TWI507562B - 多成分膜的製作方法 - Google Patents
多成分膜的製作方法 Download PDFInfo
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- TWI507562B TWI507562B TW103113480A TW103113480A TWI507562B TW I507562 B TWI507562 B TW I507562B TW 103113480 A TW103113480 A TW 103113480A TW 103113480 A TW103113480 A TW 103113480A TW I507562 B TWI507562 B TW I507562B
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- Prior art keywords
- precursor
- group
- ruthenium
- film
- substrate
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- 238000004519 manufacturing process Methods 0.000 title description 3
- 239000002243 precursor Substances 0.000 claims description 147
- 238000000034 method Methods 0.000 claims description 67
- 239000000758 substrate Substances 0.000 claims description 63
- 229910052707 ruthenium Inorganic materials 0.000 claims description 60
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 59
- 238000000151 deposition Methods 0.000 claims description 48
- 238000000576 coating method Methods 0.000 claims description 30
- 230000008021 deposition Effects 0.000 claims description 28
- 239000011248 coating agent Substances 0.000 claims description 25
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 229910052732 germanium Inorganic materials 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 20
- -1 hydrazine (trimethyldecyl) hydrazine Chemical compound 0.000 claims description 18
- 238000010926 purge Methods 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 229910052714 tellurium Inorganic materials 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 239000006227 byproduct Substances 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 125000006546 (C4-C10) cycloalkyl group Chemical group 0.000 claims description 8
- 229910052787 antimony Inorganic materials 0.000 claims description 7
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 7
- 229910052735 hafnium Inorganic materials 0.000 claims description 7
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 5
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 4
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- DJLOZGYSPCQNDS-UHFFFAOYSA-N CC(CCCCCCCCCC=1C2=CC=CC=C2C(=C2C=CC=CC12)CCCCCCCCCC(C)(C)C)(C)C Chemical compound CC(CCCCCCCCCC=1C2=CC=CC=C2C(=C2C=CC=CC12)CCCCCCCCCC(C)(C)C)(C)C DJLOZGYSPCQNDS-UHFFFAOYSA-N 0.000 claims 2
- 239000000460 chlorine Substances 0.000 claims 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims 1
- 125000004093 cyano group Chemical group *C#N 0.000 claims 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 150000002429 hydrazines Chemical class 0.000 claims 1
- 230000000269 nucleophilic effect Effects 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 239000010408 film Substances 0.000 description 99
- 238000000231 atomic layer deposition Methods 0.000 description 44
- 238000004846 x-ray emission Methods 0.000 description 21
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- 229960001701 chloroform Drugs 0.000 description 12
- 229910000618 GeSbTe Inorganic materials 0.000 description 11
- 229910004298 SiO 2 Inorganic materials 0.000 description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 11
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 11
- 239000011669 selenium Substances 0.000 description 11
- 230000008859 change Effects 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 229910018321 SbTe Inorganic materials 0.000 description 6
- 150000004770 chalcogenides Chemical class 0.000 description 6
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 6
- 239000012782 phase change material Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- LDWRUMLSXDQVHK-UHFFFAOYSA-N CC(C)(C)CCCCCCCCC[Ru]CCCCCCCCCC(C)(C)C Chemical compound CC(C)(C)CCCCCCCCC[Ru]CCCCCCCCCC(C)(C)C LDWRUMLSXDQVHK-UHFFFAOYSA-N 0.000 description 5
- 229910005872 GeSb Inorganic materials 0.000 description 5
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910052711 selenium Inorganic materials 0.000 description 5
- 229910052693 Europium Inorganic materials 0.000 description 4
- 229910000420 cerium oxide Inorganic materials 0.000 description 4
- 238000005137 deposition process Methods 0.000 description 4
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 4
- LFYYDXRFYGNQHQ-UHFFFAOYSA-N 1,2-di(nonyl)hydrazine Chemical compound CCCCCCCCCNNCCCCCCCCC LFYYDXRFYGNQHQ-UHFFFAOYSA-N 0.000 description 3
- 229910005866 GeSe Inorganic materials 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 3
- HGAYKTZIOSRHOL-UHFFFAOYSA-N 1-decyl-9h-fluorene Chemical class C1C2=CC=CC=C2C2=C1C(CCCCCCCCCC)=CC=C2 HGAYKTZIOSRHOL-UHFFFAOYSA-N 0.000 description 2
- RPDFRSKJKOQCIT-UHFFFAOYSA-N 3-ethyldodecane Chemical compound CCCCCCCCCC(CC)CC RPDFRSKJKOQCIT-UHFFFAOYSA-N 0.000 description 2
- ZMIQYPVCYSOADL-UHFFFAOYSA-N CCCCCCCCCC[Se] Chemical compound CCCCCCCCCC[Se] ZMIQYPVCYSOADL-UHFFFAOYSA-N 0.000 description 2
- UDQYOSGLMTXFPU-UHFFFAOYSA-N CN(C)NN.NN Chemical compound CN(C)NN.NN UDQYOSGLMTXFPU-UHFFFAOYSA-N 0.000 description 2
- 229910000927 Ge alloy Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical group [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
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- 239000012528 membrane Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- KHPNGCXABLTQFJ-UHFFFAOYSA-N 1,1,1-trichlorodecane Chemical compound CCCCCCCCCC(Cl)(Cl)Cl KHPNGCXABLTQFJ-UHFFFAOYSA-N 0.000 description 1
- NIIPNAJXERMYOG-UHFFFAOYSA-N 1,1,2-trimethylhydrazine Chemical compound CNN(C)C NIIPNAJXERMYOG-UHFFFAOYSA-N 0.000 description 1
- WHEZQSAGGVGZDP-UHFFFAOYSA-N 1,1-dichlorodec-1-ene Chemical compound CCCCCCCCC=C(Cl)Cl WHEZQSAGGVGZDP-UHFFFAOYSA-N 0.000 description 1
- JCMVPOVHKWWBAU-UHFFFAOYSA-N 1,2-dichlorohydrazine Chemical compound ClNNCl JCMVPOVHKWWBAU-UHFFFAOYSA-N 0.000 description 1
- XDLJIIILKATPAQ-UHFFFAOYSA-N 2,8-dichloro-7h-purine Chemical compound ClC1=NC=C2NC(Cl)=NC2=N1 XDLJIIILKATPAQ-UHFFFAOYSA-N 0.000 description 1
- KDGQCXIDQUFTSY-UHFFFAOYSA-N C(C)(C)N(C(C)C)NN.NN Chemical compound C(C)(C)N(C(C)C)NN.NN KDGQCXIDQUFTSY-UHFFFAOYSA-N 0.000 description 1
- PDSLLMHSRQJRTG-UHFFFAOYSA-N C(C)C(CCCCCCCCC[Se]CCCCCCCCCC(CC)(CC)CC)(CC)CC Chemical compound C(C)C(CCCCCCCCC[Se]CCCCCCCCCC(CC)(CC)CC)(CC)CC PDSLLMHSRQJRTG-UHFFFAOYSA-N 0.000 description 1
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- IKKDHXKSRJBGGO-UHFFFAOYSA-N CC(CCCCCCCCCNNCCCCCCCCCC(C)(C)C)(C)C Chemical compound CC(CCCCCCCCCNNCCCCCCCCCC(C)(C)C)(C)C IKKDHXKSRJBGGO-UHFFFAOYSA-N 0.000 description 1
- WXLWUEFAINUUTF-UHFFFAOYSA-N CC(CCCCCCCCC[Se]CCCCCCCCCC(C)(C)C)(C)C Chemical compound CC(CCCCCCCCC[Se]CCCCCCCCCC(C)(C)C)(C)C WXLWUEFAINUUTF-UHFFFAOYSA-N 0.000 description 1
- TUUOXGYAHCAAFN-UHFFFAOYSA-N CC1=C(C(=C(C=C1)N(N)CCCCCCCCCC)C)C Chemical compound CC1=C(C(=C(C=C1)N(N)CCCCCCCCCC)C)C TUUOXGYAHCAAFN-UHFFFAOYSA-N 0.000 description 1
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- LWUZVGFCSKAGKJ-UHFFFAOYSA-N CCC(CC)(CC)CCCCCCCCCPCCCCCCCCCC(CC)(CC)CC Chemical compound CCC(CC)(CC)CCCCCCCCCPCCCCCCCCCC(CC)(CC)CC LWUZVGFCSKAGKJ-UHFFFAOYSA-N 0.000 description 1
- SMVUUWXVFNPQIP-UHFFFAOYSA-N CCCCCCCCC(C(C)(C)C)C(C)(C)NNC(C)(C)C(CCCCCCCC)C(C)(C)C Chemical compound CCCCCCCCC(C(C)(C)C)C(C)(C)NNC(C)(C)C(CCCCCCCC)C(C)(C)C SMVUUWXVFNPQIP-UHFFFAOYSA-N 0.000 description 1
- KPEQWWDCMPJHFD-UHFFFAOYSA-N CCCCCCCCC(C(C)(C)C)C(C)(C)[Se]C(C)(C)C(CCCCCCCC)C(C)(C)C Chemical compound CCCCCCCCC(C(C)(C)C)C(C)(C)[Se]C(C)(C)C(CCCCCCCC)C(C)(C)C KPEQWWDCMPJHFD-UHFFFAOYSA-N 0.000 description 1
- LFHCNPBLHVUONJ-UHFFFAOYSA-N CCCCCCCCC(C(C)(C)NNC(C)(C)C(CCCCCCCC)C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound CCCCCCCCC(C(C)(C)NNC(C)(C)C(CCCCCCCC)C1=CC=CC=C1)C1=CC=CC=C1 LFHCNPBLHVUONJ-UHFFFAOYSA-N 0.000 description 1
- DXUWKKQDFJIIDH-UHFFFAOYSA-N CCCCCCCCC(C1=CC=CC=C1)C(C)(C)NN Chemical compound CCCCCCCCC(C1=CC=CC=C1)C(C)(C)NN DXUWKKQDFJIIDH-UHFFFAOYSA-N 0.000 description 1
- UEIQVDWLHMDSKG-UHFFFAOYSA-N CCCCCCCCC(C1=CC=CC=C1)C(C)(C)[Se]C(C)(C)C(CCCCCCCC)C2=CC=CC=C2 Chemical compound CCCCCCCCC(C1=CC=CC=C1)C(C)(C)[Se]C(C)(C)C(CCCCCCCC)C2=CC=CC=C2 UEIQVDWLHMDSKG-UHFFFAOYSA-N 0.000 description 1
- RGBZNCKRCVIGAJ-UHFFFAOYSA-N CCCCCCCCCCPC(C)(C)C(C)(C)C Chemical compound CCCCCCCCCCPC(C)(C)C(C)(C)C RGBZNCKRCVIGAJ-UHFFFAOYSA-N 0.000 description 1
- PVPSJBJRRMKGQJ-UHFFFAOYSA-N CN(N(C(C)(C)C)CCCCCCCCCC)C Chemical compound CN(N(C(C)(C)C)CCCCCCCCCC)C PVPSJBJRRMKGQJ-UHFFFAOYSA-N 0.000 description 1
- PEIBVOLUKIHRNP-UHFFFAOYSA-N CN(N(C1=CC=CC=C1)CCCCCCCCCC)C Chemical compound CN(N(C1=CC=CC=C1)CCCCCCCCCC)C PEIBVOLUKIHRNP-UHFFFAOYSA-N 0.000 description 1
- ASQXCZIYPJPNBP-UHFFFAOYSA-N C[Se](C)(CCCCCCCCCC)C Chemical compound C[Se](C)(CCCCCCCCCC)C ASQXCZIYPJPNBP-UHFFFAOYSA-N 0.000 description 1
- JPCWAQIYCADHCI-UHFFFAOYSA-N O(O)O.[Ru] Chemical compound O(O)O.[Ru] JPCWAQIYCADHCI-UHFFFAOYSA-N 0.000 description 1
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- PCBMYXLJUKBODW-UHFFFAOYSA-N [Ru].ClOCl Chemical compound [Ru].ClOCl PCBMYXLJUKBODW-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
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- JITPFBSJZPOLGT-UHFFFAOYSA-N cerium(3+);propan-2-olate Chemical compound [Ce+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] JITPFBSJZPOLGT-UHFFFAOYSA-N 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
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- 238000001816 cooling Methods 0.000 description 1
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- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
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- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
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- 150000004772 tellurides Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- LINIOGPXIKIICR-UHFFFAOYSA-L ytterbium(ii) chloride Chemical compound [Cl-].[Cl-].[Yb+2] LINIOGPXIKIICR-UHFFFAOYSA-L 0.000 description 1
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
- C23C16/45531—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations specially adapted for making ternary or higher compositions
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
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- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
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Description
本案請求2013年,4月11日申請的美國專利申請案第61/810919號的權益。在此以引用的方式將該申請案第61/810919號的揭示內容併入本文。
在此揭示的是用於沉積多成分膜的方法,各多成分膜可能是化學計量的或非化學計量的例如,但不限於,鍺碲(GT)、銻鍺(SG)、鍺銻碲(GST)、氧化鍺、氮化鍺。在此也考慮到使用本文所述的方法沉積該多成分膜的前驅物組合物或其混合物。
某些合金例如但不限於,GST(鍺銻碲合金)及GeTe(鍺碲合金)係用以裝配電子裝置,包括相變化隨機存取記憶體(PCRAM)。相變化材料根據溫度依照結晶態或非晶態存在。相變化材料依照結晶態比非晶態具有更有序的原子排列及較低電阻。相變化材料能根據操作溫度從該結晶態可逆地轉變成非晶態。這樣的特徵,也就是說,可逆的相變化及不同狀態的不同阻抗,適於新近提出的電子裝置、新型非揮
發性記憶體裝置、相變化隨機存取記憶體(PCRAM)裝置。該PCRAM的電阻可根據彼內包括的相變化材料的狀態(例如,結晶性、非晶性等等)變化。
用於記憶體裝置的各種不同類型相變化材料當中,最常用的是第14族和第15族元素的三元硫族化合物(chalcogenide),例如各種不同組成的鍺銻碲化合物,包括但不限於Ge2
Sb2
Te5
,而且常被縮寫成GST。該GST的固態能藉著加熱或冷卻循環從結晶態快速變成非晶態,或反之亦然。該非晶性GST具有相對較高電阻,而該結晶性GST具有相對較低電阻。
關於具有小於20奈米(nm)的設計要求的相變化隨機存取記憶體(PCRAM)之裝配,因為就優良步階覆蓋率、精準厚度及膜組合物控制而言ALD是最適合的沉積方法,所以對於供GeSbTe原子層沉積法(ALD)用的良好前驅物的要求逐漸提高。GST最廣為研究的組成存在於該GeTe-Sb2
Te3
擬二元結線(tie line)上。然而,這些組合物的ALD沉積由於Ge+4
前驅物比Ge+2
前驅物的安定性更高而有困難而且Ge+4
傾向於生成GeTe2
而非GeTe。在這些情況之下將會生成GeTe2
-Sb2
Te3
組合物膜。因此,需要用於形成GT及GST膜的前驅物及相關製造方法,其能生產具有高保形性及化學組成均一性的膜,特別是利用ALD沉積方法。
在此所述的是用於沉積含鍺膜的方法、前驅物及
其混合物。關此,三氯鍺烷(HGeCl3
)能於較低溫下輕易地解離成HCl及GeCl2
。此性質使HGeCl3
成為能在沉積過程中原地產生二價鍺物種的適合前驅物。在一特定具體實施例中,當其他前驅物(Me3
Si)2
Te及(EtO)3
Sb用於沉積方法時,與常用的鍺前驅物例如(MeO)4
Ge相比,HGeCl3
可能提高GST合金中的鍺組成。HGeCl3
當成鍺前驅物讓人能解決前述其他先前鍺前驅物的問題並且達成某些具體實施例中想要的Ge2
Sb2
Te5
組成。
用於將多成分膜沉積於至少一部分基材上的方法之一具體實施例包含以下步驟:a)使該基材與包含HGeCl3
的鍺前驅物接觸以與該基材反應並且提供包含Ge的第一塗層;b)引進洗淨氣體以移除任何未反應的鍺前驅物;c)使該包含Ge的第一塗層與Te前驅物接觸,其中至少一部分Te前驅物與彼內所包含的Ge反應以提供包含Ge和Te的第二塗層;d)引進洗淨氣體以移除任何未反應的Te前驅物;e)使該包含Ge和Te的第二塗層與Sb前驅物接觸,其中至少一部分Sb前驅物與至少一部分彼內所包含的Ge和Te反應以提供包含Ge、Te和Sb的第三塗層;及f)引進洗淨氣體以移除任何未反應的Sb前驅物。
在某些具體實施例中,其中步驟(a)至(f)係重複進行許多次直到達到所欲的塗層厚度為止以提供該多成分膜。在各個不同具體實施例中,該等步驟可依照以下順序進行:
e → f → → a → b → c → d。
在另一具體實施例中,提供一種將多成分膜沉積於至少一部分基材上之方法,其包含以下步驟:a.使該基材與包含HGeCl3
的鍺前驅物接觸以與該基材反應並且提供包含Ge的第一塗層;b.引進洗淨氣體以移除任何未反應的鍺前驅物;c.使該包含Ge的第一塗層與Te前驅物接觸,其中至少一部分Te前驅物與彼內所包含的Ge反應以提供包含Ge和Te的第二塗層;及d.引進洗淨氣體以移除任何未反應的Te前驅物;其中步驟(a)至(d)係重複進行以形成許多塗層並且提供該膜。
在另一具體實施例中,提供一種將含鍺膜沉積於至少一部分基材上之方法,其包含以下步驟:將該基材提供於反應器中;在足以與該基材反應以提供含鍺膜的沉積條件之下將包含HGeCl3
的鍺前驅物引進該反應器。在各個不同具體實施例中,該引進另外包含氧來源或氮來源。在此或另一具體實施例中,該含鍺膜另外包含氧來源以提供氧化鍺(GeOx
;x=1,2)膜。運用的示範性氧來源包括,但不限於,氧(O2
)、氧電漿、臭氧(O3
)、過氧化氫、空氣、一氧化氮、水電漿及水。在又另一具體實施例中,該含鍺膜另外包含氮來源以提供氮化鍺(GeN或Ge3
N4
)膜。示範性氮來源包括但不限於氨、氨電漿、氮/氫電漿及氮電漿。在此或又另一具體實施例中,該含鍺膜包含經由引進氫電漿得到的純鍺膜。在此或又另一具體實施例中,該鍺膜另外包含使用氮電漿或氨電漿或
氮/氫電漿來氮化以轉化成氮化鍺膜。
在任何前述具體實施例中,咸了解在此所述的方法的步驟可依照各種順序進行,可依序地或同時地(例如,在另一步驟中的至少一部分的期間),及其任何組合進行。在某些具體實施例中,在此所述的步驟係依序地進行以免生成沉澱物。
圖1給實施例1中沉積於該SiO2
和TiN基材上的那些膜提供該GeTe XRF與Ge脈衝時間(秒)所作的比較。
圖2給實施例2中沉積於該SiO2
和TiN基材上的那些膜提供該GeTe XRF與Ge脈衝時間(秒)所作的比較。
圖3給實施例3中沉積於該SiO2
和TiN基材上的那些膜提供該GeTe XRF與Ge脈衝時間(秒)所作的比較。
圖4給實施例4中沉積於該SiO2
和TiN基材上的那些膜提供該GeTe XRF與Ge脈衝時間(秒)所作的比較。
圖5給實施例5中沉積於該SiO2
和TiN基材上的那些膜提供該GeTe XRF與Ge脈衝時間(秒)所作的比較。
圖6a提供應用50個ALD循環的GeSbTe XRF,該ALD循環由在實施例6的氧化矽基材上的1個GeTe程序及1個SbTe程序組成。
圖6b提供應用50個ALD循環的GeSbTe XRF,該ALD循環由在實施例6的氮化鈦基材上的1個GeTe程序及1個
SbTe程序組成。
圖7a給實施例7中沉積於該氧化矽基材上的那些膜提供該GeSbTe XRF與循環次數所作的比較。
圖7b給實施例7中沉積於氮化鈦基材上的那些膜提供該GeSbTe XRF與循環次數所作的比較。
為了裝配高密度電子裝置例如相變化記憶體(PCRAM)或光伏打材料,原子層沉積法(ALD)係將膜,例如金屬硫族化合物膜,均勻地沉積於基材表面上的小尺寸結構上的較佳技術。在某些具體實施例中,該膜包含金屬硫族化合物膜。在此所用的措辭“金屬硫族化合物”表示含有一或更多第16族離子(硫族化合物)及至少一正電性元素的膜。硫族化合物材料的實例包括,但不限於,硫化物、硒化物及碲化物。習用的ALD技術涉及經常在真空之下及提高溫度下運用的ALD反應器。也有人要求該等前驅物係揮發性且熱安定性化合物以便依照蒸氣相運送至該反應器艙。ALD係用於薄膜高度控制沉積的類型之化學氣相沉積法。其係自限性(例如各反應循環所沉積的膜材料量恆常)且依順序的(例如,該等前驅物蒸氣係輪流地來到該等基材上,一次一種,由惰性氣體的洗淨期間分開)方法。咸認為ALD係用於生產非常薄的保形膜而且可能將該等膜的厚度和組成控制於原子程度最有機會的沉積方法。使用ALD,膜厚度僅取決於反應循環的數目,其使得厚度控制準確而且簡單。
在此所述的是用於含鍺膜的方法及前驅物,該等含鍺膜係多組成膜例如但不限於GeTe及GeTeSb膜。在此所述的方法之示範沉積溫度包括具有一或更多以下端點的範圍:500、400、300、200、195、190、185、180、175、170、165、160、155、150、145、140、135、130、125、120、115、110、105、100、95、90、85、80、75、70、65、60、55、50、45、40、35、30、25及/或20℃。特定溫度範圍的實例包括,但不限於,約20至約200℃或約50至約100℃。
在某些具體實施例中,該等含鍺膜另外包含碲而且係使用碲前驅物來沉積。示範性碲前驅物能選自具有以下一般結構的二矽烷基碲、矽烷基烷基碲、矽烷基胺基碲:(R1
R2
R3
Si)2
Te(R1
R2
R3
Si)TeR4
(R1
R2
R3
Si)TeN(R4
R5
)其中R1
、R2
、R3
、R4
及R5
係獨立地選自氫;無論有無雙鍵之線性、分支或環狀的1至10碳的烷基;或C3
至C10
芳基。
在ALD方法中,依照任何順序依照循環方式藉由蒸氣抽引或直接液體注射(DLI)將該等碲前驅物、醇類、鍺及銻前驅物,例如(Me2
N)4
Ge及(Me2
N)3
Sb引進沉積艙。該沉積溫度較佳為介於25°至500℃。
用於將多成分膜沉積於至少一部分基材上的方法之一具體實施例包含以下步驟:a)使該基材與包含HGeCl3
的鍺前驅物接觸以與該基材反應並且提供包含Ge的第一塗層;b)引進洗淨氣體以移除任何未反應的鍺前驅物;c)使該包含Ge的第一塗層與Te前驅物接觸,其中至少
一部分Te前驅物與彼內所包含的Ge反應以提供包含Ge和Te的第二塗層;d)引進洗淨氣體以移除任何未反應的Te前驅物;e)使該包含Ge和Te的第二塗層與Sb前驅物接觸,其中至少一部分Sb前驅物與至少一部分彼內所包含的Ge和Te反應以提供包含Ge、Te和Sb的第三塗層;及f)引進洗淨氣體以移除任何未反應的Sb前驅物。
在某些具體實施例中,其中步驟(a)至(f)係重複進行許多次直到達到所欲的塗層厚度為止以提供該多成分膜。在各個不同具體實施例中,該等步驟可依照以下順序進行:e → f → → a → b → c → d。
用於將多成分膜沉積於至少一部分基材上的方法之另一具體實施例包含以下步驟:a)引進HGeCl3
以與基材反應而使該基材表面覆蓋著Ge-Cl片斷;b)利用惰性氣體洗淨;c)引進Te前驅物以提供Te層;及d)利用惰性氣體洗淨以移除任何反應副產物。該ALD循環係重複進行一定的次數直到達成所欲的膜厚度為止。在以上具體實施例中,下一個ALD循環以步驟a)至d)開始而且該等步驟係重複持續直到獲得所欲的膜厚度為止。
在用於將多成分膜沉積於至少一部分基材上的方法之又另一具體實施例包含以下步驟:a)引進Sb前驅物以將包含胺基銻的Sb層形成於該基材
表面上;b)利用惰性氣體洗淨以移除任何反應副產物;c)引進Te前驅物以與胺基銻層反應而與包含矽烷基的Te層形成Sb-Te;d)利用惰性氣體洗淨以移除任何反應副產物;e)引進包含HGeCl3
的鍺前驅物以與碲層上剩下的矽烷基反應而與包含HGe-Cl基團的Ge層生成Te-Ge鍵;f)利用惰性氣體洗淨;g)引進Te前驅物以與胺基銻層反應而與包含矽烷基的Te層形成Sb-Te;及h)利用惰性氣體洗淨以移除任何反應副產物,該ALD循環係重複進行一定的次數直到達成所欲的膜厚度為止。在以上具體實施例中,下一個ALD循環以步驟a)至h)開始,其係接著重複持續直到獲得所欲的膜厚度為止。在各個不同具體實施例中,該等步驟可依照以下順序進行:e → f → g → h → a → b → c → d。在某些具體實施例中,該步驟a)至h)的順序能輪流進行以達成所需的GST膜例如Ge對Sb或Ge對Te的比率。
在此所述的方法所用的示範性矽烷基碲化合物具有下式:(R1
R2
R3
Si)2
Te;(R1
R2
R3
Si)TeR4
;及(R1
R2
R3
Si)TeN(R4
R5
)其中R1
、R2
、R3
、R4
及R5
係各自獨立地選自氫原子;線性、分支或環狀的1至10碳的烷基;或帶有4至10個碳的芳香
族基團。
在此所述的方法中的示範性胺基鍺烷類、胺基銻及烷氧化銻具有下式:(R1
R2
N)4
Ge(R1
R2
N)3
Sb(R1
O)3
Sb其中R1
及R2
係各自獨立地為線性、分支或環狀的1至10碳的烷基。
在上式和此說明內容各處中,該措辭“aryl”表示具有4至10個碳原子,5至10個碳原子或6至10個碳原子的芳香環族或芳香雜環族基團。示範性芳基包括,但不限於,吡咯基、苯基、苯甲基、氯苯甲基、甲苯基及鄰-二甲苯基。
在一具體實施例中,該多成分膜係利用ALD方法來沉積。本文所述的方法能用於沉積設備中提供薄膜。該沉積設備由以下零件組成。˙放置基材的反應器,前驅物蒸氣起反應並且生成膜。該反應器壁及基材固持器可於相同或不同溫度下加熱;˙一或更多液態或固態前驅物容器。必要的話也可以加熱該等容器;˙一或更多閥,其可能開啟或關閉從該等前驅物容器送往該反應器的蒸氣流。質流控制器(MFC)單元係用以控制閥3和4何時開關及開關多少;˙從該反應器抽出空氣或前驅物蒸氣的真空泵。開/關該泵送管道的閥;˙測量該反應器內的壓力位準的真空計;及˙經由閥打開或關閉的惰性或洗淨氣體(Ar或N2
)。
在典型的ALD方法中,該反應器透過入口填滿惰性氣體(例如,Ar或N2
)並且接著使用真空泵8抽至低於20mTorr的真空度。該反應器接著再填滿入口氣體(inlet gas)並且在該沉積開始時將該反應器壁及基材固持器加熱至介於25℃至500℃之間的溫度。從被加熱至一定溫度範圍的前驅物容器放出該鍺前驅物。使溫度在沉積的期間保持恆定。從被加熱至介於25℃至500℃之間的溫度的前驅物容器放出該前驅物。該溫度在沉積的期間也保持恆定。該循環的數目根據預定的膜厚度預設。該等GST膜藉由分別重複進行Ge和Sb的過程而生成。用於Ge和Sb生長的方法與Te類似。
從烷氧基鍺烷類、烷氧基銻及矽烷基碲製作GST膜的現行ALD方法產生組成為(GeTe2
)x
(Sb2
Te3
)y
,而且代表式為Ge2
Sb2
Te7
的GST膜,其中鍺係四價。工業上偏好的GST材料係依照(GeTe)x
(Sb2
Te3
)y
組成群組的Ge2
Sb2
Te5
,其中鍺係二價。為了提高該膜中的鍺含量以達成Ge2
Sb2
Te5
,必須使用二價鍺前驅物。大部分的二價鍺化合物不安定或在沉積方法例如ALD中較不具揮發性。本文所述的方法提供,但是不受理論束縛,原地產生二價鍺的方法,該二價鍺當作將二價鍺沉積於膜表面上的中間物使用。在某些具體實施例中,該三氯鍺烷前驅物係用以沉積含鍺膜,例如但不限於,二元膜類GeTe以及三元膜類例如Ge2
Sb2
Te5
。在此所述的是使用三氯鍺烷當含鍺膜,例如用於PRAM應用的GST膜,的ALD和CVD沉積用的前驅物來沉積多成分膜的方法。三氯鍺烷在該沉積艙內產生二氯鍺烯(dichlorogermylene)。二氯鍺烯與二矽烷基
碲反應生成GeTe,其進一步與Sb2
Te3
結合生成供相變化記憶分配用的相變化材料Ge2
Sb2
Te5
。
在本文所述的方法之一具體實施例中,該鍺前驅物HGeCl3
係藉由ALD沉積法用於組成為1:1的GeTe膜沉積。使用該碲前驅物例如(SiMe3
)2
Te當Te前驅物,便能按照以下方程式(1)及(2)生成GeTe。
GeCl2
+(SiMe3
)2
Te → GeTe+2Me3
SiCl-------(2)副產物或方程式(2),Me3
SiCl具有揮發性,能沉積純GeTe膜。
在本文所述的方法之另一具體實施例中,該鍺前驅物HGeCl3
係藉由ALD沉積法用於組成為1:1的GeSe膜沉積。使用矽烷基硒前驅物例如(Me3
Si)2
Se當Se前驅物,便能按照以下方程式(3)及(4)生成GeSe。
GeCl2
+(SiMe3
)2
Se → GeSe+2Me3
SiCl-------(4)副產物或方程式(4),Me3
SiCl具有揮發性,能沉積純SeTe膜。
碲前驅物或Te前驅物的實例可包含二矽烷基碲、矽烷基烷基碲或具有以下一般結構的化合物:(R1
R2
R3
Si)2
Te及(R1
R2
R3
Si)R4
Te。硒或Se前驅物的實例可包含二矽烷基硒、矽烷基烷基硒或具有以下一般結構的化合物:(R1
R2
R3
Si)2
Se或(R1
R2
R3
Si)R4
Se。在前述式中,取代基R1
、R2
、R3
及R4
係各自獨立地為:氫;線性、分支或不飽和C1-10
烷基;及C4-10
環烷基或C4-12
芳香族基團。在用所用的措辭“烷基”係選自由以下所組成的群組:線性、分支或不飽
和C1-10
烷基;及C4-10
環烷基,較佳為1至6個碳原子,更佳為1至3個碳原子,選擇性地為3至5個碳原子,又選擇性地為4至6個碳原子,或前述範圍的變化。示範性烷基包括,但不限於,甲基(Me)、乙基(Et)、正丙基、異丙基、正丁基、異丁基、第二丁基、第三丁基、第三戊基、正戊基、正己基、環戊基及環己基。該措辭“烷基”也適於其他基團例如鹵烷基、烷芳基或芳烷基中所含的烷基部分。在某些具體實施例中,在此討論的一些基團可能被一或更多其他元素例如,舉例來說,鹵原子或其他雜原子例如O、N、Si或S所取代。
該矽烷基碲前驅物的實例包括,但不限於,雙(三甲基矽烷基)碲、雙(二甲基矽烷基)碲、雙(三乙基矽烷基)碲、雙(二乙基矽烷基)碲、雙(苯基二甲基矽烷基)碲、雙(第三丁基二甲基矽烷基)碲、二甲基矽烷基甲基碲、二甲基矽烷基苯基碲、二甲基矽烷基-正丁基碲、二甲基矽烷基-第三丁基碲、三甲基矽烷基甲基碲、三甲基矽烷基苯基碲、三甲基矽烷基-正丁基碲及三甲基矽烷基-第三丁基碲。
該矽烷基硒前驅物的實例包括,但不限於,雙(三甲基矽烷基)硒、雙(二甲基矽烷基)硒、雙(三乙基矽烷基)硒、雙(二乙基矽烷基)硒、雙(苯基二甲基矽烷基)硒、雙(第三丁基二甲基矽烷基)硒、二甲基矽烷基甲基硒。
能依據在上所述的方法製作的沉積膜係選自由鍺碲(GT)、銻鍺(SG)、鍺銻碲(GST)、氧化鍺及氮化鍺所組成的群組。
在一特定具體實施例中,該GST膜係利用三氯鍺
烷來沉積。三氯鍺烷具有獨特的性質。其與二氯鍺及HCl於室溫下處於平衡狀態(參見方程式(3))。
二氯鍺及HCl生成鬆散鍵結的錯合物。此錯合物能在大氣壓力之下被餾出而不會分解(沸點75℃)。另一方面,此錯合物能藉由高真空度於低溫下被拉開並且產生固體純二氯化鍺。
在此所述的方法係使用三氯鍺烷當GST膜用的鍺前驅物。三氯鍺烷係依照蒸氣相輸送至ALD反應器艙中。藉由低壓將分子分解成二氯化鍺及HCl以令二氯化鍺拋錨於該基材表面上,而且其後在ALD循環中與二矽烷基碲反應以生成GT膜例如GeTe膜,或與二矽烷基碲和當銻(Sb)前驅物的烷氧化銻例如乙氧化銻或胺基銻例如叁(二甲基胺基)銻反應以生成GST膜。
GeCl2
+(Me3
Si)2
Te → GeTe+Me3
SiCl
Sb(OEt)3
+(Me3
Si)2
Te → Sb2
Te3
+Me3
SiOEt
Sb(NMe2
)3
+(Me3
Si)2
Te → Sb2
Te3
+Me3
SiNMe2
GeTe+Sb2
Te3
→ (GeTe)x
(Sb2
Te3
)y
二氯化鍺也與三矽烷基銻反應而生成Ge3
Sb2
膜。
GeCl2
+(Me3
Si)3
Sb → Ge3
Sb2
+Me3
SiCl
該胺基銻的實例包括,但不限於,叁(二甲基胺基)銻、叁(二乙基胺基)銻,叁(二異丙基胺基)銻、叁(二正丙基胺基)銻、叁(二第二丁基胺基)銻及叁(二第三丁基胺基)銻。
該烷氧化銻的實例包括,但不限於,乙氧化銻((EtO)3
Sb)、甲氧化銻((MeO)3
Sb)、異丙氧化銻((iPrO)3
Sb)、正丙氧化銻((nPrO)3
Sb)、第二丁氧化銻((sBuO)3
Sb)、第三丁氧化銻((tBuO)3
Sb)。
三矽烷基銻前驅物的實例包括,但不限於,叁(三甲基矽烷基)銻、叁(二甲基矽烷基)銻、叁(三乙基矽烷基)銻、叁(二乙基矽烷基)銻、叁(苯基二甲基矽烷基)銻、叁(第三丁基二甲基矽烷基)銻。
前述實例僅為了例示,而且不會依任何方式限制此揭示內容。儘管該方法及前驅物組合物已經引用特定實例及其具體實施例詳細描述過,但是熟悉此技藝者將顯而易見能於彼內完成各種不同變化及修飾而不會悖離其精神及範疇。
沉積係於帶有加裝負載鎖的噴灑頭型PEALD艙之Quros反應器所製作的ALD反應器中進行,該負載鎖能握持一個4吋晶圓。樣品及膜的相轉變性質係藉由能量分散式X-射線分析來描述其特徵。
GeTe膜係依照以下方式獲得。HGeCl3
藥罐溫度係大約1℃,而且(Me3
Si)2
Te藥罐溫度係處於40℃。典型晶圓溫度係70℃,典型的Ar氣體流速係500sccm,而且該反應器壓力係控制於3Torr。該等膜係於晶圓裝在該反應器中的受
熱接受器上而且Ar氣體流入該反應器中經過數分鐘以後依照以下方式沉積。
a)鍺前驅物脈衝步驟:使用蒸氣抽取法(vapor draw method)將HGeCl3
蒸氣引進該反應器經過通常0.1秒。在此所用的蒸氣抽取法意指該前驅物蒸氣來自藥罐而不需任何載氣的協助,所以脈衝步驟時僅打開該藥罐的出口閥。
b)Ar(Ge)脈衝步驟:使Ar氣體流入該反應器經過數秒以移除任何未反應的Ge物種及反應副產物。
c)Te前驅物脈衝步驟:藉由流過該Te藥罐的Ar載體(50sccm)將(Me3
Si)2
Te蒸氣引進該反應器經過數秒。
d)Ar(Te)洗淨步驟:使Ar氣體流入該反應器經過數秒以移除任何未反應的Te物種及反應副產物。將步驟a)至d)重複進行100次以獲得所需的膜厚度。
使用上述程序、氧化矽和氮化鈦二者當基材、三氯鍺烷當鍺前驅物及雙(三甲基矽烷基)碲當Te前驅物,試驗在各循環中依照以下順序沉積GeTe膜:(1)各個不同秒數的Ge脈衝;(2)30秒的Ar洗淨;(3)4秒的Te脈衝;及(4)40秒的Ar洗淨。XRF指示該Ge/Te原子比率係1:1。圖1給沉積於該SiO2
和TiN基材上的那些膜提供該GeTe XRF與Ge脈衝時間(秒)所作的比較。當該Te前驅物脈衝步驟能先被運用而非鍺前驅物脈衝步驟時便能獲得相同結果。
使用類似於實施例1所述的程序及氧化矽和氮化鈦當基材、三氯鍺烷當Ge前驅物及雙(三甲基矽烷基)碲當Te前驅物,經由ALD來沉積GeTe膜。試驗在各循環中依照以下順序進行100個ALD循環:(1)0.1秒的Ge脈衝;(2)20秒的Ar洗淨;(3)各個不同秒數的Te脈衝;及(4)20秒的Ar洗淨。XRF指示該Ge/Te原子比率係1:1。圖2給沉積於該SiO2
和TiN基材上的那些膜提供該GeTe XRF與Te脈衝時間(秒)所作的比較。
使用類似於實施例1所述的程序及氧化矽和氮化鈦當基材、三氯鍺烷當鍺前驅物及叁(三甲基矽烷基)銻當Sb前驅物而非Te前驅物,經由ALD來沉積GS膜。試驗在各循環中依照以下順序進行100個ALD循環:(1)各個不同秒數的鍺前驅物脈衝;(2)30秒的Ar洗淨;(3)3秒的Sb前驅物脈衝;及(4)30秒的Ar洗淨。XRF指示該Ge/Sb原子比率係1:1。圖3給沉積於該SiO2
和TiN基材上的那些膜提供該GeSb XRF與Sb脈衝時間(秒)所作的比較。
使用類似於實施例1所述的程序及氧化矽和氮化鈦當基材、三氯鍺烷當Ge前驅物及叁(三甲基矽烷基)銻當Sb
前驅物而非Te前驅物,經由ALD來沉積GeSb膜。試驗在各循環中依照以下順序進行100個ALD循環:(1)0.1秒的鍺前驅物脈衝;(2)20秒的Ar洗淨;(3)各個不同秒數的Sb前驅物脈衝;及(4)20秒的Ar洗淨。XRF指示該Ge/Sb原子比率係1:1。圖4給沉積於該SiO2
和TiN基材上的那些膜提供該GeSb XRF與Sb脈衝時間(秒)所作的比較。
使用上述程序、氧化矽和氮化鈦二者當基材、三氯鍺烷當鍺前驅物及雙(三甲基矽烷基)碲當Te前驅物。試驗在各循環中依照以下順序進行100個ALD循環:(1)0.1秒的鍺前驅物脈衝;(2)30秒的Ar洗淨;(3)4秒的Te前驅物脈衝;及(4)40秒的Ar洗淨。所得的數據顯示當該溫度範圍從50提高至110℃時GeTe沉積速率降低。圖5給沉積於該SiO2
和TiN基材上的那些膜提供該GeTe XRF與基材溫度(攝氏度)所作的比較。
上述實施例顯示GeTe膜在上述ALD沉積條件之下顯示1:1的組成。將這些前驅物調節至飽和,而且於70℃下的GeTe沉積速率係1.16埃/循環。沉積速率隨著基材溫度的提高逐漸降低。XPS結果顯示該GeTe膜中有非常少的Cl及C雜質。
Ge-Sb-Te三元膜沉積係於6吋晶圓規模的噴灑
頭型ALD反應器(CN-1,Atomic-premium)中於介於50℃至120℃的溫度下使用HGeCl3
當鍺前驅物、Sb(OEt)3
當Sb前驅物及Te(SiMe3
)2
當Te前驅物來沉積。該HGeCl3
藥罐溫度係大約1℃,Sb(OEt)3
藥罐溫度係於40℃,而且Te(SiMe3
)2
藥罐溫度係於40℃。膜組成係由XRF測定。
除了先引進銻前驅物以外,使用類似於實施例1所述的程序及氧化矽和氮化鈦當基材、雙(三甲基矽烷基)碲當Te前驅物及乙氧化銻當Sb前驅物而非鍺前驅物,經由ALD來沉積SbTe膜。聯合SbTe沉積程序及GeTe沉積程序(來自實施例1)能藉由重複a)至d)步驟在程序中使用Sb/Te或Ge/Te前驅物(分別叫做GeTe程序及SbTe程序)來沉積GeSbTe膜。圖6a及6b使用50個ALD循環提供該GeSbTe XRF,該ALD循環由分別在氧化矽基材及氮化鈦基材上的1個GeTe程序及1個SbTe程序組成。全體層密度於該SiO2
基材上係4.31ug cm-2而且於該TiN基材上係4.84ug cm-2。在一個ALD循環中的各程序次數均能調整以改變膜的組成。
使用類似於實施例6所述的程序及氧化矽和氮化鈦當基材、三氯鍺烷當鍺前驅物、乙氧化銻當Sb前驅物及雙(三甲基矽烷基)碲當Te前驅物,來沉積GeSbTe三元膜。在各循環中依照以下順序試驗各個不同數目的循環:(a)3秒的Sb前驅物脈衝;(b)15秒的Ar洗淨;(c)1秒的Te前驅物脈衝;(d)15秒的Ar洗淨;(e)5秒的Ge前驅物脈衝;(f)15秒的
Ar洗淨;(g)1秒的Te前驅物脈衝;及(h)15秒的Ar洗淨。圖7a及7b分別給中沉積於該氧化矽及氮化鈦基材上的那些膜提供該GeSbTe XRF與循環次數所作的比較。藉由該程序,沉積得到Ge:Sb:Te比率為15:35:50的膜。
Claims (20)
- 一種將多成分膜沉積於至少一部分基材上之方法,其包含以下步驟:a)使該基材與包含HGeCl3 的鍺前驅物接觸以與該基材反應並且提供包含Ge的第一塗層;b)引進洗淨氣體以移除任何未反應的鍺前驅物;c)使該包含Ge的第一塗層與Te前驅物接觸,其中至少一部分Te前驅物與彼內所包含的Ge反應以提供包含Ge和Te的第二塗層;d)引進洗淨氣體以移除任何未反應的Te前驅物;e)使該包含Ge和Te的第二塗層與Sb前驅物接觸,其中至少一部分Sb前驅物與至少一部分彼內所包含的Ge和Te反應以提供包含Ge、Te和Sb的第三塗層;f)引進洗淨氣體以移除任何未反應的Sb前驅物;其中步驟(a)至(f)係重複進行以形成許多塗層並且提供該膜。
- 如申請專利範圍第1項之方法,其中該Te前驅物包含選自由以下所組成的群組之矽烷基碲:具有以下通式的二矽烷基碲:(R1 R2 R3 Si)2 Te;具有以下通式的烷基矽烷基碲:(R1 R2 R3 Si)TeR4 ;及其混合物,其中R1 、R2 、R3 及R4 係各自獨立地選自由以下所組成的群組:氫;線性、分支或不飽和C1-10 烷基;C4-10 環烷基;及C4-12 芳香族基團。
- 如申請專利範圍第2項之方法,其中該Te前驅物包含具有下式的二矽烷基碲:(R1 R2 R3 Si)2 Te,其中R1 、R2 及R3 係獨立地選自由以下所組成的群組:氫;線性、分支或不飽和C1-10 烷基;C4-10 環烷基;及C4-12 芳香族基團。
- 如申請專利範圍第3項之方法,其中該Te前驅物包含雙(三甲基矽烷基)碲。
- 如申請專利範圍第1項之方法,其中該Sb前驅物包含選自由以下所組成的群組之化合物:具有一般結構(RO)3 Sb的化合物;具有一般結構(R1 R2 R3 Si)3 Sb的化合物;及具有一般結構(R1 R2 R3 Si)2 R4 Sb的化合物,其中取代基R、R1 、R2 、R3 及R4 係各自獨立地為:氫;線性、分支或不飽和C1-10 烷基;及C4-10 環烷基和C4-12 芳香族基團。
- 如申請專利範圍第1項之方法,其中該Sb前驅物包含具有下式的化合物:SbXn ,其中X係選自由以下所組成的群組的親核性基團:OR(烷氧基)、F(氟)、Cl(氯)、Br(溴)、NR2 (胺基)、CN(氰基)、OCN(氰酸根)、SCN(硫氰酸根)、二酮酸根、羧基及其混合物;n等於Sb的氧化態;而且R係如以上所定義。
- 如申請專利範圍第5項之方法,其中該Sb前驅物包含叁(三甲基矽烷基)銻或Sb(OEt)3 。
- 一種將多成分膜沉積於至少一部分基材上之方法,其包含以下步驟:a)使該基材與包含HGeCl3 的鍺前驅物接觸以與該基材反應並且提供包含Ge的第一塗層;b)引進洗淨氣體以移除任何未反應的鍺前驅物;c)使該包含Ge的第一塗層與Te前驅物接觸,其中至少一部分Te前驅物與彼內所包含的Ge反應以提供包含Ge和Te的第二塗層;及d)引進洗淨氣體以移除任何未反應的Te前驅物;其中步驟(a)至(d)係重複進行以形成許多塗層並且提供該膜。
- 如申請專利範圍第8項之方法,其另外包含:e)使該包含Ge和Te的第二塗層與Sb前驅物接觸,其中至少一部分Sb前驅物與至少一部分彼內所包含的Ge和Te反應以提供包含Ge、Te和Sb的第三塗層;f)引進洗淨氣體以移除任何未反應的Sb前驅物;其中步驟(a)至(f)係重複進行以形成許多塗層並且提供該GST膜。
- 一種將含鍺膜沉積於至少一部分基材上之方法,其包含以下步驟:將該基材提供於反應器中;及 將在足以與該基材反應並且提供該膜的沉積條件之下將包含HGeCl3 的鍺前驅物引進該反應器。
- 如申請專利範圍第10項之方法,其中該方法另外包含將氧來源引進該反應器以與該鍺前驅物反應並且提供氧化鍺膜。
- 如申請專利範圍第11項之方法,其中該等氧來源包含至少一選自由氧(O2 )、氧電漿、臭氧(O3 )、過氧化氫、空氣、一氧化氮、水電漿及水所組成的群組者。
- 如申請專利範圍第10項之方法,其中該方法另外包含將氮來源引進該反應器以與該鍺前驅物反應並且提供氮化鍺膜。
- 如申請專利範圍第13項之方法,其中該氮來源包含至少一選自由氨、氨電漿、氮/氫電漿及氮電漿所組成的群組者。
- 如申請專利範圍第10項之方法,其中該方法另外包含將氫電漿引進該反應器以與該鍺前驅物反應並且提供鍺膜。
- 一種將多成分膜沉積於至少一部分基材上之方法,其包含以下步驟: a)引進Sb前驅物以將包含胺基銻層的Sb層形成於該基材表面上;b)利用惰性氣體洗淨以移除任何反應副產物;c)引進Te前驅物以與該胺基銻層反應而與包含矽烷基的Te層形成Sb-Te;d)利用惰性氣體洗淨以移除任何反應副產物;e)引進包含HGeCl3 的鍺前驅物以與碲層上剩下的矽烷基反應而與包含HGe-Cl基團的Ge層生成Te-Ge鍵;f)利用惰性氣體洗淨;g)引進Te前驅物以與胺基銻層反應而與包含矽烷基的Te層形成Sb-Te;及h)利用惰性氣體洗淨以移除任何反應副產物,其中步驟a)至h)係重複進行以形成許多塗層並且提供GST膜。
- 如申請專利範圍第16項之方法,其中該Te前驅物包含選自由以下所組成的群組之矽烷基碲:具有以下通式的二矽烷基碲:(R1 R2 R3 Si)2 Te;具有以下通式的烷基矽烷基碲:(R1 R2 R3 Si)TeR4 ;及其混合物,其中R1 、R2 、R3 及R4 係各自獨立地選自由以下所組成的群組:氫;線性、分支或不飽和C1-10 烷基;C4-10 環烷基;及C4-12 芳香族基團。
- 如申請專利範圍第17項之方法,其中該Te前驅物包含具有下式的二矽烷基碲:(R1 R2 R3 Si)2 Te,其中R1 、R2 及R3 係獨立地選自由以下所組成的群組:氫;線性、分支或不飽和C1-10 烷基;C4-10 環烷基;及C4-12 芳香族基團。
- 如申請專利範圍第18項之方法,其中該Te前驅物包含雙(三甲基矽烷基)碲。
- 如申請專利範圍第16項之方法,其中該Sb前驅物包含選自由以下所組成的群組之化合物:具有一般結構(RO)3 Sb的化合物;具有一般結構(R1 R2 R3 Si)3 Sb的化合物;及具有一般結構(R1 R2 R3 Si)2 R4 Sb的化合物,其中取代基R、R1 、R2 、R3 及R4 係各自獨立地為:氫;線性、分支或不飽和C1-10 烷基;及C4-10 環烷基和C4-12 芳香族基團。
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JP6371322B2 (ja) | 2018-08-08 |
KR20160073369A (ko) | 2016-06-24 |
US9214630B2 (en) | 2015-12-15 |
JP5902743B2 (ja) | 2016-04-13 |
EP2789712A1 (en) | 2014-10-15 |
TW201447039A (zh) | 2014-12-16 |
KR101634742B1 (ko) | 2016-07-11 |
CN104099578A (zh) | 2014-10-15 |
KR102193609B1 (ko) | 2020-12-21 |
US20140308802A1 (en) | 2014-10-16 |
CN104099578B (zh) | 2018-12-07 |
US9543517B2 (en) | 2017-01-10 |
EP2789712B1 (en) | 2017-01-25 |
JP2016121403A (ja) | 2016-07-07 |
KR20140123451A (ko) | 2014-10-22 |
US20160087207A1 (en) | 2016-03-24 |
JP2015007279A (ja) | 2015-01-15 |
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