CN103145745A - Method for industrially preparing high-purity metal organic compound - Google Patents
Method for industrially preparing high-purity metal organic compound Download PDFInfo
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- CN103145745A CN103145745A CN2013100706034A CN201310070603A CN103145745A CN 103145745 A CN103145745 A CN 103145745A CN 2013100706034 A CN2013100706034 A CN 2013100706034A CN 201310070603 A CN201310070603 A CN 201310070603A CN 103145745 A CN103145745 A CN 103145745A
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- organic compound
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Abstract
The invention relates to a method for industrially preparing a high-purity metal organic compound. The method comprises the following steps of: feeding an M-magnesium alloy raw material into a reaction kettle full of inert gas, wherein M is Ga or In; adding haloalkane in the presence of an ether solvent, wherein the haloalkane is RX, X is Br or I, and R is CH3 or CH2CH3; controlling the reaction speed by controlling the adding speed of the haloalkane; after the reaction, evaporating out the solvent, and distilling in a reduced pressure condition to obtain a complex of III-group MR3 and ether; adding the complex of MR3 and ether into liquid high-boiling-point organic amine N(R')3 to form an MR3 organic amine complex; distilling to remove the ether solvent; removing the ether and low-boiling-point impurities in a reduced pressure condition; decomplexing to obtain an oxygen-free metal organic compound MR3; and rectifying the MR3 to obtain the high-purity metal organic compound. The intermediate products in the reaction process are all in a liquid state and are easy to control, the obtained product has good quality stability, and the production efficiency is high.
Description
Technical field
The present invention relates to the method for preparation of industrialization high-purity metal organic compound, relate in particular to the method for the ultra-pure metal alkylide organic compound of suitability for industrialized production, belong to the organometallics production technical field.
Background technology
At present; the method of growth compound semiconductor material has the technology such as metal organic chemical vapor deposition (MOCVD), molecular beam epitaxy (MBE), chemical beam epitaxy (CBE) and rheotaxy (LPE); special MOCVD technology; be to carry out at present the large-scale production compound semiconductor film material best approach, in the MOCVD epitaxial process, one of base mateiral of the most critical that uses is that purity is greater than 99.9999%(> 6N) organometallics source material (be called for short MO source).
The quality in MO source is the key of MOCVD technique, and purity requirement is very high.Due to the organometallics MR of III family
3(M=Ga, In; R=CH
3, CH
2cH
3) in Zn, Si, Sn, S, the Se etc. of the trace that may contain there is the ether impurity introduced in the impurity, MO source preparation process of electronically active, organo-metallic halide impurities etc., the mass formation great effect of these impurity to compound semiconductor materials.How removing the technology of these impurity, is the technology of producing the most critical in high-purity MO source.
Summary of the invention
A kind of method that the purpose of this invention is to provide preparation of industrialization high-purity metal organic compound, the ultra-pure metal alkylide organic compound of suitability for industrialized production more reliably, as trimethyl-gallium, triethyl-gallium and trimethyl indium.
Purpose of the present invention is achieved through the following technical solutions:
The method of preparation of industrialization high-purity metal organic compound, characteristics are: in being full of the reactor of rare gas element, drop into the M-raw material magnesium alloy, M is Ga or In, under ether solvent exists, progressively adds haloalkane under agitation condition, haloalkane is RX, and X is Br or I, and R is CH
3or CH
2cH
3, by what control haloalkane, add the speed control speed of response; After having reacted, solvent is steamed, then distillation obtains the MR of III family under reduced pressure
3with the title complex of ether, then by MR
3add liquid high boiling point organic amine N (R ') with the title complex of ether
3in, form MR
3the organic amine title complex, then ether solvent is removed in distillation, more further removes ethers and lower-boiling impurity under reduced pressure; Finally solution is joined, and obtains the organometallics MR of anaerobic
3; Again by MR
3obtain high-purity metal organic compound through rectifying, i.e. the MO source.
Further, the method for above-mentioned preparation of industrialization high-purity metal organic compound, described liquid high boiling point organic amine N (R ')
3it is at room temperature liquid form.
Further, the method for above-mentioned preparation of industrialization high-purity metal organic compound, described liquid high boiling point organic amine N (R ')
3, wherein three R ' are that the C3 propyl group is selected to the alkyl of C10 decyl straight or branched from C3-C10.
Further, the method for above-mentioned preparation of industrialization high-purity metal organic compound, described liquid high boiling point organic amine N (R ')
3boiling point be not less than 150
oc.
Further, the method for above-mentioned preparation of industrialization high-purity metal organic compound, in described nitrogenous liquid amine compounds and M magnesium alloy, the mol ratio of M content is 1～3:1, M is Ga or In.
Again further, the method for above-mentioned preparation of industrialization high-purity metal organic compound, the vacuum tightness of described decompression is 1～100mmHg.
Again further, the method for above-mentioned preparation of industrialization high-purity metal organic compound, the temperature that described solution is joined is 80～160 ℃, the vacuum tightness that solution is joined is 1～100mmHg.
Again further, the method for above-mentioned preparation of industrialization high-purity metal organic compound, the purity of described high-purity metal organic compound is 99.99995%.
The substantive distinguishing features that technical solution of the present invention is outstanding and significant progressive being mainly reflected in:
Adopt liquid high boiling point organic amine part, overcome traditional method and used complex technical process, material that lower boiling or SOLID ORGANIC amine part exist to supplement and the problems such as complex operation, post-processed relative risk such as transfer; In addition, also overcome that the controlling of production process difficulty that traditional method exists is large, a constant product quality not high difficult problem.Novel process of the present invention is because the intermediate product in reaction process is liquid, so production process is highly susceptible to controlling, and products obtained therefrom quality stability is good, production efficiency is high, the finished product purity can reach 99.99995%, and product is easy to separate, and is particularly suitable for large-scale industrial production.Whole production technique is simply steady, there is no industrial more numerous and diverse operations such as filtration and recrystallization, the easily control of whole production process safety; Liquid organic amine part used can recycle and reuse, and almost there is no processing waste.
Embodiment
The technique of preparation of industrialization high-purity metal organic compound of the present invention: in being full of the reactor of rare gas element, drop into M-magnesium alloy (M=Ga, In) raw material, under ether solvent exists, progressively add haloalkane under agitation condition, haloalkane is XR(X=Br, I; R=CH
3, CH
2cH
3), by controlling the speed that adds the speed control reaction of haloalkane.After having reacted, solvent is steamed, then obtain the MR of III family in the lower distillation of reduced pressure (vacuum tightness of decompression is 1～100mmHg)
3title complex with ether.Then join in liquid high boiling point organic amine, form MR
3the organic amine title complex, ether solvent is removed in distillation, further remove ether and other lower-boiling impurities under reduced pressure (vacuum tightness of decompression is 1～100mmHg), finally solution is joined (the solution temperature of joining is 80～160 ℃, and the vacuum tightness that solution is joined is 1～100mmHg) and is obtained MR again
3(M=Ga, In; R=CH
3, CH
2cH
3) thick product.Again by this MR
3thick product just obtains ultra-pure organometallics (being called for short the MO source) through high precision rectification, and it is 6.5N that purity reaches 99.99995%().
Wherein, liquid high boiling point organic amine N (R ')
3be at room temperature liquid form, liquid high boiling point organic amine N (R ')
3, wherein three R ' are that the C3 propyl group is selected to the alkyl of C10 decyl straight or branched from C3-C10, liquid high boiling point organic amine N (R ')
3boiling point be not less than 150
oc.
In the method for above-mentioned preparation of industrialization high-purity metal organic compound, organic ligand is liquid organic amine compound, and in organic amine and M-magnesium alloy, the mol ratio of M (M:Ga, In) content is 1～3:1.
embodiment 1:
In being full of the reactor of nitrogen, drop into gallium-magnesium alloy 580g, add anhydrous diethyl ether 2100g, progressively add methyl iodide (CH under agitation condition
3i) 2050g, by controlling methyl iodide (CH
3i) the speed control that adds is reacted return velocity, after having reacted, continue to keep refluxing 4 hours, then solvent is steamed, under reduced pressure, (vacuum tightness is 1～100mmHg) obtains the title complex of trimethyl-gallium and ether, the title complex of trimethyl-gallium and ether is transferred to solution and joins still, under agitation condition, progressively join in the 900g tri-n-butylamine, dropwise, opening heating makes its backflow and keeps backflow after 2 hours, ether is removed in distillation, under reduced pressure, (vacuum tightness is 1～100mmHg) removes lower-boiling impurity again, the solution that heats up is again allotted trimethyl-gallium (solution join temperature be between 80～160 ℃), obtain the trimethyl-gallium 370g of anaerobic, yield is that 90%(calculates by gallium).Again this trimethyl-gallium is just obtained to ultra-pure trimethyl-gallium through high precision rectification, it is 6.5N that purity can reach 99.99995%().
embodiment 2:
In being full of the reactor of nitrogen, drop into gallium-magnesium alloy 650g, add anhydrous diethyl ether 2200g, progressively add iodoethane (CH under agitation condition
3cH
2i) 2700g, by controlling iodoethane (CH
3cH
2i) add speed control solvent refluxing speed, after having reacted, continue to keep refluxing 4 hours, then solvent is steamed, under reduced pressure, (vacuum tightness is 1～100mmHg) obtains the title complex of triethyl-gallium and ether again, the title complex of triethyl-gallium and ether is transferred to solution and joins still, under agitation condition, progressively join in the 1000g tri-n-butylamine, dropwise, opening heating makes its backflow and keeps backflow after 2 hours, ether is removed in distillation, under reduced pressure, (vacuum tightness is 1～100mmHg) removes lower-boiling impurity again, finally solution is joined the triethyl-gallium 483g that (solution join temperature be 80～160 ℃) obtains anaerobic, yield is that 75%(calculates by gallium).Again this triethyl-gallium is just obtained to ultra-pure triethyl-gallium through high precision rectification, it is 6.5N that purity can reach 99.99995%().
embodiment 3:
In being full of the reactor of nitrogen, drop into indium-magnesium alloy 800g, add anhydrous diethyl ether 2150g, progressively add methyl iodide (CH under agitation condition
3i) 2420g, by controlling methyl iodide (CH
3i) add speed control solvent refluxing speed, after having reacted, continue to keep refluxing 4 hours, then solvent is steamed, under reduced pressure, (vacuum tightness is 1～100mmHg) obtains the title complex of trimethyl indium and ether again, the title complex of trimethyl indium and ether is transferred to solution and joins still, under agitation condition, progressively join in the 850g tri-n-butylamine, dropwise, opening heating makes its backflow and keeps backflow after 2 hours, ether is removed in distillation, under reduced pressure (vacuum tightness is 1～100mmHg) again, remove lower-boiling impurity, the solution that heats up is again allotted trimethyl indium (solution join temperature be between 80～160 ℃), obtain the trimethyl indium 492g of anaerobic, yield is that 87%(calculates by indium metal).Again this trimethyl indium is just obtained to ultra-pure trimethyl indium through being further purified processing, it is 6.5N that purity can reach 99.99995%().
The present invention prepares the method in high-purity MO source, adopt liquid high boiling point organic amine part, overcome traditional method and used complex technical process, material that lower boiling or SOLID ORGANIC amine part exist to supplement and the problems such as complex operation, post-processed relative risk such as transfer; In addition, also overcome that the controlling of production process difficulty that traditional method exists is large, a constant product quality not high difficult problem.Novel process of the present invention is because the intermediate product in reaction process is liquid, so production process is highly susceptible to controlling, and products obtained therefrom quality stability is good, production efficiency is high, the finished product purity can reach 99.99995%, and product is easy to separate, and is particularly suitable for large-scale industrial production.Whole production technique is simply steady, there is no industrial more numerous and diverse operations such as filtration and recrystallization, the easily control of whole production process safety; Liquid organic amine part used can recycle and reuse, and almost there is no processing waste.
Need to understand: the above is only the preferred embodiment of the present invention; for those skilled in the art; under the premise without departing from the principles of the invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (8)
1. the method for preparation of industrialization high-purity metal organic compound, is characterized in that: in being full of the reactor of rare gas element, drop into the M-raw material magnesium alloy, M is Ga or In, under ether solvent exists, progressively adds haloalkane under agitation condition, haloalkane is RX, and X is Br or I, and R is CH
3or CH
2cH
3, by what control haloalkane, add the speed control speed of response; After having reacted, solvent is steamed, then distillation obtains the MR of III family under reduced pressure
3with the title complex of ether, then by MR
3add liquid high boiling point organic amine N (R ') with the title complex of ether
3in, form MR
3the organic amine title complex, then ether solvent is removed in distillation, more further removes ethers and lower-boiling impurity under reduced pressure; Finally solution is joined, and obtains the organometallics MR of anaerobic
3; Again by MR
3obtain high-purity metal organic compound through rectifying.
2. the method for preparation of industrialization high-purity metal organic compound according to claim 1 is characterized in that: described liquid high boiling point organic amine N (R ')
3it is at room temperature liquid form.
3. the method for preparation of industrialization high-purity metal organic compound according to claim 1 and 2 is characterized in that: described liquid high boiling point organic amine N (R ')
3, wherein three R ' are that the C3 propyl group is selected to the alkyl of C10 decyl straight or branched from C3-C10.
4. the method for preparation of industrialization high-purity metal organic compound according to claim 1 and 2 is characterized in that: described liquid high boiling point organic amine N (R ')
3boiling point be not less than 150
oc.
5. the method for preparation of industrialization high-purity metal organic compound according to claim 1 is characterized in that: in described nitrogenous liquid amine compounds and M magnesium alloy, the mol ratio of M content is 1～3:1, and M is Ga or In.
6. the method for preparation of industrialization high-purity metal organic compound according to claim 1, it is characterized in that: the vacuum tightness of described decompression is 1～100mmHg.
7. the method for preparation of industrialization high-purity metal organic compound according to claim 1, it is characterized in that: the temperature that described solution is joined is 80～160 ℃, the vacuum tightness that solution is joined is 1～100mmHg.
8. the method for preparation of industrialization high-purity metal organic compound according to claim 1, it is characterized in that: the purity of described high-purity metal organic compound is 99.99995%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103333184A (en) * | 2013-07-05 | 2013-10-02 | 江苏南大光电材料股份有限公司 | Method for production of trimethyl gallium at high efficiency and low cost |
| CN104860972A (en) * | 2015-05-12 | 2015-08-26 | 苏州普耀光电材料有限公司 | Preparation method of high-purity trimethyl indium |
| CN105175440A (en) * | 2015-09-30 | 2015-12-23 | 江西佳因光电材料有限公司 | Preparation method of trimethylaluminium |
| CN105254654A (en) * | 2015-11-19 | 2016-01-20 | 河南承明光电新材料股份有限公司 | Method for purifying alkyl indium |
| CN108822142A (en) * | 2018-09-03 | 2018-11-16 | 上海芯渊光电科技有限公司 | A kind of preparation method of triethyl-gallium |
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| CN1410429A (en) * | 2002-08-26 | 2003-04-16 | 南京大学 | Preparation method of oxygen free trialkyl gallium |
| CN102020669A (en) * | 2010-12-22 | 2011-04-20 | 江苏南大光电材料股份有限公司 | Method for industrially preparing trimethyl gallium |
| CN102718784A (en) * | 2012-07-05 | 2012-10-10 | 广东先导稀材股份有限公司 | Decomplexation method of metal organic compound and ether complex |
-
2013
- 2013-03-06 CN CN2013100706034A patent/CN103145745A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1410429A (en) * | 2002-08-26 | 2003-04-16 | 南京大学 | Preparation method of oxygen free trialkyl gallium |
| CN102020669A (en) * | 2010-12-22 | 2011-04-20 | 江苏南大光电材料股份有限公司 | Method for industrially preparing trimethyl gallium |
| CN102718784A (en) * | 2012-07-05 | 2012-10-10 | 广东先导稀材股份有限公司 | Decomplexation method of metal organic compound and ether complex |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103333184A (en) * | 2013-07-05 | 2013-10-02 | 江苏南大光电材料股份有限公司 | Method for production of trimethyl gallium at high efficiency and low cost |
| CN104860972A (en) * | 2015-05-12 | 2015-08-26 | 苏州普耀光电材料有限公司 | Preparation method of high-purity trimethyl indium |
| CN105175440A (en) * | 2015-09-30 | 2015-12-23 | 江西佳因光电材料有限公司 | Preparation method of trimethylaluminium |
| CN105254654A (en) * | 2015-11-19 | 2016-01-20 | 河南承明光电新材料股份有限公司 | Method for purifying alkyl indium |
| CN108822142A (en) * | 2018-09-03 | 2018-11-16 | 上海芯渊光电科技有限公司 | A kind of preparation method of triethyl-gallium |
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Application publication date: 20130612 |