CN102731541A - Method for purifying trimethyl gallium - Google Patents
Method for purifying trimethyl gallium Download PDFInfo
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- CN102731541A CN102731541A CN2012102326603A CN201210232660A CN102731541A CN 102731541 A CN102731541 A CN 102731541A CN 2012102326603 A CN2012102326603 A CN 2012102326603A CN 201210232660 A CN201210232660 A CN 201210232660A CN 102731541 A CN102731541 A CN 102731541A
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- trimethyl
- gallium
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- purification
- temperature
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Abstract
The invention provides a method for purifying trimethyl gallium. The method comprises the following steps of: putting raw materials into a flask, wherein the raw materials comprise trimethyl gallium and an ether compound; dropping high polyether in a liquid form into the flask at room temperature in the presence of inert gas; after finishing dropping the liquid high polyether, stirring the raw materials and the high polyether in the flask to enable the trimethyl gallium to react with the ether compound and the high polyether to generate a compound of the high polyether and the trimethyl gallium and diethyl ether; decompressing, extracting and distilling the flask at the room temperature under an inert gas atmosphere to remove the diethyl ether; connecting the flask to distilling equipment to enable the flask to be under a decompressing and heating condition, wherein the temperature reached by heating is higher than the boiling point of the trimethyl gallium and lower than the boiling point of the high polyether to decompound the compound of the high polyether and the trimethyl gallium; and rectifying the decompounded trimethyl gallium and collecting the decompounded trimethyl gallium into a condenser pipe of the distilling equipment, wherein the decompounded high polyether is left in the flask. The method has the advantages that process and equipment are simplified and the preparation efficiency is improved.
Description
Technical field
The present invention relates to a kind of metal-organic method of purification, relate in particular to a kind of method of purification of trimethyl-gallium.
Background technology
Compound semiconductor ultra-thin film material occupies critical role in semiconductor material, it is widely used in LED equipment, semiconductor laser, infrared eye, solar cell, supercomputer etc.Metal organic chemical vapor deposition (Metal-organic Chemical Vapor Deposition is abbreviated as MOCVD) technology is the important process that obtains compound semiconductor ultra-thin film material.Trimethyl-gallium is one of important meals organic cpds of MOCVD technology.
Although industry still has distance to the existing certain research of the purification techniques of trimethyl-gallium in scale operation, need on method of purification, improve thus.
Summary of the invention
Based on the deficiency of prior art, the invention provides a kind of method of purification of trimethyl-gallium, thereby it can be simplified technology and equipment and improve preparation efficiency.
In order to realize the object of the invention, the present invention provides a kind of method of purification of trimethyl-gallium, comprises step: raw material is inserted in the flask, and said raw material contains trimethyl-gallium and etherate; The high polyethers of the form that at room temperature under atmosphere of inert gases, will be in a liquid state is added drop-wise in the flask; After high polyethers dropwises with liquid state, raw material in the flask and high polyethers are stirred, so that trimethyl-gallium and etherate and high polyethers replacement(metathesis)reaction and produce high polyethers and trimethyl-gallium title complex and ether; At room temperature under atmosphere of inert gases, flask reduced pressure to take out and heat up in a steamer, so that ether is removed; Flask is connected in rectifying device; Make flask under the decompression heating condition; The temperature that said heating reaches is more than the boiling point of trimethyl-gallium and be lower than the boiling point of high polyethers; Make high polyethers-trimethyl-gallium title complex separate and join, the trimethyl-gallium of Xie Peihou is carried out after the rectification process and collects in the prolong of rectifying device, and the high polyethers of Xie Peihou is stayed in the flask.
Beneficial effect of the present invention is following.
The method of purification of trimethyl-gallium provided by the invention, thus it can be simplified technology and equipment and improve preparation efficiency.
Embodiment
Method of purification according to trimethyl-gallium of the present invention at first is described.
Method of purification according to trimethyl-gallium of the present invention comprises step: raw material is inserted in the flask, and said raw material contains trimethyl-gallium and etherate; The high polyethers of the form that at room temperature under atmosphere of inert gases, will be in a liquid state is added drop-wise in the flask; After high polyethers dropwises with liquid state, raw material in the flask and high polyethers are stirred, so that trimethyl-gallium and etherate and high polyethers replacement(metathesis)reaction and produce high polyethers and trimethyl-gallium title complex and ether; At room temperature under atmosphere of inert gases, flask reduced pressure to take out and heat up in a steamer, so that ether is removed; Flask is connected in rectifying device; Make flask under the decompression heating condition; The temperature that said heating reaches is more than the boiling point of trimethyl-gallium and be lower than the boiling point of high polyethers; Make high polyethers-trimethyl-gallium title complex separate and join, the trimethyl-gallium of Xie Peihou is carried out after the rectification process and collects in the prolong of rectifying device, and the high polyethers of Xie Peihou is stayed in the flask.
In the method for purification according to trimethyl-gallium of the present invention, preferably, said atmosphere of inert gases adopts argon gas or nitrogen.
In the method for purification according to trimethyl-gallium of the present invention, preferably, said flask is the flask more than three mouthfuls or three mouthfuls.
In the method for purification according to trimethyl-gallium of the present invention, preferably, said high polyethers is that the polymerization degree is NHD (CH
3O (CH
2CH
2O)
nCH
3, n=3 ~ 8 wherein).
In the method for purification according to trimethyl-gallium of the present invention, preferably, the mol ratio of the high polyethers of trimethyl-gallium and dropping is 1: (0.2 ~ 5).
In the method for purification according to trimethyl-gallium of the present invention, preferably, the pressure that decompression is taken out when heating up in a steamer is 1 * 10
2~ 1 * 10
4Pa, the time is 5 ~ 10h.
In the method for purification according to trimethyl-gallium of the present invention, preferably, said decompression heating condition is 1 * 10
2~ 1 * 10
5Pa, 60 ~ 300 ℃.
In the method for purification according to trimethyl-gallium of the present invention, preferably, said rectifying device comprises thorn shape separation column, and said thorn shape separation column is connected in one of outlet of said flask.
In method of purification, preferably, make high polyethers-trimethyl-gallium title complex separate in the step of joining to be added with stirring said according to trimethyl-gallium of the present invention.
In method of purification according to trimethyl-gallium of the present invention; Preferably; The heat-processed of separating reactant ligand is two-part, and first section is heated to first temperature from room temperature, and said first temperature is more than the boiling temperature of trimethyl-gallium and be lower than the boiling point of high polyethers; Second section for being heated to the temperature of rectifying device defined from first temperature, the temperature of said regulation is the boiling point that the temperature of temperature and the said regulation of gaseous state trimethyl-gallium end liquid in the rectifying device under refluxing is lower than high polyethers.More preferably, the temperature rise rate of said second section heating is 1 ~ 2 ℃/min.
Secondly explanation is according to the embodiment of the method for purification of trimethyl-gallium of the present invention.
Embodiment 1
In the 1L there-necked flask, add raw material trimethyl-gallium and etherate 266ml, wherein the content of trimethyl-gallium is through being calculated as 0.453mol;
Add the NHD (CH that is in a liquid state at the normal pressure tap funnel
3O (CH
2CH
2O)
nCH
3, n=3 wherein) and 575ml, be 2.25mol, make the mol ratio of trimethyl-gallium and NHD be about 1:5;
At room temperature under the argon shield; Speed with 2 of per seconds is added drop-wise to the NHD in the normal pressure tap funnel in the there-necked flask; When dripping the material in the there-necked flask is stirred, so that NHD and trimethyl-gallium and etherate generation foundation replacement(metathesis)reaction and generate NHD and trimethyl-gallium title complex and ether;
After NHD is dropwised, continue stirring and make their continue reaction 5h;
At room temperature under the argon gas atmosphere and under agitation condition, 1 * 10
4Releasing reaction time 10h under the Pa is to remove ether;
There-necked flask is connected in rectifying device, and rectifying device comprises thorn shape separation column and prolong, makes the pressure of there-necked flask be in 1 * 10
5Pa is following and under agitation condition, there-necked flask is heated to 180 ℃; Making NHD and trimethyl-gallium title complex begin to separate joins; Separate that to join in the process control temperature rise rate be 2 ℃/min, up to reaching 300 ℃, omnidistance argon shield at the end liquid temp that stings the shape separation column down that refluxes; Trimethyl-gallium to Xie Peihou is collected through prolong, and the NHD of Xie Peihou is stayed in the flask.
Embodiment 2
The title complex 143ml of trimethyl-gallium and ether is inserted in the there-necked flask, and trimethyl-gallium is 0.26mol;
In the normal pressure tap funnel, add the NHD (CH that is in a liquid state
3O (CH
2CH
2O)
nCH
3, n=4 wherein) and 0.05mol, make the mol ratio of trimethyl-gallium and NHD be about 1:0.2;
At room temperature the NHD in the normal pressure tap funnel is added drop-wise in the there-necked flask under the argon gas atmosphere; The speed that is added drop-wise in the there-necked flask is 2 of per seconds; When dripping the material in the there-necked flask is stirred, so that NHD and trimethyl-gallium and etherate generation foundation replacement(metathesis)reaction and generate NHD and trimethyl-gallium title complex and ether;
, NHD stirs 1h after being dropwised;
At room temperature under argon atmosphere and 1 * 10
2Pa takes out to heat up in a steamer to there-necked flask and handles 5h, so that ether is removed;
There-necked flask is connected in rectifying device, and rectifying device comprises thorn shape separation column and prolong, makes the pressure of there-necked flask be in 1 * 10
2Pa is following and under agitation condition, there-necked flask is heated to 60 ℃; So that separating, NHD and trimethyl-gallium title complex join; Separate that to join in the process control temperature rise rate be 1 ℃/min, up to reaching 100 ℃, omnidistance argon shield at the end liquid temp that stings the shape separation column down that refluxes; The trimethyl-gallium of Xie Peihou is carried out rectification process and collects in the prolong of rectifying device, and the NHD of Xie Peihou is stayed in the there-necked flask.
Embodiment 3
The title complex 67ml of trimethyl-gallium and ether is inserted in the there-necked flask, and trimethyl-gallium is 0.183mol;
In the normal pressure tap funnel, add the NHD CH that is in a liquid state
3O (CH
2CH
2O)
nCH
3, n=8 wherein) and 0.1mol, make the mol ratio of trimethyl-gallium and NHD be about 1:0.6;
At room temperature the NHD in the normal pressure tap funnel is added drop-wise in the there-necked flask under the argon gas atmosphere; The speed that is added drop-wise in the there-necked flask is 2 of per seconds; When dripping the material in the there-necked flask is stirred, so that NHD and trimethyl-gallium and etherate generation foundation replacement(metathesis)reaction and generate NHD and trimethyl-gallium title complex and ether;
After NHD is dropwised, continue to stir 3h;
At room temperature under argon atmosphere and 4 * 10
3Under the Pa there-necked flask taken out to heat up in a steamer and handle 8h, so that ether is removed;
There-necked flask is connected in rectifying device, and rectifying device comprises thorn shape separation column and prolong, makes the pressure of there-necked flask be in 1 * 10
4Pa is following and under agitation condition, there-necked flask is heated to 120 ℃; Making NHD and trimethyl-gallium title complex begin to separate joins; Separate that to join in the process control temperature rise rate be 1.5 ℃/min, up to reaching 180 ℃, omnidistance argon shield at the end liquid temp that stings the shape separation column down that refluxes; The trimethyl-gallium of Xie Peihou is carried out rectification process and collects in the prolong of rectifying device, and the NHD of Xie Peihou is stayed in the there-necked flask.
The detected result of last illustrative embodiment 1-3.
(manufacturer is a PE company, and model is: DRC-II) detect inorganic impurity content at first to adopt icp ms (ICP-MS).
This equipment testing condition is: temperature is 18 ℃～28 ℃, and relative humidity is 30～70%, and cleanliness factor is 1000 grades.Detect principle: the icp ms detection mode: after the element process plasma high-temperature to be measured ionization, get into mass analyzer with the positive charge form, according to the difference of mass ratio, device to be detected receives, and produces signal.The signal that element to be measured produces and this element signal ratio of reference material draw constituent content process ICP-MS survey report to be measured:
Table 1 has provided the detected result of embodiment 1-3.
Foreign matter content (the unit: ppm) of the trimethyl-gallium that table 1 is purified
Find out that from table 1 purity of the trimethyl-gallium that the present invention obtained reaches 5N.
Next adopts NMR (BRUKER AVANCE III 400MHz) to detect organic impurity.In NMR detected, embodiment 1-3 did not find that all any organic impurity exists.
Claims (10)
1. the method for purification of a trimethyl-gallium comprises step:
Raw material is inserted in the flask, and said raw material contains trimethyl-gallium and etherate;
The high polyethers of the form that at room temperature under atmosphere of inert gases, will be in a liquid state is added drop-wise in the flask;
After high polyethers dropwises with liquid state, raw material in the flask and high polyethers are stirred, so that trimethyl-gallium and etherate and high polyethers replacement(metathesis)reaction and produce high polyethers and trimethyl-gallium title complex and ether;
At room temperature under atmosphere of inert gases, flask reduced pressure to take out and heat up in a steamer, so that ether is removed;
Flask is connected in rectifying device; Make flask under the decompression heating condition; The temperature that said heating reaches is more than the boiling point of trimethyl-gallium and be lower than the boiling point of high polyethers; Make high polyethers-trimethyl-gallium title complex separate and join, the trimethyl-gallium of Xie Peihou is carried out after the rectification process and collects in the prolong of rectifying device, and the high polyethers of Xie Peihou is stayed in the flask.
2. the method for purification of trimethyl-gallium according to claim 1 is characterized in that, said atmosphere of inert gases adopts argon gas or nitrogen, and said flask is the flask more than three mouthfuls or three mouthfuls.
3. the method for purification of trimethyl-gallium according to claim 1 is characterized in that, said high polyethers is NHD (CH
3O (CH
2CH
2O)
nCH
3, n=3 ~ 8 wherein).
4. the method for purification of trimethyl-gallium according to claim 3 is characterized in that, the mol ratio of the high polyethers of trimethyl-gallium and dropping is 1: (0.2 ~ 5).
5. the method for purification of trimethyl-gallium according to claim 3 is characterized in that, the pressure that decompression is taken out when heating up in a steamer is 1 * 10
2~ 1 * 10
4Pa, the time is 5 ~ 10h.
6. the method for purification of trimethyl-gallium according to claim 3 is characterized in that, said decompression heating condition is 1 * 10
2~ 1 * 10
5Pa, 60 ~ 300 ℃.
7. the method for purification of trimethyl-gallium according to claim 2 is characterized in that, said rectifying device comprises thorn shape separation column, and said thorn shape separation column is connected in one of outlet of said flask.
8. the method for purification of trimethyl-gallium according to claim 1 is characterized in that, makes high polyethers-trimethyl-gallium title complex separate in the step of joining to be added with stirring said.
9. the method for purification of trimethyl-gallium according to claim 1; It is characterized in that; The heat-processed of separating reactant ligand is two-part, and first section is heated to first temperature from room temperature, and said first temperature is more than the boiling temperature of trimethyl-gallium and be lower than the boiling point of high polyethers; Second section for being heated to the temperature of rectifying device defined from first temperature, the temperature of said regulation is lower than the boiling point of high polyethers for the temperature of the temperature of the end liquid in the rectifying device under refluxing and said regulation.
10. the method for purification of trimethyl-gallium according to claim 9 is characterized in that, the temperature rise rate of said second section heating is 1 ~ 2 ℃/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102326603A CN102731541A (en) | 2012-07-05 | 2012-07-05 | Method for purifying trimethyl gallium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102326603A CN102731541A (en) | 2012-07-05 | 2012-07-05 | Method for purifying trimethyl gallium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102731541A true CN102731541A (en) | 2012-10-17 |
Family
ID=46987915
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|---|---|---|---|
| CN2012102326603A Pending CN102731541A (en) | 2012-07-05 | 2012-07-05 | Method for purifying trimethyl gallium |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103114214A (en) * | 2012-12-28 | 2013-05-22 | 中国神华能源股份有限公司 | Production method for ultra-pure gallium |
| CN106146540A (en) * | 2015-03-26 | 2016-11-23 | 清远先导材料有限公司 | A kind of production method of triethyl-gallium |
| CN109553632A (en) * | 2018-12-29 | 2019-04-02 | 贵州威顿晶磷电子材料股份有限公司 | A kind of method of purification of trimethyl aluminium |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993010125A1 (en) * | 1991-11-19 | 1993-05-27 | Air Products And Chemicals, Inc. | Purification of tri-alkyl compounds of group 3a metals |
-
2012
- 2012-07-05 CN CN2012102326603A patent/CN102731541A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993010125A1 (en) * | 1991-11-19 | 1993-05-27 | Air Products And Chemicals, Inc. | Purification of tri-alkyl compounds of group 3a metals |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103114214A (en) * | 2012-12-28 | 2013-05-22 | 中国神华能源股份有限公司 | Production method for ultra-pure gallium |
| CN103114214B (en) * | 2012-12-28 | 2014-06-18 | 中国神华能源股份有限公司 | Production method for ultra-pure gallium |
| CN106146540A (en) * | 2015-03-26 | 2016-11-23 | 清远先导材料有限公司 | A kind of production method of triethyl-gallium |
| CN109553632A (en) * | 2018-12-29 | 2019-04-02 | 贵州威顿晶磷电子材料股份有限公司 | A kind of method of purification of trimethyl aluminium |
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Application publication date: 20121017 |