CN102139862B - Method for preparing copper indium selenium nano tablets - Google Patents
Method for preparing copper indium selenium nano tablets Download PDFInfo
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- CN102139862B CN102139862B CN201110109949A CN201110109949A CN102139862B CN 102139862 B CN102139862 B CN 102139862B CN 201110109949 A CN201110109949 A CN 201110109949A CN 201110109949 A CN201110109949 A CN 201110109949A CN 102139862 B CN102139862 B CN 102139862B
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Abstract
The invention discloses a method for preparing copper indium selenium nano tablets in the technical field of nano materials. In the method, a two-step solvothermal method is adopted. The method comprises the following steps of: loading Vc, selenium powder and dimethyl formamide (DMF) in a polytetrafluoroethylene reaction kettle and heating the selenium powder to reduce the selenium powder; and then quickly adding copper salt and indium salt, heating for the second time and reacting to prepare a copper indium selenium nano material. The problem of a selenium resource generally existing in the process of preparing the copper indium selenium nano material and the problem that the obtained copper indium selenium has an irregular shape or is agglomerated seriously and the like in the prior art are solved. The method is simple and low in production cost. And the obtained copper indium selenium nano material can further meet industrial requirements.
Description
Technical field
What the present invention relates to is a kind of method of technical field of nano material, specifically is a kind of preparation method of CIS nanometer sheet.
Background technology
Sun power is inexhaustible clean energy, and the energy that the earth is provided is huge, and annual 3x10J approximately is human now annual catabiotic 10,000 times.If the mankind can be with sun power as resource, so not only the energy dilemma of face of mankind can solve, and the ecotope crisis that is accompanied by energy consumption in the past also can be eliminated.Since silicon solar cell exploitation in 1954, the solar battery technology development rapidly.Because the aggravation of energy dilemma, people are more and more denseer for the interest of renewable energy source, and solar cell has also got into the fast-developing stage, and also making becomes research focus to solar cell material.Wherein therefore the CIS alloy is a kind of rising solar cell material owing to have good properties such as effciency of energy transfer height, large-area preparation are simple, stable performance.The copper, indium and selenium film solar cell has received people's generally attention, and development becomes the research focus of international photovoltaic circle rapidly.The situation of the over capacity that therefore, faces when present crystal silicon cell industry and the factors such as further fluctuation of international oil price provide a large amount of spaces all for the development of copper, indium and selenium film solar cell.
The method for preparing at present CIS is a lot, but its thinking mainly contains two: the one, and direct evaporation Cu, In, three kinds of independent elements of Se make its gas chemical combination make CIS; The 2nd, the copper indium diselenide alloy is to the direct added elements Se of this alloy or at H
2Add Se in the Se atmosphere.Process method mainly contains evaporation plating, magnetron sputtering, molecular beam epitaxy technique, spray pyrolysis and flash set technology etc.These methods need expensive vacuum device and gas shield mostly, the low and difficult control of pattern particle size of production efficiency.Along with rolling (roll-to-roll) but the technological innovation that equipment and print copper/indium/equipment such as selenium ink are used makes reaching its maturity of thin film technique, wet method prepare the new focus that the CIS material becomes the synthetic field of nanometer.And at present wet method to prepare the CIS major part be that what to adopt that high-temperature cracking method or quadrol etc. generally obtain as the solvent-thermal method of solvent etc. is out-of-shape or serious nano material of reuniting; That have even the distribution of sizes scope is very big, very big for the performance impact of hull cell.
Summary of the invention
The present invention is directed to the above-mentioned deficiency that prior art exists; A kind of preparation method of CIS nanometer sheet is provided; Solved and prepared problems such as ubiquitous selenium source problem and CIS out-of-shape that obtains or serious reunion in the CIS nano material process in the prior art; And technology of the present invention is simple, and production cost is low, and the CIS nano material of gained can further satisfy industrial requirement.
The present invention realizes that through following technical scheme the present invention adopts two step solvent-thermal methods: at first load Vc, selenium powder and DMF with the tetrafluoroethylene reaction kettle, selenium powder is added thermal reduction; Add mantoquita and indium salt then fast and carry out the second-heating prepared in reaction and go out the CIS nano material.
The consumption of described Vc, selenium powder and DMF is: selenium powder 2-50 weight part, Vc10-200 weight part and DMF1000 weight part; The consumption of described mantoquita and indium salt is: mantoquita 1-25 weight part, indium salt 1-25 weight part.
Described mantoquita is neutralized verdigris, cupric nitrate or copper sulfate.
Described indium salt is indium chloride, indium nitrate or indium sulfate.
Describedly add thermal reduction and be meant: the tetrafluoroethylene reaction kettle is put into 120-180 ℃ baking oven, keep 2-24 hour afterreaction still to naturally cool to room temperature.
The reaction of described second-heating is meant: to 120-200 ℃ and kept 6-96 hour, question response naturally cools to room temperature after finishing with tetrafluoroethylene reaction kettle sealing post-heating, and product is filtered and with absolute ethanol washing for several times, promptly gets the CIS nano material.
In the reaction of described second-heating preferred before heating, add Vinylpyrrolidone polymer or bent draw ketone as coating to prevent product and reunite and to change the size and the pattern of product, the consumption of this coating and the mass ratio of selenium powder are 5-100: 2-50.
The present invention relates to the gallic acid zinc nano material that method for preparing obtains, be the CuInSe2 of pure mutually cubic crystalline phase yellow copper structure, size and pattern are hexagonal sheet or the disk of about 200nm, and its band gap is wide to be 1.05～1.1eV.
The inventive method is simple, with reductive agents such as Vc selenium powder is reduced the reaction solution of gained, and cheap mantoquita and indium salt are precursor, and organism is that coating makes the product distribution of sizes little and be uniformly dispersed.DMF etc. be solvent as reaction medium, make the gained nanoparticle have homogeneity preferably.Adopted DMF solvent thermal technology, can improve the crystallization velocity of product on the one hand, operation steps is simple on the other hand, and cost is low, and speed of response is fast, and efficient is high, and has certain universality; Prepare the CIS nano material and can application well arranged aspect the solar energy film photovoltaic cell.
Description of drawings
Fig. 1 is the CIS transmission electron microscope photo of the embodiment of the invention 1 gained, and illustration is an electron-diffraction diagram.
Fig. 2 is the CIS transmission electron microscope photo of the embodiment of the invention 2 gained.
Fig. 3 is the CIS transmission electron microscope photo of the embodiment of the invention 3 gained.
Fig. 4 is the CIS transmission electron microscope photo of the embodiment of the invention 4 gained.
Embodiment
Elaborate in the face of embodiments of the invention down, present embodiment provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment being to implement under the prerequisite with technical scheme of the present invention.
Embodiment 1
1. by amount of substance part, 2 parts of selenium powders, 10 parts of Vc and 1000 parts of DMF are joined in the tetrafluoroethylene reaction kettle, with the reaction kettle sealing, put into 160 ℃ baking oven then, keep 6 hours afterreaction stills to naturally cool to room temperature.
2. open reaction kettle and add 1 part neutralized verdigris, indium nitrate and 5 parts of Vinylpyrrolidone polymers of 1 part fast, again with reaction kettle sealing, 160 ℃ of controlled temperature, 24 hours reaction times.
3. after reaction finished, reaction kettle naturally cooled to room temperature, and product is filtered, and with absolute ethanol washing for several times, vacuum is drained, and promptly obtains the CIS nano material.
Fig. 1 is the transmission electron microscope photo and the electron-diffraction diagram of the CIS nano material that obtains.Visible by figure, this material is the CuInSe of pure mutually cubic crystalline phase yellow copper structure
2, size and pattern are the monocrystalline two dimension hexagonal plate structure of about 200nm, its band gap is wide to be 1.05eV.
Embodiment 2
1. by amount of substance part, 50 parts of selenium powders, 200 parts of Vc and 1000 parts of DMF are joined in the tetrafluoroethylene reaction kettle, with the reaction kettle sealing, put into 160 ℃ baking oven then, keep 6 hours afterreaction stills to naturally cool to room temperature.
2. open reaction kettle and add 25 parts cupric nitrate, indium chloride and 100 parts of Vinylpyrrolidone polymers of 25 parts fast, again with reaction kettle sealing, 180 ℃ of controlled temperature, 6 hours reaction times.
3. after reaction finished, reaction kettle naturally cooled to room temperature, and product is filtered, and with absolute ethanol washing for several times, vacuum is drained, and promptly obtains the CIS nano material.
Fig. 2 is the transmission electron microscope photo of the CIS nano material that obtains.Visible by figure, this material is the CuInSe of the cubic crystalline phase yellow copper structure of pure phase
2, size and pattern are the monocrystalline two dimension hexagonal plate structure of about 200nm, its band gap is wide to be 1.05eV.
Embodiment 3
1. by amount of substance part, 10 parts of selenium powders, 50 parts of Vc and 1000 parts of DMF are joined in the tetrafluoroethylene reaction kettle, with the reaction kettle sealing, put into 120 ℃ baking oven then, keep 24 hours afterreaction stills to naturally cool to room temperature.
2. open reaction kettle and add 5 parts neutralized verdigris, indium chloride and 25 parts of Vinylpyrrolidone polymers of 5 parts fast, again with reaction kettle sealing, 200 ℃ of controlled temperature, 12 hours reaction times.
3. after reaction finished, reaction kettle naturally cooled to room temperature, and product is filtered, and with absolute ethanol washing for several times, vacuum is drained, and promptly obtains the CIS nano material.
Fig. 3 is the transmission electron microscope photo of the CIS nano material that obtains.Visible by figure, this material is the CuInSe of pure mutually cubic crystalline phase yellow copper structure
2, size and pattern are the two-dimensional circle chip architecture of about 200～400nm, its band gap is wide to be 1.1eV.
Embodiment 4
1. by amount of substance part, 10 parts of selenium powders, 50 parts of Vc and 1000 parts of DMF are joined in the tetrafluoroethylene reaction kettle, with the reaction kettle sealing, put into 180 ℃ baking oven then, keep 2 hours afterreaction stills to naturally cool to room temperature.
2. open that reaction kettle fast adds 5 parts indium sulfate, indium sulfate and 50 parts of songs of 5 parts draw ketone, again with reaction kettle sealing, 120 ℃ of controlled temperature, 96 hours reaction times.
3. after reaction finished, reaction kettle naturally cooled to room temperature, and product is filtered, and with absolute ethanol washing for several times, vacuum is drained, and promptly obtains the CIS nano material.
Fig. 4 is the transmission electron microscope photo of the CIS nano material that obtains.Visible by figure, this material is the CuInSe of pure mutually cubic crystalline phase yellow copper structure
2, size and pattern are the two-dimensional circle sheet structure of about 200～400nm, its band gap is wide to be 1.1eV.
Claims (4)
1. the preparation method of a CIS nanometer sheet is characterized in that, adopts two step solvent-thermal methods: at first load VC, selenium powder and DMF with the tetrafluoroethylene reaction kettle, selenium powder is added thermal reduction; Add mantoquita and indium salt then fast and carry out the second-heating prepared in reaction and go out the CIS nano material;
Describedly add thermal reduction and be meant: the tetrafluoroethylene reaction kettle is put into 120-180 ℃ baking oven, keep 2-24 hour afterreaction still to naturally cool to room temperature;
The reaction of described second-heating is meant: with tetrafluoroethylene reaction kettle sealing post-heating to 120-200 ℃ and kept 6-96 hour; Question response naturally cools to room temperature after finishing; With the product filtration and with the absolute ethanol washing several, promptly get the CIS nano material, in the second-heating reaction; To prevent the size and the pattern of product reunion and change product, the consumption of this coating and the mass ratio of selenium powder are 5-100:2-50 as coating for adding Vinylpyrrolidone polymer or Triton before heating.
2. the preparation method of CIS nanometer sheet according to claim 1 is characterized in that, the consumption of described VC, selenium powder and DMF is: selenium powder 2-50 weight part, VC10-200 weight part and DMF1000 weight part; The consumption of described mantoquita and indium salt is: mantoquita 1-25 weight part, indium salt 1-25 weight part.
3. the preparation method of CIS nanometer sheet according to claim 1 is characterized in that, described mantoquita is neutralized verdigris, cupric nitrate or copper sulfate; Described indium salt is indium chloride, indium nitrate or indium sulfate.
4. CIS nanometer sheet for preparing according to the said method of above-mentioned arbitrary claim, it is characterized in that: this nanometer sheet is the CuInSe of the cubic crystalline phase yellow copper structure of pure phase
2, size and pattern are monocrystalline two dimension hexagonal sheet or the disk shape structure of 200nm, its band gap is wide to be 1.05 ~ 1.1eV.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102923763B (en) * | 2012-09-19 | 2014-03-12 | 江苏大学 | Method for synthesizing copper indium diselenide nanosheet through ion exchange method |
| CN103243390B (en) * | 2013-05-20 | 2015-09-30 | 重庆大学 | A kind of synthetic method of ternary alkali metal-copper-chalcogmonocrystal monocrystal nano material |
| CN111071997B (en) * | 2019-12-17 | 2021-07-13 | 青海民族大学 | Preparation method of copper indium selenium nanosheet |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101698472A (en) * | 2009-11-03 | 2010-04-28 | 厦门大学 | Method for synthesizing copper-indium-selenium nanocrystalline |
| CN101804971A (en) * | 2010-04-19 | 2010-08-18 | 西安交通大学 | Preparation method of copper indium selenide nanocrystalline material |
| CN101927983A (en) * | 2010-07-26 | 2010-12-29 | 中国科学院化学研究所 | CuInSe2 nano material and preparation method and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101698472A (en) * | 2009-11-03 | 2010-04-28 | 厦门大学 | Method for synthesizing copper-indium-selenium nanocrystalline |
| CN101804971A (en) * | 2010-04-19 | 2010-08-18 | 西安交通大学 | Preparation method of copper indium selenide nanocrystalline material |
| CN101927983A (en) * | 2010-07-26 | 2010-12-29 | 中国科学院化学研究所 | CuInSe2 nano material and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Jiang Tang et al..Synthesis of Colloidal CuCaSe2, CuInSe2, and Cu(InGa)Se2 Nanoparticles.《Chem. Mater.》.2008,第20卷(第22期),6906-6910. * |
| 段学臣等.溶剂热法CuInSe2粉体的形貌可控制备与表征.《无机化学学报》.2011,第27卷(第2期),293-297. * |
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