CN102268706A - Methods for preparing ZnO/Cu2O heterojunction material and ZnO/Cu2O three-dimensional heterojunction solar cell - Google Patents
Methods for preparing ZnO/Cu2O heterojunction material and ZnO/Cu2O three-dimensional heterojunction solar cell Download PDFInfo
- Publication number
- CN102268706A CN102268706A CN2011101839937A CN201110183993A CN102268706A CN 102268706 A CN102268706 A CN 102268706A CN 2011101839937 A CN2011101839937 A CN 2011101839937A CN 201110183993 A CN201110183993 A CN 201110183993A CN 102268706 A CN102268706 A CN 102268706A
- Authority
- CN
- China
- Prior art keywords
- zno
- deposition
- preparation
- solution
- heterojunction
- 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
- 239000000463 material Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 34
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title description 20
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title description 19
- 239000010949 copper Substances 0.000 claims abstract description 119
- 239000000243 solution Substances 0.000 claims abstract description 102
- 238000002360 preparation method Methods 0.000 claims abstract description 50
- 238000000151 deposition Methods 0.000 claims abstract description 42
- 239000002073 nanorod Substances 0.000 claims abstract description 35
- 230000008021 deposition Effects 0.000 claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 23
- 239000010409 thin film Substances 0.000 claims abstract description 16
- 238000004070 electrodeposition Methods 0.000 claims abstract description 10
- 239000012266 salt solution Substances 0.000 claims abstract description 10
- 150000001879 copper Chemical class 0.000 claims abstract description 8
- 239000004065 semiconductor Substances 0.000 claims abstract description 8
- 239000007791 liquid phase Substances 0.000 claims abstract description 4
- 239000003792 electrolyte Substances 0.000 claims abstract 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 88
- 239000004310 lactic acid Substances 0.000 claims description 44
- 235000014655 lactic acid Nutrition 0.000 claims description 44
- 239000010408 film Substances 0.000 claims description 26
- 239000007787 solid Substances 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 238000005429 filling process Methods 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 238000004528 spin coating Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 229920002873 Polyethylenimine Polymers 0.000 claims 1
- 238000000137 annealing Methods 0.000 claims 1
- 238000011049 filling Methods 0.000 abstract description 16
- 230000007547 defect Effects 0.000 abstract description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 224
- 239000011787 zinc oxide Substances 0.000 description 112
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 57
- 239000002243 precursor Substances 0.000 description 30
- 238000004062 sedimentation Methods 0.000 description 30
- 239000008151 electrolyte solution Substances 0.000 description 14
- 238000007605 air drying Methods 0.000 description 9
- 238000005137 deposition process Methods 0.000 description 9
- 230000005518 electrochemistry Effects 0.000 description 9
- 238000000280 densification Methods 0.000 description 7
- 238000000407 epitaxy Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 5
- 229940112669 cuprous oxide Drugs 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 238000003491 array Methods 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- DBJUEJCZPKMDPA-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O DBJUEJCZPKMDPA-UHFFFAOYSA-N 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002061 nanopillar Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Photovoltaic Devices (AREA)
Abstract
本发明公开了一种制备ZnO/Cu2O异质结材料及ZnO/Cu2O三维结构异质结太阳电池的方法，异质结材料的制备方法包括液相生长法在基底上生长n型ZnO纳米棒阵列薄膜、以碱性铜盐溶液为电解液，在-0.4~-0.6V的沉积电位下沉积60-150s，将p型Cu2O电化学沉积在ZnO纳米棒表面，形成Cu2O种子层；以碱性铜盐溶液为沉积溶液，在-0.05～-0.3V的沉积电位下再次采用电化学沉积法将Cu2O自下而上充分填充到纳米棒阵列的空隙中形成ZnO/Cu2O三维结构异质结材料。本发明Cu2O半导体薄膜的填充深度和致密度增加，界面缺陷减少，所制异质结电池电池效率高。
The invention discloses a method for preparing a ZnO/Cu 2 O heterojunction material and a ZnO/Cu 2 O three-dimensional structure heterojunction solar cell. The preparation method of the heterojunction material includes growing an n-type solar cell on a substrate by a liquid phase growth method. ZnO nanorod array thin film, with alkaline copper salt solution as electrolyte, deposited at a deposition potential of -0.4~-0.6V for 60-150s, and electrochemically deposited p-type Cu 2 O on the surface of ZnO nanorods to form Cu 2 O seed layer: with alkaline copper salt solution as the deposition solution, Cu 2 O is fully filled into the gaps of the nanorod array from bottom to top by electrochemical deposition at the deposition potential of -0.05 ~ -0.3V to form ZnO /Cu 2 O three-dimensional structure heterojunction materials. The filling depth and density of the Cu 2 O semiconductor thin film of the invention are increased, interface defects are reduced, and the efficiency of the prepared heterojunction cell is high.
Description
Technical field
The present invention relates to prepare ZnO/Cu
2The method of O three-dimensional structure heterojunction material and with the method for this material preparation solar cell particularly adopts electrochemical deposition technique to fill p type Cu in the semiconductor nanorods array of the n type ZnO of a kind of (002) orientation
2O semiconductor fabrication ZnO/Cu
2The method of O three-dimensional structure heterojunction material and battery device belongs to semiconducter device and technical field of new energies.
Background technology
Cu
2O is a kind of found very early semiconductor material, rare can be by the semiconductor material of excited by visible light, its energy gap is about 2.17eV, can is the excited by visible light of 800 ~ 400nm, Cu in addition by wavelength
2O is nontoxic, and reserves are abundant, and preparation cost is low, theoretical utilising efficiency height, and at electrode materials, catalytic field, aspects such as electron device and gas sensor have important use.Research prepares Cu cheaply
2The O based solar battery realizes that to substituting expensive battery the extensive civil nature of solar cell is significant.By the interface structure pectinationization, preparation three-dimensional structure heterojunction solar battery can effectively increase the heterojunction boundary area, can shorten the collection length of photo-generated carrier like this when increasing the extinction degree of depth, reduce the recombination probability of photo-generated carrier, help improving battery efficiency.Because being subjected to the restriction of the shade influence relevant with complex geometry in filling process, solid inorganic p N-type semiconductorN material often can't cover or be difficult to realize its densification filling in nanoporous in the nanostructured surface conformal, therefore, explore a kind of technology of in the orientation array, fully filling inoganic solids p N-type semiconductorN and prepare the key that the 3-D heterojunction battery is the raising battery technology.Electrochemical deposition method is a kind of effective ways of filling porous material." A Simple Two-Step Electrodeposition of Cu goes up at " physical chemistry magazine " in Cui Jinbao group
2O/ZnO Nanopillar Solar Cells " (J. Phys. Chem. C, 2010,114,6408-6412.) adopt the two-step electrochemical sedimentation to prepare ZnO/Cu in the literary composition
2O three-dimensional structure heterojunction battery; H. " Strong efficient improvements in ultra-low-cost inorganic nanowire solar cells " (Advanced Energy Materials goes up in " advanced energy and material " in C. Hesse group, 2010,25, E1-E5.) the same two-step electrochemical sedimentation that adopts has been prepared ZnO/Cu in the literary composition
2O three-dimensional structure heterojunction battery.
The subject matter of the electrochemical deposition method existence of this class 3-D heterojunction battery of reporting in the document is Cu at present
2O is the single step electrochemical deposition when filling in the ZnO nanometer rod, owing to be subjected to the restriction of material diffusion transport, the maximum filling degree of depth is at 1-1.5um, and realizes the Cu of complete extinction
2The thickness of O is greater than 4um.Therefore, the battery of report has the top of very most of thickness at rod at present.Cu
2O resistance is higher and photo-generated carrier collection length is shorter, excellent top Cu
2The current carrier that O absorbs the photon generation can't fully transmit and separate.In addition, Cu
2The filling of O between nanometer rod is not to fill from bottom to top along the nanometer rod direction, and density is less, and boundary defect is more.These problems have all limited battery efficiency.
Summary of the invention
At filling the deficiency that Cu2O exists in the existing preparation ZnO/Cu2O heterojunction, a kind of method of the ZnO/Cu2O of preparation heterojunction material is provided, this method adopts the two-step electrochemical sedimentation that Cu2O is filled in the ZnO nanometer stick array, the filling degree of depth of gained Cu2O semiconductor film and density increase, and boundary defect reduces.
The present invention also provides the method that adopts this ZnO/Cu2O heterojunction material to prepare solar cell, and the battery that employing present method makes is than existing ZnO/Cu2O heterojunction battery efficient height.
Problem at present existence, the invention provides a kind of electrochemical deposition technique of in the ZnO nanometer stick array, filling Cu2O, the process that this technology will deposit Cu2O was divided into for two steps, earlier in low temperature low activity solution in ZnO nanorod surfaces conformal deposit Cu2O Seed Layer, the realization seed is grown from bottom to top in high temperature high reactivity solution then, form the Cu2O film of high crystalline quality and high-compactness, the ZnO nanometer stick array is filled in densification, has overcome the drawback that existing Cu2O filled with film exists.
Below, specifically set forth technical scheme of the present invention:
A kind of ZnO/Cu
2The preparation method of O heterojunction material, this heterojunction material comprises that substrate, liquid growth are at suprabasil n type ZnO nano-stick array thin film with adopt sedimentation to be filled in Cu in the ZnO nanometer rod
2The O film is characterized in that, Cu
2The filling process of O film may further comprise the steps:
(1) be electrolytic solution with alkaline cupric salt solution ,-0.4 ~-the sedimentation potential deposit 60-150s of 0.6V, with p type Cu
2O is electrochemically-deposited in the ZnO nanorod surfaces, forms Cu
2The O Seed Layer realizes p type Cu
2The O semi-conductor covers the conformal of ZnO nanometer rod; Described current potential refers to the reference electrode with respect to Hg/HgO
(2) be deposit solution with alkaline cupric salt solution ,-0.05～-adopt electrochemical deposition method with Cu once more under the sedimentation potential of 0.3V
2O fully is filled in the space of nanometer stick array, until Cu from bottom to top
2The O clading ZnO nano rod array also stops deposition when exceeding the array 500nm left and right sides, generally between 400-550nm, forms ZnO/Cu
2O three-dimensional structure heterojunction material.
It is that cuprous oxide film is covered the zinc oxide nano rod surface uniformly that described guarantor's row covers, and makes the film thickness unanimity on zinc oxide nano rod surface, keeps the original-shape (cross section is a hexagon) of zinc oxide nano rod, is unlikely to distortion, promptly protects row and covers.
Further, in the step (1), mode of deposition is: electrolytic solution pH 9.0 ~ 10.5, depositing temperature 15-25 ℃; Preferably, electrolytic solution pH 10.5,25 ℃ of depositing temperatures, sedimentation potential-0.5V.
Further, in the step (1), used copper salt solution is the CuSO of 0.2 ~ 0.4mol/L
4, adding lactic acid in the solution as complexing agent, lactic acid concn is 3mol/L.
Further, in the step (2), mode of deposition is: deposit solution pH 11.5 ~ 12.5,40-60 ℃ of depositing temperatures; Preferably, 60 ℃ of depositing temperature 50-, sedimentation potential-0.1～-0.2V.
Further, in the step (2), used copper salt solution is the CuSO of 0.05 ~ 0.4mol/L
4, adding lactic acid in the solution as complexing agent, lactic acid concn is 3mol/L.
Further, the shape characteristic of described n type ZnO nano-stick array thin film is: the thickness of Seed Layer is 100-200nm, and excellent diameter is 30-150nm, and excellent length is 4 μ m, and interrod spacing is 50-150nm.
When the growing ZnO nanorod arrays film, can adopt existing any liquid phase growing method to be prepared, but in order further to guarantee the performance of prepared heterojunction material, authorize the hydrothermal method synthetic technology (method of a kind of controlled oxidation zinc nanometer rod/nano-tube array orientation and shape characteristic that proposes in the patent of invention before can adopting us, CN101319370) preparation n type ZnO nanometer stick array, the gained nanometer rod is (002) orientation, and is functional.
Concrete, the preparation method of n type ZnO nano-stick array thin film is: at first, the technology that adopts sol-gel spin-coating method and rta technique to combine, at the solid or hollow ZnO Seed Layer film of substrate surface height of deposition orientation, then the ZnO Seed Layer film epitaxy in the zinc nitrate aqueous solution that adds polymine that forms is obtained height-oriented ZnO nano-stick array thin film.
Its concrete preparation method is as follows:
(1) the solid or hollow ZnO Seed Layer film of height of deposition orientation in substrate
A. prepare the Seed Layer precursor solution: will wait mole of acetic acid zinc and monoethanolamine stablizer to be dissolved into successively in the ethanol, the acetate zinc concentration is 0.075 ~ 0.3M, and after fully stirring, the sealing homogenizing is made the Seed Layer precursor solution;
B. the cleaning of deposition substrate: substrate is thoroughly cleaned;
C. deposit the ZnO Seed Layer: the Seed Layer precursor solution is spun to substrate surface with the speed of 3000-7500 commentaries on classics/min;
D. with the substrate behind the gluing 280 ℃ of following solvent evaporated or more than the pyrolysis 5min; Transfer in the quick anneal oven, under the temperature of 800 ℃ of 300-, heat-treat, obtain solid or hollow ZnO Seed Layer film;
(2) height-oriented ZnO nanometer rod/nano-pipe array thin film is prepared in epitaxy in solution
A. prepare epitaxy solution: used reagent is the Zn (NO of equimolar amount
3)
26H
2O and vulkacit H, its concentration are 0.01-0.1molL
-1, add the epitaxy conditioning agent of polymine as ZnO nanometer rod/nanotube, its concentration is 5-20mmolL
-1
B. with in the encloses container of epitaxy solution under 85-95 ℃ preheating 0.5-5 hour;
C. adopt the downward mode of end face to put into epitaxial solution solid or hollow ZnO Seed Layer film and grow, growth time is 1-48 hour;
D. the film that will grow takes out, and keep facing down put into static immersions of deionized water 30min fast after, change over to and soak in the dehydrated alcohol more than the 30min, take out final vacuum rapid drying, preservation;
Described thermal treatment is: handling under 300 ℃ the air conditions more than the 5min, handling more than the 5min under 500 ℃ of air conditionses, obtain solid ZnO Seed Layer film.
According to aforesaid method, can obtain the ZnO Seed Layer film of thickness required for the present invention by control spin coating thickness, the composition by epitaxy liquid, concentration, growth time etc. can obtain different rod footpath, interrod spacing and the long ZnO nano-stick array thin film of rod.
The used substrate of the present invention is ITO or FTO conductive glass.
The present invention adopts alkali to reconcile pH, and commonly used is sodium hydroxide.
The present invention also provides a kind of ZnO/Cu
2The preparation method of O three-dimensional structure heterojunction solar battery is characterized in that, step is: at first, utilize each described ZnO/Cu among the claim 1-10
2The preparation method of O three-dimensional structure heterojunction material prepares ZnO/Cu
2O three-dimensional structure heterojunction is then at the Cu of heterojunction
2O layer upper surface splash-proofing sputtering metal or conducting oxide electrode get ZnO/Cu
2O three-dimensional structure heterojunction solar battery.
The used metal electrode of heterojunction solar battery is Au or Pt; Used conducting oxide electrode is ITO or FTO.
Key of the present invention is to adopt two step sedimentations to prepare cuprous oxide film, makes its filling degree of depth in zinc oxide nano rod become big, and overall heterojunction material performance is improved.Two-step approach of the present invention comprises even covering last layer Red copper oxide Seed Layer film on zinc oxide nano rod earlier, and then the cuprous oxide film of fully growing on Seed Layer.
Under the guiding of foregoing invention thinking, the contriver has further explored processing parameter.When the cuprous Seed Layer of capping oxidation, in order to guarantee the even spreadability of Seed Layer on zinc oxide nano rod, guarantee the shape of zinc oxide nano rod, electrolytic solution is under the low activity (low temperature, low pH), in order to guarantee the good deposition of Seed Layer, must keep higher sedimentation potential, therefore, under a large amount of tests, drawn following processing parameter: electrolytic solution pH 9.0 ~ 10.5, depositing temperature 15-25 ℃, sedimentation potential-0.4 ~-0.6V; On the basis that forms Seed Layer, can fully fill cupric oxide by electrochemical deposition technique again, increase it and fill the degree of depth.Fill from bottom to top for controlled oxidation is cuprous, must carry out under the high temperature high reactivity, its processing condition are: deposit solution pH 11.5 ~ 12.5, and 40-60 ℃ of depositing temperatures, sedimentation potential-0.05～-0.3V.Avoided the defective that density is little, boundary defect is many according to the cuprous oxide film that present method makes, performance also is improved when heterojunction material is prepared into battery.
Beneficial effect of the present invention is:
(1) the sedimentary Seed Layer of low temperature low activity has improved Cu
2O is in the covering homogeneity of nanorod surfaces, and follow-up high-temperature high concentration high reactivity solution has guaranteed Cu
2O is growth from bottom to top in the ZnO nanometer rod.So both can improve Cu
2The crystalline quality of O has increased density again, and boundary defect is few, and the recombination probability of photo-generated carrier is low;
(2) high density high reactivity solution guarantees Cu
2O grows under the low deposition current potential, and the material diffusion no longer is sedimentary conditioning step, Cu
2The filling degree of depth of O increases, and photohole is at Cu
2The collection length of transmission route among the O and current carrier is short, is expected to improve battery efficiency.
(3) adopt special ZnO nanometer stick array preparation method, prevent the heterojunction leakage current, make the heterojunction material overall performance better.
(4) ZnO/Cu that makes among the present invention
2O heterojunction solar battery commutating ratio and electricity conversion are higher, possess aboundresources, nontoxic and advantage that cost is low, have extraordinary application potential.
Description of drawings
Fig. 1 Cu
2The preparation were established figure of O/ZnO 3-D heterojunction solar cell.
Fig. 2 is field emission scanning electron microscope (FESEM) photo of hydrothermal method synthetic ZnO nanometer stick array.
Fig. 3 is the Cu of the embodiment of the invention 1 preparation
2The field emission scanning electron microscope in the transverse section of O/ZnO heterojunction material (FESEM) photo.
Fig. 4 is not for adopting heterojunction field emission scanning electron microscope (FESEM) photo of method preparation provided by the present invention.
Fig. 5 is the Cu of the embodiment of the invention 3 preparations
2The rectification curve of O/ZnO 3-D heterojunction solar cell, among the figure, X-coordinate is a bias voltage, ordinate zou is a current density.
Fig. 6 is the Cu of the embodiment of the invention 5 preparations
2The field emission scanning electron microscope in the transverse section of O/ZnO heterojunction material (FESEM) photo.
Fig. 7 is the Cu of the embodiment of the invention 6 preparations
2The field emission scanning electron microscope in the transverse section of O/ZnO heterojunction material (FESEM) photo.
The Cu that Fig. 8 is equipped with for embodiment of the invention system 9
2The field emission scanning electron microscope in the transverse section of O/ZnO heterojunction material (FESEM) photo.
Embodiment
The present invention will be further elaborated below in conjunction with the drawings and specific embodiments, should be understood that, following explanation only is in order to explain the present invention, is not to limit it.
In following examples, the method of growing ZnO nanorod arrays film is to adopt the method for patent CN101319370 in substrate, made ZnO nano-stick array thin film as shown in Figure 2, in this patent detailed elaboration prepare the method for the ZnO nano-stick array thin film of different nanometer rod length, spacing, rod footpath, seed layer thickness, used ZnO nanometer stick array can be by epitaxy liquid composition, concentration, growth time etc. can obtain different rod footpath, interrod spacing and the long ZnO nano-stick array thin film of rod, do not repeat them here.Except that this method, also can adopt the method for other liquid phase growth ZnO nano-stick array thin film.
Below to the improved place of emphasis of the present invention---the preparation of cuprous oxide film is explained in detail.
Embodiment 1
(1) adopt hydrothermal growth ZnO nanometer stick array on the ITO conductive substrates, its seed layer thickness is 150nm, and excellent length is 4 μ m, and interrod spacing is 150nm, rod footpath 150.
(2) preparation p type Cu
2The semi-conductive precursor solution of O is with CuSO
4Solution adds lactic acid as stablizer, wherein CuSO as precursor solution
4Concentration be 0.2mol/L, concentration of lactic acid is 3mol/L, with NaOH regulator solution pH=10.5;
(3) with above-mentioned precursor solution as electrolytic solution, at ZnO nanorod surfaces electrochemistry conformal deposit Cu
2The O Seed Layer, the condition of deposition process is: 25 ℃ of temperature, sedimentation potential-0.4V, depositing time 100s.
(4) preparation p type Cu
2The semi-conductive deposit solution of O is with CuSO
4Solution adds lactic acid as stablizer, wherein CuSO as deposit solution
4Concentration be 0.2mol/L, concentration of lactic acid is 3mol/L, is 11.5 with NaOH regulator solution pH, is 50 ℃ in temperature, sedimentation potential is-0.12V deposit 8 h, with Cu
2O fully is filled in the space of ZnO nanometer stick array from bottom to top.
(5) with the air drying of post-depositional material, promptly get ZnO/Cu at 100 ℃
2The O heterojunction material.
From Fig. 3 FESEM picture Cu as can be seen
2The complete densification of O crystal shows filling characteristics from bottom to top clearly in the middle of the ZnO nanometer stick array.Fig. 4 is not for adopting heterojunction field emission scanning electron microscope (FESEM) photo of method preparation provided by the present invention, Cu as we can see from the figure
2O is single crystal grain and is dispersed on the ZnO nanometer rod, and the densification from bottom to top of being unrealized is filled.
(1) adopt hydrothermal growth ZnO nanometer stick array on the ITO conductive substrates, its seed layer thickness is 100nm, and excellent length is 4 μ m, and interrod spacing is 100nm, rod footpath 50nm.
(2) preparation p type Cu
2The semi-conductive precursor solution of O is with CuSO
4Solution adds lactic acid as stablizer, wherein CuSO as precursor solution
4Concentration be 0.2mol/L, concentration of lactic acid is 3mol/L, with NaOH regulator solution pH=9.0;
(3) with above-mentioned precursor solution as electrolytic solution, at ZnO nanorod surfaces electrochemistry conformal deposit Cu
2The O Seed Layer, the condition of deposition process is: 15 ℃ of temperature, sedimentation potential-0.5V, depositing time 100s.
(4) preparation p type Cu
2The semi-conductive deposit solution of O is with CuSO
4Solution adds lactic acid as stablizer, wherein CuSO as deposit solution
4Concentration be 0.05mol/L, concentration of lactic acid is 3mol/L, is 11.5 with NaOH regulator solution pH, is 50 ℃ in temperature, sedimentation potential is-0.3V deposit 15h, with Cu
2O fully is filled in the space of ZnO nanometer stick array from bottom to top.
(5) with the air drying of post-depositional material, promptly get ZnO/Cu at 100 ℃
2The O heterojunction material.
Embodiment 3
(1) adopt hydrothermal growth ZnO nanometer stick array on the ITO conductive substrates, its seed layer thickness is 150nm, and excellent length is 4 μ m, and interrod spacing is 150nm, rod footpath 150.
(2) preparation p type Cu
2The semi-conductive precursor solution of O is with CuSO
4Solution adds lactic acid as stablizer, wherein CuSO as precursor solution
4Concentration be 0.2mol/L, concentration of lactic acid is 3mol/L, with NaOH regulator solution pH=9.0;
(3) with above-mentioned precursor solution as electrolytic solution, at ZnO nanorod surfaces electrochemistry conformal deposit Cu
2The O Seed Layer, the condition of deposition process is: 25 ℃ of temperature, sedimentation potential-0.4V, depositing time 100s.
(4) preparation p type Cu
2The semi-conductive deposit solution of O is with CuSO
4Solution adds lactic acid as stablizer, wherein CuSO as deposit solution
4Concentration be 0.2mol/L, concentration of lactic acid is 3mol/L, is 11.5 with NaOH regulator solution pH, is 60 ℃ in temperature, sedimentation potential is-0.22V deposit 9.5 h, with Cu
2O fully is filled in the space of ZnO nanometer stick array from bottom to top.
(5) with the air drying of post-depositional material, promptly get ZnO/Cu at 100 ℃
2The O heterojunction material.
Shown in rectification curve among Fig. 5, its commutating ratio be about the 100(test voltage for+2.0V and-2.0V), Cu is described
2The O/ZnO heterojunction has interface quality preferably, Cu
2Form good electrical contact between O and the ZnO nanometer rod.
Embodiment 4
(1) adopt hydrothermal growth ZnO nanometer stick array on the ITO conductive substrates, its seed layer thickness is 150nm, and excellent length is 4 μ m, and interrod spacing is 150nm, rod footpath 150.
(2) preparation p type Cu
2The semi-conductive precursor solution of O is with CuSO
4Solution adds lactic acid as stablizer, wherein CuSO as precursor solution
4Concentration be 0.2mol/L, concentration of lactic acid is 3mol/L, with NaOH regulator solution pH=10.5;
(3) with above-mentioned precursor solution as electrolytic solution, at ZnO nanorod surfaces electrochemistry conformal deposit Cu
2The O Seed Layer, the condition of deposition process is: 15 ℃ of temperature, sedimentation potential-0.6V, depositing time 100s.
(4) preparation p type Cu
2The semi-conductive deposit solution of O is with CuSO
4Solution adds lactic acid as stablizer, wherein CuSO as deposit solution
4Concentration be 0.05mol/L, concentration of lactic acid is 3mol/L, is 11.5 with NaOH regulator solution pH, is 50 ℃ in temperature, sedimentation potential is-0.12V deposit 68 h, with Cu
2O fully is filled in the space of ZnO nanometer stick array from bottom to top.
(5) with the air drying of post-depositional material, promptly get ZnO/Cu at 100 ℃
2The O heterojunction material.
(1) adopt hydrothermal growth ZnO nanometer stick array on the ITO conductive substrates, its seed layer thickness is 100nm, and excellent length is 4 μ m, and interrod spacing is 100nm, rod footpath 50nm.
(2) preparation p type Cu
2The semi-conductive precursor solution of O is with CuSO
4Solution adds lactic acid as stablizer, wherein CuSO as precursor solution
4Concentration be 0.4mol/L, concentration of lactic acid is 3mol/L, with NaOH regulator solution pH=10.5;
(3) with above-mentioned precursor solution as electrolytic solution, at ZnO nanorod surfaces electrochemistry conformal deposit Cu
2The O Seed Layer, the condition of deposition process is: 25 ℃ of temperature, sedimentation potential-0.4V, depositing time 100s.
(4) preparation p type Cu
2The semi-conductive deposit solution of O is with CuSO
4Solution adds lactic acid as stablizer, wherein CuSO as deposit solution
4Concentration be 0.2mol/L, concentration of lactic acid is 3mol/L, is 11.5 with NaOH regulator solution pH, is 60 ℃ in temperature, sedimentation potential is-0.15V deposit 6 h, with Cu
2O fully is filled in the space of ZnO nanometer stick array from bottom to top.
(5) with the air drying of post-depositional material, promptly get ZnO/Cu at 100 ℃
2The O heterojunction material.
From Fig. 6 FESEM picture as can be seen, Cu
2The complete densification of O crystal shows filling characteristics from bottom to top clearly in the middle of the ZnO nanometer stick array.
Embodiment 6
(1) adopt hydrothermal growth ZnO nanometer stick array on the ITO conductive substrates, its seed layer thickness is 100nm, and excellent length is 4 μ m, and interrod spacing is 100nm, rod footpath 100nm.
(2) preparation p type Cu
2The semi-conductive precursor solution of O is with CuSO
4Solution adds lactic acid as stablizer, wherein CuSO as precursor solution
4Concentration be 0.4mol/L, concentration of lactic acid is 3mol/L, with NaOH regulator solution pH=9.0;
(3) with above-mentioned precursor solution as electrolytic solution, at ZnO nanorod surfaces electrochemistry conformal deposit Cu
2The O Seed Layer.The condition of deposition process is: 18 ℃ of temperature, sedimentation potential-0.6V, depositing time 60s.
(4) preparation p type Cu
2The semi-conductive deposit solution of O is with CuSO
4Solution adds lactic acid as stablizer, wherein CuSO as deposit solution
4Concentration be 0.2mol/L, concentration of lactic acid is 3mol/L, is 11.5 with NaOH regulator solution pH, is 60 ℃ in temperature, sedimentation potential is-0.13V deposit 8h, with Cu
2O fully is filled in the space of ZnO nanometer stick array from bottom to top.
(5) with the air drying of post-depositional material, promptly get ZnO/Cu at 100 ℃
2The O heterojunction material.
From Fig. 7 FESEM picture as can be seen, Cu
2The complete densification of O crystal shows filling characteristics from bottom to top clearly in the middle of the ZnO nanometer stick array.
Embodiment 7
(1) adopt hydrothermal growth ZnO nanometer stick array on the ITO conductive substrates, its seed layer thickness is 100nm, and excellent length is 4 μ m, and interrod spacing is 100nm, rod footpath 100nm.
(2) preparation p type Cu
2The semi-conductive precursor solution of O is with CuSO
4Solution adds lactic acid as stablizer, wherein CuSO as precursor solution
4Concentration be 0.4mol/L, concentration of lactic acid is 3mol/L, with NaOH regulator solution pH=9.0;
(3) with above-mentioned precursor solution as electrolytic solution, at ZnO nanorod surfaces electrochemistry conformal deposit Cu
2The O Seed Layer.The condition of deposition process is: 25 ℃ of temperature, sedimentation potential-0.4V, depositing time 100s.
(4) preparation p type Cu
2The semi-conductive deposit solution of O is with CuSO
4Solution adds lactic acid as stablizer, wherein CuSO as deposit solution
4Concentration be 0.05mol/L, concentration of lactic acid is 3mol/L, is 12.5 with NaOH regulator solution pH, is 60 ℃ in temperature, sedimentation potential is-0.12V deposit 55h, with Cu
2O fully is filled in the space of ZnO nanometer stick array from bottom to top.
(5) with the air drying of post-depositional material, promptly get ZnO/Cu at 100 ℃
2The O heterojunction material.
Embodiment 8
(1) adopt hydrothermal growth ZnO nanometer stick array on the ITO conductive substrates, its seed layer thickness is 100nm, and excellent length is 4 μ m, and interrod spacing is 150nm, rod footpath 100nm.
(2) preparation p type Cu
2The semi-conductive precursor solution of O is with CuSO
4Solution adds lactic acid as stablizer, wherein CuSO as precursor solution
4Concentration be 0.2mol/L, concentration of lactic acid is 3mol/L, with NaOH regulator solution pH=9.0;
(3) with above-mentioned precursor solution as electrolytic solution, at ZnO nanorod surfaces electrochemistry conformal deposit Cu
2The O Seed Layer, the condition of deposition process is: 25 ℃ of temperature, sedimentation potential-0.5V, depositing time 60s.
(4) preparation p type Cu
2The semi-conductive deposit solution of O is with CuSO
4Solution adds lactic acid as stablizer, wherein CuSO as deposit solution
4Concentration be 0.4mol/L, concentration of lactic acid is 3mol/L, is 12.5 with NaOH regulator solution pH, is 40 ℃ in temperature, sedimentation potential is-0.05V deposit 68h, with Cu
2O fully is filled in the space of ZnO nanometer stick array from bottom to top.
(5) with the air drying of post-depositional material, promptly get ZnO/Cu at 100 ℃
2The O heterojunction material.
Embodiment 9
(1) adopt hydrothermal growth ZnO nanometer stick array on the ITO conductive substrates, its seed layer thickness is 100nm, and excellent length is 4 μ m, and interrod spacing is 100nm, rod footpath 150nm.
(2) preparation p type Cu
2The semi-conductive precursor solution of O is with CuSO
4Solution adds lactic acid as stablizer, wherein CuSO as precursor solution
4Concentration be 0.2mol/L, concentration of lactic acid is 3mol/L, with NaOH regulator solution pH=10.0;
(3) with above-mentioned precursor solution as electrolytic solution, at ZnO nanorod surfaces electrochemistry conformal deposit Cu
2The O Seed Layer, the condition of deposition process is: 20 ℃ of temperature, sedimentation potential-0.5V, depositing time 100s.
(4) preparation p type Cu
2The semi-conductive deposit solution of O is with CuSO
4Solution adds lactic acid as stablizer, wherein CuSO as deposit solution
4Concentration be 0.2mol/L, concentration of lactic acid is 3mol/L, is 11.5 with NaOH regulator solution pH, is 50 ℃ in temperature, sedimentation potential is-0.2V deposit 18h, with Cu
2O fully is filled in the space of ZnO nanometer stick array from bottom to top.
(5) with the air drying of post-depositional material, promptly get ZnO/Cu at 100 ℃
2The O heterojunction material.
From Fig. 8 FESEM picture as can be seen, Cu
2The complete densification of O crystal shows filling characteristics from bottom to top clearly in the middle of the ZnO nanometer stick array.
ZnO/Cu with gained among the foregoing description 1-9
2The Cu of O heterojunction material
2O layer upper surface splash-proofing sputtering metal or conducting oxide electrode get ZnO/Cu
2O three-dimensional structure heterojunction solar battery, used metal electrode are Au or Pt, and conducting oxide electrode is ITO or FTO.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101839937A CN102268706A (en) | 2011-07-04 | 2011-07-04 | Methods for preparing ZnO/Cu2O heterojunction material and ZnO/Cu2O three-dimensional heterojunction solar cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101839937A CN102268706A (en) | 2011-07-04 | 2011-07-04 | Methods for preparing ZnO/Cu2O heterojunction material and ZnO/Cu2O three-dimensional heterojunction solar cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102268706A true CN102268706A (en) | 2011-12-07 |
Family
ID=45051153
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011101839937A Pending CN102268706A (en) | 2011-07-04 | 2011-07-04 | Methods for preparing ZnO/Cu2O heterojunction material and ZnO/Cu2O three-dimensional heterojunction solar cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102268706A (en) |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102732927A (en) * | 2012-07-17 | 2012-10-17 | 西北工业大学 | Preparation method of zinc oxide/ cuprous oxide heterojunction |
| CN104941644A (en) * | 2014-07-28 | 2015-09-30 | 太原科技大学 | Preparation method of three-dimensional thin film heterojunction photocatalyst based on cuprous oxide |
| CN105185859A (en) * | 2015-06-15 | 2015-12-23 | 华南师范大学 | Manufacturing method for efficient heterojunction inorganic solar energy cells |
| CN105420780A (en) * | 2015-11-06 | 2016-03-23 | 常州大学怀德学院 | Preparation method of composite nano heterojunction thin film material and preparation method of composite heterojunction solar battery |
| CN105568313A (en) * | 2015-12-11 | 2016-05-11 | 苏州大学 | 3D branch semiconductor nano heterojunction photoelectrode material and preparing method thereof |
| CN105762219A (en) * | 2016-05-11 | 2016-07-13 | 重庆大学 | Cuprous oxide-based multi-lamination heterojunction solar cell and preparation method thereof |
| CN106328750A (en) * | 2016-10-25 | 2017-01-11 | 合肥工业大学 | Heterojunction solar cell with core-shell structure based on chalcogencuprous compound and preparing method thereof |
| CN108043410A (en) * | 2017-11-07 | 2018-05-18 | 国家纳米科学中心 | Cu is modified on top2ZnO nanorod hetero-junctions of O and preparation method and application |
| CN108508070A (en) * | 2017-02-27 | 2018-09-07 | 中国科学院苏州纳米技术与纳米仿生研究所 | Au/Cu/Cu2O nanofibers ball, preparation method and application |
| CN108940281A (en) * | 2018-08-03 | 2018-12-07 | 青岛理工大学 | Novel nano photocatalytic material Ag2MoO4-WO3Method for preparing heterojunction |
| CN109507267A (en) * | 2018-11-27 | 2019-03-22 | 临沂大学 | The sensing material and preparation method thereof fast detected for biological hydrogen sulfide |
| CN109828009A (en) * | 2019-01-29 | 2019-05-31 | 吉林大学 | A kind of H based on metal oxide semiconductor films material2S gas sensor and preparation method thereof |
| CN110112225A (en) * | 2019-04-04 | 2019-08-09 | 浙江师范大学 | A kind of zinc oxide heterogeneous joint solar cell of cuprous oxide-and preparation method thereof |
| CN110634972A (en) * | 2019-09-30 | 2019-12-31 | 东北财经大学 | A cuprous oxide/zinc copper oxide/zinc oxide device with a magnesium nitride shell |
| CN111668354A (en) * | 2019-03-08 | 2020-09-15 | 华南师范大学 | InGaN-based LED epitaxial wafer and preparation method thereof |
| CN111755256A (en) * | 2020-07-14 | 2020-10-09 | 湖州师范学院 | A three-dimensional ZnO/CuO nano-heterogeneous hierarchical structure photoelectrode and its preparation method |
| CN113517374A (en) * | 2021-06-30 | 2021-10-19 | 南京邮电大学 | Preparation method of heterojunction arrays of zinc oxide-coated copper oxide nanowires |
| CN114917913A (en) * | 2022-05-26 | 2022-08-19 | 西安理工大学 | Preparation method of Cu2O/ZnO nanowire array composite thin film photocatalytic material |
| CN115101624A (en) * | 2022-06-20 | 2022-09-23 | 燕山大学 | Faraday heterojunction array electrode, preparation method thereof and light rechargeable battery |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101319370A (en) * | 2008-06-24 | 2008-12-10 | 济南大学 | A method to control the orientation and morphology characteristics of ZnO nanorod/nanotube arrays |
-
2011
- 2011-07-04 CN CN2011101839937A patent/CN102268706A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101319370A (en) * | 2008-06-24 | 2008-12-10 | 济南大学 | A method to control the orientation and morphology characteristics of ZnO nanorod/nanotube arrays |
Non-Patent Citations (3)
| Title |
|---|
| 刘维一等: "铝衬底硅颗粒太阳电池制备工艺研究", 《太阳能学报》 * |
| 刘英麟等: "用电化学沉积法制备ZnO/ Cu2O异质p-n结", 《发光学报》 * |
| 武卫兵等: "电化学法制备ｐ型Cu2O半导体薄膜及其性能的表征", 《西安交通大学学报》 * |
Cited By (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102732927A (en) * | 2012-07-17 | 2012-10-17 | 西北工业大学 | Preparation method of zinc oxide/ cuprous oxide heterojunction |
| CN104941644A (en) * | 2014-07-28 | 2015-09-30 | 太原科技大学 | Preparation method of three-dimensional thin film heterojunction photocatalyst based on cuprous oxide |
| CN105185859A (en) * | 2015-06-15 | 2015-12-23 | 华南师范大学 | Manufacturing method for efficient heterojunction inorganic solar energy cells |
| CN105185859B (en) * | 2015-06-15 | 2018-06-26 | 华南师范大学 | The preparation method of High-efficiency heterojunction inorganic solar cell |
| CN105420780A (en) * | 2015-11-06 | 2016-03-23 | 常州大学怀德学院 | Preparation method of composite nano heterojunction thin film material and preparation method of composite heterojunction solar battery |
| CN105568313A (en) * | 2015-12-11 | 2016-05-11 | 苏州大学 | 3D branch semiconductor nano heterojunction photoelectrode material and preparing method thereof |
| CN105762219A (en) * | 2016-05-11 | 2016-07-13 | 重庆大学 | Cuprous oxide-based multi-lamination heterojunction solar cell and preparation method thereof |
| CN106328750A (en) * | 2016-10-25 | 2017-01-11 | 合肥工业大学 | Heterojunction solar cell with core-shell structure based on chalcogencuprous compound and preparing method thereof |
| CN108508070A (en) * | 2017-02-27 | 2018-09-07 | 中国科学院苏州纳米技术与纳米仿生研究所 | Au/Cu/Cu2O nanofibers ball, preparation method and application |
| CN108508070B (en) * | 2017-02-27 | 2020-06-23 | 中国科学院苏州纳米技术与纳米仿生研究所 | Au/Cu/Cu2O nanofiber ball, its preparation method and application |
| CN108043410B (en) * | 2017-11-07 | 2020-05-19 | 国家纳米科学中心 | Top modified Cu2ZnO nanorod heterojunction of O, and preparation method and application thereof |
| CN108043410A (en) * | 2017-11-07 | 2018-05-18 | 国家纳米科学中心 | Cu is modified on top2ZnO nanorod hetero-junctions of O and preparation method and application |
| CN108940281B (en) * | 2018-08-03 | 2020-12-18 | 青岛理工大学 | Preparation method of a new nanometer photocatalytic material Ag2MoO4-WO3 heterojunction |
| CN108940281A (en) * | 2018-08-03 | 2018-12-07 | 青岛理工大学 | Novel nano photocatalytic material Ag2MoO4-WO3Method for preparing heterojunction |
| CN109507267B (en) * | 2018-11-27 | 2020-11-06 | 临沂大学 | Sensing material for quickly detecting biological hydrogen sulfide and preparation method thereof |
| CN109507267A (en) * | 2018-11-27 | 2019-03-22 | 临沂大学 | The sensing material and preparation method thereof fast detected for biological hydrogen sulfide |
| CN109828009B (en) * | 2019-01-29 | 2021-08-13 | 吉林大学 | A kind of H2S gas sensor based on metal oxide semiconductor thin film material and preparation method thereof |
| CN109828009A (en) * | 2019-01-29 | 2019-05-31 | 吉林大学 | A kind of H based on metal oxide semiconductor films material2S gas sensor and preparation method thereof |
| CN111668354A (en) * | 2019-03-08 | 2020-09-15 | 华南师范大学 | InGaN-based LED epitaxial wafer and preparation method thereof |
| CN111668354B (en) * | 2019-03-08 | 2021-08-17 | 华南师范大学 | InGaN-based LED epitaxial wafer and preparation method thereof |
| US12009455B2 (en) | 2019-03-08 | 2024-06-11 | Univ South China Normal | InGaN-based led epitaxial wafer and fabrication method thereof |
| CN110112225A (en) * | 2019-04-04 | 2019-08-09 | 浙江师范大学 | A kind of zinc oxide heterogeneous joint solar cell of cuprous oxide-and preparation method thereof |
| CN110634972B (en) * | 2019-09-30 | 2020-12-15 | 东北财经大学 | A cuprous oxide/zinc copper oxide/zinc oxide device with magnesium nitride shell |
| CN110634972A (en) * | 2019-09-30 | 2019-12-31 | 东北财经大学 | A cuprous oxide/zinc copper oxide/zinc oxide device with a magnesium nitride shell |
| CN111755256A (en) * | 2020-07-14 | 2020-10-09 | 湖州师范学院 | A three-dimensional ZnO/CuO nano-heterogeneous hierarchical structure photoelectrode and its preparation method |
| CN111755256B (en) * | 2020-07-14 | 2022-03-29 | 湖州师范学院 | Preparation method of three-dimensional ZnO/CuO nano heterogeneous hierarchical structure photoelectrode |
| CN113517374A (en) * | 2021-06-30 | 2021-10-19 | 南京邮电大学 | Preparation method of heterojunction arrays of zinc oxide-coated copper oxide nanowires |
| CN114917913A (en) * | 2022-05-26 | 2022-08-19 | 西安理工大学 | Preparation method of Cu2O/ZnO nanowire array composite thin film photocatalytic material |
| CN115101624A (en) * | 2022-06-20 | 2022-09-23 | 燕山大学 | Faraday heterojunction array electrode, preparation method thereof and light rechargeable battery |
| CN115101624B (en) * | 2022-06-20 | 2024-07-16 | 燕山大学 | Faraday heterojunction array electrode, preparation method thereof and photo-chargeable battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102268706A (en) | Methods for preparing ZnO/Cu2O heterojunction material and ZnO/Cu2O three-dimensional heterojunction solar cell | |
| CN103456888B (en) | A kind of Cs doping ZnO is the hybrid solar cell of electron transfer layer | |
| CN103474574A (en) | Hybrid solar cell with aluminum-doped zinc oxide nanorod as electron transfer layer | |
| CN102544214B (en) | Method for preparing ZnO nano array at window layer of solar battery | |
| CN101577228B (en) | A method for preparing a three-dimensional heterojunction device | |
| Lee et al. | Superstrate CuInS2 photovoltaics with enhanced performance using a CdS/ZnO nanorod array | |
| CN103367512A (en) | Solar battery based on inorganic bulk heterojunction and preparation method thereof | |
| CN102392282B (en) | A method for electrochemically preparing cadmium telluride semiconductor thin films under aqueous alkaline conditions | |
| CN105568313B (en) | Branched semiconductor nano heterojunction photovoltaic pole materials of 3D and preparation method thereof | |
| CN102208487B (en) | Preparation method of nanostructure heterojunction of CuInSe nanocrystal, cadmium sulfide quantum dot and zinc oxide nanowire array | |
| CN102169910B (en) | Thin film solar cell based on sulfur compound nanocrystalline | |
| CN102723208A (en) | Preparation method of composite nanowire array with one-dimensional ZnO(zinc oxide)-TiO2(titanium dioxide) core-shell structure | |
| CN103137868B (en) | Organic/ inorganic hybridization solar battery based on ternary nanometer array and preparation method thereof | |
| Xiong et al. | Fabrication and electrical characterization of ZnO rod arrays/CuSCN heterojunctions | |
| CN108281550B (en) | Based on the titania-doped perovskite solar battery and preparation method thereof of magnesium | |
| CN109728119A (en) | A kind of graphene/AlGaAs/GaAs/GaInAs multi-heterojunction solar cell and preparation method thereof | |
| US20080314435A1 (en) | Nano engineered photo electrode for photoelectrochemical, photovoltaic and sensor applications | |
| CN104241439B (en) | A kind of preparation method of cadmium telluride diaphragm solar battery | |
| CN107732014B (en) | A kind of solar cell based on ternary inorganic bulk heterojunction thin film and preparation method thereof | |
| CN109904319A (en) | Large-size perovskite flat crystal, perovskite layer preparation method and solar cell | |
| CN102790117A (en) | GaInP/GaAs/InGaNAs/Ge four-junction solar cell and preparation method thereof | |
| JP2003258278A (en) | Photoelectric conversion device and manufacturing method thereof | |
| CN112563118A (en) | In-doped CdS film, preparation method and CIGS cell prepared by same | |
| CN103074683A (en) | Coaxial homogeneous ZnO pn junction nanorod and preparation method thereof | |
| CN107364836B (en) | Tin-germanium-sulfur selenide thin film, preparation method thereof and photoelectric conversion device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20111207 |