CN106517314A - Preparing method of CZTS particulates - Google Patents
Preparing method of CZTS particulates Download PDFInfo
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- CN106517314A CN106517314A CN201611108193.8A CN201611108193A CN106517314A CN 106517314 A CN106517314 A CN 106517314A CN 201611108193 A CN201611108193 A CN 201611108193A CN 106517314 A CN106517314 A CN 106517314A
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- zinc
- czts
- copper
- tin
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- 238000000034 method Methods 0.000 title abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229960001124 trientine Drugs 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 8
- 239000012498 ultrapure water Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 150000003751 zinc Chemical class 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims abstract 2
- 239000000376 reactant Substances 0.000 claims description 18
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 claims description 12
- 239000005864 Sulphur Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 238000005119 centrifugation Methods 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000013049 sediment Substances 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 230000001186 cumulative effect Effects 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical group NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- BEAZKUGSCHFXIQ-UHFFFAOYSA-L zinc;diacetate;dihydrate Chemical compound O.O.[Zn+2].CC([O-])=O.CC([O-])=O BEAZKUGSCHFXIQ-UHFFFAOYSA-L 0.000 claims description 4
- 235000014121 butter Nutrition 0.000 claims description 3
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 2
- 239000000460 chlorine Substances 0.000 claims 2
- 229910052801 chlorine Inorganic materials 0.000 claims 2
- 229910052802 copper Inorganic materials 0.000 claims 2
- 239000010949 copper Substances 0.000 claims 2
- 230000036571 hydration Effects 0.000 claims 2
- 238000006703 hydration reaction Methods 0.000 claims 2
- 229920002472 Starch Polymers 0.000 claims 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 claims 1
- 235000019698 starch Nutrition 0.000 claims 1
- 239000008107 starch Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 abstract description 3
- 239000002244 precipitate Substances 0.000 abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 abstract 1
- 150000001879 copper Chemical class 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 15
- 239000013078 crystal Substances 0.000 description 12
- 229910000238 buergerite Inorganic materials 0.000 description 11
- 238000003760 magnetic stirring Methods 0.000 description 5
- 238000004847 absorption spectroscopy Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 235000011150 stannous chloride Nutrition 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 3
- KYRUBSWVBPYWEF-UHFFFAOYSA-N copper;iron;sulfane;tin Chemical compound S.S.S.S.[Fe].[Cu].[Cu].[Sn] KYRUBSWVBPYWEF-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910002475 Cu2ZnSnS4 Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/006—Compounds containing, besides tin, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
-
- 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
- C01P2004/30—Particle morphology extending in three dimensions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/45—Aggregated particles or particles with an intergrown morphology
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a preparing method of CZTS nanocrystallines and belongs to the field of photoelectric material preparation. The preparing method comprises the following steps: adding copper salt, zinc salt, tin salt, sulfur source and cetyl trimethylammonium bromide into a container, adding a glycol and triethylene tetramine mixed solution into the container, and ultrasonically dissolving until a precursor solution is obtained; carrying out two-step heating reaction on the precursor solution, and after reaction is finished, naturally cooling to a room temperature; separately adding absolute ethyl alcohol and ultrapure water into cooled reacting liquid, washing and carrying out centrifugal separation so as to obtain CZTS nanocrystalline precipitates; and drying the obtained CZTS nanocrystalline precipitates so as to obtain CZTS nanocrystalline powder with a controllable crystalline phase. The method is simple, is low in cost and is suitable for massive synthesis.
Description
Technical field
The present invention relates to a kind of copper-zinc-tin-sulfur（Cu2ZnSnS4, CZTS）The preparation method of particulate, belongs to photoelectric material system
Standby field.
Background technology
New quaternary compound semiconductor copper-zinc-tin-sulfur（Cu2ZnSnS4, CZTS）With the higher absorption coefficient of light (>
104cm-1), energy gap about 1.5eV（Match with the optimal energy gap required for solar cell）, component
It is rich content in the earth's crust, cheap, and composition is nontoxic and be suitable to antivacuum technology of preparing condition, therefore CZTS is a kind of green
Color, cheap, safety, the photovoltaic material for being adapted to large-scale production and application.
CZTS mainly has stannite, three kinds of crystalline structures of stannite and buergerite, and wherein custerite mutually has with stannite
There is tetragonal crystalline structure, they are thermodynamically stable phases, and buergerite mutually belongs to hexagonal system structure, is thermodynamics metastable phase.
It is reported that, reached by the photoelectric transformation efficiency for absorbing the CZTS thin-film solar cells of layer material of custerite structure C ZTS
12.6%, with wurtzite structure CZTS be absorb layer material thin-film solar cells photoelectric transformation efficiency be 4.3%；And with fibre
Zinc ore CZTS and custerite CZTS as DSSC to electrode when, the conversion efficiency of battery is respectively
6.89% and 4.89%.These results indicate that the crystal structure of photoelectric material has material impact to the photoelectric properties of photovoltaic device.
Therefore, the different CZTS of controlledly synthesis crystal structure is significant to improving photoelectric device performance.
Find by literature search, existing various preparation methods with regard to the controllable CZTS of crystalline phase.But needed for these technological reactions
It is long between seasonable（24h）, it is unfavorable for realizing efficiently, quickly preparing.Patent CN201510456207.4 uses elemental sulfur and 12
Mercaptan realizes in control CZTS nano material custerite by the ratio for regulating and controlling elemental sulfur and lauryl mercaptan as mixing sulphur source
With the ratio of buergerite, but whole course of reaction needs argon gas to protect, and reaction temperature is higher, is unfavorable for low cost, extensive
Prepare CZTS.
The content of the invention
Present invention aims to a kind of nanocrystalline preparation method of copper-zinc-tin-sulfur of offer of above-mentioned prior art, adopts
Synthesize copper-zinc-tin-sulfur particulate in atmosphere with two step heatings, the controllable CZTS of crystalline phase is obtained by simple adjustment solvent ratios and received
Meter Jing, specifically includes following steps：
（1）Mantoquita, zinc salt, pink salt, sulphur source and surfactant are added in reaction vessel, ethylene glycol are added in reaction vessel
With the mixed solution of triethylene tetramine and ultrasonic dissolution, wherein, the volume of ethylene glycol accounts for the percentage of mixed solution cumulative volume and is
>=1.25%, it is >=1.25% that the volume of triethylene tetramine accounts for the percentage of mixed solution cumulative volume.
（2）Two step heating responses are carried out to step 1 resulting solution.
（3）The reactant liquor for completing two step heating responses naturally cools to room temperature, is separately added into in the reactant liquor after cooling
Absolute ethyl alcohol and ultra-pure water carry out washing, and then be centrifuged obtaining the nanocrystalline sediments of CZTS, by the CZTS nanometers for obtaining
Brilliant drying precipitate, that is, obtain CZTS nanocrystalline.
Preferably, mantoquita of the present invention be Copper dichloride dihydrate, copper acetate monohydrate, in Salzburg vitriol one
Kind.
Preferably, zinc salt of the present invention be zinc chloride, Zinc diacetate dihydrate, the one kind in Zinc vitriol.
Preferably, pink salt of the present invention be two hydrated stannous chlorides, the one kind in butter of tin.
Preferably, sulphur source of the present invention be thiocarbamide, sulphur powder, the one kind in thioacetamide.
Preferably, the mol ratio of mantoquita of the present invention, zinc salt, pink salt and sulphur source is 2:(1-1. 5):(1-1.25):
(4-6)。
Preferably, surfactant of the present invention is cetyl trimethylammonium bromide, and its addition is 0-12.5mg/
mL。
Preferably, step of the present invention（2）In two step heating responses temperature and time be respectively 120-150 DEG C, 20min-
1h and 180-220 DEG C, 1-4h is stirred to reactant liquor by magnetic stirring apparatus in heating process, and mixing speed is 300-
900rpm。
Preferably, step of the present invention（3）In be separately added into absolute ethyl alcohol and ultra-pure water carries out washing, is then centrifuged for separating,
The number of times of " washing, centrifugation " is 3-5 time, and during centrifugation, centrifuge speed is 8000-12000rpm, and centrifugation time is 3-
5min；Dry condition is to be dried 6-12h at 60-100 DEG C.
All operations of the present invention are carried out in atmosphere.
Beneficial effects of the present invention：
（1）Raw material used in the method for the invention is easy to get, nontoxic, low cost；Whole technological operation is under air conditionses
Carry out, it is not necessary to inert gas shielding environment, preparation process is simple, directly perceived controllable；Equipment requirement is low, it is easy to accomplish extensive raw
Produce.
（2）The present invention, can be by simple regulation and control second using the ethylene glycol of low toxicity and triethylene tetramine mixed liquor as solvent
The ratio of glycol and triethylene tetramine obtains the CZTS of pure phase custerite structure, the CZTS of pure phase wurtzite structure and two-phase
The CZTS of mixing, realizes that the thing of CZTS is mutually controllable；Meanwhile, the pattern of CZTS particulates can be controlled from graininess, flowers shape, and
Change with micro-nano compound structure, is conducive to improving the conversion efficiency of photoelectric device.
（3）CZTS powder crystallinities that the method for the invention is prepared are good, size uniform, it is seen that light region has good
Good absorption, gained CZTS powders energy gap are 1.42-1.48eV, closely absorbing layer of thin film solar cell material institute
Need optimal energy gap（1.5eV）, it is adaptable to area of solar cell.
Description of the drawings
Fig. 1 is invention schematic flow sheet；
Fig. 2 is the XRD of sample prepared by embodiment 1；
Fig. 3 is the XRD of sample prepared by embodiment 2；
Fig. 4 is the XRD of sample prepared by embodiment 3；
Fig. 5 is the XRD of sample prepared by embodiment 4；
Fig. 6 is the SEM figures of the sample of a in embodiment 4；
Fig. 7 is the SEM figures of the sample of b in embodiment 4；
Fig. 8 is the SEM figures of the sample of c in embodiment 4；
Fig. 9 is the SEM figures of the sample of d in embodiment 4；
Figure 10 is the UV-vis abosrption spectrogram and (α h ν) of a samples in embodiment 42~ h ν collection of illustrative plates；
Figure 11 is the UV-vis abosrption spectrogram and (α h ν) of c samples in embodiment 42~ h ν collection of illustrative plates.
Specific embodiment
The present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings, but protection scope of the present invention is simultaneously
It is not limited to the content.
Embodiment 1
（1）By 2mmol Copper dichloride dihydrates, 1mmol Zinc diacetate dihydrates, bis- hydrated stannous chlorides of 1mmol, 4mmol sulphur powders and
During 0.1g cetyl trimethylammonium bromides add there-necked flask, 36mL ethylene glycol and 4mL triethylenes are added in there-necked flask
Tetramine mixed liquor, supersonic wave cleaning machine ultrasound 15min of the frequency for 28KHz.
（2）Two step heating responses are carried out to step 1 resulting solution.The temperature of two step heating responses, time are respectively：120
DEG C, 20min and 180 DEG C, 4h；In heating process, reactant liquor is stirred by magnetic stirring apparatus, mixing speed is
360rpm。
（3）The reactant liquor that two step heating responses are obtained is made to naturally cool to room temperature, in the reactant liquor after cooling 3 times respectively
Absolute ethyl alcohol and ultra-pure water is added to be centrifuged（Centrifuge speed：8000rpm, each centrifugation time：3min）Obtain
The nanocrystalline sediments of CZTS, the CZTS nanocrystalline colloids to obtaining are dried 8h at 60 DEG C, that is, obtain pure phase custerite structure
CZTS manocrystalline powders.
Products therefrom is prepared to the present embodiment carries out XRD tests, as shown in Fig. 22 θ=28.41 °, 32.92 °,
47.30 °, 56.15 °, (112) respectively with custerite CZTS of the diffraction maximum at 76.46 °, (200), (220),
(312), (332) crystal face is corresponding, shows that products therefrom is custerite phase CZTS crystal.
Embodiment 2
（1）2mmol copper acetate monohydrates, 1.2mmol zinc chloride, 1mmol butters of tin and 5mmol thioacetamides are added into three
In mouth flask, 8mL ethylene glycol and 32mL triethylene tetramine mixed liquors, ultrasonic wave of the frequency for 28KHz are added in there-necked flask
Cleaning machine ultrasound 45min.
（2）Two step heating responses are carried out to step 1 resulting solution.The temperature of two step heating responses, time are respectively：120
DEG C, 30min and 190 DEG C, 3h；In heating process, reactant liquor is stirred by magnetic stirring apparatus, mixing speed is
400rpm。
（3）The reactant liquor that two step heating responses are obtained is made to naturally cool to room temperature, in the reactant liquor after cooling 3 times respectively
Absolute ethyl alcohol and ultra-pure water is added to be centrifuged（Centrifuge speed：8600rpm, each centrifugation time：3min）Obtain
The nanocrystalline sediments of CZTS, the CZTS nanocrystalline colloids to obtaining are dried 8h at 80 DEG C, that is, obtain custerite and buergerite two
The CZTS manocrystalline powders for mixing.
Products therefrom is prepared to the present embodiment carries out XRD tests, as shown in figure 3,2 θ=28.41 °, 32.92 °, 47.30 °,
Diffraction maximum at 56.15 ° is corresponding with (112) of custerite CZTS, (200), (220), (312) crystal face respectively, and 2 θ=
26.91 °, 28.50 °, 30.53 °, 39.61 °, 47.56 °, 51.78 °, the diffraction maximum at 56.39 ° is respectively with buergerite CZTS's
(100), (002), (101), (102), (110), (103), (112) crystal face are corresponding, show products therefrom for custerite
The mixed crystal of phase CZTS and buergerite phase CZTS.
Embodiment 3
（1）By 2mmol Salzburg vitriols, 1.2mmol Zinc vitriols, bis- hydrated stannous chlorides of 1.2mmol and 5mmol sulphur
During urea adds there-necked flask, 20mL ethylene glycol and 20mL triethylene tetramine mixed liquors are added in there-necked flask, frequency is 28KHz
Supersonic wave cleaning machine ultrasound 1.5h.
（2）Two step heating responses are carried out to step 1 resulting solution.The temperature of two step heating responses, time are respectively：140
DEG C, 30min and 190 DEG C, 2h；In heating process, reactant liquor is stirred by magnetic stirring apparatus, mixing speed is
600rpm。
（3）The reactant liquor that two step heating responses are obtained is made to naturally cool to room temperature, in the reactant liquor after cooling 4 times respectively
Absolute ethyl alcohol and ultra-pure water is added to be centrifuged（Centrifuge speed：9000rpm, each centrifugation time：5min）Obtain
The nanocrystalline sediments of CZTS, the CZTS nanocrystalline colloids to obtaining are dried 12h at 60 DEG C, that is, obtain custerite and buergerite two
The CZTS manocrystalline powders for mixing.
Products therefrom is prepared to the present embodiment carries out XRD tests, as shown in figure 4,2 θ=26.91 °, 28.50 °, 30.53 °,
39.61 °, 47.56 °, 51.78 °, the diffraction maximum at 56.39 ° (100), (002), (101) respectively with buergerite CZTS,
(102), (110), (103), (112) crystal face are corresponding, show products therefrom for buergerite phase CZTS crystal.
Embodiment 4
（1）By 2mmol Copper dichloride dihydrates, 1.25mmol Zinc diacetate dihydrates, bis- hydrated stannous chlorides of 1mmol, 6mmol thiocarbamides
In adding there-necked flask, 40mL ethylene glycol and triethylene tetramine mixed liquor are added in there-necked flask（Ethylene glycol and triethylene four
The thing phase of the volume of amine and corresponding product, pattern are as shown in table 1）, supersonic wave cleaning machine ultrasound 2h of the frequency for 28KHz.
（2）Two step heating responses are carried out to step 1 resulting solution.The temperature of two step heating responses, time are respectively：130
DEG C, 30min and 200 DEG C, 2h；In heating process, reactant liquor is stirred by magnetic stirring apparatus, mixing speed is
800rpm。
（3）The reactant liquor that two step heating responses are obtained is made to naturally cool to room temperature, in the reactant liquor after cooling 3 times respectively
Absolute ethyl alcohol and ultra-pure water is added to be centrifuged（Centrifuge speed：12000rpm, each centrifugation time：4min）Obtain
The nanocrystalline sediments of CZTS, the CZTS nanocrystalline colloids to obtaining are dried 8h at 80 DEG C, that is, obtain the controllable CZTS of phase structure
Powder.
Products therefrom is prepared to the present embodiment carries out XRD, SEM and uv-visible absorption spectroscopy test.As shown in figure 5,
The analysis of 1,2,3 products therefrom of similar embodiment, shows in the embodiment that products therefrom a is that custerite phase CZTS crystal, b are
The mixed crystal of custerite phase CZTS and buergerite phase CZTS, c and d are buergerite phase CZTS crystal.
During SEM photograph such as Fig. 6 shows the embodiment, product a is CZTS particle of the diameter in 300-700nm；The SEM of Fig. 7
During photo shows the embodiment, product b is flowers shape CZTS of the diameter in 300-500nm；The SEM photograph of Fig. 8 shows the embodiment
Middle product c is irregular block CZTS of the diameter in 100-400nm；During the SEM photograph of Fig. 9 shows the embodiment, product d is tool
There is the CZTS of micro-nano compound structure, by a diameter of 200-800nm, thickness is for the blocky-shaped particle of 20-70nm and this for this structure
The vermiform nano wire composition of long 40-120nm that particle surface is had, width 6-15nm.
Figure 10,11 be sample a, d in the embodiment uv-visible absorption spectroscopy figure and corresponding (α h ν)2~ h ν scheme
Spectrum, uv-visible absorption spectroscopy figure is the raw-data map for measuring, (α h ν)2~ h ν collection of illustrative plates is by uv-visible absorption spectroscopy
Release, understand that sample a, d are respectively provided with very strong absorption in visible region and extend near infrared region with reference to two figures, its
Energy gap is respectively 1.43 eV, 1.48eV, is close to needed for absorbing layer of thin film solar cell material optimal energy gap
（1.5eV）, it is favourable that the performance of the solar film battery to preparing is improved.
The thing phase of ethylene glycol and triethylene tetramine volume and corresponding product, pattern in the solvent of 1. embodiment 4 of table
Claims (9)
1. a kind of preparation method of copper-zinc-tin-sulfur particulate, it is characterised in that specifically include following steps：
（1）Mantoquita, zinc salt, pink salt, sulphur source and surfactant are added in reaction vessel, ethylene glycol are added in reaction vessel
With the mixed solution of triethylene tetramine and ultrasonic dissolution, wherein, the volume of ethylene glycol accounts for the percentage of mixed solution cumulative volume and is
>=1.25%, it is >=1.25% that the volume of triethylene tetramine accounts for the percentage of mixed solution cumulative volume；
（2）Two step heating responses are carried out to step 1 resulting solution；
（3）The reactant liquor for completing two step heating responses naturally cools to room temperature, is separately added into anhydrous in the reactant liquor after cooling
Ethanol and ultra-pure water carry out washing, and then be centrifuged obtaining the nanocrystalline sediments of CZTS, will be the CZTS for obtaining nanocrystalline heavy
Starch is dried, that is, obtain CZTS nanocrystalline.
2. the preparation method of copper-zinc-tin-sulfur particulate according to claim 1, it is characterised in that：The mantoquita is two hydration chlorine
Change the one kind in copper, copper acetate monohydrate, Salzburg vitriol.
3. the preparation method of copper-zinc-tin-sulfur particulate according to claim 1, it is characterised in that：The zinc salt be zinc chloride,
One kind in Zinc diacetate dihydrate, Zinc vitriol.
4. the preparation method of copper-zinc-tin-sulfur particulate according to claim 1, it is characterised in that：The pink salt is two hydration chlorine
Change the one kind in stannous, butter of tin.
5. the preparation method of copper-zinc-tin-sulfur particulate according to claim 1, it is characterised in that：The sulphur source is thiocarbamide, sulphur
One kind in powder, thioacetamide.
6. the preparation method of the copper-zinc-tin-sulfur particulate according to claim 1-5 any one, it is characterised in that：The copper
The mol ratio of salt, zinc salt, pink salt and sulphur source is 2:(1-1. 5):(1-1.25):(4-6).
7. the preparation method of copper-zinc-tin-sulfur particulate according to claim 1, it is characterised in that：The surfactant is ten
Six alkyl trimethyl ammonium bromides, its addition are 0-12.5mg/mL.
8. the preparation method of copper-zinc-tin-sulfur particulate according to claim 1, it is characterised in that：Step（2）In two steps heating
The temperature and time of reaction is respectively 120-150 DEG C, 20min-1h and 180-220 DEG C, and 1-4h is stirred by magnetic force in heating process
Mix device to be stirred reactant liquor, mixing speed is 300-900rpm.
9. the preparation method of brilliant copper-zinc-tin-sulfur particulate according to claim 1, it is characterised in that：Step（3）In " washing, from
The number of times of heart separation " is 3-5 time, and during centrifugation, centrifuge speed is 8000-12000rpm, and centrifugation time is 3-5min；It is dried
Condition be 60-100 DEG C at be dried 6-12h.
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| CN112279306A (en) * | 2020-10-21 | 2021-01-29 | 南京晓庄学院 | Optimization method of sulfide nanocrystal, Sn-S-Co nanocrystal and optimized product thereof |
| CN113979468A (en) * | 2021-12-09 | 2022-01-28 | 山东中鸿新能源科技有限公司 | Preparation method of CZTS (Se) nano powder for solar cell module |
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| CN113979468A (en) * | 2021-12-09 | 2022-01-28 | 山东中鸿新能源科技有限公司 | Preparation method of CZTS (Se) nano powder for solar cell module |
| CN113979468B (en) * | 2021-12-09 | 2023-05-09 | 山东中鸿新能源科技有限公司 | Preparation method of CZTS (Se) series nano powder for solar cell module |
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