CN103086330A - Preparation method of CuCdSnSe semiconductor nanocrystals - Google Patents
Preparation method of CuCdSnSe semiconductor nanocrystals Download PDFInfo
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- CN103086330A CN103086330A CN2013100458335A CN201310045833A CN103086330A CN 103086330 A CN103086330 A CN 103086330A CN 2013100458335 A CN2013100458335 A CN 2013100458335A CN 201310045833 A CN201310045833 A CN 201310045833A CN 103086330 A CN103086330 A CN 103086330A
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Abstract
The invention discloses a preparation method of CuCdSnSe semiconductor nanocrystals. The method comprises the following steps: dissolving selenium powder in a high-boiling-point oily solvent to form a selenium precursor, rapidly injecting the selenium precursor into a high-temperature metal precursor composed of a copper salt, a cadmium salt, a tin salt, high-boiling-point alkylamine and the high-boiling-point oily solvent, reacting for a preset period of time, taking out the obtained reaction mixture, and injecting the reaction mixture into a precipitating agent for precipitating a product in order to obtain the high-quality CuCdSnSe semiconductor nanocrystals. The preparation method of the nano-crystals has the advantages of simplicity, safe operation process, and low cost of reaction raw materials; and the prepared nano-crystals have the advantages of uniform morphology, consistent dimension and good crystallinity. The nano-crystals prepared in the invention can be used as a thermo-electric device material.
Description
Technical field
The invention belongs to the semiconductor nanocrystal field, be specifically related to a kind of preparation method of copper cadmium tin selenium semiconductor nanocrystal.
Background technology
Just found thermoelectric effect as far back as 19 th Century French physicist Pei Erjie, the conductor that is about to differing materials couples together, and passes into the conductor that electric current forms behind the loop at point of contact place differing materials and can absorb or emit heat.Yet because the conversion efficiency of thermoelectric of metal is usually very low, so be not converted into soon application.Until the 1950's, some semiconductor materials with good thermo-electric conversion performance are found, particularly freon refrigerant disabled after, the research of thermoelectric material becomes heat subject gradually.
The performance of thermoelectric material and himself intrinsic physics parameter are closely related, and that determine the pyroelectric material performance quality is combination parameter Z=(σ α
2)/κ, σ wherein, α and κ are respectively specific conductivity, and Seebeck coefficient and thermal conductivity need make combination parameter Z increase if will improve the performance of thermoelectric material.People study more thermoelectric material and mainly contain CoSb at present
3, BaZn
2Sb
2, Bi
2Te
3With PbTe etc., because its thermoelectricity capability is that the Z value is high not enough, make the thermal power unit based on these materials be difficult to and traditional refrigeration or generating set competition.Therefore, if want to break through thermo-electric device because of the not enough suffered restriction of performance, to carry out improvement in performance to existing thermoelectric material on the one hand, need on the other hand to develop the new material with higher thermoelectricity capability and replace current material.
Recently find, by regulating Cu
2MSnQ
4(M=Zn, Cd; Q=S, Se) ratio of Cu and M can greatly be improved the thermoelectricity capability of material in the body of powder material, and this makes Cu
2MSnQ
4Become a kind of very potential thermoelectric material.As everyone knows, low-dimension nano material because having the traditional not available unique physical of body material and chemical property, becomes the main direction of present Materials science research as semiconductor nanocrystal, nano wire etc.Thermoelectric material is no exception, and increasing thermoelectric material device is made by low-dimension nano material.Therefore, preparation Cu
2CdSnSe
4Semiconductor nanocrystal also has very important significance to thermoelectric property research of its material.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of copper cadmium tin selenium semiconductor nanocrystal.
Method of the present invention is first metallic salt reactant and selenium powder to be dissolved in respectively formation metal precursor and selenium presoma in solution, then the metal precursor of selenium presoma injection high temperature is reacted to obtain nanocrystal.
In the present invention, the preparation method of copper cadmium tin selenium semiconductor nanocrystal comprises the steps:
1). the preparation of metal precursor: with mantoquita, cadmium salt and pink salt metallic salt reactant, high boiling point alkylamine and high boiling point oil-based solvent are packed in reaction vessel, are stirred to dissolving fully;
In metal precursor, material mixture ratio is:
The mol ratio of mantoquita and cadmium salt is that 3:1 is between 1:1;
The mol ratio of mantoquita and pink salt is that 3:1 is between 1:1;
The mol ratio of metallic salt and alkylamine is that 1:2 is between 1:15;
In the metal precursor of preparation, the metallic salt total concn is that 0.05mol/L is between 0.1mol/L;
2). the preparation of selenium presoma:
Selenium powder and high boiling point oil-based solvent are added in another reaction vessel, be heated to 180-220 ℃ in inert atmosphere selenium powder is dissolved fully;
Perhaps selenium powder, tri octyl phosphine and high boiling point oil-based solvent are added in sealable container, seal in inert atmosphere, then the ultrasonic selenium powder that makes dissolves fully; Wherein, tri octyl phosphine and selenium powder mol ratio are that 1.25:1 is between 2:1;
In the selenium presoma, the concentration of selenium is that 0.1mol/L is between 0.5mol/L;
3). the metal precursor for preparing is heated to 260-300 ℃ in inert atmosphere, the selenium presoma is injected wherein fast, reacted 0.5-60 minute, take out reaction mixture and inject precipitation agent, collecting precipitation is copper cadmium tin selenium semiconductor nanocrystal; The blending ratio of two kinds of presomas is: the mol ratio of metallic salt and selenium is that 1:1 is between 1:5.
Described mantoquita is cuprous iodide, cuprous chloride, neutralized verdigris or cupric acetylacetonate.
Described cadmium salt is cadmium acetate, Cadmium chloride fine powder, cadmium oleate or cadmium stearate.
Described pink salt is tin acetate, tin tetrachloride, tindichloride or dibromo acetopyruvic acid tin.
Described high boiling point alkylamine be under normal pressure boiling point greater than oleyl amine, hexadecylamine or the octadecylamine of 300 ℃.
Described high boiling point oil-based solvent be under normal pressure boiling point greater than vaccenic acid or the whiteruss of 300 ℃.
Described precipitation agent is methyl alcohol, ethanol or acetone.
The invention has the advantages that: nanocrystalline preparation method is simple, and persursor material used is with low cost, suitable synthetic in batches.The nanocrystal pattern of preparation evenly, consistent size, good crystallinity, can be used as the thermo-electric device material.
Description of drawings
Fig. 1 is the images of transmissive electron microscope of copper cadmium tin selenium semiconductor nanocrystal of the present invention.
Fig. 2 is the single particle high-resolution-ration transmission electric-lens image of copper cadmium tin selenium semiconductor nanocrystal of the present invention.
Fig. 3 is the absorption spectrum of copper cadmium tin selenium semiconductor nanocrystal of the present invention.
Embodiment
Embodiment 1:
0.5mmol cuprous iodide, 0.25mmol cadmium acetate, 0.25mmol tin acetate, 3mmol oleyl amine and 9ml vaccenic acid are packed in the reaction vessel there-necked flask, and being stirred to fully, dissolving forms metal precursor.1mmol selenium powder and 4ml vaccenic acid are added in another there-necked flask, be heated to 190 ℃ and make selenium powder dissolve formation selenium presoma fully in nitrogen atmosphere.The metal precursor temperature of reaction is elevated to 300 ° of C in nitrogen atmosphere, then the selenium presoma is injected wherein fast, react 0.5 minute taking-up reaction mixture injection methyl alcohol and make the nanocrystal precipitation, collect nanocrystal.In this embodiment, the mol ratio of mantoquita and cadmium salt is 2:1, the mol ratio of mantoquita and pink salt is 2:1, the mol ratio of metallic salt and oleyl amine is 1:3, the metallic salt total concn is 0.1mol/L, the concentration of selenium is 0.25mol/L, and the mol ratio that two kinds of presoma blending ratios are metallic salt and selenium is 1:1.
Embodiment 2:
0.6mmol cuprous chloride, 0.2mmol Cadmium chloride fine powder, 0.2mmol tin tetrachloride, 2mmol hexadecylamine and 19.4ml whiteruss are packed in the reaction vessel there-necked flask, and being stirred to fully, dissolving forms metal precursor.2mmol selenium powder and 10ml whiteruss are added in another there-necked flask, be heated to 180 ℃ and make selenium powder dissolve formation selenium presoma fully in nitrogen atmosphere.The metal precursor temperature of reaction is elevated to 260 ° of C in nitrogen atmosphere, then the selenium presoma is injected wherein fast, react 5 minutes taking-up reaction mixture injection ethanol and make the nanocrystal precipitation, collect nanocrystal.In this embodiment, the mol ratio of mantoquita and cadmium salt is 3:1, the mol ratio of mantoquita and pink salt is 3:1, the mol ratio of metallic salt and hexadecylamine is 1:2, the metallic salt total concn is 0.05mol/L, the concentration of selenium is 0.2mol/L, and the mol ratio that two kinds of presoma blending ratios are metallic salt and selenium is 1:2.
Embodiment 3:
0.4mmol cupric acetylacetonate, 0.4mmol cadmium stearate, 0.2mmol tindichloride, 9mmol octadecylamine and 13ml vaccenic acid are packed in the reaction vessel there-necked flask, and being stirred to fully, dissolving forms metal precursor.1mmol selenium powder and 10ml vaccenic acid are added in another there-necked flask, be heated to 220 ℃ and make selenium powder dissolve formation selenium presoma fully in nitrogen atmosphere.The metal precursor temperature of reaction is elevated to 280 ° of C in nitrogen atmosphere, then the selenium presoma is injected wherein fast, react 60 minutes taking-up reaction mixture injection acetone and make the nanocrystal precipitation, collect nanocrystal.In this embodiment, the mol ratio of mantoquita and cadmium salt is 1:1, the mol ratio of mantoquita and pink salt is 2:1, the mol ratio of metallic salt and octadecylamine is 1:9, the metallic salt total concn is 0.0625mol/L, the concentration of selenium is 0.1mol/L, and the mol ratio that two kinds of presoma blending ratios are metallic salt and selenium is 1:1.
Embodiment 4:
0.4mmol neutralized verdigris, 0.2mmol cadmium oleate, 0.4mmol dibromo acetopyruvic acid tin, 15mmol oleyl amine and 15ml vaccenic acid are packed in the reaction vessel there-necked flask, and being stirred to fully, dissolving forms metal precursor.2mmol selenium powder, 4mmol tri octyl phosphine and 2.2ml vaccenic acid are added in pear shape bottle, and after sealing, the ultrasonic selenium powder that makes dissolves formation selenium presoma fully in nitrogen atmosphere.The metal precursor temperature of reaction is elevated to 270 ° of C in nitrogen atmosphere, then the selenium presoma is injected wherein fast, react 35 minutes taking-up reaction mixture injection methyl alcohol and make the nanocrystal precipitation, collect nanocrystal.In this embodiment, the mol ratio of mantoquita and cadmium salt is 2:1, the mol ratio of mantoquita and pink salt is 1:1, the mol ratio of metallic salt and oleyl amine is 1:15, the metallic salt total concn is 0.05mol/L, the mol ratio of tri octyl phosphine and selenium is 2:1, the concentration of selenium is 0.5mol/L, and the mol ratio that two kinds of presoma blending ratios are metallic salt and selenium is 1:2.
Embodiment 5:
0.5mmol cuprous chloride, 0.25mmol cadmium acetate, 0.25mmol tin acetate, 3mmol oleyl amine and 11.5ml vaccenic acid are packed in the reaction vessel there-necked flask, and being stirred to fully, dissolving forms metal precursor.5mmol selenium powder, 7.5mmol tri octyl phosphine and 6.5ml vaccenic acid are added in pear shape bottle, and after sealing, the ultrasonic selenium powder that makes dissolves formation selenium presoma fully in nitrogen atmosphere.The metal precursor temperature of reaction is elevated to 300 ° of C in argon gas atmosphere, then the selenium presoma is injected wherein fast, react 15 minutes taking-up reaction mixture injection ethanol and make the nanocrystal precipitation, collect nanocrystal.In this embodiment, the mol ratio of mantoquita and cadmium salt is 2:1, the mol ratio of mantoquita and pink salt is 2:1, the mol ratio of metallic salt and oleyl amine is 1:3, the metallic salt total concn is 0.08mol/L, the mol ratio of tri octyl phosphine and selenium is 1.5:1, the concentration of selenium is 0.5mol/L, and the mol ratio that two kinds of presoma blending ratios are metallic salt and selenium is 1:5.
Embodiment 6:
0.5mmol cuprous iodide, 0.25mmol Cadmium chloride fine powder, 0.25mmol tin acetate, 6mmol oleyl amine and 13ml vaccenic acid are packed in the reaction vessel there-necked flask, and being stirred to fully, dissolving forms metal precursor.4mmol selenium powder, 5mmol tri octyl phosphine and 5.7ml vaccenic acid are added in pear shape bottle, and after sealing, the ultrasonic selenium powder that makes dissolves formation selenium presoma fully in nitrogen atmosphere.The metal precursor temperature of reaction is elevated to 290 ° of C in argon gas atmosphere, then the selenium presoma is injected wherein fast, react 25 minutes taking-up reaction mixture injection methyl alcohol and make the nanocrystal precipitation, collect nanocrystal.In this embodiment, the mol ratio of mantoquita and cadmium salt is 2:1, the mol ratio of mantoquita and pink salt is 2:1, the mol ratio of metallic salt and oleyl amine is 1:6, the metallic salt total concn is 0.067mol/L, the mol ratio of tri octyl phosphine and selenium is 1.25:1, the concentration of selenium is 0.5mol/L, and the mol ratio that two kinds of presoma blending ratios are metallic salt and selenium is 1:4.
Claims (7)
1. the preparation method of a copper cadmium tin selenium semiconductor nanocrystal is characterized in that preparation process is as follows:
1). the preparation of metal precursor: with mantoquita, cadmium salt and pink salt metallic salt reactant, high boiling point alkylamine and high boiling point oil-based solvent are packed in reaction vessel, are stirred to dissolving fully;
In metal precursor, material mixture ratio is:
The mol ratio of mantoquita and cadmium salt is that 3:1 is between 1:1;
The mol ratio of mantoquita and pink salt is that 3:1 is between 1:1;
The mol ratio of metallic salt and alkylamine is that 1:2 is between 1:15;
In the metal precursor of preparation, the metallic salt total concn is that 0.05mol/L is between 0.1mol/L;
2). the preparation of selenium presoma:
Selenium powder and high boiling point oil-based solvent are added in another reaction vessel, be heated to 180-220 ℃ in inert atmosphere selenium powder is dissolved fully;
Perhaps selenium powder, tri octyl phosphine and high boiling point oil-based solvent are added in sealable container, seal in inert atmosphere, then the ultrasonic selenium powder that makes dissolves fully; Wherein, tri octyl phosphine and selenium powder mol ratio are that 1.25:1 is between 2:1;
In the selenium presoma, the concentration of selenium is that 0.1mol/L is between 0.5mol/L;
3). the metal precursor for preparing is heated to 260-300 ℃ in inert atmosphere, the selenium presoma is injected wherein fast, reacted 0.5-60 minute, take out reaction mixture and inject precipitation agent, collecting precipitation is copper cadmium tin selenium semiconductor nanocrystal; The blending ratio of two kinds of presomas is: the mol ratio of metallic salt and selenium is that 1:1 is between 1:5.
2. the preparation method of a kind of copper cadmium tin selenium semiconductor nanocrystal according to claim 1, it is characterized in that: described mantoquita is cuprous iodide, cuprous chloride, neutralized verdigris or cupric acetylacetonate.
3. the preparation method of a kind of copper cadmium tin selenium semiconductor nanocrystal according to claim 1, it is characterized in that: described cadmium salt is cadmium acetate, Cadmium chloride fine powder, cadmium oleate or cadmium stearate.
4. the preparation method of a kind of copper cadmium tin selenium semiconductor nanocrystal according to claim 1, it is characterized in that: described pink salt is tin acetate, tin tetrachloride, tindichloride or dibromo acetopyruvic acid tin.
5. the preparation method of a kind of copper cadmium tin selenium semiconductor nanocrystal according to claim 1 is characterized in that: described high boiling point alkylamine be under normal pressure boiling point greater than oleyl amine, hexadecylamine or the octadecylamine of 300 ℃.
6. the preparation method of a kind of copper cadmium tin selenium semiconductor nanocrystal according to claim 1 is characterized in that: described high boiling point oil-based solvent be under normal pressure boiling point greater than vaccenic acid or the whiteruss of 300 ℃.
7. the preparation method of a kind of copper cadmium tin selenium semiconductor nanocrystal according to claim 1, it is characterized in that: described precipitation agent is methyl alcohol, ethanol or acetone.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110890469A (en) * | 2018-09-07 | 2020-03-17 | Tcl集团股份有限公司 | Composite material and preparation method thereof |
| CN110885674A (en) * | 2018-09-07 | 2020-03-17 | Tcl集团股份有限公司 | Composite material and preparation method thereof |
| CN110890468A (en) * | 2018-09-07 | 2020-03-17 | Tcl集团股份有限公司 | Composite material and preparation method thereof |
| CN114914710A (en) * | 2022-05-18 | 2022-08-16 | 山东大学 | Electromagnetic wave absorbing material and preparation method and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110890469A (en) * | 2018-09-07 | 2020-03-17 | Tcl集团股份有限公司 | Composite material and preparation method thereof |
| CN110885674A (en) * | 2018-09-07 | 2020-03-17 | Tcl集团股份有限公司 | Composite material and preparation method thereof |
| CN110890468A (en) * | 2018-09-07 | 2020-03-17 | Tcl集团股份有限公司 | Composite material and preparation method thereof |
| CN114914710A (en) * | 2022-05-18 | 2022-08-16 | 山东大学 | Electromagnetic wave absorbing material and preparation method and application thereof |
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Application publication date: 20130508 |