CN102249188A - Preparation method of germane gas - Google Patents
Preparation method of germane gas Download PDFInfo
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- CN102249188A CN102249188A CN 201110132107 CN201110132107A CN102249188A CN 102249188 A CN102249188 A CN 102249188A CN 201110132107 CN201110132107 CN 201110132107 CN 201110132107 A CN201110132107 A CN 201110132107A CN 102249188 A CN102249188 A CN 102249188A
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- germane
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- germane gas
- gas
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Abstract
The invention provides a preparation method of germane gas. According to the method, a sodium hydroxide solution of sodium borohydride is prepared; polyether with a volume of 0.5% to 5% of that of the solution is added to the solution; and a tetrahydrofuran solution of germanium tetrachloride is added to the solution for preparing germane gas. Compared to previously disclosed methods, according to the present method, polyether is added to the reaction solution, such that a substantial effect is brought in, generation of yellow precipitate is greatly reduced, and a conversion rate of germane is improved by approximately 7%.
Description
Technical field
The present invention relates to a kind of preparation method of Germane gas, be specifically related to a kind of by in reaction soln, adding the germane preparation method that polyethers improves transformation efficiency.
Background technology
High-purity germane is a kind of important semiconductor industry unstripped gas, progressively is applied to organometallics vapour phase epitaxy (MOVPE), is used for preparation and contains Germanium semiconductor material or device, as the germanium-silicon thin membrane solar cell.
The approach of preparation germane is a lot, and early stage method is to use LiAlH in the ether medium
4Reduction GeCl
4Prepare germane; The classical approach of preparation germane is Mg
2Ge hydrolysis in diluted acid (example hydrochloric acid) solution; With reductive agent or electrolytic process the Ge(IV in the aqueous solution) be reduced to germane; With the Ge(IV in the sodium borohydride reduction acidic solution) also can produce germane; The method for preparing germane preferably is to use NH
4Br and the Mg that is suspended in the liquefied ammonia
2The Ge effect will have the germanium of 60%-70% to be transformed into various germanes.But adopt these methods, low and by product two germanes of productive rate, three germane content height, industrial being not suitable for used.
Patent CN101723326A discloses the method that sodium hydroxide solution that a kind of tetrahydrofuran solution with germanium tetrachloride is added drop-wise to sodium borohydride prepares germane, and this method technology is simple, and cost is lower, and foreign matter content is few, is easy to purify, and is applicable to industrialization production.But easily produce yellow mercury oxide in this method reaction process, cause transformation efficiency lower.Therefore be necessary to seek to reduce the method that yellow mercury oxide produces, improve this method germane transformation efficiency.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of Germane gas, described method again to the tetrahydrofuran solution that wherein drips germanium tetrachloride, prepare Germane gas by add polyethers in the sodium hydroxide solution of the sodium borohydride for preparing.
The method of the invention is achieved through the following technical solutions: a kind of preparation method of Germane gas, the sodium hydroxide solution of preparation sodium borohydride, 0.5% ~ 5% ratio in liquor capacity is added polyethers, again to the tetrahydrofuran solution that wherein drips germanium tetrachloride, and the preparation Germane gas.
Described polyethers comprises that molecular weight is at 200 ~ 2000 polypropylene glycol and polyoxyethylene glycol.
The beneficial effect that the present invention has is:
The present invention adds polyethers in the sodium hydroxide solution of the sodium borohydride for preparing, again to the tetrahydrofuran solution that wherein drips germanium tetrachloride, and the preparation Germane gas.Compare with the CN101723326A disclosed method, this method plays a significant role by add polyethers in reaction soln, has significantly reduced the generation of yellow mercury oxide, and the germane transformation efficiency improves about 7%.
Embodiment
Comparative example:
Take by weighing 151.3g(4mol) sodium borohydride, join in the sodium hydroxide solution of 3L 1mol/L, stirring and dissolving is transferred in the reactor; Get 46.5mL(0.4mol) germanium tetrachloride is dissolved in the 280mL tetrahydrofuran (THF), transfers in the dropping funnel.With the dropping funnel germane generation systems of packing into, the resistance to air loss of inspection units.Use the vacuum pump evacuation system, treat vacuum tightness reduce to 10Pa following after, the control dropping funnel drips liquid with the speed of 30mL/min in reactor, reaction times 1.5h under agitation takes place.The gas that reaction generates feeds in the calcium chloride tube, remove moisture after the using gas collector collect.Occur yellow mercury oxide in the reaction, the germane transformation efficiency is 80.3%.
Embodiment 1:
Take by weighing 151.3g(4mol) sodium borohydride, join in the sodium hydroxide solution of 3L 1mol/L, add 15mL polypropylene glycol PPG600, stirring and dissolving is transferred in the reactor; Get 46.5mL(0.4mol) germanium tetrachloride is dissolved in the 280mL tetrahydrofuran (THF), transfers in the dropping funnel.With the dropping funnel germane generation systems of packing into, the resistance to air loss of inspection units.Use the vacuum pump evacuation system, treat vacuum tightness reduce to 10Pa following after, the control dropping funnel drips liquid with the speed of 30mL/min in reactor, under agitation react reaction times 1.5h.The gas that generates feeds in the calcium chloride tube, remove moisture after the using gas collector collect.Occur micro-yellow mercury oxide in the reaction process, the germane transformation efficiency is 86.4%.
Embodiment 2:
Change the add-on of polypropylene glycol PPG600 among the embodiment 1 into 150 mL, other condition is identical.Do not occur yellow mercury oxide in the reaction process, the germane transformation efficiency is 87.6%.
Embodiment 3:
Change the add-on of polypropylene glycol PPG600 among the embodiment 1 into 60 mL, other condition is identical.Do not occur yellow mercury oxide in the reaction process, the germane transformation efficiency is 87.3%.
Embodiment 4:
Change polypropylene glycol PPG600 among the embodiment 1 into 60 mL polyoxyethylene glycol PEG200, other condition is identical.Occur a small amount of yellow mercury oxide in the reaction process, the germane transformation efficiency is 84.5%.
Embodiment 5:
Change polypropylene glycol PPG600 among the embodiment 1 into 60 mL polyoxyethylene glycol PEG400, other condition is identical.Occur a small amount of yellow mercury oxide in the reaction process, the germane transformation efficiency is 83.9%.
Though the present invention is with preferred embodiment openly as above, be familiar with this skill person for any, in the spirit and scope that do not break away from the invention, can do various variations or retouching, same within the protection domain of the invention.
Claims (2)
1. the preparation method of a Germane gas is characterized in that: prepare the sodium hydroxide solution of sodium borohydride, add polyethers in 0.5% ~ 5% ratio of liquor capacity, again to the tetrahydrofuran solution that wherein drips germanium tetrachloride, prepare Germane gas.
2. the preparation method of Germane gas according to claim 1 is characterized in that: described polyethers refers to molecular weight at 100 ~ 3000 polypropylene glycol and polyoxyethylene glycol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110132107 CN102249188B (en) | 2011-05-21 | 2011-05-21 | Preparation method of germane gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110132107 CN102249188B (en) | 2011-05-21 | 2011-05-21 | Preparation method of germane gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102249188A true CN102249188A (en) | 2011-11-23 |
| CN102249188B CN102249188B (en) | 2012-12-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110132107 Active CN102249188B (en) | 2011-05-21 | 2011-05-21 | Preparation method of germane gas |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110612365A (en) * | 2017-05-19 | 2019-12-24 | 昭和电工株式会社 | Method for electrochemically producing germane |
| CN110621810A (en) * | 2017-05-19 | 2019-12-27 | 昭和电工株式会社 | Method for electrochemically producing germane |
| CN114655927A (en) * | 2015-08-20 | 2022-06-24 | 贺孝鸣 | Production method and device for regulating electromotive force to control germane preparation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4656013A (en) * | 1984-04-13 | 1987-04-07 | Mitsui Toatsu Chemicals, Inc. | Process for producing germanes |
| CN101723326A (en) * | 2009-12-18 | 2010-06-09 | 浙江理工大学 | Preparation method of germane |
| CN101955155A (en) * | 2010-06-07 | 2011-01-26 | 天津市泰源工业气体有限公司 | Technology for preparing germanium hydride by adopting sodium borohydride or potassium borohydride reduction germanium tetrachloride reaction |
-
2011
- 2011-05-21 CN CN 201110132107 patent/CN102249188B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4656013A (en) * | 1984-04-13 | 1987-04-07 | Mitsui Toatsu Chemicals, Inc. | Process for producing germanes |
| CN101723326A (en) * | 2009-12-18 | 2010-06-09 | 浙江理工大学 | Preparation method of germane |
| CN101955155A (en) * | 2010-06-07 | 2011-01-26 | 天津市泰源工业气体有限公司 | Technology for preparing germanium hydride by adopting sodium borohydride or potassium borohydride reduction germanium tetrachloride reaction |
Non-Patent Citations (1)
| Title |
|---|
| 《四川化工》 19971231 韩汉民 超纯锗的制备 第2-5页 1-2 , 第2期 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114655927A (en) * | 2015-08-20 | 2022-06-24 | 贺孝鸣 | Production method and device for regulating electromotive force to control germane preparation |
| CN110612365A (en) * | 2017-05-19 | 2019-12-24 | 昭和电工株式会社 | Method for electrochemically producing germane |
| CN110621810A (en) * | 2017-05-19 | 2019-12-27 | 昭和电工株式会社 | Method for electrochemically producing germane |
| CN110612365B (en) * | 2017-05-19 | 2022-04-05 | 昭和电工株式会社 | Method for electrochemically producing germane |
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| CN102249188B (en) | 2012-12-26 |
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Application publication date: 20111123 Assignee: CHINA GERMANIUM Co.,Ltd. Assignor: NANJING GERMANIUM TECHNOLOGY Co.,Ltd. Contract record no.: 2014320000338 Denomination of invention: Preparation method of germane gas Granted publication date: 20121226 License type: Exclusive License Record date: 20140424 |
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Address after: 211165 No. 718, Jiangjun Avenue, Jiangning Development Zone, Nanjing, Jiangsu Patentee after: CHINA GERMANIUM Co.,Ltd. Address before: 211165 No. 718, Jiangjun Avenue, Jiangning Development Zone, Nanjing, Jiangsu Patentee before: NANJING GERMANIUM TECHNOLOGY Co.,Ltd. |
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Effective date of registration: 20211129 Address after: 211299 No. 9, Zhongxing East Road, Lishui District, Nanjing City, Jiangsu Province Patentee after: CHINA GERMANIUM Co.,Ltd. Address before: 211165 No. 718, Jiangjun Avenue, Jiangning Development Zone, Nanjing, Jiangsu Patentee before: CHINA GERMANIUM Co.,Ltd. |