CN104862782A - Quaternary sulfide semiconductor material, and preparation method and application thereof - Google Patents
Quaternary sulfide semiconductor material, and preparation method and application thereof Download PDFInfo
- Publication number
- CN104862782A CN104862782A CN201510146636.1A CN201510146636A CN104862782A CN 104862782 A CN104862782 A CN 104862782A CN 201510146636 A CN201510146636 A CN 201510146636A CN 104862782 A CN104862782 A CN 104862782A
- Authority
- CN
- China
- Prior art keywords
- semiconductor material
- alkali metal
- preparation
- quaternary
- quaternary sulfide
- 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.)
- Granted
Links
- 239000004065 semiconductor Substances 0.000 title claims abstract description 42
- 239000000463 material Substances 0.000 title claims abstract description 38
- 125000000101 thioether group Chemical group 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000010949 copper Substances 0.000 claims abstract description 17
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- 230000003287 optical effect Effects 0.000 claims abstract description 11
- 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 10
- 150000001339 alkali metal compounds Chemical class 0.000 claims abstract description 10
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000006104 solid solution Substances 0.000 claims abstract description 10
- 150000001340 alkali metals Chemical group 0.000 claims abstract description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 150000001450 anions Chemical group 0.000 claims abstract description 6
- 150000003624 transition metals Chemical group 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 9
- -1 polyoxyethylene Polymers 0.000 claims description 9
- YPMOSINXXHVZIL-UHFFFAOYSA-N sulfanylideneantimony Chemical compound [Sb]=S YPMOSINXXHVZIL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 229910052792 caesium Inorganic materials 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 229910052701 rubidium Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 239000013078 crystal Substances 0.000 abstract description 25
- 238000000034 method Methods 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000002202 Polyethylene glycol Substances 0.000 abstract 1
- 229920001223 polyethylene glycol Polymers 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 229910052787 antimony Inorganic materials 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 150000001786 chalcogen compounds Chemical class 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 229910052742 iron Inorganic materials 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
- 125000006850 spacer group Chemical group 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 150000004770 chalcogenides Chemical class 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
- 238000010792 warming Methods 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change 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
- 238000005516 engineering process 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
- 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
- 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
- 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
- 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
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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Photovoltaic Devices (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a quaternary sulfide semiconductor material, and a preparation method and application thereof. An alkali metal compound, metallic copper, binary solid solution solid solution and elemental sulfur are used as raw materials, hydrazine hydrate and polyethylene glycol are used as solvents, and a reaction is carried out in a baking oven with a temperature of 120 to 190 DEG C for 4 to 9 d so as to prepare the quaternary sulfide semiconductor material. The chemical composition of the quaternary sulfide semiconductor material is A<x>Cu<y>Sb<z>S<x+y+3z>/2, wherein A is alkali metal atoms of a balanced anion skeleton, x represents the molar weight of the alkali metal atoms, y is the molar weight of transition metal atoms composing the skeleton and z is the molar weight of atoms composing the skeleton. The preparation method has the advantages of simple operation process, low cost of raw materials, mild reaction conditions, low synthesis temperatures, etc. Quaternary sulfide prepared by using the method has yield of 60 to 90%, a crystal grain size of 150 to 300 [mu]m and high chemical purity and can be used for preparing optical semiconductor devices.
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 field.
Background technology
FTIR radiation transmittance can be made into the optics such as second harmonic generator, frequency converter, optical parametric oscillator, has important and applies widely, thus cause extensive concern in the field such as laser communications and military technique.According to the difference of materials application wave band, nonlinear optical material is mainly divided into ultraviolet region, visible and near-infrared region and mid and far infrared light district three major types.The non-linear optic crystal of the marketization is all be made up of inorganic materials substantially, comprises KTiOPO
4(KTP), β-BaB
2o
4(BBO), AgGaS
2(AGS) etc.In recent years, multi-component sulfur compound-material, because of the constitutional features of its uniqueness and superior physical and chemical performance, has irreplaceable vital role in optical semiconductor field, particularly in mid and far infrared second order nonlinear crystal research direction, and such as AgGaSe
2and BaGa (AGSe)
4s
7(BGS) etc., this type of chalcogen compound mostly is ternary phase at present.Relative to ternary chalcogenide thing, quaternary chalcogen compound is made up of more element, the interphase interaction more complicated of element and various, and thus, the kind of crystalline obtained is more, structure is more complicated, performance is more diversified.
At present, the typical method of preparation quaternary chalcogen compound mainly comprises following three kinds both at home and abroad:
1) high temperature solid-state method: the heterogeneous phase chemical reaction that solid reactant is participated in directly, does not use solvent in reaction process, has the features such as selectivity is high, productive rate is high, technological process is simple, is present stage one of the main method preparing novel solid materials.But because temperature of reaction is compared with the shortcoming such as high, side reaction is many, experimental implementation is complicated, experimental cost is higher, limit its widespread use.
2) warm flux method in: introduce solubility promoter in high temperature solid-state method, reduce crystal growth temperature, but growth cycle extends, most fusing assistant all has toxicity in various degree, during volatilization, human body and environment are worked the mischief, and the crystal grain of preparation is less, there is by product, need to remove solubility promoter, be not thus suitable for industrial production.
3) low-temperature solvent heat (hydro-thermal) method: hydro-thermal and solvent-thermal process method are one of important means preparing chalcogen compound.Utilize low-temperature solvent heat (hydro-thermal) legal system to be grow up for nearly 30 years for chalcogen compound, early stage Sch fer etc. has prepared a series of ternary chalcogenide thing containing Main Group Metal Elements.Compared with traditional high temperature solid phase synthesis, hydrothermal preparing process easily forms the steady phase that is situated between, and physics and chemistry character there occurs larger change, can prepare the semiconductor crystalline material of structure uniqueness, excellent property thus.By conditions such as regulation and control temperature of reaction, reactant species, reaction mediums, effectively can improve solubleness and the velocity of diffusion of reactant, accelerated reaction process, affect the atom mode of connection of anion frame, the pattern of optimized product and performance.The people such as Lei Xiaowu utilize solvent-thermal method successfully to prepare [dienH
2] Hg
2sb
2s
6(Lei Xiaowu etc., Jining institute journal, 35,36 (2014)), but be included in product because of organic group, cause product thermostability poor, and productive rate is lower only has 35%.The people such as Chen Zhen have successfully prepared CsSb by solvent-thermal method
2(Se
2)
0.5se
3(Chen Zhen etc., Chinese Journal of Inorganic Chemistry, 22,27 (2006)), but need in preparation process to be first filled with argon gas protection, then tube sealing process, whole experimentation is more loaded down with trivial details, and conditional request is higher.The people such as An Yonglin (Inorganic Chemistry 53,4856 (2014)) select 1,2-propylene diamine and methanol-water mixing solutions to make solvent, react 5 days, prepared Rb at 160 DEG C
2cu
2sb
2s
5sulfide semiconductor material, experimentation relates to tube sealing operation, process more complicated, and products collection efficiency is lower only has 36%.
Therefore, develop new solvent-thermal process route, explore new synthetic system, and experimentation is more simple and convenient, reaction conditions milder, synthesis temperature is lower, and productive rate is higher, will be the key preparing multi-component sulfur compound semiconductor materials.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of quaternary sulfide semiconductor material and its production and use is provided.
The chemical constitution formula of quaternary sulfide semiconductor material is: A
xcu
ysb
zs
(x+y+3z)/2, wherein A is the alkali metal atom of balance anion skeleton, and be the one in K, Rb, Cs, x represents the molar weight of alkali metal atom, and y represents the molar weight forming skeleton transition metal atoms, and z represents the molar weight forming skeletal atom.
The preparation method of quaternary sulfide semiconductor material is: with alkali metal compound, metallic copper, binary solid solution antimony sulfide and elemental sulfur for raw material, hydrazine hydrate and polyoxyethylene glycol are solvent, in 120-190 DEG C of baking oven, react 4-9 days, obtain quaternary sulfide semiconductor material.
The mol ratio of described alkali metal compound, metallic copper, binary solid solution antimony sulfide and elemental sulfur is 0.5-1.0:2.0-3.0:0.5-1.0:2.0-2.5; The mol ratio of hydrazine hydrate and polyoxyethylene glycol is 1.0-2.0:2.5-3.0.Described alkali metal compound is: alkali metal hydroxide, carbonate or muriate.The preparation method of described binary solid solution antimony sulfide is: by mol ratio be 2:3 Sb and S load silica tube carry out tube sealing, again the silica tube of sealing is put into retort furnace, slowly be warming up to 560 DEG C, and be incubated 8 hours, naturally cool to room temperature again, open silica tube by for subsequent use for block stock grind into powder.
Quaternary sulfide semiconductor material energy gap is respectively 1.41 eV, 1.74 eV and 1.95 eV, and this semiconductor material is for the preparation of optical semiconductor device, and optical semiconductor device is solar cell buffer layer material.
Operating process of the present invention is simple and convenient, and raw materials cost is low, and reaction conditions is gentle, and synthesis temperature is low, and adopt quaternary sulfide semiconductor material prepared by present method, productive rate can reach 60%-90%, and grain-size is 150-300 μm, and chemical purity is high.The energy gap of semiconductor material is respectively 1.41 eV, 1.74 eV and 1.95 eV, has potential using value in semiconductor optical.
Accompanying drawing explanation
Fig. 1 is KCu
2sbS
3the shape appearance figure of crystal;
Fig. 2 is RbCuSb
2s
4the shape appearance figure of crystal;
Fig. 3 is Cs
2cu
2sb
2s
5the shape appearance figure of crystal;
Fig. 4 is KCu
2sbS
3the EDX collection of illustrative plates of crystal, indicates existence and the content thereof of K, Cu, Sb and S element;
Fig. 5 is RbCuSb
2s
4the EDX collection of illustrative plates of crystal, indicates existence and the content thereof of Rb, Cu, Sb and S element;
Fig. 6 is Cs
2cu
2sb
2s
5the EDX collection of illustrative plates of crystal, indicates existence and the content thereof of Cs, Cu, Sb and S element;
Fig. 7 is KCu
2sbS
3structure iron;
Fig. 8 is RbCuSb
2s
4structure iron;
Fig. 9 is Cs
2cu
2sb
2s
5structure iron;
Figure 10 is A
xcu
ysb
zs
(x+y+3z)/2the visible diffuse reflection spectrum of solid-state UV.
Embodiment
The chemical constitution formula of quaternary sulfide semiconductor material is: A
xcu
ysb
zs
(x+y+3z)/2, wherein A is the alkali metal atom of balance anion skeleton, and be the one in K, Rb, Cs, x represents the molar weight of alkali metal atom, and y represents the molar weight forming skeleton transition metal atoms, and z represents the molar weight forming skeletal atom.
The preparation method of quaternary sulfide semiconductor material is: with alkali metal compound, metallic copper, binary solid solution antimony sulfide and elemental sulfur for raw material, hydrazine hydrate and polyoxyethylene glycol are solvent, in 120-190 DEG C of baking oven, react 4-9 days, obtain quaternary sulfide semiconductor material.
The mol ratio of described alkali metal compound, metallic copper, binary solid solution antimony sulfide and elemental sulfur is 0.5-1.0:2.0-3.0:0.5-1.0:2.0-2.5; The mol ratio of hydrazine hydrate and polyoxyethylene glycol is 1.0-2.0:2.5-3.0.Described alkali metal compound is: alkali metal hydroxide, carbonate or muriate.The preparation method of described binary solid solution antimony sulfide is: by mol ratio be 2:3 Sb and S load silica tube carry out tube sealing, again the silica tube of sealing is put into retort furnace, slowly be warming up to 560 DEG C, and be incubated 8 hours, naturally cool to room temperature again, open silica tube by for subsequent use for block stock grind into powder.
Quaternary sulfide semiconductor material is for the preparation of optical semiconductor device, and optical semiconductor device is solar cell buffer layer material.
Embodiment 1:
KCu
2sbS
3crystal.Take initial feed K
2cO
30.5 mmol (0.069g), Cu 2.0 mmol (0.128g), Sb
2s
30.5 mmol (0.170g) and S 2.0 mmol (0.064g) puts into water heating kettle, then adds hydrazine hydrate 1.0 mL and polyoxyethylene glycol 2.5 mL, reacts 9 days at water heating kettle being placed in 120 DEG C.After reaction terminates, open water heating kettle, take out product, use distilled water and absolute ethanol washing 2 times respectively, obtain black bulk crystals, productive rate is 80%, grain-size 150-230 μm (see Fig. 1).Through single-crystal X-ray diffraction analysis, this crystal composition formula is KCu
2sbS
3, belong to triclinic(crystalline)system, spacer 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=610.26
3, crystalline structure figure as shown with 7.EDX ultimate analysis shows crystal only containing K, Cu, Sb, S tetra-kinds of elements, and each constituent content is than consistent with single crystal diffraction analytical results (see Fig. 4).It is 1.41 eV (see Figure 10) that UV-vis collection of illustrative plates records semiconductor material energy gap.
Embodiment 2:
RbCuSb
2s
4crystal.Take initial feed RbCl 1.0 mmol (0.121g), Cu 2.0 mmol (0.128g), Sb
2s
30.8mmol (0.170g) and S 2.0 mmol (0.064g) puts into water heating kettle, then adds hydrazine hydrate 1.6mL and polyoxyethylene glycol 2.5 mL, reacts 7 days at water heating kettle being placed in 170 DEG C.Product uses distilled water and absolute ethanol washing 2 times respectively, and obtain scarlet rhabdolith, productive rate can reach 60 %, and grain-size is 180-280 μm (see Fig. 2).Through single-crystal X-ray diffraction analysis, this crystal composition formula is RbCuSb
2s
4, belong to oblique system, spacer is C12/c1, a=7.3272, b=11.1628, c=10.7849, β=105.75 °, Z=4, V=849.01
3, crystalline structure figure as depicted in figure 8.EDX ultimate analysis shows crystal only containing Rb, Cu, Sb, S tetra-kinds of elements, and each constituent content is than consistent with single crystal diffraction analytical results (see Fig. 5).It is 1.74 eV (see Figure 10) that UV-vis collection of illustrative plates records semiconductor material energy gap.
Embodiment 3:
Cs
2cu
2sb
2s
5crystal.Weigh initial feed CsOHH
2o 1.0 mmol (0.168g), Cu 3.0 mmol (0.192g), Sb
2s
31.0mmol (0.170g) and S 2.5 mmol (0.08g) puts into water heating kettle, then adds hydrazine hydrate 2.0 mL and polyoxyethylene glycol 3.0 mL.React 4 days at water heating kettle being placed in 190 DEG C, product uses distilled water and washing with alcohol 2 times respectively, and obtain scarlet bulk crystals, productive rate can reach 72%, and grain-size is 170-300 μm (see Fig. 3).Through single-crystal X-ray diffraction analysis, this crystal composition formula is Cs
2cu
2sb
2s
5, belong to triclinic(crystalline)system, spacer 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=606.63
3, crystalline structure figure as figure 9.EDX ultimate analysis shows crystal only containing Cs, Cu, Sb, S tetra-kinds of elements, and each constituent content is than consistent with single crystal diffraction analytical results (see Fig. 6).It is 1.95 eV (see Figure 10) that UV-vis collection of illustrative plates records semiconductor material energy gap.
Claims (6)
1. quaternary sulfide semiconductor material and its production and use, is characterized in that, its chemical constitution formula is: A
xcu
ysb
zs
(x+y+3z)/2, wherein A is the alkali metal atom of balance anion skeleton, and x represents the molar weight of alkali metal atom, and y represents the molar weight forming skeleton transition metal atoms, and z represents the molar weight forming skeletal atom.
2. the preparation method of a quaternary sulfide semiconductor material as claimed in claim 1, it is characterized in that with alkali metal compound, metallic copper, binary solid solution antimony sulfide and elemental sulfur for raw material, hydrazine hydrate and polyoxyethylene glycol are solvent, in 120-190 DEG C of baking oven, react 4-9 days, obtain quaternary sulfide semiconductor material.
3. the preparation method of a kind of quaternary sulfide semiconductor material as claimed in claim 2, is characterized in that the mol ratio of described alkali metal compound, metallic copper, binary solid solution antimony sulfide and elemental sulfur is 0.5-1.0:2.0-3.0:0.5-1.0:2.0-2.5; The mol ratio of hydrazine hydrate and polyoxyethylene glycol is 1.0-2.0:2.5-3.0.
4. the preparation method of a kind of quaternary sulfide semiconductor material as claimed in claim 2, is characterized in that described alkali metal compound is: alkali metal hydroxide, carbonate or muriate.
5. a kind of quaternary sulfide semiconductor material as claimed in claim 2, is characterized in that the alkali metal atom of balance anion skeleton is the one in K, Rb, Cs.
6. as the purposes of the quaternary sulfide semiconductor material of claim 2 preparation, it is characterized in that: quaternary sulfide semiconductor material energy gap is respectively 1.41 eV, 1.74 eV and 1.95 eV, can be used for preparing optical semiconductor device, optical semiconductor device is solar cell buffer layer material.
Priority Applications (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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510146636.1A CN104862782B (en) | 2015-03-31 | 2015-03-31 | A kind of quaternary sulfide semiconductor material and its production and use |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710967035.6A Division CN107723799B (en) | 2015-03-31 | 2015-03-31 | A kind of quaternary sulfide semiconductor material and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104862782A true CN104862782A (en) | 2015-08-26 |
| CN104862782B CN104862782B (en) | 2018-01-12 |
Family
ID=53908932
Family Applications (2)
| 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 |
| 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 |
Family Applications After (1)
| 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 |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN104862782B (en) |
Cited By (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 |
| CN105244416A (en) * | 2015-10-27 | 2016-01-13 | 合肥工业大学 | Low-temperature deposition process of copper-antimony-selenium solar cell light absorption layer film |
| CN105481010A (en) * | 2015-11-26 | 2016-04-13 | 浙江大学 | High-yield quaternary chalcogenide semiconductor material and its preparation method and use |
| CN105525354A (en) * | 2016-01-29 | 2016-04-27 | 浙江大学 | Quaternary thioarsenate compound semiconductor material as well as preparation method and application thereof |
| CN105696080A (en) * | 2016-01-29 | 2016-06-22 | 浙江大学 | Quaternary chalcogenide semiconductor material, and preparation method and application thereof |
| CN105803531A (en) * | 2016-04-13 | 2016-07-27 | 浙江大学 | Four-element selenide non-linear optical crystal and preparing method and application thereof |
| CN106082327A (en) * | 2016-06-20 | 2016-11-09 | 浙江大学 | A kind of quaternary sulfide semiconductor material for antiseptic concrete and preparation method |
| CN106149059A (en) * | 2016-06-20 | 2016-11-23 | 浙江大学 | Quaternary sulfide semiconductor material and preparation method for concrete sterilization and anticorrosion |
| CN106192009A (en) * | 2016-08-03 | 2016-12-07 | 浙江大学 | A kind of for concrete surface antibacterial antiseptical quaternary sulfide semiconductor catalysis material and preparation method |
| CN106238030A (en) * | 2016-08-03 | 2016-12-21 | 浙江大学 | One is used for bordering on the sea concrete surface antibacterial antiseptical quaternary sulfide semiconductor catalysis material and preparation method and purposes |
| CN106268867A (en) * | 2016-08-03 | 2017-01-04 | 浙江大学 | One is used for concrete antibacterial antiseptical quaternary sulfide semiconductor catalysis material and preparation method and purposes |
| CN106268866A (en) * | 2016-08-03 | 2017-01-04 | 浙江大学 | A kind of quaternary sulfide semiconductor catalysis material for Marine reinforced concrete structure sterilization and anticorrosion and preparation method and purposes |
| CN106345493A (en) * | 2016-08-03 | 2017-01-25 | 浙江大学 | Quaternary sulfide semiconductor photocatalytic material for antiseptic sterilization of marine engineering concrete surface and preparation method and application of quaternary sulfide semiconductor photocatalytic material |
| CN106362770A (en) * | 2016-08-03 | 2017-02-01 | 浙江大学 | Four-component semiconductor photocatalytic material for antibiosis and anticorrosion of near-shore engineering concrete structure, and preparation method and application thereof |
| CN106423215A (en) * | 2016-08-03 | 2017-02-22 | 浙江大学 | Bacteriostatic and preservative quaternary sulfide semiconductor photocatalytic material for coastal concrete structure, preparation method and application thereof |
| 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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2015
- 2015-03-31 CN CN201510146636.1A patent/CN104862782B/en not_active Expired - Fee Related
- 2015-03-31 CN CN201710967035.6A patent/CN107723799B/en not_active Expired - Fee Related
Non-Patent Citations (4)
| Title |
|---|
| CHI ZHANG等: "Mild Solvothermal Syntheses and Characterization of Layered Copper Thioantimonates(III) and Thioarsenate(III)", 《INORG. CHEM.》 * |
| JAMES E. JEROME等: "Synthesis of New Low-Dimensional Quaternary Compounds, KCu2AsS3 and KCu4AsS4, in Supercritical Amine Solvent. Alkali Metal Derivatives of Sulfosalts", 《INORG. CHEM.》 * |
| LINA NIE等: "Surfactant-thermal method to prepare two novel two-dimensional Mn–Sb–S compounds for photocatalytic applications", 《JOURNAL OF SOLID STATE CHEMISTRY》 * |
| WEI-WEI XIONG等: "New strategies to prepare crystalline chalcogenides", 《INORG. CHEM. FRONT.》 * |
Cited By (27)
| 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 |
| CN105244416A (en) * | 2015-10-27 | 2016-01-13 | 合肥工业大学 | Low-temperature deposition process of copper-antimony-selenium solar cell light absorption layer film |
| CN105481010A (en) * | 2015-11-26 | 2016-04-13 | 浙江大学 | High-yield quaternary chalcogenide semiconductor material and its preparation method and use |
| 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 |
| CN105525354A (en) * | 2016-01-29 | 2016-04-27 | 浙江大学 | Quaternary thioarsenate compound semiconductor material as well as preparation method and application thereof |
| 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 |
| CN107779956A (en) * | 2016-01-29 | 2018-03-09 | 浙江大学 | A kind of quaternary thioarsenate compound semiconductor materials and its production and use |
| CN105803531A (en) * | 2016-04-13 | 2016-07-27 | 浙江大学 | Four-element selenide non-linear optical crystal and preparing method and application thereof |
| CN105803531B (en) * | 2016-04-13 | 2017-12-29 | 浙江大学 | Quaternary selenide nonlinear optical crystal and preparation method thereof and its purposes |
| CN106082327A (en) * | 2016-06-20 | 2016-11-09 | 浙江大学 | A kind of quaternary sulfide semiconductor material for antiseptic concrete and preparation method |
| CN106149059A (en) * | 2016-06-20 | 2016-11-23 | 浙江大学 | Quaternary sulfide semiconductor material and preparation method for concrete sterilization and anticorrosion |
| CN106345493A (en) * | 2016-08-03 | 2017-01-25 | 浙江大学 | Quaternary sulfide semiconductor photocatalytic material for antiseptic sterilization of marine engineering concrete surface and preparation method and application of quaternary sulfide semiconductor photocatalytic material |
| 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 |
| CN106423215A (en) * | 2016-08-03 | 2017-02-22 | 浙江大学 | Bacteriostatic and preservative quaternary sulfide semiconductor photocatalytic material for coastal concrete structure, preparation method and application thereof |
| CN106268866A (en) * | 2016-08-03 | 2017-01-04 | 浙江大学 | A kind of quaternary sulfide semiconductor catalysis material for Marine reinforced concrete structure sterilization and anticorrosion and preparation method and purposes |
| CN106268867A (en) * | 2016-08-03 | 2017-01-04 | 浙江大学 | One is used for concrete antibacterial antiseptical quaternary sulfide semiconductor catalysis material and preparation method and purposes |
| CN106238030A (en) * | 2016-08-03 | 2016-12-21 | 浙江大学 | One is used for bordering on the sea concrete surface antibacterial antiseptical quaternary sulfide semiconductor catalysis material 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 |
| CN106362770A (en) * | 2016-08-03 | 2017-02-01 | 浙江大学 | Four-component semiconductor photocatalytic material for antibiosis and anticorrosion of near-shore engineering concrete structure, and preparation method and application thereof |
| 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 |
| 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 |
| 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 |
| 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 |
| CN106192009A (en) * | 2016-08-03 | 2016-12-07 | 浙江大学 | A kind of for concrete surface antibacterial antiseptical quaternary sulfide semiconductor catalysis material 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104862782B (en) | 2018-01-12 |
| CN107723799A (en) | 2018-02-23 |
| CN107723799B (en) | 2019-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104862782A (en) | Quaternary sulfide semiconductor material, and preparation method and application thereof | |
| CN105951181B (en) | A kind of crystalline material, preparation method and the application as FTIR radiation transmittance | |
| CN107022793B (en) | A kind of infrared nonlinear optical crystal, preparation method and application | |
| US11187964B2 (en) | Infrared non-linear optical crystal, preparation process and application thereof | |
| CN105803531B (en) | Quaternary selenide nonlinear optical crystal and preparation method thereof and its purposes | |
| CN106835284A (en) | One class infrared nonlinear optical crystal material and its production and use | |
| CN102409407B (en) | Infrared non-linear optical material Ba3AGa5Se10Cl2 and preparation method thereof | |
| Wang et al. | Sr 4 Pb 1.5 Sb 5 O 5 Se 8: a new mid-infrared nonlinear optical material with a moderate SHG response | |
| Zhang et al. | Deep eutectic solvents synthesis of A2Sb (C2O4) Cl3 (A= NH4, K, Rb) with superior optical performance | |
| CN106629632B (en) | Selenium gallium cadmium barium compound and preparation method thereof, selenium gallium cadmium crystal of barium and its preparation method and application | |
| Zhao et al. | Na 6 Sn 3 P 4 S 16: Sn (ii)-chelated PS 4 groups inspired an ultra-strong SHG response | |
| CN111676517B (en) | Non-core mixed anion crystal material and preparation method and application thereof | |
| Cropek et al. | Revisiting two thiophosphate compounds constituting d 0 transition metal HfP 2 S 6 and d 10 transition metal α-Ag 4 P 2 S 6 as multifunctional materials for combining second harmonic generation response and photocurrent response | |
| CN102534784B (en) | Nonlinear optical crystal Rb4Ge3B6O17 | |
| CN111321455B (en) | Nonlinear optical crystal niobium oxysulfate iodate as well as preparation method and application thereof | |
| CN109750357B (en) | Infrared nonlinear optical crystal Ba10Zn7M6Q26And preparation method and application thereof | |
| Zhou et al. | Second-order nonlinear optical-active selenide borate Zn8Se2 (BO2) 12: experimental and theoretical analysis | |
| 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 | |
| Kong et al. | Explorations of new selenites of the group IIIA and IVA metals | |
| CN105525354A (en) | Quaternary thioarsenate compound semiconductor material as well as preparation method and application thereof | |
| CN105036192A (en) | Quaternary sulfo-antimonate compound semiconductor material as well as preparation method and application thereof | |
| CN103255479A (en) | Method for synthesizing MnTeMoO6 crystal by using hydrothermal method | |
| Xie et al. | A series of new rare-earth sulfide borates RE3S3BO3 (RE= Nd, Tb, Dy): Syntheses, structures and optical properties | |
| Murugadoss et al. | Solvent effect on structure and morphology of formamidinium lead tri-iodide perovskite via hydrothermal method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate 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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180112 |