A kind of product open air presentation device based on high stability height transformation efficiencyTechnical field
The present invention relates to displaying field, be specifically related to a kind of product open air presentation device based on high stability height transformation efficiency。
Background technology
Presentation device is usually for carrying out the utensil that product appearance, function etc. are shown, material has wooden, metal, plastics etc., is generally transparent or semitransparent shape。
But, existing presentation device does not generally have solar module, when using out of doors, it is impossible to effectively utilize solar energy resources。
Summary of the invention
It is an object of the invention to avoid the deficiencies in the prior art part to provide a kind of product open air presentation device based on high stability height transformation efficiency。
The purpose of the present invention is achieved through the following technical solutions:
Providing a kind of product open air presentation device based on high stability height transformation efficiency, it is characterised in that this presentation device outer surface is provided with polymer solar battery, ito glass one outward facing sides of polymer solar battery assembles；Described polymer solar battery utilizes wire to be connected with presentation device, and provides electric power support for it；Described polymer solar battery is sandwich structure, is made up of anode electrode, organic active layer, cathode electrode；Described anode electrode is followed successively by ito glass (01), WO from outside to insideXThin film (02), WOXNano wire film (04), PEDOT:PSS cushion (03), wherein, WOXNano wire film (04) is grown on WOXOn thin film (02), PEDOT:PSS cushion (03) is filled between nano thread structure, and nanowire length is more than PEDOT:PSS cushion (03) thickness；Described organic active layer (05) is between anode electrode and cathode electrode, and organic active layer (05) thickness is 610nm；Described cathode electrode is followed successively by Ti sheet (08), Al film (07), TiO from outside to inside2Thin film (06)。
Preferably, the preparation method of described polymer solar battery module is as follows:
Step one, cleans ito glass (01): taking the commercial ito glass (01) of purchase, the absorbance of visible ray is reached more than 85% by it, is cut into preliminary dimension；By the ultra-clean cloth wiped clean soaking acetone, being then passed through the ultrasonic cleaning of acetone, ethanol, deionized water, often step scavenging period is 1h, puts in vacuum drying oven dry after cleaned；Clean and dried ITO substrate are put in ozone clean machine, ozone clean 30min；
Step 2, prepares WOXThin film (02) and WOXNano wire film (04): putting in magnetic control sputtering device by the ito glass after cleaning, being evacuated to base vacuum is 5 × 104Below pa, sets Ar, O2Flow is 20sccm, 2sccm, and after gas is stable, magnetron sputtering W film, sputtering power is 320W, and thickness is 100nm；ITO substrate after magnetron sputtering is put in tube furnace, thermal oxide growth WO at 380 DEG CXNano wire, temperature retention time is 1h, so at WOXThin film (02) surface obtains WOXNano wire film (04)；
Step 3, spin coating PEDOT:PSS cushion (03): take out PEDOT:PSS solution from refrigerator and naturally thaw to room temperature, titration PEDOT:PSS solution in ITO substrate, making it cover ITO substrate surface, be then placed on sol evenning machine by substrate, setting speed is 2800r/min, spin-coating time is 55s, PEDOT:PSS buffer layer thickness is 40nm, then puts it into 120 DEG C of baking 10min in vacuum drying oven, makes PEDOT:PSS cushion (03) solidify；
Step 4, prepare organic active layer (05): this programme organic active layer adopts PCDTBT/PC71BM, weighing PCDTBT:PC71BM mass ratio is 1:4, with chlorobenzene for solvent, preparation solution, wherein the concentration of PCDTBT is 5mg/ml, is heated by solution and stirs, with abundant dissolving in 65 DEG C of water-baths；Being titrated in ITO substrate by the organic active layer prepared subsequently, and be put on sol evenning machine, spin coating rotating speed is 900r/min, and spin-coating time is 38s, can obtain organic active layer (05)；
Step 5, assembles cathode electrode:
1) cathode electrode adopts lightweight, flexible Ti sheet (08), cutting Ti sheet so that it is equivalently-sized with ITO substrate, Ti sheet thickness is 0.1mm, being immersed in the HCl solution of 0.1M, the time is 2.5h, then with water and ethanol purge, then magnetically controlled sputter method is utilized to be deposited with one layer of Al film (07) on its surface, sputtering power is 300W, and operating air pressure is 1.0Pa, and sputtering Al film thickness is 100nm；
2) take 50mL butyl titanate (Ti (OC4H9) 4) and 6mL Fluohydric acid. (HF, concentration is 40%) joins in the polytetrafluoroethylene hydro-thermal axe of 200mL, after stirring under room temperature, hydro-thermal 12 hours at 170 DEG C。Wherein, the mol ratio of titanium and fluorine is 1, after hydro-thermal reaction completes, by the TiO of gained2Precipitation is dissolved in 300mL alcoholic solution, stirs, and immerses organic active layer one end of ITO substrate dissolved with TiO2In alcoholic solution, on sol evenning machine, then under 300r/min, rotate 12s, obtain the TiO of one layer of about 10nm2Thin film (06), is then placed in vacuum drying oven 60 DEG C baking 2min；
3) cathode electrode Ti sheet is covered on ito glass (01) so that cathode electrode Al film (07) one end and organic active layer (05) end thereof contacts on ito glass,
Step 6, lead-in wire and encapsulation: connect the line to ITO electrode and cathode electrode, and with epoxy resin, device is packaged, put into and process 25min in curing oven at 70 DEG C。
Compared with prior art beneficial effects of the present invention:
1. the method adopting magnetron sputtering is deposited with one layer of WO on ITO surfaceXThin film, it is formed with ito thin film to be good Ohmic contact, reduces contact berrier, improves ito anode and collect the ability in hole；
2. configuration aspects, introduces one layer of WO between ITO and PEDOT:PSS cushionXMembrane structure, itself and PEDOT:PSS cushion form double-deck hole transmission layer, and at WOXFilm surface growth has WOXNano wire film, this nano wire directly contacts with organic active layer, increases the contact area of electrode and organic active layer, and this structure substantially increases ito anode electrode to the collection efficiency in hole in organic active layer, creates beyond thought effect；
One layer of Al film of 3.Ti cathode electrode surface magnetic control, forms reflector layer, and adopts TiO between Al film and organic active layer2Modifying, it mates with active layer bandgap, it is possible to play the effect of electron transfer layer and hole blocking layer。
Accompanying drawing explanation
Utilize accompanying drawing that invention is described further, but the embodiment in accompanying drawing does not constitute any limitation of the invention, for those of ordinary skill in the art, under the premise not paying creative work, it is also possible to obtain other accompanying drawing according to the following drawings。
Fig. 1 is the polymer solar battery module diagram of the present invention。
Wherein: 01-ITO glass, 02-WOXThin film, 03-PEDOT:PSS cushion, 04-WOXNano wire film, 05-organic active layer, 06-TiO2Thin film, 07-Al film, 08-Ti sheet。
Detailed description of the invention
Entering 21 century, along with the development of science and technology, the energy has become as the up-to-date driving force of world development and economic growth, is the bases depended on for existence of the mankind。Due to the consumption of the non-regeneration energies such as oil, coal, natural gas, seeking with Renewable Energy Development is the main method solving current energy problem。And solar energy is a kind of cleaning, environmental protection, inexhaustible alternative energy source。At present, the solar energy come into operation includes two kinds, a kind of for utilizing the heat energy of solar energy, mainly having water heater, solar cooker etc., another kind is the luminous energy utilizing the sun, namely photovoltaic effect is utilized, converting light energy into electric energy, solaode is the important devices of solar energy photoelectric conversion, and it is the device directly converting the solar into electric energy, classify according to material therefor, it is possible to be divided into inorganic solar cell and organic solar batteries。Inorganic solar cell, based on silica-base material, has the advantages such as conversion efficiency height, good stability, and shortcoming is that material purity requires high, and complicated process of preparation is expensive etc.；Organic solar batteries can be divided into again organic molecule and polymer solar battery, its material source is extensive, preparation technology is simple, the method large area such as solution spin coating, silk screen printing can be adopted to prepare, therefore organic solar batteries has more the advantage of low cost, and the research of organic solar batteries has become as the emphasis of people's extensive concern。
Simple polymer solar battery structure is single layer structure, middle one layer is served as active layer for organic material, two ends are the electrode of different work functions, wherein a termination electrode is transparent, shining intermediate layer organic material through light, it can produce the exciton of bound state, owing to the combination of exciton can be generally 0.1～1.0eV, the built in field that two end electrodes produces is difficult to be separated into electron-hole pair, therefore introduces double-decker；Active layer in double-decker is made up of two kinds of organic materials, a kind of material serves as electron donor, another kind serves as electron acceptor, under light illumination, in material, electronics is stimulated, there is electron transfer in the interface of electron donor with electron acceptor, greatly improve the separation efficiency of exciton in organic material；Introduce again body heterojunction subsequently, body heterojunction be by electron donor together with electron acceptor blended, three dimension scale is formed hetero-junctions, electron donor and electron acceptor are beneficial to electron transfer being mixed with of nanoscale on the one hand, on the other hand electron donor enrichment phase and electron acceptor enrichment phase can form continuous phase, be beneficial to the electronics after separation, hole each mutually in be transferred to two end electrodes。
At present, in polymer solar cells, generally adopting ITO is transparent anode, it is used for collecting hole, Al thin film is as negative electrode, collect electronics, the ability of electric charge is collected owing to the contact berrier between electrode and active layer determines electrode, in order to enable hole better to collect, cushion is added between ITO and active layer, most widely used at present is PEDOT (3, the polymer of 4-ethylenedioxy thiophene monomer) and the mixed solution of PSS (poly styrene sulfonate), PEDOT is good conductive material, PSS PEDOT can be made better to disperse in the solution so as film forming and regulate film conductivity。
But, the ITO contacted, in acidity, can be brought corrosivity by PSS, and PEDOT:PSS also has very strong hygroscopicity, the performance of meeting strong influence device and life-span。
Inefficient, stability and life-span for existing polymer solar battery are poor, the problem such as the structure of cushion, technique, and the present invention by introducing WO between ITO and PEDOT:PSS cushionXThin film and WOXNano thread structure, itself and PEDOT:PSS cushion form double-deck hole transmission layer, adopt Ti sheet as cathode electrode simultaneously, and one layer of Al film of magnetic control in its surface, form reflector layer, substantially increase the absorption efficiency of sunlight, and between Al film and organic active layer, adopt TiO2Modifying, to the efficiency of this polymer solar battery, stability improves, life serves beyond thought effect。
The invention will be further described with the following Examples。
Embodiment 1:
As shown in Figure 1, a kind of product open air presentation device based on high stability height transformation efficiency that embodiments of the invention provide, it is characterized in that, this presentation device outer surface is provided with polymer solar battery, and ito glass one outward facing sides of polymer solar battery assembles；Described polymer solar battery utilizes wire to be connected with presentation device, and provides electric power support for it；Described polymer solar battery is sandwich structure, is made up of anode electrode, organic active layer, cathode electrode；Described anode electrode is followed successively by ito glass (01), WO from outside to insideXThin film (02), WOXNano wire film (04), PEDOT:PSS cushion (03), wherein, WOXNano wire film (04) is grown on WOXOn thin film (02), PEDOT:PSS cushion (03) is filled between nano thread structure, and nanowire length is more than PEDOT:PSS cushion (03) thickness；Described organic active layer (05) is between anode electrode and cathode electrode, and organic active layer (05) thickness is 610nm；Described cathode electrode is followed successively by Ti sheet (08), Al film (07), TiO from outside to inside2Thin film (06)。
Preferably, the preparation method of described polymer solar battery module is as follows:
Step one, cleans ito glass (01): taking the commercial ito glass (01) of purchase, the absorbance of visible ray is reached more than 85% by it, is cut into preliminary dimension；By the ultra-clean cloth wiped clean soaking acetone, being then passed through the ultrasonic cleaning of acetone, ethanol, deionized water, often step scavenging period is 1h, puts in vacuum drying oven dry after cleaned；Clean and dried ITO substrate are put in ozone clean machine, ozone clean 30min；
Step 2, prepares WOXThin film (02) and WOXNano wire film (04): putting in magnetic control sputtering device by the ito glass after cleaning, being evacuated to base vacuum is 5 × 104Below pa, sets Ar, O2Flow is 20sccm, 2sccm, and after gas is stable, magnetron sputtering W film, sputtering power is 320W, and thickness is 100nm；ITO substrate after magnetron sputtering is put in tube furnace, thermal oxide growth WO at 380 DEG CXNano wire, temperature retention time is 1h, so at WOXThin film (02) surface obtains WOXNano wire film (04)；
Step 3, spin coating PEDOT:PSS cushion (03): take out PEDOT:PSS solution from refrigerator and naturally thaw to room temperature, titration PEDOT:PSS solution in ITO substrate, making it cover ITO substrate surface, be then placed on sol evenning machine by substrate, setting speed is 2800r/min, spin-coating time is 55s, PEDOT:PSS buffer layer thickness is 40nm, then puts it into 120 DEG C of baking 10min in vacuum drying oven, makes PEDOT:PSS cushion (03) solidify；
Step 4, prepare organic active layer (05): this programme organic active layer adopts PCDTBT/PC71BM, weighing PCDTBT:PC71BM mass ratio is 1:4, with chlorobenzene for solvent, preparation solution, wherein the concentration of PCDTBT is 5mg/ml, is heated by solution and stirs, with abundant dissolving in 65 DEG C of water-baths；Being titrated in ITO substrate by the organic active layer prepared subsequently, and be put on sol evenning machine, spin coating rotating speed is 900r/min, and spin-coating time is 38s, can obtain organic active layer (05)；
Step 5, assembles cathode electrode:
1) cathode electrode adopts lightweight, flexible Ti sheet (08), cutting Ti sheet so that it is equivalently-sized with ITO substrate, Ti sheet thickness is 0.1mm, being immersed in the HCl solution of 0.1M, the time is 2.5h, then with water and ethanol purge, then magnetically controlled sputter method is utilized to be deposited with one layer of Al film (07) on its surface, sputtering power is 300W, and operating air pressure is 1.0Pa, and sputtering Al film thickness is 100nm；
2) take 50mL butyl titanate (Ti (OC4H9) 4) and 6mL Fluohydric acid. (HF, concentration is 40%) joins in the polytetrafluoroethylene hydro-thermal axe of 200mL, after stirring under room temperature, hydro-thermal 12 hours at 170 DEG C。Wherein, the mol ratio of titanium and fluorine is 1, after hydro-thermal reaction completes, by the TiO of gained2Precipitation is dissolved in 300mL alcoholic solution, stirs, and immerses organic active layer one end of ITO substrate dissolved with TiO2In alcoholic solution, on sol evenning machine, then under 300r/min, rotate 12s, obtain the TiO of one layer of about 10nm2Thin film (06), is then placed in vacuum drying oven 60 DEG C baking 2min；
3) cathode electrode Ti sheet is covered on ito glass (01) so that cathode electrode Al film (07) one end and organic active layer (05) end thereof contacts on ito glass,
Step 6, lead-in wire and encapsulation: connect the line to ITO electrode and cathode electrode, and with epoxy resin, device is packaged, put into and process 25min in curing oven at 70 DEG C。
Polymer solar module testing result
To WOXFilm surface WOXNanowire length is measured, and obtains its length value and is about 200nm；Owing to solaode is energy conversion device, the measurement of its performance with sunlight for benchmark, to use solar simulation light, carries out performance test under the standard spectrum of AM1.5G, and this shorted devices electric current density is about 14.15mA/cm2, open-circuit voltage is about 0.95V, and energy conversion efficiency (PCE) is up to 7.9%；After repeated measure 500h, its current attenuation is less than 10%, after placing 50 days in an atmosphere, tests its energy conversion efficiency and decays to the 91% of initial value。
Test shows, the product open air presentation device of this invention to the energy conversion efficiency of sunlight up to 7.9%, the solar energy of product open air presentation device local environment can be utilized efficiently, have good stability, and circulating working time, last a long time, substantially reduce the dependence to electrical network electric energy, be effectively saved electrical network electric energy。
Embodiment 2
A kind of product open air presentation device based on high stability height transformation efficiency that embodiments of the invention provide, it is characterised in that this presentation device outer surface is provided with polymer solar battery, ito glass one outward facing sides of polymer solar battery assembles；Described polymer solar battery utilizes wire to be connected with presentation device, and provides electric power support for it；Described polymer solar battery is sandwich structure, is made up of anode electrode, organic active layer, cathode electrode；Described anode electrode is followed successively by ito glass (01), WO from outside to insideXThin film (02), WOXNano wire film (04), PEDOT:PSS cushion (03), wherein, WOXNano wire film (04) is grown on WOXOn thin film (02), PEDOT:PSS cushion (03) is filled between nano thread structure, and nanowire length is more than PEDOT:PSS cushion (03) thickness；Described organic active layer (05) is between anode electrode and cathode electrode, and organic active layer (05) thickness is 410nm；Described cathode electrode is followed successively by Ti sheet (08), Al film (07), TiO from outside to inside2Thin film (06)。
Preferably, the preparation method of described polymer solar battery module is as follows:
Step one, cleans ito glass (01): taking the commercial ito glass (01) of purchase, the absorbance of visible ray is reached more than 85% by it, is cut into preliminary dimension；By the ultra-clean cloth wiped clean soaking acetone, being then passed through the ultrasonic cleaning of acetone, ethanol, deionized water, often step scavenging period is 1h, puts in vacuum drying oven dry after cleaned；Clean and dried ITO substrate are put in ozone clean machine, ozone clean 30min；
Step 2, prepares WOXThin film (02) and WOXNano wire film (04): putting in magnetic control sputtering device by the ito glass after cleaning, being evacuated to base vacuum is 5 × 104Below pa, sets Ar, O2Flow is 20sccm, 2sccm, and after gas is stable, magnetron sputtering W film, sputtering power is 300W, and thickness is 100nm；ITO substrate after magnetron sputtering is put in tube furnace, thermal oxide growth WO at 380 DEG CXNano wire, temperature retention time is 1h, so at WOXThin film (02) surface obtains WOXNano wire film (04)；
Step 3, spin coating PEDOT:PSS cushion (03): take out PEDOT:PSS solution from refrigerator and naturally thaw to room temperature, titration PEDOT:PSS solution in ITO substrate, making it cover ITO substrate surface, be then placed on sol evenning machine by substrate, setting speed is 2800r/min, spin-coating time is 55s, PEDOT:PSS buffer layer thickness is 40nm, then puts it into 120 DEG C of baking 10min in vacuum drying oven, makes PEDOT:PSS cushion (03) solidify；
Step 4, prepare organic active layer (05): this programme organic active layer adopts PCDTBT/PC71BM, weighing PCDTBT:PC71BM mass ratio is 1:4, with chlorobenzene for solvent, preparation solution, wherein the concentration of PCDTBT is 5mg/ml, is heated by solution and stirs, with abundant dissolving in 65 DEG C of water-baths；Being titrated in ITO substrate by the organic active layer prepared subsequently, and be put on sol evenning machine, spin coating rotating speed is 900r/min, and spin-coating time is 38s, can obtain organic active layer (05)；
Step 5, assembles cathode electrode:
1) cathode electrode adopts lightweight, flexible Ti sheet (08), cutting Ti sheet so that it is equivalently-sized with ITO substrate, Ti sheet thickness is 0.1mm, being immersed in the HCl solution of 0.1M, the time is 2.5h, then with water and ethanol purge, then magnetically controlled sputter method is utilized to be deposited with one layer of Al film (07) on its surface, sputtering power is 330W, and operating air pressure is 1.0Pa, and sputtering Al film thickness is 100nm；
2) take 50mL butyl titanate (Ti (OC4H9) 4) and 6mL Fluohydric acid. (HF, concentration is 40%) joins in the polytetrafluoroethylene hydro-thermal axe of 200mL, after stirring under room temperature, hydro-thermal 12 hours at 170 DEG C。Wherein, the mol ratio of titanium and fluorine is 1, after hydro-thermal reaction completes, by the TiO of gained2Precipitation is dissolved in 300mL alcoholic solution, stirs, and immerses organic active layer one end of ITO substrate dissolved with TiO2In alcoholic solution, on sol evenning machine, then under 300r/min, rotate 12s, obtain the TiO of one layer of about 10nm2Thin film (06), is then placed in vacuum drying oven 60 DEG C baking 2min；
3) cathode electrode Ti sheet is covered on ito glass (01) so that cathode electrode Al film (07) one end and organic active layer (05) end thereof contacts on ito glass,
Step 6, lead-in wire and encapsulation: connect the line to ITO electrode and cathode electrode, and with epoxy resin, device is packaged, put into and process 25min in curing oven at 70 DEG C。
Polymer solar module testing result
To WOXFilm surface WOXNanowire length is measured, and obtains its length value and is about 200nm；Owing to solaode is energy conversion device, the measurement of its performance with sunlight for benchmark, to use solar simulation light, carries out performance test under the standard spectrum of AM1.5G, and this shorted devices electric current density is about 12.86mA/cm2, open-circuit voltage is about 0.95V, and energy conversion efficiency (PCE) is up to 7.9%；After repeated measure 500h, its current attenuation is less than 10%, after placing 50 days in an atmosphere, tests its energy conversion efficiency and decays to the 90% of initial value。
Test shows, the product open air presentation device of this invention to the energy conversion efficiency of sunlight up to 7.9%, the solar energy of product open air presentation device local environment can be utilized efficiently, have good stability, and circulating working time, last a long time, substantially reduce the dependence to electrical network electric energy, be effectively saved electrical network electric energy。
Embodiment 3:
A kind of product open air presentation device based on high stability height transformation efficiency, it is characterised in that this presentation device outer surface is provided with polymer solar battery, ito glass one outward facing sides of polymer solar battery assembles；Described polymer solar battery utilizes wire to be connected with presentation device, and provides electric power support for it；Described polymer solar battery is sandwich structure, is made up of anode electrode, organic active layer, cathode electrode；Described anode electrode is followed successively by ito glass (01), WO from outside to insideXThin film (02), WOXNano wire film (04), PEDOT:PSS cushion (03), wherein, WOXNano wire film (04) is grown on WOXOn thin film (02), PEDOT:PSS cushion (03) is filled between nano thread structure, and nanowire length is more than PEDOT:PSS cushion (03) thickness；Described organic active layer (05) is between anode electrode and cathode electrode, and organic active layer (05) thickness is 310nm；Described cathode electrode is followed successively by Ti sheet (08), Al film (07), TiO from outside to inside2Thin film (06)。
Preferably, the preparation method of described polymer solar battery module is as follows:
Step one, cleans ito glass (01): taking the commercial ito glass (01) of purchase, the absorbance of visible ray is reached more than 85% by it, is cut into preliminary dimension；By the ultra-clean cloth wiped clean soaking acetone, being then passed through the ultrasonic cleaning of acetone, ethanol, deionized water, often step scavenging period is 1h, puts in vacuum drying oven dry after cleaned；Clean and dried ITO substrate are put in ozone clean machine, ozone clean 30min；
Step 2, prepares WOXThin film (02) and WOXNano wire film (04): putting in magnetic control sputtering device by the ito glass after cleaning, being evacuated to base vacuum is 5 × 104Below pa, sets Ar, O2Flow is 20sccm, 2sccm, and after gas is stable, magnetron sputtering W film, sputtering power is 320W, and thickness is 100nm；ITO substrate after magnetron sputtering is put in tube furnace, thermal oxide growth WO at 380 DEG CXNano wire, temperature retention time is 1h, so at WOXThin film (02) surface obtains WOXNano wire film (04)；
Step 3, spin coating PEDOT:PSS cushion (03): take out PEDOT:PSS solution from refrigerator and naturally thaw to room temperature, titration PEDOT:PSS solution in ITO substrate, making it cover ITO substrate surface, be then placed on sol evenning machine by substrate, setting speed is 2800r/min, spin-coating time is 55s, PEDOT:PSS buffer layer thickness is 40nm, then puts it into 120 DEG C of baking 10min in vacuum drying oven, makes PEDOT:PSS cushion (03) solidify；
Step 4, prepare organic active layer (05): this programme organic active layer adopts PCDTBT/PC71BM, weighing PCDTBT:PC71BM mass ratio is 1:4, with chlorobenzene for solvent, preparation solution, wherein the concentration of PCDTBT is 5mg/ml, is heated by solution and stirs, with abundant dissolving in 65 DEG C of water-baths；Being titrated in ITO substrate by the organic active layer prepared subsequently, and be put on sol evenning machine, spin coating rotating speed is 900r/min, and spin-coating time is 38s, can obtain organic active layer (05)；
Step 5, assembles cathode electrode:
1) cathode electrode adopts lightweight, flexible Ti sheet (08), cutting Ti sheet so that it is equivalently-sized with ITO substrate, Ti sheet thickness is 0.1mm, being immersed in the HCl solution of 0.4M, the time is 2.5h, then with water and ethanol purge, then magnetically controlled sputter method is utilized to be deposited with one layer of Al film (07) on its surface, sputtering power is 300W, and operating air pressure is 1.0Pa, and sputtering Al film thickness is 100nm；
2) take 50mL butyl titanate (Ti (OC4H9) 4) and 6mL Fluohydric acid. (HF, concentration is 40%) joins in the polytetrafluoroethylene hydro-thermal axe of 200mL, after stirring under room temperature, hydro-thermal 12 hours at 170 DEG C。Wherein, the mol ratio of titanium and fluorine is 1, after hydro-thermal reaction completes, by the TiO of gained2Precipitation is dissolved in 300mL alcoholic solution, stirs, and immerses organic active layer one end of ITO substrate dissolved with TiO2In alcoholic solution, on sol evenning machine, then under 300r/min, rotate 12s, obtain the TiO of one layer of about 10nm2Thin film (06), is then placed in vacuum drying oven 90 DEG C baking 2min；
3) cathode electrode Ti sheet is covered on ito glass (01) so that cathode electrode Al film (07) one end and organic active layer (05) end thereof contacts on ito glass,
Step 6, lead-in wire and encapsulation: connect the line to ITO electrode and cathode electrode, and with epoxy resin, device is packaged, put into and process 25min in curing oven at 70 DEG C。
Polymer solar module testing result
To WOXFilm surface WOXNanowire length is measured, and obtains its length value and is about 200nm；Owing to solaode is energy conversion device, the measurement of its performance with sunlight for benchmark, to use solar simulation light, carries out performance test under the standard spectrum of AM1.5G, and this shorted devices electric current density is about 14.15mA/cm2, open-circuit voltage is about 0.95V, and energy conversion efficiency (PCE) is up to 7.9%；After repeated measure 500h, its current attenuation is less than 10%, after placing 50 days in an atmosphere, tests its energy conversion efficiency and decays to the 91% of initial value。
Test shows, the product open air presentation device of this invention to the energy conversion efficiency of sunlight up to 7.9%, the solar energy of product open air presentation device local environment can be utilized efficiently, have good stability, and circulating working time, last a long time, substantially reduce the dependence to electrical network electric energy, be effectively saved electrical network electric energy。
Embodiment 4
A kind of product open air presentation device based on high stability height transformation efficiency, it is characterised in that this presentation device outer surface is provided with polymer solar battery, ito glass one outward facing sides of polymer solar battery assembles；Described polymer solar battery utilizes wire to be connected with presentation device, and provides electric power support for it；Described polymer solar battery is sandwich structure, is made up of anode electrode, organic active layer, cathode electrode；Described anode electrode is followed successively by ito glass (01), WO from outside to insideXThin film (02), WOXNano wire film (04), PEDOT:PSS cushion (03), wherein, WOXNano wire film (04) is grown on WOXOn thin film (02), PEDOT:PSS cushion (03) is filled between nano thread structure, and nanowire length is more than PEDOT:PSS cushion (03) thickness；Described organic active layer (05) is between anode electrode and cathode electrode, and organic active layer (05) thickness is 360nm；Described cathode electrode is followed successively by Ti sheet (08), Al film (07), TiO from outside to inside2Thin film (06)。
Preferably, the preparation method of described polymer solar battery module is as follows:
Step one, cleans ito glass (01): taking the commercial ito glass (01) of purchase, the absorbance of visible ray is reached more than 85% by it, is cut into preliminary dimension；By the ultra-clean cloth wiped clean soaking acetone, being then passed through the ultrasonic cleaning of acetone, ethanol, deionized water, often step scavenging period is 1h, puts in vacuum drying oven dry after cleaned；Clean and dried ITO substrate are put in ozone clean machine, ozone clean 30min；
Step 2, prepares WOXThin film (02) and WOXNano wire film (04): putting in magnetic control sputtering device by the ito glass after cleaning, being evacuated to base vacuum is 5 × 104Below pa, sets Ar, O2Flow is 20sccm, 2sccm, and after gas is stable, magnetron sputtering W film, sputtering power is 320W, and thickness is 100nm；ITO substrate after magnetron sputtering is put in tube furnace, thermal oxide growth WO at 380 DEG CXNano wire, temperature retention time is 1h, so at WOXThin film (02) surface obtains WOXNano wire film (04)；
Step 3, spin coating PEDOT:PSS cushion (03): take out PEDOT:PSS solution from refrigerator and naturally thaw to room temperature, titration PEDOT:PSS solution in ITO substrate, making it cover ITO substrate surface, be then placed on sol evenning machine by substrate, setting speed is 2800r/min, spin-coating time is 55s, PEDOT:PSS buffer layer thickness is 40nm, then puts it into 120 DEG C of baking 10min in vacuum drying oven, makes PEDOT:PSS cushion (03) solidify；
Step 4, prepare organic active layer (05): this programme organic active layer adopts PCDTBT/PC71BM, weighing PCDTBT:PC71BM mass ratio is 1:4, with chlorobenzene for solvent, preparation solution, wherein the concentration of PCDTBT is 5mg/ml, is heated by solution and stirs, with abundant dissolving in 65 DEG C of water-baths；Being titrated in ITO substrate by the organic active layer prepared subsequently, and be put on sol evenning machine, spin coating rotating speed is 900r/min, and spin-coating time is 38s, can obtain organic active layer (05)；
Step 5, assembles cathode electrode:
1) cathode electrode adopts lightweight, flexible Ti sheet (08), cutting Ti sheet so that it is equivalently-sized with ITO substrate, Ti sheet thickness is 0.1mm, being immersed in the HCl solution of 0.1M, the time is 2.5h, then with water and ethanol purge, then magnetically controlled sputter method is utilized to be deposited with one layer of Al film (07) on its surface, sputtering power is 300W, and operating air pressure is 1.0Pa, and sputtering Al film thickness is 100nm；
2) take 50mL butyl titanate (Ti (OC4H9) 4) and 6mL Fluohydric acid. (HF, concentration is 40%) joins in the polytetrafluoroethylene hydro-thermal axe of 200mL, after stirring under room temperature, hydro-thermal 12 hours at 170 DEG C。Wherein, the mol ratio of titanium and fluorine is 1, after hydro-thermal reaction completes, by the TiO of gained2Precipitation is dissolved in 300mL alcoholic solution, stirs, and immerses organic active layer one end of ITO substrate dissolved with TiO2In alcoholic solution, on sol evenning machine, then under 550r/min, rotate 12s, obtain the TiO of one layer of about 10nm2Thin film (06), is then placed in vacuum drying oven 60 DEG C baking 2min；
3) cathode electrode Ti sheet is covered on ito glass (01) so that cathode electrode Al film (07) one end and organic active layer (05) end thereof contacts on ito glass,
Step 6, lead-in wire and encapsulation: connect the line to ITO electrode and cathode electrode, and with epoxy resin, device is packaged, put into and process 25min in curing oven at 70 DEG C。
Polymer solar module testing result
To WOXFilm surface WOXNanowire length is measured, and obtains its length value and is about 200nm；Owing to solaode is energy conversion device, the measurement of its performance with sunlight for benchmark, to use solar simulation light, carries out performance test under the standard spectrum of AM1.5G, and this shorted devices electric current density is about 13.63mA/cm2, open-circuit voltage is about 0.94V, and energy conversion efficiency (PCE) is up to 7.2%；After repeated measure 500h, its current attenuation is less than 10%, after placing 50 days in an atmosphere, tests its energy conversion efficiency and decays to the 91% of initial value。
Test shows, the product open air presentation device of this invention to the energy conversion efficiency of sunlight up to 7.2%, the solar energy of product open air presentation device local environment can be utilized efficiently, have good stability, and circulating working time, last a long time, substantially reduce the dependence to electrical network electric energy, be effectively saved electrical network electric energy。
Embodiment 5
A kind of product open air presentation device based on high stability height transformation efficiency, it is characterised in that this presentation device outer surface is provided with polymer solar battery, ito glass one outward facing sides of polymer solar battery assembles；Described polymer solar battery utilizes wire to be connected with presentation device, and provides electric power support for it；Described polymer solar battery is sandwich structure, is made up of anode electrode, organic active layer, cathode electrode；Described anode electrode is followed successively by ito glass (01), WO from outside to insideXThin film (02), WOXNano wire film (04), PEDOT:PSS cushion (03), wherein, WOXNano wire film (04) is grown on WOXOn thin film (02), PEDOT:PSS cushion (03) is filled between nano thread structure, and nanowire length is more than PEDOT:PSS cushion (03) thickness；Described organic active layer (05) is between anode electrode and cathode electrode, and organic active layer (05) thickness is 680nm；Described cathode electrode is followed successively by Ti sheet (08), Al film (07), TiO from outside to inside2Thin film (06)。
Preferably, the preparation method of described polymer solar battery module is as follows:
Step one, cleans ito glass (01): taking the commercial ito glass (01) of purchase, the absorbance of visible ray is reached more than 85% by it, is cut into preliminary dimension；By the ultra-clean cloth wiped clean soaking acetone, being then passed through the ultrasonic cleaning of acetone, ethanol, deionized water, often step scavenging period is 1h, puts in vacuum drying oven dry after cleaned；Clean and dried ITO substrate are put in ozone clean machine, ozone clean 30min；
Step 2, prepares WOXThin film (02) and WOXNano wire film (04): putting in magnetic control sputtering device by the ito glass after cleaning, being evacuated to base vacuum is 5 × 104Below pa, sets Ar, O2Flow is 20sccm, 2sccm, and after gas is stable, magnetron sputtering W film, sputtering power is 320W, and thickness is 100nm；ITO substrate after magnetron sputtering is put in tube furnace, thermal oxide growth WO at 380 DEG CXNano wire, temperature retention time is 1h, so at WOXThin film (02) surface obtains WOXNano wire film (04)；
Step 3, spin coating PEDOT:PSS cushion (03): take out PEDOT:PSS solution from refrigerator and naturally thaw to room temperature, titration PEDOT:PSS solution in ITO substrate, making it cover ITO substrate surface, be then placed on sol evenning machine by substrate, setting speed is 2800r/min, spin-coating time is 55s, PEDOT:PSS buffer layer thickness is 40nm, then puts it into 120 DEG C of baking 10min in vacuum drying oven, makes PEDOT:PSS cushion (03) solidify；
Step 4, prepare organic active layer (05): this programme organic active layer adopts PCDTBT/PC71BM, weighing PCDTBT:PC71BM mass ratio is 1:4, with chlorobenzene for solvent, preparation solution, wherein the concentration of PCDTBT is 5mg/ml, is heated by solution and stirs, with abundant dissolving in 65 DEG C of water-baths；Being titrated in ITO substrate by the organic active layer prepared subsequently, and be put on sol evenning machine, spin coating rotating speed is 900r/min, and spin-coating time is 38s, can obtain organic active layer (05)；
Step 5, assembles cathode electrode:
1) cathode electrode adopts lightweight, flexible Ti sheet (08), cutting Ti sheet so that it is equivalently-sized with ITO substrate, Ti sheet thickness is 0.1mm, being immersed in the HCl solution of 0.1M, the time is 2.5h, then with water and ethanol purge, then magnetically controlled sputter method is utilized to be deposited with one layer of Al film (07) on its surface, sputtering power is 300W, and operating air pressure is 1.0Pa, and sputtering Al film thickness is 100nm；
2) take 50mL butyl titanate (Ti (OC4H9) 4) and 6mL Fluohydric acid. (HF, concentration is 40%) joins in the polytetrafluoroethylene hydro-thermal axe of 200mL, after stirring under room temperature, hydro-thermal 12 hours at 170 DEG C。Wherein, the mol ratio of titanium and fluorine is 1, after hydro-thermal reaction completes, by the TiO of gained2Precipitation is dissolved in 300mL alcoholic solution, stirs, and immerses organic active layer one end of ITO substrate dissolved with TiO2In alcoholic solution, on sol evenning machine, then under 370r/min, rotate 12s, obtain the TiO of one layer of about 10nm2Thin film (06), is then placed in vacuum drying oven 60 DEG C baking 2min；
3) cathode electrode Ti sheet is covered on ito glass (01) so that cathode electrode Al film (07) one end and organic active layer (05) end thereof contacts on ito glass,
Step 6, lead-in wire and encapsulation: connect the line to ITO electrode and cathode electrode, and with epoxy resin, device is packaged, put into and process 25min in curing oven at 70 DEG C。
Polymer solar module testing result
To WOXFilm surface WOXNanowire length is measured, and obtains its length value and is about 200nm；Owing to solaode is energy conversion device, the measurement of its performance with sunlight for benchmark, to use solar simulation light, carries out performance test under the standard spectrum of AM1.5G, and this shorted devices electric current density is about 12.36mA/cm2, open-circuit voltage is about 0.95V, and energy conversion efficiency (PCE) is up to 7.9%；After repeated measure 500h, its current attenuation is less than 10%, after placing 50 days in an atmosphere, tests its energy conversion efficiency and decays to the 84% of initial value。
Test shows, the product open air presentation device of this invention to the energy conversion efficiency of sunlight up to 7.9%, the solar energy of product open air presentation device local environment can be utilized efficiently, have good stability, and circulating working time, last a long time, substantially reduce the dependence to electrical network electric energy, be effectively saved electrical network electric energy。
Finally should be noted that; above example is only in order to illustrate technical scheme; but not limiting the scope of the invention; although having made to explain to the present invention with reference to preferred embodiment; it will be understood by those within the art that; technical scheme can be modified or equivalent replacement, without deviating from the spirit and scope of technical solution of the present invention。