CN1774523A - 通过原子层沉积用于沉积铜膜的挥发性铜(ⅰ)配合物 - Google Patents
通过原子层沉积用于沉积铜膜的挥发性铜(ⅰ)配合物 Download PDFInfo
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- CN1774523A CN1774523A CNA2004800098752A CN200480009875A CN1774523A CN 1774523 A CN1774523 A CN 1774523A CN A2004800098752 A CNA2004800098752 A CN A2004800098752A CN 200480009875 A CN200480009875 A CN 200480009875A CN 1774523 A CN1774523 A CN 1774523A
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- copper
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- 239000010949 copper Substances 0.000 title claims abstract description 39
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 36
- 238000000151 deposition Methods 0.000 title abstract description 6
- 230000008021 deposition Effects 0.000 title abstract description 3
- 238000000231 atomic layer deposition Methods 0.000 title abstract 2
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical class [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 title description 5
- 238000000034 method Methods 0.000 claims abstract description 16
- 229910000071 diazene Inorganic materials 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 13
- 230000002829 reductive effect Effects 0.000 claims description 30
- 150000004699 copper complex Chemical class 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 18
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 150000001336 alkenes Chemical class 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- -1 isobutyl- Chemical group 0.000 claims description 8
- 238000002955 isolation Methods 0.000 claims description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 229910000077 silane Inorganic materials 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 6
- GCSJLQSCSDMKTP-UHFFFAOYSA-N ethenyl(trimethyl)silane Chemical compound C[Si](C)(C)C=C GCSJLQSCSDMKTP-UHFFFAOYSA-N 0.000 claims description 6
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- 229960001866 silicon dioxide Drugs 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 229910000085 borane Inorganic materials 0.000 claims description 5
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 claims description 5
- UCXUKTLCVSGCNR-UHFFFAOYSA-N diethylsilane Chemical compound CC[SiH2]CC UCXUKTLCVSGCNR-UHFFFAOYSA-N 0.000 claims description 5
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 229910000078 germane Inorganic materials 0.000 claims description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical group [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 3
- VQYPKWOGIPDGPN-UHFFFAOYSA-N [C].[Ta] Chemical compound [C].[Ta] VQYPKWOGIPDGPN-UHFFFAOYSA-N 0.000 claims description 3
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims description 3
- CFJRGWXELQQLSA-UHFFFAOYSA-N azanylidyneniobium Chemical compound [Nb]#N CFJRGWXELQQLSA-UHFFFAOYSA-N 0.000 claims description 3
- HWEYZGSCHQNNEH-UHFFFAOYSA-N silicon tantalum Chemical compound [Si].[Ta] HWEYZGSCHQNNEH-UHFFFAOYSA-N 0.000 claims description 3
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 3
- AMKGKYQBASDDJB-UHFFFAOYSA-N 9$l^{2}-borabicyclo[3.3.1]nonane Chemical group C1CCC2CCCC1[B]2 AMKGKYQBASDDJB-UHFFFAOYSA-N 0.000 claims 2
- FEJUGLKDZJDVFY-UHFFFAOYSA-N 9-borabicyclo[3.3.1]nonane Substances C1CCC2CCCC1B2 FEJUGLKDZJDVFY-UHFFFAOYSA-N 0.000 claims 2
- 239000000758 substrate Substances 0.000 abstract description 7
- 239000007787 solid Substances 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 235000012431 wafers Nutrition 0.000 description 14
- 239000012691 Cu precursor Substances 0.000 description 6
- 238000005229 chemical vapour deposition Methods 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 238000005137 deposition process Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical class COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- KCWYOFZQRFCIIE-UHFFFAOYSA-N ethylsilane Chemical compound CC[SiH3] KCWYOFZQRFCIIE-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 1
- 125000005574 norbornylene group Chemical group 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- HYWCXWRMUZYRPH-UHFFFAOYSA-N trimethyl(prop-2-enyl)silane Chemical compound C[Si](C)(C)CC=C HYWCXWRMUZYRPH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/08—Copper compounds
-
- 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
-
- 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
- C23C16/44—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
- 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]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
- Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Vapour Deposition (AREA)
- Electrodes Of Semiconductors (AREA)
Abstract
本发明涉及新型1，3－二亚胺铜配合物以及1，3－二亚胺铜配合物在原子层沉积工艺中用于在基材上或在多孔固体中或上沉积铜的用途。
Description
技术领域
本发明涉及新型1，3-二亚胺铜配合物以及1，3-二亚胺铜配合物在原子层沉积工艺中用于在基材上或在多孔固体中或上沉积铜的用途。
背景技术
原子层沉积(ALD)工艺可用于产生薄膜，作为描述通过M.Ritala和hA.Leskela的″原子层沉积″(薄膜材料手册，H.S.Nalwa，编者，Academic Press，San Diego，2001，卷1，章节2)。这些膜，尤其金属和金属氧化物膜是制造电子电路和设备的关键组分。
在用于沉积铜膜的ALD工艺中，铜前体和还原剂被交替引入反应腔。在铜前体被引入反应腔和吸附到基材上之后，过量(未吸附)前体蒸气从该腔中被泵或清除。该过程之后引入还原剂以与铜前体在基材表面上反应，这样形成铜金属和游离形式的配体。可根据需要重复该周期以实现所需膜厚度。
该工艺不同于金属配合物的分解化学中的化学蒸气沉积(CVD)。在CVD工艺中，配合物在与表面接触时分解，得到所需膜。在ALD工艺中，配合物在与表面接触时不分解成金属。相反，在引入第二试剂以与沉积的金属配合物反应时，发生金属膜的形成。在由铜(I)配合物制备铜膜时，第二试剂是还原剂。ALD工艺的优点包括能够控制膜厚度和提高覆盖适应性，因为前体在该工艺的第一步骤中自限定性吸附到基材表面上。
为了可用于ALD工艺，铜配合物必须是足够挥发性的从而在蒸发时不会热分解。通常，含三氟甲基基团的配体已被用于增加铜配合物的挥发性。但该方案在制备互连层方面存在缺陷，因为残余卤化物不利地影响互连层的性能。
用于ALD工艺的配体还必须对于分解作用稳定并能够以无金属的形式从配合物中解吸。在铜还原之后，配体被释放且必须从表面上去除以防其被引入正在形成的金属层。
US 5,464,666描述，1，3-二亚胺铜配合物在氢存在下分解形成铜。该专利还描述了1，3-二亚胺铜配合物在化学蒸气沉积工艺中用于生产铜-铝合金的用途。
DE 4202889描述了1，3-二亚胺金属配合物优选通过化学蒸气沉积工艺用于沉积涂层的用途。公开了金属配合物在减少气氛，优选氢中的分解。
S.G.McGeachin，加拿大化学杂志，46，1903-1912(1968)，描述了1，3-二亚胺和这些配体的金属配合物，包括ML2形式的二-螯合物或homoleptic配合物的合成。
US 6,464,779公开了Cu原子层CVD工艺，其中需要用氧化剂处理包含氧和氟的铜前体以形成氧化铜，随后用还原剂处理表面。
发明内容
本发明描述了一种用于在基材上形成铜沉积的方法，包括：
a.将基材与铜配合物(I)接触，以形成在基材上的铜配合物的沉积物；和
b.将沉积铜配合物与还原剂接触，
其中
L是包含2-15个碳的烯烃；
R1和R4独立地选自氢，甲基，乙基，丙基，异丙基，异丁基，和新戊基；
R2和R3独立地选自苯基和C1-C10烷基基团；和
还原剂选自9-BBN(9-硼杂双环[3.3.1]壬烷)；二硼烷；BRxH3-x形式的硼烷，其中x＝0，1或2，和R独立地选自苯基和C1-C10烷基基团；二氢苯并呋喃；吡唑啉；二硅烷；SiR′yH4-y形式的硅烷，其中y＝0，1，2或3，和R′独立地选自苯基和C1-C10烷基基团；和GeR″zH4-z形式的锗烷，其中z＝0，1，2，或3，和R″独立地选自苯基和C1-C10烷基基团。
详细描述
申请人已经发现了一种适用于产生在形成集成电路中的铜互连时用作种子层，或用于装饰或催化场合的铜膜的原子层沉积(ALD)工艺。该工艺使用挥发性的，热稳定的和衍生自仅包含C，H，Si和N的配体的铜(I)配合物。该配体选择成能够形成在合适的温度范围内是挥发性的但在该温度范围内不分解成铜金属的铜(I)配合物；相反，该配合物在加入合适的还原剂时分解成金属。该配体进一步选择使得在将铜配合物暴露于还原剂时它们会解吸而不分解。
通过容易可得还原剂将这些铜配合物还原成铜金属的过程已被表现出在中度温度下顺利地进行。
在本发明工艺中，铜利用以下步骤沉积在基材上：
a.将基材与铜配合物(I)接触，以形成在基材上的铜配合物的沉积物；和
b.将沉积的铜配合物与还原剂接触，
其中
L是包含2-15个碳的烯烃；
R1和R4独立地选自氢，甲基，乙基，丙基，异丙基，异丁基，和新戊基；
R2和R3独立地选自苯基和C1-C10烷基基团；和
还原剂选自9-BBN；二硼烷；BRxH3-x形式的硼烷，其中x＝0，1或2，和R独立地选自苯基和C1-C10烷基基团；二氢苯并呋喃；吡唑啉；二硅烷；SiR′yH4-y形式的硅烷，其中y＝0，1，2或3，和R′独立地选自苯基和C1-C10烷基基团；和GeR″zH4-z形式的锗烷，其中z＝0，1，2，或3，和R″独立地选自苯基和C1-C10烷基基团。
本发明的沉积工艺通过允许使用较低温度和产生较高质量的更均匀的膜而改进已有技术中描述的工艺。本发明的工艺还提供一种得到铜膜的更直接的路径，避免形成中间体氧化物膜。
在本发明的铜沉积工艺中，铜可沉积在基材的表面上，或孔中或孔上。
合适的基材包括导电，半导电和绝缘的基材，包括铜，硅晶片，用于制造超大规模集成电路的晶片，使用介电常数低于二氧化硅的介电材料制成的晶片，以及二氧化硅和涂有隔绝层的低k基材。
用于防止铜迁移的隔绝层包括钽，氮化钽，钛，氮化钛，氮化硅钽，氮化硅钛，氮化碳钽，和氮化铌。
该工艺可在溶液中，即，通过将铜配合物的溶液与还原剂接触而进行。但优选将基材暴露于铜配合物的蒸气，并随后通过真空或清洗而去除任何过量的铜配合物(即，未沉积的配合物)，然后将沉积的配合物暴露于还原剂的蒸气。在还原铜配合物之后，游离形式的配体可通过真空，清洗，加热，用合适的溶剂漂洗，或这些步骤的组合而去除。
可重复该工艺以构建较厚的铜层，或消除针孔。
铜配合物的沉积通常在0至200摄氏度下进行。铜配合物的还原通常在类似温度，0至200摄氏度下进行。
在本发明工艺中，起始将铜配合物沉积在基材上。金属铜膜的形成在铜配合物暴露于还原剂之前不会发生。
需要进攻性还原剂用于迅速和完全地还原铜配合物。还原剂必须是挥发性的和在加热时不分解。它们还必须具有足够的还原力以在与沉积在基材表面上的铜配合物接触时迅速反应。已经确认了一类尚未在ALD工艺中用于铜(I)还原的合适还原剂。这些试剂的一个特征在于存在质子给体。该试剂必须能够转移至少一个电子以还原配合物的铜离子和至少一个质子以质子化该配体。氧化的还原剂和质子化的配体必须能够容易从新形成的铜沉积物的表面上去除。
适用于本发明铜沉积工艺的还原剂包括9-BBN，硼烷，二硼烷，二氢苯并呋喃，吡唑啉，锗烷，二乙基硅烷，二甲基硅烷，乙基硅烷，苯基硅烷，硅烷和二硅烷。二乙基硅烷和硅烷是优选的。
在铜沉积工艺的一个实施方案中，铜配合物在能够实现配合物至基材表面上的合适流量的温度，时间和压力条件下被加入反应器。本领域熟练技术人员可以理解，对这些变量的选择取决于各个腔和体系设计，和所需工艺速率。在至少一部分铜配合物已沉积在基材(如，涂覆硅晶片)上之后，将未沉积的配合物蒸气从腔中泵或清洗并将还原剂在压力约50至760mTorr下引入腔以还原吸附的铜配合物。
基材在还原过程中保持在约0至200摄氏度的温度下。通过铜配合物和还原剂的合适组合，该还原过程迅速和完全。还原剂曝光倍可低于1秒至几分钟。重要的是，该反应的产物在还原条件下容易从基材的表面上去除。
在一个实施方案中，本发明，铜配合物是铜1，3-二亚胺配合物(1)，其中R1和R4是异丁基基团，R2和R3是甲基基团，和L＝乙烯基三甲基硅烷，和还原剂是二乙基硅烷。
本发明还提供新型1，3-二亚胺铜配合物(I)，
(1)其中L是包含2-15个碳的烯烃；
R1和R4独立地选自氢，甲基，乙基，丙基，异丙基，异丁基，和新戊基；和
R2和R3独立地选自苯基和C1-C10烷基基团。
在一个实施方案中，L是线性，端烯烃。对于具有4-15个碳的烯烃，L还可以是顺式-或反式-构型的内烯烃；顺式-是优选的。L可以是环状或双环烯烃。L还可，例如被甲硅烷基基团取代。合适的烯烃包括乙烯基三甲基硅烷，烯丙基三甲基硅烷，1-己烯，4-甲基-1-戊烯，3，3-二甲基-1-丁烯，和降冰片烯。
以下实施例1给出了可用于制造本发明铜配合物的一种特殊配体的合成。其它配体可类似地由类似氨基酮制备。
在另一实施方案中，本发明提供了一种包含沉积在基材上的1，3-二亚胺铜配合物(I)的制品。
合适的基材包括：铜，硅晶片，用于制造超大规模集成电路的晶片，使用介电常数低于二氧化硅的介电材料制成的晶片，以及二氧化硅和涂有隔绝层的低k基材。隔绝层可使用以防铜的迁移。合适的隔绝层包括：钽，氮化钽，钛，氮化钛，氮化硅钽，氮化硅钛，氮化碳钽，和氮化铌。
实施例
所有的有机试剂得自Sigma-Aldrich公司(Milwaukee，Wi，USA)。[Cu(CH3CN)4]SO3CF3可根据描述于：T.Ogura，过渡金属化学，1，179-182(976)中的方法制备。
实施例1
乙烯基三甲基硅烷(N，N′-二异丁基-2，4-戊烷二酮亚胺)铜的制备和还原
在干燥箱中在氮气氛下，向250mL圆底烧瓶中装入4-(异丁基氨基)-3-戊烯-2-酮(36.9g，237mmole)和硫酸二甲基酯(30.0g，237mmole)。反应溶液搅拌5分钟和在不搅拌的情况下放置过夜。黄色混合物变成橙色和粘稠的。异丁基胺(18g，246mmole)在剧烈搅拌下通过加料漏斗加入。搅拌溶液1小时直至凝固。中间体盐不分离，但如下所述直接转化成游离胺(基于中间体盐的理论产率)。
将NaOMe(12.8g，237mmole)在MeOH(约40mL)中的溶液加入中间体盐中并搅拌1小时。溶剂在真空下去除，得到黄色油，用戊烷提取，过滤，和浓缩得到基于质子NMR数据由所需产物(N，N′-二异丁基-2，4-戊烷二酮亚胺)(约75％)和未反应的起始原料(约25％)组成的黄色油。产物通过级分蒸馏而分离，得到黄色油(35.4g，72％产率)。
在干燥箱中，向100-mL圆底烧瓶中装入[Cu(CH3CN)4]SO3CF3(1.0g)，乙烯基三甲基硅烷(26.0mmole)，和二乙基醚(20mL)。在单独的100-mL圆底烧瓶中，将1.5M t-丁基锂(1.7mL)加入如上所述制备的N，N′-二异丁基-2，4-戊烷二酮亚胺(0.550g)的溶液。在0.5小时之后，将溶液合并。合并的溶液在吸收所有的固体之后从浑浊的白色悬浮液变成金棕色的透明溶液。在2h之后，将溶液浓缩成固体/淤泥，用戊烷(3×15mL)提取，过滤和浓缩，得到粘稠油(0.600g，62％产率)。
实施例2
将如实施例1作为最终产物分离的粘稠油用作铜前体以在基材上制成铜膜。基材由具有250埃钽层和100埃铜层的二氧化硅晶片组成。晶片具有几乎不可辨认的铜色。
约0.040g铜前体在干燥箱中装载到瓷船中。将船和晶片(约1cm2)相隔约3.5英寸放在玻璃管中。将玻璃管从干燥箱中取出并连接到真空管路。将加热线圈连接到在瓷船周围区域和晶片周围区域围绕的玻璃管；该构型使得这两个区域两个保持在不同的温度。在抽空该体系之后，氩气流通过该管而产生，首先经过船中的样品并随后经过晶片。管内的压力保持在150-200mTorr。将晶片周围的区域暖至110摄氏度。在约1小时之后，样品船周围区域的温度升至55摄氏度。这些温度和Ar气流保持约2.5小时。将样品船周围的区域冷却至室温。将管抽空至约10mTorr的压力并用二乙基硅烷回填。处于110摄氏度的管的区域迅速变成铜色。将该装置冷却和返回至干燥箱。铜色明显更深。重复该过程以得到具有光滑金属铜膜的晶片。
Claims (12)
1.一种用于在基材上形成铜沉积的方法，包括：
a.将基材与铜配合物(I)接触，以形成在基材上的铜配合物的沉积物；和
b.将沉积的铜配合物与还原剂接触，其中
L是包含2-15个碳的烯烃；
R1和R4独立地选自氢，甲基，乙基，丙基，异丙基，异丁基，和新戊基；
R2和R3独立地选自苯基和C1-C10烷基基团；和
所述还原剂选自9-BBN；二硼烷；BRxH3-x形式的硼烷，其中x＝0，1或2，和R独立地选自苯基和C1-C10烷基基团；二氢苯并呋喃；吡唑啉；二硅烷；SiR′yH4-y形式的硅烷，其中y＝0，1，2或3，和R′独立地选自苯基和C1-C10烷基基团；和GeR″zH4-z形式的锗烷，其中z＝0，1，2，或3，和R″独立地选自苯基和C1-C10烷基基团。
2.权利要求1的方法，其中R2和R3是甲基和R1和R4是异丁基。
3.权利要求1的方法，其中L是乙烯基三甲基硅烷。
4.权利要求1的方法，其中基材选自铜，硅晶片和涂有隔绝层的二氧化硅。
5.权利要求1的方法，其中基材暴露于铜配合物的蒸气。
6.权利要求1的方法，其中沉积在0至200摄氏度下进行。
7.权利要求1的方法，其中还原剂是硅烷或二乙基硅烷。
8.1，3-二亚胺铜配合物(I)，
其中
L是包含2-15个碳的烯烃；
R1和R4独立地选自氢，甲基，乙基，丙基，异丙基，异丁基，和新戊基；
R2和R3独立地选自苯基和C1-C10烷基基团；和
所述还原剂选自9-BBN；二硼烷；BRxH3-x形式的硼烷。其中x＝0，1或2，和R独立地选自苯基和C1-C10烷基基团；二氢苯并呋喃；吡唑啉；二硅烷；SiR′yH4-y形式的硅烷，其中y＝0，1，2或3，和R′独立地选自苯基和C1-C10烷基基团；和GeR″zH4-z形式的锗烷，其中z＝0，1，2，或3，和R″独立地选自苯基和C1-C10烷基基团。
9.权利要求8的1，3-二亚胺铜配合物，其中L是乙烯基三甲基硅烷；R1和R4选自氢，异丁基，和新戊基；R2是Me；和R3选自Me，Et，和苯基。
10.通过将基材与权利要求8的1，3-二亚胺铜配合物接触而制成的制品。
11.权利要求10的制品，其中基材选自基团铜，硅晶片，和涂有隔绝层的二氧化硅。
12.权利要求11的制品，其中隔绝层选自钽，氮化钽，钛，氮化钛，氮化硅钽，氮化硅钛，氮化碳钽，和氮化铌。
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| US20050227007A1 (en) * | 2004-04-08 | 2005-10-13 | Bradley Alexander Z | Volatile copper(I) complexes for deposition of copper films by atomic layer deposition |
| US20080299322A1 (en) * | 2004-07-30 | 2008-12-04 | Bradley Alexander Zak | Copper (I) Complexes for Deposition of Copper Films by Atomic Layer Deposition |
| US7205422B2 (en) | 2004-12-30 | 2007-04-17 | Air Products And Chemicals, Inc. | Volatile metal β-ketoiminate and metal β-diiminate complexes |
| US7034169B1 (en) | 2004-12-30 | 2006-04-25 | Air Products And Chemicals, Inc. | Volatile metal β-ketoiminate complexes |
| US7439338B2 (en) * | 2005-06-28 | 2008-10-21 | Micron Technology, Inc. | Beta-diketiminate ligand sources and metal-containing compounds thereof, and systems and methods including same |
| US7572731B2 (en) * | 2005-06-28 | 2009-08-11 | Micron Technology, Inc. | Unsymmetrical ligand sources, reduced symmetry metal-containing compounds, and systems and methods including same |
| US7416994B2 (en) * | 2005-06-28 | 2008-08-26 | Micron Technology, Inc. | Atomic layer deposition systems and methods including metal beta-diketiminate compounds |
| US7488435B2 (en) | 2006-08-07 | 2009-02-10 | E. I. Du Pont De Nemours And Company | Copper(I) complexes and processes for deposition of copper films by atomic layer deposition |
| WO2008018861A1 (en) * | 2006-08-07 | 2008-02-14 | E. I. Du Pont De Nemours And Company | Copper(i) complexes and processes for deposition of copper films by atomic layer deposition |
| US8263795B2 (en) * | 2007-11-05 | 2012-09-11 | Air Products And Chemicals, Inc. | Copper precursors for thin film deposition |
| US20090130466A1 (en) * | 2007-11-16 | 2009-05-21 | Air Products And Chemicals, Inc. | Deposition Of Metal Films On Diffusion Layers By Atomic Layer Deposition And Organometallic Precursor Complexes Therefor |
| DE102007058571B4 (de) * | 2007-12-05 | 2012-02-16 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Substrat mit einer Kupfer enthaltenden Beschichtung und Verfahren zu deren Herstellung mittels Atomic Layer Deposition und Verwendung des Verfahrens |
| US11505865B2 (en) * | 2018-07-12 | 2022-11-22 | Basf Se | Process for the generation of metal- or semimetal-containing films |
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| US5464666A (en) * | 1995-02-06 | 1995-11-07 | Air Products And Chemicals, Inc. | Process for chemical vapor codeposition of copper and aluminum alloys |
| KR100225686B1 (ko) * | 1995-03-20 | 1999-10-15 | 모리시다 요이치치 | 막형성용 재료 및 배선형성방법 |
| US6511936B1 (en) * | 1998-02-12 | 2003-01-28 | University Of Delaware | Catalyst compounds with β-diminate anionic ligands and processes for polymerizing olefins |
| US6281124B1 (en) * | 1998-09-02 | 2001-08-28 | Micron Technology, Inc. | Methods and systems for forming metal-containing films on substrates |
| US6642401B2 (en) * | 2000-03-14 | 2003-11-04 | Nissan Chemical Industries, Ltd. | β-diketonatocopper(I) complex containing allene compounds as ligand and process for producing the same |
| JP2001328953A (ja) * | 2000-03-14 | 2001-11-27 | Nissan Chem Ind Ltd | アレン化合物を配位子としたβ−ジケトネート銅（Ｉ）錯体およびその製造法 |
| US20020013487A1 (en) * | 2000-04-03 | 2002-01-31 | Norman John Anthony Thomas | Volatile precursors for deposition of metals and metal-containing films |
| US6464779B1 (en) * | 2001-01-19 | 2002-10-15 | Novellus Systems, Inc. | Copper atomic layer chemical vapor desposition |
| US6821891B2 (en) * | 2001-11-16 | 2004-11-23 | Applied Materials, Inc. | Atomic layer deposition of copper using a reducing gas and non-fluorinated copper precursors |
| US6939578B2 (en) * | 2002-01-18 | 2005-09-06 | E. I. Du Pont De Nemours And Company | Volatile copper(II) complexes for deposition of copper films by atomic layer deposition |
| US20050227007A1 (en) * | 2004-04-08 | 2005-10-13 | Bradley Alexander Z | Volatile copper(I) complexes for deposition of copper films by atomic layer deposition |
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- 2004-04-08 US US10/820,926 patent/US20040247905A1/en not_active Abandoned
- 2004-04-16 JP JP2006510108A patent/JP4649402B2/ja not_active Expired - Fee Related
- 2004-04-16 US US10/547,917 patent/US20060182884A1/en not_active Abandoned
- 2004-04-16 DE DE200460018627 patent/DE602004018627D1/de not_active Expired - Lifetime
- 2004-04-16 KR KR1020057019498A patent/KR101132444B1/ko not_active IP Right Cessation
- 2004-04-16 EP EP04750189A patent/EP1613789B1/en not_active Expired - Fee Related
- 2004-04-16 TW TW93110729A patent/TWI343367B/zh not_active IP Right Cessation
- 2004-04-16 WO PCT/US2004/011734 patent/WO2004094689A2/en active Application Filing
- 2004-04-16 CN CNA2004800098752A patent/CN1774523A/zh active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JP4649402B2 (ja) | 2011-03-09 |
| EP1613789A2 (en) | 2006-01-11 |
| US20040247905A1 (en) | 2004-12-09 |
| TWI343367B (en) | 2011-06-11 |
| JP2006523778A (ja) | 2006-10-19 |
| KR101132444B1 (ko) | 2012-03-30 |
| DE602004018627D1 (de) | 2009-02-05 |
| EP1613789B1 (en) | 2008-12-24 |
| TW200500327A (en) | 2005-01-01 |
| KR20060010746A (ko) | 2006-02-02 |
| WO2004094689A2 (en) | 2004-11-04 |
| WO2004094689A3 (en) | 2005-01-20 |
| US20060182884A1 (en) | 2006-08-17 |
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