CN107723799B - A kind of quaternary sulfide semiconductor material and its preparation method and application - Google Patents
A kind of quaternary sulfide semiconductor material and its preparation method and application Download PDFInfo
- Publication number
- CN107723799B CN107723799B CN201710967035.6A CN201710967035A CN107723799B CN 107723799 B CN107723799 B CN 107723799B CN 201710967035 A CN201710967035 A CN 201710967035A CN 107723799 B CN107723799 B CN 107723799B
- Authority
- CN
- China
- Prior art keywords
- preparation
- semiconductor material
- quaternary sulfide
- quaternary
- sulfide semiconductor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000004065 semiconductor Substances 0.000 title claims abstract description 35
- 239000000463 material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 125000000101 thioether group Chemical group 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 20
- 230000003287 optical effect Effects 0.000 claims abstract description 12
- 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 claims abstract description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 8
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 claims description 4
- 229910052959 stibnite Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 abstract description 20
- 229910052802 copper Inorganic materials 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 239000006104 solid solution Substances 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 5
- 150000001339 alkali metal compounds Chemical class 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
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 description 27
- 229910052787 antimony Inorganic materials 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000003708 ampul Substances 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 150000001786 chalcogen compounds Chemical class 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical group 0.000 description 4
- 229910052792 caesium Inorganic materials 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 229910052701 rubidium Inorganic materials 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 3
- 238000002050 diffraction method Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000002362 energy-dispersive X-ray chemical map Methods 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
- 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
- 239000005864 Sulphur Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 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
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- 239000012153 distilled water Substances 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
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 2
- 238000003836 solid-state method Methods 0.000 description 2
- -1 sulphur Compound Chemical class 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
- 244000170916 Paeonia officinalis Species 0.000 description 1
- 235000006484 Paeonia officinalis Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000470 constituent Substances 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
- 238000004821 distillation Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960004756 ethanol Drugs 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
- 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
- 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
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 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
- 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
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
Abstract
The invention discloses a kind of quaternary sulfide semiconductor materials and its preparation method and application.Using alkali metal compound, metallic copper, binary solid solution antimony trisulfide and elemental sulfur as raw material, hydrazine hydrate and polyethylene glycol are solvent, react 4-9 days in 120-190 DEG C of baking oven, obtain quaternary sulfide semiconductor material.Chemical constitution formula are as follows: RbCuSb2S4, belonging to monoclinic system, space group is C12/c1, β=105.75 °, Z=4,Energy gap is 1.74eV.The advantages such as this method has operating process simple, and cost of material is low, and reaction condition is mild, and 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, is used to prepare optical semiconductor device.
Description
It is on 03 31st, 2015 that the application, which is application No. is the 201510146636.1, applying date, entitled " a kind of
The divisional application of the patent of invention of quaternary sulfide semiconductor material and its preparation method and application ".
Technical field
The present invention relates to a kind of quaternary sulfide semiconductor materials and its preparation method and application, belong to inorganic semiconductor material
Material field.
Background technique
FTIR radiation transmittance can be made into the light such as second harmonic generator, frequency converter, optical parametric oscillator
Device is learned, have important in the fields such as laser communications and military technology and is widely applied, thus is attracted extensive attention.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 categories.The nonlinear optical crystal of the marketization is essentially all to be made 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 structure feature and superior
Physical and chemical performance has irreplaceable important function in optical semiconductor field, especially in mid and far infrared second order non-linear
Property Crystal study direction, such as AgGaSe2(AGSe) and BaGa4S7(BGS) etc., current such chalcogen compound is mostly ternary phase.
Relative to ternary chalcogenide object, quaternary chalcogen compound is made of more elements, is interacted between element more multiple
It is miscellaneous and various, thus, obtained crystalline is more, structure is more complicated, performance is more diversified.
Currently, the typical method of preparation quaternary chalcogen compound mainly includes the following three types both at home and abroad:
1) high temperature solid-state method: the heterogeneous phase chemical reaction that solid reactant directly participates in does not use solvent in reaction process,
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 due to reaction temperature compared with high, side reaction is more, experimental implementation is complicated, experimental cost is higher the disadvantages of, limit it and answer extensively
With.
2) medium temperature flux method: introducing cosolvent in high temperature solid-state method, reduces crystal growth temperature, but growth cycle prolongs
Long, most fluxing agent all has different degrees of toxicity, the crystal that when volatilization causes damages to human body and environment, and prepares
Grain is smaller, there are by-product, needs to remove cosolvent, thus is 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.Preparing chalcogen compound using low-temperature solvent heat (hydro-thermal) method is to grow up for nearly 30 years, early stageDeng preparation
A series of ternary chalcogenide objects containing Main Group Metal Elements.Compared with traditional high temperature solid phase synthesis, hydro-thermal preparation side
Biggish change has occurred in the method steady phase easy to form of being situated between, physics and chemical property, thus can preparation structure it is unique, function admirable
Semiconductor crystalline material.By conditions such as regulation reaction temperature, reactant species, reaction mediums, reactant can be effectively improved
Solubility and diffusion velocity accelerate reaction process, influence the atom connection type of anion frame, the pattern and property of optimized product
Energy.Lei Xiaowu 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 thermal stability poor, and yield lower 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 it needs first to be filled with argon gas in preparation process to be 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, reacts 5 days at 160 DEG C, is prepared for Rb2Cu2Sb2S5Sulfide semiconductor material, experimentation are related to tube sealing
Operation, process is more complicated, and products collection efficiency lower 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 prepare multi-component sulfur compound semiconductor materials.
Summary of the invention
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of quaternary sulfide semiconductor material and its preparation
Method and purposes.
The chemical constitution formula of quaternary sulfide semiconductor material are as follows: AxCuySbzS(x+y+3z)/2, wherein A is balance anion
The alkali metal atom of skeleton is one of K, Rb, Cs, and x indicates the mole of alkali metal atom, and y indicates to constitute skeleton transition
The mole of metallic atom, z indicate to constitute the mole of skeletal atom.
Quaternary sulfide semiconductor material the preparation method comprises the following steps: 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, react 4-9 days in 120-190 DEG C of baking oven, obtain quaternary sulphur
Compound semiconductor material.
The alkali metal compound, metallic copper, binary solid solution antimony trisulfide and elemental sulfur molar ratio be 0.5-1.0:
2.0-3.0:0.5-1.0:2.0-2.5；The molar ratio of hydrazine hydrate and polyethylene glycol is 1.0-2.0:2.5-3.0.The alkali gold
Belong to compound are as follows: alkali metal hydroxide, carbonate or chloride.The binary solid solution antimony trisulfide the preparation method comprises the following steps:
Sb and S that molar ratio is 2:3 are packed into quartz ampoule and carry out tube sealing, then the quartz ampoule of sealing is put into Muffle furnace, is slowly heated up
To 560 DEG C, and 8 hours are kept the temperature, then cooled to room temperature, opens quartz ampoule block stock grind into powder is spare.
Quaternary sulfide semiconductor material energy gap is respectively 1.41eV, 1.74eV and 1.95eV, which is used for
Optical semiconductor device is prepared, optical semiconductor device is solar battery buffer layer material.
Operation of the present invention process is simple and convenient, and cost of material is low, and reaction condition is mild, and synthesis temperature is low etc., using we
The quaternary sulfide semiconductor material of method preparation, yield can reach 60%-90%, and crystallite dimension is 150-300 μm, and chemistry is pure
Degree is high.The energy gap of semiconductor material is respectively 1.41eV, 1.74eV and 1.95eV, has in terms of semiconductor optical and potentially answers
With value.
Detailed description of the invention
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 map of crystal shows the presence and its content of K, Cu, Sb and S element；
Fig. 5 is RbCuSb2S4The EDX map of crystal shows the presence and its content of Rb, Cu, Sb and S element；
Fig. 6 is Cs2Cu2Sb2S5The EDX map of crystal shows the 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.
Specific embodiment
The chemical constitution formula of quaternary sulfide semiconductor material are as follows: AxCuySbzS(x+y+3z)/2, wherein A is balance anion
The alkali metal atom of skeleton is one of K, Rb, Cs, and x indicates the mole of alkali metal atom, and y indicates to constitute skeleton transition
The mole of metallic atom, z indicate to constitute the mole of skeletal atom.
Quaternary sulfide semiconductor material the preparation method comprises the following steps: 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, react 4-9 days in 120-190 DEG C of baking oven, obtain quaternary sulphur
Compound semiconductor material.
The alkali metal compound, metallic copper, binary solid solution antimony trisulfide and elemental sulfur molar ratio be 0.5-1.0:
2.0-3.0:0.5-1.0:2.0-2.5；The molar ratio of hydrazine hydrate and polyethylene glycol is 1.0-2.0:2.5-3.0.The alkali gold
Belong to compound are as follows: alkali metal hydroxide, carbonate or chloride.The binary solid solution antimony trisulfide the preparation method comprises the following steps:
Sb and S that molar ratio is 2:3 are packed into quartz ampoule and carry out tube sealing, then the quartz ampoule of sealing is put into Muffle furnace, is slowly heated up
To 560 DEG C, and 8 hours are kept the temperature, then cooled to room temperature, opens quartz ampoule block stock grind into powder is spare.
Quaternary sulfide semiconductor material is used to prepare optical semiconductor device, and optical semiconductor device is solar battery
Buffer layer material.
Embodiment 1:
KCu2SbS3Crystal.Weigh initial feed K2CO30.5mmol(0.069g)、Cu 2.0mmol(0.128g)、
Sb2S30.5mmol (0.170g) and S 2.0mmol (0.064g) are put into water heating kettle, add hydrazine hydrate 1.0mL and poly- second two
Water heating kettle is placed at 120 DEG C and reacts 9 days by alcohol 2.5mL.After reaction, water heating kettle is opened, product is taken out, respectively with distillation
Water and dehydrated alcohol wash 2 times, obtain black bulk crystals, yield 80%, 150-230 μm of crystallite dimension (see Fig. 1).Through list
Brilliant X-ray diffraction analysis, the crystal composition formula are KCu2SbS3, belong to anorthic system, space group is P-1(2), α=90.51 °, β=91.32 °, γ=91.49 °, Z=4,Crystal structure figure is as shown with 7.EDX elemental analysis show crystal containing only tetra- kinds of elements of K, Cu, Sb, S, and each member
Cellulose content ratio and single crystal diffraction analysis result are consistent (see Fig. 4).UV-vis map measure semiconductor material energy gap be 1.41eV (see
Figure 10).
Embodiment 2:
RbCuSb2S4Crystal.Weigh initial feed RbCl 1.0mmol (0.121g), Cu 2.0mmol (0.128g),
Sb2S30.8mmol (0.170g) and S 2.0mmol (0.064g) are put into water heating kettle, add hydrazine hydrate 1.6mL and poly- second two
Water heating kettle is placed at 170 DEG C and reacts 7 days by alcohol 2.5mL.Product is washed 2 times with distilled water and dehydrated alcohol respectively, is obtained dark red
Color 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,β=105.75 °, Z=4,Crystal structure figure such as 8
It is shown.EDX elemental analysis shows crystal containing only tetra- kinds of elements of Rb, Cu, Sb, S, and each element content ratio and single crystal diffraction analysis are tied
Fruit is consistent (see Fig. 5).It is 1.74eV that UV-vis map, which measures semiconductor material energy gap, (see Figure 10).
Embodiment 3:
Cs2Cu2Sb2S5Crystal.Weigh initial feed CsOHH2O 1.0mmol(0.168g)、Cu 3.0mmol
(0.192g)、Sb2S31.0mmol (0.170g) and S 2.5mmol (0.08g) are put into water heating kettle, add hydrazine hydrate 2.0mL
With polyethylene glycol 3.0mL.Water heating kettle is placed at 190 DEG C and is reacted 4 days, product uses distilled water and ethanol washing 2 times respectively, obtains
Peony bulk crystals, for yield up to 72%, crystallite dimension is 170-300 μm (see Fig. 3).It, should through single-crystal X-ray diffraction analysis
Crystal composition formula is Cs2Cu2Sb2S5, belong to anorthic system, space group is P-1(2),α=91.95 °, β=92.17 °, γ=101.86 °, Z=2,Crystal structure figure is as figure 9.EDX elemental analysis show crystal containing only tetra- kinds of elements of Cs, Cu, Sb, S, and it is each
Constituent content ratio and single crystal diffraction analysis result are consistent (see Fig. 6).It is 1.95eV that UV-vis map, which measures semiconductor material energy gap,
(see Figure 10).
Claims (2)
1. a kind of preparation method of quaternary sulfide semiconductor material, which is characterized in that its chemical constitution formula are as follows: 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=
849.01 Å3, energy gap is 1.74 eV；The preparation method is that: take 1.0 2.0 mmol of mmol, Cu of initial feed RbCl,
Sb2S30.8mmol and 2.0 mmol of S are put into water heating kettle, 2.5 mL of hydrazine hydrate 1.6mL and polyethylene glycol are added, by hydro-thermal
Kettle, which is placed at 170 DEG C, to react 7 days.
2. a kind of purposes of the quaternary sulfide semiconductor material of method preparation as described in claim 1, it is characterised in that: be used for
Optical semiconductor device is prepared, optical semiconductor device is solar battery buffer layer material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710967035.6A CN107723799B (en) | 2015-03-31 | 2015-03-31 | A kind of quaternary sulfide semiconductor material and its preparation method and application |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710967035.6A CN107723799B (en) | 2015-03-31 | 2015-03-31 | A kind of quaternary sulfide semiconductor material and its preparation method and application |
| CN201510146636.1A CN104862782B (en) | 2015-03-31 | 2015-03-31 | A kind of quaternary sulfide semiconductor material and its production and use |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510146636.1A Division CN104862782B (en) | 2015-03-31 | 2015-03-31 | A kind of quaternary sulfide semiconductor material and its production and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107723799A CN107723799A (en) | 2018-02-23 |
| CN107723799B true CN107723799B (en) | 2019-07-23 |
Family
ID=53908932
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710967035.6A Expired - Fee Related CN107723799B (en) | 2015-03-31 | 2015-03-31 | A kind of quaternary sulfide semiconductor material and its preparation method and application |
| CN201510146636.1A Expired - Fee Related CN104862782B (en) | 2015-03-31 | 2015-03-31 | A kind of quaternary sulfide semiconductor material and its production and use |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510146636.1A Expired - Fee Related CN104862782B (en) | 2015-03-31 | 2015-03-31 | A kind of quaternary sulfide semiconductor material and its production and use |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN107723799B (en) |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58172870A (en) * | 1982-03-22 | 1983-10-11 | エバレディ−、バッテリ−、カンパニ−、インコ−ポレ−テッド | Sulfide containing positive electrode for nonaqueous battery |
| CN101486449A (en) * | 2008-01-18 | 2009-07-22 | 北京化工大学 | Solid phase synthesis method for quaternary selenide K2CdSnSe4 |
-
2015
- 2015-03-31 CN CN201710967035.6A patent/CN107723799B/en not_active Expired - Fee Related
- 2015-03-31 CN CN201510146636.1A patent/CN104862782B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58172870A (en) * | 1982-03-22 | 1983-10-11 | エバレディ−、バッテリ−、カンパニ−、インコ−ポレ−テッド | Sulfide containing positive electrode for nonaqueous battery |
| CN101486449A (en) * | 2008-01-18 | 2009-07-22 | 北京化工大学 | Solid phase synthesis method for quaternary selenide K2CdSnSe4 |
Non-Patent Citations (2)
| Title |
|---|
| A Three-Dimensional Framework with Accessible Nanopores: RbCuSb2Se4•H2O;Jason A. Hanko et al.;《Angew. Chem. Int. Ed.》;19981231;第37卷(第3期);342-344页 |
| Surfactant-thermal methodtopreparetwonoveltwo-dimensional Mn–Sb–S compoundsforphotocatalyticapplications;Lina Nie et al.;《Journal of Solid State Chemistry》;20140826;第220卷;118-123页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104862782A (en) | 2015-08-26 |
| CN107723799A (en) | 2018-02-23 |
| CN104862782B (en) | 2018-01-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107723799B (en) | A kind of quaternary sulfide semiconductor material and its preparation method and application | |
| Wang et al. | Synthesis, structure and properties of a new nonlinear optical material: zinc cadmium tetrathiocyanate | |
| CN105951181B (en) | A kind of crystalline material, preparation method and the application as FTIR radiation transmittance | |
| Kannan et al. | Growth and characterization of Bisthiourea-zinc Acetate, a new nonlinear optical material | |
| CN105803531B (en) | Quaternary selenide nonlinear optical crystal and preparation method thereof and its purposes | |
| CN106757365B (en) | A kind of crystalline material, preparation method and the nonlinear optical crystal comprising it | |
| CN102409407B (en) | Infrared non-linear optical material Ba3AGa5Se10Cl2 and preparation method thereof | |
| Selvakumar et al. | Growth and characterization of pure and doped bis (thiourea) cadmium acetate single crystals | |
| Wang et al. | Crystal growth and characterization of a novel organometallic nonlinear-optical crystal:: MnHg (SCN) 4 (C2H6OS) 2 | |
| CN106835284A (en) | One class infrared nonlinear optical crystal material and its production and use | |
| Raj et al. | Growth and characterization of nonlinear optical active l-alanine formate crystal by modified Sankaranarayanan–Ramasamy (SR) method | |
| Baraniraj et al. | Growth and characterization of NLO based l-arginine maleate dihydrate single crystal | |
| Sun et al. | Growth and characterization of the nonlinear optical single crystal: l-lysine acetate | |
| CN111676517B (en) | Non-core mixed anion crystal material and preparation method and application thereof | |
| WO2013185453A1 (en) | Method for preparing monoclinic ga2s3 crystal and use in optics thereof | |
| Lee et al. | Bi2Te2O6 (NO3) 2 (OH) 2 (H2O): A layered bismuth tellurium nitrate hydroxide with multiple noncentrosymmetric chromophores | |
| Murugan et al. | Growth and characterization of a new metal-organic crystal: bis-thiourea cobalt chloride (BTCoC) | |
| WO2017201648A1 (en) | Infrared nonlinear optical crystal material, and preparation method therefor and use thereof | |
| Zhou et al. | Second-order nonlinear optical-active selenide borate Zn8Se2 (BO2) 12: experimental and theoretical analysis | |
| CN105036192B (en) | Quaternary sulfo-antimonate compound semiconductor material as well as preparation method and application thereof | |
| CN107779956B (en) | A kind of quaternary thioarsenate compound semiconductor materials and its preparation method and application | |
| CN109750357B (en) | Infrared nonlinear optical crystal Ba10Zn7M6Q26And preparation method and application thereof | |
| Wang et al. | Preparation and characterization of Hg (N2H4CS) 4Zn (SCN) 4 | |
| CN114318534B (en) | Second-order nonlinear optical crystal aluminophosphate and preparation method and application thereof | |
| Guo et al. | Li7Cd4. 5Ge4Se16 and Li6. 4Cd4. 8Sn4Se16: Strong Nonlinear Optical Response in Quaternary Diamond‐Like Selenide Networks |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190723 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |