CN104264211A - High temperature solvent thermal preparation method and applications of monocrystalline submicron Cu2ZnSnS4 particle - Google Patents

High temperature solvent thermal preparation method and applications of monocrystalline submicron Cu2ZnSnS4 particle Download PDF

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CN104264211A
CN104264211A CN201410426610.8A CN201410426610A CN104264211A CN 104264211 A CN104264211 A CN 104264211A CN 201410426610 A CN201410426610 A CN 201410426610A CN 104264211 A CN104264211 A CN 104264211A
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particle
monocrystalline
znsns
submicron order
solution
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CN104264211B (en
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陶杰
陈善龙
陶海军
沈一洲
朱露敏
曾小飞
蒋佳佳
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Nanjing University of Aeronautics and Astronautics
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Abstract

The invention discloses a high temperature solvent thermal preparation method and applications of a monocrystalline submicron Cu2ZnSnS4 particle, and belongs to the technical field of nano material synthesis. The method comprises the following steps: individually fetching a copper salt solution, a zinc salt solution, a tin salt solution, and a sulfur source solution, adding the solutions into a reactor in order, then diluting the mixed solution with waterless ethanol so as to obtain a precursor solution, sealing the reactor, heating to a temperature of 300 to 400 DEG C, maintaining the temperature for 1 to 12 hours, taking out the black powder in the bottom layer of the reactor, carrying out centrifugation, and washing so as to obtain the target product. Under a condition of high temperature, CZTS particles, which have excellent crystallizing performance and do not contain any impurity phase, can be synthesized within a short time period. The CZTS particle has a good crystallizing performance and a monocrystal structure, the performance of the obtained CZTS particle is similar to that of a sample which has been vulcanized and annealed, the particle size of the CZTS particle is in a submicron level, and the post annealing treatment is not required. The invention further discloses the applications of the CZTS particle in solar cell and photocatalysis.

Description

Monocrystalline submicron order Cu 2znSnS 4the high-temperature solvent hot preparation method of particle and application
Technical field
The present invention relates to a kind of Cu 2znSnS 4the preparation method of particle and application are specifically a kind of monocrystalline submicron order Cu 2znSnS 4the high-temperature solvent hot preparation method of particle and application, belong to nano material synthesis technical field.
Background technology
Along with the problem of environmental pollution that fossil oil is day by day exhausted and in use caused, the energy source device of development of new energy-conserving and environment-protective has become the important channel solving energy problem and environmental problem, wherein solar cell because of its there is applied range, the advantage of cleanliness without any pollution becomes the research object received much concern.Along with widely using of photovoltaic module, how to obtain efficient, that green, cheap solar absorptive material is current photovoltaic generation study hotspot.
1996, first Cu prepared in Japanese H.Katagiri study group 2znSnS 4solar cell, efficiency only had 0.66% at that time.But Cu 2znSnS 4narrower band gap and the characteristic of direct band-gap semicondictor still cause the concern of numerous solar cell research group.The Cu of tetragonal phase structure 2znSnS 4(CZTS) be direct band gap p-type semiconductor, energy gap is about 1.5eV, and uptake factor is up to 10 4cm -1, component is at the rich reserves of the earth, and price is low, nontoxic, is therefore considered to the ideal semiconductor material preparing solar cell.In recent years, the vacuum such as thermal evaporation, magnetron sputtering, pulsed laser deposition, chemical vapour deposition, galvanic deposit, collosol and gel and ink printing and antivacuum technology of preparing are all applied to preparation CZTS thin-film solar cells, no matter but be that the high vacuum needed for vacuum technology of preparing or the tedious steps needed for antivacuum preparation all make the preparation cost of its CZTS film higher, distance commercial production is also far apart with application.At present, solvent-thermal method is extensively adopted to prepare Cu both at home and abroad 2znSnS 4nano particle, and be configured to ink film.
On April 16th, 2014, Chinese invention patent CN102674435B discloses the nanocrystalline solvent process for thermosynthesizing of a kind of copper-zinc-tin-sulfur, it is nanocrystalline that the method reacts 15h-20h acquisition CZTS under 130-140 DEG C of environment, the characteristic peak intensity that prepared copper-zinc-tin-sulfur is nanocrystalline is less, thus the powder that preparation is described is that copper-zinc-tin-sulfur nano particle crystallinity is not good.In addition, this solvent-thermal method is generally selected about 140-200 DEG C to react and is obtained CZTS powder, the particle size obtained is Nano grade, compared with the CZTS that crystallinity cannot be prepared with vacuum method, native defect is many, density is not high yet, and it is also longer to prepare the reaction times needed for material in addition, is generally 18-30h.
Summary of the invention
Technical problem to be solved by this invention is to overcome above-mentioned defect, provides that a kind of preparation cycle is short, grain crystalline good and the monocrystalline submicron order Cu that size is large 2znSnS 4the high-temperature solvent hot preparation method of particle and application.
In order to solve the problems of the technologies described above, the invention provides a kind of monocrystalline submicron order Cu 2znSnS 4the high-temperature solvent hot preparation method of particle, comprises the following steps:
1) the sulphur source solution of the copper salt solution of 0.5-2mmol/L, the zinc solution of 0.5mmol/L, the tin-salt solution of 0.5mmol/L and 2-4mmol/L, is got respectively, the mixed solution of 1:1:1:1 formation is by volume placed in reactor, pour dehydrated alcohol again into dilute, obtain reaction precursor liquid; Described mixed solution and dehydrated alcohol volume ratio are 1:1-10;
2), by inserting in baking oven after reactor sealing, being incubated at 300-400 DEG C after 1-12h carries out solvent thermal reaction and being cooled to room temperature;
3), by step 2) cleaned powder, through absolute ethanol washing, centrifugal to solution clarification, then is carried out the dry Cu obtaining monocrystalline submicron order by the powder that obtains after reaction 2znSnS 4particle.
In the present invention, described step 1) in mantoquita be a water acetic acid copper, zinc salt is zinc acetate, pink salt is stannic chloride pentahydrate, sulphur source is Cys.
In the present invention, described step 1) in dehydrated alcohol be analytical pure rank.
In the present invention, described step 2) in the temperature rise rate of baking oven be 10 DEG C/min.
In the present invention, described step 3) in drying temperature be 80 DEG C, insulation 12h.
In the present invention, described reactor is stainless steel cauldron, to polish screw thread before use with Graphite Powder 99.
The present invention monocrystalline submicron order Cu that also claimed aforesaid method is obtained 2znSnS 4the application of particle in thin-film solar cells.
The present invention monocrystalline submicron order Cu that also claimed aforesaid method is obtained 2znSnS 4the application of particle in photochemical catalysis.
Beneficial effect of the present invention is: (1), the present invention are under the high temperature conditions, can within a short period of time synthetic crystallization excellent and not containing the CZTS particle of dephasign, compared to the polycrystalline CZTS particle that other chemical method obtains, this CZTS grain crystalline is good, in single crystal structure, the sample can annealed with sulfuration is compared, and particle size at submicron order without the need to subsequent anneal process; (2), that the present invention prepares CZTS particle preparation cycle is short, and its preparation process is environment friendly and pollution-free, and output is large; (3), the chemical reagent that uses of the CZTS particle prepared of the present invention is common agents, environmental protection, cheap and easy to get, its preparation technology is simple, with low cost, reaction conditions is gentle, energy consumption is low, be easy to large-scale application and popularization; (4) the CZTS particle that, the present invention obtains can be widely used in preparation thin-film solar cells or photochemical catalysis.
Accompanying drawing explanation
Fig. 1 is monocrystalline submicron order Cu of the present invention 2znSnS 4the process flow diagram of the high-temperature solvent hot preparation method of particle;
Fig. 2 is the XRD figure spectrum of the prepared CZTS particle of embodiment 1 in the present invention;
Fig. 3 is the laser raman collection of illustrative plates of the prepared CZTS particle of embodiment 1 in the present invention;
Fig. 4 is the transmission electron microscope picture of the prepared CZTS particle of embodiment 1 in the present invention, and wherein (a) (b) (c) is transmission electron microscope picture, (d) be electronics selected diffraction photo.
Embodiment
Be described in further detail below in conjunction with specific embodiment to the present invention.
Monocrystalline submicron order Cu prepared by the present invention 2znSnS 4(CZTS) particle carries out structure and morphology characterization by following means: select the X-ray diffractometer (XRD) of German BRUKER Advance D8 to carry out phase structure phenetic analysis to sample; The Flied emission transmission electron microscope (TEM) of U.S. FEI Tecnai G2 is selected to carry out microscopic appearance observation to sample; The laser raman of French Horiba Jobin Yvon HR800 is selected to carry out phase structure phenetic analysis to sample.
embodiment 1
As shown in Figure 1, a kind of monocrystalline submicron order Cu of the present invention 2znSnS 4(CZTS) the high-temperature solvent hot preparation method concrete steps of particle are as follows:
The first step, get the Cys of a water acetic acid copper solutions of 1mmol/L, the zinc acetate solution of 0.5mmol/L, the stannic chloride pentahydrate solution of 0.5mmol/L and 3mmol/L respectively, the mixed solution of 1:1:1:1 formation is by volume placed in stainless steel cauldron, pour analytical pure level dehydrated alcohol again into dilute, obtain reaction precursor liquid; Wherein mixed solution and analytical pure level dehydrated alcohol volume ratio are 1:1, and stainless steel cauldron to be polished screw thread with Graphite Powder 99 before use.
Second step, is positioned in high temperature blast baking oven after being sealed by stainless steel cauldron, regulates baking oven temperature rise rate to be 10 DEG C/min, and 400 DEG C of insulation 5h carry out solvent thermal reaction, take out reactor after being cooled to room temperature.
3rd step, open the reactor cooled, with dehydrated alcohol, the powder in still is transferred in beaker after outwelling supernatant liquid, transfer to again in centrifuge tube after powder sedimentation, add dehydrated alcohol eccentric cleaning for several times, until the supernatant liquid clarification in centrifuge tube, subsequently cleaned CZTS powder is placed in baking oven 80 DEG C of dry 12h, obtains the Cu of final monocrystalline submicron order 2znSnS 4particle.
Fig. 2 is the XRD figure spectrum of the present embodiment gained monocrystalline submicron order CZTS particle, and as can be seen from the figure obtained particle only has CZTS phase to exist, without other dephasign diffraction peak.
Fig. 3 is the laser raman collection of illustrative plates of the present embodiment gained monocrystalline submicron order CZTS particle, as can be seen from the figure the obtained particle obtained only have CZTS phase to exist (corresponding Raman peaks displacement is, P1:286cm -1, 338cm -1and 373cm -1), without other dephasign.
Fig. 4 is transmission electron microscope and the electronics selected diffraction figure of the present embodiment gained CZTS particle, and therefrom can find out that obtained particle size is roughly at 500nm-1 μm, shape is regular polygon, is single crystal structure from the particle of diffraction spot synthesis.
embodiment 2
The first step, get the Cys of a water acetic acid copper solutions of 0.5mmol/L, the zinc acetate solution of 0.5mmol/L, the stannic chloride pentahydrate solution of 0.5mmol/L and 4mmol/L respectively, the mixed solution of 1:1:1:1 formation is by volume placed in stainless steel cauldron, pour analytical pure level dehydrated alcohol again into dilute, obtain reaction precursor liquid; Wherein mixed solution and analytical pure level dehydrated alcohol volume ratio are 1:1, and stainless steel cauldron to be polished screw thread with Graphite Powder 99 before use; All the other steps are identical with embodiment 1.
embodiment 3
The first step, get the Cys of a water acetic acid copper solutions of 0.7mmol/L, the zinc acetate solution of 0.5mmol/L, the stannic chloride pentahydrate solution of 0.5mmol/L and 4mmol/L respectively, the mixed solution of 1:1:1:1 formation is by volume placed in stainless steel cauldron, pour analytical pure level dehydrated alcohol again into dilute, obtain reaction precursor liquid; Wherein, mixed solution and analytical pure level dehydrated alcohol volume ratio are 1:1, and stainless steel cauldron to be polished screw thread with Graphite Powder 99 before use; All the other steps are identical with embodiment 1.
embodiment 4
The first step, get the Cys of a water acetic acid copper solutions of 2mmol/L, the zinc acetate solution of 0.5mmol/L, the stannic chloride pentahydrate solution of 0.5mmol/L and 4mmol/L respectively, the mixed solution of 1:1:1:1 formation is by volume placed in stainless steel cauldron, pour analytical pure level dehydrated alcohol again into dilute, obtain reaction precursor liquid; Wherein mixed solution and analytical pure level dehydrated alcohol volume ratio are 1:3, and stainless steel cauldron to be polished screw thread with Graphite Powder 99 before use; All the other steps are identical with embodiment 1.
embodiment 5
The first step, get the Cys of a water acetic acid copper solutions of 1mmol/L, the zinc acetate solution of 0.5mmol/L, the stannic chloride pentahydrate solution of 0.5mmol/L and 2mmol/L respectively, the mixed solution of 1:1:1:1 formation is by volume placed in stainless steel cauldron, pour analytical pure level dehydrated alcohol again into dilute, obtain reaction precursor liquid; Wherein mixed solution and analytical pure level dehydrated alcohol volume ratio are 1:4, and stainless steel cauldron to be polished screw thread with Graphite Powder 99 before use; All the other steps are identical with embodiment 1.
embodiment 6
The first step, get the Cys of a water acetic acid copper solutions of 1mmol/L, the zinc acetate solution of 0.5mmol/L, the stannic chloride pentahydrate solution of 0.5mmol/L and 3mmol/L respectively, the mixed solution of 1:1:1:1 formation is by volume placed in stainless steel cauldron, pour analytical pure level dehydrated alcohol again into dilute, obtain reaction precursor liquid; Wherein mixed solution and analytical pure level dehydrated alcohol volume ratio are 1:8, and stainless steel cauldron to be polished screw thread with Graphite Powder 99 before use; All the other steps are identical with embodiment 1.
embodiment 7
The first step, get the Cys of a water acetic acid copper solutions of 1mmol/L, the zinc acetate solution of 0.5mmol/L, the stannic chloride pentahydrate solution of 0.5mmol/L and 4mmol/L respectively, the mixed solution of 1:1:1:1 formation is by volume placed in stainless steel cauldron, pour analytical pure level dehydrated alcohol again into dilute, obtain reaction precursor liquid; Wherein mixed solution and analytical pure level dehydrated alcohol volume ratio are 1:5, and stainless steel cauldron to be polished screw thread with Graphite Powder 99 before use; All the other steps are identical with embodiment 1.
embodiment 8
The first step, get the Cys of a water acetic acid copper solutions of 1mmol/L, the zinc acetate solution of 0.5mmol/L, the stannic chloride pentahydrate solution of 0.5mmol/L and 4mmol/L respectively, the mixed solution of 1:1:1:1 formation is by volume placed in stainless steel cauldron, pour analytical pure level dehydrated alcohol again into dilute, obtain reaction precursor liquid; Wherein mixed solution and analytical pure level dehydrated alcohol volume ratio are 1:10, and stainless steel cauldron to be polished screw thread with Graphite Powder 99 before use; All the other steps are identical with embodiment 1.
embodiment 9
In second step, holding temperature is 300 DEG C, soaking time 1h; All the other steps are identical with embodiment 1.
embodiment 10
In second step, holding temperature is 330 DEG C, soaking time 1h; All the other steps are identical with embodiment 1.
embodiment 11
In second step, holding temperature is 370 DEG C, soaking time 7h; All the other steps are identical with embodiment 1.
embodiment 12
In second step, holding temperature is 400 DEG C, soaking time 1h; All the other steps are identical with embodiment 1.
embodiment 13
In second step, holding temperature is 400 DEG C, soaking time 3h; All the other steps are identical with embodiment 1.
embodiment 14
In second step, holding temperature is 350 DEG C, soaking time 9h; All the other steps are identical with embodiment 1.
embodiment 15
In second step, holding temperature is 400 DEG C, soaking time 12h; All the other steps are identical with embodiment 1.
embodiment 16
The concrete number of assembling steps of thin-film solar cells is as follows:
The first step, by the Cu of monocrystalline submicron order prepared 2znSnS 4particle is with after mortar grinder 3h, get a certain amount of powder to pour ultrasonic disperse 30min in chlorobenzene into and obtain ink, draw on the molybdenum glass of a certain amount of CZTS ink droplet after cleaning with dropper, 3000r/min spin coating 30s can obtain one deck CZTS preformed layer film;
Second step, puts pre-burning on hot plate and removes chlorobenzene by performed thin film, and then repeating step 1, until obtain the film of 1-2 μm;
3rd step, selects chemical bath method CdS thin films on CZTS film;
4th step, selects the method for evaporation or magnetron sputtering on CdS, deposit ZnO:Al Window layer, and top deposits Au gate electrode more subsequently;
5th step, draw wire in Au electrode both sides, series of cells installs complete.
embodiment 17
The application of photocatalytic device is as follows:
Using monocrystalline CZTS particle as photocatalyst material, under visible light illumination, the organic photocatalytic degradations such as methylene blue, tropeolin-D, Sudan red, phenol, methyl alcohol are directly applied to.
The above is only the preferred embodiment of the present invention, it should be pointed out that for those skilled in the art, can also make some improvement under the premise without departing from the principles of the invention, and these improvement also should be considered as protection scope of the present invention.

Claims (8)

1. a monocrystalline submicron order Cu 2znSnS 4the high-temperature solvent hot preparation method of particle, is characterized in that comprising the following steps:
1) the sulphur source solution of the copper salt solution of 0.5-2mmol/L, the zinc solution of 0.5mmol/L, the tin-salt solution of 0.5mmol/L and 2-4mmol/L, is got respectively, the mixed solution of 1:1:1:1 formation is by volume placed in reactor, pour dehydrated alcohol again into dilute, obtain reaction precursor liquid; Described mixed solution and dehydrated alcohol volume ratio are 1:1-10;
2), will reactor seal after insert in baking oven, be incubated after 1-12h carries out solvent thermal reaction at 300-400 DEG C, be cooled to room temperature;
3), by step 2) cleaned powder, through absolute ethanol washing, centrifugal to solution clarification, then is carried out drying by the powder that obtains after reaction, obtains the Cu of monocrystalline submicron order 2znSnS 4particle.
2. monocrystalline submicron order Cu according to claim 1 2znSnS 4the high-temperature solvent hot preparation method of particle, is characterized in that: described step 1) in mantoquita be a water acetic acid copper, zinc salt is zinc acetate, pink salt is stannic chloride pentahydrate, sulphur source is Cys.
3. monocrystalline submicron order Cu according to claim 2 2znSnS 4the high-temperature solvent hot preparation method of particle, is characterized in that: described step 1) in dehydrated alcohol be analytical pure rank.
4. monocrystalline submicron order Cu according to claim 3 2znSnS 4the high-temperature solvent hot preparation method of particle, is characterized in that: described step 2) in the temperature rise rate of baking oven be 10 DEG C/min.
5. monocrystalline submicron order Cu according to claim 4 2znSnS 4the high-temperature solvent hot preparation method of particle, is characterized in that: described step 3) in drying temperature be 80 DEG C, insulation 12h.
6. a kind of monocrystalline submicron order Cu according to claim 5 2znSnS 4the high-temperature solvent hot preparation method of particle, is characterized in that: described reactor is stainless steel cauldron, to polish screw thread before use with Graphite Powder 99.
7. the monocrystalline submicron order Cu described in any one of claim 1 to 6 2znSnS 4the application of particle in thin-film solar cells.
8. the monocrystalline submicron order Cu described in any one of claim 1 to 6 2znSnS 4the application of particle in photochemical catalysis.
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US10453978B2 (en) 2015-03-12 2019-10-22 International Business Machines Corporation Single crystalline CZTSSe photovoltaic device
CN105006370A (en) * 2015-06-23 2015-10-28 南京航空航天大学 Method for in-situ preparing CZTS counter electrode by means of solvent thermal and application of CZTS counter electrode
CN105226131A (en) * 2015-08-24 2016-01-06 中国工程物理研究院材料研究所 A kind of chemical synthesis process of copper zinc tin sulfur absorption layer film
US10269994B2 (en) 2015-10-12 2019-04-23 International Business Machines Corporation Liftoff process for exfoliation of thin film photovoltaic devices and back contact formation
US10749050B2 (en) 2015-10-12 2020-08-18 International Business Machines Corporation Thin film CZTSSe photovoltaic device

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