CN100400705C - 有机金属络合物及其作为金属薄膜沉积前体的应用 - Google Patents
有机金属络合物及其作为金属薄膜沉积前体的应用 Download PDFInfo
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- CN100400705C CN100400705C CNB2006100089260A CN200610008926A CN100400705C CN 100400705 C CN100400705 C CN 100400705C CN B2006100089260 A CNB2006100089260 A CN B2006100089260A CN 200610008926 A CN200610008926 A CN 200610008926A CN 100400705 C CN100400705 C CN 100400705C
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 36
- 239000002184 metal Substances 0.000 title claims abstract description 35
- 125000002524 organometallic group Chemical group 0.000 title claims abstract description 25
- 239000002243 precursor Substances 0.000 title claims abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 15
- 239000010941 cobalt Substances 0.000 claims abstract description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- -1 cycloaliphatic Chemical group 0.000 claims abstract description 3
- 235000013495 cobalt Nutrition 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 20
- 238000005229 chemical vapour deposition Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000000151 deposition Methods 0.000 claims description 13
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 12
- 230000002829 reductive effect Effects 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 239000013049 sediment Substances 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 229910001507 metal halide Inorganic materials 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000000231 atomic layer deposition Methods 0.000 claims 2
- 150000002431 hydrogen Chemical class 0.000 claims 2
- 229910052742 iron Inorganic materials 0.000 abstract description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 6
- 125000003545 alkoxy group Chemical group 0.000 abstract description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052710 silicon Inorganic materials 0.000 abstract description 6
- 239000010703 silicon Substances 0.000 abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052802 copper Inorganic materials 0.000 abstract description 5
- 239000010949 copper Substances 0.000 abstract description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 3
- 125000003118 aryl group Chemical group 0.000 abstract description 3
- 238000005137 deposition process Methods 0.000 abstract description 3
- 125000003709 fluoroalkyl group Chemical group 0.000 abstract description 3
- 229910052741 iridium Inorganic materials 0.000 abstract description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052762 osmium Inorganic materials 0.000 abstract description 3
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052763 palladium Inorganic materials 0.000 abstract description 3
- 229910052697 platinum Inorganic materials 0.000 abstract description 3
- 229910052702 rhenium Inorganic materials 0.000 abstract description 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 3
- 229910052725 zinc Inorganic materials 0.000 abstract description 3
- 239000011701 zinc Substances 0.000 abstract description 3
- 150000004767 nitrides Chemical class 0.000 abstract description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 49
- 150000001875 compounds Chemical class 0.000 description 21
- 239000010408 film Substances 0.000 description 19
- 239000013078 crystal Substances 0.000 description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 238000000605 extraction Methods 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910021332 silicide Inorganic materials 0.000 description 4
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 229910020676 Co—N Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910004200 TaSiN Inorganic materials 0.000 description 1
- 229910008807 WSiN Inorganic materials 0.000 description 1
- MOKQCQYLNZHXBA-UHFFFAOYSA-N [SiH3]P(O)(O)O Chemical compound [SiH3]P(O)(O)O MOKQCQYLNZHXBA-UHFFFAOYSA-N 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- GMOWVLNENGLWNO-UHFFFAOYSA-N n'-tert-butylethanimidamide Chemical compound CC(N)=NC(C)(C)C GMOWVLNENGLWNO-UHFFFAOYSA-N 0.000 description 1
- SYCZCVFOEPCWBF-UHFFFAOYSA-N n,n'-di(propan-2-yl)ethanimidamide Chemical compound CC(C)NC(C)=NC(C)C SYCZCVFOEPCWBF-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62C—FIRE-FIGHTING
- A62C3/00—Fire prevention, containment or extinguishing specially adapted for particular objects or places
- A62C3/02—Fire prevention, containment or extinguishing specially adapted for particular objects or places for area conflagrations, e.g. forest fires, subterranean fires
- A62C3/0221—Fire prevention, containment or extinguishing specially adapted for particular objects or places for area conflagrations, e.g. forest fires, subterranean fires for tunnels
-
- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
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- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
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- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
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- C—CHEMISTRY; METALLURGY
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- 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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C16/06—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 deposition of metallic material
- C23C16/18—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 deposition of metallic material from metallo-organic compounds
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- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21F—SAFETY DEVICES, TRANSPORT, FILLING-UP, RESCUE, VENTILATION, OR DRAINING IN OR OF MINES OR TUNNELS
- E21F11/00—Rescue devices or other safety devices, e.g. safety chambers or escape ways
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- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21F—SAFETY DEVICES, TRANSPORT, FILLING-UP, RESCUE, VENTILATION, OR DRAINING IN OR OF MINES OR TUNNELS
- E21F7/00—Methods or devices for drawing- off gases with or without subsequent use of the gas for any purpose
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Abstract
本发明涉及有机金属前体,和在衬底例如硅、金属氮化物和其它金属层上制造含金属的保形薄膜的沉积方法。有机金属前体为下式的N,N’-烷基-1,1-烷基甲硅烷基氨基金属络合物:其中M为选自VIIb、VIII、IX和X族的金属,并且金属的特定实例包括钴、铁、镍、锰、钌、锌、铜、钯、铂、铱、铼、锇,并且R1-5可相同或不同并选自氢、烷基、烷氧基、氟代烷基和烷氧基、脂环族基和芳基。
Description
发明背景
厚度为或更少的金属和金属氧化物高保形薄膜在包括微电子学和磁信息存储的电子器件的制造中越来越引起人们的注意。这些薄膜通常通过化学气相沉积(CVD)和原子层沉积(ALD)法生产。随着组件器件(即晶体管)尺寸的减小以及组件器件密度的增大和电路的图案化,就相当地需要可通过CVD或ALD法制造这类薄膜的新型有机金属前体化合物。
热稳定的金属脒化物已经被选用作生产过渡金属的高保形薄膜的候选对象。其可用于生产逻辑和存储器件。用于这种金属脒化物中的示范性金属包括钴、钒、铁和镍。
已经证明,来自VIIb、VIII、IX和X族金属的金属硅化物是电子学领域,特别是在集成电路制造和微电子领域引人注目的化合物。由于其良好的热和化学稳定性、低电阻率、宽加工范围以及其对硅晶格较小的晶格失配,当器件按比例缩小时对金属硅化物的兴趣增加,这使得金属硅化物在硅上外延生长。
以下专利和文章中给出了适于通过CVD和ALD生产保形的金属或金属氧化物薄膜的有机金属化合物,以及其在电子工业中的用途。
US 6,777,565B2和US 6,753,245B2中公开了使用通式(R1)mM(PR2 3)x的有机金属化合物沉积金属薄膜,其中M为选自VIIb、VIII、IX或X族的金属,例如铁、钴、镍、锰、铑等等。还公开了甲硅烷基亚磷酸金属盐,并且其实例包括通式为H2M[(CH3)3SiOP(OC2H5)2]4和M(CH3)3SiOP(OCHH3)2]5的那些。
US 2002/0081381中公开了在ALD方法中使二(乙酰基丙酮根合)钴与氢或硅烷交替地反应形成钴膜。钴可以被用作为铜和扩散壁垒层之间的胶合层以增加粘合,扩散壁垒层例如来自TiN、TaN和WN。
US 2002/0016065中公开了使用有机金属络合物形成含金属薄膜,其中金属中心与螯合的C,N-供体配体配位。例如在一个实施例中,使用一种络合物Co{C(SiMe3)2(C5H4N)}2在硅衬底上形成钴膜。
WO 2004/046417A2和Roy G.Gordon等人在Alternate Layer Deposition ofTransition Metals,Nature Materials,第2卷,749(2003年11月)中公开了使用金属脒化物作为有机金属前体通过ALD形成高保形薄膜。双(N,N′-二异丙基乙脒根合)钴(II)、双(N,N′-叔丁基乙脒根合)锰和三(N,N′-二异丙基-2-叔丁脒根合)镧用作前体。
发明概要
本发明涉及有机金属前体以及使用这些有机金属前体在衬底,例如硅、金属氮化物和其它金属层上形成含金属保形薄膜的沉积方法。这些薄膜已经应用在计算机芯片、光学器件、磁信息存储器和涂布在载体材料上的金属催化剂上。
有机金属前体为具有下式的N,N′-烷基-1,1-烷基甲硅烷基氨基金属络合物:
其中M为选自VIIb、VIII、IX和X族的金属,并且金属的特定实例包括钴、铁、镍、锰、钒、镧、钌、锌、铜、钯、铂、铱、铼、锇,并且R1-5可相同或不同并选自氢、烷基、烷氧基、氟代烷基和烷氧基、脂环族基和芳基。
通过这些有机金属络合物(特别是N,N′-烷基-1,1-烷基甲硅烷基氨基金属络合物前体)可得到一些优点,并且这些优点包括:
以良好收率形成反应性的N,N′-烷基-1,1-烷基甲硅烷基氨基金属络合物的能力;
产生适用于各种各样电气应用的高保形金属薄膜的能力;
形成适用于微电子设备的高保形金属氧化物薄膜的能力;
由于络合物的高化学反应性,提高N,N′-烷基-1,1-烷基甲硅烷基氨基金属络合物和衬底表面之间表面反应的能力;和
通过改变N,N′烷基-1,1-烷基甲硅烷基氨基金属络合物上的R基团,来调整N,N′-烷基-1,1-烷基甲硅烷基氨基金属络合物的物理性质的能力。
发明详述
本发明涉及一类有机金属络合物,特别是具有螯合的N,N′-供体配体的N,N′-烷基-1,1-烷基甲硅烷基氨基金属络合物,以及其合成和在沉积过程中的应用。这些N,N′-烷基-1,1-烷基甲硅烷基氨基金属络合物的通式可表示如下:M{R1R2Si(NR3)(NR4R5))}2,其中M为选自VIIb、VIII、IX和X族的金属,并且金属的特定实例包括钴、铁、镍、锰、钌、锌、铜、钯、铂、铱、铼、锇,并且R1-5选自氢原子、烷基或烷氧基、氟代烷基和烷氧基以及脂环族基。
这些有机金属络合物,例如N,N′-烷基-1,1-烷基甲硅烷基氨基金属络合物可用作可能的前体,通过化学气相沉积(CVD)或原子层沉积(ALD)法在小于500℃的温度下制造薄金属或金属氧化物薄膜。CVD法可在有或没有还原剂或氧化剂的情况下进行,然而ALD法通常涉及使用其它反应物,例如还原剂或氧化剂。
有机金属络合物可通过式(MX2)的无水二价金属卤化物的反应制备,其中X优选Cl或Br。在一个优选实施方案中,使MCl2与2当量的N,N′-烷基-1,1-烷基甲硅烷基氨基锂(R1R2Si(LiNR3)(NR4R5)反应。下列反应方程式是代表性的:
MX2+R1R2Si(LiNR3)(NR4R5)→M{R1R2Si(LiNR3)(NR4R5)}+2LiX
N,N′-烷基-1,1-烷基甲硅烷基氨基锂(R1R2Si(LiNR3)(NR4R5))可通过使式R1R2Si(HNR3)(NR4R5)的有机化合物与例如LiBun的烷基锂的原位反应而得到。
作为形成热稳定化合物的一个优选方法,优选选择具有较大R基的配体,例如具有C3-4烷基、芳基或带有氮原子的环基的配体。这些大基团能够在反应期间防止聚合物类物质的形成。另一方面存在竞争问题,亦即连接到硅原子上的R基应当尽可能地小,以降低所得有机金属化合物的分子量并使得所得络合物具有较高蒸气压。连到氮原子上的优选取代基为异丙基、仲丁基和叔丁基,并且甲基和甲氧基为优选的连接到硅原子上的取代基。
多种溶剂可用于该反应。由于金属卤化物在反应介质中有较低的溶解度,建议使用极性溶剂,例如四氢呋喃(THF)。所得络合物通常高度溶于烃类溶剂,例如己烷中。因此,通过除去反应溶剂、使用己烷萃取和过滤,易于从反应混合物中分离所得络合物。
以下实施例说明N,N′-烷基-1,1-烷基甲硅烷基氨基金属络合物的制备以及其在薄膜沉积过程中作为前体的应用。
实施例1
双(N,N′-二(叔丁基)-1,1-二甲基甲硅烷基氨基)钴(II)的合成
将15克(0.116摩尔)无水CoCl2加入到装有100毫升THF的1升Schlenk烧瓶中。向该烧瓶中加入Me2Si(LiNBut)(HNBut),其通过Me2Si(HNBut)2(49.5克,0.245摩尔)与2.5MLiBun己烷溶液(98毫升,0.245摩尔)在200毫升己烷中的反应原位制备。将混合物在室温下搅拌过夜。反应完全后,真空除去所有挥发物,并使用己烷混合物(200毫升)萃取反应所得黑色固体。将己烷萃取物通过具有硅藻土垫的玻璃烧结物过滤,得到深蓝色溶液。将该溶液浓缩至约50毫升并保持在-40℃,得到黑色晶体。收集得到20克晶体并在真空干燥。通过将母液浓缩至约10毫升,另外得到5克黑色晶体。
基于钴的收率为84%。对于C20H50CoN4Si2分析计算值:Co,12.76;C,52.02;N,12.13;H,10.91。测定值:Co,13.20;C,49.52;N,11.44;H,9.72。
通过X射线单晶分析对深蓝色晶体双(N,N′-二(叔丁基)-1,1-二甲基甲硅烷基氨基)钴(II)进行结构表征。如下结构表明:钴在扭曲的四面体环境中被两个N,N′-二(叔丁基)-1,1-二甲基甲硅烷基氨基配体配位。平均Co-N距离为2.006
以上表示双(N,N′-二(叔丁基)-1,1-二甲基甲硅烷基氨基)钴(II)的晶体结构。
原子的数量由X射线单晶结构分析确定。
实施例2
双(N,N′-二(叔丁基)-1,1-二甲基甲硅烷基氨基)镍(II)的合成
除了使用NiCl2代替CoCl2外,重复实施例1的过程。将10克(0.077摩尔)无水NiCl2加入到装有80毫升THF的1升Schlenk烧瓶中。向该烧瓶中加入Me2Si(LiNBut)(HNBut),其通过Me2Si(HNBut)2(32.0克,0.154摩尔)与2.5MLiBun己烷溶液(61.6毫升,0.154摩尔)在200毫升己烷中的反应原位制备。将混合物在室温下搅拌过夜。
然后真空除去所有挥发物,并使用己烷(200毫升)萃取所得黑色固体。通过具有硅藻土垫的玻璃烧结物过滤己烷萃取物,得到深绿色溶液。将溶液浓缩至约50毫升并保持在-40℃,得到黑色晶体。收集得到25克晶体并在真空干燥。基于镍的收率为70%。
通过X射线单晶分析对深绿色晶体双(N,N′-二(叔丁基)-1,1-二甲基甲硅烷基氨基)镍(II)进行结构表征。如下结构表明:镍在扭曲的四面体环境中被两个N,N′-二(叔丁基)-1,1-二甲基甲硅烷基氨基配体配位。平均Ni-N距离为2.005双(N,N′-二(叔丁基)-1,1-二甲基甲硅烷基氨基)镍(II)的结构如下表示:
通过X射线单晶结构分析获得的双(N,N′-二(叔丁基)-1,1-二甲基甲硅烷基氨基)镍(II)的晶体结构
实施例3
双(N,N′-二(叔丁基)-1,1-二甲基甲硅烷基氨基)铁(II)的合成
除了使用FeCl2代替CoCl2外,重复实施例1的过程。将10克(0.079摩尔)无水FeCl2加入到装有50毫升THF的1升Schlenk烧瓶中。向该烧瓶中加入Me2Si(LiNBut)(HNBut),其通过Me2Si(HNBut)2(32.0克,0.158摩尔)与2.5MLiBun己烷溶液(63.1毫升,0.158摩尔)在200毫升己烷中的反应原位制备。将混合物在室温下搅拌过夜。然后真空除去所有挥发物,并使用己烷(200毫升)萃取所得黑色固体。通过具有硅藻土垫的玻璃烧结物过滤己烷萃取物,得到紫色溶液。将溶液浓缩至约50毫升并保持在-40℃,得到黑色晶体。收集得到16克晶体并在真空干燥。基于铁的收率为44%。对于C20H50FeN4Si2的分析计算值:Fe,12.18;C,52.37;N,12.22;H,10.99。测定值:Fe,11.81;C,52.37;N,11.29;H,9.21。
通过X射线单晶分析对紫色晶体双(N,N′-二(叔丁基)-1,1-二甲基甲硅烷基氨基)镍(II)进行结构表征。如下结构表明:铁在扭曲的四面体环境中被两个N,N′-二(叔丁基)-1,1-二甲基甲硅烷基氨基配体配位。平均Fe-N距离为2.048
通过X射线单晶结构分析获得的双(N,N′-二(叔丁基)-1,1-二甲基甲硅烷基氨基)铁(II)的晶体结构
实施例4
双(N,N′-二(异丙基)-1,1-二甲基甲硅烷基氨基)钴(II)的合成
将5克(0.0385摩尔)无水CoCl2加入到装有50毫升THF的500毫升Schlenk烧瓶中。向该烧瓶中加入Me2Si(LiNBut)(HNBut),其通过Me2Si(HNBut)2(14.2克,0.0815摩尔)与2.5M LiBun己烷溶液(32.6毫升,0.0815摩尔)在100毫升己烷中的反应原位制备。将混合物在室温下搅拌过夜。然后真空除去所有挥发物,并使用己烷(100毫升)萃取反应所得黑色固体。通过具有硅藻土垫的玻璃烧结物过滤己烷萃取物,得到深蓝色溶液。将溶液浓缩至约10毫升并保持在-40℃,得到黑色晶体。收集得到10克晶体并在真空干燥。基于钴的收率为64%。
实施例5
双(N,N′-二(叔丁基)-1,1-二甲基甲硅烷基氨基)钴(II)的CVD
在此实施例中,将双(N,N′-二(叔丁基)-1,1-二甲基甲硅烷基氨基)钴(II)用作形成薄膜的有机金属前体,在常规CVD设备中使用已知CVD技术在硅衬底上形成金属硅化物膜。
在此实施例中,在鼓泡器中在90℃蒸发双(N,N′-二(叔丁基)-1,1-二甲基甲硅烷基氨基)钴(II),并与100sccm N2载气一起进入CVD室。CVD室为具有加热的衬底支架的冷壁体系。衬底保持在400℃,沉积室压力保持在1托。所得薄膜的EDX分析表明,薄膜中含有钴。
由说明书和实施例可知,在用于制造固态晶体管、电容、通用接口适配器和电路的电子器件中,通式M{R1R2Si(NR3)(NR4R5))}2的N,N′-烷基-1,1-烷基甲硅烷基氨基金属络合物可用于在衬底上形成金属或准金属氧化物,包括在铜和扩散壁垒(例如TaN、TiN、WN、TaSiN、WSiN)之间形成胶合层。N,N′-烷基-1,1-烷基甲硅烷基氨基金属络合物可以与还原剂接触,或不与还原剂接触(还原剂亦即氢气、肼、单烷基肼、二烷基肼、氨以及其混合物)。含氧反应物可根据需要被加入到沉积室中,氧化剂的实例包括水、Q2、H2O2和臭氧。仅仅由于ALD方法的自约束性质,与CVD法相比,优选使用ALD法来沉积N,N′-烷基-1,1-烷基甲硅烷基氨基金属络合物。通过ALD形成的薄膜能够生成45纳米及以下的薄膜。
Claims (17)
1.以下结构表示的有机金属络合物:
其中M为选自铁、钴和镍的金属,并且R1-5可相同或不同并选自氢和烷基。
2.权利要求1所述的有机金属络合物,具有化学名称双(N,N′-二(叔丁基)-1,1-二甲基甲硅烷基氨基)钴(II)。
3.权利要求1所述的有机金属络合物,具有化学名称双(N,N′-二(叔丁基)-1,1-二甲基甲硅烷基氨基)铁(II)。
4.权利要求1所述的有机金属络合物,具有化学名称双(N,N′-二(叔丁基)-1,1-二甲基甲硅烷基氨基)镍(II)。
5.用于在衬底上形成保形金属或金属氧化物薄膜的沉积方法,其中将有机金属前体加入到沉积室、蒸发并且沉积在衬底上,其改进包括使用权利要求1中所述的有机金属络合物作为所述的有机金属前体。
6.权利要求5中所述的沉积方法,其中沉积方法为化学气相沉积法。
7.权利要求5中所述的沉积方法,其中沉积方法为原子层沉积法。
9.权利要求5所述的沉积方法,其中在引入所述有机金属前体后,向沉积室中加入还原剂以产生金属薄膜。
10.权利要求9所述的方法,其中所述还原剂选自氢气、肼、单烷基肼、二烷基肼、氨以及其混合物。
11.权利要求10所述的方法,其中所述沉积方法为化学气相沉积法。
12.权利要求10所述的方法,其中所述沉积方法为原子层沉积法。
13.权利要求5中所述的沉积方法,其中将含氧反应物引入到沉积室中以制备金属氧化物薄膜。
14.权利要求13所述的方法,其中可以通过还原剂将所得的金属氧化物薄膜还原成金属薄膜,该还原剂选自:氢气、肼、单烷基肼、二烷基肼、氨以及其混合物。
15.权利要求13所述的方法,其中含氧反应物选自水、O2、H2O2和臭氧。
17.权利要求16所述的方法,其中R1和R2为甲基,并且R3、R4和R5选自异丙基、仲丁基和叔丁基。
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- 2006-01-31 AT AT06001991T patent/ATE402184T1/de not_active IP Right Cessation
- 2006-01-31 EP EP06001991A patent/EP1688426B1/en not_active Not-in-force
- 2006-01-31 DE DE602006001873T patent/DE602006001873D1/de active Active
- 2006-02-03 KR KR1020060010775A patent/KR100665084B1/ko active IP Right Grant
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US5603988A (en) * | 1995-06-02 | 1997-02-18 | Morton International, Inc. | Method for depositing a titanium or tantalum nitride or nitride silicide |
US6753245B2 (en) * | 2000-06-29 | 2004-06-22 | Board Of Trustees, The University Of Illinois | Organometallic compounds and their use as precursors for forming films and powders of metal or metal derivatives |
WO2002027063A2 (en) * | 2000-09-28 | 2002-04-04 | President And Fellows Of Harward College | Vapor deposition of oxides, silicates and phosphates |
US20020081381A1 (en) * | 2000-10-10 | 2002-06-27 | Rensselaer Polytechnic Institute | Atomic layer deposition of cobalt from cobalt metallorganic compounds |
WO2004046417A2 (en) * | 2002-11-15 | 2004-06-03 | President And Fellows Of Harvard College | Atomic layer deposition using metal amidinates |
Also Published As
Publication number | Publication date |
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US7064224B1 (en) | 2006-06-20 |
TWI312375B (en) | 2009-07-21 |
CN1814605A (zh) | 2006-08-09 |
EP1688426B1 (en) | 2008-07-23 |
EP1688426A1 (en) | 2006-08-09 |
KR100665084B1 (ko) | 2007-01-09 |
JP2006257073A (ja) | 2006-09-28 |
KR20060089677A (ko) | 2006-08-09 |
TW200628627A (en) | 2006-08-16 |
DE602006001873D1 (de) | 2008-09-04 |
JP4388021B2 (ja) | 2009-12-24 |
ATE402184T1 (de) | 2008-08-15 |
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