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
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Abstract
The invention discloses methods for preparing a ZnO/Cu2O heterojunction material and a ZnO/Cu2O three-dimensional heterojunction solar cell. The method for preparing the heterojunction material comprises the following steps of: growing an n-type ZnO nanorod array film on a substrate by using a liquid-phase growth method, depositing for 60-150 seconds at the deposition potential from negative 0.4 volt to negative 0.6 volt by adopting an alkaline copper salt solution as the electrolyte, and electrochemically depositing p-type Cu2O on the surface of the ZnO nanorod to form a Cu2O seed layer; and by adopting the alkaline copper salt solution as the deposition solution and adopting the electrochemical deposition method again at the deposition potential from negative 0.05 volt to negative 0.3 volt, fully filling the Cu2O in clearances in the nanorod array from bottom to top to form the ZnO/Cu2O three-dimensional heterojunction material. According to the invention, the filling depth and the density of a Cu2O semiconductor film are increased, the interface defect is reduced and the cell 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)
1. 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;
(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 array 400-550nm, forms ZnO/Cu
2O three-dimensional structure heterojunction material.
2. preparation method according to claim 1 is characterized in that: in the step (1), mode of deposition is: electrolytic solution pH 9.0 ~ 10.5, depositing temperature 15-25 ℃; In the step (2), mode of deposition is: deposit solution pH 11.5 ~ 12.5,40-60 ℃ of depositing temperatures.
3. preparation method according to claim 2 is characterized in that: in the step (1), mode of deposition is: electrolytic solution pH 10.5,25 ℃ of depositing temperatures, sedimentation potential-0.5V.
4. preparation method according to claim 2 is characterized in that: in the step (2), mode of deposition is: 60 ℃ of depositing temperature 50-, and sedimentation potential-0.1～-0.2V.
5. preparation method according to claim 1 is characterized in that: 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; 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.
6. preparation method according to claim 1 is characterized in that: 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.
7. preparation method according to claim 1, the preparation method who it is characterized in that 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 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.
8. preparation method according to claim 1 is characterized in that: described substrate is ITO or FTO conductive glass.
9. 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 1-8
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.
10. preparation method according to claim 9 is characterized in that: described metal electrode is Au or Pt; Described conducting oxide electrode is ITO or FTO.
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