CN102011194A - Photovoltaic semiconductor nanocrystalline and preparation method and application thereof - Google Patents
Photovoltaic semiconductor nanocrystalline and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a Cu(In, Al) Se2 type photovoltaic semiconductor nanocrystalline and a preparation method and application thereof. The photovoltaic semiconductor nanocrystalline is obtained by using element sources of Cu, In, Al, S and Se to synthesize Cu(In, Al)Se2 nanoparticles in an organic solvent via a solvothermal method and purifying and refining. The method comprises the following steps of: (1) placing element sources of Cu, In and Al in the organic solvent to mix and reacting under protection of inert gases to obtain a solution A; (2) raising temperature of the solution A and adding one or two of element sources of S and Se to react; adjusting In/Al ratio or/and S/S2 ratio to adjust the band gap width and making the band gap width of material be matched with spectrum of sunlight; and (3) adding benzene to disperse and adding alcohol to deposit as so to obtain the target product. In the invention, by adjusting the In/Al ratio or/and the S/S2 ratio, shape and size of nanoparticles are controlled to adjust the band gap width so that the band gap width of the material is matched with the spectrum of sunlight better.
Description
Technical field
The present invention relates to a kind of Cu (In, Al) Se
2The class photovoltaic semiconductors is nanocrystalline, more specifically relates to a kind of Cu (In, Al) S
2, Cu (In, Al) Se
2Or Cu (In, and Al) (S, Se)
2Photovoltaic semiconductors is nanocrystalline.
The invention still further relates to the nanocrystalline method of the above-mentioned photovoltaic semiconductors of preparation.
The invention still further relates to the nanocrystalline application of above-mentioned photovoltaic semiconductors.
Background technology
Along with society and science and technology development, photovoltaic and electrooptical device become the great research topic of the world today.People for economical and efficient utilize sun power, wish to develop relatively inexpensive solar cell.
For example: dye sensitization solar battery, its light-electric switching mechanism is: the nanocrystalline porous film with high-specific surface area can adsorb a lot of individual layer dye molecules and absorb sunlight; The individual layer dyestuff of absorption excites the generation electronics apace electronics to be injected into later in the semi-conductive conduction band, is passed to negative electrode through external circuit then, thereby forms electric current.Switzerland scientist Michael Gratzel is oarse-grained TiO
2Crystal replaces to the spongy TiO2 of small-particle of diameter 20nm, and outer encapsulated dye thin layer forms the optical clear film of 10 micron thickness.The world record of this class battery conversion efficiency is 11%.
But dye sensitization solar battery generally adopts expensive organo-metallic dyestuff.For example, ruthenium (Ru) dyestuff is a class sensitizing dye (as: N3, N791, N945 etc.) efficiently.Ruthenium belongs to rare metal, costs an arm and a leg, and the synthetic method of purification complexity of dyestuff etc. is one of shortcoming of this class solar cell.
In addition, Cu (In, and Ga) (S, Se)
2The class solar cell adopts Mo as electrode layer, with Cu (In, Ga) (S, Se)
2As absorption layer, with CdS or ZnS as buffer layer, with ZnO as Window layer.The effciency of energy transfer of this class solar film battery has reached 19% now.U.S. Nanosolar company has developed the CIGS nano ink, in conjunction with the volume to volume technology, has released the CIGS flexible battery in the end of the year 2007.Nanosolar company use the aluminium foil end liner and on aluminium foil sputter Mo layer, not only cheap, and the specific conductivity height.
But, Cu (In, and Ga) (S, Se)
2The absorption layer Cu of class solar cell (In, and Ga) (S, Se)
2In element indium and gallium all be rare metal and dissipated metal.Gallium disperses in the Nature very much, does not have to form the gallium ore deposit of concentrating, and refines difficulty.The abundance of indium in the earth's crust is smaller, also disperses very much.Its content and silver are suitable, and output only is about 1% of silver.
Cu (In, and Ga) (S, Se)
2Mix gallium element in the absorption layer of class solar cell and can regulate its band gap width, thus better with the sunlight Spectral matching, also avoided being separated in the material simultaneously.Therefore, gallium mixes the efficient that has improved this class battery greatly.And at CuInSe
2Mix aluminium element in the semi-conductor and can play the effect of adjusting the semi-conductor band gap width and avoiding being separated equally, so just avoided using expensive gallium element.For Cu (In, Al) (S, Se)
2Material, people have prepared the battery of providing better performances by the sedimentary method of coevaporation, Cu (In, Al) Se
2The top efficiency of battery is 16.9%.
Above solar cell is a development recent years novel battery more rapidly.In addition, along with the development of nano science, people have synthesized various different types of semiconductor nanoparticles and quantum dot in succession, and are applied in the electrooptical devices such as solar cell and photodiode.As: semiconductor nanoparticles such as CdS, CdSe, PbS, PbSe and InP.The optical absorption of quantum dot derives from quantum confined effect, because tight ionising effects, make photon of every absorption can produce a plurality of electron-hole pairs, and quantum dot have higher optical extinction coefficient, the photoelectric efficiency that this helps reducing dark current and improves battery.The theoretical prediction efficient of quantum dot sensitized solar cell is higher than the theoretical prediction value of organic dye sensitized solar cell far away up to 44%.In addition, because Cu (In, and Ga) (S, Se)
2The high-level efficiency of class hull cell, synthetic CuInS
2, CuInSe
2, Cu (In, Ga) Se
2Become a new hot fields Deng narrow band gap quantum dot and nano material.As: Brian A.Korgel etc. has synthesized the CuInS with chalcopyrite crystal formation
2And CuInSe
2Nano particle (can be referring to Brian A.Korgel.etc.Chem.Mater.2009,21,1962-1966 and Brian A.Korgel.etc.J.AM.CHEM.SOC.2009,131,3134-3135).Jennifer A.Hollingsworth etc. has synthesized CuInSe
2Nano wire (can be referring to Jennifer A.Hollingsworth.etc.J.AM.CHEM.SOC.2009,131,16177-16188).Edward H.Sargent etc. has obtained Cu (In, Ga) Se by mixing gallium element
2Nanoparticle finds that mixing gallium element can obviously change CuInSe
2The absorption spectrum of nano particle, make the band gap of material broaden to the 1.5eV (can be referring to Edward H.Sargent.etc.Chem.Mater.2008,20,6906-6910).Rakesh Agrawal etc. are with Cu (In, Ga) S
2Nanoparticle deposition film forming, then to its carry out selenizing obtained Cu (In, Ga) (S, Se)
2Film, and made up efficient with it and reach solar cell about 5% (can referring to: Rakesh Agrawa.etc.Nano Lett.Vol.9, No.8,2009).
Summary of the invention
The object of the present invention is to provide a kind of Cu (In, Al) Se with chalcopyrite crystal formation
2The class photovoltaic semiconductors is nanocrystalline.
The invention still further relates to the above-mentioned Cu of preparation (In, Al) Se
2The method that the class photovoltaic semiconductors is nanocrystalline.
For achieving the above object, Cu provided by the invention (In, Al) Se
2The class photovoltaic semiconductors is nanocrystalline, is by element source in organic solvent synthetic Cu (In, Al) Se of solvent-thermal method with Cu, In, Al, S and Se
2Type nano granular carries out purification again and obtains; This method is:
1) Cu, In, Al element source place organic solvent to mix, and in protection of inert gas reaction down, obtain solution A;
2) solution A heats up, and one or both in adding S element source and the Se element source react; Adjust In/Al than or/and the S/Se ratio is regulated its band gap width, make the Spectral matching of the band gap width and the sunlight of material;
3) add the alcohol precipitation again after adding benzene disperses, obtain target product Cu (In, Al) S
2, Cu (In, Al) Se
2Or Cu (In, and Al) (S, Se)
2Photovoltaic semiconductors is nanocrystalline.
The above-mentioned Cu of preparation provided by the invention (In, Al) Se
2The method that the class photovoltaic semiconductors is nanocrystalline adopts solvent-thermal method, with element source synthetic Cu (In, Al) Se in organic solvent of Cu, In, Al, S and Se
2Type nano granular carries out purification again; Its key step is:
1) Cu, In, Al element source place organic solvent to mix, and 80-140 degree centigrade of reaction under protection of inert gas obtains solution A;
2) solution A is warming up to 200-250 degree centigrade, and one or both in adding S element source and the Se element source react; Adjust In/Al than or/and the S/Se ratio is regulated its band gap width, make the Spectral matching of the band gap width and the sunlight of material;
3) after adding benzene disperses, add the alcohol precipitation again, obtain Cu (In, Al) S
2, Cu (In, Al) Se
2Or Cu (In, and Al) (S, Se)
2Photovoltaic semiconductors is nanocrystalline.
Among the described preparation method, add tensio-active agent, the Cu that obtains (In, Al) S when Cu, In, Al element source place organic solvent to mix in the step 1
2, Cu (In, Al) Se
2Or Cu (In, and Al) (S, Se)
2Photovoltaic semiconductors is nanocrystalline to be wire or microspheroidal.
Among the described preparation method, step 2 can also comprise the steps:
A) one or both in element sulphur source and the selenium element source are mixed with organic solvent earlier, 100-120 degree centigrade of reaction under the protection of inert gas, and in 10 minutes, be warmed up to 220-250 degree centigrade of insulation, and make one or both dissolvings in element sulphur source and the selenium element source, obtain solution B;
B) stir down, solution A is added solution B, slowly cool to 100 degrees centigrade, continue to be warmed up to 180-300 degree centigrade of insulation then.
Among the described preparation method, copper (Cu) element source is selected from one or more in the following mantoquita: cuprous chloride, cupric chloride, cuprous iodide, cupric iodide, cuprous acetate, neutralized verdigris, acetylacetonate copper; Indium (In) element source is selected from one or more in the following indium salt: indium chloride, acetylacetonate indium, indium acetate, indium iodide; Aluminium (Al) element source is selected from one or more in the following aluminium salt: aluminum chloride, aluminum iodide, Burow Solution, acetylacetonate aluminium; Following one or more are selected in selenium (Se) source for use: three n-octyl phosphine oxide solution of the tri-n-octyl phosphine solution of selenium, selenium, the octadecenyl amine solution of selenium, selenourea; Following one or more are selected in sulphur (S) source for use: sulphur is dissolved in octadecenyl amine, and sulphur is dissolved in tri-n-octyl phosphine, sulphur is dissolved in three n-octyl phosphine oxides, thiocarbamide, mercaptan.
Among the described preparation method, organic solvent is octadecenyl amine, orthodichlorobenzene or anhydrous hydrazine; Alcohol is anhydrous methanol or dehydrated alcohol.
Among the described preparation method, tensio-active agent is lauryl alcohol, pyridine, polyoxyethylene glycol, cetyl trimethylammonium bromide, sodium laurylsulfonate or polyoxyethylene nonylphenol ether.
Among the described preparation method, the Cu that step 3 obtains (In, Al) S
2, Cu (In, Al) Se
2Or Cu (In, and Al) (S, Se)
2Photovoltaic semiconductors nano wire or particle with benzene, toluene or/and chloroform solvent dispersive method purify repeatedly.
Cu provided by the invention (In, Al) Se
2The class photovoltaic semiconductors is nanocrystalline can be applied in the solar cell.
Cu provided by the invention (In, Al) Se
2The class photovoltaic semiconductors is nanocrystalline can be applied in the near infrared light laser.
The invention has the advantages that:
1) adopt solvent-thermal method to synthesize the novel narrow gap semiconductor nano particle of a class.This type nano granular has potential use in field of photovoltaic materials, as can be used for comprising electrooptical devices such as photovoltaic cell, photochemical catalyst, quantum dot laser, quantum dot light emitting diode.
2) synthetic method adopts the hot method of chemical solvents, and comparing with sputter and synthetic such material of coevaporation sedimentation does not need expensive equipment and harsh synthesis condition.Lower than the method cost of equipment for preparing nano particle with mechanical disintegration such as ball mills, method is simple.Synthetic nano particle complete in crystal formation defective is less, thereby has reduced the recombination probability of photoproduction exciton.
3) by changing proportioning raw materials and synthesis condition, can adjust the band gap width of this nano material.Thereby controllably prepare the nano particle (or quantum dot) of different band gap widths and size shape.
Description of drawings
Fig. 1 be technology according to embodiment one under differing temps synthetic Cu (In, Al) (S, Se)
2The class quantum dot amplifies 30000 times transmission electron microscope electromicroscopic photograph.
Fig. 2 is Cu of the present invention (In, Al) Se
2Quantum dot is dispersed in the absorption spectrum in the toluene.
Fig. 3 is Cu of the present invention (In, Al) Se
2Quantum dot is dispersed in the fluorescence spectrum in the toluene.
Fig. 4 is Cu of the present invention (In, Al) Se
2The XRD spectra of quantum dot.
Embodiment
Preparation method of the present invention, it mainly is to adopt solvent-thermal method, with the synthetic Cu of element source such as Cu, In, Al, S, Se (as octadecenyl amine, orthodichlorobenzene, anhydrous hydrazine etc.) in organic solvent (In, Al) (S, Se)
2Type nano granular carries out purification again.
Preparation method of the present invention can by transfer In/Al and S/Se than or mix other elements (as Cd) or regulate its band gap width by the shape and size of control nano particle so that the band gap width of material better with the Spectral matching of sunlight.
The presoma of element source can select as: one or more in mantoquita such as cuprous chloride, neutralized verdigris, acetylacetonate copper and the complex compound thereof are as the copper source; In indium salt such as indium chloride, acetylacetonate indium, indium acetate and the complex compound thereof one or more are as the indium source; In aluminium salt such as aluminum chloride, Burow Solution, acetylacetonate aluminium and the complex compound thereof one or more are as the aluminium source.Selenium or sulphur are dissolved in octadecenyl amine (or orthodichlorobenzene, anhydrous hydrazine etc.) as selenium source or sulphur source.The method of purifying is for example: separate out nano particle with pure (as anhydrous methanol, dehydrated alcohol), purify several times repeatedly with benzene, toluene, chloroform equal solvent dispersive method.
The present invention mixes aluminium element can obviously change CuInSe
2Absorption spectrum and band gap.By adjust In/Al and S/Se than or mix other yuan and usually regulate its band gap width, further regulate its band gap width by the shape and size of control nano particle so that its band gap width better with the Spectral matching of sunlight.Concrete grammar can roughly satisfy under the prerequisite of 2 * Cu=2 * (In+Al)=(Se+S) at the presoma mole number, can obtain the nanoparticle of different I n/Al by the ratio that changes aluminium and indium presoma, by changing the nanoparticle that the sulphur and the ratio of selenium presoma can obtain different S/Se.If add the nano material that 1～10% suitable tensio-active agent regulation and control obtain other various patterns again, as nano wire, Nano microsphere or the like.The tensio-active agent of selecting for use can be lauryl alcohol, pyridine, polyoxyethylene glycol, cetyl trimethylammonium bromide, sodium laurylsulfonate, polyoxyethylene nonylphenol ether or the like.Replaced conventional sputter method and coevaporation sedimentation to synthesize Cu (In, Al) Se in this way
2, not needing high conversion unit and harsh preparation condition, synthetic nanoparticle monodispersity is good, and is therefore significant.
The present invention is by adjusting In/Al and S/Se than regulating its band gap width, and further regulates its band gap width by the shape and size of control nano particle so that its band gap width better with the Spectral matching of sunlight.
Technical characterictic of the present invention is:
1, by chemical process synthesized Cu (In, Al) (S, Se)
2Type nano granular.Synthetic method is to adopt element source such as Cu, In, Al, S, Se, and (as octadecenyl amine, orthodichlorobenzene, anhydrous hydrazine etc.) are synthetic in organic solvent, carry out purification again.The presoma of element can select as: one or more in mantoquita such as cuprous chloride, neutralized verdigris, acetylacetonate copper and the complex compound thereof are as the copper source; In indium salt such as indium chloride, acetylacetonate indium, indium acetate and the complex compound thereof one or more are as the indium source; In aluminium salt such as aluminum chloride, Burow Solution, acetylacetonate aluminium and the complex compound thereof one or more are as the aluminium source.Selenium or sulphur are dissolved in octadecenyl amine (or orthodichlorobenzene, anhydrous hydrazine etc.) as selenium source or sulphur source.The method of purifying is for example: separate out nano particle with pure (as anhydrous methanol, dehydrated alcohol), purify several times repeatedly with benzene, toluene, chloroform equal solvent dispersive method.
2, can by transfer In/Al and S/Se than or mix other elements (as Cd) or regulate its band gap width by the shape and size of control nano particle so that the band gap width of material better with the Spectral matching of sunlight.
Below in conjunction with example technical scheme of the present invention is described further.
Embodiment one:
0.2mmol acetylacetonate copper, 0.14mmol acetylacetonate indium, 0.06mmol acetylacetonate aluminium, 5mL 9-octadecenyl amine mixes, and 80 degrees centigrade of vacuum stirring 1h, mixture dissolve fully and obtain solution A.8mL9-octadecenyl amine and 0.4mmol selenium powder are mixed, and nitrogen protection is stirred 30min for following 120 degrees centigrade, obtains solution B.
Solution B was warmed up to 250 degrees centigrade in 10 minutes, be incubated 1 hour, and solution B becomes orangely by colourless, finally becomes sorrel.Treat that Se dissolves fully, the 5mL solution A is injected solution B with syringe, require vigorous stirring simultaneously.Solution becomes aterrimus immediately.Slowly cooling, 15min cools to 100 degrees centigrade, continues to be warmed up to 250 degrees centigrade of insulations 1 hour then.Reduce to room temperature, add the 5ml anhydrous methanol, the centrifugal 3000rpm 1min of mixture.
Precipitation is dispersed in the 10mL dry toluene, adds the centrifugation of 5mL anhydrous methanol.Add 8ml toluene and disperse, 3000rpm is centrifugal, obtains high-purity Cu (In, Al) Se
2The dispersion liquid of nano particle.
If (temperature of reaction in the above example is changed into 180～300 degrees centigrade arbitrary temp or prolongation and is shortened the reaction times by 250 degrees centigrade, can obtain the nanoparticle of different-grain diameter size.)
Embodiment two:
0.2mmol cuprous chloride (99.99%), 0.16mmol indium chloride (99.99%), 0.04mmol Burow Solution (99.99%) join in 5 milliliters the octadecenyl amine, mix, 80 degrees centigrade vacuumize 1h, obtain consoluet solution A.0.4mmol sulphur (99.98%) and 8ml octadecenyl amine mixture vacuum stripping 1h, 110 degrees centigrade obtained solution B in 30 minutes towards nitrogen protection.
Solution B was heated to 250 degrees centigrade of constant temperature 1 hour, made it to dissolve fully.Inject solution A with syringe, and slowly cool to 100 degrees centigrade, continue to be warmed up to 250 degrees centigrade of insulations 1 hour then.Reduce to room temperature, add the 5ml anhydrous methanol, the centrifugal 1min of mixture 3000rpm.
Precipitation is dispersed in the 10mL dry toluene, adds the 5mL anhydrous methanol again, centrifugation.Add 8ml toluene and disperse centrifugal Cu (In, Al) S of obtaining of 3000rpm
2Nanoparticulate dispersion.
Above method with element source S change into introduce simultaneously sulphur source and selenium source obtain Cu (In, Al) (S, Se)
2Nanocrystal.
Embodiment three:
12mL9-octadecenyl amine, 1.5mmol cuprous chloride, 1.00mmol indium chloride, 0.5mmol Burow Solution join in 100 milliliters the there-necked flask and mix, and are warmed up to 130 degrees centigrade, and argon shield is reaction 30min down.Be warmed up to 225 degrees centigrade, inject 3mL sulphur (9-octadecenyl amine dissolving 3mmol sulphur), insulation 30min with syringe.Be cooled to 60 degrees centigrade, add the 10mL dry toluene and disperse, add the 5mL dehydrated alcohol again and make it precipitation.Centrifugal 10 minutes of 10000rpm.Repeatedly several times, obtain highly purified Cu (In, Al) S with toluene dissolving/ethanol sedimentation
2Nano particle.
Embodiment four:
12mL9-octadecenyl amine, 1.5mmol cuprous chloride, 1.4mmol indium chloride, 0.1mmol Burow Solution, 0.1g lauryl alcohol join in 100 milliliters the there-necked flask and mix, and are warmed up to 130 degrees centigrade, and argon shield is reaction 30min down.Be warmed up to 225 degrees centigrade, inject 3mLTOP-Se (0.4mmol selenium is dissolved in the 3mL tri-n-octyl phosphine), insulation 90min with syringe.Be cooled to 60 degrees centigrade, add the 10mL dry toluene and disperse, add the 5mL dehydrated alcohol again and make it precipitation.Centrifugal 10 minutes of 10000rpm.Repeatedly several times, obtain highly purified Cu (In, Al) Se with toluene dissolving/ethanol sedimentation
2Nano wire.
Claims (10)
1. a Cu (In, Al) Se
2The class photovoltaic semiconductors is nanocrystalline, by element source in organic solvent synthetic Cu (In, Al) Se of solvent-thermal method with Cu, In, Al, S and Se
2Type nano granular carries out purification again and obtains; This method is:
1) Cu, In, Al element source place organic solvent to mix, and in protection of inert gas reaction down, obtain solution A;
2) solution A heats up, and one or both in adding S element source and the Se element source react; Adjust In/Al than or/and the S/Se ratio is regulated its band gap width, make the Spectral matching of the band gap width and the sunlight of material;
3) add the alcohol precipitation again after adding benzene disperses, obtain target product Cu (In, Al) S
2, Cu (In, Al) Se
2Or Cu (In, and Al) (S, Se)
2Photovoltaic semiconductors is nanocrystalline.
2. one kind prepares the described Cu of claim 1 (In, Al) Se
2The method that the class photovoltaic semiconductors is nanocrystalline adopts solvent-thermal method, with element source synthetic Cu (In, Al) Se in organic solvent of Cu, In, Al, S and Se
2Type nano granular carries out purification again; Its key step is:
1) Cu, In, Al element source place organic solvent to mix, and 80-140 degree centigrade of reaction under protection of inert gas obtains solution A;
2) solution A is warming up to 200-250 degree centigrade, and one or both in adding S element source and the Se element source react; Adjust In/Al than or/and the S/Se ratio is regulated its band gap width, make the Spectral matching of the band gap width and the sunlight of material;
3) after adding benzene disperses, add the alcohol precipitation again, obtain Cu (In, Al) S
2, Cu (In, Al) Se
2Or Cu (In, and Al) (S, Se)
2Photovoltaic semiconductors is nanocrystalline.
3. preparation method according to claim 2, wherein, in the step 1, Cu, In, Al element source add tensio-active agent, the Cu that obtains (In, Al) S when placing organic solvent to mix
2, Cu (In, Al) Se
2Or Cu (In, and Al) (S, Se)
2Photovoltaic semiconductors is nanocrystalline to be wire or microspheroidal.
4. preparation method according to claim 2, wherein, step 2 comprises the steps:
A) one or both in element sulphur source and the selenium element source are mixed with organic solvent earlier, 100-120 degree centigrade of reaction under the protection of inert gas, and in 10 minutes, be warmed up to 220-250 degree centigrade of insulation, and make one or both dissolvings in element sulphur source and the selenium element source, obtain solution B;
B) stir down, solution A is added solution B, slowly cool to 100 degrees centigrade, continue to be warmed up to 180-300 degree centigrade of insulation then.
5. preparation method according to claim 2, wherein, the Cu element source is selected from one or more in the following mantoquita: cuprous chloride, cupric chloride, cuprous iodide, cupric iodide, cuprous acetate, neutralized verdigris, acetylacetonate copper;
The In element source is selected from one or more in the following indium salt: indium chloride, acetylacetonate indium, indium acetate, indium iodide;
The Al element source is selected from one or more in the following aluminium salt: aluminum chloride, aluminum iodide, Burow Solution, acetylacetonate aluminium;
Selenium source is selected following one or more for use: three n-octyl phosphine oxide solution of the tri-n-octyl phosphine solution of selenium, selenium, the octadecenyl amine solution of selenium, selenourea;
Following one or more are selected in the sulphur source for use: sulphur is dissolved in octadecenyl amine, and sulphur is dissolved in tri-n-octyl phosphine, sulphur is dissolved in three n-octyl phosphine oxides, thiocarbamide, mercaptan.
6. preparation method according to claim 2, wherein, organic solvent is octadecenyl amine, tri-n-octyl phosphine, three n-octyl phosphine oxides, orthodichlorobenzene or anhydrous hydrazine; Alcohol is anhydrous methanol, anhydrous butanols, anhydrous propyl alcohol or dehydrated alcohol.
7. preparation method according to claim 2, wherein, tensio-active agent is lauryl alcohol, pyridine, polyoxyethylene glycol, cetyl trimethylammonium bromide, sodium laurylsulfonate or polyoxyethylene nonylphenol ether.
8. preparation method according to claim 2, wherein, the Cu that step 3 obtains (In, Al) S
2, Cu (In, Al) Se
2Or Cu (In, and Al) (S, Se)
2Photovoltaic semiconductors nano wire or particle with benzene, toluene or/and chloroform solvent dispersive method purify repeatedly.
9. the described Cu of claim 1 (In, Al) Se
2The nanocrystalline application in solar cell of class photovoltaic semiconductors.
10. the described Cu of claim 1 (In, Al) Se
2The nanocrystalline application near infrared light laser of class photovoltaic semiconductors.
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| CN102360962A (en) * | 2011-09-30 | 2012-02-22 | 中国科学院等离子体物理研究所 | Preparation method of quantum dot sensitized solar cell |
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| CN103337555A (en) * | 2013-06-09 | 2013-10-02 | 中南大学 | Method for preparing copper indium selenium sulfur powder or thin film used in thin-film solar cell |
| CN104624336A (en) * | 2015-01-22 | 2015-05-20 | 江苏启弘新材料科技有限公司 | Simple preparation method for metal oxide semiconductor quantum dot |
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| CN107573353A (en) * | 2017-09-25 | 2018-01-12 | 厦门大学 | The method that sulfo metal phthalocyanines compound is synthesized using TOPO as solvent |
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| CN102543477A (en) * | 2012-02-29 | 2012-07-04 | 中国科学院等离子体物理研究所 | Preparation method for metal sulfide catalytic electrode and application thereof |
| CN103325886A (en) * | 2013-06-09 | 2013-09-25 | 深圳市亚太兴实业有限公司 | Preparation method of CIAS membrane with energy band gradient distribution |
| CN103337555A (en) * | 2013-06-09 | 2013-10-02 | 中南大学 | Method for preparing copper indium selenium sulfur powder or thin film used in thin-film solar cell |
| CN103337555B (en) * | 2013-06-09 | 2016-08-10 | 中南大学 | A kind of copper and indium sulfur selenium powder body for thin-film solar cells or the preparation method of thin film |
| CN104624336A (en) * | 2015-01-22 | 2015-05-20 | 江苏启弘新材料科技有限公司 | Simple preparation method for metal oxide semiconductor quantum dot |
| CN107059131A (en) * | 2017-04-21 | 2017-08-18 | 南京信息工程大学 | A kind of semiconductor nano and preparation method and application |
| CN107573353A (en) * | 2017-09-25 | 2018-01-12 | 厦门大学 | The method that sulfo metal phthalocyanines compound is synthesized using TOPO as solvent |
| CN114478556A (en) * | 2017-09-25 | 2022-05-13 | 厦门大学 | Method for synthesizing sulfo metal phthalocyanine compound by taking tri-n-octyl phosphine oxide as solvent |
| CN116040589A (en) * | 2022-04-01 | 2023-05-02 | 中国计量大学 | Purification method for synthesizing nano particles from chalcopyrite type solar cell solution |
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