CN1995481A - Method for preparing diverse microcosmic appearance zinc oxide film - Google Patents
Method for preparing diverse microcosmic appearance zinc oxide film Download PDFInfo
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- CN1995481A CN1995481A CN 200610130120 CN200610130120A CN1995481A CN 1995481 A CN1995481 A CN 1995481A CN 200610130120 CN200610130120 CN 200610130120 CN 200610130120 A CN200610130120 A CN 200610130120A CN 1995481 A CN1995481 A CN 1995481A
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/005—Epitaxial layer growth
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- Crystallography & Structural Chemistry (AREA)
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Abstract
The invention discloses a making method of zinc oxide film with different microscopic shape, which comprises the following steps: (1) preparing crystal layer of substrate surface; growing oriented crystal in the growing liquid; (2) adjusting pH value of nitric acid to 9. 8; obtaining ZnO pipe-typed crystal film twice; using 25% ammonia to adjust pH value of growing liquid to 9. 2 twice; obtaining surface villus-shaped bar-crystal.
Description
Technical field
The invention relates to the preparation method of ZnO film, relate in particular to the preparation method of the ZnO film of diverse microcosmic appearance.
Background technology
Zinc oxide (ZnO) is a kind of important n of II-VI family molded breadth bandgap semiconductor functional materials, normal is stable hexagonal wurtzite crystalline structure, band gap width is 3.37eV under the room temperature, and exciton bind energy has strong free exciton transition luminescence up to 60meV at ultraviolet band.Along with the microminiaturization of electron device, the development of lighting, the ZnO film of diverse microcosmic appearance as wire, tubulose, bar-shaped etc., is an another in the world research focus after the GaN semiconductor material in recent years.Because ZnO film has unique character such as optics, electricity and acoustics, add that raw material resources is abundant, low price, toxicological harmless is suitable for the epitaxy of film and it is with a wide range of applications at aspects such as photodiode, electronic detector, surface acoustic wave strainer, gas sensor and solar cells.
Prepare at present the method that the specific morphology high quality ZnO film adopted and mainly contain gas-liquid-solid method (VLS), chemical Vapor deposition process (CVD), template, aqua-solution method etc.In these methods, VLS and CVD method need be than complex apparatus, higher temperature and metal catalysts, be not suitable for the large-area preparation film, template causes the destruction of subsiding of film and pattern easily in the process of removing template, and the uniform film of large-area preparation also has difficulties.Aqua-solution method is compared with other method, and equipment is simple, and the reaction conditions gentleness need not catalyzer, and environmental friendliness is the Perfected process of large-area preparation ZnO film.In March, 2003, Vayssieres has reported the article that is entitled as " Growth of arrayedZnO nanorods and nanowires from aqueous solutions " (aqua-solution method prepares ZnO nanometer rod and nano-wire array) first at U.S.'s periodical " Advanced materials " (advanced material), use aqua-solution method at Zn (NO
3)
26H
2O/C
6H
12N
4Architectural study the brilliant array film preparation of ZnO rod/wire.Afterwards, Zn (NO
3)
26H
2O/NaOH water solution system and Zn (NO
3)
26H
2O/NH
3H
2O water solution system etc. also is used to preparation ZnO in succession and is orientated brilliant array.Because aqua-solution method is grown to the equilibrium process of dissolution-recrystallization, and Zn (NO
3)
26H
2O/NH
3H
2In the O water solution system, the ionization equilibrium of ammoniacal liquor can be realized shock absorption, therefore helps improving the stability of growth media.Therefore, compare with other system, the ammonia soln system can realize the preparation of ZnO film in the pH value scope of broad under certain zinc concentration.
The subject matter that exists is at present: when guaranteeing that suitable growth media compositional system is kept ZnO crystal process of growth stability, in order to satisfy the requirement of multiple pattern, still do not have a kind of method of simple and easy change ZnO array film microscopic appearance.
Summary of the invention
The present invention adopts Zn (NO guaranteeing the stable of aqua-solution method ZnO orientation crystals growth process
3)
26H
2O/NH
3H
2The O water solution system, under the prerequisite of the neat bar-shaped brilliant array film of ZnO uniformly of preparation on the glass substrate, the method that provides a kind of in-site secondary to regulate growth media pH value realizes that the microscopic appearance of ZnO film changes in the aqueous solution two one-step growth modes.
The present invention is achieved by following technical solution.
(1) aqueous solution two one-step growth technologies
1. the preparation of substrate surface crystal seed layer: under the room temperature, zinc acetate is dissolved in ethylene glycol monomethyl ether and the monoethanolamine solution that is pre-mixed, zinc acetate concentration is 0.75molL
-1And the ratio of the amount of substance of monoethanolamine and zinc acetate is 1: 1; Stir 30min in 60 ℃ of lower magnetic forces and obtain evenly clarification seed solution; The cleaning glass substrate is immersed seed liquor, and dipping time is 1min, pull rate 0.85mms
-1,, repeat above operation three times in 80 ℃ of oven for drying; The substrate that will scribble film is heat-treated at last, and 550 ℃ of insulation 1.5h obtain the crystal seed film on the glass substrate;
2. be orientated crystals growth in the growth media: zinc nitrate and 25% ammoniacal liquor are added in the deionized water, the growth media of preparation 20mL, it is also airtight to stir.Initial zinc solubility scope is 0.04～0.08molL
-1, the initial pH value scope is 9.4～9.6 in the time of 90 ℃; To there be the substrate of crystal seed layer to put into the sealed beaker that growth media is housed, in 90 ℃ of water-baths, keep 4h, can obtain the bar-shaped brilliant array film of ZnO of the vertical substrate growth of preferred orientation;
(2) in-site secondary is regulated the pH value
1. use the nitric acid secondary to regulate growth media pH value to 9.8, and continue to remain on 6h in 90 ℃ of water-baths, can obtain the brilliant array film of ZnO tubulose.Last synthetic film washed with de-ionized water is dried in the air;
2. use 25% ammoniacal liquor secondary to regulate growth media pH value to 9.2, and continue to remain on 6h in 90 ℃ of water-baths, it is brilliant to obtain surperficial fine hair shape rod; Last synthetic film washed with de-ionized water is dried in the air.
The invention has the beneficial effects as follows,, adopt Zn (NO guaranteeing the stable of aqua-solution method ZnO orientation crystals growth process
3)
26H
2O/NH
3H
2The O water solution system, in the aqueous solution two one-step growth modes under the prerequisite of the neat bar-shaped brilliant array film of ZnO uniformly of preparation on the glass substrate, by the simple approach that the in-site secondary of pH value of water solution is regulated, the microscopic appearance of having finished ZnO film changes, and can realize the brilliant preparation of the brilliant and surperficial fine hair shape rod of tubulose.
Description of drawings
Fig. 1: be that the aqueous solution growth legal system is equipped with synoptic diagram;
Fig. 2: the shape appearance figure that is the bar-shaped brilliant surface scan electron microscope of ZnO of embodiment 1#;
Fig. 3: the shape appearance figure that is the brilliant surface scan electron microscope of the bar-shaped brilliant tubulose that transforms of ZnO of embodiment 1#;
Fig. 4: the shape appearance figure that is the bar-shaped brilliant surface scan electron microscope of ZnO of embodiment 2#;
Fig. 5: the shape appearance figure that is the bar-shaped brilliant brilliant surface scan electron microscope of surperficial fine hair shape rod that transforms of ZnO of embodiment 2#.
Embodiment
Below by drawings and Examples the present invention is further described.
Fig. 1 is the synoptic diagram that aqueous solution growth legal system of the present invention is equipped with the zinc oxide films film device of diverse microcosmic appearance.
The present invention is raw materials used, and it is pure to be chemical analysis as zinc acetate, monoethanolamine, ethylene glycol monomethyl ether, 25% ammoniacal liquor and nitric acid etc.
Specific embodiment sees the following form.
Can clearly be seen that by accompanying drawing the present invention has finished the transformation of the microscopic appearance of zinc-oxide film.Fig. 2, Fig. 3 are the patterns of the pattern of the bar-shaped brilliant surface scan electron microscope of ZnO before transforming and the brilliant surface scan electron microscope of ZnO tubulose after the conversion.Fig. 4, Fig. 5 are the patterns of the pattern of the bar-shaped brilliant surface scan electron microscope of ZnO before transforming and the brilliant surface scan electron microscope of ZnO surface fine hair shape rod after the conversion.Effect is highly desirable.
Claims (1)
1. a method for preparing diverse microcosmic appearance zinc oxide film is characterized in that, comprises the steps:
(1) aqueous solution two one-step growth technologies
1. the preparation of substrate surface crystal seed layer: under the room temperature, zinc acetate is dissolved in ethylene glycol monomethyl ether and the monoethanolamine solution that is pre-mixed, zinc acetate concentration is 0.75molL
-1And the ratio of the amount of substance of monoethanolamine and zinc acetate is 1: 1; Stir 30min in 60 ℃ of lower magnetic forces and obtain evenly clarification seed solution; The cleaning glass substrate is immersed seed liquor, and dipping time is 1min, pull rate 0.85mms
-1,, repeat above operation three times in 80 ℃ of oven for drying; The substrate that will scribble film is heat-treated at last, and 550 ℃ of insulation 1.5h obtain the crystal seed film on the glass substrate;
2. be orientated crystals growth in the growth media: zinc nitrate and 25% ammoniacal liquor are added in the deionized water, the growth media of preparation 20mL, it is also airtight to stir.Initial zinc solubility scope is 0.04～0.08molL
-1, the initial pH value scope is 9.4～9.6 in the time of 90 ℃; To there be the substrate of crystal seed layer to put into the sealed beaker that growth media is housed, in 90 ℃ of water-baths, keep 4h, can obtain the bar-shaped brilliant array film of ZnO of the vertical substrate growth of preferred orientation;
(2) in-site secondary is regulated the pH value
1. use the nitric acid secondary to regulate growth media pH value to 9.8, and continue to remain on 6h in 90 ℃ of water-baths, can obtain the brilliant array film of ZnO tubulose.Last synthetic film washed with de-ionized water is dried in the air;
2. use 25% ammoniacal liquor secondary to regulate growth media pH value to 9.2, and continue to remain on 6h in 90 ℃ of water-baths, it is brilliant to obtain surperficial fine hair shape rod; Last synthetic film washed with de-ionized water is dried in the air.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200610130120 CN100582320C (en) | 2006-12-13 | 2006-12-13 | Method for preparing diverse microcosmic appearance zinc oxide film |
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|---|---|---|---|
| CN 200610130120 CN100582320C (en) | 2006-12-13 | 2006-12-13 | Method for preparing diverse microcosmic appearance zinc oxide film |
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| CN1995481A true CN1995481A (en) | 2007-07-11 |
| CN100582320C CN100582320C (en) | 2010-01-20 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101800130A (en) * | 2010-04-19 | 2010-08-11 | 西安交通大学 | Method for preparing dye-sensitized solar cell compound light anode with zinc oxide nanometer structure |
| CN102776508A (en) * | 2012-06-05 | 2012-11-14 | 中国科学院合肥物质科学研究院 | Method for preparing high-porosity foamed aluminium-based reversible water absorption composite |
| CN103276445A (en) * | 2013-05-23 | 2013-09-04 | 南京理工大学 | Method for liquid-phase synthesis of one-dimensional nano array ZnO thin film by using seed auxiliary method |
-
2006
- 2006-12-13 CN CN 200610130120 patent/CN100582320C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101800130A (en) * | 2010-04-19 | 2010-08-11 | 西安交通大学 | Method for preparing dye-sensitized solar cell compound light anode with zinc oxide nanometer structure |
| CN101800130B (en) * | 2010-04-19 | 2011-06-22 | 西安交通大学 | Method for preparing dye-sensitized solar cell compound light anode with zinc oxide nanometer structure |
| CN102776508A (en) * | 2012-06-05 | 2012-11-14 | 中国科学院合肥物质科学研究院 | Method for preparing high-porosity foamed aluminium-based reversible water absorption composite |
| CN103276445A (en) * | 2013-05-23 | 2013-09-04 | 南京理工大学 | Method for liquid-phase synthesis of one-dimensional nano array ZnO thin film by using seed auxiliary method |
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| Publication number | Publication date |
|---|---|
| CN100582320C (en) | 2010-01-20 |
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