TWI835341B - 用於193nm水浸式光刻的聚合物樹脂、抗水塗層組合物、抗水塗層及其製備方法 - Google Patents
用於193nm水浸式光刻的聚合物樹脂、抗水塗層組合物、抗水塗層及其製備方法 Download PDFInfo
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- TWI835341B TWI835341B TW111138509A TW111138509A TWI835341B TW I835341 B TWI835341 B TW I835341B TW 111138509 A TW111138509 A TW 111138509A TW 111138509 A TW111138509 A TW 111138509A TW I835341 B TWI835341 B TW I835341B
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- Prior art keywords
- water
- resistant coating
- polymer resin
- acrylate
- perfluoropolyether
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000011248 coating agent Substances 0.000 title claims abstract description 44
- 238000000576 coating method Methods 0.000 title claims abstract description 44
- 239000002952 polymeric resin Substances 0.000 title claims abstract description 36
- 229920003002 synthetic resin Polymers 0.000 title claims abstract description 36
- 238000000671 immersion lithography Methods 0.000 title claims abstract description 29
- 239000008199 coating composition Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 51
- 239000000178 monomer Substances 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 25
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 23
- FQDXJYBXPOMIBX-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoro-2-methylpropan-2-ol Chemical group FC(F)(F)C(O)(C)C(F)(F)F FQDXJYBXPOMIBX-UHFFFAOYSA-N 0.000 claims abstract description 18
- -1 perfluoro chain Chemical group 0.000 claims abstract description 18
- KAKQVSNHTBLJCH-UHFFFAOYSA-N trifluoromethanesulfonimidic acid Chemical group NS(=O)(=O)C(F)(F)F KAKQVSNHTBLJCH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 4
- 239000010702 perfluoropolyether Substances 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000000839 emulsion Substances 0.000 claims description 11
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 238000005886 esterification reaction Methods 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- 230000032050 esterification Effects 0.000 claims description 9
- 239000003995 emulsifying agent Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 238000004945 emulsification Methods 0.000 claims description 5
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 claims description 5
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000012874 anionic emulsifier Substances 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 239000012875 nonionic emulsifier Substances 0.000 claims description 4
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 claims description 3
- AQZGPSLYZOOYQP-UHFFFAOYSA-N Diisoamyl ether Chemical compound CC(C)CCOCCC(C)C AQZGPSLYZOOYQP-UHFFFAOYSA-N 0.000 claims description 3
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 229920004890 Triton X-100 Polymers 0.000 claims description 2
- 239000013504 Triton X-100 Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- YENIOYBTCIZCBJ-UHFFFAOYSA-N acetic acid;1-methoxypropan-2-ol Chemical compound CC(O)=O.COCC(C)O YENIOYBTCIZCBJ-UHFFFAOYSA-N 0.000 claims 1
- 125000003368 amide group Chemical group 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 229940124530 sulfonamide Drugs 0.000 claims 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 10
- 239000011347 resin Substances 0.000 abstract description 10
- 239000003513 alkali Substances 0.000 abstract description 9
- 238000007654 immersion Methods 0.000 abstract description 8
- 238000000206 photolithography Methods 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 238000005530 etching Methods 0.000 abstract description 5
- 230000002378 acidificating effect Effects 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 229920001577 copolymer Polymers 0.000 abstract description 2
- 238000002386 leaching Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 18
- 238000005516 engineering process Methods 0.000 description 15
- 239000010410 layer Substances 0.000 description 12
- 238000001459 lithography Methods 0.000 description 12
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 10
- 239000004793 Polystyrene Substances 0.000 description 8
- 238000005227 gel permeation chromatography Methods 0.000 description 8
- 229920002223 polystyrene Polymers 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 229950000688 phenothiazine Drugs 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 2
- 239000010421 standard material Substances 0.000 description 2
- QAJCOMPEAMJMEB-UHFFFAOYSA-N 1,1,1-trifluoro-2-(trifluoromethyl)pentane-2,4-diol Chemical compound CC(O)CC(O)(C(F)(F)F)C(F)(F)F QAJCOMPEAMJMEB-UHFFFAOYSA-N 0.000 description 1
- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical compound CCCCCOCCCCC AOPDRZXCEAKHHW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 241001365789 Oenanthe crocata Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000276 deep-ultraviolet lithography Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000011011 extractables test Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012633 leachable Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 229920005548 perfluoropolymer Polymers 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
Classifications
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- 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
- C08F220/38—Esters containing sulfur
- C08F220/382—Esters containing sulfur and containing oxygen, e.g. 2-sulfoethyl (meth)acrylate
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- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
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- 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
- C08F220/22—Esters containing halogen
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- 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
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
-
- 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
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
-
- 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
- C08F220/38—Esters containing sulfur
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
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- 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
- C08F4/00—Polymerisation catalysts
- C08F4/04—Azo-compounds
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- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- G—PHYSICS
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- 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
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- 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
- G03F7/16—Coating processes; Apparatus therefor
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- 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
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/162—Coating on a rotating support, e.g. using a whirler or a spinner
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Abstract
本發明公開了一種用於193nm水浸式光刻的聚合物樹脂、抗水塗層組合物、抗水塗層及其製備方法，所述聚合物樹脂是將含六氟叔丁醇基團的丙烯酸酯單體、含全氟鏈丙烯酸酯的單體以及含三氟甲基磺醯胺基團的丙烯酸酯單體三元共聚得到。全氟烷基鏈的引入提高疏水性的同時增加了樹脂的接觸角性能和抗刻蝕能力，三氟甲基磺醯胺基團和六氟叔丁醇基的引入使樹脂有了更好的鹼溶性；採用本發明聚合物樹脂製備的抗水塗層組合物，不僅可以通過改變共聚物單體比例來匹配不同的193nm光刻膠，而且能得到線條良好的圖案；採用本發明塗層樹脂組合物製備的抗水塗層可有效避免浸沒式光刻工藝中光刻膠中酸性物質的浸出，並在顯影時自動去除，有利於簡化光刻工藝。
Description
本發明涉及積體電路製造技術領域，特別涉及積體電路製造中的光刻技術，具體涉及一種用於193nm水浸式光刻的聚合物樹脂，採用所述聚合物樹脂製備的抗水塗層組合物及抗水塗層，本發明同時還涉及所述聚合物樹脂、抗水塗層組合物及抗水塗層的製備方法。
光刻技術是積體電路製造中利用光學-化學反應原理和化學、物理刻蝕方法，將電路圖形傳遞到單晶表面或介質層上，形成有效圖形窗口或功能圖形的工藝技術。乾法光刻，尤其是193nm乾法光刻，目前已形成了成熟的技術工藝及設備，157nmF2光刻也一度被認為是繼193nm乾法光刻之後的新一代光刻技術，但由於光學鏡頭材料固有的反射光斑、掩模及保護膜材料、抗蝕劑以及污染控制等方面的技術障礙，導致乾法光刻技術發展受阻，對光刻技術的研究轉向了能克服所述技術障礙的浸沒式光刻技術，浸沒式光刻也由此成為了未來光刻技術發展的主流技術。
在對浸沒式光刻技術的研究中發現，如果將水(193nm下折射率n=1.44)作為浸沒介質填充到193nm乾法光刻設備的原空氣空間，就可以使193nm深紫外光刻技術達到65nm以下分辨率的要求。基於此，研究人員設想，若使用更高折射率的液體並對光刻工藝進行改進，即可使193nm ArF光刻技術延伸到45nm乃至32nm節點。
在193nm浸沒式光刻中，純水由於可使光學鏡頭的數值孔徑(NA值)高達1.35，而被視為首選的最佳浸沒介質；但是在光刻工藝中，由於水直接與光刻膠接觸會滲入膠膜內，導致光刻膠中所含極性物質如光致產酸劑(PAG)、曝光後產生的酸以及有機胺類添加劑等溶出，造成光刻膠圖案產生缺陷的同時也會使水本身受到污染，還會污染甚至腐蝕與之接觸的鏡頭。因此，純水作為浸沒液體的193nm光刻需在光刻膠表層再塗布一層頂部塗料等方法進行改進。D.P.Sanders等人用六氟叔丁醇基(HFA)材料作為聚合物樹脂，但其單獨使用無法滿足193nm水浸式光刻技術對鹼溶性的要求；M.Khojasteh等人選用2-丙烯醯胺-2-丙基磺酸單體(MVP)與含HFA基團的單體共聚得到了MVP系列頂部塗層材料，強酸性的磺酸基團雖然能明顯增強材料在顯影液中的鹼溶性，但也減小了與水的接觸角故而應用效果不佳。
本發明的第一個目的是為了克服現有193nm水浸式光刻膠頂部塗層材料存在的上述缺陷，提供一種用於193nm水浸式光刻的聚合物樹脂，以滿足193nm水浸式光刻技術對光刻膠頂部塗層鹼溶性、接觸角的要求。
本發明的第二個目的是提供上述聚合物樹脂的製備方法。
本發明的第三個目的是提供一種採用上述聚合物樹脂製備的
抗水塗層組合物。
本發明的第四個目的是提供一種上述抗水塗層組合物的製備方法。
本發明的第五個目的是提供一種採用上述抗水塗層組合物製備抗水塗層的方法。
本發明的第六個目的是提供一種採用上述製備方法製備的抗水塗層。
為實現其目的，本發明採用如下技術方案：一種用於193nm水浸式光刻的聚合物樹脂，是將含六氟叔丁醇基團的丙烯酸酯單體、含全氟鏈丙烯酸酯的單體以及含三氟甲基磺醯胺基團的丙烯酸酯單體進行三元共聚得到，其結構通式如下：
其中，R為氫原子或甲基；R1、R3均為C1-C6鏈狀二價的烴基；R2為C1-C18的全氟聚醚烷基；R4為C1-C6的全氟烷基；m、n、p為各單體的莫耳佔比，m：n：p=10-30：30-40：30-60。
作為本發明技術方案的優選，上述R2為C1-C6的全氟聚醚烷基。
進一步地，所述含全氟鏈丙烯酸酯的單體的合成方法包括：
步驟一、全氟聚醚醯氟合成
六氟環氧丙烷(HFPO)開環聚合，得到全氟聚醚醯氟；反應式如下：
步驟二、全氟聚醚醯氟甲酯化
取全氟聚醚醯氟置於恆壓漏斗，取1.2~2倍莫耳量甲醇置於三口燒瓶，緩慢滴加全氟聚醚醯氟於三口燒瓶中，滴加完畢升溫至30-45℃，反應2-6h，然後加入去離子水洗滌，搖晃後靜置分層，去除上層溶液，得到甲酯化產物，反應式如下：
步驟三、全氟聚醚醇的合成
取步驟三中甲酯化產物於三口燒瓶中，乙醇作溶劑，加入1.5-2倍莫耳量的硼氫化鈉，室溫下回流反應4-6h，用去離子水水洗，除去上層溶液，將下層產物在80℃下真空旋蒸除去甲醇和乙醇，得到全氟聚醚醇，反應式如下：
步驟四、全氟聚醚丙烯酸酯的合成
取全氟聚醚醇置於三口燒瓶，加入3倍莫耳量的三氟三氯乙烷和1.2-1.5倍莫耳量的三乙胺，在冰水浴條件下緩慢滴加1.2-1.5倍莫耳量的丙烯醯氯，滴加完畢升溫至25-40℃，繼續反應4-6h，反應完畢後加入去離子水洗滌，靜置分層，用無水硫酸鎂除去體系中殘留水分得到全氟聚醚丙烯酸酯，反應式如下：
上述各步驟中，0<n
4。
本發明用於193nm水浸式光刻的聚合物樹脂的製備方法，包括以下步驟：步驟一、以含六氟叔丁醇基團的丙烯酸酯單體、含全氟鏈丙烯酸酯的單體和含三氟甲基磺醯胺丙烯酸酯單體總重為100重量份，加入150~250份水，0.3~0.5份水溶性引發劑、2~5份水溶性乳化劑，磁力攪拌30-45min後，超聲乳化20-30min，得到白色乳液；所述含六氟叔丁醇基團的丙烯酸酯單體、含全氟鏈丙烯酸酯的單體、含三氟甲基磺醯胺丙烯酸酯單體的莫耳比為10-30：30-40：30-60；步驟二、將步驟一中白色乳液加入裝有攪拌器、回流冷凝管和氮氣導管的三口燒瓶中，攪拌並通入氮氣，升溫至60-75℃引發聚合，待白色乳液變成藍相後，持續反應2-2.5h，然後升溫至85℃熟化1-1.5h，降至室溫過濾出料，用丙酮破乳後在真空烘箱乾燥2h即得聚合物樹脂。
進一步地，步驟一中所述水溶性引發劑為過硫酸銨、過硫酸鉀或偶氮二異丁腈中一種或多種。
進一步地，步驟一中所述水溶性乳化劑由陰離子乳化劑與非離子乳化劑混合而成；所述陰離子乳化劑為十二烷基硫酸鈉，非離子乳化劑為曲拉通X-100。
本發明提供的一種用於193nm水浸式光刻的抗水塗層組合物，是將所述聚合物樹脂溶解於4-甲基-2-戊醇、二異戊醚、乙醇、丙二醇甲醚醋酸酯中的一種或多種溶劑中並經0.2μm PTFE過濾器過濾制得抗水塗層組合物。
優選地，所述抗水塗層組合物中，聚合物樹脂的質量分數為1-5%。
本發明提供的一種用於193nm水浸式光刻的抗水塗層的製備方法，是先將193nm光刻膠塗覆在基片上，在110℃下烘烤60s後，將請求項7所述抗水塗層組合物旋塗於光刻膠表層(在3000rpm下旋塗60s)，隨後在90℃烘烤60s即得抗水塗層。
與現有193nm水浸式光刻膠頂部塗層材料相比，本發明具有以下有益效果：
1、本發明將含六氟叔丁醇基團丙烯酸酯單體、含全氟鏈丙烯酸酯單體以及含三氟甲基磺醯胺基團丙烯酸酯單體進行三元共聚，得到了各方面性能俱佳的聚合物樹脂，其中，全氟烷基鏈的引入提高疏水性的同時增加了樹脂的接觸角性能和抗刻蝕能力，三氟甲基磺醯胺基團和六氟叔丁醇基的引入使樹脂有了更好的鹼溶性，滿足193nm水浸式光刻膠頂部塗層材料的使用要求。
2、採用本發明聚合物樹脂製備的抗水塗層組合物，不僅可以通過改變共聚物單體比例以改變材料性能，來匹配不同的193nm光刻膠，而且能得到線條良好的圖案。
3、採用本發明塗層樹脂組合物製備的抗水塗層有良好的疏水性能，可有效避免浸沒式光刻工藝中光刻膠中酸性物質的浸出。
4、採用本發明塗層樹脂製備的抗水塗層由於全氟鏈的引入使含氟量提高而具有良好的抗刻蝕能力，能進行多重曝光得到高分辨率圖案。
5、採用本發明塗層樹脂製備的抗水塗層具有良好鹼溶速率，能在顯影時自動去除，不增加額外去除工藝，從而簡化光刻工藝。
圖1為本發明實施例1全氟聚醚丙烯酸酯合成中全氟聚醚醯氟甲酯化產物的FT-IR分析圖譜；圖2為本發明實施例1全氟聚醚丙烯酸酯合成中全氟聚醚丙烯酸酯的FT-IR分析圖譜；圖3為未使用防水塗層的光學放大膠AZ 40 XT在0.26N四甲基氫氧化銨水溶液中顯影的掃描電子顯微鏡圖案；圖4為本發明實施例5中抗水塗層樣品在0.26N四甲基氫氧化銨水溶液中顯影的掃描電子顯微鏡圖案。
下面結合附圖和具體實施例對本發明進行詳細說明。
本發明實施例中單體來源如下：
一、含六氟叔丁醇基團的丙烯酸酯單體
本發明所列舉實施例中含六氟叔丁醇基團的丙烯酸酯單體為1,1,1-三氟-2-三氟甲基-2-羥基-4-甲基丙烯酸戊酯，參考文獻US2005/165249 A1，2005合成，具體為：向500ml三口燒瓶中加入攪拌磁子，加入50.0g(0.22mol)1,1,1-三氟-2-三氟甲基-2,4-戊二醇、150g甲苯，25g(0.24mol)甲基丙烯酸酐、19g吡啶、0.5g吩噻嗪，然後在油浴中攪拌加熱，使其溫度為95-100℃。6h後，停止反應。
冷卻反應液後，過濾除去副產物不溶物。所得濾液用10%鹽酸水溶液(體積百分數)洗滌。然後用10%碳酸鈉水溶液(wt%)洗滌兩次。所得有機層用30g硫酸鎂乾燥，然後過濾除去硫酸鎂。向所得濾液中加入0.7g吩噻嗪(阻聚劑)，然後蒸餾出溶劑，減壓收集80-82℃餾分，得到1,1,1-三氟-2-三氟甲基-2-羥基-4-甲基丙烯酸戊酯單體。
二、含三氟甲基磺醯胺基團的丙烯酸酯單體
本發明所列舉實施例中含三氟甲基磺醯胺基團丙烯酸酯單體為2-甲基-2-(三氟甲基磺醯胺)甲基丙烯酸丙酯，購自上海阿拉丁生化科技股份有限公司。
三、含全氟鏈丙烯酸酯的單體
本發明實施例中含全氟鏈丙烯酸酯的單體為全氟聚醚丙烯酸酯，通過以下方法合成：
(1)全氟聚醚醯氟的合成
在500ml微型高壓反應釜中加入100ml二乙二醇二甲醚和50ml乙腈，加入5g氟化鉀為催化劑，用氮氣置換釜內氣體後真空抽至負壓，開啟攪拌，30min後持續通入六氟環氧丙烷(HFPO)，用流量計控制釜內壓力小於0.5Mpa，溫度控制在10℃~30℃進行聚合反應；累計通入800gHPFO後將反應釜溫度調整至室溫，反應液靜置分層，回收下層物質，即得全氟聚醚醯氟。
(2)全氟聚醚醯氟甲酯化
用量筒分別量取全氟聚醚醯氟5mL，甲醇10mL，置於100mL三口燒瓶中，溫度設置為30℃，當溫度上升至30℃，維持反應溫度反應3h，反應完成後，將產物移至250mL分液漏斗中，加入30mL去離子水，搖晃後靜置分層，上層為去離子水，下層為粘稠產物，去除上層溶液，留下層產物，重復去離子水洗兩次。取下層產物進行傅里葉變換紅外光譜FT-IR分析，分析結果如圖1。
從圖1中結果可以看出，990cm-1處出現又尖又強的峰，對應為-C-O-C-的伸縮振動峰；1221cm-1、1195cm-1和1289cm-1處出現的吸收峰對應為-CF-、-CF2-、-CF3-的伸縮振動峰。1788cm-1左右出現的的吸收峰是-COO的伸縮振動峰，2970cm-1出現的吸收峰是脂肪族化合物中甲基吸收的不對稱伸縮振動峰，說明瞭甲基的存在。以上結果表明，全氟聚醚醯氟發生了甲酯化反應，並且全部轉化成為了全氟聚醚甲酯化產物。根據反應前後IR分析，產物正確。
(3)全氟聚醚醇的合成
向100mL三口燒瓶中加入5g全氟聚醚酯化產物，加入10mL乙醇，2g NaBH4，溫度設置為25℃，當溫度升高至25℃後維持溫度不變，在大氣壓下回流反應4h，反應結束後，將產物移至250mL分液漏斗中，向裡面加入30mL去離子水，搖晃後置於250mL分液漏斗中，靜置分層，去掉上層溶液，將下層產物在80℃下真空旋轉蒸發儀旋轉1h，去掉甲醇和乙醇，得到全氟聚醚醇。
(4)全氟聚醚丙烯酸酯的合成
將40g全氟聚醚醇加入三口瓶中，加入150ml三氟三氯乙烷，加入3g三乙胺後，在冰水浴的條件下緩慢滴加丙烯醯氯5g，半小時滴加完畢，緩慢升溫至25℃，繼續攪拌反應6h後，加入大量去離子水洗滌，靜置分層，反復三次，用無水硫酸鎂除去體系中殘留水分得到全氟聚醚丙烯酸酯產物36g，產率90%。產物FT-IR分析結果如圖2。
圖2結果顯示，全氟聚醚醇羥基峰消失，證明全氟聚醚丙烯酸酯產物反應完全。
本發明實施例中抗水塗層樣品的性能測試，是將AZ 40 XT光刻膠旋塗於矽片，在110℃下烘烤60s，然後旋塗抗水塗層樣品，在90℃下烘烤60s，然後進行動態接觸角測試、光刻膠溶出物檢測和鹼溶性檢測，並以未旋塗抗水塗層的AZ 40 XT光刻膠矽片作為對比例：
(1)動態接觸角測試：將水滴於矽片上的抗水塗層樣品表面，進行傾斜角度測試。
(2)光刻膠溶出物檢測：將整張矽片浸入水中，用液相檢測水中化學物質。
(3)鹼溶性測試：測定抗水塗層樣品在0.26N四甲基氫氧化銨水溶液中顯影的掃描電子顯微鏡圖案，以及溶解速率(nm/s)。
實施例1
本實施例提供的一種用於193nm水浸式光刻的聚合物樹脂的製備方法，包括以下步驟：步驟一、以1,1,1-三氟-2-三氟甲基-2-羥基-4-甲基丙烯酸戊酯、全氟聚醚丙烯酸酯和2-甲基-2-(三氟甲基磺醯胺)甲基丙烯酸丙酯總重為100重量份，加入150份水，0.3份水溶性引發劑(過硫酸銨)、2份水溶性乳化劑(十二烷基硫酸鈉與曲拉通質量比1；1)，磁力攪拌30min後，超聲乳化20min，得到白色乳液；所述含六氟叔丁醇基團的丙烯酸酯單體、含全氟鏈丙烯酸酯的單體、含三氟甲基磺醯胺丙烯酸酯單體的莫耳比為30：40：30；步驟二、將步驟一中白色乳液加入裝有攪拌器、回流冷凝管和氮氣導管的三口燒瓶中，攪拌並通入氮氣，升溫至60℃引發聚合，待白色乳液變成藍相後，持續反應2h，然後升溫至85℃熟化1h，降至室溫過濾出料，用丙酮破乳後在真空烘箱乾燥2h即得聚合物樹脂。
採用THF作為溶劑，通過GPC(凝膠滲透色譜法)測定的pSt(聚苯乙烯)換算分子量，即重均分子量(Mw)為18200g/mol，通過19F-NMR及1H-NMR檢測結構正確。
19F-NMR及1H-NMR檢測數據如下：
1H NMR(溶劑：CdCl3；標準物質：TMS)；6.16(q，j=0.98Hz，1H)，5.96(bs，1H)，5.66(q，j=46Hz，1H)，5.13-5.20(m，1H)，2.24-2.36(m，2H)，94(dd，j=46Hz，0.98Hz，3H)，44(d，j=6.34Hz，3H)；19FNMR(溶劑：CdCl3；標準物質：CCL3f)；-77.03(q，j=9.67Hz，3f)，-79.25(q，j=9.67Hz，3F)。
實施例2
本實施例提供的一種用於193nm水浸式光刻的聚合物樹脂的製備方法，步驟一中：加入200份水，0.4份過硫酸銨、3份水溶性乳化劑，磁力攪拌35min後，超聲乳化25min，所述含六氟叔丁醇基團的丙烯酸酯單體、含全氟鏈丙烯酸酯的單體、含三氟甲基磺醯胺丙烯酸酯單體的莫耳比為10：50：40；步驟二中：升溫至65℃引發聚合，其他條件同實施例1，得到聚合物樹脂。通過GPC(凝膠滲透色譜法)測定的pSt(聚苯乙烯)換算分子量，即重均分子量(Mw)為9000g/mol。
實施例3
本實施例提供的一種用於193nm水浸式光刻的聚合物樹脂的製備方法，步驟一中：加入250份水，0.5份過硫酸銨、5份水溶性乳化劑，磁力攪拌45min後，超聲乳化30min，所述含六氟叔丁醇基團的丙烯酸酯單體、含全氟鏈丙烯酸酯的單體、含三氟甲基磺醯胺丙烯酸酯單體的莫耳比為30：40：30；步驟二中：升溫至75℃引發聚合，待白色乳液變成藍相後，持續反應2.5h，然後升溫至85℃熟化1.5h，其他條件同實施例1，得到聚合物樹脂。通過GPC(凝膠滲透色譜法)測定的pSt(聚苯乙烯)換算分子量，即重均分子量(Mw)為11000g/mol。
實施例4
本實施例提供的一種用於193nm水浸式光刻的聚合物樹脂的製備方法，步驟一中：水溶性引發劑為偶氮二異丁腈；水溶性乳化劑為十二烷基硫酸鈉與辛基苯基聚氧乙烯醚以質量比1：1形成的混合物。
其他反應條件同實施例1，得到聚合物樹脂。通過GPC(凝膠滲透色譜法)測定的pSt(聚苯乙烯)換算分子量，即重均分子量(Mw)為16000g/mol。
實施例5
本實施例提供的一種用於193nm水浸式光刻的抗水塗層的製備方法，將1%實施例1中樹脂溶解於65%的4-甲基-2-戊醇和34%的二異戊醚的混合物中，得到抗水塗層組合物；先將光刻膠AZ 40 XT塗覆在基片上，在110℃下烘烤60s後，將所述抗水塗層組合物旋塗於光刻膠表層，在90℃烘烤60s後即得抗水塗層，標記為FS-01。其性能檢測數據見表1。
實施例6
本實施例提供的一種用於193nm水浸式光刻的抗水塗層的製備方法中，是將5%的實施例2中樹脂溶解於65%的4-甲基-2-戊醇和30%的二異戊醚的混合物中；在110℃下烘烤60s後，將所述抗水塗層組合物旋塗於光刻膠表層，在90℃烘烤60s後即得到的抗水塗層，標記為FS-02。其性能檢測數據見表1。
實施例7
本實施例提供的一種用於193nm水浸式光刻的抗水塗層的製備方法中，是將1%的實施例3中樹脂溶解於99%的PGMEA中；在110℃下烘烤60s後，將所述抗水塗層組合物旋塗於光刻膠表層，在90℃烘烤60s後即得到的抗水塗層，標記為FS-03。其性能檢測數據見表1。
根據表1數據，該抗水塗層有良好的鹼溶速率(均超過200nm/s，最高可達846nm/s)且在水中無酸性物質浸出，後接觸角均大於70°，前接觸角均大於95°，接觸性良好。
本發明未使用防水塗層的光學放大膠AZ 40 XT在0.26N四甲基氫氧化銨水溶液中顯影的掃描電子顯微鏡圖案如圖3所示；實施例5得到的FS-01抗水塗層樣品在0.26N四甲基氫氧化銨水溶液中顯影的掃描電子顯微鏡圖案如圖4所示，從圖中可以看出，在193nm水浸式光刻中，光學放大膠AZ 40 XT的半節距圖案邊緣粗糙(圖3)，而FS-01抗水塗層在193nm水浸式光刻中得到了線條良好的45nm半節距圖案(圖4)，效果顯著。
Claims (9)
- 一種用於193nm水浸式光刻的聚合物樹脂，該聚合物樹脂是將含六氟叔丁醇基團的丙烯酸酯單體、含全氟鏈丙烯酸酯的單體以及含三氟甲基磺醯胺基團的丙烯酸酯單體進行三元共聚得到，其結構通式如下：
- 如請求項1所述的一種用於193nm水浸式光刻的聚合物樹脂，其中該R2為C1-C6的全氟聚醚烷基。
- 一種如請求項1或2所述的用於193nm水浸式光刻的聚合物樹脂的製備方法，其中包括以下步驟：步驟一、以含六氟叔丁醇基團的丙烯酸酯單體、含全氟鏈丙烯酸酯的單體和含三氟甲基磺醯胺丙烯酸酯單體總重為100重量份，加入150~250份水，0.3~0.5份水溶性引發劑、2~5份水溶性乳化劑，磁力攪拌30-45min後，超聲乳化20-30min，得到白色乳液；該含六氟叔丁醇基團的丙烯酸酯單體、含全氟鏈丙烯酸酯的單體、含三氟甲基磺醯胺丙烯酸酯單體的莫耳比為10-30：30-40：30-60；步驟二、將步驟一中白色乳液加入裝有攪拌器、回流冷凝管和氮氣導管的三口燒瓶中，攪拌並通入氮氣，升溫至60-75℃引發聚合，待白色乳液變成藍相後，持續反應2-2.5h，然後升溫至85℃熟化1-1.5h，降至室溫過濾出料，用丙酮破乳後在真空烘箱乾燥2h即得聚合物樹脂。
- 如請求項3所述的一種用於193nm水浸式光刻的聚合物樹脂的製備方法，其中步驟一中該水溶性引發劑為過硫酸銨、過硫酸鉀或偶氮二異丁腈中一種或多種。
- 如請求項3所述的一種用於193nm水浸式光刻的聚合物樹脂的製備方法，其中步驟一中該水溶性乳化劑由陰離子乳化劑與非離子乳化劑混合而成；該陰離子乳化劑為十二烷基硫酸鈉，非離子乳化劑為曲拉通X-100。
- 一種用於193nm水浸式光刻的抗水塗層組合物，其中是將請求項1該聚合物樹脂溶解於4-甲基-2-戊醇、二異戊醚、乙醇、丙二醇甲醚醋酸酯中的一種或多種溶劑中，過濾得到。
- 如請求項6所述的一種用於193nm水浸式光刻的抗水塗層組合物，其中該抗水塗層組合物中聚合物樹脂的質量分數為1-5%。
- 一種用於193nm水浸式光刻的抗水塗層的製備方法，其中先將193nm光刻膠塗覆在基片上，在110℃下烘烤60s後，將請求項6該抗水塗層組合物旋塗於光刻膠表層，隨後在90℃烘烤60s即得抗水塗層。
- 一種採用如請求項8所述製備方法製備的抗水塗層。
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