CN101857270A - Method for synthesizing high-purity arsine - Google Patents
Method for synthesizing high-purity arsine Download PDFInfo
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- CN101857270A CN101857270A CN 201010233369 CN201010233369A CN101857270A CN 101857270 A CN101857270 A CN 101857270A CN 201010233369 CN201010233369 CN 201010233369 CN 201010233369 A CN201010233369 A CN 201010233369A CN 101857270 A CN101857270 A CN 101857270A
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Abstract
The invention relates to a method for synthesizing high-purity arsine, which belongs to the technical field of electron gas synthesization and purification. The method includes the following steps: (1) crude arsine synthesization process: first producing arsenic powder and zinc powder into zinc arsenide, which then reacts with dilute sulphuric acid to produce crude arsine; and (2) high-purity arsine purification process: carrying out liquid nitrogen cold trap low-temperature vacuum separation, molecular sieve adsorption and drying and gallium-indium alloy deep absorption for dehydration and deoxidation on the crude arsine. The method can deeply remove oxygen, water, carbon dioxide and other harmful impurities in electronic material, which normally can reach less than 0.01 to 0.1ppm; and gallium-indium alloy as the main body of purifying agent can be reused, and theoretically has a long service life except slight loss in chemical treatment.
Description
Technical field
The invention belongs to electronic gas synthesizing and purifying technical field, be specifically related to a kind of method of synthesizing high-purity arsine.
Background technology
Electronic gas is that electronic industries such as super large-scale integration, flat panel display device, compound semiconductor device, solar cell, optical fiber are produced indispensable starting material, and they are widely used in technologies such as film, etching, doping, vapour deposition, diffusion.For example in present Technology comparatively in the wafer manufacturing processed of advanced super large-scale integration factory, all processing steps surpass 450 roads, wherein approximately will use 50 kinds of different types of electronic gas.Arsine is one of very important group-v element in the electronic gas, AsH3 is the special gas of a kind of important electron, it is mainly used in epitaxial silicon in semi-conductor industry N type mixes, the N type diffusion in the silicon, ion implantation, growth gallium arsenide (GaAs) and gallium arsenide phosphide (GaAsP), and with IIIA/VA family element formation semiconductor compound etc.In addition, AsH3 also has very important use in photoelectron, solar cell and microwave device.
AsH3 can not be synthetic simply by simple substance, but can obtain AsH3 in the presence of the catalyzer or under the plasma irradiating.Usually use some metal arsenide and water or acid-respons to prepare AsH3, this reaction is quick and complete, do not contain H2 in the product fully, but the AsH3 yield is usually less than 90%
The arsine purity that present international most advanced level prepares gained is 6.0N, and the purity of one of special gas of China-arsine since technical reason can only production purity at the special gas of 3N～4N standard, and at many key areas, such as the manufacturing of the electronic component of the Controlling System on the research of national war preparedness weapon and No. five launch vehicle in Divine Land, and the gas of the 6N standard be badly in need of of the aspects such as manufacturing of the solar cell that uses on the satellite all relies on import; Have only developed countries such as the U.S., Russia to produce in the world at present, the SOLKATRONIC company of the U.S. sells this kind gas, China's this kind of import gas is usually hindered with changing because of international situation is nervous, so the DOMESTICATION PROBLEM of the high-purity gas material of China's urgent need has directly restricted the development of above-mentioned association area.
Summary of the invention
The detrimental impurity that reaches the arsine of 5N-6N at present mainly contains: oxygen, water, carbon monoxide, carbonic acid gas, methane .... etc., from the analytical data of the thick product of present arsine, wherein main detrimental impurity is a methane.
The objective of the invention is in order to solve can not the reach international standards shortcoming of 5N (99.999%), 6N (99.9999%) of arsine purity that the present preparation technology of China produces, disclose a kind of method of new synthesizing high-purity arsine.
For reaching the goal of the invention of above-mentioned solution prior art shortcoming, the present invention has adopted following technical scheme:
1, a kind of method of synthesizing high-purity arsine comprises the steps:
(1), the building-up process of rough arsine: make arsenic zinc with arsenic powder and zinc powder earlier, obtain rough arsine with the dilute sulphuric acid reaction again, reaction formula is as follows:
2A
S+3Zn→As
2Zn
3
A
S2Zn
3+3H
2SO
4→3ZnSO
4+2AsH
3↑；
(2), the purge process of high-purity arsine: the rough arsine that makes in the step (1) is carried out adsorption dry with the volatilization arsine after the separation of liquid nitrogen cold trap cryogenic vacuum with molecular sieve earlier, adopt gallium-dark adsorption dewatering of indium alloy liquid, oxygen at last, obtaining high-purity arsine is the arsine of 5N, 6N.
The method of the synthesizing high-purity arsine described in the technique scheme, wherein, middle arsenic powder of described step (1) and zinc powder are made arsenic zinc and are meant, arsenic powder and zinc powder are fully stirred evenly in the reactor that is placed on after vacuumizing, charge into high purity inert gas again to normal pressure, be heated to 400～450 ℃ then,, generate arsenic zinc 400～450 ℃ of reactions down; The high purity inert gas that charges in the reactor when synthesizing arsenic zinc in this step is argon gas or nitrogen, and type of heating is electrically heated.
The method of the synthesizing high-purity arsine described in the technique scheme; wherein; the process that middle arsenic zinc of described step (1) and dilute sulphuric acid reaction obtain rough arsine is; arsenic zinc is placed the arsine reactor that vacuumizes back inflated with nitrogen protection; again the dilute sulphuric acid for preparing is placed storage acid jar, progressively in the arsine reactor, add dilute sulphuric acid then, stir; arsenic zinc and dilute sulphuric acid are reacted completely, make rough arsine.
The method of the synthesizing high-purity arsine described in the technique scheme, wherein, liquid nitrogen cold trap cryogenic vacuum separation in the step (2) is meant that finishing the back in step (1) reaction captures rough arsine gas with liquid nitrogen cold trap, non-condensable gas in the cold-trap is taken out with vacuum pump, take off the liquid nitrogen container of cold-trap outside then, with the arsine volatilization, obtain the arsine that volatilizees.
The method of the synthesizing high-purity arsine described in the technique scheme wherein, also is added with metallic aluminium bits or aluminium flake in described gallium-indium alloy; Therefore the easy oxidation of aluminium powder has adopted aluminium bits or aluminium flake in the present invention, gallium-the indium alloy that has added aluminium bits or aluminium flake has intensive " absorption " to harmful trace impurity oxygen, water and carbonic acid gas etc. in the multiple special gas such as arsine, phosphine, and the multiple special gas such as arsine of main body are not had any chemical reaction.
Owing to adopted above-mentioned technical scheme, the present invention has following beneficial effect:
1, detrimental impurity in the electronic materials such as method energy deep removal oxygen of the present invention, water and carbonic acid gas generally can reach below 0.01～0.1ppm.
2, purifying agent main body gallium-indium alloy can use repeatedly, and have very long work-ing life in theory in work-ing life except that chemical treatment is lost slightly.
Embodiment:
For making technical scheme of the present invention be convenient to understand, the present invention is further illustrated below in conjunction with embodiment.
Embodiment 1:
A kind of method of synthesizing high-purity arsine comprises the steps:
(1), the building-up process of rough arsine: make arsenic zinc with arsenic powder and zinc powder earlier, obtain rough arsine with the dilute sulphuric acid reaction again; Concrete steps are: arsenic powder and zinc powder fully stirred evenly in the reactor that is placed on after vacuumizing, charge into the high purity inert gas argon gas again to normal pressure, and electrically heated to 400 then～450 ℃, reaction generates arsenic zinc under this temperature;
The arsenic zinc that generates is placed the arsine reactor that vacuumizes back inflated with nitrogen protection, again the dilute sulphuric acid for preparing is placed sour jar of storage, progressively in the arsine reactor, add dilute sulphuric acid then, stir, arsenic zinc and dilute sulphuric acid are reacted completely, the rough arsine of generation.
(2), the purge process of high-purity arsine: the rough arsine that makes in the step (1) is obtained the arsine that volatilizees with the separation of liquid nitrogen cold trap cryogenic vacuum earlier, the volatilization arsine that obtains carries out adsorption dry with molecular sieve again, adopt gallium-dark adsorption dewatering of indium alloy liquid, oxygen at last, obtain high-purity arsine; Specific operation process is:
The arsine gas that step (1) reaction is finished the back generation captures with liquid nitrogen cold trap, non-condensable gas in the cold-trap is taken out with vacuum pump, take off the liquid nitrogen container of cold-trap outside then, arsine is volatilized, obtain the arsine that volatilizees, described volatilization arsine is the adsorption dry of the adsorption desiccant molecular sieve in being arranged on the arsine purifier again, after gallium-dark adsorption dewatering of indium alloy liquid, oxygen, promptly obtains the arsine of 5N, 6N.
Embodiment 2:
The operating process of present embodiment is identical with embodiment 1, and difference is: the high purity inert gas that charges in the reactor during synthetic arsenic zinc in the building-up process of the rough arsine of step in the present embodiment (1) is a nitrogen, electrically heated to 410～430 ℃.
Embodiment 3:
The operating process of present embodiment is identical with embodiment 1, and difference is: electrically heated to 420～440 ℃ during synthetic arsenic zinc in the building-up process of the rough arsine of step in the present embodiment (1).
Embodiment 4:
The operating process of present embodiment is identical with embodiment 1, difference is: also be added with metallic aluminium bits or aluminium flake in the present embodiment in gallium-indium alloy, gallium-the indium alloy that has added aluminium powder has harmful trace impurity oxygen, water and carbonic acid gas etc. in the multiple special gas such as arsine, phosphine is had intensive " absorption ", and the multiple special gas such as arsine of main body are not had any chemical reaction.
The above, it only is preferred embodiment of the present invention, be not that the present invention is done any formal and substantial restriction, all those skilled in the art, in not breaking away from the technical solution of the present invention scope, when can utilizing the above technology contents that discloses, and a little change of making, modify the equivalent variations with differentiation, be equivalent embodiment of the present invention; Simultaneously, all foundations essence technology of the present invention all still belongs in the scope of technical scheme of the present invention change, modification and the differentiation of any equivalent variations that above embodiment did.
Claims (6)
1. the method for a synthesizing high-purity arsine comprises the steps:
(1), the building-up process of rough arsine: make arsenic zinc with arsenic powder and zinc powder earlier, obtain rough arsine with the dilute sulphuric acid reaction again;
(2), the purge process of high-purity arsine: the rough arsine that makes in the step (1) is separated with the liquid nitrogen cold trap cryogenic vacuum earlier, the volatilization arsine that obtains carries out adsorption dry with molecular sieve again, adopt gallium-dark adsorption dewatering of indium alloy liquid, oxygen at last, obtain high-purity arsine.
2. the method for synthesizing high-purity arsine according to claim 1, it is characterized in that: middle arsenic powder of described step (1) and zinc powder are made arsenic zinc and are meant, arsenic powder and zinc powder are fully stirred evenly in the reactor that is placed on after vacuumizing, charge into high purity inert gas again to normal pressure, heating then, 400～450 ℃ of reactions down, generate arsenic zinc.
3. the method for synthesizing high-purity arsine according to claim 2 is characterized in that: the high purity inert gas that charges in the reactor during synthetic arsenic zinc in the step (1) is argon gas or nitrogen, and type of heating is electrically heated.
4. the method for synthesizing high-purity arsine according to claim 1; it is characterized in that: the process that middle arsenic zinc of described step (1) and dilute sulphuric acid reaction obtain rough arsine is; arsenic zinc is placed the arsine reactor that vacuumizes back inflated with nitrogen protection; again the dilute sulphuric acid for preparing is placed storage acid jar; progressively in the arsine reactor, add dilute sulphuric acid then; stir, arsenic zinc and dilute sulphuric acid are reacted completely, make rough arsine.
5. the method for synthesizing high-purity arsine according to claim 1, it is characterized in that: the liquid nitrogen cold trap cryogenic vacuum separation in the step (2) is meant that finishing the back in step (1) reaction captures rough arsine gas with liquid nitrogen cold trap, non-condensable gas in the cold-trap is taken out with vacuum pump, take off the liquid nitrogen container of cold-trap outside then, with the arsine volatilization, obtain the arsine that volatilizees.
6. the method for synthesizing high-purity arsine according to claim 1 is characterized in that: also be added with metallic aluminium bits or aluminium flake in described gallium-indium alloy.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104944468A (en) * | 2014-03-26 | 2015-09-30 | 广东先导稀材股份有限公司 | Preparation method for zinc arsenide |
| CN106766675A (en) * | 2016-12-19 | 2017-05-31 | 清远先导材料有限公司 | The method and device of nitrogen is removed from special gas |
| CN109133019A (en) * | 2018-07-03 | 2019-01-04 | 吴来发 | The development of high-purity phosphine scale continuous producing method and device |
| CN110642227A (en) * | 2019-09-25 | 2020-01-03 | 博纯材料股份有限公司 | Synthetic purification method of arsine |
| WO2020062502A1 (en) * | 2018-09-26 | 2020-04-02 | 深圳市永盛隆科技有限公司 | Preparation method for ash3 |
| CN111348680A (en) * | 2018-12-21 | 2020-06-30 | 东泰高科装备科技有限公司 | Process for the preparation of arsine |
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| CN1751774A (en) * | 2005-08-19 | 2006-03-29 | 北京微纳捷通经贸有限公司 | Mfg. of equipment for purifying alkane gas |
| CN101380540A (en) * | 2008-10-09 | 2009-03-11 | 刘庚宇 | Gallium indium aluminum low congruent melting molten mass and use thereof in air purification |
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2010
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1751774A (en) * | 2005-08-19 | 2006-03-29 | 北京微纳捷通经贸有限公司 | Mfg. of equipment for purifying alkane gas |
| CN101380540A (en) * | 2008-10-09 | 2009-03-11 | 刘庚宇 | Gallium indium aluminum low congruent melting molten mass and use thereof in air purification |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104944468A (en) * | 2014-03-26 | 2015-09-30 | 广东先导稀材股份有限公司 | Preparation method for zinc arsenide |
| CN106766675A (en) * | 2016-12-19 | 2017-05-31 | 清远先导材料有限公司 | The method and device of nitrogen is removed from special gas |
| CN109133019A (en) * | 2018-07-03 | 2019-01-04 | 吴来发 | The development of high-purity phosphine scale continuous producing method and device |
| WO2020062502A1 (en) * | 2018-09-26 | 2020-04-02 | 深圳市永盛隆科技有限公司 | Preparation method for ash3 |
| CN110950382A (en) * | 2018-09-26 | 2020-04-03 | 东泰高科装备科技有限公司 | Process for the preparation of arsine |
| CN110950382B (en) * | 2018-09-26 | 2022-03-15 | 紫石能源有限公司 | Process for the preparation of arsine |
| CN111348680A (en) * | 2018-12-21 | 2020-06-30 | 东泰高科装备科技有限公司 | Process for the preparation of arsine |
| CN111348680B (en) * | 2018-12-21 | 2023-03-24 | 紫石能源有限公司 | Process for the preparation of arsine |
| CN110642227A (en) * | 2019-09-25 | 2020-01-03 | 博纯材料股份有限公司 | Synthetic purification method of arsine |
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Application publication date: 20101013 |