CN1158131A - 金属有机化合物 - Google Patents
金属有机化合物 Download PDFInfo
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- CN1158131A CN1158131A CN95194877A CN95194877A CN1158131A CN 1158131 A CN1158131 A CN 1158131A CN 95194877 A CN95194877 A CN 95194877A CN 95194877 A CN95194877 A CN 95194877A CN 1158131 A CN1158131 A CN 1158131A
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- 150000001875 compounds Chemical class 0.000 title description 3
- 238000000034 method Methods 0.000 claims abstract description 29
- 150000001412 amines Chemical class 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 10
- 150000004795 grignard reagents Chemical class 0.000 claims abstract description 10
- 229910001507 metal halide Inorganic materials 0.000 claims abstract description 6
- 150000005309 metal halides Chemical class 0.000 claims abstract description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 125000002524 organometallic group Chemical group 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052733 gallium Inorganic materials 0.000 claims description 10
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 claims description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 9
- -1 alkyl tertiary amine Chemical class 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 150000001350 alkyl halides Chemical class 0.000 claims description 4
- 150000003512 tertiary amines Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- OYWRDHBGMCXGFY-UHFFFAOYSA-N 1,2,3-triazinane Chemical compound C1CNNNC1 OYWRDHBGMCXGFY-UHFFFAOYSA-N 0.000 claims description 2
- 150000000182 1,3,5-triazines Chemical class 0.000 claims description 2
- JZIBVTUXIVIFGC-UHFFFAOYSA-N 2H-pyrrole Chemical class C1C=CC=N1 JZIBVTUXIVIFGC-UHFFFAOYSA-N 0.000 claims description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims 1
- 239000004065 semiconductor Substances 0.000 abstract description 5
- 150000002902 organometallic compounds Chemical class 0.000 abstract 3
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000012808 vapor phase Substances 0.000 abstract 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 12
- 239000012535 impurity Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000012043 crude product Substances 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 229910000980 Aluminium gallium arsenide Inorganic materials 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- LVKCSZQWLOVUGB-UHFFFAOYSA-M magnesium;propane;bromide Chemical compound [Mg+2].[Br-].C[CH-]C LVKCSZQWLOVUGB-UHFFFAOYSA-M 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000012263 liquid product Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910021654 trace metal Inorganic materials 0.000 description 4
- CKGXVGFLQCIASW-UHFFFAOYSA-N tri(propan-2-yl)indigane Chemical compound CC(C)[In](C(C)C)C(C)C CKGXVGFLQCIASW-UHFFFAOYSA-N 0.000 description 4
- NAMYKGVDVNBCFQ-UHFFFAOYSA-N 2-bromopropane Chemical compound CC(C)Br NAMYKGVDVNBCFQ-UHFFFAOYSA-N 0.000 description 3
- 230000031709 bromination Effects 0.000 description 3
- 238000005893 bromination reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 3
- 239000003923 scrap metal Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
- 229910021617 Indium monochloride Inorganic materials 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 2
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 2
- APFVFJFRJDLVQX-AHCXROLUSA-N indium-111 Chemical compound [111In] APFVFJFRJDLVQX-AHCXROLUSA-N 0.000 description 2
- 229940055742 indium-111 Drugs 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PFNQVRZLDWYSCW-UHFFFAOYSA-N (fluoren-9-ylideneamino) n-naphthalen-1-ylcarbamate Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1=NOC(=O)NC1=CC=CC2=CC=CC=C12 PFNQVRZLDWYSCW-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- FTWRSWRBSVXQPI-UHFFFAOYSA-N alumanylidynearsane;gallanylidynearsane Chemical compound [As]#[Al].[As]#[Ga] FTWRSWRBSVXQPI-UHFFFAOYSA-N 0.000 description 1
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 150000002258 gallium Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000000266 injurious effect Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- RGGPNXQUMRMPRA-UHFFFAOYSA-N triethylgallium Chemical compound CC[Ga](CC)CC RGGPNXQUMRMPRA-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
-
- 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/505—Preparation; Separation; Purification; Stabilisation
- C07F9/5063—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds
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- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
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- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
- C30B29/42—Gallium arsenide
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Abstract
本发明涉及一种制备金属有机化合物及金属有机胺加合物的方法。制备一种格氏试剂并让其与金属卤化物在一种胺溶剂中反应。所使用的胺可与所生成的金属有机化合物形成一种有用的加合物。应用气相取向生长技术，金属有机化合物或其胺加合物可用来生长半导体层。
Description
本发明涉及金属有机化合物，尤其那些用于应用诸如化学射束取向生长，MOVPE或ALE之类的汽相取向生长技术生长半导体层的金属有机化合物。
用于半导体生长的金属有机前体通常由诸如烷基卤化镁RMgX或烷基锂化合物之类的格氏试剂与金属卤化物反应来合成。格氏试剂的生成及其相应的与金属卤化物形成前体的反应在一种含氧溶剂(通常为醚)中进行。然后进行纯化以便将含氧的醚溶剂和其它杂质从金属有机前体中脱除。
不幸的是残余量的醚会导致由以上所制备的前体生长的半导体结构出现氧污染，从而对半导体结构的性能产生有害的影响。
本发明的目的在于提供一种可克服上述缺点的制备金属有机化合物的方法。
按照本发明，提供了由格氏试剂与金属卤化物反应制备金属有机化合物的方法，其特征在于所说的反应在一种胺溶剂中进行。
本发明的方法中使用的格氏试剂优选是在一种胺溶剂，尤其是用来制备金属有机化合物的胺中制备。
所使用的胺优选为叔胺，比如烷基叔胺或叔杂环胺。本发明中使用的胺在室温，通常18～20℃下优选为液体。本发明中使用的叔烷基胺优选是具有以下的分子式：其中R1，R2和R3为含1～4个碳原子的烷基，且R1，R2和R3可以是相同基团或R1，R2和R3中的两个可以相同。本发明中使用的烷基胺优选为三乙基胺和二甲基乙基胺。
本发明中使用的合适的杂环胺包括吡啶，2H-吡咯，嘧啶，吡嗪，哒嗪，1，3，5-三嗪和六氢三嗪。
本发明的方法可得到新型化合物，因此本发明包括这些化合物。
按照本发明的第二方面，提供了下式的新型金属有机胺加合物
MR3·A其中M是金属，R是烷基且A是叔胺，如下式叔烷胺，如下式叔烷胺
其中R1，R2和R3定义如上或叔杂环胺。
格氏试剂可用任何合适的方法，通常由镁与烷基卤化物反应制备，其中的烷基是金属有机化合物所需要的烷基。
按照本发明所制备的金属有机化合物包括第II族，第III族和第V族金属的烷基化合物。这些化合物的例子包括二烷基锌，二烷基镉。三烷基铝，三烷基镓，三烷基铟，三烷基磷，三烷基砷和三烷基锑。
据认为，本发明中的方法导致金属有机化合物与胺形成加合物。这种加合物的形成允许可挥发性的金属和非金属微观杂质从金属有机化合物中脱除。杂质很容易通过蒸馏从加合物中脱除。加合物通过除去胺(例如通过加热)加以分解，以便为一些目的(如作为MOVPE或CBE的前体)提供单独的金属有机化合物。另外，通过MOVPE，CBE和其它气相取向生长技术，加合物本身也可以用作例如第III-V族或II-VI族金属层(如砷化镓，砷化铝镓和硒化锌)的沉积的前体。
本发明中的优选方法包括以下步骤：
1.在NR3溶剂中合成RMgX；
2.将MCl3悬浮在戊烷中；
3.将RMgX加入MCl3的NR3/戊烷溶液中；
4.通过蒸馏脱除可挥发性物质并分离出MR3(NR3)；
5.从MR3(NR3)中除去挥发性杂质；
6.加合物的分离或MR3(NR3)的热分解并由分馏脱除NR3配体。
本发明将通过下面的实施例来进行进一步的描述。以下所述各反应均采用由标准纯化方法进行干燥和脱氧的试剂在常压的干燥无氧氮气中进行。
实施例1
本实例阐述采用三乙基胺为溶剂来生成三异丙基镓。
将异丙基溴(i-PrBr，280g，2.3mol)滴加到镁金属屑(60g，
2.5mol)在三乙基胺(NEt3，1000cm3)中的搅拌悬浮液中，制得异丙基
溴化镁(i-PrMgBr)的三乙胺溶液。反应剧烈放热。如果加入碘晶体，则
反应更易开始。滴加完i-PrBr后，将反应混合物于室温下搅拌4小时。
然后在搅拌下将三氯化镓(GaCl3，125g，0.7mol)的戊烷(500cm3)溶液缓慢加入i-PrMgBr的三乙胺溶液中。反应中有热量生成。GaCl3戊烷溶液加完后，将反应混合物于室温下搅拌4小时以确保反应完全。
真空蒸馏除去挥发性物质后，在100℃下真空蒸馏将粗产物收集到在液氮(-196℃)冷却下的接收器中。25-50℃下真空蒸馏将挥发性杂质从粗产物中除去，80℃下真空蒸馏到冷却的接收器(约-106℃)中而获得纯液体产物。
经质子NMR谱证明金属有机产物为三异丙基镓的三乙基胺加合物，i-Pr3Ga(NEt3)0.6
质子NMR谱数据如下：
(ppm) 归属
0.8(三重线，5.4H) NCH2CH3
1.0(多重线，3H) GaCH(CH3)2
1.4(双重线，18H) GaCH(CH3)2
2.4(四重线，3.6H) NCH2CH3
采用感应偶合的等离子发射光谱(ICP-ES)进一步分析i-Pr3Ga-NEt3加合物中的痕量金属杂质。检测到的杂质仅有硅(0.03ppm w.r.t.Ga)及锌(0.2ppm w.r.t.Ga)。
收率(i-Pr3Ga(NEt3)0.6)＝49.4g
13℃时iPr3Ga加合物的蒸汽压为0.9mBar。
在下面的条件下用由以上方法所制备的三异丙基镓通过化学射束取向生长技术在砷化镓基体上生长一层AlGaAs：
基质温度 540℃
AlGaAs生长速率 1/小时
第V族前体- 热裂解的胂
第III族前体- 三异丙基镓三乙基胺加合物+
AlH3-NMe2Et
二次离子质谱(SIMS)测定结果表明由这种方法生长的AlGaAs层(18％的铝组分)其氧水平低于4×1016cm-3。这种AlGaAs层优于由用普通方法(比如用醚作为溶剂)制备的三异丙基镓和AlH3(NMe2Et)所生长的AlGaAs层(25％的铝组分)，SIMS测得后者的氧水平高于9×1016cm-3。由三异丙基镓-三乙基胺加合物生长的AlGaAs层在氧含量上(＜4×1016cm-3)可与用三乙基镓和AlH3(NMe2Et)在相同CBE生长条件下所生长的最好的AlGaAs层相比。
附图中图1和图2依次比较了按照本实例制备的三异丙基镓加合物和按照普通方法制备的三异丙基镓的蒸汽压和生长速率。可以看出加合物的蒸汽压和生长速率都较高，这对于化学气相淀积法是有益的。
实施例2
本实例阐述采用二甲基乙基胺为溶剂来生成三异丙基镓。
将异丙基溴(i-PrBr，166g，1.4mol)滴加到镁金属屑(48g，2.0mol)在二甲基乙基胺(NMe2Et，500cm3)中的搅拌悬浮液中，制得异丙基溴化镁(i-PrBr)的二甲基乙基胺溶液。反应剧烈放热。如果加入少量碘，则反应更易开始。加完i-PrBr后，将反应混合物于室温下搅拌4小时。
然后搅拌下将三氯化镓(GaCl3，69g，0.4mol)的戊烷(260cm3)溶液缓慢加入i-PrMgBr的NMe2Et溶液中。反应剧烈放热。GaCl3戊烷溶液加完后，将反应混合物于室温下搅拌4小时以确保反应完全。
在60℃下常压蒸馏除去挥发性物质后，在100℃下真空蒸馏将粗产物收集在液氮(约-196℃)冷却下的接收器中。真空蒸馏将挥发性杂质从粗产物中除去，70℃下真空蒸馏将纯液体产物收集在接收器中。
经质子NMR谱证明金属有机产物为三异丙基镓的二甲基乙基胺加合物，i-Pr3Ga(NMe2Et)。质子NMR谱数据如下：
(ppm) 归属
0.6(三重线，3H) NCH2CH3
0.9(多重线，3H) GaCH(CH3)2
1.4(双重线，18H) GaCH(CH3)2
1.9(单线，6H) NCH3
2.4(四重线，3.6H) NCH2CH3
采用ICP-ES进一步分析i-Pr3Ga-NMe2Et加合物中的痕量金属杂质。检测到的杂质仅有硅(0.2ppm w.r.t.Ga)及锌(4.6ppm w.r.t.Ga)。
收率(i-Pr3Ga(NMe2Et)＝58.5g
实施例3
本实例阐述采用三乙基胺为溶剂来生成三异丙基铟。
滴加异丙基溴(i-PrBr，72g，0.6mol)到三乙基胺(NEt3，200cm3)中的搅拌悬浮液中，制得异丙基溴化镁(i-PrBr)的三乙胺溶液。反应剧烈放热。滴加完i-PrBr后，将反应混合物于室温下搅拌4小时。
然后搅拌下将i-PrMgBr的三乙胺溶液滴加入三氯化铟(InCl3，35g，0.2mol)的三乙基胺(200cm3)悬浮液中。反应放热。i-PrMgBr/三乙胺溶液溶液加完后，将反应混合物回流2小时以确保反应完全。
真空蒸馏除去挥发性物质后，100℃下真空蒸馏将粗产物收集在液氮(约-196℃)冷却下的接收器中。真空蒸馏将挥发性杂质从粗产物中除去，70℃下真空蒸馏将纯液体产物收集到冷却(约-196℃)接收器中。
经质子NMR谱证明金属有机产物为三异丙基铟的三乙基胺加合物，i-Pr3In(NEt3)。
质子NMR谱数据总结如下：
(ppm) 归属
0.8(三重线，9H) NCH2CH3
1.1(多重线，3H) InCH(CH3)2
1.6(双重线，18H) InCH(CH3)2
2.4(四重线，6H) NCH2CH3
采用ICP-ES进一步分析i-Pr3In-NEt3加合物中的痕量金属杂质。检测到的杂质仅有硅(0.04ppm w.r.t.In)及锌(3.8ppm w.r.t.In)。
收率(i-Pr3In(NEt3))＝8g。
实施例4
本实例阐述采用二甲基乙基胺为溶剂来生成三异丙基铟。
将i-PrBr(192g，1.6mol)滴加到镁金属屑(56g，2.3mol)在二甲基乙基胺(NMe2Et，400cm3)中的搅拌悬浮液中，制得i-PrBr的二甲基乙基胺溶液。
反应剧烈放热。滴加完i-PrBr后，将反应混合物于室温下搅拌4小时。
然后搅拌下将i-PrMgBr的NMe2Et溶液滴加入三氯化铟(InCl3，72g，0.3mol)的戊烷悬浮液中。反应放热。i-PrMgBr/NMe2Et溶液加完后，将反应混合物回流2小时。
60℃常压蒸馏除去挥发性物质后，85-90℃下真空蒸馏将粗产物收集在接收器中。25℃下真空蒸馏将挥发性杂质从粗产物中除去。
85-90℃下真空蒸馏将纯液体产物收集到冷却(约-196℃)接收器中。
经质子NMR谱证明草黄色的液体产物为三异丙基铟的二甲基乙基胺加合物，i-Pr3In(NMe2Et)。质子NMR谱数据如下：
(ppm) 归属
0.8(三重线，3H) NCH2CH3
1.0(多重线，3H) InCH(CH3)2
1.5(双重线，18H) InCH(CH3)2
2.0(单线，6H) NCH3
2.3(四重线，2H) NCH2CH3
采用ICP-EAS进一步分析i-Pr3In-NMe2Et加合物中的痕量金属杂质。检测到的杂质仅有硅(＜1ppm w.r.t.In)及锌(0.12ppm w.r.t.In)。
收率(i-Pr3In(NMe2Et)＝81.7g。
Claims (20)
1、一种由格氏试剂与金属卤化物反应制备金属有机化合物的方法，其特征在于反应是在一种胺溶剂中进行。
2、按照权利要求1所述的方法，其特征在于格氏试剂是在一种胺溶剂中制备。
3、按照权利要求2所述的方法，其特征在于制备格氏试剂所用的胺溶剂与其同金属卤化物反应所用的胺溶剂相同。
4、按照权利要求1，2或3所述的方法，其特征在于这种胺是叔胺。
5、按照权利要求1-4中任何一项中所述的方法，其特征在于这种胺是选自烷基叔胺或叔杂环胺。
6、按照权利要求1-5中任何一项中所述的方法，其特征在于这种胺在室温下是液体。
7、按照权利要求1-6中任何一项中所述的方法，其特征在于这种胺具有以下式
其中R1，R2和R3为含1～4个碳原子的烷基，且R1，R2和R3是相同基团或R1，R2和R3中的两个可以相同。
8、按照权利要求1-7中任何一项中所述的方法，其特征在于这种胺选自三乙基胺和二甲基乙基胺。
9、按照权利要求1-6中任何一项中所述的方法，其特征在于这种胺选自吡啶，2H-吡咯，嘧啶，吡嗪，哒嗪，1，3，5-三嗪和六氢三嗪。
10、按照权利要求1-9中任何一项中所述的方法，其特征在于格氏试剂由镁与烷基卤化物反应来制备，烷基卤化物中的烷基为金属有机化合物所需要的烷基。
11、按照权利要求1-10中任何一项中所述的方法，其特征在于金属有机化合物是选自第II族，第III族和第V族金属中的一种金属的烷基化合物。
12、按照权利要求11中所述的方法，其特征在于金属有机化合物是选自二烷基锌，二烷基镉，三烷基铝，三烷基镓，三烷基铟，三烷基磷，三烷基砷和三烷基锑。
13、按照权利要求11或12中所述的方法，其中的烷基为异丙基。
14、按照权利要求1-14中任何一项中所述的方法，其特征在于将金属有机化合物于与作为溶剂的胺的加合物分离出来。
15、按照权利要求14中所述的方法，其特征在于将金属有机胺加合物进一步分解得到金属有机化合物。
16、一种按照权利要求1-15中任何一项中所述的方法制备的金属有机化合物。
17、具有分子式MR3·A的金属有机胺加合物，其中M是金属
R是烷基，和
A是具有以下结构式的叔胺其中R1，R2和R3为含1～4个碳原子的烷基，且R1，R2和R3是相同基团或R1，R2和R3中的两个可以相同，或叔杂环胺。
18、一种按照权利要求17中所述的加合物，其中MR3中的烷基为C1-5直链或支链烷基。
19、一种按照权利要求18中所述的加合物，其中的烷基为异丙基。
20、一种按照权利要求1中所述的且基本上根据实施例中任何一个所描述的方法。
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| GB9417707A GB9417707D0 (en) | 1994-09-02 | 1994-09-02 | Metaloganic compounds |
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| GBGB9508702.9A GB9508702D0 (en) | 1995-04-28 | 1995-04-28 | Metalorganic compounds |
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| WO2001016101A1 (fr) * | 1999-08-26 | 2001-03-08 | Fujisawa Pharmaceutical Co., Ltd. | Procede de preparation de derives de l'indole ou de leurs sels |
| JP4757370B2 (ja) * | 2000-05-30 | 2011-08-24 | 住友化学株式会社 | エピタキシャル基板の製造方法 |
| CN100379745C (zh) * | 2001-10-26 | 2008-04-09 | 埃普切公司 | 化学气相淀积用的改良的前体 |
| TW200619222A (en) * | 2004-09-02 | 2006-06-16 | Rohm & Haas Elect Mat | Method for making organometallic compounds |
| JP4470682B2 (ja) * | 2004-10-13 | 2010-06-02 | 住友化学株式会社 | トリメチルガリウムの製造方法 |
| KR101491868B1 (ko) * | 2007-03-09 | 2015-02-09 | 오츠카 가가쿠 가부시키가이샤 | ６-히드록시에틸페남 화합물의 제조 방법 |
| US11470981B2 (en) | 2010-05-03 | 2022-10-18 | Levitation Sciences Llc | Four-in-one mattress management system |
| US9145612B2 (en) | 2012-07-06 | 2015-09-29 | Applied Materials, Inc. | Deposition of N-metal films comprising aluminum alloys |
| CN105473598B (zh) | 2013-08-22 | 2018-05-08 | 优美科股份公司及两合公司 | 用于生产烷基铟化合物的方法及其用途 |
| US9389181B2 (en) * | 2014-06-06 | 2016-07-12 | International Business Machines Corporation | Methods and apparatus for detecting metals in liquids |
| US9656239B2 (en) | 2014-06-16 | 2017-05-23 | International Business Machines Corporation | Apparatus for controlling metals in liquids |
| CN106349293B (zh) * | 2016-08-27 | 2018-07-06 | 广东先导稀材股份有限公司 | 高纯三乙基锑的制备方法 |
| US10787466B2 (en) | 2018-04-11 | 2020-09-29 | Inpria Corporation | Monoalkyl tin compounds with low polyalkyl contamination, their compositions and methods |
| US11673903B2 (en) | 2018-04-11 | 2023-06-13 | Inpria Corporation | Monoalkyl tin compounds with low polyalkyl contamination, their compositions and methods |
| KR102536479B1 (ko) | 2018-06-21 | 2023-05-24 | 인프리아 코포레이션 | 모노알킬 주석 알콕사이드 및 이들의 가수분해 및 축합 생성물의 안정적인 용액 |
| KR102261084B1 (ko) * | 2018-11-09 | 2021-06-07 | 주식회사 레이크머티리얼즈 | 유기 금속 박막 전구체 및 이의 제조 방법 |
| US11498934B2 (en) | 2019-01-30 | 2022-11-15 | Inpria Corporation | Monoalkyl tin trialkoxides and/or monoalkyl tin triamides with particulate contamination and corresponding methods |
| US11966158B2 (en) | 2019-01-30 | 2024-04-23 | Inpria Corporation | Monoalkyl tin trialkoxides and/or monoalkyl tin triamides with low metal contamination and/or particulate contamination, and corresponding methods |
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| GB2111998A (en) * | 1981-11-25 | 1983-07-13 | Secr Defence | The preparation of adducts which may be used in the preparation of compound semiconductor materials |
| JPS5988039A (ja) * | 1982-11-11 | 1984-05-21 | ライオン株式会社 | イスパグ−ラハスク含有食品生地 |
| GB8316605D0 (en) * | 1983-06-17 | 1983-07-20 | Secr Defence | Preparation of metal alkyls |
| JPH0662640B2 (ja) * | 1985-04-09 | 1994-08-17 | イギリス国 | ▲ｉｉ▼族金属アルキルの製造 |
| EP0387933B1 (en) * | 1989-03-16 | 1993-08-04 | The Procter & Gamble Company | High fiber baked cookies containing psyllium |
| JPH0360805A (ja) * | 1989-07-28 | 1991-03-15 | Sumitomo Metal Ind Ltd | 熱延鋼帯コイルの保熱方法および装置 |
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| DE4017966C2 (de) * | 1990-06-05 | 1996-05-30 | Ppm Pure Metals Gmbh | Verwendung elementorganischer Verbindungen zur Abscheidung aus der Gasphase |
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| Publication number | Publication date |
|---|---|
| ATE170525T1 (de) | 1998-09-15 |
| JPH10505199A (ja) | 1998-05-19 |
| EP0778837A1 (en) | 1997-06-18 |
| JPH10505355A (ja) | 1998-05-26 |
| GB2306165A (en) | 1997-04-30 |
| EP0778837B1 (en) | 1998-09-02 |
| US5980978A (en) | 1999-11-09 |
| EP0778838A1 (en) | 1997-06-18 |
| DE69504526T2 (de) | 1999-05-27 |
| GB9704270D0 (en) | 1997-04-16 |
| DE69504526D1 (de) | 1998-10-08 |
| KR100367023B1 (ko) | 2003-04-11 |
| CN1156996A (zh) | 1997-08-13 |
| GB2306960B (en) | 1998-07-08 |
| CA2198453C (en) | 2002-02-19 |
| CA2198453A1 (en) | 1996-03-14 |
| CA2198588A1 (en) | 1996-03-14 |
| GB9703701D0 (en) | 1997-04-09 |
| WO1996007661A1 (en) | 1996-03-14 |
| KR970705568A (ko) | 1997-10-09 |
| WO1996007660A1 (en) | 1996-03-14 |
| DE69526092T2 (de) | 2002-11-21 |
| US5886203A (en) | 1999-03-23 |
| GB2306165B (en) | 1998-07-01 |
| CN1051554C (zh) | 2000-04-19 |
| GB2306960A (en) | 1997-05-14 |
| MY112170A (en) | 2001-04-30 |
| MY112590A (en) | 2001-07-31 |
| CA2198588C (en) | 2001-08-21 |
| DE69526092D1 (de) | 2002-05-02 |
| EP0778838B1 (en) | 2002-03-27 |
| CN1051553C (zh) | 2000-04-19 |
| KR100367022B1 (ko) | 2003-04-10 |
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