CN105236482A - Quaternary sulfur-antimony compound ACuSb2S4 semiconductor material - Google Patents
Quaternary sulfur-antimony compound ACuSb2S4 semiconductor material Download PDFInfo
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- CN105236482A CN105236482A CN201510556601.5A CN201510556601A CN105236482A CN 105236482 A CN105236482 A CN 105236482A CN 201510556601 A CN201510556601 A CN 201510556601A CN 105236482 A CN105236482 A CN 105236482A
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- semiconductor material
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- acusb
- antimony compounds
- sulphur
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Abstract
The invention discloses a quaternary sulfur-antimony compound ACuSb2S4 semiconductor material, of which the chemical formula is ACuSb2S4, wherein A is one selected from the alkali metal positive ions Rb and Cs for balancing negative ion frame. A particularly preparation process includes the following steps: weighing proper amounts of alkali metal hydroxides, elementary copper, antimony powder and sulfur powder according to the molar ratio of 1:2:0.5:2; and with hydrazine hydrate and polyethylene glycol as solvents, carrying out a reaction for 7 days at 160 DEG C to obtain black-red block crystals. The method has simple operation processes and is low in raw material cost, and is mild in reaction conditions. The quaternary sulfur-antimony compound belongs to monoclinic system and has C2/c (No.15) space groups, has a novel three-dimensional opened frame structure, is about 1.7 eV in energy bond, is a narrow bandgap semiconductor material and is used for preparing optical semiconductor devices.
Description
Technical field
The present invention relates to a kind of quaternary sulphur antimony compounds ACuSb
2s
4semiconductor material, belongs to inorganic semiconductor material field.
Background technology
Along with the fast development of whole world science and technology, the world today has entered the electronic information epoch.Semiconductor material is the body material forming many solid electronic devices, in optical communication equipment, information storage, process, processing and display, have important application, as semiconductor laser, diode.Semiconductor integrated circuit, semiconductor memory and photorectifier etc.It is the energy, information, aerospace, the requisite a kind of functional materials of electronic technology, occupies extremely important status in electronic information material.Semi-conductor industry great development level is one of important symbol of a measurement advanced degree of country.
Sulphur antimony compounds has very complicated structure, abundant physics and chemistry character, having potential using value in fields such as photoelectric material, molecular recognition and catalysis, ion-exchange, nonlinear optical material (NLO), chemical sensor and semi-conductors, is one of more inorganic multifunctional material of Recent study.Because V race metal Sb (III) ion contains the active 5S of stereochemistry
2lone-pair electron, form primary structure cell S bS with S element
x(x=3,4,5).Under alkaline environment, primary structure cell S bS
xmutual polymerization forms polyanion, then coordination of metal ion, and the geometry of regulation and control substance, has enriched physical and chemical performance.
Since this century, middle low-temperature solvent process for thermosynthesizing obtains increasing concern in solid state chemistry synthesis.Solvent thermal reaction is the effective ways of synthesis sulphur antimony compounds.Solvent-thermal process system is generally in imperfect equilibrium state, at high temperature under high pressure, the solvent of building-up reactions is in critical or near critical state, reactant process based prediction model in a solvent has larger change, solvent thermal chemical reaction is made greatly to be different from normality, the functional materials be synthesized thus or crystal, have the good characteristic of self at aspect of performance.But because reaction is carried out being difficult to control in water heating kettle, so the repeatability of reaction is not good.Find according to researchist's practice for many years, solvent process for thermosynthesizing is mainly subject to the impact of following factor: the 1) polarity of solvent, viscosity, critical temperature, 2) temperature of reaction, 3) cation radius, 4) reaction times etc.By controlling the reaction process of solvent thermal, reaching optimization experiment, preparing the object of novel product.
So far, 4 quaternary sulphur antimony compoundss A-Cu-Sb-S (A=Na, K, Rb, Cs) have only been synthesized.1996, the people such as J.E.Jerome and J.W.Kolis obtained Na by the method synthesis of overcritical quadrol
2cuSbS
3(J.E.Jerome, J.W.Kolis, etal.
eur.J.SolidStateInorg.Chem., 33, 765 (1996) .), be first quaternary sulphur antimony compounds A-Cu-Sb-S (A=Na, K, Rb, Cs) be in the news; In 2005, the people such as B.Deng and J.A.Ibers obtained K by solvent method
2cuSbS
3(B.Deng, J.A.Ibers, etal.
j.SolidStateChem., 178, 3169 (2005) .).Recently, the people such as Y.L.An adopt solvent thermal process, and successfully synthesis obtains Rb
2cu
2sb
2s
5and Cs
2cu
2sb
2s
5(Y.L.An, etal.
inorg.Chem., 53, 4856 (2014) .).But the micro-space structure of these four kinds of compounds is all two-dimensional layer, in quaternary system A-Cu-Sb-S (A=Na, K, Rb, Cs), also there is no the crystalline structure of a peacekeeping three-dimensional so far.Therefore suitable reaction conditions is found, research and development novel structure and the suitable quaternary sulphur antimony compounds semiconductor material of energy gap, prepare the optical semiconductor devices such as solar cell buffer layer material, the related industrieies such as development semiconductor optoelectronic are all had important practical significance.
Summary of the invention
The object of the invention is to solve problems of the prior art, and a kind of quaternary sulphur antimony compounds ACuSb is provided
2s
4semiconductor material.Concrete technical scheme is as follows:
A kind of quaternary sulphur antimony compounds ACuSb
2s
4the chemical constitution formula of the quaternary sulphur antimony compounds in semiconductor material is ACuSb
2s
4, wherein A is the one in alkali metal cation Rb, Cs.
Described quaternary sulphur antimony compounds ACuSb
2s
4semiconductor material belongs to oblique system, and C2/c (No.15) spacer, has Three-dimensional Open skeleton structure.
Described quaternary sulphur antimony compounds ACuSb
2s
4the energy gap of semiconductor material is 1.70eV.
Another object of the present invention is to provide a kind of described quaternary sulphur antimony compounds ACuSb
2s
4the preparation method of semiconductor material, concrete preparation process is as follows: the ratio taking amount of substance is the alkali metal hydroxide of 1:2:0.5:2, copper simple substance, antimony powder and sulphur powder, with hydrazine hydrate and polyoxyethylene glycol for solvent dissolves, react at 160 DEG C after 7 days, cooling, respectively wash twice with distilled water and ethanol respectively again, quaternary sulphur antimony compounds semiconductor material can be obtained; Wherein alkali metal hydroxide is RbOH or CsOH.
Described hydrazine hydrate and the blending ratio of polyoxyethylene glycol are 1:4.
Another object of the present invention is to provide a kind of described quaternary sulphur antimony compounds ACuSb
2s
4semiconductor material is for the preparation of optical semiconductor device.
Compared with prior art, the present invention has following beneficial effect: the present invention adopts a step solvent-thermal method preparation, the advantages such as operating process is simple, and raw materials cost is low, and reaction conditions is gentle.The quaternary sulphur antimony compounds adopting present method to obtain belongs to oblique system, and C2/c (No.15) spacer, has Three-dimensional Open skeleton structure, can be with about 1.7eV, is a kind of low-gap semiconductor material, can be used for preparing optical semiconductor device.
Accompanying drawing explanation
Fig. 1 (a) is semiconductor material RbCuSb
2s
4crystal morphology figure;
Fig. 1 (b) is semiconductor material CsCuSb
2s
4crystal morphology figure;
Fig. 2 (a) is semiconductor material RbCuSb
2s
4eDS collection of illustrative plates;
Fig. 2 (b) is semiconductor material CsCuSb
2s
4eDS collection of illustrative plates;
Fig. 3 (a) is semiconductor material RbCuSb
2s
4x-ray powder diffraction figure and monocrystalline simulated diffraction figure, X-coordinate represents angle of diffraction, and ordinate zou represents intensity;
Fig. 3 (b) is semiconductor material CsCuSb
2s
4x-ray powder diffraction figure and monocrystalline simulated diffraction figure, X-coordinate represents angle of diffraction, and ordinate zou represents intensity;
Fig. 4 is semiconductor material RbCuSb
2s
4the single crystal structure figure of molecule;
Fig. 5 (a) is semiconductor material RbCuSb
2s
4solid-state UV visible absorption spectra, X-coordinate represents wavelength, and ordinate zou represents absorbancy;
Fig. 5 (b) is semiconductor material CsCuSb
2s
4solid-state UV visible absorption spectra, X-coordinate represents wavelength, and ordinate zou represents absorbancy;
Fig. 6 (a) is semiconductor material RbCuSb
2s
4thermal analysis curve, X-coordinate represents temperature, and ordinate zou represents weight percentage;
Fig. 6 (b) is semiconductor material CsCuSb
2s
4thermal analysis curve, X-coordinate represents temperature, and ordinate zou represents weight percentage.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention will be further described.
Quaternary sulphur antimony compounds ACuSb
2s
4semiconductor material chemical constitution formula is ACuSb
2s
4, wherein A is the one in alkali metal cation Rb, Cs of balance anion skeleton.
Quaternary sulphur antimony compounds ACuSb
2s
4semiconductor material belongs to oblique system, C2/c (No.15) spacer, has novel three-dimensional open-framework structure.
Quaternary sulphur antimony compounds ACuSb
2s
4the preparation method of semiconductor material is: the ratio taking amount of substance is the appropriate bases metal hydroxides of 1:2:0.5:2, copper simple substance, antimony powder, sulphur powder, with hydrazine hydrate and polyoxyethylene glycol for solvent, react at 160 DEG C after 7 days, cooling, respectively wash twice with distilled water and ethanol respectively again, quaternary sulphur antimony compounds semiconductor material can be obtained; Wherein alkali metal hydroxide is RbOH or CsOH.
Above-mentioned preparation method's kind, the blending ratio of hydrazine hydrate and polyoxyethylene glycol is 1:4.
Quaternary sulphur antimony compounds ACuSb
2s
4semiconductor material energy gap is about 1.70eV, is a kind of low-gap semiconductor material, can be used for preparing optical semiconductor device, and optical semiconductor device is solar cell buffer layer material.
In the present invention, if not refer in particular to, all equipment and raw material etc. are all directly buy from market, without what process further.Method in following embodiment, if no special instructions, is this area ordinary method.
embodiment 1:
RbCuSb
2s
4crystal:
Take initial feed RbOH1.0mmol (0.103g), Cu2.0mmol (0.128g), Sb
2s
30.5mmol (0.170g) and S2.0mmol (0.064g) puts into water heating kettle, then adds hydrazine hydrate 0.5mL and polyoxyethylene glycol 2.0mL, reacts 7 days at water heating kettle being placed in 160 DEG C.After reaction terminates, open water heating kettle, take out product, respectively wash 2 times with distilled water and dehydrated alcohol respectively, obtain dark red bulk crystals, productive rate is that 70%(is as the criterion with copper), grain-size 200*300 μm is (see Fig. 1 a).Through single-crystal X-ray diffraction analysis, this crystal composition formula is RbCuSb
2s
4, belong to oblique system, spacer is C2/c (No.15), a=7.3272 (6), b=11.1628 (8), c=10.7849 (8), α=90 °, β=105.748 (8) °, γ=90 °, Z=4, V=849.01 (11)
3, crystalline structure figure as indicated at 4.EDX ultimate analysis shows crystal only containing Rb, Cu, Sb, S tetra-kinds of elements, and each constituent content ratio is consistent with single crystal diffraction analytical results (see Fig. 2 a).The crystal that XRD analysis obtains is pure phase, and consistent with notional result (see Fig. 3 a).UV-vis collection of illustrative plates record semiconductor material energy gap be 1.71eV (see Fig. 5 a).The thermal stability that TG collection of illustrative plates describes semiconductor material is excellent, does not decompose (see Fig. 6 a) to 500 DEG C.
embodiment 2:
CsCuSb
2s
4crystal:
Take initial feed CsOH1.0mmol (0.150g), Cu2.0mmol (0.128g), Sb
2s
30.5mmol (0.170g) and S2.0mmol (0.064g) puts into water heating kettle, then adds hydrazine hydrate 0.5mL and polyoxyethylene glycol 2.0mL, reacts 7 days at water heating kettle being placed in 160 DEG C.After reaction terminates, open water heating kettle, take out product, respectively wash 2 times with distilled water and dehydrated alcohol respectively, obtain dark red bulk crystals, productive rate is that 58%(is as the criterion with copper), grain-size 250*300 μm (see Fig. 1 b).Through single-crystal X-ray diffraction analysis, this crystal composition formula is CsCuSb
2s
4, belong to oblique system, spacer is C2/c (No.15), a=7.5859 (7), b=11.1225 (9), c=10.8286 (10), α=90 °, β=105.364 (9) °, γ=90 °, Z=4, V=881.00 (14)
3.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. 2 b).The crystal that XRD analysis obtains is pure phase, and consistent with notional result (see Fig. 3 b).It is 1.70eV (see Fig. 5 b) that UV-vis collection of illustrative plates records semiconductor material energy gap.The thermal stability that TG collection of illustrative plates describes semiconductor material is excellent, does not decompose (see Fig. 6 b) to 500 DEG C.
Claims (6)
1. a quaternary sulphur antimony compounds ACuSb
2s
4semiconductor material, is characterized in that, the chemical constitution formula of quaternary sulphur antimony compounds is ACuSb
2s
4, wherein A is the one in alkali metal cation Rb, Cs.
2. a kind of quaternary sulphur antimony compounds ACuSb as claimed in claim 1
2s
4semiconductor material, is characterized in that, described quaternary sulphur antimony compounds ACuSb
2s
4semiconductor material belongs to oblique system, and C2/c (No.15) spacer, has Three-dimensional Open skeleton structure.
3. a kind of quaternary sulphur antimony compounds ACuSb as claimed in claim 1
2s
4semiconductor material, is characterized in that, described quaternary sulphur antimony compounds ACuSb
2s
4the energy gap of semiconductor material is 1.70eV.
4. a quaternary sulphur antimony compounds ACuSb as claimed in claim 1
2s
4the preparation method of semiconductor material, it is characterized in that: the ratio taking amount of substance is the alkali metal hydroxide of 1:2:0.5:2, copper simple substance, antimony powder and sulphur powder, with hydrazine hydrate and polyoxyethylene glycol for solvent dissolves, react at 160 DEG C after 7 days, cooling, respectively wash twice with distilled water and ethanol respectively again, quaternary sulphur antimony compounds semiconductor material can be obtained; Wherein alkali metal hydroxide is RbOH or CsOH.
5. preparation method as claimed in claim 4, is characterized in that: described hydrazine hydrate and the blending ratio of polyoxyethylene glycol are 1:4.
6. a quaternary sulphur antimony compounds ACuSb as claimed in claim 1
2s
4the purposes of semiconductor material, is characterized in that: for the preparation of optical semiconductor device.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN111847508A (en) * | 2019-04-24 | 2020-10-30 | 上海电机学院 | In-based semiconductor material, preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104451887A (en) * | 2014-11-28 | 2015-03-25 | 遵义师范学院 | Infrared nonlinear optical crystal Ln8Sb2S15 and preparation method thereof |
| WO2015068683A1 (en) * | 2013-11-07 | 2015-05-14 | 積水化学工業株式会社 | Coating material for forming semiconductors, semiconductor thin film, thin film solar cell and method for manufacturing thin film solar cell |
| CN104862782A (en) * | 2015-03-31 | 2015-08-26 | 浙江大学 | Quaternary sulfide semiconductor material, and preparation method and application thereof |
-
2015
- 2015-09-02 CN CN201510556601.5A patent/CN105236482A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015068683A1 (en) * | 2013-11-07 | 2015-05-14 | 積水化学工業株式会社 | Coating material for forming semiconductors, semiconductor thin film, thin film solar cell and method for manufacturing thin film solar cell |
| CN104451887A (en) * | 2014-11-28 | 2015-03-25 | 遵义师范学院 | Infrared nonlinear optical crystal Ln8Sb2S15 and preparation method thereof |
| CN104862782A (en) * | 2015-03-31 | 2015-08-26 | 浙江大学 | Quaternary sulfide semiconductor material, and preparation method and application thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| CN111847508A (en) * | 2019-04-24 | 2020-10-30 | 上海电机学院 | In-based semiconductor material, preparation method and application |
| CN111847508B (en) * | 2019-04-24 | 2022-11-18 | 上海电机学院 | In-based semiconductor material, preparation method and application |
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