CN102923763A - Method for synthesizing copper indium diselenide nanosheet through ion exchange method - Google Patents
Method for synthesizing copper indium diselenide nanosheet through ion exchange method Download PDFInfo
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- CN102923763A CN102923763A CN2012103480016A CN201210348001A CN102923763A CN 102923763 A CN102923763 A CN 102923763A CN 2012103480016 A CN2012103480016 A CN 2012103480016A CN 201210348001 A CN201210348001 A CN 201210348001A CN 102923763 A CN102923763 A CN 102923763A
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- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000005342 ion exchange Methods 0.000 title claims abstract description 11
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 title abstract description 23
- 239000002135 nanosheet Substances 0.000 title abstract description 6
- 230000002194 synthesizing effect Effects 0.000 title abstract 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims abstract description 43
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 14
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 13
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 claims abstract description 13
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229960001471 sodium selenite Drugs 0.000 claims abstract description 13
- 235000015921 sodium selenite Nutrition 0.000 claims abstract description 13
- 239000011781 sodium selenite Substances 0.000 claims abstract description 13
- JKNHZOAONLKYQL-UHFFFAOYSA-K tribromoindigane Chemical compound Br[In](Br)Br JKNHZOAONLKYQL-UHFFFAOYSA-K 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 239000000376 reactant Substances 0.000 claims abstract description 6
- 239000013335 mesoporous material Substances 0.000 claims abstract description 5
- 239000011669 selenium Substances 0.000 claims description 33
- 238000001291 vacuum drying Methods 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- UIPVMGDJUWUZEI-UHFFFAOYSA-N copper;selanylideneindium Chemical compound [Cu].[In]=[Se] UIPVMGDJUWUZEI-UHFFFAOYSA-N 0.000 claims description 14
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 12
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 8
- 229960003280 cupric chloride Drugs 0.000 claims description 6
- 230000036571 hydration Effects 0.000 claims description 6
- 238000006703 hydration reaction Methods 0.000 claims description 6
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 3
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052802 copper Inorganic materials 0.000 abstract description 4
- 239000010949 copper Substances 0.000 abstract description 4
- 229910052738 indium Inorganic materials 0.000 abstract description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- PHPKKGYKGPCPMV-UHFFFAOYSA-N [SeH-]=[Se].[In+3].[SeH-]=[Se].[SeH-]=[Se] Chemical compound [SeH-]=[Se].[In+3].[SeH-]=[Se].[SeH-]=[Se] PHPKKGYKGPCPMV-UHFFFAOYSA-N 0.000 abstract 1
- 150000001879 copper Chemical class 0.000 abstract 1
- XIMIGUBYDJDCKI-UHFFFAOYSA-N diselenium Chemical compound [Se]=[Se] XIMIGUBYDJDCKI-UHFFFAOYSA-N 0.000 abstract 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000011148 porous material Substances 0.000 abstract 1
- 239000000843 powder Substances 0.000 abstract 1
- 238000005303 weighing Methods 0.000 description 12
- 230000001186 cumulative effect Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 229910052711 selenium Inorganic materials 0.000 description 4
- 229940091258 selenium supplement Drugs 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000000851 scanning transmission electron micrograph Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- 229910000980 Aluminium gallium arsenide Inorganic materials 0.000 description 1
- 229910004613 CdTe Inorganic materials 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000002471 indium Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000002063 nanoring Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
The invention belongs to the technical field of synthesis of nano-optoelectronic material, relates to a preparation method for a copper indium diselenide (CuInSe2) nanometer material, and in particular relates to a method for synthesizing a copper indium diselenide nanosheet through an ion exchange method. The method comprises the following steps of: synthesizing an In2Se3 (DETA) 0.5 precursor in a reaction kettle by adopting indium bromide and sodium selenite as reactants, and diethylenetriamine, hydrazine hydrate and deionized water as solvents; and by adopting the precursor powder and copper salt as the reactants, and glycol as the solvent, carrying out solvent thermal reaction in the reaction kettle to obtain the copper indium diselenide (CuInSe2) nanometer material. The indium diselenide nanosheet prepared by the method provided by the invention is the mesoporous material of which the average length is 3 micrometers and the width is 1.5 micrometers; the mesoporous material is provided with a plurality of pores; each nanosheet contains three elements which are respectively copper, indium and diselenide; and each element is uniformly distributed in the whole nanosheet. The method has the advantages of high reaction reproducibility, mild reaction condition, simple preparation method, low cost, high controllability, high product crystallinity, high output and purity, and is green and environment-friendly, and is expected for being used for mass production.
Description
Technical field
The invention belongs to the photoelectric nano field of material synthesis technology, relate to copper indium diselenide (CuInSe
2) the preparations of nanomaterials method, relate in particular to the method that a kind of ion exchange method is synthesized copper indium selenium nano tablets.
Background technology
Oil, coal are Nonrenewable resources as important fossil energy.Along with the continuous exhaustion of the fossil oils such as coal and oil, the Devoting Major Efforts To Developing new and renewable sources of energy is the only way of human kind sustainable development.Sun power is human inexhaustible renewable energy source, belongs to clean energy, can not produce any environmental pollution.In the middle of effective utilization of sun power, the solar photoelectric utilization is with fastest developing speed in the last few years, the promising research field of tool.In order to make sunlight obtain more effectively utilizing, people develop and have developed solar cell.Before half a century, the human silicon single crystal such as Bell Laboratory researchist Chapin have produced first solar cell.This battery is as the conversion medium of energy, and effciency of energy transfer has reached 6%.Because the cost compare of silicon single crystal is high, popularized in order to make solar cell, people constantly explore and seek a kind of stable, high conversion, material comes substituted single crystal silicon cheaply.The Analysis on Results of obtaining from the laboratory reduces the current carrier loss and minimizing light transmission loss can improve electricity conversion to a certain extent widely.For example, the transformation efficiency of gallium arsenide (GaAs) solar cell has reached 24%, adopts the binodal solar cell AlGaAs/GaAs of stacked structure preparation and the transformation efficiency of GaInP2/GaAs to reach respectively 27.6% and 29.5%.
The development of photovoltaic solar cells is arrived II-VI compound (CdTe) again from simple IV family material list crystal silicon to III-V compound (GaAs), arrives afterwards complicated I-III-VI again
2Compound (CuInSe
2).Copper indium diselenide (CuInSe
2) being called for short CIS, the CIS material has larger uptake factor to sunlight, lower band gap (1.05eV), and preferably irradiation stability is arranged, and be suitable for use as the sunlight opto-electronic conversion, be widely used on the thin-film solar cells; In addition, there is not the light-induced degradation problem in the CIS thin-film solar cells.Therefore, CIS has also caused gazing at of people as high conversion efficiency thin-film solar cells material.CIS is as the semiconductor material of solar cell, has cheap, functional and the advantage such as technique is simple, will become an important directions of Future Development solar cell.
At present, the preparation method of CIS battery thin film mainly contains vacuum vapour deposition, selenizing method, electrodip process, chemical vapour deposition etc., and vacuum vapour deposition is evaporation source copper steam-plating, indium and the selenium that adopts separately; The selenizing method is to use H
2The selenizing of Se stack membrane, but this method is difficult to obtain uniform CIS, has certain challenge so will prepare the controlled CIS nano material of pattern.Up to now, the report of Hydrothermal Synthesis CIS nano material is not a lot: Xian seminar is that raw material has synthesized CIS nano particle and nanometer rod in ethylenediamine solution with mantoquita, indium salt and selenium simple substance, and Guo and Koo seminar are that solvent has synthesized respectively nano-rings and nano particle with oleyl amine.Because the pattern of material determines the character of material, to prepare the copper indium diselenide nano material of different-shape be necessary so seek a kind of method of gentleness.
Summary of the invention
The invention provides the synthetic copper indium diselenide (CuInSe of a kind of ion exchange method
2) the two-dimensional nano sheet.
The method of the synthetic copper indium selenium nano tablets of a kind of ion exchange method, at first take indium bromide and Sodium Selenite as reactant, with diethylenetriamine (DETA), hydrazine hydrate and deionized water are solvent, synthetic In in liner is the reactor of tetrafluoroethylene
2Se
3(DETA)
0.5Then precursor take the precursor that makes and mantoquita as reactant, take ethylene glycol as solvent, obtains copper indium diselenide (CuInSe through solvent thermal reaction in reactor
2) nanometer sheet.
In described in the present invention
2Se
3(DETA)
0.5The precursor preparation process comprises: indium bromide and Sodium Selenite are placed reactor, diethylenetriamine, hydrazine hydrate and deionized water are mixed, the interior fully dissolving of the described reactor of rear adding that stirs, the reaction solution volume is 60% of described reactor, described reactor is placed 180 ℃ of reaction 3d, be cooled to room temperature, use absolute ethanol washing, centrifugal vacuum-drying obtains In
2Se
3(DETA)
0.5Precursor.
The mol ratio of the indium bromide described in the present invention and Sodium Selenite is 2:3, and the volume ratio of described diethylenetriamine, hydrazine hydrate and deionized water is 5:2:12, and described vacuum-drying temperature is 60 ℃.
Solvent thermal reaction of the present invention comprises: with the above-mentioned In that makes
2Se
3(DETA)
0.5Precursor and mantoquita place reactor, and it is even that adding ethylene glycol is done stirring solvent, and the reaction solution volume is 60 ~ 80% of reactor volume, in 160 ~ 180 ℃ of reaction 4 ~ 8h, be cooled to room temperature, with deionized water and absolute ethanol washing, centrifugal vacuum-drying obtains copper indium selenium nano tablets.
In of the present invention
2Se
3(DETA)
0.5The mol ratio of precursor and mantoquita is 2:1, and described mantoquita is that described vacuum-drying temperature is 60 ℃ without in hydration cupric chloride, Gerhardite, the Salzburg vitriol any one.
According to the copper indium selenium nano tablets of the method for the invention preparation, nanometer sheet is mesoporous material, on average long 3 microns, wide 1.5 microns, many apertures are arranged, each nanometer sheet contains copper, indium, three kinds of elements of selenium, and also every kind of element all is to be evenly distributed in the whole nanometer sheet.
Beneficial effect
Advantage of the present invention is the reaction favorable reproducibility, and reaction conditions is gentle, and the preparation method is simple, with low cost, controllability strong, product good crystallinity, output and purity are high, and environmental protection is expected to produce in enormous quantities.
Description of drawings
Copper indium diselenide (the CuInSe that Fig. 1 is prepared
2) the X-ray diffraction analysis figure (XRD) of nanometer sheet.
Copper indium diselenide (the CuInSe that Fig. 2 is prepared
2) scanning electron microscope (SEM) photograph (SEM) of nanometer sheet.
Copper indium diselenide (the CuInSe that Fig. 3 is prepared
2) transmission electron microscope picture (TEM) of nanometer sheet.
Copper indium diselenide (the CuInSe that Fig. 4 is prepared
2) the scanning transmission electron micrograph (STEM) of nanometer sheet.
Embodiment
The present invention is described in detail below in conjunction with embodiment, so that those skilled in the art understand the present invention better, but the present invention is not limited to following examples.
Embodiment 1:
(1) take by weighing respectively 0.142g (0.4mmol) indium bromide with electronic balance, 0.1038g (0.6mmol) Sodium Selenite is in the 25ml reactor;
(2) use respectively the 5ml transfer pipet, 2ml transfer pipet, 10ml transfer pipet are measured diethylenetriamine, hydrazine hydrate, deionized water 5ml, 2ml, and 12ml stirs 2min with glass stick in the 50ml beaker, it is mixed;
(3) measuring mixing solutions 15ml reactor in (1) in (2) with transfer pipet, is that the magneton of 1cm stirs 10min with diameter under the 600rpm rotating speed, it is fully dissolved and mixes;
(4) 180 ℃ of baking oven constant temperature 3d are put in the reactor sealing, then naturally cool to room temperature, use absolute ethanol washing 5 times, drying obtains yellow In in 60 ℃ of vacuum drying ovens
2Se
3(DETA)
0.5Nanometer sheet; Repeat said process, obtain the In of capacity
2Se
3(DETA)
0.5Nanometer sheet;
(5) take by weighing the yellow In that obtains in (4)
2Se
3(DETA)
0.50.5185g (1mmol), be in the reactor of tetrafluoroethylene without hydration cupric chloride 0.0673g (0.5mmol) in the 25ml liner, measure 20ml ethylene glycol in this reactor with graduated cylinder, the volume that makes solution is 80% of reactor cumulative volume; This reactor is put into 160 ℃ of baking oven constant temperature 4h, naturally cool to room temperature, use respectively deionized water and absolute ethanol washing 3 times, dry 4h in 60 ℃ of vacuum drying ovens obtains the copper indium diselenide (CuInSe of black
2) nanometer sheet.
Fig. 1 is prepared copper indium diselenide (CuInSe
2) XRD figure of nanometer sheet, can find out that from XRD peakedness ratio is higher, and the peak is clearly, illustrate that this material has very high purity;
Fig. 2 is prepared copper indium diselenide (CuInSe
2) the SEM figure of nanometer sheet, as can be seen from the figure, this material is comprised of large-area two-dimentional sheet, and on average long 3 microns of nanometer sheet are wide 1.5 microns, and nanometer sheet is mesoporous material, and many apertures are arranged;
Fig. 3 is prepared copper indium diselenide (CuInSe
2) the TEM figure of nanometer sheet, as can be seen from the figure, this nanometer sheet is that many holes that differ in size form;
Fig. 4 is prepared copper indium diselenide (CuInSe
2) the STEM figure of nanometer sheet, as can be seen from the figure, each nanometer sheet contains copper, indium, and three kinds of elements of selenium, and also every kind of element all is to be evenly distributed in the whole nanometer sheet.
Embodiment 2:
(1) take by weighing respectively 0.142g (0.4mmol) indium bromide with electronic balance, 0.1038g (0.6mmol) Sodium Selenite is in the 25ml reactor;
(2) use respectively the 5ml transfer pipet, 2ml transfer pipet, 10ml transfer pipet are measured diethylenetriamine, hydrazine hydrate, deionized water 5ml, 2ml, and 12ml stirs 2min with glass stick in the 50ml beaker, it is mixed;
(3) measuring mixing solutions 15ml reactor in (1) in (2) with transfer pipet, is that the magneton of 1cm stirs 10min with diameter under the 600rpm rotating speed, it is fully dissolved and mixes;
(4) 180 ℃ of baking oven constant temperature 3d are put in the reactor sealing, then naturally cool to room temperature, use absolute ethanol washing 5 times, drying obtains yellow In in 60 ℃ of vacuum drying ovens
2Se
3(DETA)
0.5Nanometer sheet; Repeat said process, obtain the In of capacity
2Se
3(DETA)
0.5Nanometer sheet;
(5) take by weighing the yellow In that obtains in (4)
2Se
3(DETA)
0.50.5 0.5185g (1mmol), Gerhardite 0.121g (0.5mmol) is in the reactor of tetrafluoroethylene in the 25ml liner, measures 20ml ethylene glycol in this reactor with graduated cylinder, and the volume that makes solution is 80% of reactor cumulative volume; This reactor is put into 160 ℃ of baking oven constant temperature 4h, naturally cool to room temperature, use respectively deionized water and absolute ethanol washing 3 times, dry 4h in 60 ℃ of vacuum drying ovens obtains the copper indium diselenide (CuInSe of black
2) nanometer sheet.
Embodiment 3:
(1) take by weighing respectively 0.142g (0.4mmol) indium bromide with electronic balance, 0.1038g (0.6mmol) Sodium Selenite is in the 25ml reactor;
(2) use respectively the 5ml transfer pipet, 2ml transfer pipet, 10ml transfer pipet are measured diethylenetriamine, hydrazine hydrate, deionized water 5ml, 2ml, and 12ml stirs 2min with glass stick in the 50ml beaker, it is mixed;
(3) measuring mixing solutions 15ml reactor in (1) in (2) with transfer pipet, is that the magneton of 1cm stirs 10min with diameter under the 600rpm rotating speed, it is fully dissolved and mixes;
(4) 180 ℃ of baking oven constant temperature 3d are put in the reactor sealing, then naturally cool to room temperature, use absolute ethanol washing 5 times, drying obtains yellow In in 60 ℃ of vacuum drying ovens
2Se
3(DETA)
0.5Nanometer sheet; Repeat said process, obtain the In of capacity
2Se
3(DETA)
0.5Nanometer sheet;
(5) take by weighing the yellow In that obtains in (4)
2Se
3(DETA)
0.50.5185g (1mmol), Salzburg vitriol 0.125g (0.5mmol) is in the reactor of tetrafluoroethylene in the 25ml liner, measures 20ml ethylene glycol in this reactor with graduated cylinder, and the volume that makes solution is 80% of reactor cumulative volume; This reactor is put into 160 ℃ of baking oven constant temperature 4h, naturally cool to room temperature, use respectively deionized water and absolute ethanol washing 3 times, dry 4h in 60 ℃ of vacuum drying ovens obtains the copper indium diselenide (CuInSe of black
2) nanometer sheet.
Embodiment 4:
(1) take by weighing respectively 0.142g (0.4mmol) indium bromide with electronic balance, 0.1038g (0.6mmol) Sodium Selenite is in the 25ml reactor;
(2) use respectively the 5ml transfer pipet, 2ml transfer pipet, 10ml transfer pipet are measured diethylenetriamine, hydrazine hydrate, deionized water 5ml, 2ml, and 12ml stirs 2min with glass stick in the 50ml beaker, it is mixed;
(3) measuring mixing solutions 15ml reactor in (1) in (2) with transfer pipet, is that the magneton of 1cm stirs 10min with diameter under the 600rpm rotating speed, it is fully dissolved and mixes;
(4) 180 ℃ of baking oven constant temperature 3d are put in the reactor sealing, then naturally cool to room temperature, use absolute ethanol washing 5 times, drying obtains yellow In in 60 ℃ of vacuum drying ovens
2Se
3(DETA)
0.5Nanometer sheet; Repeat said process, obtain the In of capacity
2Se
3(DETA)
0.5Nanometer sheet;
(5) take by weighing the yellow In that obtains in (4)
2Se
3(DETA)
0.50.5185g (1mmol), be in the reactor of tetrafluoroethylene without hydration cupric chloride 0.0673g (0.5mmol) in the 25ml liner, measure 15ml ethylene glycol in this reactor with graduated cylinder, the volume that makes solution is 80% of reactor cumulative volume; This reactor is put into 160 ℃ of baking oven constant temperature 4h, naturally cool to room temperature, use respectively deionized water and absolute ethanol washing 3 times, dry 4h in 60 ℃ of vacuum drying ovens obtains the copper indium diselenide (CuInSe of black
2) nanometer sheet.
Embodiment 5:
(1) take by weighing respectively 0.142g (0.4mmol) indium bromide with electronic balance, 0.1038g (0.6mmol) Sodium Selenite is in the 25ml reactor;
(2) use respectively the 5ml transfer pipet, 2ml transfer pipet, 10ml transfer pipet are measured diethylenetriamine, hydrazine hydrate, deionized water 5ml, 2ml, and 12ml stirs 2min with glass stick in the 50ml beaker, it is mixed;
(3) measuring mixing solutions 15ml reactor in (1) in (2) with transfer pipet, is that the magneton of 1cm stirs 10min with diameter under the 600rpm rotating speed, it is fully dissolved and mixes;
(4) 180 ℃ of baking oven constant temperature 3d are put in the reactor sealing, then naturally cool to room temperature, use absolute ethanol washing 5 times, drying obtains yellow In in 60 ℃ of vacuum drying ovens
2Se
3(DETA)
0.5Nanometer sheet; Repeat said process, obtain the In of capacity
2Se
3(DETA)
0.5Nanometer sheet;
(5) take by weighing the yellow In that obtains in (4)
2Se
3(DETA)
0.50.5185g (1mmol), be in the reactor of tetrafluoroethylene without hydration cupric chloride 0.0673g (0.5mmol) in the 25ml liner, measure 15ml ethylene glycol in this reactor with graduated cylinder, the volume that makes solution is 80% of reactor cumulative volume; This reactor is put into 160 ℃ of baking oven constant temperature 8h, naturally cool to room temperature, use respectively deionized water and absolute ethanol washing 3 times, dry 4h in 60 ℃ of vacuum drying ovens obtains the copper indium diselenide (CuInSe of black
2) nanometer sheet.
Embodiment 6:
(1) take by weighing respectively 0.142g (0.4mmol) indium bromide with electronic balance, 0.1038g (0.6mmol) Sodium Selenite is in the 25ml reactor;
(2) use respectively the 5ml transfer pipet, 2ml transfer pipet, 10ml transfer pipet are measured diethylenetriamine, hydrazine hydrate, deionized water 5ml, 2ml, and 12ml stirs 2min with glass stick in the 50ml beaker, it is mixed;
(3) measuring mixing solutions 15ml reactor in (1) in (2) with transfer pipet, is that the magneton of 1cm stirs 10min with diameter under the 600rpm rotating speed, it is fully dissolved and mixes;
(4) 180 ℃ of baking oven constant temperature 3d are put in the reactor sealing, then naturally cool to room temperature, use absolute ethanol washing 5 times, drying obtains yellow In in 60 ℃ of vacuum drying ovens
2Se
3(DETA)
0.5Nanometer sheet; Repeat said process, obtain the In of capacity
2Se
3(DETA)
0.5Nanometer sheet;
(5) take by weighing the yellow In that obtains in (4)
2Se
3(DETA)
0.50.5185g (1mmol), be in the reactor of tetrafluoroethylene without hydration cupric chloride 0.0673g (0.5mmol) in the 25ml liner, measure 20ml ethylene glycol in this reactor with graduated cylinder, the volume that makes solution is 80% of reactor cumulative volume; This reactor is put into 180 ℃ of baking oven constant temperature 4h, naturally cool to room temperature, use respectively deionized water and absolute ethanol washing 3 times, dry 4h in 60 ℃ of vacuum drying ovens obtains the copper indium diselenide (CuInSe of black
2) nanometer sheet.
Claims (6)
1. the method for the synthetic copper indium selenium nano tablets of an ion exchange method is characterized in that, at first take indium bromide and Sodium Selenite as reactant, with diethylenetriamine, hydrazine hydrate and deionized water are solvent, synthetic In in liner is the reactor of tetrafluoroethylene
2Se
3(DETA)
0.5Then precursor take the precursor that makes and mantoquita as reactant, take ethylene glycol as solvent, obtains copper indium selenium nano tablets through solvent thermal reaction in reactor.
2. the method for the synthetic copper indium selenium nano tablets of ion exchange method according to claim 1 is characterized in that described In
2Se
3(DETA)
0.5The precursor preparation process comprises: indium bromide and Sodium Selenite are placed reactor, diethylenetriamine, hydrazine hydrate and deionized water are mixed, the interior fully dissolving of the described reactor of rear adding that stirs, the reaction solution volume is 60% of described reactor, described reactor is placed 180 ℃ of reaction 3d, be cooled to room temperature, use absolute ethanol washing, centrifugal vacuum-drying obtains In
2Se
3(DETA)
0.5Precursor.
3. ion exchange method according to claim 1 and 2 is synthesized the method for copper indium selenium nano tablets, it is characterized in that, the mol ratio of described indium bromide and Sodium Selenite is 2:3, the volume ratio of described diethylenetriamine, hydrazine hydrate and deionized water is 5:2:12, and described vacuum-drying temperature is 60 ℃.
4. the method for the synthetic copper indium selenium nano tablets of ion exchange method according to claim 1 is characterized in that described solvent thermal reaction comprises: with the described In that makes of claim 2
2Se
3(DETA)
0.5Precursor and mantoquita place reactor, and it is even that adding ethylene glycol is done stirring solvent, and the reaction solution volume is 60 ~ 80% of reactor volume, in 160 ~ 180 ℃ of reaction 4 ~ 8h, be cooled to room temperature, with deionized water and absolute ethanol washing, centrifugal vacuum-drying obtains copper indium selenium nano tablets.
5. according to claim 1 or the method for the synthetic copper indium selenium nano tablets of 4 described ion exchange methods, it is characterized in that described In
2Se
3(DETA)
0.5The mol ratio of precursor and mantoquita is 2:1, and described mantoquita is that described vacuum-drying temperature is 60 ℃ without in hydration cupric chloride, Gerhardite, the Salzburg vitriol any one.
6. according to the copper indium selenium nano tablets of the described method preparation of claim 1 ~ 5, it is characterized in that described copper indium selenium nano tablets is mesoporous material, on average long 3 microns, wide 1.5 microns.
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