CN1188901C - Methof for preparing 3-D orientation zinc oxide film - Google Patents
Methof for preparing 3-D orientation zinc oxide film Download PDFInfo
- Publication number
- CN1188901C CN1188901C CNB031167985A CN03116798A CN1188901C CN 1188901 C CN1188901 C CN 1188901C CN B031167985 A CNB031167985 A CN B031167985A CN 03116798 A CN03116798 A CN 03116798A CN 1188901 C CN1188901 C CN 1188901C
- Authority
- CN
- China
- Prior art keywords
- zinc
- oxide film
- substrate
- deionized water
- minutes
- 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)
- Surface Treatment Of Glass (AREA)
Abstract
The present invention relates to a method for preparing zinc oxide film with three-dimensional orientation. Firstly, zinc salt, ammonia water and ammonium salt are dissolved in deionized water according to a certain proportion for preparing reaction liquid for the growth of film; then, a treated base plate is soaked in the prepared reaction liquid for the growth of the film, the reaction liquid is heated to 94 to 97 DEG C after the base plate is presoaked for 30 to 60 minutes, and the tight zinc oxide film with the arrangement of the three-dimensional orientation can be obtained after a reaction for 30 to 60 minutes. The method of the present invention has simple operation, low cost and short production period; the prepared zinc oxide film is composed of micrometer sticks in three-dimensional arrangement, and the micrometer sticks has the average grain size of 200 nm and the length of 5 micrometer.
Description
Technical field:
The present invention relates to a kind of preparation method of 3 D tropism zinc-oxide film, be specifically related to adopt chemical solution method to prepare zinc-oxide film.Belong to the inorganic thin film preparing technical field.
Background technology:
Zinc-oxide film is a kind of good semi-conducting material, it has good photoelectric functional owing to having bigger energy gap width (similar with gallium nitride), thereby has a wide range of applications in fields such as gas sensitive, luminescent material, photoelectric conversion material, rheostat materials.Be orientated and Zinc oxide film material that three-dimensional orientation is arranged has stronger piezoelectricity and piezooptical effect according to the C axle, can with utter a word, electric installation, such as the bulk acoustic wave material with give birth to film Resonator, filter and scanning of image etc. on the surface wave material.Preparation method about zinc-oxide film reports more in recent years.But only having minority can prepare according to the C axle in these methods is orientated and the Zinc oxide film material of three-dimensional orientation arrangement, and these methods overwhelming majority concentrates on gas phase synthesis method, for example chemical vapor deposition (CVD), magnetron sputtering method, spray pyrolysis, pulsed laser deposition (PLD), atomic-layer epitaxial growth method and molecular beam epitaxy etc.There are shortcomings such as reaction temperature height, equipment complexity, cost height, efficient be low in these gas phase process.
Summary of the invention:
The objective of the invention is at the deficiencies in the prior art, provide a kind of simple to operate, the preparation method of the 3 D tropism zinc-oxide film that reaction temperature is low, cost is low, production efficiency is high.
For realizing such purpose, in the technical scheme of the present invention, adopt chemical solution method to prepare zinc-oxide film.The substrate of handling is immersed in zinc salt, ammoniacal liquor and the ammonium salt mixed solution for preparing, after 30～60 minutes, be warming up to 94～97 ℃, react the zinc-oxide film that 3 D tropism is arranged that has that can obtain densification in 30～60 minutes in pre-soaking.The zinc-oxide film of preparation is made up of the micron bar of three-dimensional arrangement, and average grain diameter is 200nm, length 5 μ m.
Preparation method of the present invention comprises following concrete steps:
1. the preparation of film growth reactant liquor: zinc salt, ammoniacal liquor and ammonium salt are dissolved in deionized water by a certain percentage, are prepared into the film growth reactant liquor.Contain zinc salt 0.01mol, 25% (mass ratio) ammoniacal liquor 5ml and ammonium salt 0.002mol in every 100ml aqueous solution.
The said zinc salt of the present invention is zinc nitrate hexahydrate or acetic anhydride zinc; Ammonium salt is anhydrous nitric acid ammonium or ammonium chloride.
2. the preliminary treatment of substrate: at first substrate was immersed in 98% the concentrated sulfuric acid of boiling 5～10 hours, was immersed in then in the acetone soln ultrasonic 30～60 minutes, next use a large amount of deionized water rinsings, at last substrate is dried in vacuum drying oven, stand-by.
The said substrate of the present invention is sheet glass or quartz substrate.
3. the 3 D tropism zinc-oxide film is synthetic: before reaction, at first substrate was soaked in the above-mentioned film growth reaction solution for preparing 30～60 minutes; Be warming up to 94～97 ℃ then, heating rate 10～20 degree/minute, reacted 30～60 minutes down at 94～97 ℃.Reaction finishes the back cools off fast with frozen water, substrate is put in deionized water for ultrasonic 1～2 minute then, uses a large amount of deionized water rinsings, can obtain the 3 D tropism zinc-oxide film through drying naturally after repeatedly washing.
Excellent results of the present invention is:
1. owing to adopted the cushioning liquid of ammoniacal liquor and ammonium salt as reactant liquor, make in the process of zinc-oxide film growth reaction solution pH value keep stable to a certain extent, this even growth for film provides good growing environment, thereby the zinc-oxide film good uniformity of preparation.
2. because the chemical solution method reaction temperature that the present invention adopts is low, have only 94～97 ℃, reaction time is short, the shortest need 30 minutes, reaction raw materials is cheap, only needs zinc salt, ammoniacal liquor and ammonium salt commonly used, thereby the inventive method is simple to operate, cost is low, the efficient height, the zinc-oxide film of preparation is by width 200 nanometers, and the hexagonal bar that length is 5 microns aligns composition.
Description of drawings:
Fig. 1 is the x-ray diffraction pattern of the embodiment of the invention 1 resulting 3 D tropism zinc-oxide film.
Fig. 2 is the electron scanning micrograph of the embodiment of the invention 1 resulting 3 D tropism zinc-oxide film.
Embodiment:
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1:
1. in the ptfe plastic bottle of a 100mL, 0.01mol zinc nitrate, 0.002mol ammonium chloride are dissolved in the 95mL deionized water, be stirred to the ammoniacal liquor that adds 5ml 25% after whole dissolvings, continue in the time of adding to stir, just be prepared into the reactant liquor of zinc-oxide film growth after the solution clarification.
2. quartz substrate that will the wide 20mm of long 50mm is immersed in the concentrated sulfuric acid of boiling, and soak and immerse again in the acetone soln after 10 hours, ultrasonic 30 minutes, use a large amount of deionized water rinsings again, it is dry to put into vacuum drying oven at last.
3. will be immersed in according to the quartz substrate that 2. step is handled according in the reactant liquor that is 1. disposed, soak 30 minutes, then reaction bulb be placed oil bath pan, according to 10 the degree/minute speed reaction temperature is risen to 95 ℃, kept 30 minutes.Then quartz substrate is immersed in the frozen water territory and cools off.After the cooling quartz substrate is immersed in deionized water for ultrasonic 2 minutes, uses a large amount of deionized water rinsings again.With airing under the quartz substrate room temperature, promptly obtain the zinc-oxide film that aligns at last.
X-ray diffraction spectrogram such as Fig. 1 of resultant zinc-oxide film, prepared as seen from Figure 1 zinc oxide are hexagonal crystal shape, and other crystal faces of the ratio of 002 crystal face exceed a lot, and the prepared zinc oxide of this explanation has very strong orientation on 001 direction.Electron scanning micrograph such as Fig. 2, prepared as seen from Figure 2 zinc-oxide film is made up of the micron bar of hexagonal prism shape, and the diameter of oxidation zinc bar is about 200 nanometers, about 5 microns of length, draw ratio is about 25.
Embodiment 2:
1. in the ptfe plastic bottle of a 100mL, 0.01mol zinc acetate, 0.002mol ammonium chloride are dissolved in the 95mL deionized water, be stirred to the ammoniacal liquor that adds 5ml 25% after whole dissolvings, continue in the time of adding to stir, just be prepared into the reactant liquor of zinc-oxide film growth after the solution clarification.
2. sheet glass that will the wide 20mm of long 50mm is immersed in the concentrated sulfuric acid of boiling, and soak and immerse again in the acetone soln after 10 hours, ultrasonic 60 minutes, use a large amount of deionized water rinsings again, it is dry to put into vacuum drying oven at last.
3. will be immersed in according to the glass substrate that 2. step is handled according in the reactant liquor that is 1. disposed, soak 60 minutes, then reaction bulb be placed oil bath pan, according to 20 the degree/minute speed reaction temperature is risen to 97 ℃, kept 60 minutes.Then glass substrate is immersed in the frozen water territory and cools off.After the cooling glass substrate is immersed in deionized water for ultrasonic 1 minute, uses a large amount of deionized water rinsings again.To dry under the glass substrate room temperature at last.Promptly obtain the zinc-oxide film that aligns.
Embodiment 3:
1. in the ptfe plastic bottle of a 100mL, 0.01mol zinc nitrate, 0.002mol ammonium nitrate are dissolved in the 95mL deionized water, be stirred to the ammoniacal liquor that adds 5ml 25% after whole dissolvings, continue in the time of adding to stir, just be prepared into the reactant liquor of zinc-oxide film growth after the solution clarification.
2. quartz plate that will the wide 20mm of long 50mm is immersed in the concentrated sulfuric acid of boiling, and soak and immerse again in the acetone soln after 8 hours, ultrasonic 45 minutes, use a large amount of deionized water rinsings again, it is dry to put into vacuum drying oven at last.
3. will be immersed in according to the quartz substrate that 2. step is handled according in the reactant liquor that is 1. disposed, soak 45 minutes, then reaction bulb be placed oil bath pan, according to 15 the degree/minute speed reaction temperature is risen to 94 ℃, kept 45 minutes.Then quartz substrate is immersed in the frozen water territory and cools off.After the cooling quartz substrate is immersed in deionized water for ultrasonic 1 minute, uses a large amount of deionized water rinsings again.To dry under the quartz substrate room temperature at last.Promptly obtain the zinc-oxide film that aligns.
Claims (2)
1, a kind of preparation method of 3 D tropism zinc-oxide film is characterized in that comprising the steps:
1. the preparation of film growth reactant liquor: zinc salt, ammoniacal liquor and ammonium salt are dissolved in deionized water, be prepared into the film growth reactant liquor, contain zinc salt 0.01mol, mass ratio in every 100ml aqueous solution and be 25% ammoniacal liquor 5ml and ammonium salt 0.002mol, wherein said zinc salt is zinc nitrate or zinc acetate, and ammonium salt is ammonium nitrate or ammonium chloride;
2. the preliminary treatment of substrate: substrate was immersed in 98% the concentrated sulfuric acid of boiling 5～10 hours, and was immersed in then in the acetone soln ultrasonic 30～60 minutes, again with in vacuum drying oven, drying substrate stand-by behind the deionized water rinsing;
3. the 3 D tropism zinc-oxide film is synthetic: substrate was soaked in the film growth reaction solution 30～60 minutes, heat up then and react, 94～97 ℃ of reaction temperatures, heating rate 10～20 degree/minute, in 30～60 minutes reaction time, reaction finishes back cooling fast, substrate is put in deionized water for ultrasonic 1～2 minute then, with drying naturally behind the deionized water rinsing, can obtain the 3 D tropism zinc-oxide film.
2, the preparation method of 3 D tropism zinc-oxide film as claimed in claim 1 is characterized in that said substrate is sheet glass or quartz plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031167985A CN1188901C (en) | 2003-05-08 | 2003-05-08 | Methof for preparing 3-D orientation zinc oxide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031167985A CN1188901C (en) | 2003-05-08 | 2003-05-08 | Methof for preparing 3-D orientation zinc oxide film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1450599A CN1450599A (en) | 2003-10-22 |
| CN1188901C true CN1188901C (en) | 2005-02-09 |
Family
ID=28684267
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031167985A Expired - Fee Related CN1188901C (en) | 2003-05-08 | 2003-05-08 | Methof for preparing 3-D orientation zinc oxide film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1188901C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100582012C (en) * | 2006-09-26 | 2010-01-20 | 中国科学院上海硅酸盐研究所 | Nano porous zinc oxide thin film with high C-axis orientation and preparation method thereof |
| CN104561964B (en) * | 2014-12-24 | 2017-01-25 | 北京科技大学 | Method for preparing ZnO thin film in a controlled manner |
-
2003
- 2003-05-08 CN CNB031167985A patent/CN1188901C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1450599A (en) | 2003-10-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lu et al. | Hydrothermal growth of large-scale micropatterned arrays of ultralong ZnO nanowires and nanobelts on zinc substrate | |
| Droepenu et al. | Zinc oxide nanoparticles synthesis methods and its effect on morphology: A review | |
| Amin et al. | Influence of pH, precursor concentration, growth time, and temperature on the morphology of ZnO nanostructures grown by the hydrothermal method | |
| Zhang et al. | Site-specific nucleation and growth kinetics in hierarchical nanosyntheses of branched ZnO crystallites | |
| CN100383049C (en) | Method of growing nano-rod shaped zinc oxide by hydrothermal decomposition | |
| Xu et al. | Synthesis and photoluminescence of assembly-controlled ZnO architectures by aqueous chemical growth | |
| Haque et al. | Study of zinc oxide nano/micro rods grown on ITO and glass substrates | |
| CN100352970C (en) | Process of preparing directionally arranged nanometer titania rods on the surface of metal titanium | |
| CN101049924A (en) | Method for producing Nano carbon tube clad by metallic sulfide | |
| CN102181927A (en) | Method for preparing zinc oxide nano-array on flexible substrate at low temperature | |
| CN100346457C (en) | Production and producer for cadmium sulfide | |
| Kardeş et al. | Photocatalyst ZnO nanorod arrays on glass substrates: the critical role of seed layer in nanorod alignment and photocatalytic efficiencies | |
| Xu et al. | Rapid fabrication of luminescent Eu: YVO4 films by microwave-assisted chemical solution deposition | |
| Kumar et al. | Synthesis of ZnO nanostructures | |
| CN1234611C (en) | Method for preparing zinc oxide nanometer material with orientation arrangement nano-tubes | |
| CN1188901C (en) | Methof for preparing 3-D orientation zinc oxide film | |
| Bobkov et al. | Fabrication of oxide heterostructures for promising solar cells of a new generation | |
| CN1234610C (en) | Method for preparing zinc oxide nanometer material with orientation arrangement nano-towers | |
| Kaneva et al. | Microwave-assisted and conventional sol-gel preparation of photocatalytically active ZnO/TiO 2/glass multilayers | |
| CN105669197A (en) | Method for preparing SBN (Sr0.5Ba0.5Nb2O6) nano-powder with improved sol-gel method | |
| Lang et al. | Synthesis and optical properties of ZnO nanorods | |
| Shaban et al. | Influence of growth time on the morphology of ZnO nanostructures prepared by low-temperature chemical bath deposition | |
| CN111730063B (en) | Preparation method of lead nanowire | |
| CN103276382B (en) | Preparation method for titanium dioxide array film with branch nano-structure and product and use thereof | |
| CN1843934A (en) | Method for preparing zinc oxide film |
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 | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |