TW201402587A - 用於矽基薄膜的低溫ald之矽前驅物 - Google Patents
用於矽基薄膜的低溫ald之矽前驅物 Download PDFInfo
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- TW201402587A TW201402587A TW102118524A TW102118524A TW201402587A TW 201402587 A TW201402587 A TW 201402587A TW 102118524 A TW102118524 A TW 102118524A TW 102118524 A TW102118524 A TW 102118524A TW 201402587 A TW201402587 A TW 201402587A
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- ruthenium
- precursor
- vapor deposition
- film
- substrate
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title abstract description 4
- 229910052710 silicon Inorganic materials 0.000 title abstract description 4
- 239000010703 silicon Substances 0.000 title abstract description 4
- 239000012686 silicon precursor Substances 0.000 title abstract description 4
- 239000010409 thin film Substances 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 114
- 239000000758 substrate Substances 0.000 claims abstract description 48
- 239000000203 mixture Substances 0.000 claims abstract description 38
- 238000000151 deposition Methods 0.000 claims abstract description 37
- 230000008569 process Effects 0.000 claims abstract description 33
- -1 silylene compound Chemical class 0.000 claims abstract description 26
- 238000005019 vapor deposition process Methods 0.000 claims abstract description 19
- 238000004377 microelectronic Methods 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims description 125
- 229910052707 ruthenium Inorganic materials 0.000 claims description 107
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 106
- 229910004129 HfSiO Inorganic materials 0.000 claims description 43
- 239000000463 material Substances 0.000 claims description 38
- 235000007586 terpenes Nutrition 0.000 claims description 30
- 229910052799 carbon Inorganic materials 0.000 claims description 29
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 26
- 238000000231 atomic layer deposition Methods 0.000 claims description 26
- 230000008021 deposition Effects 0.000 claims description 24
- 229910052760 oxygen Inorganic materials 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 239000000376 reactant Substances 0.000 claims description 21
- 238000007740 vapor deposition Methods 0.000 claims description 21
- 238000005229 chemical vapour deposition Methods 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 229910052732 germanium Inorganic materials 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 239000003990 capacitor Substances 0.000 claims description 12
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 11
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 10
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- 239000002184 metal Substances 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 8
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 8
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- PAMLGQLALQWGRO-UHFFFAOYSA-N C1(C=CC2=CC=CC=C12)C(=CCCCCCCCC)C1C=CC2=CC=CC=C12 Chemical compound C1(C=CC2=CC=CC=C12)C(=CCCCCCCCC)C1C=CC2=CC=CC=C12 PAMLGQLALQWGRO-UHFFFAOYSA-N 0.000 claims description 6
- 229910006501 ZrSiO Inorganic materials 0.000 claims description 6
- 230000005669 field effect Effects 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 238000005137 deposition process Methods 0.000 claims description 5
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 5
- GMTCPFCMAHMEMT-UHFFFAOYSA-N n-decyldecan-1-amine Chemical compound CCCCCCCCCCNCCCCCCCCCC GMTCPFCMAHMEMT-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- PQQZKESSPUGDIM-UHFFFAOYSA-N dec-1-ene-1-thiol Chemical compound CCCCCCCCC=CS PQQZKESSPUGDIM-UHFFFAOYSA-N 0.000 claims description 4
- 238000012546 transfer Methods 0.000 claims description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- 150000003973 alkyl amines Chemical class 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- UMHHBNAGKLLAHM-UHFFFAOYSA-N SC(=CCCCCCCCC)S Chemical compound SC(=CCCCCCCCC)S UMHHBNAGKLLAHM-UHFFFAOYSA-N 0.000 claims description 2
- 229910004541 SiN Inorganic materials 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims 2
- 238000000277 atomic layer chemical vapour deposition Methods 0.000 claims 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims 1
- UVLKUUBSZXVVDZ-UHFFFAOYSA-N icos-9-ene Chemical compound CCCCCCCCCCC=CCCCCCCCC UVLKUUBSZXVVDZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052758 niobium Inorganic materials 0.000 claims 1
- 239000010955 niobium Substances 0.000 claims 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims 1
- 238000001947 vapour-phase growth Methods 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 229910052581 Si3N4 Inorganic materials 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 229910003465 moissanite Inorganic materials 0.000 abstract 1
- 229910021426 porous silicon Inorganic materials 0.000 abstract 1
- 150000004760 silicates Chemical class 0.000 abstract 1
- 229910010271 silicon carbide Inorganic materials 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000010408 film Substances 0.000 description 103
- 150000003505 terpenes Chemical class 0.000 description 19
- AEVXUGUHXIUTQU-UHFFFAOYSA-N C=CCCCCCCCC.C(CN)N Chemical compound C=CCCCCCCCC.C(CN)N AEVXUGUHXIUTQU-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000010586 diagram Methods 0.000 description 5
- 238000000113 differential scanning calorimetry Methods 0.000 description 5
- 241000894007 species Species 0.000 description 5
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 3
- WJMXTYZCTXTFJM-UHFFFAOYSA-N 1,1,1,2-tetraethoxydecane Chemical compound C(C)OC(C(OCC)(OCC)OCC)CCCCCCCC WJMXTYZCTXTFJM-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
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- 229910000420 cerium oxide Inorganic materials 0.000 description 2
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- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
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- 125000005358 mercaptoalkyl group Chemical group 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- SSOLNOMRVKKSON-UHFFFAOYSA-N proguanil Chemical compound CC(C)\N=C(/N)N=C(N)NC1=CC=C(Cl)C=C1 SSOLNOMRVKKSON-UHFFFAOYSA-N 0.000 description 2
- 229960005385 proguanil Drugs 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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- 150000003303 ruthenium Chemical class 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
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- 238000006467 substitution reaction Methods 0.000 description 2
- SITVSCPRJNYAGV-UHFFFAOYSA-L tellurite Chemical compound [O-][Te]([O-])=O SITVSCPRJNYAGV-UHFFFAOYSA-L 0.000 description 2
- 125000002298 terpene group Chemical group 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
- 238000002076 thermal analysis method Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 1
- FRGJFERYCDBOQD-UHFFFAOYSA-N 1,1,1,2-tetrachlorodecane Chemical compound CCCCCCCCC(Cl)C(Cl)(Cl)Cl FRGJFERYCDBOQD-UHFFFAOYSA-N 0.000 description 1
- WYDCLGLWAMNKTO-UHFFFAOYSA-N 1-N,1-N,1-N',1-N',1-N",1-N"-hexamethyldecane-1,1,1-triamine Chemical compound CN(C)C(CCCCCCCCC)(N(C)C)N(C)C WYDCLGLWAMNKTO-UHFFFAOYSA-N 0.000 description 1
- YMEKHGLPEFBQCR-UHFFFAOYSA-N 2,2,3,3,5,5-hexachloro-1,4-dioxane Chemical compound ClC1(OC(C(OC1)(Cl)Cl)(Cl)Cl)Cl YMEKHGLPEFBQCR-UHFFFAOYSA-N 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241000219289 Silene Species 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
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- 238000003556 assay Methods 0.000 description 1
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- 150000001555 benzenes Chemical class 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012707 chemical precursor Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
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- 238000000572 ellipsometry Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 150000002290 germanium Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 125000002347 octyl 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])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000012713 reactive precursor Substances 0.000 description 1
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical class [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910003468 tantalcarbide Inorganic materials 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 238000007736 thin film deposition technique Methods 0.000 description 1
- GIRKRMUMWJFNRI-UHFFFAOYSA-N tris(dimethylamino)silicon Chemical compound CN(C)[Si](N(C)C)N(C)C GIRKRMUMWJFNRI-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl 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])[H] 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
- H01L21/28158—Making the insulator
- H01L21/28229—Making the insulator by deposition of a layer, e.g. metal, metal compound or poysilicon, followed by transformation thereof into an insulating layer
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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Abstract
描述了一種矽前驅物組合物,包括選自以下化合物的矽烯(silylene)化合物:下式的矽烯化合物:□其中每個R和R1係獨立選自有機取代基;脒基矽烯;以及雙(脒基)矽烯。該矽烯化合物可用於在微電子元件產品的製造中藉由諸如CVD、脈衝CVD、ALD以及脈衝電漿製程等氣相沉積製程形成高品質、保形的SiO2、Si3N4、SiC以及摻雜的矽酸鹽含矽膜。在一個實施方式中,這樣的矽前驅物可以在氧化劑存在下藉由在孔隙中低溫沉積氧化矽而用於密封包含多孔氧化矽的基板中的孔隙,該低溫沉積之溫度例如在50℃至200℃範圍中的溫度。
Description
本揭示案係關於用於製造微電子元件的矽基膜以及可用於藉由氣相沉積製程沉積該種膜的矽前驅物。
低溫沉積矽基薄膜對於目前半導體元件的製造和製程至關重要。在過去幾十年來,二氧化矽(SiO2)薄膜已被用來作為積體電路(IC)的基本結構部件,包括微處理器、邏輯和記憶體基礎元件。SiO2已經是半導體產業中的主要材料,並且已經被採用來作為幾乎所有已被商業化的矽基元件之絕緣介電材料。多年來SiO2已被用來作為內連線介電質、電容器以及閘極介電材料。
習知用於沉積高純度SiO2膜的產業方法一直是使用四乙氧基矽烷(TEOS)作為用於氣相沉積這種膜的薄膜前驅物。四乙氧基矽烷是一種穩定的液體材料,已被用來在化學氣相沉積(CVD)、電漿增強化學氣相沉積(PECVD)以及原子層沉積(ALD)中作為矽源試劑,以實現高純度的SiO2薄膜。其他的薄膜沉積方法(例如聚焦離子束、電子束以及其他用於形成薄膜的能量工具)也可以使用此矽源試劑來進
行。
隨著IC元件尺寸不斷地減小,以及在微影縮放方法和元件幾何形狀的收縮中相應的進步,新的沉積材料和製程也相應地受到追尋,為的是形成高完整度的SiO2薄膜。需要改良的矽基前驅物(和共反應物)來形成SiO2膜以及其他的含矽薄膜,例如氮化矽(Si3N4)、碳化矽(SiC)以及摻雜的氧化矽(SiOx)高介電常數薄膜,該等含矽薄膜可以在低溫下沉積,例如低於400℃的溫度,而且較佳為低於200℃的溫度。為了實現這些低的沉積溫度,需要能乾淨分解而產出所需膜的化學前驅物。
低溫膜的實現也需要使用和發展能確保形成均勻的保形含矽膜的沉積製程。因此,持續改進和實施化學氣相沉積(CVD)和原子層沉積(ALD)製程,同時持續尋找在處理、汽化和傳輸到反應器中為穩定的、但表現出在低溫下乾淨分解以形成所需薄膜的能力的反應前驅物化合物。在這個努力中最根本的挑戰是實現前驅物熱穩定性和前驅物用於高純度、低溫膜生長製程的適宜性之平衡。
在尋求改良的矽前驅物中,有機矽烷例如四甲氧矽烷(TMOS)、四氯矽烷(TCS)、六氯二矽烷(HCDS)以及三(二甲胺基)矽烷(TDMAS)已經被評估用於ALD沉積SiO2。可以將這種矽前驅物與氧化共反應物(例如O2、O3、N2O、水以及路易斯鹼物種)一起使用來實現SiO2薄膜,或與還原物種(例如H2或NH3)一起使用來實現氮化物薄膜。
本技藝持續尋求用於氣相沉積含矽膜的改良和新化
學品,以用於製造微電子元件。
本揭示案係關於用於藉由氣相沉積製程沉積含矽膜的矽前驅物、使用該前驅物形成的膜以及包括該膜的微電子元件。
在一個態樣中,本揭示案係關於包含矽烯化合物的矽前驅物組合物,該矽烯化合物選自以下化合物:下式的矽烯化合物:
其中每個R和R1係獨立選自有機取代基;脒基矽烯;以及雙(脒基)矽烯。
在另一個態樣中,本揭示係關於一種在基板上形成含矽膜的方法,該方法包含以下步驟:使本揭示案之矽前驅物組合物揮發,以產生相應的前驅物蒸汽,以及使該前驅物蒸汽與該基板在氣相沉積條件下接觸,以在該基板上形成該含矽膜。
在進一步的態樣中,本揭示案係關於一種包含藉由這樣的方法所沉積的含矽膜之微電子元件。
本揭示案之進一步的態樣係關於藉由這樣的方法所沉積的含矽膜。
在進一步的態樣中,本揭示案係關於一種在升溫處
理的過程中保持非晶形氧化鉿或氧化鋯材料之非晶形特性的方法,該方法包含以下步驟:將矽併入來自本揭示案之矽前驅物組合物的該非晶形氧化鉿或氧化鋯材料中。
本揭示案之另一個態樣係關於一種製作電容器的方法,該方法包含以下步驟:形成底部電極;於該底部電極上藉由氣相沉積製程、使用本揭示案之矽前驅物組合物、有機鉿前驅物以及該氣相沉積製程中的含氧介質來沉積HfSiO非晶形膜;以及於該HfSiO非晶形膜上形成頂部電極。
本揭示案之又另一個態樣係關於一種製作鐵電場效電晶體的方法,該方法包含以下步驟:形成包含源極和汲極區的基底;在該基底上沉積與該源極和汲極區接觸的氧化物層;在該氧化物層上藉由氣相沉積製程使用本揭示案之矽前驅物組合物、有機鋯前驅物以及該氣相沉積製程中的含氧介質來形成HfSiO材料;在該HfSiO材料上沉積含金屬層;以及使該HfSiO材料進行退火,以形成鐵電HfSiO材料。
在另一個態樣中,本揭示案係關於一種密封包含多孔氧化矽的基板中之孔隙的方法,該方法包含以下步驟:揮發本揭示之矽前驅物,以產生相應的前驅物蒸汽,並使該前驅物蒸汽在氣相沉積條件下與該基板接觸,該氣相沉積條件包括(i)在從50℃至200℃範圍中的溫度,以及(ii)氧化劑存
在下,以於該基板之該孔隙中沉積氧化矽,而密封該孔隙。
從以下揭示內容及所附申請專利範圍,本發明之其他態樣、特徵以及實施例將會更完全地顯而易見。
10‧‧‧電容器元件
12‧‧‧頂部電極
14‧‧‧HfSiO
16‧‧‧底部電極
20‧‧‧鐵電場效電晶體(FeFET)
22‧‧‧層
24‧‧‧鐵電HfSiO層
26‧‧‧氧化物層
28‧‧‧基底
30‧‧‧源極區
32‧‧‧汲極區
第1圖為雙(N-叔戊基)伸乙二胺矽烯之熱重分析和微差掃描熱量(TG/DSC)數據圖。
第2圖為雙(N-叔戊基)伸乙二胺矽烯之蒸汽壓(單位為托)為溫度倒數(1/T(°K))的函數之圖。
第3圖為藉由原子層沉積(ALD)使用雙(N-叔戊基)伸乙二胺矽烯作為矽前驅物所沉積的氧化矽膜之沉積膜厚度(單位為埃)為沉積膜位置(單位為公分)的函數之圖。
第4圖為雙(N-異丙基)-叔丁基-脒基雙(三甲基矽基)胺基矽烯之熱重分析和微差掃描熱量(TG/DSC)數據圖。
第5圖為使用含矽氧化鉿膜的金屬-絕緣體-金屬(MIM)電容器結構之示意圖示,該含矽氧化鉿膜係使用本揭示案之矽前驅物所形成。
第6圖為併入鐵電HfSiO膜的鐵電場效電晶體(FeFET)之示意圖示,該鐵電HfSiO膜係使用本揭示之矽前驅物所形成。
本揭示案係關於適合使用於低溫氣相沉積製程(例如CVD和ALD)以形成矽基薄膜的矽前驅物。
本文中所使用的術語「膜」係指一層沉積的材料,該材料具有小於1000微米的厚度,例如從該值降低至原子單
層的厚度值。在各種實施例中,在本發明的實施中沉積材料層的膜厚可以例如為低於100微米、10微米或1微米,或在各種薄膜制度中低於200奈米、100奈米或50奈米,視所牽涉的具體應用而定。如本文所用,術語「薄膜」意指厚度低於1微米的材料層。
值得注意的是,如同本文中以及所附申請專利範圍中所使用的,單數形「一」和「該」亦包括複數的指稱物,除非上下文另有清楚指明。
如本文中所使用的,標識的碳數範圍(例如在C1-C12烷基中)意圖包括該範圍內的每個成分碳數部分,所以每個中間碳數及任何其他陳述的或在該陳述範圍中的中間碳數值可被涵蓋,將進一步瞭解的是,在本發明之範圍內,在指定碳數範圍內的碳數子範圍可以被獨立地包含在較小的碳數範圍中,並且具體排除一碳數或多個碳數的碳數範圍係被包括在本發明中,而且排除一或兩個指定範圍之碳數限值的子範圍亦被包括在本發明中。因此,C1-C12烷基意圖包括甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基以及十二烷基,包括該等類型的直鏈和支鏈基團。因此可以理解的是,在本發明的具體實施例中,可廣泛應用於取代基部分的標識碳數範圍(例如C1-C12)使碳數範圍可被進一步局限為在更廣泛規範的取代基部分內具有碳數範圍的部分之子群組。藉由舉例的方式,在本發明的特定實施例中,碳數範圍(例如C1-C12烷基)可以被更限制性地指定,以涵蓋諸如C1-C4烷基、C2-C8烷基、C2-C4烷基、C3-C5烷基
等子範圍或該廣泛碳數範圍內的任何其他子範圍。換句話說,碳數範圍被視為肯定地提出該範圍內的每個碳數物種(以至於該範圍適用的取代基、部分或化合物)作為選擇群組,其中該選擇群組之成員中的特定者可以被選擇,無論是作為連續的碳數子範圍被選擇,或是作為該選擇群組內的特定碳數物種被選擇。
本文中使用的「烷基」包括但不限於甲基、乙基、丙基、異丙基、正丁基、第二丁基、第三丁基、戊基以及異戊基及類似者。本文中使用的「芳基」包括衍生自苯或6至10個碳原子不飽和芳族碳環基團的苯衍生物之烴類。該芳基可以具有單一個或多個環。本文中所使用的術語「芳基」還包括取代的芳基。實例包括但不限於苯基、萘基、二甲苯、苯基乙烷、取代的苯基、取代的萘基、取代的二甲苯、取代的苯基乙烷及類似者。
如同本文中關於特徵、態樣以及特徵和態樣之實施例而多方面提出的揭示內容可以在特定的實施方式中被架構為包含、組成為或基本上組成為一些或所有的該些特徵、態樣和實施例以及被集合來構成該揭示之各種進一步實施方式的元素和部件。本文在各種實施例中描述了該揭示內容,並且參考了各種特徵和態樣。該揭示內容在本說明範圍內的各種排列和組合中構思該些特徵、態樣和實施例。
本揭示案之矽前驅物為下式的矽烯(silylene)化合物:
其中每個R和R1係獨立選自有機取代基,例如H、C1-C12烷基、矽基烷基、矽基醯胺、烷基醯胺、二烷基醯胺或芳基。矽基烷基、烷基醯胺以及二烷基醯胺取代基中的烷基部分可以包括C1-C12烷基取代基,而且芳基取代基可以包括任何適當的芳族取代基,包括例如C6-C15芳基取代基。
上式的矽(II)化合物能夠以低溫化學氣相沉積及/或原子層沉積形成矽基薄膜,例如SiO2和Si3N4。這樣的化合物展現出高揮發性和化學反應性,但相對於在涉及前驅物揮發和產生的前驅物蒸汽輸送到沉積腔室的溫度下的熱降解是穩定的。這些前驅物的化學反應性允許在傳統的矽前驅物材料(例如TEOS)為惰性並因此表現出極少到無的沉積行為的低溫下生長膜。這些前驅物的熱穩定性藉由限制該矽烯在輸送和沉積過程中的不良分解而確保製程穩定性。
本揭示案的矽(II)化合物可以在本技藝內基於本文中的揭示內容而從一般的起始材料以良好的產率輕易合成,並不需過度的努力。在這樣的化合物中,可以變化取代基R和R1,以相對於諸如熔點、熱穩定性及揮發性等性能生產各種可用於氣相沉積(例如ALD或CVD)的相應前驅物。
上述通式之說明性矽前驅物為雙(N-叔戊基)伸乙二胺矽烯(bis(N-t-amyl)ethylenediamine silylene):
將這種化合物的熱分析數據圖示於第1圖中,包括熱重分析和微差掃描熱量(TG/DSC)數據。第1圖中的熱分析圖的微差掃描熱量曲線(DSC曲線)圖示出的熔點為49℃,並且熱重圖(TG圖)圖示出有效熱傳輸的t 50值為162℃(t 50為輸送一半的前驅物材料所對應的溫度)。TG圖也顯示小於1%的殘餘質量。如此低的殘餘質量表示該化合物關於在TG測定溫度下的熱降解是穩定的。
第2圖係雙(N-叔戊基)伸乙二胺矽烯之蒸汽壓(單位為托)為溫度倒數(1/T(°K))的函數之圖。該蒸氣壓係藉由校正的等溫重量損失技術所測定的,而且數據顯示在約82℃蒸氣壓為1托(133.3帕)。
除了前述之外,已經研究出雙(N-叔戊基)伸乙二胺矽烯的熱穩定性是在160℃,而且已經發現當加熱這種前驅物的純樣品24小時時,以質子核磁共振光譜觀察沒有看到該前驅物分解。
第3圖為藉由原子層沉積(ALD)使用雙(N-叔戊基)伸乙二胺矽烯作為矽前驅物所沉積的氧化矽膜之沉積膜厚度(單位為埃)為沉積膜位置(單位為公分)的函數之圖。在橫流式反應器中進行200個ALD循環,且該前驅物由溫度保持在35℃的安瓿供應,並提供30個升壓的劑量/循環。使用20重量%的臭氧作為共反應物。製程涉及第3圖中標識的循環,各在指定的溫度下進行。在溫度為50℃-200℃下,ALD
沉積速率約為0.2Å/循環。厚度係藉由假設SiO2光學性質的光譜橢圓偏振法所量測。
上述內容反映雙(N-叔戊基)伸乙二胺矽烯作為本揭示案的代表性前驅物組合物之優異特性。這樣的化合物可以在82℃和1托(133.3Pa)的壓力下以高通量被輸送到沉積反應器。在49℃以上的輸送溫度和1托(133.3Pa)的壓力下,雙(N-叔戊基)伸乙二胺矽烯在前驅物輸送系統中保持為液體,從而便利前驅物液體的輸送,並避免與固體輸送技術相關的挑戰。此外,這樣的化合物是耐熱分解的,從而藉由限制該矽烯前驅物在輸送和沉積的過程中有不良的分解而確保製程的穩定性。
為了說明上述廣泛分子式之可能前驅物化合物的廣泛範圍,如下所示合成混合配位體的矽烯前驅物(脒基雙-三甲基矽基醯胺)矽烯((amidinate bis-trimethylsilylamide)silylene)。
產品雙(N-異丙基)-叔丁基-脒基雙(三甲基矽基)胺基矽烯(bis(N-i-propyl)-t-butyl-amidinate bis(trimethylsilyl)amido silylene)之熱分析數據圖示於第4圖中,包括熱重分析和微差掃描熱量(TG/DSC)數據。在第4圖的熱分析圖中微差掃描熱量曲線(DSC曲線)顯示43℃
的熔點,並且熱重圖(TG圖)圖示出有效熱傳輸的t 50值為228℃。因此,雙(N-異丙基)-叔丁基-脒基雙(三甲基矽基)胺基矽烯表現出良好的熱穩定性和有效傳輸,特徵為小於1%的殘餘質量。
本揭示案進一步構思下式的雙(脒基)矽烯
其中每個R係獨立選自有機取代基,例如H、C1-C12烷基、矽基烷基、或矽基醯胺、烷基醯胺、二烷基醯胺或芳基。矽基烷基、烷基醯胺以及二烷基醯胺取代基中的烷基部分可以包括C1-C12烷基取代基,而且芳基取代基可以包括任何適當的芳族取代基,包括例如C6-C15芳基取代基。
可以藉由任何適當的氣相沉積技術(包括但不限於CVD、數位CVD、ALD以及脈衝電漿製程)使用本揭示案的矽烯前驅物來沉積高純度的含矽薄膜。可以使用共反應物來沉積特定的薄膜組合物。舉例來說,可以使用水、O2、O3以及N2O來與該矽烯前驅物反應而形成SiO2薄膜。可以使用NH3或烷基胺(例如二異丙基胺)與H2來形成Si3N4膜。可以使用碳源(例如甲烷或乙烷)來形成SiC膜。可以在氧化環境中以涉及摻雜劑物種與矽烯前驅物的共反應來形成摻雜的矽酸鹽高介電常數膜。其他的膜生長共反應物可以由在薄膜形成方法技術領域中具有通常知識者很容易地決定,以形
成其他在本揭示案之範圍內的含矽膜。
可以使用本揭示案之矽烯前驅物來形成保形的含矽膜,該含矽膜例如在微電子元件基板(例如高密度、高性能的積體電路元件)中的高深寬比特徵可能需要的。如此形成的含矽膜可用於需要高品質薄膜的微處理器、邏輯和記憶體元件之製造。另外,這種矽烯前驅物對於低溫沉積的順從性使含矽膜能夠被形成於熱敏基板上,例如在撓性基板應用和在平板顯示器製造中可能會遇到的熱敏基板。
可以將本揭示案的矽烯前驅物使用於固體輸送系統中,例如那些採用固體前驅物汽化器的輸送系統中,該汽化器例如ATMI公司(美國康乃迪克州丹伯里市)在商標ProE-Vap下市售的汽化器。
本揭示案的矽烯前驅物也可以在適當的有機溶劑中溶解,以便利液體輸送該前驅物進入標準的和專用的沉積反應器。
一般來說,矽烯前驅物可以以任何適當的方式被輸送來與微電子元件基板接觸。在液體輸送應用中,使用的溶劑必須與矽烯前驅物相容,並避免在輸送和製程系統中有前驅物的任何有害反應或過早分解。
因此,本揭示案構思包含選自以下化合物的矽烯化合物之矽前驅物組合物:具有下式之矽烯化合物:
其中每個R和R1係獨立選自有機取代基;脒基矽烯;以及雙(脒基)矽烯。
在這樣的矽前驅物組合物中,該矽烯化合物可以包含下式化合物:
其中每個R和R1係獨立選自H、C1-C12烷基、矽基烷基、矽基醯胺、烷基醯胺、二烷基醯胺以及芳基。在一個實施例中,該矽烯化合物包含雙(N-叔戊基)伸乙二胺矽烯。
在另一個實施例中,該矽烯化合物可以包含脒基矽烯,例如雙(N-異丙基)-叔丁基-脒基雙(三甲基矽基)胺基矽烯。
在進一步的實施例中,該矽烯化合物包含雙-脒基矽烯,一種下式之雙(脒基)矽烯
其中每個R係獨立選自有機取代基。在特定的實施例中,每個R係獨立選自H、C1-C12烷基、矽基烷基、矽基醯胺、烷基醯胺、二烷基醯胺以及芳基。
本揭示案亦構思一種在基板上形成含矽膜的方法,該方法包含以下步驟:使本揭示案之矽前驅物組合物揮發,以產生相應的前驅物蒸汽,以及使該前驅物蒸汽與該基板在氣相沉積條件下接觸,以在該基板上形成該含矽膜。該氣相沉積條件可以包含低於400℃的溫度,並且較佳包含在50℃至200℃範圍中的溫度。
以該方法形成的含矽膜可以包含SiO2或Si3N4。該方法中進行的接觸可以在化學氣相沉積製程或原子層沉積製程中進行,而且可以包括液體輸送製程、固體輸送製程或其他適當的輸送方案,藉以將該前驅物蒸汽輸送至反應器系統的沉積腔室。該接觸可以使用共反應物來進行,該共反應物例如含氧共反應物、含氮共反應物或含碳共反應物,該含氧共反應物係選自於由水、O2、O3以及N2O所組成之群組,該含氮共反應物係選自於由NH3及烷基胺/H2混合物所組成之群組,該含碳共反應物係選自於由甲烷及乙烷所組成之群組。
在具體的實施例中,該含矽膜形成方法可以包含以下步驟:摻雜該含矽膜。在各種含矽膜形成方法中,該基板可以包含微電子基板,例如包含高深寬比特徵的微電子基板,該高深寬比特徵上沉積了該含矽膜。
本揭示案進一步構思了包含含矽膜的微電子元件,該含矽膜係藉由本揭示案之方法所沉積,並且本揭示案還構思藉由該方法沉積的含矽膜,例如包含SiO2或Si3N4。
因此,本揭示案提供矽烯前驅物組合物作為低溫沉積高純度的含矽薄膜之來源。該矽烯前驅物組合物可以包含
對稱的或不對稱的烷基取代,並且可以包括混合的配位體。本揭示案之該矽烯前驅物組合物能夠藉由包括CVD、脈衝CVD、ALD以及脈衝電漿製程等技術形成高純度特性的含矽保形薄膜。藉由本揭示案之該前驅物所能夠形成的含矽薄膜包括SiO2、Si3N4、SiC以及摻雜的矽酸鹽等薄膜,例如可用於高介電常數電容器或閘極介電膜。在生產半導體產品、平板顯示器以及太陽能面板中,可以將本揭示案之該含矽膜沉積在聚合物、塑膠或其他基板上。
在各種實施例中,可以在原子層沉積(ALD)、化學氣相沉積(CVD)和脈衝CVD製程中使用本揭示案之矽前驅物來沉積含矽材料,例如沉積包含選自於由SiO、SiN、SiO2、SiON、HfSiO以及ZrSiO所組成之群組的材料之含矽膜。在這樣的製程中,該矽前驅物可以與共反應物一起被引入氣相沉積製程中,該共反應物例如NH3、N2O、NO、O2、H2O、O3、H2O2或類似者。使用本揭示案之矽前驅物的氣相沉積製程可以在低沉積溫度下進行,例如在50℃至400℃範圍中的溫度,較佳是在250℃至380℃範圍中的溫度,仍較佳是在280℃至350℃範圍中的溫度,最佳是在300℃至350℃範圍中的溫度。將理解的是,所沉積含矽材料之性質將會隨著溫度而變化,並且具體的溫度或溫度範圍可以由本技術領域中具有通常知識者基於本文之揭示內容輕易地決定,以實現特定的膜性質。
本揭示案之矽前驅物可用於各種實施例中,以將矽併入HfO2和ZrO2膜中。當在250℃至350℃等級的溫度下
使用ZrCl4和HfCl4作為前驅物並且使用H2O作為共反應物來在半導體表面上形成高介電常數膜而未過度氧化表面時,已經使用SiCl4來併入SiO2,其中需要提高高介電常數膜產物的結晶穩定性,但矽併入製程難以控制,而且在此溫度範圍中難以實現無氯膜的生產。本揭示案之矽前驅物提供了氯矽前驅物之使用替代物,藉以消除使用該種氯矽前驅物形成高介電常數膜所伴隨的缺點,特別是在例如ALD的SiO2氣相沉積製程中。
本文中揭示的矽前驅物也可用於形成矽鉿氧化物鐵電膜,其中少量的矽被併入HfO2膜中。
再者,本揭示之矽前驅物可用於將矽併入氧化鉿或氧化鋯膜中,以保持該膜之非晶形特性。為此目的,藉由以本揭示之矽烯前驅物進行的沉積而將非晶形有效量的矽併入HfO2 or ZrO2中。這樣的矽併入可以例如在原子層沉積製程中利用基板對本揭示案之矽前驅物和有機鉿或有機鋯前驅物(只要適用)與臭氧或其他含氧氣體的循環曝露來進行。本文中將產生的含矽氧化鉿膜或含矽氧化鋯膜分別指定為HfSiO和ZrSiO膜,其中該對應的HfSiO和ZrSiO材料可以具有任何適合其最終使用應用的適當化學計量組成。
因此,本揭示案亦構思將來自前驅物蒸汽的矽併入基板上的HfO2材料以形成HfSiO膜作為含矽膜的方法,其中該前驅物蒸汽係由本揭示案之矽前驅物揮發所形成的。或者,可將來自本揭示案之矽前驅物揮發所形成的前驅物蒸汽之矽併入基板上的ZrO2材料,以形成ZrSiO膜作為該含矽膜。
在具體的實施例中,本揭示案構思一種在升溫處理的過程中保持非晶形氧化鉿或氧化鋯材料之非晶形特性的方法,該方法包含以下步驟:將來自本揭示案之矽前驅物組合物的矽併入該非晶形氧化鉿或氧化鋯材料。
亦構思形成含矽膜的方法,其中氣相沉積條件包含原子層沉積製程的性能,包括沉積來自本揭示案之矽前驅物組合物的矽、沉積來自有機鉿或有機鋯前驅物的鉿或鋯以及曝露於含氧氣體。這種方法中的含氧氣體可以包含臭氧或其他適當的含氧氣體。
作為具體的實例,具有如第5圖所圖示的結構之電容器元件10可以藉由在含氧環境中沉積來自該矽烯前驅物的矽和來自適當有機鉿前驅物的鉿來形成,以在由氮化鈦或其他金屬組合物形成的底部電極16上提供HfSiO 14的非晶形膜。然後可以將由氮化鈦或其他金屬組合物形成的頂部電極12沉積在該HfSiO膜上,以構成包含該非晶形HfSiO膜的金屬-絕緣體-金屬(MIM)電容器結構,然後使該電容器結構進行升溫退火,例如在500℃至1200℃範圍中的溫度下,或更佳為在800℃至1200℃範圍中的溫度下,以在電容器元件產品中產生結晶的Si:HfO膜。
因此提供一種相應的一般化方法來製作電容器,包含以下步驟:形成底部電極;於該底部電極上藉由氣相沉積製程使用本揭示案之矽前驅物組合物、有機鉿前驅物以及該氣相沉積製程中的含氧介質來
沉積HfSiO非晶形膜;以及於該HfSiO非晶形膜上形成頂部電極。
這樣的方法可以進一步包含以下步驟:使該HfSiO非晶形膜進行退火,以實現該HfSiO非晶形膜之結晶。
在另一個應用中,可以使用該矽烯前驅物來形成鐵電場效電晶體(FeFET)20,如第6圖所圖示。這樣的電晶體元件包括基底28,基底28包含源極區30和汲極區32,在基底28上為氧化物層26,例如由二氧化矽(SiO2)形成的氧化物層。在氧化物層26上面的是鐵電HfSiO層24,鐵電HfSiO層24被氮化鈦或其他金屬組合物之層22覆蓋。
在這種FeFET元件的製造中,鐵電HfSiO層24可以藉由氣相沉積製程(例如化學氣相沉積或原子層沉積)使用本揭示案之矽烯前驅物作為矽源化合物與有機鉿前驅物(例如四-二烷基氨基鉿)和臭氧或其他含氧氣體一起形成,以實現鐵電材料層的形成,其中該HfSiO材料係處於鐵電正交晶相(ferroelectric orthorhombic phase)。
前述類型的FeFET元件可以使用於非揮發性記憶體應用,其中該非揮發性記憶體包含多重的這種HfSiO FeFET。這種FeFET中的HfSiO膜可以在3-20nm的等級,含有的矽濃度(當作SiO2量測)可以例如在該HfSiO膜之1-10莫耳百分比SiO2的範圍中。該HfSiO膜可以以非晶相沉積,並且之後接受升溫退火,例如在氮氣環境中,以引發該鐵電正交晶相的結晶和形成,例如在這樣的膜上沉積氮化鈦或其他電極材料之後。
因此,提供一種一般化方法來製作鐵電場效電晶體,該方法包含以下步驟:形成包含源極區和汲極區的基底;在該基底上沉積與該源極區和汲極區接觸的氧化物層;在該氧化物層上藉由氣相沉積製程使用本揭示案之矽前驅物組合物、有機鉿前驅物以及該氣相沉積製程中的含氧介質來形成HfSiO材料;在該HfSiO材料上沉積含金屬層;以及使該HfSiO材料進行退火,以形成鐵電HfSiO材料。
在這樣的方法中,該氧化物層可以包含SiO2,該含金屬層可以包含TiN,該有機鉿前驅物可以包含四-二烷基氨基鉿,該含氧介質可以包含臭氧,以及可以進行退火,以形成包含正交晶相的鐵電HfSiO材料。
在另一個態樣中,可以利用本揭示案之矽烯前驅物來進行元件之多孔氧化矽基板的低溫封孔,該元件包含以銅為基礎的膜,例如元件結構中的銅金屬化。這種用途利用矽烯作為高反應性Si(II)化合物的特性優勢。本揭示案之矽烯前驅物具有適當的揮發性特性,並且可用於該種前驅物可在低溫與活化矽表面反應的沉積製程中,以在該沉積製程在氧化劑(例如臭氧或水)存在下進行時沉積氧化物形式的矽。這樣的氧化物沉積可以例如在非自限的膜生長模式中在50℃到200℃範圍中的溫度下進行,以在低溫下密封多孔矽網絡中的孔隙。此低溫製程係於限制對以銅為基礎的膜造成損害的溫度下進行,該以銅為基礎的膜已經存在於元件結構中,
該元件結構包含上面沉積氧化矽的基板。
因此,本揭示案構思了一種密封包含多孔氧化矽的基板中之孔隙的方法,該方法包含以下步驟:揮發本揭示案之矽前驅物組合物,以產生相應的前驅物蒸汽,並使該前驅物蒸汽在氣相沉積條件下與該基板接觸,該氣相沉積條件包括(i)在50℃至200℃範圍中的溫度,以及(ii)氧化劑存在下,以於該基板之孔隙中沉積氧化矽,而密封該孔隙。在這樣的方法中,該基板可以包含銅,如上所討論的,該銅可受益於孔隙密封製程的低溫特性,並且也可以在該製程中採用如臭氧或水的氧化劑,以使沉積的氧化矽能夠作為基板孔隙中的密封介質。
雖然本文中已經參照具體態樣、特徵和說明性實施例提出了本揭示案,但將理解的是,本揭示案之實用性並未因此受到限制,反而延伸到包括許多其他的變化、修改和替代性實施例,例如在本揭示案所屬技術領域中具有通常知識者基於本文的描述將想到的。相應地,如以下申請專利範圍中所主張的本發明意圖在其精神和範圍內被廣義地推斷和解釋為包括所有這樣的變化、修改以及替代性實施例。
10‧‧‧電容器元件
12‧‧‧頂部電極
14‧‧‧HfSiO
16‧‧‧底部電極
Claims (54)
- 一種矽前驅物組合物,包含一選自以下化合物的矽烯(silylene)化合物:下式的矽烯化合物:
- 如請求項1所述之矽前驅物組合物,其中該矽烯化合物包含一下式化合物
- 如請求項2所述之矽前驅物組合物,其中該矽烯化合物包含雙(N-叔戊基)伸乙二胺矽烯(bis(N-t-amyl)ethylenediamine silylene)。
- 如請求項1所述之矽前驅物組合物,其中該矽烯化合物包含一脒基矽烯。
- 如請求項4所述之矽前驅物組合物,其中該矽烯化合物包含雙(N-異丙基)-叔丁基-脒基雙(三甲基矽基)胺基矽烯(bis(N-i-propyl)-t-butyl-amidinate bis(trimethylsilyl)amido silylene)。
- 如請求項1所述之矽前驅物組合物,其中該矽烯化合物包含一雙-脒基矽烯。
- 如請求項6所述之矽前驅物組合物,其中該雙(脒基)矽烯具有下式
- 如請求項7所述之矽前驅物組合物,其中每個R係獨立選自H、C1-C12烷基、矽基烷基、矽基醯胺、烷基醯胺、二烷基醯胺以及芳基。
- 一種在一基板上形成一含矽膜的方法,該方法包含以下步驟:使依據請求項1至8中任一項之一矽前驅物組合物揮發,以產生相應的前驅物蒸汽,以及使該前驅物蒸汽與該基 板在氣相沉積條件下接觸,以在該基板上形成該含矽膜。
- 如請求項9所述之方法,其中該氣相沉積條件包含低於400℃的溫度。
- 如請求項9所述之方法,其中該氣相沉積條件包含在50℃至200℃範圍中的溫度。
- 如請求項9所述之方法,其中該含矽膜包含SiO2。
- 如請求項9所述之方法,其中該含矽膜包含Si3N4。
- 如請求項9所述之方法,其中該接觸係在一化學氣相沉積製程中進行。
- 如請求項9所述之方法,其中該接觸係在一原子層沉積製程中進行。
- 如請求項9所述之方法,包括一液體輸送製程。
- 如請求項9所述之方法,包括一固體輸送製程。
- 如請求項9所述之方法,其中該接觸之步驟包含以下步驟:與一共反應物接觸。
- 如請求項18所述之方法,其中該共反應物包含一含氧共反應物,該含氧共反應物選自於由水、O2、O3以及N2O所組成之群組。
- 如請求項18所述之方法,其中該共反應物包含一含氮共反應物,該含氮共反應物選自於由NH3及烷基胺/H2混合物所組成之群組。
- 如請求項18所述之方法,其中該共反應物包含一含碳共反應物,該含碳共反應物選自於由甲烷及乙烷所組成之群組。
- 如請求項9所述之方法,進一步包含以下步驟:摻雜該含矽膜。
- 如請求項9所述之方法,其中該基板包含一微電子基板。
- 如請求項23所述之方法,其中該微電子基板包含一高深寬比特徵,該高深寬比特徵上沉積了該含矽膜。
- 一種微電子元件,包含藉由請求項9之方法所沉積的一含矽膜。
- 一種藉由請求項9之方法所沉積的含矽膜。
- 如請求項26所述之含矽膜,其中該含矽膜包含SiO2。
- 如請求項26所述之含矽膜,其中該含矽膜包含Si3N4。
- 如請求項9所述之方法,其中該含矽膜包含選自於由SiO、SiN、SiO2、SiON、HfSiO以及ZrSiO所組成之群組的材料。
- 如請求項9所述之方法,包含一氣相沉積製程,該氣相沉積製程選自於由原子層沉積、化學氣相沉積以及脈衝化學氣相沉積所組成之群組。
- 如請求項9所述之方法,其中該等氣相沉積條件包含使用一共反應物,該共反應物選自於由NH3、N2O、NO、O2、H2O、O3以及H2O2所組成之群組。
- 如請求項9所述之方法,其中該氣相沉積條件包含在一從50℃至400℃的範圍中的沉積溫度。
- 如請求項9所述之方法,其中該氣相沉積條件包含在一從250℃至380℃的範圍中的沉積溫度。
- 如請求項9所述之方法,其中該氣相沉積條件包含在一 從280℃至350℃的範圍中的沉積溫度。
- 如請求項9所述之方法,其中該氣相沉積條件包含在一從300℃至350℃的範圍中的沉積溫度。
- 如請求項9所述之方法,其中將來自該前驅物蒸汽的矽併入該基板上的HfO2材料中,以形成一HfSiO膜作為該含矽膜。
- 如請求項9所述之方法,其中將來自該前驅物蒸汽的矽併入該基板上的ZrO2材料中,以形成一ZrSiO膜作為該含矽膜。
- 如請求項9所述之方法,其中該氣相沉積條件包含一原子層沉積製程之性能,包括沉積來自請求項1之一矽前驅物組合物的矽、沉積來自一有機鉿或有機鋯前驅物的鉿或鋯以及曝露於一含氧氣體。
- 如請求項38所述之方法,其中該含氧氣體包含臭氧。
- 一種在升溫處理的過程中保持一非晶形氧化鉿或氧化鋯材料之非晶形特性的方法,該方法包含以下步驟:將矽併入來自請求項1之一矽前驅物組合物的該非晶形氧化鉿或氧化鋯材料中。
- 一種製作一電容器的方法,該方法包含以下步驟:形成一底部電極;於該底部電極上藉由一氣相沉積製程、使用請求項1之一矽前驅物組合物、一有機鉿前驅物以及該氣相沉積製程中的一含氧介質來沉積一HfSiO非晶形膜;以及於該HfSiO非晶形膜上形成一頂部電極。
- 如請求項41所述之方法,進一步包含以下步驟:使該HfSiO非晶形膜進行退火,以實現該HfSiO非晶形膜之結晶。
- 如請求項42所述之方法,其中該退火係在一從500℃至1200℃的範圍中的溫度下進行。
- 如請求項42所述之方法,其中該退火係在一從800℃至1200℃的範圍中的溫度下進行。
- 一種製作一鐵電場效電晶體的方法,該方法包含以下步驟:形成一基底,該基底包含源極區和汲極區;在該基底上沉積與該源極區和汲極區接觸的一氧化物層;在該氧化物層上藉由一氣相沉積製程使用請求項1之一矽前驅物組合物、一有機鉿前驅物以及該氣相沉積製程中的 一含氧介質來形成一HfSiO材料;在該HfSiO材料上沉積一含金屬層;以及使該HfSiO材料進行退火,以形成鐵電HfSiO材料。
- 如請求項45所述之方法,其中該氧化物層包含SiO2。
- 如請求項45所述之方法,其中該含金屬層包含TiN。
- 如請求項45所述之方法,其中該有機鉿前驅物包含四-二烷基氨基鉿。
- 如請求項45所述之方法,其中該含氧介質包含臭氧。
- 如請求項45所述之方法,其中進行該退火以形成包含一正交晶相的該鐵電HfSiO材料。
- 一種密封包含多孔氧化矽的一基板中之孔隙的方法,該方法包含以下步驟:揮發依據請求項1至8中任一項之一矽前驅物組合物,以產生相應的前驅物蒸汽,並使該前驅物蒸汽在氣相沉積條件下與該基板接觸,該氣相沉積條件包括(i)在一從50℃至200℃的一範圍中的溫度,以及(ii)氧化劑存在下,以於該基板之該孔隙中沉積氧化矽,而密封該孔隙。
- 如請求項51所述之方法,其中一包含銅的元件結構包含 該基板。
- 如請求項51所述之方法,其中該氧化劑包含水。
- 如請求項51所述之方法,其中該氧化劑包含臭氧。
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104911561A (zh) * | 2015-04-14 | 2015-09-16 | 中国计量科学研究院 | 制备高厚度均匀性纳米/亚微米SiO2薄膜的方法 |
CN110326111A (zh) * | 2017-01-20 | 2019-10-11 | 李卫民 | 铁电氧化物存储器器件 |
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Families Citing this family (17)
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---|---|---|---|---|
KR101875183B1 (ko) | 2014-06-11 | 2018-07-06 | (주)디엔에프 | 신규한 아미노실릴아민 화합물 및 원자층 증착법을 이용한 Si-N 결합을 포함하는 절연막의 제조방법 |
WO2015190749A1 (en) * | 2014-06-11 | 2015-12-17 | Dnf Co., Ltd. | Novel amino-silyl amine compound and the manufacturing method of dielectric film containing si-n bond by using atomic layer deposition |
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US10570513B2 (en) * | 2014-12-13 | 2020-02-25 | American Air Liquide, Inc. | Organosilane precursors for ALD/CVD silicon-containing film applications and methods of using the same |
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WO2016178991A1 (en) | 2015-05-02 | 2016-11-10 | Applied Materials, Inc. | Methods for depositing low k and low wet etch rate dielectric thin films |
DE102016203082A1 (de) * | 2016-02-26 | 2017-08-31 | Wacker Chemie Ag | Verfahren zur Abscheidung einer In Situ-Beschichtung auf thermisch und chemisch beanspruchten Bauteilen eines Wirbelschichtreaktors zur Herstellung von hochreinem Polysilicium |
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US11492364B2 (en) | 2020-03-31 | 2022-11-08 | Entegris, Inc. | Silicon hydrazido precursor compounds |
KR20220027026A (ko) * | 2020-08-26 | 2022-03-07 | 에이에스엠 아이피 홀딩 비.브이. | 금속 실리콘 산화물 및 금속 실리콘 산질화물 층을 형성하기 위한 방법 및 시스템 |
CN114975113B (zh) * | 2022-04-25 | 2022-12-13 | 上海陛通半导体能源科技股份有限公司 | 形成氧化硅和氮化硅复合薄膜的方法 |
Family Cites Families (178)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SU768457A1 (ru) | 1976-01-04 | 1980-10-07 | Всесоюзный научно-исследовательский и проектно-конструкторский институт добычи угля гидравлическим способом | Катализатор дл очистки выхлопных газов от окислов азота |
US4948623A (en) | 1987-06-30 | 1990-08-14 | International Business Machines Corporation | Method of chemical vapor deposition of copper, silver, and gold using a cyclopentadienyl/metal complex |
US4962214A (en) | 1988-05-11 | 1990-10-09 | Massachusettes Institute Of Technology | Catalytic enantioselective addition of hydrocarbon equivalents to alpha, beta-unsaturated carbonyl compounds |
US4915988A (en) | 1988-06-22 | 1990-04-10 | Georgia Tech Research Corporation | Chemical vapor deposition of group IIA metals and precursors therefor |
US4927670A (en) | 1988-06-22 | 1990-05-22 | Georgia Tech Research Corporation | Chemical vapor deposition of mixed metal oxide coatings |
JPH02225317A (ja) | 1989-02-23 | 1990-09-07 | Asahi Glass Co Ltd | 化学的気相蒸着法による酸化物超伝導体の製造方法 |
US5204057A (en) | 1989-07-14 | 1993-04-20 | Kabushiki Kaisha Toshiba | Highly purified titanium material and its named article, a sputtering target |
US4960916A (en) | 1989-09-29 | 1990-10-02 | United States Of America As Represented By The Secretary Of The Navy | Organometallic antimony compounds useful in chemical vapor deposition processes |
US5820664A (en) | 1990-07-06 | 1998-10-13 | Advanced Technology Materials, Inc. | Precursor compositions for chemical vapor deposition, and ligand exchange resistant metal-organic precursor solutions comprising same |
US5362328A (en) | 1990-07-06 | 1994-11-08 | Advanced Technology Materials, Inc. | Apparatus and method for delivering reagents in vapor form to a CVD reactor, incorporating a cleaning subsystem |
US6511706B1 (en) | 1990-07-06 | 2003-01-28 | Advanced Technology Materials, Inc. | MOCVD of SBT using tetrahydrofuran-based solvent system for precursor delivery |
US6111124A (en) | 1997-10-30 | 2000-08-29 | Advanced Technology Materials, Inc. | Lewis base adducts of anhydrous mononuclear tris(β-diketonate) bismuth compositions for deposition of bismuth-containing films, and method of making the same |
US5280012A (en) | 1990-07-06 | 1994-01-18 | Advanced Technology Materials Inc. | Method of forming a superconducting oxide layer by MOCVD |
US5453494A (en) | 1990-07-06 | 1995-09-26 | Advanced Technology Materials, Inc. | Metal complex source reagents for MOCVD |
US5711816A (en) | 1990-07-06 | 1998-01-27 | Advanced Technolgy Materials, Inc. | Source reagent liquid delivery apparatus, and chemical vapor deposition system comprising same |
US5204314A (en) | 1990-07-06 | 1993-04-20 | Advanced Technology Materials, Inc. | Method for delivering an involatile reagent in vapor form to a CVD reactor |
US6110529A (en) | 1990-07-06 | 2000-08-29 | Advanced Tech Materials | Method of forming metal films on a substrate by chemical vapor deposition |
US5225561A (en) | 1990-07-06 | 1993-07-06 | Advanced Technology Materials, Inc. | Source reagent compounds for MOCVD of refractory films containing group IIA elements |
US6218518B1 (en) | 1990-07-06 | 2001-04-17 | Advanced Technology Materials, Inc. | Tetrahydrofuran-adducted group II β-diketonate complexes as source reagents for chemical vapor deposition |
US5840897A (en) | 1990-07-06 | 1998-11-24 | Advanced Technology Materials, Inc. | Metal complex source reagents for chemical vapor deposition |
US6110531A (en) | 1991-02-25 | 2000-08-29 | Symetrix Corporation | Method and apparatus for preparing integrated circuit thin films by chemical vapor deposition |
FR2678621A1 (fr) | 1991-07-02 | 1993-01-08 | Atochem | Procede de preparation de ceramiques en nitrure de bore et de leurs precurseurs a partir de derives de l'hydrazine et les precurseurs ainsi mis en óoeuvre. |
US5204141A (en) | 1991-09-18 | 1993-04-20 | Air Products And Chemicals, Inc. | Deposition of silicon dioxide films at temperatures as low as 100 degree c. by lpcvd using organodisilane sources |
FR2693204A1 (fr) | 1992-08-27 | 1994-01-07 | Atochem Elf Sa | Procédé de préparation en milieu solvant de polysilylhydrazines. |
JP2799134B2 (ja) | 1992-09-22 | 1998-09-17 | 三菱電機株式会社 | チタン酸バリウムストロンチウム系誘電体薄膜用cvd原料およびメモリー用キャパシタ |
US20030152813A1 (en) | 1992-10-23 | 2003-08-14 | Symetrix Corporation | Lanthanide series layered superlattice materials for integrated circuit appalications |
US5424095A (en) | 1994-03-07 | 1995-06-13 | Eniricerche S.P.A. | Ceramic vapor deposited coating using a steam-containing carrier gas and non-alkoxy silane precursors |
JP3547471B2 (ja) | 1994-03-09 | 2004-07-28 | 富士通株式会社 | 誘電体膜の気相成長方法 |
JPH0770747A (ja) | 1994-04-06 | 1995-03-14 | Mitsubishi Materials Corp | 高純度誘電体薄膜形成用ターゲット材 |
JPH07335753A (ja) | 1994-06-06 | 1995-12-22 | Sharp Corp | 半導体装置及びその製造方法 |
JPH0822986A (ja) | 1994-07-05 | 1996-01-23 | Sony Corp | 絶縁膜の成膜方法 |
JP3282769B2 (ja) | 1994-07-12 | 2002-05-20 | ソニー株式会社 | 半導体装置の製造方法 |
US5837417A (en) | 1994-12-30 | 1998-11-17 | Clariant Finance (Bvi) Limited | Quinone diazide compositions containing low metals p-cresol oligomers and process of producing the composition |
TW285753B (zh) | 1995-01-04 | 1996-09-11 | Air Prod & Chem | |
US5919522A (en) | 1995-03-31 | 1999-07-06 | Advanced Technology Materials, Inc. | Growth of BaSrTiO3 using polyamine-based precursors |
JP3339554B2 (ja) | 1995-12-15 | 2002-10-28 | 松下電器産業株式会社 | プラズマディスプレイパネル及びその製造方法 |
US5866471A (en) * | 1995-12-26 | 1999-02-02 | Kabushiki Kaisha Toshiba | Method of forming semiconductor thin film and method of fabricating solar cell |
EP0902019A4 (en) | 1996-05-16 | 2002-03-27 | Nissan Chemical Ind Ltd | METHOD FOR PRODUCING PYRIMIDINE COMPOUNDS |
US5939333A (en) | 1996-05-30 | 1999-08-17 | Micron Technology, Inc. | Silicon nitride deposition method |
DE69704558T2 (de) | 1996-06-06 | 2001-09-13 | Clariant Finance Bvi Ltd | Metallionenreduzierung von aminoaromatischen chromophonen und ihre verwendung zur herstellung von antireflexunterschichten mit geringem gehalt an metallionen für photoresiste |
JPH10273779A (ja) | 1997-03-28 | 1998-10-13 | Nippon Sanso Kk | Cvd装置 |
US6024847A (en) | 1997-04-30 | 2000-02-15 | The Alta Group, Inc. | Apparatus for producing titanium crystal and titanium |
US6002036A (en) | 1997-07-17 | 1999-12-14 | Kabushikikaisha Kojundokagaku Kenkyusho | Process for producing bis(alkyl-cyclopentadienyl)ruthenium complexes and process for producing ruthenium-containing films by using the same |
US6177558B1 (en) | 1997-11-13 | 2001-01-23 | Protogene Laboratories, Inc. | Method and composition for chemical synthesis using high boiling point organic solvents to control evaporation |
US6277436B1 (en) | 1997-11-26 | 2001-08-21 | Advanced Technology Materials, Inc. | Liquid delivery MOCVD process for deposition of high frequency dielectric materials |
US6787186B1 (en) | 1997-12-18 | 2004-09-07 | Advanced Technology Materials, Inc. | Method of controlled chemical vapor deposition of a metal oxide ceramic layer |
US6383955B1 (en) | 1998-02-05 | 2002-05-07 | Asm Japan K.K. | Silicone polymer insulation film on semiconductor substrate and method for forming the film |
US6111122A (en) | 1998-04-28 | 2000-08-29 | Advanced Technology Materials, Inc. | Group II MOCVD source reagents, and method of forming Group II metal-containing films utilizing same |
JP2000080476A (ja) | 1998-06-26 | 2000-03-21 | Toshiba Corp | 気相成長方法および気相成長装置およびハロゲン化アンモニウム除去装置 |
US6365231B2 (en) | 1998-06-26 | 2002-04-02 | Kabushiki Kaisha Toshiba | Ammonium halide eliminator, chemical vapor deposition system and chemical vapor deposition process |
US7098163B2 (en) | 1998-08-27 | 2006-08-29 | Cabot Corporation | Method of producing membrane electrode assemblies for use in proton exchange membrane and direct methanol fuel cells |
FI108375B (fi) | 1998-09-11 | 2002-01-15 | Asm Microchemistry Oy | Menetelmõ eristõvien oksidiohutkalvojen valmistamiseksi |
US6297539B1 (en) | 1999-07-19 | 2001-10-02 | Sharp Laboratories Of America, Inc. | Doped zirconia, or zirconia-like, dielectric film transistor structure and deposition method for same |
US6013235A (en) | 1999-07-19 | 2000-01-11 | Dow Corning Corporation | Conversion of direct process high-boiling residue to monosilanes |
KR100306397B1 (ko) | 1999-12-15 | 2001-10-17 | 김응수 | 산화알미늄과 산화탄탈륨의 연속적 증착방법 |
GB0004852D0 (en) | 2000-02-29 | 2000-04-19 | Unilever Plc | Ligand and complex for catalytically bleaching a substrate |
WO2001066832A2 (en) | 2000-03-07 | 2001-09-13 | Asm America, Inc. | Graded thin films |
US6562678B1 (en) | 2000-03-07 | 2003-05-13 | Symetrix Corporation | Chemical vapor deposition process for fabricating layered superlattice materials |
KR20010088207A (ko) | 2000-03-11 | 2001-09-26 | 윤종용 | 탄탈륨산화막-티타늄산화막 복합유전막 형성방법 |
US6984591B1 (en) | 2000-04-20 | 2006-01-10 | International Business Machines Corporation | Precursor source mixtures |
US6630413B2 (en) | 2000-04-28 | 2003-10-07 | Asm Japan K.K. | CVD syntheses of silicon nitride materials |
US6342445B1 (en) | 2000-05-15 | 2002-01-29 | Micron Technology, Inc. | Method for fabricating an SrRuO3 film |
JP4621333B2 (ja) | 2000-06-01 | 2011-01-26 | ホーチキ株式会社 | 薄膜形成方法 |
US6440495B1 (en) | 2000-08-03 | 2002-08-27 | Applied Materials, Inc. | Chemical vapor deposition of ruthenium films for metal electrode applications |
JP5290488B2 (ja) * | 2000-09-28 | 2013-09-18 | プレジデント アンド フェロウズ オブ ハーバード カレッジ | 酸化物、ケイ酸塩及びリン酸塩の気相成長 |
US6660660B2 (en) | 2000-10-10 | 2003-12-09 | Asm International, Nv. | Methods for making a dielectric stack in an integrated circuit |
US20020090815A1 (en) | 2000-10-31 | 2002-07-11 | Atsushi Koike | Method for forming a deposited film by plasma chemical vapor deposition |
US6599447B2 (en) | 2000-11-29 | 2003-07-29 | Advanced Technology Materials, Inc. | Zirconium-doped BST materials and MOCVD process forming same |
EP1211333A3 (en) | 2000-12-01 | 2003-07-30 | Japan Pionics Co., Ltd. | Vaporizer for CVD apparatus |
US6464779B1 (en) | 2001-01-19 | 2002-10-15 | Novellus Systems, Inc. | Copper atomic layer chemical vapor desposition |
US7371633B2 (en) | 2001-02-02 | 2008-05-13 | Samsung Electronics Co., Ltd. | Dielectric layer for semiconductor device and method of manufacturing the same |
KR100434489B1 (ko) | 2001-03-22 | 2004-06-05 | 삼성전자주식회사 | 루테늄 산화막 씨딩층을 포함하는 루테늄막 증착 방법 |
JP2002285333A (ja) | 2001-03-26 | 2002-10-03 | Hitachi Ltd | 半導体装置の製造方法 |
US7005392B2 (en) | 2001-03-30 | 2006-02-28 | Advanced Technology Materials, Inc. | Source reagent compositions for CVD formation of gate dielectric thin films using amide precursors and method of using same |
US6479100B2 (en) | 2001-04-05 | 2002-11-12 | Applied Materials, Inc. | CVD ruthenium seed for CVD ruthenium deposition |
US6669990B2 (en) | 2001-06-25 | 2003-12-30 | Samsung Electronics Co., Ltd. | Atomic layer deposition method using a novel group IV metal precursor |
US20030020122A1 (en) | 2001-07-24 | 2003-01-30 | Joo Jae Hyun | Methods of forming integrated circuit electrodes and capacitors by wrinkling a layer that includes a noble metal oxide, and integrated circuit electrodes and capacitors fabricated thereby |
JP4921652B2 (ja) | 2001-08-03 | 2012-04-25 | エイエスエム インターナショナル エヌ.ヴェー. | イットリウム酸化物およびランタン酸化物薄膜を堆積する方法 |
KR100416602B1 (ko) | 2001-08-08 | 2004-02-05 | 삼성전자주식회사 | 스택형 캐패시터의 제조 방법 |
US7701130B2 (en) | 2001-08-24 | 2010-04-20 | Semiconductor Energy Laboratory Co., Ltd. | Luminous device with conductive film |
US6605549B2 (en) | 2001-09-29 | 2003-08-12 | Intel Corporation | Method for improving nucleation and adhesion of CVD and ALD films deposited onto low-dielectric-constant dielectrics |
JP4021653B2 (ja) | 2001-11-30 | 2007-12-12 | レール・リキード−ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード | Cvd法によるシリコン窒化物膜またはシリコンオキシ窒化物膜の製造方法 |
JP4116283B2 (ja) | 2001-11-30 | 2008-07-09 | レール・リキード−ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード | ヘキサキス(モノヒドロカルビルアミノ)ジシランおよびその製造方法 |
KR100443350B1 (ko) | 2001-12-29 | 2004-08-09 | 주식회사 하이닉스반도체 | 스트론튬루테늄산화물의 단원자층 증착 방법 |
US6824816B2 (en) | 2002-01-29 | 2004-11-30 | Asm International N.V. | Process for producing metal thin films by ALD |
US7060330B2 (en) | 2002-05-08 | 2006-06-13 | Applied Materials, Inc. | Method for forming ultra low k films using electron beam |
US7300038B2 (en) | 2002-07-23 | 2007-11-27 | Advanced Technology Materials, Inc. | Method and apparatus to help promote contact of gas with vaporized material |
US6960538B2 (en) | 2002-08-21 | 2005-11-01 | Micron Technology, Inc. | Composite dielectric forming methods and composite dielectrics |
US6730164B2 (en) | 2002-08-28 | 2004-05-04 | Micron Technology, Inc. | Systems and methods for forming strontium- and/or barium-containing layers |
US7132723B2 (en) | 2002-11-14 | 2006-11-07 | Raytheon Company | Micro electro-mechanical system device with piezoelectric thin film actuator |
US7446217B2 (en) | 2002-11-14 | 2008-11-04 | Advanced Technology Materials, Inc. | Composition and method for low temperature deposition of silicon-containing films |
US7531679B2 (en) * | 2002-11-14 | 2009-05-12 | Advanced Technology Materials, Inc. | Composition and method for low temperature deposition of silicon-containing films such as films including silicon nitride, silicon dioxide and/or silicon-oxynitride |
KR102220703B1 (ko) | 2002-11-15 | 2021-02-26 | 프레지던트 앤드 펠로우즈 오브 하바드 칼리지 | 금속 아미디네이트를 이용한 원자층 증착법 |
US7172792B2 (en) | 2002-12-20 | 2007-02-06 | Applied Materials, Inc. | Method for forming a high quality low temperature silicon nitride film |
US7972663B2 (en) | 2002-12-20 | 2011-07-05 | Applied Materials, Inc. | Method and apparatus for forming a high quality low temperature silicon nitride layer |
US6989457B2 (en) | 2003-01-16 | 2006-01-24 | Advanced Technology Materials, Inc. | Chemical vapor deposition precursors for deposition of tantalum-based materials |
US7122222B2 (en) | 2003-01-23 | 2006-10-17 | Air Products And Chemicals, Inc. | Precursors for depositing silicon containing films and processes thereof |
US7396862B2 (en) | 2003-02-06 | 2008-07-08 | Weimer Alan W | Dental composite filler particles |
KR100505674B1 (ko) | 2003-02-26 | 2005-08-03 | 삼성전자주식회사 | 루테늄 박막을 제조하는 방법 및 이를 이용한 mim캐패시터의 제조방법 |
US6794764B1 (en) | 2003-03-05 | 2004-09-21 | Advanced Micro Devices, Inc. | Charge-trapping memory arrays resistant to damage from contact hole information |
JP2004300152A (ja) | 2003-03-20 | 2004-10-28 | Mitsubishi Materials Corp | 有機金属化合物の製造方法並びに該化合物により得られた金属含有薄膜 |
US7135369B2 (en) | 2003-03-31 | 2006-11-14 | Micron Technology, Inc. | Atomic layer deposited ZrAlxOy dielectric layers including Zr4AlO9 |
US6737313B1 (en) | 2003-04-16 | 2004-05-18 | Micron Technology, Inc. | Surface treatment of an oxide layer to enhance adhesion of a ruthenium metal layer |
KR20040100766A (ko) | 2003-05-24 | 2004-12-02 | 삼성전자주식회사 | 원자층 증착법을 이용한 복합 유전막의 연속 형성방법 및이를 이용한 캐패시터의 제조방법 |
WO2004113585A2 (en) | 2003-06-18 | 2004-12-29 | Applied Materials, Inc. | Atomic layer deposition of barrier materials |
US7138332B2 (en) | 2003-07-09 | 2006-11-21 | Asm Japan K.K. | Method of forming silicon carbide films |
JP4312006B2 (ja) | 2003-08-25 | 2009-08-12 | 株式会社Adeka | 希土類金属錯体、薄膜形成用原料及び薄膜の製造方法 |
US7579496B2 (en) | 2003-10-10 | 2009-08-25 | Advanced Technology Materials, Inc. | Monosilane or disilane derivatives and method for low temperature deposition of silicon-containing films using the same |
US7601860B2 (en) | 2003-10-10 | 2009-10-13 | Advanced Technology Materials, Inc. | Composition and method for low temperature chemical vapor deposition of silicon-containing films including silicon carbonitride and silicon oxycarbonitride films |
US6960675B2 (en) * | 2003-10-14 | 2005-11-01 | Advanced Technology Materials, Inc. | Tantalum amide complexes for depositing tantalum-containing films, and method of making same |
US7285308B2 (en) | 2004-02-23 | 2007-10-23 | Advanced Technology Materials, Inc. | Chemical vapor deposition of high conductivity, adherent thin films of ruthenium |
US7005665B2 (en) | 2004-03-18 | 2006-02-28 | International Business Machines Corporation | Phase change memory cell on silicon-on insulator substrate |
US7584942B2 (en) | 2004-03-31 | 2009-09-08 | Micron Technology, Inc. | Ampoules for producing a reaction gas and systems for depositing materials onto microfeature workpieces in reaction chambers |
US7211509B1 (en) | 2004-06-14 | 2007-05-01 | Novellus Systems, Inc, | Method for enhancing the nucleation and morphology of ruthenium films on dielectric substrates using amine containing compounds |
WO2006012052A2 (en) | 2004-06-25 | 2006-02-02 | Arkema, Inc. | Amidinate ligand containing chemical vapor deposition precursors |
KR100642635B1 (ko) | 2004-07-06 | 2006-11-10 | 삼성전자주식회사 | 하이브리드 유전체막을 갖는 반도체 집적회로 소자들 및그 제조방법들 |
JP2006037123A (ja) | 2004-07-22 | 2006-02-09 | Toyoshima Seisakusho:Kk | 薄膜用cvd原料及びそれを用いて得られる薄膜 |
KR100632948B1 (ko) | 2004-08-06 | 2006-10-11 | 삼성전자주식회사 | 칼코겐화합물 스퍼터링 형성 방법 및 이를 이용한 상변화 기억 소자 형성 방법 |
US7300873B2 (en) | 2004-08-13 | 2007-11-27 | Micron Technology, Inc. | Systems and methods for forming metal-containing layers using vapor deposition processes |
US7250367B2 (en) | 2004-09-01 | 2007-07-31 | Micron Technology, Inc. | Deposition methods using heteroleptic precursors |
KR100652378B1 (ko) | 2004-09-08 | 2006-12-01 | 삼성전자주식회사 | 안티몬 프리커서 및 이를 이용한 상변화 메모리 소자의 제조방법 |
ZA200702593B (en) | 2004-09-29 | 2008-09-25 | Umicore Nv | Process for the production of Ge by reduction of GeCl4 with liquid metal |
US7390360B2 (en) | 2004-10-05 | 2008-06-24 | Rohm And Haas Electronic Materials Llc | Organometallic compounds |
US7518179B2 (en) | 2004-10-08 | 2009-04-14 | Freescale Semiconductor, Inc. | Virtual ground memory array and method therefor |
KR100889362B1 (ko) | 2004-10-19 | 2009-03-18 | 삼성전자주식회사 | 다층 유전체막으로 이루어진 트랜지스터 및 그 제조 방법 |
US7435679B2 (en) | 2004-12-07 | 2008-10-14 | Intel Corporation | Alloyed underlayer for microelectronic interconnects |
US7429402B2 (en) | 2004-12-10 | 2008-09-30 | Applied Materials, Inc. | Ruthenium as an underlayer for tungsten film deposition |
KR100618879B1 (ko) | 2004-12-27 | 2006-09-01 | 삼성전자주식회사 | 게르마늄 전구체, 이를 이용하여 형성된 gst 박막,상기 박막의 제조 방법 및 상변화 메모리 소자 |
US20060172067A1 (en) | 2005-01-28 | 2006-08-03 | Energy Conversion Devices, Inc | Chemical vapor deposition of chalcogenide materials |
KR100585175B1 (ko) | 2005-01-31 | 2006-05-30 | 삼성전자주식회사 | 화학 기상 증착법에 의한 GeSbTe 박막의 제조방법 |
US7508648B2 (en) | 2005-02-08 | 2009-03-24 | Micron Technology, Inc. | Atomic layer deposition of Dy doped HfO2 films as gate dielectrics |
KR100688532B1 (ko) | 2005-02-14 | 2007-03-02 | 삼성전자주식회사 | 텔루르 전구체, 이를 이용하여 제조된 Te-함유 칼코게나이드(chalcogenide) 박막, 상기 박막의 제조방법 및 상변화 메모리 소자 |
KR20060097807A (ko) | 2005-03-07 | 2006-09-18 | 삼성전자주식회사 | 표면처리된 복합 유전막을 갖는 반도체 장치의 제조 방법 |
KR100674848B1 (ko) | 2005-04-01 | 2007-01-26 | 삼성전기주식회사 | 고유전율 금속-세라믹-폴리머 복합 유전체 및 이를 이용한임베디드 커패시터의 제조 방법 |
US7390756B2 (en) | 2005-04-28 | 2008-06-24 | Micron Technology, Inc. | Atomic layer deposited zirconium silicon oxide films |
US20090136658A1 (en) | 2005-06-10 | 2009-05-28 | Atsuya Yoshinaka | Niobium 2-Ethylhexanoate Derivative, Method Of Producing The Derivative, Organic Acid Metal Salt Composition Containing The Derivative, And Method Of Producing Thin Film Using The Composition |
KR100724566B1 (ko) | 2005-07-29 | 2007-06-04 | 삼성전자주식회사 | 다층구조의 게이트 층간 유전막을 갖는 플래시 메모리 소자및 그 제조방법들 |
US7393736B2 (en) | 2005-08-29 | 2008-07-01 | Micron Technology, Inc. | Atomic layer deposition of Zrx Hfy Sn1-x-y O2 films as high k gate dielectrics |
US20070054487A1 (en) | 2005-09-06 | 2007-03-08 | Applied Materials, Inc. | Atomic layer deposition processes for ruthenium materials |
US20070190362A1 (en) | 2005-09-08 | 2007-08-16 | Weidman Timothy W | Patterned electroless metallization processes for large area electronics |
US20070116888A1 (en) | 2005-11-18 | 2007-05-24 | Tokyo Electron Limited | Method and system for performing different deposition processes within a single chamber |
KR100891779B1 (ko) | 2005-11-28 | 2009-04-07 | 허니웰 인터내셔날 인코포레이티드 | 증착 공정용의 유기금속 전구체 및 관련된 중간체, 이들의제조 방법, 및 이들의 사용 방법 |
US20070154637A1 (en) | 2005-12-19 | 2007-07-05 | Rohm And Haas Electronic Materials Llc | Organometallic composition |
JP2009529579A (ja) | 2006-03-10 | 2009-08-20 | アドバンスド テクノロジー マテリアルズ,インコーポレイテッド | チタネート、ランタネート及びタンタレート誘電体の膜の原子層堆積及び化学蒸着のための前駆体組成物 |
US20070262715A1 (en) | 2006-05-11 | 2007-11-15 | Matsushita Electric Industrial Co., Ltd. | Plasma display panel with low voltage material |
US8318966B2 (en) * | 2006-06-23 | 2012-11-27 | Praxair Technology, Inc. | Organometallic compounds |
US20080118731A1 (en) | 2006-11-16 | 2008-05-22 | Micron Technology, Inc. | Method of forming a structure having a high dielectric constant, a structure having a high dielectric constant, a capacitor including the structure, a method of forming the capacitor |
US20080141937A1 (en) | 2006-12-19 | 2008-06-19 | Tokyo Electron Limited | Method and system for controlling a vapor delivery system |
WO2008088563A2 (en) | 2007-01-17 | 2008-07-24 | Advanced Technology Materials, Inc. | Precursor compositions for ald/cvd of group ii ruthenate thin films |
KR100857590B1 (ko) | 2007-02-12 | 2008-09-09 | 충남대학교산학협력단 | 연성 폴리머 기판 위에 상온 화학증착법 |
KR20080076173A (ko) | 2007-02-15 | 2008-08-20 | 삼성전자주식회사 | 금속 산화막 패턴 형성 방법 및 이를 이용한 반도체 소자의형성 방법 |
US7790629B2 (en) | 2007-02-15 | 2010-09-07 | The Board Of Trustees Of The Leland Stanford Junior University | Atomic layer deposition of strontium oxide via N-propyltetramethyl cyclopentadiendyl precursor |
KR20080079514A (ko) | 2007-02-27 | 2008-09-01 | 삼성전자주식회사 | 반도체 소자의 제조방법 |
US7755128B2 (en) | 2007-03-20 | 2010-07-13 | Tokyo Electron Limited | Semiconductor device containing crystallographically stabilized doped hafnium zirconium based materials |
US20080242097A1 (en) | 2007-03-28 | 2008-10-02 | Tim Boescke | Selective deposition method |
JP2008244298A (ja) | 2007-03-28 | 2008-10-09 | Tokyo Electron Ltd | 金属膜の成膜方法、多層配線構造の形成方法、半導体装置の製造方法、成膜装置 |
US8178446B2 (en) | 2007-03-30 | 2012-05-15 | Tokyo Electron Limited | Strained metal nitride films and method of forming |
JP5571547B2 (ja) | 2007-04-09 | 2014-08-13 | プレジデント アンド フェローズ オブ ハーバード カレッジ | 銅の相互接続体のための窒化コバルト層及びそれらを形成する方法 |
WO2008128141A2 (en) | 2007-04-12 | 2008-10-23 | Advanced Technology Materials, Inc. | Zirconium, hafnuim, titanium, and silicon precursors for ald/cvd |
US20080254218A1 (en) | 2007-04-16 | 2008-10-16 | Air Products And Chemicals, Inc. | Metal Precursor Solutions For Chemical Vapor Deposition |
JP5437594B2 (ja) | 2007-06-05 | 2014-03-12 | ローム・アンド・ハース・エレクトロニック・マテリアルズ,エル.エル.シー. | 有機金属化合物 |
US8017182B2 (en) | 2007-06-21 | 2011-09-13 | Asm International N.V. | Method for depositing thin films by mixed pulsed CVD and ALD |
KR101533844B1 (ko) | 2007-06-26 | 2015-07-03 | 가부시키가이샤 코준도카가쿠 켄큐쇼 | 스트론튬 함유 박막 형성용 원료 및 그 제조 방법 |
KR100883139B1 (ko) | 2007-06-28 | 2009-02-10 | 주식회사 하이닉스반도체 | 루테늄계 전극을 구비한 캐패시터 및 그 제조 방법 |
US8455049B2 (en) | 2007-08-08 | 2013-06-04 | Advanced Technology Materials, Inc. | Strontium precursor for use in chemical vapor deposition, atomic layer deposition and rapid vapor deposition |
EP2201149B1 (en) | 2007-09-14 | 2013-03-13 | Sigma-Aldrich Co. | Methods of preparing titanium containing thin films by atomic layer deposition using monocyclopentadienyl titanium-based precursors |
US20090087561A1 (en) | 2007-09-28 | 2009-04-02 | Advanced Technology Materials, Inc. | Metal and metalloid silylamides, ketimates, tetraalkylguanidinates and dianionic guanidinates useful for cvd/ald of thin films |
US20090215225A1 (en) | 2008-02-24 | 2009-08-27 | Advanced Technology Materials, Inc. | Tellurium compounds useful for deposition of tellurium containing materials |
EP2271789A1 (en) | 2008-03-26 | 2011-01-12 | L'Air Liquide Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Deposition of ternary oxide films containing ruthenium and alkali earth metals |
US20090275164A1 (en) | 2008-05-02 | 2009-11-05 | Advanced Technology Materials, Inc. | Bicyclic guanidinates and bridging diamides as cvd/ald precursors |
US8636845B2 (en) | 2008-06-25 | 2014-01-28 | L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Metal heterocyclic compounds for deposition of thin films |
US8574675B2 (en) | 2009-03-17 | 2013-11-05 | Advanced Technology Materials, Inc. | Method and composition for depositing ruthenium with assistive metal species |
KR20120030370A (ko) | 2009-04-16 | 2012-03-28 | 어드밴스드 테크놀러지 머티리얼즈, 인코포레이티드 | 도핑된 산화지르코늄 커패시터 물질 및 구조체 |
US20100270508A1 (en) | 2009-04-24 | 2010-10-28 | Advanced Technology Materials, Inc. | Zirconium precursors useful in atomic layer deposition of zirconium-containing films |
JP5706755B2 (ja) * | 2010-06-10 | 2015-04-22 | 東ソー株式会社 | ヒドロシラン誘導体、その製造方法、ケイ素含有薄膜の製造法 |
WO2012005957A2 (en) | 2010-07-07 | 2012-01-12 | Advanced Technology Materials, Inc. | Doping of zro2 for dram applications |
WO2012177642A2 (en) | 2011-06-20 | 2012-12-27 | Advanced Technology Materials, Inc. | High-k perovskite material and methods of making and using the same |
US9177783B2 (en) * | 2013-12-10 | 2015-11-03 | Applied Materials, Inc. | Substituted silacyclopropane precursors and their use for the deposition of silicon-containing films |
-
2013
- 2013-05-22 WO PCT/US2013/042296 patent/WO2013177326A1/en active Application Filing
- 2013-05-22 US US14/400,793 patent/US9443736B2/en active Active
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104911561A (zh) * | 2015-04-14 | 2015-09-16 | 中国计量科学研究院 | 制备高厚度均匀性纳米/亚微米SiO2薄膜的方法 |
CN104911561B (zh) * | 2015-04-14 | 2017-12-26 | 中国计量科学研究院 | 制备高厚度均匀性纳米/亚微米SiO2薄膜的方法 |
TWI742022B (zh) * | 2015-11-30 | 2021-10-11 | 德商巴斯夫歐洲公司 | 生成金屬膜的方法 |
CN110326111A (zh) * | 2017-01-20 | 2019-10-11 | 李卫民 | 铁电氧化物存储器器件 |
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US9443736B2 (en) | 2016-09-13 |
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TWI558719B (zh) | 2016-11-21 |
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