CN109796051A - A kind of molten-salt growth method prepares the nanocrystalline method of copper cobalt tin sulphur - Google Patents
A kind of molten-salt growth method prepares the nanocrystalline method of copper cobalt tin sulphur Download PDFInfo
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- CN109796051A CN109796051A CN201910137636.3A CN201910137636A CN109796051A CN 109796051 A CN109796051 A CN 109796051A CN 201910137636 A CN201910137636 A CN 201910137636A CN 109796051 A CN109796051 A CN 109796051A
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- salt
- nanocrystalline
- molten
- sulphur
- copper cobalt
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- 238000000034 method Methods 0.000 title claims abstract description 39
- YYOYHASMBWYICK-UHFFFAOYSA-N [S].[Sn].[Co].[Cu] Chemical compound [S].[Sn].[Co].[Cu] YYOYHASMBWYICK-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 26
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000005864 Sulphur Substances 0.000 claims abstract description 11
- 150000001868 cobalt Chemical class 0.000 claims abstract description 7
- 239000010949 copper Substances 0.000 claims description 11
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 12
- 238000010521 absorption reaction Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000010409 thin film Substances 0.000 abstract description 6
- KYRUBSWVBPYWEF-UHFFFAOYSA-N copper;iron;sulfane;tin Chemical group S.S.S.S.[Fe].[Cu].[Cu].[Sn] KYRUBSWVBPYWEF-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004615 ingredient Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 3
- 238000003556 assay Methods 0.000 abstract 1
- 239000013078 crystal Substances 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 230000001681 protective effect Effects 0.000 abstract 1
- 230000003287 optical effect Effects 0.000 description 7
- 238000000227 grinding Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- VPRQBUKXDDOQKQ-UHFFFAOYSA-N [Sn].[Co]=S Chemical compound [Sn].[Co]=S VPRQBUKXDDOQKQ-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a kind of molten-salt growth methods to prepare the nanocrystalline method of copper cobalt tin sulphur, belongs to field of thin film solar cells.The method of the invention after mixing with fused salt, obtains mixed raw material using mantoquita, pink salt, cobalt salt, sulphur source as raw material；Gained mixed raw material is placed in protective atmosphere and is roasted, then is crushed and is cleaned, the CCTS for obtaining high-purity stannite structure is nanocrystalline.This method simple process and low cost, suitable large-scale production, assay reproducibility and stability are also relatively good, and product crystallinity is preferable, and purity is higher, thus be used to prepare the copper cobalt tin sulphur absorption layer material with the band gap that matches with thin-film solar cells.The pattern and ingredient of product can be controlled by adjusting the content of reaction temperature and fused salt；Crystal grain is grown under equilibrium state in fused salt, so the nanocrystalline characteristic of molten-salt growth is better than the absorption layer material of traditional approach preparation.
Description
Technical field
The present invention relates to a kind of molten-salt growth methods to prepare the nanocrystalline method of copper cobalt tin sulphur, belongs to field of thin film solar cells.
Background technique
The Cu of stannite type structure2CoSnS4(CCTS) be a kind of direct band-gap semicondictor material, forbidden bandwidth with partly lead
Best forbidden bandwidth (1.45 eV) required by body solar cell is very close, and the absorption coefficient of light is up to 104 cm-1, very suitable
For the absorbed layer as thin-film solar cells.For copper cobalt tin sulphur as absorbed layer, optical band gap is regulation film sun electricity
The important parameter of pond photoelectric conversion efficiency, especially with the stacked solar cell, cascade solar cell material of different band gap.Meanwhile Cu2CoSnS4By
Yu Qiyu CuIn1-xGaxSe2Structure is similar, and elemental copper, cobalt, tin, the sulphur earth reserves in CCTS are very rich, and to ring
Border is safe and non-toxic pollution-free.Therefore, CCTS is hopeful to replace CIGS to prepare inexpensive, efficient thin-film solar cells
Absorb layer material.Thus, it is intended that CCTS solar battery will be greatly improved by introducing Co atom in nanocrystalline preparation process
Open-circuit voltage and fill factor；Copper cobalt tin sulphur solar battery has the potentiality of the following scale application, is ideal film
The absorption layer material of solar battery.
Currently, the method for preparing CCTS powder mainly has Mechanical Alloying, hot injection method, water/solvent-thermal method, microwave
Heating, one pot synthesis and electrodeposition process etc..CCTS is prepared for using one pot synthesis, but is held by CCTS prepared by such method
It is also easy to produce impurity and easy to reunite.CCTS is prepared using solvent-thermal method, but this technological reaction is not easy to control, be unfavorable for realizing quickly,
Efficient preparation CNTS is nanocrystalline.
Summary of the invention
The purpose of the present invention is to provide a kind of molten-salt growth methods to prepare the nanocrystalline technique of copper cobalt tin sulphur (CCTS), specifically includes
Following steps:
(1) it is uniformly mixed after being fully ground mantoquita, cobalt salt, pink salt, sulphur source, fused salt, then in N2Add in atmosphere from room temperature
More than heat to fused salt melting temperature (650-900 DEG C) is roasted, wherein the rate of heat addition is 1-10 DEG C/min, and calcining time is
8-48h；Cool to products therefrom with the furnace room temperature；
(2) sample is taken out, eccentric cleaning (utilizes ultrapure water and alcohol eccentric cleaning, centrifugal speed 8000- after crushing
10000 rpm, to guarantee residuals on sample to clean up, entire cleaning process repeated washing 3-5 times), after having dried
Obtain pure Cu2CoSnS4It is nanocrystalline.
Preferably, mantoquita of the present invention, pink salt, cobalt salt are respectively CuS, Sn2S and CoS, sulphur source are S powder, fused salt KI
One or both of with CsCl.
The fusing point of the fused salt KI and CsCl is respectively 680 DEG C, 645 DEG C, thus is required heat to using different fused salts
On different temperature.
Preferably, mantoquita of the present invention: pink salt: cobalt salt: sulphur source: the molar ratio of fused salt is 10-30:5-20:5-20:10-20:
30-70。
Preferably, drying condition is 50-70 DEG C of dry 8-20h in step (2) of the present invention.
Beneficial effects of the present invention:
(1) reaction process of the method for the invention and washing process are conducive to the removing of impurity, high-purity reaction easy to form
Product, and the pattern of product and ingredient can be controlled by adjusting the content of reaction temperature and fused salt；Compared to its other party
Method, the method for the invention repeatability and stability are relatively good, low in cost, and product crystallinity is preferable.
(2) the absorbed layer CCTS of the method for the invention preparation is nanocrystalline, and product purity is higher, and cost is more general than at present
High-vacuum equipment is low, and introducing element is nontoxic and will not generate radiation, is more applicable for industrialization；Its optical band gap chart
It is bright, the nanocrystalline forbidden bandwidth of copper cobalt tin sulphur, with best forbidden bandwidth required by semiconductor solar cell (1.45 eV) ten
Tap is close, is adapted as the absorption layer material of solar battery.
(3) the method for the invention is prepared copper cobalt tin sulphur powder body good crystallinity, purity is high, visible light region have
Good absorption is conducive to improve photoelectric conversion efficiency.
Detailed description of the invention
Fig. 1 is the nanocrystalline XRD diagram of the copper cobalt tin sulphur of the preparation of embodiment 1.
Fig. 2 is that the nanocrystalline UV-vis of the copper cobalt tin sulphur of the preparation of embodiment 1 absorbs map.
Fig. 3 is the nanocrystalline optical band gap figure of the copper cobalt tin sulphur of the preparation of embodiment 1.
Specific embodiment
Invention is further described in detail combined with specific embodiments below, but protection scope of the present invention is not limited to
The content.
Embodiment 1
The present embodiment provides a kind of preparation methods that copper cobalt tin sulphur is nanocrystalline, specifically includes the following steps:
(1) claim 10mmol copper powder, 15 mmol cobalt powders, 5 mmol glass puttys, 20mmol sulphur powder and 70 mmol CsCl fused salts, fill
Divide grinding to be uniformly mixed later, mixture is placed in crucible.
(2) mixed sample is put into tube furnace, is passed through N2, it is made to be in N2In atmosphere.
(3) it is heated to fused salt melting temperature (850 DEG C) from room temperature, is warming up to 850 with the heating rate of 1 DEG C/min
DEG C roasting for 24 hours, cool to products therefrom with the furnace room temperature.
(4) sample in furnace is taken out, utilizes ultrapure water and alcohol eccentric cleaning after grinding, to guarantee residue on sample
Matter cleans up, and entire cleaning process repeated washing 3-5 times.
(5) cleaned sample is finally placed in 50-70 DEG C of dry 8-20h in drying box, is obtained after having dried pure
Cu2CoSnS4It is nanocrystalline, carry out the detection and analysis of object phase and performance.
Fig. 1, Fig. 2 and Fig. 3 are respectively the nanocrystalline XRD spectra of the CCTS of the preparation of embodiment 1, the CCTS nanometer according to preparation
The UV-Visible absorption map and optical band gap spectrogram that brilliant ultraviolet-visible absorption spectroscopy data are drawn.Implement as shown in Figure 1
It is nanocrystalline that example 1 is prepared for CCTS, and phase purity is high, crystallinity is preferable, without other miscellaneous phases；Embodiment 1 is prepared for as shown in Figure 2
CCTS sample visible-range near infrared spectrum region have stronger absorption, this shows them in optoelectronic areas
With potential application；The CCTS that embodiment 1 is prepared for as shown in Figure 3 nanocrystalline optical band gap is 1.4 eV, too with semiconductor
Best forbidden bandwidth (1.45 eV) required by positive electricity pond is very close, is suitable as the absorbed layer material of thin-film solar cells
Material.
Embodiment 2
The present embodiment provides a kind of preparation methods that copper cobalt tin sulphur is nanocrystalline, specifically includes the following steps:
(1) 20 mmol CuS, 5mmol CoS, 20 mmolSn are weighed2S, 10mmol sulphur powder and 50mmol KI fused salt, sufficiently
It is uniformly mixed after grinding, mixture is placed in crucible.
(2) mixed sample is put into tube furnace, is passed through N2, it is made to be in N2In atmosphere.
(3) it is heated to fused salt melting temperature (800 DEG C) from room temperature, is warming up to 800 with the heating rate of 5 DEG C/min
DEG C roasting 8h, cool to products therefrom with the furnace room temperature.
(4) sample in furnace is taken out, utilizes ultrapure water and alcohol eccentric cleaning after grinding, to guarantee residue on sample
Matter cleans up, and entire cleaning process repeated washing 3-5 times.
(5) cleaned sample is finally placed in 50-70 DEG C of dry 8-20h in drying box, is obtained after having dried
Cu2CoSnS4It is nanocrystalline, carry out the detection and analysis of object phase and performance, the results showed that Cu prepared by embodiment 22CoSnS4Nanometer
Brilliant purity with higher, optical band gap (1.43 eV) close to required by direct band-gap semicondictor solar battery most
Good 1.5 eV of band gap has preferable absorbent properties to sunlight.
Embodiment 3
The present embodiment provides a kind of preparation methods that copper cobalt tin sulphur is nanocrystalline, specifically includes the following steps:
(1) 25 mmol CuS, 20 mmol CoS, 15 mmol Sn are weighed2S, 15 mmol sulphur powders and 25 mmol KI+
25mmol CsCl fused salt is uniformly mixed after being fully ground, mixture is placed in crucible.
(2) mixed sample is put into tube furnace, is passed through N2, it is made to be in N2In atmosphere.
(3) it is heated to fused salt melting temperature (750 DEG C) from room temperature, is warming up to 750 with the heating rate of 10 DEG C/min
DEG C roasting 36h, cool to products therefrom with the furnace room temperature.
(4) sample in furnace is taken out, utilizes ultrapure water and alcohol eccentric cleaning after grinding, to guarantee residue on sample
Matter cleans up, and entire cleaning process repeated washing 3-5 times.
(5) cleaned sample is finally placed in 50-70 DEG C of dry 8-20h in drying box, is obtained after having dried
Cu2CoSnS4It is nanocrystalline, carry out the detection and analysis of object phase and performance, the results showed that Cu prepared by embodiment 32CoSnS4Nanometer
Crystalline substance has stronger absorption in visible-range near infrared spectrum region, and its optical band gap is about 1.4 eV, with semiconductor
Best forbidden bandwidth (1.45 eV) required by solar cell is very close, this show they in optoelectronic areas have compared with
High application potential.
Claims (5)
1. a kind of molten-salt growth method prepares the nanocrystalline method of copper cobalt tin sulphur, which is characterized in that specifically includes the following steps:
(1) it is uniformly mixed after being fully ground mantoquita, cobalt salt, pink salt, sulphur source, fused salt, then in N2In atmosphere, from room temperature plus
It more than heat to fused salt melting temperature is roasted, wherein the rate of heat addition is 1-10 DEG C/min, calcining time 8-48h；By gained
Product cools to room temperature with the furnace；
(2) sample is taken out, eccentric cleaning after crushing obtains pure Cu after having dried2CoSnS4It is nanocrystalline.
2. molten-salt growth method prepares the nanocrystalline method of copper cobalt tin sulphur according to claim 1, it is characterised in that: the mantoquita, tin
Salt, cobalt salt are respectively CuS, Sn2S and CoS, sulphur source are S powder, and fused salt is one or both of KI and CsCl.
3. molten-salt growth method prepares the nanocrystalline method of copper cobalt tin sulphur according to claim 1, it is characterised in that: roasting in step (1)
Burning temperature is 650-900 DEG C.
4. molten-salt growth method prepares the nanocrystalline method of copper cobalt tin sulphur according to claim 1, it is characterised in that: mantoquita: pink salt: cobalt
Salt: sulphur source: the molar ratio of fused salt is 10-30:5-20:5-20:10-20:30-70.
5. molten-salt growth method prepares the nanocrystalline method of copper cobalt tin sulphur according to claim 1, it is characterised in that: done in step (2)
Dry condition is 50-70 DEG C of dry 8-20h.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102712495A (en) * | 2009-11-25 | 2012-10-03 | 纳幕尔杜邦公司 | Syntheses of quaternary chalcogenides in cesium, rubidium, barium and lanthanum containing fluxes |
| CN103112885A (en) * | 2012-12-12 | 2013-05-22 | 南京工业大学 | Preparation method of copper-based nano solar battery material |
| CN104952979A (en) * | 2015-06-11 | 2015-09-30 | 岭南师范学院 | Micron-sized spherical copper-zinc-tin-sulfur monocrystal particle preparation method |
| CN105742385A (en) * | 2016-03-23 | 2016-07-06 | 岭南师范学院 | Preparation method for copper-iron-zinc-tin-sulfur micron monocrystal particles |
| CN105727996A (en) * | 2014-12-31 | 2016-07-06 | 清华大学 | Preparation method and application of nano-semiconductor photocatalyst |
-
2019
- 2019-02-25 CN CN201910137636.3A patent/CN109796051A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102712495A (en) * | 2009-11-25 | 2012-10-03 | 纳幕尔杜邦公司 | Syntheses of quaternary chalcogenides in cesium, rubidium, barium and lanthanum containing fluxes |
| CN103112885A (en) * | 2012-12-12 | 2013-05-22 | 南京工业大学 | Preparation method of copper-based nano solar battery material |
| CN105727996A (en) * | 2014-12-31 | 2016-07-06 | 清华大学 | Preparation method and application of nano-semiconductor photocatalyst |
| CN104952979A (en) * | 2015-06-11 | 2015-09-30 | 岭南师范学院 | Micron-sized spherical copper-zinc-tin-sulfur monocrystal particle preparation method |
| CN105742385A (en) * | 2016-03-23 | 2016-07-06 | 岭南师范学院 | Preparation method for copper-iron-zinc-tin-sulfur micron monocrystal particles |
Non-Patent Citations (1)
| Title |
|---|
| SHANSHAN WANG等: "Preparation of Cu2FeSnS4 Single Crystals by Molten Salt Method", 《NANOSCI. NANOTECHNOL. LETT.》 * |
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Application publication date: 20190524 |