CN102504816A - Method for preparing nano luminescent material ZnO/SnO2 heterostructure - Google Patents
Method for preparing nano luminescent material ZnO/SnO2 heterostructure Download PDFInfo
- Publication number
- CN102504816A CN102504816A CN2011103498123A CN201110349812A CN102504816A CN 102504816 A CN102504816 A CN 102504816A CN 2011103498123 A CN2011103498123 A CN 2011103498123A CN 201110349812 A CN201110349812 A CN 201110349812A CN 102504816 A CN102504816 A CN 102504816A
- Authority
- CN
- China
- Prior art keywords
- stove
- place
- powder
- preparation
- zno
- 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.)
- Granted
Links
Images
Landscapes
- Luminescent Compositions (AREA)
Abstract
The invention discloses a method for preparing a nano material, in particular to a method for preparing an inorganic zinc oxide/tin oxide heterostructure material. According to a chemical vapor deposition method adopted by the invention, Sn powder and Zn powder, which serve as source materials, are placed in the front end of an alumina ship, a gold plated silicon substrate is placed at a certain distance from the source materials, the alumina ship is vacuumized and heated to a high temperature, then oxygen is introduced, the temperature is kept and the white product, namely ZnO/SnO2 heterostructure nanowire luminescent material, is formed on the substrate after cooling. The method provided by the invention has the advantages that: the process can be well controlled; the operation is easy; the cost is low; and the prepared product is very pure. The material prepared by the method can be widely used in the semiconductor industry.
Description
Technical field
The present invention relates to a kind of preparation of nanomaterials, specifically be meant a kind of preparation method of inorganic materials zinc oxide/stancic oxide heterogeneous structure material.
Technical background
ZnO is a kind of broad stopband metal oxide semiconductor material, and its energy gap is 3.37eV, and exciton bind energy is 60meV, aspect photovoltaic applications, great potential is arranged.The photodiode, photocatalyst, transmitter and the solar cell that with zinc oxide are base are successfully in prepared in laboratory even be applied in the industrial production.The method for preparing at present the ZnO nano material mainly contains template, chemical Vapor deposition process, liquid phase method, solid phase method etc.Chemical Vapor deposition process is to utilize gaseous substance to carry out chemical reaction at solid surface, generates the process of solid-state deposit.Chemical gas-phase method has that device is simple, and raw materials used cost is low, realizes meliority such as large-scale industrial production easily.The most tempting characteristic of ZnO is the exciton bind energy that has up to 60meV; So high bound energy makes it at room temperature be difficult for by thermal excitation (molecular thermalmotion under the room temperature can be 26meV); Thereby improved the excitation-emission mechanism of ZnO material greatly, reduced the sharp threshold values of penetrating under the room temperature.Because the existence of zinc oxide native defect, compound luminous with band-to-band transition except exciton, it is luminous to obtain several kinds of intraband transitions.
Along with people's is goed deep into ZnO research, has had been found that multiple different luminous mechanism, has obtained a plurality of glow peaks under different wave length.This provides good selection to the multiple application of satisfying under the different situations.People are just making great efforts the luminescence phenomenon of different-energy position in the ZnO material is studied fully; Hope to choose technology of preparing as required, control preparation condition, strengthen the glow peak of required energy position; Suppress other glow peaks, thereby strengthen the using value of ZnO luminescent material aspect greatly.In recent years, also be tending towards ripe in the research aspect the heterogeneous structural nano material.
But, utilize chemical Vapor deposition process to prepare ZnO/SnO
2The heterogeneous structural nano line luminous material is not also reported.
Summary of the invention
The present invention is directed to deficiency of the prior art, proposed a kind of convenience, effective preparation method.
The present invention is achieved through following technical proposals:
A kind of ZnO/SnO
2The preparation method of heterogeneous structural nano luminescent material is characterized in that comprising the steps:
(1) is source material with Sn powder and Zn powder, mixes and place aluminium oxide boat that place gold-plated silicon substrate from source material 1.5～4cm place, place stove to aluminium oxide boat then, and stove is sealed, wherein the mol ratio of Sn powder and Zn powder is 1: 1; Sealing wherein generally is to adopt refractory brick to carry out shutoff;
(2) to vacuumizing in the stove, reach-0.08MPa, close vacuum extractor, feed the rare gas element argon gas, when furnace pressure reaches a normal atmosphere, open vacuum extractor, once more the stove internal gas pressure is evacuated to-0.08MPa up to the stove internal gas pressure; The purpose that vacuumizes among the present invention is that the air in the stove is replaced, and carries out thoroughly quite if do not reach above-mentioned vacuum tightness, carrying out repeatedly so in stove, will vacuumize as far as possible, also can realize thorough metathetical purpose;
The repetitive operation 4 times at least of above-mentioned vacuum;
(3) completing steps (2), exhaust vacuum after, stove is heated, until being warming up to 950～1050 ℃, feed 50sccm oxygen, be incubated 50～70 minutes;
(4) then stove is cooled to room temperature naturally, take out substrate, the gained white product is ZnO/SnO on the substrate
2The heterogeneous structural nano line luminous material.
As preferably, the stove described in above-mentioned preparing method's the step (1) is a tube furnace.
As preferably, leave source material 2cm place in above-mentioned preparing method's the step (1) and place gold-plated silicon substrate.
As preferably, argon flow amount is 50sccm in above-mentioned preparing method's the step (2).
As preferably, temperature of reaction is 950～980 ℃ in above-mentioned preparing method's the step (3).
Said process of the present invention is to adopt chemical Vapor deposition process; Use electronic balance to take by weighing a certain amount of Sn powder and the Zn powder places the aluminium oxide boat front end as source material; Placing gold-plated silicon substrate from source material a distance; Place the tube furnace middle part to aluminium oxide boat then, the pipe two ends respectively add a refractory brick, capping.Start mechanical pump, intraductal atmospheric pressure is reached-0.08MPa, close valve, feed an amount of argon gas, when the pipe internal pressure reaches a normal atmosphere, drive valve and be communicated with atmosphere, start mechanical pump once more and repeat the oxygen in four eliminating tube furnace furnace chambers of above operation.Start stove, be warming up to 950～1050 ℃, feed 50sccm oxygen, be incubated 50～70 minutes.Stove cools to room temperature naturally, closes gas, takes out substrate, and the gained white product is ZnO/SnO on the substrate
2The heterogeneous structural nano line luminous material.
Beneficial effect: the present invention prepares in the process, and agents useful for same is commerical prod, need not loaded down with trivial details preparation; Process controllability is strong, and is easy to operate, and cost is low, and the product purity that makes is high.
Description of drawings
Fig. 1 is the inventive method chemical vapour deposition reaction device synoptic diagram;
Fig. 2 is with 950 ℃ of ZnO/SnO that make of the present invention
2The ESEM of heterogeneous structural nano luminescent material (SEM) photo;
Fig. 3 is with 950 ℃ of ZnO/SnO that make of the present invention
2The X-ray diffraction of heterogeneous structural nano luminescent material (XRD) spectrogram;
Fig. 4 is with 950 ℃ of ZnO/SnO that make of the present invention
2The photoelectron spectrum of heterogeneous structural nano luminescent material (EDS) figure;
Fig. 5 is with 950 ℃ of ZnO/SnO that make of the present invention
2The luminescent spectrum of heterogeneous structural nano luminescent material (PL) figure;
Embodiment
Further specify the present invention below in conjunction with instance.
Embodiment 1
Be to take by weighing a certain amount of Sn powder at 1: 1 and the Zn powder is that source material places the aluminium oxide boat front end in molar ratio, place gold-plated silicon substrate from source material 2cm place, place the tube furnace middle part to aluminium oxide boat then, the pipe two ends respectively add a refractory brick, capping (like Fig. 1).Start mechanical pump, intraductal atmospheric pressure is reached-0.08MPa, close valve, feed an amount of argon gas, when the pipe internal pressure reaches a normal atmosphere, drive valve and be communicated with atmosphere, start mechanical pump once more and repeat the air in four eliminating tube furnace furnace chambers of above operation.Start stove, be warming up to 950 ℃, feed 50sccm (volumetric flow rate unit, meaning are mark condition milliliter PM) oxygen, be incubated 50 minutes.Stove cools to room temperature naturally, closes gas, takes out substrate, on substrate, has obtained one deck white product.Products therefrom is directly observed (like Fig. 2) under ESEM, can find a large amount of diameters in 50 to 100 nanometers, the nano wire of length about 10 microns generates.The XRD analysis of Fig. 3 shows that the structure of product is by hexagonal system ZnO and tetragonal system SnO
2Form, formed heterojunction structure, remaining diffraction peak is substrate and gold-plated composition.The EDS stave of Fig. 4 is understood ZnO/SnO
2Contain Zn, Sn and O element in the heterojunction structure, further proved product be ZnO/SnO
2Heterojunction structure, wherein the peak of Si is a substrate.Fig. 5 is the PL figure of product, and wherein the 379nm place is luminous corresponding to the band edge of ZnO than small peak, and this excites and results from the compound of free exciton, and this conclusion is corresponding with XRD analysis preferably.The broad peak at 505nm place is because SnO
2Intervention cause the red shift of defect luminescence peak.Therefore, exist relative stronger green luminescence peak to show among Fig. 5 and have a large amount of defectives relevant in this heterojunction structure, improved the luminescent properties of single oxide with the oxygen room.
Embodiment 2
As embodiment 1; Use electronic balance to take by weighing a certain amount of Sn powder and the Zn powder places the aluminium oxide boat front end as source material,, place the tube furnace middle part to aluminium oxide boat then place gold-plated silicon substrate from source material 2cm place; The pipe two ends respectively add a refractory brick, capping (like Fig. 1).Start mechanical pump, intraductal atmospheric pressure is reached-0.08MPa, close valve, feed an amount of argon gas, when the pipe internal pressure reaches a normal atmosphere, drive valve and be communicated with atmosphere, start mechanical pump once more and repeat the air in four eliminating tube furnace furnace chambers of above operation.Start stove, be warming up to 950 ℃, feed 50sccm oxygen, be incubated 70 minutes.Stove cools to room temperature naturally, closes gas, takes out substrate, on substrate, has obtained one deck white product.The pattern of product, structure, elementary composition and luminescent properties is all identical with embodiment 1.
Embodiment 3
As embodiment 1; Use electronic balance to take by weighing a certain amount of Sn powder and the Zn powder places the aluminium oxide boat front end as source material,, place the tube furnace middle part to aluminium oxide boat then place gold-plated silicon substrate from source material 2cm place; The pipe two ends respectively add a refractory brick, capping (like Fig. 1).Start mechanical pump, intraductal atmospheric pressure is reached-0.08MP, close valve, feed an amount of argon gas, when the pipe internal pressure reaches a normal atmosphere, drive valve and be communicated with atmosphere, start mechanical pump once more and repeat the air in four eliminating tube furnace furnace chambers of above operation.Start stove, be warming up to 1050 ℃, feed 50sccm oxygen, be incubated 50 minutes.Stove cools to room temperature naturally, closes gas, takes out substrate, on substrate, has obtained one deck white product.The pattern of product, structure, elementary composition and luminescent properties is all identical with embodiment 1.
Embodiment 4
As embodiment 1; Use electronic balance to take by weighing a certain amount of Sn powder and the Zn powder places the aluminium oxide boat front end as source material,, place the tube furnace middle part to aluminium oxide boat then place gold-plated silicon substrate from source material 2cm place; The pipe two ends respectively add a refractory brick, capping (like Fig. 1).Start mechanical pump, intraductal atmospheric pressure is reached-0.08MPa, close valve, feed an amount of argon gas, when the pipe internal pressure reaches a normal atmosphere, drive valve and be communicated with atmosphere, start mechanical pump once more and repeat the air in four eliminating tube furnace furnace chambers of above operation.Start stove, be warming up to 1050 ℃, feed 50sccm oxygen, be incubated 70 minutes.Stove cools to room temperature naturally, closes gas, takes out substrate, on substrate, has obtained one deck white product.The pattern of product, structure, elementary composition and luminescent properties is all identical with embodiment 1.
Embodiment 5
As embodiment 1; Use electronic balance to take by weighing a certain amount of Sn powder and the Zn powder places the aluminium oxide boat front end as source material,, place the tube furnace middle part to aluminium oxide boat then place gold-plated silicon substrate from source material 3cm place; The pipe two ends respectively add a refractory brick, capping (like Fig. 1).Start mechanical pump, intraductal atmospheric pressure is reached-0.08MPa, close valve, feed an amount of argon gas, when the pipe internal pressure reaches a normal atmosphere, drive valve and be communicated with atmosphere, start mechanical pump once more and repeat the air in four eliminating tube furnace furnace chambers of above operation.Start stove, be warming up to 980 ℃, feed 50sccm oxygen, be incubated 60 minutes.Stove cools to room temperature naturally, closes gas, takes out substrate, on substrate, has obtained one deck white product.The pattern of product, structure, elementary composition and luminescent properties is all identical with embodiment 1.
Claims (5)
1. ZnO/SnO
2The preparation method of heterogeneous structural nano luminescent material is characterized in that comprising the steps:
(1) is source material with Sn powder and Zn powder, mixes and place aluminium oxide boat that place gold-plated silicon substrate from source material 1.5～4cm place, place stove to aluminium oxide boat then, and stove is sealed, wherein the mol ratio of Sn powder and Zn powder is 1: 1;
(2) to vacuumizing in the stove, reach-0.08MPa, close vacuum extractor, feed the rare gas element argon gas, when furnace pressure reaches a normal atmosphere, open vacuum extractor, once more the stove internal gas pressure is evacuated to-0.08MPa up to the stove internal gas pressure;
The repetitive operation 4 times at least of above-mentioned vacuum;
(3) completing steps (2), exhaust vacuum after, stove is heated, until being warming up to 950～1050 ℃, feed 50sccm oxygen, be incubated 50～70 minutes;
(4) then stove is cooled to room temperature naturally, take out substrate, the gained white product is ZnO/SnO on the substrate
2The heterogeneous structural nano line luminous material.
2. preparation method according to claim 1 is characterized in that the stove described in the step (1) is a tube furnace.
3. preparation method according to claim 1 is characterized in that leaving in the step (1) source material 2cm place and places gold-plated silicon substrate.
4. preparation method according to claim 1 is characterized in that argon flow amount is 50sccm in the step (2).
5. preparation method according to claim 1 is characterized in that temperature of reaction is 950～980 ℃ in the step (3).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110349812.3A CN102504816B (en) | 2011-11-08 | 2011-11-08 | Method for preparing nano luminescent material ZnO/SnO2 heterostructure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110349812.3A CN102504816B (en) | 2011-11-08 | 2011-11-08 | Method for preparing nano luminescent material ZnO/SnO2 heterostructure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102504816A true CN102504816A (en) | 2012-06-20 |
| CN102504816B CN102504816B (en) | 2014-05-07 |
Family
ID=46216953
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110349812.3A Expired - Fee Related CN102504816B (en) | 2011-11-08 | 2011-11-08 | Method for preparing nano luminescent material ZnO/SnO2 heterostructure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102504816B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103627399A (en) * | 2013-12-13 | 2014-03-12 | 中国科学院长春应用化学研究所 | Semiconductor/fluorescent powder heterostructure and preparation method thereof |
| CN107091866A (en) * | 2017-04-21 | 2017-08-25 | 中国科学技术大学 | A kind of tin oxide composite nano-line, its preparation method and application |
| CN108389947A (en) * | 2018-04-27 | 2018-08-10 | 芜湖德豪润达光电科技有限公司 | Light emitting diode and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101311371A (en) * | 2008-02-27 | 2008-11-26 | 中国科学院理化技术研究所 | Preparation of SnO2Method for preparing-ZnO heterogeneous nano-wire |
| CN101323975A (en) * | 2008-07-14 | 2008-12-17 | 中国科学院理化技术研究所 | Preparation of SnO2Method for preparing -ZnO heterogeneous nano branch structure |
-
2011
- 2011-11-08 CN CN201110349812.3A patent/CN102504816B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101311371A (en) * | 2008-02-27 | 2008-11-26 | 中国科学院理化技术研究所 | Preparation of SnO2Method for preparing-ZnO heterogeneous nano-wire |
| CN101323975A (en) * | 2008-07-14 | 2008-12-17 | 中国科学院理化技术研究所 | Preparation of SnO2Method for preparing -ZnO heterogeneous nano branch structure |
Non-Patent Citations (3)
| Title |
|---|
| J. X. WANG等: "Preferential Growth of SnO2 Triangular Nanoparticles on ZnO Nanobelts", 《J. PHYS. CHEM. C》, vol. 111, no. 21, 9 May 2007 (2007-05-09), pages 7671 - 7675 * |
| ZHENYI ZHANG等: "Electrospun Nanofibers of ZnO-SnO2 Heterojunction with High Photocatalytic Activity", 《J. PHYS. CHEM. C》, vol. 114, no. 17, 13 April 2010 (2010-04-13), pages 7920 - 7925 * |
| 洪广言: "《稀土发光材料-基础与应用》", 1 April 2011, article "稀土发光材料的制备化学", pages: 517 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103627399A (en) * | 2013-12-13 | 2014-03-12 | 中国科学院长春应用化学研究所 | Semiconductor/fluorescent powder heterostructure and preparation method thereof |
| CN107091866A (en) * | 2017-04-21 | 2017-08-25 | 中国科学技术大学 | A kind of tin oxide composite nano-line, its preparation method and application |
| CN107091866B (en) * | 2017-04-21 | 2019-07-23 | 中国科学技术大学 | A kind of tin oxide composite nano-line, preparation method and application |
| CN108389947A (en) * | 2018-04-27 | 2018-08-10 | 芜湖德豪润达光电科技有限公司 | Light emitting diode and preparation method thereof |
| CN108389947B (en) * | 2018-04-27 | 2024-03-26 | 芜湖德豪润达光电科技有限公司 | Light emitting diode and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102504816B (en) | 2014-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Fan et al. | ZnO-based ternary compound nanotubes and nanowires | |
| Hsu et al. | Enhanced field emission of Al-doped ZnO nanowires grown on a flexible polyimide substrate with UV exposure | |
| CN102504816B (en) | Method for preparing nano luminescent material ZnO/SnO2 heterostructure | |
| CN107185578A (en) | In the GaN nano wire catalysis material and preparation method and application of sheet metal Grown | |
| CN102719797A (en) | Zinc oxide based transparent conductive membrane having up-conversion function and method for preparing same | |
| CN104726736B (en) | A kind of from center to edge component continuously adjustabe stratiform MoS2 (1-x)se2xalloy nano sheet material and preparation method thereof and device | |
| CN107083532A (en) | A kind of preparation method of CuI nanostructureds | |
| CN102260073A (en) | Zinc-oxide-based low-voltage voltage-sensitive ceramic thin film material and preparation method thereof | |
| CN102260907A (en) | Preparation method of ZnO nano homogeneous p-n junction array | |
| CN101328609B (en) | Method for preparing tin doping zinc oxide nanowire by vapor deposition | |
| CN101513996B (en) | An aluminum nitride nanometer comb and preparation method thereof | |
| CN103013500B (en) | Method for preparing Zn/ZnO composite luminescent material | |
| CN101476155A (en) | Electrochemical deposition preparation for Mg doped ZnO nano-wire | |
| CN101508427B (en) | Aluminum nitride single-edge nano-comb and method for preparing the same | |
| CN102618269A (en) | Method for preparing nano luminescent material with CdS/Sn alloplasmic structure | |
| CN100580155C (en) | Method for developing zinc oxide crystallite by chemical gas-phase transmitting process | |
| CN102787294B (en) | Preparation method and use of titanium-doped zinc-magnesium aluminate film | |
| CN102796517B (en) | Nitrogenous magnesium silicate film, and preparation method and application thereof | |
| CN101791566B (en) | New method for nitrating ZnO based compound nano material | |
| Rein et al. | Liquid-ammonia synthesis of microporous Mg 3 N 2 showing intense red-light emission | |
| CN103539087B (en) | A kind of method preparing aluminum nitride nanowire | |
| CN103059846B (en) | Sn/SnO2 composite luminescent material and preparation method thereof | |
| CN110003894B (en) | Yb for white light L ED2+Nitrogen oxide excitation green fluorescent material and preparation method thereof | |
| CN101760726B (en) | Preparation method of B and N codope ZnO film | |
| CN104828791B (en) | The preparation method of rare earth element ce doping GaN nano wire |
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: 20140507 Termination date: 20141108 |
|
| EXPY | Termination of patent right or utility model |