CN104851930B - All solid state electrooptical device and preparation method thereof - Google Patents
All solid state electrooptical device and preparation method thereof Download PDFInfo
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- CN104851930B CN104851930B CN201510152555.2A CN201510152555A CN104851930B CN 104851930 B CN104851930 B CN 104851930B CN 201510152555 A CN201510152555 A CN 201510152555A CN 104851930 B CN104851930 B CN 104851930B
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Classifications
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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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- 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
- 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
- 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
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- Microelectronics & Electronic Packaging (AREA)
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- Laminated Bodies (AREA)
Abstract
A kind of all solid state electrooptical device and preparation method thereof.Described electrooptical device is Zn ZnO Ag structures.The lower floor of the electrooptical device is Zn pieces, and intermediate layer is ZnO film, and upper strata is the Ag films being deposited on ZnO film.Described ZnO film is poroid, is to be generated on the Zn pieces of lower floor by anodic oxidation.The ZnO film is black-and-blue poroid for a diameter of 30~100nm's, and thickness is 2.6~5.0 μm.The present invention realizes the preparation of heterosphere using cheap anodizing technology, pass through Ag modified films, obtain all solid state electrooptical device with sun photoresponse, this method is that electrooptical device use under various conditions and the production of scale provide possibility, and then can mitigate Pressure on Energy.
Description
Technical field
The invention belongs to photovoltaic energy conversion device, and in particular to a kind of complete solid with metal-semiconductor-metal
State electrooptical device, it is possible to achieve the collection and conversion of solar energy.
Background technology
In order to realize the idea for providing electric power energy for the mankind using solar energy, research and development electrooptical device is always people
The focus of research.All solid state metal-semiconductor switching device is because its is simple in construction, sensitivity is high, can effectively break through conversion efficiency
The limit and receive much concern.The operation principle of all solid state electrooptical device of metal-semiconductor is：The metal surface of nanostructured by
Surface plasma is produced after to illumination, surface plasma deexcitation produces the thermoelectron of high-energy, and energy arrives 3eV 1, closely
The thermoelectron that metal surface area is produced is transferred at metal-semiconductor interface, a certain proportion of electricity with enough high-energy
Son can cross Schottky barrier and produce steady-state current.
Document Nano Letters, DOI：10.1021/nl2022459 in report one kind and use SiO2Do substrate preparation
TiO2/ Au electrooptical devices, SiO2、TiO2, Au thickness be respectively 200nm, 150nm, 10nm, Gao Zhen has been respectively adopted
The method such as empty chemical vapor deposition, magnetron sputtering and electron beam evaporation and high annealing.
Document The Journal of Physical Chemistry, DOI：10.1021/jp409894b in prepare respectively
With SiO2For the TiO of substrate2/ Au and TiO2The Schottky electrooptical device of/Ag structures, equally used electron beam evaporation,
The methods such as magnetron sputtering deposited the thick Au and Ag films of 10nm.
Document Applied Physics Letters, DOI：10.1063/4799156 in report SiO2In substrate
TiO2The electrooptical device of/Au/Ag nanowire composite structures, SiO2、TiO2, Au, Ag preparation method be respectively chemical gaseous phase
The method such as deposition, magnetron sputtering and high annealing, electron beam evaporation, spraying.
This laboratory discloses a kind of anodic oxidation and Photodeposition in the patent of Application No. 201210002179.5
Combine the Ti/TiO prepared2The liquid photoresponse RECTIFYING ANTENNA of/Cu structures.Its opto-electronic conversion is real only in liquid electrolyte
It is existing.
Although current metal-semiconductor-metal has certain photoelectric functional, also have the following disadvantages：
(1) TiO is generally used at present2As the heterosphere of SEMICONDUCTOR-METAL electrooptical device, but TiO2Low electronics
Mobility, high preparation cost, govern the raising of opto-electronic conversion performance.ZnO is various as a kind of cheap, nontoxic, preparation method,
Band gap scope of compromise is wide, indirect band-gap semiconductor with high exciton bind energy and electron mobility, is improving opto-electronic conversion effect
There are very big potentiality in terms of rate.
(2) each layer of solid-state electrooptical device is all very thin, generally using ultravacuum electron beam evaporation, chemical vapor deposition
The method such as product and magnetron sputtering, and TiO2To pass through high annealing.Complicated Technical investment, high preparation cost causes TiO2
The electrooptical device of base is difficult to scale industrialized production.
The content of the invention
In order to solve the TiO in current metal-semiconductor-metal2Intermediate layer transformation efficiency is low, it is difficult to prepare and
The problem of 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 structures, is specially：The lower floor of the electrooptical device is Zn pieces,
Intermediate layer is ZnO film, and upper strata is the Ag films being deposited on ZnO film.Described ZnO film is poroid, is in lower floor
Generated on Zn pieces by anodic oxidation.
Described Zn pieces are the current collector layer of the electrooptical device of full solid Zn-ZnO-Ag structures, and described ZnO film is
Heterosphere, described Ag films are photoresponsive layer.
The ZnO film is black-and-blue poroid for a diameter of 30~100nm's, and thickness is 2.6~5.0 μm.
The process proposed by the present invention for preparing all solid state electrooptical device is as follows：
Step 1：Zn pieces are pre-processed：
Step 2：Polishing fluid is configured：Configure the mixed solution of ethanol and phosphoric acid；The volume ratio of ethanol and phosphoric acid is 2:1.Match somebody with somebody
During polishing fluid processed, phosphoric acid is added dropwise in ethanol under stirring；Stirred after the phosphoric acid is all added in ethanol
Mix 30min.Stirring terminate after polishing fluid is placed in refrigerator be cooled to 0 DEG C it is stand-by.The polishing fluid can be reused.
Step 3：Electrolyte is configured：NaOH is added in deionized water and 30min is stirred, configuration concentration is 0.7M NaOH
Solution, stirring terminate after be placed in refrigerator be cooled to 0 DEG C it is stand-by.
Step 4：Constant voltage is polished：Constant voltage polishing is carried out to the Zn pieces by pretreatment using the polishing fluid configured.
Negative electrode is done with platinum electrode；Anode is done with the Zn pieces by pretreatment.During polishing, polishing voltage is 5V, by the Zn pieces and platinum electricity
Pole is placed in polishing fluid, and makes the spacing of holding 20mm between the Zn pieces and platinum electrode.The container for filling polishing fluid is placed in
In mixture of ice and water, polishing fluid is stirred with 500rpm rotating speed with agitator and keeps to polishing terminating.Polishing time
For 20min.
Step 5：The step anodic oxidation of constant voltage two：Constant voltage is carried out to the Zn pieces by polishing using the electrolyte prepared
Two step anodic oxidations, anodic oxidation voltage is 3V.
The process of first step anodic oxidation is：
Anode is done with the Zn pieces after encapsulation process, negative electrode is done with platinum electrode, the Zn pieces and platinum electrode are placed in
In electrolyte, and make the spacing of holding 20mm between the Zn pieces and platinum electrode.The encapsulation process to Zn pieces is to use asphalt mixtures modified by epoxy resin
One surface of fat covering polishing Zn pieces seals it.
The container that will be equipped with electrolyte is placed in mixture of ice and water, and is carried out 300rpm stirrings to the electrolyte and kept
Terminate to first step anodic oxidation.It is thin in ZnO of the unencapsulated Surface Creation of the Zn pieces after first step anodic oxidation
Film.The time of first step anodic oxidation is 30min.
Clean a ZnO film in the Zn pieces Surface Creation repeatedly with deionized water.It is cleaned by ultrasonic two points with acetone
Clock removes the epoxy resin of the Zn pieces sealing surfaces.
So far the first step anodic oxidation to Zn pieces is completed.
The process of second step anodic oxidation is：
The constant voltage polishing process of repeat step 4, to remove a ZnO film in the Zn pieces Surface Creation.
Anode is done with the Zn pieces Jing Guo encapsulation process, negative electrode is done with platinum electrode, the Zn pieces and platinum electrode are placed in electricity
Solve in liquid, and make the spacing of holding 20mm between the Zn pieces and platinum electrode.The encapsulation process to Zn pieces is to use epoxy resin
One surface of covering polishing Zn pieces is sealed, and the surface is the sealing surface in first step anodic oxidation.Use epoxy resin
Another surface progress of covering polishing Zn pieces is partially sealed, and sealed area is 60%~70%；Carry out partially sealed table
Face is the oxide side in first step anodic oxidation.
The container that will be equipped with electrolyte is placed in mixture of ice and water, and is carried out 300rpm stirrings to the electrolyte and kept
Terminate to second step anodic oxidation.It is thin in the secondary ZnO of the unencapsulated Surface Creation of Zn pieces after second step anodic oxidation
Film.The time of second step anodic oxidation is respectively 60~180min.
Clean the secondary ZnO film in the Zn pieces Surface Creation repeatedly with deionized water.
So far the second step anodic oxidation to Zn pieces is completed, in the secondary ZnO film of Zn piece Surface Creations after anodic oxidation
As intermediate layer.
Step 5：Deposit Ag films：The deposition Ag films are on obtained ZnO film, using conventional pulse laser
Method carries out the deposition of Ag films.
During Ag thin film depositions, target is 99.99% Ag, and target size is diameter 25mm, thickness 5mm disk, sample
The rotating speed of platform and target is 5 turns/min, and laser frequency is 10Hz.Sedimentation time is 30min, and deposit thickness is 11 ± 0.2nm.
To the Ag films for being deposited on ZnO film surface.
In the present invention, described electrooptical device is Zn-ZnO-Ag structures, and the lower floor of the electrooptical device is Zn
Piece, intermediate layer is ZnO film, and upper strata is the Ag films being deposited on ZnO film.Described ZnO film is poroid, is in lower floor
Zn pieces on generated by anodic oxidation.Described Zn pieces are the afflux of the electrooptical device of full solid Zn-ZnO-Ag structures
Layer, described ZnO film is heterosphere, and described Ag films are photoresponsive layer.
The present invention measures photoelectricity prepared by the present invention by linear sweep voltammetry, transient current method, absorption spectrometry
The current -voltage curve under simulated solar irradiation, current-time curvel and the uv-visible absorption spectra of switching device.Observation
Zn-ZnO-Ag structures compare the Zn-ZnO structures before Ag thin film depositions under different oxidization times, and it realizes all solid state photoelectricity and turned
Change.Wherein Zn pieces aoxidize pulsed laser deposition 30min Ag film preparations on the ZnO film of 60min preparations in 0.7M NaOH
Zn-ZnO-Ag conversion efficiencies it is optimal.
The realization mechanism of Zn-ZnO-Ag electrooptical devices is：Metal Ag surfaces with surface plasma effect by
After illumination, a large amount of thermoelectrons are produced, these electron energies are crossed enough forms steady-state current after Schottky barrier.Simple
ZnO film only has photoresponse to the light of ultraviolet light wave band, by depositing Ag films, has widened the photoresponse scope of device, increases
Add the absorption intensity of light, and then improve conversion efficiency.
The present invention is the improvement to all solid state electrooptical device, is realized using cheap anodizing technology heterogeneous
The preparation of layer, by Ag modified films, obtains all solid state electrooptical device with sun photoresponse, this method is
Electrooptical device use under various conditions and the production of scale provide possibility, and then can mitigate energy pressure
Power.
Present invention employs the electrooptical device of Zn-ZnO-Ag structures, main improvement has following three points：
(1) ZnO prepared with cheap easy anodizing under the conditions of liquid, air atmosphere, without high-temperature heat treatment
Film instead of the heterosphere TiO of sputtering sedimentation preparation2, preparation cost is reduced, preparation technology is simplified, environment is protected；
(2) TiO is replaced with poroid ZnO film2Amorphous membrance, adds effective contact area of metal and heterosphere, changes
It has been apt to contact performance, has added the transmission channel of electronics；
(3) all solid state electrooptical device of Direct precipitation Ag film preparations on ZnO film, has expanded electrooptical device
The scope of application.
The present invention is to prepared Zn-ZnO-Ag electrooptical devices and does not deposit the Zn-ZnO devices of Ag films and carries out
A series of photoelectric property tests, must have Ag films to realize the opto-electronic conversion of sunshine, the present invention is to implementing to verify
In example 1 prepared Zn-ZnO-Ag electrooptical devices and the Zn-ZnO devices of Ag films are not deposited comparative photoelectricity has been carried out
Property is tested.All photoelectricity tests are carried out at room temperature, using steady current source for xenon lamp simulated solar irradiation, and illumination condition is AM
1.5, power 100mW/cm2.Optical absorption properties are measured using spectrometer；Photoelectric property CHI660C electrochemical operations
Stand gathered data, sample is placed on Probe test station.Embodiment 1 and do not deposit Ag films Zn-ZnO ultraviolet-visible inhale
Spectrum is received as shown in the curve 1 and 2 in accompanying drawing 2, the absorption that Zn-ZnO 1 pair of light of corresponding curve of Ag films is not deposited is overall most
Strongly, but do not occur absworption peak；Zn-ZnO-Ag laminated films shown in curve 2 occur in that absworption peak between 400~450nm.
Using instantaneous photocurrent method testing example 1 and the current versus time curve for the Zn-ZnO devices for not depositing Ag films, bias is set
For 0.01V, light pulsing intervals 100s, as shown in Figure 3, the Zn-ZnO-Ag electrooptical devices of embodiment 1 are corresponding for test result
Curve 2 obtain 55 μ A/cm2Steady-state current, and the corresponding steady-state current of curve 1 of Zn-ZnO devices for not depositing Ag films
Close to 0.Using current -voltage curve of the linear sweep voltammetry test sample under dark-state and illumination condition, the scanning of dark-state
Scope be -0.5~0.5V, test result as shown in Figure 4, embodiment 1 and do not deposit Ag films Zn-ZnO structures it is corresponding
Curve 2 and curve 1 all form good Schottky contacts.Scanning range is -1.0~1.0V during illumination, and test result is for example attached
Shown in Fig. 5, the open-circuit voltage and short circuit current flow of the corresponding curve 2 of embodiment 1 are respectively 0.38V and 37 μ A/cm2, this result
Better than document The Journal of Physical Chemistry, DOI：10.1021/jp409894b the TiO of middle report2-
The performance of Ag structures；The corresponding zero crossing of curve 1 of Zn-ZnO structures of Ag films is not deposited, and open-circuit voltage and short circuit current flow are
0.Accompanying drawing 6 is current density-time graph of embodiment 2 and embodiment 3, and corresponding curve 3 and curve 4 can obtain photoresponse
Electric current is respectively 30,15 μ A/cm2；Accompanying drawing 7 is the illumination current density voltage curve of embodiment 2 and embodiment 3, corresponding song
Line 3 and curve 4 can obtain open-circuit voltage and short circuit current flow is respectively 0.375,0.337V and 0.046,0.038 μ A/cm2。
In summary, the Zn-ZnO-Ag electrooptical devices that prepared by the present invention realize all solid state application, and its performance is better than
TiO2- Ag structure devices.
Brief description of the drawings
Accompanying drawing 1 is the flow chart for preparing Zn-ZnO-Ag structures；
Accompanying drawing 2 is uv-visible absorption spectrum.In figure：
Curve 1 is the uv-visible absorption spectrum for the ZnO film that Zn pieces aoxidize 1h preparations in 0.7M NaOH solutions；
Curve 2 is that Zn pieces aoxidize pulsed laser deposition 30min Ag on the ZnO film of 1h preparations in 0.7M NaOH solutions
The uv-visible absorption spectrum of the laminated film of film preparation；
Curve 3 is that Zn pieces aoxidize pulsed laser deposition 30min Ag on the ZnO film of 2h preparations in 0.7M NaOH solutions
The uv-visible absorption spectrum of the laminated film of film preparation；
Curve 4 is that Zn pieces aoxidize pulsed laser deposition 30min Ag on the ZnO film of 3h preparations in 0.7M NaOH solutions
The uv-visible absorption spectrum of the laminated film of film preparation.
Accompanying drawing 3 is simulated solar irradiation transient state illumination current density-time graph.In figure：
Curve 5 is the Zn-ZnO for the ZnO film that Zn pieces aoxidize 1h preparations in 0.7M NaOH solutions instantaneous illumination electric current
Density-time graph；
Curve 6 is that Zn pieces aoxidize pulsed laser deposition 30min Ag on the ZnO film of 1h preparations in 0.7M NaOH solutions
Instantaneous illumination current density-time graph of the Zn-ZnO-Ag structures of film preparation.
Accompanying drawing 4 is dark-state current density voltage curve.In figure：
Curve 7 is that the Zn-ZnO for the ZnO film that Zn pieces aoxidize 1h preparations in 0.7M NaOH solutions dark-state electric current is close
Degree-voltage curve；
Curve 8 is that Zn pieces aoxidize pulsed laser deposition 30min Ag on the ZnO film of 1h preparations in 0.7M NaOH solutions
The dark-state current density voltage curve of the Zn-ZnO-Ag structures of film preparation.
Accompanying drawing 5 is the current density voltage curve under the conditions of simulated solar illumination.In figure：
Curve 9 is that the Zn-ZnO for the ZnO film that Zn pieces aoxidize 1h preparations in 0.7M NaOH solutions illumination electric current is close
Degree-voltage curve；
Curve 10 is that Zn pieces aoxidize pulsed laser deposition 30min on the ZnO film of 1h preparations in 0.7M NaOH solutions
The illumination current density voltage curve of the Zn-ZnO-Ag structures of Ag film preparations.
Accompanying drawing 6 is that Zn pieces aoxidize pulsed laser deposition on the ZnO film of 2,3h preparations respectively in 0.7M NaOH solutions
The Zn-ZnO-Ag structures of 30minAg film preparations instantaneous illumination current density-time graph under the conditions of simulated solar illumination.
In figure：
Curve 11 is that Zn pieces aoxidize pulsed laser deposition 30min on the ZnO film of 2h preparations in 0.7M NaOH solutions
Instantaneous illumination current density-time graph of the Zn-ZnO-Ag structures of Ag film preparations；
Curve 12 is that Zn pieces aoxidize pulsed laser deposition 30min on the ZnO film of 3h preparations in 0.7M NaOH solutions
Instantaneous illumination current density-time graph of the Zn-ZnO-Ag structures of Ag film preparations.
Accompanying drawing 7 is that Zn pieces aoxidize pulsed laser deposition on the ZnO film of 2,3h preparations respectively in 0.7M NaOH solutions
Current density voltage curve of the Zn-ZnO-Ag structures of 30minAg film preparations under the conditions of simulated solar illumination.In figure：
Curve 13 is that Zn pieces aoxidize pulsed laser deposition 30min on the ZnO film of 2h preparations in 0.7M NaOH solutions
The illumination current density voltage curve of the Zn-ZnO-Ag structures of Ag film preparations；
Curve 14 is that Zn pieces aoxidize pulsed laser deposition 30min on the ZnO film of 3h preparations in 0.7M NaOH solutions
The illumination current density voltage curve of the Zn-ZnO-Ag structures of Ag film preparations.
Example is embodied
Embodiment 1
The present embodiment is a kind of electrooptical device of metal-semiconductor-metal.Described electrooptical device is
Zn-ZnO-Ag structures, be specially：The lower floor of the electrooptical device is Zn pieces, and intermediate layer is ZnO film, and upper strata is to be deposited on
Ag films on ZnO film.Described ZnO film is poroid, is to be generated on the Zn pieces of lower floor by anodic oxidation.
Described Zn pieces are the current collector layer of the electrooptical device of full solid Zn-ZnO-Ag structures, and described ZnO film is
Heterosphere, described Ag films are photoresponsive layer.
The black-and-blue poroid of a diameter of 30~100nm is presented in described ZnO film, and thickness is 2.6 μm.
The invention also provides a kind of method for preparing Zn-ZnO-Ag structure electrooptical devices, specific preparation process
It is as follows：
Step 1：Zn pieces are pre-processed：Purity is polished for 99.9% Zn pieces with fine sandpaper, to remove surface contaminants；It will beat
Zn pieces after mill are sequentially placed into acetone, absolute ethyl alcohol and deionized water is cleaned by ultrasonic 10min respectively, to remove the Zn pieces surface
Organic matter；Finally use N2Drying is stand-by.
Step 2：Polishing fluid is configured：Configure the mixed solution of ethanol and phosphoric acid；The volume ratio of ethanol and phosphoric acid is 2:1.Match somebody with somebody
When processed, phosphoric acid is added dropwise in ethanol under stirring；Stirred after the phosphoric acid is all added in ethanol
30min.Stirring terminate after polishing fluid is placed in refrigerator be cooled to 0 DEG C it is stand-by.The polishing fluid can be reused.
Step 3：Electrolyte is configured：NaOH is added in deionized water and 30min is stirred, configuration concentration is 0.7M NaOH
Solution, stirring terminate after be placed in refrigerator be cooled to 0 DEG C it is stand-by.
Step 4：Constant voltage is polished：Constant voltage polishing is carried out to the Zn pieces by pretreatment using the polishing fluid configured.
During polishing, polishing voltage is 5V, and negative electrode is done with platinum electrode；Anode is done with the Zn pieces by pretreatment.By the Zn pieces and platinum electricity
Pole is placed in polishing fluid, and makes the spacing of holding 20mm between the Zn pieces and platinum electrode.And put the container for filling polishing fluid
In mixture of ice and water, polishing fluid is stirred with 500rpm rotating speed with agitator and keeps to polishing terminating.During polishing
Between be 20min.
Step 5：The step anodic oxidation of constant voltage two：Constant voltage is carried out to the Zn pieces by polishing using the electrolyte prepared
Two step anodic oxidations, anodic oxidation voltage is 3V.
The process of first step anodic oxidation is：
Encapsulation process is carried out to the Zn pieces, is specifically, a surface for covering polishing Zn pieces with epoxy resin makes its close
Envelope.Anode is done with the Zn pieces after encapsulation process, negative electrode is done with platinum electrode, the Zn pieces and platinum electrode are placed in electrolyte
In, and make the spacing of holding 20mm between the Zn pieces and platinum electrode.
The container that will be equipped with electrolyte is placed in mixture of ice and water, and is carried out 300rpm stirrings to the electrolyte and kept
Terminate to first step anodic oxidation.It is thin in ZnO of the unencapsulated Surface Creation of the Zn pieces after first step anodic oxidation
Film.The time of first step anodic oxidation is 30min.
Clean a ZnO film in the Zn pieces Surface Creation repeatedly with deionized water.It is cleaned by ultrasonic two points with acetone
Clock removes the epoxy resin of the Zn pieces sealing surfaces.
So far the first step anodic oxidation to Zn pieces is completed.
The process of second step anodic oxidation is：
The constant voltage polishing process of repeat step 4, to remove a ZnO film in the Zn pieces Surface Creation.
The surface that polishing Zn pieces are covered with epoxy resin is sealed, and the surface is in first step anodic oxidation
Sealing surface.With epoxy resin cover polishing Zn pieces another surface carries out it is partially sealed, sealed area be 60%~70%；
It is the oxide side in first step anodic oxidation to carry out partially sealed surface.
Anode is done with the Zn pieces Jing Guo encapsulation process, negative electrode is done with platinum electrode, the Zn pieces and platinum electrode are placed in electricity
Solve in liquid, and make the spacing of holding 20mm between the Zn pieces and platinum electrode.
The container that will be equipped with electrolyte is placed in mixture of ice and water, and is carried out 300rpm stirrings to the electrolyte and kept
Terminate to second step anodic oxidation.It is thin in the secondary ZnO of the unencapsulated Surface Creation of Zn pieces after second step anodic oxidation
Film.The time of second step anodic oxidation is respectively 60min.
Clean the secondary ZnO film in the Zn pieces Surface Creation repeatedly with deionized water.
So far the second step anodic oxidation to Zn pieces is completed, in the secondary ZnO film of Zn piece Surface Creations after anodic oxidation
As the present embodiment intermediate layer.
The step anodic oxidation of constant voltage two uses AAP- (03-150) DC POWER SUPPLY type direct currents that Hua Tai companies produce
Power supply unit.
Step 5：Deposit Ag films：The deposition Ag films are on obtained ZnO film, using conventional pulse laser
Method carries out the deposition of Ag films.
Ag thin film depositions use PLD-450 impulse laser deposition systems, and target is 99.99% Ag, and target size is straight
The rotating speed of footpath 25mm, thickness 5mm disk, sample stage and target is 5 turns/min, and laser frequency is 10Hz.Sedimentation time is
30min, deposit thickness is 11 ± 0.2nm.Obtain being deposited on the Ag films on ZnO film surface.
The invention also provides embodiment 2~6.The preparation process of the embodiment 2~6 is same as Example 1, different
Part is that the preparation parameter in each embodiment is different.The preparation parameter and effect of each embodiment are as shown in the table：
The preparation parameter and effect of each embodiment
Note：Anodizing time described in table is the time needed for carrying out second step anodic oxidation to Zn pieces.Each embodiment
In be 30min to the time needed for the first time anodic oxidation of Zn pieces.
The present invention is tested by taking embodiment 2 and embodiment 3 as an example to its photoelectric properties.
All tests are carried out at room temperature, using steady current source for xenon lamp simulated solar irradiation, and illumination condition is AM 1.5, work(
Rate 100mW/cm2.Optical absorption properties are measured with spectrometer；Photoelectric property gathers number with CHI660C electrochemical workstations
According to sample is placed on Probe test station.Curve 3 in the uv-visible absorption spectra such as accompanying drawing 2 of embodiment 2 and embodiment 3
With shown in 4, Zn-ZnO-Ag laminated films occur in that stronger absorb between 400~450nm.
Using the current versus time curve of instantaneous photocurrent method testing example 2 and embodiment 3, bias is set to 0.01V,
Light pulsing intervals 100s, as shown in Figure 6, embodiment 2 and the corresponding curve 3 and 4 of embodiment 3 are obtained test result respectively
30、15μA/cm2Steady-state current.Using current -voltage curve of the linear sweep voltammetry test sample under illumination condition,
Scanning range is 0~0.5V, and as shown in Figure 7,2 embodiment of embodiment 3 corresponding curve 3 and curve 4 can be obtained test result
It is respectively 0.375,0.337V and 0.046,0.038 μ A/cm to open-circuit voltage and short circuit current flow2。
Claims (5)
1. a kind of method for preparing all solid state electrooptical device, it is characterised in that described electrooptical device is Zn-ZnO-
Ag structures, be specially：The lower floor of the electrooptical device is Zn pieces, and intermediate layer is ZnO film, and upper strata is to be deposited on ZnO film
On Ag films；Described ZnO film is poroid, is to be generated on the Zn pieces of lower floor by anodic oxidation；
Described Zn pieces are the current collector layer of all solid state electrooptical device, and described ZnO film is heterosphere, described Ag films
For photoresponsive layer；
The ZnO film is black-and-blue poroid for a diameter of 30~100nm's, and thickness is 2.6~5.0 μm；
Specific preparation process is as follows：
Step 1：Zn pieces are pre-processed；
Step 2：Polishing fluid is configured：Configure the mixed solution of ethanol and phosphoric acid；The volume ratio of ethanol and phosphoric acid is 2:1；
Step 3：Electrolyte is configured：NaOH is added in deionized water and 30min is stirred, configuration concentration is molten for 0.7M NaOH
Liquid, stirring terminate after be placed in refrigerator be cooled to 0 DEG C it is stand-by；
Step 4：Constant voltage is polished：Constant voltage polishing is carried out to the Zn pieces by pretreatment using the polishing fluid configured；With platinum
Electrode does negative electrode；Anode is done with the Zn pieces by pretreatment；During polishing, polishing voltage is 5V, and the Zn pieces and platinum electrode is equal
It is placed in polishing fluid, and makes the spacing of holding 20mm between the Zn pieces and platinum electrode；The container for filling polishing fluid is placed in frozen water
In mixture, polishing fluid is stirred with 500rpm rotating speed with agitator and keeps to polishing terminating；Polishing time is
20min；
Step 5：The step anodic oxidation of constant voltage two：The step of constant voltage two is carried out to the Zn pieces by polishing using the electrolyte prepared
Anodic oxidation, anodic oxidation voltage is 3V；
The process of first step anodic oxidation is：
Anode is done with the Zn pieces after encapsulation process, negative electrode is done with platinum electrode, the Zn pieces and platinum electrode are placed in electrolysis
In liquid, and make the spacing of holding 20mm between the Zn pieces and platinum electrode；
The container that will be equipped with electrolyte is placed in mixture of ice and water, and is carried out 300rpm stirrings to the electrolyte and kept to the
One step anodic oxidation terminates；After first step anodic oxidation, in the Zn pieces ZnO film of unencapsulated Surface Creation；
The time of first step anodic oxidation is 30min；
Clean a ZnO film in the Zn pieces Surface Creation repeatedly with deionized water；It is cleaned by ultrasonic with acetone and is gone for two minutes
Except the epoxy resin of the Zn pieces sealing surfaces；
So far the first step anodic oxidation to Zn pieces is completed；
The process of second step anodic oxidation is：
The constant voltage polishing process of repeat step 4, to remove a ZnO film in the Zn pieces Surface Creation；
Anode is done with the Zn pieces Jing Guo encapsulation process, negative electrode is done with platinum electrode, the Zn pieces and platinum electrode are placed in electrolyte
In, and make the spacing of holding 20mm between the Zn pieces and platinum electrode；
The container that will be equipped with electrolyte is placed in mixture of ice and water, and is carried out 300rpm stirrings to the electrolyte and kept to the
Two-step anodic oxidization terminates；After second step anodic oxidation, in the secondary ZnO film of the unencapsulated Surface Creation of Zn pieces；
The time of second step anodic oxidation is respectively 60~180min；
Clean the secondary ZnO film in the Zn pieces Surface Creation repeatedly with deionized water；
So far the second step anodic oxidation to Zn pieces is completed, is in the secondary ZnO film of Zn piece Surface Creations after anodic oxidation
Intermediate layer；
Step 5：Deposit Ag films：The deposition Ag films are on obtained ZnO film, using conventional pulse laser method
Carry out the deposition of Ag films.
2. the method for all solid state electrooptical device is prepared as claimed in claim 1, it is characterised in that when preparing polishing fluid,
Phosphoric acid is added dropwise in ethanol under stirring；30min is stirred after the phosphoric acid is all added in ethanol；Stirring knot
Polishing fluid is placed in refrigerator after beam be cooled to 0 DEG C it is stand-by；The polishing fluid can be reused.
3. the method for all solid state electrooptical device is prepared as claimed in claim 1, it is characterised in that the first step anodic oxygen
It is that the surface that polishing Zn pieces are covered with epoxy resin seals it to the encapsulation process of Zn pieces during change.
4. the method for all solid state electrooptical device is prepared as claimed in claim 1, it is characterised in that the second step anodic oxygen
That the surface that polishing Zn pieces are covered with epoxy resin is sealed to the encapsulation process of Zn pieces during change, the surface for
Sealing surface during first step anodic oxidation；Another surface that polishing Zn pieces are covered with epoxy resin carries out partially sealed, sealing
Area be 60%~70%；It is the oxide side in first step anodic oxidation to carry out partially sealed surface.
5. the method for all solid state electrooptical device is prepared as claimed in claim 1, it is characterised in that during Ag thin film depositions, target
Material is 99.99% Ag, and target size is diameter 25mm, thickness 5mm disk, and the rotating speed of sample stage and target is 5 turns/min,
Laser frequency is 10Hz；Sedimentation time is 30min, and deposit thickness is 11 ± 0.2nm；Obtain being deposited on the Ag on ZnO film surface
Film.
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| Title |
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| Rectification Performance of ZnO-Zn Schottky Diode Growth by Anodization;Lirong He and Fuyi Chen;《ECS Solid State Letters》;20140205;正文第41页左栏第2段-右栏倒数第二段、图1 * |
| ZnO metal-semiconductor-metal ultraviolet sensors with various contact electrodes;S.J. Young et al.;《Journal of Crystal Grownth》;20060627;摘要、正文第43页右栏第2段-第44页左栏第1段 * |
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