WO2012033114A1 - 表面撥水処理用組成物及びこれを用いた半導体基板表面の撥水処理方法 - Google Patents
表面撥水処理用組成物及びこれを用いた半導体基板表面の撥水処理方法 Download PDFInfo
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- WO2012033114A1 WO2012033114A1 PCT/JP2011/070328 JP2011070328W WO2012033114A1 WO 2012033114 A1 WO2012033114 A1 WO 2012033114A1 JP 2011070328 W JP2011070328 W JP 2011070328W WO 2012033114 A1 WO2012033114 A1 WO 2012033114A1
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- composition
- water
- repellent treatment
- base
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- 239000005871 repellent Substances 0.000 title claims abstract description 73
- 239000000203 mixture Substances 0.000 title claims abstract description 65
- 239000000758 substrate Substances 0.000 title claims abstract description 57
- 239000004065 semiconductor Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 26
- -1 alkyl tertiary amine Chemical class 0.000 claims abstract description 69
- 239000002253 acid Substances 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 125000005210 alkyl ammonium group Chemical group 0.000 claims abstract description 14
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 69
- 230000002940 repellent Effects 0.000 claims description 48
- 125000004432 carbon atom Chemical group C* 0.000 claims description 28
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- 238000010438 heat treatment Methods 0.000 claims description 18
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- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical group C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 claims description 4
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- 150000002739 metals Chemical class 0.000 claims description 2
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical group [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 2
- QBVXKDJEZKEASM-UHFFFAOYSA-M tetraoctylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QBVXKDJEZKEASM-UHFFFAOYSA-M 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
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- UPGIACGFGCRCEH-UHFFFAOYSA-N hafnium(4+) oxygen(2-) yttrium(3+) Chemical compound [O-2].[Y+3].[Hf+4] UPGIACGFGCRCEH-UHFFFAOYSA-N 0.000 claims 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims 1
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- 125000003118 aryl group Chemical group 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 9
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- 239000010703 silicon Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- RAWVDDAJSCCYHU-CSJRWYNFSA-N Zephyramine Chemical compound C([C@@H]1O[C@@H]11)CC2N3CC(C=C(C(=C4)OC)OC)=C4[C@@]21CC3 RAWVDDAJSCCYHU-CSJRWYNFSA-N 0.000 description 6
- RAWVDDAJSCCYHU-DXEWXGHRSA-N Zephyramine Natural products O(C)c1c(OC)cc2c(c1)[C@]13[C@@H]4O[C@H]4CC[C@H]1N(C2)CC3 RAWVDDAJSCCYHU-DXEWXGHRSA-N 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
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- 125000001931 aliphatic group Chemical group 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000002950 monocyclic group Chemical group 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 3
- 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 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- MFGWMAAZYZSWMY-UHFFFAOYSA-N (2-naphthyl)methanol Chemical compound C1=CC=CC2=CC(CO)=CC=C21 MFGWMAAZYZSWMY-UHFFFAOYSA-N 0.000 description 2
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 2
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
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- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
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- PFJFNQUFMTYCHB-UHFFFAOYSA-N C[SiH2]N[SiH3] Chemical compound C[SiH2]N[SiH3] PFJFNQUFMTYCHB-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- ZBGXSVQAJGTDDB-UHFFFAOYSA-N [Y].[Hf] Chemical compound [Y].[Hf] ZBGXSVQAJGTDDB-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- XCCCHWWMLSAIOH-UHFFFAOYSA-N anthracen-1-ylmethanol Chemical compound C1=CC=C2C=C3C(CO)=CC=CC3=CC2=C1 XCCCHWWMLSAIOH-UHFFFAOYSA-N 0.000 description 1
- JCJNNHDZTLRSGN-UHFFFAOYSA-N anthracen-9-ylmethanol Chemical compound C1=CC=C2C(CO)=C(C=CC=C3)C3=CC2=C1 JCJNNHDZTLRSGN-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- HONIICLYMWZJFZ-UHFFFAOYSA-N azetidine Chemical compound C1CNC1 HONIICLYMWZJFZ-UHFFFAOYSA-N 0.000 description 1
- 125000003828 azulenyl group Chemical group 0.000 description 1
- CSNHNGDROQRZKT-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 CSNHNGDROQRZKT-UHFFFAOYSA-M 0.000 description 1
- XFBTWIOCKNNLEK-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;iodide Chemical compound [I-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 XFBTWIOCKNNLEK-UHFFFAOYSA-M 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000005380 borophosphosilicate glass Substances 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000003997 cyclic ketones Chemical class 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000006547 cyclononyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 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 1
- RMKNCYHVESPYFD-UHFFFAOYSA-N decan-1-amine;hydrochloride Chemical compound [Cl-].CCCCCCCCCC[NH3+] RMKNCYHVESPYFD-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- QLPMKRZYJPNIRP-UHFFFAOYSA-M methyl(trioctyl)azanium;bromide Chemical compound [Br-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC QLPMKRZYJPNIRP-UHFFFAOYSA-M 0.000 description 1
- AMUCTDNDAXEAOW-UHFFFAOYSA-M methyl(trioctyl)azanium;iodide Chemical compound [I-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC AMUCTDNDAXEAOW-UHFFFAOYSA-M 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 description 1
- JCRXSDBBPCPECQ-UHFFFAOYSA-N piperidine-4-thiol Chemical compound SC1CCNCC1 JCRXSDBBPCPECQ-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003254 radicals Chemical group 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- KGPZZJZTFHCXNK-UHFFFAOYSA-M tetraoctylazanium;iodide Chemical compound [I-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC KGPZZJZTFHCXNK-UHFFFAOYSA-M 0.000 description 1
- BRNULMACUQOKMR-UHFFFAOYSA-N thiomorpholine Chemical compound C1CSCCN1 BRNULMACUQOKMR-UHFFFAOYSA-N 0.000 description 1
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- SWZDQOUHBYYPJD-UHFFFAOYSA-N tridodecylamine Chemical compound CCCCCCCCCCCCN(CCCCCCCCCCCC)CCCCCCCCCCCC SWZDQOUHBYYPJD-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/022—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being a laminate, i.e. composed of sublayers, e.g. stacks of alternating high-k metal oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
Definitions
- the present invention relates to a composition for water repellent treatment of a semiconductor substrate surface having a pattern structure with a high aspect ratio, and a method of water repellent treatment of a semiconductor substrate surface using the same.
- Patent Document 1 As a conventional water-repellent treatment method, for example, for an insulating layer containing Si such as a SiO 2 layer or a silicon wafer, a solution containing various fluorine compounds is used (Patent Document 1, etc.), or a gas of various fluorine compounds is used. (Patent Document 2, Patent Document 3, etc.) and the like are known. However, since the insulating layer containing Si, such as SiO 2 layer, and the metal layer have different surface properties, there is no known composition capable of efficiently and simultaneously performing water-repellent treatment on these two layers. Its development is desired.
- the present invention has been made to solve the above-described problems, and once the entire surface of a semiconductor substrate having a pattern formed by laminating an insulating layer containing Si such as a SiO 2 layer and a metal layer is formed.
- a composition used for water-repellent treatment and a method for water-repellent treatment of the surface of a semiconductor substrate having a pattern formed by laminating an insulating layer containing Si and a metal layer using the composition are provided. The purpose is to do.
- the present invention has the following configuration. (1) a) at least one compound selected from the group consisting of long-chain alkyl tertiary amines and long-chain alkylammonium salts, b) having a condensed ring structure or generating a base or acid to form a condensed ring structure A composition for water repellent treatment of a semiconductor substrate surface, comprising a base or acid generator and c) a polar organic solvent to be formed. (2) Treating a semiconductor substrate having a pattern formed by laminating an insulating layer containing Si and a metal layer with the composition of (1) above under irradiation with light having a wavelength of 200 nm or more or under heating. A water repellent treatment method for a surface of a semiconductor substrate, which is characterized.
- the present inventors have a pattern having a high height compared to the line width, a so-called high aspect ratio pattern, and the same layer is formed by laminating an insulating layer containing Si such as a SiO 2 layer and a metal layer.
- an insulating layer containing Si such as a SiO 2 layer and a metal layer.
- the pattern has a high height compared to the line width, a so-called aspect ratio, and Since the surface of a semiconductor substrate having the same pattern formed by laminating an insulating layer containing Si, such as a SiO 2 layer, and a metal layer can be subjected to water repellent treatment in one treatment, For example, it is possible to prevent the occurrence of the problem that the pattern collapses due to the surface tension of water in the pure water rinsing process.
- R 1 to R 3 each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, provided that R 1 to R 3 Of which at least one is an alkyl group having 4 to 20 carbon atoms.
- R 1 to R 4 each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms
- X ⁇ represents an anion.
- at least one of R 1 to R 4 is an alkyl group having 4 to 20 carbon atoms.
- the alkyl group having 1 to 20 carbon atoms represented by R 1 to R 4 is preferably a linear or branched alkyl group.
- a linear alkyl group is preferable, among which a linear alkyl group having 4 to 14 carbon atoms is more preferable, and a linear alkyl group having 6 to 14 carbon atoms is preferable. More preferred is an alkyl group.
- the aryl group having 6 to 10 carbon atoms represented by R 1 to R 4 may be monocyclic or condensed polycyclic, specifically Examples thereof include a phenyl group, a naphthyl group, and azulenyl. Among them, a phenyl group having 6 carbon atoms is preferable.
- the aralkyl group having 7 to 12 carbon atoms represented by R 1 to R 4 may be monocyclic or condensed polycyclic, specifically, For example, benzyl group, phenethyl group, ⁇ -methylbenzyl group, 3-phenylpropyl group, 1-methyl-1-phenylethyl group, 4-phenylbutyl group, 2-methyl-2-phenylpropyl group, 1,2, Examples thereof include 3,4-tetrahydronaphthyl group, naphthylmethyl group, 2-naphthylethyl group, and the like. Among them, a benzyl group having 7 carbon atoms is preferable.
- the anion represented by X ⁇ in the general formula (2) is not particularly limited as long as it is usually used for this purpose in this field.
- fluoride ion, chloride ion, bromide ion, iodide ion Preferred examples include halide ions such as methanesulfonic acid and ethanesulfonic acid, anions derived from carboxylic acids such as formic acid, acetic acid, propionic acid, and butyric acid, hydroxide ions, and the like.
- R 1 to R 3 are all linear alkyl groups having 4 to 14 carbon atoms are preferable, and among them, R 1 to R 3 are all What is a C6-C14 linear alkyl group is more preferable.
- quaternary ammonium salts represented by the general formula (2) those in which at least one of R 1 to R 4 is a linear alkyl group having 4 to 14 carbon atoms are preferable, and among them, R 1 to R 4 More preferably, at least one of 4 is a linear alkyl group having 6 to 14 carbon atoms.
- the quaternary ammonium salt represented by the general formula (2) is preferable.
- tertiary amine represented by the general formula (1) for example, tri-n-butylamine, tri-n-octylamine, tri-n-dodecylamine and the like are particularly preferable.
- Examples of the quaternary ammonium salt represented by the general formula (2) include tri-n-octylmethylammonium chloride, tri-n-octylmethylammonium bromide, tri-n-octylmethylammonium iodide, tetra-n-octyl.
- Ammonium chloride tetra-n-octylammonium bromide, tetra-n-octylammonium iodide, benzyldimethyl-n-tetradecylammonium chloride, benzyldimethyl-n-tetradecylammonium bromide, benzyldimethyl-n-tetradecylammonium iodide are particularly preferred.
- long-chain alkyl tertiary amines and long-chain alkyl ammonium salts only one of them may be used, or two or more may be used in combination as appropriate.
- concentration of these long-chain alkyl tertiary amine and long-chain alkyl ammonium salt in the composition is usually 0.3 to 0.001 mol / L, preferably 0.1 to 0.001 mol / L, more preferably. Is 0.05 to 0.001 mol / L.
- commercially available products may be used, or those synthesized appropriately according to conventional methods usually used in this field may be used.
- the base or acid generator according to the present invention which has a condensed ring structure or generates a base or an acid to form a condensed ring structure, is more specifically (i) light (active energy ray) having a wavelength of 200 nm or more.
- a base or an acid is generated by irradiation with light (active energy rays) of 200 nm to 500 nm, or a base or an acid is generated by heating, and (ii) a base or an acid generated by light irradiation or heating
- Condensed ring structure It has ⁇ .
- the condensed ring structure has a planar structure such as an anthracene ring, naphthalene ring, pyrene ring, anthraquinone ring, thioxanthone ring, acenaphthene ring, coumarin ring, xanthone ring.
- bases or acid generators base generators are preferred.
- a base generator represented by the following general formula (3) is more preferable.
- R 5 and R 6 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
- R 7 and R 8 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, or These represent those forming a nitrogen-containing aliphatic ring or nitrogen-containing aromatic ring having 3 to 8 carbon atoms which may have a substituent together with the nitrogen atom to which they are bonded
- m R 9 s are each independently A halogen atom or an alkyl group having 1 to 10 carbon atoms, and m represents an integer of 0 to 9.
- examples of the alkyl group having 1 to 10 carbon atoms represented by R 5 to R 9 include a linear, branched or cyclic alkyl group. Specifically, for example, a methyl group , Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group , Neopentyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, cyclopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, neohexyl group, 2-methyl Pentyl group, 1,2-dimethylbuty
- these nitrogen-containing fat are combined to 3 carbon atoms which may have a substituent together with the nitrogen atom 1-8
- the aromatic ring or nitrogen-containing aromatic ring include azetidine, pyrrolidine, piperidine, hexamethyleneimine (azepan), heptamethyleneimine (azocan), octamethyleneimine (azonan), 2, 5-dimethylpyrrolidine, 2,6-dimethylpiperidine, 2,4,6-trimethylpiperidine, 4-hydroxypiperidine, 4-mercaptopiperidine, 4-nitropiperidine, 4-cyanopiperidine, oxazolidine, thiazolidine, morpholine, thiomorpholine, 2,3,5,6-tetramethylmorpholine, 2,3,5,6-tetramethylthiomorpholine, etc.
- Optionally substituted nitrogen-containing aliphatic ring having 3 to 8 carbon atoms such as pyrrole, imidazole, pyrazole, 2,5-dimethylpyrrole, 2,5-diethylpyrrole, 2,5-dimethylimidazole, 2 , 5-diethylimidazole, 3,5-dimethylpyrazole, 3,5-diethylpyrazole and the like, optionally containing a nitrogen-containing aromatic ring having 3 to 8 carbon atoms, and the like.
- piperidine, 4-hydroxypiperidine and imidazole are preferred.
- halogen atom represented by R 9 examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, a chlorine atom and a bromine atom are preferable, and a bromine atom. Is more preferable.
- m is preferably an integer of 0 to 5, more preferably an integer of 0 to 3, and even more preferably 0.
- the base generator having a condensed ring structure represented by the general formula (3) or generating a base to form a condensed ring structure include, for example, 9-anthrylmethyl-1-piperidinecarboxylate, Etc.
- Such bases or acid generators have been synthesized by Wako Pure Chemical Industries, Ltd., to which the present inventors belong, and patent applications have been filed. What is appropriately synthesized based on the above may be used.
- a base generator having a remaining condensed ring structure selected from an anthraquinone ring, a pyrene ring, an anthracene ring and a naphthalene ring after the base is released by light irradiation or heating.
- An anthraquinone ring, a pyrene ring, and a condensed ring structure selected from an anthracene ring are disclosed in International Publication No. WO2010 / 064631.
- a ring structure are disclosed in International Publication No. WO2010 / 064632.
- those having a condensed ring structure consisting of a xanthone ring may be synthesized according to the methods described in Synthesis Examples 1 to 3 and Examples 1 to 7 of International Publication WO2010 / 064632.
- Japanese Patent Application No. 2010-135818 discloses a base generator having a condensed ring structure composed of an alkoxyanthracene ring in the balance after the base is liberated by light irradiation or heating.
- Japanese Patent Application No. 2010-168117 discloses a base generator having a remaining condensed ring structure selected from an acenaphthene ring and a coumarin ring after light release or heating to release the base.
- an acid generator preferably has a condensed ring structure similar to that of the above-described base generator.
- bases or acid generators having a condensed ring structure or generating a base or acid to form a condensed ring structure according to the present invention may be used alone or in combination of two kinds as appropriate. A combination of the above may also be used.
- the concentration in these compositions is usually 0.5 to 0.001 mol / L, preferably 0.2 to 0.001 mol / L, more preferably 0.06 to 0.001 mol / L.
- the base generator having an anthracene ring has an amount of 0.2 to 1 w / w%, preferably 0.3 to 0.7 w / w%. .2 to 0.6 w / w%, preferably 0.2 to 0.5 w / w%.
- Examples of the c) polar organic solvent according to the present invention include alcoholic protic polar organic solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, 1-methoxy-2-propanol, and ethylene glycol.
- alcoholic protic polar organic solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, 1-methoxy-2-propanol, and ethylene glycol.
- Solvents for example, ester solvents such as ethyl acetate, n-propyl acetate, ethyl lactate, and ⁇ -butyrolactone, amide solvents such as dimethylformamide and N-methylpyrrolidone, sulfoxide solvents such as dimethyl sulfoxide, and nitriles such as acetonitrile System solvents, aprotic polar organic solvents such as cyclic ketones such as cyclohexanone, and the like. These polar organic solvents may be appropriately selected depending on the purpose.
- HMDS hexamethyldisilazane
- Substrates whose surface can be rendered water repellent by the water repellent treatment composition of the present invention include SiO 2 films (including TEOS films and thermal oxide films), SiN films, and boron phosphorus-doped silicon films (BPSG films). If it is a semiconductor substrate in which the insulating layer containing various Si used by 1 was formed, it will not specifically limit.
- the composition for water repellent treatment of the present invention is a pattern having a high height compared to the line width, a so-called high aspect ratio pattern, and the pattern contains Si such as a SiO 2 layer.
- tungsten (W) film for example, a tungsten-titanium (W / Ti) film, an aluminum (Al) film, a titanium (Ti) film, a hafnium (Hf) film, a film formed of an alloy containing these metals, for example,
- a metal layer such as a high-k film formed of hafnium (Hf) oxide or hafnium-yttrium (Hf / Y) oxide
- the metal layer can be subjected to water repellent treatment at the same time.
- the order of stacking and the number of stacks of the Si-containing insulating layer and the metal layer in the stacked pattern are not
- the water repellent treatment composition of the present invention and the semiconductor substrate to be water repellent treated can be contacted under light irradiation or heating.
- the method is not particularly limited, and there are no particular problems with methods usually employed in this field, such as an immersion method and a single wafer method.
- the temperature at the time of water repellent treatment is not particularly limited, but is preferably 10 ° C. to 30 ° C. when generating a base or acid by light irradiation, and 40 ° C. to 80 ° C. when generating a base or acid by heating. Is preferred.
- the treatment time is not particularly limited, 1 to 10 minutes is preferable when a base or acid is generated by light irradiation, and 1 to 30 minutes is preferable when a base or acid is generated by heat treatment. is there.
- the light source used for light irradiation is not particularly limited as long as it can irradiate light (active energy rays) having a wavelength of 200 nm or more, more specifically, light (active energy rays) having a wavelength of 200 nm to 500 nm.
- a mercury lamp, a xenon (Xe) lamp, etc. are mentioned.
- the light irradiation energy at this time is not particularly limited as long as the base or acid is liberated from the base or acid generator according to the present invention, but usually 40 to 100 mmJ / cm 2 , 365 nm in the vicinity of 254 nm. Irradiation is performed so that the distance is 800 to 1500 mmJ / cm 2 in the vicinity. Moreover, after using the water-repellent treatment composition of the present invention to generate a base or an acid by light irradiation or heating, the water-repellent treatment is similarly performed even if it is brought into contact with a semiconductor substrate to be subjected to the water-repellent treatment. be able to.
- the amount of light energy in the case of light irradiation in advance may be set as appropriate according to the time of light irradiation at the same time, and the heating temperature and heating time in the case of heating in advance are also set appropriately based on the processing method described above. Just do it.
- the mechanism by which the substrate surface can be subjected to water repellent treatment is not clear, but the following possibilities are high. That is, two or more cationic (or anionic) or radical units, which are generated by light irradiation or heating (which generates an acid or a base) and the structure of the compound changes (or the compound decomposes). Those formed by a condensed ring compound condensed with a ring (aliphatic ring or aromatic ring) and a long-chain alkyl tertiary amine or long-chain alkyl ammonium salt are involved in water repellency on the substrate it is conceivable that. Therefore, it is considered that the object of the present invention can be achieved by using a combination of compounds capable of generating such a mechanism other than the specific combinations described above.
- Experimental Example 1 A composition in which various chemicals were combined was prepared, and it was examined whether the surface of a thermally oxidized film wafer (that is, a silicon wafer having a SiO 2 layer) could be subjected to water repellent treatment.
- a thermally oxidized film wafer that is, a silicon wafer having a SiO 2 layer
- Method for Producing Evaluation Substrate 280 mL of an aqueous solution prepared by mixing 28% ammonia water, 35% hydrogen peroxide water and ion exchange water in a volume ratio of 1: 1: 5 to an 8-inch thermal oxide film wafer placed in a poly beaker. It was put in and immersed for 2 hours. After that, rinsing was performed while rotating at 800 rpm for 2 minutes with a single wafer washer (Caijo multispinner), and then spin drying was performed at 3000 rpm for 3 minutes. Thereafter, the wafer was cut into 2 cm ⁇ 2 cm and used as an evaluation substrate.
- aqueous solution prepared by mixing 28% ammonia water, 35% hydrogen peroxide water and ion exchange water in a volume ratio of 1: 1: 5 to an 8-inch thermal oxide film wafer placed in a poly beaker. It was put in and immersed for 2 hours. After that, rinsing was performed while rotating at 800 rpm for 2 minutes with a
- composition for study was prepared by dissolving 0.5 w / w% of each of the compounds shown in Table 1 in ⁇ -butyrolactone.
- the composition for study was prepared under a yellow lamp (FLR40SY-IC: manufactured by Mitsubishi Electric OSRAM Co., Ltd.). Moreover, in the following Examples, all% are described in w / w%.
- Method of processing the composition for examination 20 ml of the composition for examination was placed in a 30 ml poly beaker, and the composition for examination was stirred under irradiation with an ultra-high pressure mercury lamp REX-250 (center wavelength: 350 nm) manufactured by Asahi Spectroscope. The substrate for evaluation was immersed for 1 minute. Thereafter, the substrate was taken out, rinsed with running pure water for 1 minute, and dried with compressed air.
- REX-250 center wavelength: 350 nm
- Table 2 shows the structural formulas of the compounds indicated by abbreviations in Table 1.
- Example 1 Generation of a base having a condensed ring structure consisting of zephyramine (benzyldimethyl-n-tetradecylammonium chloride), which is a long-chain alkylammonium salt, and the anthracene ring, in which thermal oxide film wafer surface is the most water-repellent in Experimental Example 1 Of ⁇ -butyrolactone solution containing 9-anthrylmethyl-1-piperidinecarboxylate (WPBG-015) as a water repellent composition and the effect of immersion time It was investigated.
- the method for producing the evaluation substrate used, the treatment of the substrate with the water repellent treatment composition, and the measurement of the contact angle of pure water were carried out in accordance with Experimental Example 1. The results are shown in Table 3.
- the substrate surface is water repellent by using the composition for water repellent treatment of the present invention
- the composition for water repellent treatment of the present invention in order to confirm what properties the water repellent layer has, How the water repellency changes when the substrate for evaluation obtained by immersing under irradiation for 10 minutes is washed with isopropyl alcohol (IPA) and / or pure water, in other words, the purity of the substrate surface It was confirmed how the contact angle of water changes.
- IPA isopropyl alcohol
- Example 2 Effects of Zephyramine (benzyldimethyl-n-tetradecylammonium chloride) and 9-anthrylmethyl-1-piperidinecarboxylate (WPBG-015) in the composition for water repellent treatment
- Zephyramine in the composition for water repellent treatment The influence of the concentrations of (benzyldimethyl-n-tetradecylammonium chloride) and 9-anthrylmethyl-1-piperidinecarboxylate (WPBG-015) was examined. The results are shown in Table 5.
- concentration in Table 5 shows the density
- the method for producing the evaluation substrate used, the treatment of the substrate with the composition for water repellent treatment, and the measurement of the contact angle of pure water were performed according to Experimental Example 1.
- Example 3 Examination of influence of light irradiation time The influence of light irradiation time in water repellent treatment was examined. The results are shown in Table 6. The concentration in Table 6 indicates the concentration (w / w%) in ⁇ -butyrolactone. Further, the method for producing the evaluation substrate used, the treatment of the substrate with the composition for water repellent treatment, and the measurement of the contact angle of pure water were performed according to Experimental Example 1.
- the concentration in Table 7 indicates the concentration in ⁇ -butyrolactone, and “no light” means that the silicon wafer was immersed in the composition for water repellent treatment of the present invention for 1 minute without light irradiation, “With light” means that the silicon wafer was immersed in the composition for water repellent treatment of the present invention for 1 minute after being irradiated with light for 1 minute.
- the water-repellent treatment composition of the present invention serves as a key for light irradiation to function as a water-repellent treatment composition. Therefore, the water-repellent composition of the present invention can be stored in the dark. Long-term storage is possible.
- the Si-containing insulating layer and the metal layer are laminated easily and efficiently by a single treatment. Since the surface of the semiconductor substrate having the pattern thus formed can be subjected to water repellent treatment, for example, it can be prevented that the pattern collapses due to the surface tension of water in the pure water rinsing process.
- the composition for water repellent treatment and the method for water repellent treatment of a semiconductor substrate surface using the composition of the present invention can be suitably used for a semiconductor substrate having these structures.
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Abstract
Description
従来の撥水処理方法としては、例えばSiO2層等のSiを含有する絶縁層やシリコンウエハについて、各種フッ素化合物を含む溶液を用いたり(特許文献1等)、各種フッ素化合物のガスを用いたり(特許文献2、特許文献3等)することによって撥水処理する方法、等が知られている。
しかしながら、SiO2層等のSiを含有する絶縁層と金属層とはその表面の性質が異なるため、これら2つの層を同時に効率良く撥水処理し得る組成物は知られておらず、従って、その開発が望まれている状況にある。
(1)a)長鎖アルキル第3級アミン及び長鎖アルキルアンモニウム塩からなる群から選ばれる少なくとも1種の化合物、b)縮環構造を有するか又は塩基若しくは酸を発生して縮環構造を形成する、塩基若しくは酸発生剤、及びc)極性有機溶媒を含む、半導体基板表面撥水処理用組成物。
(2)Siを含有する絶縁層と金属層とが積層されて形成されたパターンを有する半導体基板を、波長200nm以上の光照射下又は加熱下、上記(1)の組成物で処理することを特徴とする、当該半導体基板表面の撥水処理方法。
(式中、R1~R3はそれぞれ独立して炭素数1~20のアルキル基、炭素数6~10のアリール基又は炭素数7~12のアラルキル基を示す。但し、R1~R3の内、少なくとも1つは炭素数4~20のアルキル基である。)
(式中、R1~R4はそれぞれ独立して炭素数1~20のアルキル基、炭素数6~10のアリール基又は炭素数7~12のアラルキル基を示し、X-はアニオンを示す。但し、R1~R4の内、少なくとも1つは炭素数4~20のアルキル基である。)
これら長鎖アルキル第3級アミン及び長鎖アルキルアンモニウム塩は、市販品を用いても良いし、通常この分野で用いられる常法に従って適宜合成したものを用いても良い。
(R5及びR6はそれぞれ独立して水素原子又は炭素数1~10のアルキル基を示し、R7及びR8はそれぞれ独立して水素原子又は炭素数1~10のアルキル基を示す、あるいはこれらが結合している窒素原子と共に置換基を有していても良い炭素数3~8の含窒素脂肪族環又は含窒素芳香族環を形成するものを示し、m個のR9はそれぞれ独立してハロゲン原子又は炭素数1~10のアルキル基を示し、mは0~9の整数を示す。)
このような塩基発生剤の内、アントラキノン環、ピレン環及びアントラセン環から選ばれるいずれかの縮環構造を有するものについては、国際公開公報WO2010/064631号公報に開示されている。
また、ナフタレン環からなる縮環構造を有するものについては、国際公開公報WO2010/064631号公報の合成例1及び実施例1に記載の方法に準じて合成すれば良い。即ち、先ず、同合成例1の9-アントラセンメタノールに代えて1-ナフタレンメタノール又は2-ナフタレンメタノールを用いる以外は、合成例1と同じ試薬を用い同様の操作を行って、1-(又は2-)ナフチルメチル-4’-ニトロフェニルカルボナートを得、次いでこれを同実施例1の9-アントリルメチル-4’-ニトロフェニルカルボナートの代わりに用い、それ以外は実施例1と同じ試薬を用い同様の操作を行って、1-(又は2-)ナフチルメチル-1-ピペリジンカルボキシレートを合成する、等すれば良い。
このような塩基発生剤の内、チオキサントン環からなる縮環構造を有するものについては、国際公開公報WO2010/064632号公報に開示されている。
また、キサントン環からなる縮環構造を有するものについては、国際公開公報WO2010/064632号公報の合成例1~3及び実施例1~7に記載の方法に準じて合成すれば良い。即ち、先ず、同合成例1の2,4-ジエチル-9H-チオキサンテン-9-オンに代えて2,4-ジエチル-9H-キサンテン-9-オンを用いる以外は、合成例1と同じ試薬を用い同様の操作を行って、7-ブロモ-2,4-ジエチル-9H-キサンテン-9-オンを得、次いでこれを同合成例2の7-ブロモ-2,4-ジエチル-9H-キサンテン-9-オンの代わりに用い、それ以外は実施例1と同じ試薬を用い同様の操作を行って、2,4-ジエチル-7-(3-ヒドロキシ-プロピル-1-イル)-9H-キサンテン-9-オンとし、更にこれを同実施例1の2,4-ジエチル-7-(3-ヒドロキシ-プロピル-1-イル)-9H-チオキサンテン-9-オンの代わりに用い、それ以外は実施例1と同じ試薬を用い同様の操作を行って、2,4-ジエチル-7[3-(N,N-ジエチルカルバモイルオキシ)-1-プロピル-1-イル]-9H-キサンテン-9-オンを合成する、等すれば良い。
日本特願2010-135818号に開示されている。
日本特願2010-168117号に開示されている。
また、重量比で示すと、塩基発生剤の内アントラセン環のものについては、0.2~1w/w%、好ましくは0.3~0.7w/w%、アントラキノン環のものについては、0.2~0.6w/w%、好ましくは0.2~0.5w/w%である。
これらの極性有機溶媒は、目的に応じて適宜選択すれば良いが、例えばヘキサメチルジシラザン[HMDS:ビス(トリメチルシリル)アミン]を用いたSiO2層等のSiを含有する絶縁層の撥水処理と併用する目的で本発明の撥水処理用組成物を使用する場合には非プロトン性極性有機溶媒を用いるのが望ましく、γ-ブチロラクトンを用いるのがより望ましい。
これら本発明に係る極性有機溶媒は、これらの内の1種のみを用いても良いし適宜2種以上を組み合わせて用いても良い。
各種薬剤を組み合わせた組成物を調製し、熱酸化膜ウエハ(即ちSiO2層を有するシリコンウエハ)表面を撥水処理し得るかについて検討を行った。
ポリビーカー中に置いた8インチの熱酸化膜ウエハに、28%アンモニア水、35%過酸化水素水及びイオン交換水を容積比1:1:5で混合した水溶液280mLを投入し、2時間浸漬した。その後、枚葉式洗浄機(カイジョー製マルチスピナー)で2分間、800rpmで回転させながらリンスし、次いで3000rpmで3分間スピンドライした。その後、ウエハを2cm×2cmに切断し、これを評価用基板として用いた。
γ-ブチロラクトンに、表1記載の化合物を各々0.5w/w%ずつ溶解したものを検討用組成物とした。尚、検討用組成物の調製は、イエローランプ(FLR40SY-IC:三菱電機オスラム株式会社製)の下で行った。また、以下の実施例において、%は全てw/w%で記載してある。
20mLの検討用組成物を30mLのポリビーカーに入れ、朝日分光製、超高圧水銀ランプREX-250(中心波長350nm)を照射しながら、攪拌下、検討用組成物中に評価用基板を1分間浸漬した。その後、該基板を取り出し、純水の流水で1分間リンスして圧縮空気で乾燥した。
検討用組成物で処理した基板について、接触角計(協和界面科学製、ドロップマスターDM-501)を用い、純水を1μL自動滴下して接触角を測定した。
接触角の測定結果を表1に合わせて示す。尚、表1中に略号で示した化合物の構造式を表2に示す。
尚、表1には示していないが、9-アントリルメチル-1-ピペリジンカルボキシレート(WPBG-015)の代わりにアントラセンメタノールを用いて検討を行ってみたが、ゼフィラミン(ベンジルジメチル-n-テトラデシルアンモニウムクロリド)と組み合わせて用いても基板表面に撥水性を付与することはできなかった。
実験例1で、熱酸化膜ウエハ表面が最も撥水性となった、長鎖アルキルアンモニウム塩であるゼフィラミン(ベンジルジメチル-n-テトラデシルアンモニウムクロリド)と、アントラセン環からなる縮環構造を有する塩基発生剤である9-アントリルメチル-1-ピペリジンカルボキシレート(WPBG-015)とを含有するγ-ブチロラクトン溶液を撥水処理用組成物として用いた場合の、光照射の要否並びに浸漬時間の影響を検討した。尚、用いた評価用基板の作製方法、撥水処理用組成物による該基板の処理及び純水の接触角の測定は、実験例1に準じて行った。結果を表3に示す。
本発明の撥水処理用組成物を用いることにより、基板表面が撥水化されることは分かったが、撥水化層がどのような性質を持つものであるのかを確認するために、光照射下で10分間浸漬して得られた評価用基板を、イソプロピルアルコール(IPA)又は/及び純水を用いて洗浄した場合に、撥水性がどのように変化するか、言い換えれば基板表面の純水の接触角がどのように変化するかを確認した。結果を表4に示す。
これらのことから、基板表面に形成された撥水化膜は、基板と化学結合しておらず、ファンデルワールス力程度の力で基板表面に吸着されていると推定される。
撥水処理用組成物中のゼフィラミン(ベンジルジメチル-n-テトラデシルアンモニウムクロリド)及び9-アントリルメチル-1-ピペリジンカルボキシレート(WPBG-015)の濃度による影響について検討を行った。結果を表5に示す。尚、表5中の濃度はγ-ブチロラクトン中の濃度(w/w%)を示す。また、用いた評価用基板の作製方法、撥水処理用組成物による該基板の処理及び純水の接触角の測定は、実験例1に準じて行った。
撥水処理における光照射時間の影響の検討を行った。結果を表6に示す。尚、表6中の濃度はγ-ブチロラクトン中の濃度(w/w%)を示す。また、用いた評価用基板の作製方法、撥水処理用組成物による該基板の処理及び純水の接触角の測定は、実験例1に準じて行った。
基板としてW/Ti=9:1膜が形成されたシリコンウエハを用い、本発明の撥水処理用組成物で撥水処理が可能かを検討した。結果を表7に示す。尚、表7中の濃度はγ-ブチロラクトン中の濃度を示し、「光なし」は光照射なしで上記シリコンウエハを本発明の撥水処理用組成物に1分間浸漬させたことを意味し、「光あり」は、1分間光照射してから上記シリコンウエハを本発明の撥水処理用組成物に1分間浸漬させたことを意味し、「光あてながら」は、上記シリコンウエハを本発明の撥水処理用組成物に浸漬し、その直後からシリコンウエハに直接光を1分間照射したことを意味する。また、基板としてW/Ti=9:1膜が形成されたシリコンウエハを用いた以外は、評価用基板の作製方法、撥水処理用組成物による該基板の処理及び純水の接触角の測定は、実験例1に準じて行った。
1.9-アントリルメチル-1-ピペリジンカルボキシレート(WPBG-015)と長鎖アルキル4級アンモニウム塩の組み合わせで、SiO2膜等のSiを含有する絶縁層とW膜(実験はW/Ti膜で実施)等の金属層の同時撥水化が可能である。
2.本発明の撥水処理用組成物を用いれば、1液でSiを含有する絶縁層と金属層の両層の撥水化ができるので、従来技術に比較して簡便な工程で、Siを含有する絶縁層と金属層とが積層されて形成されたパターンを有する半導体基板表面を撥水処理できる。
3.本発明の撥水処理用組成物は、光照射が撥水処理用組成物として機能を発揮するカギの役割をしているので、本発明の撥水処理用組成物は、遮光して保存すれば長期間の保存も可能である。
Claims (12)
- a)長鎖アルキル第3級アミン及び長鎖アルキルアンモニウム塩からなる群から選ばれる少なくとも1種の化合物、b)縮環構造を有するか又は塩基若しくは酸を発生して縮環構造を形成する、塩基若しくは酸発生剤、及びc)極性有機溶媒を含む、半導体基板表面撥水処理用組成物。
- 長鎖アルキル第3級アミン及び長鎖アルキルアンモニウム塩が、炭素数4~20のアルキル基を少なくとも1個以上有するものである、請求項1記載の組成物。
- a)長鎖アルキル第3級アミン及び長鎖アルキルアンモニウム塩からなる群から選ばれる少なくとも1種の化合物が、長鎖アルキルアンモニウム塩である、請求項1記載の組成物。
- 長鎖アルキルアンモニウム塩が、トリ-n-オクチルメチルアンモニウムクロリド、テトラ-n-オクチルアンモニウムブロミド又はベンジルジメチル-n-テトラデシルアンモニウムクロリドである、請求項3記載の組成物。
- b)縮環構造を有する塩基若しくは酸発生剤が、光照射又は加熱により、塩基若しくは酸となる部分以外に縮環構造を有するか又は塩基若しくは酸を発生して縮環構造を形成するものである、請求項1記載の組成物。
- 縮環構造が、アントラセン環、ナフタレン環、ピレン環、アントラキノン環、チオキサントン環、アセナフテン環、クマリン環又はキサントン環である、請求項5記載の組成物。
- 縮環構造が、アントラセン環である、請求項5記載の組成物。
- b)縮環構造を有するか又は塩基若しくは酸を発生して縮環構造を形成する、塩基若しくは酸発生剤が、9-アントリルメチル-1-ピペリジンカルボキシレートである、請求項1記載の組成物。
- c)極性有機溶媒が非プロトン性である、請求項1記載の組成物。
- c)極性有機溶媒が、γ-ブチロラクトンである、請求項1記載の組成物。
- Siを含有する絶縁層と金属層とが積層されて形成されたパターンを有する半導体基板を、波長200nm以上の光照射下又は加熱下、請求項1記載の組成物で処理することを特徴とする、当該半導体基板表面の撥水処理方法。
- 金属層が、タングステン、アルミニウム、チタン、ハフニウム、これら金属を含む合金、ハフニウム酸化物又はハフニウム-イットリウム酸化物で形成されたものである、請求項11記載の方法。
Priority Applications (6)
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EP11823588.6A EP2615633A1 (en) | 2010-09-08 | 2011-09-07 | Composition for water-repellent treatment of surface, and method for water-repellent treatment of surface of semiconductor substrate using same |
US13/821,815 US20130171835A1 (en) | 2010-09-08 | 2011-09-07 | Composition for water-repellent treatment of surface, and method for water-repellent treatment of surface of semiconductor substrate using same |
CN2011800430432A CN103098178A (zh) | 2010-09-08 | 2011-09-07 | 表面防水处理用组合物以及使用该组合物的半导体基板表面的防水处理方法 |
KR1020137007051A KR20130129360A (ko) | 2010-09-08 | 2011-09-07 | 표면 발수처리용 조성물 및 이를 사용한 반도체 기판표면의 발수처리 방법 |
SG2013016779A SG188437A1 (en) | 2010-09-08 | 2011-09-07 | Composition for water-repellent treatment of surface, and method for water-repellent treatment of surface of semiconductor substrate using same |
JP2012532992A JPWO2012033114A1 (ja) | 2010-09-08 | 2011-09-07 | 表面撥水処理用組成物及びこれを用いた半導体基板表面の撥水処理方法 |
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JP2010201276 | 2010-09-08 |
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US (1) | US20130171835A1 (ja) |
EP (1) | EP2615633A1 (ja) |
JP (1) | JPWO2012033114A1 (ja) |
KR (1) | KR20130129360A (ja) |
CN (1) | CN103098178A (ja) |
SG (1) | SG188437A1 (ja) |
TW (1) | TW201217508A (ja) |
WO (1) | WO2012033114A1 (ja) |
Cited By (3)
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JP2013161834A (ja) * | 2012-02-01 | 2013-08-19 | Central Glass Co Ltd | 撥水性保護膜形成用薬液、撥水性保護膜形成用薬液キット、及びウェハの洗浄方法 |
JP2013161833A (ja) * | 2012-02-01 | 2013-08-19 | Central Glass Co Ltd | 撥水性保護膜形成用薬液、撥水性保護膜形成用薬液キット、及びウェハの洗浄方法 |
JP2019114600A (ja) * | 2017-12-21 | 2019-07-11 | 東京応化工業株式会社 | 表面処理液、表面処理方法、及びパターン倒れの抑制方法 |
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- 2011-09-06 TW TW100132024A patent/TW201217508A/zh unknown
- 2011-09-07 KR KR1020137007051A patent/KR20130129360A/ko not_active Application Discontinuation
- 2011-09-07 US US13/821,815 patent/US20130171835A1/en not_active Abandoned
- 2011-09-07 CN CN2011800430432A patent/CN103098178A/zh active Pending
- 2011-09-07 WO PCT/JP2011/070328 patent/WO2012033114A1/ja active Application Filing
- 2011-09-07 EP EP11823588.6A patent/EP2615633A1/en not_active Withdrawn
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- 2011-09-07 JP JP2012532992A patent/JPWO2012033114A1/ja not_active Withdrawn
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Also Published As
Publication number | Publication date |
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EP2615633A1 (en) | 2013-07-17 |
US20130171835A1 (en) | 2013-07-04 |
KR20130129360A (ko) | 2013-11-28 |
SG188437A1 (en) | 2013-04-30 |
JPWO2012033114A1 (ja) | 2014-01-20 |
TW201217508A (en) | 2012-05-01 |
CN103098178A (zh) | 2013-05-08 |
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