WO2011049092A1 - 金属微細構造体のパターン倒壊抑制用処理液及びこれを用いた金属微細構造体の製造方法 - Google Patents
金属微細構造体のパターン倒壊抑制用処理液及びこれを用いた金属微細構造体の製造方法 Download PDFInfo
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- WO2011049092A1 WO2011049092A1 PCT/JP2010/068397 JP2010068397W WO2011049092A1 WO 2011049092 A1 WO2011049092 A1 WO 2011049092A1 JP 2010068397 W JP2010068397 W JP 2010068397W WO 2011049092 A1 WO2011049092 A1 WO 2011049092A1
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- treatment liquid
- metal
- group
- metal microstructure
- oxide
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 95
- 239000002184 metal Substances 0.000 title claims abstract description 95
- 238000011282 treatment Methods 0.000 title claims abstract description 85
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 238000000034 method Methods 0.000 title abstract description 30
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 22
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 19
- 125000006353 oxyethylene group Chemical group 0.000 claims abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 68
- -1 polyoxyethylene Polymers 0.000 claims description 44
- 239000010936 titanium Substances 0.000 claims description 32
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 29
- 229910052719 titanium Inorganic materials 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical group [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 18
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 15
- 229910000449 hafnium oxide Inorganic materials 0.000 claims description 15
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims description 15
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052707 ruthenium Inorganic materials 0.000 claims description 15
- 239000004065 semiconductor Substances 0.000 claims description 15
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 229910052715 tantalum Inorganic materials 0.000 claims description 12
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 12
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 11
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 10
- 229910052735 hafnium Inorganic materials 0.000 claims description 10
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 10
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 9
- 239000003112 inhibitor Substances 0.000 claims description 8
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 8
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 8
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 claims description 8
- 238000001312 dry etching Methods 0.000 claims description 7
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 6
- 238000001039 wet etching Methods 0.000 claims description 6
- TXFYZJQDQJUDED-UHFFFAOYSA-N germanium nickel Chemical compound [Ni].[Ge] TXFYZJQDQJUDED-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- RUFLMLWJRZAWLJ-UHFFFAOYSA-N nickel silicide Chemical compound [Ni]=[Si]=[Ni] RUFLMLWJRZAWLJ-UHFFFAOYSA-N 0.000 claims description 5
- 230000001629 suppression Effects 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 4
- 229910021334 nickel silicide Inorganic materials 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims 2
- PEUPIGGLJVUNEU-UHFFFAOYSA-N nickel silicon Chemical compound [Si].[Ni] PEUPIGGLJVUNEU-UHFFFAOYSA-N 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 28
- 230000005764 inhibitory process Effects 0.000 description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 229910052814 silicon oxide Inorganic materials 0.000 description 18
- 229920002120 photoresistant polymer Polymers 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 8
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 8
- 229920005591 polysilicon Polymers 0.000 description 8
- 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 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 125000002704 decyl 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])* 0.000 description 6
- 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 6
- 230000000694 effects Effects 0.000 description 6
- 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 6
- 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 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- 238000005530 etching Methods 0.000 description 5
- 229910052581 Si3N4 Inorganic materials 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 125000001400 nonyl 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])[H] 0.000 description 4
- 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 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 125000002889 tridecyl 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])[H] 0.000 description 4
- 125000002948 undecyl 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])[H] 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- FCFLBEDHHQQLCN-UHFFFAOYSA-N [Ge].[Si].[Ni] Chemical compound [Ge].[Si].[Ni] FCFLBEDHHQQLCN-UHFFFAOYSA-N 0.000 description 3
- 238000004380 ashing Methods 0.000 description 3
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 238000000206 photolithography Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000001204 arachidyl 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])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 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
- 125000005843 halogen group Chemical group 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 125000002960 margaryl 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])[H] 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000001196 nonadecyl 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])C([H])([H])[H] 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000002958 pentadecyl 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])[H] 0.000 description 2
- ZFDPAZDODACYOG-UHFFFAOYSA-M sodium;[(1,5-dimethyl-3-oxo-2-phenylpyrazol-4-yl)amino]methanesulfonate Chemical compound [Na+].CN1C(C)=C(NCS([O-])(=O)=O)C(=O)N1C1=CC=CC=C1 ZFDPAZDODACYOG-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 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 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910004129 HfSiO Inorganic materials 0.000 description 1
- 229910006137 NiGe Inorganic materials 0.000 description 1
- 229910005883 NiSi Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910004121 SrRuO Inorganic materials 0.000 description 1
- JFWLFXVBLPDVDZ-UHFFFAOYSA-N [Ru]=O.[Sr] Chemical compound [Ru]=O.[Sr] JFWLFXVBLPDVDZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- ANIPLPVHLCEBLF-UHFFFAOYSA-N strontium oxygen(2-) ruthenium(3+) Chemical compound [Ru+3].[O-2].[Sr+2] ANIPLPVHLCEBLF-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Images
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00841—Cleaning during or after manufacture
- B81C1/00849—Cleaning during or after manufacture during manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31105—Etching inorganic layers
- H01L21/31111—Etching inorganic layers by chemical means
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
- B81B2203/00—Basic microelectromechanical structures
- B81B2203/01—Suspended structures, i.e. structures allowing a movement
- B81B2203/0109—Bridges
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
- B81B2203/00—Basic microelectromechanical structures
- B81B2203/03—Static structures
- B81B2203/0361—Tips, pillars
Definitions
- the present invention relates to a processing solution for suppressing pattern collapse of a metal microstructure and a method for producing a metal microstructure using the same.
- a photolithography technique is used as a method for forming and processing an element having a fine structure used in a wide field such as a semiconductor device or a circuit board.
- a wide field such as a semiconductor device or a circuit board.
- miniaturization, high integration, and high speed of semiconductor devices and the like have advanced remarkably, and the resist pattern used for photolithography has become finer and the aspect ratio has been increasing. I'm following.
- the miniaturization or the like progresses, the collapse of the resist pattern becomes a big problem.
- the collapse of the resist pattern is caused by the surface tension of the processing solution when the processing solution used in the wet processing (mainly rinsing processing for washing away the developing solution) after developing the resist pattern is dried from the resist pattern. It is known that it is generated by the action of stress. Therefore, in order to solve the collapse of the resist pattern, a method of drying by replacing the cleaning liquid with a low surface tension liquid using a nonionic surfactant, an alcohol solvent-soluble compound or the like (for example, Patent Documents 1 and 2). And a method of hydrophobizing the surface of the resist pattern (for example, see Patent Document 3).
- metal fine structure a fine structure made of metal, metal nitride, metal oxide or the like formed by photolithography technology (hereinafter referred to as metal fine structure.
- metal, silicon-containing metal, metal nitride, or metal oxide the strength of the metal itself forming the structure is higher than the strength of the resist pattern itself or the bonding strength between the resist pattern and the substrate. Structure pattern collapse is unlikely to occur. However, as semiconductor devices and micromachines are further reduced in size, increased in integration, and speeded up, the pattern of the structure becomes finer, and the collapse of the pattern of the structure due to an increase in aspect ratio becomes a serious problem. Come.
- the resist pattern which is an organic material
- the surface state of the metal microstructure are completely different, unlike the case of the collapse of the resist pattern described above, no effective countermeasures can be found, so semiconductor devices and micromachines are downsized and highly integrated.
- the degree of freedom in pattern design is significantly hindered, such as designing a pattern that does not cause pattern collapse.
- the present invention has been made under such circumstances, and provides a treatment liquid capable of suppressing pattern collapse of a metal microstructure such as a semiconductor device or a micromachine, and a method of manufacturing a metal microstructure using the same. Objective.
- the present inventors have a hydrocarbyl group consisting of either an alkyl group or an alkenyl group, which may be partially or fully substituted with fluorine, and an oxy It has been found that the object can be achieved by a treatment liquid containing a pattern collapse inhibitor containing an ethylene structure.
- the present invention has been completed based on such findings. That is, the gist of the present invention is as follows.
- Pattern of metal microstructure having a hydrocarbyl group consisting of either an alkyl group or an alkenyl group, which may be partially or entirely substituted with fluorine, and containing a pattern collapse inhibitor containing an oxyethylene structure Treatment liquid for preventing collapse.
- the pattern collapse inhibitor is one or more selected from the group consisting of hydrocarbyl alkanolamides, polyoxyethylene hydrocarbyl amines, and perfluoroalkyl polyoxyethylene ethanol. Treatment liquid for pattern collapse suppression.
- Part or all of the metal microstructure is titanium nitride, titanium, ruthenium, ruthenium oxide, aluminum oxide, hafnium oxide, hafnium silicate, hafnium silicate, platinum, tantalum, tantalum oxide, tantalum nitride, nickel silicide
- a method for producing a metal microstructure wherein the treatment liquid according to any one of [1] to [8] is used in a cleaning step after wet etching or dry etching.
- Part or all of the metal microstructure is titanium nitride, titanium, ruthenium, ruthenium oxide, aluminum oxide, hafnium oxide, hafnium silicate, hafnium silicate, platinum, tantalum, tantalum oxide, tantalum nitride, nickel silicide
- the method for producing a metal microstructure according to [9] wherein at least one material selected from nickel silicon germanium and nickel germanium is used.
- a treatment liquid capable of suppressing pattern collapse of a metal microstructure such as a semiconductor device or a micromachine, and a method of manufacturing a metal microstructure using the same.
- FIG. 3 is a schematic cross-sectional view for each production stage of metal microstructures produced in Examples 1 to 8 and Comparative Examples 1 to 20.
- FIG. 6 is a schematic cross-sectional view for each production stage of metal microstructures produced in Examples 9 to 24 and Comparative Examples 21 to 60.
- the processing solution for suppressing pattern collapse of a metal microstructure has a hydrocarbyl group consisting of either an alkyl group or an alkenyl group, which may be partially or wholly substituted with fluorine, and suppresses pattern collapse including an oxyethylene structure.
- a hydrocarbyl group consisting of either an alkyl group or an alkenyl group, which may be partially or wholly substituted with fluorine, and suppresses pattern collapse including an oxyethylene structure.
- the oxyethylene structure in the pattern collapse inhibitor is adsorbed to the metal material used for the pattern of the metal microstructure, and the hydrocarbyl group extending from the metal material is considered to be hydrophobic, thereby hydrophobizing the pattern surface. It is done. And as a result, it is considered that the generation of stress due to the surface tension of the treatment liquid can be reduced, and the pattern collapse of the metal microstructure such as a semiconductor device or a micromachine can be suppressed.
- the pattern collapse inhibitor used in the treatment liquid of the present invention is preferably at least one selected from the group consisting of hydrocarbyl alkanolamides, polyoxyethylene hydrocarbyl amines, and perfluoroalkyl polyoxyethylene ethanol.
- the hydrocarbyl alkanolamide is preferably represented by the following general formula (1).
- R 1 represents an alkyl group having 2 to 24 carbon atoms or an alkenyl group.
- an alkyl group having 6 to 18 carbon atoms is preferable, an alkyl group having 8 to 18 carbon atoms is more preferable, and an alkyl group having 8, 10, 12, 14, 16, 18 carbon atoms is further preferable.
- the alkyl group may be linear, branched or cyclic, and may have a halogen atom or a substituent.
- n-hexyl group 1-methylhexyl group, 2-methylhexyl group, 1-pentylhexyl group, cyclohexyl group, 1-hydroxyhexyl group, 1-chlorohexyl group, 1,3-dichlorohexyl group, 1-
- various hexyl groups such as aminohexyl group, 1-cyanohexyl group, 1-nitrohexyl group, various heptyl groups, various octyl groups, various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups, various tridecyl groups
- Various tetradecyl groups various pentadecyl groups, various hexadecyl groups, various heptadecyl groups, various octadecyl groups, various nonadecyl groups, various eicosyl groups, etc., more preferably various hexyl groups, various
- the alkenyl group is preferably an alkenyl group having 2 to 24 carbon atoms, more preferably an alkenyl group having 4 to 18 carbon atoms, and further preferably an alkenyl group having 6 to 18 carbon atoms.
- the polyoxyethylene hydrocarbylamine is preferably one represented by the following general formula (2).
- R 2 represents an alkyl group having 2 to 24 carbon atoms and an alkenyl group having 2 to 24 carbon atoms.
- the alkyl group is preferably an alkyl group having 6 to 18 carbon atoms, more preferably an alkyl group having 8 to 18 carbon atoms, still more preferably an alkyl group having 8, 10, 12, 14, 16, 18 carbon atoms, 18 is particularly preferred.
- the alkyl group may be linear, branched or cyclic, and may have a halogen atom or a substituent, such as an n-hexyl group, 1-methylhexyl group, 2-methyl group.
- Hexyl group 1-pentylhexyl group, cyclohexyl group, 1-hydroxyhexyl group, 1-chlorohexyl group, 1,3-dichlorohexyl group, 1-aminohexyl group, 1-cyanohexyl group, 1-nitrohexyl group
- various heptyl groups various octyl groups, various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups, various tridecyl groups, various tetradecyl groups, various pentadecyl groups, various hexadecyl groups, various heptadecyl groups, etc.
- the alkenyl group is preferably an alkenyl group having 2 to 24 carbon atoms, more preferably an alkenyl group having 4 to 18 carbon atoms, and further preferably an alkenyl group having 6 to 18 carbon atoms.
- n and m each represent an integer of 0 to 20, preferably 0 to 14, more preferably 1 to 5 (provided that m + n is 1 or more). If n and m are within the above ranges, the polyoxyethylene hydrocarbylamine used in the present invention is water or organic, depending on the balance between the functional group represented by R 2 and the hydrophilic-hydrophobic property. It is easily dissolved in a solvent such as a solvent and can be suitably used as a treatment liquid.
- coconut oil fatty acid diethanolamide is particularly preferable, and R 1 is a mixture of 8 to 18 carbon atoms, 8, 10 or 12 carbon atoms. , 14, 16, and 18. More specifically, product name Daianol 300 (Daiichi Kogyo Seiyaku Co., Ltd.), product name Daianol CDE (Daiichi Kogyo Seiyaku Co., Ltd.), product name Amizole CDE (Kawaken Fine Chemical Co., Ltd.), product name Amizole FDE (manufactured by Kawaken Fine Chemical Co., Ltd.)
- Preferred examples of the compound represented by the general formula (2) include the product name Amit 102, the product name Amit 105, the product name Amit 105A, the product name Amit 302, the product name Amit 320 (above manufactured by Kao Corporation), and the like.
- Particularly preferred is polyoxyethylene stearylamine, and specific examples include the product name Amiradin D (Daiichi Kogyo Seiyaku Co., Ltd.), the product name Amylazine C-1802 (Daiichi Kogyo Seiyaku Co., Ltd.), and the like. Can be mentioned.
- Perfluoroalkyl polyoxyethylene ethanol is a compound represented by the following general formula (3), and specific examples include the product name FLORARD FC-170C (manufactured by Sumitomo 3M Limited).
- n and m represent an integer of 1 to 20, and n and m may be the same or different.
- the treatment liquid of the present invention preferably further contains water and is preferably an aqueous solution.
- the water is preferably water from which metal ions, organic impurities, particle particles, and the like have been removed by distillation, ion exchange treatment, filter treatment, various adsorption treatments, and the like, and pure water and ultrapure water are particularly preferred.
- the treatment liquid of the present invention contains one or more selected from the group of hydrocarbyl alkanolamides, polyoxyethylene hydrocarbyl amines, and perfluoroalkyl polyoxyethylene ethanol described above, more preferably water, and other treatment liquids.
- Various commonly used additives may be included within a range that does not impair the effect of the treatment liquid.
- the content in the treatment liquid containing one or more selected from the group of hydrocarbyl alkanolamide, polyoxyethylene hydrocarbylamine, and perfluoroalkyl polyoxyethylene ethanol in the treatment liquid of the present invention is 10 ppm to 10%. It is preferable. If the content of the compound is within the above range, the effects of these compounds can be sufficiently obtained, but it is preferable to use at a lower concentration of 5% or less in consideration of ease of handling, economy and foaming.
- the content is preferably 10 ppm to 1%, more preferably 10 to 2000 ppm, and particularly preferably 10 to 1000 ppm.
- an organic solvent such as alcohol may be added, or the solubility may be supplemented by adding an acid or an alkali.
- an organic solvent such as alcohol
- the treatment liquid of the present invention is suitably used for suppressing pattern collapse of a metal microstructure such as a semiconductor device or a micromachine.
- a metal microstructure such as a semiconductor device or a micromachine.
- TiN titanium nitride
- Ti titanium
- Ru ruthenium
- RuO Ruthenium oxide
- Sr uO 3 Sr uO 3
- Al 2 O 3 aluminum oxide
- HfO 2 hafnium oxide
- Pt platinum
- Ta tantalum
- Ta 2 O 5 tantalum oxide
- TaN tantalum nitride
- Gayori TiN (titanium nitride), Ta (tantalum), Ti (titanium), Al 2 O 3 (aluminum oxide), and HfO 2 (hafnium oxide) Ru (ruthenium) are more preferable.
- the metal microstructure and if that is patterned on the insulating film species such as SiO 2 (silicon oxide film) and TEOS (tetraethoxy ortho silane oxide film), an insulating film type in a part of the metal microstructure May be included.
- the insulating film species such as SiO 2 (silicon oxide film) and TEOS (tetraethoxy ortho silane oxide film)
- the treatment liquid of the present invention exhibits an excellent effect of suppressing pattern collapse on not only a conventional metal microstructure but also a metal microstructure having a finer and higher aspect ratio.
- the aspect ratio is a value calculated by (pattern height / pattern width)
- the treatment liquid of the present invention is an excellent pattern for patterns having a high aspect ratio of 3 or more, and further 7 or more. Has the effect of suppressing collapse.
- the treatment liquid of the present invention has a fine pattern of 1: 1 line and space, even if the pattern size (pattern width) is 300 nm or less, 150 nm or less, 100 nm or less, and even 50 nm or less.
- the fine pattern having a cylindrical or columnar structure having an interval between patterns of 300 nm or less, 150 nm or less, 100 nm or less, or 50 nm or less has an excellent effect of suppressing pattern collapse.
- the metal microstructure manufacturing method of the present invention is characterized by using the above-described treatment liquid of the present invention in a cleaning step after wet etching or dry etching. More specifically, in the cleaning step, preferably, after the metal microstructure pattern and the treatment liquid of the present invention are brought into contact with each other by dipping, spray discharge, spraying, etc., the treatment liquid is replaced with water. dry.
- the immersion time is preferably 10 seconds to 30 minutes, more preferably 15 seconds to 20 minutes, and still more preferably 20 seconds to 15 minutes.
- the temperature condition is preferably 10 to 60 ° C., more preferably 15 to 50 ° C., still more preferably 20 to 40 ° C., and particularly preferably 25 to 40 ° C.
- the surface of the pattern is hydrophobized so that the pattern collapses so that the pattern contacts the adjacent pattern. It becomes possible to suppress.
- the treatment liquid of the present invention includes a wet etching process or a dry etching process in the manufacturing process of the metal microstructure, and then a wet process (etching or cleaning, rinsing for washing away the cleaning liquid) and drying. It consists of processes and can be widely applied regardless of the type of metal microstructure. For example, (i) in the manufacture of a DRAM type semiconductor device, after wet etching is performed on an insulating film around a conductive film (see, for example, Japanese Patent Laid-Open Nos.
- a strip After a cleaning process for removing contaminants generated after dry etching or wet etching at the time of processing a gate electrode in the manufacture of a semiconductor device having a transistor having a fin-like shape for example, Japanese Patent Application Laid-Open No.
- Examples 1 to 4 As shown in FIG. 1A, after silicon nitride 103 (thickness: 100 nm) and silicon oxide 102 (thickness: 1200 nm) are formed on a silicon substrate 104, a photoresist 101 is formed, and then the photo resist is formed. By exposing and developing the resist 101, a circle-ring-shaped opening 105 ( ⁇ 125 nm, distance between circles: 70 nm) shown in FIG. 1B is formed, and dry etching is performed using the photoresist 101 as a mask. A cylindrical hole 106 shown in FIG. 1C was formed in the silicon oxide 102 by etching up to the silicon nitride 103 layer.
- the photoresist 101 was removed by ashing to obtain a structure in which a cylindrical hole 106 reaching the silicon nitride 103 layer in the silicon oxide 102 shown in FIG. Titanium nitride is filled and deposited as a metal 107 in the cylindrical hole 106 of the obtained structure (FIG. 1 (e)), and an extra portion on the silicon oxide 102 is obtained by chemical mechanical polishing (CMP).
- the metal (titanium nitride) 107 was removed to obtain a structure in which a cylinder 108 of metal (titanium nitride) was embedded in the silicon oxide 102 shown in FIG.
- the silicon oxide 102 of the obtained structure is dissolved and removed with a 0.5% hydrofluoric acid aqueous solution (25 ° C., 1 minute immersion treatment), and then rinsed with pure water, treatment liquid 1 to 4 (30 ° C., 10 minute immersion treatment). , And pure water rinse in that order, followed by drying to obtain a structure shown in FIG.
- the obtained structure has a microstructure having a cylindrical (chimney-like) pattern ( ⁇ 125 nm, height: 1200 nm (aspect ratio: 9.6), distance between cylinder: 70 nm) of metal (titanium nitride). 70% or more of the pattern did not collapse.
- Example 1 the silicon oxide 102 of the structure shown in FIG. 1 (f) was dissolved and removed with hydrofluoric acid, and then treated with pure water only. The structure shown was obtained. 50% or more of the pattern of the obtained structure caused the collapse as shown in FIG. 1 (h) (the collapse suppression rate is less than 50%).
- Table 3 shows the results of the treatment liquid, the treatment method, and the collapse inhibition rate used in Comparative Example 1.
- Example 1 the silicon oxide 102 having the structure shown in FIG. 1 (f) was dissolved and removed with hydrofluoric acid and treated with pure water, and then treated with Comparative Solutions 1 to 9 shown in Table 2 instead of Treatment Solution 1.
- a structure shown in FIG. 1G was obtained in the same manner as in Example 1 except that. More than 50% of the pattern of the obtained structure collapsed as shown in FIG. Table 3 shows the results of the treatment liquid, treatment method, and collapse suppression rate used in Examples 2 to 10.
- Collapse inhibition rate (number of cylinders not collapsed / total number of cylinders) x 100 [%]
- Examples 5-8 In Examples 1 to 4, except that tantalum was used as the metal 107 instead of titanium nitride, the structure shown in FIG. 1G was obtained. The resulting structure has a microstructure with a cylindrical pattern of metal (tantalum) cylinder 108 ( ⁇ 125 nm, height: 1200 nm (aspect ratio: 9.6), distance between cylinder: 70 nm). And 70% or more of the pattern did not collapse. Table 4 shows the results of the treatment liquid, the treatment method, and the collapse inhibition rate used in each example.
- Comparative Examples 11-20 In Comparative Examples 1 to 10, except that tantalum was used instead of titanium nitride as the metal 107, the structures shown in FIG. 1 (g) of Comparative Examples 11 to 20 were obtained in the same manner as Comparative Examples 1 to 10, respectively. . More than 50% of the pattern of the obtained structure collapsed as shown in FIG. Table 4 shows the results of the treatment liquid, the treatment method, and the collapse inhibition rate used in each example.
- Collapse inhibition rate (number of cylinders not collapsed / total number of cylinders) x 100 [%]
- a polysilicon 202 (thickness: 100 nm) is formed on a silicon oxide layer 201 formed on a silicon substrate, and a photoresist 203 is formed thereon.
- the resist 203 is exposed and developed to form a prismatic opening 204 (1000 nm ⁇ 8000 nm) shown in FIG. 2B, and dry etching is performed on the polysilicon 202 by using the photoresist 203 as a mask.
- the photoresist 203 was removed by ashing to obtain a structure in which prismatic holes 205 reaching the silicon oxide layer 201 were opened in the polysilicon 202 shown in FIG.
- the prismatic hole 205 of the obtained structure is filled and deposited with titanium as a metal to form a metal (titanium) prism 206 and a metal (titanium) layer 207 (FIG. 2 (e)), and the metal (titanium).
- a photoresist 208 was formed on the layer 207 (FIG. 2F).
- the photoresist 208 is exposed and developed to form a rectangular photomask 209 that covers the area including the two metal (titanium) prisms 206 shown in FIG. 2G, and the rectangular photomask 209 is masked.
- the metal (titanium) layer 207 was dry-etched to form a metal (titanium) plate 210 having metal (titanium) prisms 206 at both ends of the lower portion shown in FIG. Further, the rectangular photomask 209 was removed by ashing to obtain a structure made of a metal (titanium) plate 210 having polysilicon 202 and metal (titanium) prisms 206 shown in FIG.
- Example 9 Polysilicon 202 having a structure thus obtained was dissolved and removed with an aqueous tetramethylammonium hydroxide solution, and then contacted with pure water, treatment solutions 1 to 5 and pure water in that order, followed by drying.
- the obtained bridge structure 211 has a metal (titanium) plate 210 (length ⁇ width: 15000 nm ⁇ 10000 nm, thickness: 300 nm, aspect ratio: 50) and metal (titanium) prisms (length ⁇ width: 1000 nm ⁇ ) at both ends thereof.
- the metal (titanium) plate 210 of 70% or more did not collapse and the silicon oxide layer 201 was not touched.
- the collapse of the pattern was observed using “FE-SEM S-5500 (model number)” manufactured by Hitachi High-Technologies Corporation. Table 5 shows the results of the treatment liquid, the treatment method, and the collapse inhibition rate used in each example.
- Example 9 the polysilicon 202 having the structure shown in FIG. 2 (i) was dissolved and removed with an aqueous solution of tetramethylammonium hydroxide and then treated with pure water only.
- the bridge structure 211 shown in 2 (j) was obtained. More than 50% of the obtained bridge structure 211 has collapsed as shown in FIG. Table 5 shows the results of the treatment liquid, the treatment method, and the collapse inhibition rate used in Comparative Example 21.
- Example 9 the polysilicon 202 having the structure shown in FIG. 2 (i) was dissolved and removed with a tetramethylammonium hydroxide aqueous solution and treated with pure water, and then the comparative solution shown in Table 2 instead of the treatment solution 1.
- a bridge structure 211 shown in FIG. 2 (j) of Comparative Examples 22 to 30 was obtained in the same manner as in Example 9 except that the treatments in 1 to 9 were performed. 50% or more of the obtained bridge structures 211 were collapsed as shown in FIG. 2 (k) (the collapse inhibition rate was less than 50%).
- Table 5 shows the treatment liquid, the treatment method, and the collapse inhibition rate used in Comparative Example 22.
- Examples 13 to 16 In Examples 9 to 12, a bridge structure 211 shown in FIG. 2 (j) of Examples 13 to 16 was obtained in the same manner as Examples 9 to 12, except that aluminum oxide was used instead of titanium. .
- the obtained bridge structure 211 is composed of a metal (aluminum oxide) plate 210 (length ⁇ width: 15000 nm ⁇ 10000 nm, thickness: 300 nm, aspect ratio: 50) and metal (aluminum oxide) prisms (length ⁇ width: Although the microstructure has a thickness of 1000 nm ⁇ 8000 nm and height: 100 nm, the metal (aluminum oxide) plate 210 of 70% or more did not collapse and the silicon oxide layer 201 was not touched.
- Table 6 shows the results of the treatment liquid, the treatment method, and the collapse inhibition rate used in each example.
- Comparative Examples 31-40 In Comparative Examples 21 to 30, a bridge structure 211 shown in FIG. 2 (j) of Comparative Examples 31 to 40 was obtained in the same manner as Comparative Examples 21 to 30, except that aluminum oxide was used instead of titanium. . More than 50% of the obtained bridge structure collapsed as shown in FIG. 2 (k). Table 6 shows the results of the treatment liquid, the treatment method, and the collapse inhibition rate used in each example.
- Examples 17-20 a bridge structure 211 shown in FIG. 2 (j) of Examples 17 to 20 was obtained in the same manner as Examples 9 to 12 except that hafnium oxide was used instead of titanium as a metal.
- the obtained bridge structure 211 includes a metal (hafnium oxide) plate 210 (vertical ⁇ horizontal: 15000 nm ⁇ 10000 nm, thickness: 300 nm, aspect ratio: 50) and metal (hafnium oxide) prisms (vertical ⁇ horizontal: both ends).
- the microstructure has a thickness of 1000 nm ⁇ 8000 nm and height: 100 nm, 70% or more of the metal (hafnium oxide) plate 210 is not collapsed and the silicon oxide layer 201 is not touched.
- Table 7 shows the results of the treatment liquid, treatment method, and collapse inhibition rate used in each example.
- Comparative Examples 41-50 In Comparative Examples 21 to 30, the bridge structure 211 shown in FIG. 2 (j) of Comparative Examples 41 to 50 was obtained in the same manner as Comparative Examples 21 to 30 except that hafnium oxide was used instead of titanium as the metal. . More than 50% of the obtained bridge structure collapsed as shown in FIG. 2 (k). Table 7 shows the results of the treatment liquid, treatment method, and collapse inhibition rate used in each example.
- Examples 21-24 a bridge structure 211 shown in FIG. 2 (j) of Examples 21 to 24 was obtained in the same manner as Examples 9 to 12 except that ruthenium was used instead of titanium as a metal.
- the obtained bridge structure 211 includes a metal (ruthenium) plate 210 (length ⁇ width: 15000 nm ⁇ 10000 nm, thickness: 300 nm, aspect ratio: 50) and metal (ruthenium) prisms (length ⁇ width: 1000 nm ⁇ ) at both ends thereof.
- the metal (ruthenium) plate 210 of 70% or more did not collapse, and the silicon oxide layer 201 was not touched.
- the collapse of the pattern was observed using “FE-SEM S-5500 (model number)” manufactured by Hitachi High-Technologies Corporation. Table 8 shows the results of the treatment liquid, the treatment method, and the collapse inhibition rate used in each example.
- Comparative Examples 51-60 In Comparative Examples 21 to 30, a bridge structure 211 shown in FIG. 2 (j) of Comparative Examples 51 to 60 was obtained in the same manner as Comparative Examples 21 to 30, except that ruthenium was used instead of titanium as a metal. More than 50% of the obtained bridge structure collapsed as shown in FIG. 2 (k). Table 8 shows the results of the treatment liquid, the treatment method, and the collapse inhibition rate used in each example.
- the treatment liquid of the present invention can be suitably used for suppressing pattern collapse in the production of metal microstructures such as semiconductor devices and micromachines (MEMS).
- MEMS micromachines
- Photoresist 102 Silicon oxide 103. Silicon nitride 104. Silicon substrate 105. Circular opening 106. Cylindrical hole 107. Metal (titanium nitride or tantalum) 108. 201. Cylinder of metal (titanium nitride or tantalum) Silicon oxide layer 202. Polysilicon 203. Photoresist 204. Prismatic opening 205. Prismatic hole 205 206. Metal (titanium, aluminum oxide, hafnium oxide or ruthenium) prism 207. Metal (titanium, aluminum oxide, hafnium oxide or ruthenium) layer 208. Photoresist 209. Rectangular photomask 210. Metal (titanium, aluminum oxide, hafnium oxide or ruthenium) plate 211. Bridge structure
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Abstract
Description
本発明は、このような状況下になされたもので、半導体装置やマイクロマシンといった金属微細構造体のパターン倒壊を抑制しうる処理液及びこれを用いた金属微細構造体の製造方法を提供することを目的とする。
本発明は、かかる知見に基づいて完成したものである。すなわち、本発明の要旨は下記のとおりである。
[2] 前記パターン倒壊抑制剤が、ヒドロカルビルアルカノールアミド、ポリオキシエチレンヒドロカルビルアミン、およびパーフルオロアルキルポリオキシエチレンエタノールからなる群から選ばれる1種以上である[1]に記載の金属微細構造体のパターン倒壊抑制用処理液。
[7] 前記ヒドロカルビルアルカノールアミド、ポリオキシエチレンヒドロカルビルアミン、およびパーフルオロアルキルポリオキシエチレンエタノールからなる群から選ばれる1種以上の含有量が10ppm~10%である[2]~[6]のいずれかに記載の処理液。
[8] 前記金属微細構造体の一部もしくは全部が、窒化チタン、チタン、ルテニウム、酸化ルテニウム、酸化アルミニウム、酸化ハフニウム、ハフニウムシリケート、窒化ハフニウムシリケート、白金、タンタル、酸化タンタル、窒化タンタル、ニッケルシリサイド、ニッケルシリコンゲルマニウム、およびニッケルゲルマニウムから選ばれる少なくとも一種の材料を用いてなるものである[1]~[7]のいずれかに記載の処理液。
[10] 前記金属微細構造体の一部もしくは全部が、窒化チタン、チタン、ルテニウム、酸化ルテニウム、酸化アルミニウム、酸化ハフニウム、ハフニウムシリケート、窒化ハフニウムシリケート、白金、タンタル、酸化タンタル、窒化タンタル、ニッケルシリサイド、ニッケルシリコンゲルマニウム、およびニッケルゲルマニウムから選ばれる少なくとも一種の材料を用いてなるものである[9]に記載の金属微細構造体の製造方法。
[11] 前記金属微細構造体が、半導体装置またはマイクロマシンである[9]又は[10]に記載の金属微細構造体の製造方法。
なお、本発明において疎水化とは、本発明の処理液にて処理された金属の表面と水との接触角が70°以上となることをいう。また、本発明において、「オキシエチレン構造」とは、「-CH2CH2O-」の構造をいう。
例えばn-ヘキシル基、1-メチルヘキシル基、2-メチルヘキシル基、1-ペンチルへキシル基、シクロヘキシル基、1-ヒドロキシヘキシル基、1-クロロヘキシル基、1,3-ジクロロヘキシル基、1-アミノヘキシル基、1-シアノヘキシル基、1-ニトロヘキシル基などの各種ヘキシル基のほか、各種ヘプチル基、各種オクチル基、各種ノニル基、各種デシル基、各種ウンデシル基、各種ドデシル基、各種トリデシル基、各種テトラデシル基、各種ペンタデシル基、各種ヘキサデシル基、各種ヘプタデシル基、各種オクタデシル基、各種ノナデシル基、各種エイコシル基などが挙げられ、より好ましくは各種ヘキシル基のほか、各種ヘプチル基、各種オクチル基、各種ノニル基、各種デシル基、各種ウンデシル基、各種ドデシル基、各種トリデシル基、各種テトラデシル基、各種オクタデシル基であり、更に好ましくは各種オクチル基、各種デシル基、各種ドデシル基、各種テトラデシル基、各種セチル基、各種オクタデシル基である。
また相分離せず単に白濁した場合でも、その処理液の効果を害しない範囲で用いてもよいし、その処理液が均一となるように撹拌を伴って使用してもよい。また、処理液の白濁を避けるために、上記と同様にアルコールなどの有機溶剤や酸、アルカリを加えてから用いてもよい。
本発明の金属微細構造体の製造方法は、ウェットエッチング又はドライエッチングの後の洗浄工程において、上記した本発明の処理液を用いることを特徴とするものである。より具体的には、該洗浄工程において、好ましくは金属微細構造体のパターンと本発明の処理液とを浸漬、スプレー吐出、噴霧などにより接触させた後、水で該処理液を置換してから乾燥させる。ここで、金属微細構造体のパターンと本発明の処理液とを浸漬により接触させる場合、浸漬時間は10秒~30分が好ましく、より好ましくは15秒~20分、さらに好ましくは20秒~15分、特に好ましくは30秒~10分であり、温度条件は10~60℃が好ましく、より好ましくは15~50℃、さらに好ましくは20~40℃、特に好ましくは25~40℃である。また、金属微細構造体のパターンと本発明の処理液との接触の前に、あらかじめ水で洗浄を行ってもよい。このように、金属微細構造体のパターンと本発明の処理液とを接触させることにより、該パターンの表面上を疎水化することにより、パターンがその隣のパターンに接触するようなパターンの倒壊を抑制することが可能となる。
《処理液の調製》
表1に示される配合組成(質量%)に従い、実施例に係る金属微細構造体のパターン倒壊抑制用処理液1~4を調合した。なお、残部は水である。
*2:「ダイヤノールCDE(商品名)」:第一工業製薬株式会社製、比重:1.01(20℃)、粘度:約220Pas(50℃)、非イオン性、一般式(1)の範囲
*3:「アミラヂンC1802(商品名)」:第一工業製薬株式会社製、比重:0.916(20℃)、非イオン性、一般式(2)の範囲
*4:「フロラードFC-170C(商品名)」:住友スリーエム株式会社製、比重:1.32(25℃)、非イオン性、一般式(3)の範囲
*5: 各化合物が有するアルキル基の炭素数
図1(a)に示すように、シリコン基板104上に窒化珪素103(厚さ:100nm)及び酸化珪素102(厚さ:1200nm)を成膜した後、フォトレジスト101を形成した後、該フォトレジスト101を露光、現像することにより、図1(b)に示す円-リング状開口部105(φ125nm、円と円との距離:70nm)を形成し、該フォトレジスト101をマスクとしてドライエッチングにより酸化珪素102に図1(c)に示す円筒状の孔106を、窒化珪素103の層までエッチングして形成した。次いで、フォトレジスト101をアッシングにより除去し、図1(d)に示す酸化珪素102に窒化珪素103の層に達する円筒状孔106が開孔された構造体を得た。得られた構造体の円筒状孔106に、金属107として窒化チタンを充填・堆積し(図1(e))、化学的機械研磨(ケミカルメカニカルポリッシング;CMP)により、酸化珪素102上の余分な金属(窒化チタン)107を除去し、図1(f)に示す酸化珪素102中に金属(窒化チタン)の円筒108が埋め込まれた構造体を得た。得られた構造体の酸化珪素102を0.5%フッ酸水溶液により溶解除去(25℃、1分浸漬処理)した後、純水リンス、処理液1~4(30℃、10分浸漬処理)、及び純水リンスの順で接液処理し、乾燥を行い、図1(g)に示す構造体を得た。
得られた構造体は、金属(窒化チタン)の円筒-煙突状のパターン(φ125nm,高さ:1200nm(アスペクト比:9.6),円筒と円筒との間の距離:70nm)を有する微細構造であり、70%以上の該パターンは倒壊することがなかった。
ここで、パターンの倒壊は、「FE-SEM S-5500(型番)」:日立ハイテクノロジーズ社製を用いて観察し、倒壊抑制率は、パターン全本数中の倒壊しなかったパターンの割合を算出して求めた数値であり、該倒壊抑制率が50%以上であれば合格と判断した。各例において使用した処理液、処理方法及び倒壊抑制率の結果を表3に示す。
実施例1において、図1(f)に示される構造体の酸化珪素102をフッ酸により溶解除去した後、純水のみで処理した以外は、実施例1と同様にして図1(g)に示す構造体を得た。得られた構造体のパターンの50%以上は、図1(h)に示されるような倒壊をおこしていた(倒壊抑制率は50%未満となる。)。比較例1において使用した処理液、処理方法及び倒壊抑制率の結果を表3に示す。
実施例1において、図1(f)に示される構造体の酸化珪素102をフッ酸により溶解除去し純水で処理した後、処理液1の代わりに表2に示す比較液1~9で処理する以外は、実施例1と同様にして図1(g)に示す構造体を得た。得られた構造体のパターンの50%以上は、図1(h)に示されるような倒壊をおこしていた。各例2~10において使用した処理液、処理方法及び倒壊抑制率の結果を表3に示す。
*2:「カチオーゲンTML(商品名)」:第一工業製薬株式会社製,0.01%水
*3:「サーフィノール104(商品名)」:日信化学工業株式会社製,0.01%水
*4:「エパン420(商品名)」:第一工業製薬株式会社製,0.01%水
*5:「フロラードFC-93(商品名)」:3M社製,0.01%水
*6:「サーフロンS-111(商品名)」:AGCセイミケミカル(株)製,0.01%水
実施例1~4において、金属107として窒化チタンの代わりにタンタルを用いた以外は実施例1~4と同様にして図1(g)に示す構造体を得た。得られた構造体は、金属(タンタル)の円筒108の円筒状のパターン(φ125nm,高さ:1200nm(アスペクト比:9.6)、円筒と円筒との間の距離:70nm)を有する微細構造であり、70%以上の該パターンは倒壊することがなかった。各例において使用した処理液、処理方法及び倒壊抑制率の結果を表4に示す。
比較例1~10において、金属107として窒化チタンの代わりにタンタルを用いた以外は比較例1~10と同様にして、各々比較例11~20の図1(g)に示す構造体を得た。得られた構造体のパターンの50%以上は、図1(h)に示されるような倒壊をおこしていた。各例において使用した処理液、処理方法及び倒壊抑制率の結果を表4に示す。
図2(a)に示すように、シリコン基板上に形成された酸化珪素層201上にポリシリコン202(厚さ:100nm)を成膜し、その上にフォトレジスト203を形成した後、該フォトレジスト203を露光、現像することにより、図2(b)に示す角柱状開口部204(1000nm×8000nm)を形成し、該フォトレジスト203をマスクとしてドライエッチングによりポリシリコン202に図2(c)に示す角柱状孔205を、酸化珪素層201までエッチングして形成した。次いで、フォトレジスト203をアッシングにより除去し図2(d)に示すポリシリコン202に酸化珪素層201に達する角柱状孔205が開孔された構造体を得た。得られた構造体の角柱状孔205に金属としてチタンを充填・堆積して、金属(チタン)角柱206及び金属(チタン)層207を形成し(図2(e))、該金属(チタン)層207上にフォトレジスト208を形成した(図2(f))。次いで、フォトレジスト208を露光、現像することにより、図2(g)に示す2つの金属(チタン)角柱206を含む範囲を覆う長方形型フォトマスク209を形成し、該長方形型フォトマスク209をマスクとして、金属(チタン)層207をドライエッチングすることにより、図2(h)に示す下部の両端に金属(チタン)角柱206を有する金属(チタン)板210を形成した。さらに、長方形フォトマスク209をアッシングにより除去し、図2(i)に示すポリシリコン202と金属(チタン)角柱206とを有する金属(チタン)板210からなる構造体を得た。得られた構造体のポリシリコン202を水酸化テトラメチルアンミニウム水溶液により溶解除去した後、純水、処理液1~5、及び純水の順で接液処理し、乾燥を行い、実施例9~12の図2(j)に示す橋梁構造体211を得た。
実施例9において、図2(i)に示される構造体のポリシリコン202を水酸化テトラメチルアンミニウム水溶液により溶解除去した後、純水のみで処理した以外は、実施例9と同様にして図2(j)に示す橋梁構造体211を得た。得られた橋梁構造体211の50%以上は、図2(k)に示されるような倒壊をおこしていた。比較例21において使用した処理液、処理方法及び倒壊抑制率の結果を表5に示す。
実施例9において、図2(i)に示される構造体のポリシリコン202を水酸化テトラメチルアンミニウム水溶液により溶解除去し純水で処理した後、処理液1の代わりに表2に示す比較液1~9で処理する以外は、実施例9と同様にして、比較例22~30の図2(j)に示す橋梁構造体211を得た。得られた橋梁構造体211の50%以上は、図2(k)に示されるような倒壊をおこしていた(倒壊抑制率は50%未満となった。)。比較例22において使用した処理液、処理方法及び倒壊抑制率を表5に示す。
実施例9~12において、金属としてチタンの代わりに酸化アルミニウムを用いた以外は実施例9~12と同様にして、実施例13~16の図2(j)に示す橋梁構造体211を得た。
得られた橋梁構造体211は、金属(酸化アルミニウム)板210(縦×横:15000nm×10000nm,厚さ:300nm,アスペクト比:50)及びその両端に金属(酸化アルミニウム)角柱(縦×横:1000nm×8000nm,高さ:100nm)を有する微細構造であるが、70%以上の金属(酸化アルミニウム)板210が倒壊することなく、酸化珪素層201に触れることはなかった。各例において使用した処理液、処理方法及び倒壊抑制率の結果を表6に示す。
比較例21~30において、金属としてチタンの代わりに酸化アルミニウムを用いた以外は比較例21~30と同様にして、比較例31~40の図2(j)に示す橋梁構造体211を得た。得られた橋梁構造体の50%以上は、図2(k)に示されるような倒壊をおこしていた。各例において使用した処理液、処理方法及び倒壊抑制率の結果を表6に示す。
実施例9~12において、金属としてチタンの代わりに酸化ハフニウムを用いた以外は実施例9~12と同様にして、実施例17~20の図2(j)に示す橋梁構造体211を得た。
得られた橋梁構造体211は、金属(酸化ハフニウム)板210(縦×横:15000nm×10000nm,厚さ:300nm,アスペクト比:50)及びその両端に金属(酸化ハフニウム)角柱(縦×横:1000nm×8000nm,高さ:100nm)を有する微細構造であるが、70%以上の金属(酸化ハフニウム)板210が倒壊することがなく、酸化珪素層201に触れることはなかった。各例において使用した処理液、処理方法及び倒壊抑制率の結果を表7に示す。
比較例21~30において、金属としてチタンの代わりに酸化ハフニウムを用いた以外は比較例21~30と同様にして、比較例41~50の図2(j)に示す橋梁構造体211を得た。得られた橋梁構造体の50%以上は、図2(k)に示されるような倒壊をおこしていた。各例において使用した処理液、処理方法及び倒壊抑制率の結果を表7に示す。
実施例9~12において、金属としてチタンの代わりにルテニウムを用いた以外は実施例9~12と同様にして、実施例21~24の図2(j)に示す橋梁構造体211を得た。
得られた橋梁構造体211は、金属(ルテニウム)板210(縦×横:15000nm×10000nm,厚さ:300nm,アスペクト比:50)及びその両端に金属(ルテニウム)角柱(縦×横:1000nm×8000nm,高さ:100nm)を有する微細構造であるが、70%以上の金属(ルテニウム)板210が倒壊することはなく、酸化珪素層201に触れることはなかった。ここで、パターンの倒壊は、「FE-SEM S-5500(型番)」:日立ハイテクノロジーズ社製を用いて観察した。各例において使用した処理液、処理方法及び倒壊抑制率の結果を表8に示す。
比較例21~30において、金属としてチタンの代わりにルテニウムを用いた以外は比較例21~30と同様にして、比較例51~60の図2(j)に示す橋梁構造体211を得た。得られた橋梁構造体の50%以上は、図2(k)に示されるような倒壊をおこしていた。各例において使用した処理液、処理方法及び倒壊抑制率の結果を表8に示す。
102.酸化珪素
103.窒化珪素
104.シリコン基板
105.円状開口部
106.円筒状孔
107.金属(窒化チタンまたはタンタル)
108.金属(窒化チタンまたはタンタル)の円筒
201.酸化珪素層
202.ポリシリコン
203.フォトレジスト
204.角柱状開口部
205.角柱状孔205
206.金属(チタン、酸化アルミニウム、酸化ハフニウムまたはルテニウム)角柱
207.金属(チタン、酸化アルミニウム、酸化ハフニウムまたはルテニウム)層
208.フォトレジスト
209.長方形型フォトマスク
210.金属(チタン、酸化アルミニウム、酸化ハフニウムまたはルテニウム)板
211.橋梁構造体
Claims (11)
- 一部または全部がフッ素で置換されていてもよいアルキル基およびアルケニル基のいずれかからなるヒドロカルビル基を有し、オキシエチレン構造を含むパターン倒壊抑制剤を含有する金属微細構造体のパターン倒壊抑制用処理液。
- 前記パターン倒壊抑制剤が、ヒドロカルビルアルカノールアミド、ポリオキシエチレンヒドロカルビルアミン、およびパーフルオロアルキルポリオキシエチレンエタノールからなる群から選ばれる1種以上である請求項1に記載の金属微細構造体のパターン倒壊抑制用処理液。
- さらに水を含む請求項1~5のいずれかに記載の処理液。
- 前記ヒドロカルビルアルカノールアミド、ポリオキシエチレンヒドロカルビルアミン、およびパーフルオロアルキルポリオキシエチレンエタノールからなる群から選ばれる1種以上の含有量が10ppm~10%である請求項2~6のいずれかに記載の処理液。
- 前記金属微細構造体の一部もしくは全部が、窒化チタン、チタン、ルテニウム、酸化ルテニウム、酸化アルミニウム、酸化ハフニウム、ハフニウムシリケート、窒化ハフニウムシリケート、白金、タンタル、酸化タンタル、窒化タンタル、ニッケルシリサイド、ニッケルシリコンゲルマニウム、およびニッケルゲルマニウムから選ばれる少なくとも一種の材料を用いてなるものである請求項1~7のいずれかに記載の処理液。
- ウェットエッチング又はドライエッチングの後の洗浄工程において、請求項1~8のいずれかに記載の処理液を用いることを特徴とする金属微細構造体の製造方法。
- 前記金属微細構造体の一部もしくは全部が、窒化チタン、チタン、ルテニウム、酸化ルテニウム、酸化アルミニウム、酸化ハフニウム、ハフニウムシリケート、窒化ハフニウムシリケート、白金、タンタル、酸化タンタル、窒化タンタル、ニッケルシリサイド、ニッケルシリコンゲルマニウム、およびニッケルゲルマニウムから選ばれる少なくとも一種の材料を用いてなるものである請求項9に記載の金属微細構造体の製造方法。
- 前記金属微細構造体が、半導体装置またはマイクロマシンである請求項9又は10に記載の金属微細構造体の製造方法。
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- 2010-10-19 KR KR1020177017709A patent/KR20170078867A/ko active Search and Examination
- 2010-10-19 CN CN201080047543.9A patent/CN102640264B/zh active Active
- 2010-10-19 KR KR1020187023186A patent/KR102008117B1/ko active IP Right Grant
- 2010-10-19 DE DE112010003836.8T patent/DE112010003836B4/de active Active
- 2010-10-19 WO PCT/JP2010/068397 patent/WO2011049092A1/ja active Application Filing
- 2010-10-19 KR KR1020127010126A patent/KR20120116390A/ko active Search and Examination
- 2010-10-21 TW TW099135937A patent/TW201122736A/zh unknown
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JPWO2016117656A1 (ja) * | 2015-01-23 | 2017-10-12 | 富士フイルム株式会社 | パターン処理方法、半導体基板製品の製造方法およびパターン構造の前処理液 |
Also Published As
Publication number | Publication date |
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KR20120116390A (ko) | 2012-10-22 |
KR102008117B1 (ko) | 2019-08-06 |
JP5720575B2 (ja) | 2015-05-20 |
CN102640264A (zh) | 2012-08-15 |
US20120205345A1 (en) | 2012-08-16 |
JPWO2011049092A1 (ja) | 2013-03-14 |
KR20170078867A (ko) | 2017-07-07 |
TW201122736A (en) | 2011-07-01 |
DE112010003836T5 (de) | 2012-11-22 |
CN102640264B (zh) | 2015-04-01 |
KR20180093133A (ko) | 2018-08-20 |
DE112010003836B4 (de) | 2020-01-30 |
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