JP5655352B2 - Radiation-sensitive resin composition and polymer used therefor - Google Patents
Radiation-sensitive resin composition and polymer used therefor Download PDFInfo
- Publication number
- JP5655352B2 JP5655352B2 JP2010084494A JP2010084494A JP5655352B2 JP 5655352 B2 JP5655352 B2 JP 5655352B2 JP 2010084494 A JP2010084494 A JP 2010084494A JP 2010084494 A JP2010084494 A JP 2010084494A JP 5655352 B2 JP5655352 B2 JP 5655352B2
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- radiation
- group
- resin composition
- sensitive resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920000642 polymer Polymers 0.000 title claims description 69
- 230000005855 radiation Effects 0.000 title claims description 48
- 239000011342 resin composition Substances 0.000 title claims description 41
- 239000002253 acid Substances 0.000 claims description 50
- 238000006116 polymerization reaction Methods 0.000 claims description 24
- 239000003513 alkali Substances 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 11
- 238000005227 gel permeation chromatography Methods 0.000 claims description 11
- 239000007870 radical polymerization initiator Substances 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 5
- 229920002223 polystyrene Polymers 0.000 claims description 5
- 150000005676 cyclic carbonates Chemical group 0.000 claims description 4
- 230000002829 reductive effect Effects 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 239000001301 oxygen Chemical group 0.000 claims description 2
- 229910052760 oxygen Chemical group 0.000 claims description 2
- 125000000686 lactone group Chemical group 0.000 claims 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 2
- 239000000178 monomer Substances 0.000 description 41
- -1 alicyclic hydrocarbon Chemical class 0.000 description 39
- 239000002904 solvent Substances 0.000 description 34
- 238000000034 method Methods 0.000 description 28
- 239000011347 resin Substances 0.000 description 24
- 229920005989 resin Polymers 0.000 description 24
- 239000000243 solution Substances 0.000 description 24
- 230000007547 defect Effects 0.000 description 17
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 14
- 238000011161 development Methods 0.000 description 14
- 230000018109 developmental process Effects 0.000 description 14
- 229910052731 fluorine Inorganic materials 0.000 description 14
- 239000011737 fluorine Substances 0.000 description 14
- 238000007654 immersion Methods 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- 229920002120 photoresistant polymer Polymers 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 125000002723 alicyclic group Chemical group 0.000 description 11
- 238000009792 diffusion process Methods 0.000 description 11
- 239000003999 initiator Substances 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 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
- 230000035945 sensitivity Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 5
- 239000012986 chain transfer agent Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical compound C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 5
- 239000012953 triphenylsulfonium Substances 0.000 description 5
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000005456 alcohol based solvent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 150000002596 lactones Chemical group 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 4
- 238000001226 reprecipitation Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- CEZIJESLKIMKNL-UHFFFAOYSA-N 1-(4-butoxynaphthalen-1-yl)thiolan-1-ium Chemical compound C12=CC=CC=C2C(OCCCC)=CC=C1[S+]1CCCC1 CEZIJESLKIMKNL-UHFFFAOYSA-N 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 3
- GPIUUMROPXDNRH-UHFFFAOYSA-N 3647-74-3 Chemical compound C1C2C3C(=O)NC(=O)C3C1C=C2 GPIUUMROPXDNRH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- SMEROWZSTRWXGI-UHFFFAOYSA-N Lithocholsaeure Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)CC2 SMEROWZSTRWXGI-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 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 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
- 239000004210 ether based solvent Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- VLLPVDKADBYKLM-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate;triphenylsulfanium Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 VLLPVDKADBYKLM-UHFFFAOYSA-M 0.000 description 2
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- QWOZZTWBWQMEPD-UHFFFAOYSA-N 1-(2-ethoxypropoxy)propan-2-ol Chemical compound CCOC(C)COCC(C)O QWOZZTWBWQMEPD-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 description 2
- GRCVHLCFMAVQCF-UHFFFAOYSA-M 2-(1-adamantyl)-1,1-difluoroethanesulfonate;triphenylsulfanium Chemical compound C1C(C2)CC3CC2CC1(CC(F)(F)S(=O)(=O)[O-])C3.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 GRCVHLCFMAVQCF-UHFFFAOYSA-M 0.000 description 2
- ZKCAGDPACLOVBN-UHFFFAOYSA-N 2-(2-ethylbutoxy)ethanol Chemical compound CCC(CC)COCCO ZKCAGDPACLOVBN-UHFFFAOYSA-N 0.000 description 2
- GZMAAYIALGURDQ-UHFFFAOYSA-N 2-(2-hexoxyethoxy)ethanol Chemical compound CCCCCCOCCOCCO GZMAAYIALGURDQ-UHFFFAOYSA-N 0.000 description 2
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- UPGSWASWQBLSKZ-UHFFFAOYSA-N 2-hexoxyethanol Chemical compound CCCCCCOCCO UPGSWASWQBLSKZ-UHFFFAOYSA-N 0.000 description 2
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 2
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Natural products CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 2
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 2
- LDMRLRNXHLPZJN-UHFFFAOYSA-N 3-propoxypropan-1-ol Chemical compound CCCOCCCO LDMRLRNXHLPZJN-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- RZKSECIXORKHQS-UHFFFAOYSA-N Heptan-3-ol Chemical compound CCCCC(O)CC RZKSECIXORKHQS-UHFFFAOYSA-N 0.000 description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical group C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical class C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229960003964 deoxycholic acid Drugs 0.000 description 2
- KXGVEGMKQFWNSR-UHFFFAOYSA-N deoxycholic acid Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)C(O)C2 KXGVEGMKQFWNSR-UHFFFAOYSA-N 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- OZLBDYMWFAHSOQ-UHFFFAOYSA-N diphenyliodanium Chemical compound C=1C=CC=CC=1[I+]C1=CC=CC=C1 OZLBDYMWFAHSOQ-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 229940116333 ethyl lactate Drugs 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- NGAZZOYFWWSOGK-UHFFFAOYSA-N heptan-3-one Chemical compound CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- XAOGXQMKWQFZEM-UHFFFAOYSA-N isoamyl propanoate Chemical compound CCC(=O)OCCC(C)C XAOGXQMKWQFZEM-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- YCMDNBGUNDHOOD-UHFFFAOYSA-N n -((trifluoromethylsulfonyl)oxy)-5-norbornene-2,3-dicarboximide Chemical compound C1=CC2CC1C1C2C(=O)N(OS(=O)(=O)C(F)(F)F)C1=O YCMDNBGUNDHOOD-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- GJQIMXVRFNLMTB-UHFFFAOYSA-N nonyl acetate Chemical compound CCCCCCCCCOC(C)=O GJQIMXVRFNLMTB-UHFFFAOYSA-N 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- JGTNAGYHADQMCM-UHFFFAOYSA-N perfluorobutanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-N 0.000 description 2
- 229960005323 phenoxyethanol Drugs 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 230000007261 regionalization Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical class C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- FAYMLNNRGCYLSR-UHFFFAOYSA-M triphenylsulfonium triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 FAYMLNNRGCYLSR-UHFFFAOYSA-M 0.000 description 2
- LHXDLQBQYFFVNW-OIBJUYFYSA-N (-)-Fenchone Chemical compound C1C[C@@]2(C)C(=O)C(C)(C)[C@@H]1C2 LHXDLQBQYFFVNW-OIBJUYFYSA-N 0.000 description 1
- XNUYPROIFFCXAE-UHFFFAOYSA-N (4-cyclohexylphenyl)-diphenylsulfanium Chemical compound C1CCCCC1C1=CC=C([S+](C=2C=CC=CC=2)C=2C=CC=CC=2)C=C1 XNUYPROIFFCXAE-UHFFFAOYSA-N 0.000 description 1
- RUDFKNNFTLQMGW-UHFFFAOYSA-M (4-cyclohexylphenyl)-diphenylsulfanium;(7,7-dimethyl-3-oxo-4-bicyclo[2.2.1]heptanyl)methanesulfonate Chemical compound C1CC2(CS([O-])(=O)=O)C(=O)CC1C2(C)C.C1CCCCC1C1=CC=C([S+](C=2C=CC=CC=2)C=2C=CC=CC=2)C=C1 RUDFKNNFTLQMGW-UHFFFAOYSA-M 0.000 description 1
- UFADEYDBOXASBQ-UHFFFAOYSA-M (4-cyclohexylphenyl)-diphenylsulfanium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F.C1CCCCC1C1=CC=C([S+](C=2C=CC=CC=2)C=2C=CC=CC=2)C=C1 UFADEYDBOXASBQ-UHFFFAOYSA-M 0.000 description 1
- QEYKXSMQZGHJSX-UHFFFAOYSA-M (4-cyclohexylphenyl)-diphenylsulfanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1CCCCC1C1=CC=C([S+](C=2C=CC=CC=2)C=2C=CC=CC=2)C=C1 QEYKXSMQZGHJSX-UHFFFAOYSA-M 0.000 description 1
- HQGTWZUOVIZAKX-UHFFFAOYSA-N (4-methylsulfonylphenyl)-diphenylsulfanium Chemical compound C1=CC(S(=O)(=O)C)=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 HQGTWZUOVIZAKX-UHFFFAOYSA-N 0.000 description 1
- VHXIWNNSPUGPEI-UHFFFAOYSA-M (7,7-dimethyl-3-oxo-4-bicyclo[2.2.1]heptanyl)methanesulfonate;(4-methylsulfonylphenyl)-diphenylsulfanium Chemical compound C1CC2(CS([O-])(=O)=O)C(=O)CC1C2(C)C.C1=CC(S(=O)(=O)C)=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 VHXIWNNSPUGPEI-UHFFFAOYSA-M 0.000 description 1
- PQONLZARMHVIPW-UHFFFAOYSA-N (7,7-dimethyl-3-oxo-4-bicyclo[2.2.1]heptanyl)methanesulfonate;2,6-dimethyl-4-(thiolan-1-ium-1-yl)phenol Chemical compound CC1=C(O)C(C)=CC([S+]2CCCC2)=C1.C1CC2(CS([O-])(=O)=O)C(=O)CC1C2(C)C PQONLZARMHVIPW-UHFFFAOYSA-N 0.000 description 1
- HHYVKZVPYXHHCG-UHFFFAOYSA-M (7,7-dimethyl-3-oxo-4-bicyclo[2.2.1]heptanyl)methanesulfonate;diphenyliodanium Chemical compound C=1C=CC=CC=1[I+]C1=CC=CC=C1.C1CC2(CS([O-])(=O)=O)C(=O)CC1C2(C)C HHYVKZVPYXHHCG-UHFFFAOYSA-M 0.000 description 1
- FJALTVCJBKZXKY-UHFFFAOYSA-M (7,7-dimethyl-3-oxo-4-bicyclo[2.2.1]heptanyl)methanesulfonate;triphenylsulfanium Chemical compound C1CC2(CS([O-])(=O)=O)C(=O)CC1C2(C)C.C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 FJALTVCJBKZXKY-UHFFFAOYSA-M 0.000 description 1
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 1
- WYPDFLYUYKDLGV-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoro-2-(4-tetracyclo[6.2.1.13,6.02,7]dodecanylmethyl)propan-2-ol Chemical compound C12C(C3)CCC3C2C2CC(CC(O)(C(F)(F)F)C(F)(F)F)C1C2 WYPDFLYUYKDLGV-UHFFFAOYSA-N 0.000 description 1
- VIDOPANCAUPXNH-UHFFFAOYSA-N 1,2,3-triethylbenzene Chemical compound CCC1=CC=CC(CC)=C1CC VIDOPANCAUPXNH-UHFFFAOYSA-N 0.000 description 1
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 description 1
- BXGYVRIBHDBIJQ-UHFFFAOYSA-M 1-(4-butoxynaphthalen-1-yl)thiolan-1-ium;(7,7-dimethyl-3-oxo-4-bicyclo[2.2.1]heptanyl)methanesulfonate Chemical compound C1CC2(CS([O-])(=O)=O)C(=O)CC1C2(C)C.C12=CC=CC=C2C(OCCCC)=CC=C1[S+]1CCCC1 BXGYVRIBHDBIJQ-UHFFFAOYSA-M 0.000 description 1
- WNDABSCBNOUSTE-UHFFFAOYSA-M 1-(4-butoxynaphthalen-1-yl)thiolan-1-ium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F.C12=CC=CC=C2C(OCCCC)=CC=C1[S+]1CCCC1 WNDABSCBNOUSTE-UHFFFAOYSA-M 0.000 description 1
- JQIQJUCEFIYYOJ-UHFFFAOYSA-M 1-(4-butoxynaphthalen-1-yl)thiolan-1-ium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C12=CC=CC=C2C(OCCCC)=CC=C1[S+]1CCCC1 JQIQJUCEFIYYOJ-UHFFFAOYSA-M 0.000 description 1
- WXWSNMWMJAFDLG-UHFFFAOYSA-N 1-(6-butoxynaphthalen-2-yl)thiolan-1-ium Chemical compound C1=CC2=CC(OCCCC)=CC=C2C=C1[S+]1CCCC1 WXWSNMWMJAFDLG-UHFFFAOYSA-N 0.000 description 1
- PIUKSJQPBWVFHQ-UHFFFAOYSA-M 1-(6-butoxynaphthalen-2-yl)thiolan-1-ium;(7,7-dimethyl-3-oxo-4-bicyclo[2.2.1]heptanyl)methanesulfonate Chemical compound C1CC2(CS([O-])(=O)=O)C(=O)CC1C2(C)C.C1=CC2=CC(OCCCC)=CC=C2C=C1[S+]1CCCC1 PIUKSJQPBWVFHQ-UHFFFAOYSA-M 0.000 description 1
- WRMXJRZJMAXZNC-UHFFFAOYSA-M 1-(6-butoxynaphthalen-2-yl)thiolan-1-ium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F.C1=CC2=CC(OCCCC)=CC=C2C=C1[S+]1CCCC1 WRMXJRZJMAXZNC-UHFFFAOYSA-M 0.000 description 1
- WFZZYWQSLJQVOT-UHFFFAOYSA-M 1-(6-butoxynaphthalen-2-yl)thiolan-1-ium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C1=CC2=CC(OCCCC)=CC=C2C=C1[S+]1CCCC1 WFZZYWQSLJQVOT-UHFFFAOYSA-M 0.000 description 1
- KZVBBTZJMSWGTK-UHFFFAOYSA-N 1-[2-(2-butoxyethoxy)ethoxy]butane Chemical compound CCCCOCCOCCOCCCC KZVBBTZJMSWGTK-UHFFFAOYSA-N 0.000 description 1
- MQGIBEAIDUOVOH-UHFFFAOYSA-N 1-[2-[2-[2-(2-butoxyethoxy)ethoxy]ethoxy]ethoxy]butane Chemical compound CCCCOCCOCCOCCOCCOCCCC MQGIBEAIDUOVOH-UHFFFAOYSA-N 0.000 description 1
- FUWDFGKRNIDKAE-UHFFFAOYSA-N 1-butoxypropan-2-yl acetate Chemical compound CCCCOCC(C)OC(C)=O FUWDFGKRNIDKAE-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 description 1
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 1
- DMFAHCVITRDZQB-UHFFFAOYSA-N 1-propoxypropan-2-yl acetate Chemical compound CCCOCC(C)OC(C)=O DMFAHCVITRDZQB-UHFFFAOYSA-N 0.000 description 1
- BHQDJBBBEDFPAL-UHFFFAOYSA-N 1-tricyclo[5.2.1.02,6]decanyl prop-2-enoate Chemical compound C12CCCC2C2(OC(=O)C=C)CC1CC2 BHQDJBBBEDFPAL-UHFFFAOYSA-N 0.000 description 1
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- KWBZODMYTRHRIU-UHFFFAOYSA-N 2,3,4,5,6,7,8,8a-octahydro-1h-naphthalen-4a-yl prop-2-enoate Chemical compound C1CCCC2CCCCC21OC(=O)C=C KWBZODMYTRHRIU-UHFFFAOYSA-N 0.000 description 1
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 1
- AWBIJARKDOFDAN-UHFFFAOYSA-N 2,5-dimethyl-1,4-dioxane Chemical compound CC1COC(C)CO1 AWBIJARKDOFDAN-UHFFFAOYSA-N 0.000 description 1
- WFQNMENFJSZTGD-UHFFFAOYSA-O 2,6-dimethyl-4-(thiolan-1-ium-1-yl)phenol Chemical compound CC1=C(O)C(C)=CC([S+]2CCCC2)=C1 WFQNMENFJSZTGD-UHFFFAOYSA-O 0.000 description 1
- GNZYDSUXCMLOMM-UHFFFAOYSA-N 2,6-dimethyl-4-(thiolan-1-ium-1-yl)phenol;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound CC1=C(O)C(C)=CC([S+]2CCCC2)=C1.[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F GNZYDSUXCMLOMM-UHFFFAOYSA-N 0.000 description 1
- VAOHUAFTTHSCRT-UHFFFAOYSA-N 2,6-dimethyl-4-(thiolan-1-ium-1-yl)phenol;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CC1=C(O)C(C)=CC([S+]2CCCC2)=C1 VAOHUAFTTHSCRT-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- CKCGJBFTCUCBAJ-UHFFFAOYSA-N 2-(2-ethoxypropoxy)propyl acetate Chemical compound CCOC(C)COC(C)COC(C)=O CKCGJBFTCUCBAJ-UHFFFAOYSA-N 0.000 description 1
- BJINVQNEBGOMCR-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethyl acetate Chemical compound COCCOCCOC(C)=O BJINVQNEBGOMCR-UHFFFAOYSA-N 0.000 description 1
- DRLRGHZJOQGQEC-UHFFFAOYSA-N 2-(2-methoxypropoxy)propyl acetate Chemical compound COC(C)COC(C)COC(C)=O DRLRGHZJOQGQEC-UHFFFAOYSA-N 0.000 description 1
- DJCYDDALXPHSHR-UHFFFAOYSA-N 2-(2-propoxyethoxy)ethanol Chemical compound CCCOCCOCCO DJCYDDALXPHSHR-UHFFFAOYSA-N 0.000 description 1
- XYVAYAJYLWYJJN-UHFFFAOYSA-N 2-(2-propoxypropoxy)propan-1-ol Chemical compound CCCOC(C)COC(C)CO XYVAYAJYLWYJJN-UHFFFAOYSA-N 0.000 description 1
- CIEPNGYYAZJVPI-UHFFFAOYSA-M 2-(3-bicyclo[2.2.1]heptanyl)-1,1,2,2-tetrafluoroethanesulfonate;(4-methylsulfonylphenyl)-diphenylsulfanium Chemical compound C1CC2C(C(F)(F)C(F)(F)S(=O)(=O)[O-])CC1C2.C1=CC(S(=O)(=O)C)=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 CIEPNGYYAZJVPI-UHFFFAOYSA-M 0.000 description 1
- CDSOWTBAXZQSFF-UHFFFAOYSA-M 2-(3-bicyclo[2.2.1]heptanyl)-1,1,2,2-tetrafluoroethanesulfonate;1-(4-butoxynaphthalen-1-yl)thiolan-1-ium Chemical compound C1CC2C(C(F)(F)C(F)(F)S(=O)(=O)[O-])CC1C2.C12=CC=CC=C2C(OCCCC)=CC=C1[S+]1CCCC1 CDSOWTBAXZQSFF-UHFFFAOYSA-M 0.000 description 1
- COAPLGOCHZYBCI-UHFFFAOYSA-M 2-(3-bicyclo[2.2.1]heptanyl)-1,1,2,2-tetrafluoroethanesulfonate;1-(6-butoxynaphthalen-2-yl)thiolan-1-ium Chemical compound C1CC2C(C(F)(F)C(F)(F)S(=O)(=O)[O-])CC1C2.C1=CC2=CC(OCCCC)=CC=C2C=C1[S+]1CCCC1 COAPLGOCHZYBCI-UHFFFAOYSA-M 0.000 description 1
- JDUWLFYXEJGUET-UHFFFAOYSA-N 2-(3-bicyclo[2.2.1]heptanyl)-1,1,2,2-tetrafluoroethanesulfonate;2,6-dimethyl-4-(thiolan-1-ium-1-yl)phenol Chemical compound CC1=C(O)C(C)=CC([S+]2CCCC2)=C1.C1CC2C(C(F)(F)C(F)(F)S(=O)(=O)[O-])CC1C2 JDUWLFYXEJGUET-UHFFFAOYSA-N 0.000 description 1
- AHFWIRXJWWWORD-UHFFFAOYSA-N 2-(3-bicyclo[2.2.1]heptanyl)-1,1,2,2-tetrafluoroethanesulfonic acid Chemical compound C1CC2C(C(F)(F)C(F)(F)S(=O)(=O)O)CC1C2 AHFWIRXJWWWORD-UHFFFAOYSA-N 0.000 description 1
- HQLKZWRSOHTERR-UHFFFAOYSA-N 2-Ethylbutyl acetate Chemical compound CCC(CC)COC(C)=O HQLKZWRSOHTERR-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- GQKZRWSUJHVIPE-UHFFFAOYSA-N 2-Pentanol acetate Chemical compound CCCC(C)OC(C)=O GQKZRWSUJHVIPE-UHFFFAOYSA-N 0.000 description 1
- SPSNALDHELHFIJ-UHFFFAOYSA-N 2-[(1-cyano-1-cyclopropylethyl)diazenyl]-2-cyclopropylpropanenitrile Chemical compound C1CC1C(C)(C#N)N=NC(C)(C#N)C1CC1 SPSNALDHELHFIJ-UHFFFAOYSA-N 0.000 description 1
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- WFSMVVDJSNMRAR-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]ethanol Chemical compound CCOCCOCCOCCO WFSMVVDJSNMRAR-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- SDHQGBWMLCBNSM-UHFFFAOYSA-N 2-[2-(2-methoxyethoxy)ethoxy]ethyl acetate Chemical compound COCCOCCOCCOC(C)=O SDHQGBWMLCBNSM-UHFFFAOYSA-N 0.000 description 1
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 description 1
- ZVUNTIMPQCQCAQ-UHFFFAOYSA-N 2-dodecanoyloxyethyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCCOC(=O)CCCCCCCCCCC ZVUNTIMPQCQCAQ-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- TZYRSLHNPKPEFV-UHFFFAOYSA-N 2-ethyl-1-butanol Chemical compound CCC(CC)CO TZYRSLHNPKPEFV-UHFFFAOYSA-N 0.000 description 1
- WOYWLLHHWAMFCB-UHFFFAOYSA-N 2-ethylhexyl acetate Chemical compound CCCCC(CC)COC(C)=O WOYWLLHHWAMFCB-UHFFFAOYSA-N 0.000 description 1
- CETWDUZRCINIHU-UHFFFAOYSA-N 2-heptanol Chemical compound CCCCCC(C)O CETWDUZRCINIHU-UHFFFAOYSA-N 0.000 description 1
- PFNHSEQQEPMLNI-UHFFFAOYSA-N 2-methyl-1-pentanol Chemical compound CCCC(C)CO PFNHSEQQEPMLNI-UHFFFAOYSA-N 0.000 description 1
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical class OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- BRRVXFOKWJKTGG-UHFFFAOYSA-N 3,3,5-trimethylcyclohexanol Chemical compound CC1CC(O)CC(C)(C)C1 BRRVXFOKWJKTGG-UHFFFAOYSA-N 0.000 description 1
- PKNKULBDCRZSBT-UHFFFAOYSA-N 3,4,5-trimethylnonan-2-one Chemical compound CCCCC(C)C(C)C(C)C(C)=O PKNKULBDCRZSBT-UHFFFAOYSA-N 0.000 description 1
- YHCCCMIWRBJYHG-UHFFFAOYSA-N 3-(2-ethylhexoxymethyl)heptane Chemical compound CCCCC(CC)COCC(CC)CCCC YHCCCMIWRBJYHG-UHFFFAOYSA-N 0.000 description 1
- JFUOAGBSDGCVES-UHFFFAOYSA-N 3-but-2-enyl-4-methylpyrrolidine-2,5-dione Chemical compound CC=CCC1C(C)C(=O)NC1=O JFUOAGBSDGCVES-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- JSGVZVOGOQILFM-UHFFFAOYSA-N 3-methoxy-1-butanol Chemical compound COC(C)CCO JSGVZVOGOQILFM-UHFFFAOYSA-N 0.000 description 1
- QMYGFTJCQFEDST-UHFFFAOYSA-N 3-methoxybutyl acetate Chemical compound COC(C)CCOC(C)=O QMYGFTJCQFEDST-UHFFFAOYSA-N 0.000 description 1
- IICCLYANAQEHCI-UHFFFAOYSA-N 4,5,6,7-tetrachloro-3',6'-dihydroxy-2',4',5',7'-tetraiodospiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 IICCLYANAQEHCI-UHFFFAOYSA-N 0.000 description 1
- WGUJUIMHWNHXGB-UHFFFAOYSA-N 4-bicyclo[2.2.1]heptanyl prop-2-enoate Chemical compound C1CC2CCC1(OC(=O)C=C)C2 WGUJUIMHWNHXGB-UHFFFAOYSA-N 0.000 description 1
- MQWCXKGKQLNYQG-UHFFFAOYSA-N 4-methylcyclohexan-1-ol Chemical compound CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 1
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 1
- LBKMJZAKWQTTHC-UHFFFAOYSA-N 4-methyldioxolane Chemical compound CC1COOC1 LBKMJZAKWQTTHC-UHFFFAOYSA-N 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 1
- LIZXBEVIORHARS-UHFFFAOYSA-L C(C)(C)(C)C1=CC=C(C=C1)[I+]C1=CC=C(C=C1)C(C)(C)C.FC(C(C(C(S(=O)(=O)[O-])(F)F)(F)F)(F)F)(F)F.C(C)(C)(C)C1=CC=C(C=C1)[I+]C1=CC=C(C=C1)C(C)(C)C.FC(C(C(C(S(=O)(=O)[O-])(F)F)(F)F)(F)F)(F)F Chemical compound C(C)(C)(C)C1=CC=C(C=C1)[I+]C1=CC=C(C=C1)C(C)(C)C.FC(C(C(C(S(=O)(=O)[O-])(F)F)(F)F)(F)F)(F)F.C(C)(C)(C)C1=CC=C(C=C1)[I+]C1=CC=C(C=C1)C(C)(C)C.FC(C(C(C(S(=O)(=O)[O-])(F)F)(F)F)(F)F)(F)F LIZXBEVIORHARS-UHFFFAOYSA-L 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- YYLLIJHXUHJATK-UHFFFAOYSA-N Cyclohexyl acetate Chemical compound CC(=O)OC1CCCCC1 YYLLIJHXUHJATK-UHFFFAOYSA-N 0.000 description 1
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- HXQPUEQDBSPXTE-UHFFFAOYSA-N Diisobutylcarbinol Chemical compound CC(C)CC(O)CC(C)C HXQPUEQDBSPXTE-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 206010073306 Exposure to radiation Diseases 0.000 description 1
- OGMPMTBETWGGJV-UHFFFAOYSA-N FC(C(C(C(S(=O)(=O)[O-])(F)F)(F)F)(F)F)(F)F.CC=1C(=C(C=C(C1)C)[S+]1CCCC1)O Chemical compound FC(C(C(C(S(=O)(=O)[O-])(F)F)(F)F)(F)F)(F)F.CC=1C(=C(C=C(C1)C)[S+]1CCCC1)O OGMPMTBETWGGJV-UHFFFAOYSA-N 0.000 description 1
- LZOIMKRQKPPEQH-UHFFFAOYSA-L FC(C(C(C(S(=O)(=O)[O-])(F)F)(F)F)(F)F)(F)F.CS(=O)(=O)C1=CC=C(C=C1)[S+](C1=CC=CC=C1)C1=CC=CC=C1.FC(S(=O)(=O)[O-])(F)F.CS(=O)(=O)C1=CC=C(C=C1)[S+](C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound FC(C(C(C(S(=O)(=O)[O-])(F)F)(F)F)(F)F)(F)F.CS(=O)(=O)C1=CC=C(C=C1)[S+](C1=CC=CC=C1)C1=CC=CC=C1.FC(S(=O)(=O)[O-])(F)F.CS(=O)(=O)C1=CC=C(C=C1)[S+](C1=CC=CC=C1)C1=CC=CC=C1 LZOIMKRQKPPEQH-UHFFFAOYSA-L 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- JKRZOJADNVOXPM-UHFFFAOYSA-N Oxalic acid dibutyl ester Chemical compound CCCCOC(=O)C(=O)OCCCC JKRZOJADNVOXPM-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000007877 V-601 Substances 0.000 description 1
- NVJPBZCLWGTJKD-UHFFFAOYSA-N [bis(4-tert-butylphenyl)-lambda3-iodanyl] trifluoromethanesulfonate Chemical compound CC(C)(C)c1ccc(cc1)[I](OS(=O)(=O)C(F)(F)F)c1ccc(cc1)C(C)(C)C NVJPBZCLWGTJKD-UHFFFAOYSA-N 0.000 description 1
- MSAVICZWFPQFPO-UHFFFAOYSA-N acetic acid;ethene Chemical compound C=C.C=C.CC(O)=O MSAVICZWFPQFPO-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- JIMXXGFJRDUSRO-UHFFFAOYSA-N adamantane-1-carboxylic acid Chemical compound C1C(C2)CC3CC2CC1(C(=O)O)C3 JIMXXGFJRDUSRO-UHFFFAOYSA-N 0.000 description 1
- IYKFYARMMIESOX-UHFFFAOYSA-N adamantanone Chemical compound C1C(C2)CC3CC1C(=O)C2C3 IYKFYARMMIESOX-UHFFFAOYSA-N 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 229940007550 benzyl acetate Drugs 0.000 description 1
- DNFSNYQTQMVTOK-UHFFFAOYSA-N bis(4-tert-butylphenyl)iodanium Chemical compound C1=CC(C(C)(C)C)=CC=C1[I+]C1=CC=C(C(C)(C)C)C=C1 DNFSNYQTQMVTOK-UHFFFAOYSA-N 0.000 description 1
- MDUKBVGQQFOMPC-UHFFFAOYSA-M bis(4-tert-butylphenyl)iodanium;(7,7-dimethyl-3-oxo-4-bicyclo[2.2.1]heptanyl)methanesulfonate Chemical compound C1CC2(CS([O-])(=O)=O)C(=O)CC1C2(C)C.C1=CC(C(C)(C)C)=CC=C1[I+]C1=CC=C(C(C)(C)C)C=C1 MDUKBVGQQFOMPC-UHFFFAOYSA-M 0.000 description 1
- DJBAOXYQCAKLPH-UHFFFAOYSA-M bis(4-tert-butylphenyl)iodanium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F.C1=CC(C(C)(C)C)=CC=C1[I+]C1=CC=C(C(C)(C)C)C=C1 DJBAOXYQCAKLPH-UHFFFAOYSA-M 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BTMVHUNTONAYDX-UHFFFAOYSA-N butyl propionate Chemical compound CCCCOC(=O)CC BTMVHUNTONAYDX-UHFFFAOYSA-N 0.000 description 1
- 125000000609 carbazolyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- CGZZMOTZOONQIA-UHFFFAOYSA-N cycloheptanone Chemical compound O=C1CCCCCC1 CGZZMOTZOONQIA-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- IIRFCWANHMSDCG-UHFFFAOYSA-N cyclooctanone Chemical compound O=C1CCCCCCC1 IIRFCWANHMSDCG-UHFFFAOYSA-N 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 229940009976 deoxycholate Drugs 0.000 description 1
- KXGVEGMKQFWNSR-LLQZFEROSA-N deoxycholic acid Chemical class C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)[C@@H](O)C1 KXGVEGMKQFWNSR-LLQZFEROSA-N 0.000 description 1
- XXTZHYXQVWRADW-UHFFFAOYSA-N diazomethanone Chemical class [N]N=C=O XXTZHYXQVWRADW-UHFFFAOYSA-N 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- ORPDKMPYOLFUBA-UHFFFAOYSA-M diphenyliodanium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound C=1C=CC=CC=1[I+]C1=CC=CC=C1.[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ORPDKMPYOLFUBA-UHFFFAOYSA-M 0.000 description 1
- SBQIJPBUMNWUKN-UHFFFAOYSA-M diphenyliodanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.C=1C=CC=CC=1[I+]C1=CC=CC=C1 SBQIJPBUMNWUKN-UHFFFAOYSA-M 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229940052761 dopaminergic adamantane derivative Drugs 0.000 description 1
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000012156 elution solvent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- JFCFIXGDCBSLRW-UHFFFAOYSA-N heptan-2-yl 1,1,2,2-tetrafluoroethanesulfonate Chemical compound CC(CCCCC)OS(=O)(=O)C(C(F)F)(F)F JFCFIXGDCBSLRW-UHFFFAOYSA-N 0.000 description 1
- XVEOUOTUJBYHNL-UHFFFAOYSA-N heptane-2,4-diol Chemical compound CCCC(O)CC(C)O XVEOUOTUJBYHNL-UHFFFAOYSA-N 0.000 description 1
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 description 1
- OHMBHFSEKCCCBW-UHFFFAOYSA-N hexane-2,5-diol Chemical compound CC(O)CCC(C)O OHMBHFSEKCCCBW-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- KXUHSQYYJYAXGZ-UHFFFAOYSA-N isobutylbenzene Chemical compound CC(C)CC1=CC=CC=C1 KXUHSQYYJYAXGZ-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M isovalerate Chemical compound CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- SMEROWZSTRWXGI-HVATVPOCSA-N lithocholic acid Chemical class C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)CC1 SMEROWZSTRWXGI-HVATVPOCSA-N 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- IMXBRVLCKXGWSS-UHFFFAOYSA-N methyl 2-cyclohexylacetate Chemical compound COC(=O)CC1CCCCC1 IMXBRVLCKXGWSS-UHFFFAOYSA-N 0.000 description 1
- GFVQBVDJRHZKPO-UHFFFAOYSA-N methyl 2-hydroxy-5-oxo-4-oxatricyclo[4.2.1.03,7]nonane-9-carboxylate Chemical compound O1C(=O)C2C(C(=O)OC)C3C(O)C1C2C3 GFVQBVDJRHZKPO-UHFFFAOYSA-N 0.000 description 1
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- JESXATFQYMPTNL-UHFFFAOYSA-N mono-hydroxyphenyl-ethylene Natural products OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 1
- HEPOEAALKWFVLE-UHFFFAOYSA-N n -((perfluorooctanesulfonyl)oxy)-5-norbornene-2,3-dicarboximide Chemical compound C1=CC2CC1C1C2C(=O)N(OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C1=O HEPOEAALKWFVLE-UHFFFAOYSA-N 0.000 description 1
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229940017144 n-butyl lactate Drugs 0.000 description 1
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- QJQAMHYHNCADNR-UHFFFAOYSA-N n-methylpropanamide Chemical compound CCC(=O)NC QJQAMHYHNCADNR-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical group C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 description 1
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 1
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 1
- WYNVIVRXHYGNRT-UHFFFAOYSA-N octane-3,5-diol Chemical compound CCCC(O)CC(O)CC WYNVIVRXHYGNRT-UHFFFAOYSA-N 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 1
- GTCCGKPBSJZVRZ-UHFFFAOYSA-N pentane-2,4-diol Chemical compound CC(O)CC(C)O GTCCGKPBSJZVRZ-UHFFFAOYSA-N 0.000 description 1
- GXOHBWLPQHTYPF-UHFFFAOYSA-N pentyl 2-hydroxypropanoate Chemical compound CCCCCOC(=O)C(C)O GXOHBWLPQHTYPF-UHFFFAOYSA-N 0.000 description 1
- 125000005004 perfluoroethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001484 phenothiazinyl group Chemical class C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 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
- 125000006239 protecting group Chemical group 0.000 description 1
- 150000003220 pyrenes Chemical class 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229940081623 rose bengal Drugs 0.000 description 1
- 229930187593 rose bengal Natural products 0.000 description 1
- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- BRGJIIMZXMWMCC-UHFFFAOYSA-N tetradecan-2-ol Chemical compound CCCCCCCCCCCCC(C)O BRGJIIMZXMWMCC-UHFFFAOYSA-N 0.000 description 1
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 description 1
- 229940103494 thiosalicylic acid Drugs 0.000 description 1
- 125000004665 trialkylsilyl group Chemical group 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- XMUJIPOFTAHSOK-UHFFFAOYSA-N undecan-2-ol Chemical compound CCCCCCCCCC(C)O XMUJIPOFTAHSOK-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Materials For Photolithography (AREA)
Description
本発明は、半導体素子等の微細加工用ポジ型フォトレジスト膜を得るための感放射線性樹脂組成物及びそれに用いる重合体に関するものである。 The present invention relates to a radiation-sensitive resin composition for obtaining a positive photoresist film for microfabrication such as a semiconductor element and a polymer used therefor.
化学増幅型の感放射線性樹脂組成物は、KrFエキシマレーザーやArFエキシマレーザーに代表される遠紫外線や電子線の照射により露光部に酸を生成させ、この酸を触媒とする化学反応により、露光部と未露光部の現像液に対する溶解速度に差を生じさせ、基板上にレジストパターンを形成させる組成物である。 The chemically amplified radiation-sensitive resin composition generates an acid in an exposed portion by irradiation with far ultraviolet rays or electron beams typified by a KrF excimer laser or an ArF excimer laser, and is exposed by a chemical reaction using this acid as a catalyst. It is a composition that causes a difference in the dissolution rate of the part and the unexposed part in the developer to form a resist pattern on the substrate.
例えば、KrFエキシマレーザー(波長248nm)を光源として用いる場合には、248nm領域での吸収が小さい、ポリ(ヒドロキシスチレン)(以下、「PHS」と記す場合がある。)を基本骨格とする重合体を構成成分とする化学増幅型感放射線性樹脂組成物が用いられている。この組成物によれば、高感度、高解像度、且つ良好なパターン形成を実現することが可能である。 For example, when a KrF excimer laser (wavelength 248 nm) is used as a light source, a polymer having a basic skeleton of poly (hydroxystyrene) (hereinafter sometimes referred to as “PHS”) that has low absorption in the 248 nm region. A chemically amplified radiation-sensitive resin composition containing as a constituent is used. According to this composition, high sensitivity, high resolution, and good pattern formation can be realized.
しかし、更なる微細加工を目的として、より短波長の光源、例えば、ArFエキシマレーザー(波長193nm)を光源として用いる場合には、193nm領域に大きな吸収を示すPHS等の芳香族化合物を使用することが困難であるという問題があった。 However, when a shorter wavelength light source, for example, an ArF excimer laser (wavelength 193 nm) is used as a light source for the purpose of further microfabrication, an aromatic compound such as PHS having a large absorption in the 193 nm region should be used. There was a problem that was difficult.
そこで、ArFエキシマレーザーを光源とするリソグラフィー材料としては、193nm領域に大きな吸収を有しない脂環式炭化水素を骨格中に有する重合体を構成成分とする樹脂組成物が用いられている。 Therefore, as a lithographic material using an ArF excimer laser as a light source, a resin composition containing a polymer having an alicyclic hydrocarbon that does not have large absorption in the 193 nm region in its skeleton is used.
上記のような感放射線性樹脂組成物としては、例えば、その繰り返し単位中に、アダマンタン骨格やノルボルナン骨格、シクロヘキサン骨格を有する重合体を構成成分とする感放射線性樹脂組成物が開示されている(特許文献1〜4参照)。 As the radiation sensitive resin composition as described above, for example, a radiation sensitive resin composition containing a polymer having an adamantane skeleton, a norbornane skeleton or a cyclohexane skeleton in its repeating unit is disclosed ( (See Patent Documents 1 to 4).
特許文献1〜4に示す感放射線性樹脂組成物は、その繰り返し単位中に、酸の作用によりアルカリ可溶性となるアルカリ不溶性又はアルカリ難溶性の重合体と、ラクトン骨格を有することで、レジストとしての解像性能が飛躍的に向上することが見出されている。しかしながら、未だ現像欠陥が発生するという問題点があり、さらなる改善が求められている。 The radiation-sensitive resin composition shown in Patent Documents 1 to 4 has an alkali-insoluble or hardly-soluble alkali-soluble polymer that becomes alkali-soluble by the action of an acid and a lactone skeleton in its repeating unit. It has been found that the resolution performance is dramatically improved. However, there is a problem that development defects still occur, and further improvement is required.
本発明は、このような従来技術の有する課題に鑑みて成されたものであり、現像欠陥の少ない感放射線性樹脂組成物を提供するものである。 The present invention has been made in view of such problems of the prior art, and provides a radiation-sensitive resin composition with few development defects.
本発明により、以下の感放射線性樹脂組成物及びそれに用いる重合体が提供される。 The present invention provides the following radiation-sensitive resin composition and a polymer used therefor.
[1] (A)分子鎖の少なくとも一方の末端にカルボニル基を有し、かつ、ゲルパーミエーションクロマトグラフィーによるポリスチレン換算重量平均分子量が11000以上である、酸の作用により分解しアルカリ現像液に対する溶解度が増大する重合体(以下、「重合体(A)」ともいう)、及び、(B)感放射線性酸発生剤(以下、「酸発生剤(B)」ともいう)を含有することを特徴とする、感放射線性樹脂組成物。
[2] (A)重合体が、さらにラクトン構造を有する繰り返し単位及び環状カーボネート構造を有する繰り返し単位から選ばれる少なくとも一種を有する、[1]に記載の感放射線性樹脂組成物。
[3] 分子鎖の少なくとも一方の末端にカルボニル基を有し、かつ、ゲルパーミエーションクロマトグラフィーによるポリスチレン換算重量平均分子量が11000以上である、酸の作用により分解しアルカリ現像液に対する溶解度が増大する重合体。
[1] (A) A carbonyl group at least at one end of the molecular chain, and a polystyrene-reduced weight average molecular weight by gel permeation chromatography of 11,000 or more, which is decomposed by the action of an acid and is soluble in an alkali developer. Containing a polymer (hereinafter also referred to as “polymer (A)”) and (B) a radiation-sensitive acid generator (hereinafter also referred to as “acid generator (B)”). A radiation-sensitive resin composition.
[2] The radiation sensitive resin composition according to [1], wherein the polymer (A) further includes at least one selected from a repeating unit having a lactone structure and a repeating unit having a cyclic carbonate structure.
[3] It has a carbonyl group at at least one end of the molecular chain and has a polystyrene-equivalent weight average molecular weight of 11,000 or more by gel permeation chromatography, which is decomposed by the action of an acid and increases the solubility in an alkali developer. Polymer.
本発明により、現像欠陥の少ない感放射線性樹脂組成物及びそれに用いる重合体を提供することができる。 According to the present invention, a radiation-sensitive resin composition with few development defects and a polymer used therefor can be provided.
以下、本発明を実施するための形態について説明するが、本発明は以下の実施の形態に限定されるものではない。 Hereinafter, although the form for implementing this invention is demonstrated, this invention is not limited to the following embodiment.
<感放射線性樹脂組成物>
本発明の感放射線性樹脂組成物は、分子鎖(主鎖)の少なくとも一方の末端にカルボニル基を有し、ゲルパーミエーションクロマトグラフィーによるポリスチレン換算重量平均分子量が11000以上である、酸の作用により分解しアルカリ現像液に対する溶解度が増大する重合体(A)と、酸発生剤(B)とを含有する。
重合体(A)は、酸の作用前にはアルカリ不溶性またはアルカリ難溶性を示し、酸の作用により酸解離性基が解離してアルカリ易溶性を示す重合体である。重合体(A)が、分子鎖の末端にカルボニル基を含有し、かつ高分子量体であることで、現像欠陥の少ない感放射線性樹脂組成物を得ることができると考えられる。
<Radiation sensitive resin composition>
The radiation-sensitive resin composition of the present invention has a carbonyl group at least at one end of a molecular chain (main chain), and has a polystyrene-reduced weight average molecular weight of 11,000 or more by gel permeation chromatography. The polymer (A) which decomposes | disassembles and the solubility with respect to an alkali developing solution increases, and an acid generator (B) are contained.
The polymer (A) is a polymer that exhibits alkali insolubility or alkali insolubility before the action of an acid, and is readily soluble in alkali by dissociation of an acid dissociable group by the action of an acid. It is thought that the radiation sensitive resin composition with few development defects can be obtained because the polymer (A) contains a carbonyl group at the end of the molecular chain and is a high molecular weight product.
なお、本明細書にいう「アルカリ不溶性またはアルカリ難溶性」とは、当該感放射線性樹脂組成物から形成されたレジスト被膜からレジストパターンを形成する際に採用されるアルカリ現像条件下で、レジスト被膜の代わりに[A]成分の重合体のみを用いた被膜を現像した場合に、被膜の初期膜厚の50%以上が現像後に残存する性質を意味する。また、本明細書にいう「感放射線性樹脂組成物」および「感放射線性酸発生体」の「放射線」とは、可視光線、紫外線、遠紫外線、X線、荷電粒子線等を含む概念である。
以下、各成分について詳細に説明する。
As used herein, “alkali-insoluble or alkali-insoluble” refers to a resist film under the alkali development conditions employed when a resist pattern is formed from a resist film formed from the radiation-sensitive resin composition. In the case where a film using only the polymer of the component [A] is developed instead of the above, it means that 50% or more of the initial film thickness of the film remains after development. The “radiation” of the “radiation-sensitive resin composition” and “radiation-sensitive acid generator” in the present specification is a concept including visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams, and the like. is there.
Hereinafter, each component will be described in detail.
重合体(A):
本発明の感放射線性樹脂組成物に用いられる重合体(A)は、本発明の重合体であり、分子鎖の少なくとも一方の末端にカルボニル基を有する。なお、ここで言う「分子鎖」とは重合体主鎖を示す。すなわち、重合体(A)は、例えば下記一般式(a)で表される構造を有する。なお、重合体(A)の主鎖は、直鎖状であっても分岐鎖状であってもよい。
Polymer (A):
The polymer (A) used in the radiation-sensitive resin composition of the present invention is the polymer of the present invention and has a carbonyl group at least at one end of the molecular chain. The “molecular chain” referred to here indicates a polymer main chain. That is, the polymer (A) has a structure represented by the following general formula (a), for example. The main chain of the polymer (A) may be linear or branched.
(一般式(a)中、A1、A2およびAnは重合体中の各構造単位を示し、XおよびYは1価の有機基を示す。但し、XおよびYの少なくともひとつは、脂環式炭化水素基を有する有機基である。) (In the general formula (a), A 1, A 2 and A n represents a respective structural units in the polymer, X and Y represents a monovalent organic group. However, at least one of X and Y, fat (It is an organic group having a cyclic hydrocarbon group.)
重合体末端にカルボニル基を有する重合体は、例えば下記のいずれかの方法によって得ることができる。
(1)カルボニル基を有するラジカル重合開始剤を用いて重合する方法。
(2)カルボニル基を有する連鎖移動剤の存在下で重合する方法。
(3)カルボニル基を有するラジカル停止剤を用いる方法。
(4)カルボン酸エステル基を有するアニオン重合開始剤を用いて重合し、アルコールで重合停止させ、得られた重合体を加水分解する方法。
(5)アニオン重合した後、カルボン酸エステル基を有する重合停止剤または二酸化炭素を用いて重合停止させ、得られた重合体を加水分解する方法。
(6)2つの水酸基をトリアルキルシリル基で保護したエノレート開始剤を用いてグループトランスファー重合した後、得られた重合体を加水分解する方法。
(7)重合体末端に水酸基、アミノ基等を有する重合体を得た後、高分子反応によりカルボキシル基を導入する方法。
これらのうち、(1)または(2)の方法が特に好ましく用いられる。
A polymer having a carbonyl group at the end of the polymer can be obtained, for example, by any of the following methods.
(1) A method of polymerizing using a radical polymerization initiator having a carbonyl group.
(2) A method of polymerizing in the presence of a chain transfer agent having a carbonyl group.
(3) A method using a radical terminator having a carbonyl group.
(4) A method of polymerizing using an anionic polymerization initiator having a carboxylic acid ester group, terminating the polymerization with an alcohol, and hydrolyzing the resulting polymer.
(5) A method in which, after anionic polymerization, polymerization is terminated using a polymerization terminator having a carboxylic acid ester group or carbon dioxide, and the resulting polymer is hydrolyzed.
(6) A method of hydrolyzing the polymer obtained after group transfer polymerization using an enolate initiator in which two hydroxyl groups are protected with a trialkylsilyl group.
(7) A method of introducing a carboxyl group by a polymer reaction after obtaining a polymer having a hydroxyl group, an amino group or the like at the polymer terminal.
Of these, the method (1) or (2) is particularly preferably used.
前記ラジカル重合開始剤としては、例えば下記式(a1)〜(a3)で表される化合物等を挙げることができる。 Examples of the radical polymerization initiator include compounds represented by the following formulas (a1) to (a3).
また、前記連鎖移動剤としては、例えば、メルカプト酢酸、メルカプトプロピオン酸、チオサリチル酸などを挙げることができる。 Examples of the chain transfer agent include mercaptoacetic acid, mercaptopropionic acid, and thiosalicylic acid.
また、本発明の重合体(A)の重合に用いることができるその他のラジカル重合開始剤としては、公知のものを挙げることができ、具体的には、2,2’−アゾビス(4−メトキシ−2,4−ジメチルバレロニトリル)、2,2’−アゾビス(2−シクロプロピルプロピオニトリル)、2,2’−アゾビス(2,4−ジメチルバレロニトリル)等を挙げることができる。これらは1種または2種以上を混合して使用することができる。これらのラジカル重合開始剤は、上述したカルボニル基を有するラジカル重合開始剤と併用することができるとともに、上述した連鎖移動剤を用いる場合に、ラジカル重合開始剤として用いることができる。 Examples of other radical polymerization initiators that can be used for the polymerization of the polymer (A) of the present invention include known ones. Specifically, 2,2′-azobis (4-methoxy -2,4-dimethylvaleronitrile), 2,2'-azobis (2-cyclopropylpropionitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), and the like. These can be used alone or in combination of two or more. These radical polymerization initiators can be used in combination with the above-described radical polymerization initiator having a carbonyl group, and can be used as a radical polymerization initiator when the above-described chain transfer agent is used.
重合体(A)の合成法としては、ラジカル重合の常法に従って合成することができる。例えば、(1)単量体およびラジカル開始剤を含有する溶液を、反応溶剤または単量体を含有する溶液に滴下して重合反応させる方法;(2)単量体を含有する溶液と、ラジカル開始剤を含有する溶液とを各別に、反応溶剤または単量体を含有する溶液に滴下して重合反応させる方法;(3)各々の単量体を含有する、複数種の溶液と、ラジカル開始剤を含有する溶液とを各別に、反応溶剤または単量体を含有する溶液に滴下して重合反応させる方法;(4)単量体、ラジカル開始剤および連鎖移動剤を含有する溶液を、反応溶剤または単量体を含有する溶液に滴下して重合反応させる方法;等の方法で合成することが好ましい。 As a method for synthesizing the polymer (A), it can be synthesized according to a conventional method of radical polymerization. For example, (1) a method in which a solution containing a monomer and a radical initiator is dropped into a reaction solvent or a solution containing a monomer to cause a polymerization reaction; (2) a solution containing the monomer and a radical A method in which a solution containing an initiator is dropped into a reaction solvent or a solution containing a monomer separately to cause a polymerization reaction; (3) a plurality of types of solutions containing each monomer, and radical initiation A method in which a solution containing an agent is separately added to a reaction solvent or a solution containing a monomer to cause a polymerization reaction; (4) a solution containing a monomer, a radical initiator, and a chain transfer agent is reacted. It is preferable to synthesize by a method such as a method of dropping a solvent or a monomer-containing solution to cause a polymerization reaction.
なお、単量体溶液に対して、単量体溶液を滴下して反応させる場合、滴下される単量体溶液中の単量体量は、重合に用いられる単量体総量に対して30モル%以上であることが好ましく、50モル%以上であることが更に好ましく、70モル%以上であることが特に好ましい。 In addition, when the monomer solution is dropped and reacted with respect to the monomer solution, the monomer amount in the dropped monomer solution is 30 mol with respect to the total amount of monomers used for polymerization. % Or more, more preferably 50 mol% or more, and particularly preferably 70 mol% or more.
これらの方法における反応温度は開始剤種によって適宜決定すればよい。通常、30〜180℃であり、40〜160℃が好ましく、50〜140℃が更に好ましい。滴下時間は、反応温度、開始剤の種類、反応させる単量体等の条件によって異なるが、通常、30分〜8時間であり、45分〜6時間が好ましく、1〜5時間が更に好ましい。また、滴下時間を含む全反応時間も、滴下時間と同様に条件により異なるが、通常、30分〜8時間であり、45分〜7時間が好ましく、1〜6時間が更に好ましい。 What is necessary is just to determine the reaction temperature in these methods suitably with initiator seed | species. Usually, it is 30-180 degreeC, 40-160 degreeC is preferable and 50-140 degreeC is still more preferable. Although dripping time changes with conditions, such as reaction temperature, the kind of initiator, and the monomer made to react, it is 30 minutes-8 hours normally, 45 minutes-6 hours are preferable, and 1-5 hours are still more preferable. Further, the total reaction time including the dropping time varies depending on the conditions as well as the dropping time, but is usually 30 minutes to 8 hours, preferably 45 minutes to 7 hours, and more preferably 1 to 6 hours.
ラジカル開始剤の用いる量は、単量体総量に対して好ましくは0.1モル%〜30モル%以下、更に好ましくは0.1モル%〜25モル%以下、特に好ましくは0.1モル%〜20モル%以下である。連鎖移動剤の用いる量は、開始剤量に対して70モル%以下が好ましく、50%以下が特に好ましい。このような範囲とすることにより、重合体のゲルパーミエーションクロマトグラフィ(GPC)によるポリスチレン換算重量平均分子量(以下、「Mw」と記す。)が、11,000以上となる。重合体のMwが11,000未満であると、現像欠陥低減の効果が得られないこともある。Mwは、11,000〜200,000であることが更に好ましく、11,000〜50,000であることが特に好ましい。 The amount of radical initiator used is preferably 0.1 mol% to 30 mol% or less, more preferably 0.1 mol% to 25 mol% or less, particularly preferably 0.1 mol%, based on the total amount of monomers. ˜20 mol% or less. The amount of the chain transfer agent used is preferably 70 mol% or less, particularly preferably 50% or less, based on the initiator amount. By setting it as such a range, the polystyrene conversion weight average molecular weight (henceforth "Mw") by the gel permeation chromatography (GPC) of a polymer will be 11,000 or more. If the Mw of the polymer is less than 11,000, the effect of reducing development defects may not be obtained. Mw is more preferably 11,000 to 200,000, and particularly preferably 11,000 to 50,000.
重合溶剤としては、重合を阻害する溶剤(重合禁止効果を有するニトロベンゼン、連鎖移動効果を有するメルカプト化合物等)以外の溶剤であって、その単量体を溶解可能な溶剤であれば使用することができる。例えば、アルコール類、エーテル類、ケトン類、アミド類、エステル・ラクトン類、ニトリル類およびその混合溶剤等を挙げることができる。これらの溶剤は、単独でまたは2種以上を混合して使用することができる。 As a polymerization solvent, a solvent other than a solvent that inhibits polymerization (nitrobenzene having a polymerization inhibiting effect, mercapto compound having a chain transfer effect, or the like) and a solvent that can dissolve the monomer may be used. it can. Examples thereof include alcohols, ethers, ketones, amides, esters / lactones, nitriles, and mixed solvents thereof. These solvents can be used alone or in admixture of two or more.
重合反応により得られた樹脂は、再沈殿法により回収することが好ましい。即ち、重合反応終了後、重合液を再沈溶剤に投入することにより、目的の樹脂を粉体として回収する。再沈溶剤としては、前記重合溶剤として例示した溶剤を単独でまたは2種以上を混合して使用することができる。再沈殿法の他に、分液操作により、単量体、オリゴマー等の低分子成分を除去して、樹脂を回収することもできる。即ち、重合反応終了後、重合溶液を適宜濃縮して、例えば、メタノール/ヘプタンなどの2液に分離する溶剤系を選択して加え、樹脂溶液から低分子成分を除去し適宜必要な溶剤系(プロピレングリコールモノメチルエーテル等)に置換し、目的の樹脂を溶液として回収する。 The resin obtained by the polymerization reaction is preferably recovered by a reprecipitation method. That is, after the polymerization reaction is completed, the target resin is recovered as a powder by putting the polymerization solution into a reprecipitation solvent. As a reprecipitation solvent, the solvent illustrated as the said polymerization solvent can be used individually or in mixture of 2 or more types. In addition to the reprecipitation method, the resin can be recovered by removing low molecular components such as monomers and oligomers by a liquid separation operation. That is, after completion of the polymerization reaction, the polymerization solution is appropriately concentrated, for example, a solvent system that separates into two liquids such as methanol / heptane is selected and added, and the low molecular components are removed from the resin solution, and the necessary solvent system ( And the desired resin is recovered as a solution.
なお、重合体(A)には、単量体由来の低分子量成分が含まれるが、その含有率は、重合体(A)の総量(100質量%)に対して、0.1質量%以下であることが好ましく、0.07質量%以下であることが更に好ましく、0.05質量%以下であることが特に好ましい。 In addition, although the polymer (A) contains a low molecular weight component derived from a monomer, the content thereof is 0.1% by mass or less with respect to the total amount (100% by mass) of the polymer (A). It is preferable that it is 0.07 mass% or less, and it is especially preferable that it is 0.05 mass% or less.
この低分子量成分の含有率が0.1質量%以下である場合には、この重合体(A)を使用してレジスト膜を作製し、液浸露光を行う際に、レジスト膜に接触した水への溶出物の量を少なくすることができる。更に、レジスト保管時に、レジスト中に異物が析出することがなく、レジスト塗布時においても塗布ムラが発生することない。従って、レジストパターン形成時における欠陥の発生を十分に抑制することができる。 When the content of this low molecular weight component is 0.1% by mass or less, a resist film is prepared using this polymer (A), and the water in contact with the resist film is subjected to immersion exposure. It is possible to reduce the amount of eluate in Furthermore, no foreign matter is deposited in the resist during resist storage, and coating unevenness does not occur during resist application. Therefore, it is possible to sufficiently suppress the occurrence of defects when forming a resist pattern.
なお、本明細書において、単量体由来の「低分子量成分」というときは、ゲルパーミエーションクロマトグラフィ(GPC)によるポリスチレン換算重量平均分子量(以下、「Mw」と記す場合がある。)が、Mw500以下の成分を意味するものとする。具体的には、モノマー、ダイマー、トリマー、オリゴマー等の成分である。この「低分子量成分」は、例えば、水洗、液々抽出等の化学的精製法、化学的精製法と限外ろ過、遠心分離等の物理的精製法とを組み合わせた方法等により除去することができる。 In the present specification, when the term “low molecular weight component” derived from a monomer is used, the polystyrene-equivalent weight average molecular weight (hereinafter sometimes referred to as “Mw”) by gel permeation chromatography (GPC) is Mw500. It shall mean the following ingredients. Specifically, it is a component such as a monomer, dimer, trimer or oligomer. This “low molecular weight component” can be removed by, for example, chemical purification methods such as washing with water, liquid-liquid extraction, and the like, and chemical purification methods combined with physical purification methods such as ultrafiltration and centrifugation. it can.
また、この低分子量成分は、重合体(A)を高速液体クロマトグラフィー(HPLC)による分析で定量することができる。なお、重合体(A)は、低分子量成分の他、ハロゲン、金属等の不純物が少ないほど好ましく、それにより、レジストとしたときの感度、解像度、プロセス安定性、パターン形状等を更に改善することができる。 The low molecular weight component can be quantified by analyzing the polymer (A) by high performance liquid chromatography (HPLC). In addition to the low molecular weight component, the polymer (A) is preferably as low as possible impurities such as halogen and metal, thereby further improving the sensitivity, resolution, process stability, pattern shape, etc. when used as a resist. Can do.
重合体(A)は、下記一般式(1)で表される繰り返し単位(1)を有することが好ましい。 The polymer (A) preferably has a repeating unit (1) represented by the following general formula (1).
(一般式(1)中、R1は水素原子またはメチル基を示し、R2は、炭素数1〜4のアルキル基または炭素数4〜20の1価の脂環式炭化水素基を示し、R3およびR4は、相互に独立に、炭素数1〜4のアルキル基または炭素数4〜20の1価の脂環式炭化水素基を示すか、あるいはR3とR4が相互に結合して、両者が結合している炭素原子と共に形成される炭素数4〜20の2価の脂環式炭化水素基を示す。) (In General Formula (1), R 1 represents a hydrogen atom or a methyl group, R 2 represents an alkyl group having 1 to 4 carbon atoms or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, R 3 and R 4 are each independently an alkyl group having 1 to 4 carbon atoms or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or R 3 and R 4 are bonded to each other And a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms formed together with the carbon atom to which both are bonded.
上記一般式(1)中のR2、R3およびR4が示す炭素数1〜4のアルキル基としては、メチル基、エチル基、n−プロピル基、i−プロピル基、n−ブチル基、i−ブチル基等を挙げることができ、中でもメチル基、エチル基、i−プロピル基が好ましい。また、R2、R3およびR4が示す炭素数4〜20の1価の脂環式炭化水素基としては、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロオクチル基、ノルボルニル基、トリシクロデシル基、テトラシクロドデシル基、アダマンチル基等が挙げられる。さらに、R3とR4が相互に結合して、両者が結合している炭素原子と共に形成される炭素数4〜20の2価の脂環式炭化水素基としては、上記1価の脂環式炭化水素基から水素原子1つを除いた基が挙げられる。 Examples of the alkyl group having 1 to 4 carbon atoms represented by R 2 , R 3 and R 4 in the general formula (1) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, An i-butyl group can be exemplified, and among them, a methyl group, an ethyl group, and an i-propyl group are preferable. Examples of the monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms represented by R 2 , R 3 and R 4 include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a norbornyl group, and a tricyclodecyl group. , Tetracyclododecyl group, adamantyl group and the like. Furthermore, R 3 and R 4 are bonded to each other, and the divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms formed together with the carbon atom to which both are bonded includes the above monovalent alicyclic ring. And a group obtained by removing one hydrogen atom from the formula hydrocarbon group.
繰り返し単位(1)としては、下記一般式(1−1)〜(1−20)で示される繰り返し単位が特に好ましい。これらは一種単独でも、二種以上が含まれていてもよい。 As the repeating unit (1), repeating units represented by the following general formulas (1-1) to (1-20) are particularly preferable. These may be used alone or in combination of two or more.
(式中、R1の定義は上記式(1)と同じである。) (In the formula, the definition of R 1 is the same as in the above formula (1).)
繰り返し単位(1)の含有率は、重合体[A]を構成する全繰り返し単位に対して、1モル%以上80モル%以下が好ましく、1モル%以上70モル%以下がより好ましく、5モル%以上70モル%以下が特に好ましい。繰り返し単位(1)の含有率が上記範囲であることで、当該感放射線性樹脂組成物は、解像度、MEEFおよびLWRが高度にバランスされたレジスト特性を発揮することができる。1モル%未満の場合、あるいは80モル%を超える場合、レジストとしての解像性能が劣化する恐れがある。 The content of the repeating unit (1) is preferably 1 mol% or more and 80 mol% or less, more preferably 1 mol% or more and 70 mol% or less, based on all repeating units constituting the polymer [A]. % To 70 mol% is particularly preferable. When the content of the repeating unit (1) is in the above range, the radiation-sensitive resin composition can exhibit resist characteristics in which resolution, MEEF, and LWR are highly balanced. When the amount is less than 1 mol% or exceeds 80 mol%, the resolution performance as a resist may deteriorate.
重合体(A)は、ラクトン骨格を有する繰り返し単位および環状カーボネート骨格を有する繰り返し単位から選ばれる少なくとも一種(以下、「繰り返し単位(2)」ともいう)を含有することが好ましい。繰り返し単位(2)としては、下記式で表される繰り返し単位が好ましいものとして挙げられる。 The polymer (A) preferably contains at least one selected from repeating units having a lactone skeleton and repeating units having a cyclic carbonate skeleton (hereinafter also referred to as “repeating unit (2)”). As the repeating unit (2), a repeating unit represented by the following formula is preferred.
(前記一般式中、R5およびR6は相互に独立に水素またはメチル基を示し、R7は水素原子またはメトキシ基を示し、R8は水素原子、炭素数1〜4のアルキル基またはシアノ基を示し、Aは単結合またはメチレンを示し、Bはメチレンまたは酸素を示し、l,mは0または1の整数である。) (In the above general formula, R 5 and R 6 each independently represent hydrogen or a methyl group, R 7 represents a hydrogen atom or a methoxy group, R 8 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a cyano group. Represents a group, A represents a single bond or methylene, B represents methylene or oxygen, and l and m are integers of 0 or 1.)
繰り返し単位(2)としては、下記式で示される繰り返し単位が特に好ましい。 As the repeating unit (2), a repeating unit represented by the following formula is particularly preferable.
重合体(A)において、繰り返し単位(2)の含有率は、重合体(A)を構成する全繰り返し単位に対して、繰り返し単位(2)の総量が、10〜70モル%であることが好ましく、20〜60モル%であることが更に好ましい。このような含有率とすることによって、レジストとしての現像性、欠陥性、低LWR、低PEB温度依存性等を向上させることができる。一方、70モル%を超えると、レジストとしての解像性、LWR、が低下するおそれがある。 In the polymer (A), the content of the repeating unit (2) is such that the total amount of the repeating unit (2) is 10 to 70 mol% with respect to all the repeating units constituting the polymer (A). Preferably, it is 20-60 mol%, and it is still more preferable. By setting it as such a content rate, the developability as a resist, defect property, low LWR, low PEB temperature dependence, etc. can be improved. On the other hand, if it exceeds 70 mol%, the resolution as a resist and LWR may be lowered.
また、重合体(A)は下記式で表される極性基を有する繰り返し単位を1種類以上含有してもよい。 Moreover, a polymer (A) may contain 1 or more types of repeating units which have a polar group represented by a following formula.
さらに、重合体(A)は、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸ブチル、ラウリル(メタ)アクリレート、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸−ビシクロ[2.2.1]ヘプチルエステル、(メタ)アクリル酸−シクロヘキシルエステル、(メタ)アクリル酸−ビシクロ[4.4.0]デカニルエステル、(メタ)アクリル酸−ビシクロ[2.2.2]オクチルエステル、(メタ)アクリル酸−トリシクロ[5.2.1.02,6]デカニルエステル、(メタ)アクリル酸−アダマンチル、(メタ)アクリル酸−トリシクロ[3.3.1.13,7]デカニルエステル等のアルキル(メタ)アクリレート由来の繰り返し単位を含有してもよい。 Furthermore, the polymer (A) includes methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid-bicyclo [2.2.1] heptyl ester, (meth) acrylic acid-cyclohexyl ester, (meth) acrylic acid-bicyclo [4.4.0] decanyl ester, (meth) acrylic acid-bicyclo [2.2.2] ] Octyl ester, (meth) acrylic acid-tricyclo [5.2.1.0 2,6 ] decanyl ester, (meth) acrylic acid-adamantyl, (meth) acrylic acid-tricyclo [3.3.1.1] 3,7 ] It may contain a repeating unit derived from an alkyl (meth) acrylate such as decanyl ester.
本発明の感放射線性樹脂組成物は、上記重合体(A)を単独または2種以上併用してもよい。また、重合体(A)と、分子鎖の末端に脂環式炭化水素骨格を含有しない他の重合体とを混合して用いてもよい。この場合、全重合体における重合体(A)の割合は5質量%以上、好ましくは10質量%以上、特に好ましくは15質量%以上である。5質量%未満では、解像度、MEEFおよびLWRが高度にバランスされたレジスト特性を発揮することができない恐れがある。 In the radiation-sensitive resin composition of the present invention, the polymer (A) may be used alone or in combination of two or more. Moreover, you may mix and use a polymer (A) and the other polymer which does not contain an alicyclic hydrocarbon skeleton at the terminal of a molecular chain. In this case, the ratio of the polymer (A) in the total polymer is 5% by mass or more, preferably 10% by mass or more, and particularly preferably 15% by mass or more. If it is less than 5% by mass, there is a possibility that resist characteristics in which resolution, MEEF and LWR are highly balanced cannot be exhibited.
溶剤(B):
本発明の感放射線性樹脂組成物は、溶剤を含有する。該溶剤は、少なくとも上記の重合体(A)、および任意成分を溶解可能であれば、特に限定されない。例えば、アルコール系溶剤、ケトン系溶剤、アミド系溶剤、エーテル系溶剤、エステル系溶剤およびその混合溶剤等が挙げられる。
Solvent (B):
The radiation sensitive resin composition of the present invention contains a solvent. The solvent is not particularly limited as long as it can dissolve at least the polymer (A) and optional components. Examples thereof include alcohol solvents, ketone solvents, amide solvents, ether solvents, ester solvents, and mixed solvents thereof.
アルコール系溶剤としては、例えば、メタノール、エタノール、n−プロパノール、iso−プロパノール、n−ブタノール、iso−ブタノール、sec−ブタノール、tert−ブタノール、n−ペンタノール、iso−ペンタノール、2−メチルブタノール、sec−ペンタノール、tert−ペンタノール、3−メトキシブタノール、n−ヘキサノール、2−メチルペンタノール、sec−ヘキサノール、2−エチルブタノール、sec−ヘプタノール、3−ヘプタノール、n−オクタノール、2−エチルヘキサノール、sec−オクタノール、n−ノニルアルコール、2,6−ジメチル−4−ヘプタノール、n−デカノール、sec−ウンデシルアルコール、トリメチルノニルアルコール、sec−テトラデシルアルコール、sec−ヘプタデシルアルコール、フルフリルアルコール、フェノール、シクロヘキサノール、メチルシクロヘキサノール、3,3,5−トリメチルシクロヘキサノール、ベンジルアルコール、ジアセトンアルコール等のモノアルコール系溶剤;
エチレングリコール、1,2−プロピレングリコール、1,3−ブチレングリコール、2,4−ペンタンジオール、2−メチル−2,4−ペンタンジオール、2,5−ヘキサンジオール、2,4−ヘプタンジオール、2−エチル−1,3−ヘキサンジオール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、トリプロピレングリコール等の多価アルコール系溶剤;
エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノヘキシルエーテル、エチレングリコールモノフェニルエーテル、エチレングリコールモノ−2−エチルブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノプロピルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノヘキシルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノプロピルエーテル等の多価アルコール部分エーテル系溶剤等が挙げられる。
Examples of alcohol solvents include methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-pentanol, iso-pentanol, and 2-methylbutanol. , Sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethyl Hexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, se - heptadecyl alcohol, furfuryl alcohol, phenol, cyclohexanol, methyl cyclohexanol, 3,3,5-trimethyl cyclohexanol, benzyl alcohol, mono-alcohol solvents such as diacetone alcohol;
Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2 Polyhydric alcohol solvents such as ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, polyhydric alcohol partial ether solvents such as dipropylene glycol monopropyl ether.
ケトン系溶剤としては、例えば、アセトン、メチルエチルケトン、メチル−n−プロピルケトン、メチル−n−ブチルケトン、ジエチルケトン、メチル−iso−ブチルケトン、メチル−n−ペンチルケトン、エチル−n−ブチルケトン、メチル−n−ヘキシルケトン、ジ−iso−ブチルケトン、トリメチルノナノン、シクロペンタノン、シクロヘキサノン、シクロヘプタノン、シクロオクタノン、2−ヘキサノン、メチルシクロヘキサノン、2,4−ペンタンジオン、アセトニルアセトン、ジアセトンアルコール、アセトフェノン、フェンチョン等のケトン系溶剤が挙げられる。 Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n. -Hexyl ketone, di-iso-butyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonyl acetone, diacetone alcohol, Examples include ketone solvents such as acetophenone and fenchon.
アミド系溶剤としては、例えば、N,N−ジメチルイミダゾリジノン、N−メチルホルムアミド、N,N−ジメチルホルムアミド、N,N−ジエチルホルムアミド、アセトアミド、N−メチルアセトアミド、N,N−ジメチルアセトアミド、N−メチルプロピオンアミド、N−メチルピロリドン等が挙げられる。 Examples of the amide solvent include N, N-dimethylimidazolidinone, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide, N-methylpyrrolidone and the like can be mentioned.
エーテル系溶剤としては、例えば、エチルエーテル、iso−プロピルエーテル、n−ブチルエーテル、n−ヘキシルエーテル、2−エチルヘキシルエーテル、ジオキソラン、4−メチルジオキソラン、ジオキサン、ジメチルジオキサン、エチレングリコールモノメチルエーテル、エチレングリコールジメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールジエチルエーテル、エチレングリコールモノ−n−ブチルエーテル、エチレングリコールモノ−n−ヘキシルエーテル、エチレングリコールモノフェニルエーテル、エチレングリコールモノ−2−エチルブチルエーテル、エチレングリコールジブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールモノ−n−ブチルエーテル、ジエチレングリコールジ−n−ブチルエーテル、ジエチレングリコールモノ−n−ヘキシルエーテル、エトキシトリグリコール、テトラエチレングリコールジ−n−ブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、トリプロピレングリコールモノメチルエーテル、テトラヒドロフラン、2−メチルテトラヒドロフラン、ジフェニルエーテル、アニソール等が挙げられる。 Examples of ether solvents include ethyl ether, iso-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether. , Ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, ethylene glycol dibutyl ether, diethylene glycol Monomethyl ether, diethylene glycol dimethyl ether, diethylene Recall monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether, propylene Examples include glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, diphenyl ether, and anisole.
エステル系溶剤としては、例えば、ジエチルカーボネート、プロピレンカーボネート、酢酸メチル、酢酸エチル、γ−ブチロラクトン、γ−バレロラクトン、酢酸n−プロピル、酢酸iso−プロピル、酢酸n−ブチル、酢酸iso−ブチル、酢酸sec−ブチル、酢酸n−ペンチル、酢酸sec−ペンチル、酢酸3−メトキシブチル、酢酸メチルペンチル、酢酸2−エチルブチル、酢酸2−エチルヘキシル、酢酸ベンジル、酢酸シクロヘキシル、酢酸メチルシクロヘキシル、酢酸n−ノニル、アセト酢酸メチル、アセト酢酸エチル、酢酸エチレングリコールモノメチルエーテル、酢酸エチレングリコールモノエチルエーテル、酢酸ジエチレングリコールモノメチルエーテル、酢酸ジエチレングリコールモノエチルエーテル、酢酸ジエチレングリコールモノ−n−ブチルエーテル、酢酸プロピレングリコールモノメチルエーテル、酢酸プロピレングリコールモノエチルエーテル、酢酸プロピレングリコールモノプロピルエーテル、酢酸プロピレングリコールモノブチルエーテル、酢酸ジプロピレングリコールモノメチルエーテル、酢酸ジプロピレングリコールモノエチルエーテル、ジ酢酸グリコール、酢酸メトキシトリグリコール、プロピオン酸エチル、プロピオン酸n−ブチル、プロピオン酸iso−アミル、シュウ酸ジエチル、シュウ酸ジ−n−ブチル、乳酸メチル、乳酸エチル、乳酸n−ブチル、乳酸n−アミル、マロン酸ジエチル、フタル酸ジメチル、フタル酸ジエチル等が挙げられる。 Examples of the ester solvent include diethyl carbonate, propylene carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, iso-propyl acetate, n-butyl acetate, iso-butyl acetate, and acetic acid. sec-butyl, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, n-nonyl acetate, aceto Methyl acetate, ethyl acetoacetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene acetate Recall mono-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, diacetic acid Glycol, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, iso-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate , Diethyl malonate, dimethyl phthalate, diethyl phthalate and the like.
その他の溶剤としては、例えば、n−ペンタン、iso−ペンタン、n−ヘキサン、iso−ヘキサン、n−ヘプタン、iso−ヘプタン、2,2,4−トリメチルペンタン、n−オクタン、iso−オクタン、シクロヘキサン、メチルシクロヘキサン等の脂肪族炭化水素系溶剤;
ベンゼン、トルエン、キシレン、メシチレン、エチルベンゼン、トリメチルベンゼン、メチルエチルベンゼン、n−プロピルベンセン、iso−プロピルベンセン、ジエチルベンゼン、iso−ブチルベンゼン、トリエチルベンゼン、ジ−iso−プロピルベンセン、n−アミルナフタレン等の芳香族炭化水素系溶剤;
ジクロロメタン、クロロホルム、フロン、クロロベンゼン、ジクロロベンゼン等の含ハロゲン溶剤を挙げることができる。
Examples of other solvents include n-pentane, iso-pentane, n-hexane, iso-hexane, n-heptane, iso-heptane, 2,2,4-trimethylpentane, n-octane, iso-octane, and cyclohexane. , Aliphatic hydrocarbon solvents such as methylcyclohexane;
Fragrances such as benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propyl benzene, iso-propyl benzene, diethylbenzene, iso-butylbenzene, triethylbenzene, di-iso-propylbenzene, n-amylnaphthalene Group hydrocarbon solvents;
Mention may be made of halogen-containing solvents such as dichloromethane, chloroform, freon, chlorobenzene and dichlorobenzene.
これらの溶剤のうちでも、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、シクロヘキサノンおよびγ−ブチロラクトン、乳酸エチルが好ましい。これらの溶剤は、単独または2種以上を併用できる。これらの溶剤を用いると、レジストとしての塗布性、保存安定性、レジスト膜形成後のレジスト膜中の残溶剤率がバランスされたものとなる。 Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, γ-butyrolactone, and ethyl lactate are preferable. These solvents can be used alone or in combination of two or more. When these solvents are used, the resist coating properties, the storage stability, and the residual solvent ratio in the resist film after forming the resist film are balanced.
任意成分
本発明の感放射線性樹脂組成物は、上記の重合体(A)および溶剤(B)に加え、本発明の効果を損なわない範囲で、任意成分として酸発生体、フッ素含有樹脂、脂環式骨格含有化合物、界面活性剤、酸拡散制御体、増感剤等を含有することができる。任意成分の配合量は、その目的に応じて適宜決定することができる。
Optional component In addition to the polymer (A) and the solvent (B), the radiation-sensitive resin composition of the present invention includes, as an optional component, an acid generator, fluorine, as long as the effects of the present invention are not impaired Containing resin, alicyclic skeleton containing compound, surfactant, acid diffusion controller, sensitizer and the like can be contained. The compounding quantity of an arbitrary component can be suitably determined according to the purpose.
(酸発生体)
酸発生体は、露光により酸を発生する成分である。その酸により重合体(A)中に存在する酸解離性基が解離し、その結果、重合体(A)がアルカリ現像液に易溶性となる。酸発生体の当該感放射線性樹脂組成物における含有形態としては、後述するような遊離の化合物の形態でも、重合体(A)または前述の他の重合体の一部として組み込まれた形態でも、これらの両方の形態でもよい。
(Acid generator)
The acid generator is a component that generates an acid upon exposure. The acid dissociable group present in the polymer (A) is dissociated by the acid, and as a result, the polymer (A) becomes readily soluble in an alkali developer. As the inclusion form in the radiation sensitive resin composition of the acid generator, either in the form of a free compound as described later, in the form incorporated as part of the polymer (A) or the other polymer described above, Both of these forms may be used.
上記酸発生体としては、例えば、オニウム塩化合物、スルホンイミド化合物、ハロゲン含有化合物、ジアゾケトン化合物等が挙げられる。これらの酸発生体のうち、オニウム塩化合物が好ましい。 Examples of the acid generator include onium salt compounds, sulfonimide compounds, halogen-containing compounds, diazoketone compounds, and the like. Of these acid generators, onium salt compounds are preferred.
オニウム塩化合物としては、例えば、スルホニウム塩(テトラヒドロチオフェニウム塩を含む。)、ヨードニウム塩、ホスホニウム塩、ジアゾニウム塩、ピリジニウム塩等を挙げることができる。これらのオニウム塩化合物のうち、スルホニウム塩が好ましい。 Examples of the onium salt compounds include sulfonium salts (including tetrahydrothiophenium salts), iodonium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like. Of these onium salt compounds, sulfonium salts are preferred.
スルホニウム塩としては、例えば、トリフェニルスルホニウムトリフルオロメタンスルホネート、トリフェニルスルホニウムノナフルオロ−n−ブタンスルホネート、トリフェニルスルホニウムパーフルオロ−n−オクタンスルホネート、トリフェニルスルホニウム2−ビシクロ[2.2.1]ヘプト−2−イル−1,1,2,2−テトラフルオロエタンスルホネート、トリフェニルスルホニウムカンファースルホネート、4−シクロヘキシルフェニルジフェニルスルホニウムトリフルオロメタンスルホネート、4−シクロヘキシルフェニルジフェニルスルホニウムノナフルオロ−n−ブタンスルホネート、4−シクロヘキシルフェニルジフェニルスルホニウムパーフルオロ−n−オクタンスルホネート、4−シクロヘキシルフェニルジフェニルスルホニウム2−ビシクロ[2.2.1]ヘプト−2−イル−1,1,2,2−テトラフルオロエタンスルホネート、4−シクロヘキシルフェニルジフェニルスルホニウムカンファースルホネート、4−メタンスルホニルフェニルジフェニルスルホニウムトリフルオロメタンスルホネート、4−メタンスルホニルフェニルジフェニルスルホニウムノナフルオロ−n−ブタンスルホネート、4−メタンスルホニルフェニルジフェニルスルホニウムパーフルオロ−n−オクタンスルホネート、4−メタンスルホニルフェニルジフェニルスルホニウム2−ビシクロ[2.2.1]ヘプト−2−イル−1,1,2,2−テトラフルオロエタンスルホネート、4−メタンスルホニルフェニルジフェニルスルホニウムカンファースルホネート等が挙げられる。これらのうち、トリフェニルスルホニウムトリフルオロメタンスルホネート、トリフェニルスルホニウムノナフルオロ−n−ブタンスルホネートおよびトリフェニルスルホニウムパーフルオロ−n−ブタンスルホネートが好ましく、トリフェニルスルホニウムパーフルオロ−n−ブタンスルホネートがより好ましい。 Examples of the sulfonium salt include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium 2-bicyclo [2.2.1] hept. 2-yl-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium camphorsulfonate, 4-cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4- Cyclohexylphenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-cyclohexylphenyldiphenyl Rusulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium camphorsulfonate, 4-methanesulfonylphenyldiphenylsulfonium trifluoromethanesulfonate 4-methanesulfonylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium 2-bicyclo [2.2.1] hept- 2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium camphorsulfonate, etc. It is. Of these, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate and triphenylsulfonium perfluoro-n-butanesulfonate are preferable, and triphenylsulfonium perfluoro-n-butanesulfonate is more preferable.
テトラヒドロチオフェニウム塩としては、例えば、1−(4−n−ブトキシナフタレン−1−イル)テトラヒドロチオフェニウムトリフルオロメタンスルホネート、1−(4−n−ブトキシナフタレン−1−イル)テトラヒドロチオフェニウムノナフルオロ−n−ブタンスルホネート、1−(4−n−ブトキシナフタレン−1−イル)テトラヒドロチオフェニウムパーフルオロ−n−オクタンスルホネート、1−(4−n−ブトキシナフタレン−1−イル)テトラヒドロチオフェニウム2−ビシクロ[2.2.1]ヘプト−2−イル−1,1,2,2−テトラフルオロエタンスルホネート、1−(4−n−ブトキシナフタレン−1−イル)テトラヒドロチオフェニウムカンファースルホネート、1−(6−n−ブトキシナフタレン−2−イル)テトラヒドロチオフェニウムトリフルオロメタンスルホネート、1−(6−n−ブトキシナフタレン−2−イル)テトラヒドロチオフェニウムノナフルオロ−n−ブタンスルホネート、1−(6−n−ブトキシナフタレン−2−イル)テトラヒドロチオフェニウムパーフルオロ−n−オクタンスルホネート、1−(6−n−ブトキシナフタレン−2−イル)テトラヒドロチオフェニウム2−ビシクロ[2.2.1]ヘプト−2−イル−1,1,2,2−テトラフルオロエタンスルホネート、1−(6−n−ブトキシナフタレン−2−イル)テトラヒドロチオフェニウムカンファースルホネート、1−(3,5−ジメチル−4−ヒドロキシフェニル)テトラヒドロチオフェニウムトリフルオロメタンスルホネート、1−(3,5−ジメチル−4−ヒドロキシフェニル)テトラヒドロチオフェニウムノナフルオロ−n−ブタンスルホネート、1−(3,5−ジメチル−4−ヒドロキシフェニル)テトラヒドロチオフェニウムパーフルオロ−n−オクタンスルホネート、1−(3,5−ジメチル−4−ヒドロキシフェニル)テトラヒドロチオフェニウム2−ビシクロ[2.2.1]ヘプト−2−イル−1,1,2,2−テトラフルオロエタンスルホネート、1−(3,5−ジメチル−4−ヒドロキシフェニル)テトラヒドロチオフェニウムカンファースルホネート等が挙げられる。これらのテトラヒドロチオフェニウム塩のうち、1−(4−n−ブトキシナフタレン−1−イル)テトラヒドロチオフェニウムノナフルオロ−n−ブタンスルホネート、1−(4−n−ブトキシナフタレン−1−イル)テトラヒドロチオフェニウムパーフルオロ−n−オクタンスルホネートおよび1−(3,5−ジメチル−4−ヒドロキシフェニル)テトラヒドロチオフェニウムノナフルオロ−n−ブタンスルホネートが好ましい。 Examples of the tetrahydrothiophenium salt include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium. Nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothio Phenium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium camphor Sulfonate, 1- (6-n-butoxynaphthalen-2-yl) Tetrahydrothiophenium trifluoromethanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothio Phenium perfluoro-n-octanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium 2-bicyclo [2.2.1] hept-2-yl-1,1,2, 2-tetrafluoroethanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium camphorsulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (3,5-dimethyl- -Hydroxyphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (3,5-dimethyl -4-hydroxyphenyl) tetrahydrothiophenium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (3,5-dimethyl-4- Hydroxyphenyl) tetrahydrothiophenium camphorsulfonate and the like. Of these tetrahydrothiophenium salts, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) Tetrahydrothiophenium perfluoro-n-octane sulfonate and 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium nonafluoro-n-butane sulfonate are preferred.
ヨードニウム塩としては、例えば、ジフェニルヨードニウムトリフルオロメタンスルホネート、ジフェニルヨードニウムノナフルオロ−n−ブタンスルホネート、ジフェニルヨードニウムパーフルオロ−n−オクタンスルホネート、ジフェニルヨードニウム2−ビシクロ[2.2.1]ヘプト−2−イル−1,1,2,2−テトラフルオロエタンスルホネート、ジフェニルヨードニウムカンファースルホネート、ビス(4−t−ブチルフェニル)ヨードニウムトリフルオロメタンスルホネート、ビス(4−t−ブチルフェニル)ヨードニウムノナフルオロ−n−ブタンスルホネート、ビス(4−t−ブチルフェニル)ヨードニウムパーフルオロ−n−オクタンスルホネート、ビス(4−t−ブチルフェニル)ヨードニウム2−ビシクロ[2.2.1]ヘプト−2−イル−1,1,2,2−テトラフルオロエタンスルホネート、ビス(4−t−ブチルフェニル)ヨードニウムカンファースルホネート等が挙げられる。これらのヨードニウム塩のうち、ビス(4−t−ブチルフェニル)ヨードニウムノナフルオロ−n−ブタンスルホネートが好ましい。 Examples of the iodonium salt include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 2-bicyclo [2.2.1] hept-2-yl. -1,1,2,2-tetrafluoroethanesulfonate, diphenyliodonium camphorsulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate Bis (4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4-t-butylphenyl) iodonium 2-bicyclo [2. .1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, bis (4-t- butylphenyl) iodonium camphorsulfonate, and the like. Of these iodonium salts, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate is preferred.
スルホンイミド化合物としては、例えば、N−(トリフルオロメタンスルホニルオキシ)ビシクロ[2.2.1]ヘプト−5−エン−2,3−ジカルボキシイミド、N−(ノナフルオロ−n−ブタンスルホニルオキシ)ビシクロ[2.2.1]ヘプト−5−エン−2,3−ジカルボキシイミド、N−(パーフルオロ−n−オクタンスルホニルオキシ)ビシクロ[2.2.1]ヘプト−5−エン−2,3−ジカルボキシイミド、N−(2−ビシクロ[2.2.1]ヘプト−2−イル−1,1,2,2−テトラフルオロエタンスルホニルオキシ)ビシクロ[2.2.1]ヘプト−5−エン−2,3−ジカルボキシイミド、N−(2−(3−テトラシクロ[4.4.0.12,5.17,10]ドデカニル)−1,1−ジフルオロエタンスルホニルオキシ)ビシクロ[2.2.1]ヘプト−5−エン−2,3−ジカルボキシイミド、N−(カンファースルホニルオキシ)ビシクロ[2.2.1]ヘプト−5−エン−2,3−ジカルボキシイミド等を挙げることができる。これらのスルホンイミド化合物のうち、N−(トリフルオロメタンスルホニルオキシ)ビシクロ[2.2.1]ヘプト−5−エン−2,3−ジカルボキシイミドが好ましい。 Examples of the sulfonimide compound include N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo. [2.2.1] Hept-5-ene-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide, N- (2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy) bicyclo [2.2.1] hept-5 Ene-2,3-dicarboximide, N- (2- (3-tetracyclo [4.4.0.12,5.17,10] dodecanyl) -1,1-difluoroethanesulfonyl Xyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-di Carboximide etc. can be mentioned. Of these sulfonimide compounds, N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide is preferred.
酸発生体は、単独または2種以上を併用できる。酸発生体を用いる場合の使用量は、レジストとしての感度および現像性を確保する観点から、重合体(A)100質量部に対して、通常、0.1質量部以上10質量部以下、好ましくは0.5質量部以上9質量部以下である。この場合、酸発生体の使用量が0.1質量部未満では、感度および現像性が低下する傾向があり、一方10質量部を超えると、放射線に対する透明性が低下して、矩形のレジストパターンを得られ難くなる傾向がある。 The acid generator can be used alone or in combination of two or more. The amount used in the case of using the acid generator is usually 0.1 parts by mass or more and 10 parts by mass or less, preferably 100 parts by mass or less, with respect to 100 parts by mass of the polymer (A), from the viewpoint of ensuring sensitivity and developability as a resist. Is 0.5 parts by mass or more and 9 parts by mass or less. In this case, if the amount of the acid generator used is less than 0.1 parts by mass, the sensitivity and developability tend to decrease. On the other hand, if it exceeds 10 parts by mass, the transparency to radiation decreases and a rectangular resist pattern. Tends to be difficult to obtain.
(酸拡散制御体)
酸拡散制御体は、露光により酸発生体から生じる酸のレジスト被膜中における拡散現象を制御する成分である。具体的には、非露光領域における好ましくない化学反応を抑制する効果を奏し、その結果、得られる感放射線性樹脂組成物の貯蔵安定性がさらに向上し、またレジストとしての解像度がさらに向上するとともに、露光から現像処理までの引き置き時間の変動によるレジストパターンの線幅変化を抑えることができ、プロセス安定性に極めて優れた組成物が得られる。酸拡散制御体の当該感放射線性樹脂組成物における含有形態としては、遊離の化合物の形態でも、重合体(A)または前述の他の重合体の一部として組み込まれた形態でも、これらの両方の形態でもよい。
(Acid diffusion controller)
The acid diffusion controller is a component that controls the diffusion phenomenon of the acid generated from the acid generator upon exposure in the resist film. Specifically, it has the effect of suppressing undesirable chemical reactions in the non-exposed areas, and as a result, the storage stability of the resulting radiation-sensitive resin composition is further improved, and the resolution as a resist is further improved. Thus, a change in the line width of the resist pattern due to a change in the holding time from exposure to development processing can be suppressed, and a composition having excellent process stability can be obtained. The inclusion form of the acid diffusion controller in the radiation-sensitive resin composition may be either a free compound form or a form incorporated as part of the polymer (A) or the other polymer mentioned above. It may be a form.
酸拡散制御体としては、一般に、非露光領域で塩基性を示す化合物が用いられる。具体的には、3級アミン化合物、4級アンモニウムヒドロキシド化合物等の窒素含有塩基性化合物;窒素原子に−COOR基(但し、Rは酸解離性基を示す)が結合した構造を有する化合物;露光により弱酸を生じることにより塩基性を喪失するオニウム塩等を挙げることができる。
酸拡散抑制体は、1種を単独でまたは2種以上を混合して使用することができる。低分子の酸拡散制御剤の含有割合は、全重合体100質量部に対して、5質量部未満が好ましく、1質量部未満が更に好ましい。合計使用量が5質量部を超えると、レジストとしての感度が著しく低下する傾向にある。
As the acid diffusion controller, a compound showing basicity in a non-exposed region is generally used. Specifically, a nitrogen-containing basic compound such as a tertiary amine compound or a quaternary ammonium hydroxide compound; a compound having a structure in which a —COOR group (where R represents an acid-dissociable group) is bonded to a nitrogen atom; Examples include onium salts that lose basicity by generating weak acids upon exposure.
The acid diffusion inhibitor can be used alone or in combination of two or more. The content ratio of the low-molecular acid diffusion controller is preferably less than 5 parts by mass, more preferably less than 1 part by mass with respect to 100 parts by mass of the total polymer. When the total amount used exceeds 5 parts by mass, the sensitivity as a resist tends to be remarkably lowered.
(フッ素含有樹脂)
フッ素含有樹脂は、特に液浸露光においてレジスト膜表面に撥水性を発現させる作用を示す。また、レジスト膜から液浸液への成分の溶出を抑制する効果を奏し、さらに高速スキャンにより液浸露光を行ったとしても液滴を残さない為、結果としてウォーターマーク欠陥等の液浸由来欠陥を抑制する効果がある。
(Fluorine-containing resin)
The fluorine-containing resin exhibits an action of developing water repellency on the resist film surface particularly in immersion exposure. In addition, it has the effect of suppressing elution of components from the resist film to the immersion liquid, and even when immersion exposure is performed by high-speed scanning, it does not leave droplets, resulting in immersion-derived defects such as watermark defects. There is an effect to suppress.
フッ素含有樹脂の構造としては、例えば、
それ自体が現像液に不溶で、酸の作用によりアルカリ可溶性となるフッ素含有樹脂;
それ自体が現像液に可溶で、酸の作用によりアルカリ可溶性が増大するフッ素含有樹脂;
それ自体が現像液に不溶で、アルカリの作用によりアルカリ可溶性となるフッ素含有樹脂;
それ自体が現像液に可溶であり、アルカリの作用によりアルカリ可溶性が増大するフッ素含有樹脂等を挙げることができる。
As the structure of the fluorine-containing resin, for example,
A fluorine-containing resin which itself is insoluble in a developer and becomes alkali-soluble by the action of an acid;
A fluorine-containing resin which is itself soluble in a developer and whose alkali solubility is increased by the action of an acid;
A fluorine-containing resin which itself is insoluble in a developer and becomes alkali-soluble by the action of alkali;
Examples thereof include a fluorine-containing resin which is itself soluble in a developer and whose alkali solubility is increased by the action of an alkali.
フッ素含有樹脂としては、フッ素含有繰り返し単位を有する重合体が好ましい。フッ素含有繰り返し単位を与える単量体としては、例えば、トリフルオロメチル(メタ)アクリル酸エステル、2,2,2−トリフルオロエチル(メタ)アクリル酸エステル、パーフルオロエチル(メタ)アクリル酸エステル、パーフルオロn−プロピル(メタ)アクリル酸エステル、パーフルオロi−プロピル(メタ)アクリル酸エステル、パーフルオロn−ブチル(メタ)アクリル酸エステル、パーフルオロi−ブチル(メタ)アクリル酸エステル、パーフルオロt−ブチル(メタ)アクリル酸エステル、2−(1,1,1,3,3,3−ヘキサフルオロプロピル)(メタ)アクリル酸エステル、1−(2,2,3,3,4,4,5,5−オクタフルオロペンチル)(メタ)アクリル酸エステル、パーフルオロシクロヘキシルメチル(メタ)アクリル酸エステル、1−(2,2,3,3,3−ペンタフルオロプロピル)(メタ)アクリル酸エステル、1−(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10−ヘプタデカフルオロデシル)(メタ)アクリル酸エステル、1−(5−トリフルオロメチル−3,3,4,4,5,6,6,6−オクタフルオロヘキシル)(メタ)アクリル酸エステル等が挙げられる。 As the fluorine-containing resin, a polymer having a fluorine-containing repeating unit is preferable. Examples of the monomer that gives a fluorine-containing repeating unit include trifluoromethyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, Perfluoro n-propyl (meth) acrylic acid ester, perfluoro i-propyl (meth) acrylic acid ester, perfluoro n-butyl (meth) acrylic acid ester, perfluoro i-butyl (meth) acrylic acid ester, perfluoro t-butyl (meth) acrylic acid ester, 2- (1,1,1,3,3,3-hexafluoropropyl) (meth) acrylic acid ester, 1- (2,2,3,3,4,4 , 5,5-octafluoropentyl) (meth) acrylic acid ester, perfluorocyclohexylmethyl (meth) ) Acrylic acid ester, 1- (2,2,3,3,3-pentafluoropropyl) (meth) acrylic acid ester, 1- (3,3,4,4,5,5,6,6,7, 7,8,8,9,9,10,10,10-heptadecafluorodecyl) (meth) acrylic acid ester, 1- (5-trifluoromethyl-3,3,4,4,5,6,6 , 6-octafluorohexyl) (meth) acrylic acid ester and the like.
フッ素含有樹脂としては、例えば、上記フッ素含有繰り返し単位と、重合体(A)を構成する繰り返し単位とを有する共重合体等が好ましい。これらのフッ素含有樹脂は、単独または2種以上を併用できる。 As a fluorine-containing resin, the copolymer etc. which have the said fluorine-containing repeating unit and the repeating unit which comprises a polymer (A) are preferable, for example. These fluorine-containing resins can be used alone or in combination of two or more.
(脂環式骨格含有化合物)
脂環式骨格含有化合物は、ドライエッチング耐性、パターン形状、基板との接着性等を改善する効果を奏する。
(Alicyclic skeleton-containing compound)
The alicyclic skeleton-containing compound has an effect of improving dry etching resistance, pattern shape, adhesion to the substrate, and the like.
脂環式骨格含有化合物としては、例えば、1−アダマンタンカルボン酸、2−アダマンタノン、1−アダマンタンカルボン酸t−ブチル等のアダマンタン誘導体類;
デオキシコール酸t−ブチル、デオキシコール酸t−ブトキシカルボニルメチル、デオキシコール酸2−エトキシエチル等のデオキシコール酸エステル類;
リトコール酸t−ブチル、リトコール酸t−ブトキシカルボニルメチル、リトコール酸2−エトキシエチル等のリトコール酸エステル類;
3−〔2−ヒドロキシ−2,2−ビス(トリフルオロメチル)エチル〕テトラシクロ[4.4.0.12,5.17,10]ドデカン、2−ヒドロキシ−9−メトキシカルボニル−5−オキソ−4−オキサ−トリシクロ[4.2.1.03,7]ノナン等を挙げることができる。これらの脂環式骨格含有化合物は、単独または2種以上を併用できる。
Examples of the alicyclic skeleton-containing compound include adamantane derivatives such as 1-adamantanecarboxylic acid, 2-adamantanone, and 1-adamantanecarboxylate t-butyl;
Deoxycholic acid esters such as t-butyl deoxycholate, t-butoxycarbonylmethyl deoxycholic acid, 2-ethoxyethyl deoxycholic acid;
Lithocholic acid esters such as t-butyl lithocholic acid, t-butoxycarbonylmethyl lithocholic acid, 2-ethoxyethyl lithocholic acid;
3- [2-hydroxy-2,2-bis (trifluoromethyl) ethyl] tetracyclo [4.4.0.12,5.17,10] dodecane, 2-hydroxy-9-methoxycarbonyl-5-oxo- 4-oxa-tricyclo [4.2.1.03,7] nonane and the like can be mentioned. These alicyclic skeleton-containing compounds can be used alone or in combination of two or more.
(界面活性剤)
界面活性剤は、塗布性、ストリエーション、現像性等を改良する効果を奏する。
(Surfactant)
Surfactants have the effect of improving coatability, striation, developability, and the like.
界面活性剤としては、例えば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンn−オクチルフェニルエーテル、ポリオキシエチレンn−ノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート等のノニオン系界面活性剤の他、以下商品名で、KP341(信越化学工業社)、ポリフローNo.75、同No.95(共栄社化学社)、エフトップEF301(トーケムプロダクツ社)、エフトップEF303(トーケムプロダクツ社)、エフトップEF352(トーケムプロダクツ社)、メガファックF171(大日本インキ化学工業社)、メガファックF173(大日本インキ化学工業社)、フロラードFC430(住友スリーエム社)、フロラードFC431(住友スリーエム社)、アサヒガードAG710、サーフロンS−382(旭硝子工業社)、サーフロンSC−101(旭硝子工業社)、サーフロンSC−102(旭硝子工業社)、サーフロンSC−103(旭硝子工業社)、サーフロンSC−104(旭硝子工業社)、サーフロンSC−105(旭硝子工業社)、サーフロンSC−106(旭硝子工業社)等を挙げることができる。これらの界面活性剤は、単独または2種以上を併用できる。 Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol In addition to nonionic surfactants such as distearate, KP341 (Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no. 95 (Kyoeisha Chemical Co., Ltd.), Ftop EF301 (Tochem Products), Ftop EF303 (Tochem Products), Ftop EF352 (Tochem Products), MegaFuck F171 (Dainippon Ink and Chemicals), Mega Fax F173 (Dainippon Ink and Chemicals), Florard FC430 (Sumitomo 3M), Florard FC431 (Sumitomo 3M), Asahi Guard AG710, Surflon S-382 (Asahi Glass Industry), Surflon SC-101 (Asahi Glass Industry) Surflon SC-102 (Asahi Glass Industrial Co., Ltd.), Surflon SC-103 (Asahi Glass Industrial Co., Ltd.), Surflon SC-104 (Asahi Glass Industrial Co., Ltd.), Surflon SC-105 (Asahi Glass Industrial Co., Ltd.), Surflon SC-106 (Asahi Glass Industrial Co., Ltd.) Etc. These surfactants can be used alone or in combination of two or more.
(増感剤)
増感剤は、酸発生体に吸収される放射線のエネルギー以外のエネルギーを吸収して、そのエネルギーを電子やラジカル等の形で酸発生体に伝達し、それにより酸の生成量を増加する作用を示すものであり、感放射線性樹脂組成物の「みかけの感度」を向上させる効果を奏する。
(Sensitizer)
The sensitizer absorbs energy other than the energy of the radiation absorbed by the acid generator and transmits the energy to the acid generator in the form of electrons or radicals, thereby increasing the amount of acid produced. And has the effect of improving the “apparent sensitivity” of the radiation-sensitive resin composition.
増感剤としては、例えば、カルバゾール類、アセトフェノン類、ベンゾフェノン類、ナフタレン類、フェノール類、ビアセチル、エオシン、ローズベンガル、ピレン類、アントラセン類、フェノチアジン類等を挙げることができる。これらの増感剤は、単独または2種以上を併用できる。 Examples of the sensitizer include carbazoles, acetophenones, benzophenones, naphthalenes, phenols, biacetyl, eosin, rose bengal, pyrenes, anthracenes, and phenothiazines. These sensitizers can be used alone or in combination of two or more.
(その他の任意成分)
その他の任意成分としては、例えば、染料、顔料、接着助剤、アルカリ可溶性樹脂、酸解離性の保護基を有する低分子のアルカリ溶解性制御剤、ハレーション防止剤、保存安定化剤、消泡剤等が挙げられる。これらのうち、例えば、染料または顔料を配合すると、露光部の潜像を可視化させて、露光時のハレーションの影響を緩和できる。また、接着助剤を配合すると、基板との接着性を改善できる。これらのその他の任意成分は、単独または2種以上を併用できる。
(Other optional ingredients)
Other optional components include, for example, dyes, pigments, adhesion aids, alkali-soluble resins, low-molecular alkali solubility control agents having acid-dissociable protecting groups, antihalation agents, storage stabilizers, antifoaming agents. Etc. Among these, for example, when a dye or a pigment is blended, the latent image in the exposed area can be visualized and the influence of halation during exposure can be reduced. Further, when an adhesion assistant is blended, the adhesion to the substrate can be improved. These other optional components can be used alone or in combination of two or more.
(フォトレジストパターンの形成方法)
フォトレジストパターンの形成方法は、例えば、以下に示す方法が一般的である。感放射線性樹脂組成物を用いて、基板上にフォトレジスト膜を形成する工程(以下、工程(i)ともいう。)、形成されたフォトレジスト膜に、必要に応じて液浸媒体を介し、所定のパターンを有するマスクを通して放射線を照射して露光する工程(以下、工程(ii)ともいう。)、基板(露光されたフォトレジスト膜)を加熱する工程(以下、工程(iii)ともいう。)、現像工程(以下、工程(iv)ともいう。)を経て、フォトレジストパターンを形成することができる。
(Photoresist pattern formation method)
As a method for forming a photoresist pattern, for example, the following method is generally used. Using the radiation-sensitive resin composition, a step of forming a photoresist film on the substrate (hereinafter also referred to as step (i)), the formed photoresist film through an immersion medium as necessary, It is also referred to as a step of exposing by exposure to radiation through a mask having a predetermined pattern (hereinafter also referred to as step (ii)) and a step of heating the substrate (exposed photoresist film) (hereinafter referred to as step (iii)). ) And a development step (hereinafter also referred to as step (iv)), a photoresist pattern can be formed.
工程(i)では、感放射線性樹脂組成物またはこれを溶剤に溶解させて得られた組成物溶液を、回転塗布、流延塗布、ロール塗布等の塗布手段によって、基板(シリコンウエハー、二酸化シリコン、反射防止膜で被覆されたウエハー等)上に所定の膜厚となるように樹脂組成物溶液を塗布し、次いでプレベークすることにより塗膜中の溶剤を揮発させることにより、フォトレジスト膜を形成する。 In the step (i), a radiation sensitive resin composition or a composition solution obtained by dissolving it in a solvent is applied to a substrate (silicon wafer, silicon dioxide) by a coating means such as spin coating, cast coating, roll coating or the like. A photoresist film is formed by applying a resin composition solution to a predetermined film thickness on a wafer coated with an antireflection film, etc., and then pre-baking to volatilize the solvent in the coating film. To do.
工程(ii)では、工程(i)で形成されたフォトレジスト膜に(場合によっては、水等の液浸媒体を介して)、放射線を照射し、露光させる。なお、この際、所定のパターンを有するマスクを通して放射線を照射する。放射線としては、目的とするパターンの線幅に応じて、可視光線、紫外線、遠紫外線、X線、荷電粒子線等から適宜選択して照射する。ArFエキシマレーザー(波長193nm)、KrFエキシマレーザー(波長248nm)に代表される遠紫外線が好ましく、ArFエキシマレーザーがより好ましい。 In step (ii), the photoresist film formed in step (i) is irradiated with radiation (possibly through an immersion medium such as water) and exposed. At this time, radiation is irradiated through a mask having a predetermined pattern. As the radiation, irradiation is performed by appropriately selecting from visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams and the like according to the line width of the target pattern. Far ultraviolet rays represented by ArF excimer laser (wavelength 193 nm) and KrF excimer laser (wavelength 248 nm) are preferable, and ArF excimer laser is more preferable.
工程(iii)は、PEBと呼ばれ、工程(ii)でフォトレジスト膜の露光された部分において、酸発生体[B]から発生した酸が重合体を脱保護する工程である。PEBは、通常50℃から180℃の範囲で適宜選択して実施される。 Step (iii) is called PEB and is a step in which the acid generated from the acid generator [B] deprotects the polymer in the exposed portion of the photoresist film in step (ii). PEB is usually carried out by appropriately selecting in the range of 50 ° C to 180 ° C.
工程(iv)では、露光されたフォトレジスト膜を、現像液で現像することにより、所定のフォトレジストパターンを形成する。現像後は、水で洗浄し、乾燥することが一般的である。現像液としては、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、ケイ酸ナトリウム、メタケイ酸ナトリウム、アンモニア水、エチルアミン、n−プロピルアミン、ジエチルアミン、ジ−n−プロピルアミン、トリエチルアミン、メチルジエチルアミン、エチルジメチルアミン、トリエタノールアミン、テトラメチルアンモニウムヒドロキシド、ピロール、ピペリジン、コリン、1,8−ジアザビシクロ−[5.4.0]−7−ウンデセン、1,5−ジアザビシクロ−[4.3.0]−5−ノネン等のアルカリ性化合物の少なくとも1種を溶解したアルカリ水溶液が好ましい。 In step (iv), the exposed photoresist film is developed with a developer to form a predetermined photoresist pattern. After development, it is common to wash with water and dry. Examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, Ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0 An alkaline aqueous solution in which at least one alkaline compound such as -5-nonene is dissolved is preferable.
また、液浸露光を行う場合は、工程(ii)の前に、液浸液とレジスト膜との直接の接触を保護するために、液浸液不溶性の液浸用保護膜をレジスト膜上に設けてもよい。液浸用保護膜としては、工程(iv)の前に溶剤により剥離する、溶剤剥離型保護膜(例えば、特開2006−227632号公報参照)、工程(iv)の現像と同時に剥離する、現像液剥離型保護膜(例えば、WO2005−069076号公報、WO2006−035790号公報参照)のいずれを用いてもよい。但し、スループットの観点からは、現像液剥離型液浸用保護膜を用いることが好ましい。 In addition, when performing immersion exposure, before the step (ii), in order to protect the direct contact between the immersion liquid and the resist film, an immersion liquid insoluble immersion protective film is formed on the resist film. It may be provided. Examples of the immersion protective film include a solvent-peelable protective film (see, for example, JP-A-2006-227632) that is peeled off by a solvent before the step (iv), and a development that peels off simultaneously with the development in the step (iv). Any of liquid-removable protective films (see, for example, WO2005-069096 and WO2006-035790) may be used. However, from the viewpoint of throughput, it is preferable to use a developer peeling type immersion protective film.
このようにして得られるレジストパターンは、トップロスが防止されて矩形性が良好であり、LWRおよびパターン倒れも抑制されているので、リソグラフィー技術を応用した微細加工に好適である。 The resist pattern thus obtained is suitable for fine processing using a lithography technique because the top loss is prevented, the rectangularity is good, and the LWR and pattern collapse are suppressed.
以下、本発明を実施例に基づいて具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、実施例、比較例中の「部」及び「%」は、特に断らない限り質量基準である。また、各種物性値の測定方法、及び諸特性の評価方法を以下に示す。 EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified. Moreover, the measuring method of various physical-property values and the evaluation method of various characteristics are shown below.
[重量平均分子量(Mw)及び数平均分子量(Mn)]:東ソー社製GPCカラム(G2000HXL2本、G3000HXL1本、G4000HXL1本)を用い、流量:1.0ミリリットル/分、溶出溶媒:テトラヒドロフラン、カラム温度:40℃の分析条件で、単分散ポリスチレンを標準とするゲルパーミエーションクロマトグラフィ(GPC)により測定した。また、分散度(Mw/Mn)は測定結果より算出した。 [Weight average molecular weight (Mw) and number average molecular weight (Mn)]: GPC columns (2 G2000HXL, 1 G3000HXL, 1 G4000HXL) manufactured by Tosoh Corporation, flow rate: 1.0 ml / min, elution solvent: tetrahydrofuran, column temperature : Measured by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard under analysis conditions of 40 ° C. The degree of dispersion (Mw / Mn) was calculated from the measurement results.
[13C−NMR分析]:13C−NMR分析は、日本電子社製「JNM−EX270」を用いて測定した。 [ 13 C-NMR analysis]: The 13 C-NMR analysis was measured using “JNM-EX270” manufactured by JEOL Ltd.
以下、樹脂(A)の合成例について説明する。なお、樹脂(A)の合成に用いた単量体の種類を式(M−1)〜(M−12)として以下に示す。 Hereinafter, synthesis examples of the resin (A) will be described. In addition, the kind of monomer used for the synthesis | combination of resin (A) is shown below as Formula (M-1)-(M-12).
(合成例1 樹脂(A−1)の調製)
式(M−1)で表される単量体(以下、「単量体(M−1)」ともいう)13.0g(50mol%)、式(M−7)で表される単量体(以下、「単量体(M−7)」ともいう)2.9g(10mol%)及び式(M−11)で表される単量体(以下、「単量体(M−9)」ともいう)10.3g(30mol%)を、2−ブタノン60gに溶解し、更に上記式(a3)の構造を有する和光純薬工業(株)製重合開始剤「V−601」0.36gを投入した単量体溶液を準備した。一方で、式(M−5)で表される単量体(以下、「単量体(M−5)」ともいう)3.8g(10mol%)を30gの2−ブタノンに溶解した単量体溶液を200mlの三口フラスコに投入し、30分窒素パージした後、反応釜を攪拌しながら80℃に加熱し、事前に準備した単量体溶液を滴下漏斗を用いて3時間かけて滴下した。滴下開始を重合開始時間とし、重合反応を6時間実施した。重合終了後、重合溶液を水冷することにより30℃以下に冷却し、600gのメタノールへ投入して、析出した白色粉末をろ別した。ろ別した白色粉末を150gのメタノールにて2度スラリー状で洗浄した後、再度ろ別し、50℃にて17時間乾燥して白色粉末の共重合体を得た。得られた共重合体のMwは18000であり、Mw/Mnは1.74であり、収率は82.4%であり、共重合体中の各単量体に由来する繰り返し単位の割合(単量体(M−1)/単量体(M−5)/単量体(M−7)/単量体(M−11))はmol%で、49.0/9.2/10.1/31.6であった。この共重合体を樹脂(A−1)とする。合成例1で用いた単量体の種類、及び配合処方を表1に示す。また、得られた共重合体のMw、Mw/Mn、収率、及び共重合体中の各単量体に由来する繰り返し単位の割合の測定結果を表2に示す。
(Synthesis Example 1 Preparation of Resin (A-1))
13.0 g (50 mol%) of a monomer represented by the formula (M-1) (hereinafter also referred to as “monomer (M-1)”), a monomer represented by the formula (M-7) (Hereinafter also referred to as “monomer (M-7)”) 2.9 g (10 mol%) and a monomer represented by formula (M-11) (hereinafter “monomer (M-9)”) (Also called) 10.3 g (30 mol%) is dissolved in 60 g of 2-butanone, and 0.36 g of a polymerization initiator “V-601” manufactured by Wako Pure Chemical Industries, Ltd. having the structure of the above formula (a3) is further added. A charged monomer solution was prepared. On the other hand, a monomer represented by the formula (M-5) (hereinafter also referred to as “monomer (M-5)”) 3.8 g (10 mol%) dissolved in 30 g of 2-butanone The body solution was put into a 200 ml three-necked flask and purged with nitrogen for 30 minutes, and then the reaction kettle was heated to 80 ° C. with stirring, and the monomer solution prepared in advance was dropped over 3 hours using a dropping funnel. . The polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time. After the completion of the polymerization, the polymerization solution was cooled with water to 30 ° C. or less, poured into 600 g of methanol, and the precipitated white powder was filtered off. The filtered white powder was washed twice with 150 g of methanol in the form of a slurry and then filtered again and dried at 50 ° C. for 17 hours to obtain a white powder copolymer. Mw of the obtained copolymer was 18000, Mw / Mn was 1.74, the yield was 82.4%, and the ratio of repeating units derived from each monomer in the copolymer ( The monomer (M-1) / monomer (M-5) / monomer (M-7) / monomer (M-11)) are mol%, 49.0 / 9.2 / 10. 1 / 31.6. This copolymer is referred to as “resin (A-1)”. Table 1 shows the types of monomers used in Synthesis Example 1 and the formulation. In addition, Table 2 shows the measurement results of Mw, Mw / Mn, yield, and the ratio of repeating units derived from each monomer in the copolymer.
(合成例2〜20 樹脂(A−2)〜(A−20)の合成)
表1に示す種類の単量体及び開始剤を、表1に示す配合処方で使用したこと以外は、合成例1と同様の方法によって、共重合体を調製した。表中の重合開始剤の記載は、「V−501」が上記式(a2)の構造を有する和光純薬製開始剤、「パーロイルSA」が上記式(a1)の構造を有する日油株式会社製開始剤である。なお、得られた共重合体のMw、Mw/Mn、収率、及び共重合体中の各単量体に由来する繰り返し単位の割合の測定結果を表2に示す。各共重合体を樹脂(A−2)〜(A−20)とする。
(Synthesis Examples 2 to 20 Synthesis of Resins (A-2) to (A-20))
A copolymer was prepared in the same manner as in Synthesis Example 1 except that the types of monomers and initiators shown in Table 1 were used in the formulation shown in Table 1. The description of the polymerization initiator in the table is as follows: “V-501” is an initiator made by Wako Pure Chemicals having the structure of the above formula (a2), and “Paroyl SA” is NOF Corporation having the structure of the above formula (a1). It is a manufacturing initiator. In addition, Table 2 shows the measurement results of Mw, Mw / Mn, yield of the obtained copolymer, and the ratio of the repeating unit derived from each monomer in the copolymer. Let each copolymer be resin (A-2)-(A-20).
(実施例1 感放射線性樹脂組成物の調製)
合成例1で調製した樹脂(A−1)100部、酸発生剤(B−1)3.6部、酸発生剤(B−2)10.6部、酸拡散抑制剤(C)1.7部、添加剤(D)0.02部、溶剤(E−1)1700部、溶剤(E−2)700部、及び溶剤(E−3)30部を混合して感放射線性樹脂組成物を調製した。
(Example 1 Preparation of radiation-sensitive resin composition)
Resin (A-1) 100 parts prepared in Synthesis Example 1, acid generator (B-1) 3.6 parts, acid generator (B-2) 10.6 parts, acid diffusion inhibitor (C) 1. 7 parts, 0.02 part of additive (D), 1700 parts of solvent (E-1), 700 parts of solvent (E-2), and 30 parts of solvent (E-3) are mixed to produce a radiation sensitive resin composition. Was prepared.
(実施例2〜11及び比較例1〜9 感放射線性樹脂組成物の調製)
表3に示す配合処方としたこと以外は実施例1と同様にして感放射線性樹脂組成物を調製した。
(Examples 2 to 11 and Comparative Examples 1 to 9 Preparation of radiation-sensitive resin composition)
A radiation sensitive resin composition was prepared in the same manner as in Example 1 except that the formulation shown in Table 3 was used.
尚、酸発生剤(B)、酸拡散抑制剤(C)、添加剤(D)及び溶剤(E)の詳細を以下に示す。 Details of the acid generator (B), the acid diffusion inhibitor (C), the additive (D), and the solvent (E) are shown below.
酸発生剤(B) Acid generator (B)
(B−1):トリフェニルスルホニウム2−(アダマンタン−1−イル)−1,1−ジフルオロエタン−1−スルホナート
(B−2):トリフェニルスルホニウム2−(アダマンタンカルボニルオキシ)−1,1,2,2−テトラフルオロヘキサン−1−スルホネート
(B-1): Triphenylsulfonium 2- (adamantan-1-yl) -1,1-difluoroethane-1-sulfonate (B-2): Triphenylsulfonium 2- (adamantanecarbonyloxy) -1,1,2 , 2-Tetrafluorohexane-1-sulfonate
酸拡散抑制剤(C)
(C):N−t−ブトキシカルボニル−4−ヒドロキシピペリジン
Acid diffusion inhibitor (C)
(C): Nt-butoxycarbonyl-4-hydroxypiperidine
添加剤(D)
(D):DAINAFLOW(株式会社ネオス製)
Additive (D)
(D): DAINAFLOW (manufactured by Neos)
溶剤(E)
(E−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
(E−2):シクロヘキサノン
(E−3):γ−ブチロラクトン
Solvent (E)
(E-1): Propylene glycol monomethyl ether acetate (E-2): Cyclohexanone (E-3): γ-butyrolactone
感放射線性樹脂組成物の評価
実施例1〜11及び比較例1〜9の感放射線性樹脂組成物について、以下のようにして各種評価を行った。これらの評価結果を表4に示す。
Evaluation of Radiation Sensitive Resin Composition The radiation sensitive resin compositions of Examples 1 to 11 and Comparative Examples 1 to 9 were subjected to various evaluations as follows. These evaluation results are shown in Table 4.
[現像欠陥]:
まず、下層反射防止膜(「ARC66」、日産化学社製)を形成した12インチシリコンウェハ上に、感放射線性樹脂組成物によって、膜厚110nmの被膜を形成し、100℃又は130℃で60秒間ソフトベーク(SB)を行った。次に、この被膜を、ArFエキシマレーザー液浸露光装置(「NSR S610C」、NIKON社製)を用い、NA=1.3、ratio=0.800、Dipoleの条件により、マスクパターンを介して露光した。露光後、95℃又は120℃で60秒間ポストベーク(PEB)を行った。その後、2.38質量%のテトラメチルアンモニウムヒドロキシド水溶液により現像し、水洗し、乾燥して、ポジ型のレジストパターンを形成した。このとき、幅45nmのラインアンドスペースを形成する露光量を最適露光量とした。この最適露光量にてウェハ全面に線幅45nmのラインアンドスペースを形成し、欠陥検査用ウェハとした。なお、測長には走査型電子顕微鏡(「CC−4000」、日立ハイテクノロジーズ社製)を用いた。
[Development defects]:
First, a film having a film thickness of 110 nm is formed from a radiation-sensitive resin composition on a 12-inch silicon wafer on which an underlayer antireflection film (“ARC66”, manufactured by Nissan Chemical Co., Ltd.) is formed. Soft bake (SB) was performed for 2 seconds. Next, this film is exposed through a mask pattern using an ArF excimer laser immersion exposure apparatus (“NSR S610C”, manufactured by NIKON) under the conditions of NA = 1.3, ratio = 0.800, Dipole. did. After the exposure, post-baking (PEB) was performed at 95 ° C. or 120 ° C. for 60 seconds. Thereafter, the resist film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution, washed with water, and dried to form a positive resist pattern. At this time, the exposure amount for forming a line and space having a width of 45 nm was determined as the optimum exposure amount. With this optimum exposure amount, a line and space having a line width of 45 nm was formed on the entire surface of the wafer to obtain a defect inspection wafer. A scanning electron microscope (“CC-4000”, manufactured by Hitachi High-Technologies Corporation) was used for length measurement.
その後、欠陥検査用ウェハ上の欠陥数を、KLA−Tencor社製の「KLA2810」を用いて測定した。更に、「KLA2810」にて測定された欠陥を、レジスト由来と判断されるものと外部由来の異物とに分類した。分類後、レジスト被膜由来と判断されるものの数(欠陥数)の合計が500個/wafer未満であった場合「良好」とし、500個以上1000個未満であった場合「やや良好」とし、1000個/waferを超える場合は「不良」とした。 Thereafter, the number of defects on the defect inspection wafer was measured using “KLA2810” manufactured by KLA-Tencor. Furthermore, the defects measured by “KLA2810” were classified into those judged to be resist-derived and foreign matters derived from the outside. After classification, when the total number of defects (number of defects) determined to be derived from the resist film was less than 500 / wafer, it was judged as “good”, and when it was 500 or more and less than 1000, “somewhat good”, 1000 When it exceeded the number of pieces / wafer, it was determined as “defective”.
表4からわかるように、本発明の感放射線性樹脂組成物は、比較例1〜9に比べて、現像欠陥数が少ないことを確認できた。 As can be seen from Table 4, it was confirmed that the radiation-sensitive resin composition of the present invention had fewer development defects than Comparative Examples 1-9.
本発明の感放射線性樹脂組成物は、今後、益々レジストパターンの線幅の微細化が要求されるフォトレジストに好適に利用可能なものである。 The radiation-sensitive resin composition of the present invention can be suitably used for photoresists that require increasingly finer line widths of resist patterns in the future.
Claims (2)
(A) It has a carbonyl group at at least one end of the molecular chain, and has a polystyrene-reduced weight average molecular weight of 11,000 or more by gel permeation chromatography, and is decomposed by the action of an acid to increase the solubility in an alkali developer. A polymer having at least two types of repeating units selected from a repeating unit having a lactone structure and a repeating unit having a cyclic carbonate structure, and a radical polymerization initiator represented by the following formula (a1 ): A radiation-sensitive resin composition comprising a polymer obtained by polymerization and (B) a radiation-sensitive acid generator.
(前記一般式中、R5およびR6は相互に独立に水素またはメチル基を示し、R7は水素原子またはメトキシ基を示し、R8は水素原子、炭素数1〜4のアルキル基またはシアノ基を示し、Aは単結合またはメチレンを示し、Bはメチレンまたは酸素を示し、l,mは0または1の整数である。)
(A) In the polymer, at least two kinds of repeating units selected from a repeating unit having a lactone structure and a repeating unit having a cyclic carbonate structure are at least two kinds of repeating units selected from repeating units represented by the following formula: The radiation sensitive resin composition of Claim 1 which exists.
(In the above general formula, R 5 and R 6 each independently represent hydrogen or a methyl group, R 7 represents a hydrogen atom or a methoxy group, R 8 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a cyano group. Represents a group, A represents a single bond or methylene, B represents methylene or oxygen, and l and m are integers of 0 or 1.)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010084494A JP5655352B2 (en) | 2010-03-31 | 2010-03-31 | Radiation-sensitive resin composition and polymer used therefor |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010084494A JP5655352B2 (en) | 2010-03-31 | 2010-03-31 | Radiation-sensitive resin composition and polymer used therefor |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2011215429A JP2011215429A (en) | 2011-10-27 |
JP5655352B2 true JP5655352B2 (en) | 2015-01-21 |
Family
ID=44945195
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2010084494A Active JP5655352B2 (en) | 2010-03-31 | 2010-03-31 | Radiation-sensitive resin composition and polymer used therefor |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP5655352B2 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113024714A (en) * | 2021-03-12 | 2021-06-25 | 深圳力合博汇光敏材料有限公司 | (meth) acrylic polymer having crosslinkable functional group at terminal position |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3700276B2 (en) * | 1996-08-09 | 2005-09-28 | Jsr株式会社 | Radiation sensitive resin composition |
JP2001142214A (en) * | 1999-11-12 | 2001-05-25 | Fuji Photo Film Co Ltd | Positive photoresist composition |
JP4414069B2 (en) * | 2000-07-11 | 2010-02-10 | ダイセル化学工業株式会社 | Method for producing polymer compound for photoresist and method for producing photoresist composition |
JP4187949B2 (en) * | 2001-06-21 | 2008-11-26 | 富士フイルム株式会社 | Positive resist composition |
JP2006096965A (en) * | 2004-02-20 | 2006-04-13 | Tokyo Ohka Kogyo Co Ltd | Polymer compound, photoresist composition containing such polymer compound, and method for forming resist pattern |
WO2005085301A1 (en) * | 2004-03-08 | 2005-09-15 | Mitsubishi Rayon Co., Ltd. | Resist polymer, resist composition, process for pattern formation, and starting compounds for production of the resist polymer |
JP2006023692A (en) * | 2004-06-09 | 2006-01-26 | Fuji Photo Film Co Ltd | Photosensitive composition and pattern forming method using the same |
JP4668048B2 (en) * | 2005-12-02 | 2011-04-13 | 東京応化工業株式会社 | Positive resist composition and resist pattern forming method |
JP2007256640A (en) * | 2006-03-23 | 2007-10-04 | Fujifilm Corp | Positive photosensitive composition and pattern forming method using same |
-
2010
- 2010-03-31 JP JP2010084494A patent/JP5655352B2/en active Active
Also Published As
Publication number | Publication date |
---|---|
JP2011215429A (en) | 2011-10-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR102166206B1 (en) | Radiation-sensitive resin composition, resist pattern forming method, acid diffusion control agent, compound and method for producing compound | |
WO2018070327A1 (en) | Radiation-sensitive resin composition and resist-pattern forming method | |
KR102164849B1 (en) | Radiation-sensitive resin composition, resist pattern forming method, polymer and method for producing compound | |
JP5835319B2 (en) | Resist pattern forming method, radiation-sensitive resin composition, and resist film | |
JP2013225094A (en) | Photoresist composition and method for forming resist pattern | |
JP5724791B2 (en) | Radiation-sensitive resin composition and method for forming resist pattern | |
JP6421757B2 (en) | Radiation sensitive resin composition, resist pattern forming method, polymer and compound | |
JP5609980B2 (en) | Radiation sensitive resin composition, polymer and compound | |
WO2012063840A1 (en) | Radiation-sensitive resin composition, pattern forming method, and acid diffusion regulator | |
JP6171774B2 (en) | Radiation sensitive resin composition, resist pattern forming method and radiation sensitive acid generator | |
JP5540818B2 (en) | Radiation-sensitive resin composition and polymer | |
WO2021220648A1 (en) | Radiation-sensitive resin composition, method for forming resist pattern using same, and sulfonic acid salt compound and radiation-sensitive acid generator comprising same | |
KR20110013315A (en) | Radiation-sensitive resin composition and compound used therein | |
JP5857522B2 (en) | Compound and photoresist composition | |
JP5783111B2 (en) | Photoresist composition and resist pattern forming method | |
JP5569402B2 (en) | Radiation sensitive resin composition, polymer and compound | |
JP6528692B2 (en) | Radiation sensitive resin composition, resist pattern forming method, polymer and compound | |
JP5655352B2 (en) | Radiation-sensitive resin composition and polymer used therefor | |
WO2014141979A1 (en) | Radiation-sensitive resin composition, resist pattern forming method, radiation-sensitive acid generator and compound | |
JP6191684B2 (en) | Radiation sensitive resin composition, resist pattern forming method, and polymer | |
JP2012203401A (en) | Radiation-sensitive resin composition | |
KR101996088B1 (en) | Photoresist composition, process for forming resist pattern and acid generator | |
JP2017181696A (en) | Radiation-sensitive resin composition and method for forming resist pattern | |
JP2011215428A (en) | Radiation-sensitive resin composition and polymer used therein | |
JP2013088763A (en) | Photoresist composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20120816 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20131111 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20131119 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140120 |
|
A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20140513 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140808 |
|
A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20140815 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20140916 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20141001 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20141028 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20141110 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 5655352 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |