CN101565313A - Method for preparing copper-zinc-tin-sulfur photoelectric material - Google Patents
Method for preparing copper-zinc-tin-sulfur photoelectric material Download PDFInfo
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- CN101565313A CN101565313A CNA2009100516457A CN200910051645A CN101565313A CN 101565313 A CN101565313 A CN 101565313A CN A2009100516457 A CNA2009100516457 A CN A2009100516457A CN 200910051645 A CN200910051645 A CN 200910051645A CN 101565313 A CN101565313 A CN 101565313A
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Abstract
A method for preparing a copper-zinc-tin-sulfur photoelectric material in the field of new energy resource comprises the following steps of: respectively treating copper powders, zinc powders and tin powders by sulphuric acid or hydrochloric acid, depressurizing, filtering, drying the powders in vacuum, and mixing the powders with sulfur powders; ball-grinding the powders under the protection of inert gases, statically pressing the ball-grinded materials to obtain a block; sintering the block under the protection of the inert gases, thus obtaining the copper-zinc-tin-sulfur photoelectric material. The method is green, has no pollution and simple requirement for equipment and is suitable for large-scale industrial production.
Description
Technical field
That the present invention relates to is a kind of preparation method of photoelectric material technical field, is specifically related to a kind of preparation method of copper-zinc-tin-sulfur photoelectric material.
Background technology
Copper-zinc-tin-sulfur (Cu
2ZnSnS
4, english abbreviation is CZTS) and have the custerite structure, the desired best energy gap of its energy gap and semiconductor solar cell (1.5eV) is very approaching, and has bigger uptake factor and (can reach 10
4Cm
-1).In addition, this material is that utilization higher zinc and tin element of the amount of containing on the earth's crust replaced copper-indium-galliun-selenium (Cu
2InGaSe
2English abbreviation is CIGS) in phosphide element, also do not contain poisonous composition and environmentally friendly, become the optimal candidate material that substitutes copper-indium-galliun-selenium solar cell absorption layer, be called the next generation's one of the most promising cheap solar cell material in the world, might be become the main product of following photovoltaic cell.
Find that through literature search R.Nitsche etc. rolled up the 52nd～53 page of the 1st phase in 1967 the 1st in " Journal of CrystalGrowth " (crystal growth) and deliver " Crystal growth ofquaternary 1 to prior art
2246
4Chalcogenides by iodine vapor transport " (iodine gas phase transportation act prepares single crystal Cu
2ZnSnS
4) since, the professional has developed Cu such as atomic beam sputter, magnetron sputtering, laser splash, thermal evaporation vacuum plating
2ZnSnS
4Preparation method, but the shortcomings such as hydrogen sulfide that these methods exist apparatus expensive, are not easy to the big area deposition and need to use severe toxicity.Therefore, proposed a kind of can the preparation in a large number, with low cost, environmental friendliness, nontoxic Cu
2ZnSnS
4The preparation method, significant for the present technique field.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of preparation method of copper-zinc-tin-sulfur photoelectric material is provided.Method green non-pollution of the present invention, equipment requirements is simple, is fit to large-scale industrialization production.
The present invention is achieved by the following technical solutions, may further comprise the steps:
1. with copper powder, zinc powder and glass putty are respectively with sulfuric acid or salt acid treatment;
2. filtration under diminished pressure, vacuum-drying;
3. mix ball milling under protection of inert gas with the sulphur powder after;
4. ball milling is good material static pressure obtains block;
5. sintering under protection of inert gas obtains copper-zinc-tin-sulfur photoelectric material.
Described copper powder, the purity of zinc powder and glass putty is 4N～6N.
Described sulfuric acid or hydrochloric acid are treated to, and are 1～5% sulfuric acid or hydrochloric acid stir process 5～60 minutes with massfraction.
Described vacuum-drying is, 30～80 ℃ of dryings are 6～24 hours under the vacuum.
The mol ratio of copper powder, zinc powder, glass putty and sulphur powder is: (2～2.2): (1～1.2): (1～1.2): (4～4.2).
The quality that adds agate ball is 5～100 times of ball milling material.
Described ball milling is that 50～300rpm handled 6～96 hours.
Described static pressure is static pressure such as the pressure of 10～60MPa 5～60 minutes.
Described being sintered to, 300 ℃～1500 ℃ sintering 1～12 hour.
The present invention passes through to select copper, zinc, tin, four kinds of suitable stoicheiometries of monomer of sulphur, the high energy mechanical ball mill mixing, and isostatic pressing, then high temperature sintering under the protection of inert gas obtains a large amount of Cu fast
2ZnSnS
4Photoelectric material.Principle of the present invention is under the protection of inert gas state and the condition of high temperature; monomeric substance obtains very big energy from the external world; the atom out-shell electron is very active; trend towards between atom toward the minimum stable state development of energy; and copper, zinc, tin, four kinds of monomers of sulphur are through ball milling thorough mixing in advance, so can obtain Cu behind the high temperature sintering
2ZnSnS
4Photoelectric material.
Method of the present invention has been avoided the apparatus expensive of sputtering method existence, the shortcomings such as hydrogen sulfide that are not easy to the big area deposition and need to use severe toxicity, has green non-pollution, and equipment requirements is simple, the advantage that suitable large-scale industrialization is produced.
Description of drawings
Fig. 1 is the Cu of embodiment 1 preparation
2ZnSnS
4The X ray diffracting spectrum of photoelectric material;
Fig. 2 is the Cu of embodiment 2 preparations
2ZnSnS
4The X ray diffracting spectrum of photoelectric material;
Fig. 3 is the Cu of embodiment 4 preparations
2ZnSnS
4The X ray diffracting spectrum of photoelectric material;
Fig. 4 is the Cu of embodiment 4 preparations
2ZnSnS
4The X ray diffracting spectrum of photoelectric material;
Fig. 5 is the Cu of embodiment 5 preparations
2ZnSnS
4The X ray diffracting spectrum of photoelectric material.
Embodiment
Below in conjunction with accompanying drawing embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
With copper powder (4N), zinc powder (4N) and glass putty (4N) is 5%, 1%, 5% dilute sulphuric acid stir process filtration under diminished pressure after 20 minutes with massfraction respectively, 40 ℃ of dryings of vacuum 12 hours; Again with the copper handled well, zinc, glass putty and high purity sulphur powder 2: 1: 1 in molar ratio: 4 add in the ball grinders, add the agate ball that is about 5 times of quality of material, vacuumize earlier after the sealing, logical again high-pure helium gas shiled.On planetary ball mill with the rotating speed ball mill mixing of 50rpm 24 hours; The material that ball milling is good is put into mould with the static pressure such as pressure of 30MPa 10 minutes, obtains fine and close material block; At last the material piece behind the isostatic pressing is put into silica tube, feed high-purity argon gas, high temperature sintering is 12 hours in 300 ℃, obtains Cu
2ZnSnS
4Photoelectric material, the X-ray diffractogram of material such as Fig. 1.
Embodiment 2
With copper powder (6N), zinc powder (6N) and glass putty (6N) is 1% dilute sulphuric acid stir process filtration under diminished pressure after 60 minutes with massfraction respectively, 80 ℃ of dryings of vacuum 6 hours; Again with the copper handled well, zinc, glass putty and high purity sulphur powder 2.2: 1.2: 1.2 in molar ratio: 4.2 add in the ball grinders, add the agate ball that is about 40 times of quality of material, vacuumize earlier after the sealing, logical again high-purity argon gas protection.On planetary ball mill with the rotating speed ball mill mixing of 300rpm 6 hours; The material that ball milling is good is put into mould with the static pressure such as pressure of 10MPa 60 minutes, obtains fine and close material block; At last the material piece behind the isostatic pressing is put into silica tube, feed high-purity argon gas, high temperature sintering is 1 hour in 1500 ℃, obtains Cu
2ZnSnS
4Photoelectric material, the X-ray diffractogram of material such as Fig. 2.
Embodiment 3
With copper powder (4N), zinc powder (4N) and glass putty (4N) is 5% dilute sulphuric acid stir process filtration under diminished pressure after 5 minutes with massfraction respectively, 30 ℃ of dryings of vacuum 24 hours; Again with the copper handled well, zinc, glass putty and high purity sulphur powder 2.1: 1.1: 1.1 in molar ratio: 4.1 add in the ball grinders, add the agate ball that is about 100 times of quality of material, vacuumize earlier after the sealing, logical again high-purity argon gas protection.On planetary ball mill with the rotating speed ball mill mixing of 180rpm 96 hours; The material that ball milling is good is put into mould with the static pressure such as pressure of 60MPa 5 minutes, obtains fine and close material block; At last the material piece behind the isostatic pressing is put into silica tube, feed high-purity argon gas, high temperature sintering is 4 hours in 700 ℃, obtains Cu
2ZnSnS
4Photoelectric material, the X-ray diffractogram of material such as Fig. 3.
Embodiment 4
With copper powder (5N), zinc powder (5N) and glass putty (5N) is 1% dilute hydrochloric acid stir process filtration under diminished pressure after 60 minutes with massfraction respectively, 40 ℃ of dryings of vacuum 10 hours; Again with the copper handled well, zinc, glass putty and high purity sulphur powder 2.2: 1.2: 1.2 in molar ratio: 4.2 add in the ball grinders, add the agate ball that is about 40 times of quality of material, vacuumize earlier after the sealing, logical again high pure nitrogen protection.On planetary ball mill with the rotating speed ball mill mixing of 300rpm 6 hours; The material that ball milling is good is put into mould with the static pressure such as pressure of 10MPa 60 minutes, obtains fine and close material block; At last the material piece behind the isostatic pressing is put into silica tube, feed high pure nitrogen, high temperature sintering is 4 hours in 1500 ℃, obtains Cu
2ZnSnS
4Photoelectric material, the X-ray diffractogram of material such as Fig. 4.
Embodiment 5
With copper powder (5N), zinc powder (5N) and glass putty (5N) is 5% dilute hydrochloric acid stir process filtration under diminished pressure after 5 minutes with massfraction respectively, 50 ℃ of dryings of vacuum 10 hours; Again with the copper handled well, zinc, glass putty and high purity sulphur powder 2.1: 1.1: 1.1 in molar ratio: 4.1 add in the ball grinders, add the agate ball that is about 100 times of quality of material, vacuumize earlier after the sealing, logical more high-purity CO
2Protection.On planetary ball mill with the rotating speed ball mill mixing of 180rpm 96 hours; The material that ball milling is good is put into mould with the static pressure such as pressure of 20MPa 15 minutes, obtains fine and close material block; At last the material piece behind the isostatic pressing is put into silica tube, feed high-purity helium, high temperature sintering is 12 hours in 700 ℃, obtains Cu
2ZnSnS
4Photoelectric material, the X-ray diffractogram of material such as Fig. 5.
Claims (8)
1, a kind of preparation method of copper-zinc-tin-sulfur photoelectric material is characterized in that, comprises the steps:
1. with copper powder, zinc powder and glass putty are respectively with sulfuric acid or salt acid treatment;
2. filtration under diminished pressure, vacuum-drying;
3. mix ball milling under protection of inert gas with the sulphur powder after;
4. ball milling is good material static pressure obtains block;
5. sintering under protection of inert gas obtains copper-zinc-tin-sulfur photoelectric material.
2, the preparation method of copper-zinc-tin-sulfur photoelectric material according to claim 1 is characterized in that, described copper powder, and the purity of zinc powder and glass putty is 4N～6N.
3, the preparation method of copper-zinc-tin-sulfur photoelectric material according to claim 1 is characterized in that, described sulfuric acid or hydrochloric acid are treated to, and is 1～5% sulfuric acid or hydrochloric acid stir process 5～60 minutes with massfraction.
4, the preparation method of copper-zinc-tin-sulfur photoelectric material according to claim 1 is characterized in that, described vacuum-drying is, 30～80 ℃ of dryings are 6～24 hours under the vacuum.
According to the preparation method of claim 1 or 2 described copper-zinc-tin-sulfur photoelectric materials, it is characterized in that 5, the mol ratio of copper powder, zinc powder, glass putty and sulphur powder is: (2～2.2): (1～1.2): (1～1.2): (4～4.2).
6, the preparation method of copper-zinc-tin-sulfur photoelectric material according to claim 1 is characterized in that, described ball milling is to be incorporated as the agate ball of 5～100 times of ball milling quality of material, 50～300rpm processing 6～96 hours.
7, the preparation method of copper-zinc-tin-sulfur photoelectric material according to claim 1 is characterized in that, described static pressure is static pressure such as the pressure of 10～60MPa 5～60 minutes.
8, the preparation method of copper-zinc-tin-sulfur photoelectric material according to claim 1 is characterized in that, described being sintered to, 300 ℃～1500 ℃ sintering 1～12 hour.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101792175A (en) * | 2010-03-11 | 2010-08-04 | 山东大学 | Cu-Sn-Zn-S semiconductor material with adjustable forbidden band width and preparation method thereof |
| CN102070121A (en) * | 2009-11-20 | 2011-05-25 | 正峰新能源股份有限公司 | Method for preparing copper-indium-gallium-selenium nanoparticles |
| CN102320647A (en) * | 2011-08-17 | 2012-01-18 | 北京科技大学 | Preparation method of copper sulphide nano-powder with different stoichiometric ratios |
| CN101780974B (en) * | 2009-12-31 | 2012-02-01 | 合肥工业大学 | Preparation method of Cu2ZnSnS4 semiconductor material |
| CN102372302A (en) * | 2010-08-20 | 2012-03-14 | 华东师范大学 | Copper-zinc-tin-sulfur or copper-zinc-tin-selenium target for absorbed layer of thin-film solar battery, preparation method for target and application of target |
| CN102593252A (en) * | 2012-02-23 | 2012-07-18 | 中国科学院合肥物质科学研究院 | Method for preparing copper-zinc-tin-sulfur light absorbing layer of film solar batter |
| US8470287B2 (en) | 2009-11-25 | 2013-06-25 | E I Du Pont De Nemours And Company | Preparation of copper zinc tin sulfide |
| CN103178154A (en) * | 2012-09-28 | 2013-06-26 | 吉林大学 | High-pressure production method of high-density single-tetragon CZTS (copper zinc tin sulfide) material |
| CN103861617A (en) * | 2014-03-28 | 2014-06-18 | 西北师范大学 | Preparation method and application of copper-zinc-tin-sulfur nano-crystalline powder photo-catalyst |
| CN104245573A (en) * | 2012-02-27 | 2014-12-24 | 日本麦可罗尼克斯股份有限公司 | Method for fabricating alloy for czts solar cell |
| CN104801317A (en) * | 2015-03-27 | 2015-07-29 | 电子科技大学 | Photocatalytic water splitting hydrogen production catalyst responding to visible light and preparation method of catalyst |
| CN109956504A (en) * | 2019-03-29 | 2019-07-02 | 昆明理工大学 | A kind of preparation method that cuprum-nickel-stannum sulphur is nanocrystalline |
| CN111924874A (en) * | 2020-08-17 | 2020-11-13 | 华北理工大学 | Preparation method of copper-zinc-tin-based powder |
-
2009
- 2009-05-21 CN CNA2009100516457A patent/CN101565313A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070121A (en) * | 2009-11-20 | 2011-05-25 | 正峰新能源股份有限公司 | Method for preparing copper-indium-gallium-selenium nanoparticles |
| US8470287B2 (en) | 2009-11-25 | 2013-06-25 | E I Du Pont De Nemours And Company | Preparation of copper zinc tin sulfide |
| CN101780974B (en) * | 2009-12-31 | 2012-02-01 | 合肥工业大学 | Preparation method of Cu2ZnSnS4 semiconductor material |
| CN101792175A (en) * | 2010-03-11 | 2010-08-04 | 山东大学 | Cu-Sn-Zn-S semiconductor material with adjustable forbidden band width and preparation method thereof |
| CN102372302A (en) * | 2010-08-20 | 2012-03-14 | 华东师范大学 | Copper-zinc-tin-sulfur or copper-zinc-tin-selenium target for absorbed layer of thin-film solar battery, preparation method for target and application of target |
| CN102320647A (en) * | 2011-08-17 | 2012-01-18 | 北京科技大学 | Preparation method of copper sulphide nano-powder with different stoichiometric ratios |
| CN102593252A (en) * | 2012-02-23 | 2012-07-18 | 中国科学院合肥物质科学研究院 | Method for preparing copper-zinc-tin-sulfur light absorbing layer of film solar batter |
| CN104245573B (en) * | 2012-02-27 | 2016-06-08 | 日本麦可罗尼克斯股份有限公司 | The manufacture method of CZTS system alloy used for solar batteries |
| CN104245573A (en) * | 2012-02-27 | 2014-12-24 | 日本麦可罗尼克斯股份有限公司 | Method for fabricating alloy for czts solar cell |
| CN103178154B (en) * | 2012-09-28 | 2015-11-25 | 吉林大学 | The high pressure method for preparing of a kind of high densification, single tetragonal copper-zinc-tin-sulfur material |
| CN103178154A (en) * | 2012-09-28 | 2013-06-26 | 吉林大学 | High-pressure production method of high-density single-tetragon CZTS (copper zinc tin sulfide) material |
| CN103861617A (en) * | 2014-03-28 | 2014-06-18 | 西北师范大学 | Preparation method and application of copper-zinc-tin-sulfur nano-crystalline powder photo-catalyst |
| CN104801317A (en) * | 2015-03-27 | 2015-07-29 | 电子科技大学 | Photocatalytic water splitting hydrogen production catalyst responding to visible light and preparation method of catalyst |
| CN104801317B (en) * | 2015-03-27 | 2017-06-16 | 电子科技大学 | A kind of photolytic hydrogen production catalyst of responding to visible light and preparation method thereof |
| CN109956504A (en) * | 2019-03-29 | 2019-07-02 | 昆明理工大学 | A kind of preparation method that cuprum-nickel-stannum sulphur is nanocrystalline |
| CN111924874A (en) * | 2020-08-17 | 2020-11-13 | 华北理工大学 | Preparation method of copper-zinc-tin-based powder |
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Open date: 20091028 |