CN105047821A - Inverse type polymer solar cell based on modification of active layer and transmission layer and preparation method of solar cell - Google Patents
Inverse type polymer solar cell based on modification of active layer and transmission layer and preparation method of solar cell Download PDFInfo
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Abstract
The invention relates to an inverse type polymer solar cell based on modification of an active layer and a transmission layer, and belongs to the technical field of polymer solar cells. The polymer solar cell is of a typical inverse structure. UV processing and hydroxylation are carried out on a titanium dioxide electron transmission layer, and polyethylene imine modification is then carried out; an active layer is doped with inorganic quantum dots to further adjust the energy level among acceptors and enhance transmission of carriers; and a hole transmission layer employs water-soluble molybdenum trioxide, and doped with gold nano-particles. Spin coating of aqueous solution saves more energy compared with vapor deposition; surface plasmon resonance caused by doping of the gold nano-particles can reflect light back to an active layer, further to utilize light and help transmission of charges in a transmission layer; and carrier transmission is smoother, and a more balanced electro-hole transfer speed can be achieved.
Description
Technical field
The invention belongs to polymer solar battery technical field, be specifically related to a kind of transoid polymer solar battery of modifying based on active layer and transport layer and preparation method.
Background technology
The research of polymer solar battery can greatly alleviating energy crisis and environmental protect pollution problem, has been subjected to increasing concern, has become the research topic of very attractive in recent years.But the low commercial applications that still govern polymer solar battery of energy conversion efficiency.The efficiency of single-unit solar cell reaches 10.2%, restrict the mainly unmatched electron-hole migration of its reason improved further, be separated, transmit and recombination rate, cause the very low photoelectric current method that therefore resilient coating is modified more to be applied, comprise cathode buffer layer and modify and anode buffer layer modification; On the other hand, the research of current solar cell exists a general problem is exactly that spectrum utilization factor is low; The method of the evaporation that simultaneous buffering layer adopts more, consumes the energy greatly, and inevitable also by the granule of remaining transport layer material in evaporation cavity during evaporation transport layer, and this affects to the evaporation of next step electrode.
Summary of the invention
The object of this invention is to provide a kind of transoid polymer solar battery of modifying based on active layer and transport layer and preparation method.
Polymer solar battery prepared by the present invention, is characterized in that: from bottom to up, successively by ITO electro-conductive glass, the TiO as substrate and negative electrode
2electron transfer layer, polymine PEI decorative layer, PCDTBT:PCBM active layer, MoO
3hole transmission layer, Ag anode form, and namely structure is ITO/TiO
2/ PEI/PCDTBT:PCBM/MoO
3/ Ag; Mix in active layer with PCDTBT:PCBM mass ratio be 0.0286% ~ 0.114% inorganic-quantum-dot (cadmium selenide, cadmium telluride, cadmium sulfide etc.); At MoO
3mix in hole transmission layer and MoO
3mass ratio is the Au nano particle (NPs) of 3.0% ~ 5.0%; Three kinds of diverse ways are used to modify spin coating PEI layer modified titanic oxide battery transport layer.
Wherein, TiO
2the thickness of electron transfer layer is the thickness of 20 ~ 40nm, PEI decorative layer is 4 ~ 10nm, and the thickness mixing the PCDTBT:PCBM active layer of inorganic-quantum-dot is 80 ~ 150nm, mixes the MoO of Au nano particle (NPs)
3the thickness of hole transmission layer is the thickness of 4 ~ 10nm, Ag anode is 80 ~ 120nm;
In addition, for TiO
2electron transfer layer, we additionally use three kinds of modes and carry out preliminary treatment, and then carry out PEI finishing; For active layer, we will mix inorganic-quantum-dot material, improve active layer to the level-density parameter between acceptor material; For hole transmission layer, our water miscible molybdenum trioxide that adopted hydro thermal method to prepare, and mix the golden nanometer particle of certain mass, the mode then adopting the mode of spin-coating film to replace evaporation prepares molybdenum trioxide hole transmission layer.Above-mentioned all transferring charge be all more conducive in device of improving one's methods.
In the present invention, the hole transmission layer of gold doping is spun to after on active layer and carries out annealing in process, forms good configuration of surface after annealing.Golden nanometer particle represents good surface plasmon resonance effect, light is reflected back active layer and is utilized again; Meanwhile, golden nanometer particle be mixed with the transmission being beneficial to electric charge; Obtain the molybdenum trioxide hole transport layer film of gold doping in the present invention by the method for spin-coating film, compare with traditional vacuum thermal evaporation, operate more simple and convenient, and the consumption of the energy can be reduced.
Concrete method is as follows: dissolve in water by the ammonium molybdate of certain mass under room temperature, form the solution of 0.01 ~ 0.1mol/L, added in above-mentioned solution by the aqueous hydrochloric acid solution of 2mol/L, until the pH value of mixed solution is between 1 ~ 1.5, gained is water-soluble molybdenum trioxide solution again; Get the above-mentioned solution of 5 ~ 10mL, add the golden nanometer particle of 0.5 ~ 1.0mg, ultrasonic process 20 ~ 40min, namely obtain the molybdenum trioxide aqueous solution of gold doping.
The preparation method of the transoid polymer solar battery modified based on active layer and transport layer of the present invention, its step and condition as follows:
1) ITO electro-conductive glass is put into beaker, use acetone, absolute ethyl alcohol, deionized water ultrasonic cleaning 10 ~ 20min respectively, dry up with nitrogen after cleaning;
2) under room temperature condition, the butyl titanate (Yi Li chemical plant, Beijing) of 10 ~ 20mL is added drop-wise in the absolute ethyl alcohol (Beijing Chemical Plant) of 90 ~ 100mL, drip the glacial acetic acid (Beijing Chemical Plant) of 10 ~ 20mL again, magnetic agitation 30 ~ 40min, obtains the yellow solution of homogeneous transparent; Then the acetylacetone,2,4-pentanedione (Tianjin chemical reagent factory) of 10 ~ 20mL is added, stir 20 ~ 30min, again 10 ~ 20mL deionized water is slowly added drop-wise in above-mentioned solution with the speed of 2 ~ 4mL/min, continue stirring 1 ~ 2h, obtain the faint yellow colloidal sol of homogeneous transparent, place ageing 6 ~ 8h, obtained TiO
2colloidal sol; By obtained TiO
2colloidal sol is spin-coated on step 1) the ITO conductive glass surface that obtains, spin speed is 3000 ~ 5000rpm; Then will with TiO
2iTO electro-conductive glass roasting 2 ~ 3h under 450 ~ 600 DEG C of conditions of colloidal sol, Temperature fall 10 ~ 12h, can obtain TiO on ITO electro-conductive glass
2electron transfer layer, the thickness of electron transfer layer is 20 ~ 40nm;
3) adopt three kinds of diverse ways to TiO
2electron transfer layer carries out surface treatment,
Method one is TiO
2electron transfer layer surface, without any process, directly with the PEI solution of 3000 ~ 4000rmp spin coating, 1 ~ 5mg/mL, obtains the PEI decorative layer that thickness is 4 ~ 10nm;
Method two is by step 2) in spin coating have TiO
2the ITO electro-conductive glass wavelength of electron transfer layer is the UV-irradiation 10 ~ 20min of 200 ~ 400nm, then the PEI solution of 1 ~ 5mg/mL is spun to the TiO after ultraviolet process with the revolution of 3000 ~ 4000rmp
2on electron transfer layer, obtain the PEI decorative layer that thickness is 4 ~ 10nm;
Method three is with TiO
2electron transfer layer is basis material, using non-conjugated electrolyte polymine (PEI) as interface-modifying layer.First, by step 2) TiO that obtains
2it is that in the ethylene glycol solution of the KOH of 1 ~ 3mg/mL, 10 ~ 20h carries out hydroxylating process that electron transfer layer is immersed in concentration; Then, then by the PEI solution of 1 ~ 5mg/mL be spin-coated on the TiO after hydroxylating process with the revolution of 3000 ~ 4000rmp
2on electron transfer layer, owing to containing a large amount of protonated amido energy and TiO in PEI solution
2the hydroxyl generation electrostatic self-assembled on electron transfer layer surface, thus the interface dipole sublayer forming thin layer, obtain the PEI decorative layer that thickness is 4 ~ 10nm;
4) under room temperature condition, by donor material PCDTBT (Poly-[and N-9 "-hepta-decanyl-2, 7-carbazolealt-5, 5-(40, 70-di-2-thienyl-20, 10, 30ben-zothia-diazole)], conjugated polymer, sigma-ardrich) with acceptor material PCBM ([6, 6]-phenyl – C61 – butyricacidmethylester, fullerene derivate, the accurate Science and Technology Ltd. of Nichem) be dissolved in organic solvent dichloro-benzenes (Beijing lark prestige company) according to mass ratio 1:4, be configured to the active layer solution of 5 ~ 10mg/mL, 10 ~ 40 μ L are added in above-mentioned active layer solution, the CdSe inorganic-quantum-dot solution of 1 ~ 5mg/mL, then under the speed of 600 ~ 800rpm, 24 ~ 48h is stirred, namely can be configured to the mixed solution of the PCDTBT:PCBM doped with inorganic-quantum-dot,
5) on PEI decorative layer, spin coating is doped with the PCDTBT:PCBM active layer solution of inorganic-quantum-dot, and rotating speed is 2000 ~ 3000rpm; Then, put into the glove box being full of inert gas, with 50 ~ 100 DEG C of annealing 10 ~ 20min in thermal station, thus at TiO
2the obtained PCDTBT:PCBM active layer doped with inorganic-quantum-dot on electron transfer layer, thickness is 80 ~ 150nm;
6) at the molybdenum trioxide aqueous solution of the gold doping obtained doped with spin coating on the PCDTBT:PCBM active layer of inorganic-quantum-dot, rotating speed is 3000 ~ 5000rpm; Then put into the glove box being full of inert atmosphere, with 80 ~ 120 DEG C of annealing 10 ~ 20min in thermal station, thus obtain molybdenum trioxide hole transmission layer on active layer, thickness is 4 ~ 10nm;
7) device is taken out, at pressure 1 × 10
-4~ 5 × 10
-4under Pa condition, evaporation Ag (Chemical Reagent Co., Ltd., Sinopharm Group) electrode on molybdenum trioxide hole transmission layer, thickness is 80 ~ 120nm, and the speed of growth is
thus prepare the transoid polymer solar battery modified based on active layer and transport layer.
The transoid polymer solar battery modified based on active layer and transport layer made by us can be good at solving the problem mentioned in background technology: the PEI 1) adopted modifies the transmission that cathode buffer layer can be good at improving electric charge and balances; 2); Molybdenum trioxide anode buffer layer gold doping can carry high light reflectivity later, increases spectrum and utilizes, and adopt the way of solution spin coating, avoid the series of problems that evaporation coating method brings; 3) active layer mixes inorganic-quantum-dot, the energy level between can better regulating to acceptor, is conducive to strengthening transferring charge, improves the coupling of electron-hole mobility.
Accompanying drawing explanation
Fig. 1: the structural representation of polymer solar battery of the present invention;
Fig. 2: molybdenum trioxide gold doping hole transmission layer polymer solar battery photocurrent curve under different revolutions prepared by the embodiment of the present invention 1.
Fig. 3: after the process of the embodiment of the present invention 2 ultraviolet, the photocurrent curve of the polymer solar battery that PEI modifies under the different revolutions of preparation;
Fig. 4: after the process of the embodiment of the present invention 3 hydroxylating, the photocurrent curve of the polymer solar battery that PEI modifies under the different revolutions of preparation;
Fig. 5: in the embodiment of the present invention 1,2,3 under three kinds of different conditions PEI modify and not have modification polymer solar battery photocurrent curve.
As shown in Figure 1,1 be ITO electro-conductive glass as substrate and negative electrode, 2 is TiO
2electron transfer layer, 3 is PEI decorative layer, 4 is PCDTBT:PCBM:CdSe active layer, 5 for MoO
3: Au hole transmission layer, 6 is Ag electrode.
As shown in Figure 2, at 100mw/cm
2xenon light shining under recorded V-I characteristic curve, we use Keithley, SMU2601 digital sourcemeter.When curve one, two, three is respectively and does not carry out PEI modification, the revolution of molybdenum trioxide hole transmission layer is the photocurrent curve of 2000,3000 and 4000 turns of lower devices, we can see that the efficiency of device presents one and first raises rear downward trend, are issued to the best at 3000 turns.Therefore, in follow-up experimentation, 3000 turns are chosen as the revolution of molybdenum trioxide hole transmission layer is unified.
As shown in Figure 3, curve one is after ultraviolet process, and revolution is the photocurrent curve of the solar cell that the PEI under 3000 turns modifies; Curve two is after ultraviolet process, and revolution is the photocurrent curve of the solar cell that the PEI under 4000 turns modifies; Curve three is after ultraviolet process, and revolution is the photocurrent curve of the solar cell that the PEI under 5000 turns modifies.From figure, we can clearly compare, solar cell prepared by the present invention, the best results of device when PEI revolution is 4000 turns.
Curve one is after hydroxylating process as shown in Figure 4, and revolution is the photocurrent curve of the solar cell that the PEI under 3000 turns modifies; Curve two is after hydroxylating process, and revolution is the photocurrent curve of the solar cell that the PEI under 4000 turns modifies; Curve three is after hydroxylating process, and revolution is the photocurrent curve of the solar cell that the PEI under 5000 turns modifies.From figure, we can clearly compare, solar cell prepared by the present invention, the best results of device when PEI revolution is 4000 turns.
As shown in Figure 5, curve one, two, three represents TiO respectively
2pEI modification, TiO is carried out under electron transfer layer is untreated
2pEI modification and TiO is carried out under the process of electron transfer layer ultraviolet
2the photocurrent curve of the device of PEI modification is carried out under the process of electron transfer layer hydroxylating.As can be seen from figure we, at TiO
2when electron transfer layer does not process, PEI modifies can produce good device effect, carries out PEI modification again the energy conversion efficiency of device can be made to increase further after ultraviolet and hydroxylating process.
Embodiment
Embodiment 1:
(1) the ITO electro-conductive glass of 15mm × 20mm is put into beaker, use acetone, absolute ethyl alcohol, deionized water ultrasonic cleaning 15min successively, the substrate nitrogen gun after cleaning dries up, and puts into culture dish stand-by;
(2) at room temperature 25 DEG C by the Ti (OC of 10mL
4h
9)
4be added drop-wise in the absolute ethyl alcohol of 90mL, then drip the glacial acetic acid of 10mL, magnetic agitation 40min, obtain the yellow solution of homogeneous transparent; Then add the acetylacetone,2,4-pentanedione of 10mL, stir 30min, then 10mL deionized water is slowly added drop-wise in above-mentioned solution with the speed of 3mL/min, continue to stir 1h, obtain the faint yellow colloidal sol of homogeneous transparent, still aging 7h, obtained TiO
2colloidal sol;
By TiO
2colloidal sol is spin-coated on clean ito glass surface, and spin speed is 3000rpm; Then will with TiO
2muffle furnace put into by the ITO electro-conductive glass of colloidal sol, roasting 2h under 450 DEG C of conditions, and powered-down is by Temperature fall 12h in stove subsequently, can obtain TiO on ITO electro-conductive glass
2electron transfer layer;
(3) at TiO
2the PEI solution of direct spin coating 2mg/mL on electron transfer layer, revolution is 4000rmp, obtains PEI decorative layer;
(4) under room temperature condition, PCDTBT and PCBM is dissolved in 1mL dichloro-benzenes organic solvent according to mass ratio 1:4, be configured to the solution of 7mg/mL, add the oil-soluble CdSe inorganic-quantum-dot solution of 20 μ L, 1mg/mL again, after then stirring 48h, obtain PCDTBT:PCBM:CdSe active layer solution;
(5) spin coating PCDTBT:PCBM:CdSe active layer solution on PEI decorative layer, rotating speed is 2000rpm; Then, the sample that spin coating is good is put into the glove box being full of ar gas environment, 70 DEG C of annealing 20min in thermal station, can obtain PCDTBT:PCBM:CdSe active layer on PEI decorative layer, thickness is about 100nm;
(6) at room temperature 25 DEG C, the ammonium molybdate of 39.2mg is dissolved in the deionized water of 20mL, forms the solution of 0.01mol/L, then the aqueous hydrochloric acid solution of 2mol/L is dropwise added in above-mentioned solution, until the pH value of mixed solution is 1.5, finally stirs and obtain the molybdenum trioxide aqueous solution in 2 hours.Ultrasonic process 30min after the molybdenum trioxide aqueous solution taking-up 10mL prepared adds the golden nanometer particle of 0.58mg.
The water-soluble molybdenum trioxide gold doping solution that spin coating is obtained on PCDTBT:PCBM:CdSe active layer, rotating speed is 3000rpm; Then sample is put into the glove box being full of argon gas, with 160 DEG C of annealing 10min in thermal station, thus the Molybdenum Oxide Thin Films by Sol-Gel thickness of obtained gold doping is 6nm on PCDTBT:PCBM:CdSe active layer;
(7) taken out by sample, putting into SD400B type multi-source temperature control organic vapors molecule deposition system, is 5 × 10 at pressure
-4under Pa, evaporation Ag electrode on the Molybdenum Oxide Thin Films by Sol-Gel of gold doping, thickness is 100nm, and the speed of growth is
Embodiment 2:
(1) the ITO electro-conductive glass of 15mm × 20mm is put into beaker, use acetone, absolute ethyl alcohol, deionized water ultrasonic cleaning 15min successively, the substrate nitrogen gun after cleaning dries up, and puts into culture dish stand-by;
(2) at room temperature 25 DEG C by the Ti (OC of 10mL
4h
9)
4be added drop-wise in the absolute ethyl alcohol of 90mL, then drip the glacial acetic acid of 10mL, magnetic agitation 40min, obtain the yellow solution of homogeneous transparent; Then add the acetylacetone,2,4-pentanedione of 10mL, stir 30min, then 10mL deionized water is slowly added drop-wise in above-mentioned solution with the speed of 3mL/min, continue to stir 1h, obtain the faint yellow colloidal sol of homogeneous transparent, still aging 7h, obtained TiO
2colloidal sol;
By TiO
2colloidal sol is spin-coated on clean ito glass surface, and spin speed is 3000rpm; Then will with TiO
2muffle furnace put into by the ITO electro-conductive glass of colloidal sol, roasting 2h under 450 DEG C of conditions, and powered-down is by Temperature fall 12h in stove subsequently, can obtain TiO on ITO electro-conductive glass
2electron transfer layer;
(3) by TiO
2electron transfer layer 250nm UV-irradiation 10min.Again the PEI solution of 2mg/mL is spun to the TiO after ultraviolet process with 4000rmp
2on electron transfer layer, obtain PEI decorative layer;
(4) under room temperature condition, PCDTBT and PCBM is dissolved according to mass ratio 1:4 in the dichloro-benzenes of organic solvent 1mL, be configured to the solution of 7mg/mL, then add the CdSe inorganic-quantum-dot solution of 1mg/mL of 20 μ L, after then stirring 48h, obtain PCDTBT:PCBM:CdSe active layer solution;
(5) spin coating PCDTBT:PCBM:CdSe active layer solution on PEI decorative layer, rotating speed is 2000rpm; Then, the sample that spin coating is good is put into the glove box being full of ar gas environment, 70 DEG C of annealing 20min in thermal station, can obtain PCDTBT:PCBM:CdSe active layer on PEI decorative layer, thickness is about 100nm;
(6) at room temperature 25 DEG C, the ammonium molybdate of 39.2mg is dissolved in the deionized water of 20mL, form the solution of 0.01mol/L, then the aqueous hydrochloric acid solution of 2mol/L is dropwise added in above-mentioned solution, until the pH value of mixed solution is 1.5.It is for subsequent use that finally stirring obtains the molybdenum trioxide aqueous solution in 2 hours.Ultrasonic process 30min after the molybdenum trioxide solution taking-up 10mL prepared adds the golden nanometer particle of 0.58mg.
The water-soluble molybdenum trioxide gold doping solution that spin coating is obtained on PCDTBT:PCBM:CdSe active layer, rotating speed is 3000rpm; Then sample is put into the glove box being full of argon gas, with 160 DEG C of annealing 10min in thermal station, thus on PCDTBT:PCBM:CdSe active layer, obtain the Molybdenum Oxide Thin Films by Sol-Gel of gold doping, thickness is 6nm;
(7) taken out by sample, putting into SD400B type multi-source temperature control organic vapors molecule deposition system, is 5 × 10 at pressure
-4under Pa, evaporation Ag electrode on the Molybdenum Oxide Thin Films by Sol-Gel of gold doping, thickness is 100nm, and the speed of growth is
Embodiment 3:
(1) the ITO electro-conductive glass of 15mm × 20mm is put into beaker, use acetone, absolute ethyl alcohol, deionized water ultrasonic cleaning 15min successively, the substrate nitrogen gun after cleaning dries up, and puts into culture dish stand-by;
(2) at room temperature 25 DEG C by the Ti (OC of 10mL
4h
9)
4be added drop-wise in the absolute ethyl alcohol of 90mL, then drip the glacial acetic acid of 10mL, magnetic agitation 40min, obtain the yellow solution of homogeneous transparent; Then add the acetylacetone,2,4-pentanedione of 10mL, stir 30min, then 10mL deionized water is slowly added drop-wise in above-mentioned solution with the speed of 3mL/min, continue to stir 1h, obtain the faint yellow colloidal sol of homogeneous transparent, still aging 7h, obtained TiO
2colloidal sol;
By TiO
2colloidal sol is spin-coated on clean ito glass surface, and spin speed is 3000rpm; Then will with TiO
2muffle furnace put into by the ITO electro-conductive glass of colloidal sol, roasting 2h under 450 DEG C of conditions, and powered-down is by Temperature fall 12h in stove subsequently, can obtain TiO on ITO electro-conductive glass
2electron transfer layer;
(3) with the TiO spun above
2electron transfer layer is basis material, using non-conjugated electrolyte polymine (PEI) as interface-modifying layer.The electron transfer layer prepared is carried out hydroxylating process, and hydroxylacion method is the TiO that will prepare
2electron transfer layer is immersed in 20h in the ethylene glycol solution of the KOH of 1mg/mL.Then, then by the PEI solution of 2mg/mL be spin-coated on the TiO after hydroxylating process with revolution 4000rmp
2on electron transfer layer.Owing to containing a large amount of protonated amido energy and TiO in PEI solution
2the hydroxyl generation electrostatic self-assembled process on surface, forms the interface dipole sublayer of thin layer.
(4) under room temperature condition, PCDTBT and PCBM is dissolved according to mass ratio 1:4 in the dichloro-benzenes of organic solvent 1mL, be configured to the solution of 7mg/mL, then add the CdSe inorganic-quantum-dot solution of 1mg/mL of 20 μ L, after then stirring 48h, obtain PCDTBT:PCBM:CdSe active layer solution;
(5) spin coating PCDTBT:PCBM:CdSe active layer solution on PEI decorative layer, rotating speed is 2000rpm; Then, the sample that spin coating is good is put into the glove box being full of ar gas environment, 70 DEG C of annealing 20min in thermal station, can obtain PCDTBT:PCBM:CdSe active layer on PEI decorative layer, thickness is about 100nm;
(6) at room temperature 25 DEG C, the ammonium molybdate of 39.2mg is dissolved in the deionized water of 20mL, form the solution of 0.01mol/L, then the aqueous hydrochloric acid solution of 2mol/L is dropwise added in above-mentioned solution, until the pH value of mixed solution is 1.5.It is for subsequent use that finally stirring obtains the molybdenum trioxide aqueous solution in 2 hours.Ultrasonic process 30min after the molybdenum trioxide solution taking-up 10mL prepared adds the golden nanometer particle of 0.58mg.
The water-soluble molybdenum trioxide gold doping solution that spin coating is obtained on PCDTBT:PCBM:CdSe active layer, rotating speed is 3000rpm; Then sample is put into the glove box being full of argon gas, with 160 DEG C of annealing 10min in thermal station, thus on PCDTBT:PCBM:CdSe active layer, obtain the Molybdenum Oxide Thin Films by Sol-Gel of gold doping, thickness is 6nm;
(7) taken out by sample, putting into SD400B type multi-source temperature control organic vapors molecule deposition system, is 5 × 10 at pressure
-4under Pa, evaporation Ag electrode on the Molybdenum Oxide Thin Films by Sol-Gel of gold doping, thickness is 100nm, and the speed of growth is
Claims (8)
1. based on the transoid polymer solar battery that active layer and transport layer are modified, it is characterized in that: from bottom to up, successively by ITO electro-conductive glass, the TiO as substrate and negative electrode
2electron transfer layer, polymine PEI decorative layer, PCDTBT:PCBM active layer, MoO
3hole transmission layer and Ag anode composition, mixing in active layer with PCDTBT:PCBM mass ratio is the inorganic-quantum-dot of 0.0286% ~ 0.114%; Mix in hole transmission layer and MoO
3mass ratio is the Au nano particle of 3.0% ~ 5.0%.
2. a kind of transoid polymer solar battery modified based on active layer and transport layer as claimed in claim 1, is characterized in that: inorganic-quantum-dot is cadmium selenide, cadmium telluride or cadmium sulfide.
3. a kind of transoid polymer solar battery modified based on active layer and transport layer as claimed in claim 1, is characterized in that: TiO
2the thickness of electron transfer layer is the thickness of 20 ~ 40nm, PEI decorative layer is 4 ~ 10nm, and the thickness mixing the PCDTBT:PCBM active layer of inorganic-quantum-dot is 80 ~ 150nm, mixes the MoO of Au nano particle
3the thickness of hole transmission layer is the thickness of 4 ~ 10nm, Ag anode is 80 ~ 120nm.
4. a kind of transoid polymer solar battery modified based on active layer and transport layer as claimed in claim 1, is characterized in that: TiO
2electron transfer layer carries out UV-irradiation process.
5. a kind of transoid polymer solar battery modified based on active layer and transport layer as claimed in claim 1, is characterized in that: TiO
2electron transfer layer carries out hydroxylating process.
6. a preparation method for the transoid polymer solar battery modified based on active layer and transport layer, its step is as follows:
1) ITO electro-conductive glass is put into beaker, use acetone, absolute ethyl alcohol, deionized water ultrasonic cleaning 10 ~ 20min respectively, dry up with nitrogen after cleaning;
2) by TiO
2colloidal sol is spin-coated on step 1) the ITO conductive glass surface that obtains, spin speed is 3000 ~ 5000rpm; Then will with TiO
2iTO electro-conductive glass roasting 2 ~ 3h under 450 ~ 600 DEG C of conditions of colloidal sol, Temperature fall 10 ~ 12h, can obtain TiO on ITO electro-conductive glass
2electron transfer layer, the thickness of electron transfer layer is 20 ~ 40nm;
3) method of one of following three kinds of employing is to TiO
2electron transfer layer carries out surface treatment,
Method one is TiO
2electron transfer layer surface, without any process, directly with the PEI solution of 3000 ~ 4000rmp spin coating, 1 ~ 5mg/mL, obtains the PEI decorative layer that thickness is 4 ~ 10nm;
Method two is by step 2) in spin coating have TiO
2the ITO electro-conductive glass wavelength of electron transfer layer is the UV-irradiation 10 ~ 20min of 200 ~ 400nm, then the PEI solution of 1 ~ 5mg/mL is spun to the TiO after ultraviolet process with the revolution of 3000 ~ 4000rmp
2on electron transfer layer, obtain the PEI decorative layer that thickness is 4 ~ 10nm;
First method three is by step 2) TiO that obtains
2it is that in the ethylene glycol solution of the KOH of 1 ~ 3mg/mL, 10 ~ 20h carries out hydroxylating process that electron transfer layer is immersed in concentration; Then, then by the PEI solution of 1 ~ 5mg/mL be spin-coated on the TiO after hydroxylating process with the revolution of 3000 ~ 4000rmp
2on electron transfer layer, obtain the PEI decorative layer that thickness is 4 ~ 10nm;
4) under room temperature condition, donor material PCDTBT and acceptor material PCBM is dissolved in organic solvent dichloro-benzenes according to mass ratio 1:4, be configured to the active layer solution of 5 ~ 10mg/mL, the inorganic-quantum-dot solution of 10 ~ 40 μ L, 1 ~ 5mg/mL is added in above-mentioned active layer solution, then under the speed of 600 ~ 800rpm, stir 24 ~ 48h, namely can be configured to the mixed solution of the PCDTBT:PCBM doped with inorganic-quantum-dot;
5) on PEI decorative layer, spin coating is doped with the PCDTBT:PCBM active layer solution of inorganic-quantum-dot, and rotating speed is 2000 ~ 3000rpm; Then, put into the glove box being full of inert gas, with 50 ~ 100 DEG C of annealing 10 ~ 20min in thermal station, thus at TiO
2the obtained PCDTBT:PCBM active layer doped with inorganic-quantum-dot on electron transfer layer, thickness is 80 ~ 150nm;
6) at the molybdenum trioxide aqueous solution of the gold doping obtained doped with spin coating on the PCDTBT:PCBM active layer of inorganic-quantum-dot, rotating speed is 3000 ~ 5000rpm; Then put into the glove box being full of inert atmosphere, with 80 ~ 120 DEG C of annealing 10 ~ 20min in thermal station, thus obtain molybdenum trioxide hole transmission layer on active layer, thickness is 4 ~ 10nm;
7) device is taken out, at pressure 1 × 10
-4~ 5 × 10
-4under Pa condition, evaporation Ag electrode on molybdenum trioxide hole transmission layer, thickness is 80 ~ 120nm, and the speed of growth is
thus prepare the transoid polymer solar battery modified based on active layer and transport layer.
7. the preparation method of a kind of transoid polymer solar battery modified based on active layer and transport layer as claimed in claim 6, is characterized in that: step 2) described in TiO
2the preparation of colloidal sol is the glacial acetic acid being added drop-wise to the butyl titanate of 10 ~ 20mL in the absolute ethyl alcohol of 90 ~ 100mL, then dripping 10 ~ 20mL at ambient temperature, and magnetic agitation 30 ~ 40min, obtains the yellow solution of homogeneous transparent; Then add the acetylacetone,2,4-pentanedione of 10 ~ 20mL, stir 20 ~ 30min, then 10 ~ 20mL deionized water is slowly added drop-wise in above-mentioned solution with the speed of 2 ~ 4mL/min, continue stirring 1 ~ 2h, obtain the faint yellow colloidal sol of homogeneous transparent, place ageing 6 ~ 8h, obtained TiO
2colloidal sol.
8. the preparation method of a kind of transoid polymer solar battery modified based on active layer and transport layer as claimed in claim 6, it is characterized in that: step 6) described in the preparation of the molybdenum trioxide aqueous solution of gold doping be at room temperature the ammonium molybdate of certain mass is dissolved in water, form the solution of 0.01 ~ 0.1mol/L, again the aqueous hydrochloric acid solution of 2mol/L is added in above-mentioned solution, until the pH value of mixed solution is between 1 ~ 1.5, gained is water-soluble molybdenum trioxide solution; Get the above-mentioned solution of 5 ~ 10mL, add the golden nanometer particle of 0.5 ~ 1.0mg, ultrasonic process 20 ~ 40min, namely obtain the molybdenum trioxide aqueous solution of gold doping.
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