CN102086393B - Preparation method of ZnO, CuO and ZnS quantum dot film - Google Patents
Preparation method of ZnO, CuO and ZnS quantum dot film Download PDFInfo
- Publication number
- CN102086393B CN102086393B CN2010105883188A CN201010588318A CN102086393B CN 102086393 B CN102086393 B CN 102086393B CN 2010105883188 A CN2010105883188 A CN 2010105883188A CN 201010588318 A CN201010588318 A CN 201010588318A CN 102086393 B CN102086393 B CN 102086393B
- Authority
- CN
- China
- Prior art keywords
- quantum dot
- solution
- cuo
- zno
- coo
- 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
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Luminescent Compositions (AREA)
Abstract
The invention relates to a preparation method of a ZnO, CuO and ZnS quantum dot film. The preparation method comprises the following steps: preparing Cu ion modified ZnO quantum dot precipitate, CuO quantum dot precipitate and ZnS quantum dot precipitate; adding trichloromethane in the prepared quantum dot precipitates respectively to fully dissolve, then adding n-octylamine dispersant to obtain Cu ion modified ZnO colloidal quantum dot solution, CuO colloidal quantum dot solution and ZnS colloidal quantum dot solution; diluting the three kinds of colloidal quantum dot solutions with the same amount of trichloromethane, filtering with a polytetrafluoroethylene (PTFE) filter, coating one or more of the colloidal quantum dot solutions on an indium-tin oxide (ITO) substrate through the spin-coating method, prebaking, and annealing in the air to obtain the quantum dot single-layer or multi-layer film. The preparation process of the invention is simple; the coated quantum dot film is compact and smooth and has good adhesion performance and controllable film thickness; and the quantum dot multi-layer structure is easy to realize and the quantum dot film is suitable for the multi-layer quantum dot film element.
Description
Technical field
The present invention relates to the preparation method of quantum dot film, especially the preparation method of ZnO, CuO and ZnS quantum dot film.
Background technology
Quantum dot receives the effect of restraint on the size, has adjustable luminescent properties, makes it as visible light source still be very advantageous all on large-area flat-plate shows.Preparing quantum dot with the conventional gas-phase epitaxy method compares; The colloid quantum dot is synthetic controlled; And possess higher monodispersity, be easy to be compatible with inkjet printing, seal and spin coating proceeding and prepare quantum dot single/multiple layer film, become a kind of luminescence system of the novel raising gain of light.Meanwhile, the compatibility of inorganic quantum dot and various luminescent materials is all relatively good, no matter is on the full-inorganic quantum dot device therefore, or can both embodies its advantage on the hybrid inorganic-organic quantum device.It will be further appreciated that; Compare luminescent organic molecule, its metastable photochemistry attribute has brought many opportunities for its practicability, has done some fruitful trials in this field with a collection of searcher headed by the scientist Bawendi; But preparing the complex process that quantum dot was introduced on this step; Productive rate is not high, and has more and relate to poisonous heavy metal ion, also has certain distance from real industrialization.At present; It is ripe gradually to adopt low temperature water-bath legal system to be equipped with inorganic quantum dot; Manyly all be applied on the biological fluorescent labelling, but the example that is applied on the thin-film device also rarely has report, relatively success also mainly concentrates on the ZnO quantum dot; People such as Jin and Sun has carried out a few thing with regard to the application of its ultraviolet detection and field-effect transistor aspect respectively, and more deep application is attempted being still waiting to carry out.Therefore, widen the scope of the synthetic quantum dot material system of low temperature, rationally constructing novel quantum dot device structure is a very significant job.
Summary of the invention
The objective of the invention is to provide a kind of preparation method of simple and easy to do ZnO, CuO and ZnS quantum dot film for quantum device.
The preparation method of ZnO of the present invention, CuO and ZnS quantum dot film comprises the steps:
1) with Zn (CH
3COO)
2And Cu (CH
3COO)
2(1: 0.005～1: 0.04) fully is dissolved in the methyl alcohol in molar ratio, adds deionized water then as catalyst for reaction, and 60 ℃ of following water-baths refluxed 30 minutes, obtained precursor solution;
2) the KOH methanol solution with 0.167mol/L drops in the precursor solution of step 1) Zn (CH
3COO)
2And Cu (CH
3COO)
2Mixture and the mol ratio of KOH be 1: 1.67～1: 2,60 ℃ of following water-baths 2.5 hours, with the frozen water cooling, the methyl alcohol centrifuge washing, the ZnO quantum dot deposition of Cu ion modification;
3) with Cu (CH
3COO)
2Be dissolved in the methyl alcohol Cu (CH of preparation 0.0083mol/L
3COO)
2Methanol solution adds glacial acetic acid as catalysts, and 80 ℃ of water-baths refluxed 120 minutes, obtained precursor solution;
4) the KOH methanol solution with 0.167mol/L drops in the precursor solution of step 3), 60 ℃ of water-baths 1 hour, and with the frozen water cooling, the methyl alcohol centrifuge washing obtains CuO quantum dot deposition;
5) with Zn (CH
3COO)
2Be dissolved in respectively in the methyl alcohol in 1: 1.67 in molar ratio with thioacetamide, obtain Zn (CH
3COO)
2Methanol solution and thioacetamide methanol solution;
6) with Zn (CH
3COO)
2Methanol solution drips the thioacetamide methanol solution then 70 ℃ of following water bath heat preservation half an hour, adds glacial acetic acid at last as catalyst for reaction, 60 ℃ of waters bath with thermostatic control reactions 30 minutes, and with the frozen water cooling, the methyl alcohol centrifuge washing obtains ZnS quantum dot deposition;
7) in ZnO quantum dot deposition, CuO quantum dot deposition and the ZnS quantum dot deposition of the above-mentioned Cu ion modification that makes, adding chloroform respectively fully dissolves it; Add the n-octyl amine dispersant then respectively; Shake up, obtain ZnO colloid quantum dot solution, CuO colloid quantum dot solution and the ZnS colloid quantum dot solution of Cu ion modification;
8) ZnO colloid quantum dot solution, CuO colloid quantum dot solution and the ZnS colloid quantum dot solution with the Cu ion modification dilutes with the chloroform of equivalent respectively; The PTFE filter in each personal 0.22 μ m aperture filters then; With the rotating speed of 2000～4000rpm in ZnO colloid quantum dot solution, CuO colloid quantum dot solution and the ZnS colloid quantum dot solution of Cu ion modification one or more are spin-coated on the ITO substrate that cleaned; After 80 ℃ of prebakes; In 250 ℃ of following air, annealed 1～2 hour, obtain quantum dot single or multiple lift film.
Among the present invention, raw materials used pureness specifications is respectively: Zn (CH
3COO)
2(99.99%), Cu (CH
3COO)
2(99.99%), KOH particle (85+%), thioacetamide (99.0+%), deionized water (R=18.2M Ω), n-octyl amine (99+%), chloroform (chromatographically pure), methyl alcohol (analyzing pure), glacial acetic acid (analyzing pure).Substrate can be ITO sheet, quartz plate or Si sheet.
The present invention can control the size of quantum dot preferably through regulating parameters such as raw material ratio, temperature, time, optimizes spin coating proceeding and can obtain the transparent quantum dot film that thickness is adjustable, luminescent properties is different with annealing time.Beneficial effect of the present invention is:
1. use comparatively simple solwution method to prepare the many body system quantum dot, technology is simple, and is with low cost;
2. the quantum dot film of spin coating is not only fine and close smooth, and tack is all good, and controllable film thickness, is prone to realize the quantum dot sandwich construction;
3. single ZnO quantum dot defect luminescence is serious, through the finishing effect of Cu ion, has compensated surperficial outstanding key effectively, has suppressed defect luminescence, and the band edge emission is effectively strengthened;
4. realized the preparation of CuO quantum dot at low temperatures, be expected to aspect air-sensitive, catalysis, magnetic storage, solar energy, realize using;
5. the realization of broad stopband ZnS quantum dot film; Not only can apply it on the deep ultraviolet field of detecting; More an approach that well realizes being with coupling is provided at LED and photovoltaic field; Optimize the separation of electron hole and compound, for the design of multi-layer quantum point device architecture provides the universality method.
Description of drawings
Fig. 1 is ZnO, CuO, the XRD figure spectrum of ZnS quantum dot powder;
Fig. 2 is the ZnO quantum dot PL contrast collection of illustrative plates before and after the Cu ion modification;
Fig. 3 is high-resolution-ration transmission electric-lens (HRTEM) photo of quantum dot, and wherein (a) is the ZnO quantum dot, (b) is the CuO quantum dot, (c) is the ZnS quantum dot;
Fig. 4 is the SEM vertical view (a) and sectional drawing (b) of CuO quantum dot spin coating rear film;
Fig. 5 is the SEM vertical view (a) and sectional drawing (b) of ZnO/ZnS quantum dot bilayer film;
Fig. 6 is the SEM vertical view (a) and sectional drawing (b) of CuO/ZnO/ZnS quantum dot three-layer thin-film;
Fig. 7 is the I-V characteristic curve of ZnO/ZnS quantum dot bilayer film device;
Fig. 8 is the I-V characteristic curve of CuO/ZnO/ZnS quantum dot three-layer thin-film device.
Embodiment
Further specify the present invention below in conjunction with instance.
Embodiment
1) with 0.7925g (purity 99.99%) Zn (CH
3COO)
2Powder and 0.0327g (purity 99.99%) Cu (CH
3COO)
2Powder is dissolved in the methanol solution of 40mL, adds 250 μ L deionized waters after the stirring fully, and 60 ℃ of following water-baths refluxed 30 minutes, obtained precursor solution;
2) the KOH methanol solution with 20mL 0.167mol/L drops in the precursor solution of step 1); 60 ℃ of water-baths 2.5 hours are with frozen water cooling, methyl alcohol centrifuge washing 3 times; Obtain the ZnO quantum dot deposition of Cu ion modification; Characterize its thing phase (see figure 1) with XRD, PL characterizes its characteristics of luminescence (see figure 2), and high-resolution-ration transmission electric-lens characterizes its pattern and size (is seen Fig. 3 a);
3) with 0.2724g (purity 99.99%) Cu (CH
3COO)
2Powder is dissolved in the 60mL methanol solution, adds 100 μ L glacial acetic acid, and 80 ℃ of water-baths refluxed 120 minutes, obtained Cu (CH
3COO)
2The methyl alcohol precursor solution;
4) the KOH methanol solution with 10mL 0.167mol/L drops in the precursor solution of step 3); 60 ℃ of water-baths 1 hour; With the frozen water cooling, methyl alcohol centrifuge washing 6 times obtains CuO quantum dot deposition; Characterize its thing phase (see figure 1) with XRD, high-resolution-ration transmission electric-lens characterizes its pattern and size (seeing Fig. 3 b);
5) with 0.8192g (purity 99.99%) Zn (CH
3COO)
2Powder and 0.6732g (purity 99.0+%) thioacetamide powder, be dissolved in respectively 40 with the methyl alcohol of 20mL in, obtain Zn (CH
3COO)
2Methanol solution and thioacetamide methanol solution;
6) with Zn (CH
3COO)
2Methanol solution drips the thioacetamide methanol solution then 70 ℃ of following water bath heat preservation half an hour, adds 50 μ L glacial acetic acid at last as catalyst for reaction; 60 ℃ of waters bath with thermostatic control were reacted 30 minutes; With the frozen water cooling, methyl alcohol centrifuge washing 3 times obtains ZnS quantum dot deposition; Characterize its thing phase (see figure 1) with XRD, high-resolution-ration transmission electric-lens characterizes its pattern and size (seeing Fig. 3 c);
7) in ZnO quantum dot, CuO quantum dot and the ZnS quantum dot of the above-mentioned Cu ion modification that makes, adding the 5mL chloroform respectively fully dissolves it; Add 200 μ L n-octyl amine dispersants then respectively; Shake up, obtain ZnO colloid quantum dot solution, CuO colloid quantum dot solution and the ZnS colloid quantum dot solution of Cu ion modification;
8) get gained colloid quantum dot solution in the 1mL step 7) respectively; With isopyknic chloroform dilution; Filter with the PTFE filter in 0.22 μ m aperture successively then, CuO colloid quantum dot solution is spun on the ITO substrate that cleaned, after 80 ℃ of prebakes with the rotating speed of 3000rpm; Annealing is 1 hour in 250 ℃ of following air, obtains CuO quantum dot single thin film (see figure 4).
Be spun on successively on the ITO substrate that cleaned with the rotating speed of 3000rpm ZnO colloid quantum dot solution and ZnS colloid quantum dot solution the Cu ion modification; After 80 ℃ of prebakes; Annealing is 1 hour in 250 ℃ of following air, obtains ZnO/ZnS quantum dot bilayer film (see figure 5).
Be spun on successively on the ITO substrate that cleaned with the rotating speed of 3000rpm ZnO colloid quantum dot solution and ZnS colloid quantum dot solution CuO colloid quantum dot solution, Cu ion modification; After 80 ℃ of prebakes; Annealing is 1 hour in 250 ℃ of following air, obtains CuO/ZnO/ZnS quantum dot three-layer thin-film (see figure 6)
Three kinds of quantum dot films that this example makes are used patterned mask plate evaporating Al electrode respectively, test different quantum dot thin-film device I-V characteristics;
ZnO/ZnS quantum dot bilayer film device has rectification characteristic (see figure 7) preferably; The I-V characteristic curve of CuO/ZnO/ZnS quantum dot three-layer thin-film device is as shown in Figure 8; The three-layer thin-film device is compared with the bilayer film device; Have better rectification characteristic and lower cut-in voltage, explain that the CuO quantum dot film that increases can effectively improve the injection efficiency in hole.
Claims (1)
1. the preparation method of a single or multiple lift quantum dot film comprises the steps:
1) with Zn (CH
3COO)
2And Cu (CH
3COO)
21:0.005 ~ 1:0.04 fully is dissolved in the methyl alcohol in molar ratio, adds deionized water then as catalyst for reaction, and 60 ℃ of following water-baths refluxed 30 minutes, obtained precursor solution;
2) the KOH methanol solution with 0.167mol/L drops in the precursor solution of step 1) Zn (CH
3COO)
2And Cu (CH
3COO)
2Mixture and the mol ratio of KOH be 1:1.67 ~ 1:2,60 ℃ of following water-baths 2.5 hours, with the frozen water cooling, the methyl alcohol centrifuge washing, the ZnO quantum dot deposition of Cu ion modification;
3) with Cu (CH
3COO)
2Be dissolved in the methyl alcohol Cu (CH of preparation 0.0083mol/L
3COO)
2Methanol solution adds glacial acetic acid as catalysts, and 80 ℃ of water-baths refluxed 120 minutes, obtained precursor solution;
4) the KOH methanol solution with 0.167mol/L drops in the precursor solution of step 3), 60 ℃ of water-baths 1 hour, and with the frozen water cooling, the methyl alcohol centrifuge washing obtains CuO quantum dot deposition;
5) with Zn (CH
3COO)
2With thioacetamide in molar ratio 1:1.67 be dissolved in respectively in the methyl alcohol, obtain
Zn (CH
3COO)
2Methanol solution and thioacetamide methanol solution;
6) with Zn (CH
3COO)
2Methanol solution drips the thioacetamide methanol solution then 70 ℃ of following water bath heat preservation half an hour, adds glacial acetic acid at last as catalyst for reaction, 60 ℃ of waters bath with thermostatic control reactions 30 minutes, and with the frozen water cooling, the methyl alcohol centrifuge washing obtains ZnS quantum dot deposition;
7) in ZnO quantum dot deposition, CuO quantum dot deposition and the ZnS quantum dot deposition of the above-mentioned Cu ion modification that makes, adding chloroform respectively fully dissolves it; Add the n-octyl amine dispersant then respectively; Shake up, obtain ZnO colloid quantum dot solution, CuO colloid quantum dot solution and the ZnS colloid quantum dot solution of Cu ion modification;
8) ZnO colloid quantum dot solution, CuO colloid quantum dot solution and the ZnS colloid quantum dot solution with the Cu ion modification dilutes with the chloroform of equivalent respectively; The PTFE filter in each personal 0.22 μ m aperture filters then; With the rotating speed of 2000 ~ 4000rpm in ZnO colloid quantum dot solution, CuO colloid quantum dot solution and the ZnS colloid quantum dot solution of Cu ion modification one or more are spin-coated on the ITO substrate that cleaned; After 80 ℃ of prebakes; In 250 ℃ of following air, annealed 1 ~ 2 hour, obtain ZnO, CuO and ZnS quantum dot single or multiple lift film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105883188A CN102086393B (en) | 2010-12-07 | 2010-12-07 | Preparation method of ZnO, CuO and ZnS quantum dot film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105883188A CN102086393B (en) | 2010-12-07 | 2010-12-07 | Preparation method of ZnO, CuO and ZnS quantum dot film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102086393A CN102086393A (en) | 2011-06-08 |
| CN102086393B true CN102086393B (en) | 2012-12-26 |
Family
ID=44098399
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105883188A Expired - Fee Related CN102086393B (en) | 2010-12-07 | 2010-12-07 | Preparation method of ZnO, CuO and ZnS quantum dot film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102086393B (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102336928B (en) * | 2011-07-08 | 2012-11-28 | 北京理工大学 | Flexible, environmentally-friendly, transparent and adjustable-illuminant-color film material and preparation method thereof |
| CN102559172A (en) * | 2011-11-29 | 2012-07-11 | 天津理工大学 | Semiconductor luminescent material with adjustable luminescent colours and preparation method |
| CN102730749A (en) * | 2012-06-26 | 2012-10-17 | 湖南工业大学 | Method for preparing water-soluble ZnS quantum point |
| CN104591262B (en) * | 2015-01-26 | 2016-09-21 | 河南科技大学 | The method that cinnabar nanoparticle is prepared in dropping backflow |
| CN105420780B (en) * | 2015-11-06 | 2017-11-17 | 常州大学怀德学院 | Composite Nano heterogenous junction film material and composite heterogenous junction solar cell preparation method |
| CN106328009A (en) * | 2016-09-09 | 2017-01-11 | Tcl集团股份有限公司 | Optical display system and preparation method and application thereof |
| CN106356470A (en) * | 2016-09-13 | 2017-01-25 | Tcl集团股份有限公司 | Core/shell semiconductor nanorod film, polarization light emitting diode and preparation method thereof |
| EP3537138B1 (en) * | 2016-11-02 | 2023-12-27 | LG Chem, Ltd. | Quantum dot biosensor |
| CN106711283B (en) * | 2016-12-27 | 2019-05-24 | 南京理工大学 | A kind of all print zinc oxide nanocrystalline base ultraviolet light electric explorer preparation method |
| CN106952826A (en) * | 2017-03-30 | 2017-07-14 | 深圳市华星光电技术有限公司 | A kind of field-effect transistor and preparation method thereof |
| CN108754528B (en) * | 2018-06-08 | 2020-07-03 | 西北大学 | High-performance photocatalytic nano material |
| CN110679609B (en) * | 2019-09-30 | 2021-03-19 | 广明源光科技股份有限公司 | Copper-doped zinc oxide quantum dot nano antibacterial agent and preparation method thereof |
| CN112916348B (en) * | 2021-01-22 | 2022-05-17 | 中国计量大学 | Controllable quantum dot preparation method based on spin coating technology and quantum dot |
| CN113571600B (en) * | 2021-07-01 | 2023-08-18 | 深圳先进技术研究院 | Infrared detector and preparation method thereof |
| CN118073528A (en) * | 2024-04-18 | 2024-05-24 | 湖南金阳烯碳新材料股份有限公司 | Positive electrode composite material suitable for dry electrode process and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101275073A (en) * | 2007-09-26 | 2008-10-01 | 浙江大学 | Preparation for ZnO quantum dot |
-
2010
- 2010-12-07 CN CN2010105883188A patent/CN102086393B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101275073A (en) * | 2007-09-26 | 2008-10-01 | 浙江大学 | Preparation for ZnO quantum dot |
Non-Patent Citations (2)
| Title |
|---|
| ZnO量子点的制备及其光电性能研究进展;杨玲敏等;《纳米材料与结构》;20041231(第12期);22-25 * |
| 杨玲敏等.ZnO量子点的制备及其光电性能研究进展.《纳米材料与结构》.2004,(第12期),22-25. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102086393A (en) | 2011-06-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102086393B (en) | Preparation method of ZnO, CuO and ZnS quantum dot film | |
| CN108529690B (en) | Preparation method and application of nickel oxide nanocrystal | |
| CN103840047B (en) | A kind of be hole transmission layer with colloid NiO nano-crystal film photoelectric device and preparation method thereof | |
| US8173205B2 (en) | Method for fabricating ZnO thin films | |
| JP5881045B2 (en) | Quantum dot-containing titanium compound and method for producing the same, and photoelectric conversion element using the quantum dot-containing titanium compound | |
| CN102244010B (en) | Preparation method of p-CuAlO2/n-ZnO:Al transparent thin film heterojunction of glass substrate | |
| CN108929670B (en) | Core-shell quantum dot, preparation method thereof, device and composition | |
| US20070298160A1 (en) | Thin film containing nanocrystal particles and method for preparing the same | |
| KR20100124802A (en) | Copper indium sulfide nanoparticles and a preparation method thereof | |
| CN101538713A (en) | Titanium dioxide thin film with dual-layer nano-ordered structure and preparation method thereof | |
| CN105694893A (en) | Langmiur-Blodgett composite lighting film of cadmium telluride quantum dots and layered double hydroxide and manufacturing method thereof | |
| CN103700725A (en) | Preparation method of nano-particle-based copper indium sulphur selenium film for solar battery | |
| CN113046083B (en) | CdSeS magic number nanocluster, preparation method and application thereof | |
| Xu et al. | The dependence of the optical properties of ZnO nanorod arrays on their growth time | |
| CN105540641B (en) | A kind of preparation method of the mg-doped zinc oxide material of flower-like microsphere | |
| CN100582012C (en) | Nano porous zinc oxide thin film with high C-axis orientation and preparation method thereof | |
| CN109935731A (en) | Composite membrane and its preparation method and application | |
| CN110054212B (en) | Compound NH4GaS2And preparation method and application thereof | |
| CN109988370B (en) | Light wave conversion material, preparation method thereof and solar cell | |
| CN110010770A (en) | A kind of preparation of the perovskite solar battery of gold bipyramid plasma enhancing | |
| CN110776000B (en) | All-inorganic perovskite nanocrystalline, preparation method thereof and application thereof in semiconductor device | |
| CN112680212B (en) | Synthesis method of halogen perovskite film with low lead and high fluorescence efficiency | |
| CN103880062A (en) | Zinc oxide nano-column thin film and preparation method thereof | |
| CN115637426A (en) | Method for depositing mesoporous tin dioxide film by chemical bath | |
| CN103077831A (en) | ZnO nano-crystal/nano-rod aggregate film material and preparation method thereof |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121226 Termination date: 20201207 |