TWI745542B - 組成物對於正型光阻親水化處理劑之用途、組成物對於正型光阻顯影劑之用途、及半導體元件之製造方法 - Google Patents
組成物對於正型光阻親水化處理劑之用途、組成物對於正型光阻顯影劑之用途、及半導體元件之製造方法 Download PDFInfo
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- TWI745542B TWI745542B TW107104435A TW107104435A TWI745542B TW I745542 B TWI745542 B TW I745542B TW 107104435 A TW107104435 A TW 107104435A TW 107104435 A TW107104435 A TW 107104435A TW I745542 B TWI745542 B TW I745542B
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- Prior art keywords
- photoresist
- component
- coating film
- treatment agent
- hydrophilization treatment
- Prior art date
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 250
- 238000011282 treatment Methods 0.000 title claims abstract description 116
- 238000004519 manufacturing process Methods 0.000 title claims description 30
- 239000004065 semiconductor Substances 0.000 title claims description 28
- 239000000203 mixture Substances 0.000 title claims description 13
- 238000000576 coating method Methods 0.000 claims abstract description 122
- 239000011248 coating agent Substances 0.000 claims abstract description 120
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 90
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229920000223 polyglycerol Polymers 0.000 claims abstract description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 15
- 125000002252 acyl group Chemical group 0.000 claims abstract description 13
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 49
- 239000000758 substrate Substances 0.000 claims description 47
- 230000002093 peripheral effect Effects 0.000 claims description 13
- 125000003342 alkenyl group Chemical group 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 238000000206 photolithography Methods 0.000 claims description 5
- 239000004615 ingredient Substances 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 2
- 239000000470 constituent Substances 0.000 claims 1
- 230000006866 deterioration Effects 0.000 abstract description 7
- -1 2-hydroxyethyl (N,N-dimethyl-N-lauryl) ammonium hydroxide Chemical compound 0.000 description 72
- 238000011161 development Methods 0.000 description 25
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 14
- 238000005498 polishing Methods 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 125000001931 aliphatic group Chemical group 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 229910052911 sodium silicate Inorganic materials 0.000 description 4
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 125000005645 linoleyl group Chemical group 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 2
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 2
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 2
- 101150065749 Churc1 gene Proteins 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- 102100038239 Protein Churchill Human genes 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 235000010980 cellulose Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 2
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 229960002887 deanol Drugs 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- 239000012972 dimethylethanolamine Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000007756 gravure coating Methods 0.000 description 2
- 125000006038 hexenyl group Chemical group 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—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
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
-
- 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
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
-
- 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
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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Abstract
本發明提供能抑制光阻塗膜之劣化,同時可將光阻塗膜之表面快速且安定地親水化的光阻親水化處理劑。
本發明之光阻親水化處理劑至少含有下述成分(A)、及成分(B):成分(A):下述式(a)所示之聚甘油或其衍生物
RaO-(C3H6O2)n-H (a)
(式中,Ra表示氫原子、可具有羥基之碳數1~18的烴基、或碳數2~24之醯基;n表示括弧內所示之甘油單元的平均聚合度,為2~60之整數);成分(B):水。
Description
本發明係關於應用於光阻塗膜表面,將光阻塗膜表面親水化之光阻親水化處理劑,及含該光阻親水化處理劑之顯影液,以及使用該光阻親水化處理劑之半導體元件的製造方法。本案主張於2017年2月10日在日本申請之特願2017-023181號的優先權,並在此處引用其內容。
就在半導體裝置(電晶體、電容器、記憶體、發光元件、太陽能電池等)或電子機器(各種顯示器等)之製造中,於基板上形成電路之方法而言,例如,可利用包含下述步驟之光刻法:
[1]在基板上塗布光阻,形成光阻塗膜。
[2]在光阻塗膜上,隔著描繪有電路之圖案的光罩照射光,刻印電路圖案。
[3]浸入顯影液,將圖案部分以外之部分的光阻塗膜除去。
[4]使顯影後殘留之光阻塗膜硬化,形成光罩。
[5]利用所得到之光罩,蝕刻基板。
在前述步驟中所形成之光阻塗膜,由於其表面為疏水性,例如,將基板之周緣部分(斜角部分或邊緣部分等)產生之粗糙研磨而進行平坦化時,即使一面供給水至光阻塗膜表面,一面進行研磨,由於水被排開,無法用水覆蓋光阻塗膜表面,所以研磨屑容易附著在光阻塗膜表面,研磨屑一旦附著,要除去非常困難。於是,附著之研磨屑成為配線之短路或電阻上升的原因,有導致可靠度降低的問題。
又,光阻塗膜由於其表面為疏水性,顯影時顯影液之濡濕性差,發生顯影不均,而在基板上精度良好地形成期望之圖案有時會變得困難。再者,將顯影後之光阻塗膜水洗、乾燥時,作用在光阻塗膜與水之間的界面張力有時會將光阻圖案破壞。此問題隨著光阻圖案之微細化、高長寬比化而變得顯著。
就解決上述問題之方法而言,可列舉賦予光阻塗膜表面親水性,提高光阻塗膜與水之親和力的方法。就賦予光阻塗膜表面親水性之方法而言,專利文獻1中揭示將光阻塗膜表面以界面活性劑或水溶性高分子化合物進行塗覆之方法。然而,此方法由於供給水至光阻塗膜表面時,塗膜容易剝落,有親水性賦予效果無法持續的問題。
就使親水性賦予效果持續之方法而言,可列舉使用鹼溶液,使光阻塗膜表面略為溶解而賦予親水性的方法。就此方法中所使用之鹼溶液而言,在專利文獻2中揭示TMAH(=氫氧化四甲基銨)溶液等。又,在專利文獻3中記載含有2-羥基乙基(N,N-二甲基-N-月桂基)銨氫氧化物等氫氧化第四級銨之水溶液。然而,若使用 此等鹼溶液進行親水化處理,有因光阻塗膜薄化,光罩特性降低,而產率降低的問題。
專利文獻1 日本特開2005-277050號公報
專利文獻2 日本特開平9-106081號公報
專利文獻3 日本特開2008-46153號公報
因此,本發明之目的,為提供可抑制光阻塗膜之劣化,將光阻塗膜之表面快速且安定地親水化的光阻親水化處理劑。
本發明之其他目的,為提供對光阻塗膜之濡濕性優良,可抑制顯影不均的發生,且可抑制顯影後之水洗‧乾燥時光阻圖案損壞的顯影液。
本發明之其他目的,為提供能抑制研磨屑之附著或顯影不均,產率良好地製造具有高精度之配線圖案之半導體元件的方法。
本發明人為解決上述課題而專心檢討之結果,發現:含有下述成分之組成物,可抑制光阻塗膜之劣化,同時可將光阻塗膜之表面快速且安定地親水化;在研磨半導體基板時,若於光阻塗膜表面應用該組成物,一面供給水,一面研磨半導體基板,則可使光阻塗膜不 會劣化,且可抑制研磨屑附著於光阻塗膜;顯影時若將該組成物應用於光阻塗膜表面,可使顯影液對光阻塗膜之濡濕性提高,抑制顯影不均之發生,且於顯影後之水洗‧乾燥時,能抑制光阻圖案損壞。本發明為基於此等見解而完成者。
亦即,本發明提供至少含有下述成分(A)、及成分(B)之光阻親水化處理劑。
成分(A):下述式(a)所示之聚甘油或其衍生物RaO-(C3H6O2)n-H (a)
(式中,Ra表示氫原子、可具有羥基之碳數1~18之烴基、或碳數2~24之醯基;n表示括弧內所示之甘油單元的平均聚合度,為2~60之整數);成分(B):水。
本發明又提供如前述之光阻親水化處理劑,其中成分(A)之含量為光阻親水化處理劑全量之0.1重量%以上。
本發明又提供如前述之光阻親水化處理劑,其中光阻為正型光阻。
本發明又提供一種光阻顯影液,其包含前述光阻親水化處理劑。
本發明又提供一種半導體元件之製造方法,其為經由對基板上之光阻塗膜施行曝光及顯影,形成光刻用之光阻圖案,並利用所得到之光阻圖案蝕刻基板之步驟,而製造半導體元件的方法,其特徵為施行下述處理[1]及/或[2]: [1]使用前述光阻親水化處理劑,將基板上之光阻塗膜的表面親水化後進行顯影,或使用含有前述光阻親水化處理劑的顯影液進行顯影;[2]於使用上述光阻親水化處理劑將前述光阻塗膜親水化後,一面供給水至光阻塗膜,一面研磨具備光阻塗膜之基板之周緣部分的粗糙處。
本發明之光阻親水化處理劑由於具有上述構成,容易在光阻塗膜之表面快速地附著,形成親水性被覆膜,藉由形成被覆膜,可將光阻塗膜之表面安定地親水化,與藉由使用鹼溶液使光阻塗膜表面溶解而賦予親水性之方法比較,可將光阻塗膜之劣化抑制至極低。
又,含有本發明之光阻親水化處理劑的顯影液,對光阻塗膜之濡濕性高,可抑制顯影不均之發生,顯影後之水洗‧乾燥時,可防止藉由界面張力造成光阻圖案損壞。
於是,在半導體元件之製造中,只要使用本發明之光阻親水化處理劑,將基板上之光阻塗膜的表面親水化後進行顯影,或使用含本發明之光阻親水化處理劑的顯影液進行顯影,即可抑制顯影不均之發生,顯影後之水洗‧乾燥時,可防止藉由界面張力造成光阻圖案損壞。又,只要將前述光阻塗膜使用本發明之光阻親水化處理劑親水化後,一面供給水至光阻塗膜,一面研磨具備光阻塗膜之基板之周緣部分的粗糙處,即可抑制研磨屑附著於光阻塗膜。因此,可防止先前因前述研磨屑之附著 所引起之配線之短路或電阻上升,防止產率之降低,而可有效率地製造高精度之半導體元件。
本發明之光阻親水化處理劑至少含有下述成分(A)、及成分(B):成分(A):式(a)所示之聚甘油或其衍生物;成分(B):水。
本發明之光阻親水化處理劑,以下述式(a)所示之聚甘油或其衍生物作為必需成分。
RaO-(C3H6O2)n-H (a)
(式中,Ra表示氫原子、可具有羥基之碳數1~18的烴基、或碳數2~24之醯基;n表示甘油單元之平均聚合度,為2~60之整數)。
式(a)中之n個C3H6O2為相同或相異,且具有下述式(a-1)或(a-2)所示之結構:-CH2-CHOH-CH2O- (a-1)
-CH(CH2OH)CH2O- (a-2)
Ra中之碳數1~18之烴基,包含碳數1~18之烷基、碳數2~18之烯基、及碳數2~18之多烯基、碳數3~18之脂環式烴基、碳數6~18之芳香族烴基、及此等2個以上連結而成之基。
就前述碳數1~18之烷基而言,例如,可列舉甲基、乙基、正丙基、2-甲基-1-丙基、正丁基、三級丁基、3,3-二甲基-2-丁基、正戊基、異戊基、三級戊基、正己基、2-乙基己基、正辛基、異辛基、正癸基、4-癸基、異癸基、十二基(=正月桂基)、異十二基、十四基(=肉豆蔻基)、異肉豆蔻基、鯨蠟基、異鯨蠟基、正己基癸基、2-己基癸基、硬脂基、異硬脂基等直鏈狀或分枝鏈狀的烷基。此等之中,以碳數8~18之直鏈狀或分枝鏈狀的烷基為較佳。
就前述碳數2~18之烯基而言,例如,可列舉乙烯基、烯丙基、2-丁烯基、丙烯基、己烯基、2-乙基己烯基、油基等直鏈狀或分枝鏈狀的烯基。
就前述碳數2~18之多烯基而言,例如,可列舉丁二烯基、戊二烯基、己二烯基、庚二烯基、辛二烯基、亞油醯基、亞油基等二烯基;1,2,3-戊三烯基等三烯基;四烯基。
就前述碳數3~18之脂環式烴基而言,例如,可列舉環丁基、環戊基、環己基、環辛基、環十二基、2-環庚烯基、2-環己烯基等飽和或不飽和脂環式烴基(尤其環烷基、環烯基)。
就前述碳數6~18之芳香族烴基而言,例如,可列舉苯基、萘基等。
就前述基2個以上連結而成之基而言,例如,可列舉苄基、2-苯基乙烯基、1-環戊基乙基、1-環己基乙基、環己基甲基、2-環己基乙基、1-環己基-1-甲基乙基等。
前述碳數2~24之醯基中,包含脂肪族醯基及芳香族醯基。就前述脂肪族醯基而言,例如,可列舉乙醯基、丙醯基、丁醯基、異丁醯基、硬脂醯基、油醯基等飽和或不飽和脂肪族醯基。就前述芳香族醯基而言,例如,可列舉苄醯基、甲苯甲醯基、萘甲醯基等。
就Ra而言,其中以氫原子、直鏈狀或分枝鏈狀烷基(其中更佳為碳數8~18之直鏈狀或分枝鏈狀烷基,特佳為碳數10~18之直鏈狀或分枝鏈狀烷基)、直鏈狀或分枝鏈狀烯基(其中更佳為碳數2~18之直鏈狀或分枝鏈狀烯基,特佳為碳數2~8之直鏈狀或分枝鏈狀烯基)、或脂肪族醯基(特佳為碳數10~18之飽和脂肪族醯基)為較佳,尤其,以氫原子、前述烷基、或前述烯基為特佳。
式(a)中,n表示括弧內所示之甘油單元的平均聚合度。n之值為2~60之整數,n之值的下限,較佳為5,更佳為10,進一步更佳為15,特佳為20,最佳為25、極佳為30。n之值的上限,較佳為55,更佳為50,特佳為45,最佳為40。n之值為前述範圍的聚甘油或其衍生物,容易附著於光阻塗膜之表面,形成被覆膜,藉由被覆膜形成,可將光阻塗膜表面安定地親水化。
前述聚甘油或其衍生物之重量平均分子量,為例如200~20000,較佳為600~15000,更佳為1000~10000,特佳為1500~5000,最佳為2000~4500。具有上述範圍之重量平均分子量的聚甘油或其衍生物,由於對光阻塗膜之表面的密著性特別優良,即使供給水至光阻塗膜表面,亦不會剝離,隨著時間的經過仍可安定地維持對光阻塗膜表面之親水性賦予效果。再者,本說明書中之重量平均分子量,為藉由凝膠滲透層析(GPC)測定之以標準聚苯乙烯換算的分子量。
就前述聚甘油或其衍生物而言,其中以使用選自下式所示之化合物中的至少1種為較佳:HO-(C3H6O2)10-H
HO-(C3H6O2)20-H
HO-(C3H6O2)30-H
HO-(C3H6O2)40-H
CH2=CHCH2-O-(C3H6O2)6-H
C12H25O-(C3H6O2)4-H
C12H25O-(C3H6O2)10-H
C18H37O-(C3H6O2)4-H
C18H37O-(C3H6O2)10-H。
前述聚甘油或其衍生物中,就聚甘油(亦即,式(a)中之Ra為氫原子的化合物)而言,例如,可適當使用商品名「PGL 03P」(聚(3)甘油)、「PGL 06」(聚(6)甘油)、「PGL 10PSW」(聚(10)甘油)、「PGL 20PW」(聚(20)甘油)、「PGL XPW」(聚(40)甘油)(以上,Daicel股份有限公司製)等市售品。
前述聚甘油或其衍生物中,聚甘油衍生物(亦即,式(a)中之Ra為可具有羥基之碳數1~18之烴基、或碳數2~24之醯基的化合物),可使用各種方法製造。就聚甘油衍生物之製造方法而言,例如,可列舉下述方法等,然而本發明中之聚甘油衍生物,不限定於藉由該等方法製造。
(1)將2,3-環氧基-1-丙醇進行加成聚合於RaOH(Ra與前述相同)之方法;(2)使聚甘油與烷基鹵化物(例如,Ra1X:X表示鹵素原子;Ra1表示碳數1~18之烴基)、羧酸(例如,Ra2OH:Ra2表示碳數2~24之醯基)、或其衍生物(例如,羧酸鹵化物、酸酐等)縮合之方法。
在上述方法(1)中,加成反應以在鹼觸媒存在下進行為較佳。就鹼觸媒而言,例如,可列舉氫氧化鈉、氫氧化鉀、氫氧化鋰、金屬鈉、氫化鈉等。此等,可單獨使用1種,或將2種以上組合使用。
在上述方法(2)中,就作為原料使用之聚甘油而言,適合使用上述之市售品。
本發明之光阻親水化處理劑,含有作為成分(A)之選自聚甘油及聚甘油衍生物(具體而言,聚甘油單醚、聚甘油單酯等)的1種、或2種以上。又,本發明之光阻親水化處理劑,亦可含有對應於式(a)所示之聚甘油或其衍生物的聚甘油二醚或聚甘油二酯,然而在此情況,式(a)所示之聚甘油或其衍生物與對應之聚甘油二醚、及聚甘油二酯的合計量中,式(a)所示之聚甘油或其 衍生物所佔的比率以75%以上為較佳,尤其以90%以上為特佳。又,聚甘油二醚及聚甘油二酯之比率,以5%以下為較佳,尤其以1%以下為特佳。再者,各成分所佔之比率,係以高速液體層析將各成分溶離,然後從以示差折射率檢測器算出峰面積時的面積比求得。
本發明之光阻親水化處理劑中之成分(A)的含量,為光阻親水化處理劑全量(100重量%)之例如0.1重量%以上,較佳為0.1~5.0重量%,更佳為0.3~4.0重量%,特佳為0.5~3.0重量%,最佳為0.5~2.5重量%。
本發明之光阻親水化處理劑以水作為必需成分。就水而言,可為硬水、軟水之任一種,例如,可使用工業用水、自來水、離子交換水、蒸餾水等。
在本發明之光阻親水化處理劑中,就水之含量而言,為光阻親水化處理劑全量(100重量%)之例如80.0~99.9重量%,較佳為85.0~99.9重量%,更佳為90.0~99.8重量%,特佳為95.0~99.5重量%。
本發明之光阻親水化處理劑係以成分(A)及成分(B)作為必需成分。本發明之光阻親水化處理劑除成分(A)、成分(B)以外,亦可含有其他成分。
就前述其他成分而言,例如,可為陰離子系界面活性劑(聚羧酸系、聚丙烯酸系、烷基苯磺酸系 等)、陽離子系界面活性劑(氯化烷基三甲基銨、氯化烷基吡啶鎓鹽等之第四級銨鹽等)、非離子系界面活性劑(乙炔二醇系、聚氧伸烷基烷基醚、聚氧伸乙基烷基胺、聚乙烯基吡咯啶酮等)、水溶性高分子化合物(纖維素類、幾丁聚醣類等)、有機鹼(TMAH、二乙基乙醇胺等)、醇類(甲醇、乙醇、異丙醇等)等。此等可單獨使用1種,或將2種以上組合使用。
在本發明之光阻親水化處理劑全量(100重量%)中,成分(A)及成分(B)之合計含量所佔的比率為例如70重量%以上,較佳為80重量%以上,特佳為90重量%以上,最佳為95重量%以上。再者,上限為100重量%。因此,上述其他成分之含量(含有2種以上之情況,為其總量)為本發明之光阻親水化處理劑全量(100重量%)的例如30重量%以下,較佳為20重量%以下,特佳為10重量%以下,最佳為5重量%以下。
本發明之光阻親水化處理劑可視需要,在成分(A)、成分(B)中混合其他成分而調製。
本發明之光阻顯影液,其特徵為包含上述光阻親水化處理劑。
在本發明之光阻顯影液全量(100重量%)中,成分(A)的含量為例如0.1重量%以上,較佳為0.1~5.0重量%,更佳為0.3~4.0重量%,特佳為0.5~3.0重量%,最佳為0.5~2.5重量%。
本發明之光阻顯影液,除上述光阻親水化處理劑以外,含有周知慣用之顯影液成分。例如,在光阻為正型光阻之情況,光阻顯影液可含有選自無機鹼(氫氧化鈉、氫氧化鉀、碳酸鈉、矽酸鈉、偏矽酸鈉、氨水等)、第一級胺類(乙基胺、正丙基胺等)、第二級胺類(二乙基胺、二正丁基胺等)、第三級胺類(三乙基胺、甲基二乙基胺等)、醇胺類(二甲基乙醇胺、三乙醇胺等)、第四級銨鹽(氫氧化四甲基銨、氫氧化四乙基銨等)、環狀胺類(吡咯、哌啶等)、醇類、界面活性劑等中的1種或2種以上。
本發明之光阻顯影液,由於含有上述光阻親水化處理劑(尤其成分(A)),對光阻塗膜之濡濕性優良,可抑制顯影不均之發生,且顯影後之水洗‧乾燥時,可緩和光阻圖案與水之間的界面張力,而抑制光阻圖案損壞。
本發明之半導體元件的製造方法,為經由「對基板上之光阻塗膜施行曝光及顯影,形成光刻用的光阻圖案,利用所得到之光阻圖案蝕刻基板」之步驟,而製造半導體元件的方法(亦即,藉由光刻製造半導體元件之方法),其特徵為施行下述處理[1]及/或[2]:[1]使用本發明之光阻親水化處理劑,將基板上之光阻塗膜的表面親水化後進行顯影,或使用含有本發明之光阻親水化處理劑的顯影液進行顯影; [2]於使用本發明之光阻親水化處理劑將前述光阻塗膜親水化後,一面供給水至光阻塗膜,一面研磨具備光阻塗膜之基板之周緣部分的粗糙處。
形成光阻塗膜之光阻方面,包含正型光阻及負型光阻。在本發明中,其中使用正型光阻,從可形成更高精度之微細圖案的觀點,為較佳。
就正型光阻而言,無特別限制,例如,可列舉酚醛樹脂、聚丙烯酸、聚對羥基苯乙烯、聚降莰烯樹脂、及於此等中導入氟之樹脂等。
就在基板上形成光阻塗膜之方法而言、例如,可列舉使用旋轉塗布法、滾筒塗布法、浸漬法、噴霧法、簾幕流動塗布法、網版印刷法、平板印刷法、凹版塗布法將光阻塗布在基板上之方法等。光阻塗膜之厚度,例如為約數百nm~數μm。
所得到之光阻塗膜在施行曝光處理前可施行預烘烤處理。又,亦可在曝光處理後施行烘烤處理。藉由施行預烘烤處理或烘烤處理,可提高基板與光阻塗膜之密著性。處理溫度為例如100~150℃,處理時間為例如約1~30分鐘。
再者,顯影後以施行水洗‧乾燥處理為較佳。在本發明中,由於使用上述光阻親水化處理劑將光阻塗膜表面親水化,即使水洗,亦可緩和水與光阻圖案之間的界面張力,而可抑制光阻圖案之損壞。
就使用本發明之光阻親水化處理劑,將光阻塗膜之表面親水化的方法而言,只要能使本發明之光 阻親水化處理劑與光阻塗膜表面接觸,則無特別限制。就使本發明之光阻親水化處理劑與光阻塗膜表面接觸之方法而言,可列舉例如(1)噴霧法、(2)滴入法、及(3)浸漬法等。
例如,就(1)噴霧法或(2)滴入法而言,藉由使具備光阻塗膜之基板旋轉,同時從配置在前述基板之上方的噴嘴將本發明之光阻親水化處理劑噴霧或滴入,可對基板上之整面光阻塗膜全面地塗布本發明之光阻親水化處理劑,而將光阻塗膜表面親水化。
就(3)浸漬法而言,藉由將具備光阻塗膜之基板浸漬於本發明之光阻親水化處理劑中,可將光阻塗膜表面親水化。
在任一種方法中,親水化處理所需要之時間,均為例如5秒~60秒,較佳為10秒~30秒。若處理時間短,親水化變得不充分,又,若處理時間過長,則作業效率降低,因此不佳。又,本發明之光阻親水化處理劑由於對光阻塗膜表面之濡濕性高,故在採用(2)滴入法之情況,要將半導體基板表面全體被覆所需之光阻親水化處理劑的量只要少許即已足夠,而可達到成本之削減。
在本發明中,施行顯影處理時,其特徵為預先使用本發明之光阻親水化處理劑,將基板上之光阻塗膜的表面親水化,或使用含有本發明之光阻親水化處理劑的顯影液進行顯影。因此,顯影液對光阻塗膜之濡濕性變得良好,可抑制顯影不均之發生。又,顯影後之水洗‧乾燥時,可抑制光阻圖案因界面張力而造成損壞。
又,在本發明中,其特徵為於使用本發明之光阻親水化處理劑將前述光阻塗膜親水化後,一面供給水至該光阻塗膜,一面研磨具備光阻塗膜之基板之周緣部分的粗糙處。
就將基板之周緣部分的粗糙處研磨之方法而言,例如,可列舉於使基板旋轉之狀態下,對基板之周緣部分按壓研磨墊片、研磨膠帶等研磨工具的方法等。研磨中亦可使用研磨材料。
就水之供給方法而言,例如,可列舉從給水噴嘴將水連續地或間歇地滴入的方法。若於使具備光阻塗膜之基板旋轉的狀態下將水滴入,則水藉由離心力向外側流動,而將具備光阻塗膜之基板整面覆蓋。水之供給速度、及供給量無特別限制,可適宜調整。
又,就所供給之水而言,可只使用水(例如,超純水等),亦可使用在水中添加其他成分(例如,界面活性劑等)者。再者,供給水時,亦可合併進行光阻塗膜表面之物理性洗淨(例如,超音波洗淨、毛刷洗淨、噴射洗淨等)。
若藉由上述方法對基板之周緣部分施行研磨處理,可抑制研磨屑附著於光阻塗膜,能防止因研磨屑所引起之配線的短路或電阻上升。再者,由於將基板之周緣部分的粗糙處藉由研磨而平坦化(或者,鏡面化),亦可防止基板之周緣部分的粗糙部分在隨後之步驟(例如,搬運等)中粉塵化,而防止因粉塵所引起之配線之短路或電阻上升。
再者,本發明中所用之光阻親水化處理劑、及光阻顯影液係藉由成分(A)附著於光阻塗膜之表面,形成被覆膜,而將光阻塗膜表面安定地親水化者,由於可在不引起光阻塗膜之薄化下進行親水化,無損於光阻塗膜之光罩特性。
依據以上,若藉由本發明之半導體元件的製造方法,可效率良好地製造高精度之半導體元件。
以下,藉由實施例更具體地說明本發明,然而本發明並不受此等實施例限定。
依照表1所記載之處方摻入各成分,得到光阻親水化處理劑。關於所得到之光阻親水化處理劑,藉由以下之方法評價光阻塗膜表面之親水化力、及光阻塗膜之劣化防止性。
在矽晶圓上將正型光阻(長瀨產業股份有限公司製,商品名「Nagase Positive Resist 820」)藉由旋轉塗布法塗布後,於120℃進行10分鐘烘烤,得到試驗片(光阻塗膜厚度:約1700nm)。
在實施例及比較例所得到之光阻親水化處理劑中,將前述試驗片於25℃、不攪拌下浸漬10秒,然後,以超純水進行3分鐘流水淋洗。淋洗後,拉起試驗片,以目視觀察光阻塗膜表面之濡濕性,並依據下述基準評價親水化力。又,藉由光學干擾式膜厚計測定處理前後之膜 厚減少量,評價對光阻塗膜之損傷。再者,光阻膜厚之減少量較少者,表示光阻塗膜之損傷較小,光阻塗膜之劣化防止性優良。將結果示於表1。
○:即使拉起試驗片,試驗片表面仍為濡濕狀態
×:若拉起試驗片,水為立刻被排開或逐漸地被排開之狀態
再者,表中之記號表示以下之化合物。
a-1:聚(40)甘油,商品名「PGL XPW」,Daicel股份有限公司製
b-1:TMAH
b-2:氫氧化2-羥基乙基-(N,N-二甲基-N-月桂基)銨
b-3:氫氧化2-羥基乙基-(N,N-二甲基-N-肉豆蔻基)銨
b-4:氫氧化2-羥基乙基-(N,N-二甲基-N-硬脂基)銨
將本發明之構成及其變化摘記如下,作為以上之總整理。
[1]一種光阻親水化處理劑,其中至少含有下述成分(A)、及成分(B):成分(A):下述式(a)所示之聚甘油或其衍生物RaO-(C3H6O2)n-H (a)
(式中,Ra表示氫原子、可具有羥基之碳數1~18之烴基、或碳數2~24之醯基;n表示括弧內所示之甘油單元之平均聚合度,為2~60之整數);成分(B):水。
[2]如[1]記載之光阻親水化處理劑,其中成分(A)之含量為光阻親水化處理劑全量的0.1重量%以上。
[3]如[1]或[2]記載之光阻親水化處理劑,其中光阻為正型光阻。
[4]如[1]至[3]中任1項記載之光阻親水化處理劑,其中正型光阻為選自包含酚醛樹脂、聚丙烯酸、聚對羥基苯乙烯、聚降莰烯樹脂、及於此等中導入氟之樹脂的群組。
[5]如[1]至[4]中任1項記載之光阻親水化處理劑,其中式(a)中之n個C3H6O2具有下述式(a-1)或(a-2)所示之結構:-CH2-CHOH-CH2O- (a-1)
-CH(CH2OH)CH2O- (a-2)。
[6]如[1]至[5]中任1項記載之光阻親水化處理劑,其中Ra中之碳數1~18之烴基包含碳數1~18之烷基、碳 數2~18之烯基、及碳數2~18之多烯基、碳數3~18之脂環式烴基、碳數6~18之芳香族烴基、及此等2個以上連結而成之基。
[7]如[1]至[6]中任1項記載之光阻親水化處理劑,其中碳數1~18之烴基選自包含甲基、乙基、正丙基、2-甲基-1-丙基、正丁基、三級丁基、3,3-二甲基-2-丁基、正戊基、異戊基、三級戊基、正己基、2-乙基己基、正辛基、異辛基、正癸基、4-癸基、異癸基、十二基(=正月桂基)基、異十二基、十四基(=肉豆蔻基)、異肉豆蔻基、鯨蠟基、異鯨蠟基、正己基癸基、2-己基癸基、硬脂基、異硬脂基;乙烯基、烯丙基、2-丁烯基、丙烯基、己烯基、2-乙基己烯基、油基;丁二烯基、戊二烯基、己二烯基、庚二烯基、辛二烯基、亞油醯基、亞油基;1,2,3-戊三烯基;四烯基;環丁基、環戊基、環己基、環辛基、環十二基、2-環庚烯基、2-環己烯基;苯基、萘基;苄基、2-苯基乙烯基、1-環戊基乙基、1-環己基乙基、環己基甲基、2-環己基乙基、及1-環己基-1-甲基乙基之群組。
[8]如[1]至[7]中任1項記載之光阻親水化處理劑,其中碳數2~24之醯基,選自包含乙醯基、丙醯基、丁醯基、異丁醯基、硬脂醯基、油醯基、苄醯基、甲苯甲醯基、及萘甲醯基之群組。
[9]如[1]至[8]中任1項記載之光阻親水化處理劑,其中式(a)中之n為2~60之整數,n之值之下限選自包含5、10、15、20、25、及30之群組,n之值之上限選自包含55、50、45、及40之群組。
[10]如[1]至[9]中任1項記載之光阻親水化處理劑,其中聚甘油或其衍生物之重量平均分子量,選自包含200~20000、600~15000、1000~10000、1500~5000、及2000~4500之群組。
[11]如[1]至[10]中任1項記載之光阻親水化處理劑,其中聚甘油或其衍生物,選自包含下述式所表示之化合物的群組:HO-(C3H6O2)10-H
HO-(C3H6O2)20-H
HO-(C3H6O2)30-H
HO-(C3H6O2)40-H
CH2=CHCH2-O-(C3H6O2)6-H
C12H25O-(C3H6O2)4-H
C12H25O-(C3H6O2)10-H
C18H37O-(C3H6O2)4-H
C18H37O-(C3H6O2)10-H。
[12]如[1]至[11]中任1項記載之光阻親水化處理劑,其中式(a)所示之聚甘油或其衍生物、與對應之聚甘油二醚及聚甘油二酯的合計中,式(a)所示之聚甘油或其衍生物所佔的比率為75%以上或90%以上,聚甘油二醚及聚甘油二酯之比率為5%以下或1%以下。
[13]如[1]至[12]中任1項記載之光阻親水化處理劑,其中光阻親水化處理劑中之成分(A)的含量,相對於光阻親水化處理劑全量(100重量%),為選自包含0.1重量%以上、0.1~5.0重量%、0.3~4.0重量%、0.5~3.0重量%、及0.5~2.5重量%之群組。
[14]如[1]至[13]中任1項記載之光阻親水化處理劑,其中水之含量,相對於光阻親水化處理劑全量(100重量%),為選自包含80.0~99.9重量%、85.0~99.9重量%、90.0~99.8重量%、及95.0~99.5重量%之群組。
[15]如[1]至[14]中任1項記載之光阻親水化處理劑,其進一步含有成分(A)及成分(B)以外的成分,前述其他成分,包含選自包含聚羧酸系界面活性劑、聚丙烯酸系界面活性劑、烷基苯磺酸系界面活性劑、烷基三甲基銨氯化物、烷基吡啶鎓氯化物、乙炔二醇系界面活性劑、聚氧伸烷基烷基醚、聚氧伸乙基烷基胺、聚乙烯基吡咯啶酮、纖維素類、幾丁聚醣類、TMAH、二乙基乙醇胺、甲醇、乙醇、及異丙基醇之群組中的1種以上。
[16]如[1]至[15]中任1項記載之光阻親水化處理劑,其中光阻親水化處理劑全量(100重量%)中成分(A)及成分(B)之合計含量所佔的比率,為選自包含70重量%以上、80重量%以上、90重量%以上、95重量%以上、及100重量%之群組,成分(A)及成分(B)以外之成分的含量為本發明之光阻親水化處理劑全量(100重量%)中的選自包含30重量%以下、20重量%以下、10重量%以下、及5重量%以下之群組。
[17]一種光阻顯影液,其包含[1]至[16]中任1項記載之光阻親水化處理劑。
[18]如[17]記載之光阻顯影液,其中光阻顯影液全量(100重量%)中之成分(A)的含量,係選自包含0.1重量%以上、0.1~5.0重量%、0.3~4.0重量%、0.5~3.0重量%、及0.5~2.5重量%之群組。
[19]如[17]或[18]記載之光阻顯影液,其進一步含有選自包含氫氧化鈉、氫氧化鉀、碳酸鈉、矽酸鈉、偏矽酸鈉、氨水、乙基胺、正丙基胺、二乙基胺、二-正丁基胺、三乙基胺、甲基二乙基胺、二甲基乙醇胺、三乙醇胺、氫氧化四甲基銨、氫氧化四乙基銨、吡咯、哌啶、醇、界面活性劑之群組中的1種以上。
[20]一種半導體元件之製造方法,其為經由「對基板上之光阻塗膜施行曝光及顯影,形成光刻用之光阻圖案,利用所得到之光阻圖案蝕刻基板」的步驟,而製造半導體元件之方法,其特徵為施行下述處理[i]及/或[ii]:[i]將基板上之光阻塗膜的表面,使用[1]至[16]中任1項記載之光阻親水化處理劑親水化後進行顯影,或使用含有[1]至[16]中任1項記載之光阻親水化處理劑的顯影液進行顯影;[ii]於使用[1]至[15]中任1項記載之光阻親水化處理劑將前述光阻塗膜親水化後,一面供給水至光阻塗膜,一面研磨具備光阻塗膜之基板之周緣部分的粗糙處。
[21]如[20]記載之半導體元件的製造方法,其中在基板上形成光阻塗膜之方法,為使用選自包含旋轉塗布法、滾筒塗布法、浸漬法、噴霧法、簾幕流動塗布法、網版印刷法、平板印刷法、凹版塗布法之群組的方法,在基板上塗布光阻之方法,光阻塗膜之厚度約為數百nm~數μm。
[22]如[20]或[21]記載之半導體元件的製造方法,其係在所得到之光阻塗膜施行曝光處理前施行預烘烤處 理,或在曝光處理後施行烘烤處理,處理溫度為100~150℃,處理時間為1~30分鐘。
[23]如[20]至[22]中任1項記載之半導體元件的製造方法,其中進一步於顯影後施行水洗‧乾燥處理。
[24]如[20]至[23]中任1項記載之半導體元件的製造方法,其中光阻塗膜之表面的親水化,為藉由使光阻親水化處理劑與光阻塗膜表面接觸而進行,前述接觸方法為選自包含(1)噴霧法、(2)滴入法、及(3)浸漬法之群組。
[25]如[20]至[24]中任1項記載之半導體元件的製造方法,其中研磨為於使基板旋轉之狀態下,將研磨墊片或研磨膠帶按壓於基板之周緣部分,或使用研磨材料。
[26]如[20]至[25]中任1項記載之半導體元件的製造方法,其中水之供給為藉由將水從給水噴嘴連續地或間歇地滴入而進行。
[27]如[20]至[26]中任1項記載之半導體元件的製造方法,其中進一步在供給水時,合併進行光阻塗膜表面之物理性洗淨(例如,超音波洗淨、毛刷洗淨、噴射洗淨等)。
本發明係提供能抑制光阻塗膜之劣化,同時可將光阻塗膜之表面快速且安定地親水化的光阻親水化處理劑。又,本發明提供對光阻塗膜之濡濕性優良,可抑制顯影不均之發生,且顯影後之水洗‧乾燥時可抑制光阻圖案損壞之顯影液。再者,本發明提供抑制研磨屑之附著或顯影不均,而產率良好地製造具有高精度之配線圖案之半導體元件的方法。
Claims (6)
- 一種組成物對於正型光阻親水化處理劑之用途,該組成物至少含有下述成分(A)、及成分(B):成分(A):下述式(a’)所示之聚甘油衍生物Ra’O-(C3H6O2)n’-H (a’)(式中,Ra’表示可具有羥基之碳數1~18的烷基、可具有羥基之碳數2~18的烯基、或碳數2~24之醯基;n’表示括弧內所示之甘油單元的平均聚合度,為15~60之整數);成分(B):水。
- 一種組成物對於正型光阻親水化處理劑之用途,該組成物至少含有下述成分(A)、及成分(B):成分(A):下述式(a”)所示之聚甘油Ra”O-(C3H6O2)n-H (a”)(式中,Ra”表示氫原子;n表示括弧內所示之甘油單元的平均聚合度,為2~60之整數);成分(B):水。
- 如請求項1或2之用途,其中成分(A)之含量為組成物全量之0.1重量%以上。
- 一種組成物對於正型光阻顯影液之用途,該組成物至少含有下述成分(A)、及成分(B):成分(A):下述式(a’)所示之聚甘油衍生物Ra’O-(C3H6O2)n’-H (a’)(式中,Ra’表示可具有羥基之碳數1~18的烷基、可具有羥基之碳數2~18的烯基、或碳數2~24之醯基; n’表示括弧內所示之甘油單元的平均聚合度,為15~60之整數);成分(B):水。
- 一種組成物對於正型光阻顯影液之用途,該組成物至少含有下述成分(A)、及成分(B):成分(A):下述式(a”)所示之聚甘油Ra”O-(C3H6O2)n-H (a”)(式中,Ra”表示氫原子;n表示括弧內所示之甘油單元的平均聚合度,為2~60之整數);成分(B):水。
- 一種半導體元件之製造方法,其為經由對基板上之光阻塗膜施行曝光及顯影,形成光刻用之光阻圖案,並利用所得到之光阻圖案蝕刻基板之步驟,而製造半導體元件的方法,其特徵為施行下述處理[1]及[2]:[1]使用下述光阻親水化處理劑,將基板上之光阻塗膜的表面親水化後進行顯影,或使用含有下述光阻親水化處理劑的顯影液進行顯影;[2]於使用下述光阻親水化處理劑將前述光阻塗膜親水化後,一面供給水至光阻塗膜,一面研磨具備光阻塗膜之基板之周緣部分的粗糙處;光阻親水化處理劑:至少含有下述成分(A)、及成分(B);成分(A):下述式(a)所示之聚甘油或其衍生物RaO-(C3H6O2)n-H (a)(式中,Ra表示氫原子、可具有羥基之碳數1~18 的烴基、或碳數2~24之醯基;n表示括弧內所示之甘油單元的平均聚合度,為2~60之整數);成分(B):水。
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