CN105036192B - 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 PDFInfo
- Publication number
- CN105036192B CN105036192B CN201510310461.3A CN201510310461A CN105036192B CN 105036192 B CN105036192 B CN 105036192B CN 201510310461 A CN201510310461 A CN 201510310461A CN 105036192 B CN105036192 B CN 105036192B
- Authority
- CN
- China
- Prior art keywords
- baagsbs
- quaternary
- preparation
- compound semiconductor
- crystal
- 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
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
Technical field
The present invention relates to a kind of quaternary sulfantimoniate compound semiconductor materials and its production and use, belong to no
Machine field of semiconductor materials.
Background technology
Multi-element metal chalcogenide has extremely complex structure, also has abundant physics and chemical property, is solid
A chemical very active research field, this kind of compound is in nonlinear optics, ion exchange, photocatalysis, ionic conduction
Etc. aspect all present certain application prospect.These special properties of chalcogenide come from their various compositions and crystal knot
Structure.Therefore, carry out the synthesis of multi-element metal chalcogenide, inquire into the relation of their structure and properties, be by multi-element metal sulfur
Belong to the focus of compound research.
With respect to traditional ternary chalcogenide thing, quaternary chalcogen compound is made up of more elements, phase between element
Interaction is more various, thus, the kind of crystalline obtaining is more, structure is more complicated, be likely to more performances.In recent years
Come, the study on the synthesis of multi-element metal chalcogenide achieves impressive progress, scientist, by various methods, has synthesized a large amount of
There is the quaternary chalcogen compound of new structure and peculiar property, be greatly enriched chalcogenide structure chemical and materialized
Learn.
Because sb (iii) enlivens the presence of lone pair electrons, antimony chalcogen compound has very abundant structure type, its base
This construction unit is the sbq of pyrometric cone3With tetrahedral sbq4.Using different cationes as structure directing agent, [sb (iii) q
]3-Unit can form the anion [sb of different structure by the polymerization on common side and common summitxqy]z-, form chain, stratiform or three
Dimension network.Transition metal ionss equally can form more complicated inorganic anion skeleton with antimony sulfur network connection.
At present, the typical method of preparation quaternary chalcogen compound mainly includes high temperature solid-state method both at home and abroad, middle temperature cosolvent
Method and low-temperature solvent full-boiled process.Wherein high temperature solid-state method yield is high, and selectivity is high, but reaction temperature is high, and experimental implementation is complicated；In
Warm flux method is practical but how toxic cosolvent is, during volatilization, human body and environment is worked the mischief.Low-temperature solvent full-boiled process is near
The synthesis being just used for inorganic crystal material in 30 years, compared with conventional high-temperature synthetic method, due to can easily be accommodated solvent thermal bar
Ambiance under part, thus be conducive to the generation of lower valency, middle valence state and special valence state compound, and can uniformly be mixed
Miscellaneous, also help the synthesis of cenotype, new construction.
Solvent process for thermosynthesizing has become the important synthetic method of chalcogenide in recent years, is situated between by selecting suitable reaction
Matter, can not only be greatly enhanced dissolubility and the diffusance of reactant, accelerate reaction process, and can affect chalcogen anion bone
The structure of frame.Therefore, develop new solvent-thermal process route, find new synthetic system, be synthesizing new multi-component sulfur compound
Key.
Content of the invention
It is an object of the invention to provide a kind of quaternary sulfantimoniate compound semiconductor materials and preparation method thereof and use
On the way.
Quaternary sulfantimoniate compound semiconductor materials chemical constitution formula is respectively as follows: baagsbs3, baagsbs3·h2O,
Wherein baagsbs3Crystal structure is as shown in Figure 5, baagsbs3·h2O crystal structure is as shown in Figure 6.
Described baagsbs3Belong to monoclinic system,c2/c space group, cell parameter 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, dc=4.898g/cm3,
Monocrystal is orange red bulk, and energy gap is 2.21 ev；
baagsbs3·h2O belongs to rhombic system,pAn2 space group, cell parameter 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, dc=4.435g/cm3, monocrystal is Huang
Color chips shape, energy gap is 2.43ev.
A kind of preparation method of quaternary sulfantimoniate compound semiconductor materials is: mol ratio is 1.0:0.4-1.0:
The hydronium(ion) Barium monoxide of 0.2:2.0-3.0, argent, binary solid solution antimony trisulfide and elemental sulfur mixing, add 3-5ml hydration
Hydrazine, reacts 7 days in 160 DEG C of baking ovens, obtains baagsbs after deionized water and washing with alcohol3.
The preparation method of another kind of quaternary sulfantimoniate compound semiconductor materials is: mol ratio is 1.0-1.5:
1.0-1.2:0.25-0.5:2.0-2.5 hydronium(ion) Barium monoxide, argent, binary solid solution antimony trisulfide and elemental sulfur mixing,
Add 3-5ml hydrazine hydrate, react 7 days in 160 DEG C of baking ovens, after deionized water and washing with alcohol, obtain baagsbs3·h2o.
Quaternary sulfantimoniate compound semiconductor materials is used for preparing optical semiconductor device or solaode transition
Layer material.
Beneficial effects of the present invention: synthetic method is simple, cost of material is low, and reaction condition is gentle.Using this method
The quaternary sulfantimoniate compound semiconductor materials of preparation, yield can reach 40%-50%.The energy gap of semi-conducting material is respectively
2.21 ev and 2.43 ev, have potential using value in terms of semiconductor optical.
Brief description
Fig. 1 is baagsbs3The shape appearance figure of crystal；
Fig. 2 is baagsbs3·h2The shape appearance figure of o crystal；
Fig. 3 is baagsbs3The edx collection of illustrative plates of crystal, indicates presence and its content of ba, ag, sb and s element；
Fig. 4 is baagsbs3·h2The edx collection of illustrative plates of o crystal, indicates presence and its content of ba, ag, sb and s element；
Fig. 5 is baagsbs3Structure chart；
Fig. 6 is baagsbs3·h2The structure chart of o；
Fig. 7 is according to the baagsbs in embodiment 13What crystal obtained xrd collection of illustrative plates with monocrystalline simulated diffraction figure；
Fig. 8 is according to the baagsbs in embodiment 23·h2What o crystal obtained xrd collection of illustrative plates with monocrystalline simulated diffraction figure；
Fig. 9 is baagsbs3Thermal analysis curve；
Figure 10 is baagsbs3·h2The thermal analysis curve of o；
Figure 11 is baagsbs3And baagsbs3·h2The visible diffusing reflection spectrum of solid-state UV of o.
Specific embodiment
Quaternary sulfantimoniate compound semiconductor materials chemical constitution formula is respectively as follows: baagsbs3, baagsbs3·h2O,
Wherein said baagsbs3Belong to monoclinic system,c2/c space group, cell parameter 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, dc=4.898g/cm3, monocrystalline
Body is orange red bulk, and energy gap is 2.21 ev；
baagsbs3·h2O belongs to rhombic system,pAn2 space group, cell parameter 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, dc=4.435g/cm3, monocrystal is Huang
Color chips shape, energy gap is 2.43ev.
A kind of preparation method of quaternary sulfantimoniate compound semiconductor materials is: mol ratio is 1.0:0.4-1.0:
The hydronium(ion) Barium monoxide of 0.2:2.0-3.0, argent, binary solid solution antimony trisulfide and elemental sulfur mixing, add 3-5ml hydration
Hydrazine, reacts 7 days in 160 DEG C of baking ovens, obtains baagsbs after deionized water and washing with alcohol3.
The preparation method of another kind of quaternary sulfantimoniate compound semiconductor materials is: mol ratio is 1.0-1.5:
1.0-1.2:0.25-0.5:2.0-2.5 hydronium(ion) Barium monoxide, argent, binary solid solution antimony trisulfide and elemental sulfur mixing,
Add 3-5ml hydrazine hydrate, react 7 days in 160 DEG C of baking ovens, after deionized water and washing with alcohol, obtain baagsbs3·h2o.
Quaternary sulfantimoniate compound semiconductor materials is used for preparing optical semiconductor device or solaode transition
Layer material.
Embodiment 1:
baagsbs3Crystal.Weigh initial feed ba (oh)2·8h2o 1.0 mmol(0.316g)、ag 0.4 mmol
(0.043g)、sb2s30.2 mmol (0.068g) and s 2.0 mmol (0.064g) puts in water heating kettle, adds hydrazine hydrate
3ml, water heating kettle is placed at 160 DEG C and reacts 7 days.Product uses distilled water and absolute ethanol washing 2 times respectively, obtains orange red on a small quantity
Color bulk crystals and a large amount of yellow flat crystal, orange red bulk crystals yield is 15%.Edx elementary analysiss show crystal containing only
Tetra- kinds of elements of ba, ag, sb, s, and each element content is than about 1:1:1:3.
Embodiment 2:
baagsbs3Crystal.Weigh initial feed ba (oh)2·8h2o 1.0 mmol(0.316g)、ag 0.5 mmol
(0.054g)、sb2s30.2 mmol (0.068g) and s 2.5 mmol (0.080g) puts in water heating kettle, adds hydrazine hydrate
4ml, water heating kettle is placed at 160 DEG C and reacts 7 days.Product uses distilled water and absolute ethanol washing 2 times respectively, obtains orange red color lump
Shape crystal and a small amount of yellow flat crystal, orange red bulk crystals yield is 38%.Through single-crystal x x ray diffraction analysis, this crystal group
An accepted way of doing sth is baagsbs3, belong to monoclinic system,c2/c space group, cell parameter a=9.3675 (7), b=7.9328 (5), c=
17.2651 (12), α=90 °, β=101.734 °, γ=90 °, v=1256.17 (15)3, crystal structure figure is as figure 5 illustrates.Edx unit
Plain analysis shows crystal containing only tetra- kinds of elements of ba, ag, sb, s, and each element content than consistent with single crystal diffraction analysis result (see
Fig. 3).It is 2.21 ev (see Figure 11) that uv-vis collection of illustrative plates records semi-conducting material energy gap.
Embodiment 3:
baagsbs3Crystal.Weigh initial feed ba (oh)2·8h2o 1.0 mmol(0.316g)、ag 0.5 mmol
(0.054g)、sb2s30.2 mmol (0.068g) and s 3.0 mmol (0.080g) puts in water heating kettle, adds hydrazine hydrate
5ml, water heating kettle is placed at 160 DEG C and reacts 7 days.Product uses distilled water and absolute ethanol washing 2 times respectively, obtains orange red on a small quantity
Color bulk crystals and a small amount of yellow flat crystal, orange red bulk crystals yield is 10%.Edx elementary analysiss show crystal containing only
Tetra- kinds of elements of ba, ag, sb, s, and each element content is than about 1:1:1:3.
Embodiment 4:
baagsbs3·h2O crystal.Weigh initial feed ba (oh)2·8h2o 1.0 mmol(0.316g)、 ag 1.0
mmol(0.108g)、 sb2s30.25 mmol (0.085g) and s 2.5 mmol (0.080g) puts in water heating kettle, adds
Hydrazine hydrate 3.0 ml.Water heating kettle is placed at 160 DEG C and reacts 7 days, product uses distilled water and washing with alcohol 2 times respectively, obtains Huang
Color flat crystal, yield is up to 80%, but crystalline size is less.Edx elementary analysiss show crystal containing only tetra- kinds of ba, ag, sb, s
Element, and each element content is than about 1:1:1:3.
Embodiment 5:
baagsbs3·h2O crystal.Weigh initial feed ba (oh)2·8h2o 1.0 mmol(0.316g)、 ag 1.0
mmol(0.108g)、 sb2s30.5 mmol (0.170g) and s 2.0 mmol (0.064g) puts in water heating kettle, adds water
Close hydrazine 4.0 ml.Water heating kettle is placed at 160 DEG C and reacts 7 days, product uses distilled water and washing with alcohol 2 times respectively, obtains yellow
Flat crystal, yield is up to 50%.Through single-crystal x x ray diffraction analysis, this crystal composition formula is baagsbs3, belong to rhombic system,pAn2 space group, cell parameter a=18.8527 (7), b=8.8232 (3), c=8.6649 (3), α=90 °, β=90 °, γ=
90 °, v=1441.33 (9)3, crystal structure figure is as indicated with 6.Edx elementary analysiss show that crystal contains tetra- kinds of elements of ba, ag, sb, s,
And each element content is than consistent with single crystal diffraction analysis result (see Fig. 4).Uv-vis collection of illustrative plates records semi-conducting material energy gap
2.43 ev (see Figure 11).
Embodiment 6:
baagsbs3·h2O crystal.Weigh initial feed ba (oh)2·8h2o 1.5 mmol(0.474g)、 ag 1.2
mmol(0.0.130g)、 sb2s30.5 mmol (0.170g) and s 2.0 mmol (0.064g) puts in water heating kettle, adds
Hydrazine hydrate 5.0 ml.Water heating kettle is placed at 160 DEG C and reacts 7 days, product uses distilled water and washing with alcohol 2 times respectively, obtains Huang
Color flat crystal, yield is 30%.Edx elementary analysiss show crystal containing only tetra- kinds of elements of ba, ag, sb, s, and each element content ratio
It is about 1:1:1:3.
Claims (3)
1. a kind of quaternary sulfantimoniate compound semiconductor materials is it is characterised in that its chemical constitution formula is respectively as follows:
baagsbs3, baagsbs3·h2O, wherein baagsbs3Crystal structure is:
baagsbs3·h2O crystal structure is:
Described baagsbs3Belong to monoclinic system, c2/c space group, cell parameter α=90 °, β=101.734 °, γ=90 °,Z=8, dc=4.898g/cm3,
Monocrystal is orange red bulk, and energy gap is 2.21ev；
baagsbs3·h2O belongs to rhombic system, pan2 space group, cell parameter α=90 °, β=90 °, γ=90 °,Z=8, dc=4.435g/cm3, monocrystal is
Yellow lamellar, energy gap is 2.43ev.
2. a kind of preparation method of quaternary sulfantimoniate compound semiconductor materials as claimed in claim 1, its feature exists
In by the hydronium(ion) Barium monoxide for 1.0:0.4-1.0:0.2:2.0-3.0 for the mol ratio, argent, binary solid solution antimony trisulfide and list
Matter sulfur mixes, and adds 3-5ml hydrazine hydrate, reacts 7 days, obtain after deionized water and washing with alcohol in 160 DEG C of baking ovens
baagsbs3.
3. a kind of preparation method of quaternary sulfantimoniate compound semiconductor materials as claimed in claim 1, its feature exists
In by the hydronium(ion) Barium monoxide for 1.0-1.5:1.0-1.2:0.25-0.5:2.0-2.5 for the mol ratio, argent, binary solid solution
Antimony trisulfide and elemental sulfur mixing, add 3-5ml hydrazine hydrate, react 7 days, through deionized water and washing with alcohol in 160 DEG C of baking ovens
After obtain baagsbs3·h2o.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510310461.3A CN105036192B (en) | 2015-06-08 | 2015-06-08 | Quaternary sulfo-antimonate compound semiconductor material as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510310461.3A CN105036192B (en) | 2015-06-08 | 2015-06-08 | Quaternary sulfo-antimonate compound semiconductor material as well as preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105036192A CN105036192A (en) | 2015-11-11 |
| CN105036192B true CN105036192B (en) | 2017-01-25 |
Family
ID=54443244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510310461.3A Expired - Fee Related CN105036192B (en) | 2015-06-08 | 2015-06-08 | Quaternary sulfo-antimonate compound semiconductor material as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105036192B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101376492A (en) * | 2007-08-30 | 2009-03-04 | 中国科学院福建物质结构研究所 | Preparation of transient metal chalcogenide compound |
| CN101486449A (en) * | 2008-01-18 | 2009-07-22 | 北京化工大学 | Solid phase synthesis method for quaternary selenide K2CdSnSe4 |
-
2015
- 2015-06-08 CN CN201510310461.3A patent/CN105036192B/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| Zhimin Ma et al..Low temperature synthesis and structures of alkaline earth metal chalcogenides Ba3Cu4SbS6OH，BaCuSbS3 and BaCu2S2.《RSC Advances》.2016,第28937-28940页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105036192A (en) | 2015-11-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109369725A (en) | A kind of unleaded hydridization two dimension double perovskite materials and preparation method | |
| CN105036192B (en) | Quaternary sulfo-antimonate compound semiconductor material as well as preparation method and application thereof | |
| CN101219783A (en) | Method for producing electrode material with ferrophosphorus | |
| CN105680045B (en) | A kind of preparation method of high stability amorphous manganous silicate | |
| CN103288122A (en) | Rhombus zinc oxide nanorod array and preparation method thereof | |
| CN103213956A (en) | Preparation method of CuInSe2 with a chalcopyrite structure and CuIn1-xGazSe2 nano particles | |
| CN103903872A (en) | Method for preparing perovskite phase organic and inorganic mixed crystal materials | |
| CN105645469A (en) | Nano rodlike lanthanum titanate powder and preparation method thereof | |
| CN104477934A (en) | Method for low-temperature synthesis of pollucite | |
| CN106542569A (en) | A kind of preparation method of flower ball-shaped tin ash | |
| CN105481010B (en) | A kind of high yield quaternary sulfide compound semiconductor material and its production and use | |
| CN105696080A (en) | Quaternary chalcogenide semiconductor material, and preparation method and application thereof | |
| CN102689920A (en) | Method for producing copper-tin-zinc-sulfur (CTZS) materials through solvent-thermal synthesis | |
| CN106277050A (en) | A kind of novel light absorbent and preparation method thereof | |
| CN105036148B (en) | Preparation method for flowerlike Li2Si2O5 powder | |
| CN105382254B (en) | A kind of Bi2Te3‑Sb2Te3Nuclear shell structure nano line and preparation method thereof | |
| CN103466688A (en) | Method for preparing ZnS nanosheet | |
| CN106904652B (en) | A kind of pentatomic sulphur antimonial semi-conducting material and its production and use | |
| CN102786038B (en) | Hydro-thermal synthesis method of cubic phase InSe nano sheet | |
| CN101838155B (en) | Method for preparing hexagonal flaky cadmium sulphide membrane in microwave hydrothermal mode | |
| CN103613115A (en) | Method for synthesizing ZnO/ZnSe (zinc oxide/zinc selenide) coaxial nano structure through gas-phase anion exchange | |
| CN105600814B (en) | One kind prepares flower-like structure Cu2The method of O photoelectric materials | |
| CN107779956B (en) | A kind of quaternary thioarsenate compound semiconductor materials and its preparation method and application | |
| CN104860272A (en) | New method for quick preparation of high-purity cadmium telluride powder | |
| CN102517625A (en) | Boric acid strontium lithium micropore crystal and preparation method thereof and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170125 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |