CN104749905A - 定向自组装图案形成方法和组合物 - Google Patents
定向自组装图案形成方法和组合物 Download PDFInfo
- Publication number
- CN104749905A CN104749905A CN201410858452.3A CN201410858452A CN104749905A CN 104749905 A CN104749905 A CN 104749905A CN 201410858452 A CN201410858452 A CN 201410858452A CN 104749905 A CN104749905 A CN 104749905A
- Authority
- CN
- China
- Prior art keywords
- layer
- pattern
- self
- group
- crosslinked
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 60
- 238000002408 directed self-assembly Methods 0.000 title claims abstract description 30
- 230000007261 regionalization Effects 0.000 title description 2
- 125000003118 aryl group Chemical group 0.000 claims abstract description 26
- 239000004065 semiconductor Substances 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 238000000059 patterning Methods 0.000 claims abstract description 9
- 125000000524 functional group Chemical group 0.000 claims abstract description 6
- 125000005647 linker group Chemical group 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims description 53
- 239000000126 substance Substances 0.000 claims description 52
- 239000000178 monomer Substances 0.000 claims description 38
- 239000000463 material Substances 0.000 claims description 35
- 229920001577 copolymer Polymers 0.000 claims description 25
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 238000001259 photo etching Methods 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 150000001721 carbon Chemical group 0.000 claims description 3
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 238000007385 chemical modification Methods 0.000 claims 1
- 238000000137 annealing Methods 0.000 abstract description 15
- 238000004132 cross linking Methods 0.000 abstract description 15
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 229920001400 block copolymer Polymers 0.000 abstract description 3
- 229920006037 cross link polymer Polymers 0.000 abstract description 3
- 238000013500 data storage Methods 0.000 abstract description 2
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 60
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 56
- 239000010410 layer Substances 0.000 description 42
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 31
- -1 vinyl BCB Chemical compound 0.000 description 29
- 229910052757 nitrogen Inorganic materials 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 239000000243 solution Substances 0.000 description 26
- 239000002904 solvent Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 16
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 15
- 239000003963 antioxidant agent Substances 0.000 description 14
- 230000008569 process Effects 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 235000006708 antioxidants Nutrition 0.000 description 13
- 238000001914 filtration Methods 0.000 description 13
- 239000004094 surface-active agent Substances 0.000 description 13
- 230000003078 antioxidant effect Effects 0.000 description 11
- 125000004494 ethyl ester group Chemical group 0.000 description 10
- 239000003999 initiator Substances 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 9
- 229920002120 photoresistant polymer Polymers 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 7
- DTGDMPJDZKDHEP-UHFFFAOYSA-N 4-ethenylbicyclo[4.2.0]octa-1(6),2,4-triene Chemical compound C=CC1=CC=C2CCC2=C1 DTGDMPJDZKDHEP-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- 238000004528 spin coating Methods 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 5
- 239000004926 polymethyl methacrylate Substances 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000005240 physical vapour deposition Methods 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000000206 photolithography Methods 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 2
- 125000006274 (C1-C3)alkoxy group Chemical group 0.000 description 2
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N 2-Methylheptane Chemical compound CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 2
- RXGUIWHIADMCFC-UHFFFAOYSA-N 2-Methylpropyl 2-methylpropionate Chemical compound CC(C)COC(=O)C(C)C RXGUIWHIADMCFC-UHFFFAOYSA-N 0.000 description 2
- CFAKWWQIUFSQFU-UHFFFAOYSA-N 2-hydroxy-3-methylcyclopent-2-en-1-one Chemical compound CC1=C(O)C(=O)CC1 CFAKWWQIUFSQFU-UHFFFAOYSA-N 0.000 description 2
- LAIUFBWHERIJIH-UHFFFAOYSA-N 3-Methylheptane Chemical compound CCCCC(C)CC LAIUFBWHERIJIH-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 2
- 229920003026 Acene Polymers 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001312 dry etching Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 description 2
- ZOCHHNOQQHDWHG-UHFFFAOYSA-N hexan-3-ol Chemical compound CCCC(O)CC ZOCHHNOQQHDWHG-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- VOMJJZIGGPFTCI-UHFFFAOYSA-N n-tert-butyl-n-(2-methyl-1-phenylpropyl)hydroxylamine Chemical class CC(C)(C)N(O)C(C(C)C)C1=CC=CC=C1 VOMJJZIGGPFTCI-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- NMRPBPVERJPACX-UHFFFAOYSA-N octan-3-ol Chemical compound CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- JCZPMGDSEAFWDY-SQOUGZDYSA-N (2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanamide Chemical compound NC(=O)[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO JCZPMGDSEAFWDY-SQOUGZDYSA-N 0.000 description 1
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- JAMNSIXSLVPNLC-UHFFFAOYSA-N (4-ethenylphenyl) acetate Chemical compound CC(=O)OC1=CC=C(C=C)C=C1 JAMNSIXSLVPNLC-UHFFFAOYSA-N 0.000 description 1
- LFNVRNWBMJBTKZ-UHFFFAOYSA-N 1-fluorohexan-1-ol Chemical compound CCCCCC(O)F LFNVRNWBMJBTKZ-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- RLPGDEORIPLBNF-UHFFFAOYSA-N 2,3,4-trimethylpentane Chemical compound CC(C)C(C)C(C)C RLPGDEORIPLBNF-UHFFFAOYSA-N 0.000 description 1
- SKDGWNHUETZZCS-UHFFFAOYSA-N 2,3-ditert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(O)=C1C(C)(C)C SKDGWNHUETZZCS-UHFFFAOYSA-N 0.000 description 1
- MXSKJYLPNPYQHH-UHFFFAOYSA-N 2,4-dimethyl-6-(1-methylcyclohexyl)phenol Chemical compound CC1=CC(C)=C(O)C(C2(C)CCCCC2)=C1 MXSKJYLPNPYQHH-UHFFFAOYSA-N 0.000 description 1
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 description 1
- TUIWMHDSXJWXOH-UHFFFAOYSA-N 2,5-dimethylhexan-3-one Chemical group CC(C)CC(=O)C(C)C TUIWMHDSXJWXOH-UHFFFAOYSA-N 0.000 description 1
- HNURKXXMYARGAY-UHFFFAOYSA-N 2,6-Di-tert-butyl-4-hydroxymethylphenol Chemical compound CC(C)(C)C1=CC(CO)=CC(C(C)(C)C)=C1O HNURKXXMYARGAY-UHFFFAOYSA-N 0.000 description 1
- BVUXDWXKPROUDO-UHFFFAOYSA-N 2,6-di-tert-butyl-4-ethylphenol Chemical compound CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BVUXDWXKPROUDO-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- IEORSVTYLWZQJQ-UHFFFAOYSA-N 2-(2-nonylphenoxy)ethanol Chemical compound CCCCCCCCCC1=CC=CC=C1OCCO IEORSVTYLWZQJQ-UHFFFAOYSA-N 0.000 description 1
- QNVRIHYSUZMSGM-LURJTMIESA-N 2-Hexanol Natural products CCCC[C@H](C)O QNVRIHYSUZMSGM-LURJTMIESA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- AKNMPWVTPUHKCG-UHFFFAOYSA-N 2-cyclohexyl-6-[(3-cyclohexyl-2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound OC=1C(C2CCCCC2)=CC(C)=CC=1CC(C=1O)=CC(C)=CC=1C1CCCCC1 AKNMPWVTPUHKCG-UHFFFAOYSA-N 0.000 description 1
- 239000001837 2-hydroxy-3-methylcyclopent-2-en-1-one Substances 0.000 description 1
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-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
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 description 1
- KUMXLFIBWFCMOJ-UHFFFAOYSA-N 3,3-dimethylhexane Chemical class CCCC(C)(C)CC KUMXLFIBWFCMOJ-UHFFFAOYSA-N 0.000 description 1
- IEJUDCCSASQBJM-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid;octadecane Chemical compound CCCCCCCCCCCCCCCCCC.CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O IEJUDCCSASQBJM-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- NMRPBPVERJPACX-QMMMGPOBSA-N 3-Octanol Natural products CCCCC[C@@H](O)CC NMRPBPVERJPACX-QMMMGPOBSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 1
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 6-tert-butyl-m-cresol Natural products CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 1
- OOVQLEHBRDIXDZ-UHFFFAOYSA-N 7-ethenylbicyclo[4.2.0]octa-1,3,5-triene Chemical compound C1=CC=C2C(C=C)CC2=C1 OOVQLEHBRDIXDZ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 description 1
- AQZGPSLYZOOYQP-UHFFFAOYSA-N Diisoamyl ether Chemical compound CC(C)CCOCCC(C)C AQZGPSLYZOOYQP-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229920000028 Gradient copolymer Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical class COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910003089 Ti–OH Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 239000006117 anti-reflective coating Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 229920001585 atactic polymer Polymers 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- UMIVXZPTRXBADB-UHFFFAOYSA-N benzocyclobutene Chemical compound C1=CC=C2CCC2=C1 UMIVXZPTRXBADB-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical class CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 235000019282 butylated hydroxyanisole Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 229960005082 etohexadiol Drugs 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 229910000078 germane Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229930182478 glucoside Natural products 0.000 description 1
- 150000008131 glucosides Chemical class 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- BGYICJVBGZQOCY-UHFFFAOYSA-N heptyl propanoate Chemical compound CCCCCCCOC(=O)CC BGYICJVBGZQOCY-UHFFFAOYSA-N 0.000 description 1
- GOKKOFHHJFGZHW-UHFFFAOYSA-N hexyl propanoate Chemical compound CCCCCCOC(=O)CC GOKKOFHHJFGZHW-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000000671 immersion lithography Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- RGFNRWTWDWVHDD-UHFFFAOYSA-N isobutyl butyrate Chemical group CCCC(=O)OCC(C)C RGFNRWTWDWVHDD-UHFFFAOYSA-N 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- XURVRZSODRHRNK-UHFFFAOYSA-N o-quinodimethane Chemical compound C=C1C=CC=CC1=C XURVRZSODRHRNK-UHFFFAOYSA-N 0.000 description 1
- WOFPPJOZXUTRAU-UHFFFAOYSA-N octan-4-ol Chemical compound CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 150000002931 p-cresols Chemical class 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- TWSRVQVEYJNFKQ-UHFFFAOYSA-N pentyl propanoate Chemical compound CCCCCOC(=O)CC TWSRVQVEYJNFKQ-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000885 poly(2-vinylpyridine) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-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
- 238000000746 purification Methods 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 description 1
- FVEFRICMTUKAML-UHFFFAOYSA-M sodium tetradecyl sulfate Chemical compound [Na+].CCCCC(CC)CCC(CC(C)C)OS([O-])(=O)=O FVEFRICMTUKAML-UHFFFAOYSA-M 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1803—C3-(meth)acrylate, e.g. (iso)propyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/32—Monomers containing only one unsaturated aliphatic radical containing two or more rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1807—C7-(meth)acrylate, e.g. heptyl (meth)acrylate or benzyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/16—Homopolymers or copolymers of alkyl-substituted styrenes
-
- 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
-
- 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
- G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/38—Treatment before imagewise removal, e.g. prebaking
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02118—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/02227—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process
- H01L21/02255—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by thermal treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
- C08F220/302—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and two or more oxygen atoms in the alcohol moiety
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Computer Hardware Design (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
一种通过定向自组装形成图案的方法,包括:(a)提供半导体基材,其包括一个或多个将被图案化的层;(b)在一个或多个将被图案化的层上施加可交联的底层组合物以形成可交联底层,其中所述可交联的底层组合物包括可交联聚合物,其包括具有以下通式(I-A)或(I-B)的第一单元:其中:P是可聚合官能团;L是单键或m+1价连接基团;X1是单价供电子基团;X2是二价供电子基团;Ar1和Ar2分别为三价和二价芳基,且环丁烯的环碳原子与Ar1或Ar2的相同芳环上的邻近碳原子键合;m和n均为1以上的整数;且每个R1是独立的单价基团;(c)加热可交联底层以形成交联的底层;(d)在交联的底层上形成包括嵌段共聚物的自组装层;和(e)将自组装层退火。所述方法和组合物被发现特别适用于形成高分辨率图案的半导体装置和数据存储装置的制备。
Description
本申请以根据35U.S.C.§119(e)要求2013年12月31日提出的美国临时申请No.61/922,767为优先权,其全部内容通过引用全部并入本申请。
技术领域
本发明一般涉及电子设备的制造。更具体地,本发明涉及通过定向自组装形成图案的方法,以及用于该方法的底层组合物。所述方法和组合物适用于例如半导体设备制造中精细图案的形成,或适用于数据存储如硬盘驱动器的制备。
背景技术
在半导体制造工业中,使用光致抗蚀剂材料的光学光刻技术是将图像转移到设置在半导体基材上的一个或多个底层,例如金属层、半导体层和介电层,以及基材本身的标准技术。为了提高半导体设备的集成度并允许形成具有纳米范围尺寸的结构,具有高分辨率能力的光致抗蚀剂和光刻加工工具已经被开发。目前的先进光学光刻技术的制造标准是193nm浸没式光刻。然而,这种方法的物理分辨率极限使得其难于直接形成超过大约36nm半-节距线和空间图形的图案。虽然EUV光学曝光工具被发展用于产生更高分辨率的图案,但是这样的工具的价格惊人且此技术的采用仍然为不确定的。
定向自组装(DSA)工艺被用于将分辨率极限提高到超过目前的光学光刻技术,例如,到小于15nm。DSA工艺依赖于某些类型的嵌段共聚物在基材表面上退火重排为有序结构的能力。所述嵌段共聚物的重排基于所述嵌段中的一种嵌段与底层表面上的预形成图案的亲合力。
已知的用于DSA底层的可交联聚合物系统包括无规聚合物,其包括乙烯基苯并环丁烯(BCB)和苯乙烯。这样的聚合物被公开于,例如,Du Yeol Ryu等的“A Generalized Approach to the modification of Solid Surfaces”,《Science》,第308卷,第236页(2005)。然而,由于需要相对高的退火温度(例如,大约250℃)和/或长的退火时间以诱导通过异构化环丁烯的环与反应性邻奎诺二甲烷(o-quinodimethane)中间体的交联,因此包含乙烯基BCB的聚合物在DSA底层中的广泛应用受到了限制。高交联温度的使用会通过导致这些层的热降解和/或氧化对底层造成不利影响,底层包括例如,抗反射涂层和硬掩模。高交联温度进一步会造成去湿,导致图案成形差,和由氧化引起的表面能变化。另外,较高的交联温度会限制其他用于DSA底层组合物中的官能化单体的种类。高的交联温度对于以下情况来说是不利的:需要更复杂的加热工具处理基材来提供惰性气氛环境,以阻止不想要的会造成底层的表面能的增加的氧化发生。因此,需要提供允许底层组合物在相当短的时间低温交联的DSA工艺,以及用于该工艺的可交联聚合物和底层组合物。
存在对定向自组装工艺的持续需求,和对可交联聚合物和包括这样的聚合物的DSA底层组合物的需求,其解决了一个或多个与现有技术相关的问题。
发明概述
根据本发明的第一方面,提供了一种通过定向自组装形成图案的方法。所述方法包括:(a)提供半导体基材,其包括一个或多个将被图案化的层;(b)在所述一个或多个将被图案化的层上施加可交联的底层组合物,以形成可交联底层,其中所述可交联底层组合物包括可交联聚合物,该聚合物包括具有以下通式(I-A)或(I-B)的第一单元:
其中:P是可聚合官能团;L是单键或m+1价连接基团;X1是单价供电子基团;X2是二价供电子基团;Ar1和Ar2分别为三价和二价芳基,且环丁烯的环的碳原子与Ar1或Ar2的相同芳环上的邻近碳原子键合;m和n均为1以上的整数;且每个R1是独立的单价基团;(c)加热可交联底层以形成交联的底层;(d)在交联的底层上形成包括嵌段共聚物的自组装层;和(e)将自组装层退火。所述方法特别适用于在半导体装置的制备中形成高分辨率图案。
本文所使用的术语仅是为了描述特定的实施方式,且不被认为是对本发明的限制。在本文中使用的,单数形式的“一个”、“一种”和“所述”被认为也包括复数形式,除非上下文中另有说明。除非另有说明,用于聚合物的单元比率以摩尔%表示。
附图说明
下面将参考下列附图讨论本发明,其中同样的附图标记表示同样的特征,并且其中:
图1A-F显示了根据本发明的示例性DSA工艺相应流程的截面图和俯视图;和
图2A-C是在本发明的底层组合物上的自排列DSA层的原子力显微镜(AFM)图像。
具体实施方式
本发明的定向自组装(DSA)方法包括在一个或多个将被图案化的层上施加可交联的底层组合物。可交联的底层组合物包括可交联聚合物、溶剂,且可以包括一种或多种另外的任选组分。
可在所述组合物中使用的可交联聚合物可以为均聚物,或可以为具有多种不同重复单元的共聚物,例如,两种、三种、四种或更多不同的重复单元。通常地,可交联聚合物为共聚物。共聚物可以为无规共聚物、嵌段共聚物或梯度共聚物,且典型地为无规共聚物。
可交联聚合物包括第一单元,其包括稠合到环丁烯环的芳香基团,下文中称为“芳基环丁烯”。所述芳香基团可以包括单个或多个芳香环,例如,一个、两个、三个、四个或更多芳香环。当多个芳香环存在于所述单元内时,芳香环可以自己形成稠合(例如萘基、蒽基、芘基)和/或栓系(例如联苯)结构。所述芳香基团是可任选被取代的,例如,被一个或多个烷基、环烷基或卤素取代。环丁烯基团是可任选被取代的,例如,由一个或多个羟基、烷氧基、胺或酰胺取代。
可交联聚合物包括以下通式(I-A)或(I-B)表示的单元:
其中,P为可聚合官能基团,例如,乙烯基、(烷基)丙烯酸酯或环烯烃;L为单键或m+1-价连接基团,其选自可任选取代的线性或支化脂肪族和芳香族烃,和它们的组合,任选地具有一个或多个连接部分,选自例如,-O-、-S-、-COO-、-CONR3-、-CONH-和-OCONH-,其中R3选自氢和取代和未取代的C1到C10线性、支化或环状烃,优选为烷基;X1选自单价供电子基团,例如,C1-C10烷氧基、胺、硫、-OCOR9、-NHCOR10-,其中R9选自取代和未取代的C1到C10线性、支化和环状烃,R10选自取代和未取代的C1到C10线性、支化和环状烃;X2选自二价供电子基团,例如,-O-、-S-、-COO-、-CONR11-、-CONH-和-OCONH-,其中R11选自氢和取代和未取代的C1到C10线性、支化或环状烃,优选为烷基,优选为-O-;Ar1和Ar2分别为三价和二价芳基,且环丁烯的环碳原子与Ar1或Ar2的相同芳环上的邻近碳原子键合;且m和n均为1以上的整数;每个R1为独立的单价基团。优选地,Ar1和Ar2包括1、2或3个芳香碳环或杂芳环。优选地,芳基包括单芳环,且更优选地为苯环。芳基任选地由1到3个基团取代,所述基团选自(C1-C6)烷基、(C1-C6)烷氧基、和卤素,优选地由一个或多个(C1-C6)烷基、(C1-C3)烷氧基、和氯取代,且更优选地由一个或多个(C1-C3)烷基和(C1-C3)烷氧基取代。优选地芳基为未取代的。优选地m=1或2,且更优选地m=1。优选地n=1-4,更优选地n=1或2,且进一步优选地n=1。优选地,R1选自H和(C1-C6)烷基,且更优选地选自H和(C1-C3)烷基。优选地,R2选自单键、(C1-C6)亚烷基,且更优选地选自单键和(C1-C3)亚烷基。为了清楚的目的,当m和n大于1,通式(I-A)和(I-B)中限定的不同基团中存在多个这样的基团时,可以对这些基团各自独立地进行选择。
可聚合官能基团P可以选自,例如,以下通式(II-A)和(II-B):
其中R4选自氢、氟、C1-C3烷基、和C1-C3氟烷基;且X为氧或由结构式NR5表示,其中R5选自氢和取代和未取代的C1到C10线性、支化和环状烃;且
其中R6选自氢、氟、C1-C3烷基、和C1-C3氟烷基。另外的适合的可聚合官能基团包括,例如,降冰片烯、环硅氧烷、环醚、烷氧基硅烷、酚醛树脂、官能团例如苯酚和/或醛、羧酸、醇和胺。
用于本发明的芳基环丁烯单体可以通过任何合适的方法准备,例如在M.Azadi-Ardakani等的3,6-Dimethoxybenzocyclobutenone:A Reagent for QuinoneSynthesis,Tetrahedron,第44卷,第18期,第5939-5952页,1988;J.Dobish等,Polym.Chem.,2012,3,857-860(2012);美国专利第4540763,4812588,5136069和5138081;和国际专利申请公开号WO94/25903中所描述的。用于制备单体的芳基环丁烯是商业可获得的,CycloteneTM牌,购于陶氏化学公司。
适合的芳基环丁烯单体包括,例如,形成以下聚合单元的那些:
第一单元通常存在于自交联聚合物中,其量为从1到100摩尔%,例如从1到50摩尔%、从2到20摩尔%、或从3到10摩尔%,基于聚合物的量。
可交联聚合物可以包括一种或多种其它单元。聚合物可以,例如,包括一种或多种能够调整自交联聚合物的表面能,光学特性(例如n和k值)和/或玻璃态转变温度的其它单元。通过为聚合物选择合适的单元,所述聚合物可以制成对覆盖在底层上的DSA嵌段共聚物的特定嵌段具有亲合性,或对DSA嵌段共聚物的每个嵌段均为中性的。合适的单元包括,例如,选自以下通式(III)和(IV)的一个或多个单元:
其中R11独立地选自氢、氟、C1-C3烷基、和C1-C3氟烷基,R12选自任选地取代的C1到C10烷基;和Ar3为芳基。优选地,Ar3包括1、2或3个芳香碳环和/或杂芳环。优选地,芳基包括单芳香环,且更优选地为苯环。芳基任选地由例如(C1-C6)烷基、(C1-C6)烷氧基或卤素取代。优选地芳基为未取代的。
其它单元的示例性的合适的结构包括以下的:
所述一个或多个其它单元如果存在于自交联聚合物中,可以以高达99摩尔%的量使用,优选地从80到98摩尔%,基于聚合物的量。
可交联聚合物优选地具有小于100,000的重均分子量Mw,优选地Mw为1,000到50,000。可交联聚合物通常的多分散指数(PDI=Mw/Mn)为小于2.0,且更优选为小于1.8。分子量,Mw和Mn的确定都可以通过例如采用通用的校准方法的凝胶渗透色谱法,并以聚苯乙烯标样校准。
优选地,聚合物交联的起始温度(T0)为小于250℃,优选地从100到225℃,更优选地从100到200℃。这样的相对低的起始温度将使得聚合物的交联在相对低的温度和时间下进行,通过这样避免或最小化上述的在使用较高的起始温度和交联温度时可能发生的问题。
可交联聚合物通常以从80到100wt%的量存在于底层组合物中,例如,从90到100wt%或从95到100wt%,基于组合物的总固体量。
合适的无规可交联聚合物包括,例如,以下的(比率为摩尔%):
其中单元比率基于聚合物的量以摩尔%计。
所述底层组合物进一步包括溶剂,其可以包括单一溶剂或溶剂混合物。配制或铸塑底层组合物的合适的溶剂材料对于组合物中的非溶剂组分表现出很好的溶解性,但是不会明显地溶解基材表面的接触底层组合物的下层材料。溶剂通常地选自水、水性溶液、有机溶剂和其混合物。用于底层组合物的合适的有机溶剂包括,例如:醇例如直链、支化或环状C4-C9一元醇,如1-丁醇、2-丁醇、异丁醇、叔丁醇、2-甲基-1-丁醇、1-戊醇、2-戊醇、4-甲基-2-戊醇、1-己醇、1-庚醇、1-辛醇、2-己醇、2-庚醇、2-辛醇、3-己醇、3-庚醇、3-辛醇和4-辛醇;2,2,3,3,4,4-六氟-1-丁醇、2,2,3,3,4,4,5,5-八氟-1-戊醇和2,2,3,3,4,4,5,5,6,6-十氟-1-己醇,和C5-C9氟化二元醇,如2,2,3,3,4,4-六氟-1,5-戊二醇、2,2,3,3,4,4,5,5,-八氟-1,6-己二醇和2,2,3,3,4,4,5,5,6,6,7,7-十二氟-1,8-辛二醇;烷基酯如乙酸烷基酯如乙酸正丁基酯,丙酸酯例如丙酸正丁基酯、丙酸正戊基酯、丙酸正己基酯和丙酸正庚基酯,和丁酸烷基酯例如丁酸正丁基酯、丁酸异丁基酯和异丁酸异丁基酯;酮例如2,5-二甲基-4-己酮和2,6-二甲基-4-庚酮;脂肪族烃例如n-庚烷、n-壬烷、n-辛烷、n-癸烷、2-甲基庚烷、3-甲基庚烷、3,3-二甲基己烷和2,3,4-三甲基戊烷,和氟化脂肪族烃例如全氟庚烷;醚例如异戊醚和双丙二醇单甲基醚;和包含一种或多种这些溶剂的混合物。这些有机溶剂中,醇、脂肪族烃和醚是优选的。组合物中的溶剂组分通常以从80到99wt%的量存在,更典型地,从90到99wt%或从95到99wt%的量,基于底层组合物的总重量。
所述底层组合物可以包括一种或多种任选的添加剂,包括例如,表面活性剂和抗氧化剂。典型的表面活性剂包括那些表现出两亲性的,意思是它们可以同时是既亲水又疏水的。两亲性表面活性剂具有亲水性端部基团或多个亲水性端部基团,其对于水具有强烈的亲合力且包括长的疏水性尾部,该尾部亲有机物质且斥水。合适的表面活性剂可以是离子型的(即阳离子、阴离子)或非离子型的。表面活性剂的进一步的示例包括硅酮表面活性剂、聚(环氧烷)表面活性剂、和含氟化合物表面活性剂。合适的非离子型表面活性剂包括但是不限于,辛基苯酚乙氧基化物和壬基苯酚乙氧基化物如X-114、X-110、X-45、X-15和支化仲醇乙氧基化物如TERGITOLTMTMN-6(陶氏化学公司,米德兰,美国密歇根州)。进一步的表面活性剂的示例包括醇(伯醇和仲醇)乙氧基化物、胺乙氧基化物、葡糖苷、葡糖胺、聚乙二醇、聚(乙二醇-共-丙二醇)或McCutcheon’s Emulsifiers and Detergents(North American Edition for theYear 2000,由Manufacturers Confectioners Publishing Co.of Glen Rock,N.J出版)公开的其他表面活性剂。非离子表面活性剂如炔二醇衍生物也是适合的。这样的表面活性剂可从宾夕法尼亚州阿伦敦的空气产品和化学品有限公司(Air Products and Chemicals,Inc.ofAllentown)商业获得,以商品名和销售。其他适合的表面活性剂包括其它聚合物如三嵌段EO-PO-EO共聚物25R2、L121、L123、L31、L81、L101和P123(巴斯夫公司(BASF,Inc.))。这样的表面活性剂和其他任选的添加剂(如果使用的话)通常以较小的量存在于所述组合物中,如基于底层组合物的总固体量从0.01到10wt%。
在底层组合物中可加入抗氧化剂以阻止或最小化底层组合物中的有机材料的氧化。适合的抗氧化剂包括,例如,酚基抗氧化剂、由有机酸衍生物组成的抗氧化剂、含硫的抗氧化剂、磷基抗氧化剂、胺基抗氧化剂、由胺醛缩合物组成的抗氧化剂和由胺酮缩合物组成的抗氧化剂。酚基抗氧化剂的示例包括取代苯酚如1-氧-3-甲基-4-异丙基苯、2,6-二叔丁基酚、2,6-二叔丁基-4-乙基酚、2,6-二叔丁基-4-甲基酚、4-羟甲基-2,6-二叔丁基酚、丁基羟基苯甲醚、2-(1-甲基环己基)-4,6-二甲基酚、2,4-二甲基-6-叔丁基酚、2-甲基-4,6-二壬基酚、2,6-二叔丁基-α-二甲氨基对甲酚、6-(4-羟基-3,5-二叔丁基苯胺基)2,4-二辛基-硫-1,3,5-三嗪、3-(4’羟基3’,5’-二叔丁基苯基)丙酸正十八烷基酯、辛基化酚、芳烷基取代酚、烷基化对甲酚和受阻酚;双、三和聚酚如4,4’-二羟基二苯基、亚甲基-双(二甲基-4,6-酚)、2,2’-亚甲基-双-(4-甲基-6-叔丁基酚)、2,2’-亚甲基-双-(4-甲基-6-环己基酚)、2,2’-亚甲基-双-(4-乙基-6-叔丁基酚)、4,4’-亚甲基-双-(2,6-二-叔丁基酚)、2,2’-亚甲基-双-(6-α-甲基-苯基-对甲酚)、亚甲基-交联的多价烷基酚、4,4’-亚丁基双-(3-甲基-6-叔丁基酚)、1,1-双-(4-羟苯基)-环己烷、2,2’-二羟基-3,3’-二-(α-甲基环己基)-5,5’-二甲基二苯基甲烷、烷基化双酚、受阻双酚、1,3,5-三甲基-2,4,6-三(3,5-二-叔丁基-4-羟苯基)苯,三-(2-甲基-4-羟基-5-叔丁基苯基)丁烷、和四-[亚甲基-3-(3’,5’-二-叔丁基-4’-羟苯基)丙酸酯]甲烷。合适的抗氧化剂是商业可获得的,例如,IrganoxTM抗氧化剂(汽巴专业化学公司(Ciba Specialty Chemicals Corp.))。如果使用的话,抗氧化剂以通常从0.01到10wt%的量存在于所述底层组合物中,基于底层组合物的总固体量。
因为聚合物是自交联的,底层组合物不需要附加的交联剂来影响聚合物的交联。优选地,所述底层组合物不含有这样的附加的交联剂。
所述底层组合物以下述已知过程制备。例如,所述组合物可以通过将组合物的固体成分溶解于溶剂成分中制备。需要的组合物的总固体量依赖于一些因素例如需要的最终层厚度。典型地,底层组合物的固体量为从0.05到10wt%,更典型地,从0.1到5wt%,基于组合物的总重量。
所述底层组合物在布置于基材上之前可以实施纯化步骤。纯化可以包括例如离心、过滤、蒸馏、倾析、蒸发、用离子交换珠处理等。
本发明的底层组合物被发现特别适用于DSA工艺中,其用作底层,与覆盖的DSA嵌段共聚物的嵌段具有亲合性,或其对于DSA嵌段共聚物的嵌段是中性的。所述组合物可以,例如用于需要这样的底层的化学外延(chemoepitaxy)工艺。
为了阐释的目的,本发明将参考图1A-F进行描述,其描述了根据本发明的示例性的DSA化学外延工艺流程。因为图1的示例性工艺中使用了本发明的底层组合物作为垫层,应该清楚的是其可替代的可以用作刷层或其他类型的底层。
图1A描述了基材100,其包括一个或多个在其表面上将被图案化的层。所述一个或多个将被图案化的层可以为底层的基材材料本身和/或一个或多个与基材材料不同的形成于基材上的层。基材可以为例如半导体的材料,如硅或化合物半导体(例如III-V或II-VI)、玻璃、石英、陶瓷、铜等。通常地,所述基材为半导体晶片,例如单晶硅或化合物半导体晶片,且可以具有一个或多个层且在其表面上形成有图案化的特征。基材上的层可以包括,例如,一个或多个传导层如铝、铜、钼、钽、钛、钨、合金、这些金属的氮化物或硅化物、掺杂的无定形硅或掺杂的多晶硅、无定形碳的层,一个或多个介电层如氧化硅、氮化硅、氧氮化硅、或金属氧化物的层,半导体层例如单晶硅、和它们的结合。所述层可以包括硬掩模层,例如含硅的或碳硬掩模层,或抗反射涂层例如底部抗反射涂层(BARC)。所述层可以通过多种技术制备,例如,化学气相沉积(CVD)如等离子体增强CVD、低压CVD或外延生长,物理气相沉积(PVD)例如溅射或蒸镀、电镀或通过旋涂。
这里所描述的底层组合物被施加于基材表面以形成底层102。所述底层组合物可以施加到基材,例如通过旋涂、浸渍、辊涂或其他传统的涂覆技术。在这些技术中,旋涂是典型的且优选的。对于旋涂来说,所述底层组合物的固体含量可以根据使用的特定涂覆设备、溶液粘度、涂覆工具的旋涂速度和旋涂的时间调节以提供想要的膜厚度。所述底层组合物的典型厚度为从2到15nm,优选的从5到10nm。
任选地,底层102可以接着进行软烘焙以将层内的溶剂含量最小化,由此形成无粘性涂层且改善所述层和基材之间的粘附。软烘焙可以在烤盘上或烤炉里进行,通常使用烤盘。软烘焙温度和时间依赖于,例如光致抗蚀剂的特定材料和厚度。软烘焙通常在从大约90到150℃的温度下进行,且时间为从大约30到120秒钟。
底层组合物层102在能够有效地引起可交联聚合物进行交联的温度和时间下加热以得到交联的聚合物网。交联烘烤可以在烤盘上或烤炉内进行。交联烘烤可以,例如在晶片轨迹的烤盘上进行,其也用于底层组合物的涂覆。交联烘烤温度和时间将依赖于,例如底层的特定结构和厚度。交联烘烤通常在从大约100到250℃的温度下进行,且持续从大约30秒到30分钟的时间,优选的为从30秒到5分钟,更优选的为从30秒到120秒。交联烘烤的进行例如可以通过在单一温度下加热底层、在烘烤过程中提高温度或使用阶梯形加热曲线。因为交联反应可以在相对低的温度下进行,烘烤可以在空气环境中进行,它也可以任选地在其他气氛下例如惰性气氛下进行。
交联的底层接着被图案化以形成引导图案。引导图案的图案化可以使用光刻和刻蚀方法完成,如图1B和1C所示。图案化可替代地可以通过化学法完成,例如,通过对底层的与引导图案相关或不相关的区域的酸催化极性转换来完成。适合的极性转换工艺和组合物的描述见美国专利申请公开US2012/0088188A1。
图案化通常通过光刻工艺完成,其中光致抗蚀剂组合物被覆盖在交联的底层上,且进行软烘焙以从所述层内去除溶剂。光致抗蚀剂层通常涂覆为从50nm到120nm的厚度。合适的光致抗蚀剂材料为本领域公知的和/或商业可获得的。光致抗蚀剂层通过图案化的光掩模曝光于活性辐射以图案化,且图像通过合适的显影剂,例如水基(例如2.38wt%TMAH)或有机溶剂显影剂进行显影。光致抗蚀剂通常为化学增强的且可以使用短波辐射(例如低于200nm辐射包括193nm和EUV辐射(例如13.5nm))或电子束进行成像。光致抗蚀剂可以为正性-或负性-作用。理想的是,抗蚀剂图案由负性显影(NTD)形成时,其中传统的正型光致抗蚀剂被成像并在有机溶剂显影剂中显影。得到的光致抗蚀剂图案104形成于交联的底层102上,如图1B所示。
光致抗蚀剂图案104接着通过刻蚀转移到底层102上,以形成下面的基材上通过开口分离的引导图案102’,如图1C所示。刻蚀工艺通常为采用合适的刻蚀化学法的干法刻蚀。合适的刻蚀化学包括例如,采用O2、CHF3、CF4、Ar、SF6和其结合的等离子体工艺。其中,氧和氟化等离子体刻蚀是典型的。任选地,刻蚀可以包括修整刻蚀以进一步减少引导图案的宽度以形成更精细的图案。引导图案的典型宽度为例如从1到30nm,且中心至中心的节距为从5到500nm。这对于例如针扎垫层来说是典型的。如果对于中性垫层,引导图案典型地具有例如从5到300nm的宽度,且中心至中心的节距为从12到500nm。
残留的光致抗蚀剂图案104采用合适的剥离剂从基材上移除,如图1D所示。合适的剥离剂为商业可获得的,且其包括例如,乳酸乙酯、γ戊内酯、γ丁内酯或N-甲基-2-吡咯烷酮(NMP)。
刷状组合物接着覆盖到基材上,这样它设置在引导图案之间形成的凹槽内以形成刷状层106,如图1E所示。为了使得刷状层和基材之间发生共价键合,基材通常在上表面链接有羟基。共价键合通常在基材的羟基如Si-OH(其中基材包括SiO2)或Ti-OH(其中基材包括TiO2)和刷状聚合物之间的缩合反应中发生。刷状聚合物和基材的共价连接通常例如通过旋涂刷状聚合物的溶液完成,所述刷状聚合物包括连接基团,其包括至少一个羟基作为聚合物主链的端基团或作为聚合物侧链的端基团。应该意识到可以使用其他的或可替代的技术来键合聚合物,例如,通过环氧基、酯基、羧酸基、酰胺基、硅氧烷基、或(甲基)丙烯酸酯基键合,其中这些官能基团还可以存在于聚合物内或通过表面处理连接到基材的表面上。刷状聚合物通常为无规共聚物,其选自例如,羟基封端的聚(2-乙烯基吡啶)、羟基封端的聚苯乙烯-无规-聚(甲基丙烯酸甲酯),或可以包含羟基苯乙烯或丙烯酸甲2-羟乙酯单元来代替封端的羟基。
刷状组合物层被加热,由此移除溶剂并使得聚合物与基材表面键合。加热以键合刷状层可以在任何适合的温度和时间实施,例如,通常在从70到250℃的温度下进行从30秒到2分钟的时间。
定向自组装层108接着在刷状层106和引导图案102’上形成,如图1F所示。自组装层包括嵌段共聚物,其具有与底层引导图案102’有亲合性的第一嵌段,和与引导图案没有亲合性的第二、分散(也称为“中性”)嵌段。如在本文中所用的,“与......有亲合性”的意思是第一嵌段是与引导图案表面能匹配且吸引的,这样在铸造和退火过程中,可移动的第一嵌段选择性地沉积在引导图案上并与引导图案对齐。在这种方式下,第一嵌段在底层上形成与引导图案对齐的第一微区。类似地,嵌段共聚物的第二、分散嵌段对于底层的引导图案的亲合性较小,在底层上形成了邻近第一微区对齐的第二微区。所述微区通常具有最短平均尺寸为1到100nm,例如,从5到75nm或从10到50nm。
嵌段可以通常为任何合适的区域-形成嵌段,另一不相似的嵌段可以连接其上。嵌段可以从不同的可聚合单体衍生得到,其中所述嵌段可以包括但不限于:聚烯烃包括聚二烯,聚醚包括聚(环氧烷)如聚(环氧乙烷)、聚(环氧丙烷)、聚(环氧丁烷),或这些物质的无规或嵌段共聚物;聚((甲基)丙烯酸酯),聚苯乙烯,聚酯,聚有机硅氧烷,聚有机锗烷,或由基于Fe、Sn、Al、或Ti如聚(有机苯基甲硅烷基二茂铁)的可聚合有机金属单体制备的有机金属聚合物。
嵌段共聚物的嵌段可以,例如包括单体C2-30烯单体,从C1-30醇衍生得到的(甲基)丙烯酸酯单体,含无机物的单体,其包括那些基于Fe、Si、Ge、Sn、Al、Ti的单体,或包括至少一种前述单体的组合。用于嵌段的示例性单体可以包括,如C2-30烯单体、乙烯、丙烯、1-丁烯、1,3-丁二烯、异戊二烯、乙酸乙烯酯、二氢吡喃、降冰片烯、马来酸酐、苯乙烯、4-羟基苯乙烯、4-乙酰氧基苯乙烯、4-甲基苯乙烯、或α-甲基苯乙烯;且可以包括如(甲基)丙烯酸酯单体、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸异丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸正戊酯、(甲基)丙烯酸异戊酯、(甲基)丙烯酸新戊酯、(甲基)丙烯酸正己酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸异冰片酯、或(甲基)丙烯酸羟乙酯。可以使用这些单体中的两种或多种的结合。
有用的嵌段共聚物包括至少两种嵌段,且可以为双嵌段、三嵌段、四嵌段等具有离散嵌段的共聚物。示例性嵌段共聚物包括聚苯乙烯-b-聚乙烯吡啶、聚苯乙烯-b-聚丁二烯、聚苯乙烯-b-聚异戊二烯、聚苯乙烯-b-聚甲基丙烯酸甲酯、聚苯乙烯-b聚链烯基芳香烃、聚异戊二烯-b-聚环氧乙烷、聚苯乙烯-b-聚(乙烯-丙烯)、聚环氧乙烷-b-聚己内酯、聚丁二烯-b-聚环氧乙烷、聚苯乙烯-b-聚(叔丁基(甲基)丙烯酸酯)、聚甲基丙烯酸甲酯-b-聚(甲基丙烯酸叔丁酯)、聚环氧乙烷-b-聚环氧丙烷、聚苯乙烯-b-聚四氢呋喃、聚苯乙烯-b-聚异戊二烯-b-聚环氧乙烷、聚(苯乙烯-b-二甲基硅氧烷)、聚(甲基丙烯酸甲酯-b-二甲基硅氧烷)、聚((甲基)丙烯酸甲酯-r-苯乙烯)-b-聚甲基丙烯酸甲酯、聚((甲基)丙烯酸甲酯-r-苯乙烯)-b-聚苯乙烯、聚(对羟基苯乙烯-r-苯乙烯)-b-聚甲基丙烯酸甲酯、聚(对羟基苯乙烯-r-苯乙烯)-b-聚环氧乙烷、聚异戊二烯-b-聚苯乙烯-b-聚二茂铁基硅烷、或包括至少一种上述嵌段共聚物的结合。
需要的嵌段共聚物具有适合于进一步处理的总分子量和多分散度。嵌段共聚物通常具有重均分子量(Mw)为1,000到200,000g/mol。嵌段共聚物通常具有多分散度(Mw/Mn)为从1.01到6,从1.01到1.5,从1.01到1.2或从1.01到1.1。分子重量,Mw和Mn均可以通过例如凝胶渗透色谱确定,采用通用的校正方法,且以聚苯乙烯为标准校准。
嵌段共聚物通常从溶液中涂覆到底层(引导图案和刷状层)表面上,通过旋涂在底层表面上形成自组装层108。嵌段共聚物被退火以在退火过程中形成微区。退火条件将依赖于DSA层的特定材料。退火通常在从100到380℃的温度下进行从30秒到2小时的时间。退火可以在恒定的或变化的温度下进行,例如,移动的梯度加热有利于在嵌段共聚物中形成想要的自组装形态结构。另一有利于在嵌段共聚物中形成想要的自组装形态结构的适合的退火技术包括将膜与溶剂蒸汽接触,在室温或高温下进行。溶剂蒸汽可以例如,由单一溶剂或溶剂混合而来。溶剂蒸汽的组成可以随时间改变。溶剂蒸汽退火技术已经被公开于,例如,Jung和Ross,“Solvent-Vapor-Induced Tunability of Self-AssembledBlock Copolymer Patterns”,《Adv.Mater.》,第21卷,第24期,第2540-2545页,Wiley-VCH,第1521-4095(2009)页和美国专利No.2011/0272381。
所述微区形成其中第一嵌段在底层上形成与引导图案对齐的第一微区110,和第二嵌段在底层上形成相邻第一微区对齐的第二微区112。当底层的引导图案形成其间隔大于第一和第二微区的空间间隔的稀疏图案时,如图所示的另外的第一和第二微区形成在底层上以填充稀疏图案的间隔空间。另外的第一微区,其没有对齐引导图案,而是对齐之前形成的第二(分散)微区,且另外的第二微区对齐另外的第一微区。
接着通过移除第一或第二微区和任选的底层的下方部分来形成浮雕图案。移除步骤可以通过例如采用氧等离子体的例如湿法刻蚀方法或干法刻蚀方法完成,或它们的结合。
以上方法和结构可以用于包括存储设备的半导体装置的制备,其需要密集线/间距图案,例如动态随机存储器(DRAM)、同步动态随机存储器(SDRAM)或密集特征的数据存储如在硬盘驱动器中。应该意识到这样的装置是示例性的且不应被视为对本发明的限制。
对基材进行进一步处理以形成最终的装置。进一步处理可以包括,例如,在基材上的一个或多个其他的层的制备、打磨、化学-机械抛光(CMP)、离子注入、退火、CVD、PVD、外延生长、电镀、刻蚀和平版印刷技术例如DSA和光刻。
以下非限定性实施例用于描述本发明。
实施例
甲基丙烯酸2-(1,2-二氢环丁烷并苯-1-基氧基)乙酯的合成
1-溴-1,2-二氢环丁烷并苯(1.2)
向圆底烧瓶内,于室温下加入N-溴代琥珀酰亚胺(102克,0.573摩尔)和600ml氯苯。过氧化苯甲酰(1.2克,0.005摩尔)接着被加入,接着加入二环[4.2.0]八-1(6),2,4-三烯(1.1)(50克,0.48摩尔)。反应混合物在85℃下搅拌2天。在冷却到室温后,加入400ml庚烷,且混合物在室温下搅拌20分钟。混合物通过硅胶短垫进行过滤并使用庚烷洗涤。在减压浓缩后,得到的油在大约2托的真空和70-74℃下提取,得到作为油的产物(1.2)(64克,73%产率)。
2-(1,2-二氢环丁烷并苯-1-基氧基)乙醇(1.3)
向圆底烧瓶内,加入1-溴-1,2-二氢环丁烷并苯(1.2)(30克,0.164摩尔)和乙二醇(150ml)。四氟硼酸银(I)(35克,0.18摩尔)接着被缓缓加入,同时使用冰浴以保持温度在大约30℃。在添加过后,反应混合物在50℃下搅拌3小时。一旦冷却到室温,加入200ml水和400ml醚。得到的混合物通过硅藻土过滤。有机层使用水洗涤三遍(每次30ml)且通过Na2SO4干燥,并浓缩得到作为油的产物(1.3)(21.8克,产率79%)。
甲基丙烯酸2-(1,2-二氢环丁烷并苯-1-基氧基)乙酯(1.5)
2-(1,2-二氢环丁烷并苯-1-基氧基)乙醇(1.3)(20克,0.122摩尔)溶解在500ml的含有三乙基胺(37克,0.366摩尔)和大约100ppm丁基化羟基甲苯(BHT)的二氯甲烷(DCM)中。混合物采用冰浴冷却到大约0℃。接着甲基丙烯酰氯(1.4)(15.27克,0.146摩尔)被逐滴加入。得到的混合物在大约0℃下搅拌4小时。在水相反应后,有机相用10%NH4OH和水洗涤。有机相用Na2SO4干燥并浓缩。采用EA/庚烷0-40%进行快速柱层析得到需要的产品(1.5)(21克,产率74%)。
可交联聚合物(CP)的制备
实施例1:可交联聚合物1(CP1)(对比)
苯乙烯和4-乙烯基苯并环丁烯(VBCB)单体通过氧化铝柱以去除所有的抑制物。28.883克苯乙烯,1.116克VBCB,0.225克N-叔丁基-N-(2-甲基-1-苯丙基)-O-(1-苯乙基)羟胺,和0.011克2,2,5-三甲基-4-苯基-3-氮杂己烷-3-氮氧化物被注入100mL的Schlenk瓶内。反应混合物由三个冷冻解冻泵循环进行脱气,并且接着瓶内注入氮气且密封。接下来,反应瓶加热到120℃保持19小时。在甲醇/水(80/20)内进行沉淀。过滤收集析出的聚合物,空气干燥过夜,再溶解于THF中,再沉淀到甲醇/水(80/20)中。过滤最终聚合物,空气干燥过夜并进一步在25℃下真空干燥48小时得到可交联聚合物1(CP1)。
实施例2:可交联聚合物2(CP2)(对比)
苯乙烯和4-乙烯基苯并环丁烯(VBCB)单体通过氧化铝柱以去除所有的抑制物。26.341克苯乙烯,3.658克VBCB,0.229克N-叔丁基-N-(2-甲基-1-苯丙基)-O-(1-苯乙基)羟胺,和0.011克2,2,5-三甲基-4-苯基-3-氮杂己烷-3-氮氧化物被注入100mL的Schlenk瓶内。反应混合物由三个冷冻解冻泵循环进行脱气,并且接着瓶内注入氮气且密封。接下来,反应瓶加热到120℃保持19小时。在甲醇/水(80/20)内进行沉淀。过滤收集析出的聚合物,空气干燥过夜,再溶解于THF中,再沉淀到甲醇/水(80/20)中。过滤最终聚合物,空气干燥过夜并进一步在25℃下真空干燥48小时得到可交联聚合物2(CP2)。
实施例3:可交联聚合物3(CP3)
17.899克苯乙烯和2.101克甲基丙烯酸2-(1,2-二氢环丁烷并苯-1-基氧基)乙酯(BCBMA)溶解在30.000克丙二醇甲基醚醋酸酯(PGMEA)中。所述单体溶液用氮气鼓泡20分钟脱气。将PGMEA(15.097克)加入到装有冷凝器和机械搅拌器的250mL三颈烧瓶中并通过氮气鼓泡20分钟脱气。随后将反应瓶中的溶剂加热至80℃。在4.000克PGMEA中溶解V601(2,2-偶氮二异丁酸二甲酯)(1.041克),引发剂溶液用氮气鼓泡20分钟脱气。引发剂溶液加入到反应烧瓶中,然后在强力搅拌和氮气环境下,在3小时内将单体溶液滴加到反应器中。单体完成进料后,聚合混合物在80℃下再静置1小时。总共4小时的聚合时间(3小时进料和1小时进料后搅拌)后,聚合混合物被冷却至室温。在甲醇/水(80/20)内进行沉淀。过滤收集沉淀的聚合物,空气干燥过夜,再溶解于THF中,再沉淀到甲醇/水(80/20)中。过滤最终聚合物,空气干燥过夜并进一步在25℃下真空干燥48小时得到可交联聚合物3(CP3)。
实施例4:可交联聚合物4(CP4)
16.028克苯乙烯和3.792克甲基丙烯酸2-(1,2-二氢环丁烷并苯-1-基氧基)乙酯(BCBMA)溶解在30.000克丙二醇甲基醚醋酸酯(PGMEA)中。所述单体溶液用氮气鼓泡20分钟脱气。将PGMEA(14.964克)加入到装有冷凝器和机械搅拌器的250mL三颈烧瓶中并通过氮气鼓泡20分钟脱气。随后将反应瓶中的溶剂加热至80℃。在4.000克PGMEA中溶解V601(2,2-偶氮二异丁酸二甲酯)(0.984克),引发剂溶液用氮气鼓泡20分钟。引发剂溶液加入到反应烧瓶中,然后在强力搅拌和氮气环境下,在3小时内将单体溶液滴加到反应器中。单体完成进料后,聚合混合物在80℃下再静置1小时。总共4小时的聚合时间(3小时进料和1小时进料后搅拌)后,聚合混合物被冷却至室温。在甲醇/水(80/20)内进行沉淀。过滤收集沉淀的聚合物,空气干燥过夜,再溶解于THF中,在沉淀到甲醇/水(80/20)中。过滤最终聚合物,空气干燥过夜并进一步在25℃下真空干燥48小时得到可交联聚合物4(CP4)。
实施例5:可交联聚合物5(CP5)
15.901克甲基丙烯酸甲酯(MMA)和4.099克甲基丙烯酸2-(1,2-二氢环丁烷并苯-1-基氧基)乙酯(BCBMA)溶解在30.000克丙二醇甲基醚醋酸酯(PGMEA)中。所述单体溶液用氮气鼓泡20分钟脱气。将PGMEA(15.037克)加入到装有冷凝器和机械搅拌器的250mL三颈烧瓶中并通过氮气鼓泡20分钟脱气。随后将反应瓶中的溶剂加热至80℃。在4.000克PGMEA中溶解V601(2,2-偶氮二异丁酸二甲酯)(1.016克),引发剂溶液也用氮气鼓泡20分钟脱气。引发剂溶液加入到反应烧瓶中,然后在强力搅拌和氮气环境下,在3小时内将单体溶液滴加到反应器中。单体完成进料后,聚合混合物在80℃下再静置1小时。总共4小时的聚合时间(3小时进料和1小时进料后搅拌)后,聚合混合物被冷却至室温。在甲醇/水(80/20)内进行沉淀。过滤收集沉淀的聚合物,空气干燥过夜,再溶解于THF中,再沉淀到甲醇/水(80/20)中。过滤最终聚合物,空气干燥过夜并进一步在25℃下真空干燥48小时得到可交联聚合物5(CP5)。
实施例6:可交联聚合物6(CP6)
17.445克甲基丙烯酸苄基酯(BZMA)和2.555克甲基丙烯酸2-(1,2-二氢环丁烷并苯-1-基氧基)乙基酯(BCBMA)溶解在30.000克丙二醇甲基醚醋酸酯(PGMEA)中。所述单体溶液用氮气鼓泡20分钟脱气。将PGMEA(14.144克)加入到装有冷凝器和机械搅拌器的250mL三颈烧瓶中并通过氮气鼓泡20分钟脱气。随后将反应瓶中的溶剂加热至80℃。在4.000克PGMEA中溶解V601(2,2-偶氮二异丁酸二甲酯)(0.633克),引发剂溶液也用氮气鼓泡20分钟以脱气。引发剂溶液加入到反应烧瓶中,然后在强力搅拌和氮气环境下,在3小时内将单体溶液滴加到反应器中。单体完成进料后,聚合混合物在80℃下再静置1小时。总共4小时的聚合时间(3小时进料和1小时进料后搅拌)后,聚合混合物被冷却至室温。在甲醇/水(80/20)内进行沉淀。过滤收集沉淀的聚合物,空气干燥过夜,再溶解于THF中,再沉淀到甲醇/水(80/20)中。过滤最终聚合物,空气干燥过夜并进一步在25℃下真空干燥48小时得到可交联聚合物6(CP6)。
实施例7:可交联聚合物7(CP7)
17.254克甲基丙烯酸苯基酯(PHMA)和2.746克甲基丙烯酸2-(1,2-二氢环丁烷苯并-1-基氧基)乙酯(BCBMA)溶解在30.000克丙二醇甲基醚醋酸酯(PGMEA)中。所述单体溶液用氮气鼓泡20分钟脱气。将PGMEA(14.254克)加入到装有冷凝器和机械搅拌器的250mL三颈烧瓶中并通过氮气鼓泡20分钟脱气。随后将反应瓶中的溶剂加热至80℃。在4.000克PGMEA中溶解V601(2,2-偶氮二异丁酸二甲酯)(0.680克),引发剂溶液也用氮气鼓泡20分钟以脱气。引发剂溶液加入到反应烧瓶中,然后在强力搅拌和氮气环境下,在3小时内将单体溶液滴加到反应器中。单体完成进料后,聚合混合物在80℃下再静置1小时。总共4小时的聚合时间(3小时进料和1小时进料后搅拌)后,聚合混合物被冷却至室温。在甲醇/水(80/20)内进行沉淀。过滤收集沉淀的聚合物,空气干燥过夜,再溶解于THF中,再沉淀到甲醇/水(80/20)中。过滤最终聚合物,空气干燥过夜并进一步在25℃下真空干燥48小时得到可交联聚合物7(CP7)。
实施例8:可交联聚合物8(CP8)
16.415克4-甲基苯乙烯(4MS)、3.585克甲基丙烯酸2-(1,2-二氢环丁烷并苯-1-基氧基)乙酯(BCBMA)和0.178克V601(2,2-偶氮二异丁酸二甲酯)溶解在20.000克丙二醇甲基醚醋酸酯(PGMEA)中,且加入到装有冷凝器和机械搅拌器的250mL三颈烧瓶中。所述单体溶液用氮气鼓泡20分钟脱气。随后将反应瓶中的溶剂加热至60℃。在24小时的聚合后,反应混合物被冷却至室温。在甲醇/水(80/20)内进行沉淀。过滤收集沉淀的聚合物,空气干燥过夜,再溶解于THF中,再沉淀到甲醇/水(80/20)中。过滤最终聚合物,空气干燥过夜并进一步在25℃下真空干燥48小时得到可交联聚合物8(CP8)。
实施例9:可交联聚合物9(CP9)
18.125克4-甲基苯乙烯(4MS)、1.875克甲基丙烯酸2-(1,2-二氢环丁烷并苯-1-基氧基)乙酯(BCBMA)和0.130克V601(2,2-偶氮二异丁酸二甲酯)溶解在20.000克丙二醇甲基醚醋酸酯(PGMEA)中,且加入到装有冷凝器和机械搅拌器的250mL三颈烧瓶中。所述单体溶液用氮气鼓泡20分钟脱气。随后将反应瓶中的溶剂加热至60℃。在24小时的聚合后,反应混合物被冷却至室温。在甲醇/水(80/20)内进行沉淀。过滤收集沉淀的聚合物,空气干燥过夜,再溶解于THF中,再沉淀到甲醇/水(80/20)中。过滤最终聚合物,空气干燥过夜并进一步在25℃下真空干燥48小时得到可交联聚合物9(CP9)。
实施例10:可交联聚合物10(CP10)
18.258克甲基丙烯酸正丙基酯(nPMA)、1.742克甲基丙烯酸2-(1,2-二氢环丁烷苯并-1-基氧基)乙酯(BCBMA)和0.121克V601(2,2-偶氮二异丁酸二甲酯)溶解在20.000克丙二醇甲基醚醋酸酯(PGMEA)中,且加入到装有冷凝器和机械搅拌器的250mL三颈烧瓶中。所述单体溶液用氮气鼓泡20分钟脱气。随后将反应瓶中的溶剂加热至60℃。在24小时的聚合后,反应混合物被冷却至室温。在甲醇/水(80/20)内进行沉淀。过滤收集沉淀的聚合物,空气干燥过夜,再溶解于THF中,再沉淀到甲醇/水(80/20)中。过滤最终聚合物,空气干燥过夜并进一步在25℃下真空干燥48小时得到可交联聚合物10(CP10)。
溶剂剥离试验
可交联聚合物的热交联反应通过实施溶剂剥离试验来进行非直接监控。实施例1到10中制备的每一可交联聚合物溶解在丙二醇甲基醚醋酸酯(PGMEA)中且旋涂到裸露的Si晶片上。涂覆的晶片在氮气环境中以不同温度和不同时间长度加热,如表1所示,以研究热交联的效率。接着,膜全部用PGMEA彻底冲洗以去除未交联的材料。残留在基材上的不溶解的交联聚合物的厚度被检测。结果如表1所示。
表1
表1显示了对比可交联聚合物1和2的有效交联仅在高温下退火后得到,例如在250℃下对CP1进行30分钟和在250℃下对CP2进行5分钟。本发明的可交联聚合物3-10中的每一个在较低温度和较短时间的退火后可以获得有效交联。
在交联的底层上的嵌段共聚物自组装
通过将可交联聚合物CP4、CP5和CP8溶解于PGMEA中制备可交联的底层组合物。得到的组合物旋涂在各硅晶片上以制成厚度为8到9nm的底层。底层进行退火以诱发交联,在下面的表2所示的条件下进行。DSA组合物包括在PGMEA中的聚苯乙烯-嵌段-聚甲基丙烯酸甲酯(PS-b-PMMA)嵌段共聚物,其被涂覆在底层上得到CP4和CP5的厚度为32nm,CP8的厚度为50nm,且在250℃下进行退火2分钟。对得到的晶片进行原子力显微镜(AFM)成像以观察表面上形成的图像。得到的聚合物CP4的AFM图像为指纹图案,说明底层对DSA聚合物的聚苯乙烯和聚甲基丙烯酸甲酯嵌段是中性的。聚合物CP5和CP8的AFM图像分别为聚甲基丙烯酸甲酯-优先的和聚苯乙烯-优先的岛/孔状图案。这些结果说明了底层组合物的表面能可以调整为对DSA嵌段共聚物的不同嵌段优先或对这些嵌段都中性。
表2
Claims (10)
1.一种通过定向自组装形成图案的方法,包括:
(a)提供半导体基材,其包括一个或多个将被图案化的层;
(b)在所述一个或多个将被图案化的层上施加可交联的底层组合物以形成可交联底层,其中所述可交联底层组合物包括可交联聚合物,其包括具有以下通式(I-A)或(I-B)的第一单元:
其中:P是可聚合官能团;L是单键或m+1价连接基团;X1是一价供电子基团;X2是二价供电子基团;Ar1和Ar2分别为三价和二价芳基,且环丁烯的环碳原子与Ar1或Ar2的相同芳环上的邻近碳原子键合;m和n均为大于或等于1的整数;且每个R1独立地是单价基团;
(c)加热所述可交联底层以形成交联的底层;
(d)在所述交联的底层上形成包括嵌段共聚物的自组装层;和
(e)将所述自组装层退火。
2.根据权利要求1的方法,所述方法进一步包括图案化交联的底层。
3.根据权利要求2的方法,其中图案化的交联的底层通过光刻和刻蚀制成,其中暴露基材的凹槽设置于交联的底层的邻近图案之间。
4.根据权利要求3的方法,所述方法进一步包括在邻近图案之间的凹槽内形成刷状层,其中自组装层形成于图案和刷状层上。
5.根据权利要求2的方法,其中所述图案通过化学改变交联的底层的选定区域而形成。
6.根据权利要求1到5的任一项的方法,其中所述可聚合官能团P选自下面的通式(II-A)和(H-B):
其中R4选自氢、氟、C1-C3烷基、和C1-C3氟烷基;且X为氧或由结构式NR5表示,其中R5选自氢和取代和未取代的C1到C10线性、支化和环状烃;且
其中R6选自氢、氟、C1-C3烷基、和C1-C3氟烷基;且其中L选自任选地取代的线性或支化的脂肪族和芳香族烃,和它们的组合,任选地带有一个或多个选自-O-、-S-、-COO-、-CONR3-、-CONH-和-OCONH-的连接部分,其中R3选自氢和取代和未取代的C1到C10线性、支化和环状烃。
7.根据权利要求1到6的任一项的方法,其中所述第一单元为通式(I-A),其中X1选自C1-C10烷氧基、胺、硫、-OCOR9,-NHCOR10,和它们的组合,其中R9选自取代和未取代的C1到C10线性、支化和环状烃,R10选自取代或未取代的C1到C10线性、支化和环状烃。
8.根据权利要求1到6的任一项的方法,其中所述第一单元为通式(I-B),其中X2为-O-、-S-、-COO-、-CONR11-、-CONH-和-OCONH-,其中R11选自氢和取代和未取代的C1到C10线性、支化或环状烃,优选地为烷基,优选地为-O-,和其组合。
9.根据权利要求1到8的任一项的方法,其中所述第一单元由选自一种或多种以下单体的单体形成:
10.根据权利要求1到9的任一项的方法,其中所述聚合物进一步包括第二单元,所述第二单元选自通式(III)和(IV):
其中R7选自氢、氟、C1-C3烷基、和C1-C3氟烷基,R8选自任选地取代的C1到C10烷基,和Ar3为任选地取代的芳基。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201361922767P | 2013-12-31 | 2013-12-31 | |
US61/922,767 | 2013-12-31 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN104749905A true CN104749905A (zh) | 2015-07-01 |
CN104749905B CN104749905B (zh) | 2018-02-13 |
Family
ID=53589804
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201410858452.3A Active CN104749905B (zh) | 2013-12-31 | 2014-12-31 | 定向自组装图案形成方法和组合物 |
Country Status (5)
Country | Link |
---|---|
US (1) | US9490117B2 (zh) |
JP (1) | JP6545463B2 (zh) |
KR (1) | KR102422401B1 (zh) |
CN (1) | CN104749905B (zh) |
TW (1) | TWI573808B (zh) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108137313A (zh) * | 2015-10-16 | 2018-06-08 | Az电子材料卢森堡有限公司 | 用于嵌段共聚物自组装的组合物和方法 |
CN109206605A (zh) * | 2018-08-31 | 2019-01-15 | 江苏汉拓光学材料有限公司 | 用于定向自组装的嵌段共聚物和使用其的定向自组装方法 |
CN109748997A (zh) * | 2017-11-02 | 2019-05-14 | 罗门哈斯电子材料有限责任公司 | 来自含有氮杂环的单体和含有乙烯基芳基环丁烯的单体的加成聚合物 |
CN109749000A (zh) * | 2017-11-02 | 2019-05-14 | 罗门哈斯电子材料有限责任公司 | 来自含乙烯基芳基环丁烯单体的低温可固化加成聚合物和其制备方法 |
CN109867590A (zh) * | 2017-12-01 | 2019-06-11 | 罗门哈斯电子材料有限责任公司 | 以改进固化动力学制备稳定且可热聚合的乙烯基、氨基或低聚苯氧基苯并环丁烯单体的方法 |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3095127B1 (en) * | 2014-01-16 | 2020-05-20 | Brewer Science, Inc. | High-chi block copolymers for directed self-assembly |
KR20160133511A (ko) * | 2014-03-15 | 2016-11-22 | 보드 오브 리전츠, 더 유니버시티 오브 텍사스 시스템 | 블록 공중합체의 정돈 |
JP2016058620A (ja) * | 2014-09-11 | 2016-04-21 | 株式会社東芝 | 半導体装置の製造方法 |
KR102651697B1 (ko) * | 2015-09-07 | 2024-03-27 | 아이엠이씨 브이제트더블유 | 트렌치 보조 케모에피탁시(trac) dsa 흐름 |
JP6346132B2 (ja) * | 2015-09-11 | 2018-06-20 | 株式会社東芝 | パターン形成方法 |
TWI612108B (zh) * | 2015-10-31 | 2018-01-21 | Rohm And Haas Electronic Materials Llc | 嵌段共聚物及圖案處理組合物以及方法 |
KR102402958B1 (ko) * | 2015-11-11 | 2022-05-27 | 삼성전자주식회사 | 반도체 장치의 패턴 형성 방법 및 반도체 장치의 제조 방법 |
EP3500637B1 (en) * | 2016-08-18 | 2022-06-22 | Merck Patent GmbH | Polymer compositions for self-assembly applications |
JP6926939B2 (ja) * | 2017-10-23 | 2021-08-25 | 東京エレクトロン株式会社 | 半導体装置の製造方法 |
US10529552B2 (en) | 2017-11-29 | 2020-01-07 | Taiwan Semiconductor Manufacturing Co., Ltd. | Method for manufacturing a semiconductor device and a coating material |
KR102484630B1 (ko) * | 2018-08-16 | 2023-01-04 | 주식회사 엘지화학 | 패턴화 기판의 제조 방법 |
KR102498631B1 (ko) * | 2018-08-16 | 2023-02-10 | 주식회사 엘지화학 | 패턴화 기판의 제조 방법 |
TW202307048A (zh) * | 2021-05-18 | 2023-02-16 | 德商馬克專利公司 | 用於圖案化苯乙烯-嵌段-甲基丙烯酸甲酯(ps-b-pmma)型嵌段共聚物之定向自組裝之具有改良乾蝕刻能力的疏水性可交聯釘壓底層 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4540763A (en) * | 1984-09-14 | 1985-09-10 | The Dow Chemical Company | Polymers derived from poly(arylcyclobutenes) |
WO2013005026A2 (en) * | 2011-07-04 | 2013-01-10 | Cambridge Display Technology Limited | Polymers, monomers and methods of forming polymers |
US20130078576A1 (en) * | 2011-09-23 | 2013-03-28 | Az Electronic Materials Usa Corp. | Compositions of neutral layer for directed self assembly block copolymers and processes thereof |
US20130224635A1 (en) * | 2012-02-27 | 2013-08-29 | Yoko Takekawa | Mask pattern creation method, recording medium, and semiconductor device manufacturing method |
US20130284698A1 (en) * | 2012-04-27 | 2013-10-31 | Shin-Etsu Chemical Co., Ltd. | Patterning process |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4661193A (en) * | 1984-08-27 | 1987-04-28 | The Dow Chemical Company | Adhesive compositions for arylcyclobutene monomeric compositions |
US4965329A (en) | 1984-08-27 | 1990-10-23 | The Dow Chemical Company | N-substituted arylcyclo butenyl-unsaturated cyclic imides |
US4698394A (en) * | 1985-12-23 | 1987-10-06 | Shell Oil Company | Reactive styrene polymers |
US5198527A (en) * | 1990-12-24 | 1993-03-30 | The Dow Chemical Company | Arylcyclobutene terminated carbonate polymer |
US5318827A (en) * | 1992-06-15 | 1994-06-07 | The Dow Chemical Company | Carbonate polymer laminate structure |
US6565968B1 (en) * | 2000-04-12 | 2003-05-20 | Avery Dennison Corporation | UV-curable pressure-sensitive adhesives and protective coatings |
US6780567B2 (en) | 2001-08-02 | 2004-08-24 | Fuji Photo Film Co., Ltd. | Lithographic process using reaction of o-quinodimethane |
WO2004073018A2 (en) * | 2003-02-05 | 2004-08-26 | Dow Global Technologies Inc. | Sacrificial benzocyclobutene/norbornene polymers for making air gaps within semiconductor devices |
US8999492B2 (en) | 2008-02-05 | 2015-04-07 | Micron Technology, Inc. | Method to produce nanometer-sized features with directed assembly of block copolymers |
PL2389852T3 (pl) * | 2010-05-25 | 2015-03-31 | Electrolux Home Products Corp Nv | Układ ramienia myjącego do zmywarki |
JP6035017B2 (ja) | 2010-10-04 | 2016-11-30 | ローム アンド ハース エレクトロニック マテリアルズ エルエルシーRohm and Haas Electronic Materials LLC | 下層組成物および下層を像形成する方法 |
WO2013158527A1 (en) | 2012-04-16 | 2013-10-24 | Brewer Science Inc. | Silicon hardmask layer for directed self-assembly |
US8940810B2 (en) * | 2012-06-07 | 2015-01-27 | Canon Kabushiki Kaisha | Optical component, electronic board, method for producing the optical component, and method for producing the electronic board |
CN104701238B (zh) * | 2013-11-14 | 2019-10-08 | 罗门哈斯电子材料有限公司 | 间隙填充方法 |
US20150210793A1 (en) * | 2013-12-31 | 2015-07-30 | Rohm And Haas Electronic Materials Llc | Crosslinkable polymers and underlayer compositions |
-
2014
- 2014-12-31 TW TW103146518A patent/TWI573808B/zh active
- 2014-12-31 US US14/588,410 patent/US9490117B2/en active Active
- 2014-12-31 KR KR1020140195926A patent/KR102422401B1/ko active IP Right Grant
- 2014-12-31 CN CN201410858452.3A patent/CN104749905B/zh active Active
-
2015
- 2015-01-05 JP JP2015000582A patent/JP6545463B2/ja active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4540763A (en) * | 1984-09-14 | 1985-09-10 | The Dow Chemical Company | Polymers derived from poly(arylcyclobutenes) |
WO2013005026A2 (en) * | 2011-07-04 | 2013-01-10 | Cambridge Display Technology Limited | Polymers, monomers and methods of forming polymers |
US20130078576A1 (en) * | 2011-09-23 | 2013-03-28 | Az Electronic Materials Usa Corp. | Compositions of neutral layer for directed self assembly block copolymers and processes thereof |
US20130224635A1 (en) * | 2012-02-27 | 2013-08-29 | Yoko Takekawa | Mask pattern creation method, recording medium, and semiconductor device manufacturing method |
US20130284698A1 (en) * | 2012-04-27 | 2013-10-31 | Shin-Etsu Chemical Co., Ltd. | Patterning process |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108137313A (zh) * | 2015-10-16 | 2018-06-08 | Az电子材料卢森堡有限公司 | 用于嵌段共聚物自组装的组合物和方法 |
CN108137313B (zh) * | 2015-10-16 | 2019-10-18 | Az电子材料卢森堡有限公司 | 用于嵌段共聚物自组装的组合物和方法 |
CN109748997A (zh) * | 2017-11-02 | 2019-05-14 | 罗门哈斯电子材料有限责任公司 | 来自含有氮杂环的单体和含有乙烯基芳基环丁烯的单体的加成聚合物 |
CN109749000A (zh) * | 2017-11-02 | 2019-05-14 | 罗门哈斯电子材料有限责任公司 | 来自含乙烯基芳基环丁烯单体的低温可固化加成聚合物和其制备方法 |
CN109748997B (zh) * | 2017-11-02 | 2022-03-04 | 罗门哈斯电子材料有限责任公司 | 来自含有氮杂环的单体和含有乙烯基芳基环丁烯的单体的加成聚合物 |
CN109867590A (zh) * | 2017-12-01 | 2019-06-11 | 罗门哈斯电子材料有限责任公司 | 以改进固化动力学制备稳定且可热聚合的乙烯基、氨基或低聚苯氧基苯并环丁烯单体的方法 |
CN109867590B (zh) * | 2017-12-01 | 2022-06-21 | 罗门哈斯电子材料有限责任公司 | 以改进固化动力学制备稳定且可热聚合的乙烯基、氨基或低聚苯氧基苯并环丁烯单体的方法 |
CN109206605A (zh) * | 2018-08-31 | 2019-01-15 | 江苏汉拓光学材料有限公司 | 用于定向自组装的嵌段共聚物和使用其的定向自组装方法 |
CN109206605B (zh) * | 2018-08-31 | 2020-11-24 | 江苏汉拓光学材料有限公司 | 用于定向自组装的嵌段共聚物和使用其的定向自组装方法 |
Also Published As
Publication number | Publication date |
---|---|
KR102422401B1 (ko) | 2022-07-18 |
KR20150079486A (ko) | 2015-07-08 |
US20150287592A1 (en) | 2015-10-08 |
TW201602138A (zh) | 2016-01-16 |
JP6545463B2 (ja) | 2019-07-17 |
CN104749905B (zh) | 2018-02-13 |
TWI573808B (zh) | 2017-03-11 |
JP2015130508A (ja) | 2015-07-16 |
US9490117B2 (en) | 2016-11-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104749905A (zh) | 定向自组装图案形成方法和组合物 | |
CN104788598A (zh) | 可交联聚合物和底层组合物 | |
TWI588896B (zh) | 圖案收縮方法 | |
JP6742686B2 (ja) | ギャップ充填方法 | |
TWI487755B (zh) | 熱退火製程 | |
CN106243514B (zh) | 用于图案处理的组合物和方法 | |
TW201643565A (zh) | 圖案處理方法 | |
KR20210044691A (ko) | 오버코팅 포토레지스트와 함께 사용하기 위한 코팅 조성물 | |
CN110114377B (zh) | 嵌段共聚物自组装的新组合物和方法 | |
CN105304550A (zh) | 间隙填充方法 | |
KR20140009065A (ko) | 고온 열 어닐링 가공법 | |
US20240182701A1 (en) | Resin composition for forming phase-separated structure, method of producing structure containing phase-separated structure, and block copolymer | |
JP2017082220A (ja) | 実質的に対称な3アーム星型ブロックコポリマー |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |