CN103523818A - Preparation method of height-oriented ZnO nanocone array structure material - Google Patents
Preparation method of height-oriented ZnO nanocone array structure material Download PDFInfo
- Publication number
- CN103523818A CN103523818A CN201310532848.4A CN201310532848A CN103523818A CN 103523818 A CN103523818 A CN 103523818A CN 201310532848 A CN201310532848 A CN 201310532848A CN 103523818 A CN103523818 A CN 103523818A
- Authority
- CN
- China
- Prior art keywords
- zno
- substrate
- height
- preparation
- array
- 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.)
- Granted
Links
Images
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses a liquid chemistry growing method of a height-oriented ZnO nanocone array. According to the liquid chemistry growing method of the height-oriented ZnO nanocone array, ZnO colloidal sol coats a substrate through a spin coating film method, and a uniform nanoscale ZnO crystal seed layer is prepared through heat treatment; ZnO array growth liquid is prepared with KOH and Zn (NO3)2; a growing face (the face containing the crystal seed layer) of the substrate is suspended and immersed in the growth liquid in an inverse buckling mode, the reaction lasts for 1-12 hours under the condition of water bath at 20-50 DEG C, and the ZnO nanocone array is prepared on the substrate. The liquid chemistry growing method of the height-oriented ZnO nanocone array has the advantages of being simple in equipment and process, easy to operate, low in cost, suitable for industrial production and the like. The prepared ZnO nanocone array has the advantages of being highly compact, uniform in thickness, good in orientation, high in flatness, stable in performance, capable of being firmly combined with the substrate and the like, and has wide application prospects and great market benefits on the aspects of super-hydrophobic surfaces, detectors, piezoelectric frequency converters, ultraviolet laser, solar cells and the like.
Description
Technical field
The invention belongs to low-dimensional nano structure technical field of semiconductor, particularly a kind of wet-chemical growth method of height-oriented ZnO nano cone array.
Background technology
ZnO has the direct broad-band gap (3.37eV of wurtzite structure as II-VI family, 300K) compound semiconductor materials, because of its excellent physicochemical property, as high Young's modulus, extremely low thermal expansivity, high thermostability, large exciton bind energy and negative electron affinity energy etc., at numerous areas such as sensor, UV transmitting, opto-electronic conversion, super-hydrophobic interface, photochemical catalysis and photodiodes, there is potential application, in recent years, be subject to worldwide showing great attention to.At present, in the numerous fine structure materials based on ZnO that have been successfully prepared, one dimension Nano structure array material is as ZnO nanowire array, nanometer stick array, nano-tube array, nano needle arrays, nano-cone array etc., because thering is single crystal, low dimension, quantum confined effect, small-size effect, the special propertys such as surface effects, and extremely investigator's favor.
Up to now, the preparation method of ZnO one-dimensional nano structure material mainly contains: template assisting growth method, metal organic vapor method (MOVPE), pulsed laser deposition (PLD), chemical Vapor deposition process (CVD), electrochemical vapor deposition and wet chemistry method etc.Wherein, the methods such as template assisting growth method, MOVPE, PLD, CVD, need expensive plant and instrument and harsh processing condition, are difficult to carry out large-scale industrial production; Wet chemistry method desired reaction temperature lower (comparing with vapor phase process), simple to operate, is applicable to scale operation.But, the ZnO array structure materials that uses the method to obtain, the oriented of its crystallographic axis is bad, and homogeneity and repeatable poor, is difficult to practical application, needs further to be improved.
At the wet chemistry method of all reports, prepare in one dimension Nano structure array, comparatively common based on kind of brilliant solution method.The Chinese patent that is 200610025353.2 as application number discloses a kind of " hydrothermal growth method of self-assembling ZnO array ", and the method is utilized sol-gel method and lifted filming technology, through 600 ℃ of annealing 2h, prepares crystal seed layer; Bar-shaped or the tube array of recycling hydrothermal method synthetic ZnO at 150～200 ℃.Application number is that 200810122113.3 Chinese patent discloses a kind of " method of growing ZnO nano-wire array on flexible substrate ", and the method is utilized pulsed laser deposition crystal seed layer, is utilizing solution method 70～100 ℃ of synthesis of nano linear arrays.Yet, the ZnO nano-structure array material that at present the method obtains, the oriented of its crystallographic axis is good not, quality purity is not high enough, homogeneity and repeatability good not; Preparation technology needs further to be improved.The more important thing is, the temperature of the synthetic ZnO nano-structure array of solution method is all more than 60 ℃ at present.
According to existing document, find that the synthetic ZnO of current solution method mainly exists following problem: the first, the temperature of reaction of the synthetic ZnO nano array of solution method is high.In reaction soln, contain organic coordination compound composition, in the process that generates ZnO, need this organic coordination compound thermolysis, so need higher temperature of reaction, increase energy consumption.The second, solution synthesizes the of low quality of ZnO nano-structure array, and powder grains a large amount of in solution can be deposited on substrate surface in reaction.Because heterogeneous nucleation and homogeneous nucleation coexist in solution, heterogeneous nucleation can occur than homogeneous nucleation under lower degree of supersaturation, and the degree of supersaturation of solution is the main drive of ZnO growth.If solution degree of supersaturation is too high, on the one hand, a large amount of homogeneous nucleations of ZnO are also grown up, on the other hand, and the OH of zinc
-ligand [Zn (OH)]
(n-2) -nbetween be easy to flock together by hydrolysis reaction, in solution, form a large amount of solution powders, these powder grains can be deposited on substrate surface in reaction, have a strong impact on crystallization and the growth of ZnO crystal grain on substrate surface, thus cause the ZnO quality of generation and purity not high.The 3rd, it is good not that solution synthesizes ZnO nano-structure array orientation, density and homogeneity, and this is mainly homogeneity good the causing not of crystal seed layer.
Summary of the invention
The object of the invention is that the temperature of reaction that above-mentioned prior art exists is high, the imperfect problem of homogeneity in order to overcome, provide a kind of preparation method of height-oriented ZnO nano cone array structure materials, to obtain the neat ZnO nano cone array of preparation height preferred orientation in different base.The method required equipment, technique are simple, and cost is low, easy to operate, and reaction conditions is gentle, pollution-free, is easy to accomplish scale production.
Technical scheme of the present invention is: a kind of preparation method of height-oriented ZnO nano cone array structure materials, adopt wet-chemical growth method, utilize sol-gel method making ZnO seed presoma, then in substrate, apply described ZnO seed presoma, form film, through thermal treatment, obtain the uniform nano level ZnO of one deck crystal seed layer; In reaction vessel, by substrate, the unsettled back-off of face with crystal seed layer is immersed in ZnO growth solution, and under water bath condition, reaction obtains ZnO nano cone array; Described ZnO growth solution is KOH and Zn (NO
3)
2the concentration of preparation is 0.10～0.25molL
-1zn (OH)
4 2-the aqueous solution, and the pH value of controlling solution is between 10～12.
ZnO seed presoma is with Zn (Ac)
22H
2o is that precursors, monoethanolamine are stablizer, CH
3oCH
2cH
2oH is that solvent, PEG4000 are that tensio-active agent prepares.
In substrate, the described ZnO seed presoma of coating, forms film, and the concrete method adopting is for adopting the method for sol evenning machine spin coating plated film.
Heat treated temperature is 350 ℃～500 ℃, and the time is 10min～2h.
20～50 ℃ of bath temperatures, water-bath time 1-12h.
Described substrate is conductor or isolator.
Described substrate is Cu sheet, conductive glass or slide glass.
Technical solution of the present invention:------potassium hydroxide/zinc nitrate aqueous solution system------is to reduce temperature of reaction to adopt cheap inorganic growth system; Adopt the unsettled back-off of substrate grown face to be placed in reaction solution, this not only can effectively avoid the deposition of solution powder in reaction solution, improves the ZnO quality and the purity that generate, but also can improve the adhesivity of ZnO crystal and substrate; Adopt the method for sol evenning machine spin coating plated film to prepare crystal seed layer, to improve homogeneity, density and the planeness of crystal seed layer.
The present invention can be by regulating the parameters such as temperature, time, growth media concentration and crystal seed layer thermal treatment temp and time of array growth to control the growth size of ZnO nano cone.
Beneficial effect:
1. the inventive method equipment used, technique are simple, easy to operate, and reaction conditions is gentle, environmental friendliness, and energy consumption is little, and cost is low, reproducible, is suitable for scale operation.
2. the ZnO nano cone array that the inventive method is prepared, favorable orientation, crystal mass purity are high, even thickness, array is good, and the aspects such as emission nanometer electron device on the scene, piezoelectric generator, dye sensitization solar battery, photonic crystal and super-hydrophobic interface have a wide range of applications.In crystal seed layer preparation, add appropriate polyoxyethylene glycol, make crystal seed layer film of nanoparticles evenly without reuniting, to such an extent as to good than the nano-pillar of report in the past of the nano-cone array planeness of growing below and uniformity coefficient.And nano-cone array transmitting on the scene and super-hydrophobic aspect are better than nano column array.
Accompanying drawing explanation:
Fig. 1 is process flow sheet of the present invention.
Fig. 2 is the FESEM figure of direct growth ZnO array in 35 ℃ of 12hCu substrates.
Fig. 3 is the FESEM figure of the ZnO crystal seed layer prepared in 350 ℃ of annealing 10minCu substrates.
Fig. 4 is the FESEM figure of the ZnO array of growing in 35 ℃ of 4hCu substrates.
Fig. 5 is the FESEM figure of the ZnO array of growing in 35 ℃ of 8hCu substrates.
Fig. 6 is the FESEM figure of the ZnO array of growing in 35 ℃ of 12hCu substrates.
Fig. 7 is the XRD figure of the ZnO array of growing in 35 ℃ of 12hCu substrates.
Fig. 8 is the TEM figure of the ZnO array of growing in 35 ℃ of 12hCu substrates.
Fig. 9 is the FESEM figure of the ZnO array of growing in 35 ℃ of 12hFTO substrates.
Figure 10 is the FESEM figure of the ZnO array of growing in 25 ℃ of 12hCu substrates.
Figure 11 is the FESEM figure of the ZnO array of growing in 45 ℃ of 12hCu substrates.
Figure 12 is 0.20molL
-1zn (OH)
4 2-the FESEM figure of the ZnO array of growing in 35 ℃ of 12hCu substrates.
Figure 13 is that sample of the present invention is placed schematic diagram in reaction vessel.
In figure: 1-reaction vessel 2-array growth media 3-substrate sheet 4-foam block (effect is that substrate is suspended) 5-sealing cover.
Embodiment:
Below in conjunction with embodiment, the invention will be further described.
The concrete technology of the wet-chemical growth method of the ZnO nano cone array that the present invention is height-oriented is as follows:
1. the preparation of colloidal sol: take 5.488g Zinc diacetate dihydrate [Zn (Ac)<sub TranNum="116">2</sub>2H<sub TranNum="117">2</sub>o], put into beaker, and add wherein the ethylene glycol monomethyl ether [CH of 25ml<sub TranNum="118">3</sub>oCH<sub TranNum="119">2</sub>cH<sub TranNum="120">2</sub>oH], magnetic agitation 15min; Measure 1.5ml thanomin [MEA] and join in the ethylene glycol monomethyl ether of 15ml, mechanical stirring ultrasonic dispersion 5min; By in the ethylene glycol monomethyl ether solution of the thanomin ethylene glycol monomethyl ether solution that is added drop-wise to the zinc acetate that magnetic agitation dropwise, drip again the deionized water of 0.9ml, then add proper amount of glycol methyl ether to adjust liquor capacity and reach 50ml, sealed beaker, and at 60 ℃ of strong magnetic agitation 2h of water-bath, still aging 24h.Finally add 0.25g polyoxyethylene glycol [HO (CH<sub TranNum="121">2</sub>cH<sub TranNum="122">2</sub>o)<sub TranNum="123">n</sub>h] 4000(tensio-active agent), 60 ℃ of stirring in water bath 30min, obtain the precursor sol of ZnO.(Xia Yongmei. the preparation of dye-sensitized solar cell anode and performance study thereof: [Lanzhou University of Science & Technology's master thesis] [D]. Lanzhou: college of science of Lanzhou University of Science & Technology, 2010).With the difference of having reported: for making up the disappearance of Zn (Ac) 22H2O crystal water, and make hydrolysis reaction fully carry out being conducive to form required colloidal sol, the deionized water adding.In colloid, add appropriate polyoxyethylene glycol, the even nothing of crystal seed layer film of nanoparticles of preparing is reunited, to such an extent as to the nano-pillar of reporting before the nano-cone array planeness of growing and uniformity coefficient ratio is better below.
2. the cleaning of substrate: according to a conventional method substrate used is cleaned up.Such as substrate is that copper sheet is first used deionized water ultrasonic cleaning 10min, then use acetone ultrasonic washing 10min; Put into 10%(volume ratio) HCl aqueous solution soaking 30s; Take out, rinse successively with deionized water and dehydrated alcohol, cold wind dries up, standby.Substrate is that the words of FTO glass or slide glass can first be cleaned with cleaning agent, and tap water rinses, then uses acetone ultrasonic washing 10min, put into subsequently after deionized water for ultrasonic ripple washing 5min, take out, with rinsed with deionized water and dehydrated alcohol, rinse successively, dry up standby.
3. the preparation of crystal seed layer: adopt the method for spin coating plated film at the upper preparation of cleaned substrate (as Cu sheet or FTO glass) layer of ZnO colloidal film; Through 350 ℃ of annealing 10min, at substrate surface, form the nano level ZnO crystal seed layer of one deck even compact.
4. the preparation of array growth solution: with KOH and Zn (NO
3)
2compound concentration is 0.10～0.25molL
-1zn (OH)
4 2-the aqueous solution, and the pH value of controlling solution is between 10～12, fully magnetic agitation, obtains a settled solution, is required array growth media.
5. the preparation of array: array growth media is poured in reaction vessel, then substrate is prepared with to facing down of crystal seed layer and is suspended in (as shown in Figure 8) in array growth media, good seal reaction vessel afterwards, be placed in electric heating constant temperature tank, under 20～50 ℃ of water bath condition, insulation 1-12h, take out, use successively rinsed with deionized water, dehydrated alcohol rinses, room temperature vacuum drying.By floatation of foam, under liquid convection, can move around, aufwuchsplate is conducive to avoid precipitating in solution vertically downward.
As a comparison, in substrate, do not prepare crystal seed layer in advance, take the step solution method ZnO array of directly growing in substrate.At KOH and Zn (NO
3)
2in reaction system, the cleaned unsettled back-off of Cu substrate grown face is immersed in array growth media, after 35 ℃ of water-bath growth 12h, the sample preparing, compactness, planeness and orientation (crystal orientation) are all relative poor, as shown in Figure 2.
Embodiment 1: the preparation of substrate crystal seed layer
Utilize the above-mentioned colloid preparing in advance, by using the desk-top sol evenning machine spin coating of KW-4A type plated film, in Cu substrate sheet, prepare layer of ZnO colloid film; Through the lower 350 ℃ of annealing 10min of argon atmosphere, at substrate surface, form the nano level ZnO crystal seed rete of one deck even compact, as shown in Figure 3.
Embodiment 2:Cu substrate is at 35 ℃ of growth ZnO nano cone arrays
Adopt substrate modes of emplacement of the present invention, by KOH and Zn (NO
3)
2the 0.25molL of the pH=12 of preparation
-1zn (OH)
4 2-in reaction system, the Cu sheet that is prepared with crystal seed layer of take is substrate, the ZnO array film making after 35 ℃ of water-baths growths 4h, 8h, 12h, and pattern is respectively as shown in Fig. 4, Fig. 5, Fig. 6.Sample F ESEM result shows that ZnO is taper, and nano level has shown preferred orientation highly; Integral arrayization is good.Sample XRD(Fig. 7 of growth 12h) result shows the ZnO phase that the array composition of gained is hexagonal wurtzite structure, the diffraction data of collection of illustrative plates and standard card (PDF#36-1451) is in full accord, compare with the standard diagram of ZnO powder, (002) diffraction peak has relatively high intensity, shows that array films has the c-axis orientation of height.In order further to analyze the cone crystal structure generating, carried out tem analysis, as Fig. 8, low power TEM image shows that the brilliant surface of cone is essentially smooth and gradually little along the direction of growth diameter of cone, is rendered as elongated cone brilliant; In illustration, diffraction spot style result shows that this cone crystalline substance is hexagonal wurtzite single crystal structure; By analyzing the HRTEM image in illustration, two groups of spacings be can clearly observe and 0.26nm and 0.16nm are about respectively, correspond respectively to (001) and (110) family of crystal planes; Result also shows that monocrystalline cone grows along c-axis direction preferred orientation.
The ZnO nano of growing on embodiment 3:FTO glass substrate cone array
Adopt substrate modes of emplacement of the present invention, by KOH and Zn (NO
3)
2the 0.25molL of the pH=12 of preparation
-1zn (OH)
4 2-in reaction system, the FTO glass that is prepared with crystal seed layer of take is substrate, the ZnO array film making after 35 ℃ of water-baths growth 12h, and pattern is as shown in Figure 9.
The embodiment 4:Cu substrate ZnO nano cone array of growing under differing temps
Adopt substrate modes of emplacement of the present invention, by KOH and Zn (NO
3)
2the 0.25molL of the pH=12 of preparation
-1zn (OH)
4 2-in reaction system, the Cu sheet that is prepared with crystal seed layer of take is substrate, the ZnO array film making after 25 ℃ and 45 ℃ of water-baths growth 12h, and pattern is respectively as shown in Figure 10 and Figure 11.
Embodiment 5:Cu substrate is at 0.20molL
-1zn (OH)
4 2-the ZnO nano cone array of growing in reaction system
Adopt substrate modes of emplacement of the present invention, by KOH and Zn (NO
3)
2the 0.20molL of the pH=11 of preparation
-1zn (OH)
4 2-in reaction system, the Cu sheet that is prepared with crystal seed layer of take is substrate, the ZnO array film making after 35 ℃ of water-baths growth 12h, and pattern is respectively as shown in figure 12.
Claims (7)
1. the preparation method of a height-oriented ZnO nano cone array structure materials, adopt wet-chemical growth method, utilize sol-gel method making ZnO seed presoma, then in substrate, apply described ZnO seed presoma, form film, through thermal treatment, obtain the uniform nano level ZnO of one deck crystal seed layer; In reaction vessel, by substrate, the unsettled back-off of face with crystal seed layer is immersed in ZnO growth solution, and under water bath condition, reaction obtains ZnO nano cone array; It is characterized in that: described ZnO growth solution is KOH and Zn (NO
3)
2the concentration of preparation is 0.10～0.25molL
-1zn (OH)
4 2-the aqueous solution, and the pH value of controlling solution is between 10～12.
2. the preparation method of height-oriented ZnO nano cone array structure materials according to claim 1, is characterized in that, ZnO seed presoma is with Zn (Ac)
22H
2o is that precursors, monoethanolamine are stablizer, CH
3oCH
2cH
2oH is that solvent, PEG4000 are that tensio-active agent prepares.
3. the preparation method of height-oriented ZnO nano cone array structure materials according to claim 1, is characterized in that, in substrate, the described ZnO seed presoma of coating, forms film, and the concrete method adopting is for adopting the method for sol evenning machine spin coating plated film.
4. the preparation method of height-oriented ZnO nano cone array structure materials according to claim 1, is characterized in that, heat treated temperature is 350 ℃～500 ℃, and the time is 10min～2h.
5. the preparation method of height-oriented ZnO nano cone array structure materials according to claim 1, is characterized in that 20～50 ℃ of bath temperatures, water-bath time 1-12h.
6. the preparation method of height-oriented ZnO nano cone array structure materials according to claim 1, is characterized in that, described substrate is conductor or isolator.
7. the preparation method of height-oriented ZnO nano cone array structure materials according to claim 1, is characterized in that, described substrate is Cu sheet, conductive glass or slide glass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310532848.4A CN103523818B (en) | 2013-10-31 | 2013-10-31 | A kind of preparation method of height-oriented ZnO nano cone array structure materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310532848.4A CN103523818B (en) | 2013-10-31 | 2013-10-31 | A kind of preparation method of height-oriented ZnO nano cone array structure materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103523818A true CN103523818A (en) | 2014-01-22 |
| CN103523818B CN103523818B (en) | 2015-09-09 |
Family
ID=49926241
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310532848.4A Expired - Fee Related CN103523818B (en) | 2013-10-31 | 2013-10-31 | A kind of preparation method of height-oriented ZnO nano cone array structure materials |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103523818B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105463564A (en) * | 2015-11-30 | 2016-04-06 | 东南大学 | ZnO nanorod and ZnO cluster composite structure and preparation method thereof |
| CN105776317A (en) * | 2016-04-05 | 2016-07-20 | 东南大学 | Transparent super-hydrophobic nano-array and preparation method thereof |
| CN106290481A (en) * | 2015-05-11 | 2017-01-04 | 北京化工大学 | ZnO nano cone gas sensitive of Au load and its production and use |
| CN109865527A (en) * | 2017-12-04 | 2019-06-11 | 天津发洋环保科技有限公司 | A kind of preparation method of the nanometer cone cell film for air cleaning |
| CN114163138A (en) * | 2021-12-16 | 2022-03-11 | 南京工程学院 | Preparation method of spectrum conversion nanorod array |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1865526A (en) * | 2006-03-31 | 2006-11-22 | 中国科学院上海光学精密机械研究所 | Hydrothermal method growth process for self-assembling ZnO array |
| CN101319370A (en) * | 2008-06-24 | 2008-12-10 | 济南大学 | Method for controlling orientation and profile characteristic of zinc oxide nano-stick/nano-tube array |
| JP2012144384A (en) * | 2011-01-07 | 2012-08-02 | Tokyo Institute Of Technology | Method for producing conductive zinc oxide film |
-
2013
- 2013-10-31 CN CN201310532848.4A patent/CN103523818B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1865526A (en) * | 2006-03-31 | 2006-11-22 | 中国科学院上海光学精密机械研究所 | Hydrothermal method growth process for self-assembling ZnO array |
| CN101319370A (en) * | 2008-06-24 | 2008-12-10 | 济南大学 | Method for controlling orientation and profile characteristic of zinc oxide nano-stick/nano-tube array |
| JP2012144384A (en) * | 2011-01-07 | 2012-08-02 | Tokyo Institute Of Technology | Method for producing conductive zinc oxide film |
Non-Patent Citations (3)
| Title |
|---|
| JUAN ZHAO ET AL.: "Growth and morphology of ZnO nanorods prepared from Zn(NO3)2/NaOH solutions", 《JOURNAL OF THE EUROPEAN CERAMIC SOCIETY》, vol. 26, 28 February 2006 (2006-02-28), pages 3745 - 3752 * |
| SEA-FUE WANG ET AL.: "Effect of ZnO seed layers on the solution chemical growth of ZnO nanorod arrays", 《CERAMICS INTERNATIONAL》, vol. 35, 22 July 2008 (2008-07-22), pages 1255 - 1260, XP025915328, DOI: doi:10.1016/j.ceramint.2008.06.012 * |
| XUFENG WU ET AL.: "Controlled one-step fabrication of highly oriented ZnO nanoneedle/nanorods arrays at near room temperature", 《CHEM. COMMUN.》, 8 March 2006 (2006-03-08), pages 1655 - 1657 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106290481A (en) * | 2015-05-11 | 2017-01-04 | 北京化工大学 | ZnO nano cone gas sensitive of Au load and its production and use |
| CN105463564A (en) * | 2015-11-30 | 2016-04-06 | 东南大学 | ZnO nanorod and ZnO cluster composite structure and preparation method thereof |
| CN105776317A (en) * | 2016-04-05 | 2016-07-20 | 东南大学 | Transparent super-hydrophobic nano-array and preparation method thereof |
| CN109865527A (en) * | 2017-12-04 | 2019-06-11 | 天津发洋环保科技有限公司 | A kind of preparation method of the nanometer cone cell film for air cleaning |
| CN114163138A (en) * | 2021-12-16 | 2022-03-11 | 南京工程学院 | Preparation method of spectrum conversion nanorod array |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103523818B (en) | 2015-09-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103523818B (en) | A kind of preparation method of height-oriented ZnO nano cone array structure materials | |
| Li et al. | Single crystalline Cu 2 ZnSnS 4 nanosheet arrays for efficient photochemical hydrogen generation | |
| CN101786026B (en) | n-shaped titanium oxide nanotube/p-shaped diamond heterojunction photocatalytic material and preparation method | |
| CN104724758A (en) | Method for preparing WO3 nano-layer material | |
| CN101800130B (en) | Method for preparing dye-sensitized solar cell compound light anode with zinc oxide nanometer structure | |
| Guo et al. | Hierarchical TiO 2–CuInS 2 core–shell nanoarrays for photoelectrochemical water splitting | |
| CN101857382B (en) | Method for preparing sheet-shaped bismuth oxyiodide (BiOI) nano-film electrode | |
| CN108409157A (en) | A kind of ZnIn2S4 nanometer wafer arrays structure and preparation method thereof | |
| CN108023017A (en) | A kind of monocrystal thin films of organo-mineral complexing perovskite material and its preparation method and application | |
| CN102881462B (en) | A kind of preparation method of ZnO nano rod array/nano grain cluster microballoon sphere composite film | |
| CN114016077B (en) | Cadmium sulfide-indium zinc sulfide heterojunction nanorod array composite material and preparation method thereof | |
| CN105714377A (en) | Method for preparing nanometer flower-shaped WO3 thin-film photo-anodes | |
| Shen et al. | Enhancing efficiency of CdS/TiO2 nanorod arrays solar cell through improving the hydrophilicity of TiO2 nanorod surface | |
| KR20090110090A (en) | Synthesis method for indium selenide nanoparticles by ultrasonic waves and a compound semiconductor solar cell comprising the said | |
| CN110882707A (en) | CoP/Si hydrogen evolution catalytic material and preparation method thereof | |
| Chen et al. | Morphology selective electrodeposition of Cu2O microcrystals on ZnO nanotube arrays as efficient visible-light-driven photo-electrode | |
| CN106119922B (en) | A kind of cuprous oxide is electrodeposited in composite material on TiOx nano chip arrays film and preparation method thereof | |
| CN108355688A (en) | A kind of photoelectrocatalysis water decomposition BiVO4/Ag3PO4The preparation method of film | |
| CN102807248A (en) | Method for preparing cuprous sulfide nanoarray | |
| Yao et al. | Hierarchical TiO 2 nanoflowers/nanosheets array film: synthesis, growth mechanism and enhanced photoelectrochemical properties | |
| CN105236472A (en) | Preparation method of SnO2 nano-wire array | |
| CN102509648B (en) | Preparation method for Ga-doped ZnO nanometer material | |
| CN112588303B (en) | Preparation method of selenium-bismuth oxide nanosheet and heterojunction type photoelectrode based on selenium-bismuth oxide nanosheet | |
| CN102030315A (en) | Method for preparing nano Cu2-xSe array on copper substrate by hydrothermal process | |
| CN108545960A (en) | A kind of Y doping zinc oxide nanometers stick array preparation method |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150909 Termination date: 20211031 |