CN108793232A - A kind of preparation method of the copper silver-colored zinc tin sulfur particle of buergerite phase micro-nano compound structure - Google Patents
A kind of preparation method of the copper silver-colored zinc tin sulfur particle of buergerite phase micro-nano compound structure Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 79
- 239000010949 copper Substances 0.000 title claims abstract description 79
- YGSCHSPBVNFNTD-UHFFFAOYSA-N [S].[Sn].[Zn] Chemical compound [S].[Sn].[Zn] YGSCHSPBVNFNTD-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000002245 particle Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 150000001875 compounds Chemical group 0.000 title claims abstract description 21
- 229910000238 buergerite Inorganic materials 0.000 title claims abstract description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 39
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000005864 Sulphur Substances 0.000 claims abstract description 23
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012046 mixed solvent Substances 0.000 claims abstract description 20
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000011701 zinc Substances 0.000 claims abstract description 17
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 14
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229960001124 trientine Drugs 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 11
- 238000013019 agitation Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical group NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 16
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical group [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 11
- 229940071536 silver acetate Drugs 0.000 claims description 11
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical group C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 8
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 8
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical group Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 8
- 235000011150 stannous chloride Nutrition 0.000 claims description 8
- 239000001119 stannous chloride Substances 0.000 claims description 8
- 239000004246 zinc acetate Substances 0.000 claims description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 4
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 3
- 235000014121 butter Nutrition 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- YCKOAAUKSGOOJH-UHFFFAOYSA-N copper silver Chemical compound [Cu].[Ag].[Ag] YCKOAAUKSGOOJH-UHFFFAOYSA-N 0.000 claims description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- XDNDXYZWMMAEPS-UHFFFAOYSA-N silver sulfuric acid Chemical compound [Ag].OS(O)(=O)=O XDNDXYZWMMAEPS-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 16
- 238000010586 diagram Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical group S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000000224 chemical solution deposition Methods 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000000527 sonication Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- SEUJAMVVGAETFN-UHFFFAOYSA-N [Cu].[Zn].S=[Sn]=[Se] Chemical compound [Cu].[Zn].S=[Sn]=[Se] SEUJAMVVGAETFN-UHFFFAOYSA-N 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical group [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
- C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Hybrid Cells (AREA)
Abstract
The present invention relates to a kind of preparation methods of the copper silver-colored zinc tin sulfur particle of buergerite phase micro-nano compound structure, belong to photocatalysis and solar cell material technical field.Copper source, Yin Yuan, zinc source, tin source, sulphur source are dissolved in organic in the mixed solvent and obtain precursor solution by the present invention, wherein organic mixed solvent is the mixed solvent of ethylene glycol and triethylene tetramine；Under agitation, it is 120 ~ 140 DEG C of 20 ~ 40 min of reaction precursor solution to be heated to temperature, and it is 180 ~ 200 DEG C of 30 ~ 60 min of reaction to be again heated to temperature, and cooling is separated by solid-liquid separation, and is washed solid and is drying to obtain the copper silver-colored zinc tin sulfur particle of buergerite phase structure.The preparation method of buergerite phase structure copper silver-colored zinc tin sulfur particle of the present invention is simple, and synthesis temperature is relatively low, and precursor material used is of low cost, product excellent in crystallinity, and batch is suitble to synthesize.
Description
Technical field
The present invention relates to a kind of preparation methods of the copper silver-colored zinc tin sulfur particle of buergerite phase micro-nano compound structure, belong to light and urge
Change and solar cell material technical field.
Background technology
Direct band-gap semicondictor material copper-zinc-tin-sulfur have match with solar spectrum band gap width (1.5 or so), compared with
The high absorption coefficient of light (is more than 104cm-1), the advantages that ingredient is nontoxic, the earth's crust is with respect to rich reserves, be extremely potential thin
Film solar cell absorbs layer material；Copper silver-colored zinc tin sulphur is mainly with three kinds of custerite, stannite and wurtzite crystalline structures
In the presence of compared to the copper-zinc-tin-sulfur of custerite and stannite structure, the copper-zinc-tin-sulfur of wurtzite structure has higher current-carrying
Sub- concentration, low resistivity and very strong photoelectric respone, thus increasingly cause the attention of researcher.Meanwhile it if can be into
One step obtains the structure of nanometer scale on the surface of copper silver-colored zinc tin sulphur micron particles（Obtain the micro-nano composite junction of copper silver-colored zinc tin sulphur
Structure）, will make copper silver-colored zinc tin sulphur that there is the surface area of bigger, and be more conducive to and generate light scattering, enhance electron-transport, be also more suitable for
Prepare efficient solar cell.
At present about the preparation method of such polynary photocatalytic semiconductor material mainly include magnetron sputtering method, liquid phase method,
Thermal evaporation and chemical bath deposition method etc..Search document Yeh L Y, Cheng K W. Preparation of the Ag-
Zn–Sn–S quaternary photoelectrodes using chemical bath deposition for
photoelectrochemical applications[J]. Thin Solid Films, 2014, 558(6):289-293.
It is prepared for that silver-colored zinc tin sulphur is nanocrystalline, and the method preparation temperature is low, and substrate is selectively more using chemical bath deposition method, but it is chemical
The bath sedimentation reaction time is slow, needs to anneal in vacuum environment, and obtained sample surfaces are coarse, while substrate deposition,
Also a large amount of deposition film is had on chamber wall, causes a large amount of wastes of raw material.Document Solution-phase
Synthesis of Stannite-type Ag2ZnSnS4 Nanoparticles for Application to
Photoelectrode Materials" T. Sasamura, T. Osaki, T. Kameyama, T. Shibayama,
A. Kudo, S. Kuwabata, and T. Torimoto, Chem. Lett., 41,1009 (2012) use liquid phase
The method that method and sedimentation are combined, synthesis silver-colored zinc tin sulphur is nanocrystalline, and the method need to first prepare AZT presomas, and in protection gas
Lower high-temperature process, then Multiple depositions obtain silver-colored zinc tin sulphur nano thin-film on ITO, and process is extremely complex, and obtained
Sample, purity is relatively low, and impurity is various, and solvent for use oleyl amine is expensive, strong toxicity.Patent 106298995A discloses a kind of use
Spin coating method prepares the CZTS precursor thin-films of Ag doping, the Ag doping copper zinc tin sulfur selenium that after prepared by selenization
(ACZTSSe) layer film is absorbed, but this reaction needs under high temperature environment spin coating repeatedly and needs to be continually fed into protective gas so that
Process is not easy to control, is unfavorable for realizing efficient, large-scale prepare.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of copper silver-colored zinc tin sulfur particles of buergerite phase micro-nano compound structure
Preparation method micro-nano is prepared using simple two steps heating in air that is, using ethylene glycol and triethylene tetramine as solvent
Composite construction copper silver-colored zinc tin sulfur particle, simple for process, reaction condition is mild, the time is short, and environmental-friendly, preparation process intuitively may be used
Control.
A kind of preparation method of the copper silver-colored zinc tin sulfur particle of buergerite phase micro-nano compound structure, the specific steps are：
（1）Copper source, Yin Yuan, zinc source, tin source, sulphur source are dissolved in organic in the mixed solvent and obtain precursor solution, wherein organic
Mixed solvent is the mixed solvent of ethylene glycol and triethylene tetramine；
（2）Under agitation, by step（1）It is 120 ~ 140 DEG C of reactions 20 ~ 40 that gained precursor solution, which is heated to temperature,
Min, it is 180 ~ 200 DEG C of 30 ~ 240 min of reaction to be again heated to temperature, and cooling, separation of solid and liquid is washed solid and is simultaneously drying to obtain micro-
The copper silver-colored zinc tin sulfur particle of nano compound structure；
The step（1）Middle copper source, the molar ratio in silver-colored source are (9 ~ 1):1, the integral molar quantity in copper source and silver-colored source and zinc source, tin source,
The molar ratio of sulphur source is 2:(1~1.25):(1~1.25):(4~6)；
The step（1）Middle copper source is copper chloride, cuprous iodide, copper acetate or copper sulphate, and silver-colored source is silver acetate, silver nitrate or sulphur
Sour silver, zinc source are zinc chloride, zinc acetate or zinc sulfate, and tin source is stannous chloride or butter of tin, and sulphur source is thiocarbamide, sulphur powder, two
Nitric sulfid, lauryl mercaptan or thioacetamide；
The step（1）In the volume ratio of organic in the mixed solvent ethylene glycol and triethylene tetramine be 1:(1~8).
Using ethylene glycol and triethylene tetramine mixed liquor as solvent in the present invention, can by change presoma with ratio,
The reaction conditions such as system reaction time and temperature with ensure higher nucleation rate, good particle size distribution and pattern,
The controllability of component.
Beneficial effects of the present invention：
（1）Raw material used in the method for the present invention is easy to get, at low cost, this method have it is easy to operate, preparation process is intuitively controllable, if
It is standby to require low advantage；By changing presoma with reaction conditions such as ratio, system reaction time and temperature to ensure nucleation speed
Rate is high, particle diameter distribution is narrow and pattern, component are controllable；
（2）Copper silver-colored zinc tin sulphur powder body good crystallinity that the method for the present invention is prepared, visible light region have to be absorbed well, is had
Conducive to raising photoelectric conversion efficiency.
Description of the drawings
Fig. 1 is the XRD diagram of copper silver-colored zinc tin sulfur particle prepared by embodiment 1；
Fig. 2 is the XRD diagram of copper silver-colored zinc tin sulfur particle prepared by embodiment 2；
Fig. 3 is the XRD diagram of copper silver-colored zinc tin sulfur particle prepared by embodiment 3；
Fig. 4 is the UV-vis abosrption spectrograms of copper silver-colored zinc tin sulfur particle prepared by embodiment 2；
Fig. 5 is the SEM figures of copper silver-colored zinc tin sulfur particle prepared by embodiment 2.
Specific implementation mode
Invention is further described in detail With reference to embodiment, but protection scope of the present invention and unlimited
In the content.
Embodiment 1：A kind of preparation method of copper silver-colored zinc tin sulfur particle, the specific steps are：
（1）By copper source（Copper source is copper chloride）, silver-colored source（Silver-colored source is silver acetate）, zinc source（Zinc source is zinc acetate）, tin source（Tin source is
Stannous chloride）, sulphur source（Sulphur source is thiocarbamide）It is dissolved in organic in the mixed solvent, is placed in the ultrasonic wave that frequency is 40KHz and surpasses
Sonication 1h obtains precursor solution, wherein organic mixed solvent is the mixed solvent of ethylene glycol and triethylene tetramine, ethylene glycol
Volume ratio with triethylene tetramine is 1:1, copper source（Copper chloride）With silver-colored source（Silver acetate）Molar ratio be 9:1, copper source（Chlorination
Copper）With silver-colored source（Silver acetate）Integral molar quantity and zinc source（Zinc acetate）, tin source（Stannous chloride）, sulphur source（Thiocarbamide）Molar ratio be
2:1:1:4；
（2）Under agitation, by step（1）It is 120 DEG C of reaction 30min that gained precursor solution, which is heated to temperature, is reheated
It is 180 DEG C of reaction 120min to temperature, cooling, separation of solid and liquid is respectively with absolute ethyl alcohol and distillation water washing solid and drying
Obtain the copper silver-colored zinc tin sulfur particle of micro-nano compound structure；
The XRD diagram of the copper silver-colored zinc tin sulfur particle of micro-nano compound structure manufactured in the present embodiment as shown in Figure 1, from fig. 1, it can be seen that 2 θ=
Diffraction maximum at 26.98 °, 28.46 °, 30.52 °, 39.58 °, 47.56 °, 51.52 °, 56.22 ° respectively with copper silver-colored zinc tin sulphur
PDF cards（W-CZTS）(100), (002), (101), (102), (110), (103), (112) crystal face is corresponding, table
Bright products therefrom is copper silver-colored zinc tin sulfur particle.
Embodiment 2：A kind of preparation method of copper silver-colored zinc tin sulfur particle, the specific steps are：
（1）By copper source（Copper source is copper chloride）, silver-colored source（Silver-colored source is silver acetate）, zinc source（Zinc source is zinc acetate）, tin source（Tin source is
Stannous chloride）, sulphur source（Sulphur source is thiocarbamide）It is dissolved in organic in the mixed solvent, is placed in the ultrasonic wave that frequency is 40KHz and surpasses
Sonication 2h obtains precursor solution, wherein organic mixed solvent is the mixed solvent of ethylene glycol and triethylene tetramine, ethylene glycol
Volume ratio with triethylene tetramine is 1:4, copper source（Copper chloride）With silver-colored source（Silver acetate）Molar ratio be 7:3, copper source（Chlorination
Copper）With silver-colored source（Silver acetate）Integral molar quantity and zinc source（Zinc acetate）, tin source（Stannous chloride）, sulphur source（Thiocarbamide）Molar ratio be
2:1:1:5；
（2）Under agitation, by step（1）It is 140 DEG C of reaction 30min that gained precursor solution, which is heated to temperature, is reheated
It is 190 DEG C of reaction 120min to temperature, cooling, separation of solid and liquid is respectively with absolute ethyl alcohol and distillation water washing solid and drying
Obtain the copper silver-colored zinc tin sulfur particle of micro-nano compound structure；
The XRD diagram of the copper silver-colored zinc tin sulfur particle of micro-nano compound structure manufactured in the present embodiment as shown in Fig. 2, as can be seen from Figure 2,2 θ=
Diffraction maximum at 26.94 °, 28.42 °, 30.46 °, 39.46 °, 47.5 °, 51.44 °, 56.14 ° respectively with copper silver-colored zinc tin sulphur
PDF cards（W-CZTS）(100), (002), (101), (102), (110), (103), (112) crystal face is corresponding, table
Bright products therefrom is copper silver-colored zinc tin sulfur particle.
UV-vis abosrption spectrograms such as Fig. 4 institutes of the copper silver-colored zinc tin sulfur particle of micro-nano compound structure manufactured in the present embodiment
Show, as can be seen from Figure 4, the copper silver-colored zinc tin sulfur particle of the micro-nano compound structure of the present embodiment has in visible light near infrared spectrum region
There are very strong absorption, optical band gap about 1.66eV to be suitable as close to the best band gap 1.5eV needed for thin-film solar cells
The absorption layer material of thin-film solar cells.
The SEM of the copper silver-colored zinc tin sulfur particle of micro-nano compound structure manufactured in the present embodiment schemes as shown in figure 5, as can be seen from Figure 5,
Sample is made of three-dimensional flower-shaped spherical microcrystal grain, and about 300 ~ 500 nm of diameter, size is relatively uniform, while can clearly see
To single flower-shaped particle be by petal shaped nano piece it is that the basic unit self assembly that randomly intersects forms, nanometer sheet thickness is about
10 nm, surface smoother.
Embodiment 3：A kind of copper silver-colored zinc tin sulfur particle preparation method, the specific steps are：
（1）By copper source（Copper source is copper chloride）, silver-colored source（Silver-colored source is silver acetate）, zinc source（Zinc source is zinc acetate）, tin source（Tin source is
Stannous chloride）, sulphur source（Sulphur source is thiocarbamide）It is dissolved in organic in the mixed solvent, is placed in the ultrasonic wave that frequency is 40KHz and surpasses
Sonication 2h obtains precursor solution, wherein organic mixed solvent is the mixed solvent of ethylene glycol and triethylene tetramine, ethylene glycol
Volume ratio with triethylene tetramine is 1:8, copper source（Copper chloride）With silver-colored source（Silver acetate）Molar ratio be 1:1, copper source（Chlorination
Copper）With silver-colored source（Silver acetate）Integral molar quantity and zinc source（Zinc acetate）, tin source（Stannous chloride）, sulphur source（Thiocarbamide）Molar ratio be
2:1.25:1.25:6；
（2）Under agitation, by step（1）It is 130 DEG C of reaction 30min that gained precursor solution, which is heated to temperature, is reheated
It is 200 DEG C of reaction 30min to temperature, it is cooling, it is separated by solid-liquid separation, with absolute ethyl alcohol and distillation water washing solid and is drying to obtain respectively
The copper silver-colored zinc tin sulfur particle of micro-nano compound structure；
The XRD diagram of the copper silver-colored zinc tin sulfur particle of micro-nano compound structure manufactured in the present embodiment as shown in figure 3, as can be seen from Figure 3,2 θ=
Diffraction maximum at 26.92 °, 28.4 °, 30.52 °, 39.5 °, 47.54 °, 51.44 °, the 56.22 ° PDF with copper silver-colored zinc tin sulphur respectively
Card（W-CZTS）(100), (002), (101), (102), (110), (103), (112) crystal face is corresponding, shows
Products therefrom is copper silver-colored zinc tin sulfur particle.
Embodiment 4：Copper silver-colored zinc tin sulfur particle preparation method and embodiment 1 are essentially identical in the present embodiment, difference
It is：Step（1）Middle copper source is copper acetate.
Embodiment 5：Copper silver-colored zinc tin sulfur particle preparation method and embodiment 1 are essentially identical in the present embodiment, difference
It is：Step（1）Middle copper source is cuprous iodide.
Embodiment 6：Copper silver-colored zinc tin sulfur particle preparation method and embodiment 1 are essentially identical in the present embodiment, difference
It is：Step（1）Middle copper source is copper sulphate.
Embodiment 7：Copper silver-colored zinc tin sulfur particle preparation method and embodiment 1 are essentially identical in the present embodiment, difference
It is：Step（1）Middle silver source is silver nitrate.
Embodiment 8：Copper silver-colored zinc tin sulfur particle preparation method and embodiment 1 are essentially identical in the present embodiment, difference
It is：Step（1）Middle silver source is silver sulfate.
Embodiment 9：Copper silver-colored zinc tin sulfur particle preparation method and embodiment 1 are essentially identical in the present embodiment, difference
It is：Step（1）Middle zinc source is zinc chloride.
Embodiment 10：Copper silver-colored zinc tin sulfur particle preparation method and embodiment 1 are essentially identical in the present embodiment, difference
It is：Step（1）Middle tin source is butter of tin.
Embodiment 11：Copper silver-colored zinc tin sulfur particle preparation method and embodiment 1 are essentially identical in the present embodiment, difference
It is：Step（1）Middle sulphur source is sulphur powder.
Embodiment 12：Copper silver-colored zinc tin sulfur particle preparation method and embodiment 1 are essentially identical in the present embodiment, difference
It is：Step（1）Middle sulphur source is carbon disulfide.
Claims (4)
1. a kind of preparation method of the copper silver-colored zinc tin sulfur particle of buergerite phase micro-nano compound structure, which is characterized in that specific steps
For：
（1）Copper source, Yin Yuan, zinc source, tin source, sulphur source are dissolved in organic in the mixed solvent and obtain precursor solution, wherein organic
Mixed solvent is the mixed solvent of ethylene glycol and triethylene tetramine；
（2）Under agitation, by step（1）It is 120 ~ 140 DEG C of reactions 20 ~ 40 that gained precursor solution, which is heated to temperature,
Min, it is 180 ~ 200 DEG C of 30 ~ 240 min of reaction to be again heated to temperature, and cooling, separation of solid and liquid is washed solid and is simultaneously drying to obtain micro-
The copper silver-colored zinc tin sulfur particle of nano compound structure.
2. the preparation method of the copper silver-colored zinc tin sulfur particle of buergerite phase micro-nano compound structure according to claim 1, feature
It is：Step（1）Middle copper source, the molar ratio in silver-colored source are (9 ~ 1):1, the integral molar quantity and zinc source, tin source, sulphur source of copper source and silver-colored source
Molar ratio be 2:(1~1.25):(1~1.25):(4~6).
3. the preparation method of the copper silver-colored zinc tin sulfur particle of buergerite phase micro-nano compound structure according to claim 1, feature
It is：Step（1）Middle copper source is copper chloride, cuprous iodide, copper acetate or copper sulphate, and silver-colored source is silver acetate, silver nitrate or sulfuric acid
Silver, zinc source are zinc chloride, zinc acetate or zinc sulfate, and tin source is stannous chloride or butter of tin, and sulphur source is thiocarbamide, sulphur powder, two sulphur
Change carbon, lauryl mercaptan or thioacetamide.
4. the preparation method of the copper silver-colored zinc tin sulfur particle of buergerite phase micro-nano compound structure according to claim 1, feature
It is：Step（1）In the volume ratio of organic in the mixed solvent ethylene glycol and triethylene tetramine be 1:(1~8).
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| CN106277038A (en) * | 2016-07-27 | 2017-01-04 | 昆明理工大学 | A kind of preparation method of micro-nano compound structure buergerite copper-zinc-tin-sulfur microgranule |
| CN106298995A (en) * | 2016-11-03 | 2017-01-04 | 中国科学院兰州化学物理研究所 | A kind of Ag doping copper zinc tin sulfur selenium light absorbing zone thin-film material and application in solar cells thereof |
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| CN106277038A (en) * | 2016-07-27 | 2017-01-04 | 昆明理工大学 | A kind of preparation method of micro-nano compound structure buergerite copper-zinc-tin-sulfur microgranule |
| CN106298995A (en) * | 2016-11-03 | 2017-01-04 | 中国科学院兰州化学物理研究所 | A kind of Ag doping copper zinc tin sulfur selenium light absorbing zone thin-film material and application in solar cells thereof |
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