CN102049529B - Method for preparing Ge material by adopting Ge acid radical ion water-solubility precursor - Google Patents
Method for preparing Ge material by adopting Ge acid radical ion water-solubility precursor Download PDFInfo
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- CN102049529B CN102049529B CN201010594317.4A CN201010594317A CN102049529B CN 102049529 B CN102049529 B CN 102049529B CN 201010594317 A CN201010594317 A CN 201010594317A CN 102049529 B CN102049529 B CN 102049529B
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Abstract
The invention relates to a preparation method for Ge (germanium) material, particularly relates to the preparation for Ge nanometer powder and Ge film, and belongs to the technical field of inorganic material. Ge material comprises Ge nanometer power, Ge film, Ge porous film material and the like, wherein the preparation method for Ge nanometer powder comprises the following steps: firstly, Ge acid radical ion water-solubility precursor is reacted with sodium borohydride, then the reaction product is centrifuged, washed, and dried, and finally receives heat treatment. The Ge acid radical ion water-solubility precursor adopted in the invention to prepare Ge material can be obtained only by dissolving germanium dioxide into alkaline solution, the price of the germanium dioxide is low, and no toxicity or pollution is generated, so that germanium dioxide is particularly suitable for industrialized production. In the invention, compared with other reducing agents such as Na (Natrium) and metal Naphthalene chemical compound, sodium borohydride being adopted as the reducing agent can enable the reaction to be mild, the reaction can be generated under the ordinary temperature and the normal pressure, and the problems in the Ge material preparation such as high cost, excessively complicated technology and potential safety hazard are solved.
Description
Technical field
The present invention relates to a kind of preparation method of germanium material, particularly the preparation of germanium nano-powder and germanium film, belongs to technical field of inorganic material.
Background technology
The electronics of germanium and hole mobility are higher than silicon, and saturation resistance is very little, and the performance in high frequency and large power semiconductor device is better than silicon.In addition the low-pressure performance of germanium transistor is good, and power consumption is little, almost there is no heat radiation, the device that to be therefore also applicable to take battery be power supply or require athermic micro electric power apparatus.Germanium has fabulous detection feature, and to gamma-rays, infra-red radiation and temperature have high resolution ratio.In recent years, the phenomenon that nano level germanium crystal has strong luminescence generated by light has caused concern widely, and has been applied in the middle of bio-imaging technology.
The existing method of preparing germanium nano material has: under HTHP, decompose the organic compound of germanium, for example tetraethyl germanium and diphenyl germanium; In germanium tetrachloride and glycol dimethyl ether, make NaGe that disproportionated reaction occurs; Utilize the compound of strong reductant reduction germanium.Wherein, the gaseous compound of germanium (as germane) is mostly inflammable and poisonous, and the liquefied compound of germanium (as germanium tetrachloride) is violent with strong reductant abnormal reaction, can produce a large amount of harmful Germane gas; Conventional reducing agent is as sodium, and metal naphthalene compound etc. are very responsive to hydrone, needs harsh reaction environment (as reacted in organic solvent or inert atmosphere).In addition, the price of above-mentioned germanium presoma is higher, although and germanium dioxide low price, due to its stable chemical nature, is not also prepared the method for germanium under gentle condition with germanium dioxide.Therefore, develop a kind of cost low, reaction condition is simple, and the preparation method that potential safety hazard is few is very significant.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of germanium material, can solve in existing germanium material preparation method cost high, the problem such as the too complicated and potential potential safety hazard of technique is many.
Germanium material of the present invention comprises germanium nano-powder, germanium film and germanium porous film material etc.Wherein:
The preparation method of germanium nano-powder, utilizes germanic acid radical ion water-soluble precursor to react with sodium borohydride, product is centrifugal, washing, dry after, through further heat treatment and get final product.
In course of reaction, the mol ratio of controlling germanium dioxide in sodium borohydride and presoma is 4: 1～6: 1, and adding the reaction time after sodium borohydride is 12～48 hours, and heat treatment temperature is 120～180 ℃.
Product can be removed impurity by centrifugal and washing repeatedly.
Germanium nano-powder is turned out to be the germanium of face-centered cubic crystal formation by X-ray diffraction (XRD).Illustrate that this kind of method can access the germanium nano-powder of good crystallinity.
The preparation method of germanium film, utilizes germanic acid radical ion water-soluble precursor to react with sodium borohydride, product is centrifugal, washing, dry after, through thermal evaporation, obtain germanium film.
Thermal evaporation temperature is 400～1000 ℃.
Germanium film material, thus the product of diverse microcosmic appearance can be obtained by controlling the reaction conditions such as acid extraction.
The preparation method of germanium porous film material, adopts germanic acid radical ion water-soluble precursor, slowly separates out germanium dioxide and deposits film forming after presoma is adjusted to acidity, and then in hydrogen atmosphere, heat treatment germanium dioxide film obtains germanium porous film material.
Wherein:
In hydrogen atmosphere, heat treatment temperature is 500～700 ℃.
Germanium dioxide film forms on substrate, and substrate can have any shape, flat shape or molded non-planar.
The product of germanic acid radical ion water-soluble precursor of the present invention and sodium borohydride, can be used as germanium source and is applied in germanium film preparation.
The present invention adopts germanic acid radical ion water-soluble precursor to prepare germanium material, and presoma is dissolved in alkaline solution with germanium dioxide and can obtains, germanium dioxide low price, and nontoxic pollution-free, is particularly suitable for suitability for industrialized production.Reducing agent adopts sodium borohydride, and with respect to reducing agents such as sodium and metal naphthalene compounds, its course of reaction is gentle, and just can react under normal temperature and pressure.Can be high for solving in germanium material preparation cost, the too complicated and potential potential safety hazard of technique is many etc., and problem provides a kind of feasible thinking.
Accompanying drawing explanation
Fig. 1 is the XRD photo of prepared germanium nano-powder;
Fig. 2 is the SEM photo of prepared germanium nano-powder;
Fig. 3 is the SEM photo of the germanium film prepared on 400 ℃ of lower-glass substrates;
Fig. 4 is the SEM photo of the germanium film prepared on 600 ℃ of lower-glass substrates;
Fig. 5 is the SEM photo of the germanium film prepared on silver-colored substrate at 600 ℃;
Fig. 6 is the SEM photo of the germanium film prepared in Sapphire Substrate at 800 ℃;
Fig. 7 is the SEM photo of the germanium perforated membrane prepared in glass substrate;
Fig. 8 is the photo in kind of quartz glass tube;
Fig. 9 is the photo in kind that is formed with the quartz glass tube of germanium perforated membrane on inwall;
The specific embodiment
Below in conjunction with embodiment and accompanying drawing, the invention will be further described.
Embodiment 1
The preparation method of germanium nano-powder of the present invention, carries out according to the following step successively:
(1) 0.3g germanium dioxide being dissolved under heating condition to 10ml mass concentration is to obtain germanic acid radical ion water-soluble precursor in 3% ammonia spirit;
(2) 0.542g sodium borohydride is added in above-mentioned presoma, stir after standing 24 hours;
(3) above-mentioned product is carried out repeatedly to centrifuge washing until centrifuge tube at the middle and upper levels the pH value of clear liquid be 7, collect centrifuge tube bottom precipitation and in air atmosphere 120 ℃ of heating within 4 hours, obtain grey black powder, the X-ray diffraction spectrogram of product is shown in Fig. 1, shown diffraction maximum is attributed to the diffraction maximum of face-centered cubic germanium, and Fig. 2 is shown in by the SEM photo of product.Fig. 1 illustrates that in conjunction with Fig. 2 grey black powder is the germanium nano-powder of crystalline state.
Crystalline state germanium nano-powder presoma prepared by this kind of method is easy to obtain, and easy and simple to handle, equipment is simple, can produce in enormous quantities.
Embodiment 2
The preparation method of germanium nano-powder of the present invention, carries out according to the following step successively:
(1) 0.3g germanium dioxide being dissolved under heating condition to 10ml mass concentration is to obtain germanic acid radical ion water-soluble precursor in 3% ammonia spirit;
(2) 0.365g sodium borohydride is added in above-mentioned presoma, stir after standing 24 hours;
(3) above-mentioned product is carried out repeatedly to centrifuge washing until centrifuge tube at the middle and upper levels the pH value of clear liquid be 7, collect centrifuge tube bottom precipitation and 180 ℃ of heating obtain crystalline state for 4 hours in air atmosphere germanium nano-powder.
Embodiment 3
The preparation method of germanium nano-powder of the present invention, carries out according to the following step successively:
(1) 0.3g germanium dioxide being dissolved under heating condition to 10ml mass concentration is to obtain germanic acid radical ion water-soluble precursor in 3% ammonia spirit;
(2) 0.645g sodium borohydride is added in above-mentioned presoma, stir after standing 48 hours;
(3) above-mentioned product is carried out repeatedly to centrifuge washing until centrifuge tube at the middle and upper levels the pH value of clear liquid be 7, collect centrifuge tube bottom precipitation and 160 ℃ of heating obtain crystalline state for 4 hours in air atmosphere germanium nano-powder.
Embodiment 4
The preparation method of germanium film material in glass substrate of the present invention, carries out according to the following step successively:
(1) the precipitation adding distil water stirring of embodiment 1 (3) described centrifuge tube bottom is made to suspension and move into flat porcelain boat, in air atmosphere, 120 ℃ of heating form one deck crystalline state germanium deposit in porcelain boat bottom after 4 hours.Take this deposit as germanium source, locate to cover a clean glass sheet for 3 millimeters above it.
(2) porcelain boat that is stamped sheet glass in (1) is put into 400 ℃ of heating of vacuum furnace 2 hours, at sheet glass lower surface, by thermal evaporation, formed germanium film.The SEM photo of the germanium film that Fig. 3 is prepared for this kind of method.Above-mentioned crystalline state germanium nano-powder can evaporate and obtain germanium film at 400 ℃, and evaporating temperature is far below the fusing point (947 ℃) of germanium, and take the evaporating temperature of traditional germanium film preparation technique that block germanium is germanium source, all needs to surpass the fusing point of germanium.
Embodiment 5
The preparation method of germanium film material in glass substrate of the present invention, carries out according to the following step successively:
(1) the precipitation adding distil water stirring of embodiment 1 (3) described centrifuge tube bottom is made to suspension and move into flat porcelain boat, in air atmosphere, 120 ℃ of heating form one deck crystalline state germanium deposit in porcelain boat bottom after 4 hours.Take this deposit as germanium source, locate to cover a clean glass sheet for 3 millimeters above it.
(2) porcelain boat that is stamped sheet glass in (1) is put into 600 ℃ of heating of vacuum furnace 1 hour, at sheet glass lower surface, by thermal evaporation, formed germanium film.The SEM photo of the germanium film that Fig. 4 is prepared for this kind of method, can find that the surface of film is uniformly distributed with the spheroidal particle that is less than 10 nanometers, and the compactness of film integral and crystallinity are better than the germanium film of preparation at 400 ℃.
Embodiment 6
The preparation method of germanium film material on silver-colored substrate of the present invention, carries out according to the following step successively:
(1) the precipitation adding distil water stirring of embodiment 1 (3) described centrifuge tube bottom is made to suspension and move into flat porcelain boat, in air atmosphere, 120 ℃ of heating form one deck crystalline state germanium deposit in porcelain boat bottom after 4 hours.Take this deposit as germanium source, 3 millimeters of sheet glass of locating to cover an electroplate above it, silvered face is downward.
(2) porcelain boat that is stamped silvered glass sheet in (1) is put into 600 ℃ of heating of vacuum furnace 2 hours, at sheet glass silvered face, by thermal evaporation, formed germanium film.Germanium film prepared by this kind of method has the feature of oriented growth, and film surface is parallel to (111) crystal face of germanium.The SEM photo of the germanium film that Fig. 5 is prepared for this kind of method, can find out that film surface has island pattern.
Embodiment 7
The preparation method of germanium film material in Sapphire Substrate of the present invention, carries out according to the following step successively:
(1) get the tubular container of an end opening, the germanium nano-powder of embodiment 1 preparation is put into one end of close sealing in container, Sapphire Substrate is put into one end of opening.
(2) tubular container is put into vacuum furnace, heating is placed with one end of germanium nano-powder, and 800 ℃ of heating-up temperatures, 6 hours heat times, form germanium film at Sapphire Substrate upper surface by thermal evaporation.The SEM photo of the germanium film that Fig. 6 is prepared for this kind of method, this kind of method can be on the surface that is difficult for closing with germanium junction, and as sapphire, germanium film is prepared on the surface of quartz glass.
Embodiment 8
The preparation method of germanium porous film material in planar substrate of the present invention, carries out according to the following step successively:
(1) 0.7g germanium dioxide being dissolved under heating condition to 10ml mass concentration is to obtain germanic acid radical ion water-soluble precursor in 1.5% sodium hydroxide solution;
(2) sulfuric acid is added dropwise in the germanic acid radical ion aqueous solution to pH be 5;
(3) in above-mentioned solution, put into clean sheet glass, within 3 days, take out afterwards, at sheet glass upper surface, form a surface sediments;
(4) by heat treatment 1 hour in hydrogen atmosphere after dry with sedimental sheet glass in (3), 600 ℃ of heat treatment temperatures obtain the more uniform germanium porous film material of one deck on sheet glass.The SEM photo of the germanium perforated membrane that Fig. 7 is prepared for this kind of method, it has unique loose structure as seen from the figure.
Embodiment 9
The preparation method of germanium porous film material in Non-planar substrates of the present invention, carries out according to the following step successively:
(1) 0.7g germanium dioxide being dissolved under heating condition to 10ml mass concentration is to obtain germanic acid radical ion water-soluble precursor in 1.5% sodium hydroxide solution;
(2) sulfuric acid being added dropwise to the germanic acid radical ion aqueous solution to pH is 5;
(3) above-mentioned solution to be injected to clean internal diameter be the quartz glass tube of 2 millimeters and seal the mouth of pipe, and quartz glass tube is vertically standing.After 3 days, open the mouth of pipe, pour out solution, on quartz glass pipe internal surface, form a surface sediments;
(4) by heat treatment 1 hour in hydrogen atmosphere after dry with sedimental quartz glass tube in (3), 600 ℃ of heat treatment temperatures obtain the more uniform germanium porous film material of one deck on quartz glass inside pipe wall.Fig. 8 is the photo in kind of quartz glass tube, and Fig. 9 is the photo in kind of the inwall quartz glass tube that has germanium perforated membrane, illustrates that this kind of method can obtain at complex-shaped substrate surface more uniform germanium porous film material.
Evidence, the present invention can prepare a series of germanium material by germanic acid radical ion water-soluble precursor, comprises germanium nano-powder, germanium film and germanium porous film material.
The above, be only preferred embodiment of the present invention, is not the present invention to be done to the restriction of other form, and any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the equivalent embodiment of equivalent variations.But every technical solution of the present invention content that do not depart from, any simple modification, equivalent variations and the remodeling above embodiment done according to technical spirit of the present invention, still belong to the protection domain of technical solution of the present invention.
Claims (6)
1. a preparation method for germanium film material, is characterized in that:
(1) germanium dioxide powder is dissolved in ammoniacal liquor, obtains the germanic acid radical ion aqueous solution, add sodium borohydride, by product through repeatedly centrifugal, washing, to supernatant liquor pH value be 7, centrifuge tube bottom precipitation suspension is moved in flat porcelain boat dry, obtain crystalline state germanium deposit;
(2) above crystalline state germanium deposit, 3mm place covers a clean glass sheet, and at 400～1000 ℃, heating in vacuum is 1～6 hour, makes germanium film.
2. the preparation method of germanium film material according to claim 1, is characterized in that, the mol ratio of sodium borohydride and germanium dioxide is 4:1～6:1, and be 12～48 hours drying time, and baking temperature is 120～180 ℃.
3. the preparation method of germanium film material according to claim 1, is characterized in that, heating in vacuum temperature is 400～600 ℃.
4. the preparation method of a germanium porous film material, it is characterized in that, germanium dioxide powder is dissolved in and in sodium hydroxide solution, makes the germanic acid radical ion aqueous solution, it is that the clean internal diameter of 5 rear injections is the quartz glass tube of 2 millimeters and seals the mouth of pipe that the germanic acid radical ion aqueous solution is adjusted to pH value, after 3 days, separate out germanium dioxide and deposit film forming, then in hydrogen atmosphere, heat treatment germanium dioxide film obtains germanium porous film material for 1 hour.
5. the preparation method of germanium porous film material according to claim 4, is characterized in that, in hydrogen atmosphere, heat treatment temperature is 500～700 ℃.
6. according to the preparation method of the germanium porous film material described in claim 4 or 5, it is characterized in that, germanium oxide film forms on quartz glass tube substrate.
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| CN102764896A (en) * | 2012-06-27 | 2012-11-07 | 暨南大学 | Germanium nanoparticle preparation method capable of stabilizing nanometer germanium |
| CN106159247B (en) * | 2015-04-13 | 2019-04-05 | 中国科学院宁波材料技术与工程研究所 | A kind of porous germanium negative electrode material of lithium ion battery and its preparation method and application |
| CN111661872B (en) * | 2020-06-16 | 2022-10-04 | 华东师范大学 | Preparation method of nano germanium oxide |
| CN112830511B (en) * | 2021-03-15 | 2023-01-03 | 广东先导稀材股份有限公司 | Germanium dioxide dechlorination method |
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| CN1706577A (en) * | 2005-04-28 | 2005-12-14 | 浙江大学 | Supersonic liquid phase reduction process for preparing monodisperse nano germanium crystal |
| CN101117708A (en) * | 2006-07-31 | 2008-02-06 | 敬承斌 | Liquid deposition preparing method for germanium dioxide material |
| CN101186974A (en) * | 2006-11-15 | 2008-05-28 | 云南临沧鑫圆锗业股份有限公司 | Reclamation of germanium from germanium waste material by wet method |
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| US6645444B2 (en) * | 2001-06-29 | 2003-11-11 | Nanospin Solutions | Metal nanocrystals and synthesis thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1706577A (en) * | 2005-04-28 | 2005-12-14 | 浙江大学 | Supersonic liquid phase reduction process for preparing monodisperse nano germanium crystal |
| CN101117708A (en) * | 2006-07-31 | 2008-02-06 | 敬承斌 | Liquid deposition preparing method for germanium dioxide material |
| CN101186974A (en) * | 2006-11-15 | 2008-05-28 | 云南临沧鑫圆锗业股份有限公司 | Reclamation of germanium from germanium waste material by wet method |
Non-Patent Citations (2)
| Title |
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| "液相沉积法合成二氧化锗类材料的研究";侯金霞;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;中国学术期刊电子杂志社;20090515;第10-12、43-44及50页 * |
| 侯金霞."液相沉积法合成二氧化锗类材料的研究".《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》.中国学术期刊电子杂志社,2009,第10-12、43-44及50页. |
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Address after: 200241 room 243, School of information, East China Normal University, 500 Dongchuan Road, Shanghai, Minhang District Applicant after: Jing Chengbin Address before: 266042 Qingdao University of Science & Technology, 53 Zhengzhou Road, Sifang District, Shandong, Qingdao Applicant before: Jing Chengbin |
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