CN1171894C - Preparation method of oxygen free trialkyl gallium - Google Patents
Preparation method of oxygen free trialkyl gallium Download PDFInfo
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- CN1171894C CN1171894C CNB021381674A CN02138167A CN1171894C CN 1171894 C CN1171894 C CN 1171894C CN B021381674 A CNB021381674 A CN B021381674A CN 02138167 A CN02138167 A CN 02138167A CN 1171894 C CN1171894 C CN 1171894C
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- Prior art keywords
- gallium
- preparation
- trialkyl gallium
- oxygen free
- trialkyl
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- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 47
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000001301 oxygen Substances 0.000 title claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 150000001350 alkyl halides Chemical class 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 150000001412 amines Chemical class 0.000 claims abstract description 6
- 238000004821 distillation Methods 0.000 claims abstract description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- FWLGASJILZBATH-UHFFFAOYSA-N gallium magnesium Chemical compound [Mg].[Ga] FWLGASJILZBATH-UHFFFAOYSA-N 0.000 claims description 4
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 2
- RGGPNXQUMRMPRA-UHFFFAOYSA-N triethylgallium Chemical compound CC[Ga](CC)CC RGGPNXQUMRMPRA-UHFFFAOYSA-N 0.000 claims 2
- 239000012429 reaction media Substances 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- -1 methyl halide Chemical class 0.000 abstract description 4
- 230000006837 decompression Effects 0.000 abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 abstract description 3
- 239000011777 magnesium Substances 0.000 abstract description 3
- 150000002259 gallium compounds Chemical class 0.000 abstract description 2
- 150000003512 tertiary amines Chemical class 0.000 abstract 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 150000002430 hydrocarbons Chemical class 0.000 abstract 1
- 239000011261 inert gas Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000007818 Grignard reagent Substances 0.000 description 8
- 150000004795 grignard reagents Chemical class 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 150000002170 ethers Chemical class 0.000 description 5
- 238000005804 alkylation reaction Methods 0.000 description 3
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 150000005826 halohydrocarbons Chemical class 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910000980 Aluminium gallium arsenide Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910002601 GaN Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
Abstract
The present invention relates to a preparation method of oxygen free trialkyl gallium. In the preparation method, organic tertiary amine and the mixture of gallium and magnesium are put in a reaction container; air in the system is eliminated, and inert gas is filled; alkyl halide is added under stirring and heating; when all alkyl halide is added, stirring continues to be carried out until reaction is sufficient; or hydrocarbon solvents are added; alkyl halide is added under stirring and heating; when all alkyl halide is added, stirring continues to be carried out until reaction is sufficient; excessive organic tertiary amine, solvents and volatile substances are removed under decompression; the mixture of trialkyl gallium and amine can be obtained at normal pressure or through decompression and distillation; or coordination compound decomplexation is directly carried out for obtaining trialkyl gallium. The present invention has the advantages that the present invention can realize the direct action of methyl halide and gallium metal for generating trialkyl gallium under the condition of organic tertiary amine as an oxygen free auxiliary reagent and the assistance of other metal; the yield is more than 30%. The method realizes the oxygen free preparation of trialkyl gallium compounds and has simple and convenient operation.
Description
One, technical field
The present invention relates to a kind of preparation method's who is used for the trialkyl gallium in photoelectron technology field, particularly a kind of oxygen free trialkyl gallium preparation method.
Two, background technology
High-purity trialkyl gallium, it is one of important support material of advanced metal organic chemical vapor deposition (MOCVD) technology epitaxy compound semiconductor, the compound semiconductor materials such as GaAs, GaN, AlGaAs, GaInN that are widely used in growing have important use to be worth in development of opto-electronic devices such as high brightness luminescent pipe, semiconductor laser, various band detector, solar cell and producer mask.
The quality purity of high-purity trialkyl gallium is the of paramount importance quality index in high-purity trialkyl gallium source, the height of the quality purity of high-purity trialkyl gallium directly influences the performance of the compound semiconductor of being grown, along with the develop rapidly of MOCVD technology and the quickening of industrialization process, more and more higher requirement has been proposed in the trialkyl gallium source.The quality purity of high-purity trialkyl gallium is main relevant with the amount of its contained element impurity, and the content of element impurity is low more, and the quality of high-purity trialkyl gallium is just good more.Paying close attention to maximum to the trialkyl gallium source for a long time mainly is metallic impurity such as iron, silicon, copper, tin.Nearest studies show that oxygen is to influence one of most important impurity element of compound semiconductor materials performance, and using oxo solvent in the preparation process in source is an important reasons [M.S.Ravetz who causes epitaxial film oxygen to stain, L.M.Smith, S.A.Rushworth, A.B.Leese, R.Kanijola, J.I.Davies, R.T.Blunt, J.Electron.Mater., 2000,29,157. (electronic material magazine, 2000)].
At present, preparation method with trialkyl gallium of industrial application value mainly contains Grignard reagent method and two kinds of direct alkylation process, and the Grignard reagent method promptly generates Grignard reagent with halohydrocarbon and MAGNESIUM METAL effect earlier, with the Grignard reagent and the gallium halide effect that obtain, obtain alkylate then; Direct alkylation process, i.e. down auxiliary at metal reagent, a step is realized the alkylation of halohydrocarbon to gallium.These two kinds of methods all need medium and the auxiliary reagent as reaction such as organic ethers such as ether usually.Studies show that the organic ethers reagent that uses in the preparation process is difficult to thoroughly remove in purge process, residual a small amount of organic ethers reagent will cause the oxygen of compound to stain, thereby influence the performance of compound semiconductor.For this reason, proposed the notion of low oxygen source and no oxygen source recently, so-called low oxygen source manages to go to deal with problems from purge process exactly, utilizes the oxygenate impurities such as organic ethers that may exist in purification technique (as the title complex purification technique) the removal source; So-called no oxygen source from the head product preparation process in source, is just got rid of and is used aerobic reagent exactly, under complete anaerobic system
Realize the preparation and the purifying of source compound, thoroughly get rid of of the contamination of oxygenate impurity such as organic ethers the source.The quality perspective in collateral security and raising source considers that no oxygen source should be ideal.Document [A.C.Jones, S.A.Rushworth, T.Martin, T.J.Whittaker, R.W.Freer, US Patent 5,980,978 (1999) (United States Patent (USP)s, the patent No. 5,980,978,1999)] reported and under oxygen free condition, utilized the Grignard reagent legal system to be equipped with the method for trialkyl gallium, promptly elder generation by MAGNESIUM METAL and alkylogen effect, prepares the alkyl Grignard reagent in the presence of trimethylamine, and then, obtain the mixture of trialkyl gallium and amine complex with the Grignard reagent and the gallium trichloride effect that obtain.This preparation method need prepare Grignard reagent and gallium trichloride earlier, and then allow both react, in fact need three-step reaction, obviously there is the cumbersome shortcoming of operation, Fan Ying productive rate is not high yet in addition, even do not considering that gallium trichloride prepares under the situation of productive rate, the productive rate of preparation is also lower, as obtains (i-pr)
3Ga (NEt
3)
0.6Productive rate be 27%.
Three, summary of the invention
1, goal of the invention: purpose of the present invention provides a kind of method for preparing trialkyl gallium under the condition of complete anaerobic auxiliary reagent.
2, technical scheme: for achieving the above object, the preparation method of oxygen free trialkyl gallium of the present invention is characterized in that this method is:
Method one: trimethylamine, the gallium magnesium mixture of excessive (double as solvent) are placed reaction vessel, adopt the air in the anhydrous technology eliminating of western cold gram (Schlenk) the anaerobic system and charge into rare gas element, stir, under the heating (room temperature to 100 ℃), slowly add haloalkane, after adding, continue to stir 1-4 hour, to react fully; Filter when needing, the reaction mixture that obtains is under reduced pressure removed excessive trimethylamine, and normal pressure or underpressure distillation obtain the mixture of trialkyl gallium and amine, or directly carries out title complex and separate and join, and obtains trialkyl gallium.
Method two:
Trimethylamine, gallium magnesium mixture are placed reaction vessel, adopt the air in the anhydrous technology eliminating of western cold gram (Schlenk) the anaerobic system and charge into rare gas element, add suitable varsol such as hexane, stirring, heating under (below the boiling point of solvent), slowly add haloalkane, after adding, continue to stir 1-10 hour, to react fully; Filter when needing, the reaction mixture that obtains under reduced pressure removes and desolvates and other volatile matter, and normal pressure or underpressure distillation obtain the mixture of trialkyl gallium and amine complex.Or directly carry out title complex and separate and join, obtain trialkyl gallium.
3, beneficial effect
The present invention compared with prior art, its remarkable advantage is: under the condition of trimethylamine as the anaerobic auxiliary reagent, assisting down of other metals (as MAGNESIUM METAL), can realize the direct effect of methyl halide and gallium, generate trialkyl gallium, productive rate is more than 30%.This method has realized the anaerobic preparation of trialkyl gallium compound, and is easy and simple to handle.
Four, embodiment
Embodiment 1: in reaction flask, add triethylamine (excessive), magnesium gallium mixture, adopt the air in the anhydrous technology eliminating of the Schlenk anaerobic system and charge into nitrogen, under heating (about 40-80 ℃), stirring, slowly add methyl iodide, after adding, continued stirring reaction 4 hours, the triethylamine that pressure reducing and steaming is excessive, underpressure distillation get the title complex of trimethyl-gallium and triethylamine, and productive rate is in gallium 40%.
Embodiment 2: in reaction flask, add N, N-Diethyl Aniline, magnesium gallium mixture, adopt the air in the anhydrous technology eliminating of the Schlenk anaerobic system and charge into nitrogen, add toluene as solvent, heating (about 40-80 ℃), stirring slowly add methyl iodide, after adding down, continued stirring reaction 6 hours, filter, filtrate boils off solvent and other volatile impurity under normal pressure or decompression, under the vacuum to trimethyl-gallium and N, the title complex of N-Diethyl Aniline is separated and is joined, and obtains trimethyl-gallium, and productive rate is in gallium 36%.
Claims (6)
1, a kind of preparation method of oxygen free trialkyl gallium is characterized in that this preparation method is:
1) trimethylamine, gallium magnesium mixture are placed reaction vessel, the air in the eliminating system also charges into rare gas element;
2) under stirring, heating, add haloalkane, continue to be stirred to sufficient reacting after adding; The temperature of heating is a room temperature to 100 ℃;
3) under reduced pressure remove excessive trimethylamine, normal pressure or underpressure distillation obtain the mixture of trialkyl gallium and amine, or directly carry out title complex and separate and join, and obtain trialkyl gallium;
Described trimethylamine is triethylamine, N, the N-Diethyl Aniline; Described rare gas element is a nitrogen; Haloalkane is a methyl iodide; Trialkyl gallium is a triethyl-gallium.
2, the preparation method of oxygen free trialkyl gallium according to claim 1 is characterized in that 1) in adopt air in the western cold gram anaerobic anhydrous process eliminating system.
3, the preparation method of oxygen free trialkyl gallium according to claim 1 is characterized in that 2) in time of continue stirring be 1-4 hour.
4, a kind of preparation method of oxygen free trialkyl gallium is characterized in that this preparation method is:
1) with trimethylamine as reaction medium, trimethylamine, gallium magnesium mixture are placed reaction vessel, the air in the eliminating system also charges into rare gas element;
2) add varsol, under stirring, heating, add haloalkane, continue to be stirred to sufficient reacting after adding; The temperature of heating is below the boiling point of solvent;
3) under reduced pressure remove and desolvate and volatile matter, normal pressure or underpressure distillation obtain the mixture of trialkyl gallium and amine complex, or directly carry out title complex and separate and join, and obtain trialkyl gallium;
Described trimethylamine is triethylamine, N, the N-Diethyl Aniline; Described rare gas element is a nitrogen; Haloalkane is a methyl iodide; Trialkyl gallium is a triethyl-gallium; Varsol is a toluene.
5, the preparation method of oxygen free trialkyl gallium according to claim 4 is characterized in that 1) in adopt air in the western cold gram anaerobic anhydrous process eliminating system.
6, the preparation method of oxygen free trialkyl gallium according to claim 4 is characterized in that 2) in time of continue stirring be 1-10 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021381674A CN1171894C (en) | 2002-08-26 | 2002-08-26 | Preparation method of oxygen free trialkyl gallium |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021381674A CN1171894C (en) | 2002-08-26 | 2002-08-26 | Preparation method of oxygen free trialkyl gallium |
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| Publication Number | Publication Date |
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| CN1410429A CN1410429A (en) | 2003-04-16 |
| CN1171894C true CN1171894C (en) | 2004-10-20 |
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| CNB021381674A Expired - Fee Related CN1171894C (en) | 2002-08-26 | 2002-08-26 | Preparation method of oxygen free trialkyl gallium |
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| CN103145745A (en) * | 2013-03-06 | 2013-06-12 | 江苏南大光电材料股份有限公司 | Method for industrially preparing high-purity metal organic compound |
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| CN1410429A (en) | 2003-04-16 |
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