CN105417503A - Method for preparing CuGaSe2 nano-crystals through water phase method - Google Patents

Method for preparing CuGaSe2 nano-crystals through water phase method Download PDF

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CN105417503A
CN105417503A CN201511026900.4A CN201511026900A CN105417503A CN 105417503 A CN105417503 A CN 105417503A CN 201511026900 A CN201511026900 A CN 201511026900A CN 105417503 A CN105417503 A CN 105417503A
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reaction
gallium
nanocrystalline
nano
cugase
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CN105417503B (en
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房永征
郑新峰
刘玉峰
侯京山
张娜
赵国营
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Shanghai Institute of Technology
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Shanghai Institute of Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/30—Three-dimensional structures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention discloses a method for preparing CuGaSe2 nano-crystals through a water phase method. The method includes the steps that firstly, a copper salt precursor, a gallium salt precursor, selenosulfate and deionized water are added to a three-opening flask and stirred in the inert atmosphere, then the temperature is raised for a reaction, heating is stopped after the reaction is completed, a reactant is cooled, methyl alcohol is added to the cooled reactant, nano-particles settle, and finally the nano-crystals are centrifugally collected. The method has the advantages that experiment operation is easy, the reaction precursors are cheap, the reaction temperature is low, and the obtained nano-crystals are uniform in diameter.

Description

A kind of Aqueous phase prepares CuGaSe 2nanocrystalline method
Technical field
The invention belongs to photovoltaic material technical field, be specifically related to a kind of Aqueous phase and prepare CuGaSe 2nanocrystalline method.
Background technology
Along with the progress of society, energy problem has become the significant problem that human survival and development faces.Be the photovoltaic technology of electric energy by solar energy converting be do not solve the important means of energy problem.Reduce device cost, improving device efficiency is be engaged in the major objective that solar cell material and device investigator pursue.
Copper base sulfide is the important semiconductor compound of a class, and these compounds are widely used in the fields such as solar cell, transistor, photo-detector and temperature-sensitive device.Copper base sulfide film, as solar battery obsorbing layer, mainly comprises the Cu of binary 2s, the CuInS of ternary 2, CuGaSe 2, CuInSe 2with quaternary compound Cu 2znSnS 4deng.Recently find these copper base sulfide to be prepared into nanocrystalline ink, nanocrystalline ink solar cell material cost is low, manufacture craft is simple, copper base sulfide film can be prepared by printing simple technique, effectively reduce the cost of manufacture of film absorption layer and the dependence to expensive huge vacuum installations, for the solar cell device of lower price high efficiency provides wide prospect.Existing a lot of about Cu at present 2s, CdTe, PbSe, CuInS 2, CuInSe 2with Cu (In, Ga) Se 2etc. the report of nanocrystalline device.In numerous semiconductor nano, chalcopyrite structure semiconductor is nanocrystalline is the photovoltaic device material of excellent performance.CuGaSe 2be a kind of copper base sulfide material of yellow copper structure, it has the direct band gap that mates very much with solar spectrum and the high absorption coefficient to visible ray, becomes most potential novel thin film solar cell material, CuGaSe 2thin-film material is widely studied as solar cell absorption layer.In addition, CuGaSe 2middle Cu, Ga and Se element does not have toxicity, can not work the mischief to environment.
Current synthesis CuGaSe 2nanocrystalline main method is by liquid phase process such as heat injection and solvent thermal, usually the organic solvent of Long carbon chain is used in these methods, as oleyl amine, oleic acid, octadecylene etc., and Se source needs can dissolve at comparatively high temps usually, the temperature of reaction that Syntheses needs 200-280 DEG C is usually carried out in these solvents, there be limited evidence currently of has experiment by water solution system, and namely the temperature of less than 100 DEG C prepares CuGaSe 2nanocrystalline.Therefore, how to obtain the Se presoma of dissolution in low temperature, and at low temperature (less than 100 DEG C) synthesis CuGaSe 2nanocrystalline is a job with practical significance.
Summary of the invention
In order to overcome the deficiencies in the prior art, object of the present invention aims to provide a kind of Aqueous phase and prepares CuGaSe 2nanocrystalline method.The inventive method is simple to operate, and temperature of reaction is low, and element chemistry metering is more accurate than controlling, and persursor material used is with low cost, nontoxicity.
Method of the present invention is: by mantoquita presoma, gallium salt precursor body, sodium thiosulfate and deionized water, join in there-necked flask, stirs all presomas in an inert atmosphere and dissolves; Then temperature is raised reaction, reacted and stopped heating that reactant is cooled; Add methyl alcohol in the most backward cooled reaction product and make nanoparticle sedimentation, collected by centrifugation is nanocrystalline.Technical solution of the present invention is specifically described as follows.
The invention provides a kind of Aqueous phase and prepare CuGaSe 2nanocrystalline method, concrete steps are as follows:
First the deionized water of 0.1-10mmol mantoquita presoma, 0.1-10mmol gallium salt precursor body, 0.5-20mmol sodium thiosulfate and 5-20mL is joined in there-necked flask, stir in an inert atmosphere; Then temperature of reaction is increased to 70-90 DEG C of reaction 10-60min, after reaction terminates, naturally cooling; Add methyl alcohol in the most backward cooled reaction solution, make nanoparticle sedimentation, then collected by centrifugation is nanocrystalline.
In the present invention, described mantoquita presoma to be selected from cupric chloride, cupric acetylacetonate, neutralized verdigris, cupric nitrate or copper sulfate any one.
In the present invention, described gallium salt precursor body to be selected from gallium nitrate, gallium trichloride, methyl ethyl diketone gallium or gallium oxide any one.
In the present invention, during collected by centrifugation, rotating speed is that 3000-14000 turns/min, and centrifugation time is 1-10 minute.
Beneficial effect of the present invention is: experimental implementation is simple, and precursors is cheap, and temperature of reaction is lower, the nanocrystalline uniform particle diameter obtained.
Accompanying drawing explanation
Fig. 1 is CuGaSe prepared by the embodiment of the present invention 1 2nanocrystalline X ray diffracting spectrum.
Fig. 2 is that the embodiment of the present invention 1 prepares CuGaSe 2nanocrystalline scanning electron microscope (SEM) photograph.
Fig. 3 is that the embodiment of the present invention 1 prepares CuGaSe 2nanocrystalline crystalline structure figure.
Embodiment
Below in conjunction with drawings and Examples, the present invention is elaborated further.
Embodiment 1
Successively by the deionized water of reactant presoma 10mL, 0.5mmol cupric chloride, 0.5mmol gallium nitrate, 0.5mmol sodium thiosulfate adds in there-necked flask, is stirred to presoma and all dissolves in argon atmosphere, then temperature of reaction is increased to 80 DEG C of reaction 10min, stop heating, reactant is cooled, then in cooled reaction product, adds methyl alcohol make nanoparticle sedimentation, then within 1 minute, collect nanocrystalline with the centrifugation of 3000 turns/min.Fig. 1 is CuGaSe prepared by the present invention 2nanocrystalline X ray diffracting spectrum.Fig. 2 is that the present invention prepares CuGaSe 2nanocrystalline scanning electron microscope (SEM) photograph, nanocrystalline median size is 260 nanometers.Fig. 3 is that the present invention prepares CuGaSe 2nanocrystalline crystalline structure figure.
Embodiment 2
Successively the deionized water of reactant presoma 5mL, 0.1mmol cupric nitrate, 0.1mmol gallium chloride, 0.1mmol sodium thiosulfate are added in there-necked flask, in argon atmosphere, be stirred to presoma all dissolve, then temperature of reaction is increased to 85 DEG C of reaction 20min, stop heating, reactant is cooled, in cooled reaction product, add methyl alcohol again and make nanoparticle sedimentation, then within 7 minutes, collect nanocrystalline with the centrifugation of 6000 turns/min, nanocrystalline median size is 265 nanometers.
Embodiment 3
Successively the deionized water of reactant presoma 20mL, 10mmol neutralized verdigris, 10mmol methyl ethyl diketone gallium, 10mmol sodium thiosulfate are added in there-necked flask, in argon atmosphere, be stirred to presoma all dissolve, then temperature of reaction is increased to 90 DEG C of reaction 50min, stop heating, reactant is cooled, in cooled reaction product, add methyl alcohol again and make nanoparticle sedimentation, then within 80 minutes, collect nanocrystalline with the centrifugation of 8000 turns/min, nanocrystalline median size is 265 nanometers.
Embodiment 4
Successively the deionized water of reactant presoma 17mL, 0.6mmol copper sulfate, 0.6mmol gallium oxide, 0.6mmol sodium thiosulfate are added in there-necked flask, in argon atmosphere, be stirred to presoma all dissolve, then temperature of reaction is increased to 70 DEG C of reaction 60min, stop heating, reactant is cooled, in cooled reaction product, add methyl alcohol again and make nanoparticle sedimentation, then within 10 minutes, collect nanocrystalline with the centrifugation of 14000 turns/min, nanocrystalline median size is 250 nanometers.
Embodiment 5
Successively the deionized water of reactant presoma 12mL, 0.7mmol acetylacetone copper, 0.7mmol gallium nitrate, 0.7mmol sodium thiosulfate are added in there-necked flask, in argon atmosphere, be stirred to presoma all dissolve, then temperature of reaction is increased to 75 DEG C of reaction 30min, stop heating, reactant is cooled, in cooled reaction product, add methyl alcohol again and make nanoparticle sedimentation, then within 5 minutes, collect nanocrystalline with the centrifugation of 9000 turns/min, nanocrystalline median size is 255 nanometers.
Embodiment 6
Successively the deionized water of reactant presoma 16mL, 0.8mmol cupric chloride, 0.8mmol gallium chloride, 0.8mmol sodium thiosulfate are added in there-necked flask, in argon atmosphere, be stirred to presoma all dissolve, then temperature of reaction is increased to 78 DEG C of reaction 40min, stop heating, reactant is cooled, in cooled reaction product, add methyl alcohol again and make nanoparticle sedimentation, then within 6 minutes, collect nanocrystalline with the centrifugation of 7000 turns/min, nanocrystalline median size is 258 nanometers.

Claims (4)

1. an Aqueous phase prepares CuGaSe 2nanocrystalline method, is characterized in that, concrete steps are as follows:
First the deionized water of 0.1-10mmol mantoquita presoma, 0.1-10mmol gallium salt precursor body, 0.5-20mmol sodium thiosulfate and 5-20mL is joined in there-necked flask, stir in an inert atmosphere; Then temperature of reaction is increased to 70-90 DEG C of reaction 10-60min, after reaction terminates, naturally cooling; Add methyl alcohol in the most backward cooled reaction solution, make nanoparticle sedimentation, then collected by centrifugation CuGaSe 2nanocrystalline.
2. method according to claim 1, is characterized in that: described mantoquita presoma to be selected from cupric chloride, cupric acetylacetonate, neutralized verdigris, cupric nitrate or copper sulfate any one.
3. method according to claim 1, is characterized in that: described gallium salt precursor body to be selected from gallium nitrate, gallium trichloride, methyl ethyl diketone gallium or gallium oxide any one.
4. method according to claim 1, is characterized in that: during collected by centrifugation, and rotating speed is that 3000-14000 turns/min, and centrifugation time is 1-10 minute.
CN201511026900.4A 2015-12-31 2015-12-31 A kind of Aqueous phase prepares CuGaSe2Nanocrystalline method Expired - Fee Related CN105417503B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113104819A (en) * 2021-04-08 2021-07-13 河南大学 Copper-gallium-selenium nanocrystalline and perovskite solar cell prepared by using same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1443707A (en) * 2003-04-17 2003-09-24 上海交通大学 Preparation method of nano copper selenide
CN101804971A (en) * 2010-04-19 2010-08-18 西安交通大学 Preparation method of copper indium selenide nanocrystalline material
CN102476791A (en) * 2010-11-25 2012-05-30 马瑞新 Method for preparing copper indium diselenide nanometer powder

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1443707A (en) * 2003-04-17 2003-09-24 上海交通大学 Preparation method of nano copper selenide
CN101804971A (en) * 2010-04-19 2010-08-18 西安交通大学 Preparation method of copper indium selenide nanocrystalline material
CN102476791A (en) * 2010-11-25 2012-05-30 马瑞新 Method for preparing copper indium diselenide nanometer powder

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JIANG TANG ET AL.: "Synthesis of Colloidal CuGaSe2,CuInSe2,and Cu(InGa)Se2 Nanoparticles", 《CHEMISTRY OF MATERIALS》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113104819A (en) * 2021-04-08 2021-07-13 河南大学 Copper-gallium-selenium nanocrystalline and perovskite solar cell prepared by using same

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