CN102304735A - Silver-copper bimetallic thin film for light anode and laser-induced membrane-changing method - Google Patents
Silver-copper bimetallic thin film for light anode and laser-induced membrane-changing method Download PDFInfo
- Publication number
- CN102304735A CN102304735A CN201110246562A CN201110246562A CN102304735A CN 102304735 A CN102304735 A CN 102304735A CN 201110246562 A CN201110246562 A CN 201110246562A CN 201110246562 A CN201110246562 A CN 201110246562A CN 102304735 A CN102304735 A CN 102304735A
- Authority
- CN
- China
- Prior art keywords
- silver
- film
- electrolytic solution
- laser
- deionized water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Photovoltaic Devices (AREA)
- Hybrid Cells (AREA)
Abstract
The invention relates to a silver-copper bimetallic thin film for a light anode and a laser-induced membrane-changing method. In the silver-copper bimetallic thin film, the molar ratio of silver to copper is (1-7):(1-8). Dye sensitized solar cell light anode with an Ag-Cu bimetallic-TiO2 composite structure is prepared by substituting a laser-induced membrane-changing preparation method for an electron beam photoetching method and substituting an Ag-Cu bimetallic material for Au to serve as a surface plasma medium. A metallic titanium-supported titanium oxide membrane serves as a receiving substrate; the silver-copper thin film serves as a source matrix; the metallic titanium-supported titanium oxide membrane is placed below indium tin oxide (ITO) glass where the silver-copper thin film is deposited to perform laser-induced membrane changing. By the silver-copper bimetallic thin film for the light anode and the laser-induced membrane-changing method, dependence on high-cost noble metal in the prior art can be reduced, photovoltaic property of the dye sensitized solar cell is further improved, solar energy can be utilized to a larger degree, energy pressure can be relieved, and environment-friendly and low-cost development of the dye sensitized solar cell technique can be further promoted.
Description
Technical field
The present invention relates to technical field of solar batteries, be specifically related to a kind of method that light anodic film and induced with laser change film that is used for.
Background technology
Solar energy converting is meant that be the process of chemical energy and electric energy through photochromics from conversion of solar energy, and from the eighties in last century, the research group of the Gratzel of Lausanne, SUI higher technical school has reported a kind of with dye sensitization TiO
2Be light anodic solar cell, " A low-cost, the high-efficiency solar-cell based on dye-sensitized colloidal TiO that on Nature (1991,353:737～740), deliver
2Films " paper, indicate the birth of dye sensitization solar battery (DS SC), this battery is with TiO
2For the light anode, with organic coordination compound, pure organic dye is a photosensitizers, and the theoretical conversion stabilised efficiency is 10%.The main drawback of this battery is that dyestuff costs an arm and a leg, and is 8000 yuan of every grams like the price of dyestuff N719, so the development of new dyestuff becomes one of main direction of research DS SC.
The main method that addresses this problem at present is to utilize noble metal nano particles that the plasma resonance effect takes place under visible light; Thereby generation light induced electron; Use metal-oxide titanium composite structure manufacturing solar cells; For example; Japan scholar Nishijima etc. J Phys.Chem.Lett (2010,1,2031-2036) disclosed document " Plasmon-Assisted Photocurrent Generation from Visible to Near-Infrared Wavelength Using a Au-Nanorods/TiO
2Electrode " in, at TiO
2Single-crystal surface deposition Au nanometer stick array is found Au-TiO
2Structure can have photovoltaic performance in visible light-near infrared range.
But this method shortcoming is very tangible, this Au-TiO
2Structure is to use the electron beam lithography preparation, and preparation time is long, and cost is expensive, can not be used for extensive, low-cost suitability for industrialized production.
At APPLIED PHYSICS LETTERS 92; In 233107 (2008) the document; Korea S Shin etc. has reported the method for using induced with laser prepared electrode; This method has been used by ABC Nanotec Solution and is provided, and the Nano silver grain China ink that is of a size of 25nm uses spin coating method the nanoparticle China ink to be deposited on the source matrix of using as induced with laser on the glass basis as raw material.Thisly induce that to change the silver material cost that film uses very high.
Summary of the invention
For overcoming the deficiency that the preparation time that exists in the prior art is long, cost is expensive, the present invention proposes a kind of method that light anodic silver-bearing copper bimetal film and induced with laser change film that is used for.
The silver in the light anodic silver-bearing copper bimetal film that the present invention proposes and the mol ratio of copper are 1～7: 1～8.
The invention allows for a kind of silver-bearing copper bimetal film and carry out the method that induced with laser changes film, detailed process is following:
Polishing electrolytic solution is that 5% hydrofluoric acid, 45% nitric acid and 50% deionized water are formed by mass ratio.The hydrofluoric acid of said amount and nitric acid are added in the deionized water successively and stirs, obtain polishing the electrolytic solution of usefulness.
Galvanic deposit electrolytic solution is made up of 11.89g/L polyoxyethylene glycol, 0.004-0.014mol/L Silver Nitrate, 0.006-0.016mol/L cupric nitrate, 0.1mol/L saltpetre and deionized water.Polyoxyethylene glycol, Silver Nitrate, cupric nitrate and the saltpetre of said amount is added in the 50ml deionized water successively and stirs, obtain galvanic deposit electrolytic solution.
Test electrolytic solution is made up of 0.01mol/L sodium sulfate and deionized water.The sodium sulfate of said amount is added in the 50ml deionized water and stirs, obtain testing electrolytic solution.
Step 4, preparation salt bridge: be dissolved in the saltpetre particle of 90g in the 100g deionized water, obtain potassium nitrate solution.Through water-bath potassium nitrate solution is heated to 60 ℃ and be incubated 1h.In potassium nitrate solution, adding quality is the agar of 9.5g.The potassium nitrate solution that is added with agar is warming up to 90 ℃.Pour into the dissolved potassium nitrate solution in the U-shaped pipe, be cooled to 20 ℃, obtain being equipped with the salt bridge of saltpetre and agar solid mixture.
Step 5, clean ito glass: ito glass is soaked 15min in sodium hydroxide solution, in the described sodium hydroxide solution, the content of sodium hydroxide is 0.5mol/L.With the ito glass after the deionized water rinsing immersion.Ito glass is cleaned 15min at acetone soln and deionized water for ultrasonic successively.The ultrasonic power of ultrasonic cleaning is 200W.The ito glass that obtains cleaning up.
Step 6, preparation silver-bearing copper bimetal film:, adopt three-electrode system galvanic deposit silver-bearing copper through electrochemical workstation.With platinum guaze with ito glass is corresponding is placed in the galvanic deposit electrolytic solution, the distance between platinum guaze and the ito glass adjacently situated surfaces is 2cm.SCE is placed in the saturated Repone K electrolytic solution.Through salt bridge galvanic deposit electrolytic solution is connected with saturated Repone K electrolytic solution.Obtain being deposited on the silver-bearing copper bimetal film on the ito glass.Deposition constant potential E=-4V
SCE, depositing time is 10min.
Step 7, induced with laser changes film: adopt the laser apparatus induced with laser to change film.When induced with laser changed film, the oxidation titanium film that supports with metal titanium was as receiving substrate, to be deposited on silver-bearing copper bimetal film on the ito glass as the source matrix.The oxidation titanium film that metal titanium is supported places the ito glass below that deposits the silver-bearing copper film, carries out induced with laser and changes film.Induced with laser changes in the film, and laser power is 6～10W, and laser frequency is 20KHZ, and laser speed is 500mm/s, and the induced with laser time is 0.2s.Obtain the film modified TiO of silver-bearing copper bimetal
2The light anode.
The present invention adopts three-electrode system that resulting silver-bearing copper is modified TiO
2The light anode carries out the photovoltaic property detection.In the test, platinum guaze and silver-bearing copper are modified TiO
2The light anode is corresponding to be placed in the test electrolytic solution; SCE is placed in the saturated Repone K electrolytic solution; To test electrolytic solution through salt bridge is connected with saturated Repone K electrolytic solution; Use xenon lamp simulated solar irradiation and visible light to make radiation source; The light intensity of said xenon lamp is 100mWcm
-2Solar spectrum; Adopt linear sweep voltammetry at short-circuit current-time curve of measuring between-0.1～1.2Vsce under xenon lamp mimic sunshine and two kinds of illumination of visible light; The changing conditions of short-circuit current density and open circuit voltage from curve obtains silver-bearing copper and modifies TiO
2The light anode is compared the photovoltaic character before modifying.
The present invention is to use induced with laser to change film (LIFT) preparation method to replace electron beam lithography, uses the Ag-Cu bimetallic material to replace Au to make surperficial plasma medium, preparation Ag-Cu bimetal-TiO
2The dye-sensitized solar cell anode of composite structure.
Smooth anode of the present invention is by TiO
2Film and Ag-Cu bimetal are formed, TiO
2Film is the layer oxide film that metal titanium supports, and is the rutile phase mutually.The Ag-Cu bimetal is to change the sedimentary particulate material that is of membrane technique through induced with laser, and the size of particulate material is between 5～10 μ m, and it is the Ag-Cu nanoparticle of 1～5nm that equally distributed diameter is wherein arranged, and is fcc structure silver and fcc structure copper mutually.
Preparing above-mentioned smooth anodic principal character is:
1. adopt LSF 10T type laser apparatus to carry out induced with laser and change film processing.Source of the present invention matrix is placed with the reception substrate naturally, and the composition that changes laser power and silver-bearing copper film makes an experiment.The present invention has three laser powers, and laser parameter is that power is elected 6-10W as, and frequency is 20KHZ, and speed is 500mm/s, and the time is 0.2s.
2. the source matrix of induced with laser is a silver-bearing copper bimetal film; Three-electrode system is adopted in the preparation of silver-bearing copper bimetal film, utilizes potentiostatic method electrochemical deposition on ito glass to go out silver-copper nano dendrite; Electrolytic solution is 0.004-0.014mol/L Silver Nitrate, 0.006-0.016mol/L cupric nitrate; 0.1mol/L saltpetre and 11.89g/L polyoxyethylene glycol, depositing time 600s, 25 ℃ of temperature.
3. receiving substrate is the oxidation titanium film that metal titanium supports.The oxidation titanium film that metal titanium supports is that the titanium foil after the polishing is put into tube type resistance furnace 500 degree left and right sides oxidations 60 minutes.
Six kinds of light anodes have been prepared according to the method described above.Use linear sweep voltammetry, measured the current-voltage curve under simulated solar illumination and visible light.Six kinds of light anodic performance perameters see the following form, and can find the silver-bearing copper bimetal-TiO after modifying through metal
2Short-circuit current density and open circuit voltage all improved a lot before the composite anode was compared and modified.Short-circuit current density and open circuit voltage are high more, show that its light collection efficiency and electron injection efficiency are high more.
Electric current and the magnitude of voltage of anode under simulated solar illumination and visible light of not sharing the same light
Silver-bearing copper is modified TiO
2The reaction mechanism that the light anode improves electricity conversion is: the silver-bearing copper particle is modified the photoelectronic generation approach on the light anode of having widened effectively; Mainly contain two aspects; The one, the phototransformation that the nano silver copper particle absorbs is surface plasma and electron-hole pair, and this excite state electronics is injected into TiO
2Conduction band has increased light anodic light collection efficiency; The 2nd, silver-copper nano particle edge's electric field space and The limited time have improved near field intensity, have promoted the electron excitation of silver-copper nano particle at visible light wave range, have improved the injection efficiency of electronics.
The present invention is comprehensively existing method of modifying, adopts low cost process to realize precious metal silver-bearing copper bimetal modifying, preparation silver-bearing copper bimetal-TiO
2The dye-sensitized solar cell anode of composite structure.The present invention can reduce in the prior art the undue dependence to expensive precious metal; And further improve the photovoltaic performance of dye sensitization solar battery; Make sun power obtain to a greater degree utilizing; Finally reach the purpose of alleviating energy pressure, further promote the green low-cost development of dye sensitization solar battery technology.
Description of drawings
Accompanying drawing 1 is silver-bearing copper bimetal modifying TiO
2Light anodic preparation flow figure;
Accompanying drawing 2 is that light anodic induced with laser changes film machining principle figure;
Accompanying drawing 3 is silver-bearing copper bimetal modifying TiO
2Light anodic X-ray diffractogram;
Accompanying drawing 4 is silver-bearing copper bimetal modifying TiO under the different capacity
2Light anodic current-voltage curve, wherein a is that full exposure is penetrated, b is a radiation of visible light;
Accompanying drawing 5 is that the silver-bearing copper under the different silver-bearing copper compositions is modified light anodic current-voltage curve, and wherein a is that full exposure is penetrated, and b is a radiation of visible light.In the accompanying drawing:
1. laser beam 2. deposits the oxidation titanium film of the ito glass 3. metal titaniums support of silver-bearing copper film
Embodiment
Present embodiment is the film modified TiO of a kind of silver-bearing copper bimetal
2The light anode, the light anode dimension of modification is 1cm * 1cm.
The mol ratio of silver and copper is 1: 1 in the light anodic silver-bearing copper bimetal film that present embodiment proposes.
Present embodiment has also proposed the method that a kind of photo-anode film induced with laser changes film, is to utilize above-mentioned silver and copper bi-metal film to modify TiO through the method that induced with laser changes film
2The light anode, its detailed process is following:
Step 4, preparation salt bridge: be dissolved in the saltpetre particle of 90g in the 100g deionized water, obtain potassium nitrate solution.Through water-bath potassium nitrate solution is heated to 60 ℃ and be incubated 1h; In insulation, in potassium nitrate solution, adding quality is the agar of 9.5g.The potassium nitrate solution that is added with agar is warming up to 90 ℃.With diameter is that the Glass tubing of 5-6mm curves the U-shaped pipe, pours into the dissolved potassium nitrate solution in the U-shaped pipe, is cooled to 20 ℃, obtains being equipped with the salt bridge of saltpetre and agar solid mixture.
Step 5, clean ito glass: ito glass is cut into the strip of 1cm * 5cm, in sodium hydroxide solution, soak 15min, in the described sodium hydroxide solution, the content of sodium hydroxide is 0.5mol/L, to increase the wetting ability of ito glass matrix.With the ito glass after the deionized water rinsing immersion.Ito glass is cleaned 15min at acetone soln and deionized water for ultrasonic successively.The ultrasonic power of ultrasonic cleaning is 200W.The ito glass that obtains cleaning up
Step 6, preparation silver-bearing copper bimetal film: utilize the CHI660C electrochemical workstation, adopt three-electrode system.Described three-electrode system is to be working electrode with the ito glass, and platinum guaze is a supporting electrode, and saturated calomel is a reference electrode.With platinum guaze with ito glass is corresponding is placed in the galvanic deposit electrolytic solution, the distance between platinum guaze and the ito glass adjacently situated surfaces is 2cm.SCE is placed in the saturated Repone K electrolytic solution.The two ends of salt bridge are immersed respectively in galvanic deposit electrolytic solution and the saturated Repone K electrolytic solution, galvanic deposit electrolytic solution is connected with saturated Repone K electrolytic solution, obtain being deposited on the silver-bearing copper bimetal film on the ito glass through salt bridge.In the present embodiment, depositing temperature is a room temperature, deposition constant potential E=-4V
SCE, depositing time is 10min.
Step 7, induced with laser changes film: utilize LSF 10T type laser apparatus, the oxidation titanium film 3 that supports with metal titanium is as the reception substrate, to be deposited on silver-bearing copper bimetal film on the ito glass as the source matrix.Metal titanium oxidation titanium film 3 that supports and the ito glass 2 that deposits the silver-bearing copper film are placed laser beam 1 below, carry out induced with laser and change film.Induced with laser changes in the film, and laser power is 8W, and laser frequency is 20KHZ, and laser speed is 500mm/s, and the induced with laser time is 0.2s.Obtain the film modified TiO of silver-bearing copper bimetal
2The light anode.
Present embodiment is the film modified TiO of a kind of silver-bearing copper bimetal
2The light anode, the light anode dimension of modification is 1cm * 1cm.
The mol ratio of silver and copper is 7: 3 in the light anodic silver-bearing copper bimetal film that present embodiment proposes.
Present embodiment has also proposed the method that a kind of photo-anode film induced with laser changes film, is to utilize above-mentioned silver and copper bi-metal film to modify TiO through the method that induced with laser changes film
2The light anode, its detailed process is following:
Step 4, preparation salt bridge: be dissolved in the saltpetre particle of 90g in the 100g deionized water, obtain potassium nitrate solution.Through water-bath potassium nitrate solution is heated to 60 ℃ and be incubated 1h; In insulation, in potassium nitrate solution, adding quality is the agar of 9.5g.The potassium nitrate solution that is added with agar is warming up to 90 ℃.With diameter is that the Glass tubing of 5-6mm curves the U-shaped pipe, pours into the dissolved potassium nitrate solution in the U-shaped pipe, is cooled to 20 ℃, obtains being equipped with the salt bridge of saltpetre and agar solid mixture.
Step 5, clean ito glass: ito glass is cut into the strip of 1cm * 5cm, in sodium hydroxide solution, soak 15min, in the described sodium hydroxide solution, the content of sodium hydroxide is 0.5mol/L, to increase the wetting ability of ito glass matrix.With the ito glass after the deionized water rinsing immersion.Ito glass is cleaned 15min at acetone soln and deionized water for ultrasonic successively.The ultrasonic power of ultrasonic cleaning is 200W.The ito glass that obtains cleaning up
Step 6, preparation silver-bearing copper bimetal film: utilize the CHI660C electrochemical workstation, adopt three-electrode system.Described three-electrode system is to be working electrode with the ito glass, and platinum guaze is a supporting electrode, and saturated calomel is a reference electrode.With platinum guaze with ito glass is corresponding is placed in the galvanic deposit electrolytic solution, the distance between platinum guaze and the ito glass adjacently situated surfaces is 2cm.SCE is placed in the saturated Repone K electrolytic solution.The two ends of salt bridge are immersed respectively in galvanic deposit electrolytic solution and the saturated Repone K electrolytic solution, galvanic deposit electrolytic solution is connected with saturated Repone K electrolytic solution, obtain being deposited on the silver-bearing copper bimetal film on the ito glass through salt bridge.In the present embodiment, depositing temperature is a room temperature, deposition constant potential E=-4V
SCE, depositing time is 10min.
Step 7, induced with laser changes film: utilize LSF 10T type laser apparatus, the oxidation titanium film 3 that supports with metal titanium is as the reception substrate, to be deposited on silver-bearing copper bimetal film on the ito glass as the source matrix.Metal titanium oxidation titanium film 3 that supports and the ito glass 2 that deposits the silver-bearing copper film are placed laser beam 1 below, carry out induced with laser and change film.Induced with laser changes in the film, and laser power is 6W, and laser frequency is 20KHZ, and laser speed is 500mm/s, and the induced with laser time is 0.2s.Obtain the film modified TiO of silver-bearing copper bimetal
2The light anode.
Present embodiment is the film modified TiO of a kind of silver-bearing copper bimetal
2The light anode, the light anode dimension of modification is 1cm * 1cm.
The mol ratio of silver and copper is 2: 8 in the light anodic silver-bearing copper bimetal film that present embodiment proposes.
Present embodiment has also proposed the method that a kind of photo-anode film induced with laser changes film, is to utilize above-mentioned silver and copper bi-metal film to modify TiO through the method that induced with laser changes film
2The light anode, its detailed process is following:
Step 4, preparation salt bridge: be dissolved in the saltpetre particle of 90g in the 100g deionized water, obtain potassium nitrate solution.Through water-bath potassium nitrate solution is heated to 60 ℃ and be incubated 1h; In insulation, in potassium nitrate solution, adding quality is the agar of 9.5g.The potassium nitrate solution that is added with agar is warming up to 90 ℃.With diameter is that the Glass tubing of 5-6mm curves the U-shaped pipe, pours into the dissolved potassium nitrate solution in the U-shaped pipe, is cooled to 20 ℃, obtains being equipped with the salt bridge of saltpetre and agar solid mixture.
Step 5, clean ito glass: ito glass is cut into the strip of 1cm * 5cm, in sodium hydroxide solution, soak 15min, in the described sodium hydroxide solution, the content of sodium hydroxide is 0.5mol/L, to increase the wetting ability of ito glass matrix.With the ito glass after the deionized water rinsing immersion.Ito glass is cleaned 15min at acetone soln and deionized water for ultrasonic successively.The ultrasonic power of ultrasonic cleaning is 200W.The ito glass that obtains cleaning up
Step 6, preparation silver-bearing copper bimetal film: utilize the CHI660C electrochemical workstation, adopt three-electrode system.Described three-electrode system is to be working electrode with the ito glass, and platinum guaze is a supporting electrode, and saturated calomel is a reference electrode.With platinum guaze with ito glass is corresponding is placed in the galvanic deposit electrolytic solution, the distance between platinum guaze and the ito glass adjacently situated surfaces is 2cm.SCE is placed in the saturated Repone K electrolytic solution.The two ends of salt bridge are immersed respectively in galvanic deposit electrolytic solution and the saturated Repone K electrolytic solution, galvanic deposit electrolytic solution is connected with saturated Repone K electrolytic solution, obtain being deposited on the silver-bearing copper bimetal film on the ito glass through salt bridge.In the present embodiment, depositing temperature is a room temperature, deposition constant potential E=-4V
SCE, depositing time is 10min.
Step 7, induced with laser changes film: utilize LSF 10T type laser apparatus, the oxidation titanium film 3 that supports with metal titanium is as the reception substrate, to be deposited on silver-bearing copper bimetal film on the ito glass as the source matrix.Metal titanium oxidation titanium film 3 that supports and the ito glass 2 that deposits the silver-bearing copper film are placed laser beam 1 below, carry out induced with laser and change film.Induced with laser changes in the film, and laser power is 10W, and laser frequency is 20KHZ, and laser speed is 500mm/s, and the induced with laser time is 0.2s.Obtain the film modified TiO of silver-bearing copper bimetal
2The light anode.
Embodiment 4
Present embodiment is the film modified TiO of a kind of silver-bearing copper bimetal
2The light anode, the light anode dimension of modification is 1cm * 1cm.
The mol ratio of silver and copper is 4: 6 in the light anodic silver-bearing copper bimetal film that present embodiment proposes.
Present embodiment has also proposed the method that a kind of photo-anode film induced with laser changes film, is to utilize above-mentioned silver and copper bi-metal film to modify TiO through the method that induced with laser changes film
2The light anode, its detailed process is following:
Step 4, preparation salt bridge: be dissolved in the saltpetre particle of 90g in the 100g deionized water, obtain potassium nitrate solution.Through water-bath potassium nitrate solution is heated to 60 ℃ and be incubated 1h; In insulation, in potassium nitrate solution, adding quality is the agar of 9.5g.The potassium nitrate solution that is added with agar is warming up to 90 ℃.With diameter is that the Glass tubing of 5-6mm curves the U-shaped pipe, pours into the dissolved potassium nitrate solution in the U-shaped pipe, is cooled to 20 ℃, obtains being equipped with the salt bridge of saltpetre and agar solid mixture.
Step 5, clean ito glass: ito glass is cut into the strip of 1cm * 5cm, in sodium hydroxide solution, soak 15min, in the described sodium hydroxide solution, the content of sodium hydroxide is 0.5mol/L, to increase the wetting ability of ito glass matrix.With the ito glass after the deionized water rinsing immersion.Ito glass is cleaned 15min at acetone soln and deionized water for ultrasonic successively.The ultrasonic power of ultrasonic cleaning is 200W.The ito glass that obtains cleaning up
Step 6, preparation silver-bearing copper bimetal film: utilize the CHI660C electrochemical workstation, adopt three-electrode system.Described three-electrode system is to be working electrode with the ito glass, and platinum guaze is a supporting electrode, and saturated calomel is a reference electrode.With platinum guaze with ito glass is corresponding is placed in the galvanic deposit electrolytic solution, the distance between platinum guaze and the ito glass adjacently situated surfaces is 2cm.SCE is placed in the saturated Repone K electrolytic solution.The two ends of salt bridge are immersed respectively in galvanic deposit electrolytic solution and the saturated Repone K electrolytic solution, galvanic deposit electrolytic solution is connected with saturated Repone K electrolytic solution, obtain being deposited on the silver-bearing copper bimetal film on the ito glass through salt bridge.In the present embodiment, depositing temperature is a room temperature, deposition constant potential E=-4V
SCE, depositing time is 10min.
Step 7, induced with laser changes film: utilize LSF 10T type laser apparatus, the oxidation titanium film 3 that supports with metal titanium is as the reception substrate, to be deposited on silver-bearing copper bimetal film on the ito glass as the source matrix.Metal titanium oxidation titanium film 3 that supports and the ito glass 2 that deposits the silver-bearing copper film are placed laser beam 1 below, carry out induced with laser and change film.Induced with laser changes in the film, and laser power is 8W, and laser frequency is 20KHZ, and laser speed is 500mm/s, and the induced with laser time is 0.2s.Obtain the film modified TiO of silver-bearing copper bimetal
2The light anode.
The present invention adopts three-electrode system that resulting silver-bearing copper in the foregoing description is modified TiO
2The light anode carries out the photovoltaic property detection.The photovoltaic property detection at room temperature carries out, and uses CHI660C type electrochemical workstation to carry out data gathering.Three-electrode system is adopted in test.Described three-electrode system is to modify TiO with silver-bearing copper
2The light anode is a negative electrode, and platinum guaze is an anode, and saturated calomel is a reference electrode, and electrolyzer is selected quartz beaker for use.Platinum guaze and silver-bearing copper are modified TiO
2The light anode is corresponding to be placed in the test electrolytic solution; SCE is placed in the saturated Repone K electrolytic solution.The two ends of salt bridge are immersed test electrolytic solution and saturated Repone K electrolytic solution respectively, will test electrolytic solution through salt bridge and be connected with saturated Repone K electrolytic solution.Use xenon lamp simulated solar irradiation and visible light to make radiation source; It is 100mWcm that said xenon lamp can produce light intensity
-2Solar spectrum.Adopt linear sweep voltammetry at short-circuit current-time curve of measuring between-0.1～1.2Vsce under xenon lamp mimic sunshine and two kinds of illumination of visible light.The changing conditions of short-circuit current density and open circuit voltage from curve obtains silver-bearing copper and modifies TiO
2The light anode is compared the photovoltaic character before modifying.
Claims (2)
1. one kind is used for light anodic silver-bearing copper bimetal film, it is characterized in that, the silver in the said silver-bearing copper bimetal film and the mol ratio of copper are 1～7: 1～8;
2. one kind is utilized the said light anodic silver-bearing copper bimetal film that is used for of claim 1 to carry out the method that induced with laser changes film, it is characterized in that detailed process is following:
Step 1, handle titanium foil: to the titanium foil polishing, and with acetone, absolute ethyl alcohol and deionized water each ultrasonic cleaning 5min successively; Ultrasonic power is 200W;
Step 2, preparing electrolyte: described electrolytic solution comprises polishing electrolytic solution, galvanic deposit electrolytic solution and test electrolytic solution;
Wherein:
Polishing electrolytic solution is that 5% hydrofluoric acid, 45% nitric acid and 50% deionized water are formed by mass ratio; The hydrofluoric acid of said amount and nitric acid are added in the deionized water successively and stirs, obtain polishing the electrolytic solution of usefulness;
Galvanic deposit electrolytic solution is made up of 11.89g/L polyoxyethylene glycol, 0.004-0.014mol/L Silver Nitrate, 0.006-0.016mol/L cupric nitrate, 0.1mol/L saltpetre and deionized water; Polyoxyethylene glycol, Silver Nitrate, cupric nitrate and the saltpetre of said amount is added in the 50ml deionized water successively and stirs, obtain galvanic deposit electrolytic solution;
Test electrolytic solution is made up of 0.01mol/L sodium sulfate and deionized water; The sodium sulfate of said amount is added in the 50ml deionized water and stirs, obtain testing electrolytic solution;
Step 3, the oxidation titanium film that the preparation metal titanium supports: with using the deionized water rinsing specimen surface behind the 1min in the titanium foil immersion polishing electrolytic solution; Dried titanium foil is put into resistance furnace oxidation 1h and furnace cooling, and oxidizing temperature is 500 degree; Obtain the oxidation titanium film that metal titanium supports;
Step 4, preparation salt bridge: be dissolved in the saltpetre particle of 90g in the 100g deionized water, obtain potassium nitrate solution; Through water-bath potassium nitrate solution is heated to 60 ℃ and be incubated 1h; In potassium nitrate solution, adding quality is the agar of 9.5g; The potassium nitrate solution that is added with agar is warming up to 90 ℃; Pour into the dissolved potassium nitrate solution in the U-shaped pipe, be cooled to 20 ℃, obtain being equipped with the salt bridge of saltpetre and agar solid mixture;
Step 5, clean ito glass: ito glass is soaked 15min in sodium hydroxide solution, in the described sodium hydroxide solution, the content of sodium hydroxide is 0.5mol/L; With the ito glass after the deionized water rinsing immersion; Ito glass is cleaned 15min at acetone soln and deionized water for ultrasonic successively; The ultrasonic power of ultrasonic cleaning is 200W; The ito glass that obtains cleaning up;
Step 6, preparation silver-bearing copper bimetal film:, adopt three-electrode system galvanic deposit silver-bearing copper through electrochemical workstation; With platinum guaze with ito glass is corresponding is placed in the galvanic deposit electrolytic solution, the distance between platinum guaze and the ito glass adjacently situated surfaces is 2cm; SCE is placed in the saturated Repone K electrolytic solution; Through salt bridge galvanic deposit electrolytic solution is connected with saturated Repone K electrolytic solution; Obtain being deposited on the silver-bearing copper bimetal film on the ito glass; Deposition constant potential E=-4V
SCE, depositing time is 10min;
Step 7, induced with laser changes film: adopt the laser apparatus induced with laser to change film; When induced with laser changed film, the oxidation titanium film that supports with metal titanium was as receiving substrate, to be deposited on silver-bearing copper bimetal film on the ito glass as the source matrix; The oxidation titanium film that metal titanium is supported places the ito glass below that deposits the silver-bearing copper film, carries out induced with laser and changes film; Induced with laser changes in the film, and laser power is 6～10W, and laser frequency is 20KHZ, and laser speed is 500mm/s, and the induced with laser time is 0.2s; Obtain the film modified TiO of silver-bearing copper bimetal
2The light anode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110246562.0A CN102304735B (en) | 2011-08-25 | 2011-08-25 | Silver-copper bimetallic thin film for light anode and laser-induced membrane-changing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110246562.0A CN102304735B (en) | 2011-08-25 | 2011-08-25 | Silver-copper bimetallic thin film for light anode and laser-induced membrane-changing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102304735A true CN102304735A (en) | 2012-01-04 |
| CN102304735B CN102304735B (en) | 2014-02-05 |
Family
ID=45378646
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110246562.0A Expired - Fee Related CN102304735B (en) | 2011-08-25 | 2011-08-25 | Silver-copper bimetallic thin film for light anode and laser-induced membrane-changing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102304735B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110993739A (en) * | 2019-12-13 | 2020-04-10 | 陕西易莱德新材料科技有限公司 | Production method of membrane electrode for solar cell |
| CN114380361A (en) * | 2021-12-10 | 2022-04-22 | 中国科学院生态环境研究中心 | Method for recovering uranium from uranium-containing wastewater and underground water through electrochemical reduction and enrichment in coexistence of nitrates |
| CN117637246A (en) * | 2023-11-27 | 2024-03-01 | 广东工业大学 | Laser-induced forward transfer method for forming high-conductivity metal structure |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101383384A (en) * | 2008-10-24 | 2009-03-11 | 昆明理工大学 | Silver copper composite oxide film material for photoelectric semiconductor |
| CN101908582A (en) * | 2010-06-29 | 2010-12-08 | 通用光伏能源(烟台)有限公司 | Method for manufacturing transparent thin-film solar cell component |
-
2011
- 2011-08-25 CN CN201110246562.0A patent/CN102304735B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101383384A (en) * | 2008-10-24 | 2009-03-11 | 昆明理工大学 | Silver copper composite oxide film material for photoelectric semiconductor |
| CN101908582A (en) * | 2010-06-29 | 2010-12-08 | 通用光伏能源(烟台)有限公司 | Method for manufacturing transparent thin-film solar cell component |
Non-Patent Citations (1)
| Title |
|---|
| 刘婧等: "银铜双金属薄膜的激光诱导换膜和光伏性质", 《贵金属》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110993739A (en) * | 2019-12-13 | 2020-04-10 | 陕西易莱德新材料科技有限公司 | Production method of membrane electrode for solar cell |
| CN114380361A (en) * | 2021-12-10 | 2022-04-22 | 中国科学院生态环境研究中心 | Method for recovering uranium from uranium-containing wastewater and underground water through electrochemical reduction and enrichment in coexistence of nitrates |
| CN117637246A (en) * | 2023-11-27 | 2024-03-01 | 广东工业大学 | Laser-induced forward transfer method for forming high-conductivity metal structure |
| CN117637246B (en) * | 2023-11-27 | 2024-05-07 | 广东工业大学 | Laser-induced forward transfer method for forming high-conductivity metal structure |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102304735B (en) | 2014-02-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jung et al. | Dye sensitized solar cells for economically viable photovoltaic systems | |
| Sedghi et al. | Influence of TiO2 electrode properties on performance of dye-sensitized solar cells | |
| Ahmad et al. | 2-D Mxene flakes as potential replacement for both TCO and Pt layers for Dye-Sensitized Solar cell | |
| Liu et al. | Composite photoanodes of Zn2SnO4 nanoparticles modified SnO2 hierarchical microspheres for dye-sensitized solar cells | |
| Zhao et al. | Thickness-dependent electron transport performance of mesoporous TiO2 thin film for dye-sensitized solar cells | |
| CN103560013B (en) | A kind of sulfide is to DSSC of electrode and preparation method thereof | |
| Lin et al. | Flexible dye-sensitized solar cells with one-dimensional ZnO nanorods as electron collection centers in photoanodes | |
| Rakhunde et al. | Effect of dye absorption time on the performance of a novel 2-HNDBA sensitized ZnO photo anode based dye-sensitized solar cell | |
| Yue et al. | Enhanced performance of flexible dye-sensitized solar cell based on nickel sulfide/polyaniline/titanium counter electrode | |
| Fan et al. | Low-cost, quasi-solid-state and TCO-free highly bendable dye-sensitized cells on paper substrate | |
| Chen et al. | High catalytic activity of a PbS counter electrode prepared via chemical bath deposition for quantum dots-sensitized solar cells | |
| Liu et al. | Jalpaite Ag 3 CuS 2: a novel promising ternary sulfide absorber material for solar cells | |
| Peng et al. | Influence of ZnO nano-array interlayer on the charge transfer performance of quantum dot sensitized solar cells | |
| Wang et al. | A novel organic ionic plastic crystal electrolyte for solid-state dye-sensitized solar cells | |
| Thambidurai et al. | Chemical bath deposition of ZnO nanorods for dye sensitized solar cell applications | |
| Bhattacharya et al. | CdTe nanoparticles decorated titania for dye sensitized solar cell: a novel co-sensitizer approach towards highly efficient energy conversion | |
| Feng et al. | A ZnO/TiO2 composite nanorods photoanode with improved performance for dye‐sensitized solar cells | |
| Ghayoor et al. | Enhancement of photovoltaic performance of dye-sensitized solar cells based on TiO2-graphene quantum dots photoanode | |
| Thambidurai et al. | Synthesis and characterization of flower like ZnO nanorods for dye-sensitized solar cells | |
| CN102304735B (en) | Silver-copper bimetallic thin film for light anode and laser-induced membrane-changing method | |
| Li et al. | Orientation modulation of ZnO nanorods on charge transfer performance enhancement for Sb2S3 quantum dot sensitized solar cells | |
| Chan et al. | Influence of nanomaterial fillers in biopolymer electrolyte system for squaraine-based dye-sensitized solar cells | |
| Erten-Ela | Photovoltaic performance of ZnO nanorod and ZnO: CdO nanocomposite layers in dye-sensitized solar cells (DSSCs) | |
| Javed et al. | Anatase TiO2 nanotubes as photoanode for dye-sensitized solar cells | |
| CN102290250B (en) | Method for preparing solar cell photo-anode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140205 Termination date: 20170825 |