CN105110363B - Method for preparing zinc oxide microtubes - Google Patents
Method for preparing zinc oxide microtubes Download PDFInfo
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- CN105110363B CN105110363B CN201510493163.2A CN201510493163A CN105110363B CN 105110363 B CN105110363 B CN 105110363B CN 201510493163 A CN201510493163 A CN 201510493163A CN 105110363 B CN105110363 B CN 105110363B
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- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
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Abstract
The invention provides a method for preparing a zinc oxide micron tube, which is applied to the field of micron tube preparation and comprises the following steps: providing a gallium nitride substrate with the surface coated with photoresist in a spinning mode, and a mixed solution obtained by mixing zinc nitrate and hexamethylene tetramine according to the same preparation proportion; photoetching one surface of the gallium nitride substrate, which is coated with the photoresist in a rotating mode, and preparing a hole array on the gallium nitride substrate; and placing the gallium nitride substrate with the prepared hole array in the mixed solution for reaction, and preparing the zinc oxide microtubes growing longitudinally at the edge of each hole of the hole array. Compared with the existing preparation method of the micron tube, the preparation method of the invention has the advantages of simple preparation process, low equipment requirement, good controllability and capability of realizing rapid, efficient and large-scale controllable preparation.
Description
Technical Field
The invention relates to the technical field of micron tube preparation, in particular to a method for preparing a zinc oxide micron tube.
Background
In the prior art, there are documents [1] and [2] that report CVD preparation schemes of ZnO nanotubes. The method takes ZnO nanobelts and pure NaCl as raw materials, takes an Au film as a catalyst, carries out reaction in a horizontal high-temperature furnace under the protection of argon, and carries out reaction for 2H at the reaction temperature of 860 ℃ and cooling to room temperature to obtain the nano-ZnO/NaCl/Au. The basic principle is as follows: (a) dissolving gaseous Zn, O2 raw material into the interface of the molten NaCl melt and Au; (b) because the specific surface area of the Au particles is high, ZnO nucleates at the edges of the Au particles, and then tubular ZnO nuclei are formed at the interfaces of Au and Nacl; (c) the tubular nucleus grows upwards to form a ZnO micron tube.
There is also a document [3] that reports another method for preparing a ZnO nanotube by a high-temperature CVD method, which realizes a tubular structure by changing the partial pressure of Zn vapor in a reaction atmosphere. Firstly, synthesizing a Zn-rich ZnO column in high Zn steam partial pressure, and then reducing the Zn partial pressure to volatilize or reoxidize Zn-rich in ZnO to generate a micron tubular structure.
In practical implementation, the two existing methods have the disadvantages that the reaction is carried out at high temperature, the reaction conditions are harsh, the requirements on equipment are high, and the energy consumption is high.
In addition, in the prior art, there is also a document [4] that reports that a ZnO microtube is grown by a hydrothermal method in which a ZnO microtube is grown first (day 1), and then a (002) plane is dissolved in the [001] direction in the next day by utilizing the difference in stability of different crystal planes of the ZnO column. The method has the disadvantages that long reaction time is needed, and the control of parameters such as pipe diameter and the like is difficult.
In conclusion, the existing technology for preparing the ZnO micron tube is difficult to control parameters such as the growth position, the tube diameter and the like of the micron tube, has high preparation cost, and is not energy-saving and environment-friendly. Therefore, there is a need for improvements in the prior art.
With the information of the documents involved:
[1]Kong,X.H.and Y.D.Li,Ultraviolet-emitting ZnOmicrotube arraysynthesized by a catalyst-assisted flux method.Chemistry Letters,2003.32(11):p.1062-1063.
[2] wangzhou, Zhang Shuanmin, an Liutaiqi, micron tube preparation and application progress in the chemical world, 2005(12) p.52-56.
[3]Yan,Y.G.,etal.,Afeasible routeto prepare hollow ZnOmicrotube viamodulating reagent's vapor pressure and growth temperature.Journal ofMaterials Research,2013.28(6):p.897-904.
[4]Vayssieres,L.,etal.,Three-dimensional array of highly orientedcrystalline ZnOmicrotubes.Chemistry of Materials,2001.13(12):p.4395-+.
Disclosure of Invention
In view of the above drawbacks of the prior art, an object of the present invention is to provide a method for preparing a zinc oxide microtube, which is used to solve the problems that the control of the parameters such as the growth position and the diameter of the microtube is difficult, the preparation cost is high, and the energy saving and environmental protection are not sufficient in the prior art for preparing the ZnO microtube.
In order to achieve the above objects and other related objects, the present invention provides the following technical solutions:
a method of making a zinc oxide microtube, comprising: providing a gallium nitride substrate with the surface coated with photoresist in a spinning mode, and a mixed solution obtained by mixing zinc nitrate and hexamethylene tetramine according to the same preparation proportion; photoetching one surface of the gallium nitride substrate, which is coated with the photoresist in a rotating mode, and preparing a hole array on the gallium nitride substrate; placing the gallium nitride substrate with the prepared hole array in the mixed solution for reaction, and preparing a longitudinally-grown zinc oxide micron tube at the edge of each hole of the hole array; after the photolithography is completed, the gallium nitride substrate with the etched hole array needs to be subjected to plasma cleaning.
As a preferable embodiment of the above method for preparing the zinc oxide microtube, the tube diameter of the prepared zinc oxide microtube is determined by the aperture of each hole in the hole array.
As a preferable embodiment of the above method for preparing the zinc oxide microtube, the wall thickness of the prepared zinc oxide microtube is determined by the pore diameter of each pore in the pore array, the concentration of the mixed solution and the reaction time.
As a preferable embodiment of the above method for preparing the zinc oxide microtube, the length of the prepared zinc oxide microtube is determined by the concentration of the mixed solution and the reaction time.
As a preferable embodiment of the above method for producing a zinc oxide microtube, the method for performing plasma cleaning includes: and cleaning the gallium nitride substrate for 1-3 minutes in an air atmosphere at the power of 100W.
As a preferable embodiment of the above method for preparing a zinc oxide microtube, the method for preparing the zinc oxide microtube in the mixed solution comprises: and placing the gallium nitride substrate prepared with the hole array in the mixed solution for 3-5 hours, and keeping the reaction temperature at a constant temperature of 90 ℃.
As a further optimization of the method for preparing the zinc oxide microtube and the preferable scheme thereof, the concentration of the zinc nitrate solution is 0.5mol/L, and the concentration of the Hexamethylenetetramine (HMTA) solution is 0.5 mol/L.
As a further optimization of the method for preparing the zinc oxide micron tube and the preferable scheme thereof, the photoresist is s1805 photoresist.
The invention processes the substrate by means of photoetching, thus realizing the control of parameters such as growth position, pipe diameter and the like of the micron pipe, and compared with the high-temperature method in the prior art, the method has the advantages of energy saving, environmental protection and low cost; compared with other hydrothermal growth schemes, the method has the advantages of good controllability, rapid synthesis and convenience.
Drawings
Fig. 1 shows a flow chart of a method for preparing a zinc oxide microtube.
FIGS. 2-1 to 2-3 are schematic views showing the process for preparing the zinc oxide micron tube according to the present invention.
Description of the reference numerals
1 growth substrate
11 lithographic aperture
2 nucleation of nuclear factor
3 zinc oxide micron tube
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It is to be noted that the features in the following embodiments and examples may be combined with each other without conflict.
It should be noted that the drawings provided in the following embodiments are only for illustrating the basic idea of the present invention, and the components related to the present invention are only shown in the drawings rather than drawn according to the number, shape and size of the components in actual implementation, and the type, quantity and proportion of the components in actual implementation may be changed freely, and the layout of the components may be more complicated.
Referring to fig. 1, a flow chart of a method for preparing a zinc oxide microtube is provided, and the following will explain the technical scheme of the method in detail:
s11, providing a gallium nitride substrate with a surface coated with a photoresist in a spinning mode and a mixed solution obtained by mixing zinc nitrate and hexamethylene tetramine according to the same preparation proportion.
In the specific implementation, before the photoresist is spin-coated on the gallium nitride substrate, the surface of the gallium nitride substrate needs to be cleaned and then coated with the photoresist. In addition, the photoresist spin-coated on the surface of the gallium nitride substrate is s1805 photoresist.
In addition, zinc nitrate (Zn (NO) is added to the mixed solution3)2) The concentration of (1) is 0.5mol/L, and the concentration of hexamethylene tetramine (HMTA) is 0.5mol/L, wherein, zinc nitrate and hexamethylene tetramine are mixed according to the preparation ratio of 1:1, and the mixed solution for reaction is obtained.
And S13, performing photoetching treatment on the surface of the gallium nitride substrate coated with the photoresist in a rotating mode, and preparing a hole array on the gallium nitride substrate.
In a specific implementation, an array of holes is etched in a gallium nitride substrate, i.e., a plurality of holes are etched in an array in a gallium nitride substrate. After the completion of the photolithography, the gallium nitride substrate on which the hole array is etched needs to be plasma-cleaned for several minutes, and generally, the photoresist remaining in the hole portion on the gallium nitride substrate is removed by cleaning for about 2 minutes in an air atmosphere at a power of 100W.
S15, placing the gallium nitride substrate with the prepared hole array in the mixed solution for reaction, and preparing the zinc oxide microtubes growing longitudinally at the edge of each hole of the hole array.
In specific implementation, the gallium nitride substrate with the prepared hole array is placed in the mixed solution to react under the general condition that the gallium nitride substrate is placed in the mixed solution and is kept at a constant temperature of 90 ℃ to react for about 4 hours, and the hole-shaped zinc oxide microtube array can be prepared on the gallium nitride substrate along the hole array.
In particular implementations, the size of the lithographic aperture, growth time, and mixing can be variedThe solution concentration is combined to control the parameters of the pipe diameter, the wall thickness and the like of the micron pipe. Specifically, the diameter of the micron tube is mainly controlled by the photoetching aperture: phiOuter (ZnOMT)≈ΦHole(s). The length depends on the concentration and the time of the growth mother liquor, and under the same growth time condition, the concentration is increased and the length is increased; under the same concentration condition, the time and the length are increased, wherein the first 1.5 hours is a rapid increase period, and the later increase is slow. The thickness of the micron tube wall is related to the size of a photoetching hole and the concentration and time of growth mother liquor, and under the condition of the same aperture and growth time, the concentration is increased and the thickness is increased; under the same conditions of pore size and concentration, the time is increased, and the thickness is also increased.
Specifically, please refer to the following experimental examples:
experiment 1:
the diameter of the photoetching hole is 6 mu m, in Zn (NO)3)2(0.05molL-1) With HMTA (0.05mol L-1)1/1 the resultant microtube was hexagonal side by side at a distance of about 6 μm and diagonal side at a distance of about 7 μm at 90 deg.C for 12 hours. The length is about 4 μm and the wall thickness is 2 to 3 μm.
Experiment 2:
the diameter of the photoetching hole is 2 mu m, in Zn (NO)3)2(0.05molL-1) With HMTA (0.05mol L-1)1/1 the resultant microtube was hexagonal with a side-to-side distance of about 2 μm and a diagonal distance of about 3 μm at 90 deg.C for 12 hours in a mixed solution. The length is about 4 μm and the wall thickness is 1 μm.
Experiment 3:
the diameter of the photoetching hole is 6 mu m, in Zn (NO)3)2(0.05molL-1) With HMTA (0.05mol L-1)1/1 the resultant microtube had a hexagonal side-to-side distance of about 6 μm and a diagonal distance of about 7 μm at 90 deg.C for 2 hours. The length is about 2 μm and the wall thickness is 2 μm.
Experiment 4:
the diameter of the photoetching hole is 6 mu m, in Zn (NO)3)2(0.5molL-1) With HMTA (0.5mol L)-1)1/1 the resultant microtube had a hexagonal side-to-side distance of about 6 μm and a diagonal distance of about 7 μm at 90 deg.C for 2 hours.The length is about 3 μm and the wall thickness is 2 μm.
With reference to FIGS. 2-1 to 2-3, a schematic diagram of the process for preparing the zinc oxide micron tube of the present invention is shown. Wherein, fig. 2-1 is a growth substrate 1 (gallium nitride substrate) of the photolithographic aperture array 11; FIG. 2-2 is a graph showing that nucleation 2 is formed along the edge of a photo-etched hole by zinc oxide (ZnO) generated after the growth substrate 1 in FIG. 2-1 is placed in a mixed solution; fig. 2-3 shows that based on fig. 2-2, the nucleation 2 continues the ZnO growth and fusion to generate a tubular structure, namely a zinc oxide microtube 3.
In summary, the present invention photolithographically processes the ZnO growth substrate to nucleate ZnO along the edges of the photolithograph holes, the grown ZnO seeds are fused together with a void in the middle, thereby forming a tubular structure. Compared with the existing preparation method, the preparation process of the ZnO micron tube is simple, the equipment requirement is low, the controllability is good, and the rapid, efficient and large-scale controllable preparation can be realized.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (9)
1. A method for preparing a zinc oxide microtube, comprising:
providing a gallium nitride substrate with the surface coated with photoresist in a spinning mode, and a mixed solution obtained by mixing zinc nitrate and hexamethylene tetramine according to the same preparation proportion;
photoetching one surface of the gallium nitride substrate, which is coated with the photoresist in a rotating mode, and preparing a hole array on the gallium nitride substrate, wherein the diameter of a photoetching hole is 2-6 micrometers;
placing the gallium nitride substrate with the prepared hole array in the mixed solution for reaction, and preparing a zinc oxide micron tube growing longitudinally at the edge of each hole of the hole array, wherein the tube diameter of the zinc oxide micron tube is 2-6 microns, the wall thickness of the zinc oxide micron tube is 1-3 microns, and the length of the zinc oxide micron tube is 1-4 microns;
after the photolithography is completed, the gallium nitride substrate on which the array is etched needs to be subjected to plasma cleaning.
2. The method of claim 1, wherein the diameter of the prepared zinc oxide microtube is determined by the diameter of each hole in the hole array.
3. The method of claim 1, wherein the wall thickness of the prepared zinc oxide nanotubes is determined by the pore size of each pore in the pore array, the concentration of the mixed solution and the reaction time.
4. The method of preparing zinc oxide nanotubes according to claim 1, wherein the length of the prepared zinc oxide nanotubes is determined by the concentration of the mixed solution and the reaction time.
5. The method for preparing zinc oxide microtubes according to claim 3, wherein the method of performing plasma cleaning comprises: and cleaning the gallium nitride substrate for 1-3 minutes in an air atmosphere at the power of 100W.
6. The method for preparing a zinc oxide microtube according to claim 1, wherein the method for preparing the zinc oxide microtube in the mixed solution comprises:
and placing the gallium nitride substrate with the prepared hole array in the mixed solution for 3-5 hours, and keeping the reaction temperature at 90 ℃ for constant temperature.
7. The method for preparing zinc oxide microtubes according to any one of claims 1 to 5, wherein the concentration of the solution of zinc nitrate is 0.5 mol/L.
8. The method for preparing zinc oxide microtubes according to claim 6, wherein the solution concentration of Hexamethylenetetramine (HMTA) is 0.5 mol/L.
9. The method for preparing zinc oxide microtubes according to any one of claims 1-5, wherein the photoresist is s1805 photoresist.
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| CN105154974B (en) * | 2015-09-28 | 2018-01-26 | 中国科学院重庆绿色智能技术研究院 | A kind of method for retouching side growth ZnO |
Citations (4)
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| CN101618852A (en) * | 2009-08-07 | 2010-01-06 | 复旦大学 | Method for growing patterned zinc oxide nano rod array based on nano stamping technology |
| CN102476823A (en) * | 2010-11-23 | 2012-05-30 | 国家纳米科学中心 | Zinc oxide micro-nano array and preparation method thereof |
| CN102553812A (en) * | 2012-01-04 | 2012-07-11 | 兰州大学 | Preparation method of super-hydrophobic surface |
| CN102751418A (en) * | 2012-07-24 | 2012-10-24 | 山东大学 | LED (light-emitting diode) tube core with ZnO-micron and nano composite structure and preparation method thereof |
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| CN102799063B (en) * | 2012-07-20 | 2013-11-20 | 北京科技大学 | Method for preparing photoresist template and patterned ZnO nanorod array |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101618852A (en) * | 2009-08-07 | 2010-01-06 | 复旦大学 | Method for growing patterned zinc oxide nano rod array based on nano stamping technology |
| CN102476823A (en) * | 2010-11-23 | 2012-05-30 | 国家纳米科学中心 | Zinc oxide micro-nano array and preparation method thereof |
| CN102553812A (en) * | 2012-01-04 | 2012-07-11 | 兰州大学 | Preparation method of super-hydrophobic surface |
| CN102751418A (en) * | 2012-07-24 | 2012-10-24 | 山东大学 | LED (light-emitting diode) tube core with ZnO-micron and nano composite structure and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| Direct-current nanogenerator based on ZnO nanotube arrays;Y. Xi, et al.;《Physica status solidi(RRL)-Rapid Research Letters》;20111231;第5卷(第2期);77-79 * |
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