CN104979428B - A kind of nanocrystalline synthetic method of copper indium gallium sulphur selenium - Google Patents
A kind of nanocrystalline synthetic method of copper indium gallium sulphur selenium Download PDFInfo
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- CN104979428B CN104979428B CN201510290298.9A CN201510290298A CN104979428B CN 104979428 B CN104979428 B CN 104979428B CN 201510290298 A CN201510290298 A CN 201510290298A CN 104979428 B CN104979428 B CN 104979428B
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- sulphur
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- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims abstract description 14
- ZQRRBZZVXPVWRB-UHFFFAOYSA-N [S].[Se] Chemical compound [S].[Se] ZQRRBZZVXPVWRB-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 14
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000010189 synthetic method Methods 0.000 title claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 11
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000005864 Sulphur Substances 0.000 claims abstract description 10
- 238000005119 centrifugation Methods 0.000 claims abstract description 8
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims abstract description 8
- 238000001556 precipitation Methods 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 5
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims abstract description 5
- -1 chlorination Chemical compound 0.000 claims abstract description 3
- 239000012467 final product Substances 0.000 claims abstract description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 3
- 238000010926 purge Methods 0.000 claims abstract description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- 229920002678 cellulose Polymers 0.000 claims 1
- 239000001913 cellulose Substances 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000000376 reactant Substances 0.000 abstract description 4
- 230000004044 response Effects 0.000 abstract description 3
- 230000003749 cleanliness Effects 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 239000011669 selenium Substances 0.000 description 14
- 238000013019 agitation Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 230000003252 repetitive effect Effects 0.000 description 10
- 239000006228 supernatant Substances 0.000 description 10
- 238000010792 warming Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000010409 thin film Substances 0.000 description 8
- 229960004756 ethanol Drugs 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 5
- 229910005267 GaCl3 Inorganic materials 0.000 description 5
- 229960000935 dehydrated alcohol Drugs 0.000 description 5
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 239000013049 sediment Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- CDZGJSREWGPJMG-UHFFFAOYSA-N copper gallium Chemical compound [Cu].[Ga] CDZGJSREWGPJMG-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
-
- 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
Abstract
A kind of nanocrystalline synthetic method of copper indium gallium sulphur selenium, is related to a kind of solar cell material.The synthetic method that a kind of processing step is simple, the adjustable copper indium gallium sulphur selenium of energy gap is nanocrystalline is provided.1) by Cu-lyt., indium chloride, chlorination, sulphur powder, selenium powder is mixed with oleyl amine, adds dithioglycol regulation and control element sulphur ratio, obtains mixed solution；2) by step 1) gained mixed solution heated and stirred, evacuation, inflated with nitrogen, in nitrogen atmosphere reaction, obtain dark brown solution；3) by step 2) in gained dark brown solution centrifugation, gained precipitation respectively use chloroform and ethanol purge, obtain final product copper indium gallium sulphur selenium nanocrystalline.Reaction temperature is low, and the response time is short, synthesizer simple it is only necessary to simple container, synthetic route is simple, workable, and the equal environmentally safe of reactant used, course of reaction cleanliness without any pollution, reaction efficiency is high, and reaction cost is cheap, has larger synthesis application prospect.
Description
Technical field
The present invention relates to a kind of solar cell material, especially relate to that a kind of copper indium gallium sulphur selenium is nanocrystalline (to be designated as
CuIn1-xGax(SySe1-y)2) synthetic method.
Background technology
The energy is the basis of human society survival and development, and the energy crisis of today's society has been instant asking
Topic.People are making great efforts to seek new energy, to solve growing energy demand.Solar energy is that the mankind are inexhaustible, uses it
Inexhaustible clean energy resource.In the application of solar energy, the most extensive and the most great-hearted field is photovoltaic generation, and its operation principle is just
It is to convert solar energy into using the photovoltaic effect of quasiconductor to be available for the wide variety of electric energy of the mankind.Find light from 1800
Volt effect solar cell material is also developing always.After first generation monocrystal silicon and polysilicon solar cell, it is also at present
The widest solaode of industrialization.Second filial generation solaode is the solaode based on thin film technique, thin film technique
Application significantly reduces cost also large area can carry out industrialization production.At present, thin-film solar cells mainly have amorphous
Silicon and polycrystalline silicon thin film solar cell, cadmium telluride and CuInSe2Hull cell.
I-III-VI2Semiconductor nano becomes in thin-film solar cells research because having outstanding electro optic properties
One of most potential material, in the novel solar battery based on semiconductor nano or quantum dot, with colloid nano crystalline substance be
" ink " is come to prepare photovoltaic layer be an important direction.Wherein, the I-III-VI as representative with CIGS (CIGS)2Pyrite
Ore deposit type compound nano crystalline substance is especially noticeable, becomes the ideal body of scientists study inorganic semiconductor novel solar battery
System (Q.J.Guo, S.J.Kim, M.Kar, W.N.Shafarman, R.W.Birkmire, E.A.Stach, R.Agrawal,
H.W.Hillhouse.Nano Lett.,2008,8,2982.)：1)I-III-VI2Semiconductor optoelectronic high conversion efficiency, performance is steady
Fixed, capability of resistance to radiation is strong, there is not light-induced degradation problem；2)I-III-VI2Quasiconductor obtains in thin-film solar cells
Original application, CIGS hull cell laboratory peak efficiency is 20.8%, is not less than the 20.4% of polycrystalline silicon thin film solar cell.Become
Product component efficiency has reached 13%, is one of efficiency highest battery in current thin film battery；3) different I-III-VI2Quasiconductor
Bandwidth excursion big, such as CIS (CuInSe2) it is 1.04eV, copper gallium selenium (CuGaSe2) it is 1.68eV, copper gallium sulfur
(CuGaS2) it is 2.43eV, similar also can the change by component due to structure fine-tunes bandwidth further, such as CuIn1-xGax
(SySe1-y)2(CIGSSe) energy gap can be adjusted between 0.98-2.40, for the design of different solaodes
Supremacy clause is provided.On the other hand, when matter dimensions are in nanoscale, its a series of chemical physical property is as well as changing
Become.So working as I-III-VI2In nanosized, its energy gap also can change the size Control of semiconductor nano therewith
Become, to show more excellent optical absorption property, the final solar cell material photoelectric transformation efficiency that improves reaches more effectively
Using sunlight.So how to prepare the controlled I-III-VI of energy gap2Semiconductor nano be one very meaningful
Work.
Content of the invention
It is an object of the invention to provide a kind of processing step is simple, the adjustable copper indium gallium sulphur selenium of energy gap is nanocrystalline
Synthetic method.
A kind of nanocrystalline synthetic method of described copper indium gallium sulphur selenium, comprises the following steps：
1) by Cu-lyt., indium chloride, chlorination, sulphur powder, selenium powder is mixed with oleyl amine, adds dithioglycol regulation and control element sulphur
Ratio, obtains mixed solution；
2) by step 1) gained mixed solution heated and stirred, evacuation, inflated with nitrogen, in nitrogen atmosphere reaction, obtain dark-brown
Solution；
3) by step 2) in gained dark brown solution centrifugation, gained precipitation respectively use chloroform and ethanol purge, obtain final product
Copper indium gallium sulphur selenium is nanocrystalline.
In step 1) in, in molar ratio, indium chloride: chlorination=1: 8～8: 1；Selenium powder: sulphur powder content=1: 8～8: 1；
By sulfur content mol ratio, dithioglycol: sulphur powder=1: 15～1: 5.
Step 2) in, described reaction is preferably first reacts 1h at 130 DEG C, subsequently temperature is increased to reaction at 240 DEG C
1.5h.
Described evacuation, preferably 80 DEG C of the temperature conditionss of inflated with nitrogen, described evacuation, inflated with nitrogen preferably repeatedly 3 times.
Step 3) in, the number of times of described cleaning generally 3 times.
Compared with the prior art, the having the prominent advantages that of the present invention：
1) add dithioglycol can Effective Regulation each element ratio, this is because dithioglycol belongs to liquid, compared to solid-state
Reactant is easier to fully react with other reactants, and the addition of liquid dithioglycol makes crystal be more easy to nucleation, the crystalline substance obtaining
Grain is less；In addition, can effectively regulate and control CuIn by adding dithioglycol1-xGax(SySe1-y)2The ratio of middle each element, from
And adjust their energy gap, so it is adapted to the demand of different solaode preparations.And liquid dithioglycol plus
Enter to regulate and control nano-crystalline granule size in 10nm.2) reaction temperature is than with respect to conventional synthesis CuInSe2Nanometer
Even 280 DEG C low of 260 DEG C brilliant of reaction temperature.3) response time also will shorten much than traditional method.4) present invention is not only
Using synthesizer simple it is only necessary to simple container, synthetic route is simply, workable, and reaction used
The equal environmentally safe of thing, course of reaction cleanliness without any pollution, reaction efficiency is high, and reaction cost is cheap, has larger synthesis application
Prospect.
Brief description
Fig. 1 adopts, for the present invention, the CuIn that oleyl amine is reaction dissolvent gained0.5Ga0.5(S0.5Se0.5)2Nanocrystalline TEM figure.
Fig. 2 adopts, for the present invention, the CuIn that oleyl amine is reaction dissolvent gained0.3Ga0.7(S0.7Se0.3)2Nanocrystalline TEM figure.
Fig. 3 adopts, for the present invention, the CuIn that oleyl amine is reaction dissolvent gained0.5Ga0.5(S0.5Se0.5)2Nanocrystalline EDX figure.
In figure 3, abscissa is energy/KeV；Show Cu, In, Ga, S, Se.
Fig. 4 adopts the CuIn of the different proportion that oleyl amine is reaction dissolvent gained for the present invention1-xGax(SySe1-y)2XRD
Figure, in Fig. 4, abscissa is angle of diffraction 2Theta/ °, and vertical coordinate is diffracted intensity Intensity；Diffraction maximum is distinguished from left to right
111,220,311,400,331,422 and 511.Curve a is CuIn0.2Ga0.8(S0.8Se0.2)2；Curve b is CuIn0.3Ga0.7
(S0.7Se0.3)2；Curve c is CuIn0.5Ga0.5(S0.5Se0.5)2；Curve d is CuInSe2.
Specific embodiment
Example below will combine accompanying drawing, and the invention will be further described.
From Fig. 1 and Fig. 2, the CuIn of present invention preparation1-xGax(SySe1-y)2Nano-crystalline granule is less, granular size phase
To more uniformly, granule-morphology is essentially close to circular granular.Nano-crystalline granule is averagely about between 5 to 10nm.
As seen from Figure 3, may certify that Cu, the presence of In, Ga, S, Se, and can determine whether product each element ratio and rate of charge
Close.
As seen from Figure 4 it can be seen that the CuIn obtaining1-xGax(SySe1-y)2For pure phase, impurity peaks are there is no.
The specific embodiment of the present invention is given below：
Embodiment 1
(1) take 250L three-neck flask, glove box weighs 0.2475g CuCl, 0.1105g InCl3,0.3520g
GaCl3, 0.0640g S powder, 0.0395g Se powder simultaneously measures 50mL oleyl amine, 16.8 μ L dithioglycols, adds in three-neck flask.
(3) reaction unit is installed：One side side port rubber stopper of three-necked bottle seals, and another side side pipe connects in glass bushing
Put the temperature probe of heating mantle, to measure reacting liquid temperature.Middle mouth connects reflux condensing tube, connects vacuum spool above condensing tube
In order to evacuation and logical nitrogen.Finally three-necked bottle is positioned in magnetic force heating stirrer.
(4) at room temperature system evacuation is then passed to nitrogen repetitive operation 3 times, each pumpdown time is at least
10min, the system vacuum of making reaches -0.1MPa, so that system is in the protection of blanket of nitrogen.
(5) it is warming up to the 80 DEG C of logical nitrogen repetitive operation of evacuation 2 times again in magnetic agitation, each pumpdown time is extremely
Few 10min, the system vacuum of making reaches -0.1MPa, eventually forms dark-brown solution.
(6) it is warming up to 130 DEG C in magnetic agitation and maintain heated and stirred reaction 1h.
(7) continue to stir and be brought rapidly up to maintain heated and stirred reaction 1.5h to 240 DEG C.
(8) be cooled to 100 DEG C, add 10mL chloroform so that reaction is stopped, and add 5mL dehydrated alcohol, under 8000rpm from
Heart 10min, removes supernatant, precipitation is dispersed in 10mL chloroform, is centrifuged 5min, takes supernatant under 7000rpm, adds
0.2mL oleyl amine, so that nanocrystalline be uniformly dispersed, in order to remove unnecessary Organic substance, adds 5mL ethanol, under 8000rpm
Centrifugation 10min, then lower sediment is dispersed in 10mL chloroform, so repeatedly obtain purer CuIn 3 times1-xGax
(SySe1-y)2Nanocrystalline.
Referring to Fig. 1～4, can be seen that the nano-crystalline granule size obtaining between 5～10nm from Fig. 1 and Fig. 2；By Fig. 3
EDX figure can obtain prepare CuIn1-xGax(SySe1-y)2Nanocrystalline middle each element ratio is mated with rate of charge, and each unit is described
The ratio of element has obtained Effective Regulation；Can be seen that the CuIn obtaining by the XRD figure of Fig. 41-xGax(SySe1-y)2It is no miscellaneous peak, say
The bright product obtaining is pure phase.
Embodiment 2
(1) take 50mL three-neck flask, glove box weighs 0.0495g CuCl, 0.0553g InCl3,0.0440g
GaCl3, 0.0160g S powder, 0.0395g Se powder simultaneously measures 10mL oleyl amine, 2.1 μ L dithioglycols, adds in three-neck flask.
(3) reaction unit is installed：One side side port rubber stopper of three-necked bottle seals, and another side side pipe connects in glass bushing
Put the temperature probe of heating mantle, to measure reacting liquid temperature.Middle mouth connects reflux condensing tube, connects vacuum spool above condensing tube
In order to evacuation and logical nitrogen.Finally three-necked bottle is positioned in magnetic force heating stirrer.
(4) at room temperature system evacuation is then passed to nitrogen repetitive operation 3 times, each pumpdown time is at least
10min, the system vacuum of making reaches -0.1MPa, so that system is in the protection of blanket of nitrogen.
(5) it is warming up to the 80 DEG C of logical nitrogen repetitive operation of evacuation 2 times again in magnetic agitation, each pumpdown time is extremely
Few 10min, the system vacuum of making reaches -0.1MPa, eventually forms dark-brown solution.
(6) it is warming up to 130 DEG C in magnetic agitation and maintain heated and stirred reaction 1h.
(7) continue to stir and be brought rapidly up to maintain heated and stirred reaction 1.5h to 240 DEG C.
(8) be cooled to 100 DEG C, add 10mL chloroform so that reaction is stopped, and add 5mL dehydrated alcohol, under 8000rpm from
Heart 10min, removes supernatant, precipitation is dispersed in 10mL chloroform, is centrifuged 5min, takes supernatant under 7000rpm, adds
0.2mL oleyl amine, so that nanocrystalline be uniformly dispersed, in order to remove unnecessary Organic substance, adds 5mL ethanol, under 8000rpm
Centrifugation 10min, then lower sediment is dispersed in 10mL chloroform, so repeatedly obtain purer CuIn 3 times1-xGax
(SySe1-y)2Nanocrystalline.
Embodiment 3
(1) take 50mL three-neck flask, glove box weighs 0.0495g CuCl, 0.0443g InCl3,0.0528g
GaCl3, 0.0096g S powder, 0.0158g Se powder simultaneously measures 10mL oleyl amine, 2.52 μ L dithioglycols, adds in three-neck flask.
(3) reaction unit is installed：One side side port rubber stopper of three-necked bottle seals, and another side side pipe connects in glass bushing
Put the temperature probe of heating mantle, to measure reacting liquid temperature.Middle mouth connects reflux condensing tube, connects vacuum spool above condensing tube
In order to evacuation and logical nitrogen.Finally three-necked bottle is positioned in magnetic force heating stirrer.
(4) at room temperature system evacuation is then passed to nitrogen repetitive operation 3 times, each pumpdown time is at least
10min, the system vacuum of making reaches -0.1MPa, so that system is in the protection of blanket of nitrogen.
(5) it is warming up to the 80 DEG C of logical nitrogen repetitive operation of evacuation 2 times again in magnetic agitation, each pumpdown time is extremely
Few 10min, the system vacuum of making reaches -0.1MPa, eventually forms dark-brown solution.
(6) it is warming up to 130 DEG C in magnetic agitation and maintain heated and stirred reaction 1h.
(7) continue to stir and be brought rapidly up to maintain heated and stirred reaction 1.5h to 240 DEG C.
(8) be cooled to 100 DEG C, add 10mL chloroform so that reaction is stopped, and add 5mL dehydrated alcohol, under 8000rpm from
Heart 10min, removes supernatant, precipitation is dispersed in 10mL chloroform, is centrifuged 5min, takes supernatant under 7000rpm, adds
0.2mL oleyl amine, so that nanocrystalline be uniformly dispersed, in order to remove unnecessary Organic substance, adds 5mL ethanol, under 8000rpm
Centrifugation 10min, then lower sediment is dispersed in 10mL chloroform, so repeatedly obtain purer CuIn 3 times1-xGax
(SySe1-y)2Nanocrystalline.
Embodiment 4
(1) take 50mL three-neck flask, glove box weighs 0.0495g CuCl, 0.0332g InCl3,0.0616g
GaCl3, 0.0112g S powder, 0.0118g Se powder simultaneously measures 10mL oleyl amine, 2.94 μ L dithioglycols, adds in three-neck flask.
(3) reaction unit is installed：One side side port rubber stopper of three-necked bottle seals, and another side side pipe connects in glass bushing
Put the temperature probe of heating mantle, to measure reacting liquid temperature.Middle mouth connects reflux condensing tube, connects vacuum spool above condensing tube
In order to evacuation and logical nitrogen.Finally three-necked bottle is positioned in magnetic force heating stirrer.
(4) at room temperature system evacuation is then passed to nitrogen repetitive operation 3 times, each pumpdown time is at least
10min, the system vacuum of making reaches -0.1MPa, so that system is in the protection of blanket of nitrogen.
(5) it is warming up to the 80 DEG C of logical nitrogen repetitive operation of evacuation 2 times again in magnetic agitation, each pumpdown time is extremely
Few 10min, the system vacuum of making reaches -0.1MPa, eventually forms dark-brown solution.
(6) it is warming up to 130 DEG C in magnetic agitation and maintain heated and stirred reaction 1h.
(7) continue to stir and be brought rapidly up to maintain heated and stirred reaction 1.5h to 240 DEG C.
(8) be cooled to 100 DEG C, add 10mL chloroform so that reaction is stopped, and add 5mL dehydrated alcohol, under 8000rpm from
Heart 10min, removes supernatant, precipitation is dispersed in 10mL chloroform, is centrifuged 5min, takes supernatant under 7000rpm, adds
0.2mL oleyl amine, so that nanocrystalline be uniformly dispersed, in order to remove unnecessary Organic substance, adds 5mL ethanol, under 8000rpm
Centrifugation 10min, then lower sediment is dispersed in 10mL chloroform, so repeatedly obtain purer CuIn 3 times1-xGax
(SySe1-y)2Nanocrystalline.
Embodiment 5
(1) take 50mL three-neck flask, glove box weighs 0.0495g CuCl, 0.0553g InCl3,0.0440g
GaCl3, 0.0160g S powder, 0.0395g Se powder simultaneously measures 10mL oleyl amine, 2.1 μ L dithioglycols, adds in three-neck flask.
(3) reaction unit is installed：One side side port rubber stopper of three-necked bottle seals, and another side side pipe connects in glass bushing
Put the temperature probe of heating mantle, to measure reacting liquid temperature.Middle mouth connects reflux condensing tube, connects vacuum spool above condensing tube
In order to evacuation and logical nitrogen.Finally three-necked bottle is positioned in magnetic force heating stirrer.
(4) at room temperature system evacuation is then passed to nitrogen repetitive operation 3 times, each pumpdown time is at least
10min, the system vacuum of making reaches -0.1MPa, so that system is in the protection of blanket of nitrogen.
(5) it is warming up to the 80 DEG C of logical nitrogen repetitive operation of evacuation 2 times again in magnetic agitation, each pumpdown time is extremely
Few 10min, the system vacuum of making reaches -0.1MPa, eventually forms dark-brown solution.
(6) it is warming up to 130 DEG C in magnetic agitation and maintain heated and stirred reaction 1h.
(7) continue to stir and be brought rapidly up to maintain heated and stirred reaction 1.5h to 240 DEG C.
(8) be cooled to 100 DEG C, add 10mL chloroform so that reaction is stopped, and add 5mL dehydrated alcohol, under 8000rpm from
Heart 10min, removes supernatant, precipitation is dispersed in 10mL chloroform, is centrifuged 5min, takes supernatant under 7000rpm, adds
0.2mL oleyl amine, so that nanocrystalline be uniformly dispersed, in order to remove unnecessary Organic substance, adds 5mL ethanol, under 8000rpm
Centrifugation 10min, then lower sediment is dispersed in 10mL chloroform, so repeatedly obtain purer CuIn 3 times1-xGax
(SySe1-y)2Nanocrystalline.
When increasing reaction vessel size, when expanding inventory, the controlled CuIn of ratio still can be obtained1-xGax
(SySe1-y)2Nanocrystalline, illustrate that this method is practicable.
Main advantages of the present invention are：1) add liquid dithioglycol can Effective Regulation each element ratio, and permissible
Regulation and control nano-crystalline granule size, in 10nm, has some superiority (can make anti-compared to common all solid state reactant
Should carry out is more abundant).2) reaction temperature is compared to conventional synthesis CuInSe2Even 280 DEG C of 260 DEG C of nanocrystalline reaction temperature
Low.3) response time also will shorten much than the 4h in traditional method.4) present invention not only with synthesizer simple, only
Need simple container (three-neck flask, biexhaust pipe, electric jacket), synthetic route is simple, workable, reaction efficiency is high
(proportion of products obtaining is close with rate of charge), reaction cost is cheap, has larger synthesis application prospect, and is adapted to difference
The demand of solaode preparation.
Claims (4)
1. a kind of nanocrystalline synthetic method of copper indium gallium sulphur selenium is it is characterised in that comprise the following steps：
1) by Cu-lyt., indium chloride, chlorination, sulphur powder, selenium powder is mixed with oleyl amine, adds dithioglycol regulation and control element sulphur ratio
Example, obtains mixed solution；In molar ratio, indium chloride: chlorination=1: 8～8: 1；Selenium powder: sulphur powder content=1: 8～8: 1；By sulfur unit
Cellulose content mol ratio, dithioglycol: sulphur powder=1: 15～1: 5；
2) by step 1) gained mixed solution heated and stirred, evacuation, inflated with nitrogen, in nitrogen atmosphere reaction, obtain dark brown solution；
3) by step 2) in gained dark brown solution centrifugation, gained precipitation respectively use chloroform and ethanol purge, obtain final product copper and indium
Gallium sulfur selenium is nanocrystalline.
2. as claimed in claim 1 a kind of nanocrystalline synthetic method of copper indium gallium sulphur selenium it is characterised in that step 2) in, described
Reaction is first to react 1h at 130 DEG C, subsequently temperature is increased to reaction 1.5h at 240 DEG C.
3. as claimed in claim 1 a kind of nanocrystalline synthetic method of copper indium gallium sulphur selenium it is characterised in that step 2) in, described
Evacuation, the temperature conditionss of inflated with nitrogen are 80 DEG C, described evacuation, inflated with nitrogen 3 times repeatedly.
4. as claimed in claim 1 a kind of nanocrystalline synthetic method of copper indium gallium sulphur selenium it is characterised in that step 3) in, described
The number of times of cleaning is 3 times.
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