JP6717862B2 - タングステン及びgst膜のためのエッチング溶液 - Google Patents
タングステン及びgst膜のためのエッチング溶液 Download PDFInfo
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- JP6717862B2 JP6717862B2 JP2018008709A JP2018008709A JP6717862B2 JP 6717862 B2 JP6717862 B2 JP 6717862B2 JP 2018008709 A JP2018008709 A JP 2018008709A JP 2018008709 A JP2018008709 A JP 2018008709A JP 6717862 B2 JP6717862 B2 JP 6717862B2
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- Prior art keywords
- etching solution
- hydroxide
- metal
- tungsten
- gst
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- 238000005530 etching Methods 0.000 title claims description 92
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims description 53
- 239000010937 tungsten Substances 0.000 title claims description 53
- 229910052721 tungsten Inorganic materials 0.000 title claims description 53
- 239000000203 mixture Substances 0.000 claims description 88
- 229910052751 metal Inorganic materials 0.000 claims description 66
- 239000002184 metal Substances 0.000 claims description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000002585 base Substances 0.000 claims description 26
- 238000004377 microelectronic Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- -1 poly(oxyethylene) Polymers 0.000 claims description 21
- 150000002739 metals Chemical class 0.000 claims description 20
- 150000007524 organic acids Chemical class 0.000 claims description 20
- 150000003863 ammonium salts Chemical class 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 15
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 14
- 239000007800 oxidant agent Substances 0.000 claims description 14
- 150000001412 amines Chemical class 0.000 claims description 12
- 238000005260 corrosion Methods 0.000 claims description 11
- 230000007797 corrosion Effects 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 11
- 239000003112 inhibitor Substances 0.000 claims description 11
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 10
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 9
- 150000004692 metal hydroxides Chemical class 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229940074391 gallic acid Drugs 0.000 claims description 7
- 235000004515 gallic acid Nutrition 0.000 claims description 7
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 7
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical group [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 7
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 235000005985 organic acids Nutrition 0.000 claims description 6
- 150000002978 peroxides Chemical class 0.000 claims description 6
- 150000005622 tetraalkylammonium hydroxides Chemical group 0.000 claims description 6
- 239000001393 triammonium citrate Substances 0.000 claims description 6
- 235000011046 triammonium citrate Nutrition 0.000 claims description 6
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 3
- JPIGSMKDJQPHJC-UHFFFAOYSA-N 1-(2-aminoethoxy)ethanol Chemical compound CC(O)OCCN JPIGSMKDJQPHJC-UHFFFAOYSA-N 0.000 claims description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 2
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 claims description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 claims description 2
- YSAANLSYLSUVHB-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]ethanol Chemical compound CN(C)CCOCCO YSAANLSYLSUVHB-UHFFFAOYSA-N 0.000 claims description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- 239000004251 Ammonium lactate Substances 0.000 claims description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 2
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 claims description 2
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical group NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 2
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- 235000019286 ammonium lactate Nutrition 0.000 claims description 2
- 229940059265 ammonium lactate Drugs 0.000 claims description 2
- NHJPVZLSLOHJDM-UHFFFAOYSA-N azane;butanedioic acid Chemical compound [NH4+].[NH4+].[O-]C(=O)CCC([O-])=O NHJPVZLSLOHJDM-UHFFFAOYSA-N 0.000 claims description 2
- RZOBLYBZQXQGFY-HSHFZTNMSA-N azanium;(2r)-2-hydroxypropanoate Chemical compound [NH4+].C[C@@H](O)C([O-])=O RZOBLYBZQXQGFY-HSHFZTNMSA-N 0.000 claims description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- YXVFQADLFFNVDS-UHFFFAOYSA-N diammonium citrate Chemical compound [NH4+].[NH4+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O YXVFQADLFFNVDS-UHFFFAOYSA-N 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 2
- 150000003462 sulfoxides Chemical class 0.000 claims description 2
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 claims description 2
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 claims 2
- QVOFCQBZXGLNAA-UHFFFAOYSA-M tributyl(methyl)azanium;hydroxide Chemical compound [OH-].CCCC[N+](C)(CCCC)CCCC QVOFCQBZXGLNAA-UHFFFAOYSA-M 0.000 claims 2
- OZHIYEINSCNALY-UHFFFAOYSA-N 1-aminobutan-1-ol Chemical compound CCCC(N)O OZHIYEINSCNALY-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 description 48
- 239000000463 material Substances 0.000 description 34
- 239000000758 substrate Substances 0.000 description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 9
- 239000010408 film Substances 0.000 description 9
- 230000001590 oxidative effect Effects 0.000 description 9
- 150000002989 phenols Chemical class 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- 239000004615 ingredient Substances 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 239000012782 phase change material Substances 0.000 description 8
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- 239000002738 chelating agent Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
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- 230000008859 change Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000003989 dielectric material Substances 0.000 description 6
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910001080 W alloy Inorganic materials 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- 229940093915 gynecological organic acid Drugs 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
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- 150000003852 triazoles Chemical group 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- 229940117960 vanillin Drugs 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/32—Alkaline compositions
- C23F1/38—Alkaline compositions for etching refractory metals
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
- C09K13/02—Etching, surface-brightening or pickling compositions containing an alkali metal hydroxide
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/32—Alkaline compositions
- C23F1/40—Alkaline compositions for etching other metallic material
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/011—Manufacture or treatment of multistable switching devices
- H10N70/061—Shaping switching materials
- H10N70/063—Shaping switching materials by etching of pre-deposited switching material layers, e.g. lithography
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/20—Multistable switching devices, e.g. memristors
- H10N70/231—Multistable switching devices, e.g. memristors based on solid-state phase change, e.g. between amorphous and crystalline phases, Ovshinsky effect
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/801—Constructional details of multistable switching devices
- H10N70/881—Switching materials
- H10N70/882—Compounds of sulfur, selenium or tellurium, e.g. chalcogenides
- H10N70/8828—Tellurides, e.g. GeSbTe
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- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- ing And Chemical Polishing (AREA)
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- Cleaning Or Drying Semiconductors (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
- Electrodes Of Semiconductors (AREA)
- Semiconductor Memories (AREA)
Description
本発明のエッチング溶液組成物は、水性ベースであり、したがって水を含む。本発明において、水は様々な形態で作用する、例えば、組成物の1つ又は複数の固形成分を溶解するため、成分のキャリアとして、金属残留物の除去の補助として、組成物の粘度改質剤として、及び希釈液として作用する。好ましくは、洗浄組成物中で用いられる水は脱イオン(DI)水である。
本発明のエッチング溶液組成物は、少なくとも2つのヒドロキシル基を有する少なくとも1つのフェノール誘導体化合物を含む。
本発明のエッチング溶液組成物は、強塩基、例えば、4級アンモニウム化合物(例えば、水酸化テトラアルキルアンモニウム)、有機アミン、アルカリ金属水酸化物、又はそれらの混合物を含む。
本発明のエッチング溶液組成物は、任意選択で、有機酸のアンモニウム塩をさらに含むことができる。アンモニウムとは、式N(RaRbRcRd)+の任意のアミンの塩であって、式中、Ra、Rb、Rc、Rdは全て同一であるか又は異なることができ、独立して、H、CH3、C2H5、及びC3H7を有する塩を意味する。例示の有機酸のアンモニウム塩としては、クエン酸三アンモニウム(TAC)、酢酸アンモニウム、乳酸アンモニウム、クエン酸二アンモニウム、コハク酸二アンモニウム、及びそれらの組み合わせが挙げられる。
本発明のエッチング溶液組成物は、任意選択で、1つ又は複数の水混和性有機溶媒を含む。使用することができる水混和性有機溶媒の例は、エチレングリコール、プロピレングリコール、1,4−ブタンジオール、トリプロピレングリコールメチルエーテル、プロピレングリコールプロピルエーテル、ジエチレングリコールn−ブチルエーテル(例えば、販売名Dowanol DBの下で商業的に入手可能)、ヘキシルオキシプロピルアミン、ポリ(オキシエチレン)ジアミン、ジメチルスルホキシド、テトラヒドロフルフリルアルコール、グリセロール、アルコール、スルホキシド、又はそれらの混合物である。好ましい溶媒は、アルコール、ジオール、又はそれらの混合物である。最も好ましい溶媒は、ジオール、例えば、プロピレングリコールである。
洗浄組成物中で使用することができる別の任意選択の成分は金属キレート剤であり、それは、典型的に、溶液中で金属を保持するため及び金属残留物の溶解を促進させるための組成物の能力を増加させるために機能する。この目的に有用なキレート剤の典型的な例は、以下の有機酸:(エチレンジニトリロ)テトラ酢酸(EDTA)、ブチレンジアミンテトラ酢酸、(1,2−シクロヘキシレンジニトロリロ−)テトラ酢酸(CyDTA)、ジエチレントリアミンペンタ酢酸(DETPA)、エチレンジアミンテトラプロピオン酸、(ヒドロキシエチル)エチレンジアミントリ酢酸(HEDTA)、N,N,N’,N’−エチレンジアミンテトラ(メチレンホスホン酸)(EDTMP)、トリエチレンテトラミンヘキサ酢酸(TTHA)、1,3−ジアミノ−2−ヒドロキシプロパン−N,N,N’,N’−テトラ酢酸(DHPTA)、メチルイミノジ酢酸、プロピレンジアミンテトラ酢酸、ニトリロトリ酢酸(NTA)、クエン酸、酒石酸、グルコン酸、サッカリン酸、グリセリン酸、シュウ酸、フタル酸、マレイン酸、マンデル酸、マロン酸、乳酸、サリチル酸、カテコール、没食子酸、没食子酸プロピル、ピロガロール、8−ヒドロキシキノリン、及びシステイン、並びにそれらの異性体及び塩である。好ましいキレート剤は、アミノカルボン酸、例えば、EDTA、CyDTA、及びアミノホスホン酸、例えば、EDTMPである。
本発明の組成物は、任意選択で、少なくとも1つの腐食防止剤を含む。腐食防止剤は、金属、特に銅、又は非金属であることができる、洗浄されるべき基材の表面と反応して、表面を不動態化させ、洗浄中の過剰なエッチングを防止するために提供される。
本発明の洗浄組成物はまた、以下の添加剤:界面活性剤、化学改質剤、染料、殺生物剤、及び他の添加剤のうち1つ又は複数を含むことができる。1つ又は複数の添加剤を、それらが組成物のpH範囲に不利に影響を与えない範囲で加えることができる。
本発明のエッチング組成物のpHは、意図される最終的な使用に最適化された組成物を製造するために変更することができる。一般的に、pHは塩基性であり、例えば、約8.5超、より好ましくは10.0以上、又は約10〜14以上、又は約10〜約14である。最も好ましくは、エッチング組成物のpHは12以上、又は約12〜14以上、又は約12〜約14である。使用において、エッチング組成物のpHは12超又は約12であることが好ましい。
別の態様において、マイクロ電子デバイスの製造中に、GST金属及びタングステン金属の少なくとも1つを含むマイクロ電子デバイスからGST金属及びタングステン金属の両方をエッチングするための方法であって、方法が、室温において、約1〜約40Å/分の速度で、デバイスからGST金属及びタングステン金属を少なくとも部分的に除去するのに十分な時間、マイクロ電子デバイスを水性エッチング溶液に接触させる工程を含み、水性エッチング溶液が、水と;少なくとも2つのヒドロキシル基を有する少なくとも1つのフェノール誘導体と;(i)一般式NR1R2R3R4OHを有し、式中、R1、R2、R3及びR4が同一であるか又は互いに異なることができ、水素、直鎖状又は分枝状C1〜C6アルキル、及び置換又は非置換C6〜C10アリールからなる群より選択される4級塩基、(ii)一般式NR1R2R3を有し、式中、R1、R2及びR3が同一であるか又は互いに異なることができ、水素、直鎖状又は分枝状C1〜C6アルキル、及び直鎖状又は分枝状C1〜C6アルコールからなる群より選択される有機アミン、並びに(iii)金属水酸化物からなる群より選択される少なくとも1つの強塩基と;任意選択で、有機酸のアンモニウム塩と;任意選択で水混和性溶媒とを含むか、それらから本質的になるか、又はそれらからなり、エッチング溶液のpHが8.5以上又は10以上であり、エッチング溶液が過酸化物酸化剤及び金属イオン含有酸化剤を実質的に含まない、方法が提供される。幾つかの実施形態において、リンス工程及び乾燥工程を含む少なくとも1つの追加の工程が存在する場合がある。
本例の対象である全ての組成物を、1”テフロン(登録商標)コーティング撹拌棒を用いて250mLビーカー内で100gの材料を混合することで調製した。水混和性有機溶媒を含まない組成物のために、ビーカーに加えられた第1材料は脱イオン(DI)水であった。次いで、残りの成分は任意の順番で加えることができる。表中で示された例において、各組成物の残部は水である。
本例で使用される各基材は、シリコンウエハ上のTEOS有機ケイ酸ガラス(OSG)誘電体材料上にタングステン膜を含む。試験したGST膜をシリコンウエハ上に直接適用した。
エッチング試験を、400rmpで設定された1/2”の円形テフロン(登録商標)撹拌棒を用いて250mLビーカー内で100gの洗浄組成物を使用して行った。洗浄組成物を、必要に応じて、ホットプレート上で、以下で示す所望の温度にまで加熱した。およそ1”×1”サイズのウエハ部分を、以下の組の条件下で組成物中に浸漬した。
10分間@25℃
20分間@25℃
10分間@35℃
20分間@35℃
GST及びタングステン金属層の厚さについて、ウエハのクーポンを、Creative Design Engineering,Inc製のResMap(商標)モデル273抵抗率設備を用いて層の抵抗率を測定することで測定した。次いで、クーポンを、10分間以下、所望の温度で組成物中に浸水した。次いで、クーポンを脱イオン水でリンスし、乾燥して、金属層の厚さを測定した。浸水時間の関数としての厚さ変化のグラフを作成し、曲線の傾きからオングストローム/分においてエッチ速度を決定した。
Claims (15)
- タングステン含有金属及びGST金属の両方に適したエッチング溶液であって、
水と;
没食子酸と;
(i)一般式NR1R2R3R4OHを有し、式中、R1、R2、R3及びR4が同一であるか又は互いに異なることができ、直鎖状又は分枝状C1〜C6アルキル、及び置換又は非置換C6〜C10アリールからなる群より選択される4級塩基、(ii)一般式NR1R2R3を有し、式中、R1、R2及びR3が同一であるか又は互いに異なることができ、水素、直鎖状又は分枝状C1〜C6アルキル、及び直鎖状又は分枝状C1〜C6アルコールからなる群より選択される有機アミン、並びに(iii)金属水酸化物からなる群より選択される少なくとも1つの強塩基と;
有機酸のアンモニウム塩と;
任意選択で、水混和性溶媒とを含み、pHが10以上であり、かつ、過酸化物酸化剤及び金属イオン含有酸化剤を実質的に含まない、エッチング溶液。 - 前記少なくとも1つの強塩基が、水酸化テトラアルキルアンモニウムである、請求項1に記載のエッチング溶液。
- 前記水酸化テトラアルキルアンモニウムが、水酸化テトラエチルアンモニウム(TEAH)、水酸化テトラメチルアンモニウム(TMAH)、水酸化テトラプロピルアンモニウム(TPAH)、水酸化テトラブチルアンモニウム(TBAH)、水酸化トリブチルメチルアンモニウム(TBMAH)、水酸化ベンジルトリメチルアンモニウム(BTMAH)、及びそれらの組み合わせからなる群より選択される、請求項2に記載のエッチング溶液。
- 前記少なくとも1つの強塩基が金属水酸化物である、請求項1に記載のエッチング溶液。
- 前記金属水酸化物が、水酸化リチウム、水酸化セシウム、水酸化ナトリウム、及び水酸化カリウムからなる群より選択される少なくとも1つである、請求項4に記載のエッチング溶液。
- 前記少なくとも1つの強塩基が有機アミンである、請求項1に記載のエッチング溶液。
- 前記有機アミンが、アミノエチルエタノールアミン、N−メチルアミノエタノール、アミノエトキシエタノール、ジメチルアミノエトキシエタノール、ジエタノールアミン、N−メチルジエタノールアミン、モノエタノールアミン、トリエタノールアミン、1−アミノ−2−プロパノール、2−アミノ−1−ブタノール、イソブタノールアミン、トリエチレンジアミン、及びそれらの組み合わせからなる群より選択される少なくとも1つである、請求項6に記載のエッチング溶液。
- 前記強塩基が水酸化テトラエチルアンモニウムである、請求項1に記載のエッチング溶液。
- 前記有機酸のアンモニウム塩が、クエン酸三アンモニウム、酢酸アンモニウム、乳酸アンモニウム、クエン酸二アンモニウム、コハク酸二アンモニウム、及びそれらの組み合わせからなる群より選択される、請求項1に記載のエッチング溶液。
- 前記有機酸のアンモニウム塩を含み、前記有機酸のアンモニウム塩がクエン酸三アンモニウムである、請求項1又は8に記載のエッチング溶液。
- 前記水混和性溶媒が存在しており、エチレングリコール、プロピレングリコール、1,4−ブタンジオール、トリプロピレングリコールメチルエーテル、プロピレングリコールプロピルエーテル、ジエチレングリコールn−ブチルエーテル、ヘキシルオキシプロピルアミン、ポリ(オキシエチレン)ジアミン、ジメチルスルホキシド、テトラヒドロフルフリルアルコール、グリセロール、アルコール、スルホキシド、及びそれらの混合物からなる群より選択される、請求項1に記載のエッチング溶液。
- 腐食防止剤をさらに含む、請求項1に記載のエッチング溶液。
- 室温において、約1〜約40Å/分の速度でGST金属及びタングステン金属の両方をエッチングすることができる、請求項1に記載のエッチング溶液。
- 約20〜約99wt%の前記水と;
約0.1〜約15wt%の没食子酸と;
約1〜約60wt%の前記少なくとも1つの強塩基と;
約0〜約20wt%の前記有機酸のアンモニウム塩と;
約0〜約75wt%の前記水混和性溶媒とを含む、請求項1に記載のエッチング溶液。 - GST金属及びタングステン金属の少なくとも1つを含むマイクロ電子デバイスから、前記マイクロ電子デバイスの製造中にGST金属及びタングステン金属の両方をエッチングするための方法であって、
室温において、約1〜約40Å/分の速度で前記マイクロ電子デバイスからGST金属及びタングステン金属を少なくとも部分的に除去するのに十分な時間、前記マイクロ電子デバイスを請求項1〜12及び14のいずれか1項に記載の水性のエッチング溶液と接触させる工程を含む、方法。
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EP3351658B1 (en) | 2022-02-09 |
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