CN104862782B - A kind of quaternary sulfide semiconductor material and its production and use - Google Patents
A kind of quaternary sulfide semiconductor material and its production and use Download PDFInfo
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 title claims abstract description 29
- 125000000101 thioether group Chemical group 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000006104 solid solution Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 7
- 150000001339 alkali metal compounds Chemical class 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 5
- 229910052959 stibnite Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 241001124569 Lycaenidae Species 0.000 claims 1
- 235000014987 copper Nutrition 0.000 claims 1
- 235000001508 sulfur Nutrition 0.000 claims 1
- 239000010949 copper Substances 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 18
- 229910052802 copper Inorganic materials 0.000 abstract description 11
- 230000003287 optical effect Effects 0.000 abstract description 10
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 6
- 150000001340 alkali metals Chemical group 0.000 abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 5
- 229940007424 antimony trisulfide Drugs 0.000 abstract description 5
- NVWBARWTDVQPJD-UHFFFAOYSA-N antimony(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Sb+3].[Sb+3] NVWBARWTDVQPJD-UHFFFAOYSA-N 0.000 abstract description 5
- 150000001450 anions Chemical group 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 150000003624 transition metals Chemical group 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 239000003708 ampul Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 150000001786 chalcogen compounds Chemical class 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 229910052792 caesium Inorganic materials 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 229910052701 rubidium Inorganic materials 0.000 description 4
- 238000002050 diffraction method Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 241000736199 Paeonia Species 0.000 description 2
- 235000006484 Paeonia officinalis Nutrition 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 150000004770 chalcogenides Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006184 cosolvent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 description 2
- 238000003836 solid-state method Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007716 flux method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000009022 nonlinear effect Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B28/00—Production of homogeneous polycrystalline material with defined structure
- C30B28/04—Production of homogeneous polycrystalline material with defined structure from liquids
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
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Abstract
The invention discloses a kind of quaternary sulfide semiconductor material and its production and use.Using alkali metal compound, metallic copper, binary solid solution antimony trisulfide and elemental sulfur as raw material, hydrazine hydrate and polyethylene glycol are solvent, are reacted 49 days in 120 190 DEG C of baking ovens, obtain quaternary sulfide semiconductor material.Chemical constitution formula is：AxCuySbzS(x+y+3z)/2, wherein A is the alkali metal atom of balance anion skeleton, and x represents the mole of alkali metal atom, and y represents to form the mole of skeleton transition metal atoms, and z represents to form the mole of skeletal atom.This method has operating process simple, and cost of material is low, and reaction condition is gentle, the advantages such as synthesis temperature is low.The quaternary sulfide obtained using this method, yield can reach 60% 90%, and crystallite dimension is 150 300 μm, and chemical purity is high, for preparing optical semiconductor device.
Description
Technical field
The present invention relates to a kind of quaternary sulfide semiconductor material and its production and use, belong to inorganic semiconductor material
Material field.
Background technology
FTIR radiation transmittance can be made into the light such as second harmonic generator, frequency converter, optical parametric oscillator
Device is learned, has in the field such as laser communicationses and military technology important and is widely applied, thus causes extensive concern.According to material
Expect the difference of application band, nonlinear optical material is broadly divided into ultraviolet region, visible and near-infrared region and mid-infrared and far-infrared light
Area's three major types.The nonlinear optical crystal of the marketization is essentially all to be made up of inorganic material, including KTiOPO4(KTP)、β-
BaB2O4(BBO)、AgGaS2(AGS) etc..In recent years, multi-component sulfur compound-material is because of its unique architectural feature and superior
Physical and chemical performance, there is irreplaceable important function in optical semiconductor field, particularly in mid and far infrared second order non-linear
Property Crystal study direction, such as AgGaSe2And BaGa (AGSe)4S7(BGS) etc., current such chalcogen compound is mostly ternary phase.
Relative to ternary chalcogenide thing, quaternary chalcogen compound is made up of more elements, and the interphase interaction of element is more multiple
Miscellaneous and various, thus, obtained kind of crystalline is more, structure is more complicated, performance is more diversified.
At present, preparing the typical method of quaternary chalcogen compound both at home and abroad mainly includes following three kinds：
1）High temperature solid-state method：The heterogeneous phase chemical reaction that solid reactant directly participates in, without using solvent in course of reaction,
Have the characteristics that it is selective it is high, yield is high, technical process is simple, be prepare at this stage novel solid materials main method it
One.But because reaction temperature is compared with the shortcomings of high, side reaction is more, experimental implementation is complicated, experimental cost is higher, limits it and extensively should
With.
2）Medium temperature flux method：Cosolvent is introduced in high temperature solid-state method, reduces crystal growth temperature, but growth cycle prolongs
Long, most fluxing agent all has different degrees of toxicity, human body and environment is damaged during volatilization, and the crystal of preparation
Grain is smaller, accessory substance be present, it is necessary to remove cosolvent, thus be not suitable for industrial production.
3）Low-temperature solvent heat（Hydro-thermal）Method：Hydro-thermal and solvent-thermal process method be prepare chalcogen compound important means it
One.Utilize low-temperature solvent heat（Hydro-thermal）It is to grow up for nearly 30 years that method, which prepares chalcogen compound, prepared by early stage Sch fer etc.
A series of ternary chalcogenide things containing Main Group Metal Elements.Compared with traditional high temperature solid phase synthesis, hydro-thermal preparation side
Method easily forms be situated between steady phase, physics and chemical property there occurs larger change, thus can preparation structure it is unique, function admirable
Semiconductor crystalline material.By regulating and controlling the conditions such as reaction temperature, reactant species, reaction medium, reactant can be effectively improved
Solubility and diffusion velocity, accelerate reaction process, influence the atom connected mode of anion frame, the pattern and property of optimized product
Energy.Thunder dawn force et al. is successfully prepared [dienH using solvent-thermal method2]Hg2Sb2S6(thunder dawn force etc., Jining institute journal, 35,
36 (2014)), but because organic group is included in product, cause product heat endurance poor, and yield relatively low only 35%.It is old
Shake et al. is successfully prepared CsSb by solvent-thermal method2(Se2)0.5Se3(Chen Zhen etc., Chinese Journal of Inorganic Chemistry, 22,27 (2006)),
But need first to be filled with argon gas in preparation process and protected, then tube sealing is handled, and whole experiment process is comparatively laborious, condition requirement
It is higher.An Yonglin et al. (Inorganic Chemistry 53,4856 (2014)) selects 1,2- propane diamine and methanol-water mixing
Solution makees solvent, is reacted 5 days at 160 DEG C, is prepared for Rb2Cu2Sb2S5Sulfide semiconductor material, experimentation are related to envelope
Pipe operates, and process is more complicated, and products collection efficiency relatively low only 36%.
Therefore, new solvent-thermal process route is developed, explores new synthetic system, and experimentation is more simple and convenient, instead
Condition milder is answered, synthesis temperature is lower, and yield is higher, will be the key for preparing multi-component sulfur compound semiconductor materials.
The content of the invention
The purpose of the present invention is overcome the deficiencies in the prior art, there is provided a kind of quaternary sulfide semiconductor material and its preparation
Method and purposes.
The chemical constitution formula of quaternary sulfide semiconductor material is：AxCuySbzS(x+y+3z)/2, wherein A is balance anion
The alkali metal atom of skeleton, it is one kind in K, Rb, Cs, x represents the mole of alkali metal atom, and y represents to form skeleton transition
The mole of metallic atom, z represent to form the mole of skeletal atom.
The preparation method of quaternary sulfide semiconductor material is：With alkali metal compound, metallic copper, binary solid solution vulcanization
Antimony and elemental sulfur are raw material, and hydrazine hydrate and polyethylene glycol are solvent, are reacted 4-9 days in 120-190 DEG C of baking oven, obtain quaternary
Sulfide semiconductor material.
Described alkali metal compound, metallic copper, the mol ratio of binary solid solution antimony trisulfide and elemental sulfur are 0.5-1.0：
2.0-3.0：0.5-1.0：2.0-2.5；The mol ratio of hydrazine hydrate and polyethylene glycol is 1.0-2.0：2.5-3.0.Described alkali gold
Belonging to compound is：Alkali metal hydroxide, carbonate or chloride.The preparation method of described binary solid solution antimony trisulfide is：
It is 2 by mol ratio:3 Sb and S loads quartz ampoule and carries out tube sealing, then the quartz ampoule of sealing is put into Muffle furnace, slowly heating
To 560 DEG C, and 8 hours are incubated, then naturally cool to room temperature, open quartz ampoule block stock grind into powder is standby.
Quaternary sulfide semiconductor material energy gap is respectively 1.41 eV, 1.74 eV and 1.95 eV, and the semi-conducting material is used
In preparing optical semiconductor device, optical semiconductor device is solar cell buffer layer material.
Operating process of the present invention is simple and convenient, and cost of material is low, and reaction condition is gentle, and synthesis temperature is low etc., using we
Quaternary sulfide semiconductor material prepared by method, yield can reach 60%-90%, and crystallite dimension is 150-300 μm, and chemistry is pure
Degree is high.The energy gap of semi-conducting material is respectively 1.41 eV, 1.74 eV and 1.95 eV, is had in terms of semiconductor optical potential
Application value.
Brief description of the drawings
Fig. 1 is KCu2SbS3The shape appearance figure of crystal；
Fig. 2 is RbCuSb2S4The shape appearance figure of crystal；
Fig. 3 is Cs2Cu2Sb2S5The shape appearance figure of crystal；
Fig. 4 is KCu2SbS3The EDX collection of illustrative plates of crystal, indicate presence and its content of K, Cu, Sb and S element；
Fig. 5 is RbCuSb2S4The EDX collection of illustrative plates of crystal, indicate presence and its content of Rb, Cu, Sb and S element；
Fig. 6 is Cs2Cu2Sb2S5The EDX collection of illustrative plates of crystal, indicate presence and its content of Cs, Cu, Sb and S element；
Fig. 7 is KCu2SbS3Structure chart；
Fig. 8 is RbCuSb2S4Structure chart；
Fig. 9 is Cs2Cu2Sb2S5Structure chart；
Figure 10 is AxCuySbzS(x+y+3z)/2The visible diffusing reflection spectrum of solid-state UV.
Embodiment
The chemical constitution formula of quaternary sulfide semiconductor material is：AxCuySbzS(x+y+3z)/2, wherein A is balance anion
The alkali metal atom of skeleton, it is one kind in K, Rb, Cs, x represents the mole of alkali metal atom, and y represents to form skeleton transition
The mole of metallic atom, z represent to form the mole of skeletal atom.
The preparation method of quaternary sulfide semiconductor material is：With alkali metal compound, metallic copper, binary solid solution vulcanization
Antimony and elemental sulfur are raw material, and hydrazine hydrate and polyethylene glycol are solvent, are reacted 4-9 days in 120-190 DEG C of baking oven, obtain quaternary
Sulfide semiconductor material.
Described alkali metal compound, metallic copper, the mol ratio of binary solid solution antimony trisulfide and elemental sulfur are 0.5-1.0：
2.0-3.0：0.5-1.0：2.0-2.5；The mol ratio of hydrazine hydrate and polyethylene glycol is 1.0-2.0：2.5-3.0.Described alkali gold
Belonging to compound is：Alkali metal hydroxide, carbonate or chloride.The preparation method of described binary solid solution antimony trisulfide is：
It is 2 by mol ratio:3 Sb and S loads quartz ampoule and carries out tube sealing, then the quartz ampoule of sealing is put into Muffle furnace, slowly heating
To 560 DEG C, and 8 hours are incubated, then naturally cool to room temperature, open quartz ampoule block stock grind into powder is standby.
Quaternary sulfide semiconductor material is used to prepare optical semiconductor device, and optical semiconductor device is solar cell
Buffer layer material.
Embodiment 1：
KCu2SbS3Crystal.Weigh initial feed K2CO30.5 mmol (0.069g)、Cu 2.0 mmol(0.128g)、
Sb2S30.5 mmol (0.170g) and the mmol of S 2.0 (0.064g) are put into water heating kettle, are added the mL of hydrazine hydrate 1.0 and are gathered
The mL of ethylene glycol 2.5, water heating kettle is placed at 120 DEG C and reacted 9 days.After reaction terminates, water heating kettle is opened, product is taken out, uses respectively
Distilled water and absolute ethyl alcohol wash 2 times, obtain black bulk crystals, yield 80%, 150-230 μm of crystallite dimension (see Fig. 1).
Through single-crystal X-ray diffraction analysis, the crystal composition formula is KCu2SbS3, belong to anorthic system, space group is P-1(2), a=
6.3857, b=9.1361, c=10.4672, α=90.51 °, β=91.32 °, γ=91.49 °, Z=4, V=610.263,
Crystal structure figure is as shown with 7.EDX elementary analyses show crystal containing only tetra- kinds of elements of K, Cu, Sb, S, and each element content ratio with
Single crystal diffraction analysis result is consistent (see Fig. 4).It is 1.41 eV that UV-vis collection of illustrative plates, which measures semi-conducting material energy gap, (see Figure 10).
Embodiment 2：
RbCuSb2S4Crystal.Weigh the mmol of initial feed RbCl 1.0 (0.121g), the mmol of Cu 2.0 (0.128g),
Sb2S30.8mmol (0.170g) and the mmol of S 2.0 (0.064g) are put into water heating kettle, add hydrazine hydrate 1.6mL and poly- second
The mL of glycol 2.5, water heating kettle is placed at 170 DEG C and reacted 7 days.Product is washed 2 times with distilled water and absolute ethyl alcohol respectively, is obtained
Peony rhabdolith, for yield up to 60 %, crystallite dimension is 180-280 μm (see Fig. 2).Through single-crystal X-ray diffraction analysis,
The crystal composition formula is RbCuSb2S4, belonging to monoclinic system, space group is C12/c1, a=7.3272, b=11.1628, c=
10.7849, β=105.75 °, Z=4, V=849.013, crystal structure figure is as depicted in figure 8.EDX elementary analyses show crystal containing only
Tetra- kinds of elements of Rb, Cu, Sb, S, and each element content ratio is consistent with single crystal diffraction analysis result (see Fig. 5).UV-vis collection of illustrative plates measures
Semi-conducting material energy gap is 1.74 eV (see Figure 10).
Embodiment 3：
Cs2Cu2Sb2S5Crystal.Weigh initial feed CsOHH2O 1.0 mmol(0.168g)、Cu 3.0 mmol
(0.192g)、Sb2S31.0mmol (0.170g) and the mmol of S 2.5 (0.08g) are put into water heating kettle, add hydrazine hydrate 2.0
The mL and mL of polyethylene glycol 3.0.Water heating kettle is placed at 190 DEG C and reacted 4 days, product is washed 2 times with distilled water and ethanol respectively,
Peony bulk crystals are obtained, for yield up to 72%, crystallite dimension is 170-300 μm (see Fig. 3).Through single crystal X-ray diffraction point
Analysis, the crystal composition formula is Cs2Cu2Sb2S5, belong to anorthic system, space group is P-1(2), a=7.3965, b=8.5390,
C=9.8302, α=91.95 °, β=92.17 °, γ=101.86 °, Z=2, V=606.633, crystal structure figure is as figure 9.EDX
Elementary analysis shows crystal containing only tetra- kinds of elements of Cs, Cu, Sb, S, and each element content ratio is consistent with single crystal diffraction analysis result
(see Fig. 6).It is 1.95 eV that UV-vis collection of illustrative plates, which measures semi-conducting material energy gap, (see Figure 10).
Claims (1)
1. a kind of preparation method of quaternary sulfide semiconductor material, it is characterised in that its chemical constitution formula is：KCu2SbS3, category
In anorthic system, space group is P-1(2), a=6.3857, b=9.1361, c=10.4672, α=90.51 °, β=91.32 °,
γ=91.49 °, Z=4, V=610.263, energy gap is 1.41 eV；The preparation method of quaternary sulfide semiconductor material is：With
0.5 mmol alkali metal compound potassium carbonate K2CO3, 2.0 mmol metallic coppers, 0.5 mmol binary solid solution antimony trisulfides Sb2S3With
2.0 mmol elemental sulfurs are raw material, and 1.0 mL hydrazine hydrates and 2.5 mL polyethylene glycol are solvent, react 9 in 120 DEG C of baking ovens
My god, obtain quaternary sulfide semiconductor material.
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| CN105236482A (en) * | 2015-09-02 | 2016-01-13 | 浙江大学 | Quaternary sulfur-antimony compound ACuSb2S4 semiconductor material |
| CN105244416B (en) * | 2015-10-27 | 2017-06-30 | 合肥工业大学 | A kind of low temperature deposition process of copper antimony Se solar cell light absorbing zone film |
| CN105481010B (en) * | 2015-11-26 | 2017-11-03 | 浙江大学 | A kind of high yield quaternary sulfide compound semiconductor material and its production and use |
| CN105696080A (en) * | 2016-01-29 | 2016-06-22 | 浙江大学 | Quaternary chalcogenide semiconductor material, and preparation method and application thereof |
| CN107779956B (en) * | 2016-01-29 | 2019-10-11 | 浙江大学 | A kind of quaternary thioarsenate compound semiconductor materials and its preparation method and application |
| CN105803531B (en) * | 2016-04-13 | 2017-12-29 | 浙江大学 | Quaternary selenide nonlinear optical crystal and preparation method thereof and its purposes |
| CN106149059B (en) * | 2016-06-20 | 2019-10-25 | 浙江大学 | Quaternary sulfide semiconductor material and preparation method for concrete sterilization and anticorrosion |
| CN106082327B (en) * | 2016-06-20 | 2018-02-06 | 浙江大学 | A kind of quaternary sulfide semiconductor material and preparation method for antiseptic concrete |
| CN106238030B (en) * | 2016-08-03 | 2018-11-20 | 浙江大学 | One kind is for the border on the sea antibacterial corrosion-resistant quaternary sulfide semiconductor catalysis material of concrete surface and preparation method and purposes |
| CN106362770B (en) * | 2016-08-03 | 2018-12-25 | 浙江大学 | A kind of quaternary sulfide semiconductor catalysis material and preparation method and its usage for nearshore engineering construction concrete structure Antimicrobial preservative |
| CN106268866B (en) * | 2016-08-03 | 2019-02-22 | 浙江大学 | A kind of quaternary sulfide semiconductor catalysis material and preparation method and purposes for Marine reinforced concrete structure sterilization and anticorrosion |
| CN106345493B (en) * | 2016-08-03 | 2018-11-20 | 浙江大学 | One kind is for the antibacterial corrosion-resistant quaternary sulfide semiconductor catalysis material in ocean engineering concrete surface and preparation method and purposes |
| CN106268867B (en) * | 2016-08-03 | 2018-11-20 | 浙江大学 | One kind is for the antibacterial corrosion-resistant quaternary sulfide semiconductor catalysis material of concrete and preparation method and purposes |
| CN106423215B (en) * | 2016-08-03 | 2019-02-22 | 浙江大学 | One kind is for the border on the sea antibacterial corrosion-resistant quaternary sulfide semiconductor catalysis material of concrete structure and preparation method and purposes |
| CN106192009B (en) * | 2016-08-03 | 2019-10-25 | 浙江大学 | One kind being used for the antibacterial corrosion-resistant quaternary sulfide semiconductor catalysis material of concrete surface and preparation method |
| CN109778317A (en) * | 2019-01-24 | 2019-05-21 | 中国科学院福建物质结构研究所 | A kind of crystalline material and the preparation method and application thereof of the non-heart sulfide of quaternary |
| CN111573631A (en) * | 2020-05-25 | 2020-08-25 | 安阳师范学院 | Quaternary copper-containing chalcogenide and preparation method and application thereof |
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| US4419422A (en) * | 1982-03-22 | 1983-12-06 | Union Carbide Corporation | Sulfide-containing cathode for nonaqueous cells |
| CN101486449A (en) * | 2008-01-18 | 2009-07-22 | 北京化工大学 | Solid phase synthesis method for quaternary selenide K2CdSnSe4 |
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| Mild Solvothermal Syntheses and Characterization of Layered Copper Thioantimonates(III) and Thioarsenate(III);Chi Zhang等;《Inorg. Chem.》;20140507;第53卷;4856-4860 * |
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| CN104862782A (en) | 2015-08-26 |
| CN107723799A (en) | 2018-02-23 |
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