CN103213956B - Preparation method of CuInSe2 with a chalcopyrite structure and CuIn1-xGazSe2 nano particles - Google Patents

Preparation method of CuInSe2 with a chalcopyrite structure and CuIn1-xGazSe2 nano particles Download PDF

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CN103213956B
CN103213956B CN201310078754.4A CN201310078754A CN103213956B CN 103213956 B CN103213956 B CN 103213956B CN 201310078754 A CN201310078754 A CN 201310078754A CN 103213956 B CN103213956 B CN 103213956B
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nano particle
cuinse
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indium
solution
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CN103213956A (en
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韩朝霞
张大伟
洪瑞金
陶春先
凌进中
黄元申
陈勤妙
庄松林
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University of Shanghai for Science and Technology
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Abstract

The invention relates to a preparation method of CuInSe2 with a chalcopyrite structure and CuIn1-xGazSe2 nano particles. Firstly, a metal precursor solution containing Cu+ or Cu2+, In3 or Ga3+ cation and a Se powder precursor solution are respectively prepared, and then the metal precursor solution and the Se powder precursor solution are mixed and uniformly stirred, and the solution is heated to 200-285 DEG C. with high purity nitrogen protection and reacted for 0.5-2 hours, and then the CuInSe2 or CuIn1-xGazSe2 nano particle solution is obtained, after high speed centrifugation, cleaning and drying steps, the CuInSe2 or CuIn1-xGazSe2 nano particles are obtained. The CuInSe2 or CuIn1-xGazSe2 nano particle has the advantages of chalcopyrite crystal structure, good dispersibility and high phase purity, and the element ingredient approaches to the stoichiometric ratio, thereby laying a foundation for preparing a high conversion efficiency film solar energy battery. The invention employs cheap metal salt and selenium powder as precursors, and employs a simple one-pot synthetic method, and has the advantages of simple operation, short synthesis period, strong repeatability without injection, and is suitable for mass production.

Description

A kind of CuInSe with yellow copper structure 2and CuIn 1-xga xse 2the preparation method of nano particle
Technical field
The present invention relates to a kind of CuInSe with yellow copper structure 2and CuIn 1-xga xse 2the preparation method of nano particle.
Technical background
CuInSe 2and CuIn 1-xga xse 2belong to compounds of group, is direct band-gap semicondictor material, has chalcopyrite crystalline structure at low temperatures.CuInSe 2and CuIn 1-xga xse 2there is high uptake factor (10 5cm -1), good photovoltaic stability, high conversion efficiency of solar cell (20.3%), therefore obtain and pay close attention to widely, be considered to very promising solar battery obsorbing layer material.
At present, high efficiency solar cell absorption layer adopts vacuum method to prepare usually.Vacuum method has that preparation cost is high, process is complicated and not easily realizes large-area a lot of shortcoming such as to commercially produce.For making sun power can really become the pillar energy, low cost technology of preparing must be developed.Antivacuum preparation method has essential characteristic at a low price, and in numerous antivacuum preparation method, because of it, there is low production cost, high material use efficiency based on the print process of nano particle and be beneficial to the preparation method that the advantages such as volume to volume production are considered to be hopeful most to realize low cost, big area is produced.For printing nanoparticles method, high dispersive, yellow copper structure, near stoichiometric proportion CuInSe 2and CuIn 1-xga xse 2the preparation of nano particle is the technology of most critical.
In recent years, CuInSe 2and CuIn 1-xga xse 2the preparation method of nano particle mainly contains solvent-thermal method, thermal decomposition method, hot injection method, ball milled, polyvalent alcohol circumfluence method etc.But most of method wherein can not control the size of nano particle, pattern, component, degree of crystallinity or phase purity effectively.And the nano particle of synthesis is reunited severity usually, easily introduces space in absorption layer film, is unfavorable for the preparation of the fine and close absorption layer film of high quality.Up to the present, Rapid Thermal injection method is the most successful, most widely used method in nanocrystal synthesis.The nano particle of hot injection method synthesis is less, evenly and good dispersity, but this method is owing to being difficult to volume production by the restriction of monomer rate of injection and mass transfer, and first need prepare stock solution, this for improve solar cell production efficiency, to reduce costs be disadvantageous.
Summary of the invention
The present invention carries out to solve the problem, object be to provide a kind of easy, quick, be suitable for mass production and the high CuInSe with yellow copper structure of synthesis quality 2and CuIn 1-xga xse 2the preparation method of nano particle.
The present invention to achieve these goals, have employed following steps:
The invention provides a kind of CuInSe 2the preparation method of nano particle, is characterized in that, comprises the following steps:
(1). mantoquita and indium salt are joined in oleyl amine (OLA), heats and stir, after solution clarification, be cooled to room temperature, obtain the metal front liquid solution containing cupric ion and indium ion;
(2). Se powder is joined in oleyl amine (OLA), stir and obtain Se powder precursor solution after ultrasonic vibration;
(3). metal front liquid solution is mixed with Se powder precursor solution, obtains mixing solutions;
(4). under high pure nitrogen protection, be constantly uniformly mixed solution and be heated to 200 ~ 285 DEG C, reaction 0.5 ~ 2 h, obtains CuInSe 2nanoparticles solution;
(5). cooling CuInSe 2nanoparticles solution to 30 ~ 60 DEG C, add normal hexane and dehydrated alcohol, obtain CuInSe through high speed centrifugation, cleaning, drying step 2nano particle.
In preparation method of the present invention, such feature can also be had: in step (1), mantoquita is cupric chloride, cuprous chloride or cuprous iodide, indium salt is indium chloride, indium acetate or indium iodide, the mol ratio of cupric ion and indium ion is 1:1, and total volumetric molar concentration of cupric ion and indium ion is 0.04 ~ 0.4mol/L.
In preparation method of the present invention, can also have such feature: in step (1), Heating temperature is 40 ~ 70 DEG C, and churning time is 2 ~ 4 h.In step (2), in Se powder precursor solution, the volumetric molar concentration of Se is 0.04 ~ 0.4mol/L.In step (3), mixing process is carried out in there-necked flask, and there-necked flask is connected with Shi Lanke line, and Shi Lanke line is for providing the reaction conditions of anhydrous and oxygen-free, and in mixing solutions, the mol ratio of cupric ion, indium ion and Se is 1:1:2.In step (4), heat-processed adopts electric mantle to heat and adopts thermopair to control temperature of reaction.In step (5), the volume ratio of normal hexane and dehydrated alcohol is 0 ~ 1:1, and the centrifugal speed of centrifugal process is 6000 ~ 10000r/min, and centrifugation time is 5 ~ 15 min, and drying process is carried out in loft drier, and drying temperature is 60 ~ 80 oc, time of drying is 6 ~ 15 h.
In addition, present invention also offers a kind of aforesaid method that uses and prepare CuIn 1-xga xse 2the method of nano particle, is characterized in that: in step (1), also add gallium salt.
Further, in this kind of preparation method, such feature can also be had: gallium salt is gallium chloride or gallium iodide.
The effect of invention and effect
The present invention, using the metal-salt of cheapness and selenium powder as presoma, adopts simple One-step Synthesis method, does not need to inject, and easy and simple to handle, synthesis cycle is short, repeatable strong, is suitable for mass production.In addition, the CuInSe adopting method of the present invention to synthesize 2and CuIn 1-xga xse 2nano particle has yellow copper structure, good dispersity, and phase purity is high, and elementary composition is close to stoichiometric ratio, lays the foundation for preparing high conversion efficiency thin-film solar cells.
Accompanying drawing explanation
Fig. 1 is the CuInSe prepared by the method for embodiment one 2the XRD figure spectrum of nano particle.
Fig. 2 is the CuInSe prepared by the method for embodiment two 2the XRD figure spectrum of nano particle.
Fig. 3 is the CuInSe prepared by the method for embodiment two 2the SEM collection of illustrative plates of nano particle.
Fig. 4 is the CuInSe prepared by the method for embodiment three 2the TEM collection of illustrative plates of nano particle.
Fig. 5 is the CuInSe prepared by the method for embodiment three 2the Vis-IR abosrption spectrogram of nano particle.
Fig. 6 is the CuIn prepared by the method for embodiment four 1-xga xse 2the XRD collection of illustrative plates of nano particle.
Embodiment
Below in conjunction with accompanying drawing to the CuInSe that the present invention relates to 2and CuIn 1-xga xse 2the preparation method of nano particle is described in detail.The present embodiment is implemented under premised on technical solution of the present invention, given detailed embodiment and process, is to further illustrate of the present invention, instead of limits the scope of the invention.
Embodiment one
The implementation process of the embodiment of the present invention one is as follows:
(1). take 170mg CuCl 22H 2and 293mg InCl O(1mmol) 34H 2o (1mmol) is also placed in the there-necked flask of 50ml, adds 15ml oleyl amine (OLA), is heated to 60 DEG C and magnetic agitation 3 h, naturally cools to room temperature, obtain the metal front liquid solution of glassy yellow after solution clarification.
(2). take the there-necked flask that 158mg simple substance Se powder (2mmol) is placed in another 50ml, add 10ml oleyl amine (OLA), room temperature lower magnetic force stirs 0.5h, ultrasonic vibration 10min, obtains Se powder precursor solution.
(3). by metal front liquid solution and the mixing of Se powder precursor solution, and the mixing solutions of gained is placed in the there-necked flask be connected with Shi Lanke line.
(4). under room temperature, 5min is vacuumized to there-necked flask, then heat gained mixing solutions with electric mantle and constantly carry out magnetic agitation, temperature of reaction is controlled with thermopair, when mixing solutions temperature rises to 110 DEG C, continue to vacuumize 5 points, then in there-necked flask, pass into high pure nitrogen, repeat 3 times.To mixing solutions heating, when temperature rises to 200 DEG C, isothermal reaction 1.5h, obtains CuInSe 2nanoparticles solution.
(5). naturally cooling gained CuInSe 2nanoparticles solution, adds 6ml normal hexane and 6ml dehydrated alcohol stopped reaction when temperature is down to 60 DEG C.When temperature is down to room temperature, by CuInSe 2nanoparticles solution loads centrifuge tube, with the centrifugation 10min of 8000 r/min, removes supernatant liquor, then with dehydrated alcohol, black precipitate is cleaned three times, be placed in loft drier with 70 oc freeze-day with constant temperature 10h, obtains CuInSe 2nano particle.
In the present embodiment, the oleyl amine (OLA) in step (1) and step (2) is used for as reaction solvent and reductive agent.Oleyl amine (OLA) is a kind of conventional organic solvent, and molecular formula is CH 3(CH 2) 7cH=CH(CH 2) 7cH 2nH 2.
Directly Se powder is dissolved in oleyl amine (OLA) in step (2).Because the solubleness of Se powder in oleyl amine (OLA) is very low under low temperature, so stir and can only obtain after ultrasonic vibration the aaerosol solution of Se powder, this aaerosol solution is Se powder precursor solution.
Select there-necked flask as reaction vessel in step (4), and be connected with there-necked flask with Shi Lanke line.Shi Lanke line is used for as reacting the reaction conditions creating anhydrous and oxygen-free.Vacuumized by Shi Lanke line and pass into high pure nitrogen in there-necked flask, the impact on reaction of moisture and oxygen can be got rid of, reaction is carried out under the condition of anhydrous and oxygen-free.
Fig. 1 is the CuInSe prepared by the method for embodiment one 2the XRD figure spectrum of nano particle.
As shown in Figure 1, CuInSe 2all diffraction peaks of nano particle and chalcopyrite CuInSe 2corresponding fine of standard card JCPDF No.40-1487, the CuInSe made by the preparation method of embodiment one is described 2nano particle has chalcopyrite crystalline structure.
Embodiment two
Temperature of reaction in the step (4) of embodiment two is 230 oc, the reaction times is 1h, and other each step is all identical with the corresponding step of embodiment one.
Fig. 2 is the CuInSe prepared by the method for embodiment two 2the XRD figure spectrum of nano particle.
As shown in Figure 2, CuInSe 2all diffraction peaks of nano particle and chalcopyrite CuInSe 2corresponding fine of standard card JCPDF No.40-1487, the CuInSe made by the preparation method of embodiment two is described 2nano particle has chalcopyrite crystalline structure, and crystallinity is fine.
Fig. 3 is the CuInSe prepared by the method for embodiment two 2the SEM collection of illustrative plates of nano particle.
As shown in Figure 3, CuInSe 2the dispersiveness of nano particle is fine, and particle size is between 50-300 nm.
Embodiment three
The implementation process of the embodiment of the present invention three is as follows:
(1). take 119.3mg CuCl 22H 2and 205.3mg InCl O(0.7mmol) 34H 2o(0.7mmol) and be placed in the there-necked flask of 50ml, add 15ml oleyl amine (OLA), be heated to 50 oc magnetic agitation 4 h, naturally cool to room temperature, obtain the metal front liquid solution of glassy yellow after solution clarification.
(2). take the there-necked flask that 110.5mg simple substance Se powder (1.4mmol) is placed in another 50ml, add 10ml oleyl amine, room temperature lower magnetic force stirs 1h, and ultrasonic vibration 10min, obtain Se powder precursor solution.
(3). by metal front liquid solution and the mixing of Se powder precursor solution, and the mixing solutions of gained is placed in the there-necked flask be connected with Shi Lanke line.
(4). under room temperature, 5min is vacuumized to there-necked flask, then heat gained mixing solutions with electric mantle and constantly carry out magnetic agitation, temperature of reaction is controlled with thermopair, when mixing solutions temperature rises to 110 DEG C, continue to vacuumize 5 points, then in there-necked flask, pass into high pure nitrogen, repeat 3 times.To mixing solutions heating, when temperature rises to 265 DEG C, isothermal reaction 1h, obtains CuInSe 2nanoparticles solution.
(5). naturally cooling gained CuInSe 2nanoparticles solution, 5ml normal hexane and 8ml dehydrated alcohol stopped reaction is added when temperature is down to 50 DEG C, when temperature is down to room temperature, nanoparticles solution is loaded centrifuge tube, with the centrifugation 8min of 10000 r/min, remove supernatant liquor, and then add 10ml normal hexane and black precipitate is cleaned three times by 40ml dehydrated alcohol, be placed in loft drier with 80 oc freeze-day with constant temperature 8h, obtains CuInSe 2nano particle.
Fig. 4 is the CuInSe prepared by the method for embodiment three 2the TEM collection of illustrative plates of nano particle.
As shown in Figure 4, by CuInSe prepared by the method for embodiment three 2the particle dispersion of nano particle is fine, and particle size is between 50-300 nm.To prepared CuInSe 2nano particle carries out electron energy analysis (EDX), show that the atomic ratio of Cu:In:Se is 25.6:23.6:50.8, close to stoichiometric ratio.
Fig. 5 is the CuInSe prepared by the method for embodiment three 2the Vis-IR abosrption spectrogram of nano particle.
As shown in Figure 5, by CuInSe prepared by the method for embodiment three 2nano particle has good absorption at whole visible ray to near-infrared band, proves this CuInSe 2nano particle is good light absorption layer material.
Embodiment four
The implementation process of the embodiment of the present invention four is as follows:
(1). take 170mg CuCl 22H 2o(1mmol), 205.3mg InCl 34H 2the super dry GaCl of O (0.7mmol) and 52.8mg 3(0.3mmol), be placed in the there-necked flask of a 50ml, add 12ml oleyl amine (OLA), be heated to 60 oc and magnetic agitation 2 h, naturally cool to room temperature, obtain the metal front liquid solution of glassy yellow after solution clarification.
(2). take the there-necked flask that 158mg simple substance Se powder (2mmol) is placed in another 50ml, add 10ml oleyl amine, room temperature lower magnetic force stirs 1h, ultrasonic vibration 15min, obtains Se powder precursor solution.
(3). by metal front liquid solution and the mixing of Se powder precursor solution, and the mixing solutions of gained is placed in the there-necked flask be connected with Shi Lanke line.
(4). under room temperature, 5min is vacuumized to there-necked flask, then heat gained mixing solutions with electric mantle and constantly carry out magnetic agitation, temperature of reaction is controlled with thermopair, when mixing solutions temperature rises to 110 DEG C, continue to vacuumize 5 points, then in there-necked flask, pass into high pure nitrogen, repeat 3 times.To mixing solutions heating, when temperature rises to 280 DEG C, isothermal reaction 1.5h, obtains CuIn 1-xga xse 2nanoparticles solution.
4) naturally cooling gained CuIn 1-xga xse 2nanoparticles solution, 10ml normal hexane and 10ml dehydrated alcohol stopped reaction is added when temperature is down to 50 DEG C, treat that temperature is down to room temperature, nanoparticles solution is loaded centrifuge tube, with the centrifugation 9min of 9000 r/min, remove supernatant liquor, and then add 5ml normal hexane and black precipitate is cleaned three times by 40ml dehydrated alcohol, be placed in loft drier with 70 oc freeze-day with constant temperature 10h, obtains CuIn 1-xga xse 2nano particle.
Fig. 6 is the CuIn prepared by the method for embodiment one 1-xga xse 2the XRD collection of illustrative plates of nano particle.
As shown in Figure 6, CuIn 1-xga xse 2nano particle has chalcopyrite crystalline structure.CuIn 1-xga xse 2the XRD figure spectrum of nano particle and CuInSe 2the XRD figure spectrum of nano particle is basically identical, and its difference is, CuIn 1-xga xse 2nano particle is because of Ga 3+the diffraction peak of mixing of particle offsets to the right.

Claims (10)

1. a CuInSe 2the preparation method of nano particle, is characterized in that, comprises the following steps:
(1). mantoquita and indium salt are joined in oleyl amine, heats and stir, after solution clarification, be cooled to room temperature, obtain the metal front liquid solution containing cupric ion and indium ion;
(2). Se powder is joined in oleyl amine, stirs and obtain Se powder precursor solution after ultrasonic vibration;
(3). described metal front liquid solution is mixed with described Se powder precursor solution, obtains mixing solutions;
(4). under high pure nitrogen protection, constantly stir described mixing solutions and be heated to 200 ~ 285 DEG C, reaction 0.5 ~ 2h, obtains CuInSe 2nanoparticles solution;
(5). cool described CuInSe 2nanoparticles solution to 30 ~ 60 DEG C, add normal hexane and dehydrated alcohol, obtain CuInSe through high speed centrifugation, cleaning, drying step 2nano particle.
2. CuInSe according to claim 1 2the preparation method of nano particle, it is characterized in that: in step (1), described mantoquita is cupric chloride, cuprous chloride or cuprous iodide, described indium salt is indium chloride, indium acetate or indium iodide, the mol ratio of described cupric ion and described indium ion is 1:1, and total volumetric molar concentration of described cupric ion and described indium ion is 0.04 ~ 0.4mol/L.
3. CuInSe according to claim 1 2the preparation method of nano particle, is characterized in that: in step (1), and described Heating temperature is 40 ~ 70 DEG C, and churning time is 2 ~ 4h.
4. CuInSe according to claim 1 2the preparation method of nano particle, is characterized in that: in step (2), and in described Se powder precursor solution, the volumetric molar concentration of Se is 0.04 ~ 0.4mol/L.
5. CuInSe according to claim 1 2the preparation method of nano particle, is characterized in that: in step (3), mixing process is carried out in there-necked flask, and described there-necked flask is connected with Shi Lanke line, and described Shi Lanke line is for providing the reaction conditions of anhydrous and oxygen-free.
6. CuInSe according to claim 1 2the preparation method of nano particle, is characterized in that: in step (3), and in described mixing solutions, the mol ratio of cupric ion, indium ion and Se is 1:1:2.
7. CuInSe according to claim 1 2the preparation method of nano particle, is characterized in that: in step (4), and heat-processed adopts electric mantle to heat and adopts thermopair to control temperature of reaction.
8. CuInSe according to claim 1 2the preparation method of nano particle, it is characterized in that: in step (5), the volume ratio of described normal hexane and described dehydrated alcohol is greater than 0 and is less than or equal to 1, the centrifugal speed of centrifugal process is 6000 ~ 10000r/min, centrifugation time is 5 ~ 15min, drying process is carried out in loft drier, and drying temperature is 60 ~ 80 DEG C, and time of drying is 6 ~ 15h.
9. one kind uses the method according to any one of claim 1 ~ 8 to prepare CuIn 1-xga xse 2the method of nano particle, is characterized in that: in step (1), also add gallium salt.
10. preparation Cuaccording to claim 9 1-xga xse 2the method of nano particle, is characterized in that: described gallium salt is gallium chloride or gallium iodide.
CN201310078754.4A 2013-02-25 2013-02-25 Preparation method of CuInSe2 with a chalcopyrite structure and CuIn1-xGazSe2 nano particles Expired - Fee Related CN103213956B (en)

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CN104064628B (en) * 2014-07-01 2016-07-06 扬州大学 A kind of preparation method of CIS tellurium nano-wire
CN104057101B (en) * 2014-07-01 2015-12-09 扬州大学 The method of copper indium tellurium nano-wire is prepared in a kind of catalysis
CN104810431A (en) * 2015-03-31 2015-07-29 安徽省嘉信包装印务有限公司 Method for preparing copper indium gallium selenide thin film through screen printing process
CN105802630A (en) * 2016-04-14 2016-07-27 中国科学院合肥物质科学研究院 One-pot method for green synthesis of copper indium diselenide quantum dots and application thereof
CN106191986B (en) * 2016-07-13 2018-09-07 中国科学技术大学 Liquid-phase reflux one-step method controllable preparation orthorhombic phase AgIn1-xGaxSe2The method of nanometer monocrystalline particle
CN106833647B (en) * 2017-01-20 2019-05-21 温州大学 A kind of synthetic method of copper indium selenide quantum dot
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