CN103523818B - A kind of preparation method of height-oriented ZnO nano cone array structure materials - Google Patents
A kind of preparation method of height-oriented ZnO nano cone array structure materials Download PDFInfo
- Publication number
- CN103523818B CN103523818B CN201310532848.4A CN201310532848A CN103523818B CN 103523818 B CN103523818 B CN 103523818B CN 201310532848 A CN201310532848 A CN 201310532848A CN 103523818 B CN103523818 B CN 103523818B
- Authority
- CN
- China
- Prior art keywords
- zno
- substrate
- array
- preparation
- 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.)
- Expired - Fee Related
Links
Abstract
The invention discloses the wet-chemical growth method of a kind of height-oriented ZnO nano cone array, ZnO sol coating in substrate, is prepared one deck uniform nano level ZnO crystal seed layer through thermal treatment by employing spin coating plating method; With KOH and Zn (NO
3)
2preparation ZnO array growth liquid; Substrate grown face (face namely containing crystal seed layer) unsettled back-off is immersed in above-mentioned growth media, under 20 ~ 50 DEG C of water bath condition, reaction 1 ~ 12h, making ZnO nano-cone array in described substrate.The method has that instrument and supplies is simple, easy to operate, cost is low and the advantage such as applicable suitability for industrialized production.ZnO nano that the present invention prepares cone array has that high compaction, even thickness, favorable orientation, planeness are high, stable performance, with substrate in conjunction with the feature such as firm, have broad application prospects and huge market efficiency in super hydrophobic surface, detector, piezoelectric variable-frequency device, Ultra-Violet Laser and solar cell etc.
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 race, 300K) compound semiconductor materials, because of the physicochemical property of its excellence, 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, worldwide showing great attention to is received.At present, numerous in the fine structure material of ZnO what be 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 having single crystal, low dimension, quantum confined effect, small-size effect, the special propertys such as surface effects, and the favor of extremely investigator.
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 method such as template assisting growth method, MOVPE, PLD, CVD, needs expensive plant and instrument and harsh processing condition, is difficult to carry out large-scale industrial production; Wet chemistry method desired reaction temperature lower (compared with vapor phase process), simple to operate, be applicable to scale operation.But use the ZnO array structure materials that obtains of the method, the oriented of its crystallographic axis is bad, homogeneity and repeatable poor, is difficult to practical application, needs to be improved further.
Prepare in one dimension Nano structure array at the wet chemistry method of all reports, comparatively common based on kind of brilliant solution method.The Chinese patent being 200610025353.2 as application number discloses one " hydrothermal growth method of self-assembling ZnO array ", and the method utilizes sol-gel method and lift filming technology, prepares crystal seed layer through 600 DEG C of annealing 2h; Recycling hydrothermal method synthesizes the bar-shaped or tube array of ZnO at 150 ~ 200 DEG C.Application number be 200810122113.3 Chinese patent disclose one " method of growing ZnO nano-wire array on flexible substrate ", the method utilizes pulsed laser deposition crystal seed layer, is utilizing solution method 70 ~ 100 DEG C of synthesis of nano linear arrays.But, the ZnO nano-structure array material that current 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 to be improved further.The more important thing is, the temperature of current solution method synthesis ZnO nano-structure array is all more than 60 DEG C.
Find that current solution method synthesis ZnO mainly exists following problem according to existing document: the first, the temperature of reaction of solution method synthesis ZnO nano array remains high.Containing organic coordination compound composition in reaction soln, in the process generating 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 the reaction.Because heterogeneous nucleation and homogeneous nucleation coexist in solution, heterogeneous nucleation can occur compared to 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 nucleation of ZnO is also grown up, on the other hand, and the OH of zinc
-ligand [Zn (OH)]
(n-2) -nbetween flock together easily via hydrolysis reaction, form a large amount of solution powders in the solution, these powder grains can be deposited on substrate surface in the 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.3rd, solution synthesis ZnO nano-structure array orientation, density and homogeneity are good not, and the homogeneity of this mainly crystal seed layer is good not to be caused.
Summary of the invention
The object of the invention is high, the imperfect problem of homogeneity of temperature of reaction existed to overcome above-mentioned prior art, there is provided 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 on different substrates.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, obtain one deck uniform nano level ZnO crystal seed layer through thermal treatment; In reaction vessel, substrate is immersed in ZnO growth solution with the unsettled back-off in face of crystal seed layer, under water bath condition, is obtained by reacting 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 controlling solution is between 10 ~ 12.
ZnO seed presoma is with Zn (Ac)
22H
2o is precursors, monoethanolamine is stablizer, CH
3oCH
2cH
2oH is solvent, PEG4000 is that tensio-active agent prepares.
Substrate applies described ZnO seed presoma, forms film, the concrete method adopted is the method adopting sol evenning machine spin coating plated film.
Heat treated temperature is 350 DEG C ~ 500 DEG C, and the time is 10min ~ 2h.
Bath temperature 20 ~ 50 DEG C, 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 in substrate grown face to be placed in reaction solution, this not only effectively can avoid the deposition of solution powder in reaction solution, improves the ZnO quality and purity that generate, but also can improve the adhesivity of ZnO crystal and substrate; The method of sol evenning machine spin coating plated film is adopted to prepare crystal seed layer, to improve the homogeneity of crystal seed layer, density and planeness.
The growth size of the present invention by regulating the temperature of array growth, time, growth media concentration and the parameter such as crystal seed layer thermal treatment temp and time to carry out controlling ZnO nano cone.
Beneficial effect:
1. the inventive method equipment used, technique are simply, easy to operate, and reaction conditions is gentle, and environmental friendliness, energy consumption is little, and cost is low, reproducible, is suitable for scale operation.
2. the ZnO nano that the inventive method is prepared bores array, 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 the even soilless sticking of crystal seed layer film of nanoparticles, to such an extent as to good than the nano-pillar reported in the past of the nano-cone array planeness grown below and uniformity coefficient.And nano-cone array Flied emission and super-hydrophobic in be better than nano column array.
Accompanying drawing illustrates:
Fig. 1 is process flow sheet of the present invention.
Fig. 2 is the FESEM figure of direct growth ZnO array in 35 DEG C of 12hCu substrates.
Fig. 3 is the FESEM figure of ZnO crystal seed layer prepared by 350 DEG C of annealing 10minCu substrate.
Fig. 4 is the FESEM figure of the ZnO array that 35 DEG C of 4hCu substrates grow.
Fig. 5 is the FESEM figure of the ZnO array that 35 DEG C of 8hCu substrates grow.
Fig. 6 is the FESEM figure of the ZnO array that 35 DEG C of 12hCu substrates grow.
Fig. 7 is the XRD figure of the ZnO array that 35 DEG C of 12hCu substrates grow.
Fig. 8 is the TEM figure of the ZnO array that 35 DEG C of 12hCu substrates grow.
Fig. 9 is the FESEM figure of the ZnO array that 35 DEG C of 12hFTO substrates grow.
Figure 10 is the FESEM figure of the ZnO array that 25 DEG C of 12hCu substrates grow.
Figure 11 is the FESEM figure of the ZnO array that 45 DEG C of 12hCu substrates grow.
Figure 12 is 0.20molL
-1zn (OH)
4 2-the FESEM figure of the ZnO array that 35 DEG C of 12hCu substrates grow.
Figure 13 is that inventive samples places schematic diagram in reaction vessel.
In figure: 1-reaction vessel 2-array growth liquid 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)
22H
2o], put into beaker, and add the ethylene glycol monomethyl ether [CH of 25ml wherein
3oCH
2cH
2oH], magnetic agitation 15min; Measuring 1.5ml thanomin [MEA] joins in the ethylene glycol monomethyl ether of 15ml, mechanical stirring ultrasonic disperse 5min; The ethylene glycol monomethyl ether dropwise of thanomin is added drop-wise in the ethylene glycol monomethyl ether solution of the zinc acetate that magnetic agitation, drip the deionized water of 0.9ml again, then add proper amount of glycol methyl ether adjustment liquor capacity and reach 50ml, sealed beaker, and stir 2h, still aging 24h at 60 DEG C of water-bath vigorous magnetic.Finally add 0.25g polyoxyethylene glycol [HO (CH
2cH
2o)
nh] 4000(tensio-active agent), 60 DEG C 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 reported: for making up the disappearance of Zn (Ac) 22H2O crystal water, and make hydrolysis reaction fully carry out being conducive to forming required colloidal sol, the deionized water added.In colloid, add appropriate polyoxyethylene glycol, make the even soilless sticking of crystal seed layer film of nanoparticles prepared, to such an extent as to better than the nano-pillar reported before of the nano-cone array planeness grown below and uniformity coefficient.
2. the cleaning of substrate: according to a conventional method substrate used is cleaned up.Such as substrate is that copper sheet then first uses deionized water ultrasonic cleaning 10min, then uses acetone ultrasonic washing 10min; Put into 10%(volume ratio) HCl aqueous solution soaking 30s; Take out, rinse with deionized water and dehydrated alcohol successively, cold wind dries up, for subsequent use.Substrate is that the words of FTO glass or slide glass can first with cleaning agent cleaning, tap water, then uses acetone ultrasonic washing 10min, after putting into deionized water for ultrasonic ripple washing 5min subsequently, take out, rinse with rinsed with deionized water and dehydrated alcohol successively, dry up for subsequent use.
3. the preparation of crystal seed layer: adopt the method for spin coating plated film at cleaned substrate (as Cu sheet or FTO glass) upper preparation layer of ZnO colloidal film; Through 350 DEG C of annealing 10min, namely form the nano level ZnO crystal seed layer of one deck even compact at substrate surface.
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 controlling solution is between 10 ~ 12, abundant magnetic agitation, obtains a settled solution, is required array growth liquid.
5. the preparation of array: array growth liquid is poured in reaction vessel, then facing down of crystal seed layer there is is to be suspended in (as shown in Figure 8) in array growth liquid substrate preparation, good seal reaction vessel afterwards, be placed in electric heating constant temperature tank, under 20 ~ 50 DEG C of water bath condition, insulation 1-12h, take out, use rinsed with deionized water successively, dehydrated alcohol rinses, and room temperature in vacuo is dried.By floatation of foam, can move around under liquid convection, aufwuchsplate is conducive to avoiding precipitating in solution vertically downward.
As a comparison, in substrate, do not prepare crystal seed layer in advance, take a step solution method directly in substrate, to grow ZnO array.At KOH and Zn (NO
3)
2in reaction system, be immersed in array growth liquid by the cleaned unsettled back-off in Cu substrate grown face, after 35 DEG C of water-bath growth 12h, the sample prepared, compactness, planeness are all relative with orientation (crystal orientation) poor, as shown in Figure 2.
Embodiment 1: the preparation of substrate crystal seed layer
Utilizing the above-mentioned colloid prepared in advance, by using KW-4A type desk-top sol evenning machine spin coating plated film, Cu substrate sheet being prepared layer of ZnO colloid film; Through the lower 350 DEG C of annealing 10min of argon atmosphere, namely form the nano level ZnO crystal seed rete of one deck even compact at substrate surface, as shown in Figure 3.
Embodiment 2:Cu substrate is at 35 DEG C 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, with prepare have crystal seed layer Cu sheet for substrate, ZnO array film obtained after 35 DEG C of water-baths growth 4h, 8h, 12h, pattern is respectively as shown in Fig. 4, Fig. 5, Fig. 6.Sample F ESEM result display ZnO is taper, and nano level, shows the preferred orientation of height; Integral arrayization is good.Sample XRD(Fig. 7 of growth 12h) array elements of result display gained is the ZnO phase of hexagonal wurtzite structure, the diffraction data of collection of illustrative plates and standard card (PDF#36-1451) is completely the same, compared 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 to analyze the cone crystal structure of generation further, carried out tem analysis, as Fig. 8, the brilliant surface of low power TEM image display cone is essentially smooth and direction of growth diameter along cone is gradually little, 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, clearly can observe two groups of spacings and being about 0.26nm and 0.16nm respectively, corresponding respectively to (001) and (110) family of crystal planes; Result also shows that monocrystalline cone grows along c-axis direction preferred orientation.
Embodiment 3:FTO glass substrate grows ZnO nano 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, with prepare have crystal seed layer FTO glass for substrate, ZnO array film obtained after 35 DEG C of water-baths growth 12h, pattern is as shown in Figure 9.
Embodiment 4:Cu substrate grows ZnO nano cone array at different temperatures
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, with prepare have crystal seed layer Cu sheet for substrate, ZnO array film obtained after 25 DEG C and 45 DEG C of water-baths growth 12h, 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 grown 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, with prepare have crystal seed layer Cu sheet for substrate, ZnO array film obtained after 35 DEG C of water-baths growth 12h, pattern is respectively as shown in figure 12.
Claims (2)
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, obtain one deck uniform nano level ZnO crystal seed layer through thermal treatment; In reaction vessel, substrate is suspended, and make its face level with crystal seed layer downward, be immersed in ZnO growth solution, under water bath condition, be obtained by reacting 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 ~ 0.25 molL
-1zn (OH)
4 2-the aqueous solution, and the pH value controlling solution is between 10 ~ 12; Bath temperature is 20 ~ 50 DEG C, water bath time 1-12h; After sampling, use rinsed with deionized water successively, dehydrated alcohol rinses, and room temperature in vacuo is dried; Substrate is copper sheet, conductive glass or slide glass;
ZnO seed presoma is with Zn (Ac)
22H
2o is precursors, monoethanolamine is stablizer, CH
3oCH
2cH
2oH is solvent, PEG4000 is that tensio-active agent prepares;
Substrate applies described ZnO seed presoma, forms film, the concrete method adopted is the method adopting sol evenning machine spin coating plated film.
2. the preparation method of height-oriented ZnO nano cone array structure materials according to claim 1, it is characterized in that, heat treated temperature is 350 DEG C ~ 500 DEG C, and the time is 10min ~ 2h.
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 CN103523818A (en) | 2014-01-22 |
| CN103523818B true 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) |
Families Citing this family (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 |
| CN105776317B (en) * | 2016-04-05 | 2018-02-06 | 东南大学 | A kind of transparent 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 |
| CN114163138B (en) * | 2021-12-16 | 2023-03-03 | 南京工程学院 | Preparation method of spectrum conversion nanorod array |
Citations (2)
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 (2)
| 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 |
Non-Patent Citations (3)
| Title |
|---|
| Controlled one-step fabrication of highly oriented ZnO nanoneedle/nanorods arrays at near room temperature;Xufeng Wu et al.;《Chem. Commun.》;20060308;1655-1657 * |
| Effect of ZnO seed layers on the solution chemical growth of ZnO nanorod arrays;Sea-Fue Wang et al.;《Ceramics International》;20080722;第35卷;1255-1260 * |
| Growth and morphology of ZnO nanorods prepared from Zn(NO3)2/NaOH solutions;Juan Zhao et al.;《Journal of the European Ceramic Society》;20060228;第26卷;3745-3752 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103523818A (en) | 2014-01-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103523818B (en) | A kind of preparation method of height-oriented ZnO nano cone array structure materials | |
| CN101786026B (en) | n-shaped titanium oxide nanotube/p-shaped diamond heterojunction photocatalytic material and preparation method | |
| CN108409157A (en) | A kind of ZnIn2S4 nanometer wafer arrays structure and preparation method thereof | |
| CN101800130B (en) | Method for preparing dye-sensitized solar cell compound light anode with zinc oxide nanometer structure | |
| CN104724758A (en) | Method for preparing WO3 nano-layer material | |
| 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 | |
| CN100360420C (en) | Method of growing nano-tube shaped zinc oxide by hydrothermal decomposition | |
| CN106833647B (en) | A kind of synthetic method of copper indium selenide quantum dot | |
| CN112588303B (en) | Preparation method of selenium-bismuth oxide nanosheet and heterojunction type photoelectrode based on selenium-bismuth oxide nanosheet | |
| CN110054224A (en) | A kind of stratiform tungsten trioxide photoelectrode material and preparation method thereof | |
| CN105714377A (en) | Method for preparing nanometer flower-shaped WO3 thin-film photo-anodes | |
| CN102030315B (en) | Method for preparing nano Cu2-xSe array on copper substrate by hydrothermal process | |
| 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 | |
| CN106119922B (en) | A kind of cuprous oxide is electrodeposited in composite material on TiOx nano chip arrays film and preparation method thereof | |
| Chen et al. | Morphology selective electrodeposition of Cu2O microcrystals on ZnO nanotube arrays as efficient visible-light-driven photo-electrode | |
| CN105236472A (en) | Preparation method of SnO2 nano-wire array | |
| CN102509648B (en) | Preparation method for Ga-doped ZnO nanometer material | |
| CN108545960A (en) | A kind of Y doping zinc oxide nanometers stick array preparation method | |
| CN103066154B (en) | A kind of ZnO/CdS/Cu 2znSnS 4pn ties the preparation method of nanometer stick array | |
| CN107937969A (en) | A kind of GN Sb2Se3The preparation method of laminated film | |
| CN102795665B (en) | Preparation method of titanium dioxide nanotube (rod) array | |
| CN113620342B (en) | Shuttle-shaped silver bismuth disulfide nano material and preparation method thereof | |
| CN103603040B (en) | A kind of low temperature liquid phase growing method preparing ZnO nano cone array |
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 |
Granted publication date: 20150909 Termination date: 20211031 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |