CN104851930A - All-solid-state photoelectric conversion device and preparation method thereof - Google Patents
All-solid-state photoelectric conversion device and preparation method thereof Download PDFInfo
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- CN104851930A CN104851930A CN201510152555.2A CN201510152555A CN104851930A CN 104851930 A CN104851930 A CN 104851930A CN 201510152555 A CN201510152555 A CN 201510152555A CN 104851930 A CN104851930 A CN 104851930A
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- 238000006243 chemical reaction Methods 0.000 title abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000010408 film Substances 0.000 claims description 124
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 78
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 54
- 238000005498 polishing Methods 0.000 claims description 54
- 238000007254 oxidation reaction Methods 0.000 claims description 49
- 230000003647 oxidation Effects 0.000 claims description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 229910052697 platinum Inorganic materials 0.000 claims description 27
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 24
- 239000003792 electrolyte Substances 0.000 claims description 24
- 239000012530 fluid Substances 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 18
- 238000000151 deposition Methods 0.000 claims description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 12
- 239000003822 epoxy resin Substances 0.000 claims description 12
- 229920000647 polyepoxide Polymers 0.000 claims description 12
- 230000008021 deposition Effects 0.000 claims description 11
- 238000005538 encapsulation Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 230000000717 retained effect Effects 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 238000004062 sedimentation Methods 0.000 claims description 4
- 238000000427 thin-film deposition Methods 0.000 claims description 4
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000007517 polishing process Methods 0.000 claims description 3
- -1 under stirring Substances 0.000 claims description 2
- 238000007743 anodising Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000004044 response Effects 0.000 abstract description 2
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- 238000012986 modification Methods 0.000 abstract 1
- 238000005286 illumination Methods 0.000 description 21
- 238000004549 pulsed laser deposition Methods 0.000 description 17
- 229910007605 Zn—ZnO Inorganic materials 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 8
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- 229910010413 TiO 2 Inorganic materials 0.000 description 7
- 238000005229 chemical vapour deposition Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000005566 electron beam evaporation Methods 0.000 description 4
- 238000001755 magnetron sputter deposition Methods 0.000 description 4
- 230000005693 optoelectronics Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 4
- 238000001429 visible spectrum Methods 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002784 hot electron Substances 0.000 description 3
- 238000004502 linear sweep voltammetry Methods 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
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- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
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- 238000004847 absorption spectroscopy Methods 0.000 description 1
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- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
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- 238000002256 photodeposition Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/0296—Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1828—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/543—Solar cells from Group II-VI materials
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- 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
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Abstract
An all-solid-state photoelectric conversion device and a preparation method thereof. The photoelectric conversion device is of a Zn-ZnO-Ag structure. A lower layer of the photoelectric conversion device is a Zn sheet, a middle layer is a ZnO film, and an upper layer is a Ag film deposited on the ZnO film. The ZnO film is poriform, and is generated on the Zn sheet located at the lower layer by anodizing. The ZnO film is black blue poriform, the diameter is 30 to 100nm, and the thickness is 2.6 to 5.0[mu]m. Low-cost anodizing technology is adopted to realize preparation of a heterogeneous layer, through AG film modification, an all-solid-state photoelectric conversion device having sunlight response is obtained, and the method provides possibilities of use of the photoelectric conversion device under various conditions and large-scale production, and thus can alleviate energy pressure.
Description
Technical field
The invention belongs to photovoltaic energy conversion device, be specifically related to a kind of all solid state electrooptical device with metal-semiconductor-metal, collection and the conversion of solar energy can be realized.
Background technology
In order to realize utilizing solar energy to provide the idea of electric power energy for the mankind, research and development electrooptical device is the focus that people study always.All solid state metal-semiconductor switching device because its structure is simple, highly sensitive, can effectively break through the conversion efficiency limit and receive much concern.The operation principle of all solid state electrooptical device of metal-semiconductor is: produce surface plasma after the metal surface of nanostructure is subject to illumination, surface plasma deexcitation produces high-octane hot electron, energy is 1 to 3eV, the hot electron that nearly metal surface area produces is transferred to metal-semiconductor interface place, and a certain proportion of have enough high-octane electronics and can pass over Schottky barrier and produce steady-state current.
Document Nano Letters, reports a kind of use SiO in DOI:10.1021/nl2022459
2be TiO prepared by substrate
2/ Au electrooptical device, SiO
2, TiO
2, Au thickness be respectively 200nm, 150nm, 10nm, have employed the chemical vapour deposition (CVD) of high vacuum, magnetron sputtering and the method such as electron beam evaporation and high annealing respectively.
Document The Journal of Physical Chemistry, has prepared respectively with SiO in DOI:10.1021/jp409894b
2for the TiO of substrate
2/ Au and TiO
2the Schottky electrooptical device of/Ag structure, the method such as electron beam evaporation, magnetron sputtering that employs equally deposited thick Au and the Ag film of 10nm.
Document Applied Physics Letters, reports SiO in DOI:10.1063/4799156
2suprabasil TiO
2the electrooptical device of/Au/Ag nanowire composite structures, SiO
2, TiO
2, Au, Ag preparation method be respectively the methods such as chemical vapour deposition (CVD), magnetron sputtering and high annealing, electron beam evaporation, spraying.
This laboratory is disclose the Ti/TiO that a kind of anodic oxidation and Photodeposition combine preparation in the patent of 201210002179.5 at application number
2the liquid photoresponse RECTIFYING ANTENNA of/Cu structure.Its opto-electronic conversion realizes only in liquid electrolyte.
Although metal current-SEMICONDUCTOR-METAL structure has certain photoelectric functional, also there is following shortcoming:
(1) usually TiO is adopted at present
2as the heterosphere of SEMICONDUCTOR-METAL electrooptical device, but TiO
2low electron mobility, high preparation cost, govern the raising of opto-electronic conversion performance.ZnO is cheap, nontoxic as one, preparation method is various, and band gap scope of compromise is wide, the indirect gap semiconductor with high exciton bind energy and electron mobility, has very large potentiality improving in photoelectric conversion efficiency.
(2) each layer of solid-state light power conversion device is all very thin, generally all adopts the methods such as ultravacuum electron beam evaporation, chemical vapour deposition (CVD) and magnetron sputtering, and TiO
2will through high annealing.Complicated Technical investment, high preparation cost makes TiO
2the electrooptical device of base is difficult to realize scale suitability for industrialized production.
Summary of the invention
In order to solve the TiO in metal current-SEMICONDUCTOR-METAL structure
2the problem that intermediate layer transformation efficiency is low, preparation is difficult and cost is high, the present invention proposes a kind of all solid state electrooptical device and preparation method thereof.
Described electrooptical device is Zn-ZnO-Ag structure, is specially: the lower floor of this electrooptical device is Zn sheet, and intermediate layer is ZnO film, and upper strata is the Ag film be deposited on ZnO film.Described ZnO film is poroid, is to be generated by anodic oxidation on the Zn sheet of lower floor.
Described Zn sheet is the current collector layer of the electrooptical device of full solid Zn-ZnO-Ag structure, and described ZnO film is heterosphere, and described Ag film is photoresponsive layer.
Described ZnO film is diameter is the black-and-blue poroid of 30 ~ 100nm, and thickness is 2.6 ~ 5.0 μm.
The process of the described all solid state electrooptical device of preparation that the present invention proposes is as follows:
The preliminary treatment of step 1:Zn sheet:
Step 2: polishing fluid configures: the mixed solution of configuration ethanol and phosphoric acid; The volume ratio of ethanol and phosphoric acid is 2:1.During preparation polishing fluid, under stirring, phosphoric acid is dropwise added in ethanol; 30min is stirred when all being joined after in ethanol by described phosphoric acid.After stirring terminates, polishing fluid is placed on refrigerator and cooled but to 0 DEG C stand-by.This polishing fluid can be reused.
Step 3: electrolyte configures: being added by NaOH in deionized water and to stir 30min, configuration concentration is the NaOH solution of 0.7M, stir to be placed in refrigerator after terminating be cooled to 0 DEG C stand-by.
Step 4: constant voltage polishing: utilize the polishing fluid configured to carry out constant voltage polishing to through pretreated Zn sheet.Negative electrode is done with platinum electrode; To do anode through pretreated Zn sheet.During polishing, polishing voltage is 5V, and described Zn sheet and platinum electrode are all placed in polishing fluid, and makes the spacing keeping 20mm between this Zn sheet and platinum electrode.The container filling polishing fluid is placed in mixture of ice and water, with blender polishing fluid is stirred with the rotating speed of 500rpm and be retained to polishing and terminate.Polishing time is 20min.
Step 5: constant voltage two step anodic oxidation: utilize the electrolyte prepared to carry out the anodic oxidation of constant voltage two step to the Zn sheet through polishing, anodic oxidation voltage is 3V.
The anodised process of the first step is:
Do anode with the Zn sheet after encapsulation process, do negative electrode with platinum electrode, described Zn sheet and platinum electrode are all placed in electrolyte, and make the spacing keeping 20mm between this Zn sheet and platinum electrode.The described encapsulation process to Zn sheet makes it seal with a surface of epoxy resin covering polishing Zn sheet.
The container that electrolyte is housed is placed in mixture of ice and water, and carries out 300rpm stirring to this electrolyte and be retained to first step anodic oxidation terminating.After first step anodic oxidation, at described Zn sheet unencapsulated Surface Creation ZnO film.The first step anodised time is 30min.
A ZnO film at described Zn sheet Surface Creation is repeatedly cleaned with deionized water.The epoxy resin of described Zn sheet sealing surfaces within two minutes, is removed with acetone ultrasonic cleaning.
So far the first step anodic oxidation to Zn sheet is completed.
The anodised process of second step is:
Repeat the constant voltage polishing process of step 4, to remove a ZnO film at described Zn sheet Surface Creation.
Do anode with the Zn sheet through encapsulation process, do negative electrode with platinum electrode, described Zn sheet and platinum electrode are all placed in electrolyte, and make the spacing keeping 20mm between this Zn sheet and platinum electrode.The described encapsulation process to Zn sheet seals with a surface of epoxy resin covering polishing Zn sheet, and this surface is the sealing surface when first step anodic oxidation.Another surface covering polishing Zn sheet with epoxy resin is carried out partially sealed, and the area of sealing is 60% ~ 70%; Carrying out partially sealed surface is oxide side when first step anodic oxidation.
The container that electrolyte is housed is placed in mixture of ice and water, and carries out 300rpm stirring to this electrolyte and be retained to second step anodic oxidation terminating.After second step anodic oxidation, at described Zn sheet unencapsulated Surface Creation secondary ZnO film.The second step anodised time is respectively 60 ~ 180min.
The secondary ZnO film at described Zn sheet Surface Creation is repeatedly cleaned with deionized water.
So far complete the second step anodic oxidation to Zn sheet, after anodic oxidation, be intermediate layer at the secondary ZnO film of Zn sheet Surface Creation.
Step 5: deposition Ag film: described deposition Ag film is on the ZnO film obtained, adopts conventional pulse laser method to carry out the deposition of Ag film.
During Ag thin film deposition, target is the Ag of 99.99%, and target size is the disk of diameter 25mm, thickness 5mm, and the rotating speed of sample stage and target is 5 turns/min, and laser frequency is 10Hz.Sedimentation time is 30min, and deposit thickness is 11 ± 0.2nm.Obtain the Ag film being deposited on ZnO film surface.
In the present invention, described electrooptical device is Zn-ZnO-Ag structure, and the lower floor of this electrooptical device is Zn sheet, and intermediate layer is ZnO film, and upper strata is the Ag film be deposited on ZnO film.Described ZnO film is poroid, is to be generated by anodic oxidation on the Zn sheet of lower floor.Described Zn sheet is the current collector layer of the electrooptical device of full solid Zn-ZnO-Ag structure, and described ZnO film is heterosphere, and described Ag film is photoresponsive layer.
The present invention measures the current-voltage curve under simulated solar irradiation of electrooptical device prepared by the present invention, current-time curvel and uv-visible absorption spectra by linear sweep voltammetry, transient current method, absorption spectrometry.Observe Zn-ZnO-Ag structure under different oxidization time compare Ag thin film deposition before Zn-ZnO structure, it achieves all solid state opto-electronic conversion.Wherein in 0.7M NaOH, be oxidized the Zn-ZnO-Ag conversion efficiency of pulsed laser deposition 30min Ag film preparation on ZnO film prepared by 60min best for Zn sheet.
The realization mechanism of Zn-ZnO-Ag electrooptical device is: after the metal A g surface with surface plasma effect is subject to illumination, produce a large amount of hot electron, these electron energies define steady-state current after enough crossing Schottky barrier.Simple ZnO film only has photoresponse to the light of ultraviolet light wave band, by deposition Ag film, has widened the photoresponse scope of device, has added the absorption intensity of light, and then improve conversion efficiency.
The present invention is the improvement to all solid state electrooptical device, cheap anodizing technology is adopted to realize the preparation of heterosphere, by Ag modified film, obtain all solid state electrooptical device with sunlight response, this method is that the production of electrooptical device use under various conditions and scale provides possibility, and then can alleviate Pressure on Energy.
Present invention employs the electrooptical device of Zn-ZnO-Ag structure, main improvement has following 3 points:
(1) with the easy anode oxidation method of cheapness liquid state, air atmosphere, without high-temperature heat treatment condition under the ZnO film prepared instead of heterosphere TiO prepared by sputtering sedimentation
2, reduce preparation cost, simplify preparation technology, protect environment;
(2) TiO is replaced with poroid ZnO film
2amorphous membrance, adds effective contact area of metal and heterosphere, improves contact performance, add the transmission channel of electronics;
(3) all solid state electrooptical device of Direct precipitation Ag film preparation on ZnO film, has expanded the scope of application of electrooptical device.
The present invention has carried out a series of photoelectric property test to prepared Zn-ZnO-Ag electrooptical device and the Zn-ZnO device that do not deposit Ag film, in order to verify the opto-electronic conversion that Ag film must be had could to realize sunlight, the present invention has carried out comparative photoelectric property to Zn-ZnO-Ag electrooptical device prepared in embodiment 1 and the Zn-ZnO device that do not deposit Ag film and has tested.All photoelectricity tests all at room temperature carry out, and use steady current source for xenon lamp simulated solar irradiation, illumination condition is AM 1.5, power 100mW/cm
2.Optical absorption properties uses spectrometer to measure; Photoelectric property CHI660C electrochemical workstation image data, sample is placed on Probe test station.Embodiment 1 and do not deposit Ag film the uv-visible absorption spectra of Zn-ZnO as shown in the curve 1 and 2 in accompanying drawing 2, the curve 1 not depositing the Zn-ZnO of Ag film corresponding is the strongest to the absorption entirety of light, but does not occur absworption peak; Absworption peak has been there is in the Zn-ZnO-Ag laminated film shown in curve 2 between 400 ~ 450nm.Adopt instantaneous photocurrent method testing example 1 and do not deposit the current versus time curve of Zn-ZnO device of Ag film, bias voltage is set to 0.01V, light pulsing intervals 100s, as shown in Figure 3, the curve 2 that the Zn-ZnO-Ag electrooptical device of embodiment 1 is corresponding obtains 55 μ A/cm to test result
2steady-state current, and curve 1 steady-state current corresponding to the Zn-ZnO device not depositing Ag film is close to 0.Adopt the current-voltage curve of linear sweep voltammetry test sample under dark-state and illumination condition, the sweep limits of dark-state is-0.5 ~ 0.5V, test result as shown in Figure 4, embodiment 1 and do not deposit curve 2 corresponding to the Zn-ZnO structure of Ag film and curve 1 all defines good Schottky contacts.During illumination, sweep limits is-1.0 ~ 1.0V, and as shown in Figure 5, the open circuit voltage of the curve 2 of embodiment 1 correspondence and short circuit current are respectively 0.38V and 37 μ A/cm to test result
2, this result is better than document The Journal of Physical Chemistry, the TiO reported in DOI:10.1021/jp409894b
2the performance of-Ag structure; Do not deposit curve 1 zero crossing that the Zn-ZnO structure of Ag film is corresponding, open circuit voltage and short circuit current are 0.Accompanying drawing 6 is current density-time graphs of embodiment 2 and embodiment 3, and corresponding curve 3 and curve 4 can obtain photoresponse electric current and be respectively 30,15 μ A/cm
2; Accompanying drawing 7 is illumination current density voltage curves of embodiment 2 and embodiment 3, and corresponding curve 3 and curve 4 can obtain that open circuit voltage and short circuit current are respectively 0.375,0.337V and 0.046,0.038 μ A/cm
2.
In sum, Zn-ZnO-Ag electrooptical device prepared by the present invention achieves all solid state application, and its performance is better than TiO
2-Ag structure devices.
Accompanying drawing explanation
Accompanying drawing 1 is the flow chart of preparation Zn-ZnO-Ag structure;
Accompanying drawing 2 is uv-visible absorption spectrums of the ZnO-Ag laminated film of pulsed laser deposition 30min Ag film preparation on the ZnO film prepared of Zn sheet Anodic oxidation different time.In figure:
Curve 1 is the UV-Vis spectrum visible spectrum that Zn sheet is oxidized ZnO film prepared by 1h in 0.7M NaOH solution
Curve 2 is UV-Vis spectrum visible spectrums that Zn sheet is oxidized the laminated film of pulsed laser deposition 30minAg film preparation on ZnO film prepared by 1h in 0.7M NaOH solution
Curve 3 is UV-Vis spectrum visible spectrums that Zn sheet is oxidized the laminated film of pulsed laser deposition 30minAg film preparation on ZnO film prepared by 2h in 0.7M NaOH solution
Curve 4 is UV-Vis spectrum visible spectrums that Zn sheet is oxidized the laminated film of pulsed laser deposition 30minAg film preparation on ZnO film prepared by 3h in 0.7M NaOH solution
Accompanying drawing 3 is simulated solar irradiation transient state illumination current density-time graphs that Zn sheet is oxidized the Zn-ZnO-Ag structure of Zn-ZnO structure prepared by 1h and pulsed laser deposition 30min Ag film preparation on ZnO film in 0.7M NaOH solution.In figure:
Curve 1 is instantaneous illumination current density-time graph that Zn sheet is oxidized the Zn-ZnO of ZnO film prepared by 1h in 0.7M NaOH solution
Curve 2 is instantaneous illumination current density-time graphs that Zn sheet is oxidized the Zn-ZnO-Ag structure of pulsed laser deposition 30minAg film preparation on ZnO film prepared by 1h in 0.7M NaOH solution
Accompanying drawing 4 is that Zn sheet is oxidized Zn-ZnO structure prepared by 1h and the dark-state current density voltage curve of the Zn-ZnO-Ag structure of pulsed laser deposition 30min Ag film preparation on ZnO film in 0.7M NaOH solution.In figure:
Curve 1 is the dark-state current density voltage curve that Zn sheet is oxidized the Zn-ZnO of ZnO film prepared by 1h in 0.7M NaOH solution
Curve 2 is dark-state current density voltage curves that Zn sheet is oxidized the Zn-ZnO-Ag structure of pulsed laser deposition 30minAg film preparation on ZnO film prepared by 1h in 0.7M NaOH solution
Accompanying drawing 5 be Zn sheet be oxidized in 0.7M NaOH solution the Zn-ZnO-Ag structure of Zn-ZnO structure prepared by 1h and pulsed laser deposition 30min Ag film preparation on ZnO film under simulated solar illumination condition in current density voltage curve figure:
Curve 1 is the illumination current density voltage curve that Zn sheet is oxidized the Zn-ZnO of ZnO film prepared by 1h in 0.7M NaOH solution
Curve 2 is illumination current density voltage curves that Zn sheet is oxidized the Zn-ZnO-Ag structure of pulsed laser deposition 30minAg film preparation on ZnO film prepared by 1h in 0.7M NaOH solution
Accompanying drawing 6 be the Zn-ZnO-Ag structure of pulsed laser deposition 30min Ag film preparation on Zn sheet is oxidized 2 respectively in 0.7M NaOH solution, prepared by 3h ZnO film under simulated solar illumination condition in instantaneous illumination current density-time plot:
Curve 3 is instantaneous illumination current density-time graphs that Zn sheet is oxidized the Zn-ZnO-Ag structure of pulsed laser deposition 30minAg film preparation on ZnO film prepared by 2h in 0.7M NaOH solution
Curve 4 is instantaneous illumination current density-time graphs that Zn sheet is oxidized the Zn-ZnO-Ag structure of pulsed laser deposition 30minAg film preparation on ZnO film prepared by 3h in 0.7M NaOH solution
Accompanying drawing 7 is Zn-ZnO-Ag structure current density voltage curves under simulated solar illumination condition of pulsed laser deposition 30min Ag film preparation on Zn sheet is oxidized 2 respectively in 0.7M NaOH solution, prepared by 3h ZnO film.In figure:
Curve 3 is illumination current density voltage curves that Zn sheet is oxidized the Zn-ZnO-Ag structure of pulsed laser deposition 30minAg film preparation on ZnO film prepared by 2h in 0.7M NaOH solution
Curve 4 is illumination current density voltage curves that Zn sheet is oxidized the Zn-ZnO-Ag structure of pulsed laser deposition 30minAg film preparation on ZnO film prepared by 3h in 0.7M NaOH solution
Concrete embodiment
Embodiment 1
The present embodiment is a kind of electrooptical device of metal-semiconductor-metal.Described electrooptical device is Zn-ZnO-Ag structure, is specially: the lower floor of this electrooptical device is Zn sheet, and intermediate layer is ZnO film, and upper strata is the Ag film be deposited on ZnO film.Described ZnO film is poroid, is to be generated by anodic oxidation on the Zn sheet of lower floor.
Described Zn sheet is the current collector layer of the electrooptical device of full solid Zn-ZnO-Ag structure, and described ZnO film is heterosphere, and described Ag film is photoresponsive layer.
It is the black-and-blue poroid of 30 ~ 100nm that described ZnO film presents diameter, and thickness is 2.6 μm.
The invention allows for a kind of method preparing Zn-ZnO-Ag structured light power conversion device, concrete preparation process is as follows:
The preliminary treatment of step 1:Zn sheet: by purity be 99.9% Zn sheet fine sandpaper polish, to remove surface contaminants; Zn sheet after polishing is put into successively acetone, absolute ethyl alcohol and deionized water ultrasonic cleaning 10min respectively, to remove this Zn sheet surface organic matter; Finally use N
2dry up stand-by.
Step 2: polishing fluid configures: the mixed solution of configuration ethanol and phosphoric acid; The volume ratio of ethanol and phosphoric acid is 2:1.During preparation, under stirring, phosphoric acid is dropwise added in ethanol; 30min is stirred when all being joined after in ethanol by described phosphoric acid.After stirring terminates, polishing fluid is placed on refrigerator and cooled but to 0 DEG C stand-by.This polishing fluid can be reused.
Step 3: electrolyte configures: being added by NaOH in deionized water and to stir 30min, configuration concentration is the NaOH solution of 0.7M, stir to be placed in refrigerator after terminating be cooled to 0 DEG C stand-by.
Step 4: constant voltage polishing: utilize the polishing fluid configured to carry out constant voltage polishing to through pretreated Zn sheet.During polishing, polishing voltage is 5V, does negative electrode with platinum electrode; To do anode through pretreated Zn sheet.Described Zn sheet and platinum electrode are all placed in polishing fluid, and make the spacing keeping 20mm between this Zn sheet and platinum electrode.And the container filling polishing fluid is placed in mixture of ice and water, with blender polishing fluid stirred with the rotating speed of 500rpm and be retained to polishing and terminate.Polishing time is 20min.
Step 5: constant voltage two step anodic oxidation: utilize the electrolyte prepared to carry out the anodic oxidation of constant voltage two step to the Zn sheet through polishing, anodic oxidation voltage is 3V.
The anodised process of the first step is:
Carry out encapsulation process to described Zn sheet, specifically, the surface covering polishing Zn sheet with epoxy resin makes it seal.Do anode with the Zn sheet after encapsulation process, do negative electrode with platinum electrode, described Zn sheet and platinum electrode are all placed in electrolyte, and make the spacing keeping 20mm between this Zn sheet and platinum electrode.
The container that electrolyte is housed is placed in mixture of ice and water, and carries out 300rpm stirring to this electrolyte and be retained to first step anodic oxidation terminating.After first step anodic oxidation, at described Zn sheet unencapsulated Surface Creation ZnO film.The first step anodised time is 30min.
A ZnO film at described Zn sheet Surface Creation is repeatedly cleaned with deionized water.The epoxy resin of described Zn sheet sealing surfaces within two minutes, is removed with acetone ultrasonic cleaning.
So far the first step anodic oxidation to Zn sheet is completed.
The anodised process of second step is:
Repeat the constant voltage polishing process of step 4, to remove a ZnO film at described Zn sheet Surface Creation.
The surface covering polishing Zn sheet with epoxy resin seals, and this surface is the sealing surface when first step anodic oxidation.Another surface covering polishing Zn sheet with epoxy resin is carried out partially sealed, and the area of sealing is 60% ~ 70%; Carrying out partially sealed surface is oxide side when first step anodic oxidation.
Do anode with the Zn sheet through encapsulation process, do negative electrode with platinum electrode, described Zn sheet and platinum electrode are all placed in electrolyte, and make the spacing keeping 20mm between this Zn sheet and platinum electrode.
The container that electrolyte is housed is placed in mixture of ice and water, and carries out 300rpm stirring to this electrolyte and be retained to second step anodic oxidation terminating.After second step anodic oxidation, at described Zn sheet unencapsulated Surface Creation secondary ZnO film.The second step anodised time is respectively 60min.
The secondary ZnO film at described Zn sheet Surface Creation is repeatedly cleaned with deionized water.
So far complete the second step anodic oxidation to Zn sheet, after anodic oxidation, be the present embodiment intermediate layer at the secondary ZnO film of Zn sheet Surface Creation.
AAP-(03-150) the DC POWER SUPPLY type DC power supply that the anodic oxidation of constant voltage two step adopts Hua Tai company to produce.
Step 5: deposition Ag film: described deposition Ag film is on the ZnO film obtained, adopts conventional pulse laser method to carry out the deposition of Ag film.
Ag thin film deposition adopts PLD-450 impulse laser deposition system, and target is the Ag of 99.99%, and target size is the disk of diameter 25mm, thickness 5mm, and the rotating speed of sample stage and target is 5 turns/min, and laser frequency is 10Hz.Sedimentation time is 30min, and deposit thickness is 11 ± 0.2nm.Obtain the Ag film being deposited on ZnO film surface.
The invention allows for embodiment 2 ~ 6.The preparation process of described embodiment 2 ~ 6 is all identical with embodiment 1, and difference is that the preparation parameter in each embodiment is different.Preparation parameter and the effect of each embodiment are as shown in the table:
The preparation parameter of each embodiment and effect
Note: anodizing time described in table is for carrying out the time needed for second step anodic oxidation to Zn sheet.In each embodiment, 30min is to the time needed for the first time anodic oxidation of Zn sheet.
The present invention, for embodiment 2 and embodiment 3, tests its photoelectric properties.
All tests are all at room temperature carried out, and use steady current source for xenon lamp simulated solar irradiation, illumination condition is AM 1.5, power 100mW/cm
2.Optical absorption properties spectrometer is measured; Photoelectric property CHI660C electrochemical workstation image data, sample is placed on Probe test station.The uv-visible absorption spectra of embodiment 2 and embodiment 3 is as shown in the curve 3 and 4 in accompanying drawing 2, and absorbing more by force has all appearred in Zn-ZnO-Ag laminated film between 400 ~ 450nm.Adopt the current versus time curve of instantaneous photocurrent method testing example 2 and embodiment 3, bias voltage is set to 0.01V, light pulsing intervals 100s, and as shown in Figure 6, the curve 3 and 4 of embodiment 2 and embodiment 3 correspondence obtains 30,15 μ A/cm to test result respectively
2steady-state current.Adopt the current-voltage curve of linear sweep voltammetry test sample under illumination condition, sweep limits is 0 ~ 0.5V, as shown in Figure 7, the curve 3 of embodiment 2 embodiment 3 correspondence and curve 4 can obtain that open circuit voltage and short circuit current are respectively 0.375,0.337V and 0.046,0.038 μ A/cm to test result
2.
Claims (7)
1. an all solid state electrooptical device, is characterized in that, described electrooptical device is Zn-ZnO-Ag structure, is specially: the lower floor of this electrooptical device is Zn sheet, and intermediate layer is ZnO film, and upper strata is the Ag film be deposited on ZnO film; Described ZnO film is poroid, is to be generated by anodic oxidation on the Zn sheet of lower floor;
Described Zn sheet is the current collector layer of all solid state electrooptical device, and described ZnO film is heterosphere, and described Ag film is photoresponsive layer.
2. all solid state electrooptical device as claimed in claim 1, it is characterized in that, described ZnO film is diameter is the black-and-blue poroid of 30 ~ 100nm, and thickness is 2.6 ~ 5.0 μm.
3. prepare a method for all solid state electrooptical device described in claim 1, it is characterized in that, concrete preparation process is as follows:
The preliminary treatment of step 1:Zn sheet:
Step 2: polishing fluid configures: the mixed solution of configuration ethanol and phosphoric acid; The volume ratio of ethanol and phosphoric acid is 2:1;
Step 3: electrolyte configures: being added by NaOH in deionized water and to stir 30min, configuration concentration is the NaOH solution of 0.7M, stir to be placed in refrigerator after terminating be cooled to 0 DEG C stand-by;
Step 4: constant voltage polishing: utilize the polishing fluid configured to carry out constant voltage polishing to through pretreated Zn sheet; Negative electrode is done with platinum electrode; To do anode through pretreated Zn sheet; During polishing, polishing voltage is 5V, and described Zn sheet and platinum electrode are all placed in polishing fluid, and makes the spacing keeping 20mm between this Zn sheet and platinum electrode; The container filling polishing fluid is placed in mixture of ice and water, with blender polishing fluid is stirred with the rotating speed of 500rpm and be retained to polishing and terminate; Polishing time is 20min;
Step 5: constant voltage two step anodic oxidation: utilize the electrolyte prepared to carry out the anodic oxidation of constant voltage two step to the Zn sheet through polishing, anodic oxidation voltage is 3V;
The anodised process of the first step is: do anode with the Zn sheet after encapsulation process, do negative electrode with platinum electrode, and described Zn sheet and platinum electrode are all placed in electrolyte, and makes the spacing keeping 20mm between this Zn sheet and platinum electrode;
The container that electrolyte is housed is placed in mixture of ice and water, and carries out 300rpm stirring to this electrolyte and be retained to first step anodic oxidation terminating; After first step anodic oxidation, at described Zn sheet unencapsulated Surface Creation ZnO film; The first step anodised time is 30min;
A ZnO film at described Zn sheet Surface Creation is repeatedly cleaned with deionized water; The epoxy resin of described Zn sheet sealing surfaces within two minutes, is removed with acetone ultrasonic cleaning;
So far the first step anodic oxidation to Zn sheet is completed;
The anodised process of second step is:
Repeat the constant voltage polishing process of step 4, to remove a ZnO film at described Zn sheet Surface Creation;
Do anode with the Zn sheet through encapsulation process, do negative electrode with platinum electrode, described Zn sheet and platinum electrode are all placed in electrolyte, and make the spacing keeping 20mm between this Zn sheet and platinum electrode;
The container that electrolyte is housed is placed in mixture of ice and water, and carries out 300rpm stirring to this electrolyte and be retained to second step anodic oxidation terminating; After second step anodic oxidation, at described Zn sheet unencapsulated Surface Creation secondary ZnO film; The second step anodised time is respectively 60 ~ 180min;
The secondary ZnO film at described Zn sheet Surface Creation is repeatedly cleaned with deionized water;
So far complete the second step anodic oxidation to Zn sheet, after anodic oxidation, be intermediate layer at the secondary ZnO film of Zn sheet Surface Creation;
Step 5: deposition Ag film: described deposition Ag film is on the ZnO film obtained, adopts conventional pulse laser method to carry out the deposition of Ag film.
4. prepare the method for all solid state electrooptical device as claimed in claim 3, it is characterized in that, during preparation polishing fluid, under stirring, phosphoric acid is dropwise added in ethanol; 30min is stirred when all being joined after in ethanol by described phosphoric acid; After stirring terminates, polishing fluid is placed on refrigerator and cooled but to 0 DEG C stand-by; This polishing fluid can be reused.
5. preparing the method for all solid state electrooptical device as claimed in claim 3, it is characterized in that, is make it seal with the surface that epoxy resin covers polishing Zn sheet to the encapsulation process of Zn sheet in described first step anode oxidation process.
6. prepare the method for all solid state electrooptical device as claimed in claim 3, it is characterized in that, be seal with the surface that epoxy resin covers polishing Zn sheet to the encapsulation process of Zn sheet in described second step anode oxidation process, this surface is the sealing surface when first step anodic oxidation; Another surface covering polishing Zn sheet with epoxy resin is carried out partially sealed, and the area of sealing is 60% ~ 70%; Carrying out partially sealed surface is oxide side when first step anodic oxidation.
7. prepare the method for all solid state electrooptical device as claimed in claim 3, it is characterized in that, during Ag thin film deposition, target is the Ag of 99.99%, and target size is the disk of diameter 25mm, thickness 5mm, the rotating speed of sample stage and target is 5 turns/min, and laser frequency is 10Hz; Sedimentation time is 30min, and deposit thickness is 11 ± 0.2nm; Obtain the Ag film being deposited on ZnO film surface.
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| LIRONG HE AND FUYI CHEN: "Rectification Performance of ZnO-Zn Schottky Diode Growth by Anodization", 《ECS SOLID STATE LETTERS》 * |
| P.K. BASU ET AL: "Hydrogen Gas Sensors Using Anodically Prepared and Surface Modified Nanoporous ZnO Thin Films", 《SENSORS LETTERS》 * |
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