolution. Become.
- the surfactant it is particularly preferable to use a fluorine-based and/or silicon-based surfactant.
- the description in paragraphs [0183] to [0184] of WO2019/058890 can be considered, and the contents thereof are incorporated herein.
- composition of the present invention contains a surfactant
- its content is preferably greater than 0 to 2% by mass, more preferably 0.0001 to 2% by mass, based on the total solid content of the composition, More preferably, it is 0.0005 to 1% by mass.
- the composition of the present invention contains a carboxylic acid, a carboxylic acid onium salt, a dissolution inhibiting compound having a molecular weight of 3000 or less described in Proceeding of SPIE, 2724, 355 (1996), a dye, and a plasticizer. , a photosensitizer, a light absorber, an antioxidant, and the like can be appropriately contained.
- Carboxylic acid in particular, can be suitably used to improve performance.
- Preferred carboxylic acids are aromatic carboxylic acids such as benzoic acid and naphthoic acid.
- the content of the carboxylic acid is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, based on the total solid content of the composition. It is preferably 0.01 to 3% by mass.
- the composition of the present invention relates to an actinic ray- or radiation-sensitive resin composition that reacts with irradiation of actinic rays or radiation to change its properties. More specifically, the composition of the present invention can be used in semiconductor manufacturing processes such as IC (Integrated Circuit), circuit board manufacturing such as liquid crystals or thermal heads, manufacturing of imprint mold structures, other photofabrication processes, or The present invention relates to an actinic ray- or radiation-sensitive resin composition used for producing a lithographic printing plate or an acid-curable composition.
- the pattern formed in the present invention can be used in an etching process, an ion implantation process, a bump electrode forming process, a rewiring forming process, MEMS (Micro Electro Mechanical Systems), and the like.
- the present invention also relates to an actinic ray- or radiation-sensitive film (preferably a resist film) formed from the actinic ray- or radiation-sensitive composition of the present invention described above.
- a film is formed, for example, by applying the composition of the present invention onto a support such as a substrate.
- the thickness of the actinic ray-sensitive or radiation-sensitive film is not particularly limited, it is preferably 0.02 to 0.1 ⁇ m.
- a suitable coating method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, etc.
- the coated film is prebaked at 60 to 150° C. for 1 to 20 minutes, preferably at 80 to 120° C. for 1 to 10 minutes to form a thin film.
- the topcoat that may be provided on the substrate, the actinic ray-sensitive or radiation-sensitive film, the descriptions in paragraphs [0342] to [0358] of International Publication No. 2017/056832 can be referred to, and these contents are the specification of the present application. incorporated into the book.
- the present invention a resist film forming step of forming a resist film using the actinic ray-sensitive or radiation-sensitive resin composition of the present invention; an exposure step of exposing the resist film; A developing step of developing the exposed resist film using a developer; It also relates to a patterning method comprising
- the exposure is preferably performed using an electron beam (EB), an ArF excimer laser or extreme ultraviolet (EUV), more preferably an electron beam or extreme ultraviolet.
- EB electron beam
- EUV extreme ultraviolet
- the resist film is exposed (pattern forming step).
- the exposure amount is about 1 to 100 mJ/cm 2 , preferably about 20 to 60 mJ/cm 2 in the case of ArF excimer laser, and about 0.1 to 20 ⁇ C/cm 2 , preferably 3 to 10 ⁇ C/cm in the case of electron beam. 2 , and in the case of extreme ultraviolet rays, about 0.1 to 20 mJ/cm 2 , preferably about 3 to 15 mJ/cm 2 .
- post-exposure heating on a hot plate preferably at 60 to 150°C for 5 seconds to 20 minutes, more preferably at 80 to 120°C for 15 seconds to 10 minutes, still more preferably at 80 to 120°C for 1 to 10 minutes.
- Post-exposure baking is performed, followed by development, rinsing, and drying to form a pattern.
- post-exposure heating is appropriately adjusted depending on the acid decomposability of the repeating unit having an acid decomposable group in the resin (A).
- the post-exposure heating temperature is 110° C. or higher and the heating time is 45 seconds or longer.
- an alkaline developer typically an alkaline aqueous solution
- a developer containing an organic solvent also referred to as an organic developer
- the developer is an alkaline aqueous solution
- TMAH tetramethylammonium hydroxide
- TBAH tetrabutylammonium hydroxide
- Development is carried out for 0.1 to 3 minutes, preferably 0.5 to 2 minutes, by a conventional method such as dip method, puddle method or spray method. Suitable amounts of alcohols and/or surfactants may be added to the alkaline developer.
- the unexposed portion of the film dissolves and the exposed portion is difficult to dissolve in the developer, and in the formation of a positive pattern, the exposed portion of the film is dissolved, and the unexposed portion of the film is difficult to dissolve in the developer, so that the desired pattern is formed on the substrate.
- the alkali concentration of the alkali developer is usually 0.1 to 20 mass %.
- the pH of the alkaline developer is usually 10.0-15.0. In particular, a 2.38% by weight aqueous solution of tetramethylammonium hydroxide is desirable.
- Pure water may be used as the rinse solution in the rinse treatment performed after alkali development, and an appropriate amount of surfactant may be added. Further, after the development processing or the rinsing processing, a processing for removing the developer or the rinsing liquid adhering to the pattern with a supercritical fluid can be performed.
- the developer in the above step may be a ketone solvent, an ester solvent, or an ester solvent.
- Polar solvents such as solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents can be used.
- the concentration of the organic solvent (in the case of multiple mixtures, the total) in the organic developer is preferably 50% by mass or more, more preferably 50 to 100% by mass, still more preferably 85 to 100% by mass, still more preferably 90 to 100% by weight, particularly preferably 95 to 100% by weight. Most preferably, it consists essentially of an organic solvent.
- the case where it consists substantially only of the organic solvent includes the case where a small amount of surfactant, antioxidant, stabilizer, antifoaming agent, etc. are contained.
- the organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. .
- composition for use in the present invention does not contain impurities such as components containing metals, halogen-containing metal salts, acids, alkalis, sulfur atoms or phosphorus atoms.
- impurities containing metal atoms include Na, K, Ca, Fe, Cu, Mn, Mg, Al, Cr, Ni, Zn, Ag, Sn, Pb, Li, and salts thereof. can.
- the content of impurities contained in these materials is preferably 1 ppm (parts per million) or less, more preferably 1 ppb (parts per billion) or less, further preferably 100 ppt (parts per trillion) or less, particularly preferably 10 ppt or less, Most preferably, it is substantially free (below the detection limit of the measuring device).
- impurities such as metals from various materials
- the descriptions in paragraphs [0384] to [0402] of International Publication No. 2017/056832 can be referred to, and the contents thereof are incorporated herein.
- the present invention also relates to a method of manufacturing an electronic device, including the pattern forming method described above.
- the electronic device manufactured by the method for manufacturing an electronic device of the present invention is suitably mounted in electrical and electronic equipment (for example, home appliances, OA (Office Automation) related equipment, media related equipment, optical equipment, communication equipment, etc.). be done.
- electrical and electronic equipment for example, home appliances, OA (Office Automation) related equipment, media related equipment, optical equipment, communication equipment, etc.
- Photoacid generator (B) The structure of the photoacid generator (B) used is shown below.
- Table 1 below shows the pKa of the conjugate acids of the acid diffusion controllers (D-1) to (D-10), (DX-1) and (DX-2).
- FIG. 1 shows an NMR (nuclear magnetic resonance) chart (solvent: deuterated acetone) of the compound (D-1) obtained in Synthesis Example 2.
- W-1 Megafac F176 (manufactured by Dainippon Ink and Chemicals Co., Ltd.; fluorine-based)
- W-2 Megafac R08 (manufactured by Dainippon Ink and Chemicals Co., Ltd.; fluorine and silicon type)
- W-3 Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.; silicone-based)
- W-4 Troisol S-366 (manufactured by Troy Chemical Co., Ltd.)
- W-5 KH-20 (manufactured by Asahi Glass Co., Ltd.)
- W-6 PolyFox PF-6320 (manufactured by OMNOVA Solutions Inc.; fluorine-based)
- SL-1 Propylene glycol monomethyl ether acetate (PGMEA)
- SL-2 propylene glycol monomethyl ether propionate
- SL-3 2-heptanone
- SL-4 ethyl lactate
- SL-5 propylene glycol monomethyl ether
- SL-6 cyclohexanone
- SL-7 ⁇ -butyrolactone
- SL-8 propylene carbonate
- the resulting resist composition was coated on a 6-inch Si (silicon) wafer previously treated with hexamethyldisilazane (HMDS) using a spin coater Mark 8 manufactured by Tokyo Electron, and coated on a hot plate at 130° C. for 300 seconds. After drying, a resist film with a film thickness of 100 nm was obtained. Similar results can be obtained by replacing the Si wafer with a chromium substrate.
- HMDS hexamethyldisilazane
- the wafer coated with the resist film obtained above was subjected to pattern irradiation using an electron beam lithography system (manufactured by Advantest Co., Ltd.; F7000S, acceleration voltage 50 keV). At this time, drawing was performed so as to form a line and space of 1:1. After electron beam drawing, the sheet was heated on a hot plate at 100° C. for 60 seconds, immersed in a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, rinsed with water for 30 seconds, and dried. . After that, the wafer was rotated at a rotation speed of 4000 rpm for 30 seconds, and then dried by baking at 95° C. for 60 seconds.
- TMAH tetramethylammonium hydroxide
- TMAH tetramethylammonium hydroxide
- the resist compositions of Examples 1 to 14 contain a resin (A) whose polarity increases under the action of an acid, and a compound represented by the general formula (DA1). It can be seen that the performance and LWR performance are excellent and development defects can be reduced. On the other hand, the resist compositions of Comparative Examples 1 and 2 do not contain the compound represented by the general formula (DA1), and are inferior to the resist compositions of Examples in terms of EL performance, LWR performance and development defects. was
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Materials For Photolithography (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
Abstract
Description
酸の作用により極性が増大する樹脂(A)、及び下記一般式(DA1)で表される化合物を含む、感活性光線性又は感放射線性樹脂組成物。
X1は硫黄原子又はNQ3を表す。
Q3は水素原子、有機基、-OH又は-NH2を表す。
Q1は水素原子又は置換基を表す。
X2は連結基Xz又は単結合を表す。
上記連結基Xzは、炭素原子、酸素原子、窒素原子及び硫黄原子からなる群より選択される少なくとも1つの原子からなる2価の連結基である。ただし、上記窒素原子は水素原子、アルキル基、アリール基又は芳香族ヘテロ環基と結合していてもよく、上記硫黄原子は炭化水素基と結合していてもよい。
Ara1は芳香族基を表す。
Q2は水素原子又はアルキル基を表す。
Q1とQ2とは結合して環を形成してもよい。
Q1及びQ2からなる群より選択される少なくとも1つとQ3とは結合して環を形成してもよい。
kは1~5の整数を表す。
mは1~3の整数を表す。
n及びpは各々独立に0~2の整数を表す。
ただし、m+n+p=3である。
X1、X2、Q1、Q2、Q3及びAra1は、複数存在する場合は、それぞれ同一であっても異なっていてもよい。
ただし、nが0を表す場合、下記条件(i)又は(ii)を満たす。
条件(i):X2が単結合を表し、かつAra1が芳香族ヘテロ環基を表す。
条件(ii):X2が上記連結基Xzを表す。
[2]
上記一般式(DA1)中のX2が、下記式(X2-1)~(X2-11)のいずれかで表される2価の連結基又は単結合を表す、[1]に記載の感活性光線性又は感放射線性樹脂組成物。
[3]
上記樹脂(A)が下記一般式(3)で表される繰り返し単位、下記一般式(6)で表される繰り返し単位及び下記一般式(7)で表される繰り返し単位からなる群より選択される少なくとも1つを有する、[1]又は[2]に記載の感活性光線性又は感放射線性樹脂組成物。
R5~R7は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。
L2は、2価の連結基を表す。
R8~R10は、各々独立に、アルキル基、シクロアルキル基、アリール基、アラルキル基又はアルケニル基を表す。R8~R10のうち2つが結合して環を形成してもよい。
R22~R24は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。
L4は、単結合又は2価の連結基を表す。
Ar1は、芳香族基を表す。
R25~R27は、各々独立に水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基又はアルケニル基を表す。
R26とR27とは結合して環を形成してもよい。
R24又はR25はAr1と結合してもよい。
R28~R30は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。
L5は、単結合又は2価の連結基を表す。
R31及びR32は、各々独立に、水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基又はアルケニル基を表す。
R33は、アルキル基、シクロアルキル基、アリール基、アラルキル基又はアルケニル基を表す。
R32とR33とは結合して環を形成してもよい。
[4]
上記樹脂(A)が、下記一般式(A2)で表される繰り返し単位を有する、[1]~[3]のいずれか1つに記載の感活性光線性又は感放射線性樹脂組成物。
R101、R102及びR103は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。
LAは、単結合又は2価の連結基を表す。
ArAは、芳香族基を表す。
kは、1~5の整数を表す。
ただし、R102はArAと結合してもよく、R102とArAが結合する場合、R102は単結合又はアルキレン基を表す。
[5]
上記一般式(DA1)中のnが1又は2を表す、[1]~[4]のいずれか1つに記載の感活性光線性又は感放射線性樹脂組成物。
[6]
一般式(DA1)中のQ1が窒素原子を含む置換基を表す、[5]に記載の感活性光線性又は感放射線性樹脂組成物。
[7]
上記一般式(DA1)中のnが0を表し、上記条件(i)を満たし、かつAra1が窒素原子を含む芳香族ヘテロ環基を表す、[1]~[4]のいずれか1つに記載の感活性光線性又は感放射線性樹脂組成物。
[8]
上記一般式(DA1)で表される化合物の共役酸のpKaが2以上である、[1]~[7]のいずれか1つに記載の感活性光線性又は感放射線性樹脂組成物。
[9]
上記一般式(DA1)で表される化合物が、非イオン性の化合物である、[1]~[8]のいずれか1つに記載の感活性光線性又は感放射線性樹脂組成物。
[10]
[1]~[9]のいずれか1つに記載の感活性光線性又は感放射線性樹脂組成物を用いて形成された感活性光線性又は感放射線性膜。
[11]
[1]~[9]のいずれか1つに記載の感活性光線性又は感放射線性樹脂組成物を用いてレジスト膜を形成する工程と、
上記レジスト膜を露光する工程と、
上記露光されたレジスト膜を現像液を用いて現像する工程と、
を有するパターン形成方法。
[12]
[11]に記載のパターン形成方法を含む電子デバイスの製造方法。
以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に限定されない。
置換基Tとしては、フッ素原子、塩素原子、臭素原子及びヨウ素原子等のハロゲン原子;メトキシ基、エトキシ基及びtert-ブトキシ基等のアルコキシ基;フェノキシ基及びp-トリルオキシ基等のアリールオキシ基;メトキシカルボニル基、ブトキシカルボニル基及びフェノキシカルボニル基等のアルコキシカルボニル基;アセトキシ基、プロピオニルオキシ基及びベンゾイルオキシ基等のアシルオキシ基;アセチル基、ベンゾイル基、イソブチリル基、アクリロイル基、メタクリロイル基及びメトキサリル基等のアシル基;メチルスルファニル基及びtert-ブチルスルファニル基等のアルキルスルファニル基;フェニルスルファニル基及びp-トリルスルファニル基等のアリールスルファニル基;アルキル基(例えば、炭素数1~10);シクロアルキル基(例えば、炭素数3~20);アリール基(例えば、炭素数6~20);ヘテロアリール基;水酸基;カルボキシ基;ホルミル基;スルホ基;シアノ基;アルキルアミノカルボニル基;アリールアミノカルボニル基;スルホンアミド基;シリル基;アミノ基;モノアルキルアミノ基;ジアルキルアミノ基;アリールアミノ基、ニトロ基;並びにこれらの組み合わせが挙げられる。
ソフトウェアパッケージ1: Advanced Chemistry Development (ACD/Labs) Software V8.14 for Solaris (1994-2007 ACD/Labs)。
H+解離自由エネルギーの計算方法については、例えばDFT(密度汎関数法)により計算できるが、他にも様々な手法が文献等で報告されており、これに制限されるものではない。なお、DFTを実施できるソフトウェアは複数存在するが、例えば、Gaussian16が挙げられる。
本発明の感活性光線性又は感放射線性樹脂組成物(「本発明の組成物」ともいう。)は、酸の作用により極性が増大する樹脂(A)、及び下記一般式(DA1)で表される化合物を含む、感活性光線性又は感放射線性樹脂組成物である。
X1は硫黄原子又はNQ3を表す。
Q3は水素原子、有機基、-OH又は-NH2を表す。
Q1は水素原子又は置換基を表す。
X2は連結基Xz又は単結合を表す。
上記連結基Xzは、炭素原子、酸素原子、窒素原子及び硫黄原子からなる群より選択される少なくとも1つの原子からなる2価の連結基である。ただし、上記窒素原子は水素原子、アルキル基、アリール基又は芳香族ヘテロ環基と結合していてもよく、上記硫黄原子は炭化水素基と結合していてもよい。
Ara1は芳香族基を表す。
Q2は水素原子又はアルキル基を表す。
Q1とQ2とは結合して環を形成してもよい。
Q1及びQ2からなる群より選択される少なくとも1つとQ3とは結合して環を形成してもよい。
kは1~5の整数を表す。
mは1~3の整数を表す。
n及びpは各々独立に0~2の整数を表す。
ただし、m+n+p=3である。
X1、X2、Q1、Q2、Q3及びAra1は、複数存在する場合は、それぞれ同一であっても異なっていてもよい。
ただし、nが0を表す場合、下記条件(i)又は(ii)を満たす。
条件(i):X2が単結合を表し、かつAra1が芳香族ヘテロ環基を表す。
条件(ii):X2が上記連結基Xzを表す。
本発明の組成物は、ポジ型のレジスト組成物であることが好ましい。
本発明の組成物は、アルカリ現像用のレジスト組成物であることが好ましい。
また、本発明の組成物は、化学増幅型のレジスト組成物であることが好ましく、化学増幅ポジ型レジスト組成物であることがより好ましい。
本発明の組成物は、一般式(DA1)で表される化合物を含む。一般式(DA1)で表される化合物は、ヨウ素原子が置換した芳香族基を有する含窒素化合物であり、窒素原子の周辺に窒素原子の塩基性を低下させない極性基を有する。このような構造により、一般式(DA1)で表される化合物は塩基性が高く、発生した酸をクエンチする能力が充分に高いため、良好なLWR性能を有すると考えられる。また、極性基を有することにより水素結合による酸の拡散抑制効果が高く、EL性能が良好であると考えられる。更に、極性基の親水性により典型的な現像液であるアルカリ現像液などの水性現像液への溶解性が向上し現像欠陥を抑制することができると考えられる。
一般式(DA1)で表される化合物について説明する。
一般式(DA1)で表される化合物は、酸拡散制御剤として機能することができる。
X1はNQ3を表すことが好ましい。
Q3が有機基を表す場合の有機基は特に限定されないが、炭素数1~20の有機基であることが好ましく、炭素数1~10の有機基であることがより好ましい。
Q3が有機基を表す場合の有機基は、アルキル基、シクロアルキル基、アルケニル基、アリール基、ヘテロ環基、-OQ3a又は-NQ3bQ3cであることが好ましい。Q3aは有機基を表す。Q3bは有機基を表す。Q3cは水素原子又は有機基を表す。
芳香族ヘテロ環基としては、例えば、ピロール、イミダゾール、ピラゾール、オキサゾール、イソオキサゾール、チアゾール、イソチアゾール、トリアゾール等の窒素原子を1つ以上含む五員環芳香族ヘテロ環化合物から1つの水素原子を取り除いた基、及び、ピリジン、ピラジン、ピリミジン、ピリダジン、トリアジン、チアジン、オキサジン等の窒素原子を1つ以上含む六員環芳香族ヘテロ環化合物から1つの水素原子を取り除いた基などが挙げられる。
また、芳香族ヘテロ環基は、上記五員環芳香族ヘテロ環化合物又は上記六員環芳香族ヘテロ環化合物が、上記五員環芳香族ヘテロ環化合物、上記六員環芳香族ヘテロ環化合物、芳香族炭化水素(例えば、ベンゼン、ナフタレン等)、シクロアルカン(例えば、シクロペンタン、シクロヘキサン等)、及び非芳香族ヘテロ環化合物(例えば、後述する五員環非芳香族ヘテロ環化合物、六員環非芳香族ヘテロ環化合物等)からなる群より選択される少なくとも1つと縮環した化合物(例えば、インドール、キノリン、イソキノリン等)から1つの水素原子を取り除いた基であってもよい。
上記芳香族ヘテロ環基は置換基を有していてもよい。
上記芳香族ヘテロ環基に環員として含まれる炭素原子には、オキソ基(=O)が置換してもよい。
非芳香族ヘテロ環基としては、例えば、ピロリジン、ピロリン、2-オキサゾリドン等の窒素原子を1つ以上含む五員環非芳香族ヘテロ環化合物から1つの水素原子を取り除いた基、及び、モルホリン、ピペリジン、ピペラジン等の窒素原子を1つ以上含む六員環非芳香族ヘテロ環化合物から1つの水素原子を取り除いた基などが挙げられる。
また、非芳香族ヘテロ環基は、上記五員環非芳香族ヘテロ環化合物又は上記六員環非芳香族ヘテロ環化合物が、上記五員環非芳香族ヘテロ環化合物、上記六員環非芳香族ヘテロ環化合物及びシクロアルカン(例えば、シクロペンタン、シクロヘキサン等)からなる群より選択される少なくとも1つと縮環した化合物から1つの水素原子を取り除いた基であってもよい。
上記非芳香族ヘテロ環基は置換基を有していてもよい。
上記非芳香族ヘテロ環基に環員として含まれる炭素原子には、オキソ基(=O)が置換してもよい。
Q1が置換基を表す場合の置換基としては特に限定されないが、アルキル基、シクロアルキル基、アルケニル基、アリール基、ヘテロ環基、シアノ基、ニトロ基又はアミノ基が好ましい。
Q1がアミノ基を表す場合のアミノ基は、-NQ1aQ1bで表されることが好ましい。Q1a及びQ1bはそれぞれ独立に水素原子又は置換基を表し、Q1aとQ1bとは結合して環を形成してもよい。
Q1a及びQ1bが置換基を表す場合の置換基は特に限定されないが、有機基が好ましい。上記有機基としては、例えば、アルキル基、シクロアルキル基、アルケニル基、アリール基、ヘテロ環基又は下記一般式(na1)で表される基が挙げられる。上記アルキル基、シクロアルキル基、アルケニル基、アリール基及びヘテロ環基の説明、具体例及び好ましい範囲は、Q3がアルキル基、シクロアルキル基、アルケニル基、アリール基又はヘテロ環基を表す場合の各基について記載したものと同様である。
連結基Xzは、炭素原子、酸素原子、窒素原子及び硫黄原子からなる群より選択される少なくとも1つの原子からなる2価の連結基である。ただし、上記窒素原子は水素原子、アルキル基、アリール基又は芳香族ヘテロ環基と結合していてもよく、上記硫黄原子は炭化水素基と結合していてもよい。
また、X2は2価の炭化水素基と、エステル結合及びエーテル結合から選ばれる少なくとも1種とからなることはない。
Q4及びQ5がアルキル基、アリール基又は芳香族ヘテロ環基を表す場合の各基の説明、具体例及び好ましい範囲は、Q3がアルキル基、アリール基又は芳香族ヘテロ環基を表す場合の各基について記載したものと同様である。
上記炭化水素基は、炭素数1~20の炭化水素基であることが好ましく、炭素数1~10の炭化水素基であることが好ましい。上記炭化水素基は、アルキル基、シクロアルキル基、アルケニル基又はアリール基であることが好ましい。上記アルキル基、シクロアルキル基、アルケニル基又はアリール基の説明、具体例及び好ましい範囲は、Q3がアルキル基、シクロアルキル基、アルケニル基又はアリール基を表す場合の各基について記載したものと同様である。
Q6がアルキル基、アリール基又は芳香族ヘテロ環基を表す場合の各基の説明、具体例及び好ましい範囲は、Q3がアルキル基、アリール基又は芳香族ヘテロ環基を表す場合の各基について記載したものと同様である。
G1がアルキル基、アリール基又は芳香族ヘテロ環基を表す場合の各基の説明、具体例及び好ましい範囲は、Q3がアルキル基、アリール基又は芳香族ヘテロ環基を表す場合の各基について記載したものと同様である。
X5は酸素原子を表すことが好ましい。
G2が表す炭化水素基の説明、具体例及び好ましい範囲は、X3及びX4が炭化水素基を表す場合に記載したものと同様である。
G3及びG4がアルキル基、アリール基又は芳香族ヘテロ環基を表す場合の各基の説明、具体例及び好ましい範囲は、Q3がアルキル基、アリール基又は芳香族ヘテロ環基を表す場合の各基について記載したものと同様である。
X6は-NG3G4を表すことが好ましい。
Ara1が表す芳香族基としては、アリール基又は芳香族ヘテロ環基が好ましい。
Ara1がアリール基又は芳香族ヘテロ環基を表す場合の具体例及び好ましい範囲は、Q3がアリール基又は芳香族ヘテロ環基を表す場合の各基について記載したものと同様である。
条件(i):X2が単結合を表し、かつAra1が芳香族ヘテロ環基を表す。
条件(ii):X2が上記連結基Xzを表す。
Q2がアルキル基を表す場合の具体例及び好ましい範囲は、Q3がアルキル基を表す場合に記載したものと同様である。
Q1とQ2とが結合して環を形成する場合の環を「環Qr」とも呼ぶ。
環Qrは単環であっても多環であってもよい。単環の場合は、五員環又は六員環が好ましい。
環Qrは少なくとも1つの窒素原子を環員として含むが、更に窒素原子、酸素原子及び硫黄原子からなる群より選択される少なくとも1つを環員として含んでもよい。
環Qrは芳香環であっても非芳香環であってもよい。
環Qrが芳香環である場合の芳香環としては、例えば、Q3が芳香族ヘテロ環基を表す場合に記載した窒素原子を1つ以上含む五員環芳香族ヘテロ環化合物、窒素原子を1つ以上含む六員環芳香族ヘテロ環化合物、上記五員環芳香族ヘテロ環化合物又は上記六員環芳香族ヘテロ環化合物が、上記五員環芳香族ヘテロ環化合物、上記六員環芳香族ヘテロ環化合物、芳香族炭化水素、シクロアルカン、及び非芳香族ヘテロ環化合物からなる群より選択される少なくとも1つと縮環した化合物等が有する環構造が挙げられる。
環Qrが非芳香環である場合の非芳香環としては、例えば、Q3が非芳香族ヘテロ環基を表す場合に記載した窒素原子を1つ以上含む五員環非芳香族ヘテロ環化合物、窒素原子を1つ以上含む六員環非芳香族ヘテロ環化合物、上記五員環非芳香族ヘテロ環化合物又は上記六員環非芳香族ヘテロ環化合物が、上記五員環非芳香族ヘテロ環化合物、上記六員環非芳香族ヘテロ環化合物、及びシクロアルカンからなる群より選択される少なくとも1つと縮環した化合物等が有する環構造が挙げられる。
環Qrは置換基を有していてもよい。
Q1及びQ2からなる群より選択される少なくとも1つとQ3とが結合して環を形成する場合の環を「環Qs」とも呼ぶ。
環Qsの説明、具体例及び好ましい範囲は、環Qrについて記載したものと同様である。
現像欠陥をより低減できるという理由から、nは1若しくは2を表すか、又は、nが0を表し、上記条件(ii)を満たし、かつX2が上記式(X2-11)で表される2価の連結基を表すことが好ましい。
一般式(DA1)中のnが1又は2を表し、かつ一般式(DA1)で表される化合物の共役酸のpKaが2以上であることが特に好ましい。
本発明の組成物中、一般式(DA1)で表される化合物の含有量(複数種存在する場合はその合計)は、本発明の組成物の全固形分を基準として、0.001~40質量%が好ましく、0.01~30質量%がより好ましく、0.1~20質量%が更に好ましい。
なお、固形分とは、組成物中の溶剤を除いた成分を意図し、溶剤以外の成分であれば液状成分であっても固形分とみなす。
また、対応する芳香族化合物のヨウ素化によっても合成することができる。ヨウ素化については、例えば、「鈴木二美監修,マナック(株)研究所,臭素およびヨウ素化合物の有機合成 試薬と合成法(2017).丸善出版」等を参照することができる。
酸の作用により極性が増大する樹脂(A)(「樹脂(A)」ともいう。)について説明する。
樹脂(A)は、酸の作用により分解し極性が増大する樹脂である。
樹脂(A)は、酸の作用により分解し極性が増大する基(「酸分解性基」ともいう。)を含むことが好ましく、酸分解性基を有する繰り返し単位を含むことがより好ましい。
樹脂(A)は、酸の作用により極性が増大してアルカリ現像液に対する溶解度が増大し、有機溶剤に対する溶解度が減少する。
樹脂(A)を含む本発明の組成物を用いたパターン形成では、典型的には、現像液としてアルカリ現像液を採用した場合にはポジ型パターンが形成され、現像液として有機系現像液を採用した場合にはネガ型パターンが形成される。
上記極性基としては、アルカリ可溶性基が好ましく、例えば、カルボキシ基、フェノール性水酸基、フッ素化アルコール基、スルホン酸基、リン酸基、スルホンアミド基、スルホニルイミド基、(アルキルスルホニル)(アルキルカルボニル)メチレン基、(アルキルスルホニル)(アルキルカルボニル)イミド基、ビス(アルキルカルボニル)メチレン基、ビス(アルキルカルボニル)イミド基、ビス(アルキルスルホニル)メチレン基、ビス(アルキルスルホニル)イミド基、トリス(アルキルカルボニル)メチレン基、及びトリス(アルキルスルホニル)メチレン基等の酸性基、並びにアルコール性水酸基等が挙げられる。
上記極性基としては、カルボキシ基、フェノール性水酸基、フッ素化アルコール基(好ましくはヘキサフルオロイソプロパノール基)、又はスルホン酸基が好ましく、カルボキシ基又はフェノール性水酸基がより好ましい。つまり、酸分解性基としては、酸の作用により分解してカルボキシ基を生じる基、又は酸の作用により分解してフェノール性水酸基を生じる基が好ましい。
樹脂(A)が、酸の作用により分解してカルボキシ基を生じる基及び酸の作用により分解してフェノール性水酸基を生じる基からなる群より選ばれる少なくとも1つの酸分解性基を有する繰り返し単位を有することが好ましい。
式(Y1):-C(Rx1)(Rx2)(Rx3)
式(Y2):-C(=O)OC(Rx1)(Rx2)(Rx3)
式(Y3):-C(R36)(R37)(OR38)
式(Y4):-C(Rn)(H)(Ar)
なかでも、Rx1~Rx3は、それぞれ独立に、直鎖状又は分岐鎖状のアルキル基を表すことが好ましく、Rx1~Rx3は、それぞれ独立に、直鎖状のアルキル基を表すことがより好ましい。
Rx1~Rx3の2つが互いに結合して環(単環及び多環のいずれであってもよい)を形成してもよい。
Rx1~Rx3のシクロアルキル基としては、シクロペンチル基、及びシクロヘキシル基等の単環のシクロアルキル基、並びにノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及びアダマンチル基等の多環のシクロアルキル基が好ましい。
Rx1~Rx3のアリール基としては、炭素数6~10のアリール基が好ましく、例えば、フェニル基、ナフチル基、及びアントリル基等が挙げられる。
Rx1~Rx3のアラルキル基としては、上述したRx1~Rx3のアルキル基中の1個の水素原子を炭素数6~10のアリール基(好ましくはフェニル基)で置換した基が好ましく、例えば、ベンジル基等が挙げられる。
Rx1~Rx3のアルケニル基としては、ビニル基が好ましい。
Rx1~Rx3の2つが結合して形成されるシクロアルキル基は、例えば、環を構成するメチレン基の1つが、酸素原子等のヘテロ原子、カルボニル基等のヘテロ原子を有する基、又はビニリデン基で置き換わっていてもよい。また、これらのシクロアルキル基は、シクロアルカン環を構成するエチレン基の1つ以上が、ビニレン基で置き換わっていてもよい。
式(Y1)又は式(Y2)で表される基は、例えば、Rx1がメチル基又はエチル基であり、Rx2とRx3とが結合して上述のシクロアルキル基を形成している態様が好ましい。
なお、上記アルキル基、シクロアルキル基、アリール基、及びアラルキル基には、酸素原子等のヘテロ原子及び/又はカルボニル基等のヘテロ原子を有する基が含まれていてもよい。例えば、上記アルキル基、シクロアルキル基、アリール基、及びアラルキル基は、例えば、メチレン基の1つ以上が、酸素原子等のヘテロ原子及び/又はカルボニル基等のヘテロ原子を有する基で置き換わっていてもよい。
また、R38は、繰り返し単位の主鎖が有する別の置換基と互いに結合して、環を形成してもよい。R38と繰り返し単位の主鎖が有する別の置換基とが互いに結合して形成する基は、メチレン基等のアルキレン基が好ましい。
Mは、単結合又は2価の連結基を表す。
Qは、ヘテロ原子を含んでいてもよいアルキル基、ヘテロ原子を含んでいてもよいシクロアルキル基、ヘテロ原子を含んでいてもよいアリール基、アミノ基、アンモニウム基、メルカプト基、シアノ基、アルデヒド基、又はこれらを組み合わせた基(例えば、アルキル基とシクロアルキル基とを組み合わせた基)を表す。
アルキル基及びシクロアルキル基は、例えば、メチレン基の1つが、酸素原子等のヘテロ原子、又はカルボニル基等のヘテロ原子を有する基で置き換わっていてもよい。
なお、L1及びL2のうち一方は水素原子であり、他方はアルキル基、シクロアルキル基、アリール基、又はアルキレン基とアリール基とを組み合わせた基であることが好ましい。
Q、M、及びL1の少なくとも2つが結合して環(好ましくは、5員若しくは6員環)を形成してもよい。
パターンの微細化の点では、L2が2級又は3級アルキル基であることが好ましく、3級アルキル基であることがより好ましい。2級アルキル基としては、イソプロピル基、シクロヘキシル基又はノルボルニル基が挙げられ、3級アルキル基としては、tert-ブチル基又はアダマンタン基が挙げられる。これらの態様では、Tg(ガラス転移温度)及び活性化エネルギーが高くなるため、膜強度の担保に加え、かぶりの抑制ができる。
R5~R7は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。
L2は、2価の連結基を表す。
R8~R10は、各々独立に、アルキル基、シクロアルキル基、アリール基、アラルキル基又はアルケニル基を表す。R8~R10のうち2つが結合して環を形成してもよい。
R22~R24は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。
L4は、単結合又は2価の連結基を表す。
Ar1は、芳香族基を表す。
R25~R27は、各々独立に水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基又はアルケニル基を表す。
R26とR27とは結合して環を形成してもよい。
R24又はR25はAr1と結合してもよい。
R28~R30は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。
L5は、単結合又は2価の連結基を表す。
R31及びR32は、各々独立に、水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基又はアルケニル基を表す。
R33は、アルキル基、シクロアルキル基、アリール基、アラルキル基又はアルケニル基を表す。
R32とR33とは結合して環を形成してもよい。
一般式(3)で表される繰り返し単位は、酸分解性基を有する繰り返し単位である。
R5、R6、及びR7で表されるシクロアルキル基としては、シクロペンチル基、及びシクロヘキシル基等の単環のシクロアルキル基、並びにノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及びアダマンチル基等の多環のシクロアルキル基が好ましい。
R5、R6、及びR7で表されるハロゲン原子としては、フッ素原子、塩素原子、臭素原子、及びヨウ素原子が挙げられ、フッ素原子又はヨウ素原子が好ましい。
R5、R6、及びR7で表されるアルコキシカルボニル基中に含まれるアルキル基としては直鎖状及び分岐鎖状のいずれであってもよい。アルコキシカルボニル基中に含まれるアルキル基の炭素数は特に制限されないが、1~5が好ましく、1~3がより好ましい。
R8~R10で表されるシクロアルキル基としては、シクロペンチル基、及びシクロヘキシル基等の単環のシクロアルキル基、並びにノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及びアダマンチル基等の多環のシクロアルキル基が好ましい。
R8~R10で表されるアリール基としては、フェニル基が好ましい。
R8~R10で表されるアラルキル基としては、上述したR8~R10で表されるアルキル基中の1個の水素原子を炭素数6~10のアリール基(好ましくはフェニル基)で置換した基が好ましく、例えば、ベンジル基等が挙げられる。
R8~R10で表されるアルケニル基としては、ビニル基が好ましい。
R8~R10の2つが結合して形成される環としては、シクロアルキル基が好ましい。R8~R10の2つが結合して形成されるシクロアルキル基としては、シクロペンチル基、若しくは、シクロヘキシル基等の単環のシクロアルキル基、又はノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、若しくは、アダマンチル基等の多環のシクロアルキル基が好ましく、炭素数5~6の単環のシクロアルキル基がより好ましい。
R8~R10の2つが結合して形成されるシクロアルキル基は、例えば、環を構成するメチレン基の1つが、酸素原子等のヘテロ原子、カルボニル基等のヘテロ原子を有する基、又はビニリデン基で置き換わっていてもよい。また、これらのシクロアルキル基は、シクロアルカン環を構成するエチレン基の1つ以上が、ビニレン基で置き換わっていてもよい。
一般式(6)で表される繰り返し単位は、酸分解性基を有する繰り返し単位である。
L4が2価の連結基を表す場合の2価の連結基としては、-CO-、-O-、-S-、-SO-、-SO2-、炭化水素基(例えば、アルキレン基、シクロアルキレン基、アルケニレン基、アリーレン基等)、及びこれらの複数が連結した連結基等が挙げられる。
Ar1で表される芳香族基としては特に制限されないが、例えばフェニレン基又はナフチレン基が挙げられ、フェニレン基が好ましい。
R25~R27で表されるアルキル基、シクロアルキル基、アリール基、アラルキル基、及びアルケニル基としては、上述した一般式(3)中のR8~R10で表されるアルキル基、シクロアルキル基、アリール基、アラルキル基、及びアルケニル基と同様の基が挙げられる。
R25~R27で表される、上記アルキル基、シクロアルキル基、アリール基、アラルキル基、及びアルケニル基は置換基を有していてもよく、置換基としては、例えば、上記置換基Tが挙げられる。
R26とR27、Ar1とR24、及びR25とAr1が結合して形成されるシクロアルキル基は、例えば、環を構成するメチレン基の1つが、酸素原子等のヘテロ原子、カルボニル基等のヘテロ原子を有する基、又はビニリデン基で置き換わっていてもよい。また、これらのシクロアルキル基は、シクロアルカン環を構成するエチレン基の1つ以上が、ビニレン基で置き換わっていてもよい。
一般式(7)で表される繰り返し単位は、酸分解性基を有する繰り返し単位である。
R31、R32、及びR33で表されるアルキル基、シクロアルキル基、アリール基、アラルキル基、及びアルケニル基としては、上述した一般式(3)中のR8~R10で表されるアルキル基、シクロアルキル基、アリール基、アラルキル基、及びアルケニル基と同様の基が挙げられる。
R31、R32、及びR33で表される、上記アルキル基、シクロアルキル基、アリール基、アラルキル基、及びアルケニル基は置換基を有していてもよく、置換基としては、例えば、上記置換基Tが挙げられる。
R32とR33が結合して形成される環としては、シクロアルキル基が好ましい。R32とR33が結合して形成されるシクロアルキル基としては、シクロペンチル基、若しくは、シクロヘキシル基等の単環のシクロアルキル基、又はノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、若しくは、アダマンチル基等の多環のシクロアルキル基が好ましく、炭素数5~6の単環のシクロアルキル基がより好ましい。
R32とR33が結合して形成されるシクロアルキル基は、例えば、環を構成するメチレン基の1つが、酸素原子等のヘテロ原子、カルボニル基等のヘテロ原子を有する基、又はビニリデン基で置き換わっていてもよい。また、これらのシクロアルキル基は、シクロアルカン環を構成するエチレン基の1つ以上が、ビニレン基で置き換わっていてもよい。
樹脂(A)は、下記一般式(A2)で表される繰り返し単位を有することが好ましい。
R101、R102及びR103は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。
LAは、単結合又は2価の連結基を表す。
ArAは、芳香族基を表す。
kは、1~5の整数を表す。
ただし、R102はArAと結合してもよく、R102とArAが結合する場合、R102は単結合又はアルキレン基を表す。
一般式(A2)中のR103は水素原子又はメチル基であることが好ましく、水素原子であることがより好ましい。
(k+1)価の芳香族基は、更に置換基を有していてもよい。
LAが2価の連結基を表す場合の2価の連結基としては、特に限定されないが、例えば、-COO-、-CONR64-、アルキレン基、又はこれらの基の2種以上を組み合わせてなる基が挙げられる。上記R64は水素原子又はアルキル基を表す。
上記アルキレン基としては、特に限定されないが、メチレン基、エチレン基、プロピレン基、ブチレン基、ヘキシレン基、及びオクチレン基等の炭素数1~8のアルキレン基が好ましい。
R64がアルキル基を表す場合のアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、sec-ブチル基、ヘキシル基、2-エチルヘキシル基、オクチル基、ドデシル基等の炭素数20以下のアルキル基が挙げられ、炭素数8以下のアルキル基が好ましい。
kは1~3の整数を表すことが好ましく、1又は2を表すことがより好ましい。
樹脂(A)は、上述した繰り返し単位以外のその他の繰り返し単位を含んでいてもよい。
樹脂(A)が、上述した繰り返し単位以外のその他の繰り返し単位を含む場合、その他の繰り返し単位の含有量は特に限定されないが、樹脂(A)中の全繰り返し単位に対して1モル%以上60モル%以下であることが好ましく、3モル%以上50モル%以下であることがより好ましく、5モル%以上40モル%以下であることが更に好ましい。
樹脂(A)は、上記した繰り返し単位以外に、更に、酸基を有する繰り返し単位を有していてもよい。
酸基としては、例えば、カルボキシ基、フッ素化アルコール基(好ましくはヘキサフルオロイソプロパノール基)、スルホン酸基、スルホンアミド基、イソプロパノール基等が好ましい。
また、上記ヘキサフルオロイソプロパノール基は、フッ素原子の1つ以上(好ましくは1~2つ)が、フッ素原子以外の基(例えばアルキルオキシカルボニル基等)で置換されてもよい。このように形成された-C(CF3)(OH)-CF2-も、酸基として好ましい。また、フッ素原子の1つ以上がフッ素原子以外の基に置換されて、-C(CF3)(OH)-CF2-を含む環を形成してもよい。
酸基を有する繰り返し単位の具体例としては、例えば国際公開第2019/054282号の段落[0205]の記載を参酌でき、これらの内容は本願明細書に組み込まれる。ただし、酸基を有する繰り返し単位はこれらに限定されるものではない。
樹脂(A)は、上記した繰り返し単位以外に、更に、フッ素原子又はヨウ素原子を有し、酸分解性を示さない繰り返し単位を有していてもよい。
樹脂(A)は、上記した繰り返し単位以外に、更に、ラクトン基、スルトン基又はカーボネート基を有する繰り返し単位を有していてもよい。
樹脂(A)は、下記一般式(LC1-1)~(LC1-21)のいずれかで表されるラクトン構造、又は下記一般式(SL1-1)~(SL1-3)のいずれかで表されるスルトン構造の環員原子から、水素原子を1つ以上引き抜いてなるラクトン基又はスルトン基を有する繰り返し単位を有することが好ましい。
また、ラクトン基又はスルトン基が主鎖に直接結合していてもよい。例えば、ラクトン基又はスルトン基の環員原子が、樹脂(A)の主鎖を構成してもよい。
ラクトン構造を有する繰り返し単位の具体例として、例えば国際公開第2018/193954号の段落[0088]の記載を参酌でき、これらの内容は本願明細書に組み込まれる。ただし、ラクトン構造を有する繰り返し単位はこれらに限定されるものではない。
樹脂(A)は光酸発生基を有する繰り返し単位を有していてもよい。光酸発生基を有する繰り返し単位としては、国際公開第2018/193954号の段落[0090]~[0096]の記載を参酌でき、これらの内容は本願明細書に組み込まれる。
樹脂(A)は、上記の繰り返し単位以外に、例えば、ドライエッチング耐性、標準現像液適性、基板密着性、レジストプロファイル、解像力、耐熱性、感度等を調節する目的で様々な繰り返し単位を有していてもよい。
上記以外のその他の繰り返し単位としては、国際公開第2018/193954号の段落[0097]~[0100]、[0102]~[0133]の記載を参酌でき、これらの内容は本願明細書に組み込まれる。
樹脂(A)の重量平均分子量は、特に限定されないが、1000~200000であることが好ましく、2000~30000であることがより好ましく、3000~20000であることが更に好ましい。
樹脂(A)の分散度(分子量分布)は、通常1.0~5.0であり、1.0~3.0であることが好ましく、1.0~2.5であることがより好ましく、1.0~2.0であることが更に好ましい。
なお、固形分とは、組成物中の溶剤を除いた成分を意図し、溶剤以外の成分であれば液状成分であっても固形分とみなす。
また、本発明の組成物に含まれる樹脂(A)は1種のみであってもよいし、2種以上であってもよい。
本発明の感活性光線性又は感放射線性樹脂組成物は、活性光線又は放射線の照射により酸を発生する化合物(光酸発生剤)を含むことが好ましい。
活性光線又は放射線の照射により酸を発生する化合物を「化合物(B)」又は「光酸発生剤(B)」とも呼ぶ。
化合物(B)が、低分子化合物の形態である場合、化合物(B)の分子量は3000以下が好ましく、2000以下がより好ましく、1000以下が更に好ましい。下限は特に制限されないが、100以上が好ましい。
化合物(B)が、重合体の一部に組み込まれた形態である場合、樹脂(A)の一部に組み込まれてもよく、樹脂(A)とは異なる樹脂に組み込まれてもよい。
化合物(B)は、低分子化合物であることが好ましい。
上記有機酸として、例えば、スルホン酸(脂肪族スルホン酸、芳香族スルホン酸、及び、カンファースルホン酸等)、カルボン酸(脂肪族カルボン酸、芳香族カルボン酸、及び、アラルキルカルボン酸等)、カルボニルスルホニルイミド酸、ビス(アルキルスルホニル)イミド酸、及び、トリス(アルキルスルホニル)メチド酸が挙げられる。
「M+ X-」で表される化合物において、M+は、有機カチオンを表す。
上記有機カチオンの構造は特に制限されない。また、有機カチオンの価数は、1又は2価以上であってもよい。
上記有機カチオンとしては、下記一般式(ZaI)で表されるカチオン(以下「カチオン(ZaI)」ともいう。)、又は、下記一般式(ZaII)で表されるカチオン(以下「カチオン(ZaII)」ともいう。)が好ましい。
一般式(ZaII)中、R204及びR205は、それぞれ独立に、有機基を表す。
上記一般式(ZaI)及び(ZaII)については以下に詳述するが、上記一般式(ZaI)中のR201、R202、及びR203の少なくとも1つがアリール基であるか、又は、上記一般式(ZaII)中のR204及びR205の少なくとも1つがアリール基であることが好ましい。上記アリール基は置換基を有していてもよく、置換基としては、ハロゲン原子(好ましくはフッ素原子又はヨウ素原子)又は有機基が好ましい。
また、上記一般式(ZaI)中のR201、R202、及びR203の少なくとも1つが酸分解性基を有するか、又は、上記一般式(ZaII)中のR204及びR205の少なくとも1つが酸分解性基を有することも好ましい。酸分解性基については樹脂(A)におけるものと同様である。上記一般式(ZaI)中のR201、R202、及びR203の少なくとも1つが酸分解性基を有する形態としては、R201、R202、及びR203の少なくとも1つが酸分解性基を含む有機基で置換されたアリール基であることが好ましい。上記一般式(ZaII)中のR204及びR205の少なくとも1つが酸分解性基を有する形態としては、R204及びR205の少なくとも1つが酸分解性基を含む有機基で置換されたアリール基であることが好ましい。
R201、R202、及びR203としての有機基の炭素数は、通常1~30であり、1~20が好ましい。また、R201~R203のうち2つが結合して環構造を形成してもよく、環内に酸素原子、硫黄原子、エステル基、アミド基、又はカルボニル基を含んでいてもよい。R201~R203の内の2つが結合して形成する基としては、例えば、アルキレン基(例えば、ブチレン基及びペンチレン基)、及び-CH2-CH2-O-CH2-CH2-が挙げられる。
カチオン(ZaI-1)は、上記式(ZaI)のR201~R203の少なくとも1つがアリール基である、アリールスルホニウムカチオンである。
アリールスルホニウムカチオンは、R201~R203の全てがアリール基でもよいし、R201~R203の一部がアリール基であり、残りがアルキル基又はシクロアルキル基であってもよい。
また、R201~R203のうちの1つがアリール基であり、R201~R203のうちの残りの2つが結合して環構造を形成してもよく、環内に酸素原子、硫黄原子、エステル基、アミド基、又はカルボニル基を含んでいてもよい。R201~R203のうちの2つが結合して形成する基としては、例えば、1つ以上のメチレン基が酸素原子、硫黄原子、エステル基、アミド基、及び/又はカルボニル基で置換されていてもよいアルキレン基(例えば、ブチレン基、ペンチレン基、及び-CH2-CH2-O-CH2-CH2-)が挙げられる。
アリールスルホニウムカチオンとしては、例えば、トリアリールスルホニウムカチオン、ジアリールアルキルスルホニウムカチオン、アリールジアルキルスルホニウムカチオン、ジアリールシクロアルキルスルホニウムカチオン、及びアリールジシクロアルキルスルホニウムカチオンが挙げられる。
アリールスルホニウムカチオンが必要に応じて有しているアルキル基又はシクロアルキル基は、炭素数1~15の直鎖状アルキル基、炭素数3~15の分岐鎖状アルキル基、又は炭素数3~15のシクロアルキル基が好ましく、メチル基、エチル基、プロピル基、n-ブチル基、sec-ブチル基、t-ブチル基、シクロプロピル基、シクロブチル基、又は、シクロヘキシル基がより好ましい。
上記置換基は可能な場合更に置換基を有していてもよく、上記アルキル基が置換基としてハロゲン原子を有して、トリフルオロメチル基等のハロゲン化アルキル基となっていることも好ましい。
また、上記置換基は任意の組み合わせにより、酸分解性基を形成することも好ましい。
なお、酸分解性基とは、酸の作用により分解して極性基を生じる基を意図し、酸の作用により脱離する脱離基で極性基が保護された構造であるのが好ましい。上記の極性基及び脱離基としては、上述の通りである。
カチオン(ZaI-2)は、式(ZaI)におけるR201~R203が、それぞれ独立に、芳香環を有さない有機基を表すカチオンである。芳香環とは、ヘテロ原子を含む芳香族環も包含する。
R201~R203としての芳香環を有さない有機基は、一般的に炭素数1~30であり、炭素数1~20が好ましい。
R201~R203は、それぞれ独立に、アルキル基、シクロアルキル基、アリル基、又はビニル基が好ましく、直鎖状又は分岐鎖状の2-オキソアルキル基、2-オキソシクロアルキル基、又はアルコキシカルボニルメチル基がより好ましく、直鎖状又は分岐鎖状の2-オキソアルキル基が更に好ましい。
R201~R203は、ハロゲン原子、アルコキシ基(例えば、炭素数1~5)、水酸基、シアノ基、又はニトロ基によって更に置換されていてもよい。
また、R201~R203の置換基は、それぞれ独立に、置換基の任意の組み合わせにより、酸分解性基を形成することも好ましい。
カチオン(ZaI-3b)は、下記式(ZaI-3b)で表されるカチオンである。
R1c~R5cは、それぞれ独立に、水素原子、アルキル基、シクロアルキル基、アリール基、アルコキシ基、アリールオキシ基、アルコキシカルボニル基、アルキルカルボニルオキシ基、シクロアルキルカルボニルオキシ基、ハロゲン原子、水酸基、ニトロ基、アルキルチオ基、又はアリールチオ基を表す。
R6c及びR7cは、それぞれ独立に、水素原子、アルキル基(例えば、t-ブチル基等)、シクロアルキル基、ハロゲン原子、シアノ基、又はアリール基を表す。
Rx及びRyは、それぞれ独立に、アルキル基、シクロアルキル基、2-オキソアルキル基、2-オキソシクロアルキル基、アルコキシカルボニルアルキル基、アリル基、又はビニル基を表す。
また、R1c~R7c、並びに、Rx及びRyの置換基は、それぞれ独立に、置換基の任意の組み合わせにより、酸分解性基を形成することも好ましい。
上記環としては、芳香族又は非芳香族の炭化水素環、芳香族又は非芳香族のヘテロ環、及びこれらの環が2つ以上組み合わされてなる多環縮合環が挙げられる。環としては、3~10員環が挙げられ、4~8員環が好ましく、5又は6員環がより好ましい。
R5cとR6c、及びR5cとRxが結合して形成する基としては、単結合又はアルキレン基が好ましい。アルキレン基としては、メチレン基及びエチレン基が挙げられる。
カチオン(ZaI-4b)は、下記式(ZaI-4b)で表されるカチオンである。
lは0~2の整数を表す。
rは0~8の整数を表す。
R13は、水素原子、ハロゲン原子(例えば、フッ素原子及びヨウ素原子等)、水酸基、アルキル基、ハロゲン化アルキル基、アルコキシ基、カルボキシ基、アルコキシカルボニル基、又はシクロアルキル基を含む基(シクロアルキル基そのものであってもよく、シクロアルキル基を一部に含む基であってもよい)を表す。これらの基は置換基を有してもよい。
R14は、水酸基、ハロゲン原子(例えば、フッ素原子及びヨウ素原子等)、アルキル基、ハロゲン化アルキル基、アルコキシ基、アルコキシカルボニル基、アルキルカルボニル基、アルキルスルホニル基、シクロアルキルスルホニル基、又はシクロアルキル基を含む基(シクロアルキル基そのものであってもよく、シクロアルキル基を一部に含む基であってもよい)を表す。これらの基は置換基を有してもよい。R14は、複数存在する場合は、それぞれ独立して、水酸基等の上記基を表す。
R15は、それぞれ独立して、アルキル基、シクロアルキル基、又はナフチル基を表す。2つのR15が互いに結合して環を形成してもよい。2つのR15が互いに結合して環を形成するとき、環骨格内に、酸素原子、又は窒素原子等のヘテロ原子を含んでもよい。一態様において、2つのR15がアルキレン基であり、互いに結合して環構造を形成するのが好ましい。なお、上記アルキル基、上記シクロアルキル基、及び上記ナフチル基、並びに、2つのR15が互いに結合して形成する環は置換基を有してもよい。
また、R13~R15、並びに、Rx及びRyの各置換基は、それぞれ独立に、置換基の任意の組み合わせにより、酸分解性基を形成するのも好ましい。
式(ZaII)中、R204及びR205は、それぞれ独立に、有機基を表し、好ましくは、アリール基、アルキル基又はシクロアルキル基を表す。
R204及びR205のアリール基は、フェニル基、又はナフチル基が好ましく、フェニル基がより好ましい。R204及びR205のアリール基は、酸素原子、窒素原子、又は硫黄原子等を有するヘテロ環を有するアリール基であってもよい。ヘテロ環を有するアリール基の骨格としては、例えば、ピロール、フラン、チオフェン、インドール、ベンゾフラン、及びベンゾチオフェンが挙げられる。
R204及びR205のアルキル基及びシクロアルキル基は、炭素数1~10の直鎖状アルキル基又は炭素数3~10の分岐鎖状アルキル基(例えば、メチル基、エチル基、プロピル基、ブチル基、又はペンチル基)、又は炭素数3~10のシクロアルキル基(例えばシクロペンチル基、シクロヘキシル基、又はノルボルニル基)が好ましい。
「M+ X-」で表される化合物において、X-は、有機アニオンを表す。
有機アニオンとしては、特に制限されず、1又は2価以上の有機アニオンが挙げられる。
有機アニオンとしては、求核反応を起こす能力が著しく低いアニオンが好ましく、非求核性アニオンがより好ましい。
上記アルキル基は、例えば、フルオロアルキル基(フッ素原子以外の置換基を有していてもよい。パーフルオロアルキル基であってもよい)であってもよい。
炭素数7~14のアラルキル基としては、例えば、ベンジル基、フェネチル基、ナフチルメチル基、ナフチルエチル基、及び、ナフチルブチル基が挙げられる。
また、ビス(アルキルスルホニル)イミドアニオンにおけるアルキル基は、互いに結合して環構造を形成してもよい。これにより、酸強度が増加する。
Lが複数存在する場合、Lは、それぞれ同一でも異なっていてもよい。
2価の連結基としては、例えば、-O-CO-O-、-COO-、-CONH-、-CO-、-O-、-S-、-SO-、-SO2-、アルキレン基(炭素数1~6が好ましい)、シクロアルキレン基(炭素数3~15が好ましい)、アルケニレン基(炭素数2~6が好ましい)、及び、これらの複数を組み合わせた2価の連結基が挙げられる。なかでも、2価の連結基としては、-O-CO-O-、-COO-、-CONH-、-CO-、-O-、-SO2-、-O-CO-O-アルキレン基-、-COO-アルキレン基-、又は、-CONH-アルキレン基-が好ましく、-O-CO-O-、-O-CO-O-アルキレン基-、-COO-、-CONH-、-SO2-、又は、-COO-アルキレン基-がより好ましい。
*a-(CR2a 2)X-Q-(CR2b 2)Y-*b (AN4-2)
*bは、式(AN4)における-C(R1)(R2)-との結合位置を表す。
X及びYは、それぞれ独立に、0~10の整数を表し、0~3の整数が好ましい。
R2a及びR2bは、それぞれ独立に、水素原子又は置換基を表す。
R2a及びR2bがそれぞれ複数存在する場合、複数存在するR2a及びR2bは、それぞれ同一でも異なっていてもよい。
ただし、Yが1以上の場合、式(AN4)における-C(R1)(R2)-と直接結合するCR2b 2におけるR2bは、フッ素原子以外である。
Qは、*A-O-CO-O-*B、*A-CO-*B、*A-CO-O-*B、*A-O-CO-*B、*A-O-*B、*A-S-*B、又は、*A-SO2-*Bを表す。
ただし、式(AN4-2)中のX+Yが1以上かつ、式(AN4-2)中のR2a及びR2bのいずれもが全て水素原子である場合、Qは、*A-O-CO-O-*B、*A-CO-*B、*A-O-CO-*B、*A-O-*B、*A-S-*B、又は、*A-SO2-*Bを表す。
*Aは、式(AN4)におけるR3側の結合位置を表し、*Bは、式(AN4)における-SO3 -側の結合位置を表す。
上記有機基は、炭素原子を1以上有していれば制限はなく、直鎖状の基(例えば、直鎖状のアルキル基)でも、分岐鎖状の基(例えば、t-ブチル基等の分岐鎖状のアルキル基)でもよく、環状の基であってもよい。上記有機基は、置換基を有していても、有していなくてもよい。上記有機基は、ヘテロ原子(酸素原子、硫黄原子、及び/又は、窒素原子等)を有していても、有してなくてもよい。
上記有機基の例としては、電子求引性基ではない置換基も挙げられる。
上記電子求引性基ではない置換基としては、例えば、炭化水素基、水酸基、オキシ炭化水素基、オキシカルボニル炭化水素基、アミノ基、炭化水素置換アミノ基、及び、炭化水素置換アミド基が挙げられる。
また、電子求引性基ではない置換基としては、それぞれ独立に、-R’、-OH、-OR’、-OCOR’、-NH2、-NR’2、-NHR’、又は、-NHCOR’が好ましい。R’は、1価の炭化水素基である。
なかでも、R1及びR2は、それぞれ独立に、炭化水素基(シクロアルキル基が好ましい)又は水素原子が好ましい。
上記環状構造を有する有機基は、例えば、ヘテロ原子(酸素原子、硫黄原子、及び/又は、窒素原子等)を有していても、有してなくてもよい。ヘテロ原子は、環状構造を形成する炭素原子の1つ以上と置換していてもよい。
上記環状構造を有する有機基は、例えば、環状構造の炭化水素基、ラクトン環基、及び、スルトン環基が好ましい。なかでも、上記環状構造を有する有機基は、環状構造の炭化水素基が好ましい。
上記環状構造の炭化水素基は、単環又は多環のシクロアルキル基が好ましい。これらの基は、置換基を有していてもよい。
上記シクロアルキル基は、単環(シクロヘキシル基等)でも多環(アダマンチル基等)でもよく、炭素数は5~12が好ましい。
上記ラクトン基及びスルトン基としては、例えば、前述の式(LC1-1)~(LC1-21)で表される構造、及び、式(SL1-1)~(SL1-3)で表される構造のいずれかにおいて、ラクトン構造又はスルトン構造を構成する環員原子から、水素原子を1つ除いてなる基が好ましい。
少なくとも1つのXfは、フッ素原子又は炭素数1~4のパーフルオロアルキル基であることが好ましく、フッ素原子又はCF3であることがより好ましく、双方のXfがフッ素原子であることが更に好ましい。
R4及びR5で表されるアルキル基は、炭素数1~4が好ましい。上記アルキル基は置換基を有していてもよい。R4及びR5としては、水素原子が好ましい。
少なくとも1つのフッ素原子で置換されたアルキル基の具体例及び好適な態様は式(AN1)中のXfの具体例及び好適な態様と同じである。
Lが複数存在する場合、Lは、それぞれ同一でも異なっていてもよい。
2価の連結基としては、例えば、-O-CO-O-、-COO-、-CONH-、-CO-、-O-、-S-、-SO-、-SO2-、アルキレン基(炭素数1~6が好ましい)、シクロアルキレン基(炭素数3~15が好ましい)、アルケニレン基(炭素数2~6が好ましい)、及び、これらの複数を組み合わせた2価の連結基が挙げられる。なかでも、2価の連結基としては、-O-CO-O-、-COO-、-CONH-、-CO-、-O-、-SO2-、-O-CO-O-アルキレン基-、-COO-アルキレン基-、又は、-CONH-アルキレン基-が好ましく、-O-CO-O-、-O-CO-O-アルキレン基-、-COO-、-CONH-、-SO2-、又は、-COO-アルキレン基-がより好ましい。
環状の有機基としては、例えば、脂環基、アリール基、及び、複素環基が挙げられる。
脂環基は、単環であってもよく、多環であってもよい。単環の脂環基としては、例えば、シクロペンチル基、シクロヘキシル基、及び、シクロオクチル基等の単環のシクロアルキル基が挙げられる。多環の脂環基としては、例えば、ノルボルニル基、トリシクロデカニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及び、アダマンチル基等の多環のシクロアルキル基が挙げられる。なかでも、ノルボルニル基、トリシクロデカニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及び、アダマンチル基等の炭素数7以上の嵩高い構造を有する脂環基が好ましい。
複素環基は、単環又は多環であってもよい。なかでも、多環の複素環基である場合、より酸の拡散を抑制できる。また、複素環基は、芳香族性を有していてもよいし、芳香族性を有していなくてもよい。芳香族性を有している複素環としては、例えば、フラン環、チオフェン環、ベンゾフラン環、ベンゾチオフェン環、ジベンゾフラン環、ジベンゾチオフェン環、及び、ピリジン環が挙げられる。芳香族性を有していない複素環としては、例えば、テトラヒドロピラン環、ラクトン環、スルトン環、及び、デカヒドロイソキノリン環が挙げられる。複素環基における複素環としては、フラン環、チオフェン環、ピリジン環、又は、デカヒドロイソキノリン環が好ましい。
態様(AN2):式(AN1)中、oは2を表し、pは0を表し、-SO3 -と直接結合している炭素原子(以下、この炭素原子を「炭素原子Z1」とも呼ぶ。)に結合した2つのXfは、それぞれ独立に、水素原子、又はフッ素原子を有さない有機基を表し、上記炭素原子に隣接している炭素原子(以下、この炭素原子を「炭素原子Z2」とも呼ぶ。)に結合した2つのXfは、それぞれ独立に、水素原子、又は有機基を表す。q、L、及び、Wの好ましい態様は、前述したものと同様である。
炭素原子Z1に結合した2つのXfは、水素原子であることが好ましい。
炭素原子Z2に結合した2つのXfの少なくとも一方がフッ素原子又はフッ素原子を有する有機基であることが好ましく、両方がフッ素原子又はフッ素原子を有する有機基であることがより好ましく、両方が、フッ素で置換されたアルキル基であることが更に好ましい。
また、Bは更に、「-(L)q-W」で表される置換基を有していてもよい。L、q及びWは、上記式(AN1)中のL、q及びWと同じ意味を表し、具体例及び好ましい範囲も同様である。
ジスルホンアミドアニオンは、例えば、N-(SO2-Rq)2で表されるアニオンである。
ここで、Rqは置換基を有していてもよいアルキル基を表し、フルオロアルキル基が好ましく、パーフルオロアルキル基がより好ましい。2個のRqは互いに結合して環を形成してもよい。2個のRqが互いに結合して形成される基は、置換基を有していてもよいアルキレン基が好ましく、フルオロアルキレン基が好ましく、パーフルオロアルキレン基が更に好ましい。上記アルキレン基の炭素数は2~4が好ましい。
Z2cにおける上記炭化水素基は、直鎖状でも分岐鎖状でもよく、環状構造を有していてもよい。また、上記炭化水素基における炭素原子(好ましくは、上記炭化水素基が環状構造を有する場合における、環員原子である炭素原子)は、カルボニル炭素(-CO-)であってもよい。上記炭化水素基としては、例えば、置換基を有していてもよいノルボルニル基を有する基が挙げられる。上記ノルボルニル基を形成する炭素原子は、カルボニル炭素であってもよい。
また、式(d1-2)中の「Z2c-SO3 -」は、上述の式(AN4)、(AN1)又は(AN5)で表されるアニオンとは異なるのが好ましい。例えば、Z2cは、アリール基以外が好ましい。また、例えば、Z2cにおける、-SO3 -に対してα位及びβ位の原子は、置換基としてフッ素原子を有する炭素原子以外の原子が好ましい。例えば、Z2cは、-SO3 -に対してα位の原子及び/又はβ位の原子は環状基中の環員原子であるのが好ましい。
化合物(B)は、下記化合物(I)及び下記化合物(II)からなる群より選択される少なくとも1種であることも好ましい。
化合物(I)は、1つ以上の下記構造部位X及び1つ以上の下記構造部位Yを有する化合物であって、活性光線又は放射線の照射によって、下記構造部位Xに由来する下記第1の酸性部位と下記構造部位Yに由来する下記第2の酸性部位とを含む酸を発生する化合物である。
構造部位X:アニオン部位A1 -とカチオン部位M1 +とからなり、且つ活性光線又は放射線の照射によって、HA1で表される第1の酸性部位を形成する構造部位
構造部位Y:アニオン部位A2 -とカチオン部位M2 +とからなり、且つ活性光線又は放射線の照射によって、HA2で表される第2の酸性部位を形成する構造部位
カチオン部位M1 +とカチオン部位M2 +とはそれぞれ独立に有機カチオンを表すことが好ましく、具体例及び好ましい範囲は前述のM+で表される有機カチオンと同様である。
また、上記化合物(I)は、下記条件Iを満たす。
化合物(I)が、例えば、上記構造部位Xに由来する上記第1の酸性部位を1つと、上記構造部位Yに由来する上記第2の酸性部位を1つ有する酸を発生する化合物である場合、化合物PIは「HA1とHA2とを有する化合物」に該当する。
このような化合物PIの酸解離定数a1及び酸解離定数a2とは、より具体的に説明すると、化合物PIの酸解離定数を求めた場合において、化合物PIが「A1 -とHA2とを有する化合物」となる際のpKaが酸解離定数a1であり、上記「A1 -とHA2とを有する化合物」が「A1 -とA2 -とを有する化合物」となる際のpKaが酸解離定数a2である。
このような化合物PIの酸解離定数を求めた場合、化合物PIが「1つのA1 -と1つのHA1と1つのHA2とを有する化合物」となる際の酸解離定数、及び「1つのA1 -と1つのHA1と1つのHA2とを有する化合物」が「2つのA1 -と1つのHA2とを有する化合物」となる際の酸解離定数が、上述の酸解離定数a1に該当する。また、「2つのA1 -と1つのHA2とを有する化合物」が「2つのA1 -とA2 -を有する化合物」となる際の酸解離定数が酸解離定数a2に該当する。つまり、このような化合物PIの場合、上記構造部位X中の上記カチオン部位M1 +をH+に置き換えてなるHA1で表される酸性部位に由来する酸解離定数を複数有する場合、複数の酸解離定数a1のうち最も大きい値よりも、酸解離定数a2の値の方が大きい。なお、化合物PIが「1つのA1 -と1つのHA1と1つのHA2とを有する化合物」となる際の酸解離定数をaaとし、「1つのA1 -と1つのHA1と1つのHA2とを有する化合物」が「2つのA1 -と1つのHA2とを有する化合物」となる際の酸解離定数をabとしたとき、aa及びabの関係は、aa<abを満たす。
上記化合物PIとは、化合物(I)に活性光線又は放射線を照射した場合に、発生する酸に該当する。
化合物(I)が2つ以上の構造部位Xを有する場合、構造部位Xは、それぞれ同一であっても異なっていてもよい。また、2つ以上の上記A1 -、及び2つ以上の上記M1 +は、それぞれ同一であっても異なっていてもよい。
また、化合物(I)中、上記A1 -及び上記A2 -、並びに、上記M1 +及び上記M2 +は、それぞれ同一であっても異なっていてもよいが、上記A1 -及び上記A2 -は、それぞれ異なっているのが好ましい。
アニオン部位A1 -としては、酸解離定数の小さい酸性部位を形成し得るものが好ましく、なかでも、式(AA-1)~(AA-3)のいずれかであるのがより好ましく、式(AA-1)及び(AA-3)のいずれかであるのが更に好ましい。
また、アニオン部位A2 -としては、アニオン部位A1 -よりも酸解離定数の大きい酸性部位を形成し得るものが好ましく、式(BB-1)~(BB-6)のいずれかであるのがより好ましく、式(BB-1)及び(BB-4)のいずれかであるのが更に好ましい。
なお、以下の式(AA-1)~(AA-3)及び式(BB-1)~(BB-6)中、*は、結合位置を表す。
以下において、まず、式(Ia-1)で表される化合物について述べる。
A11 -及びA12 -は、それぞれ独立に、1価のアニオン性官能基を表す。
L1は、2価の連結基を表す。
M11 +及びM12 +は、それぞれ同一であっても異なっていてもよい。
A11 -及びA12 -は、それぞれ同一であっても異なっていてもよいが、互いに異なっているのが好ましい。
但し、上記式(Ia-1)において、M11 +及びM12 +で表されるカチオンをH+に置き換えてなる化合物PIa(HA11-L1-A12H)において、A12Hで表される酸性部位に由来する酸解離定数a2は、HA11で表される酸性部位に由来する酸解離定数a1よりも大きい。なお、酸解離定数a1と酸解離定数a2との好適値については、上述した通りである。また、化合物PIaと、活性光線又は放射線の照射によって式(Ia-1)で表される化合物とから発生する酸は同じである。
また、M11 +、M12 +、A11 -、A12 -、及びL1の少なくとも1つが、置換基として、酸分解性基を有していてもよい。
A11 -及びA12 -で表される1価のアニオン性官能基としては、上述した式(AA-1)~(AA-3)及び式(BB-1)~(BB-6)のいずれかのアニオン部位を含む1価のアニオン性官能基であるのが好ましく、式(AX-1)~(AX-3)、及び式(BX-1)~(BX-7)からなる群から選ばれる1価のアニオン性官能基であるのがより好ましい。A11 -で表される1価のアニオン性官能基としては、なかでも、式(AX-1)~(AX-3)のいずれかで表される1価のアニオン性官能基であるのが好ましい。また、A12 -で表される1価のアニオン性官能基としては、なかでも、式(BX-1)~(BX-7)のいずれかで表される1価のアニオン性官能基が好ましく、式(BX-1)~(BX-6)のいずれかで表される1価のアニオン性官能基がより好ましい。
上記アルキル基の炭素数は1~15が好ましく、1~10がより好ましく、1~6が更に好ましい。
上記アルキル基は、置換基を有していてもよい。置換基としては、フッ素原子又はシアノ基が好ましく、フッ素原子がより好ましい。上記アルキル基が置換基としてフッ素原子を有する場合、パーフルオロアルキル基であってもよい。
上記アリール基は、置換基を有していてもよい。置換基としては、フッ素原子、ヨウ素原子、パーフルオロアルキル基(例えば、炭素数1~10が好ましく、炭素数1~6がより好ましい。)、又はシアノ基が好ましく、フッ素原子、ヨウ素原子、パーフルオロアルキル基がより好ましい。
RBで表される1価の有機基としては、直鎖状、分岐鎖状、若しくは環状のアルキル基、又はアリール基が好ましい。
上記アルキル基の炭素数は1~15が好ましく、1~10がより好ましく、1~6が更に好ましい。
上記アルキル基は、置換基を有していてもよい。置換基として特に制限されないが、置換基としては、フッ素原子又はシアノ基が好ましく、フッ素原子がより好ましい。上記アルキル基が置換基としてフッ素原子を有する場合、パーフルオロアルキル基であってもよい。
なお、アルキル基において結合位置となる炭素原子(例えば、式(BX-1)及び(BX-4)の場合、アルキル基中の式中に明示される-CO-と直接結合する炭素原子が該当し、式(BX-2)及び(BX-3)の場合、アルキル基中の式中に明示される-SO2-と直接結合する炭素原子が該当し、式(BX-6)の場合、アルキル基中の式中に明示されるN-と直接結合する炭素原子が該当する。)が置換基を有する場合、フッ素原子又はシアノ基以外の置換基であるのも好ましい。
また、上記アルキル基は、炭素原子がカルボニル炭素で置換されていてもよい。
上記アリール基は、置換基を有していてもよい。置換基としては、フッ素原子、ヨウ素原子、パーフルオロアルキル基(例えば、炭素数1~10が好ましく、炭素数1~6がより好ましい。)、シアノ基、アルキル基(例えば、炭素数1~10が好ましく、炭素数1~6がより好ましい。)、アルコキシ基(例えば、炭素数1~10が好ましく、炭素数1~6がより好ましい。)、又はアルコキシカルボニル基(例えば、炭素数2~10が好ましく、炭素数2~6がより好ましい。)が好ましく、フッ素原子、ヨウ素原子、パーフルオロアルキル基、アルキル基、アルコキシ基、又はアルコキシカルボニル基がより好ましい。
また、上記アルキレン基、上記シクロアルキレン基、上記アルケニレン基、上記2価の脂肪族複素環基、2価の芳香族複素環基、及び2価の芳香族炭化水素環基は、置換基を有していてもよい。置換基としては、例えば、ハロゲン原子(好ましくはフッ素原子)が挙げられる。
L111で表される2価の連結基としては特に制限されず、例えば、-CO-、-NH-、-O-、-SO-、-SO2-、置換基を有していてもよいアルキレン基(好ましくは炭素数1~6がより好ましい。直鎖状及び分岐鎖状のいずれでもよい)、置換基を有していてもよいシクロアルキレン基(好ましくは炭素数3~15)、置換基を有していてもよいアリール基(好ましくは炭素数6~10)、及びこれらの複数を組み合わせた2価の連結基が挙げられる。置換基としては特に制限されず、例えば、ハロゲン原子が挙げられる。
pは、0~3の整数を表し、1~3の整数を表すのが好ましい。
vは、0又は1の整数を表す。
Xf1は、それぞれ独立に、フッ素原子、又は少なくとも1つのフッ素原子で置換されたアルキル基を表す。このアルキル基の炭素数は、1~10が好ましく、1~4がより好ましい。また、少なくとも1つのフッ素原子で置換されたアルキル基としては、パーフルオロアルキル基が好ましい。
Xf2は、それぞれ独立に、水素原子、置換基としてフッ素原子を有していてもよいアルキル基、又はフッ素原子を表す。このアルキル基の炭素数は、1~10が好ましく、1~4がより好ましい。Xf2としては、なかでも、フッ素原子、又は少なくとも1つのフッ素原子で置換されたアルキル基を表すのが好ましく、フッ素原子、又はパーフルオロアルキル基がより好ましい。
なかでも、Xf1及びXf2としては、それぞれ独立に、フッ素原子又は炭素数1~4のパーフルオロアルキル基であることが好ましく、フッ素原子又はCF3であることがより好ましい。特に、Xf1及びXf2が、いずれもフッ素原子であることが更に好ましい。
*は結合位置を表す。
式(Ia-1)中のL11が式(L1)で表される2価の連結基を表す場合、式(L1)中のL111側の結合手(*)が、式(Ia-1)中のA12 -と結合するのが好ましい。
次に、式(Ia-2)~(Ia-4)で表される化合物について説明する。
A22 -は、2価のアニオン性官能基を表す。ここで、A22 -で表される2価のアニオン性官能基とは、上述したアニオン部位A2 -を含む2価の基を意図する。A22 -で表される2価のアニオン性官能基としては、例えば、以下に示す式(BX-8)~(BX-11)で表される2価のアニオン性官能基が挙げられる。
L21及びL22は、それぞれ独立に、2価の有機基を表す。
なお、A21a -及びA21b -は、互いに同一であっても異なっていてもよい。また、M21a +、M21b +、及びM22 +は、互いに同一であっても異なっていてもよい。
また、M21a +、M21b +、M22 +、A21a -、A21b -、L21、及びL22の少なくとも1つが、置換基として、酸分解性基を有していてもよい。
A32 -で表される1価のアニオン性官能基は、上述したアニオン部位A2 -を含む1価の基を意図する。A32 -で表される1価のアニオン性官能基としては特に制限されないが、例えば、上述の式(BX-1)~(BX-7)からなる群から選ばれる1価のアニオン性官能基が挙げられる。
A31b -は、2価のアニオン性官能基を表す。ここで、A31b -で表される2価のアニオン性官能基とは、上述したアニオン部位A1 -を含む2価の基を意図する。A31b -で表される2価のアニオン性官能基としては、例えば、以下に示す式(AX-4)で表される2価のアニオン性官能基が挙げられる。
L31及びL32は、それぞれ独立に、2価の有機基を表す。
なお、A31a -及びA32 -は、互いに同一であっても異なっていてもよい。また、M31a +、M31b +、及びM32 +は、互いに同一であっても異なっていてもよい。
また、M31a +、M31b +、M32 +、A31a -、A32 -、L31、及びL32の少なくとも1つが、置換基として、酸分解性基を有していてもよい。
M41a +、M41b +、及びM42 +は、それぞれ独立に、有機カチオンを表す。
L41は、3価の有機基を表す。
なお、A41a -、A41b -、及びA42 -は、互いに同一であっても異なっていてもよい。また、M41a +、M41b +、及びM42 +は、互いに同一であっても異なっていてもよい。
また、M41a +、M41b +、M42 +、A41a -、A41b -、A42 -、及びL41の少なくとも1つが、置換基として、酸分解性基を有していてもよい。
また、上記アルキレン基、上記シクロアルキレン基、上記アルケニレン基、上記2価の脂肪族複素環基、2価の芳香族複素環基、及び2価の芳香族炭化水素環基は、置換基を有していてもよい。置換基としては、例えば、ハロゲン原子(好ましくはフッ素原子)が挙げられる。
Xfは、それぞれ独立に、フッ素原子、又は少なくとも1つのフッ素原子で置換されたアルキル基を表す。このアルキル基の炭素数は、1~10が好ましく、1~4がより好ましい。また、少なくとも1つのフッ素原子で置換されたアルキル基としては、パーフルオロアルキル基が好ましい。
Xfは、フッ素原子又は炭素数1~4のパーフルオロアルキル基であることが好ましく、フッ素原子又はCF3であることがより好ましい。特に、双方のXfがフッ素原子であることが更に好ましい。
LAで表される2価の連結基としては特に制限されず、例えば、-CO-、-O-、-SO-、-SO2-、アルキレン基(好ましくは炭素数1~6。直鎖状でも分岐鎖状でもよい)、シクロアルキレン基(好ましくは炭素数3~15)、2価の芳香族炭化水素環基(6~10員環が好ましく、6員環が更に好ましい。)、及びこれらの複数を組み合わせた2価の連結基が挙げられる。
また、上記アルキレン基、上記シクロアルキレン基、及び2価の芳香族炭化水素環基は、置換基を有していてもよい。置換基としては、例えば、ハロゲン原子(好ましくはフッ素原子)が挙げられる。
式(Ia-2)中のL21及びL22が式(L2)で表される2価の有機基を表す場合、式(L2)中のLA側の結合手(*)が、式(Ia-2)中のA21a -及びA21b -と結合するのが好ましい。
また、式(Ia-3)中のL31及びL32が式(L2)で表される2価の有機基を表す場合、式(L2)中のLA側の結合手(*)が、式(Ia-3)中のA31a -及びA32 -と結合するのが好ましい。
次に、式(Ia-5)について説明する。
A52a -及びA52b -は、2価のアニオン性官能基を表す。ここで、A52a -及びA52b -で表される2価のアニオン性官能基とは、上述したアニオン部位A2 -を含む2価の基を意図する。A22 -で表される2価のアニオン性官能基としては、例えば、上述の式(BX-8)~(BX-11)からなる群から選ばれる2価のアニオン性官能基が挙げられる。
L51及びL53は、それぞれ独立に、2価の有機基を表す。L51及びL53で表される2価の有機基としては、上述した式(Ia-2)中のL21及びL22と同義であり、好適態様も同じである。
L52は、3価の有機基を表す。L52で表される3価の有機基としては、上述した式(Ia-4)中のL41と同義であり、好適態様も同じである。
なお、A51a -、A51b -、及びA51c -は、互いに同一であっても異なっていてもよい。また、A52a -及びA52b -は、互いに同一であっても異なっていてもよい。また、M51a +、M51b +、M51c +、M52a +、及びM52b +は、互いに同一であっても異なっていてもよい。
また、M51b +、M51c +、M52a +、M52b +、A51a -、A51b -、A51c -、L51、L52、及びL53の少なくとも1つが、置換基として、酸分解性基を有していてもよい。
化合物(II)は、2つ以上の上記構造部位X及び1つ以上の下記構造部位Zを有する化合物であって、活性光線又は放射線の照射によって、上記構造部位Xに由来する上記第1の酸性部位を2つ以上と上記構造部位Zとを含む酸を発生する化合物とを含む酸を発生する化合物である。
構造部位Z:酸を中和可能な非イオン性の部位
なお、化合物(II)が、例えば、上記構造部位Xに由来する上記第1の酸性部位を2つと上記構造部位Zとを有する酸を発生する化合物である場合、化合物PIIは「2つのHA1を有する化合物」に該当する。この化合物PIIの酸解離定数を求めた場合、化合物PIIが「1つのA1 -と1つのHA1とを有する化合物」となる際の酸解離定数、及び「1つのA1 -と1つのHA1とを有する化合物」が「2つのA1 -を有する化合物」となる際の酸解離定数が、酸解離定数a1に該当する。
上記化合物PIIとは、化合物(II)に活性光線又は放射線を照射した場合に、発生する酸に該当する。
なお、上記2つ以上の構造部位Xは、それぞれ同一であっても異なっていてもよい。また、2つ以上の上記A1 -、及び2つ以上の上記M1 +は、それぞれ同一であっても異なっていてもよい。
プロトンと静電的に相互作用し得る基、又は、電子を有する官能基としては、環状ポリエーテル等のマクロサイクリック構造を有する官能基、又は、π共役に寄与しない非共有電子対をもった窒素原子を有する官能基が挙げられる。π共役に寄与しない非共有電子対を有する窒素原子とは、例えば、下記式に示す部分構造を有する窒素原子である。
上記式(IIa-1)中、L61及びL62は、それぞれ上述した式(Ia-1)中のL1と同義であり、好適態様も同じである。
また、上記アルキレン基、上記シクロアルキレン基、及び上記アルケニレン基は、置換基を有していてもよい。置換基としては、特に制限されないが、例えば、ハロゲン原子(好ましくはフッ素原子)が挙げられる。
なお、上記化合物(IIa-1)において上記構造部位X中の上記カチオン部位M61a +及びM61b +をH+に置き換えてなる化合物PIIa-1は、HA61a-L61-N(R2X)-L62-A61bHが該当する。また、化合物PIIa-1と、活性光線又は放射線の照射によって式(IIa-1)で表される化合物から発生する酸は同じである。
また、M61a +、M61b +、A61a -、A61b -、L61、L62、及びR2Xの少なくとも1つが、置換基として、酸分解性基を有していてもよい。
上記式(IIa-2)中、L71、L72、及びL73は、それぞれ上述した式(Ia-1)中のL1と同義であり、好適態様も同じである。
なお、上記化合物(IIa-1)において上記構造部位X中の上記カチオン部位M71a +、M71b +、及び、M71c +をH+に置き換えてなる化合物PIIa-2は、HA71a-L71-N(L73-A71cH)-L72-A71bHが該当する。また、化合物PIIa-2と、活性光線又は放射線の照射によって式(IIa-2)で表される化合物から発生する酸は同じである。
また、M71a +、M71b +、M71c +、A71a -、A71b -、A71c -、L71、L72、及びL73の少なくとも1つが、置換基として、酸分解性基を有していてもよい。
化合物(B)は、1種単独で使用してもよく、2種以上を使用してもよい。
本発明の組成物は、一般式(DA1)で表される化合物に加えて、更に、その他の酸拡散制御剤を含有することができる。酸拡散制御剤は、露光時に光酸発生剤等から発生する酸をトラップし、余分な発生酸による、未露光部における樹脂(A)の反応を抑制するクエンチャーとして作用する。
酸拡散制御剤としては、例えば、塩基性化合物(DA)、活性光線又は放射線の照射により塩基性が低下又は消失する塩基性化合物(DB)、光酸発生剤(B)から発生する酸に対して相対的に弱酸となる酸を発生するオニウム塩(DC)、窒素原子を有し、酸の作用により脱離する基を有する低分子化合物(DD)、又はカチオン部に窒素原子を有するオニウム塩化合物(DE)等を酸拡散制御剤として使用できる。本発明の組成物においては、公知の酸拡散制御剤を適宜使用できる。例えば、米国特許出願公開2016/0070167A1号明細書の段落[0627]~[0664]、米国特許出願公開2015/0004544A1号明細書の段落[0095]~[0187]、米国特許出願公開2016/0237190A1号明細書の段落[0403]~[0423]、及び、米国特許出願公開2016/0274458A1号明細書の段落[0259]~[0328]に開示された公知の化合物を酸拡散制御剤として好適に使用できる。
R200、R201及びR202は、同一でも異なってもよく、各々独立に、水素原子、アルキル基(好ましくは炭素数1~20)、シクロアルキル基(好ましくは炭素数3~20)又はアリール基(炭素数6~20)を表す。R201とR202は、互いに結合して環を形成してもよい。
R203、R204、R205及びR206は、同一でも異なってもよく、各々独立に、炭素数1~20のアルキル基を表す。
上記アルキル基について、置換基を有するアルキル基としては、炭素数1~20のアミノアルキル基、炭素数1~20のヒドロキシアルキル基、又は炭素数1~20のシアノアルキル基が好ましい。
一般式(A)及び(E)中のアルキル基は無置換であることがより好ましい。
プロトンアクセプター性は、pH測定を行うことによって確認することができる。
化合物(DCA)としては、下記一般式(C-1)~(C-3)のいずれかで表される化合物が好ましい。
R1、R2、及びR3は、各々独立に炭素数1以上の置換基を表す。
L1は、カチオン部位とアニオン部位とを連結する2価の連結基又は単結合を表す。
-X-は、-COO-、-SO3 -、-SO2 -、及び-N--R4から選択されるアニオン部位を表す。R4は、隣接するN原子との連結部位に、カルボニル基(-C(=O)-)、スルホニル基(-S(=O)2-)、及びスルフィニル基(-S(=O)-)のうち少なくとも1つを有する1価の置換基を表す。
R1、R2、R3、R4、及びL1は、互いに結合して環構造を形成してもよい。また、一般式(C-3)において、R1~R3のうち2つを合わせて1つの2価の置換基を表し、N原子と2重結合により結合していてもよい。
酸の作用により脱離する基としては、アセタール基、カルボネート基、カルバメート基、3級エステル基、3級水酸基、又はヘミアミナールエーテル基が好ましく、カルバメート基、又はヘミアミナールエーテル基がより好ましい。
化合物(DD)の分子量は、100~1000が好ましく、100~700がより好ましく、100~500が更に好ましい。
化合物(DD)は、窒素原子上に保護基を有するカルバメート基を有してもよい。カルバメート基を構成する保護基としては、下記一般式(d-1)で表される。
Rbは、各々独立に、水素原子、アルキル基(好ましくは炭素数1~10)、シクロアルキル基(好ましくは炭素数3~30)、アリール基(好ましくは炭素数3~30)、アラルキル基(好ましくは炭素数1~10)、又はアルコキシアルキル基(好ましくは炭素数1~10)を表す。Rbは相互に結合して環を形成していてもよい。
Rbが示すアルキル基、シクロアルキル基、アリール基、及びアラルキル基は、各々独立にヒドロキシル基、シアノ基、アミノ基、ピロリジノ基、ピペリジノ基、モルホリノ基、オキソ基等の官能基、アルコキシ基、又はハロゲン原子で置換されていてもよい。Rbが示すアルコキシアルキル基についても同様である。
2つのRbが相互に連結して形成する環としては、脂環式炭化水素、芳香族炭化水素、複素環式炭化水素及びその誘導体等が挙げられる。
一般式(d-1)で表される基の具体的な構造としては、米国特許公報US2012/0135348A1号明細書の段落[0466]に開示された構造が挙げられるが、これに限定されない。
lは0~2の整数を表し、mは1~3の整数を表し、l+m=3を満たす。
Raは、水素原子、アルキル基、シクロアルキル基、アリール基又はアラルキル基を表す。lが2のとき、2つのRaは同じでも異なっていてもよく、2つのRaは相互に連結して式中の窒素原子と共に複素環を形成していてもよい。この複素環には式中の窒素原子以外のヘテロ原子を含んでいてもよい。
Rbは、上記一般式(d-1)におけるRbと同義であり、好ましい例も同様である。
一般式(6)において、Raとしてのアルキル基、シクロアルキル基、アリール基、及びアラルキル基は、各々独立にRbとしてのアルキル基、シクロアルキル基、アリール基、及びアラルキル基が置換されていてもよい基として前述した基と同様な基で置換されていてもよい。
本発明における特に好ましい化合物(DD)の具体例としては、米国特許出願公開2012/0135348A1号明細書の段落[0475]に開示された化合物が挙げられるが、これに限定されない。
化合物(DE)の好ましい具体例としては、米国特許出願公開2015/0309408A1号明細書の段落[0203]に開示された化合物が挙げられるが、これに限定されない。
本発明の組成物が、一般式(DA1)で表される化合物に加えて、更に、その他の酸拡散制御剤を含有する場合、本発明の組成物中のその他の酸拡散制御剤の含有量(複数種存在する場合はその合計)は、本発明の組成物の全固形分に対して、0.001~20質量%が好ましく、0.01~15質量%がより好ましい。
本発明の組成物は、溶剤を含有することが好ましい。
本発明の組成物においては溶剤として公知のレジスト溶剤を適宜使用できる。
溶剤としては、例えば、アルキレングリコールモノアルキルエーテルカルボキシレート、アルキレングリコールモノアルキルエーテル、乳酸アルキルエステル、アルコキシプロピオン酸アルキル、環状ラクトン(好ましくは炭素数4~10)、環を有してもよいモノケトン化合物(好ましくは炭素数4~10)、アルキレンカーボネート、アルコキシ酢酸アルキル、及びピルビン酸アルキル等の有機溶剤が挙げられる。
溶剤に関しては、国際公開第2019/058890号の段落[0187]~[0197]の記載を参酌でき、これらの内容は本願明細書に組み込まれる。
固形分濃度とは、感活性光線性又は感放射線性樹脂組成物の総質量に対する、溶剤を除く他の成分の質量の質量百分率である。
本発明の組成物は、界面活性剤を更に含んでいてもよい。界面活性剤を含有することにより、波長が250nm以下、特には220nm以下の露光光源を使用した場合に、良好な感度及び解像度で、密着性及び現像欠陥のより少ないパターンを形成することが可能となる。
界面活性剤としては、フッ素系及び/又はシリコン系界面活性剤を用いることが特に好ましい。
界面活性剤に関しては、国際公開第2019/058890号の段落[0183]~[0184]の記載を参酌でき、これらの内容は本願明細書に組み込まれる。
本発明の組成物は、上記に説明した成分以外にも、カルボン酸、カルボン酸オニウム塩、Proceeding of SPIE, 2724,355 (1996)等に記載の分子量3000以下の溶解阻止化合物、染料、可塑剤、光増感剤、光吸収剤、酸化防止剤などを適宜含有することができる。
本発明の組成物は、活性光線又は放射線の照射により反応して性質が変化する感活性光線性又は感放射線性樹脂組成物に関する。更に詳しくは、本発明の組成物は、IC(Integrated Circuit)等の半導体製造工程、液晶若しくはサーマルヘッド等の回路基板の製造、インプリント用モールド構造体の作製、その他のフォトファブリケーション工程、又は平版印刷版、若しくは酸硬化性組成物の製造に使用される感活性光線性又は感放射線性樹脂組成物に関する。本発明において形成されるパターンは、エッチング工程、イオンインプランテーション工程、バンプ電極形成工程、再配線形成工程、及びMEMS(Micro Electro Mechanical Systems)等において使用できる。
本発明は、前述した本発明の感活性光線又は感放射線性組成物により形成された感活性光線性又は感放射線性膜(好ましくはレジスト膜)にも関する。このような膜は、例えば、本発明の組成物が基板等の支持体上に塗布されることにより形成される。感活性光線性又は感放射線性膜の厚みは特に限定されないが、0.02~0.1μmが好ましい。基板上に塗布する方法としては、スピンコート、ロールコート、フローコート、ディップコート、スプレーコート、ドクターコート等の適当な塗布方法により基板上に塗布されるが、スピン塗布が好ましく、その回転数は1000~3000rpm(rotations per minute)が好ましい。塗布膜は60~150℃で1~20分間、好ましくは80~120℃で1~10分間プリベークして薄膜を形成する。
基板、感活性光線性又は感放射線性膜上に設けてもよいトップコートに関しては、国際公開第2017/056832号の段落[0342]~[0358]の記載を参酌でき、これらの内容は本願明細書に組み込まれる。
本発明は、
本発明の感活性光線性又は感放射線性樹脂組成物を用いてレジスト膜を形成するレジスト膜形成工程と、
レジスト膜を露光する露光工程と、
露光されたレジスト膜を現像液を用いて現像する現像工程と、
を含むパターン形成方法にも関する。
本発明において、上記露光は、電子線(EB)、ArFエキシマレーザー又は極紫外線(EUV)を用いて行われることが好ましく、電子線又は極紫外線を用いて行われることがより好ましい。
次いで、ホットプレート上で、好ましくは60~150℃で5秒~20分間、より好ましくは80~120℃で15秒~10分間、さらに好ましくは80~120℃で1~10分間、露光後加熱(ポストエクスポージャーベーク)を行い、次いで、現像、リンス、乾燥することによりパターンを形成する。ここで、露光後加熱は、樹脂(A)における酸分解性基を有する繰り返し単位の酸分解性によって、適宜調整される。酸分解性が低い場合、露光後加熱の温度は110℃以上、加熱時間は45秒以上であることも好ましい。
現像液は適宜選択されるが、アルカリ現像液(代表的にはアルカリ水溶液)又は有機溶剤を含有する現像液(有機系現像液ともいう)を用いることが好ましい。現像液がアルカリ水溶液である場合には、テトラメチルアンモニウムヒドロキシド(TMAH)、テトラブチルアンモニウムヒドロキシド(TBAH)等の、0.1~5質量%、好ましくは2~3質量%アルカリ水溶液で、0.1~3分間、好ましくは0.5~2分間、浸漬(dip)法、パドル(puddle)法、スプレー(spray)法等の常法により現像する。
アルカリ現像液には、アルコール類及び/又は界面活性剤を、適当量添加してもよい。こうして、ネガ型パターンの形成おいては、未露光部分の膜は溶解し、露光された部分は現像液に溶解し難いことにより、またポジ型パターンの形成おいては、露光された部分の膜は溶解し、未露光部の膜は現像液に溶解し難いことにより、基板上に目的のパターンが形成される。
アルカリ現像液のpHは、通常10.0~15.0である。
特に、テトラメチルアンモニウムヒドロキシドの2.38質量%の水溶液が望ましい。
また、現像処理又はリンス処理の後に、パターン上に付着している現像液又はリンス液を超臨界流体により除去する処理を行うことができる。
有機系現像液における有機溶剤(複数混合の場合は合計)の濃度は、好ましくは50質量%以上、より好ましくは50~100質量%、さらに好ましくは85~100質量%、さらにより好ましくは90~100質量%、特に好ましくは95~100質量%である。
最も好ましくは、実質的に有機溶剤のみからなる場合である。なお、実質的に有機溶剤のみからなる場合とは、微量の界面活性剤、酸化防止剤、安定剤、消泡剤などを含有する場合を含むものとする。
特に、有機系現像液は、ケトン系溶剤、エステル系溶剤、アルコール系溶剤、アミド系溶剤及びエーテル系溶剤からなる群より選択される少なくとも1種類の有機溶剤を含有する現像液であるのが好ましい。
これら材料に含まれる不純物の含有量としては、1ppm(parts per million)以下が好ましく、1ppb(parts per billion)以下がより好ましく、100ppt(parts per trillion)以下が更に好ましく、10ppt以下が特に好ましく、実質的に含まないこと(測定装置の検出限界以下であること)が最も好ましい。
各種材料から金属等の不純物を除去する方法等に関しては、国際公開第2017/056832号の段落[0384]~[0402]の記載を参酌でき、これらの内容は本願明細書に組み込まれる。
また、本発明は、上記したパターン形成方法を含む、電子デバイスの製造方法にも関する。本発明の電子デバイスの製造方法により製造された電子デバイスは、電気電子機器(例えば、家電、OA(Office Automation)関連機器、メディア関連機器、光学用機器、及び通信機器等)に、好適に搭載される。
使用した樹脂(A)の繰り返し単位の構造及びその含有量(モル比率)、重量平均分子量(Mw)、及び分散度(Pd=Mw/Mn)を以下に示す。
シクロヘキサノン(57g)を窒素気流下にて85℃に加熱した。この液に攪拌しながら、下記式(M-1)で表されるモノマー(50.5g)、下記式(M-2)で表されるモノマー(37.1g)、シクロヘキサノン(106g)、及び、2,2’-アゾビスイソ酪酸ジメチル〔V-601、富士フイルム和光純薬社製〕(8.6g)の混合溶液を3時間かけて滴下し、反応液を得た。滴下終了後、反応液を85℃にて更に3時間攪拌した。得られた反応液を放冷後、4100gの酢酸エチル/ヘプタン(質量比1:9)で再沈殿した後、ろ過し、得られた固体を真空乾燥することで、樹脂(A-1)(86g)を得た。
使用した光酸発生剤(B)の構造を以下に示す。
使用した酸拡散制御剤の構造を以下に示す。
テトラヒドロフラン(THF)20gに2,3,5-トリヨード安息香酸5gを溶解させた後、カルボニルジイミダゾールを1.6g加え室温で30分間攪拌した。その後、1,1,3,3-テトラメチルグアニジン2.3gを添加し、40℃で1時間攪拌した。反応液を室温まで冷却後、水100g、酢酸エチル100gを加え分液し、有機相を水100gで3回洗浄した。得られた有機相を濃縮し化合物(D-1)を3.1g淡黄色結晶として得た。
界面活性剤としては下記のものを使用した。
W-1: メガファックF176(大日本インキ化学工業(株)製;フッ素系)
W-2: メガファックR08(大日本インキ化学工業(株)製;フッ素及びシリコン系)
W-3: ポリシロキサンポリマーKP-341(信越化学工業(株)製;シリコン系)
W-4: トロイゾルS-366(トロイケミカル(株)製)
W-5: KH-20(旭硝子(株)製)
W-6: PolyFox PF-6320(OMNOVA Solutions Inc.製;フッ素系)
溶剤としては下記のものを使用した。
SL-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(PGMEA)
SL-2: プロピレングリコールモノメチルエーテルプロピオネート
SL-3: 2-ヘプタノン
SL-4: 乳酸エチル
SL-5: プロピレングリコールモノメチルエーテル(PGME)
SL-6: シクロヘキサノン
SL-7: γ-ブチロラクトン
SL-8: プロピレンカーボネート
下記表2に示す成分を下記表2に示す溶剤に溶解させ、固形分濃度2.7質量%の溶液を調製し、これを0.02μmのポアサイズを有するポリエチレンフィルターでろ過して、レジスト組成物R-1~R-14、RX-1及びRX-2を得た。
なお、下記表2において、各成分を2種以上使用した場合は、それぞれの種類と使用量を「/」で区切って表した。例えば、実施例11で「(A-1)/(A-3)」は、樹脂(A)として(A-1)と(A-3)の2種を使用したことを表し、「5/5」は(A-1)と(A-3)をそれぞれ5gずつ使用したことを表す。
得られたレジスト組成物を、予めヘキサメチルジシラザン(HMDS)処理を施した6インチSi(シリコン)ウェハ上に東京エレクトロン製スピンコーターMark8を用いて塗布し、130℃、300秒間ホットプレート上で乾燥して、膜厚100nmのレジスト膜を得た。
なお、上記Siウェハをクロム基板に変更しても、同様の結果が得られるものである。
上記で得られたレジスト膜が塗布されたウェハを、電子線描画装置((株)アドバンテスト製;F7000S、加速電圧50keV)を用いて、パターン照射を行った。この際、1:1のラインアンドスペースが形成されるように描画を行った。電子線描画後、100℃、60秒ホットプレート上で加熱し、2.38質量%テトラメチルアンモニウムハイドロオキサイド(TMAH)水溶液を用いて60秒間浸漬した後、30秒間、水でリンスして乾燥した。その後、4000rpmの回転数で30秒間ウェハを回転させた後、95℃で60秒間ベークを行い乾燥した。
(1)ラフネス性能(LWR性能)の評価方法
測長走査型電子顕微鏡((株)日立製作所S-9380II)により線幅50nm(1:1)のラインアンドスペースのパターンを解像する時の最適露光量を感度(Eopt)(μC/cm2)とした。
上記感度(Eopt)を示す露光量にて解像した線幅50nm(1:1)のラインアンドスペースのパターンに対して、測長走査型電子顕微鏡(SEM((株)日立製作所S-9380II))を使用してパターン上部から観察する際、線幅を任意のポイントで観測し、その測定ばらつきを3σ(nm)で評価した。値が小さいほど良好な性能であることを示す。
測長走査型電子顕微鏡((株)日立製作所S-9380II)により線幅50nm(1:1)のラインアンドスペースのパターンを解像する時の最適露光量を感度(Eopt)(μC/cm2)とした。
求めた感度(Eopt)を基準とし、次いで目的の値である50nmの±10%(即ち、45nmおよび55nm)となるときの露光量を求めた。そして、次式で定義される露光ラチチュード(EL、単位:%)を算出した。ELの値が大きいほど、露光量変化による性能変化が小さく、良好である(EL性能に優れる)。
EL(%)=[〔(ラインの線幅が55nmとなる露光量)-(ラインの線幅が45nmとなる露光量)〕/Eopt]×100
得られた線幅50nm(1:1)のラインアンドスペースのレジストパターンの観測において、KLAテンコール社製2360を用い、欠陥検査装置のピクセルサイズを0.16μmに、また閾値を20に設定して、ランダムモードで測定し、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現像欠陥を検出した。その後、SEMVISION G3(APPLIED MATERIALS社製)により、ウエハ上の単位面積あたりの欠陥数(個数/cm2)を測定した。値が0.5未満のものをA、0.5以上0.8未満のものをB、0.8以上のものをCとした。
上記で得られたレジスト膜が塗布されたウェハを、EUV露光装置(Exitech社製 Micro Exposure Tool、NA(開口数)0.3、Quadrupole、アウターシグマ0.68、インナーシグマ0.36)を用い、露光マスク(ライン/スペース=1/1)を使用して、パターン露光を行った。露光後、ホットプレート上で、100℃で90秒間加熱した後、2.38質量%のテトラメチルアンモニウムハイドロオキサイド(TMAH)水溶液を用いて60秒間浸漬した後、30秒間、水でリンスした。その後、4000rpmの回転数で30秒間ウェハを回転させた後、95℃で60秒間ベークを行い乾燥した。
(1)露光ラチチュード(EL)の評価方法
測長走査型電子顕微鏡((株)日立製作所S-9380II)により線幅50nm(1:1)のラインアンドスペースのパターンを解像する時の最適露光量を感度(Eopt)(mJ/cm2)とした。
求めた感度(Eopt)を基準とし、次いで目的の値である50nmの±10%(即ち、45nmおよび55nm)となるときの露光量を求めた。そして、次式で定義される露光ラチチュード(EL、単位:%)を算出した。ELの値が大きいほど、露光量変化による性能変化が小さく、良好である(EL性能に優れる)。
EL(%)=[〔(ラインの線幅が55nmとなる露光量)-(ラインの線幅が45nmとなる露光量)〕/Eopt]×100
Claims (12)
- 酸の作用により極性が増大する樹脂(A)、及び下記一般式(DA1)で表される化合物を含む、感活性光線性又は感放射線性樹脂組成物。
一般式(DA1)中、
X1は硫黄原子又はNQ3を表す。
Q3は水素原子、有機基、-OH又は-NH2を表す。
Q1は水素原子又は置換基を表す。
X2は連結基Xz又は単結合を表す。
前記連結基Xzは、炭素原子、酸素原子、窒素原子及び硫黄原子からなる群より選択される少なくとも1つの原子からなる2価の連結基である。ただし、前記窒素原子は水素原子、アルキル基、アリール基又は芳香族ヘテロ環基と結合していてもよく、前記硫黄原子は炭化水素基と結合していてもよい。
Ara1は芳香族基を表す。
Q2は水素原子又はアルキル基を表す。
Q1とQ2とは結合して環を形成してもよい。
Q1及びQ2からなる群より選択される少なくとも1つとQ3とは結合して環を形成してもよい。
kは1~5の整数を表す。
mは1~3の整数を表す。
n及びpは各々独立に0~2の整数を表す。
ただし、m+n+p=3である。
X1、X2、Q1、Q2、Q3及びAra1は、複数存在する場合は、それぞれ同一であっても異なっていてもよい。
ただし、nが0を表す場合、下記条件(i)又は(ii)を満たす。
条件(i):X2が単結合を表し、かつAra1が芳香族ヘテロ環基を表す。
条件(ii):X2が前記連結基Xzを表す。 - 前記一般式(DA1)中のX2が、下記式(X2-1)~(X2-11)のいずれかで表される2価の連結基又は単結合を表す、請求項1に記載の感活性光線性又は感放射線性樹脂組成物。
- 前記樹脂(A)が下記一般式(3)で表される繰り返し単位、下記一般式(6)で表される繰り返し単位及び下記一般式(7)で表される繰り返し単位からなる群より選択される少なくとも1つを有する、請求項1又は2に記載の感活性光線性又は感放射線性樹脂組成物。
一般式(3)中、
R5~R7は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。
L2は、2価の連結基を表す。
R8~R10は、各々独立に、アルキル基、シクロアルキル基、アリール基、アラルキル基又はアルケニル基を表す。R8~R10のうち2つが結合して環を形成してもよい。
一般式(6)中、
R22~R24は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。
L4は、単結合又は2価の連結基を表す。
Ar1は、芳香族基を表す。
R25~R27は、各々独立に水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基又はアルケニル基を表す。
R26とR27とは結合して環を形成してもよい。
R24又はR25はAr1と結合してもよい。
R28~R30は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。
L5は、単結合又は2価の連結基を表す。
R31及びR32は、各々独立に、水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基又はアルケニル基を表す。
R33は、アルキル基、シクロアルキル基、アリール基、アラルキル基又はアルケニル基を表す。
R32とR33とは結合して環を形成してもよい。 - 前記一般式(DA1)中のnが1又は2を表す、請求項1~4のいずれか1項に記載の感活性光線性又は感放射線性樹脂組成物。
- 一般式(DA1)中のQ1が窒素原子を含む置換基を表す、請求項5に記載の感活性光線性又は感放射線性樹脂組成物。
- 前記一般式(DA1)中のnが0を表し、前記条件(i)を満たし、かつAra1が窒素原子を含む芳香族ヘテロ環基を表す、請求項1~4のいずれか1項に記載の感活性光線性又は感放射線性樹脂組成物。
- 前記一般式(DA1)で表される化合物の共役酸のpKaが2以上である、請求項1~7のいずれか1項に記載の感活性光線性又は感放射線性樹脂組成物。
- 前記一般式(DA1)で表される化合物が、非イオン性の化合物である、請求項1~8のいずれか1項に記載の感活性光線性又は感放射線性樹脂組成物。
- 請求項1~9のいずれか1項に記載の感活性光線性又は感放射線性樹脂組成物を用いて形成された感活性光線性又は感放射線性膜。
- 請求項1~9のいずれか1項に記載の感活性光線性又は感放射線性樹脂組成物を用いてレジスト膜を形成する工程と、
前記レジスト膜を露光する工程と、
前記露光されたレジスト膜を現像液を用いて現像する工程と、
を有するパターン形成方法。 - 請求項11に記載のパターン形成方法を含む電子デバイスの製造方法。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020247004350A KR20240031384A (ko) | 2021-08-12 | 2022-07-13 | 감활성광선성 또는 감방사선성 수지 조성물, 감활성광선성 또는 감방사선성막, 패턴 형성 방법 및 전자 디바이스의 제조 방법 |
JP2023541376A JPWO2023017702A1 (ja) | 2021-08-12 | 2022-07-13 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2021131754 | 2021-08-12 | ||
JP2021-131754 | 2021-08-12 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2023017702A1 true WO2023017702A1 (ja) | 2023-02-16 |
Family
ID=85200456
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2022/027517 WO2023017702A1 (ja) | 2021-08-12 | 2022-07-13 | 感活性光線性又は感放射線性樹脂組成物、感活性光線性又は感放射線性膜、パターン形成方法及び電子デバイスの製造方法 |
Country Status (4)
Country | Link |
---|---|
JP (1) | JPWO2023017702A1 (ja) |
KR (1) | KR20240031384A (ja) |
TW (1) | TW202311241A (ja) |
WO (1) | WO2023017702A1 (ja) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104985914A (zh) * | 2015-07-10 | 2015-10-21 | 中国科学院理化技术研究所 | 包含两层感光层的可水显影的光聚合型平版印刷版材料及其应用 |
JP2018155908A (ja) * | 2017-03-17 | 2018-10-04 | 信越化学工業株式会社 | レジスト材料及びパターン形成方法 |
JP2020098330A (ja) * | 2018-12-18 | 2020-06-25 | 信越化学工業株式会社 | レジスト材料及びパターン形成方法 |
JP2021047396A (ja) * | 2019-09-13 | 2021-03-25 | 信越化学工業株式会社 | レジスト材料及びパターン形成方法 |
JP2021081708A (ja) * | 2019-11-20 | 2021-05-27 | 信越化学工業株式会社 | レジスト材料及びパターン形成方法 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7114242B2 (ja) | 2016-12-14 | 2022-08-08 | 住友化学株式会社 | レジスト組成物及びレジストパターンの製造方法 |
JP7156199B2 (ja) | 2018-08-09 | 2022-10-19 | 信越化学工業株式会社 | レジスト材料及びパターン形成方法 |
-
2022
- 2022-07-13 JP JP2023541376A patent/JPWO2023017702A1/ja active Pending
- 2022-07-13 WO PCT/JP2022/027517 patent/WO2023017702A1/ja active Application Filing
- 2022-07-13 KR KR1020247004350A patent/KR20240031384A/ko unknown
- 2022-07-20 TW TW111127101A patent/TW202311241A/zh unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104985914A (zh) * | 2015-07-10 | 2015-10-21 | 中国科学院理化技术研究所 | 包含两层感光层的可水显影的光聚合型平版印刷版材料及其应用 |
JP2018155908A (ja) * | 2017-03-17 | 2018-10-04 | 信越化学工業株式会社 | レジスト材料及びパターン形成方法 |
JP2020098330A (ja) * | 2018-12-18 | 2020-06-25 | 信越化学工業株式会社 | レジスト材料及びパターン形成方法 |
JP2021047396A (ja) * | 2019-09-13 | 2021-03-25 | 信越化学工業株式会社 | レジスト材料及びパターン形成方法 |
JP2021081708A (ja) * | 2019-11-20 | 2021-05-27 | 信越化学工業株式会社 | レジスト材料及びパターン形成方法 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2023017702A1 (ja) | 2023-02-16 |
KR20240031384A (ko) | 2024-03-07 |
TW202311241A (zh) | 2023-03-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4961324B2 (ja) | 電子線、x線又はeuv用ポジ型レジスト組成物及びそれを用いたパターン形成方法 | |
JP6613020B2 (ja) | カルバメート成分を含むフォトレジスト | |
JP6007100B2 (ja) | 感活性光線性または感放射線性樹脂組成物、感活性光線性または感放射線性膜及びパターン形成方法 | |
JP5140354B2 (ja) | 感光性組成物、該感光性組成物に用いる化合物及び該感光性組成物を用いたパターン形成方法 | |
JP2007293250A (ja) | ポジ型レジスト組成物およびそれを用いたパターン形成方法 | |
JP7318129B2 (ja) | 感活性光線性又は感放射線性樹脂組成物、レジスト膜、パターン形成方法、電子デバイスの製造方法 | |
JPWO2020066342A1 (ja) | 感活性光線性又は感放射線性樹脂組成物、レジスト膜、パターン形成方法、電子デバイスの製造方法 | |
WO2022209733A1 (ja) | 感活性光線性又は感放射線性樹脂組成物、レジスト膜、パターン形成方法、電子デバイスの製造方法 | |
JP5520489B2 (ja) | リソグラフィ用基板被覆方法、及び該方法に用いられる感活性光線または感放射線性樹脂組成物 | |
WO2022172689A1 (ja) | 感活性光線性又は感放射線性樹脂組成物、レジスト膜、パターン形成方法、電子デバイスの製造方法 | |
WO2021220851A1 (ja) | 感活性光線性又は感放射線性樹脂組成物、感活性光線性又は感放射線性膜、マスクブランクス、パターン形成方法及び電子デバイスの製造方法 | |
WO2023032794A1 (ja) | 感活性光線性又は感放射線性樹脂組成物、感活性光線性又は感放射線性膜、パターン形成方法、電子デバイスの製造方法、及び化合物 | |
WO2023054127A1 (ja) | 感活性光線性又は感放射線性樹脂組成物、レジスト膜、パターン形成方法及び電子デバイスの製造方法 | |
WO2023162837A1 (ja) | ポジ型感活性光線性又は感放射線性樹脂組成物、感活性光線性又は感放射線性膜、パターン形成方法、電子デバイスの製造方法、及び化合物 | |
JP7434592B2 (ja) | 感活性光線性又は感放射線性樹脂組成物、レジスト膜、パターン形成方法、電子デバイスの製造方法 | |
WO2023145564A1 (ja) | 感活性光線性又は感放射線性樹脂組成物、感活性光線性又は感放射線性膜、パターン形成方法、及び電子デバイスの製造方法 | |
WO2023145488A1 (ja) | 感活性光線性又は感放射線性樹脂組成物、レジスト膜、パターン形成方法及び電子デバイスの製造方法 | |
JP7373070B2 (ja) | 感活性光線性又は感放射線性樹脂組成物、感活性光線性又は感放射線性膜、パターン形成方法及び電子デバイスの製造方法 | |
WO2022172597A1 (ja) | 感活性光線性又は感放射線性樹脂組成物、レジスト膜、ポジ型パターン形成方法、電子デバイスの製造方法 | |
WO2023017702A1 (ja) | 感活性光線性又は感放射線性樹脂組成物、感活性光線性又は感放射線性膜、パターン形成方法及び電子デバイスの製造方法 | |
WO2022220189A1 (ja) | 感活性光線性又は感放射線性樹脂組成物、レジスト膜、パターン形成方法、電子デバイスの製造方法 | |
WO2022158323A1 (ja) | パターン形成方法、及び電子デバイスの製造方法 | |
WO2023017703A1 (ja) | 感活性光線性又は感放射線性樹脂組成物、感活性光線性又は感放射線性膜、パターン形成方法及び電子デバイスの製造方法 | |
WO2019044547A1 (ja) | 感活性光線性又は感放射線性樹脂組成物、レジスト膜、パターン形成方法、及び電子デバイスの製造方法 | |
WO2024024691A1 (ja) | 感活性光線性又は感放射線性樹脂組成物、感活性光線性又は感放射線性膜、パターン形成方法、及び電子デバイスの製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 22855766 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2023541376 Country of ref document: JP |
|
ENP | Entry into the national phase |
Ref document number: 20247004350 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020247004350 Country of ref document: KR |
|
NENP | Non-entry into the national phase |
Ref country code: DE |