CN100494068C - Method for preparing monodisperse ternary sulfide CuInS2 - Google Patents
Method for preparing monodisperse ternary sulfide CuInS2 Download PDFInfo
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- CN100494068C CN100494068C CNB2007100407573A CN200710040757A CN100494068C CN 100494068 C CN100494068 C CN 100494068C CN B2007100407573 A CNB2007100407573 A CN B2007100407573A CN 200710040757 A CN200710040757 A CN 200710040757A CN 100494068 C CN100494068 C CN 100494068C
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- mantoquita
- sulfide
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Abstract
The invention relates to a method for preparing single-dispersive 3D sulfide CuInS2, which belongs to the field of nano-materials preparation. Chemical solution method is used to prepare the single-dispersive 3D sulfide CuInS2 nano-crystal by using alkylamine as the surfactant. First, cupric salt, indium salt, sulfer source and alkylamine are dispersed in the solvent to prepare the reaction solution, which is for solvent heat treatment to produce single-dispersive 3D sulfide CuInS2 nano-crystal with uniform shape. The invention is characterized in simple preparation, low cost and capable of synthersizing the single-dispersive 3D sulfide CuInS2 nano-crystal in large scale. And the prepared CuInS2 nano-crystal is of polyhedron shape, which is of 13-17nm in size and capable of self assembly in a wide range to produce single-layer nano-superlattice.
Description
Technical field
The present invention relates to a kind of monodisperse ternary sulfide CuInS
2The preparation method, adopt the hot method of chemical solvents to prepare monodispersed ternary sulfide CuInS
2Belong to the nano material preparation technical field.
Background technology
Because the physicochemical property of size and morphology control and in the important application in fields such as optics, electricity, catalysis, biosensor, data storage, monodispersed inorganic nanocrystal has attracted increasing attention in the more than ten years in the past.Especially semi-conductor binary sulfide (as CdS, CdSe, CdTe, PbS, ZnS, MnS etc.), because the optical property that its quantum confined effect and size rely on, the preparation of its gluey dispersed nano material and performance study have been obtained significant achievement.Yet owing to lack suitable synthetic method, the research of monodisperse ternary sulfide has lagged far behind the research of binary sulfide.Therefore, how to control synthetic gluey monodispersed ternary sulfide and still have very big difficulty.I-III-VI
2(I=Cu, Ag; III=Ga, In; VI=S, Se Te) is the functional materials of a series of excellent performances, it has important use at aspects such as photovoltaic solar cell, light emitting diode, linearity and nonlinear optics instruments.Wherein, CuInS
2Be a kind of very important functional materials, its distinctive high specific absorbance (α ≈ 5 * 10
5Cm
-1), (1.45eV approaches sunlight 1.1≤Eg≤1.5eV), lower production cost and nontoxicity makes it to become the good photoelectric conversion material that can be applied to solar cell for best band-gap energy.At present, based on CuInS
2The solar cell of material can reach light turnover ratio near 18% in breadboard scale.Theoretical investigation thinks that this higher light turnover ratio generally is because the hole energy barrier of grain boundary has stoped the P-N knot of the compound and random formation in electronics-hole to cause.Therefore, synthetic monodispersed monocrystalline CuInS
2Nanocrystallinely a large amount of grain boundaries and P-N knot will be produced, thereby its opto-electronic conversion performance might be improved greatly.Yet just present CuInS
2Synthetic method, quadrol solvent-thermal method, chemical heat solution and high temperature roast method etc. generally obtain is erose product or serious random nano material of reuniting, have or even body phase material.Though and metal organic supramolecular precursor pyrolysis method also can obtain monodispersed CuInS
2Nanocrystalline, but because the building-up process of its used unit molecule precursor is very loaded down with trivial details, production cost is very high and the hypertoxicity of precursor itself, makes this method be subjected to great restriction in the further popularization of Application Areass such as photovoltaic solar cell.
Summary of the invention
The object of the invention is at the prior art deficiency, provide a kind of simple to operate, production cost is low, can obtain monodispersed Cu InS
2Preparation of nano crystal.
For realizing such purpose, in the technical scheme of the present invention, be tensio-active agent with the alkylamine, be the sulphur source with dithiocarbonic anhydride, with the methyl-phenoxide reaction solvent, adopt chemical solution methyl-phenoxide solvent thermal to prepare ternary sulfide CuInS
2Nanocrystalline.At first mantoquita, indium salt, sulphur source and alkylamine are dissolved in the methyl-phenoxide preparation feedback liquid; The reaction solution that just prepares is then handled under the solvent thermal condition, can obtain the monodisperse ternary sulfide CuInS of pattern rule
2Nanocrystalline.
Preparation method of the present invention comprises following concrete steps:
1. the preparation of chemical reaction liquid: mantoquita, indium salt, alkylamine surfactant, dithiocarbonic anhydride mixing are dissolved in the methyl-phenoxide, preparation feedback liquid, wherein the concentration of mantoquita is 0.01～0.05mol1
-1, indium salt and mantoquita mol ratio be that the mol ratio of 1:1, tensio-active agent and mantoquita is 6～15, the mol ratio of dithiocarbonic anhydride and mantoquita is 20～40.
The said mantoquita of the present invention is that neutralized verdigris, indium salt are indium chloride, and described tensio-active agent is cetylamine, stearylamine or oleyl amine, and reaction solvent is a methyl-phenoxide, and the sulphur source is a dithiocarbonic anhydride.
2. monodisperse ternary sulfide CuInS
2Nanocrystalline is synthetic: reaction solution is moved into the autoclave that has polytetrafluoroethylliner liner, after 200 ℃ of solvent heat treatment 12-24 hours, naturally cool to about 60-70 ℃, the methyl alcohol that adds reaction solution cumulative volume 20～30%, then with the product centrifugation, with absolute ethanol washing for several times, vacuum is drained, and promptly obtains monodisperse ternary sulfide CuInS
2Nanocrystalline.
Excellent results of the present invention is:
1. because to have adopted alkylamine be tensio-active agent, make CuInS
2Nanocrystal in the process of growth, reach better controlled growth, to CuInS
2Nanocrystal played the better protecting effect, prevented nanocrystalline reunion, make it to have good distribution of sizes and pattern homogeneity.
2. because the present invention has adopted the chemical solution method reaction, and raw material is cheap, simple to operate, cost is low, efficient is high, is easy to further industrial production.The CuInS of preparation
2Nanocrystalline is polyhedron-shaped, and its size is the 13-17 nanometer, and can be on a large scale self-assembly form the nano super-lattice of individual layer.
Description of drawings
Fig. 1 is the ternary sulfide CuInS of the embodiment of the invention 1 gained
2Nanocrystalline thing phase composite collection of illustrative plates wherein, (a) is X-ray diffraction collection of illustrative plates, (b) is energy dispersive X-ray spectra.
Fig. 2 is the ternary sulfide CuInS of the embodiment of the invention 1 gained
2The transmission electron microscope photo of nanocrystalline different amplification.
Fig. 3 is the embodiment of the invention 2 gained ternary sulfide CuInS
2Nanocrystalline high-resolution-ration transmission electric-lens photo.
Fig. 4 is the embodiment of the invention 3 gained ternary sulfide CuInS
2Nanocrystalline transmission electron microscope photo.
Embodiment
Below by specific embodiment technical scheme of the present invention is further described.The following examples are to further specify of the present invention, and do not limit the scope of the invention.
Embodiment 1
1. in the flask of a 100ml, the neutralized verdigris of 0.4mmol, the indium chloride of 0.4mmol, the stearylamine of 4mmol are joined in the methyl-phenoxide of 39ml, be heated to 60 ℃ and keep after 1 hour adding 0.5ml dithiocarbonic anhydride, continue magnetic agitation in the time of adding, be prepared into CuInS
2Nanocrystalline reaction solution.
2. will move into according to the reaction solution that 1. step prepares and have in the autoclave of 50ml polytetrafluoroethylliner liner, 200 ℃ the reaction 12 hours after, reactor naturally cools to 60 ℃, add 10ml methyl alcohol, after the centrifugation, with absolute ethanol washing for several times, vacuum is drained sample, can obtain monodisperse ternary sulfide CuInS
2Nanocrystalline.
Resulting monodisperse ternary sulfide CuInS
2Nanocrystalline X-x ray diffration pattern x such as Fig. 1 a.Prepared as seen from the figure material is the CuInS of tetragonal structure
2Fig. 1 b obtains CuInS
2Nanocrystalline energy dispersive X-X-ray analysis X collection of illustrative plates, the contained element of prepared as seen from the figure material is copper, indium and sulphur, three's atom content meets CuInS than for 1:0.92:2.06
2Nanocrystalline stoichiometric ratio.Carbon signal wherein comes from CuInS
2The cetylamine that nanocrystal surface coats, the oxygen carbon signal comes from CuInS
2The oxygen of nanocrystalline a spot of oxidation or air the inside.Fig. 2 is gained CuInS
2The transmission electron microscope photo of different amplification.By Fig. 2 a as seen, this CuInS
2Nanocrystalline can be on a large scale self-assembly form the nano super-lattice of individual layer, illustrate that this method can synthesize gelationus monodispersed Cu InS on a large scale
2Nanocrystalline.From transmission electron microscope photo Fig. 2 b of bigger magnification as can be seen, gained CuInS
2The nanocrystalline 13-17 nanometer that is of a size of has good distribution of sizes, and its pattern is polyhedron-shaped.
1. in the flask of a 100ml, the neutralized verdigris of 0.4mmol, the indium chloride of 0.4mmol, the cetylamine of 3.6mmol are joined in the methyl-phenoxide of 39ml, be heated to 60 ℃ and keep after 1 hour adding 1ml dithiocarbonic anhydride, continue magnetic agitation in the time of adding, be prepared into CuInS
2Nanocrystalline reaction solution.
2. will move into according to the reaction solution that 1. step prepares and have in the autoclave of 50ml polytetrafluoroethylliner liner, in 200 ℃ of solvent thermal after 24 hours, reactor naturally cools to 60 ℃, add 10ml methyl alcohol, after the centrifugation, with absolute ethanol washing for several times, vacuum is drained sample, promptly can obtain to be similar to the monodisperse ternary sulfide CuInS of embodiment 1
2Nanocrystalline.
Fig. 3 is resulting ternary sulfide CuInS
2Nanocrystalline high-resolution-ration transmission electric-lens photo.As seen from the figure, this ternary sulfide CuInS
2Nanocrystalline have a lattice fringe clearly, and synthetic CuInS is described
2Nanocrystalline is the single crystal structure of highly crystalline.Wherein 2.80
Spacing corresponding to cubic CuInS
2The d value of [004] face, CuInS is described
2Nanocrystalline edge＜001 the quick growth of direction, and it is at＜00-1 growth restriction on the direction, thereby it is nanocrystalline to have formed pyramidal polyhedron.
Embodiment 3
1. in the flask of a 100ml, the neutralized verdigris of 0.8mmol, the indium chloride of 0.8mmol, the oleyl amine of 12mmol are joined in the methyl-phenoxide of 39ml, be heated to 60 ℃ and keep after 1 hour adding 0.5ml dithiocarbonic anhydride, continue magnetic agitation in the time of adding, be prepared into CuInS
2Nanocrystalline reaction solution.
2. will move into according to the reaction solution that 1. step prepares and have in the autoclave of 50ml polytetrafluoroethylliner liner, in 200 ℃ of solvent thermal after 24 hours, reactor naturally cools to 60 ℃, add 10ml methyl alcohol, after the centrifugation, with absolute ethanol washing for several times, vacuum is drained sample, promptly can obtain monodisperse ternary sulfide CuInS
2Nanocrystalline.
Fig. 4 is resulting monodisperse ternary sulfide CuInS
2Nanocrystalline transmission electron microscope photo.As seen from the figure, the pattern of the product of this embodiment, size and embodiment 1 and can be self-assembled into the nano super-lattice of individual layer similar to Example 1 much at one.
Claims (1)
1, a kind of monodisperse ternary sulfide CuInS
2The preparation method, it is characterized in that may further comprise the steps:
1) preparation of chemical reaction liquid: mantoquita, indium salt, tensio-active agent, dithiocarbonic anhydride mixing are dissolved in the methyl-phenoxide, are mixed with reaction solution; Wherein the concentration of mantoquita is 0.01～0.05moll
-1, the mol ratio of indium salt and mantoquita is 1:1, and the mol ratio of tensio-active agent and mantoquita is 6～15, and the mol ratio of dithiocarbonic anhydride and mantoquita is 20～40; Described mantoquita is a neutralized verdigris, and described indium salt is indium chloride, and described tensio-active agent is cetylamine, stearylamine or oleyl amine;
2) monodisperse ternary sulfide CuInS
2Nanocrystalline is synthetic: reaction solution is moved into the autoclave that has polytetrafluoroethylliner liner, after 200 ℃ of solvent heat treatment 12-24 hours, naturally cool to 60-70 ℃, the methyl alcohol that adds reaction solution cumulative volume 20～30%, with the product centrifugation, with absolute ethanol washing for several times, vacuum is drained, and promptly obtains monodisperse ternary sulfide CuInS
2Nanocrystalline.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101844799A (en) * | 2010-06-17 | 2010-09-29 | 安阳师范学院 | Preparation method of hexagon stannic disulphide nano slice |
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| CN101870458B (en) * | 2009-04-22 | 2012-05-09 | 钟润文 | Preparation methods of multi-element metal chalcogen compound, target and coating material |
| CN101885509B (en) * | 2010-07-23 | 2013-01-09 | 河南大学 | Method for preparing nanometer CuInS2 |
| CN102041555A (en) * | 2011-01-14 | 2011-05-04 | 南开大学 | Preparation method of CuInS2 nanocrystalline material |
| WO2012163976A1 (en) | 2011-06-03 | 2012-12-06 | Bayer Intellectual Property Gmbh | Continuous process for the synthesis of ternary or quaternary semiconducting nanoparticles based on ib, iiia, via elements of the periodic classification |
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| CN108380169B (en) * | 2018-02-11 | 2020-07-14 | 华北电力大学 | Layered metal sulfide NaInS for removing radionuclide U (VI)2And preparation thereof |
| CN112520716B (en) * | 2020-11-27 | 2022-11-01 | 国家纳米科学中心 | Two-dimensional layered CuInP2S6 semiconductor material and preparation method thereof |
| CN115197695B (en) * | 2021-04-14 | 2024-01-19 | 中国科学院理化技术研究所 | CuInS 2 Preparation method of quantum dot superlattice structure |
| CN114250473B (en) * | 2022-03-01 | 2022-06-07 | 青岛理工大学 | Iron oxide based Z-shaped heterojunction composite photo-anode film and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101844799A (en) * | 2010-06-17 | 2010-09-29 | 安阳师范学院 | Preparation method of hexagon stannic disulphide nano slice |
| CN101844799B (en) * | 2010-06-17 | 2012-05-09 | 安阳师范学院 | Preparation method of hexagon stannic disulphide nano slice |
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