CN100523297C - Method for hydrothermally synthesizing series flower shape zinc oxide micron/nano structure - Google Patents
Method for hydrothermally synthesizing series flower shape zinc oxide micron/nano structure Download PDFInfo
- Publication number
- CN100523297C CN100523297C CNB2006101175649A CN200610117564A CN100523297C CN 100523297 C CN100523297 C CN 100523297C CN B2006101175649 A CNB2006101175649 A CN B2006101175649A CN 200610117564 A CN200610117564 A CN 200610117564A CN 100523297 C CN100523297 C CN 100523297C
- Authority
- CN
- China
- Prior art keywords
- zno
- nanostructure
- flower
- zinc oxide
- reaction vessels
- 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
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The present invention discloses hydrothermal process of synthesizing efflorescent zinc oxide in micron and nanometer structure. The process includes adopting zinc chloride and ammonia water as material, regulating solution pH value to 10.40-12.00, setting the treated substrate and the compounded solution inside reaction utensil with cover, heating in a stove to react, eliminating transparent liquid while leaving white precipitate, sealing the precipitate in the utensil at room temperature for hours, washing and air drying to obtain the efflorescent zinc oxide in micron and nanometer structure on the substrate. The prepared efflorescent zinc oxide is used mainly in making chemical sensor, optical memory, photocatalyst, etc. and the process is simple, low in cost, controllable, pollution-free and suitable for industrial production.
Description
Technical field
The invention belongs to the semiconductor nano material preparation field, be specifically related to a kind of micron and nano-ZnO preparation, particularly a kind of preparation method who utilizes hydrothermal synthesis method to prepare series flower shape ZnO micron and nanostructure.
Background technology
(band gap is 3.37eV as the wide bandgap semiconductor compound, room-temperature exciton can be 60meV), ZnO has characteristics such as its unique optics, electricity, photoelectricity and piezoelectricity, has been widely used in that opto-electronic device, solar battery light wave are led, device such as power device, transmitter, flat pannel display and optical storage.Preparation methods such as different up to now chemistry, physics and electrochemistry mainly contain methods such as molecular beam epitaxy, metal organic chemical vapor deposition, laser deposition, sputtering method, thermal evaporation and hydro-thermal be synthetic.The molecular beam epitaxy cost is too high, is not suitable for the requirement of scale operation; Chemical Vapor deposition process is a method relatively preferably, but improves also needing aspect the controllability of nanostructure; Thermal evaporation is because its cost is low, easy handling and can prepare advantage such as multiple pattern and become one of main method of preparation ZnO nanostructure, but its shortcoming is: high temperature requires, controllability is relatively poor.These synthetic methods cut both ways.Solution synthetic method since advantage such as it is simple, low temperature, cost are low, easy handling and big area are synthetic enjoy people's favor, and utilize this synthetic method, the nano material of preparing differing materials and having different-shape.
Summary of the invention
The object of the present invention is to provide the hydrothermally synthesizing series flower shape zinc oxide micron of characteristics such as a kind of simple, low-cost, pollution-free and large-area preparation and the method for nanostructure.
In order to realize goal of the invention of the present invention, adopt following technical scheme:
A kind of method of utilizing hydrothermally synthesizing series flower shape zinc oxide micron and nanostructure comprises the steps:
1) be that 25% ammoniacal liquor splashes in the middle of the liquor zinci chloridi that concentration is 0.2～0.5mol/l with mass percent, the pH value of adjusting solution is between 10.40-12.00.
2) cleaning of substrate, the good substrate of electroconductibility (as iron, aluminium, copper etc. or be coated with other substrates of metallic film, as silicon chip, glass etc.) place acetone and deionized water mixed solution or the beaker of alcoholic solution, ultrasonic 5min keeps flat in the reaction vessels that has connector behind 1.5h.
3) solution for preparing places the reaction vessels that has connector, builds reaction vessels (not being absolute seal, so the air pressure of solution is almost near normal pressure), puts into temperature then and be 80～150 ℃ drying oven and heating 4-8h, takes out reaction vessels.
4) pour out reacted transparent liquid and stay white depositions, again the reaction vessels good seal, at room temperature preserve 2-6h after, take out sample, with drying naturally after the washed with de-ionized water.
5) by changing the concentration and the pH value of liquor zinci chloridi, can prepare the flower-shaped ZnO nanometer and the micrometer structure of different-shape.Single flower-shapedly have 6～18 μ m sizes, and the hexagonal length of side of sheet is between 500nm～2 μ m, and thickness is between 80nm～300nm.
Adopt the method for the ZnO micron of technique scheme preparation and nanostructure can realize large-area synthetic and have that method is simple, cost is low, advantages such as mild condition and environmentally safe, thereby can realize suitability for industrialized production.Problems such as (especially in Field Emission Display) big area, low cost and controllability preparation in the micro-nano level ZnO application have been solved.Moreover compare with other chemical synthesis process, the inventive method has only adopted two kinds of chemical reagent, does not add any promoting agent or organism, so cost is lower and synthetic micro Nano material purity is higher.The flower-like structure of the present invention's preparation is made up of the sheet hexagon, because it has big specific surface area, at aspects such as chemical sensor, photochemical catalysis and optical storages great application prospect is arranged.
Description of drawings
Fig. 1 is the stereoscan photograph under the differential responses pH value of solution value.
Fig. 2 is the stereoscan photograph under the differential responses strength of solution.
Fig. 3 is the ZnO micron of one of them floriform appearance and the XRD figure spectrum of nanostructure.
Embodiment
Following specific embodiment just further specifies the present invention and how to realize, and does not limit the scope of the invention:
Embodiment 1
1) be that 25% ammoniacal liquor splashes in the middle of the liquor zinci chloridi that concentration is 0.35mol/l with mass percent, the pH value of adjusting solution is respectively 10.40,10.80 and 11.15.
2) cleaning of substrate places acetone and deionized water mixed solution or the beaker of alcoholic solution to copper sheet, and ultrasonic 5min does not keep flat in the reaction vessels that has connector after not waiting to 1.5h.
3) solution for preparing is placed the reaction vessels that has connector, build reaction vessels (not being absolute seal), put into temperature then and be 95 ℃ drying oven and heating 5.5h, take out reaction vessels so the air pressure of solution is almost near normal pressure.
4) pour out reacted transparent liquid and stay white depositions, again the reaction vessels good seal, at room temperature preserve 4h after, take out sample, with drying naturally after the washed with de-ionized water.Substrate deposition one deck white film on copper sheet, field emission scanning electron microscope (FESEM) show that further this white thing is respectively the flower-shaped ZnO nanometer and the micro-crystal of different-shape, see shown in a, b among Fig. 1, the c.
X-ray diffraction (XRD) collection of illustrative plates of the flower-like structure ZnO micro-nano material sample of present embodiment growth is seen Fig. 3, and the result is shown as typical six side's pricker zinc ore ZnO crystals, and does not have other any impurity.
1) with mass percent be 25% ammoniacal liquor splash into concentration be respectively 0.2,0.35 and the liquor zinci chloridi of 0.45mol/l in the middle of, the pH value of adjusting solution is about 10.60.
2) cleaning of substrate places acetone and deionized water mixed solution or the beaker of alcoholic solution to copper sheet, and ultrasonic 5min does not keep flat in the reaction vessels that has connector after not waiting to 1.5h.
3) solution for preparing places the reaction vessels that has connector, builds reaction vessels (not being absolute seal, so the air pressure of solution is almost near normal pressure), puts into temperature then and be 95 ℃ drying oven and heating 5.5h, takes out reaction vessels.
4) pour out reacted transparent liquid and stay white depositions, again the reaction vessels good seal, at room temperature preserve 4h after, take out sample, with drying naturally after the washed with de-ionized water.Substrate deposition one deck white film on copper sheet, field emission scanning electron microscope (FESEM) show that further this white thing is respectively the flower-shaped ZnO nanometer and the micro materials of different-shape, see that a among Fig. 2 is to shown in the c.
Claims (5)
1. a method of utilizing hydrothermally synthesizing series flower shape zinc oxide micron and nanostructure comprises the steps:
1), be that 25% ammoniacal liquor splashes in the middle of the liquor zinci chloridi that concentration is 0.2～0.5mol/l with mass percent, the pH value of adjusting solution is between 10.40-12.00;
2), the cleaning of substrate: the good substrate of electroconductibility is placed acetone and deionized water mixed solution or the anhydrous beaker of alcohol, and ultrasonic 5min keeps flat in the reaction vessels that has connector behind 1.5h;
3), with 1) solution for preparing of step places the reaction vessels that has connector to build, put into temperature then and be 80～150 ℃ drying oven and heating 4-8h after, take out reaction vessels;
4), pour out reacted transparent liquid and stay white depositions, again the reaction vessels good seal, at room temperature preserve 2-6h after, take out sample, with drying flower-shaped ZnO nanometer and the micrometer structure that promptly gets different-shape after the washed with de-ionized water naturally.
2. the preparation method of a kind of ZnO micron according to claim 1 and nanostructure is characterized in that, described substrate is iron, aluminium, copper or the silicon chip that is coated with metallic film, be coated with a kind of in the glass of metallic film.
3. the preparation method of a kind of ZnO micron according to claim 1 and nanostructure is characterized in that, described reaction is near carrying out under the normal pressure.
4. the preparation method of a kind of ZnO micron according to claim 1 and nanostructure is characterized in that, by changing the concentration and the pH value of liquor zinci chloridi, can prepare the flower-shaped ZnO nanometer and the micrometer structure of different-shape.
5. the preparation method of a kind of ZnO micron according to claim 1 and nanostructure, it is characterized in that, the single ZnO flower-like structure that is obtained is made up of dozens of hexagon sheet structure, single flower has 6～18 μ m sizes, and the hexagonal length of side of sheet is between 500nm～2 μ m, and thickness is between 80nm～300nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101175649A CN100523297C (en) | 2006-10-25 | 2006-10-25 | Method for hydrothermally synthesizing series flower shape zinc oxide micron/nano structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101175649A CN100523297C (en) | 2006-10-25 | 2006-10-25 | Method for hydrothermally synthesizing series flower shape zinc oxide micron/nano structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1944708A CN1944708A (en) | 2007-04-11 |
| CN100523297C true CN100523297C (en) | 2009-08-05 |
Family
ID=38044356
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006101175649A Expired - Fee Related CN100523297C (en) | 2006-10-25 | 2006-10-25 | Method for hydrothermally synthesizing series flower shape zinc oxide micron/nano structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100523297C (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100563881C (en) * | 2008-01-23 | 2009-12-02 | 厦门大学 | A kind of method of polyacrylic acid hydro-thermal synthesis of nano gold |
| CN101580405B (en) * | 2009-06-05 | 2011-07-27 | 华东师范大学 | Semiconductor material with ZnO cone-shaped nano structure compounded on silicon chip and preparation method thereof |
| CN101811727A (en) * | 2010-04-16 | 2010-08-25 | 广西民族大学 | Method for synthesizing flaky nano zinc oxide by low-temperature control |
| CN102249284B (en) * | 2011-05-13 | 2013-04-17 | 陕西师范大学 | Preparation method for micrometer barium-doped zinc oxide |
| CN102502783B (en) * | 2011-10-14 | 2014-04-02 | 中国科学院上海硅酸盐研究所 | Method for preparing alkali zinc chloride nano-powder in hexagonal flake structures |
| CN103894171A (en) * | 2012-12-26 | 2014-07-02 | 吉林师范大学 | Preparation method for photocatalyst with flower-cluster-like zinc oxide micrometer structure |
| CN103241764B (en) * | 2013-05-30 | 2015-02-18 | 中国科学院上海光学精密机械研究所 | Preparation method of three-dimensional zinc oxide flower-like structure |
| CN103818875B (en) * | 2014-02-17 | 2017-02-01 | 中国科学技术大学 | Growth method of micro-nano functional material and application thereof in quantum dot cell |
| CN104561964B (en) * | 2014-12-24 | 2017-01-25 | 北京科技大学 | Method for preparing ZnO thin film in a controlled manner |
| CN114956159A (en) * | 2022-06-20 | 2022-08-30 | 江南大学 | Preparation method of hydrangea-shaped nano zinc oxide |
-
2006
- 2006-10-25 CN CNB2006101175649A patent/CN100523297C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| 花状氧化锌的制备与控制生长. 张艳辉，田彦文，邵忠财等.过程工程学报，第6卷第2期. 2006 |
| 花状氧化锌的制备与控制生长. 张艳辉，田彦文，邵忠财等.过程工程学报，第6卷第2期. 2006 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1944708A (en) | 2007-04-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100523297C (en) | Method for hydrothermally synthesizing series flower shape zinc oxide micron/nano structure | |
| CN100383049C (en) | Method of growing nano-rod shaped zinc oxide by hydrothermal decomposition | |
| Liu et al. | Synthesis of single-crystalline anatase nanorods and nanoflakes on transparent conducting substrates | |
| CN100590893C (en) | II-VI family semiconductor thin film used for the photovoltaic cell | |
| CN102583504B (en) | Method for preparation and regulation of surface-roughness ZnO nano-cone or nanorod array | |
| Li et al. | Photo-to-current response of Bi 2 Fe 4 O 9 nanocrystals synthesized through a chemical co-precipitation process | |
| CN108409157A (en) | A kind of ZnIn2S4 nanometer wafer arrays structure and preparation method thereof | |
| CN106986373A (en) | A kind of preparation method of ZnO nanorod | |
| CN102383114A (en) | Vanadium dioxide thin film and preparation method thereof | |
| CN100376473C (en) | Method for preparing polycrystalline Nano film of zinc selenide | |
| CN101880054A (en) | Method for preparing hollow zinc oxide microspheres | |
| CN109694101B (en) | SnO (stannic oxide)2@ ZnO nano composite material and preparation method thereof | |
| CN100567163C (en) | A kind of method for preparing copper doped zinc oxide nanoline | |
| CN101439873B (en) | Method for titania film growth in fluorine-based aqueous solution | |
| CN103489942A (en) | Light trapping structure based on nano-zinc oxide silicon heterojunction battery, and preparation method of the light trapping structure | |
| CN101235475A (en) | Method for preparing copper indium sulfide thin film | |
| CN104264211A (en) | High temperature solvent thermal preparation method and applications of monocrystalline submicron Cu2ZnSnS4 particle | |
| Ravichandran et al. | CdS films from two different low cost techniques for solar cell applications–a comparative study | |
| Ma et al. | Synthesis of Cu2ZnSnS4 thin film through chemical successive ionic layer adsorption and reactions | |
| CN109052988A (en) | A kind of preparation method of zinc indium sulphur nano-chip arrays film | |
| CN101863451A (en) | Method for preparing zinc oxide in three-dimensional nanostructure with cryogenic fluid method | |
| CN102219253A (en) | Solution method for preparing zinc oxide with ultra-two-dimensional nano structure | |
| CN107937969A (en) | A kind of GN Sb2Se3The preparation method of laminated film | |
| CN102181850B (en) | In-situ synthesis method for zinc oxide nano film | |
| CN101445267B (en) | Method for Preparing black zinc oxide and application of black zinc oxide |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090805 Termination date: 20111025 |