CN102254985B - Hydro-thermal synthesis method for copper-zinc-tin-sulfur photoelectric material - Google Patents
Hydro-thermal synthesis method for copper-zinc-tin-sulfur photoelectric material Download PDFInfo
- Publication number
- CN102254985B CN102254985B CN2011100940066A CN201110094006A CN102254985B CN 102254985 B CN102254985 B CN 102254985B CN 2011100940066 A CN2011100940066 A CN 2011100940066A CN 201110094006 A CN201110094006 A CN 201110094006A CN 102254985 B CN102254985 B CN 102254985B
- Authority
- CN
- China
- Prior art keywords
- zinc
- copper
- tin
- sulfur
- photoelectric material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Photovoltaic Devices (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a hydro-thermal synthesis method for a copper-zinc-tin-sulfur photoelectric material, belonging to the field of preparation of inorganic nano materials. The method comprises the following steps of: dissolving a zinc salt, a tin salt and a cupric salt into a solvent in the molar ratio (0.5-6):(0.3-1):(0.5-2), adding a sulfur-containing compound of which the mole number is 1-4 times of the total mole number of the metal salts and 0-1 millimole of surfactant and reacting at 150-220 DEG C for 5-48 hours; and centrifuging and drying to obtain copper-zinc-tin-sulfur photoelectric material powder. In the method, tetragonal-phase copper-zinc-tin-sulfur photoelectric material powder and orthogonal-phase copper-zinc-tin-sulfur photoelectric material powder are synthesized respectively with a hydro-thermal method and an ethylene diamine-assisted hydro-thermal method; and the method is easy to operate, has high repeatability and low cost, and is easy for realizing mass production.
Description
Technical field
The present invention relates to a kind of hydrothermal synthesis method of copper-zinc-tin-sulfur photoelectric material, belong to field of inorganic nano-material preparation.
Background technology
Along with society and economic development, people replace existing non-renewable energy resources in the urgent need to seeking a kind of cleaning and reproducible new forms of energy, to alleviate day by day serious energy crisis.Solar energy, but as a kind of infinite regeneration and the abundant clean energy resource of reserves, caused people's extensive concern.How further to develop solar energy and become current study hotspot.The photovoltaic technology that can convert solar energy into electrical energy is one of important means that does not solve energy problem.Transformation efficiency is high, stable performance, cheap solar cell are the targets that the scientific worker pursues.
The emphasis of current solar cell research is the exploration of photovoltaic device material.The requirements such as a new generation's solar cell material should meet that environmental friendliness, reserves are abundant, band gap and sunlight coupling.In numerous semi-conducting materials, the desired best energy gap of the energy gap of copper-zinc-tin-sulfur and semiconductor solar cell (1.5eV) is very approaching, in addition, the absorption coefficient of this material is larger, contained element reserves on earth are all very abundant, and do not contain hypertoxic composition, be one of optimal candidate material of environmentally friendly solar cell device.
Through prior art and literature search are found, mainly contain the methods such as atomic beam sputter, magnetron sputtering, spray pyrolysis when preparation copper-zinc-tin-sulfur material.Above these methods are had relatively high expectations to the instrument and equipment that uses, and sulfuration process is complicated, and process conditions are comparatively harsh.Chinese patent CN101844797A (201010174921.1) discloses a kind of method that Hydrothermal Synthesis prepares solar absorption layer material copper-zinc-tin-sulfur, comprise the steps: step 1, get mol ratio and be cupric salt, divalent zinc, the stannous salt of 2: 1: 1, add ethylene glycol wiring solution-forming A; Step 2 is got slaine total mole number 1-5 vulcanized sodium doubly, adds ethylene glycol wiring solution-forming B; Step 3 adds solution B in A, is transferred in autoclave, and heating separates, and obtains the copper-zinc-tin-sulfur nanosphere.The method has selected organic reagent ethylene glycol as solvent, and the copper-zinc-tin-sulfur of preparation contains other phases except Emission in Cubic.Xiaotang Lu etc. are at the 3141st～3143 page of " Wurtzite Cu that delivers of " Chemical Communications " (chemical communication) the 47th phase o. 11th in 2011
2ZnSnS
4Nanocrystals:a novel quaternary semiconductor " (copper-zinc-tin-sulfur of Wurtzite structure is nanocrystalline: the copper-zinc-tin-sulfur nano material of a kind of novel quaternary semiconductor compound) having announced a kind of Wurtzite structure. and the method is used high boiling organic solvent and protective agent in preparation process; easy carbonization when heat treatment; easily form the complex centre, can limit to a certain extent the transformation efficiency of prepared solar cell.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of hydrothermal synthesis method of copper-zinc-tin-sulfur photoelectric material.The powder that has synthesized respectively the copper-zinc-tin-sulfur photoelectric material of Tetragonal, quadrature phase by hydro-thermal, ethylenediamine assisting alcohol-hydrothermal method.Synthetic method environmental protection of the present invention, cost is low, and reaction condition is gentle, is suitable for large-scale production.
Technical scheme of the present invention is as follows:
A kind of hydrothermal synthesis method of copper-zinc-tin-sulfur photoelectric material, step is as follows:
1) zinc salt, pink salt, mantoquita are pressed (0.5～6): (0.3～1): the mol ratio of (0.5～2) is dissolved in solvent, add again slaine total mole number 1-4 sulfur-containing compound doubly, slaine total mole number 0-0.5 surfactant doubly, ultrasonic or magnetic agitation mixes it, and getting concentration is the 0.05-0.2mol/L precursor solution.
2) with step 1) the precursor solution of gained is transferred in the stainless steel cauldron of inner liner polytetrafluoroethylene, and reaction is 5-48 hour under 150-220 ℃ of condition.React and naturally cool to room temperature after complete.Products therefrom is at ambient temperature with ethanol washing 3-6 time and centrifugation.Namely obtain the powder of copper-zinc-tin-sulfur photoelectric material after product drying after separation.
Step 1) described in " concentration be the 0.05-0.2mol/L precursor solution, mol wherein refers to the total mole number of slaine.
Preferably, a kind of hydrothermal synthesis method of copper-zinc-tin-sulfur photoelectric material, step is as follows:
1) zinc salt, pink salt, mantoquita are pressed (1～4): (0.3～1): the mol ratio of (0.6～2) is dissolved in solvent, add again slaine total mole number 1-4 sulfur-containing compound doubly, slaine total mole number 0-0.5 surfactant doubly, ultrasonic or magnetic agitation mixes it, and getting concentration is the 0.1mol/L precursor solution.
2) with step 1) the precursor solution of gained is transferred in the stainless steel cauldron of inner liner polytetrafluoroethylene, and reaction is 10-48 hour under 180-220 ℃ of condition.React and naturally cool to room temperature after complete.Products therefrom is at ambient temperature with ethanol washing 3-6 time and centrifugation.Namely obtain the powder of copper-zinc-tin-sulfur photoelectric material after product drying after separation.
Step 1) described in " concentration be the 0.1mol/L precursor solution, mol wherein refers to the total mole number of slaine.
Step 1) described mantoquita is a kind of in copper chloride, copper nitrate, Schweinfurt green, copper sulphate, stannous chloride, cuprous sulfate, cuprous nitrate.
Step 1) described pink salt is a kind of in stannous chloride, stannous sulfate, in stannic chloride.
Step 1) described zinc salt is a kind of in zinc chloride, zinc nitrate, zinc acetate, zinc sulfate, trbasic zinc phosphate.
Step 1) described sulfur-containing compound is a kind of in thiocarbamide, vulcanized sodium, potassium sulfide, cupferron, thioacetamide.
Step 1) described surfactant is a kind of in softex kw, hexadecyldimethyl benzyl ammonium ammonium chloride, OTAC, DDAO, brocide, lauryl sodium sulfate, neopelex.
Step 1) described solvent is a kind of in water, water and the ethylenediamine mixed solvent of 1: 1 by volume～10: 1.
Further preferred, a kind of hydrothermal synthesis method of copper-zinc-tin-sulfur photoelectric material, step is as follows:
1) take respectively 0.5 mM of zinc chloride, 0.5 mM of stannous chloride, 1 mM of copper chloride, 4 mMs of thiocarbamides, 20 ml waters, magnetic agitation mixes it, gets precursor solution.
2) with step 1) the precursor solution of gained is transferred in the stainless steel cauldron that liner is polytetrafluoroethylene, 200 ℃ of lower isothermal reactions 10 hours.React and naturally cool to room temperature after complete.Products therefrom is used centrifugation after absolute ethanol washing 4 times at ambient temperature.After product drying after separation, namely obtain the powder of copper-zinc-tin-sulfur photoelectric material.
Another kind of preferred version is as follows:
1) taking respectively 0.5 mM of zinc chloride, 0.5 mM of stannous chloride, 1 mM of copper chloride, 4 mMs of thiocarbamides, 20 ml volumes ratios is the water of 1: 1 and the mixed solvent of ethylenediamine, ultrasonic it is mixed, and gets precursor solution.
2) with step 1) the precursor solution of gained is transferred in the stainless steel cauldron that liner is polytetrafluoroethylene, 180 ℃ of lower isothermal reactions 24 hours.React and naturally cool to room temperature after complete.Products therefrom is used centrifugation after absolute ethanol washing 4 times at ambient temperature.After product drying after separation, namely obtain the powder of copper-zinc-tin-sulfur photoelectric material.
Another kind of preferred version is as follows:
1) take respectively 1 mM of zinc chloride, 0.33 mM of stannous chloride, 0.67 mM of copper chloride, 4 mMs of thiocarbamides, 0.26 gram softex kw, 20 ml waters, magnetic agitation mixes it, gets precursor solution.
2) with step 1) the precursor solution of gained is transferred in the stainless steel cauldron that liner is polytetrafluoroethylene, 220 ℃ of lower isothermal reactions 16 hours.React and naturally cool to room temperature after complete.Products therefrom is used centrifugation after absolute ethanol washing 6 times at ambient temperature.After product drying after separation, namely obtain the powder of copper-zinc-tin-sulfur photoelectric material
The phase of product adopts Bruker D8X-x ray diffractometer x with Cu-K alpha ray (wavelength X=1.54178 by X-ray diffraction spectra (XRD) test
) for diffraction light sources, product is made X light diffracting analysis.
The present invention has synthesized the powder of copper-zinc-tin-sulfur photoelectric material according to the homogeneous nucleation principle by hydro thermal method.In water, add or do not add surfactant, what obtain is all the powder of the copper-zinc-tin-sulfur photoelectric material of Emission in Cubic; In the mixed solvent of water and ethylenediamine, what obtain is the powder of the copper-zinc-tin-sulfur photoelectric material of quadrature phase.
The present invention does not introduce the organic solvent of the long-chain such as oleyl amine when preparation copper-zinc-tin-sulfur powder body material, do not need purifying can obtain the split material, and is simple to operate, good reproducibility, and cost is low, is easy to realize large-scale production.
Description of drawings
Fig. 1 is the X ray diffracting spectrum of the copper-zinc-tin-sulfur photoelectric material powder of embodiment 1 preparation;
Fig. 2 is the X ray diffracting spectrum of the copper-zinc-tin-sulfur photoelectric material powder of embodiment 2 preparations;
Fig. 3 is the X ray diffracting spectrum of the copper-zinc-tin-sulfur photoelectric material powder of embodiment 3 preparations.
Embodiment
The present invention will be further described below in conjunction with embodiment, but be not limited to this.
The embodiment of the present invention is raw materials used is commercial analysis net product, is not further purified before use.
The phase of the copper-zinc-tin-sulfur photoelectric material powder of embodiment of the present invention preparation adopts Bruker D8X-x ray diffractometer x with Cu-K alpha ray (wavelength X=1.54178 by X-ray diffraction spectra (XRD) test
) for diffraction light sources, product is made X light diffracting analysis.
Embodiment 1: a kind of hydrothermal synthesis method of copper-zinc-tin-sulfur photoelectric material, and concrete steps are as follows:
1) take respectively 0.5 mM of zinc chloride, 0.5 mM of stannous chloride, 1 mM of copper chloride, 4 mMs of thiocarbamides, 20 ml waters, magnetic agitation mixes it, gets precursor solution.
2) with step 1) the precursor solution of gained is transferred in the stainless steel cauldron that liner is polytetrafluoroethylene, 200 ℃ of lower isothermal reactions 10 hours.React and naturally cool to room temperature after complete.Products therefrom is used centrifugation after absolute ethanol washing 4 times at ambient temperature.After product drying after separation, namely obtain the powder of copper-zinc-tin-sulfur photoelectric material.
Embodiment 2: a kind of hydrothermal synthesis method of copper-zinc-tin-sulfur photoelectric material, and concrete steps are as follows:
1) taking respectively 0.5 mM of zinc chloride, 0.5 mM of stannous chloride, 1 mM of copper chloride, 4 mMs of thiocarbamides, 20 ml volumes ratios is the water of 1: 1 and the mixed solvent of ethylenediamine, and magnetic agitation mixes it, gets precursor solution.
2) with step 1) the precursor solution of gained is transferred in the stainless steel cauldron that liner is polytetrafluoroethylene, 180 ℃ of lower isothermal reactions 24 hours.React and naturally cool to room temperature after complete.Products therefrom is used centrifugation after absolute ethanol washing 4 times at ambient temperature.After product drying after separation, namely obtain the powder of copper-zinc-tin-sulfur photoelectric material.
Embodiment 3: a kind of hydrothermal synthesis method of copper-zinc-tin-sulfur photoelectric material, and concrete steps are as follows:
1) take respectively 1 mM of zinc chloride, 0.33 mM of stannous chloride, 0.67 mM of copper chloride, 4 mMs of thiocarbamides, 0.26 gram softex kw, 20 ml waters, magnetic agitation mixes it, gets precursor solution.
2) with step 1) the precursor solution of gained is transferred in the stainless steel cauldron that liner is polytetrafluoroethylene, 220 ℃ of lower isothermal reactions 16 hours.React and naturally cool to room temperature after complete.Products therefrom is used centrifugation after absolute ethanol washing 6 times at ambient temperature.After product drying after separation, namely obtain the powder of copper-zinc-tin-sulfur photoelectric material.
Embodiment 4: a kind of hydrothermal synthesis method of copper-zinc-tin-sulfur photoelectric material, and concrete steps are as follows:
1) take respectively 1.4 mMs of zinc chloride, 0.2 mM of stannous chloride, 0.4 mM of copper chloride, 4 mMs of thiocarbamides, 20 ml waters, magnetic agitation mixes it, gets precursor solution.
2) with step 1) the precursor solution of gained is transferred in the stainless steel cauldron that liner is polytetrafluoroethylene, 180 ℃ of lower isothermal reactions 16 hours.React and naturally cool to room temperature after complete.Products therefrom is used centrifugation after absolute ethanol washing 5 times at ambient temperature.After product drying after separation, namely obtain the powder of copper-zinc-tin-sulfur photoelectric material.
Embodiment 5: a kind of hydrothermal synthesis method of copper-zinc-tin-sulfur photoelectric material, and concrete steps are as follows:
1) take respectively 1 mM of zinc chloride, 0.33 mM of stannous chloride, 0.67 mM of copper chloride, 4 mMs of thiocarbamides, 20 ml waters, magnetic agitation mixes it, gets precursor solution.
2) with step 1) the precursor solution of gained is transferred in the stainless steel cauldron that liner is polytetrafluoroethylene, 200 ℃ of lower isothermal reactions 16 hours.React and naturally cool to room temperature after complete.Products therefrom is used centrifugation after absolute ethanol washing 6 times at ambient temperature.After product drying after separation, namely obtain the powder of copper-zinc-tin-sulfur photoelectric material.
Embodiment 6: as described in Example 1, difference is to replace thiocarbamide with vulcanized sodium.
Embodiment 7: as described in Example 1, difference is to replace copper chloride with cuprous nitrate, and stannic chloride replaces stannous chloride.
Embodiment 8: as described in Example 1, difference is that copper nitrate replaces copper chloride.
Embodiment 9: as described in Example 1, difference is to replace zinc chloride with zinc nitrate.
Embodiment 10: as described in Example 1, difference is to replace zinc chloride with zinc acetate.
Embodiment 11: as described in Example 1, difference is to replace zinc chloride with zinc sulfate.
Embodiment 12: as described in Example 2, difference is to be that the water of 4: 3 and the mixed solvent of ethylenediamine replace water with volume ratio.
Embodiment 13: as described in Example 2, difference is to be that the water of 2: 1 and the mixed solvent of ethylenediamine replace water with volume ratio.
Embodiment 14: as described in Example 2, difference is to be that the water of 4: 1 and the mixed solvent of ethylenediamine replace water with volume ratio.
Embodiment 15: as described in Example 3, difference is that lauryl sodium sulfate replaces softex kw.
Embodiment 16: as described in Example 3, difference is that neopelex replaces softex kw.
Claims (4)
1. the hydrothermal synthesis method of a copper-zinc-tin-sulfur photoelectric material, step is as follows:
1) zinc salt, pink salt, mantoquita are pressed (0.5～6): (0.3～1): the mol ratio of (0.5～2) is dissolved in solvent, add again slaine total mole number 1-4 sulfur-containing compound doubly, slaine total mole number 0-0.5 surfactant doubly, ultrasonic or magnetic agitation mixes it, and getting concentration is the 0.05-0.2mol/L precursor solution; Described solvent is water and the ethylenediamine mixed solvent of 1:1～10:1 by volume;
2) precursor solution with the step 1) gained is transferred in the stainless steel cauldron of inner liner polytetrafluoroethylene, reaction is 5-48 hour under 150-220 ℃ of condition, react and naturally cool to room temperature after complete, products therefrom namely obtains the powder of copper-zinc-tin-sulfur photoelectric material at ambient temperature with ethanol washing 3-6 time and centrifugation after the product drying after separation.
2. the hydrothermal synthesis method of a kind of copper-zinc-tin-sulfur photoelectric material as claimed in claim 1, step is as follows:
1) zinc salt, pink salt, mantoquita are pressed (1～4): (0.3～1): the mol ratio of (0.6～2) is dissolved in solvent, add again slaine total mole number 1-4 sulfur-containing compound doubly, slaine total mole number 0-0.5 surfactant doubly, ultrasonic or magnetic agitation mixes it, and getting concentration is the 0.1mol/L precursor solution; Described solvent is water and the ethylenediamine mixed solvent of 1:1～10:1 by volume;
2) precursor solution with the step 1) gained is transferred in the stainless steel cauldron of inner liner polytetrafluoroethylene, reaction is 10-48 hour under 180-220 ℃ of condition, react and naturally cool to room temperature after complete, products therefrom namely obtains the powder of copper-zinc-tin-sulfur photoelectric material at ambient temperature with ethanol washing 3-6 time and centrifugation after the product drying after separation.
3. the hydrothermal synthesis method of a kind of copper-zinc-tin-sulfur photoelectric material as claimed in claim 1 or 2, is characterized in that, the described mantoquita of step 1) is a kind of in copper chloride, copper nitrate, Schweinfurt green, copper sulphate, stannous chloride, cuprous sulfate, cuprous nitrate; The described pink salt of step 1) is a kind of in stannous chloride, stannous sulfate, in stannic chloride; The described zinc salt of step 1) is a kind of in zinc chloride, zinc nitrate, zinc acetate, zinc sulfate, trbasic zinc phosphate; Step 2) described sulfur-containing compound is a kind of in thiocarbamide, vulcanized sodium, potassium sulfide, cupferron, thioacetamide; Step 2) described surfactant is a kind of in softex kw, hexadecyldimethyl benzyl ammonium ammonium chloride, OTAC, DDAO, brocide, lauryl sodium sulfate, neopelex.
4. the hydrothermal synthesis method of a kind of copper-zinc-tin-sulfur photoelectric material as claimed in claim 1 or 2, is characterized in that, step is as follows:
1) take respectively 0.5 mM of zinc chloride, 0.5 mM of stannous chloride, 1 mM of copper chloride, 4 mMs of thiocarbamides, 20 ml volumes than the mixed solvent for the water of 1:1 and ethylenediamine, ultrasonic it is mixed, get precursor solution;
2) precursor solution with the step 1) gained is transferred in the stainless steel cauldron that liner is polytetrafluoroethylene, 180 ℃ of lower isothermal reactions 24 hours, react and naturally cool to room temperature after complete, products therefrom is used centrifugation after absolute ethanol washing 4 times at ambient temperature, after product drying after separation, namely obtain the powder of copper-zinc-tin-sulfur photoelectric material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100940066A CN102254985B (en) | 2011-04-14 | 2011-04-14 | Hydro-thermal synthesis method for copper-zinc-tin-sulfur photoelectric material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100940066A CN102254985B (en) | 2011-04-14 | 2011-04-14 | Hydro-thermal synthesis method for copper-zinc-tin-sulfur photoelectric material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102254985A CN102254985A (en) | 2011-11-23 |
| CN102254985B true CN102254985B (en) | 2013-05-08 |
Family
ID=44982099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100940066A Expired - Fee Related CN102254985B (en) | 2011-04-14 | 2011-04-14 | Hydro-thermal synthesis method for copper-zinc-tin-sulfur photoelectric material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102254985B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103303970A (en) * | 2013-06-26 | 2013-09-18 | 吉林大学 | Preparation method of band gaps adjustable magnesium-doped copper-zinc-tin-sulfur film |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557117A (en) * | 2012-03-08 | 2012-07-11 | 桂林理工大学 | Method for thermally synthesizing Cu2ZnSnS4 semiconductor material by solvent through microwaves |
| CN103359777B (en) * | 2012-03-29 | 2016-04-27 | 上海交通大学 | A kind of Cu 2znSnS 4hydrothermal preparation method and Cu 2znSnS 4material and purposes |
| CN102674435B (en) * | 2012-05-10 | 2014-04-16 | 北京工业大学 | Solvothermal synthesis method for copper, zinc, tin and sulfur nanocrystals |
| CN102674436B (en) * | 2012-05-18 | 2014-08-27 | 中国科学院合肥物质科学研究院 | Preparation method of non-organic-coated crystalline-phase-controllable Cu2ZnSnS4 nanocrystals |
| CN102689920A (en) * | 2012-06-20 | 2012-09-26 | 上海大学 | Method for producing copper-tin-zinc-sulfur (CTZS) materials through solvent-thermal synthesis |
| CN103400903A (en) * | 2013-08-15 | 2013-11-20 | 吉林大学 | Preparation method for improving grain size and density of CZTS film |
| CN103613120B (en) * | 2013-11-29 | 2015-07-15 | 上海交通大学 | Synthesis of copper-zinc-tin-sulfur nanoparticles and method for compounding graphene by using copper-zinc-tin-sulfur nanoparticles |
| CN103771495B (en) * | 2013-12-24 | 2015-08-19 | 上海交通大学 | Prepare Shi Mo Xi the method of copper-zinc-tin-sulfur nanocrystalline composite material |
| CN104085917B (en) * | 2014-04-28 | 2015-12-02 | 上海大学 | Wurtzite structure Cu 2cdSnS 4the solvothermal preparation method of nano wire |
| CN104393103B (en) * | 2014-10-17 | 2016-06-22 | 广东工业大学 | A kind of Cu2ZnSnS4The preparation method of semiconductive thin film and application thereof |
| CN105226131B (en) * | 2015-08-24 | 2017-09-29 | 中国工程物理研究院材料研究所 | A kind of chemical synthesis process of copper zinc tin sulfur absorption layer film |
| CN106517314A (en) * | 2016-12-06 | 2017-03-22 | 昆明理工大学 | Preparing method of CZTS particulates |
| CN107364891A (en) * | 2017-06-28 | 2017-11-21 | 常州市尚泽纺织品有限公司 | A kind of preparation method of copper zinc cadmium molybdenum sulfur photoelectric material |
| CN109211851B (en) * | 2017-07-07 | 2021-01-22 | 天津师范大学 | PH detection method based on copper-zinc-tin-sulfur alloy quantum dots |
| CN107935060B (en) * | 2017-11-24 | 2019-11-05 | 上海材料研究所 | Stratiform sulfur family photoelectric material and preparation method thereof |
| CN114649532B (en) * | 2022-03-10 | 2024-04-02 | 中国地质大学（武汉） | Nest CuS-Zn lithium ion battery cathode material and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102009009550A1 (en) * | 2009-02-19 | 2010-09-02 | Carl Von Ossietzky Universität Oldenburg | A process for wet chemically synthesizing dicopper-zinc-tin-tetrasulfide and / or tetraselenide (CZTS), a process for producing a semiconductor layer from CZTS and a colloidal suspension |
| CN101780974B (en) * | 2009-12-31 | 2012-02-01 | 合肥工业大学 | Preparation method of Cu2ZnSnS4 semiconductor material |
| CN101794826B (en) * | 2010-02-05 | 2011-12-28 | 合肥工业大学 | Copper-zinc-tin-sulfur quaternary compound, thin film solar cell formed by same, and preparation method thereof |
| CN101844797B (en) * | 2010-05-14 | 2011-12-14 | 东华大学 | Method for preparing solar energy absorbing layer material Cu2ZnSnS4 by hydrothermal synthesis |
-
2011
- 2011-04-14 CN CN2011100940066A patent/CN102254985B/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| A mild solvothermal route to kesterite quaternary Cu2ZnSnS4 nanoparticles;M.Cao等;《Journal of Crystal Growth》;20101027;第318卷;1117-1120 * |
| M.Cao等.A mild solvothermal route to kesterite quaternary Cu2ZnSnS4 nanoparticles.《Journal of Crystal Growth》.2010,第318卷 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103303970A (en) * | 2013-06-26 | 2013-09-18 | 吉林大学 | Preparation method of band gaps adjustable magnesium-doped copper-zinc-tin-sulfur film |
| CN103303970B (en) * | 2013-06-26 | 2015-03-11 | 吉林大学 | Preparation method of band gaps adjustable magnesium-doped copper-zinc-tin-sulfur film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102254985A (en) | 2011-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102254985B (en) | Hydro-thermal synthesis method for copper-zinc-tin-sulfur photoelectric material | |
| CN101844797B (en) | Method for preparing solar energy absorbing layer material Cu2ZnSnS4 by hydrothermal synthesis | |
| CN102826594A (en) | Microwave synthesis method of Cu2ZnSnS nanoparticles | |
| CN101648696A (en) | Method for preparing graphene-phthalocyanin nano composite material by mercaptan-alkene clicking chemical method | |
| CN109746011A (en) | Composite photo-catalyst derived from a kind of MOF base and preparation method thereof | |
| CN104817120A (en) | Preparation method of sea urchin-like Ni/Co composite basic carbonate | |
| CN108745391A (en) | A kind of New Two Dimensional black phosphorus nanometer sheet-MoS2Composite solar hydrogen manufacturing material and its preparation method and application | |
| CN104588045A (en) | Ultra-thin BiOCl nano-sheet, preparation method and application thereof | |
| CN107486221B (en) | Copper sulfide photocatalyst and preparation method thereof | |
| CN102557116A (en) | Method for preparing CuInS2 hollow solar absorbing material | |
| CN105568314A (en) | Preparation method of CuWO4/WO3 heterostructured nanosheet array film | |
| CN102931286A (en) | Method for preparing absorption layer of copper-zinc-tin-sulfide thin film solar cell | |
| CN104275200B (en) | A kind of nucleocapsid structure ZnS/Ni 2the preparation method of P composite inorganic membranes | |
| CN102161477B (en) | Method for preparing copper zinc tin selenium nanoparticles through aqueous phase synthesis | |
| CN102897722B (en) | Alpha-In2Se3 nano-grade flower-ball solvothermal synthesizing method | |
| CN102249199A (en) | Microwave-assisted solvothermal synthesis method of I-III-VI semiconductor material nano-powder | |
| CN109133158B (en) | Locally oxidized SnS2Method for preparing thin slice and its product and use | |
| CN102219192A (en) | Solar battery material SnS nanocrystal synthesized under conditions of high temperature and liquid phase by non-injection method | |
| CN102689920A (en) | Method for producing copper-tin-zinc-sulfur (CTZS) materials through solvent-thermal synthesis | |
| CN102344166B (en) | Preparation method for Cu2ZnSnS4 solar energy absorption layer material | |
| CN102887538B (en) | Preparation method of surfactant-modified CuInS2 nanocrystal | |
| CN107059131A (en) | A kind of semiconductor nano and preparation method and application | |
| CN102205950B (en) | Chalcopyrite-structured CIS powder material and liquid phase preparation method thereof | |
| CN105970253A (en) | Method for preparing three-band-gap tin-doped copper-gallium-sulfur solar cell thin film material through sulfuration annealing after double-potential deposition | |
| CN103253698A (en) | Method for preparing CuInS2 nanocrystals by mixed solvent thermal process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130508 Termination date: 20180414 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |