CN107344730A - A kind of preparation method of zinc-oxide nano column array - Google Patents
A kind of preparation method of zinc-oxide nano column array Download PDFInfo
- Publication number
- CN107344730A CN107344730A CN201710693227.2A CN201710693227A CN107344730A CN 107344730 A CN107344730 A CN 107344730A CN 201710693227 A CN201710693227 A CN 201710693227A CN 107344730 A CN107344730 A CN 107344730A
- Authority
- CN
- China
- Prior art keywords
- array
- solution
- zinc
- growth
- nano
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/11—Particle morphology extending in one dimension, e.g. needle-like with a prismatic shape
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
- C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Abstract
The present invention provides a kind of preparation method of zinc-oxide nano column array.Using the microelectronic processing technique of current technical maturity, the present invention is in the GaN template with nano-array pattern, with Zn (NO3)2With precursor aqueous solution of the HPT aqueous solution as ZnO nano post array growth, aid in being inverted growth using hydro-thermal normal gravity and prepare the ZnO nano post array of high-sequential, size uniform.Different zinc-oxide nano column arrays is grown by the nanoarray templates for making different pattern；By adjusting Zn (NO3)2Regulate and control a nanometer column dimension with HPT concentration and nano column array growth temperature.The present invention can prepare the ZnO nano post array of various high-sequentials, size uniform by adjusting different technological parameters.
Description
Technical field
The invention belongs to technical field of nano material, and in particular to a kind of preparation method of zinc-oxide nano column array.
Background technology
Zinc oxide is a kind of semiconductor material with wide forbidden band of direct band gap, short-wave long light-emitting diode, laser diode,
There is very tempting application prospect with fields such as capacity storages.ZnO nano-arrays have unique photoelectric characteristic, and having can
As the flat end face of miniature Fa-Po cavity, provided convenience condition for construction ZnO nano lasers.Apply in microelectronics and light
Electrical domain can improve the working characteristics of device, such as make ZnO nano array structures on LED surfaces, utilize surface scattering
With fiber waveguide mechanism, LED light extraction efficiency is improved；ZnO nano-arrays are assembled as reflection-proof in solar cell surface
Coating, effectively improve the photovoltaic efficiency of solar cell；Have using micro-electromechanical technology ZnO nano-arrays solid state gas sensors
There are height sensitivity and fast response time.The present invention is expected to improve photoelectric efficiency in microelectronic, in gas sensing field
Improving sensitivity, response time etc. has important application.
Patent（CN105780118 A）Disclose and a kind of zinc-oxide nano column array is prepared using electrochemical deposition method
Preparation method.Patent（CN105858712 A）Disclose one kind and utilize the adjustable zinc-oxide nano column of Hydrothermal Synthesiss optical band gap
The zinc-oxide nano column array material that the preparation method and this method of array material obtain.But this above method is prepared into
The size heterogeneity of the zinc-oxide nano column array arrived, the array degree of order are poor.
The content of the invention
In view of the above the shortcomings that prior art, it is an object of the invention to provide one kind to prepare high-sequential, size
The preparation method of uniform zinc-oxide nano column array.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of zinc-oxide nano column array, it is characterised in that specifically include following steps：
Step 1, utilize plasma enhanced chemical vapor deposition technology（PECVD）One layer of Si is deposited on GaN3N4Film, so
Nanometer embossing (nanoimprinting lithography) or electron beam lithography (electron beam are utilized afterwards
Lithography) Si3N4Film etches required nano-array pattern, and it is molten that the GaN template prepared is immersed into watery hydrochloric acid
In liquid, it is cleaned by ultrasonic；700 DEG C of rapid thermal annealing 10min in a nitrogen atmosphere；GaN template is cleaned with deionized water, finally uses nitrogen
Air-blowing is done, for future use.
Step 2, prepare Zn (NO3)2With HPT solution, the solution prepared is put into refrigerator, stood
More than 3h, the above-mentioned solution iced is mixed, is sufficiently stirred using magnetic stirring apparatus, recycle supersonic cleaning machine ultrasound shake
Swing, centrifuge removes sediment, precursor aqueous solution of the stable mixed solution as ZnO nano post array growth.
Step 3, ZnO nano post array growth step：Oven temperature is set, growth temperature is controlled at 70-95 DEG C, uses copper
Adhesive tape is fixed on GaN template on slide, is inverted in precursor aqueous solution and seals, and gravity auxiliary is inverted growth ZnO in an oven
Nano column array 3-5 hours.
Step 4, after the completion of growth, quickly sample is taken out from solution, is put into deionized water, in 80 DEG C of heating
Thermal cleaning method is used to clean up the various residues on sample on disk；The sample cleaned up is carefully picked up and is put into 70 DEG C
Baking oven in baking 10min dry, obtain ZnO nano array sample.
Further, the GaN template after being annealed in step 1 is again dipped into dilute hydrochloric acid solution, is cleaned by ultrasonic, nitrogen gas
Rapid thermal annealing under atmosphere.To remove the organic matter of remained on surface and the impurity of absorption in GaN template preparation process.
Further, Zn (NO are prepared in step 23)2With HPT solution, the solution prepared is put into
Refrigerator, more than 3h is stood, the above-mentioned solution iced is mixed.Sediment is removed using centrifuge.Fully to be mixed
Get togather, the precursor aqueous solution needed for the ZnO nano post array growth that chemical property is stable.
Further, precursor aqueous solution is preheated 5min in baking oven after the medium oven temperature of step 3 is stable, with copper adhesive tape
GaN template is fixed on slide, is inverted in preheated precursor aqueous solution and seals, gravity auxiliary is inverted growth in an oven
ZnO nano post array 3-5 hours.
This step is key of the invention, using copper adhesive tape rather than normal tape（Or other modes）It is possible to prevente effectively from
Additional impurities are introduced in precursor aqueous solution；Growth apparatus sealing reduces influence of the external environment condition to growth（Nano material growth by
Environment influences very big）；Gravity auxiliary is inverted growth and is on the one hand advantageous to ZnO nano post array length direction（Vertically downward direction）
Growth, while it is possible to prevente effectively from growth course ZnO molecules be deposited on growth templates influence nano column array life
It is long, improve the degree of order and nano-pillar surface, the flatness of side of ZnO nano post array.
Further, cleaning process is to carry out thermal cleaning in deionized water in step 4, in 80 DEG C of heating dish repeatedly
Cleaning sample.Growth terminates to adsorb or remain Zn (NO in rear ZnO nano post array3)2And HPT, use
Multiple thermal cleaning is to clean up the Zn (NO between nano column array gap3)2And HPT.
Beneficial effects of the present invention：
Nano material of the present invention, is made up of hydrothermal growth process, and zinc-oxide nano column array material is prepared in GaN template.
Under current ripe microelectronic processing technique background, using hydrothermal growth process, without using extra particular device, it is not required to valuable
Under conditions of chemical reagent, the degree of order, the size uniformity degree of zinc-oxide nano column array material are substantially increased.The present invention's
The method of zinc-oxide nano column array, preparation cost is low, and technique is simple, easy to operate, easy to spread.
Brief description of the drawings
Fig. 1 is that the zinc-oxide nano column array scanning of materials electron microscopic mirror plane that preparation method of the present invention is prepared regards
Figure.
Fig. 2 is 30 ° of angled views of SEM.
Embodiment
The present invention is expanded on further with most preferred embodiment below in conjunction with the accompanying drawings, but does not limit the protection model of claim
Enclose.
Embodiment 1
First, using plasma enhanced chemical vapor deposition method (PECVD), deposit thickness is that 40 nanometers of Si3N4 is thin on GaN
Film, then utilize nanometer embossing（nanoimprint lithography）Nano-array pattern is made, is carved with reactive ion
The GaN template with nano-array pattern is prepared in erosion technology etching Si3N4.The GaN template prepared is immersed into watery hydrochloric acid
（4%）In solution, cleaned 10 minutes in instrument is cleaned by ultrasonic；700 DEG C of rapid thermal annealings 10 minutes in a nitrogen atmosphere（Remove GaN
The organic matter of template surface remaining）；GaN template after annealing is again dipped into watery hydrochloric acid（4%）In solution, in instrument is cleaned by ultrasonic
Cleaning 10 minutes；GaN template is cleaned with deionized water, is finally dried up with nitrogen, for future use.
2nd, Zn (NO3) 2 and HPT solution (hexamethylenetetramine, abbreviation are prepared
HMTA), the solution prepared is put into refrigerator, stands more than 3h, the solution of iced mistake is mixed, fully stirred with magnetic stirring apparatus
10min is mixed, then is shaken 10 minutes with ultrasonic vibration instrument, centrifuge removes sediment, as ZnO nano post array growth
Precursor aqueous solution.
3rd, specific growth step：Oven temperature is set as 80 DEG C, precursor aqueous solution dried after waiting oven temperature stable
Case preheat 5 minutes, GaN template is fixed on slide with copper adhesive tape, be inverted in it is closed in preheated solution, in an oven
Gravity auxiliary is inverted growth ZnO nano post array 3 hours.
4th, after the completion of growing, quickly sample is taken out from solution with clip, is put into deionized water, is cleaned multiple times；Again
It is secondary to carry out thermal cleaning in deionized water, sample is cleaned multiple times in 80 DEG C of heating dish；The sample cleaned up is carefully pressed from both sides
Rise to be put into 70 DEG C of baking oven and toast 10 minutes, obtain ZnO nano array sample.Electron scanning micrograph such as Fig. 1 and figure
2.It can be seen that the zinc-oxide nano column array that preparation method of the present invention is prepared, size uniformity, arrangement are high from two secondary figures
Degree is orderly.
Claims (5)
1. a kind of preparation method of zinc-oxide nano column array, it is characterised in that specifically include following steps：
Step 1, one layer of Si is deposited on GaN using plasma enhanced chemical vapor deposition technology3N4Film, then using receiving
Rice stamping technique or electron beam lithography are Si3N4Film etches the nano-array pattern of design, is prepared and carries
Si3N4The GaN template of film nano array pattern, the GaN template prepared is immersed in dilute hydrochloric acid solution, be cleaned by ultrasonic；In nitrogen
The lower 700 DEG C of rapid thermal annealing 10min of gas atmosphere；GaN template is cleaned with deionized water, is finally dried up with nitrogen, for future use；
Step 2, prepare Zn (NO3)2With HPT solution, the solution prepared is put into refrigerator, stand 3h with
On, the above-mentioned solution iced is mixed, is sufficiently stirred using magnetic stirring apparatus, recycles supersonic cleaning machine ultrasonic vibration, from
Scheming centrifugation removes sediment, precursor aqueous solution of the stable mixed solution as ZnO nano post array growth；
Step 3, ZnO nano post array growth step：Oven temperature is set, growth temperature is controlled at 70-95 DEG C, with copper adhesive tape
GaN template is fixed on slide, is inverted in precursor aqueous solution and seals, gravity auxiliary is inverted growth ZnO nano in an oven
Post array 3-5 hours；
Step 4, after the completion of growth, sample is taken out from solution rapidly, is put into deionized water, it is clear using thermal cleaning method
Various residues on wash clean sample；The sample cleaned up is carefully picked up be put into 70 DEG C of baking oven toast 10min bake
It is dry, obtain ZnO nano array sample.
2. the preparation method of zinc-oxide nano column array according to claim 1, it is characterised in that after being annealed in step 1
GaN template be again dipped into dilute hydrochloric acid solution, be cleaned by ultrasonic, rapid thermal annealing under nitrogen atmosphere.
3. the preparation method of zinc-oxide nano column array according to claim 1, it is characterised in that Zn is prepared in step 2
(NO3)2With HPT solution, the solution prepared is put into refrigerator, stands more than 3h, iced above-mentioned
Solution mixes, and is sufficiently stirred using magnetic stirring apparatus, recycles supersonic cleaning machine ultrasonic vibration, and centrifuge removes precipitation
Thing.
4. the preparation method of zinc-oxide nano column array according to claim 1, it is characterised in that the medium baking oven of step 3
Precursor aqueous solution is preheated 5min in baking oven after interior temperature stabilization, GaN template is fixed on slide with copper adhesive tape, is inverted in pre-
In the good precursor aqueous solution of heat, gravity auxiliary is inverted growth ZnO nano post array in an oven.
5. the preparation method of zinc-oxide nano column array according to claim 1, it is characterised in that cleaned in step 4
Journey is to carry out thermal cleaning in deionized water, and sample is cleaned multiple times in 80 DEG C of heating dish.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710693227.2A CN107344730A (en) | 2017-08-14 | 2017-08-14 | A kind of preparation method of zinc-oxide nano column array |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710693227.2A CN107344730A (en) | 2017-08-14 | 2017-08-14 | A kind of preparation method of zinc-oxide nano column array |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107344730A true CN107344730A (en) | 2017-11-14 |
Family
ID=60257618
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710693227.2A Pending CN107344730A (en) | 2017-08-14 | 2017-08-14 | A kind of preparation method of zinc-oxide nano column array |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107344730A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108982600A (en) * | 2018-05-30 | 2018-12-11 | 杨丽娜 | Based on gallium oxide/gallic acid zinc hetero-junctions nano-array flexible gas sensor and preparation method thereof |
| CN111787681A (en) * | 2020-07-16 | 2020-10-16 | 上海大学 | Electrode, electrode preparation method and liquid phase discharge plasma device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102184846A (en) * | 2011-04-22 | 2011-09-14 | 东莞市中镓半导体科技有限公司 | Preparation method of patterned substrate |
| CN102942207A (en) * | 2012-11-13 | 2013-02-27 | 北京科技大学 | Method for preparing patterned ZnO nanorod array |
| CN105271361A (en) * | 2015-10-28 | 2016-01-27 | 中国科学院上海微系统与信息技术研究所 | Preparation method of dendritic zinc oxide nanowire array |
-
2017
- 2017-08-14 CN CN201710693227.2A patent/CN107344730A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102184846A (en) * | 2011-04-22 | 2011-09-14 | 东莞市中镓半导体科技有限公司 | Preparation method of patterned substrate |
| CN102942207A (en) * | 2012-11-13 | 2013-02-27 | 北京科技大学 | Method for preparing patterned ZnO nanorod array |
| CN105271361A (en) * | 2015-10-28 | 2016-01-27 | 中国科学院上海微系统与信息技术研究所 | Preparation method of dendritic zinc oxide nanowire array |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108982600A (en) * | 2018-05-30 | 2018-12-11 | 杨丽娜 | Based on gallium oxide/gallic acid zinc hetero-junctions nano-array flexible gas sensor and preparation method thereof |
| CN111787681A (en) * | 2020-07-16 | 2020-10-16 | 上海大学 | Electrode, electrode preparation method and liquid phase discharge plasma device |
| CN111787681B (en) * | 2020-07-16 | 2021-06-22 | 上海大学 | Electrode, electrode preparation method and liquid phase discharge plasma device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1312034C (en) | Process for preparing monocrystalline silicon nano line array with single axial arranging | |
| Xu et al. | Density-controlled growth of aligned ZnO nanowire arrays by seedless chemical approach on smooth surfaces | |
| CN101937946B (en) | Surface texture method of solar battery silicon slice | |
| CN102126724A (en) | Method for preparing silicon nanowire array with smooth surface | |
| CN104692827B (en) | A kind of Ag nanometers of preparation method of ball array of Ag SiO2 | |
| CN108470777B (en) | Preparation method of material testing unit with nano-scale interval small electrodes for in-situ power-on chip of transmission electron microscope | |
| CN105261671A (en) | Method for preparing thin-film antireflection structure employing laser direct writing | |
| CN114211121A (en) | Femtosecond laser ablation-surface film coating composite processing method for super-hydrophobic surface | |
| CN107344730A (en) | A kind of preparation method of zinc-oxide nano column array | |
| CN103337449A (en) | Method for transplanting silicon nanowire array and preparing simple device thereof | |
| Kohlmann et al. | Fabrication of ZnO Nanobrushes by H2–C2H2 Plasma Etching for H2 Sensing Applications | |
| CN103296141A (en) | Method for producing dendritic heterojunction nanowire array structural materials | |
| CN102299211A (en) | Two-step method for manufacturing cadmium sulphide film | |
| CN103073048B (en) | Method for preparing patterned ZnO film by liquid phase self-assembly technology | |
| CN103413865A (en) | Black silicon super-hydrophobic material and manufacturing method thereof | |
| CN103320753B (en) | The preparation method of the controlled aluminum nanoparticles array of a kind of size density | |
| CN102856434A (en) | Preparation method for square silicon nano-porous array | |
| CN105347345A (en) | Silicon micro-nano structure preparing method | |
| Iqbal et al. | Rapid anisotropic chemical etching for quick formation of novel octagonal pyramids on silicon surface for photovoltaics | |
| US8945794B2 (en) | Process for forming silver films on silicon | |
| CN104761154A (en) | Method for preparation of ITO nanowire under catalysis of organic macromolecular material | |
| Lévy‐Clément et al. | Applications of colloidal crystal patterning for synthesis of 1D and 3D nanostructured semiconductors | |
| CN108663387A (en) | A kind of method that wet etching prepares nano particle TEM sample | |
| Zhang et al. | Fabrication and characterization of silicon nanostructures based on metal-assisted chemical etching | |
| CN109560195A (en) | A kind of preparation method based on the uniform MXene film of silicon-based semiconductor devices and its in the application of memristor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 210044 Ning six road, Pukou District, Nanjing, Jiangsu Province, No. 219 Applicant after: Nanjing University of Information Science and Technology Address before: No. 69, Jianye District, Jianye District, Nanjing, Jiangsu Applicant before: Nanjing University of Information Science and Technology |
|
| CB02 | Change of applicant information | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20171114 |
|
| RJ01 | Rejection of invention patent application after publication |