CN101084229A - 用作铜薄膜沉积前体的铜(i)化合物 - Google Patents
用作铜薄膜沉积前体的铜(i)化合物 Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 47
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 42
- 239000002243 precursor Substances 0.000 title claims abstract description 31
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical class [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000010409 thin film Substances 0.000 title abstract description 9
- 230000008021 deposition Effects 0.000 title description 4
- 239000000758 substrate Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 239000012691 Cu precursor Substances 0.000 claims description 30
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- 229910052799 carbon Inorganic materials 0.000 claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- 125000003118 aryl group Chemical group 0.000 claims description 24
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000012530 fluid Substances 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 229910021332 silicide Inorganic materials 0.000 claims description 6
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- -1 tungsten nitride Chemical class 0.000 claims description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- CFJRGWXELQQLSA-UHFFFAOYSA-N azanylidyneniobium Chemical compound [Nb]#N CFJRGWXELQQLSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 claims description 3
- 229910021341 titanium silicide Inorganic materials 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- WQJQOUPTWCFRMM-UHFFFAOYSA-N tungsten disilicide Chemical compound [Si]#[W]#[Si] WQJQOUPTWCFRMM-UHFFFAOYSA-N 0.000 claims description 2
- 229910021342 tungsten silicide Inorganic materials 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims 1
- 238000000231 atomic layer deposition Methods 0.000 abstract description 15
- 238000000151 deposition Methods 0.000 abstract description 6
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 150000001409 amidines Chemical class 0.000 description 6
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 6
- 238000001465 metallisation Methods 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical group [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000001301 oxygen Chemical group 0.000 description 4
- 229910052760 oxygen Chemical group 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 238000004377 microelectronic Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- GCSJLQSCSDMKTP-UHFFFAOYSA-N ethenyl(trimethyl)silane Chemical compound C[Si](C)(C)C=C GCSJLQSCSDMKTP-UHFFFAOYSA-N 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- YDGSUPBDGKOGQT-UHFFFAOYSA-N lithium;dimethylazanide Chemical compound [Li+].C[N-]C YDGSUPBDGKOGQT-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
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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
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
- C07F1/08—Copper compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
- C07C257/10—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines
- C07C257/14—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines having carbon atoms of amidino groups bound to acyclic carbon atoms
-
- 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 System
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic System without C-Metal linkages
-
- 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
-
- 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
Abstract
用于在制造半导体器件中形成铜薄膜的脒铜(I)前体,以及使用化学汽相沉积或原子层沉积工艺在衬底上沉积脒铜(I)前体的方法。
Description
技术领域
本发明通常涉及新型的脒铜(I)及其合成,并且涉及用于在微电子器件结构中利用该新型铜前体制造铜电路的方法。
背景技术
由于铜的低电阻率、低接触电阻、以及通过降低RC延时而增强器件性能的能力,铜已经成为金属化很大尺寸集成(VLSI)装置的优选金属。铜金属化已经被许多半导体器件制造商用来生产微电子芯片、薄膜记录磁头和封装元件。
铜的化学汽相沉积(CVD)为金属化提供均匀的覆盖。原子层沉积(ALD),其是改进的CVD工艺,也提供对铜种子层而言是关键的均匀覆盖。流体CVD前体和/或溶解于溶剂中的固态前体使得可以直接将前体注入和/或流体输送至CVD或ALD蒸发器单元内。准确和精确的输送速率可以通过体积测量而获得,以达到在VLSI装置的CVD或ALD金属化期间的再现性。
许多氟和/或含氧铜CVD前体是商业上可获得的,包括(hfac)Cu(MHY)、(hfac)Cu(3-己炔)、(hfac)Cu(DMCOD)和(hfac)Cu(VTMS),其中hfac=1,1,1,5,5,5-六氟乙酰丙酮根(acetonato)、MHY=2-甲基-1-己烯-3-炔、DMCOD=二甲基环辛二烯、以及VTMS=乙烯基三甲基硅烷。
集成电路制造中的铜金属化通常在铜层和下层结构(underlyingstructure)之间利用隔离层,来防止由于铜层与集成电路其他部分的相互作用而引起的有害效应。通常使用的隔离材料范围较宽,包括含金属、金属氮化物、金属硅化物、和金属氮化硅的材料。示例性的隔离材料包括氮化钛、硅化钛、氮化钽、硅化钽、氮硅化钽、氮化铌、氮硅化铌、氮化钨、和硅化钨。在(hfac)CuL型前体用于铜金属化的情况中,在隔离层和铜层之间形成界面层,其导致金属化具有较差的附着力和较高的接触电阻率。
当使用(hfac)CuL铜前体时,较差附着力和过高接触电阻率的缺点很容易形成含氧和/或含氟界面层,这归因于同时包含氧和氟的hfac配体。为了克服这种缺点,提供具有降低氧/氟含量的铜前体将是本领域的重大进步。提供具有无氧特征的铜前体是尤其有利的。
因此,本发明的目的是提供新型缺氧的(无氧和无氟的)铜前体和制剂(配方),以及利用这些前体和制剂在集成电路和其他微电子器件结构制造中形成铜的方法。
发明内容
本发明通常涉及脒铜(I)(copper(I)amidinate)化合物,其有利地具有无氧和无氟的特性,可作为源反应物用于在衬底上形成具有改善的附着力的铜,并涉及利用这种脒铜(I)化合物的方法。
在一个方面,本发明涉及以下结构式的铜前体化合物:
其中:
R1和R2可以相同或彼此不同,并且各自独立地选自由H、C1-C6烷基、C3-C7环烷基、芳基、和甲硅烷基的烃基衍生物组成的组(例如,-SiR3,其中R独立地选自由C1-C6烷基组成的组);
R3选自由H、C1-C6烷基、C3-C7环烷基、芳基、甲硅烷基的烃基衍生物以及NR4R5组成的组,其中R4和R5可以相同或彼此不同并且独立地选自由H、C1-C6烷基、C3-C7环烷基、芳基、以及甲硅烷基的烃基衍生物组成的组;
条件是,当R1和R2是异丙基时,R3不是甲基。
在另一个方面,本发明涉及铜前体制剂,包括:
(a)以下结构式的铜前体化合物:
其中:
R1和R2可以相同或彼此不同,并且各自独立地选自由H、C1-C6烷基、C3-C7环烷基、芳基、和甲硅烷基的烃基衍生物组成的组;
R3选自由H、C1-C6烷基、C3-C7环烷基、芳基、甲硅烷基的烃基衍生物以及NR4R5组成的组,其中R4和R5可以相同或彼此不同并且独立地选自由H、C1-C6烷基、C3-C7环烷基、芳基、和甲硅烷基的烃基衍生物组成的组;
(b)用于前体化合物的溶剂组合物。
在又一个方面,本发明涉及在衬底上沉积铜的方法,包括挥发以下结构式的铜前体:
其中:
R1和R2可以相同或彼此不同,并且各自独立地选自由H、C1-C6烷基、C3-C7环烷基、芳基、和甲硅烷基的烃基衍生物组成的组;
R3选自由H、C1-C6烷基、C3-C7环烷基、芳基、甲硅烷基的烃基衍生物以及NR4R5组成的组,其中R4和R5可以相同或彼此不同并且独立地选自由H、C1-C6烷基、C3-C7环烷基、芳基、和甲硅烷基的烃基衍生物组成的组;
限制条件是,当R1和R2是异丙基时,R3不是甲基,
以形成前体蒸汽并在升高温度蒸汽热分解条件下使前体蒸汽与衬底接触,使铜沉积在衬底上。
随后的说明和所附的权利要求将使本发明的其它方面、特征和具体实施方式更加显而易见。
附图说明
图1是2-异丙基-1,3-二异丙基脒铜(I)的1H-NMR谱图。
图2是2-异丙基-1,3-二异丙基脒铜(I)的同步热分析(STA)/差示扫描量热法(DSC)曲线图。
图3是2-异丙基-1,3-二异丙基脒铜(I)的ORTEP结构。
图4是2-二甲基氨基-1,3-二异丙基脒铜(I)的STA/DSC曲线图。
图5是2-二甲基氨基-1,3-二异丙基脒铜(I)的ORTEP结构。
具体实施方式
本发明涉及在衬底上CVD或ALD形成铜薄膜的新型脒铜(I)前体,以及利用这些前体的相应工艺。
脒根(amidinate)是大体积单阴离子配体,其具有基本化学结构:
在一个方面,本发明提供以下结构的化合物:
其中:
R1和R2可以相同或彼此不同,并且各自独立地选自由H、C1-C6烷基、C3-C7环烷基、芳基、和甲硅烷基的烃基衍生物组成的组(例如,-SiR3,其中R独立地选自由C1-C6烷基组成的组);
R3选自由H、C1-C6烷基、C3-C7环烷基、芳基、甲硅烷基的烃基衍生物以及NR4R5组成的组,其中R4和R5可以相同或彼此不同并且独立地选自由H、C1-C6烷基、C3-C7环烷基、芳基、和甲硅烷基的烃基衍生物组成的组;
限制条件是,当R1和R2是异丙基时,R3不是甲基。
结构式(I)的化合物可用于通过CVD或ALD工艺形成铜膜,其中利用在特定应用领域技术人员可以容易地确定的包括附属的温度、压力、浓度、流速和CVD技术的工艺条件。
优选的结构式(I)的化合物包括2-异丙基-1,3-二异丙基脒铜(I):
以及2-二甲基氨基-1,3-二异丙基脒铜(I):
根据以下的化学方程式(2)和(3)可以很容易的合成结构式(I)的化合物:
R1-N=C=N-R2中R3Li→(R1-N=C(R3)-N-R2)Li+ (2)
以下将在本文实施例中更全面的描述。
在使用CVD或ALD时,挥发本发明的铜(I)前体,以形成前体蒸汽,然后该蒸汽在升高温度的汽相热分解条件下接触衬底,将铜沉积在衬底上。
2-异丙基-1,3-二异丙基脒铜(I)和2-二甲基氨基-1,3-二异丙基脒铜(I)都是易挥发和热稳定的,并且在降低CVD或ALD反应器中的环境沉积条件(ambient deposition condition)下可用作铜CVD或ALD前体。固态前体可以溶解于有机溶剂中,可用流体输送将溶液计量进蒸发器内,以便转移到反应器。。
更具体地说,作为举例,在形成半导体集成电路、薄膜电路、薄膜封装元件以及薄膜记录磁头线圈中的铜连接线过程中,可以使用本发明的脒铜(I)前体成分。为了形成这样的集成电路或薄膜电路,使用的半导体衬底可以具有多个形成在衬底上和/或内的介电和导电层(多层)。半导体衬底可以包括裸衬底或在裸衬底上形成的任意数目的构成层(constitient layer)。
在本发明的广泛实践中,含铜层可以利用脒铜(I)前体形成于半导体衬底上,用在第一、第二、第三或更多金属化层中。这种铜层通常用于需要低电阻率、高性能和/或高速度电路通道的电路位置。如在本文背景技术中所论述的,在半导体衬底上形成铜层之前,可在衬底上沉积或以其他方式形成隔离层。
然后,利用本文描述的铜前体组合物,可以利用CVD或ALD系统将铜沉积在晶片上,这种系统在半导体制造领域是众所周知的。此外,水、产生水的化合物、或前体制剂的其它辅助剂可以在CVD或ALD设备的上游或内部与铜前体混合。同样的,可以以类似白方式使用还原剂。
作为另一个变体,当铜合金组分要沉积到衬底上时,铜前体制剂可以包含或混合其它金属源反应物质,或这些其它反应物质可以分别被蒸发并引入到沉积室。
本发明的组合物可以以各种途径输送到CVD或ALD反应器。例如,可以使用流体输送系统。可替换地,可以使用组合的流体输送和闪蒸工艺单元,例如LDS300流体输送和蒸发器单元(商业上可获自Advanced Technology Materials,Inc.,Danbury,CT),以能够按体积输送低挥发性物质,实现可再现的转送和沉积而无前体的热分解。兼顾可再生的转送和沉积又无热分解的这些考虑对于提供商业可接受的铜CVD或ALD工艺是重要的。
在流体输送制剂中,液体的铜前体可以以纯液体形式使用,或者液体或固体铜前体可以以含有它的溶剂制剂使用。因此,本发明的铜前体制剂可以包括适宜性质的溶剂成分,该适宜性质可以是对在衬底上形成铜的特定最终应用是理想和有利的。适合的溶剂可以包括例如烷烃溶剂如己烷、庚烷、辛烷、戊烷、或芳烃溶剂例如苯或甲苯、胺以及酰胺。用于特定铜前体的具体溶剂组合物的使用可以容易地以经验来确定,以便为流体输送蒸发和所用具体铜前体的转送选择适当的单一成分或多成分溶剂介质。
在本发明的另一个具体实施方式中,可以使用固体输送系统,例如使用ProE-Vap固体输送和蒸发器单元(商业上获自AdvancedTechnology Materials,Inc.,Danbury,CT)。
对于本发明的前体组合物可以使用种类广泛的CVD或ALD工艺条件。普遍的工艺条件可以包括150~400℃范围的衬底温度、0.05~5托(Torr)范围的压力;以及在大约与蒸发器温度相同的50至120℃、在25~750sccm的氦、氢、氮、或氩的载气流。
具有有利电特性(低电阻率)和对隔离层(例如,由TiN或TaN形成的)良好附着力的铜薄膜的沉积,也可以通过本发明的工艺和前体来完成。实际上,沉积的薄膜的共形性(conformality)通过CVD或ALD技术是可以达到的,该技术优选地对实现“完全填充”(full-fill)铜金属化提供解决途径。本发明的流体输送方法,包括“闪蒸”蒸发和如本文所披露的铜前体化学的使用,能够获得下一代器件的几何结构和尺寸,例如65nm线宽的共形垂直互连。这些关键尺寸的互连的共形沉积不能通过目前可获得的物理沉积法来实现。因此,本发明的方法能给将来的换代器件提供可行的途径,实现在本领域的重大进步。
通过以下例举性和非限制性的实施例,更充分显示本发明的特征和优点。
实施例1 2-异丙基-1,3-二异丙基脒铜(I)的合成
反应是在稳定的氮气流下进行。将6.3g 1,3-二异丙基碳二亚胺((CH3)2CHN=C=NCH(CH3),49.9mmol)和50ml干醚装入Schlenk烧瓶并将烧瓶放置在冰水浴中。然后,在约0℃下向磁力搅拌的混合物中逐滴地加入异丙基锂(在1.6M的醚中,51.2mmol)32ml。在完成加入后,在室温下将混合物再搅拌两小时。将混合物转移到另一个装有悬浮在50ml醚中的6gCuCl(60.6mmol)的烧瓶中。将这种混合物在室温下搅拌过夜,然后汽提至干燥。固体残留物用戊烷(3×50mL)萃取。萃取后,将戊烷滤液浓缩至稍微混浊。将饱和溶液放置在-39℃的冷冻机中,获得的结晶产品的产率约为60%。
图1示出了2-异丙基-1,3-二异丙基脒铜(I)的1H NMR(C6D6)谱,其具有以下峰值:δ1.20(d,6H,(CH3)2CH-C),1.23(br,12H,(CH3)2CH-N),3.20(hept,1H,CH),3.45(br,1H,CH),3.95(br,1H,CH)。
图2示出了2-异丙基-1,3-二异丙基脒铜(I)的STA/DSC曲线图。融融峰为约160℃而残留物为约19%。
图3是2-异丙基-1,3-二异丙基脒铜(I)的ORTEP结构,示出了化合物的二聚物结构和30%概率的热椭圆体。
实施例2 2-二甲基氨基-1,3-二异丙基脒铜(I)的合成
将纯的1,3-二异丙基碳二亚胺(12.37g,98mmol,15.2mL)缓慢地加入到LiNMe2(5g,98mmol)溶于125ml四氢呋喃(THF)的溶液中。观察到放热现象。将反应混合物搅拌1小时。此后,在干箱中向反应混合物加入9.7g固体CuCl(98mmol)。所得的淡绿悬浮液搅拌过夜,并在真空下去除所有的挥发物。在150ml己烷中清洗残留物。滤液在真空下浓缩并放置在冰箱中,由此在夜间生长出纯晶体。总产率为60%,晶体的熔点为108℃。1H NMR(C6D6):δ3.42(七重峰,1H,J(H-H)=6Hz,CH(CH3)2),2.55(单峰,3H,N(CH3)2),1.30(双重峰,6H,J(H-H)=6Hz,CH(CH3)2)。13CNMR(C6D6):δ171.95(Me2NC(N(iPr))2),48.61(CH(CH3)2),41.29(N(CH3)2),27.98(CH(CH3)2)。
图4是2-二甲基氨基-1,3-二异丙基脒铜(I)的STA/DSC曲线图,其在低于230℃的转送温度下是挥发性的并且残留质量低于5%。
图5是2-二甲基氨基-1,3-二异丙基脒铜(I)的ORTEP结构,示出了处于固态的化合物的二聚结构。2.4152(17)的相对短的Cu-Cu距离可以表明弱金属-金属相互作用。平均Cu-N距离是1.875(3),其与在类似化合物中观察到的非常相似。
如本领域技术人员所明了的,尽管本文参照各种具体实施方式描述了本发明,但应该理解到本发明并不限制于此,而是延伸到和涵盖各种其他改进和具体实施方式。因此,应根据所附的权利要求广泛地对本发明进行解释和说明。
Claims (20)
1. 一种铜前体化合物,其结构式为:
其中:
R1和R2可以相同或彼此不同,并且各自独立地选自由H、C1-C6烷基、C3-C7环烷基、芳基、和甲硅烷基的烃基衍生物组成的组;
R3选自由H、C1-C6烷基、C3-C7环烷基、芳基、甲硅烷基的烃基衍生物以及NR4R5组成的组,其中R4和R5可以相同或彼此不同并且独立地选自由H、C1-C6烷基、C3-C7环烷基、芳基、以及甲硅烷基的烃基衍生物组成的组;
限制条件是,当R1和R2是异丙基时,R3不是甲基。
2. 根据权利要求1所述的化合物,其为2-异丙基-1,3-二异丙基脒铜(I)或2-二甲基氨基-1,3-二异丙基脒铜(I)。
3. 根据权利要求1所述的化合物,其中,R1和R2是异丙基。
4. 一种铜前体制剂,包括:
(a)以下结构式的铜前体化合物:
其中:
R1和R2可以相同或彼此不同,并且各自独立地选自由H、C1-C6烷基、C3-C7环烷基、芳基、以及甲硅烷基的烃基衍生物组成的组;
R3选自由H、C1-C6烷基、C3-C7环烷基、芳基、甲硅烷基的烃基衍生物以及NR4R5组成的组,其中R4和R5可以相同或彼此不同并且独立地选自由H、C1-C6烷基、C3-C7环烷基、芳基、以及甲硅烷基的烃基衍生物组成的组;以及
(b)用于所述前体化合物的溶剂成分。
5. 根据权利要求4所述的铜前体制剂,其中,所述溶剂成分包括有机溶剂。
6. 根据权利要求4所述的铜前体制剂,其中,所述溶剂成分包括选自由烷烃、芳烃、胺和酰胺溶剂组成的组的溶剂。
7. 根据权利要求4所述的铜前体制剂,其中,所述溶剂成分包括选自由己烷、庚烷、辛烷、戊烷、苯、甲苯、以及二甲基甲酰胺溶剂组成的组的溶剂。
9. 根据权利要求8所述的方法,其中,在化学汽相沉积条件下沉积所述铜。
10. 根据权利要求8所述的方法,其中,在原子层沉积条件下沉积所述铜。
11. 根据权利要求8所述的方法,所述铜前体为2-异丙基-1,3-二异丙基脒铜(I)或2-二甲基氨基-1,3-二异丙基脒铜(I)。
12. 根据权利要求8所述的方法,其中,所述衬底是隔离材料。
13.根据权利要求12所述的方法,其中,所述隔离材料包括选自由氮化钛、硅化钛、氮化钽、硅化钽、氮硅化钛、氮化铌、氮硅化铌、氮化钨、以及硅化钨组成的组的化合物。
14.根据权利要求8所述的方法,其中,铜的沉积在集成电路的制造过程中发生。
15.根据权利要求8所述的方法,包括通过使用流体输送系统将所述铜前体化合物输送至加工装置。
16. 根据权利要求8所述的方法,包括通过使用固体输送系统将所述铜前体化合物输送至加工装置。
17. 根据权利要求8所述的方法,其中,所述衬底的温度为约150℃至约400℃。
18. 一种将铜沉积到衬底上的方法,包括:
(a)挥发铜前体制剂,其包括:
(i)以下结构式的铜前体化合物:
其中:
R1和R2可以相同或彼此不同,并且各自独立地选自由H、C1-C6烷基、C3-C7环烷基、芳基、和甲硅烷基的烃基衍生物组成的组;
R3选自由H、C1-C6烷基、C3-C7环烷基、芳基、甲硅烷基的烃基衍生物以及NR4R5组成的组,其中R4和R5可以相同或彼此不同并且独立地选自由H、C1-C6烷基、C3-C7环烷基、芳基、以及甲硅烷基的烃基衍生物组成的组; 以及
(ii)用于所述前体化合物的溶剂成分,以形成前体蒸汽;以及
(b)在升高温度的汽相热分解条件下,使所述前体蒸汽与所述衬底接触,将铜沉积到所述衬底上。
19. 根据权利要求18所述的方法,其中,在化学汽相沉积条件下沉积所述铜。
20. 根据权利要求18所述的方法,其中,在原子层沉积条件下沉积所述铜。
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CN106498361A (zh) * | 2016-11-22 | 2017-03-15 | 江南大学 | 一种以肼类为还原剂单原子层沉积技术生长金属Cu的方法 |
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US7531031B2 (en) | 2009-05-12 |
KR20120105057A (ko) | 2012-09-24 |
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EP1765834A1 (en) | 2007-03-28 |
US7166732B2 (en) | 2007-01-23 |
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