CN102516983A - Copper indium/gallium sulfur quantum dot compounds with luminescent properties, synthesized under ionothermal conditions, and application thereof - Google Patents
Copper indium/gallium sulfur quantum dot compounds with luminescent properties, synthesized under ionothermal conditions, and application thereof Download PDFInfo
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- CN102516983A CN102516983A CN2011103496787A CN201110349678A CN102516983A CN 102516983 A CN102516983 A CN 102516983A CN 2011103496787 A CN2011103496787 A CN 2011103496787A CN 201110349678 A CN201110349678 A CN 201110349678A CN 102516983 A CN102516983 A CN 102516983A
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Abstract
The invention provides copper indium/gallium sulfur quantum dot compounds with luminescent properties, synthesized under ionothermal conditions and application thereof. Under the ionothermal conditions, two copper indium (gallium) sulfur quantum dot compounds are synthesized, and the compounds have the structural characteristics that a series of long-range ordered discrete ultra-tetrahedron T5 cluster quantum dots are stacked by weak hydrogen bond action to form a three-dimensional structure, and the quantum dots are partitioned by positive ions of an ionic liquid. Due to strong absorption and emission in a visible light range, the two compounds are expected to have a potential application value in the aspect of semiconductor photoelectric conversion materials.
Description
Technical field
The present invention relates to one type under the ion heat condition synthetic have the copper indium/gallium sulphur quantum dot compounds of luminescent properties.This is under the ion heat condition, to obtain the metal chalcogenide constructed by ultra tetrahedral cluster first.This compounds is the ultra tetrahedron T5 bunch of quantum dot formation of copper indium (gallium) sulphur by the separation of a series of long-range orders; Ion liquid positively charged ion plays charge balance and separates the effect of these quantum dots; Fluorescence property research shows that this compounds can launch strong fluorescence under the irradiation of UV-light, is expected to be used for the semiconductor optoelectronic converting material.
Background technology
CuIn (Ga) S (Se)
2(CIS/CIGS) solar conversion efficiency of Yin Qigao and receiving much attention
[1]Mainly be to be main at present with inorganic nano material preparation and performance for the research of this compounds
[2]Yet copper indium (gallium) sulphur (selenium) compound of nanotopography often lacks long-range order, is difficult to satisfy the requirement that some requires narrow spectral line, high-intensity photovoltaic applications.Thereby the high nuclear of the class CIS/CIGS quantum dot cluster compound of the crystalline state of synthetic long-range order, and to study its quantum effect be that a very significant job is arranged
[3]Early stage people adopt the solution at room temperature method, and introducing organic sulfur-containing, phosphorus-containing ligand have synthesized some low nuclear type CIS duster compounds
[4]P. people such as Y. Feng has prepared the multidimensional structure compound that is interconnected to form by the ultra tetrahedral cluster of copper indium sulphur T5 under the solvent thermal condition; Its structural unit also is the ultra tetrahedral cluster of the maximum check figure of present report for T5 bunch, and finds that it has luminescent properties preferably
[5]Compare with the superlattice compound, some discrete nanometer sulfides bunch are owing to have quantum confined effect and solubility, are expected to be applied to the semiconductor-quantum-point device and are used to make up the chalkogenide and preparation film of three-dimensional porous structure as presoma
[6-8]With hydro-thermal, solvent thermal is the polymkeric substance that the preparation method of the metal chalcogenide of constructing based on ultra tetrahedral cluster of representative is easy to form multidimensional structure, and the example that forms high nuclear separate structure is limited.Up to recently, P. Y. Feng etc. has reported ultra tetrahedron T4 bunch of maximum separation
[9]We uniquely are incorporated into the synthetic of metal chalcogenide with the ion thermal synthesis; Regulate ion liquid performance through adding a spot of organic amine; Two examples have been prepared by the ultra tetrahedron T5 bunch of class CIS compound of constructing; This also is the ultra tetrahedral cluster of separation of the present maximum of being reported, and has studied its luminescent properties.
Summary of the invention
The present invention relates to the synthetic of one type of copper indium (gallium) sulphur quantum dot compounds and luminescent properties research, promptly under the ion heat condition, prepared two routine copper indium (gallium) sulphur quantum dot compounds, its molecular formula is respectively: [Bmmim]
13[Cu
5In
30S
52(SH)
4] (
1) and [Bmmim]
13[Cu
5Ga
30S
52(SH)
4] (
2) (Bmmim=1-butyl-2,3-methylimidazole), the constructional feature of this compounds is to be piled into three-dimensional structure by the ultra tetrahedral cluster quantum dot of T5 of a series of separations through hydrogen bond action, ionic liquid is separated these quantum dots.Fluorescence property research shows that this compounds can launch strong fluorescence under the irradiation of UV-light, is expected to be used for semiconductor optoelectronic conversion device.
The present invention adopts following technical scheme:
With a certain amount of In
2S
3, CuI, (Bmmim) Cl (1-butyl-2,3-methylimidazole villaumite) ionic liquid and small amount of amine are mixed to join in the 20 mL stainless steel cauldrons that liner is a tetrafluoroethylene, after 160 ° of C react a couple of days, can obtain yellow bulk crystals (compound
1), under similar reaction conditions, with [enH]
2Ga
4S
7(en)
2Substitute In
2S
3, Cu (NO
3) 3H
2O substitutes CuI can obtain compound
2
Compound
1Belong to oblique system, spacer does
C2/c, cell parameter is:
a=23.5771 (6),
b=40.8575 (7),
c=46.2697 (15),
β=94.313 (2) °,
V=44445 (2)
3,
Z=8.Compound
1Most important characteristic is that its structure is to separate discrete [Cu by the ionic liquid positively charged ion
5In
30S
52(SH)
4]
13-Ultra tetrahedron T5 bunch of quantum dot constitutes each [Cu
5In
30S
52(SH)
4]
13-Bunch summit, the unit cornerwise distance of metal be approximately 1.5 nm and T5 bunch of superlattice compound of copper indium sulphur of having reported approaching, obviously greater than some T4 duster compounds, ion liquid positively charged ion plays charge balance and separates the effect of these quantum dots.
Compound
2Belong to hexagonal system, spacer does
P6
3 / m, cell parameter is:
a=22.8807 (4),
c=42.7120 (11),
V=19365.1 (7)
3,
Z=4, compound
2Have with
1Similarly ultra tetrahedron T5 bunch, owing to the minute differences of accumulation mode causes two compounds to belong to different spacers.Compound
2It is the T5 copper gallium sulphur duster compound of the non-surface ligand hydridization of present reported first.
This compounds has strong fluorescent emission in the visible region under the irradiation of UV-light, can be used for the semiconductor optoelectronic converting material.Fluorescence property research is illustrated under the ultraviolet excitation of 370 nm compound
1The class CIS compound of the three-dimensional structure that at 540 nm places of visible region strong fluorescent emission is arranged and reported has similar luminescent properties; Compound
2There is strong yellow emission at 630 nm places in the visible region.This strong absorption and the emission of two compounds in visible-range, especially compound
2Light emitting region from 480-800 nm, cover most of visible-range, and ABSORPTION EDGE decays gradually, the potential using value is being arranged aspect the semiconductor optoelectronic converting material.
Description of drawings
Fig. 1. compound
1With
2Building-up reactions and T5 clustering architecture;
Fig. 2. compound
1(a) and
2(b) three-dimensional packed structures;
Fig. 3. compound
1With
2Fluorescence emission spectrum.
Embodiment
The ultra tetrahedral cluster quantum dot compounds of embodiment 1:T5
1-
2Preparation
[Bmmim]
13[Cu
5In
30S
52(SH)
4] (
1) synthetic
With In
2S
3(0.49 mmol, 0.159 g), CuI (0.16 mmol; 0.031 g), thioacetamide (1.53 mmol, 0.115 g); [Bmmim] Cl (1.435 g, 1-butyl-2,3-methylimidazole villaumite); It is in the 20 mL stainless steel cauldrons of tetrafluoroethylene, in 160 ℃ of isothermal reactions 6 days that pyridine (0.5 mL) and dimethylamine agueous solution (0.2 mL, 33%) are enclosed liner; Naturally be cooled to room temperature then, with N, N '-N washing back is chosen yellow bulk crystals (title product) 5 mg by hand.
[Bmmim]
13[Cu
5Ga
30S
52(SH)
4] synthetic
With [enH]
2Ga
4S
7(en)
2(0.25 mmol, 0.188 g), Cu (NO
3) 3H
2O (0.18 mmol, 0.043 g), thioacetamide (2.48 mmol; 0.186 g), 1,3-two (4-pyridine) propane (1.74 mmol; 0.345 g), [Bmmim] Cl (1.132 g, 1-butyl-2; 3-methylimidazole villaumite) and dimethylamine agueous solution (0.3 mL, 33%) to enclose liner be in the 20 mL stainless steel cauldrons of tetrafluoroethylene, in 160 ℃ of isothermal reactions 6 days; Naturally be cooled to room temperature then, with N, N '-N washing back is chosen light green bulk crystals (title product) 24 mg by hand.
Claims (3)
1. one type of copper indium/gallium sulphur quantum dot compounds with luminescent properties, its molecular formula is [Bmmim]
13[Cu
5X
30S
52(SH)
4], wherein X=In, Ga, Bmmim=1-butyl-2,3-methylimidazole; When X=In, [Bmmim]
13[Cu
5In
30S
52(SH)
4] belonging to oblique system, spacer does
C2/c, cell parameter is:
a=23.5771 (6),
b=40.8575 (7),
c=46.2697 (15),
β=94.313 (2) °,
V=44445 (2)
3,
Z=8; When X=Ga, [Bmmim]
13[Cu
5Ga
30S
52(SH)
4] belonging to hexagonal system, spacer does
P6
3 / m, cell parameter is:
a=22.8807 (4),
c=42.7120 (11),
V=19365.1 (7)
3,
Z=4.
2. the compound method of copper indium according to claim 1/gallium sulphur quantum dot compounds is characterized in that: with a certain amount of In
2S
3, CuI, (Bmmim) Cl ionic liquid and small amount of amine are mixed, and obtain compound [Bmmim] in 160 ° of C isothermal reaction a couple of days
13[Cu
5In
30S
52(SH)
4]; With a certain amount of [enH]
2Ga
4S
7(en)
2, Cu (NO
3) 3H
2O, thioacetamide, 1,3-two (4-pyridine) propane, [Bmmim] Cl and dimethylamine agueous solution mix, and obtain compound [Bmmim] in 160 ℃ of isothermal reaction a couple of days
13[Cu
5Ga
30S
52(SH)
4].
3. the purposes of copper indium according to claim 1/gallium sulphur quantum dot compounds is characterized by: compound has strong fluorescent emission in the visible region under the irradiation of UV-light, can be used for the semiconductor optoelectronic converting material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105099358A (en) * | 2015-07-28 | 2015-11-25 | 南方科技大学 | Solar fluorescent focusing power generation system of quantum dot doped type, and manufacturing method therefor |
| CN106497556A (en) * | 2016-10-21 | 2017-03-15 | 景德镇陶瓷大学 | A kind of ionic liquid assisted microwave synthesis synthesize the preparation method of the polynary quantum dot of I III VI races and its obtained product |
| CN109675595A (en) * | 2017-10-18 | 2019-04-26 | 中国科学院福建物质结构研究所 | A kind of tungsten carbide/porous carbon composite and preparation method thereof and the application in hydrogen is produced in electrochemistry |
| CN110171806A (en) * | 2019-05-08 | 2019-08-27 | 桂林理工大学 | A kind of preparation method of water solubility feux rouges sulphur quantum dot |
-
2011
- 2011-11-08 CN CN2011103496787A patent/CN102516983A/en active Pending
Non-Patent Citations (5)
| Title |
|---|
| PINGYUN FENG等: "The Interface Chemistry between Chalcogenide Clusters and Open Framework Chalcogenides", 《AMERICAN CHEMICAL SOCIETY》 * |
| XIANHUI BU等: "Pushing up the size limit of chalcogenide supertetrahedral clusters: two-and three-dimensional photoluminescent open frameworks from (Cu5In30S54) 13-clusters", 《J. AM. CHEM. SOC》 * |
| 李建荣: "以离子液体为模板的晶态Sn_Se基硫属化物", 《中国化学会第27届学术年会第08分会场摘要集》 * |
| 李春英: "镓_铟硫属化合物溶剂热合成及配位修饰", 《苏州大学 博士学位论文》 * |
| 陈晓霞: "铟硫属化合物及螯合胺配阳离子的结构研究", 《苏州大学 硕士学位论文》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105099358A (en) * | 2015-07-28 | 2015-11-25 | 南方科技大学 | Solar fluorescent focusing power generation system of quantum dot doped type, and manufacturing method therefor |
| CN105099358B (en) * | 2015-07-28 | 2018-06-05 | 深圳扑浪创新科技有限公司 | A kind of manufacturing method of quantum dot-doped type solar energy fluorescence concentrating generating system |
| CN106497556A (en) * | 2016-10-21 | 2017-03-15 | 景德镇陶瓷大学 | A kind of ionic liquid assisted microwave synthesis synthesize the preparation method of the polynary quantum dot of I III VI races and its obtained product |
| CN106497556B (en) * | 2016-10-21 | 2018-08-03 | 景德镇陶瓷大学 | A kind of preparation method of the polynary quantum dot of ionic liquid assisted microwave synthesis synthesis I-III-VI races and its product obtained |
| CN109675595A (en) * | 2017-10-18 | 2019-04-26 | 中国科学院福建物质结构研究所 | A kind of tungsten carbide/porous carbon composite and preparation method thereof and the application in hydrogen is produced in electrochemistry |
| CN109675595B (en) * | 2017-10-18 | 2020-05-05 | 中国科学院福建物质结构研究所 | Tungsten carbide/porous carbon composite material, preparation method thereof and application thereof in electrochemical hydrogen production |
| CN110171806A (en) * | 2019-05-08 | 2019-08-27 | 桂林理工大学 | A kind of preparation method of water solubility feux rouges sulphur quantum dot |
| CN110171806B (en) * | 2019-05-08 | 2022-04-22 | 桂林理工大学 | Preparation method of water-soluble red light sulfur quantum dots |
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Application publication date: 20120627 |