JP2019050365A - 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−ゲルマニウム合金を選択的に除去するためのエッチング液 Download PDFInfo
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- JP2019050365A JP2019050365A JP2018157455A JP2018157455A JP2019050365A JP 2019050365 A JP2019050365 A JP 2019050365A JP 2018157455 A JP2018157455 A JP 2018157455A JP 2018157455 A JP2018157455 A JP 2018157455A JP 2019050365 A JP2019050365 A JP 2019050365A
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- 229910000577 Silicon-germanium Inorganic materials 0.000 title claims abstract description 53
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000010703 silicon Substances 0.000 title claims description 29
- 229910052710 silicon Inorganic materials 0.000 title claims description 27
- 229910045601 alloy Inorganic materials 0.000 title abstract description 6
- 239000000956 alloy Substances 0.000 title abstract description 6
- 238000005389 semiconductor device fabrication Methods 0.000 title 1
- 239000000203 mixture Substances 0.000 claims abstract description 147
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 36
- 238000004377 microelectronic Methods 0.000 claims abstract description 26
- 239000007800 oxidant agent Substances 0.000 claims abstract description 26
- 239000004094 surface-active agent Substances 0.000 claims abstract description 25
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 238000005530 etching Methods 0.000 claims description 46
- -1 poly (oxyethylene) Polymers 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 29
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 19
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 229920002873 Polyethylenimine Polymers 0.000 claims description 15
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 15
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- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 claims description 8
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
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- ZUQAPLKKNAQJAU-UHFFFAOYSA-N acetylenediol Chemical compound OC#CO ZUQAPLKKNAQJAU-UHFFFAOYSA-N 0.000 claims description 6
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 6
- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-UHFFFAOYSA-N 0.000 claims description 6
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 5
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- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 150000004673 fluoride salts Chemical class 0.000 claims description 4
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 claims description 4
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 4
- 150000003462 sulfoxides Chemical class 0.000 claims description 4
- 150000003512 tertiary amines Chemical class 0.000 claims description 4
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 claims description 4
- ASVMCHUOIVTKQQ-UHFFFAOYSA-M triethyl(methyl)azanium;fluoride Chemical compound [F-].CC[N+](C)(CC)CC ASVMCHUOIVTKQQ-UHFFFAOYSA-M 0.000 claims description 4
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 3
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 claims description 3
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 claims description 3
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical group OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 3
- 229940043276 diisopropanolamine Drugs 0.000 claims description 3
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 3
- 150000003335 secondary amines Chemical class 0.000 claims description 3
- BZWNJUCOSVQYLV-UHFFFAOYSA-H trifluoroalumane Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[Al+3].[Al+3] BZWNJUCOSVQYLV-UHFFFAOYSA-H 0.000 claims description 3
- IQVLXQGNLCPZCL-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) 2,6-bis[(2-methylpropan-2-yl)oxycarbonylamino]hexanoate Chemical compound CC(C)(C)OC(=O)NCCCCC(NC(=O)OC(C)(C)C)C(=O)ON1C(=O)CCC1=O IQVLXQGNLCPZCL-UHFFFAOYSA-N 0.000 claims description 2
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 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
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-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
- HHPDFYDITNAMAM-UHFFFAOYSA-N 2-[cyclohexyl(2-hydroxyethyl)amino]ethanol Chemical compound OCCN(CCO)C1CCCCC1 HHPDFYDITNAMAM-UHFFFAOYSA-N 0.000 claims description 2
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 claims description 2
- GPICKHDXBPTBLD-UHFFFAOYSA-N 2-methylpropane-1,2,3-tricarboxylic acid Chemical compound OC(=O)CC(C)(CC(O)=O)C(O)=O GPICKHDXBPTBLD-UHFFFAOYSA-N 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
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 2
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 claims description 2
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 2
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 claims description 2
- 229940091181 aconitic acid Drugs 0.000 claims description 2
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 2
- QNSOHXTZPUMONC-UHFFFAOYSA-N benzene pentacarboxylic acid Natural products OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O QNSOHXTZPUMONC-UHFFFAOYSA-N 0.000 claims description 2
- GGAUUQHSCNMCAU-UHFFFAOYSA-N butane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)CC(C(O)=O)C(C(O)=O)CC(O)=O GGAUUQHSCNMCAU-UHFFFAOYSA-N 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 2
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 claims description 2
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 150000003141 primary amines Chemical class 0.000 claims 2
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 150000003868 ammonium compounds Chemical class 0.000 claims 1
- CVXBEEMKQHEXEN-UHFFFAOYSA-N carbaryl Chemical compound C1=CC=C2C(OC(=O)NC)=CC=CC2=C1 CVXBEEMKQHEXEN-UHFFFAOYSA-N 0.000 claims 1
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- 239000012972 dimethylethanolamine Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 4
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- 229920005591 polysilicon Polymers 0.000 abstract description 3
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- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- UELAIMNOXLAYRW-UHFFFAOYSA-M sodium;1,4-dicyclohexyloxy-1,4-dioxobutane-2-sulfonate Chemical compound [Na+].C1CCCCC1OC(=O)C(S(=O)(=O)[O-])CC(=O)OC1CCCCC1 UELAIMNOXLAYRW-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- FBWNMEQMRUMQSO-UHFFFAOYSA-N tergitol NP-9 Polymers CCCCCCCCCC1=CC=C(OCCOCCOCCOCCOCCOCCOCCOCCOCCO)C=C1 FBWNMEQMRUMQSO-UHFFFAOYSA-N 0.000 description 1
- YNJQKNVVBBIPBA-UHFFFAOYSA-M tetrabutylazanium;trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CCCC[N+](CCCC)(CCCC)CCCC YNJQKNVVBBIPBA-UHFFFAOYSA-M 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- BVQJQTMSTANITJ-UHFFFAOYSA-N tetradecylphosphonic acid Chemical compound CCCCCCCCCCCCCCP(O)(O)=O BVQJQTMSTANITJ-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- YQIVQBMEBZGFBY-UHFFFAOYSA-M tetraheptylazanium;bromide Chemical compound [Br-].CCCCCCC[N+](CCCCCCC)(CCCCCCC)CCCCCCC YQIVQBMEBZGFBY-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- AHNISXOXSNAHBZ-UHFFFAOYSA-M tetrakis-decylazanium;bromide Chemical compound [Br-].CCCCCCCCCC[N+](CCCCCCCCCC)(CCCCCCCCCC)CCCCCCCCCC AHNISXOXSNAHBZ-UHFFFAOYSA-M 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 150000003627 tricarboxylic acid derivatives Chemical class 0.000 description 1
- JAJRRCSBKZOLPA-UHFFFAOYSA-M triethyl(methyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(CC)CC JAJRRCSBKZOLPA-UHFFFAOYSA-M 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- 150000008648 triflates Chemical class 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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Abstract
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。以下で説明する水の範囲は、任意の源由来の組成物中の水の全てを含む。多くの用途において、組成物中の水の重量パーセントは、以下の数字群:0.5、1、5、10、15、20、25、30、40、45、50、55、60、65、70、75、80、85及び90から選択される始点及び終点を有する範囲であると考えられる。組成物中で使用することができる水の範囲の例としては、例えば、約0.5〜約90wt%、又は1〜約85wt%、又は約5.0〜約80wt%、又は約10〜約70wt%、又は約40〜約80wt%の水が挙げられる。本発明のまた別の好ましい実施形態では、他の成分の所望の重量パーセントを達成するための量で水を含むことができる。
本発明のエッチング組成物は、「オキシダイザー」とも称される酸化剤を含む。酸化剤は、関連する酸化物(すなわちゲルマニウム又はシリコンの酸化物)を形成することで、シリコン−ゲルマニウム合金をエッチングするために主に機能する。酸化剤は、任意の適切な酸化剤であることができる。適切な酸化剤としては、限定されないが、1つ又は複数のペルオキシ化合物、すなわち、少なくとも1つのペルオキシ基(−O−O−)を含む化合物が挙げられる。適切なプレオキシ化合物としては、例えば、過酸化物、過硫化物(例えば、モノ過硫化物及びジ過硫化物)、過炭酸塩、それらの酸、それらの塩、及びそれらの混合物が挙げられる。他の適切な酸化剤としては、例えば、酸化ハライド(例えば、ヨウ化物、過ヨウ化物、それらの酸、及びそれらの混合物など)、過ホウ酸、過ホウ酸塩、ペルオキシ酸(例えば、過酢酸、過安息香酸、それらの塩、それらの混合物など)、過マンガン酸塩、セリウム化合物、フェリシアン化物(例えば、フェリシアン化カリウム)、それらの混合物などが挙げられる。
本発明のエッチング組成物はまた、1つ又は複数のフッ化物イオン源を含む。フッ化物イオンは、酸化剤の作用の下で形成されたシリコン又はゲルマニウムの酸化物の除去を補助するために主に機能する。本発明に係るフッ化物イオン源を提供する典型的な化合物は、フッ化水素酸、フッ化アンモニウム、4級フッ化アンモニウム、フルオロホウ酸塩、フルオロホウ酸、テトラフルオロホウ酸テトラブチルアンモニウム、六フッ化アルミニウム、並びに、以下の式:R1NR2R3R4Fであって、式中、R1、R2、R3及びR4が独立して、H又は(C1〜C4)アルキル基を示す式を有する脂肪族1級、2級又は3級アミンのフッ化物塩である。典型的に、R1、R2、R3及びR4基中の炭素原子の総数は12個以下の炭素原子である。脂肪族1級、2級又は3級アミンのフッ化物塩の例としては、フッ化テトラメチルアンモニウム、フッ化テトラエチルアンモニウム、フッ化メチルトリエチルアンモニウム、及びフッ化テトラブチルアンモニウムが挙げられる。
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、ブチルジグリコール、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、スルホラン、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ことができる。幾つかの実施形態において、好ましい溶媒は、スルホラン又はスルホキシド、例えばジメチルスルホキシドであることができる。幾つかの実施形態において、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。他の実施形態において、好ましい溶媒はグリコールエーテルである。
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。
エッチング組成物は、任意選択で緩衝組成物を含む。典型的に、緩衝組成物は、以下で詳細に述べるように、アミン化合物及び多官能性有機酸を含むか、それらから本質的になるか、又はそれらからなる。
幾つかの実施形態において、本発明のエッチング組成物の任意選択の緩衝組成物は、2級又は3級有機アミンを含む。2級又は3級有機アミンは、緩衝剤の共役塩基成分を提供するために主に機能する。
幾つかの実施形態において、本発明のエッチング組成物の任意選択の緩衝組成物は、1つ又は複数の多官能性有機酸を含み、それは、緩衝剤の共役酸部として主に機能する。本明細書で使用される場合、「多官能性有機酸」という用語は、2つ以上のカルボキシレート基を有する酸又は多酸を言い表し、例えば、限定されないが、(i)ジカルボン酸(例えば、マロン酸、リンゴ酸など);芳香族部を含むジカルボン酸(例えば、フタル酸など)及びそれらの組み合わせ、並びに(ii)トリカルボン酸(例えば、クエン酸塩など)、芳香族部を含むトリカルボン酸(例えば、トリメット酸など)、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組成物はまた、以下の添加剤:キレート剤、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は、それらが組成物の性能に悪影響を与えない範囲で加えることができる。
別の態様において、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(複合半導体)デバイス上でのシリコンに対するシリコン−ゲルマニウムのエッチング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(複合半導体)デバイスを、水、酸化剤、水混和性有機溶媒、フッ化物イオン源、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−ゲルマニウムが少なくとも部分的に除去された後にマイクロ電子(複合半導体)デバイスをリンスする工程とを含み、シリコンに対するシリコン−ゲルマニウムのエッチ選択性が、約5超又は10超又は15超又は20超又は25超又は30超又は65超又は80超である方法が提供される。幾つかの実施形態において、シリコンに対するシリコン−ゲルマニウムのエッチ選択性は、例えば、複数(2つ以上)の交互のSiGe層及びSi層を有する図1に示されるような水平積層体から得られる。追加の乾燥工程をまた、方法に含めることができる。「少なくとも部分的に除去」とは、材料の少なくとも50%の除去、好ましくは材料の少なくとも80%の除去を意味する。最も好ましくは、本発明の組成物を使用して、シリコン−ゲルマニウムの100%除去が達成される。
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、ビーカーに加えられた第1の材料は脱イオン(DI)水であり、その後、特定の順番なくその他の成分を加えた。典型的に、酸化剤(例えば、過酸化水素)を使用する直前に加えた。
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を示す。SiGe/Si多層体堆積は、Si基材10上の厚いSiGe層12で開始した。次いで、Si/SiGe多層体堆積を行った。(Si層は表示14で示され、SiGe層は表示16で示される。)酸化物層18及び窒化物ハードマスク(HM)層20を、Si/Ge(及び酸化物)多層体の上部に堆積し、平行なフィン22にパターン化した。SiGe/Siナノワイヤのフィンを、選択的にエッチングして、Siナノワイヤを得た。図の側Aはエッチング前のマイクロ電子デバイスを示し、図の側Bはエッチング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
この例は、2.0wt%の過酸化水素がSiGeのエッチ速度に影響を及ぼすことを示している。
この例は、過酸化水素の存在下において、フッ化物源を加えることがSiGeのエッチ速度に影響を及ぼすことを示している。
特定の溶媒の選択性への影響を決定するために以下の組成物を調製した。ブチルジグリコール(BDG)は溶媒として役割を示し、SiGeエッチ速度を向上させることができた。
以下の例は、シリコンエッチングを抑制するための腐食防止剤を評価した。PEI Lupasol(登録商標)800は、所望の選択性の改善に貢献した。
以下の例は、シリコンエッチングを抑制するための腐食防止剤を評価した。非イオン性界面活性剤Surfynol(登録商標)485は、ポリSiエッチ速度の抑制を補助した。
Claims (25)
- 水、
酸化剤、
水混和性有機溶媒、
フッ化物イオン源、及び
任意選択で、界面活性剤
を含み、マイクロ電子デバイスから、シリコンに対してシリコン−ゲルマニウムを選択的に除去するのに適したエッチング液。 - 前記酸化剤が過酸化水素である、請求項1に記載のエッチング液。
- 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、ブチルジグリコール、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、ジプロピレングリコールモノメチルエーテル、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、スルホラン、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ブチルジグリコールである、請求項3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又はアセチレンジオール又は変性アセチレンジオール又はそれらの混合物を含む、請求項5に記載のエッチング組成物。
- 前記ポリアルキレンイミンがポリエチレンイミンである、請求項6に記載のエッチング組成物。
- 前記フッ化物イオン源が、フッ化水素酸、フッ化アンモニウム、重フッ化アンモニウム、4級フッ化アンモニウム、フルオロホウ酸塩、フルオロホウ酸、テトラフルオロホウ酸テトラブチルアンモニウム、六フッ化アルミニウム、及び、式:R1NR2R3R4Fであって、式中、R1、R2、R3及びR4が独立して、H又は(C1〜C4)アルキル基を示す式を有する脂肪族1級、2級又は3級アミンのフッ化物塩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。
- 前記フッ化物イオン源が、フッ化アンモニウム、重フッ化アンモニウム、フッ化テトラメチルアンモニウム、フッ化テトラエチルアンモニウム、フッ化メチルトリエチルアンモニウム、及びフッ化テトラブチルアンモニウムからなる群より選択される、請求項8に記載のエッチング組成物。
- 前記フッ化物イオン源が、フッ化アンモニウム又は重フッ化アンモニウムを含む、請求項8に記載のエッチング組成物。
- 緩衝組成物をさらに含む、請求項1に記載のエッチング組成物。
- 前記緩衝組成物が、アミン化合物及び多官能性有機酸を含む、請求項11に記載のエッチング組成物。
- 前記アミン化合物がアルカノールアミンを含み、前記多官能性有機酸が、少なくとも3つのカルボン酸基を有する多塩基酸を含む、請求項12に記載のエッチング組成物。
- 前記アルカノールアミンが、ジエタノールアミン、ジイソプロパノールアミン、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、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、及びそれらの混合物からなる群より選択される、請求項13に記載のエッチング組成物。
- 前記多塩基酸が、クエン酸、2−メチルプロパン−1,2,3−トリカルボン酸、ベンゼン−1,2,3−トリカルボン酸(ヘミメリト酸)、プロパン−1,2,3−トリカルボン酸(トリカルバリル酸)、1,シス−2,3−プロペントリカルボン酸(アコニット酸)、ブタン−1,2,3,4−テトラカルボン酸、シクロペンタンテトラ−1,2,3,4−カルボン酸、ベンゼン−1,2,4,5−テトラカルボン酸(ピロメリット酸)、ベンゼンペンタカルボン酸、ベンゼンヘキサカルボン酸(メリト酸)、及びそれらの混合物からなる群より選択される、請求項13に記載のエッチング組成物。
- 前記緩衝組成物が、アンモニウム化合物及び多官能性有機酸を含む、請求項11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に対するシリコン−ゲルマニウム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、水、酸化剤、水混和性有機溶媒、フッ化物イオン源、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−ゲルマニウム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工程とを含み、シリコンに対するシリコン−ゲルマニウムのエッチ選択性が約10超である、方法。 - 前記半導体デバイスを乾燥する工程をさらに含む、請求項17に記載の方法。
- シリコンに対するシリコン−ゲルマニウムのエッチ選択性が10超である、請求項17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17に記載の方法。
- 前記水混和性溶媒がブチルジグリコールである、請求項17に記載の方法。
- 前記界面活性剤が存在している、請求項17に記載の方法。
- 前記界面活性剤がポリアルキレンイミンを含む、請求項17に記載の方法。
- 前記フッ化物イオン源が、フッ化水素酸、フッ化アンモニウム、4級フッ化アンモニウム、フルオロホウ酸塩、フルオロホウ酸、テトラフルオロホウ酸テトラブチルアンモニウム、六フッ化アルミニウム、及び、式:R1NR2R3R4Fであって、式中、R1、R2、R3及びR4が独立して、H又は(C1〜C4)アルキル基を示す式を有する脂肪族1級、2級又は3級アミンのフッ化物塩からなる群より選択される、請求項17に記載の方法。
- 前記フッ化物イオン源が、フッ化アンモニウム、重フッ化アンモニウム、フッ化テトラメチルアンモニウム、フッ化テトラエチルアンモニウム、フッ化メチルトリエチルアンモニウム、及びフッ化テトラブチルアンモニウムからなる群より選択される、請求項24に記載の方法。
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CN113161234A (zh) * | 2021-04-27 | 2021-07-23 | 上海新阳半导体材料股份有限公司 | 一种含氟清洗液组合物的应用 |
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EP3447791A1 (en) | 2019-02-27 |
US20190088492A1 (en) | 2019-03-21 |
JP6855420B2 (ja) | 2021-04-07 |
CN109423291B (zh) | 2022-09-30 |
US10879076B2 (en) | 2020-12-29 |
CN109423291A (zh) | 2019-03-05 |
EP3447791B1 (en) | 2023-07-26 |
TW201920767A (zh) | 2019-06-01 |
IL261351A (en) | 2019-02-28 |
IL261351B (en) | 2022-10-01 |
KR102327914B1 (ko) | 2021-11-18 |
SG10201807212VA (en) | 2019-03-28 |
TWI683038B (zh) | 2020-01-21 |
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IL261351B2 (en) | 2023-02-01 |
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