JP6892418B2 - 半導体デバイスの製造中にシリコン−ゲルマニウム/シリコン積層体からシリコン−ゲルマニウム合金に対してシリコンを選択的に除去するためのエッチング液 - Google Patents
半導体デバイスの製造中にシリコン−ゲルマニウム/シリコン積層体からシリコン−ゲルマニウム合金に対してシリコンを選択的に除去するためのエッチング液 Download PDFInfo
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- JP6892418B2 JP6892418B2 JP2018157295A JP2018157295A JP6892418B2 JP 6892418 B2 JP6892418 B2 JP 6892418B2 JP 2018157295 A JP2018157295 A JP 2018157295A JP 2018157295 A JP2018157295 A JP 2018157295A JP 6892418 B2 JP6892418 B2 JP 6892418B2
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- 229910000577 Silicon-germanium Inorganic materials 0.000 title claims description 57
- 238000005530 etching Methods 0.000 title claims description 47
- 239000010703 silicon Substances 0.000 title claims description 46
- 229910052710 silicon Inorganic materials 0.000 title claims description 45
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 title claims description 30
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title description 39
- 239000004065 semiconductor Substances 0.000 title description 15
- 238000004519 manufacturing process Methods 0.000 title description 8
- 229910045601 alloy Inorganic materials 0.000 title description 4
- 239000000956 alloy Substances 0.000 title description 4
- 239000000203 mixture Substances 0.000 claims description 114
- -1 amine compound Chemical class 0.000 claims description 41
- 150000001875 compounds Chemical class 0.000 claims description 35
- 239000000908 ammonium hydroxide Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 31
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 29
- 238000004377 microelectronic Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000004094 surface-active agent Substances 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 17
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- 230000007797 corrosion Effects 0.000 claims description 15
- 238000005260 corrosion Methods 0.000 claims description 15
- 239000003112 inhibitor Substances 0.000 claims description 15
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- KVFVBPYVNUCWJX-UHFFFAOYSA-M ethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(C)C KVFVBPYVNUCWJX-UHFFFAOYSA-M 0.000 claims description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 7
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 claims description 6
- 239000005725 8-Hydroxyquinoline Substances 0.000 claims description 6
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- 229960003540 oxyquinoline Drugs 0.000 claims description 6
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 claims description 6
- HHPDFYDITNAMAM-UHFFFAOYSA-N 2-[cyclohexyl(2-hydroxyethyl)amino]ethanol Chemical compound OCCN(CCO)C1CCCCC1 HHPDFYDITNAMAM-UHFFFAOYSA-N 0.000 claims description 5
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 claims description 5
- 235000010323 ascorbic acid Nutrition 0.000 claims description 5
- 229960005070 ascorbic acid Drugs 0.000 claims description 5
- 239000011668 ascorbic acid Substances 0.000 claims description 5
- GWOLZNVIRIHJHB-UHFFFAOYSA-N 11-mercaptoundecanoic acid Chemical compound OC(=O)CCCCCCCCCCS GWOLZNVIRIHJHB-UHFFFAOYSA-N 0.000 claims description 4
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 4
- HQDAZDGXZONBTK-UHFFFAOYSA-N 1-amino-1-ethoxyethanol Chemical group CCOC(C)(N)O HQDAZDGXZONBTK-UHFFFAOYSA-N 0.000 claims description 3
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 claims description 3
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 claims description 3
- KIZQNNOULOCVDM-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].C[N+](C)(C)CCO KIZQNNOULOCVDM-UHFFFAOYSA-M 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 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 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 3
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 claims description 3
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 3
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 claims description 3
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 3
- FKPSBYZGRQJIMO-UHFFFAOYSA-M benzyl(triethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC1=CC=CC=C1 FKPSBYZGRQJIMO-UHFFFAOYSA-M 0.000 claims description 3
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 3
- 229940043276 diisopropanolamine Drugs 0.000 claims description 3
- 150000003462 sulfoxides Chemical class 0.000 claims description 3
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 claims description 3
- JAJRRCSBKZOLPA-UHFFFAOYSA-M triethyl(methyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(CC)CC JAJRRCSBKZOLPA-UHFFFAOYSA-M 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 2
- 239000000463 material Substances 0.000 description 23
- 239000000758 substrate Substances 0.000 description 15
- 239000002070 nanowire Substances 0.000 description 14
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 12
- 239000003989 dielectric material Substances 0.000 description 11
- 229920002873 Polyethylenimine Polymers 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 239000002131 composite material Substances 0.000 description 9
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000003093 cationic surfactant Substances 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 235000012431 wafers Nutrition 0.000 description 4
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- SVMUEEINWGBIPD-UHFFFAOYSA-N dodecylphosphonic acid Chemical compound CCCCCCCCCCCCP(O)(O)=O SVMUEEINWGBIPD-UHFFFAOYSA-N 0.000 description 3
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
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- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 3
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- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 3
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 2
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 2
- QDCPNGVVOWVKJG-VAWYXSNFSA-N 2-[(e)-dodec-1-enyl]butanedioic acid Chemical compound CCCCCCCCCC\C=C\C(C(O)=O)CC(O)=O QDCPNGVVOWVKJG-VAWYXSNFSA-N 0.000 description 2
- WYMDDFRYORANCC-UHFFFAOYSA-N 2-[[3-[bis(carboxymethyl)amino]-2-hydroxypropyl]-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)CN(CC(O)=O)CC(O)=O WYMDDFRYORANCC-UHFFFAOYSA-N 0.000 description 2
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 2
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- FCKYPQBAHLOOJQ-UHFFFAOYSA-N Cyclohexane-1,2-diaminetetraacetic acid Chemical compound OC(=O)CN(CC(O)=O)C1CCCCC1N(CC(O)=O)CC(O)=O FCKYPQBAHLOOJQ-UHFFFAOYSA-N 0.000 description 2
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- ZTHYODDOHIVTJV-UHFFFAOYSA-N Propyl gallate Chemical compound CCCOC(=O)C1=CC(O)=C(O)C(O)=C1 ZTHYODDOHIVTJV-UHFFFAOYSA-N 0.000 description 2
- 229910000676 Si alloy Inorganic materials 0.000 description 2
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- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 2
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- 229940111121 antirheumatic drug quinolines Drugs 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
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- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
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- 229940093915 gynecological organic acid Drugs 0.000 description 2
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- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
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Images
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- 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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- 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
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- 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
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- 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
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Description
本発明のエッチング組成物は水系であり、したがって水を含む。本発明において、水は様々に機能し、例えば、組成物の1つ又は複数の成分を溶解するため、成分のキャリアとして、残留物の除去の助剤として、組成物の粘度改質剤として、及び希釈液として機能する。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。次の段落で説明する水の範囲は、あらゆる源由来の組成物中の全ての水を含む。
本発明のエッチング組成物は、4級水酸化アンモニウム及びアミン化合物のうちの少なくとも1つであるシリコンエッチング液を含む。幾つかの実施形態において、シリコンエッチング液は、4級水酸化アンモニウム及びアミン化合物の両方を含む。
本発明のエッチング組成物は、水混和性溶媒を含む。用い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(BDG)(例えば、販売名Dowanol DBの下で商業的に入手可能)、ジプロピレングリコールメチルエーテル(DPM)、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(DMSO)、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、スルホラン、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、ポリオール、例えば、プロピレングリコールのようなジオール、及び、グリセロールのようなトリオールである。
本発明のエッチング組成物は、任意選択で少なくとも1つの界面活性剤を含む。界面活性剤は、エッチングからシリコン−ゲルマニウムを保護するために機能する。本明細書で説明する組成物中で使用するための界面活性剤としては、限定されないが、両性塩、カチオン性界面活性剤、アニオン性界面活性剤、両性界面活性剤、非イオン性界面活性剤、及びそれらの組み合わせが挙げられ、例えば、限定されないが、ビス(2−エチルヘキシル)リン酸塩、ペルフルオロヘプタン酸、ペルフルオロデカン酸、トリフルオロメタンスルホン酸、ホスホノ酢酸、ドデセニルコハク酸、ジオクタデシルリン酸水素、オクタデシルリン酸二水素、ドデシルアミン、ドデシルコハク酸モノジエタノールアミド、ラウリン酸、パルミチン酸、オレイン酸、ジュニペル酸、12−ヒドロキシステアリン酸、ドデシルリン酸塩が挙げられる。
本発明のエッチング組成物はまた、1つ又は複数の腐食防止剤を含むことができる。存在する場合、腐食防止剤は、エッチングからシリコン−ゲルマニウムを保護することができる。腐食防止剤の例としては、アミノカルボン酸、例えば、トリエチレンテトラミン六酢酸(TTHA)、1,3−ジアミノ−2−ヒドロキシプロパン−N,N,N’,N’−四酢酸(DHPTA)、メチルイミノ二酢酸、プロピレンジアミン四酢酸、エチレンジアミン四酢酸(EDTA)、ブチレンジアミン四酢酸、(1,2−シクロへキシレンジアミン)四酢酸(CyDTA)、ジエチレントリアミン五酢酸(DETPA)、エチレンジアミン四プロピオン酸、(ヒドロキシエチル)エチレンジアミン三酢酸(HEDTA)、及びニトロ三酢酸(NTA)、アミノホスホン酸、例えば、N,N,N’,N’−エチレンジアミン四(メチレンホスホン)酸(EDTMP);カルボン酸、例えば、デカン酸、クエン酸、酒石酸、グルコン酸、糖酸、グリセリン酸、シュウ酸、アスコルビン酸、フタル酸、安息香酸、メルカプト安息香酸、マレイン酸、マンデル酸、マロン酸、乳酸、及びサリチル酸が挙げられる。他の可能性のある腐食防止剤としては、没食子酸プロピル、ピロガロール、キノリン、例えば、8−ヒドロキシキノリン、ピペラジン、例えば、1−(2−アミノエチル)ピペラジン、システイン、及びN,N,N’,N”,N”−ペンタメチルジエチレントリアミン(Polycat5)が挙げられる。別の腐食防止剤はヘキシルアミンを含むことができる。幾つかの好ましい腐食防止剤は、硫黄含有基を含むことができる。他の好ましい腐食防止剤は、アミノカルボン酸、例えば、EDTA、CyDTA、キノリン、例えば、8−ヒドロキシキノリン、デカン酸、11−メルカプトウンデカン酸、ピペラジン、例えば、1−(2−アミノエチル)ピペラジン、ベンズイミダゾール、例えば、2−メルカプト−5−メチルベンズイミダゾール、並びにカルボン酸、例えば、シュウ酸、デカン酸、及びアスコルビン酸が挙げられる。より好ましい腐食防止剤としては、デカン酸、アスコルビン酸、11−メルカプトウンデカン酸、1−(2−アミノエチル)ピペラジン、及び8−ヒドロキシキノリンが挙げられる。最も好ましくは8−ヒドロキシキノリンである。
別の態様において、水、4級水酸化アンモニウム化合物及びアミン化合物のうち少なくとも1つ、水混和性溶媒、及び任意選択で界面活性剤を含むか、それらから本質的になるか、又はそれらからなる組成物中でマイクロ電子デバイス(複合半導体デバイス)をエッチングすることによって、シリコン及びシリコン−ゲルマニウムを含むマイクロ電子デバイス、例えば複合半導体デバイスにおいて、シリコン−ゲルマニウムに対するシリコンのエッチ速度を選択的に向上させる方法が提供される。方法は、シリコン及びシリコン−ゲルマニウムを含むマイクロ電子デバイス(複合半導体デバイス)上でのシリコン−ゲルマニウムに対するシリコンのエッチ速度を選択的に向上する工程を含み、本方法は、シリコン及びシリコン−ゲルマニウムを含むマイクロ電子デバイス(複合半導体デバイス)を、水、4級水酸化アンモニウム化合物及びアミン化合物のうち少なくとも1つ、水混和性溶媒、及び任意選択で界面活性剤を含む水性組成物に接触させる接触工程と、シリコンが少なくとも部分的に除去された後に複合半導体デバイスをリンスする工程とを含み、シリコン−ゲルマニウムに対するシリコンのエッチ選択性は約50超である。追加の乾燥工程をまた本方法に加えることができる。「少なくとも部分的に除去」とは、本発明の方法で本発明の組成物を使用して、材料を50%以上の除去すること、好ましくは材料を70%以上の除去すること、最も好ましくは材料の80%以上を除去することを意味する。
洗浄組成物を調製するための一般手順
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ビーカー中で成分を混合することで調製した。典型的に、ビーカーに加えた第1の材料は脱イオン(DI)水であり、その後、特定の順序なく他の成分を加えた。
Siウエハ上にヘテロエピタキシーによりSiGe/Si多層体を堆積した。図1の側Aは、例において処理されたマイクロ電子デバイスの概略図である。SiGe/Si多層体堆積は、Si基材10上の厚いSiGe層12で始まった。次いで、Si/SiGe多層体堆積を行った。(Si層は14で表示される。SiGe層は16で表示される。)酸化物層18及び窒化物ハードマスク(HM)層20を多層体の上部に堆積し、平行FIN22にパターン化した。SiGe/SiナノワイヤFINを選択的にエッチングして、SiGeナノワイヤを得た。図1の側Aは、デバイスを本発明の組成物と接触させる前における本例で処理されたマイクロ電子デバイスを示す。図の側Bは、処理後のマイクロ電子デバイスを示す。
400rpmに設定した1/2”円形テフロン(登録商標)コーティング撹拌棒を用いて250mLビーカー中で、100gのエッチング組成物を使用してエッチング試験を行った。エッチング組成物をホットプレート上で約45℃の温度に加熱した。試験クーポンを約20分間撹拌しながら組成物中に浸漬した。
例1:溶媒の効果
表2の組成物で詳細に示されるように、エッチング及び選択性への効果を決定するために様々な溶媒を評価した。
SiGeナノワイヤがアルカリ環境においてエッチングされることから保護することについて、様々な機能の腐食防止剤を評価した。特にSiGe合金中でGe濃度が25mol%に近い又はそれ未満である場合に、SiGeのダメージは従来のSiエッチング液で容易に発生した。評価した組成物を表3〜6にまとめた。
以下の配合物をさらに評価した。
Claims (18)
- 水、
4級水酸化アンモニウム化合物及びアミン化合物のうち少なくとも1つ、
水混和性溶媒、
任意選択で界面活性剤、及び
デカン酸、アスコルビン酸、1−(2−アミノエチル)ピペラジン、臭化(1−ヘキサデシル)トリメチルアンモニウム、8−ヒドロキシキノリン、及び11−メルカプトウンデカン酸、及びそれらの混合物からなる群より選択される腐食防止剤
を含み、マイクロ電子デバイスからシリコン−ゲルマニウムに対してシリコンを選択的に除去するためのエッチング液。 - 前記4級水酸化アンモニウム化合物及び前記アミン化合物が存在している、請求項1に記載のエッチング液。
- 前記4級水酸化アンモニウム化合物が、アルキル基の全てが同一なわけではない水酸化テトラアルキルアンモニウム化合物であり、前記アミン化合物がアルカノールアミンである、請求項2に記載のエッチング液。
- 前記4級水酸化アンモニウム化合物が、水酸化ベンジルトリメチルアンモニウム、水酸化メチルトリエチルアンモニウム、水酸化エチルトリメチルアンモニウム(ETMAH)、水酸化2−ヒドロキシエチルトリメチルアンモニウム、水酸化ベンジルトリエチルアンモニウム、水酸化ヘキサデシルトリメチルアンモニウム、及びそれらの混合物からなる群より選択され、
前記アルカノールアミン化合物が、N−メチルエタノールアミン(NMEA)、モノエタノールアミン(MEA)、ジエタノールアミン、トリエタノールアミン、トリイソプロパノールアミン、2−(2−アミノエチルアミノ)エタノール、2−(2−アミノエトキシ)エタノール(AEE)、トリエタノールアミン、N−エチルエタノールアミン、N,N−ジメチルエタノールアミン、N,N−ジエチルエタノールアミン、N−メチルジエタノールアミン、N−エチルジエタノールアミン、シクロヘキシルアミンジエタノール、ジイソプロパノールアミン、シクロヘキシルアミンジエタノール、及びそれらの混合物からなる群より選択される、請求項3に記載のエッチング液。 - 前記4級水酸化アンモニウム化合物が、水酸化エチルトリメチルアンモニウム(ETMAH)であり、前記アルカノールアミンがアミノ(エトキシ)エタノール(AEE)である、請求項4に記載のエッチング組成物。
- 前記水混和性溶媒が、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、又は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組成物。
- 前記水混和性溶媒がグリセロールである、請求項6に記載のエッチング組成物。
- 前記界面活性剤が存在している、請求項1に記載のエッチング組成物。
- 前記界面活性剤がポリアルキレンイミンである、請求項8に記載のエッチング組成物。
- シリコン及びシリコン−ゲルマニウムを含むマイクロ電子デバイス上でのシリコン−ゲルマニウムに対するシリコンのエッチ速度を選択的に向上させる方法であって、
シリコン及びシリコン−ゲルマニウムを含むマイクロ電子デバイスを、請求項1に記載のエッチング組成物に接触させる接触工程と、
シリコンが少なくとも部分的に除去された後に前記マイクロ電子デバイスをリンスするリンス工程とを含み、前記リンス工程の後に測定される、シリコン−ゲルマニウムに対するシリコンのエッチ選択性が約50超である、方法。 - 前記マイクロ電子デバイスを乾燥する工程をさらに含む、請求項10に記載の方法。
- 前記リンス工程の後に測定される、シリコン−ゲルマニウムに対するシリコンのエッチ選択性が約50〜約200である、請求項10に記載の方法。
- 前記接触工程が約25〜約100℃の温度で行われる、請求項10に記載の方法。
- 前記4級水酸化アンモニウム化合物及び前記アミン化合物が存在している、請求項10に記載の方法。
- 前記4級水酸化アンモニウム化合物が、アルキル基の全てが同一なわけではない水酸化テトラアルキルアンモニウム化合物であり、前記アミン化合物がアルカノールアミンである、請求項14に記載の方法。
- 前記4級水酸化アンモニウム化合物が、水酸化ベンジルトリメチルアンモニウム、水酸化メチルトリエチルアンモニウム、水酸化エチルトリメチルアンモニウム(ETMAH)、水酸化2−ヒドロキシエチルトリメチルアンモニウム、水酸化ベンジルトリエチルアンモニウム、水酸化ヘキサデシルトリメチルアンモニウム、及びそれらの混合物からなる群より選択され、
前記アルカノールアミン化合物が、N−メチルエタノールアミン(NMEA)、モノエタノールアミン(MEA)、ジエタノールアミン、トリエタノールアミン、トリイソプロパノールアミン、2−(2−アミノエチルアミノ)エタノール、2−(2−アミノエトキシ)エタノール(AEE)、トリエタノールアミン、N−エチルエタノールアミン、N,N−ジメチルエタノールアミン、N,N−ジエチルエタノールアミン、N−メチルジエタノールアミン、N−エチルジエタノールアミン、シクロヘキシルアミンジエタノール、ジイソプロパノールアミン、シクロヘキシルアミンジエタノール、及びそれらの混合物からなる群より選択される、請求項15に記載の方法。 - 前記4級水酸化アンモニウム化合物が、水酸化エチルトリメチルアンモニウム(ETMAH)であり、前記アルカノールアミンがアミノ(エトキシ)エタノール(AEE)である、請求項16に記載の方法。
- 前記水混和性溶媒が、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からなる群より選択される、請求項10に記載の方法。
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