CN105036192A - Quaternary sulfo-antimonate compound semiconductor material as well as preparation method and application thereof - Google Patents

Quaternary sulfo-antimonate compound semiconductor material as well as preparation method and application thereof Download PDF

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CN105036192A
CN105036192A CN201510310461.3A CN201510310461A CN105036192A CN 105036192 A CN105036192 A CN 105036192A CN 201510310461 A CN201510310461 A CN 201510310461A CN 105036192 A CN105036192 A CN 105036192A
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quaternary
baagsbs
preparation
compound semiconductor
thioantimoniate
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CN105036192B (en
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刘毅
刘畅
沈亚英
候佩佩
张家正
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Zhejiang University ZJU
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Abstract

The invention discloses a quaternary sulfo-antimonate compound semiconductor material as well as a preparation method and application thereof. A quaternary sulfide semiconductor material is obtained by using hydrated barium hydroxide, metallic silver, a binary solid solution antimony sulfide and elemental sulfur as raw materials and hydrazine hydrate as a solvent to react for 7 days in a backing oven at 160 DEG C and has chemical composition formulae of BaAgSbS3 and BaAgSbS3.H2O. The preparation method has the advantages of simple operation process, simple raw materials, low cost, mild reaction condition, low synthetic temperature and the like. The yield of the quaternary sulfide obtained by adopting the preparation method disclosed by the invention can reach 40-50%, the chemical purity of the quaternary sulfide is high, and the quaternary sulfide can be used for preparing optical semiconductor devices or solar battery transition layer materials.

Description

A kind of quaternary thioantimoniate compound semiconductor materials and its production and use
Technical field
The present invention relates to a kind of quaternary thioantimoniate compound semiconductor materials and its production and use, belong to inorganic semiconductor material field.
Background technology
Multi-element metal chalkogenide has very complicated structure, also has abundant physics and chemistry character, is the very active research field of solid state chemistry one, this compounds is in nonlinear optics, ion-exchange, photochemical catalysis, the aspects such as ionic conduction all present certain application prospect.These special character of chalkogenide come from their various composition and crystalline structure.Therefore, carrying out the synthesis of multi-element metal chalkogenide, inquire into the relation of their structure and properties, is the focus carrying out the research of multi-element metal chalkogenide.
Relative to traditional ternary chalcogenide thing, quaternary chalcogen compound is made up of more element, and the interphase interaction of element is more various, and thus, the kind of crystalline obtained is more, structure is more complicated, also may occur more performance.In recent years, the study on the synthesis of multi-element metal chalkogenide achieves impressive progress, scientist, by various method, has synthesized the quaternary chalcogen compound in a large number with novel texture and peculiar property, has greatly enriched chalcogenide structure chemistry and materials chemistry.
Because Sb (III) enlivens the existence of lone-pair electron, antimony chalcogen compound has very abundant structure type, and its basic building unit is the SbQ of pyrometric cone 3with tetrahedral SbQ 4.Using different positively charged ions as structure directing agent, [Sb (III) Q] 3-unit forms the negatively charged ion [Sb of different structure by common limit and the polymerization being total to summit xq y] z-, composition chain, stratiform or three-dimensional network.Transition metal ion can be connected with antimony sulphur network equally, forms more complicated inorganic anion skeleton.
At present, the typical method of preparation quaternary chalcogen compound mainly comprises high temperature solid-state method, middle temperature flux method and low-temperature solvent heat method both at home and abroad.Wherein high temperature solid-state method productive rate is high, and selectivity is high, but temperature of reaction is high, and experimental implementation is complicated; Middle temperature flux method is practical but how toxic solubility promoter is, works the mischief during volatilization to human body and environment.The nearly synthesis being just used to inorganic crystal material for 30 years of low-temperature solvent heat method, compared with conventional high-temperature synthetic method, owing to being easy to regulate the ambiance under solvent thermal condition, thus the generation of lower valency, middle valence state and special valence state compound is conducive to, and can evenly adulterate, also help the synthesis of cenotype, new texture.
Solvent process for thermosynthesizing has become the important synthetic method of chalkogenide in recent years, by selecting suitable reaction medium, greatly can not only improve solubleness and the diffusibleness of reactant, accelerates reaction process, and can affect the structure of chalcogen anion frame.Therefore, developing new solvent-thermal process route, find new synthetic system, is the key of synthesizing new multi-component sulfur compound.
Summary of the invention
The object of this invention is to provide a kind of quaternary thioantimoniate compound semiconductor materials and its production and use.
Quaternary thioantimoniate compound semiconductor materials chemical constitution formula is respectively: BaAgSbS 3, BaAgSbS 3h 2o, wherein said BaAgSbS 3belong to oblique system, c2/c spacer, unit cell parameters a=9.3675 (7), b=7.9328 (5), c=17.2651 (12), α=90 °, β=101.734 °, γ=90 °, V=1256.17 (15) 3, Z=8, D c=4.898g/cm 3, single crystal is orange red bulk, and energy gap is 2.21eV;
BaAgSbS 3h 2o belongs to rhombic system, pan2 spacer, unit cell parameters a=18.8527 (7), b=8.8232 (3), c=8.6649 (3), α=90 °, β=90 °, γ=90 °, V=1441.33 (9) 3, Z=8, D c=4.435g/cm 3, single crystal is yellow sheet, and energy gap is 2.43eV.
A kind of preparation method of quaternary thioantimoniate compound semiconductor materials is: be the mixing of the hydronium(ion) barium oxide of 1.0:0.4-1.0:0.2:2.0-3.0, argent, binary solid solution antimony sulfide and elemental sulfur by mol ratio, add 3-5mL hydrazine hydrate, react 7 days in 160 DEG C of baking ovens, after deionized water and washing with alcohol, obtain BaAgSbS 3.
The preparation method of another kind of quaternary thioantimoniate compound semiconductor materials is: be the mixing of the hydronium(ion) barium oxide of 1.0-1.5:1.0-1.2:0.25-0.5:2.0-2.5, argent, binary solid solution antimony sulfide and elemental sulfur by mol ratio, add 3-5mL hydrazine hydrate, react 7 days in 160 DEG C of baking ovens, after deionized water and washing with alcohol, obtain BaAgSbS 3h 2o.
Quaternary thioantimoniate compound semiconductor materials is for the preparation of optical semiconductor device or solar cell buffer layer material.
Beneficial effect of the present invention: synthetic method is simple, raw materials cost is low, and reaction conditions is gentle.Adopt quaternary thioantimoniate compound semiconductor materials prepared by present method, productive rate can reach 40%-50%.The energy gap of semiconductor material is respectively 2.21eV and 2.43eV, has potential using value in semiconductor optical.
Accompanying drawing explanation
Fig. 1 is BaAgSbS 3the shape appearance figure of crystal;
Fig. 2 is BaAgSbS 3h 2the shape appearance figure of O crystal;
Fig. 3 is BaAgSbS 3the EDX collection of illustrative plates of crystal, indicates existence and the content thereof of Ba, Ag, Sb and S element;
Fig. 4 is BaAgSbS 3h 2the EDX collection of illustrative plates of O crystal, indicates existence and the content thereof of Ba, Ag, Sb and S element;
Fig. 5 is BaAgSbS 3structure iron;
Fig. 6 is BaAgSbS 3h 2the structure iron of O;
Fig. 7 is according to the BaAgSbS in embodiment 1 3crystal obtain XRD figure spectrum with monocrystalline simulated diffraction figure;
Fig. 8 is according to the BaAgSbS in embodiment 2 3h 2o crystal obtain XRD figure spectrum with monocrystalline simulated diffraction figure;
Fig. 9 is BaAgSbS 3thermal analysis curve;
Figure 10 is BaAgSbS 3h 2the thermal analysis curve of O;
Figure 11 is BaAgSbS 3and BaAgSbS 3h 2the visible diffuse reflection spectrum of solid-state UV of O.
Embodiment
Quaternary thioantimoniate compound semiconductor materials chemical constitution formula is respectively: BaAgSbS 3, BaAgSbS 3h 2o, wherein said BaAgSbS 3belong to oblique system, c2/c spacer, unit cell parameters a=9.3675 (7), b=7.9328 (5), c=17.2651 (12), α=90 °, β=101.734 °, γ=90 °, V=1256.17 (15) 3, Z=8, D c=4.898g/cm 3, single crystal is orange red bulk, and energy gap is 2.21eV;
BaAgSbS 3h 2o belongs to rhombic system, pan2 spacer, unit cell parameters a=18.8527 (7), b=8.8232 (3), c=8.6649 (3), α=90 °, β=90 °, γ=90 °, V=1441.33 (9) 3, Z=8, D c=4.435g/cm 3, single crystal is yellow sheet, and energy gap is 2.43eV.
A kind of preparation method of quaternary thioantimoniate compound semiconductor materials is: be the mixing of the hydronium(ion) barium oxide of 1.0:0.4-1.0:0.2:2.0-3.0, argent, binary solid solution antimony sulfide and elemental sulfur by mol ratio, add 3-5mL hydrazine hydrate, react 7 days in 160 DEG C of baking ovens, after deionized water and washing with alcohol, obtain BaAgSbS 3.
The preparation method of another kind of quaternary thioantimoniate compound semiconductor materials is: be the mixing of the hydronium(ion) barium oxide of 1.0-1.5:1.0-1.2:0.25-0.5:2.0-2.5, argent, binary solid solution antimony sulfide and elemental sulfur by mol ratio, add 3-5mL hydrazine hydrate, react 7 days in 160 DEG C of baking ovens, after deionized water and washing with alcohol, obtain BaAgSbS 3h 2o.
Quaternary thioantimoniate compound semiconductor materials is for the preparation of optical semiconductor device or solar cell buffer layer material.
Embodiment 1:
BaAgSbS 3crystal.Take initial feed Ba (OH) 28H 2o1.0mmol (0.316g), Ag0.4mmol (0.043g), Sb 2s 30.2mmol (0.068g) and S2.0mmol (0.064g) puts into water heating kettle, then adds hydrazine hydrate 3mL, reacts 7 days at water heating kettle being placed in 160 DEG C.Product uses distilled water and absolute ethanol washing 2 times respectively, and obtain a small amount of orange red bulk crystals and a large amount of yellow tabular crystal, orange red bulk crystals productive rate is 15%.EDX ultimate analysis shows crystal only containing Ba, Ag, Sb, S tetra-kinds of elements, and each constituent content ratio is about 1:1:1:3.
Embodiment 2:
BaAgSbS 3crystal.Take initial feed Ba (OH) 28H 2o1.0mmol (0.316g), Ag0.5mmol (0.054g), Sb 2s 30.2mmol (0.068g) and S2.5mmol (0.080g) puts into water heating kettle, then adds hydrazine hydrate 4mL, reacts 7 days at water heating kettle being placed in 160 DEG C.Product uses distilled water and absolute ethanol washing 2 times respectively, and obtain orange red bulk crystals and a small amount of yellow tabular crystal, orange red bulk crystals productive rate is 38%.Through single-crystal X-ray diffraction analysis, this crystal composition formula is BaAgSbS 3, belong to oblique system, c2/c spacer, unit cell parameters a=9.3675 (7), b=7.9328 (5), c=17.2651 (12), α=90 °, β=101.734 °, γ=90 °, V=1256.17 (15) 3, crystalline structure figure as figure 5 illustrates.EDX ultimate analysis shows crystal only containing Ba, Ag, Sb, S tetra-kinds of elements, and each constituent content is than consistent with single crystal diffraction analytical results (see Fig. 3).It is 2.21eV (see Figure 11) that UV-vis collection of illustrative plates records semiconductor material energy gap.
Embodiment 3:
BaAgSbS 3crystal.Take initial feed Ba (OH) 28H 2o1.0mmol (0.316g), Ag0.5mmol (0.054g), Sb 2s 30.2mmol (0.068g) and S3.0mmol (0.080g) puts into water heating kettle, then adds hydrazine hydrate 5mL, reacts 7 days at water heating kettle being placed in 160 DEG C.Product uses distilled water and absolute ethanol washing 2 times respectively, and obtain a small amount of orange red bulk crystals and a small amount of yellow tabular crystal, orange red bulk crystals productive rate is 10%.EDX ultimate analysis shows crystal only containing Ba, Ag, Sb, S tetra-kinds of elements, and each constituent content ratio is about 1:1:1:3.
Embodiment 4:
BaAgSbS 3h 2o crystal.Weigh initial feed Ba (OH) 28H 2o1.0mmol (0.316g), Ag1.0mmol (0.108g), Sb 2s 30.25mmol (0.085g) and S2.5mmol (0.080g) puts into water heating kettle, then adds hydrazine hydrate 3.0mL.React 7 days at water heating kettle being placed in 160 DEG C, product uses distilled water and washing with alcohol 2 times respectively, and obtain yellow tabular crystal, productive rate can reach 80%, but crystalline size is less.EDX ultimate analysis shows crystal only containing Ba, Ag, Sb, S tetra-kinds of elements, and each constituent content ratio is about 1:1:1:3.
Embodiment 5:
BaAgSbS 3h 2o crystal.Weigh initial feed Ba (OH) 28H 2o1.0mmol (0.316g), Ag1.0mmol (0.108g), Sb 2s 30.5mmol (0.170g) and S2.0mmol (0.064g) puts into water heating kettle, then adds hydrazine hydrate 4.0mL.React 7 days at water heating kettle being placed in 160 DEG C, product uses distilled water and washing with alcohol 2 times respectively, and obtain yellow tabular crystal, productive rate can reach 50%.Through single-crystal X-ray diffraction analysis, this crystal composition formula is BaAgSbS 3, belong to rhombic system, pan2 spacer, unit cell parameters a=18.8527 (7), b=8.8232 (3), c=8.6649 (3), α=90 °, β=90 °, γ=90 °, V=1441.33 (9) 3, crystalline structure figure as indicated with 6.EDX ultimate analysis shows that crystal contains Ba, Ag, Sb, S tetra-kinds of elements, and each constituent content is than consistent with single crystal diffraction analytical results (see Fig. 4).It is 2.43eV (see Figure 11) that UV-vis collection of illustrative plates records semiconductor material energy gap.
Embodiment 6:
BaAgSbS 3h 2o crystal.Weigh initial feed Ba (OH) 28H 2o1.5mmol (0.474g), Ag1.2mmol (0.0.130g), Sb 2s 30.5mmol (0.170g) and S2.0mmol (0.064g) puts into water heating kettle, then adds hydrazine hydrate 5.0mL.React 7 days at water heating kettle being placed in 160 DEG C, product uses distilled water and washing with alcohol 2 times respectively, and obtain yellow tabular crystal, productive rate is 30%.EDX ultimate analysis shows crystal only containing Ba, Ag, Sb, S tetra-kinds of elements, and each constituent content ratio is about 1:1:1:3.

Claims (4)

1. a quaternary thioantimoniate compound semiconductor materials, is characterized in that, its chemical constitution formula is respectively: BaAgSbS 3, BaAgSbS 3h 2o, wherein said BaAgSbS 3belong to oblique system, c2/c spacer, unit cell parameters a=9.3675 (7), b=7.9328 (5), c=17.2651 (12), α=90 °, β=101.734 °, γ=90 °, V=1256.17 (15) 3, Z=8, D c=4.898g/cm 3, single crystal is orange red bulk, and energy gap is 2.21eV; BaAgSbS 3h 2o belongs to rhombic system, pan2 spacer, unit cell parameters a=18.8527 (7), b=8.8232 (3), c=8.6649 (3), α=90 °, β=90 °, γ=90 °, V=1441.33 (9) 3, Z=8, D c=4.435g/cm 3, single crystal is yellow sheet, and energy gap is 2.43eV.
2. the preparation method of a quaternary thioantimoniate compound semiconductor materials as claimed in claim 1, it is characterized in that being the mixing of the hydronium(ion) barium oxide of 1.0:0.4-1.0:0.2:2.0-3.0, argent, binary solid solution antimony sulfide and elemental sulfur by mol ratio, add 3-5mL hydrazine hydrate, react 7 days in 160 DEG C of baking ovens, after deionized water and washing with alcohol, obtain BaAgSbS 3.
3. the preparation method of a quaternary thioantimoniate compound semiconductor materials as claimed in claim 1, it is characterized in that being the mixing of the hydronium(ion) barium oxide of 1.0-1.5:1.0-1.2:0.25-0.5:2.0-2.5, argent, binary solid solution antimony sulfide and elemental sulfur by mol ratio, add 3-5mL hydrazine hydrate, react 7 days in 160 DEG C of baking ovens, after deionized water and washing with alcohol, obtain BaAgSbS 3h 2o.
4. the purposes of quaternary thioantimoniate compound semiconductor materials as claimed in claim 2, is characterized in that: for the preparation of optical semiconductor device or solar cell buffer layer material.
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Cited By (3)

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Publication number Priority date Publication date Assignee Title
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

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

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