TWI837424B - 阻劑用交聯型聚合物 - Google Patents
阻劑用交聯型聚合物 Download PDFInfo
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- TWI837424B TWI837424B TW109133765A TW109133765A TWI837424B TW I837424 B TWI837424 B TW I837424B TW 109133765 A TW109133765 A TW 109133765A TW 109133765 A TW109133765 A TW 109133765A TW I837424 B TWI837424 B TW I837424B
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- Taiwan
- Prior art keywords
- polymer
- phenolic hydroxyl
- parts
- group
- cross
- Prior art date
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- 229920006037 cross link polymer Polymers 0.000 title claims abstract description 29
- 229920000642 polymer Polymers 0.000 claims abstract description 88
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 47
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 40
- 239000002253 acid Substances 0.000 claims abstract description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 5
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 5
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 229930195734 saturated hydrocarbon Natural products 0.000 claims abstract description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 4
- 239000002904 solvent Substances 0.000 claims description 22
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 14
- 239000003112 inhibitor Substances 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 9
- 150000002989 phenols Chemical class 0.000 claims description 8
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 150000001299 aldehydes Chemical class 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 6
- 229920003986 novolac Polymers 0.000 claims description 6
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- 238000001459 lithography Methods 0.000 abstract description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 80
- 239000011259 mixed solution Substances 0.000 description 29
- 239000000243 solution Substances 0.000 description 25
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 24
- 238000003756 stirring Methods 0.000 description 23
- 238000005342 ion exchange Methods 0.000 description 20
- 125000006239 protecting group Chemical group 0.000 description 15
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 14
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 13
- 229960000834 vinyl ether Drugs 0.000 description 13
- 230000032683 aging Effects 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 239000003377 acid catalyst Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- DQNSRQYYCSXZDF-UHFFFAOYSA-N 1,4-bis(ethenoxymethyl)cyclohexane Chemical compound C=COCC1CCC(COC=C)CC1 DQNSRQYYCSXZDF-UHFFFAOYSA-N 0.000 description 10
- 229920001429 chelating resin Polymers 0.000 description 10
- 230000001681 protective effect Effects 0.000 description 10
- 238000006359 acetalization reaction Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 230000035945 sensitivity Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- -1 tricyclodecene Chemical compound 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 6
- 230000035800 maturation Effects 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- 125000000962 organic group Chemical group 0.000 description 5
- 238000000206 photolithography Methods 0.000 description 5
- 239000002966 varnish Substances 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical group COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229940116333 ethyl lactate Drugs 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000012643 polycondensation polymerization Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 description 2
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 150000003973 alkyl amines Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229940057867 methyl lactate Drugs 0.000 description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RJTJPFYIGZWFMK-UHFFFAOYSA-N 1-[2-(2-ethenoxyethoxy)ethoxy]-2-methoxyethane Chemical compound COCCOCCOCCOC=C RJTJPFYIGZWFMK-UHFFFAOYSA-N 0.000 description 1
- HWCLMKDWXUGDKL-UHFFFAOYSA-N 1-ethenoxy-2-ethoxyethane Chemical compound CCOCCOC=C HWCLMKDWXUGDKL-UHFFFAOYSA-N 0.000 description 1
- GXZPMXGRNUXGHN-UHFFFAOYSA-N 1-ethenoxy-2-methoxyethane Chemical compound COCCOC=C GXZPMXGRNUXGHN-UHFFFAOYSA-N 0.000 description 1
- UVHXEHGUEKARKZ-UHFFFAOYSA-N 1-ethenylanthracene Chemical compound C1=CC=C2C=C3C(C=C)=CC=CC3=CC2=C1 UVHXEHGUEKARKZ-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-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
- WVXLLHWEQSZBLW-UHFFFAOYSA-N 2-(4-acetyl-2-methoxyphenoxy)acetic acid Chemical compound COC1=CC(C(C)=O)=CC=C1OCC(O)=O WVXLLHWEQSZBLW-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
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- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical compound OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
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- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
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- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical class C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 description 1
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
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- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 1
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- 229910017604 nitric acid Inorganic materials 0.000 description 1
- IZJVVXCHJIQVOL-UHFFFAOYSA-N nitro(phenyl)methanesulfonic acid Chemical class OS(=O)(=O)C([N+]([O-])=O)C1=CC=CC=C1 IZJVVXCHJIQVOL-UHFFFAOYSA-N 0.000 description 1
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Abstract
本發明提供一種高感度微影用交聯型聚合物。
本發明之因酸的作用,對顯影液之溶解性產生變化之阻劑用交聯型聚合物係聚合物中之酚性羥基之至少一部分,具有被以下式(1):
(式(1)中,R1
表示碳數1~5之烷基,n表示1~5之整數,*表示對自酚性羥基中去除氫原子後之殘基的鍵結部)
表示之基團保護的結構,且
聚合物中之酚性羥基之至少一部分,具有被以下式(2):
(式(2)中,R2
表示可包含脂肪族環式基之碳數2~17之2價之飽和烴基、或包含芳香環之碳數6~17之2價烴基,*表示對自酚性羥基中去除氫原子後之殘基之鍵結部)
表示之基團保護,且聚合物彼此交聯的結構。
Description
本發明係有關因酸的作用,對顯影液之溶解性產生變化之阻劑用交聯型聚合物。更詳細而言,有關可用於厚膜阻劑之交聯型聚合物及包含該聚合物的厚膜阻劑用組成物。
用於半導體製造的光微影係使用以各種酚醛清漆系聚合物或丙烯酸系聚合物、羥基苯乙烯為首之氧苯乙烯系聚合物等作為基底聚合物的阻劑用組成物。例如,在LSI等之半導體積體電路或、FPD之顯示面之製造、感熱頭(thermal head)等之電路基板之製造等之寬廣領域中,為了微細元件之形成或進行微細加工,以往使用光微影技術。在需要磁頭或凸塊等之厚膜步驟的領域,需要牆面垂直性良好形成高長寬比的阻劑圖型。但是上述以往的阻劑,有膜厚變厚所致之膜之光線穿透性的問題等,而無法充分地保有解析性或感度,或無法得到所期望之阻劑圖型等的問題。為了解決此等問題時,提案可藉由酸等切斷聚合物鏈的化合物進行交聯的方法(參照專利文獻1~4)。使用這種交聯聚合物時,未曝光的部分顯示高分子量,且充分的強度,又,曝光的部分因曝光發生的酸,交聯被切斷,藉由鹼顯影液顯影時,成為小的結構單元而溶解。因此,曝光部之脫落單元變小,解析性提高。
另外,交聯聚合物在曝光後,交聯部位未被分解時,對鹼顯影液,無法發揮充分的溶解力,故膜厚需要以更少的曝光能量進行去保護的高感度樹脂。
[先前技術文獻]
[專利文獻]
[專利文獻1] 日本特開2004-144905號
[專利文獻2] 日本特開2002-72480號
[專利文獻3] 日本特開2008-46594號
[專利文獻4] 日本特開平6-148889號
[用以解決課題之手段]
為了解決上述課題,精心檢討的結果,發現因酸的作用,對顯影液之溶解性產生變化之阻劑用聚合物中,將聚合物中之酚性羥基,以具有氧乙烯基之親水性的酸解離性保護基保護,且以具有交聯性結構之保護基保護,適合用於光微影之高感度的阻劑用交聯型聚合物,而完成本發明。
亦即,本發明提供以下<1>~<7>者。
<1>一種阻劑用交聯型聚合物,其係因酸的作用,對顯影液之溶解性產生變化之阻劑用交聯型聚合物,
聚合物中之酚性羥基之至少一部分,具有被以下式(1):
(式(1)中,R1
表示碳數1~5之烷基,n表示1~5之整數,*表示對由酚性羥基中去除氫原子後之殘基的鍵結部)
表示之基團保護的結構,且
聚合物中之酚性羥基之至少一部分,具有被以下式(2):
(式(2)中,R2
表示可包含脂肪族環式基之碳數2~17之2價之飽和烴基、或包含芳香環之碳數6~17之2價烴基,*表示對自酚性羥基中去除氫原子後之殘基之鍵結部)
表示之基團保護,且聚合物彼此交聯的結構。
<2>如<1>之阻劑用交聯型聚合物,其中具有酚性羥基的聚合物為具有來自p-羥基苯乙烯或4-羥基苯基(甲基)丙烯酸酯之結構單元的聚合物。
<3>如<1>之阻劑用交聯型聚合物,其中具有酚性羥基的聚合物為藉由酚類與醛類或酮類之縮聚合所得的酚醛清漆型聚合物。
<4>如<1>~<3>中任一項之阻劑用交聯型聚合物,其中相對於前述聚合物所含有之全苯酚數100莫耳%,前述酚性羥基之被前述式(1)表示之基團的保護率為20~60莫耳%。
<5>如<1>~<4>中任一項之阻劑用交聯型聚合物,其中相對於前述聚合物所含有之全苯酚數100莫耳%,前述酚性羥基之被前述式(2)表示之基團的保護率為1~10莫耳%。
<6>如<1>~<5>中任一項之阻劑用交聯型聚合物,其中重量平均分子量為5,000~400,000。
<7>一種厚膜阻劑用組成物,其係至少包含如<1> ~<6>中任一項之交聯型聚合物、溶劑及酸產生劑。
[發明效果]
依據本發明時,可提供高感度的阻劑用交聯型聚合物,特別是光微影用之高感度的厚膜阻劑用交聯型聚合物。
[實施發明之形態]
<阻劑用聚合物>
本發明之聚合物,可適用於因酸的作用,對顯影液之溶解性產生變化的阻劑。
本發明之聚合物中之酚性羥基之至少一部分,具有被以下式(1)表示之基團保護的結構。
式(1)中,R1
為碳數1~5之烷基,較佳為碳數1~3之烷基,又更佳為甲基或乙基。n為1~5之整數,較佳為1~4之整數。*表示對酚性羥基中去除氫原子後之殘基的鍵結部。
本發明之聚合物中之酚性羥基之至少一部分,因被式(1)表示之基團保護,相較於以往交聯型的阻劑用聚合物,可提高感度。
式(1)表示之基團,可列舉例如以下者。
本發明之聚合物中之酚性羥基之至少一部分,可進一步具有被以下式(2)表示之基團保護,聚合物彼此交聯的結構。本發明之聚合物係具有因這種酸的作用產生分解的交聯部,而聚合物的分子量變大,使未曝光部之鹼對顯影液之溶解性降低,曝光部中,交聯部分解,聚合物分子量大幅降低,藉由提高對顯影液之溶解性,可充分地提高感度及顯影對比。
式(2)中,R2
表示可包含脂肪族環式基之碳數2~17之2價之飽和烴基、或包含芳香環之碳數6~17之2價之烴基,較佳為可包含脂肪族環式基之碳數2~17之2價之飽和烴基,更佳為1,4-環己烷二伸甲基、三環癸烷二伸甲基。*表示對酚性羥基中去除氫原子後之殘基的鍵結部。
式(2)表示之基團,可列舉例如以下者。
作為本發明之聚合物,具有來自p-羥基苯乙烯或4-羥基苯基(甲基)丙烯酸酯之結構單元之聚合物中之酚性羥基之一部分,被式(1)表示之基團保護,且被式(2)表示之基團保護,具有聚合物彼此交聯之結構者為佳。又,本說明書中,「(甲基)丙烯酸酯」係指「丙烯酸酯及甲基丙烯酸酯之至少一種」。
本發明之較佳的態樣,p-羥基苯乙烯之均聚物(聚p-羥基苯乙烯)之酚性羥基之一部分被式(1)表示之基團保護,且被式(2)表示之基團保護,具有聚合物彼此交聯的結構者如下述。
又,作為本發明之聚合物,藉由酚類與、醛類或酮類之縮聚合所得之酚醛清漆型聚合物中之酚性羥基之一部分,被式(1)表示之基團保護,且被式(2)表示之基團保護,具有聚合物彼此交聯之結構者為佳。
本發明之聚合物係藉由使結構中具有酚性羥基的聚合物,在溶劑與酸觸媒之存在下,與以下式(3)表示之乙烯醚反應(縮醛化),可導入式(1)表示之保護基。以下式(3)表示之乙烯醚,可使用1種類或複數種類。
式(3)中,R1
及n之定義及較佳的態樣係與式(1)相同。
式(3)表示之乙烯醚,可列舉例如以下者。
又,本發明之聚合物係藉由將結構中具有酚性羥基的聚合物,在溶劑與酸觸媒之存在下,與以下式(4)表示之乙烯醚反應(縮醛化),導入式(2)表示之保護基,可進行交聯。以下式(4)表示之乙烯醚,可使用1種類或複數種類。
式(4)中,R2
之定義及較佳的態樣係與式(2)相同。
式(4)表示之乙烯醚,可列舉例如以下者。
例如,本發明之聚合物係將具有來自p-羥基苯乙烯或4-羥基苯基(甲基)丙烯酸酯之結構單元的聚合物,在溶劑與酸觸媒之存在下,藉由與式(2)及式(4)表示之乙烯醚反應(縮醛化)而得。同樣地,本發明之聚合物係藉由將酚類與醛類或酮類之縮聚合所得之酚醛清漆型聚合物,在溶劑與酸觸媒之存在下,與式(2)及式(4)表示之乙烯醚反應(縮醛化)而得。不論何者,式(2)及式(4)表示之乙烯醚,各自皆可使用1種類或複數種類。
縮醛化反應所使用的酸觸媒,可列舉例如硫酸、硝酸、鹽酸、磷酸等之無機酸類;如甲酸、乙酸、丁酸、三氟乙酸等的羧酸類;甲磺酸、苯磺酸、甲苯磺酸等的磺酸類;如甲烷膦酸、苯膦酸之膦酸類等。其中,就乙烯醚之聚合反應抑制的觀點,較佳為磷酸或磺酸。
酸觸媒之使用量係因使用之酸的種類而異,無法一概限定,但是相對於反應系,通常為1~5000ppm,較佳為1~2000ppm。酸觸媒之使用量在上述範圍內時,不易產生乙烯醚之聚合反應等之副反應,又,容易得到充分的反應速度。
縮醛化反應所使用之溶劑,只要是可穩定溶解原料之具有酚性羥基的聚合物、乙烯醚、酸觸媒、及縮醛化反應所得之產物的溶劑即可,具體而言,可列舉乙酸甲酯、乙酸乙酯、乙酸異丙酯、乙酸丙酯、乙酸丁酯、丙酸甲酯、乳酸甲酯、乳酸乙酯等之酯類;乙二醇單甲醚乙酸酯、乙二醇單***乙酸酯、丙二醇單甲醚乙酸酯、丙二醇單***乙酸酯等之醚酯類;四氫呋喃、1,4-二噁烷、乙二醇二甲醚等之醚類;甲苯、二甲苯等之芳香族烴類,彼等可單獨使用或混合2種以上使用。
縮醛化反應之溫度,較佳為25~120℃,更佳為30~100℃,又更佳為30~80℃。
本發明之聚合物中之酚性羥基之藉由式(1)表示之基團的保護率(保護基導入率)係相對於聚合物所含有之全苯酚數100莫耳%,較佳為20~60莫耳%,更佳為25~55莫耳%,又更佳為30~50莫耳%。保護基導入率為20莫耳%以上時,容易調節保護基導入率,故更容易調節鹼溶解速度,又,60莫耳%以下時,調節鹼溶解速度,可容易形成所期望之阻劑圖型。
本發明之聚合物中之酚性羥基之藉由式(2)表示之基團的保護率(保護基導入率)係相對於聚合物所含有之全苯酚數100莫耳%,較佳為1~10莫耳%,更佳為2~8莫耳%。保護基導入率為上述範圍內時,調節鹼溶解速度,可容易形成所期望之阻劑圖型。
縮醛化反應後,添加鹼性化合物,也可將酸觸媒進行中和。具體而言,可列舉鈉、鉀等之鹼金屬之氫氧化物、碳酸鹽、碳酸氫鹽等之鹼金屬化合物;氨水及氨氣體;如三甲基胺、三乙基胺之胺類;如吡啶、甲基吡啶之吡啶類;如氫氧化四烷基銨之四級銨化合物;及鹼性離子交換樹脂等,較佳為胺類、四級銨化合物,又更佳為胺類。
本發明之聚合物,也可含有其他的結構。提供其他結構單元的單體,為了調整對微影溶劑或鹼顯影液之溶解性或基板密著性等,可使用公知阻劑用聚合物所使用的各種單體。
具有酚性羥基的聚合物為具有來自p-羥基苯乙烯或4-羥基苯基(甲基)丙烯酸酯之結構單元的聚合物時,作為共聚單體,可列舉例如苯乙烯、乙烯基萘、乙烯基蒽等所衍生之苯乙烯系單體;丙烯酸、甲基丙烯酸所衍生之各種的(甲基)丙烯酸酯系單體;降莰烯、三環癸烯、四環十二碳烯等所衍生之降莰烯系單體等。又,茚、苊烯等也可共聚合。但是上述單體中,具有酸解離性基之單體之使用,必須注意避免因縮醛化反應時使用之酸觸媒的作用,酸解離性基產生脫離。
具有來自p-羥基苯乙烯或4-羥基苯基(甲基)丙烯酸酯之結構單元的聚合物,可藉由例如日本特開平02-047109、日本特開平10-251315、日本再表2012/081619等所記載之習知的方法製造。
又,聚p-羥基苯乙烯可由丸善石油化學(股)或日本曹達(股)取得。
具有酚性羥基的聚合物為藉由酚類與、醛類或酮類之縮聚合所得的酚醛清漆型聚合物時,可藉由習知的方法製造。亦即,藉由將酚類與、醛類或酮類在酸觸媒之存在下,使反應的方法製造。又,許多種類的酚醛清漆型樹脂有市售,因此,可使用該等市售品。
交聯型聚合物之重量平均分子量(Mw)及分散度(Mw/Mn),可配合其用途適宜設定者,無特別限定。例如,重量平均分子量(Mw),就展現高分子性的觀點,較佳為5,000~400,000,更佳為7,000~100,000,又更佳為10,000~50,000,又更佳為20,000~40,000。又,分散度(Mw/Mn),其上限值較佳為20以下,更佳為15以下,又更佳為12以下,又更佳為10以下,下限值較佳為2以上,更佳為3以上,又更佳為4以上。
又,本發明中,交聯型聚合物之重量平均分子量(Mw)及分散度(Mw/Mn)係藉由GPC(凝膠滲透層析)而得的測定值,可以後述的測定條件測定。
<厚膜阻劑用組成物>
包含上述聚合物的組成物,例如可用於半導體微影所需要之阻劑等的用途。特別是適用於形成膜厚1μm以上,較佳為膜厚1μm以上、100μm以下之厚膜阻劑的用途。本發明之厚膜阻劑用組成物,至少包含聚合物、溶劑、及酸產生劑,也可再含有酸擴散抑制劑等。
酸產生劑可適宜選擇使用以往作為化學增強型阻劑用之酸產生劑所提案者。這種例,可列舉錪鹽或鋶鹽等之鎓鹽、肟磺酸鹽類、雙烷基或雙芳基磺醯基重氮甲烷類等之重氮甲烷類、硝基苄基磺酸鹽類、亞胺基磺酸鹽類、二碸類等,其中較佳為鎓鹽。此等可單獨使用,也可組合2種以上使用。
酸擴散抑制劑可適宜選擇使用以往作為化學增強型阻劑用之酸擴散抑制劑所提案者。這種例,可列舉含氮有機化合物,較佳為一級~三級之烷基胺或羥基烷基胺。特別是三級烷基胺、三級羥基烷基胺為佳,其中特佳為三乙醇胺、三異丙醇胺。此等可單獨使用,也可組合2種以上使用。
溶劑只要是可將構成阻劑用組成物之各成分溶解,作為均勻的溶液者即可,可將作為塗膜形成用溶劑之公知之任意者,以1種單獨溶劑或2種以上之混合溶劑使用。因溶解性優異,故具有選自酮鍵、酯鍵、醚鍵、及羥基之至少1種以上之極性基的溶劑為佳。其中,在常壓下之沸點為110~220℃的溶劑,在旋轉塗佈後之烘烤中,蒸發速度適當,製膜性優異,故特佳。這種溶劑的具體例,可列舉甲基異丁酮、甲基異戊基酮、甲基戊基酮、環己酮等之具有酮鍵的溶劑、丙二醇單甲醚(PGME)、丙二醇單***等之具有醚鍵與羥基的溶劑、丙二醇單甲醚乙酸酯(PGMEA)、丙二醇單***乙酸酯、3-乙氧基丙酸乙酯等之具有醚鍵與酯鍵的溶劑、乳酸甲酯、乳酸乙酯等之具有酯鍵與羥基的溶劑、γ-丁內酯等之具有酯鍵的溶劑等。其中,較佳為PGMEA、PGME、γ-丁內酯、乳酸乙酯。
阻劑用組成物,必要時可適宜含有酸產生劑之感度劣化防止或提高阻劑圖型的形狀、曝光後安定性等為目的之有機羧酸類或磷之含氧酸類、改良阻劑膜性能用的加成樹脂、提高塗佈性用的界面活性劑、溶解抑止劑、可塑劑、安定劑、著色劑、光暈防止劑、染料等、作為阻劑用添加劑慣用的化合物。
[實施例]
以下舉實施例,更具體地說明本發明之實施形態。但是本發明不限定於此等實施例者。以下,無特別聲明時,份為質量基準。
[重量平均分子量・分散度]
下述合成之聚合物的重量平均分子量(Mw)及分散度(Mw/Mn)係將聚苯乙烯作為標準品,藉由GPC(凝膠滲透層析)測定。將純化後之聚合物0.02g溶解於四氫呋喃1ml中,調製分析用試料。對裝置之試料注入量為50μl。
測定裝置:東曹公司製 HPLC-8320GPC
檢測器:示差折射率(RI)檢測器
管柱:Shodex GPC KF804×3(昭和電工製)
溶離液:四氫呋喃
流速:1.0mL/分鐘
溫度:40℃
檢量線:使用聚苯乙烯標準樣品(東曹公司製)製作
[聚合物組成比・保護基導入率]
下述合成之聚合物之保護基導入率係以13
C-NMR分析。將純化後之聚合物溶液2.0g與Cr(III)乙醯丙酮0.1g溶解於重丙酮1.0g中,調製分析用試料。
裝置:Bruker製「AVANCE400」
核種:13
C
測定法:反閘控去耦(inverse gated decoupling)
積算次數:6000次
測定管徑:10mmϕ
[微影評價]
相對於聚合物1.0份,添加界面活性劑(DIC製、
Megafac F477)0.1份與光酸產生劑(ADEKA製、SP606)0.2份,將此溶解於丙二醇單甲醚乙酸酯(以下稱為PGMEA),旋轉塗佈於基板上時,使膜厚成為10μm來調整濃度。將混合液以孔徑0.04μm尼龍過濾器過濾,得到阻劑用組成物。
在室溫24℃下使用旋轉塗佈機,將上述阻劑用組成物塗佈於進行了六甲基二矽氮烷處理(100℃×60秒)的6吋晶圓晶圓基板上。塗佈後的基板以100℃烘烤60秒後,使用i線光源改變曝光量進行曝光後,在室溫下放置180秒。然後,將基板設置於顯影速度測定裝置RDA-800上,在23℃下使用2.38質量%氫氧化四甲銨水溶液,顯影180秒鐘,測定各曝光量之顯影中之阻劑膜厚的經時變化。解析數據,得到阻劑之感度Eth(作為阻劑之殘膜率0%用所需的曝光量(mJ/cm2
)。Eth表示值越小,越高感度。
[調整例1]聚p-羥基苯乙烯(聚PHS)溶液之調製
在具備溫度計、冷凝管及攪拌裝置之茄型燒瓶中,投入聚p-羥基苯乙烯(丸善石油化學製、MARUKA
LYNCURM S-2P)1000份、丙二醇單甲醚乙酸酯(以下稱為「PGMEA」)5000份,邊攪拌邊將體系內進行氮取代,加熱昇溫至60℃。其次,減壓濃縮下,將PGMEA濃縮,去除剩餘的水分與PGMEA,進行濃度調整成為30wt%。
所得之聚合物為Mw=5,700,Mw/Mn=2.03。
[調製例2]酚醛清漆樹脂溶液之調製
在具備溫度計、冷凝管及攪拌裝置之茄型燒瓶中,投入酚醛清漆樹脂(DIC製PHENOLITE TD-2090)272份、PGMEA 1565份,40℃下減壓濃縮,去除剩餘的水分與PGMEA,將酚醛清漆樹脂濃度調整成為30wt%。
調製後之酚醛清漆樹脂為Mw=7600,Mw/Mn=4.70。
[實施例1]聚PHS-MOVE35-CHDVE保護聚合物
在具備溫度計、冷凝管及攪拌裝置之茄型燒瓶中,投入調製例1所得之30wt%聚-p-羥基苯乙烯/PGMEA溶液206.8份、PGMEA 31.2份、0.1wt%甲磺酸(以下稱為「MSA」)之PGMEA溶液0.8份,邊攪拌邊將體系內進行氮取代,加熱昇溫至40℃。其次,將(2-甲氧基乙基)乙烯醚(以下稱為「MOVE」)19.6份、PGMEA 18.4份的混合溶液以30分鐘滴下。進行2小時熟成,將1,4-環己烷二甲醇二乙烯醚(日本Kabaido工業製、以下稱為「CHDVE」)3.0份、PGMEA 6.3份的混合溶液以10分鐘滴下。進行2小時熟成,將三乙基胺(和光純藥工業製、以下稱為「TEA」)0.008份、PGMEA 25.0份的混合溶液停止反應。然後,以Amberlyst B20-HG・DRY(organo公司製)1.1份花費約6小時,使用管柱進行離子交換。離子交換後,40℃減壓濃縮去除PGMEA,濃度調整成為50wt%。
[實施例2]聚PHS-MOVE25-CHDVE保護聚合物
在具備溫度計、冷凝管及攪拌裝置之茄型燒瓶中,投入調製例1所得之30wt%聚-p-羥基苯乙烯/PGMEA溶液331.5份、PGMEA 54.2份、0.1wt%MSA之PGMEA溶液1.2份,邊攪拌邊將體系內進行氮取代,加熱昇溫至40℃。其次,將MOVE 20.7份、PGMEA 19.7份的混合溶液以30分鐘滴下。進行2小時熟成,將CHDVE 4.8份、PGMEA 10.8份的混合溶液,以10分鐘滴下。進行2小時熟成,以TEA 0.013份、PGMEA 43.3份的混合溶液停止反應。然後,以AmberlystB20-HG・DRY(organo公司製)1.7份花費約6小時,使用管柱進行離子交換。離子交換後,40℃減壓濃縮去除PGMEA,濃度調整成為50wt%。
[實施例3]聚PHS-MOVE45-CHDVE保護聚合物
在具備溫度計、冷凝管及攪拌裝置之茄型燒瓶中,投入調製例1所得之30wt%聚-p-羥基苯乙烯/PGMEA溶液329.9份、PGMEA 37.5份、0.1wt%MSA之PGMEA溶液1.2份,邊攪拌邊將體系內進行氮取代,加熱昇溫至40℃。其次,將MOVE 37.1份、PGMEA 37.1份的混合溶液以30分鐘滴下。進行2小時熟成,將CHDVE 4.8份、PGMEA 9.1份的混合溶液以10分鐘滴下。進行2小時熟成,以TEA 0.013份、PGMEA 36.5份的混合溶液停止反應。然後,以AmberlystB20-HG・DRY(organo公司製)1.7份花費約6小時,使用管柱進行離子交換。離子交換後,40℃減壓濃縮去除PGMEA,濃度調整成為50wt%。
[實施例4]聚PHS-EOVE35-CHDVE保護聚合物
在具備溫度計、冷凝管及攪拌裝置之茄型燒瓶中,投入調製例1所得之30wt%聚-p-羥基苯乙烯/PGMEA溶液197.6份、PGMEA 25.4份、0.1wt%MSA之PGMEA溶液1.5份,邊攪拌邊將體系內進行氮取代,加熱昇溫至40℃。其次,將(2-乙氧基乙基)乙烯醚(以下稱為「EOVE」)20.8份、PGMEA 18.8份的混合溶液以30分鐘滴下。進行2小時熟成,將CHDVE 3.0份、PGMEA 5.1份的混合溶液以10分鐘滴下。進行2小時熟成,以TEA 0.015份、PGMEA 20.3份的混合溶液停止反應。然後,以Amberlyst B20-HG・DRY (organo公司製)2.0份花費約6小時進行離子交換。離子交換後,減壓濃縮下,將PGMEA濃縮,濃度調整成為50wt%。
[實施例5]聚PHS-TEGVE35-CHDVE保護聚合物
在具備溫度計、冷凝管及攪拌裝置之茄型燒瓶中,投入調製例1所得之30wt%聚-p-羥基苯乙烯/PGMEA溶液195.1份、PGMEA 11.8份、0.1wt%MSA的PGMEA溶液1.4份,邊攪拌邊將體系內進行氮取代,加熱昇溫至40℃。其次,將2-(2-(2-甲氧基乙氧基)乙氧基)乙基乙烯醚(以下稱為「TEGVE」)33.7份、PGMEA 31.8份的混合溶液以30分鐘滴下。進行2小時熟成,將CHDVE 3.0份、PGMEA 2.4份的混合溶液以10分鐘滴下。進行2小時熟成,以TEA 0.015份、PGMEA 9.5份的混合溶液停止反應。然後,以AmberlystB20-HG・DRY(organo公司製)2.0份花費約6小時進行離子交換。離子交換後,減壓濃縮下,將PGMEA濃縮,濃度調整成為50wt%。
[實施例6]酚醛清漆-MOVE35-CHDVE保護聚合物
在具備溫度計、冷凝管及攪拌裝置之茄型燒瓶中,投入調製例2所得之酚醛清漆樹脂溶液193.4份、PGMEA 26.7份、0.1wt%MSA的PGMEA溶液0.8份,邊攪拌邊將體系內進行氮取代,加熱昇溫至40℃。其次,將MOVE 20.6份、PGMEA 19.6份的混合溶液以30分鐘滴下。進行2小時熟成,將CHDVE 3.4份、PGMEA 5.3份的混合溶液以10分鐘滴下。進行2小時熟成,以TEA 0.009份、PGMEA 21.4份的混合溶液停止反應。然後,以AmberlystB20-HG・DRY (organo公司製)1.1份花費約6小時進行離子交換。離子交換後,減壓濃縮下,將PGMEA濃縮,濃度調整成為50 wt%。
[比較例1]聚PHS-EVE35-CHDVE保護聚合物
在具備溫度計、冷凝管及攪拌裝置之茄型燒瓶中,投入調製例1所得之30wt%聚-p-羥基苯乙烯/PGMEA溶液325.2份、PGMEA 60.5份、0.1wt%MSA的PGMEA溶液1.2份,邊攪拌邊將體系內進行氮取代,加熱昇溫至40℃。其次,將乙基乙烯醚(以下稱為「EVE」)21.5份、PGMEA 12.0份的混合溶液以30分鐘滴下。將CHDVE5.0份、PGMEA 5.3份的混合溶液以10分鐘滴下。進行1小時熟成,以TEA 0.013份、PGMEA 48.4份的混合溶液停止反應。然後,以AmberlystB20-HG・DRY(organo公司製)2.5份花費約6小時進行離子交換。離子交換後,減壓濃縮下,將PGMEA濃縮,濃度調整成為50wt%。
[比較例2]聚PHS-CHVE35-CHDVE保護聚合物
在具備溫度計、冷凝管及攪拌裝置之茄型燒瓶中,投入調製例1所得之30wt%聚-p-羥基苯乙烯/PGMEA溶液197.2份、PGMEA 22.3份、0.1wt%MSA的PGMEA溶液1.5份,邊攪拌邊將體系內進行氮取代,加熱昇溫至40℃。其次,將環己基乙烯醚(丸善石油化學製、以下稱為「CHVE」)23.8份、PGMEA 21.3份的混合溶液以30分鐘滴下。進行2小時熟成,將CHDVE 3.4份、PGMEA 5.3份的混合溶液以10分鐘滴下。進行2小時熟成,以TEA 0.015份、PGMEA 18.2份的混合溶液停止反應。然後,以
AmberlystB20-HG・DRY(organo公司製)2.0份花費約6小時進行離子交換。離子交換後,減壓濃縮下,將PGMEA濃縮,濃度調整成為50wt%。
[比較例3]聚PHS-DHP35-CHDVE保護聚合物
在具備溫度計、冷凝管及攪拌裝置之茄型燒瓶中,投入調製例1所得之30wt%聚-p-羥基苯乙烯/PGMEA溶液200.9份、PGMEA 30.9份、1.0wt%MSA的PGMEA溶液0.3份,邊攪拌邊將體系內進行氮取代,加熱昇溫至40℃。其次,將二氫吡喃(以下稱為「DHP」)15.4份、PGMEA 14.5份的混合溶液以30分鐘滴下。進行4小時熟成,將CHDVE 3.3份、PGMEA 6.2份的混合溶液以10分鐘滴下。進行30分鐘熟成,以TEA 0.015份、PGMEA 18.2份的混合溶液停止反應。然後,以Amberlyst B20-HG・DRY(organo公司製)2.7份花費約6小時進行離子交換。離子交換後、減壓濃縮下,將PGMEA濃縮,濃度調整成為50wt%。
[比較例4]聚PHS-MOVE35保護聚合物
在具備溫度計、冷凝管及攪拌裝置之茄型燒瓶中,投入調製例1所得之30wt%聚-p-羥基苯乙烯/PGMEA溶液 2211份、PGMEA 350份、0.1wt%MSA的PGMEA溶液 8.5份,邊攪拌邊將體系內進行氮取代,加熱昇溫至40℃。其次,將MOVE 214份、PGMEA 198份的混合溶液以30分鐘滴下。進行2小時熟成,以PGMEA 351份停止反應。然後,以AmberlystB20-HG・DRY(organo公司製)7.7份花費約6小時,使用管柱進行離子交換。離子交換後,以40℃減壓濃縮去除PGMEA,濃度調整成為50wt%。
測定實施例及比較例所得之聚合物之重量平均分子量(Mw)、分散度(Mw/Mn)、及保護基導入率,將微影評價結果(Eth)記載於表1。酚性羥基之保護率係確認以13
C-NMR定量進行。又,13
C-NMR無法將以單乙烯醚保護的單元與以二乙烯醚保護的單元分離、定量,故各自之導入率係記載以原料之投入量為基礎算出的值。
實施例1~6之以特定親水性之酸解離性保護基及交聯性保護基保護的交聯型聚合物,相較於比較例1~3之以往的疏水性的酸解離性保護基及交聯性保護基保護的聚合物,感度充分地提高。又,比較例4的聚合物,無交聯性保護基,僅以親水性之酸解離性保護基保護者,感度過佳,在光微影中之操作困難。
Claims (6)
- 一種阻劑用交聯型聚合物,其係因酸的作用,對顯影液之溶解性產生變化之阻劑用交聯型聚合物,聚合物中之酚性羥基之至少一部分,具有被以下式(1):
- 如請求項1之阻劑用交聯型聚合物,其中具有酚性羥基的聚合物為具有來自p-羥基苯乙烯或4-羥基苯基(甲基)丙烯酸酯之結構單元的聚合物。
- 如請求項1之阻劑用交聯型聚合物,其中具有酚性羥基的聚合物為藉由酚類與醛類或酮類之縮聚合所得的酚醛清漆型聚合物。
- 如請求項1~3中任一項之阻劑用交聯型聚合物,其中相對於前述聚合物所含有之全苯酚數100莫耳%,前述酚性羥基之被前述式(2)表示之基團的保護率為1~10莫耳%。
- 如請求項1~3中任一項之阻劑用交聯型聚合物,其中重量平均分子量為5,000~400,000。
- 一種厚膜阻劑用組成物,其係至少包含如請求項1~5中任一項之交聯型聚合物、溶劑及酸產生劑。
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