CN102942164B - Copper-zinc-tin-selenium-sulfur allotropic nanoparticle and preparation method and application thereof - Google Patents
Copper-zinc-tin-selenium-sulfur allotropic nanoparticle and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a copper-zinc-tin-selenium-sulfur allotropic nanoparticle and a preparation method and an application thereof. The prepared nanoparticle is provided with a wurtzite nucleus and two sphalerite ends, wherein the nucleus and the ends are arranged in a linear way; the nanoparticle is in a shape of a rugby football, a cylinder or a shuttle; and the average particle diameter is 10 to 80 nm. The copper-zinc-tin-selenium-sulfur allotropic nanoparticle prepared by using the preparation method has novel structural features and can be applied to solar cell absorption layers, photoconductivity switches and thermoelectric conversion materials.
Description
Technical field
The present invention relates to field of nanometer material technology, particularly a kind of copper-zinc-tin-selenium sulphur allotropy nanoparticle, and its preparation method and application.
Background technology
If there is the nanostructure of two or more chemical composition to form a nano heterogeneous particle by particular crystal plane symbiosis, the nanostructure of so this particle is exactly the standard nano-heterogeneous structure being well known.In this particle, have two kinds can or the two or more different chemical substances of electronic band structure, kind and content by two kinds of materials of suitable regulation and control can regulate and control the electronic band structure of nano heterogeneous particle, make nano-heterogeneous structure in the arrangement of energy gap and valence band conduction band, obtain new regulation and control chance.In view of this,, at material science, synthetic and research standard nano-heterogeneous structure has become in recent years a study hotspot and has arrived development fast.
The not jljl of same substance also has different electronic band structures mutually, if obtain two kinds of thing phases so can be in a nanostructure controlled, also just can be by regulating two-phase proportion to realize the regulation and control of electronic band structure, but because the thing of material is determined jointly by Material Thermodynamics and growth kinetics mutually, so it is more much more difficult than synthetic standards nano heterojunction controllably in a nanostructure, to design two kinds of thing phases of introducing (homoatomic multiform nanoparticle is synthesized in namely design).
Up to the present, controllably synthetic allotropy nanoparticle only had report in II-VI family dendritic " polypody " nanoparticle.Dendritic " polypody " II-VI nanoparticle has the core of a zincblende lattce structure and the branch of multiple wurtzites, wherein (001) face coherence epitaxy of wurtzite is on (111) of zink sulphide core face, because zink sulphide has eight (111) equivalent crystal planes, so dendritic " polypody " nanoparticle can have maximum eight " foots ".But the synthetic and property research of right and wrong " polypody " allotropy nanoparticle is not also seen in report at present.
Summary of the invention
The object of the present invention is to provide a kind of copper-zinc-tin-selenium sulphur allotropy nanoparticle.
Another object of the present invention is to provide a kind of preparation method of copper-zinc-tin-selenium sulphur allotropy nanoparticle.
The present invention also has an object to be to provide the application of above-mentioned copper-zinc-tin-selenium sulphur allotropy nanoparticle in solar battery obsorbing layer, photoconductivity switching and thermoelectricity conversion.
To achieve these goals, the present invention proposes a kind of copper-zinc-tin-selenium sulphur allotropy nanoparticle, it has the core of a wurtzite and the end points of two zink sulphide, and described core and described end points are arranged with linear mode.
Preferably, described copper-zinc-tin-selenium sulphur allotropy nanoparticle has the pattern of rugby shape or cylindrical or fusiformis, and the median size of nanoparticle is 10～80nm.
The invention allows for a kind of method of preparing above-mentioned copper-zinc-tin-selenium sulphur allotropy nanoparticle, it comprises the steps:
(1) copper zinc-tin metal-salt added to the mixed solution post-heating of alkyl sulfhydryl and organic solvent and be incubated, obtaining solution A;
(2) two organic radical selenides are added to organic solvent post-heating insulation, obtain solution B;
(3) described solution A and described solution B are mixed and be heated to 200～320 DEG C after insulation, thereby make copper-zinc-tin-selenium sulphur allotropy nanoparticle.
Preferably, in step (1), mantoquita is cupprous salt, the salt that zinc salt is divalent zinc, and pink salt is stannous salt, and Cu
+, Zn
2+, Sn
2+amount of substance be 2.5～3.1:1.25～1.55:1.25～1.55:2～10, wherein Cu with the ratio of the volume of alkyl sulfhydryl
+, Zn
2+, Sn
2+the unit of amount of substance be mole that the unit of the volume of alkyl sulfhydryl is for rising.
Preferably, described in step (1), the temperature of heating is 50～150 DEG C, and the time of described insulation is 1min～1h.
Preferably, described in step (1), the molecular formula of alkyl sulfhydryl is C
nh
2n+1sH, described organic solvent is oleyl amine or octadecylene or tributylphosphine or triphenylphosphine, wherein 11<n<17.
Preferably, described in step (2), described in two organic radical selenides and step (1), the amount of substance ratio of mantoquita is 10～12.4:2.5～3.1.
Preferably, described in step (2), the temperature of heating is 50～150 DEG C, and the time of described insulation is 1min～1h, and described organic solvent is oleyl amine or octadecylene or tributylphosphine or triphenylphosphine.
More preferably, described in step (3), the time of insulation is 5min～2h, and the temperature rise rate of described heating is 5～15 DEG C/min.
The present invention also provides the application in solar battery obsorbing layer, photoconductivity switching and thermoelectricity conversion of above-mentioned copper-zinc-tin-selenium sulphur allotropy nanoparticle.
The core of the synthetic copper-zinc-tin-selenium sulphur allotropy nanoparticle of method that the present invention adopts is wurtzite, two ends are zink sulphide, with traditional allotropy nanoparticle core be zink sulphide, epitaxy wurtzite is compared, there is brand-new constructional feature, not only can be used as a brand-new structural models for theoretical investigation, also can be used as " nanoparticle inks " and pass through scraper for coating, rotary coating or other thin film-forming methods are made solar battery obsorbing layer, to obtain better photic electron hole separating effect, can also be used as main light absorbing material and be applied to photoconductivity switching, or after compressed one-tenth piece for thermoelectricity transition material.
Brief description of the drawings
Fig. 1 a is the transmission electron micrograph of the copper-zinc-tin-selenium sulphur allotropy nanoparticle prepared of the embodiment of the present invention 1.
Fig. 1 b is the high resolution transmission electron microscopy picture of the copper-zinc-tin-selenium sulphur allotropy nanoparticle prepared of the embodiment of the present invention 1.
Fig. 2 a is the transmission electron micrograph of the copper-zinc-tin-selenium sulphur allotropy nanoparticle prepared of the embodiment of the present invention 2.
Fig. 2 b is the high resolution transmission electron microscopy picture of the copper-zinc-tin-selenium sulphur allotropy nanoparticle prepared of the embodiment of the present invention 2.
Fig. 3 is the transmission electron micrograph of the copper-zinc-tin-selenium sulphur allotropy nanoparticle prepared of the embodiment of the present invention 3.
Fig. 4 a is the transmission electron micrograph of the copper-zinc-tin-selenium sulphur allotropy nanoparticle prepared of the embodiment of the present invention 4.
Fig. 4 b is the high resolution transmission electron microscopy picture of the copper-zinc-tin-selenium sulphur allotropy nanoparticle prepared of the embodiment of the present invention 4.
Fig. 5 a is the transmission electron micrograph of the copper-zinc-tin-selenium sulphur allotropy nanoparticle prepared of the embodiment of the present invention 5.
Fig. 5 b is the high resolution transmission electron microscopy picture of the copper-zinc-tin-selenium sulphur allotropy nanoparticle prepared of the embodiment of the present invention 5.
Fig. 6 is the X ray diffracting spectrum of the copper-zinc-tin-selenium sulphur allotropy nanoparticle prepared of the embodiment of the present invention 3.
Fig. 7 is the X ray diffracting spectrum of the copper-zinc-tin-selenium sulphur allotropy nanoparticle of inventive embodiments 1,2,4,5 preparations.
Embodiment
For the above-mentioned purpose, the feature and advantage that make invention can become apparent more, below the specific embodiment of the present invention is described in detail.
A lot of details are set forth in the following description so that fully understand the present invention, but the present invention can also adopt other to be different from alternate manner described here and implement, those skilled in the art can do similar popularization without prejudice to intension of the present invention in the situation that, and therefore the present invention is not subject to the restriction of following public specific embodiment.
Prepare in the method for copper-zinc-tin-selenium sulphur allotropy nanoparticle in the present invention, first two kinds of required solution of preparation reaction, it comprises:
The first step: copper zinc-tin metal-salt is added to mixed solution post-heating the insulation of alkyl sulfhydryl and organic solvent, obtain solution A.
Heating is mainly for copper zinc-tin metal-salt is fully dissolved, and preferably the temperature of heating is 50～150 DEG C, and the time of insulation is 1min～1h.Copper zinc-tin metal-salt is for copper source, He Xi source, zinc source are provided, it can have multiple choices, preferential selection mantoquita is cupprous salt, for example, in cuprous chloride or cuprous bromide or cuprous iodide one or more, select the salt that zinc salt is divalent zinc, for example, in zinc acetylacetonate or zinc chloride or zinc acetate one or more, selecting pink salt is stannous salt, for example, in tindichloride or dibromo acetopyruvic acid tin one or more, and can select Cu
+, Zn
2+, Sn
2+amount of substance be 2.5～3.1:1.25～1.55:1.25～1.55:2～10, wherein Cu with the ratio of the volume of alkyl sulfhydryl
+, Zn
2+, Sn
2+the unit of amount of substance be mole that the unit of the volume of alkyl sulfhydryl is for rising.For the more sulphur source of high-quality is provided, the preferably molecular formula of alkyl sulfhydryl is C
nh
2n+1sH(11<n<17) alkyl sulfhydryl, such as 1-Dodecyl Mercaptan or tetradecanylthioalcohol or 15 mercaptan etc.Organic solvent, for dissolved copper zinc-tin metal-salt, is preferably oleyl amine or octadecylene or tributylphosphine or triphenylphosphine.The add-on of organic solvent does not need strict restriction, from angle expediently, the amount of substance of mantoquita may be selected to be 2.4～3:10～600 with the ratio of the volume of organic solvent, and wherein the unit of the amount of substance of mantoquita is mole, and the unit of the volume of organic solvent is for rising.
Second step: two organic radical selenides are added to organic solvent post-heating insulation, obtain solution B.
Heating is mainly for two organic radical selenides are fully dissolved, and preferably the temperature of heating is 50～150 DEG C, and the time of insulation is 1min～1h.Adding of two organic radical selenides is for selenium source is provided, it refers to the selenide with two organic groups, such as phenylbenzene selenide or dibutyl selenide etc., two organic groups can be the same or different, and organic group comprises alkyl, hydroxyl, phenyl, carboxyl etc.Organic solvent in this step is used for dissolving two organic radical selenides, is preferably oleyl amine or octadecylene or tributylphosphine or triphenylphosphine, can be identical or different with organic solvent used in the first step.The add-on of organic solvent does not need strict restriction, and from angle expediently, the amount of substance of two organic radical selenides and the volume ratio of organic solvent may be selected to be 1～3:1.8～27.Preferably, the amount of substance ratio of the mantoquita in two organic radical selenides and the first step is 10～12.4:2.5～3.1.
Obtaining, after solution A and solution B, carrying out next step reaction:
The 3rd step: solution A and solution B are mixed and be heated to 200～320 DEG C after insulation, thereby make copper-zinc-tin-selenium sulphur allotropy nanoparticle.In order to make reaction more abundant, preferably the temperature rise rate of heating is 5～15 DEG C/min, and soaking time is 5min～2h.
The Anke TGL-10B whizzer that adopts in an embodiment Anting Scientific Instrument Factory, Shanghai to produce carries out centrifugal; The 104A/PL912 heating jacket that adopts U.S. Glas-col to produce heats; The JEOL-F2010 transmission electron microscope that adopts Japan to produce is observed the pattern of copper-zinc-tin-selenium sulphur allotropy nanoparticle; Philips X ' the Pert PRO SUPER x-ray diffractometer that adopts Dutch Philip to produce is analyzed mutually to the thing of copper-zinc-tin-selenium sulphur allotropy nanoparticle.
Embodiment 1
(1) in three mouthfuls of beakers that are 25mL at volume, add 10mL oleyl amine and 600 μ L tetradecanylthioalcohols, add again 0.25mmol cuprous chloride, 0.128mmol zinc chloride, 0.14mmol tindichloride, and be incubated 10min after three mouthfuls of beakers are heated to 140 DEG C, obtain faint yellow transparent solution A.
(2) 1.12mmol dibutyl selenide and 5mL octadecylene are added in three mouthfuls of beakers of another 25mL, and three mouthfuls of beakers are heated to be incubated 5min after 70 ° of C, obtain the solution B of yellow transparent.
(3) solution A and solution B are mixed, and be incubated 10min after solution being heated to 240 DEG C with the temperature rise rate of 8 DEG C/min, thereby make copper-zinc-tin-selenium sulphur allotropy nanoparticle.After question response finishes, be cooled to room temperature, replace eccentric cleaning copper-zinc-tin-selenium sulphur allotropy nanoparticle with normal hexane and ethanol.
The characteristic of the final product obtaining by this method is as follows:
Refer to Fig. 1, as shown in the figure, the size of the copper-zinc-tin-selenium sulphur allotropy nanoparticle making is comparatively even, and most of particle is rugby shape pattern, the cylindrical and fusiformis pattern of small portion, and particle diameter is 10-28nm.Described nanoparticle is carried out to high-resolution-ration transmission electric-lens and observe discovery, the two ends of nanoparticle are zincblende lattce structure, and centre is wurtzite structure.
Refer to (a) in Fig. 7, as shown in the figure, the nanoparticle making is wurtzite and zink sulphide coexisting phase, and crystal property is good.
Embodiment 2
(1) in three mouthfuls of beakers that are 25mL at volume, add 15mL oleyl amine and 800 μ L 15 mercaptan, add again 0.29mmol cuprous chloride, 0.13mmol zinc acetate, 0.15mmol dibromo acetopyruvic acid tin, and be incubated 5min after three mouthfuls of beakers are heated to 100 DEG C, obtain faint yellow transparent solution A.
(2) 1.13mmol phenylbenzene selenide and 10mL oleyl amine are added in three mouthfuls of beakers of another 25mL, and three mouthfuls of beakers are heated to be incubated approximately one minute after 70 ° of C, obtain the solution B of yellow transparent.
(3) mixed liquor A and mixed liquid B are mixed, and be incubated 30min after solution being heated to 260 DEG C with the temperature rise rate of 12 DEG C/min, thereby make copper-zinc-tin-selenium sulphur allotropy nanoparticle.After question response finishes, be cooled to room temperature, and replace eccentric cleaning copper-zinc-tin-selenium sulphur allotropy nanoparticle with normal hexane and ethanol.
The characteristic of the final product obtaining by this method is as follows:
Refer to Fig. 2, as shown in the figure, the size of the copper-zinc-tin-selenium sulphur allotropy nanoparticle making is comparatively even, and most of particle is rugby shape pattern, the cylindrical and fusiformis pattern of small portion, and particle diameter is 10-30nm.Described nanoparticle is carried out to high-resolution-ration transmission electric-lens and observe discovery, the two ends of nanoparticle are zincblende lattce structure, and centre is wurtzite structure.
Refer to (b) in Fig. 7, as shown in the figure, the nanoparticle making is wurtzite and zink sulphide coexisting phase, and crystal property is good.
Embodiment 3
(1) in three mouthfuls of beakers that are 25mL at volume, add 10mL oleyl amine and 600 μ L 1-Dodecyl Mercaptans, add again 0.28mmol cuprous iodide, 0.14mmol zinc acetate, 0.14mmol tindichloride, and be incubated 2min after three mouthfuls of beakers are heated to 140 DEG C, obtain faint yellow transparent solution A.
(2) 1.12mmol phenylbenzene selenide and 5mL oleyl amine are added in three mouthfuls of beakers of another 25mL, and three mouthfuls of beakers are heated to be incubated 1min after 70 ° of C, obtain the mixed liquid B of yellow transparent.
(3) mixed liquor A and mixed liquid B are mixed, and be incubated 30min after solution being heated to 280 DEG C with the temperature rise rate of 10 DEG C/min, thereby make copper-zinc-tin-selenium sulphur allotropy nanoparticle.After question response finishes, be cooled to room temperature, and replace eccentric cleaning copper-zinc-tin-selenium sulphur allotropy nanoparticle with normal hexane and ethanol.
The characteristic of the final product obtaining by this method is as follows:
Refer to Fig. 3, as shown in the figure, the size of the copper-zinc-tin-selenium sulphur allotropy nanoparticle making is comparatively even, and most of particle is rugby shape pattern, the cylindrical and fusiformis pattern of small portion, and particle size range is 11-32nm.Described nanoparticle is carried out to high-resolution-ration transmission electric-lens and observe discovery, the two ends of nanoparticle are zincblende lattce structure, and centre is wurtzite structure.
Refer to Fig. 3, as shown in the figure, the nanoparticle making is wurtzite and zink sulphide coexisting phase, and crystal property is good.
Embodiment 4
(1) in three mouthfuls of beakers that are 25mL at volume, add 10mL tributylphosphine and 500 μ L 1-Dodecyl Mercaptans, add again 0.3mmol cuprous bromide, 0.15mmol zinc chloride, 0.127mmol dibromo acetopyruvic acid tin, and be incubated 40min after three mouthfuls of beakers are heated to 130 DEG C, obtain faint yellow transparent solution A.
(2) 1.2mmol phenylbenzene selenide and 8mL oleyl amine are added in three mouthfuls of beakers of another 25mL, and three mouthfuls of beakers are heated to be incubated 1h after 140 ° of C, obtain the solution B of yellow transparent.
(3) mixed liquor A and mixed liquid B are mixed, and be incubated 1h after solution being heated to 300 DEG C with the temperature rise rate of 5 DEG C/min, thereby make copper-zinc-tin-selenium sulphur allotropy nanoparticle.After question response finishes, be cooled to room temperature, and replace eccentric cleaning copper-zinc-tin-selenium sulphur allotropy nanoparticle with normal hexane and ethanol.
The characteristic of the final product obtaining by this method is as follows:
Refer to Fig. 4, as shown in the figure, the size of the copper-zinc-tin-selenium sulphur allotropy nanoparticle making is comparatively even, and most of particle is rugby shape pattern, the cylindrical and fusiformis pattern of small portion, particle diameter 13-34nm.Described nanoparticle is carried out to high-resolution-ration transmission electric-lens and observe discovery, the two ends of nanoparticle are zincblende lattce structure, and centre is wurtzite structure.
Refer to (c) in Fig. 7, as shown in the figure, the nanoparticle making is wurtzite and zink sulphide coexisting phase, and crystal property is good.
Embodiment 5
(1) in three mouthfuls of beakers that are 25mL at volume, add 10mL octadecylene and 500 μ 15 mercaptan, add again 0.27mmol cuprous chloride, 0.15mmol zinc acetylacetonate, 0.129mmol dibromo acetopyruvic acid tin, and be incubated 30min after three mouthfuls of beakers are heated to 60 DEG C, obtain faint yellow transparent solution A.
(2) 1.12mmol dibutyl selenide and 5mL oleyl amine are added in three mouthfuls of beakers of another 25mL, and be incubated 10min after three mouthfuls of beakers are heated to 90 DEG C, obtain the mixed liquid B of yellow transparent.
(3) mixed liquor A and mixed liquid B are mixed, and be incubated 1.5h after solution being heated to 320 DEG C with the temperature rise rate of 8 DEG C/min, thereby make copper-zinc-tin-selenium sulphur allotropy nanoparticle.After question response finishes, be cooled to room temperature, and replace eccentric cleaning copper-zinc-tin-selenium sulphur allotropy nanoparticle with normal hexane and ethanol.
The characteristic of the final product obtaining by this method is as follows:
Refer to Fig. 5, as shown in the figure, the size of the copper-zinc-tin-selenium sulphur allotropy nanoparticle making is comparatively even, and most of particle is rugby shape pattern, the cylindrical and fusiformis pattern of small portion, and particle size range is 15-35nm.Described nanoparticle is carried out to high-resolution-ration transmission electric-lens and observe discovery, the two ends of nanoparticle are zincblende lattce structure, and centre is wurtzite structure.
Refer to (d) in Fig. 7, as shown in the figure, the nanoparticle making is wurtzite and zink sulphide coexisting phase, and crystal property is good.
Although the present invention is described in conjunction with above embodiment, but the present invention is not defined to above-described embodiment, and being only subject to the restriction of claims, those of ordinary skill in the art can easily modify to it and change, but do not leave essence design of the present invention and scope.
Claims (10)
1. a copper-zinc-tin-selenium sulphur allotropy nanoparticle, is characterized in that, has the core of a wurtzite and the end points of two zink sulphide, and described core and described end points are arranged with linear mode.
2. nanoparticle as claimed in claim 1, is characterized in that, described copper-zinc-tin-selenium sulphur allotropy nanoparticle has the pattern of rugby shape or cylindrical or fusiformis, and the median size of nanoparticle is 10～80nm.
3. a method of preparing the copper-zinc-tin-selenium sulphur allotropy nanoparticle described in claim 1 or 2, is characterized in that, comprises the steps:
(1) copper zinc-tin metal-salt added to the mixed solution post-heating of alkyl sulfhydryl and organic solvent and be incubated, obtaining solution A;
(2) two organic radical selenides are added to organic solvent post-heating insulation, obtain solution B;
(3) described solution A and described solution B are mixed and be heated to 200～320 DEG C after insulation, thereby make copper-zinc-tin-selenium sulphur allotropy nanoparticle.
4. method as claimed in claim 3, is characterized in that, the mantoquita in step (1) is cupprous salt, the salt that zinc salt is divalent zinc, and pink salt is stannous salt, and Cu
+, Zn
2+, Sn
2+amount of substance be 2.5～3.1:1.25～1.55:1.25～1.55:2～10, wherein Cu with the ratio of the volume of alkyl sulfhydryl
+, Zn
2+, Sn
2+the unit of amount of substance be mole that the unit of the volume of alkyl sulfhydryl is for rising.
5. method as claimed in claim 3, is characterized in that, described in step (1), the temperature of heating is 50～150 DEG C, and the time of described insulation is 1min～1h.
6. method as claimed in claim 3, is characterized in that, described in step (1), the molecular formula of alkyl sulfhydryl is C
nh
2n+1sH, described organic solvent is oleyl amine or octadecylene or tributylphosphine or triphenylphosphine, wherein 11<n<17.
7. method as claimed in claim 3, is characterized in that, described in step (2), described in two organic radical selenides and step (1), the amount of substance ratio of mantoquita is 10～12.4:2.5～3.1.
8. method as claimed in claim 3, is characterized in that, described in step (2), the temperature of heating is 50～150 DEG C, and the time of described insulation is 1min～1h, and described organic solvent is oleyl amine or octadecylene or tributylphosphine or triphenylphosphine.
9. the method as described in any one in claim 3 to 8, is characterized in that, described in step (3), the time of insulation is 5min～2h, and the temperature rise rate of described heating is 5～15 DEG C/min.
10. the application of the copper-zinc-tin-selenium sulphur allotropy nanoparticle described in any one in solar battery obsorbing layer, photoconductivity switching and thermoelectricity transition material in claim 1 to 2.
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| CN1271170A (en) * | 1999-04-19 | 2000-10-25 | 三菱电机株式会社 | Switch for converter of tapping on load |
| CN101830444A (en) * | 2010-05-28 | 2010-09-15 | 上海交通大学 | Method for preparing copper zinc tin sulfur selenium nano particles |
| CN102712495A (en) * | 2009-11-25 | 2012-10-03 | 纳幕尔杜邦公司 | Syntheses of quaternary chalcogenides in cesium, rubidium, barium and lanthanum containing fluxes |
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| US20120097234A1 (en) * | 2010-10-26 | 2012-04-26 | International Business Machines Corporation | Using Diffusion Barrier Layer for CuZnSn(S,Se) Thin Film Solar Cell |
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| CN1271170A (en) * | 1999-04-19 | 2000-10-25 | 三菱电机株式会社 | Switch for converter of tapping on load |
| CN102712495A (en) * | 2009-11-25 | 2012-10-03 | 纳幕尔杜邦公司 | Syntheses of quaternary chalcogenides in cesium, rubidium, barium and lanthanum containing fluxes |
| CN101830444A (en) * | 2010-05-28 | 2010-09-15 | 上海交通大学 | Method for preparing copper zinc tin sulfur selenium nano particles |
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