CN108028174A - 锗表面的钝化 - Google Patents
锗表面的钝化 Download PDFInfo
- Publication number
- CN108028174A CN108028174A CN201680055157.1A CN201680055157A CN108028174A CN 108028174 A CN108028174 A CN 108028174A CN 201680055157 A CN201680055157 A CN 201680055157A CN 108028174 A CN108028174 A CN 108028174A
- Authority
- CN
- China
- Prior art keywords
- acid
- ester
- sulfenyl
- dipropionic
- ether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 55
- 238000002161 passivation Methods 0.000 title claims description 54
- 239000000203 mixture Substances 0.000 claims abstract description 70
- 239000000463 material Substances 0.000 claims abstract description 59
- 238000004377 microelectronic Methods 0.000 claims abstract description 44
- 239000002253 acid Substances 0.000 claims description 39
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 28
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 24
- 150000002148 esters Chemical class 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- -1 1- octyl groups Chemical group 0.000 claims description 20
- 229910001868 water Inorganic materials 0.000 claims description 20
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 18
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 13
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 13
- 150000003568 thioethers Chemical class 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 11
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 11
- VMKYTRPNOVFCGZ-UHFFFAOYSA-N 2-sulfanylphenol Chemical compound OC1=CC=CC=C1S VMKYTRPNOVFCGZ-UHFFFAOYSA-N 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 10
- HRKQOINLCJTGBK-UHFFFAOYSA-N dihydroxidosulfur Chemical compound OSO HRKQOINLCJTGBK-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 150000002334 glycols Chemical class 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 150000001735 carboxylic acids Chemical class 0.000 claims description 8
- 150000002019 disulfides Chemical class 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N n-propyl alcohol Natural products CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- ODJQKYXPKWQWNK-UHFFFAOYSA-N 3,3'-Thiobispropanoic acid Chemical compound OC(=O)CCSCCC(O)=O ODJQKYXPKWQWNK-UHFFFAOYSA-N 0.000 claims description 7
- 150000004662 dithiols Chemical class 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000005864 Sulphur Substances 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 6
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003989 dielectric material Substances 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 150000007513 acids Chemical class 0.000 claims description 5
- 239000006184 cosolvent Substances 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 4
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 claims description 4
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- GVPWHKZIJBODOX-UHFFFAOYSA-N dibenzyl disulfide Chemical compound C=1C=CC=CC=1CSSCC1=CC=CC=C1 GVPWHKZIJBODOX-UHFFFAOYSA-N 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims description 4
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 claims description 4
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 claims description 3
- 229910000577 Silicon-germanium Inorganic materials 0.000 claims description 3
- 125000002228 disulfide group Chemical group 0.000 claims description 3
- 238000011010 flushing procedure Methods 0.000 claims description 3
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- 239000012212 insulator Substances 0.000 claims description 3
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 3
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 claims description 2
- 150000000178 1,2,4-triazoles Chemical class 0.000 claims description 2
- 150000004869 1,3,4-thiadiazoles Chemical class 0.000 claims description 2
- 229940058015 1,3-butylene glycol Drugs 0.000 claims description 2
- MCMFEZDRQOJKMN-UHFFFAOYSA-N 1-butylimidazole Chemical class CCCCN1C=CN=C1 MCMFEZDRQOJKMN-UHFFFAOYSA-N 0.000 claims description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical class CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 2
- TZOVOULUMXXLOJ-UHFFFAOYSA-N 1-methyl-4-[(4-methylphenyl)disulfanyl]benzene Chemical compound C1=CC(C)=CC=C1SSC1=CC=C(C)C=C1 TZOVOULUMXXLOJ-UHFFFAOYSA-N 0.000 claims description 2
- KLMZKZJCMDOKFE-UHFFFAOYSA-N 1-octylimidazole Chemical class CCCCCCCCN1C=CN=C1 KLMZKZJCMDOKFE-UHFFFAOYSA-N 0.000 claims description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 2
- WMDZKDKPYCNCDZ-UHFFFAOYSA-N 2-(2-butoxypropoxy)propan-1-ol Chemical compound CCCCOC(C)COC(C)CO WMDZKDKPYCNCDZ-UHFFFAOYSA-N 0.000 claims description 2
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 2
- XYVAYAJYLWYJJN-UHFFFAOYSA-N 2-(2-propoxypropoxy)propan-1-ol Chemical compound CCCOC(C)COC(C)CO XYVAYAJYLWYJJN-UHFFFAOYSA-N 0.000 claims description 2
- RFCQDOVPMUSZMN-UHFFFAOYSA-N 2-Naphthalenethiol Chemical class C1=CC=CC2=CC(S)=CC=C21 RFCQDOVPMUSZMN-UHFFFAOYSA-N 0.000 claims description 2
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 claims description 2
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-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
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- JKRDADVRIYVCCY-UHFFFAOYSA-N 2-hydroxyoctanoic acid Chemical class CCCCCCC(O)C(O)=O JKRDADVRIYVCCY-UHFFFAOYSA-N 0.000 claims description 2
- BHJWUUSAMQADIT-UHFFFAOYSA-N 2-methylbenzenecarbothioic s-acid Chemical compound CC1=CC=CC=C1C(O)=S BHJWUUSAMQADIT-UHFFFAOYSA-N 0.000 claims description 2
- CMNQZZPAVNBESS-UHFFFAOYSA-N 6-sulfanylhexanoic acid Chemical class OC(=O)CCCCCS CMNQZZPAVNBESS-UHFFFAOYSA-N 0.000 claims description 2
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 claims description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 2
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 claims description 2
- VPIAKHNXCOTPAY-UHFFFAOYSA-N Heptane-1-thiol Chemical class CCCCCCCS VPIAKHNXCOTPAY-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical class CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 2
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 claims description 2
- 229910006990 Si1-xGex Inorganic materials 0.000 claims description 2
- 229910007020 Si1−xGex Inorganic materials 0.000 claims description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims description 2
- AKPLSMYRLYRCQN-UHFFFAOYSA-N [(benzhydryldisulfanyl)-phenylmethyl]benzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)SSC(C=1C=CC=CC=1)C1=CC=CC=C1 AKPLSMYRLYRCQN-UHFFFAOYSA-N 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims description 2
- HAXFWIACAGNFHA-UHFFFAOYSA-N aldrithiol Chemical class C=1C=CC=NC=1SSC1=CC=CC=N1 HAXFWIACAGNFHA-UHFFFAOYSA-N 0.000 claims description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 2
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical class CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 claims description 2
- HPVVIIKTKWMIGP-UHFFFAOYSA-N butyl 3-(3-butoxy-3-oxopropyl)sulfanylpropanoate Chemical compound CCCCOC(=O)CCSCCC(=O)OCCCC HPVVIIKTKWMIGP-UHFFFAOYSA-N 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 2
- VTXVGVNLYGSIAR-UHFFFAOYSA-N decane-1-thiol Chemical class CCCCCCCCCCS VTXVGVNLYGSIAR-UHFFFAOYSA-N 0.000 claims description 2
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 claims description 2
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 claims description 2
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical class CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002220 fluorenes Chemical class 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- FHKSXSQHXQEMOK-UHFFFAOYSA-N hexane-1,2-diol Chemical class CCCCC(O)CO FHKSXSQHXQEMOK-UHFFFAOYSA-N 0.000 claims description 2
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229960002510 mandelic acid Drugs 0.000 claims description 2
- PMRYVIKBURPHAH-UHFFFAOYSA-N methimazole Chemical compound CN1C=CNC1=S PMRYVIKBURPHAH-UHFFFAOYSA-N 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 2
- FAQJJMHZNSSFSM-UHFFFAOYSA-N phenylglyoxylic acid Chemical class OC(=O)C(=O)C1=CC=CC=C1 FAQJJMHZNSSFSM-UHFFFAOYSA-N 0.000 claims description 2
- YWOQNRUBCZGGTI-UHFFFAOYSA-N phenylsulfanylmethanamine Chemical compound NCSC1=CC=CC=C1 YWOQNRUBCZGGTI-UHFFFAOYSA-N 0.000 claims description 2
- 235000013772 propylene glycol Nutrition 0.000 claims description 2
- 229940107700 pyruvic acid Drugs 0.000 claims description 2
- 229960003080 taurine Drugs 0.000 claims description 2
- 229960002178 thiamazole Drugs 0.000 claims description 2
- 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 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- HCZMHWVFVZAHCR-UHFFFAOYSA-N 2-[2-(2-sulfanylethoxy)ethoxy]ethanethiol Chemical class SCCOCCOCCS HCZMHWVFVZAHCR-UHFFFAOYSA-N 0.000 claims 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims 2
- CKFGINPQOCXMAZ-UHFFFAOYSA-N methanediol Chemical compound OCO CKFGINPQOCXMAZ-UHFFFAOYSA-N 0.000 claims 2
- JMTFLSQHQSFNTE-UHFFFAOYSA-N 1-dodecylimidazole Chemical class CCCCCCCCCCCCN1C=CN=C1 JMTFLSQHQSFNTE-UHFFFAOYSA-N 0.000 claims 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 claims 1
- GPPUPQFYDYLTIY-UHFFFAOYSA-N 2-oxooctanoic acid Chemical class CCCCCCC(=O)C(O)=O GPPUPQFYDYLTIY-UHFFFAOYSA-N 0.000 claims 1
- VGUWZCUCNQXGBU-UHFFFAOYSA-N 3-[(4-methylpiperazin-1-yl)methyl]-5-nitro-1h-indole Chemical compound C1CN(C)CCN1CC1=CNC2=CC=C([N+]([O-])=O)C=C12 VGUWZCUCNQXGBU-UHFFFAOYSA-N 0.000 claims 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- SJSWRKNSCWKNIR-UHFFFAOYSA-N azane;dihydrochloride Chemical compound N.Cl.Cl SJSWRKNSCWKNIR-UHFFFAOYSA-N 0.000 claims 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical class OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims 1
- 235000019256 formaldehyde Nutrition 0.000 claims 1
- 150000004702 methyl esters Chemical class 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims 1
- 229960002446 octanoic acid Drugs 0.000 claims 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims 1
- LZOZLBFZGFLFBV-UHFFFAOYSA-N sulfene Chemical class C=S(=O)=O LZOZLBFZGFLFBV-UHFFFAOYSA-N 0.000 claims 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 11
- 239000010703 silicon Substances 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 9
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- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
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- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- 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 1
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 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
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- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910021341 titanium silicide Inorganic materials 0.000 description 1
- 238000003949 trap density measurement Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- WQJQOUPTWCFRMM-UHFFFAOYSA-N tungsten disilicide Chemical compound [Si]#[W]#[Si] WQJQOUPTWCFRMM-UHFFFAOYSA-N 0.000 description 1
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- 229910001928 zirconium oxide 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
Classifications
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- 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
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/28008—Making conductor-insulator-semiconductor electrodes
- H01L21/28255—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor belonging to Group IV and not being elemental silicon, e.g. Ge, SiGe, SiGeC
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02367—Substrates
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- H01L21/02381—Silicon, silicon germanium, germanium
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- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
- H01L21/02178—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing aluminium, e.g. Al2O3
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
- H01L21/0228—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
- H01L21/02299—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment
- H01L21/02304—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment formation of intermediate layers, e.g. buffer layers, layers to improve adhesion, lattice match or diffusion barriers
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
- H01L21/02299—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment
- H01L21/02307—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment treatment by exposure to a liquid
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- H—ELECTRICITY
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- H01L21/02532—Silicon, silicon germanium, germanium
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- 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
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/28008—Making conductor-insulator-semiconductor electrodes
- H01L21/28017—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon
- H01L21/28247—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon passivation or protection of the electrode, e.g. using re-oxidation
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/76—Making of isolation regions between components
- H01L21/762—Dielectric regions, e.g. EPIC dielectric isolation, LOCOS; Trench refilling techniques, SOI technology, use of channel stoppers
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Abstract
本发明涉及可用于在具有含锗材料的微电子装置上钝化所述含锗材料的组合物。
Description
技术领域
本发明涉及一种用于使微电子装置表面上的含锗材料钝化的组合物及过程。
背景技术
在过去的几十年里,集成电路中的特征的扩展已使半导体芯片上的功能单元的密度增加。举例来说,缩减晶体管大小允许将更多的存储器装置并入于芯片上,从而使得制造容量增加的产品。
对于集成电路装置,在金属氧化物半导体场效应晶体管(MOSFET)的制造中,除了硅之外的半导电结晶材料可为有利的。一种此材料的实例是Ge,其相对于硅提供若干潜在有利的特征,例如(但不限于)高载流子(电洞)迁移率、带隙偏移、不同晶格常数及与硅成合金以形成半导体二元合金SiGe的能力。
在现代晶体管设计中使用Ge的一个问题是目前针对这些年来积极缩放的硅FET所实现的极细特征(例如,22nm及以下)现在于Ge中难以实现,当以较不积极缩放的形式实施时通常使潜在基于材料的性能增益重新开始。举例来说,MOSFET的性能强烈地受通道栅极电介质界面处的电活性缺陷影响。在具有硅通道的装置中,可通过在通道表面上谨慎形成薄氧化物来实现低界面陷阱密度(Dit)。对于具有锗通道的装置,不可通过此氧化过程轻易地实现低Dit。
本发明的目的是提供用于使微电子装置上的含锗表面钝化的组合物。不受理论的束缚,认为在含锗表面上形成表面层(即钝化)将抑制含锗表面处的氧化及提供低界面陷阱密度。
发明内容
本发明涉及一种用于使包括含锗表面的微电子装置上的含锗表面钝化的组合物及过程。
一方面,描述一种使微电子装置表面上的含锗材料钝化的方法,所述方法包括使包括所述含锗材料的所述微电子装置接触包括水及从由以下各物组成的群组选出的至少一种表面活性化合物的钝化组合物:α-羟基酸、胺类、唑类、羧酸类、二醇类、二硫化物类、二硫醇类、硒化物类、亚硫酸盐、硫醚、硫醇类、硫醇、硫甘醇、邻羟基苯硫酚及其组合。
从随后揭示内容及所附技术方案将更全面地了解本发明的其它方面、特征及实施例。
具体实施方式
一般来说,本发明涉及使微电子装置表面上的含锗材料钝化的组合物。
为了参考起见,“微电子装置”对应于半导体衬底、平板显示器、相变存储器装置、太阳能面板及包含太阳能电池装置、光生伏打及微机电系统(MEMS)的其它产品,经制造用于微电子设备、集成电路、能量收集或计算机芯片应用中。应理解,术语“微电子装置”、“微电子衬底”及“微电子装置结构”并不意味着以任何方式具限制性,而是包含将最终变成微电子装置或微电子组合件的任何衬底或结构。微电子装置可经图案化、毯覆、为控制装置及/或测试装置。
“硅”可经定义包含Si、多晶Si及单晶Si。硅包括于绝缘体上硅(SOI)晶片中,所述SOI晶片可用作(例如)电子装置(例如FET)及集成电路的衬底或衬底的部分。其它类型的晶片也可包括硅。
如本文使用,“含硅材料”对应于硅、p掺杂硅、n掺杂硅、氧化硅(包含栅极氧化物(例如,以热方式或化学方式生长的SiO2)及TEOS)、氮化硅、热氧化硅、SiOH、SiCOH、硅化钛、硅化钨、硅化镍、硅化钴及低k电介质材料。如本文定义,“低k电介质材料”对应于用作分层微电子装置中的电介质材料的任何材料,其中所述材料具有小于约3.5的介电常数。优选地,低k电介质材料包含低极性材料,例如含硅有机聚合物、含硅混合有机/无机材料、有机硅酸盐玻璃(OSG)、TEOS、掺杂氟的硅玻璃(FSG)、二氧化硅及掺杂碳的氧化物(CDO)玻璃。应了解,低k电介质材料可具有不同的密度及不同的孔隙度。
如本文描述,“氧化硅”或“SiO2”材料对应于从氧化硅前体源沉积的材料,例如,TEOS、以热方式沉积的氧化硅或使用商业可用的前体(例如SiLKTM、AURORATM、CORALTM或BLACK DIAMONDTM)沉积的掺杂碳的氧化物(CDO)。出于本说明的目的,“氧化硅”意味着广泛地包含SiO2、CDO、硅氧烷及热氧化物。氧化硅或SiO2材料对应于纯氧化硅(SiO2),也对应于结构中包含杂质的不纯的氧化硅。
如本文定义,“含锗材料”可为块状锗晶片、n掺杂锗、p掺杂锗、绝缘体上锗(GOI)晶片,在此情况层是形成于衬底顶部上的电介质层上的锗层及衬底上的锗层。含锗材料可为至少部分延伸于衬底之上的连续层或可被划分成分离区域。应了解,出于本申请案的目的,含锗材料还可包含具有通式Si1-xGex的硅锗(SiGe)合金,其中Ge的含量大于约70wt%,更优选地大于80wt%,且最优选地大于90wt%。
如本文使用,“约”打算对应于所述值的±5%。
如本文定义,“高k电介质”材料对应于铪氧化物(例如,HfO2);锆氧化物(例如,ZrO2);氧硅酸铪;硅酸铪;硅酸锆;硅酸钛;铝氧化物;其掺杂镧类似物(例如,LaAlO3);硅酸铝;钛酸盐(例如,Ta2O5);铪及硅的氧化物及氮化物(例如,HfSiON);其掺杂镧类似物(例如,HFSiON(La));钛酸钡锶(BST);铪及铝的氧化物(例如,HfxAlyOz);钛酸锶(SrTiO3);钛酸钡(BaTiO3)及其组合。
如本文使用,微电子装置表面上的含锗材料的“钝化”对应于在含锗表面上形成至少一个表面层。
在第一方面中,描述一种用于使微电子装置表面上的含锗材料钝化的钝化组合物及使用钝化组合物的方法,所述钝化组合物包括水及从由以下各物组成的群组选出的至少一种表面活性化合物、由水及从由以下各物组成的群组选出的至少一种表面活性化合物组成或基本上由水及从由以下各物组成的群组选出的至少一种表面活性化合物组成:α-羟基酸、胺类、唑类、羧酸类、二醇类、二硫化物类、二硫醇类、硒化物类、亚硫酸盐、硫醚、硫醇类、硫醇、硫甘醇、邻羟基苯硫酚及其组合。
在必要情况下,可能需要将至少一种表面活性化合物溶于助溶剂中。对此钝化组合物合适的助溶剂物质包含(但不限于):四亚甲砜、直链或支链的C1-C6醇(包含(但不限于)甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、叔丁醇、1-戊醇、己醇、环己醇、2-乙基-1-己醇)、苯甲醇、糠醇、二醇类(例如乙二醇、二甘醇、丙二醇(1,2-丙二醇)、四亚甲基二醇(1,4-丁二醇)、2,3-丁二醇、1,3-丁二醇及新戊二醇);或乙二醇醚(例如二甘醇单甲醚、三甘醇单甲醚、二甘醇单乙醚、三甘醇单乙醚、乙二醇单丙醚、乙二醇单丁醚、二甘醇单丁醚、三甘醇单丁醚、丙二醇甲醚、二丙二醇甲醚、三丙二醇甲基醚、丙二醇正丙醚、二丙二醇正丙醚、三丙二醇正丙醚、丙二醇正丁醚、二丙二醇正丁基醚及三丙二醇正丁醚)。其它有用的溶剂是典型的极性溶剂,例如二甲基乙酰胺、甲酰胺、二甲基甲酰胺、1-甲基-2-吡咯烷酮、二甲亚砜、四氢糠醇(THFA)及其它极性溶剂。本文也预期两种或两种以上助溶剂物质的组合。
不受理论的束缚,认为表面活性化合物被强烈地吸附到含锗材料表面且在冲洗之后仍留在那里。举例来说,如果表面活性化合物包括硫(例如,二硫化物、二硫醇、亚硫酸盐、硫醚、硫醇类、硫醇、硫甘醇、邻羟基苯硫酚),那么硫基钝化层可形成于含锗材料表面上,或者,如果表面活性化合物包括硒(例如,硒化物),那么硒基钝化层可形成于含锗材料表面上。本文预期的表面活性化合物包含(但不限于)α-羟基酸、胺、唑类、羧酸、二醇、二硫化物、二硫醇、硒化物、亚硫酸盐、硫醚、硫醇、硫基醇、硫二醇、邻羟基硫酚、及其组合。举例来说,该至少一种表面活性化合物可选自由下列各项组成之群:α-羟基酸(例如,2-羟基-正辛酸)、胺(例如,牛磺酸、硫脲)、唑(例如,咪唑、氯化1-己基-3-甲基咪唑鎓、1,2,4-三唑、1-十二烷基咪唑、N-辛基咪唑、1-辛基苯并咪唑、1-(正丁基)咪唑、1-甲基咪唑、4-甲基咪唑)、羧酸(例如,苯乙醇酸、丙酮酸、2-酮基辛酸、苯基乙醛酸、2-羟基辛酸)、二醇(例如,1,2-丁二醇、1,2-己二醇)、二硫化物(例如,对甲苯基二硫化物、二苯甲基二硫醚、苯甲基二硫醚、丙基二硫化物、胱胺二盐酸盐、二硫基二羟乙酸、2,2'-二硫基二吡啶)、二硫醇(例如,3,6-二氧杂-1,8-辛烷二硫醇、双(2-巯乙基)醚、七乙二醇二硫醇、四乙二醇二硫醇、3,3'-硫基二丙酸双(2-巯乙基)酯、双(2-巯乙基)硫醚)、硒化物(例如,二氧化硒)、亚硫酸盐(例如,亚硫酸铵)、硫醚(例如,2,2'-硫基二乙酸、3,3'-硫基二丙酸、硫基二丙酸二(十六烷基)酯、硫基苯甲醚(甲基苯基硫醚)、3,3'-硫基二丙酸双(2-乙基己基)酯、硫基二丙酸二(十三烷基)酯、硫基二丙酸二月桂基酯、二苯基硫醚、3,3'-二硫基二丙酸二甲基酯、3,3'-二硫基二丙酸二乙基酯、3,3'-三硫基二丙酸二甲基酯、3,3'-硫基二丙酸二异丁基酯、硫代二苯酚、硫基二丙酸二-十二烷基酯、3,3'-二硫基二丙酸二异辛基酯、3,3'-硫基二丙酸二甲基酯、1,3二硫环己烷、3,3'-硫基二丙酸二乙基酯、3,3'-二硫基二丙酸双(2,3-二羟丙基)酯、3,3'-硫基二丙酸双(2,3-二羟丙基)酯、3,3'-硫基二丙酸二丁基酯、苯基二硫醚、3,3'-硫基二丙酸月桂基硬脂基酯、硫基二丙酸二肉豆蔻基酯、3,3'-硫基二丙酸二油基酯、硫基二丙酸二-十八烷基酯、3,3'-硫基二丙酸二辛基锡、3,3'-二硫基丙酸二硬脂基酯、硫基二丙酸二硬脂基酯、3,3'-硫基二丙酸、1,3,4-噻二唑-2,5-二硫醇)、硫醇(例如,硫基羟乙酸甲酯、1-辛烷硫醇、1-十二烷硫醇、1-癸烷硫醇、6-巯基己酸、环己烷硫醇、1-庚烷硫醇、9-巯基芴、联苯-4-硫醇、硫基羟乙酸、11-巯基-1-十一烷醇、2-萘硫醇、硫基苯甲酸、甲硫咪唑、半胱氨酸)、硫基醇及硫二醇(例如,2-巯基乙醇、1-巯基-2-丙醇、3-巯基-1-丙醇、1-硫基甘油)及邻羟基硫代苯酚(例如,2-羟基硫代苯酚)。优选地,从由以下各物组成的群组选出表面活性化合物:3,3'-硫代二丙酸、2,2'-硫代二乙酸、3,6-二氧杂-1,8-辛二硫醇、巯基乙酸甲酯及其组合。基于钝化组合物的总重量,钝化组合物中的至少一种表面活性化合物的浓度在从约0.00001wt%到约10wt%的范围内。
应了解,通常的做法是在使用之前稀释浓缩形式的钝化组合物。举例来说,钝化组合物可以更浓缩形式制造,且在此之后,在使用之前及/或在工厂使用期间,在制造商处用额外的水进行稀释。稀释率可在从约0.1部分稀释剂:1部分钝化组合物浓度到约100部分稀释剂:1部分钝化组合物浓度的范围内。
本文描述的钝化组合物通过简单地添加相应成分并混合成均匀状态很容易制定。在钝化组合物的具体倍数中,相应成分的浓度可能广泛地变化,即,更稀释或更浓缩,且应了解,钝化组合物可不同地且替代地包括符合本文的揭示内容的成分的任何组合、由符合本文的揭示内容的成分的任何组合组成或基本上由符合本文的揭示内容的成分的任何组合组成。
在第二方面中,一种使微电子装置表面上的含锗材料钝化的方法,所述方法包括使包括所述含锗材料的所述微电子装置接触包括水及从以下各物组成的群组选出的至少一种表面活性化合物、由水及从以下各物组成的群组选出的至少一种表面活性化合物组成或基本上由水及从以下各物组成的群组选出的至少一种表面活性化合物组成的钝化组合物:α-羟基酸、胺类、唑类、羧酸类、二醇类、二硫化物类、二硫醇类、硒化物类、亚硫酸盐、硫醚、硫醇类、硫醇、硫甘醇、邻羟基苯硫酚及其组合,如本文描述。以任何合适的方式使钝化组合物接触微电子装置表面,例如,通过在装置表面上喷涂钝化组合物、通过浸泡(在钝化组合物的静态或动态容积中)装置、通过使装置接触其上具有吸附的钝化组合物的另一材料(例如,垫)或纤维状吸附剂施配器元件、通过使装置接触循环钝化组合物、或通过任何其它合适的方法、方式或技术,通过所述方法、方式或技术,使钝化组合物与含锗材料可移除式接触。针对动态或静态清洁,所述应用可在一批晶片设备或单一晶片设备中进行。
在本文描述的钝化组合物的使用中,钝化组合物通常在从约20℃到约100℃(优选地约20℃到约40℃)的范围内的温度下接触装置结构达从约10秒到约100分钟(优选地约30秒到约30分钟)的充足时间。此类接触时间及温度是说明性的,且可采用有效地实现所需钝化的任何其它合适的时间及温度条件。
在实现所期望的钝化之后,可从先前已将钝化组合物施加到其的微电子装置容易地移除多余的钝化组合物,例如,通过冲洗、清洗或其它移除步骤,如在本发明的钝化组合物的给定最终使用应用中可期望及有效的。举例来说,装置可用包含去离子水的冲洗溶液冲洗及/或干燥(例如,旋转干燥、N2、蒸气干燥等等)。替代地,冲洗可基本上是无水的,例如,异丙醇(IPA),接着进行干燥步骤(例如,旋转干燥、N2、蒸气干燥等等)。在冲洗之后,认为来自从以下各物组成的群组选出的至少一种表面活性化合物的分子被吸附(即,以化学方式及/或以物理方式)于含锗材料上:α-羟基酸、胺类、唑类、羧酸类、二醇类、二硫化物类、二硫醇类、硒化物类、亚硫酸盐、硫醚、硫醇类、硫醇、硫甘醇、邻羟基苯硫酚及其组合,如本文描述。
在第二方面的一个实施例中,使微电子装置表面上的含锗材料钝化的方法包括:
使包括所述含锗材料的所述微电子装置接触氧化物移除组合物;及
使包括所述含锗材料的所述微电子装置接触钝化组合物,
其中所述钝化组合物包括水及从以下各物组成的群组选出的至少一种表面活性化合物、由水及从以下各物组成的群组选出的至少一种表面活性化合物组成或基本上由水及从以下各物组成的群组选出的至少一种表面活性化合物组成:α-羟基酸、胺类、唑类、羧酸类、二醇类、二硫化物类、二硫醇类、硒化物类、亚硫酸盐、硫醚、硫醇类、硫醇、硫甘醇、邻羟基苯硫酚及其组合,如本文描述。氧化物移除组合物包含(但不限于)氢氟酸溶液、盐酸溶液、HCl/H2O2/水溶液(即,SC-2)及NH4OH/H2O2/水溶液(即,SC-1)。任选冲洗步骤可在接触氧化物移除组合物与接触钝化组合物之间进行。
在第二方面的另一实施例中,使微电子装置表面上的含锗材料钝化的方法包括:
使包括所述含锗材料的所述微电子装置接触氧化物移除组合物;
使包括所述含锗材料的所述微电子装置接触钝化组合物;
冲洗包括所述含锗材料的所述微电子装置;及
将包括所述含锗材料的所述微电子装置干燥,
其中所述钝化组合物包括水及从以下各物组成的群组选出的至少一种表面活性化合物、由水及从以下各物组成的群组选出的至少一种表面活性化合物组成或基本上由水及从以下各物组成的群组选出的至少一种表面活性化合物组成:α-羟基酸、胺类、唑类、羧酸类、二醇类、二硫化物类、二硫醇类、硒化物类、亚硫酸盐、硫醚、硫醇类、硫醇、硫甘醇、邻羟基苯硫酚及其组合,如本文描述。所述氧化物移除组合物包含(但不限于)氢氟酸溶液、盐酸溶液、HCl/H2O2/水溶液(即,SC-2)及NH4OH/H2O2/水溶液(即,SC-1)。任选冲洗步骤可在接触氧化物移除组合物与接触钝化组合物之间进行。
在另一实施例中,使微电子装置表面上的含锗材料钝化的方法包括:
使包括所述含锗材料的所述微电子装置接触氧化物移除组合物;
使包括所述含锗材料的所述微电子装置接触钝化组合物;
冲洗包括所述含锗材料的所述微电子装置;
将包括所述含锗材料的所述微电子装置干燥;及
在包括所述含锗材料的所述微电子装置上沉积高k电介质材料,
其中所述钝化组合物包括水及从以下各物组成的群组选出的至少一种表面活性化合物、由水及从以下各物组成的群组选出的至少一种表面活性化合物组成或基本上由水及从以下各物组成的群组选出的至少一种表面活性化合物组成:α-羟基酸、胺类、唑类、羧酸类、二醇类、二硫化物类、二硫醇类、硒化物类、亚硫酸盐、硫醚、硫醇类、硫醇、硫甘醇、邻羟基苯硫酚及其组合,如本文描述。所述氧化物移除组合物包含(但不限于)氢氟酸溶液、盐酸溶液、HCl/H2O2/水溶液(即,SC-2)及NH4OH/H2O2/水溶液(即,SC-1)。任选冲洗步骤可在接触氧化物移除组合物与接触钝化组合物之间进行。
本发明的另一方面涉及一种制造物品,其包括本文所描述的微电子装置衬底、含锗材料及钝化组合物、由本文所描述的微电子装置衬底、含锗材料及钝化组合物组成或基本上由本文所描述的微电子装置衬底、含锗材料及钝化组合物组成。
通过下文论述的说明性实例更完整地展示本发明的特征及优点。
实例1
使用下列六步骤氧化物移除过程清理掺杂镓的具有0.02ohm-cm的电阻率的p型锗衬底及具有0.04ohm-cm的电阻率的n型锗衬底:
1.HCl/H2O2/H2O(100:1:500)冲洗达20s
2.DIW冲洗
3.NH4OH/H2O2/H2O(1:1:100)冲洗达40s
4.DIW冲洗
5.4%HF冲洗达1分钟
6.DIW冲洗
接着,将锗衬底暴露到包括以下各物中的一者的钝化组合物达五分钟:硫化铵(1%水溶液)、巯基乙酸甲酯(1%水溶液)、3,6-二氧杂-1,8-辛二硫醇(1%DMSO),接着进行DIW冲洗及氮气干燥。所有处理都在环境温度下完成。使用来自625nm、700mW的光电二极管的照明测量光致发光(PL)。在以下表1中展示集成PL强度。表面缺陷导致非辐射重合及较低PL强度。巯基乙酸甲酯的较高PL强度证实其比硫化铵更能有效用于表面钝化。
表1:
实例2
使掺杂镓的具有0.02ohm-cm的电阻率的p型锗衬底经受以下过程:
1.使用丙酮然后使用异丙醇清理
2.暴露到包括以下各者中的一者的钝化组合物达20分钟:硫化铵(1%水溶液)、3,3'-硫代二丙酸(1%水溶液)、2,2'-硫代二乙酸(1%水溶液)、3,6-二氧杂-1,8-辛二硫醇(1%DMSO)
3.DI水冲洗
4.氮气吹干
5.10个脉冲的三甲基铝(在ALD反应器中)
6.在250℃下使用三甲基铝进行Al2O3的ALD 100个循环
7.在氮气中450℃退火达2分钟
8.通过荫罩进行Ni/Au上电极沉积
9.Ti/Au欧姆接触到Ge衬底的底部
10.后金属退火(300℃,在氮气中30s)
11.电容对电压测量。
以100Hz与1MHz之间的25个频率进行电容对电压测量,其中栅极电压在2.25与-2.25伏特之间。这些测量经模型化以提取界面状态的密度。下文给出若干配方的结果。3,3'-硫基二丙酸展示Dit降低而无Q-时间以及Dit的较少增加及24小时的Q-时间。2,2'-硫基二乙酸展示比硫化铵低的Dit与24小时的队列时间。对于p型Ge,在具有可比较的Dit及迟滞的情况下,3,6-二氧杂-1,8-辛二硫醇及巯基乙酸甲酯展示比硫化铵更少的频率分散。
表2:
虽然本文已参考本发明的具体方面、特征及说明性实施例描述了本发明,但应了解,本发明的实用性并不因此而受限,而是延伸到且涵盖众多其它变化、修改及替代实施例,如将基于本文揭示内容向本发明领域的一般技术人员论述所述其它变化、修改及替代实施例。对应地,希望将下文所主张的本发明广泛地解释及解译为包含在其精神及范围内的所有此类变化、修改及替代实施例。
Claims (12)
1.一种钝化微电子装置表面上的含锗材料的方法,所述方法包括使包括所述含锗材料的所述微电子装置接触包括水及从由以下各物组成的群组选出的至少一种表面活性化合物的钝化组合物:α-羟基酸、胺类、唑类、羧酸类、二醇类、二硫化物类、二硫醇类、硒化物类、亚硫酸盐、硫醚、硫醇类、硫醇、硫甘醇、邻羟基苯硫酚及其组合。
2.根据权利要求1所述的方法,其中所述接触包括从由以下各方法组成的群组选出的方法:在所述装置的所述表面上喷涂所述钝化组合物、将所述装置浸入所述钝化组合物中、使所述装置接触其上具有吸附的所述钝化组合物的另一材料及使所述装置接触循环钝化组合物。
3.根据权利要求1或2所述的方法,其中所述至少一种表面活性化合物包括从由以下各物组成的群组选出的至少一种物质:2-羟基-正辛酸、牛磺酸、硫脲、咪唑、氯化1-己基-3-甲基咪唑鎓、1,2,4-三唑、1-十二烷基咪唑、N-辛基咪唑、1-辛基苯并咪唑、1-(正丁基)咪唑、1-甲基咪唑、4-甲基咪唑、苯乙醇酸、丙酮酸、2-氧代辛酸、苯基乙醛酸、2-羟基辛酸、1,2-丁二醇、1,2-己二醇、对甲苯基二硫化物、二苯甲基二硫醚、苯甲基二硫醚、丙基二硫化物、胱胺二盐酸盐、二硫基二羟乙酸、2,2'-二硫基二吡啶、3,6-二氧杂-1,8-辛烷二硫醇、双(2-巯乙基)醚、七乙二醇二硫醇、四乙二醇二硫醇、3,3'-硫基二丙酸双(2-巯乙基)酯、双(2-巯乙基)硫醚、二氧化硒、亚硫酸铵、2,2'-硫基二乙酸、3,3'-硫基二丙酸、硫基二丙酸二(十六烷基)酯、硫基苯甲醚(甲基苯基硫醚)、3,3'-硫基二丙酸双(2-乙基己基)酯、硫基二丙酸二(十三烷基)酯、硫基二丙酸二月桂基酯、二苯基硫醚、3,3'-二硫基二丙酸二甲基酯、3,3'-二硫基二丙酸二乙基酯、3,3'-三硫基二丙酸二甲基酯、3,3'-硫基二丙酸二异丁基酯、硫代二苯酚、硫基二丙酸二-十二烷基酯、3,3'-二硫基二丙酸二异辛基酯、3,3'-硫基二丙酸二甲基酯、1,3二硫环己烷、3,3'-硫基二丙酸二乙基酯、3,3'-二硫基二丙酸双(2,3-二羟丙基)酯、3,3'-硫基二丙酸双(2,3-二羟丙基)酯、3,3'-硫基二丙酸二丁基酯、苯基二硫醚、3,3'-硫基二丙酸月桂基硬脂基酯、硫基二丙酸二肉豆蔻基酯、3,3'-硫基二丙酸二油基酯、硫基二丙酸二-十八烷基酯、3,3'-硫基二丙酸二辛基锡、3,3'-二硫基丙酸二硬脂基酯、硫基二丙酸二硬脂基酯、3,3'-硫基二丙酸、1,3,4-噻二唑-2,5-二硫醇、硫基羟乙酸甲酯、1-辛烷硫醇、1-十二烷硫醇、1-癸烷硫醇、6-巯基己酸、环己烷硫醇、1-庚烷硫醇、9-巯基芴、联苯-4-硫醇、硫基羟乙酸、11-巯基-1-十一烷醇、2-萘硫醇、硫基苯甲酸、甲硫咪唑、半胱氨酸、2-巯基乙醇、1-巯基-2-丙醇、3-巯基-1-丙醇、1-硫基甘油、2-羟基硫代苯酚、及其组合,优选地为3,3'-硫基二丙酸、2,2'-硫基二乙酸、3,6-二氧杂-1,8-辛烷二硫醇、硫基羟乙酸甲酯及其组合。
4.根据前述权利要求中任一权利要求所述的方法,其中所述钝化组合物进一步包括至少一种助溶剂,其中所述至少一种助溶剂包括从由以下各物组成的群组选出的物质:四亚甲砜、甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、叔丁醇、1-戊醇、己醇、环己醇、2-乙基-1-己醇、苯甲醇、糠醇、乙二醇、二甘醇、丙二醇(1,2-丙二醇)、四亚甲二醇(1,4-丁二醇)、2,3-丁二醇、1,3-丁二醇、新戊二醇、二甘醇单甲醚、三甘醇单甲醚、二甘醇单乙醚、三甘醇单乙醚、乙二醇单丙醚、乙二醇单丁醚、二甘醇单丁醚、三甘醇单丁醚、丙二醇甲基醚、二丙二醇甲基醚、三丙二醇甲基醚、丙二醇正丙醚、二丙二醇正丙醚、三丙二醇正丙醚、丙二醇正丁醚、二丙二醇正丁醚、三丙二醇正丁醚、二甲基乙酰胺、甲酰胺、二甲基甲酰胺、1-甲基-2-吡咯烷酮、二亚甲砜、四氢糠醇(THFA)及其组合。
5.根据前述权利要求中任一权利要求所述的方法,其中所述接触包括从约10秒到约100分钟、优选地约30秒到约30分钟的时间。
6.根据前述权利要求中任一权利要求所述的方法,其中所述接触包括从约20℃到约100℃、优选地约20℃到约40℃的温度。
7.根据前述权利要求中任一权利要求所述的方法,其进一步包括使包括所述含锗材料的所述微电子装置在接触所述钝化组合物之前接触氧化物移除组合物。
8.根据权利要求7所述的方法,其中所述氧化物移除组合物包括氢氟酸溶液、盐酸溶液、HCl/H2O2/水溶液或NH4OH/H2O2/水溶液。
9.根据前述权利要求中任一权利要求所述的方法,其进一步包括在接触所述钝化组合物之后冲洗包括所述含锗材料的所述微电子装置。
10.根据权利要求9所述的方法,其进一步包括在所述冲洗之后干燥包括所述含锗材料的所述微电子装置。
11.根据权利要求10所述的方法,其进一步包括在所述干燥之后将高k电介质材料沉积于包括所述含锗材料的所述微电子装置上。
12.根据前述权利要求中任一权利要求所述的方法,其中所述含锗材料包括以下各物中的至少一者:块状锗晶片、n掺杂锗、p掺杂锗;绝缘体上锗GOI晶片,在此情况所述层是形成于衬底顶部上的电介质层上的锗层、衬底上的锗层;及具有通式Si1-xGex的硅锗SiGe合金,其中Ge的含量大于约70wt%,更优选地大于80wt%,且最优选地大于90wt%。
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- 2016-08-12 CN CN201680055157.1A patent/CN108028174A/zh active Pending
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CN113745965A (zh) * | 2020-05-27 | 2021-12-03 | 山东华光光电子股份有限公司 | 一种液体环境下解理钝化半导体激光器腔面的方法 |
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TW201714219A (zh) | 2017-04-16 |
JP2018525833A (ja) | 2018-09-06 |
CN116759290A (zh) | 2023-09-15 |
JP6735337B2 (ja) | 2020-08-05 |
TWI714618B (zh) | 2021-01-01 |
WO2017030967A1 (en) | 2017-02-23 |
EP3335238A1 (en) | 2018-06-20 |
US20180240674A1 (en) | 2018-08-23 |
KR20180030714A (ko) | 2018-03-23 |
EP3335238A4 (en) | 2019-03-13 |
US10290505B2 (en) | 2019-05-14 |
KR102066438B1 (ko) | 2020-01-16 |
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