US20040137359A1 - Positive photoresist composition - Google Patents
Positive photoresist composition Download PDFInfo
- Publication number
- US20040137359A1 US20040137359A1 US10/742,878 US74287803A US2004137359A1 US 20040137359 A1 US20040137359 A1 US 20040137359A1 US 74287803 A US74287803 A US 74287803A US 2004137359 A1 US2004137359 A1 US 2004137359A1
- Authority
- US
- United States
- Prior art keywords
- positive photoresist
- compound represented
- photoresist composition
- formula
- compound
- 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.)
- Abandoned
Links
- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 41
- 239000000203 mixture Substances 0.000 title claims abstract description 39
- 150000001875 compounds Chemical class 0.000 claims abstract description 62
- -1 quinonediazide ester Chemical class 0.000 claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 239000003504 photosensitizing agent Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 4
- 230000035945 sensitivity Effects 0.000 abstract description 17
- 239000004615 ingredient Substances 0.000 description 33
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- 230000032050 esterification Effects 0.000 description 11
- 238000005886 esterification reaction Methods 0.000 description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 10
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- 229920003986 novolac Polymers 0.000 description 8
- 235000013824 polyphenols Nutrition 0.000 description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 8
- WTQZSMDDRMKJRI-UHFFFAOYSA-N 4-diazoniophenolate Chemical class [O-]C1=CC=C([N+]#N)C=C1 WTQZSMDDRMKJRI-UHFFFAOYSA-N 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- 150000002576 ketones Chemical class 0.000 description 7
- OGRAOKJKVGDSFR-UHFFFAOYSA-N 2,3,5-trimethylphenol Chemical compound CC1=CC(C)=C(C)C(O)=C1 OGRAOKJKVGDSFR-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 6
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 6
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical class OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 4
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 description 4
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 4
- 238000000206 photolithography Methods 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 236TMPh Natural products CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 3
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229940116333 ethyl lactate Drugs 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229940079877 pyrogallol Drugs 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 2
- FJJYHTVHBVXEEQ-UHFFFAOYSA-N 2,2-dimethylpropanal Chemical compound CC(C)(C)C=O FJJYHTVHBVXEEQ-UHFFFAOYSA-N 0.000 description 2
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 2
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 2
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- HMNKTRSOROOSPP-UHFFFAOYSA-N 3-Ethylphenol Chemical compound CCC1=CC=CC(O)=C1 HMNKTRSOROOSPP-UHFFFAOYSA-N 0.000 description 2
- IAVREABSGIHHMO-UHFFFAOYSA-N 3-hydroxybenzaldehyde Chemical compound OC1=CC=CC(C=O)=C1 IAVREABSGIHHMO-UHFFFAOYSA-N 0.000 description 2
- ASHGTJPOSUFTGB-UHFFFAOYSA-N 3-methoxyphenol Chemical class COC1=CC=CC(O)=C1 ASHGTJPOSUFTGB-UHFFFAOYSA-N 0.000 description 2
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 2
- XXRCUYVCPSWGCC-UHFFFAOYSA-N Ethyl pyruvate Chemical compound CCOC(=O)C(C)=O XXRCUYVCPSWGCC-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical class OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000002801 charged material Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- VFLDPWHFBUODDF-FCXRPNKRSA-N curcumin Chemical compound C1=C(O)C(OC)=CC(\C=C\C(=O)CC(=O)\C=C\C=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-FCXRPNKRSA-N 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- UHKJHMOIRYZSTH-UHFFFAOYSA-N ethyl 2-ethoxypropanoate Chemical compound CCOC(C)C(=O)OCC UHKJHMOIRYZSTH-UHFFFAOYSA-N 0.000 description 2
- 229940117360 ethyl pyruvate Drugs 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 2
- CWKLZLBVOJRSOM-UHFFFAOYSA-N methyl pyruvate Chemical compound COC(=O)C(C)=O CWKLZLBVOJRSOM-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- BTFQKIATRPGRBS-UHFFFAOYSA-N o-tolualdehyde Chemical compound CC1=CC=CC=C1C=O BTFQKIATRPGRBS-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical class OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MFVGRLIGGZNHRJ-UHFFFAOYSA-N (2,4-dihydroxyphenyl)-[4-(dimethylamino)phenyl]methanone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(O)C=C1O MFVGRLIGGZNHRJ-UHFFFAOYSA-N 0.000 description 1
- ZRDYULMDEGRWRC-UHFFFAOYSA-N (4-hydroxyphenyl)-(2,3,4-trihydroxyphenyl)methanone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C(O)=C1O ZRDYULMDEGRWRC-UHFFFAOYSA-N 0.000 description 1
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 1
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical class CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- HTQNYBBTZSBWKL-UHFFFAOYSA-N 2,3,4-trihydroxbenzophenone Chemical compound OC1=C(O)C(O)=CC=C1C(=O)C1=CC=CC=C1 HTQNYBBTZSBWKL-UHFFFAOYSA-N 0.000 description 1
- ZCONCJFBSHTFFD-UHFFFAOYSA-N 2,3,5-triethylphenol Chemical compound CCC1=CC(O)=C(CC)C(CC)=C1 ZCONCJFBSHTFFD-UHFFFAOYSA-N 0.000 description 1
- GOWFRAUGTCYVPS-UHFFFAOYSA-N 2,6-bis[(4-hydroxy-2,5-dimethylphenyl)methyl]-4-methylphenol Chemical compound OC=1C(CC=2C(=CC(O)=C(C)C=2)C)=CC(C)=CC=1CC1=CC(C)=C(O)C=C1C GOWFRAUGTCYVPS-UHFFFAOYSA-N 0.000 description 1
- XXXFZKQPYACQLD-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl acetate Chemical compound CC(=O)OCCOCCO XXXFZKQPYACQLD-UHFFFAOYSA-N 0.000 description 1
- IXQGCWUGDFDQMF-UHFFFAOYSA-N 2-Ethylphenol Chemical compound CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 1
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical compound ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 description 1
- SUKZIEQXDVGCJR-UHFFFAOYSA-N 2-ethyl-4-prop-1-en-2-ylphenol Chemical class CCC1=CC(C(C)=C)=CC=C1O SUKZIEQXDVGCJR-UHFFFAOYSA-N 0.000 description 1
- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-UHFFFAOYSA-N 0.000 description 1
- PPPFYBPQAPISCT-UHFFFAOYSA-N 2-hydroxypropyl acetate Chemical compound CC(O)COC(C)=O PPPFYBPQAPISCT-UHFFFAOYSA-N 0.000 description 1
- UITUMGKYHZMNKN-UHFFFAOYSA-N 2-methyl-4-prop-1-en-2-ylphenol Chemical class CC(=C)C1=CC=C(O)C(C)=C1 UITUMGKYHZMNKN-UHFFFAOYSA-N 0.000 description 1
- WUQYBSRMWWRFQH-UHFFFAOYSA-N 2-prop-1-en-2-ylphenol Chemical class CC(=C)C1=CC=CC=C1O WUQYBSRMWWRFQH-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- VZIRCHXYMBFNFD-HNQUOIGGSA-N 3-(2-Furanyl)-2-propenal Chemical compound O=C\C=C\C1=CC=CO1 VZIRCHXYMBFNFD-HNQUOIGGSA-N 0.000 description 1
- SRWILAKSARHZPR-UHFFFAOYSA-N 3-chlorobenzaldehyde Chemical compound ClC1=CC=CC(C=O)=C1 SRWILAKSARHZPR-UHFFFAOYSA-N 0.000 description 1
- VBIKLMJHBGFTPV-UHFFFAOYSA-N 3-ethoxyphenol Chemical class CCOC1=CC=CC(O)=C1 VBIKLMJHBGFTPV-UHFFFAOYSA-N 0.000 description 1
- YYMPIPSWQOGUME-UHFFFAOYSA-N 3-propoxyphenol Chemical class CCCOC1=CC=CC(O)=C1 YYMPIPSWQOGUME-UHFFFAOYSA-N 0.000 description 1
- CYEKUDPFXBLGHH-UHFFFAOYSA-N 3-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC(O)=C1 CYEKUDPFXBLGHH-UHFFFAOYSA-N 0.000 description 1
- SGJZXXPWUDGJSV-UHFFFAOYSA-N 4,6-bis[2-(4-hydroxyphenyl)propan-2-yl]benzene-1,3-diol Chemical compound C=1C(C(C)(C)C=2C=CC(O)=CC=2)=C(O)C=C(O)C=1C(C)(C)C1=CC=C(O)C=C1 SGJZXXPWUDGJSV-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- LKVFCSWBKOVHAH-UHFFFAOYSA-N 4-Ethoxyphenol Chemical class CCOC1=CC=C(O)C=C1 LKVFCSWBKOVHAH-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- CLAQXRONBVEWMK-UHFFFAOYSA-N 4-[(2-hydroxyphenyl)-(4-hydroxy-2,3,5-trimethylphenyl)methyl]-2,3,6-trimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C=2C(=CC=CC=2)O)C=2C(=C(C)C(O)=C(C)C=2)C)=C1C CLAQXRONBVEWMK-UHFFFAOYSA-N 0.000 description 1
- AYKNBEUSHQHYSX-UHFFFAOYSA-N 4-[(4-ethoxyphenyl)diazenyl]-n,n-diethylaniline Chemical compound C1=CC(OCC)=CC=C1N=NC1=CC=C(N(CC)CC)C=C1 AYKNBEUSHQHYSX-UHFFFAOYSA-N 0.000 description 1
- YNICUQBUXHBYCH-UHFFFAOYSA-N 4-[(4-hydroxy-2,5-dimethylphenyl)-(2-hydroxyphenyl)methyl]-2,5-dimethylphenol Chemical compound C1=C(O)C(C)=CC(C(C=2C(=CC=CC=2)O)C=2C(=CC(O)=C(C)C=2)C)=C1C YNICUQBUXHBYCH-UHFFFAOYSA-N 0.000 description 1
- BMCUJWGUNKCREZ-UHFFFAOYSA-N 4-[(4-hydroxy-3,5-dimethylphenyl)-(2-hydroxyphenyl)methyl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C=2C=C(C)C(O)=C(C)C=2)C=2C(=CC=CC=2)O)=C1 BMCUJWGUNKCREZ-UHFFFAOYSA-N 0.000 description 1
- MOXSMAJIGCIVQY-UHFFFAOYSA-N 4-[(5-amino-3-methyl-1-phenylpyrazol-4-yl)diazenyl]phenol Chemical compound CC1=NN(C=2C=CC=CC=2)C(N)=C1N=NC1=CC=C(O)C=C1 MOXSMAJIGCIVQY-UHFFFAOYSA-N 0.000 description 1
- TWCUWADOIBLGAU-UHFFFAOYSA-N 4-[2-[3-[2-(2,4-dihydroxyphenyl)propan-2-yl]-2-hydroxy-5-methylphenyl]propan-2-yl]benzene-1,3-diol Chemical compound C=1C(C)=CC(C(C)(C)C=2C(=CC(O)=CC=2)O)=C(O)C=1C(C)(C)C1=CC=C(O)C=C1O TWCUWADOIBLGAU-UHFFFAOYSA-N 0.000 description 1
- QBFWOUJDPJACIQ-UHFFFAOYSA-N 4-[2-[4-[1,1-bis(4-hydroxy-3-methylphenyl)ethyl]phenyl]propan-2-yl]-2-methylphenol Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=CC(=CC=2)C(C)(C=2C=C(C)C(O)=CC=2)C=2C=C(C)C(O)=CC=2)=C1 QBFWOUJDPJACIQ-UHFFFAOYSA-N 0.000 description 1
- WXYSZTISEJBRHW-UHFFFAOYSA-N 4-[2-[4-[1,1-bis(4-hydroxyphenyl)ethyl]phenyl]propan-2-yl]phenol Chemical compound C=1C=C(C(C)(C=2C=CC(O)=CC=2)C=2C=CC(O)=CC=2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WXYSZTISEJBRHW-UHFFFAOYSA-N 0.000 description 1
- SIDYFHJPUCRHJY-UHFFFAOYSA-N 4-[2-[4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]phenyl]propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=CC(=CC=2)C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 SIDYFHJPUCRHJY-UHFFFAOYSA-N 0.000 description 1
- FVLYIHYVIMGFNV-UHFFFAOYSA-N 4-[[2-hydroxy-5-methyl-3-[(2,3,4-trihydroxyphenyl)methyl]phenyl]methyl]benzene-1,2,3-triol Chemical compound OC=1C(CC=2C(=C(O)C(O)=CC=2)O)=CC(C)=CC=1CC1=CC=C(O)C(O)=C1O FVLYIHYVIMGFNV-UHFFFAOYSA-N 0.000 description 1
- ZXBUEKCCOHOCGJ-UHFFFAOYSA-N 4-[[3-[(2,4-dihydroxy-5-methylphenyl)methyl]-2-hydroxy-5-methylphenyl]methyl]-6-methylbenzene-1,3-diol Chemical compound OC=1C(CC=2C(=CC(O)=C(C)C=2)O)=CC(C)=CC=1CC1=CC(C)=C(O)C=C1O ZXBUEKCCOHOCGJ-UHFFFAOYSA-N 0.000 description 1
- CQKQINNUKSBEQR-UHFFFAOYSA-N 4-[[4-(dimethylamino)phenyl]diazenyl]phenol Chemical compound CN(C)c1ccc(cc1)N=Nc1ccc(O)cc1 CQKQINNUKSBEQR-UHFFFAOYSA-N 0.000 description 1
- LBDYXGSGBKXKIL-UHFFFAOYSA-N 4-[[4-hydroxy-3-[(4-hydroxy-3,5-dimethylphenyl)methyl]-5-methylphenyl]methyl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(CC=2C=C(CC=3C=C(C)C(O)=C(C)C=3)C(O)=C(C)C=2)=C1 LBDYXGSGBKXKIL-UHFFFAOYSA-N 0.000 description 1
- UWFUILMHBCVIMK-UHFFFAOYSA-N 4-[bis(4-hydroxy-3,5-dimethylphenyl)methyl]benzene-1,2-diol Chemical compound CC1=C(O)C(C)=CC(C(C=2C=C(O)C(O)=CC=2)C=2C=C(C)C(O)=C(C)C=2)=C1 UWFUILMHBCVIMK-UHFFFAOYSA-N 0.000 description 1
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 description 1
- JAGRUUPXPPLSRX-UHFFFAOYSA-N 4-prop-1-en-2-ylphenol Chemical class CC(=C)C1=CC=C(O)C=C1 JAGRUUPXPPLSRX-UHFFFAOYSA-N 0.000 description 1
- KIIIPQXXLVCCQP-UHFFFAOYSA-N 4-propoxyphenol Chemical class CCCOC1=CC=C(O)C=C1 KIIIPQXXLVCCQP-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical class COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- SJJISKLXUJVZOA-UHFFFAOYSA-N Solvent yellow 56 Chemical compound C1=CC(N(CC)CC)=CC=C1N=NC1=CC=CC=C1 SJJISKLXUJVZOA-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical class OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical class C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 229940117916 cinnamic aldehyde Drugs 0.000 description 1
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 229940109262 curcumin Drugs 0.000 description 1
- 235000012754 curcumin Nutrition 0.000 description 1
- 239000004148 curcumin Substances 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- KVFDZFBHBWTVID-UHFFFAOYSA-N cyclohexanecarbaldehyde Chemical compound O=CC1CCCCC1 KVFDZFBHBWTVID-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- VFLDPWHFBUODDF-UHFFFAOYSA-N diferuloylmethane Natural products C1=C(O)C(OC)=CC(C=CC(=O)CC(=O)C=CC=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical class CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229960004337 hydroquinone Drugs 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- OVWYEQOVUDKZNU-UHFFFAOYSA-N m-tolualdehyde Chemical compound CC1=CC=CC(C=O)=C1 OVWYEQOVUDKZNU-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical class COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 229940100595 phenylacetaldehyde Drugs 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
Definitions
- the present invention relates to a positive photoresist composition that is excellent in sensitivity and definition and is advantageously used for patterning a resist with less shrink.
- photoresist materials that can form an ultrafine resist pattern of not more than half a micrometer, particularly of not more than 0.35 ⁇ m.
- positive photoresist compositions each comprising an alkali-soluble novolak resin and a non-benzophenone naphthoquinonediazido-group-containing compound (a photosensitizer) have been proposed.
- Japanese Patent Laid-Open No. 6-167805 mentions that a positive photoresist material using an esterified product between a tetra- to hepta-nuclear linear polyphenol compound and a naphthoquinonediazidosulfonic acid compound is a high-definition material for use in photolithography processes using i-line.
- Photolithography processes using short-wavelength light sources such as KrF excimer laser (248 nm) and ArF excimer laser (193 nm) are suitable for the formation of resist patterns of not more than 0.35 ⁇ m.
- manufacturing lines using these light sources require a large amount of spending on new plants and equipment, and such spending is nearly unrecoverable.
- an object of the present invention is to solve the above problems and to provide a positive photoresist composition that is excellent in sensitivity and definition and can form a resist pattern with less shrink upon shifting of the focus even in the formation of an ultrafine resist pattern of not more than 0.35 ⁇ m.
- a positive photoresist composition containing an alkali-soluble resin, a specific quinonediazide ester (a photosensitizer) and a specific compound (a sensitizer) is excellent in sensitivity and definition and causes less shrink.
- the present invention has been accomplished based on these findings.
- the present invention provides a positive photoresist composition including (A) an alkali-soluble resin, (B) a photosensitizer including a quinonediazide ester between a naphthoquinonediazidosulfonic acid compound and at least one of a compound represented by following Formula (I):
- R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom or an alkyl group having from 1 to 3 carbon atoms, and a compound represented by following Formula (II):
- R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are each independently a hydrogen atom, an alkyl group having from 1 to 3 carbon atoms or a cyclohexyl group, and (C) a sensitizer including at least one of a compound represented by following Formula (III):
- the compound represented by Formula (I) in the positive photoresist composition is preferably a compound represented by the following formula:
- the compound represented by Formula (II) is preferably a compound represented by the following formula:
- the compound represented by Formula (III) is preferably a compound represented by the following formula:
- the compound represented by Formula (III) is preferably a compound represented by the following formula:
- the present invention can therefore provide a positive photoresist composition that is excellent in sensitivity and definition and can form a resist pattern with less shrink upon shifting of the focus even in the formation of an ultrafine resist pattern of not more than 0.35 ⁇ m.
- Alkali-soluble resins for use as the ingredient (A) are not specifically limited and can be optionally chosen from those generally used as film-forming substances in positive photoresist compositions. Of these resins, condensates of aromatic hydroxy compounds and aldehydes or ketones, polyhydroxystyrenes and derivatives thereof are preferable.
- aromatic hydroxy compounds include, but are not limited to, phenol, m-cresol, p-cresol, o-cresol, and other cresols; 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, and other xylenols ; m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,3,5-triethylphenol, 4-tert-butylphenol, 3-tert-butylphenol, 2-tert-butylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butyl-5-methylphenol, and other alkyl-substituted phenols; p-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol, p-propoxyphenol, m-propoxyphenol, and other alkyl-
- the aldehydes include, but are not limited to, formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, butylaldehyde, trimethylacetaldehyde, acrolein (acrylaldehyde), crotonaldehyde, cyclohexanealdehyde, furfural, furylacrolein, benzaldehyde, terephthalaldehyde, phenylacetaldehyde, ⁇ -phenylpropylaldehyde, ⁇ -phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, m-
- Each of these aldehydes can be used alone or in combination.
- formaldehyde is desirable for its availability.
- the combination use of a hydroxybenzaldehyde and formaldehyde is specifically preferred in order to improve heat resistance.
- the ketones include, for example, acetone, methyl ethyl ketone, diethyl ketone, and diphenyl ketone. Each of these ketones may be used alone or in combination. Further, an appropriate combination of an aldehyde and a ketone can be employed.
- the condensate of an aromatic hydroxy compound and an aldehyde or a ketone can be prepared in the presence of an acidic catalyst according to a known technique.
- acidic catalysts include, but are not limited to, hydrochloric acid, sulfuric acid, formic acid, oxalic acid, and p-toluenesulfonic acid.
- the polyhydroxystyrenes and derivatives thereof include, but are not limited to, vinylphenol homopolymers, and copolymers of vinylphenol and a copolymerizable comonomer.
- Such comonomers include, for example, acrylic acid derivatives, acrylonitrile, methacrylic acid derivatives, methacrylonitrile, styrene, ⁇ -methylstyrene, p-methylstyrene, o-methylstyrene, p-methoxystyrene, p-chlorostyrene, and other styrene derivatives.
- alkali-soluble resins for use in the present invention as the ingredient (A), preferred resins are alkali-soluble novolak resins each having a weight average molecular weight (Mw) of from 2000 to 20000, and typically from 3000 to 12000. These alkali-soluble resins preferably have a molecular weight dispersion (Mw/Mn) of from 2 to 5.
- alkali-soluble novolak resins obtained by a condensation reaction of m-cresol and p-cresol with formaldehyde and alkali-soluble novolak resins obtained by a condensation reaction of m-cresol, p-cresol and 2,3,5-trimethylphenol with formaldehyde are preferred to yield positive photoresist compositions having high sensitivity and wide exposure margin.
- an ester (hereinafter referred to as “quinonediazide ester”) of a napthoquinonediazidosulfonic acid compound with at least one of the compounds represented by Formulae (I) and (II) is used as the ingredient (B) (photosensitizer).
- the ingredient (B) photosensitizer
- the quinonediazide ester of the compound represented by Formula (I) has an average esterification rate of preferably from 25% to 90% and more preferably from 45% to 75%. If the average esterification rate is less than 25%, the resulting photoresist composition may exhibit deteriorated film residual rate and definition, and in contrast, if it exceeds 90%, the photoresist composition may exhibit deteriorated sensitivity and increased scum.
- the quinonediazide ester of the compound represented by Formula (II) has an average esterification rate of preferably from 20% to 90% and more preferably from 30% to 80%. If the average esterification rate is less than 20%, the resulting photoresist composition may exhibit deteriorated film residual rate and definition, and in contrast, if it exceeds 90%, the photoresist composition may exhibit deteriorated sensitivity and increased scum.
- the resulting positive photoresist composition has further improved sensitivity and definition and causes less shrink.
- the resulting positive photoresist composition has further improved sensitivity and definition and causes less shrink.
- the positive photoresist composition of the present invention may further comprise additional quinonediazide esters as the ingredient (B) according to necessity, in addition to the quinonediazide esters of the compounds represented by Formulae (I) and (II).
- additional quinonediazide esters include, but are not limited to, quinonediazide esters of polyphenol compounds represented by following Formula (IV):
- R 19 to R 26 are each independently a hydrogen atom, a halogen atom, an alkyl group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, or a cycloalkyl group
- R 27 to R 29 are each independently a hydrogen atom or an alkyl group having from 1 to 6 carbon atoms
- Q is a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms, or Q is combined with R 27 to form a cyclic ring having from 3 to 6 carbon atoms, or a residue represented by the following formula:
- R 30 and R 31 are each independently a hydrogen atom, a halogen atom, an alkyl group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, or a cycloalkyl group; and c is an integer of from 1 to 3; a and b are each an integer of from 1 to 3; d is an integer of from 0 to 3; and n is an integer of from 0 to 3.
- Such polyphenol compounds include, for example, linear trinuclear compounds, linear tetranuclear compounds, linear pentanuclear compounds, and trisphenol polyphenol compounds, other than the compounds represented by Formulae (I) and (II).
- the amount of these additional quinonediazide esters is preferably less than or equal to 75% by weight, and more preferably less than or equal to 50% by weight based on the weight of the ingredient (B). If the amount of the additional quinonediazide esters exceeds 75% by weight, the resulting positive photoresist composition may have deteriorated definition.
- the content of the ingredient (B) in the positive photoresist composition of the present invention is preferably from 20% to 60% by weight, and more preferably from 30% to 50% by weight relative to the total weight of the alkali-soluble resin ingredient (A) and the sensitizer (intensifier) ingredient (C) described below. If the content of the ingredient (B) is less than 20% by weight, images in exact accordance with patterns may not be obtained, and transferring property may be deteriorated. In contrast, if the content exceeds 60% by weight, sensitivity and uniformity of the resulting resist film tend to be deteriorated to thereby deteriorate definition.
- the sensitizer (intensifier) for use in the present invention is an alkali-soluble low molecular weight compound having a molecular weight of less than or equal to about 1000 and having a phenolic hydroxyl group.
- the specific compound represented by Formula (III) as the sensitizer (C) is used in combination with the specific quinonediazide esters.
- the resulting positive photoresist composition has high definition, causes less shrink and is therefore suitable in the fields of the formation of complicated circuit traces such as in logical ICs.
- the resulting positive photoresist composition has further improved sensitivity and definition and causes less shrink.
- the compound represented by Formula (III) is preferably a compound represented by the following formula:
- the resulting positive photoresist composition has further improved sensitivity and definition and causes less shrink.
- the positive photoresist composition may further comprise additional alkali-soluble low molecular weight compounds each having a phenolic hydroxyl group as the ingredient (C), in addition to the compounds represented by Formula (III).
- Such low molecular weight compounds include, for example, the polyphenol compounds represented by Formula (IV), such as 2,6-bis(2,5-dimethyl-4-hydroxyphenylmethyl)-4-methylphenol, bis(4-hydroxy-2,3,5-trimethylphenyl)-2-hydroxyphenylmethane, 1,4-bis[1-(3,5-dimethyl-4-hydroxyphenyl)isopropyl]benzene, 2,4-bis(3,5-dimethyl-4-hydroxyphenylmethyl)-6-methylphenol, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, 1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl]benzen
- the content of these additional alkali-soluble low molecular weight compounds each having a phenolic hydroxyl group, if any, is preferably less than or equal to 75% by weight and more preferably less than or equal to 50% by weight based on the total weight of the ingredient (C). If the content exceeds 75% by weight, the formation of shrink may not effectively be suppressed.
- the amount of the ingredient (C) is preferably from 20% to 50% by weight and more preferably from 30% to 40% by weight, relative to the weight of the ingredient (A) alkali-soluble resin.
- the positive photoresist composition of the present invention may further comprise any of compatible additives including, for example, ultraviolet absorbents for inhibition of halation and surfactants for prevention of striation within ranges not adversely affecting the objects of the invention.
- Such ultraviolet absorbents include, for example, 2,2′4,4′-tetrahydroxybenzophenone, 4-dimethylamino-2′,4′-dihydroxybenzophenone, 5-amino-3-methyl-1-phenyl-4-(4-hydroxyphenylazo)pyrazole, 4-dimethylamino-4′-hydroxyazobenzene, 4-diethylamino-4′-ethoxyazobenzene, 4-diethylaminoazobenzene and curcumin.
- the surfactants include, but are not limited to, Fluorad FC-430 and FC-431 (trade names, available from Fluorochemical-Sumitomo 3M Co.), EFTOP EF122A, EF122B, EF122C and EF126 (trade names, available from Tohkem Products Corporation) and other fluorine-containing surfactants.
- the positive photoresist composition of the present invention is preferably used as a solution prepared by dissolving each of the ingredients (A), (B) and (C) and other additional ingredients in an appropriate solvent.
- solvents include those conventionally used in positive photoresist compositions, such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone, and other ketones; ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol monoacetate, or monomethyl ethers, monoethyl ethers, monopropyl ethers, monobutyl ethers or monophenyl ethers thereof, and other polyhydric alcohols and derivatives thereof; dioxane and other cyclic ethers; and ethyl lactate, methyl acetate, ethyl acetate, butyl acetate,
- solvents can be used alone or in combination.
- typically preferred solvents are acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone, and other ketones; and ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, and other esters.
- the positive photoresist composition of the present invention may preferably be used, for example, in the following manner: Each of the ingredients (A), (B) and (C) and other ingredients added according to necessity is dissolved in an appropriate solvent as mentioned above to yield a coating solution; the coating solution is then applied, using a spinner or the like, onto a substrate such as a silicon wafer or a substrate carrying an anti-reflection coating formed thereon, and is then dried to form a photosensitive layer; next, the photosensitive layer is irradiated with and is exposed to light through a desired mask pattern; and the exposed portions of the film are then dissolved and removed by dipping the substrate in a developer solution, for example, an alkaline aqueous solution such as a 1% to 10% by weight tetramethylammonium hydroxide (TMAH) aqueous solution, thus forming an image being in exact accordance with the mask pattern.
- TMAH tetramethylammonium hydroxide
- a sample was applied onto a silicon wafer using a spinner, and was dried on a hot plate at 90° C. for 90 sec. to form a resist film 1.0 ⁇ m thick.
- the film was then post-exposure baked (PEB) at 110° C.
- the sensitivity was defined as the exposure time period (Eop) in milliseconds (ms) to exactly reproduce a 0.35- ⁇ m mask pattern with a line-and-space (L&S) width of 1:1.
- the definition was defined as the critical definition at an exposure to reproduce a 0.35- ⁇ m mask pattern.
- a sample was applied onto a silicon wafer using a spinner and was dried on a hot plate at 90° C. for 90 sec. to form a resist film 1.0- ⁇ m thick.
- the resist film was irradiated at the optimum exposure time period (Eop) under the condition that the focus was shifted 1.0 ⁇ m from the optimum position of the focus toward the minus side (the upper side of the substrate).
- the film was then post-exposure baked (PEB) at 110° C. for 90 sec.; was subjected to developing in a 2.38% by weight tetramethylammonium hydroxide aqueous solution at 23° C. for 60 sec., was rinsed with water for 30 sec., and was dried.
- the shrink was evaluated in accordance with the following criteria by taking the lengths in a longitudinal direction of the two resist traces at both ends of the five parallel resist traces as an index.
- Mw weight average molecular weight
- Mw/Mn molecular weight distribution
- a series of positive photoresist compositions was prepared in the same manner as in Example 1, except that the ingredients (B) and (C) used in Example 1 were changed to those indicated in Table 1.
- Ingredient (B) Ingredient (C) (compositional (compositional ratio (wt. %)) ratio (wt.
- Example 1 b1 (100) c1 (100)
- Example 2 b2 (100) c1 (100)
- Example 3 b1 (100) c2 (100)
- Example 4 b1/b3 (80/20) c1 (100)
- Example 5 b1/b4 (80/20) c1 (100)
- Example 6 b1 (100) c1/c3 (50/50)
- Example 7 b1 (100) c1/c4 (50/50) Comp. Ex. 1 b1 (100) c5 (100) Comp. Ex. 2 b1 (100) c6 (100) Comp. Ex. 3 b1 (100) c7 (100) Comp. Ex. 4 b5 (100) c1 (100) Comp. Ex. 5 b6 (100) c1 (100)
- Table 2 shows that the photoresist compositions according to the present invention comprising the specific photosensitizers and sensitizers cause less shrink and are excellent in sensitivity and definition.
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
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- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A composition includes (A) an alkali-soluble resin, (B) a quinonediazide ester of a compound represented by the following formula:
This composition is a positive photoresist composition that is excellent in sensitivity and definition and causes less shrink.
Description
- This is a continuation of application Ser. No. 10/035,137 filed Jan. 4, 2002; the disclosure of which is incorporated herein by reference.
- 1. Field of the Invention
- The present invention relates to a positive photoresist composition that is excellent in sensitivity and definition and is advantageously used for patterning a resist with less shrink.
- 2. Description of the Related Art
- In photolithography processes using i-line (365 nm), demands have been made on photoresist materials that can form an ultrafine resist pattern of not more than half a micrometer, particularly of not more than 0.35 μm. As such photoresist materials, positive photoresist compositions each comprising an alkali-soluble novolak resin and a non-benzophenone naphthoquinonediazido-group-containing compound (a photosensitizer) have been proposed.
- For example, Japanese Patent Laid-Open No. 6-167805 mentions that a positive photoresist material using an esterified product between a tetra- to hepta-nuclear linear polyphenol compound and a naphthoquinonediazidosulfonic acid compound is a high-definition material for use in photolithography processes using i-line.
- Photolithography processes using short-wavelength light sources such as KrF excimer laser (248 nm) and ArF excimer laser (193 nm) are suitable for the formation of resist patterns of not more than 0.35 μm. However, manufacturing lines using these light sources require a large amount of spending on new plants and equipment, and such spending is nearly unrecoverable.
- Under these circumstances, strong demands have been made on the use of the photolithography processes using i-line (365 nm) from now on, which are widely used at present, and techniques of ultrafine processing of resist patterns of not more than 0.35 μm using photoresist materials for i-line irradiation have been examined.
- However, it has been believed that by using a light source having a wavelength greater than the size of the resulting resist pattern, a resist pattern having satisfactory sensitivity, definition, focal depth range properties and other properties cannot be obtained. For example, this type of resist patterns exhibits “shrink”, the phenomenon that the resist pattern shrinks in a length direction upon shifting of the focus on the order of submicron from an optimal position during exposure. The shrink is often observed in both edges of a resist pattern comprising regular line-and-space (L&S) traces or in an isolation pattern or irregular resist pattern. Accordingly, the resulting pattern in, for example, a logical IC having complicated traces cannot be obtained in a good yield.
- Accordingly, an object of the present invention is to solve the above problems and to provide a positive photoresist composition that is excellent in sensitivity and definition and can form a resist pattern with less shrink upon shifting of the focus even in the formation of an ultrafine resist pattern of not more than 0.35 μm.
- After intensive investigations to achieve the above objects, the present inventors have found that a positive photoresist composition containing an alkali-soluble resin, a specific quinonediazide ester (a photosensitizer) and a specific compound (a sensitizer) is excellent in sensitivity and definition and causes less shrink. The present invention has been accomplished based on these findings.
-
-
-
- wherein x is 0 or 1.
-
-
-
-
- In this connection, one type of the compounds represented by Formula (III) is disclosed as a sensitizer in Japanese Patent No. 2629990. However, such conventional technologies fail to disclose the combination use of the compound represented by Formula (III) with the compound represented by Formula (I) and/or the compound represented by Formula (II).
- The present invention can therefore provide a positive photoresist composition that is excellent in sensitivity and definition and can form a resist pattern with less shrink upon shifting of the focus even in the formation of an ultrafine resist pattern of not more than 0.35 μm.
- The present invention will be illustrated in detail below.
- Ingredient (A): Alkali-Soluble Resin
- Alkali-soluble resins for use as the ingredient (A) are not specifically limited and can be optionally chosen from those generally used as film-forming substances in positive photoresist compositions. Of these resins, condensates of aromatic hydroxy compounds and aldehydes or ketones, polyhydroxystyrenes and derivatives thereof are preferable.
- Such aromatic hydroxy compounds include, but are not limited to, phenol, m-cresol, p-cresol, o-cresol, and other cresols; 2,3-xylenol, 2,5-xylenol, 3,5-xylenol, 3,4-xylenol, and other xylenols ; m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,3,5-triethylphenol, 4-tert-butylphenol, 3-tert-butylphenol, 2-tert-butylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butyl-5-methylphenol, and other alkyl-substituted phenols; p-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol, p-propoxyphenol, m-propoxyphenol, and other alkoxy-substituted phenols; o-isopropenylphenol, p-isopropenylphenol, 2-methyl-4-isopropenylphenol, 2-ethyl-4-isopropenylphenol, and other isopropenyl-substituted phenols; phenylphenol, and other aryl-substituted phenols; 4,4′-dihydroxybiphenyl, bisphenol A, resorcinol, hydroquinone, pyrogallol, and other polyhydroxyphenols. Each of these compounds can be used alone or in combination.
- The aldehydes include, but are not limited to, formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, butylaldehyde, trimethylacetaldehyde, acrolein (acrylaldehyde), crotonaldehyde, cyclohexanealdehyde, furfural, furylacrolein, benzaldehyde, terephthalaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, and cinnamaldehyde. Each of these aldehydes can be used alone or in combination. Of these aldehydes, formaldehyde is desirable for its availability. The combination use of a hydroxybenzaldehyde and formaldehyde is specifically preferred in order to improve heat resistance.
- The ketones include, for example, acetone, methyl ethyl ketone, diethyl ketone, and diphenyl ketone. Each of these ketones may be used alone or in combination. Further, an appropriate combination of an aldehyde and a ketone can be employed.
- The condensate of an aromatic hydroxy compound and an aldehyde or a ketone can be prepared in the presence of an acidic catalyst according to a known technique. Such acidic catalysts include, but are not limited to, hydrochloric acid, sulfuric acid, formic acid, oxalic acid, and p-toluenesulfonic acid.
- The polyhydroxystyrenes and derivatives thereof include, but are not limited to, vinylphenol homopolymers, and copolymers of vinylphenol and a copolymerizable comonomer. Such comonomers include, for example, acrylic acid derivatives, acrylonitrile, methacrylic acid derivatives, methacrylonitrile, styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, p-methoxystyrene, p-chlorostyrene, and other styrene derivatives.
- Of these alkali-soluble resins for use in the present invention as the ingredient (A), preferred resins are alkali-soluble novolak resins each having a weight average molecular weight (Mw) of from 2000 to 20000, and typically from 3000 to 12000. These alkali-soluble resins preferably have a molecular weight dispersion (Mw/Mn) of from 2 to 5. Among them, alkali-soluble novolak resins obtained by a condensation reaction of m-cresol and p-cresol with formaldehyde, and alkali-soluble novolak resins obtained by a condensation reaction of m-cresol, p-cresol and 2,3,5-trimethylphenol with formaldehyde are preferred to yield positive photoresist compositions having high sensitivity and wide exposure margin.
- Ingredient (B): Photosensitizer
- According to the present invention, an ester (hereinafter referred to as “quinonediazide ester”) of a napthoquinonediazidosulfonic acid compound with at least one of the compounds represented by Formulae (I) and (II) is used as the ingredient (B) (photosensitizer). By this configuration, the resulting positive photoresist composition has excellent definition.
- The quinonediazide ester of the compound represented by Formula (I) has an average esterification rate of preferably from 25% to 90% and more preferably from 45% to 75%. If the average esterification rate is less than 25%, the resulting photoresist composition may exhibit deteriorated film residual rate and definition, and in contrast, if it exceeds 90%, the photoresist composition may exhibit deteriorated sensitivity and increased scum.
- The quinonediazide ester of the compound represented by Formula (II) has an average esterification rate of preferably from 20% to 90% and more preferably from 30% to 80%. If the average esterification rate is less than 20%, the resulting photoresist composition may exhibit deteriorated film residual rate and definition, and in contrast, if it exceeds 90%, the photoresist composition may exhibit deteriorated sensitivity and increased scum.
-
- By using this compound, the resulting positive photoresist composition has further improved sensitivity and definition and causes less shrink.
-
- By using this compound, the resulting positive photoresist composition has further improved sensitivity and definition and causes less shrink.
- The positive photoresist composition of the present invention may further comprise additional quinonediazide esters as the ingredient (B) according to necessity, in addition to the quinonediazide esters of the compounds represented by Formulae (I) and (II). Such quinonediazide esters include, but are not limited to, quinonediazide esters of polyphenol compounds represented by following Formula (IV):
-
- wherein R30 and R31 are each independently a hydrogen atom, a halogen atom, an alkyl group having from 1 to 6 carbon atoms, an alkoxy group having from 1 to 6 carbon atoms, or a cycloalkyl group; and c is an integer of from 1 to 3; a and b are each an integer of from 1 to 3; d is an integer of from 0 to 3; and n is an integer of from 0 to 3. Such polyphenol compounds include, for example, linear trinuclear compounds, linear tetranuclear compounds, linear pentanuclear compounds, and trisphenol polyphenol compounds, other than the compounds represented by Formulae (I) and (II).
- The amount of these additional quinonediazide esters, if any, is preferably less than or equal to 75% by weight, and more preferably less than or equal to 50% by weight based on the weight of the ingredient (B). If the amount of the additional quinonediazide esters exceeds 75% by weight, the resulting positive photoresist composition may have deteriorated definition.
- The content of the ingredient (B) in the positive photoresist composition of the present invention is preferably from 20% to 60% by weight, and more preferably from 30% to 50% by weight relative to the total weight of the alkali-soluble resin ingredient (A) and the sensitizer (intensifier) ingredient (C) described below. If the content of the ingredient (B) is less than 20% by weight, images in exact accordance with patterns may not be obtained, and transferring property may be deteriorated. In contrast, if the content exceeds 60% by weight, sensitivity and uniformity of the resulting resist film tend to be deteriorated to thereby deteriorate definition.
- Ingredient (C): Sensitizer
- the sensitizer (intensifier) for use in the present invention is an alkali-soluble low molecular weight compound having a molecular weight of less than or equal to about 1000 and having a phenolic hydroxyl group.
- According to the present invention, the specific compound represented by Formula (III) as the sensitizer (C) is used in combination with the specific quinonediazide esters. By this configuration, the resulting positive photoresist composition has high definition, causes less shrink and is therefore suitable in the fields of the formation of complicated circuit traces such as in logical ICs.
-
- By using this compound, the resulting positive photoresist composition has further improved sensitivity and definition and causes less shrink.
-
- By using this compound, the resulting positive photoresist composition has further improved sensitivity and definition and causes less shrink.
- The positive photoresist composition may further comprise additional alkali-soluble low molecular weight compounds each having a phenolic hydroxyl group as the ingredient (C), in addition to the compounds represented by Formula (III).
- Such low molecular weight compounds include, for example, the polyphenol compounds represented by Formula (IV), such as 2,6-bis(2,5-dimethyl-4-hydroxyphenylmethyl)-4-methylphenol, bis(4-hydroxy-2,3,5-trimethylphenyl)-2-hydroxyphenylmethane, 1,4-bis[1-(3,5-dimethyl-4-hydroxyphenyl)isopropyl]benzene, 2,4-bis(3,5-dimethyl-4-hydroxyphenylmethyl)-6-methylphenol, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, 1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene, 1-[1-(3-methyl-4-hydroxyphenyl)isopropyl]-4-[1,1-bis(3-methyl-4-hydroxyphenyl)ethyl]benzene, 2,6-bis[1-(2,4-dihydroxyphenyl)isopropyl]-4-methylphenol, 4,6-bis[1-(4-hydroxyphenyl)isopropyl]resorcin, 4,6-bis(3,5-dimethoxy-4-hydroxyphenylmethyl)pyrogallol, 4,6-bis(3,5-dimethyl-4-hydroxyphenylmethyl)pyrogallol, 2,6-bis(3-methyl-4,6-dihydroxyphenylmethyl)-4-methylphenol, 2,6-bis(2,3,4-trihydroxyphenylmethyl)-4-methylphenol, and 1,1-bis(4-hydroxyphenyl)cyclohexane.
- The content of these additional alkali-soluble low molecular weight compounds each having a phenolic hydroxyl group, if any, is preferably less than or equal to 75% by weight and more preferably less than or equal to 50% by weight based on the total weight of the ingredient (C). If the content exceeds 75% by weight, the formation of shrink may not effectively be suppressed.
- The amount of the ingredient (C) is preferably from 20% to 50% by weight and more preferably from 30% to 40% by weight, relative to the weight of the ingredient (A) alkali-soluble resin.
- In addition to the above specified ingredients, where necessary, the positive photoresist composition of the present invention may further comprise any of compatible additives including, for example, ultraviolet absorbents for inhibition of halation and surfactants for prevention of striation within ranges not adversely affecting the objects of the invention. Such ultraviolet absorbents include, for example, 2,2′4,4′-tetrahydroxybenzophenone, 4-dimethylamino-2′,4′-dihydroxybenzophenone, 5-amino-3-methyl-1-phenyl-4-(4-hydroxyphenylazo)pyrazole, 4-dimethylamino-4′-hydroxyazobenzene, 4-diethylamino-4′-ethoxyazobenzene, 4-diethylaminoazobenzene and curcumin. The surfactants include, but are not limited to, Fluorad FC-430 and FC-431 (trade names, available from Fluorochemical-Sumitomo 3M Co.), EFTOP EF122A, EF122B, EF122C and EF126 (trade names, available from Tohkem Products Corporation) and other fluorine-containing surfactants.
- The positive photoresist composition of the present invention is preferably used as a solution prepared by dissolving each of the ingredients (A), (B) and (C) and other additional ingredients in an appropriate solvent. Such solvents include those conventionally used in positive photoresist compositions, such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone, and other ketones; ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol monoacetate, or monomethyl ethers, monoethyl ethers, monopropyl ethers, monobutyl ethers or monophenyl ethers thereof, and other polyhydric alcohols and derivatives thereof; dioxane and other cyclic ethers; and ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, and other esters. Each of these solvents can be used alone or in combination. Of these solvents, typically preferred solvents are acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone, and other ketones; and ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, and other esters.
- Practically, the positive photoresist composition of the present invention may preferably be used, for example, in the following manner: Each of the ingredients (A), (B) and (C) and other ingredients added according to necessity is dissolved in an appropriate solvent as mentioned above to yield a coating solution; the coating solution is then applied, using a spinner or the like, onto a substrate such as a silicon wafer or a substrate carrying an anti-reflection coating formed thereon, and is then dried to form a photosensitive layer; next, the photosensitive layer is irradiated with and is exposed to light through a desired mask pattern; and the exposed portions of the film are then dissolved and removed by dipping the substrate in a developer solution, for example, an alkaline aqueous solution such as a 1% to 10% by weight tetramethylammonium hydroxide (TMAH) aqueous solution, thus forming an image being in exact accordance with the mask pattern.
- The present invention will be further illustrated in detail with reference to several examples and comparative examples below which are not intended to limit the scope of the invention. The properties of the resulting positive photoresist compositions were evaluated by the following methods, and the results are shown in Table 2.
- (1) Sensitivity
- A sample was applied onto a silicon wafer using a spinner, and was dried on a hot plate at 90° C. for 90 sec. to form a resist film 1.0 μm thick. The resist film was then irradiated with light through a mask (reticle) corresponding to a 0.35-μm resist pattern with a line-and-space (L&S) width of 1:1 for an increasing period from 0.1 sec. at intervals of 0.01 sec. using a reducing-type projection aligner NSR-2005i10D (available from Nikon Corporation, Japan; NA=0.57). The film was then post-exposure baked (PEB) at 110° C. for 90 sec.; was subjected to developing in a 2.38% by weight tetramethylammonium hydroxide aqueous solution at 23° C. for 60 sec., was rinsed with water for 30 sec., and was dried. In this procedure, the sensitivity was defined as the exposure time period (Eop) in milliseconds (ms) to exactly reproduce a 0.35-μm mask pattern with a line-and-space (L&S) width of 1:1.
- (2) Definition
- The definition was defined as the critical definition at an exposure to reproduce a 0.35-μm mask pattern.
- (3) Shrink Evaluation
- A sample was applied onto a silicon wafer using a spinner and was dried on a hot plate at 90° C. for 90 sec. to form a resist film 1.0-μm thick. The resist film was then irradiated with light through a mask (reticle) corresponding to five parallel resist traces 0.35-μm wide and 1.0-μm long with a line-and-space (L&S) width of 1:1 for an increasing period from 0.1 sec. at intervals of 0.01 sec. using a reducing-type projection aligner NSR-2005i10D (available from Nikon Corporation, Japan; NA=0.57).
- In this procedure, the resist film was irradiated at the optimum exposure time period (Eop) under the condition that the focus was shifted 1.0 μm from the optimum position of the focus toward the minus side (the upper side of the substrate).
- The film was then post-exposure baked (PEB) at 110° C. for 90 sec.; was subjected to developing in a 2.38% by weight tetramethylammonium hydroxide aqueous solution at 23° C. for 60 sec., was rinsed with water for 30 sec., and was dried. In this procedure, the shrink was evaluated in accordance with the following criteria by taking the lengths in a longitudinal direction of the two resist traces at both ends of the five parallel resist traces as an index.
- Criteria on Shrink Evaluation
- Excellent: The lengths of the resulting traces were equal to or more than 0.9 μm and less than or equal to 1.0 μm, indicating that almost no shrink occurred.
- Good: The lengths of the resulting traces were equal to or more than 0.8 μm and less than 0.9 μm, indicating that some shrink occurred.
- Fair: The lengths of the resulting traces were equal to or more than 0.7 μm and less than 0.8 μm.
- Failure: The lengths of the resulting traces were less than 0.7 μm.
- Ingredient (A): An alkali-soluble resin comprising 50 parts by weight of a novolak resin (a1) and 50 parts by weight of a novolak resin (a2). The novolak resin (a1) had a weight average molecular weight (Mw) in terms of polystyrene of 5000 and a molecular weight distribution (Mw/Mn) of 3.0 and was prepared from m-cresol/p-cresol/2,3,5-trimethylphenol=35/40/25 (by mole of charged material) using formaldehyde as a condensing agent. The novolak resin (a2) had a weight average molecular weight (Mw) in terms of polystyrene of 5000 and a molecular weight distribution (Mw/Mn) of 3.0 and was prepared from m-cresol/p-cresol=42.5/57.5 (by mole of charged material) using formaldehyde as a condensing agent.
-
-
- In 510 parts by weight of solvent mixture [ethyl lactate/butyl acetate=9/1 (by weight)], 100 parts by weight of the ingredient (A), 50 parts by weight of the ingredient (B), and 30 parts by weight of the ingredient (C) were dissolved, the resulting solution was filtrated through a 0.2-μm membrane filter and thereby yielded a positive photoresist composition.
- A series of positive photoresist compositions was prepared in the same manner as in Example 1, except that the ingredients (B) and (C) used in Example 1 were changed to those indicated in Table 1.
TABLE 1 Ingredient (B) Ingredient (C) (compositional (compositional ratio (wt. %)) ratio (wt. %)) Example 1 b1 (100) c1 (100) Example 2 b2 (100) c1 (100) Example 3 b1 (100) c2 (100) Example 4 b1/b3 (80/20) c1 (100) Example 5 b1/b4 (80/20) c1 (100) Example 6 b1 (100) c1/c3 (50/50) Example 7 b1 (100) c1/c4 (50/50) Comp. Ex. 1 b1 (100) c5 (100) Comp. Ex. 2 b1 (100) c6 (100) Comp. Ex. 3 b1 (100) c7 (100) Comp. Ex. 4 b5 (100) c1 (100) Comp. Ex. 5 b6 (100) c1 (100) -
-
-
-
- b5: A reaction product (esterification rate: 67%) between 1 mole of 2,3,4-trihydroxybenzophenone and 2 moles of 5-NQD.
- b6: A reaction product (esterification rate: 75%) of 1 mole of 2,3,4,4′-tetrahydroxybenzophenone and 3 moles of 5-NQD.
-
-
-
-
-
-
-
- Table 2 shows that the photoresist compositions according to the present invention comprising the specific photosensitizers and sensitizers cause less shrink and are excellent in sensitivity and definition.
- Other embodiments and variations will be obvious to those skilled in the art, and this invention is not to be limited to the specific matters stated above.
Claims (4)
1. A positive photoresist composition comprising;
(A) an alkali-soluble resin;
(B) a photosensitizer comprising a quinonediazide ester between a naphthoquinonediazidosulfonic acid compound and a compound represented by following Formula (I):
wherein R1, R2, R3, R4, R5, R6, R7 and R8 are each independently a hydrogen atom or an alkyl group having from 1 to 3 carbon atoms, and
(C) a sensitizer comprising at least one of compounds represented by following Formula (III):
wherein x is 0 or 1.
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KR20130032071A (en) * | 2011-09-22 | 2013-04-01 | 주식회사 동진쎄미켐 | I-line photoresist composition and method of forming fine pattern using the same |
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-
2002
- 2002-01-04 TW TW091100079A patent/TWI263864B/en not_active IP Right Cessation
- 2002-01-04 US US10/035,137 patent/US6964838B2/en not_active Expired - Fee Related
- 2002-01-15 KR KR10-2002-0002258A patent/KR100531593B1/en not_active IP Right Cessation
- 2002-01-16 DE DE10201452A patent/DE10201452A1/en not_active Withdrawn
-
2003
- 2003-12-23 US US10/742,878 patent/US20040137359A1/en not_active Abandoned
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5652081A (en) * | 1995-09-20 | 1997-07-29 | Fuji Photo Film Co., Ltd. | Positive working photoresist composition |
US5738968A (en) * | 1996-03-25 | 1998-04-14 | Tokyo Ohka Kogyo Co., Ltd. | Positive photoresist composition |
US5985507A (en) * | 1998-02-18 | 1999-11-16 | Olin Microelectronic Chemicals, Inc. | Selected high thermal novolaks and positive-working radiation-sensitive compositions |
US20020132178A1 (en) * | 2001-01-17 | 2002-09-19 | Tokyo Ohka Kogyo Co., Ltd. | Positive photoresist composition |
Also Published As
Publication number | Publication date |
---|---|
US20020132178A1 (en) | 2002-09-19 |
KR100531593B1 (en) | 2005-11-28 |
TWI263864B (en) | 2006-10-11 |
DE10201452A1 (en) | 2002-09-26 |
KR20020062161A (en) | 2002-07-25 |
US6964838B2 (en) | 2005-11-15 |
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Legal Events
Date | Code | Title | Description |
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STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |