CN105047821B - The transoid polymer solar battery and preparation method modified based on active layer and transport layer - Google Patents

The transoid polymer solar battery and preparation method modified based on active layer and transport layer Download PDF

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CN105047821B
CN105047821B CN201510296545.6A CN201510296545A CN105047821B CN 105047821 B CN105047821 B CN 105047821B CN 201510296545 A CN201510296545 A CN 201510296545A CN 105047821 B CN105047821 B CN 105047821B
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solution
tio
active layer
electron transfer
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CN105047821A (en
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郭文滨
刘春雨
沈亮
董玮
周敬然
温善鹏
张歆东
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Jilin University
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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Abstract

The invention belongs to polymer solar battery technical field, and in particular to a kind of transoid polymer solar battery modified based on active layer and transport layer.Device architecture of the present invention is typical reciprocal form structure.Ultraviolet processing and hydroxylating processing are carried out firstly, for titanic oxide electronic transport layer, polyethyleneimine is then carried out amine-modified；Secondly, inorganic-quantum-dot doping is carried out for active layer, further to adjust to the energy level between acceptor, strengthens the transmission of carrier；Finally, hole transmission layer uses water miscible molybdenum trioxide, and carry out the doping of golden nanometer particle, aqueous solution spin coating is conducive to saving the energy compared to vapour deposition method, surface plasmon resonance effect produced by the incorporation of golden nanometer particle can reflect light back into active layer to be further employed, while also will be helpful to transmission of the electric charge in transport layer.Using the transmission of carrier will be made more smooth while three, the migration rate of an electron-hole more balanced is reached.

Description

The transoid polymer solar battery modified based on active layer and transport layer and preparation Method
Technical field
The invention belongs to polymer solar battery technical field, and in particular to one kind is modified based on active layer with transport layer Transoid polymer solar battery and preparation method.
Background technology
The research of polymer solar battery can greatly alleviating energy crisis and improve problem of environmental pollution, be subjected to To increasing concern, the research topic as very attractive in recent years.But energy conversion efficiency is low still to be govern The commercial applications of polymer solar battery.The efficiency of single-unit solar cell has reached 10.2%, restricts it and further carries High the reason for, is mainly the migration of unmatched electron-hole, separation, transmission and recombination rate, cause one very low photoelectric current because The method of this cushion modification is more applied, including cathode buffer layer modification and anode buffer layer modification；On the other hand, mesh The problem of research of preceding solar cell has one generally is exactly that spectrum utilization factor is low；The simultaneous buffering layer evaporation used more Method, greatly consumes the energy, and inevitable also by the small of remaining transmission layer material in evaporation cavity when being deposited with transport layer Particle, this affects the evaporation to next step electrode.
The content of the invention
It is an object of the invention to provide a kind of transoid polymer solar battery modified based on active layer and transport layer and Preparation method.
Polymer solar battery prepared by the present invention, it is characterised in that：From bottom to up, successively by being used as substrate and the moon The ITO electro-conductive glass of pole, TiO2Electron transfer layer, polyethyleneimine PEI decorative layers, PCDTBT:PCBM active layers, MoO3Hole Transport layer, Ag anodes composition, i.e. structure are ITO/TiO2/PEI/PCDTBT:PCBM/MoO3/Ag；In active layer incorporation with PCDTBT:PCBM mass ratioes are 0.0286%~0.114% inorganic-quantum-dot (cadmium selenide, cadmium telluride, cadmium sulfide etc.)； MoO3Incorporation and MoO in hole transmission layer3Mass ratio is 3.0%~5.0% Au nano-particles (NPs)；It is different using three kinds Method modifies PEI layers of modified titanic oxide battery transport layer of spin coating.
Wherein, TiO2The thickness of electron transfer layer is 20~40nm, and the thickness of PEI decorative layers is 4~10nm, mixes inorganic amount The PCDTBT of son point:The thickness of PCBM active layers is 80~150nm, mixes Au nano-particles (NPs) MoO3Hole transmission layer Thickness is 4~10nm, and the thickness of Ag anodes is 80~120nm；
In addition, for TiO2Electron transfer layer, we additionally use three kinds of modes and pre-processed, and PEI is then carried out again Surface modification；For active layer, we will mix inorganic-quantum-dot material, to improve active layer to the energy level between acceptor material Matching；For hole transmission layer, we are prepared for water miscible molybdenum trioxide using hydro-thermal method, and mix the gold of certain mass Nano-particle, then replaces the mode of evaporation to prepare molybdenum trioxide hole transmission layer by the way of spin-coating film.It is above-mentioned all Improved method is all more beneficial for the electric charge transmission in device.
The hole transmission layer of gold doping is made annealing treatment after being spun on active layer in the present invention, is formed well after annealing Configuration of surface.Golden nanometer particle represents good surface plasmon resonance effect, reflects light back into active layer by sharp again With；Meanwhile, the transmission being mixed with beneficial to electric charge of golden nanometer particle；In the present invention the three of gold doping are obtained with the method for spin-coating film Molybdenum oxide hole transport layer film, is compared with traditional vacuum thermal evaporation, operates simpler convenience, and can reduce energy The consumption in source.
Specific method is as follows：The ammonium molybdate of certain mass is dissolved in water at room temperature, forms 0.01~0.1mol/L's Solution, then 2mol/L aqueous hydrochloric acid solution is added in above-mentioned solution, until the pH value of mixed solution is between 1~1.5, gained As water-soluble molybdenum trioxide solution；5~10mL above-mentioned solution is taken, is added at 0.5~1.0mg golden nanometer particle, ultrasound 20~40min is managed, that is, obtains the molybdenum trioxide aqueous solution of gold doping.
The preparation method of the transoid polymer solar battery of the present invention modified based on active layer and transport layer, it is walked Suddenly it is as follows with condition：
1) ITO electro-conductive glass is put into beaker, respectively with acetone, absolute ethyl alcohol, deionized water be cleaned by ultrasonic 10~ 20min, is dried up after cleaning with nitrogen；
2) 10~20mL butyl titanate (Beijing Yi Li chemical plant) is added drop-wise to 90~100mL nothing under room temperature condition In water-ethanol (Beijing Chemical Plant), then 10~20mL glacial acetic acid (Beijing Chemical Plant) is added dropwise, 30~40min of magnetic agitation is obtained To the yellow solution of homogeneous transparent；Then add 10~20mL acetylacetone,2,4-pentanedione (Tianjin chemical reagent factory), stirring 20~ 30min, then 10~20mL deionized waters are slowly dropped in above-mentioned solution with 2~4mL/min speed, continuation stirring 1~ 2h, obtains the faint yellow colloidal sol of homogeneous transparent, places ageing 6~8h, obtained TiO2Colloidal sol；By obtained TiO2Colloidal sol spin coating In step 1) obtained ITO conductive glass surfaces, spin speed is 3000~5000rpm；Then TiO will be carried2The ITO of colloidal sol Electro-conductive glass is calcined 2~3h, 10~12h of Temperature fall under the conditions of 450~600 DEG C, you can be made on ITO electro-conductive glass TiO2Electron transfer layer, the thickness of electron transfer layer is 20~40nm；
3) using three kinds of different methods to TiO2Electron transfer layer is surface-treated,
Method one is TiO2Electric transmission layer surface is without any processing, directly with 3000~4000rmp spin coatings, 1~5mg/ ML PEI solution, obtains the PEI decorative layers that thickness is 4~10nm；
Method two is by step 2) in spin coating have TiO2The ITO electro-conductive glass wavelength of electron transfer layer is 200~400nm 10~20min of ultraviolet light, then 1~5mg/mL PEI solution is spun to ultraviolet place with 3000~4000rmp revolution TiO after reason2On electron transfer layer, the PEI decorative layers that thickness is 4~10nm are obtained；
Method three is with TiO2Electron transfer layer is matrix material, using non-conjugated electrolyte polyethyleneimine (PEI) as Interface-modifying layer.First, by step 2) obtained TiO2Electron transfer layer is immersed in the second two for the KOH that concentration is 1~3mg/mL 10~20h carries out hydroxylating processing in alcoholic solution；Then, then by 1~5mg/mL PEI solution with 3000~4000rmp turn Number is spin-coated on the TiO after hydroxylating processing2On electron transfer layer, due to containing the amido energy of substantial amounts of protonation in PEI solution With TiO2Electrostatic self-assembled occurs for the hydroxyl of electric transmission layer surface, so as to form a thin layer of interface dipole sublayer, obtains Thickness is 4~10nm PEI decorative layers；
4) under room temperature condition, by donor material PCDTBT (Poly- [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-butyric acid methyl ester, fowler Ene derivative, Nichem precisions Science and Technology Ltd.) according to mass ratio 1：4 are dissolved in organic solvent dichloro-benzenes, and (Beijing lark prestige is public Department) in, 5~10mg/mL active layer solution is configured to, 10~40 μ L, 1~5mg/mL are added in above-mentioned active layer solution CdSe inorganic-quantum-dot solution, then stirs 24~48h, you can be configured to doped with inorganic under 600~800rpm speed The PCDTBT of quantum dot:PCBM mixed solution；
5) PCDTBT of the spin coating doped with inorganic-quantum-dot on PEI decorative layers:PCBM active layer solution, rotating speed is 2000 ~3000rpm；Then, it is put into the glove box full of inert gas, with 50~100 DEG C of 10~20min of annealing in thermal station, from And in TiO2The PCDTBT doped with inorganic-quantum-dot is made on electron transfer layer:PCBM active layers, thickness is 80~150nm；
6) in the PCDTBT doped with inorganic-quantum-dot:The molybdenum trioxide of gold doping is water-soluble made from spin coating on PCBM active layers Liquid, rotating speed is 3000~5000rpm；It is then placed in the glove box full of inert atmosphere, with 80~120 DEG C of annealing in thermal station 10~20min, so that molybdenum trioxide hole transmission layer be made on active layer, thickness is 4~10nm；
7) device is taken out, in pressure 1 × 10-4~5 × 10-4Under the conditions of Pa, it is deposited with molybdenum trioxide hole transmission layer Ag (Chemical Reagent Co., Ltd., Sinopharm Group) electrode, thickness is 80~120nm, and the speed of growth isSo as to be prepared into To 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 solution The problem of certainly being referred in background technology：1) transmission that the PEI modification cathode buffer layers used can be good at improving electric charge is put down Weighing apparatus；2)；High light reflectivity can be carried after molybdenum trioxide anode buffer layer gold doping, increase spectrum is utilized, and uses solution spin coating Method, it is to avoid a series of problems that evaporation coating method is brought；3) active layer incorporation inorganic-quantum-dot, can preferably be adjusted to receipts Energy level between body, is conducive to enhancing electric charge transmission, improves the matching of electron-hole mobility.
Brief description of the drawings
Fig. 1：The structural representation of polymer solar battery of the present invention；
Fig. 2：Molybdenum trioxide gold doping hole transmission layer polymer solar electricity under different revolutions prepared by the embodiment of the present invention 1 Pond photocurrent curve.
Fig. 3：After the ultraviolet processing of the embodiment of the present invention 2, the polymer solar battery that PEI is modified under the different revolutions of preparation Photocurrent curve；
Fig. 4：After the processing of the hydroxylating of the embodiment of the present invention 3, the polymer solar electricity that PEI is modified under the different revolutions of preparation The photocurrent curve in pond；
Fig. 5：In the embodiment of the present invention 1,2,3 under three kinds of different conditions PEI modify and without modify the polymer sun Can cell photoelectric flow curve.
As shown in figure 1,1 be ITO electro-conductive glass as substrate and negative electrode, 2 be TiO2Electron transfer layer, 3 are that PEI is modified Layer, 4 are PCDTBT:PCBM：CdSe active layers, 5 are MoO3：Au hole transmission layers, 6 are Ag electrodes.
As shown in Fig. 2 in 100mw/cm2Xenon light shining under measured V-I characteristic curves, we use Keithley, SMU2601 digital sourcemeter.In the case that curve one, two, three does not respectively carry out PEI modifications, molybdenum trioxide is empty The revolution of cave transport layer is 2000, the photocurrent curve of 3000 and 4000 turns of lower devices, and we can see that the efficiency of device is in Downward trend after existing one first rise, is issued to optimal at 3000 turns.Therefore, for three oxidations in follow-up experimentation The unified selection of the revolution of molybdenum hole transmission layer is 3000 turns.
As shown in figure 3, curve one be ultraviolet processing after, revolution be 3000 turns under PEI modification solar cell light Current curve；Curve two be ultraviolet processing after, revolution be 4000 turns under PEI modification solar cell photocurrent curve； Curve three be ultraviolet processing after, revolution be 5000 turns under PEI modification solar cell photocurrent curve.From figure we Can clearly it compare, solar cell prepared by the present invention, the best results of device when PEI revolutions are 4000 turns.
After curve one as shown in Figure 4 is hydroxylating processing, revolution is the light of the solar cell of the PEI modifications under 3000 turns Current curve；Curve two is that after hydroxylating is handled, revolution is bent for the photoelectric current of the solar cell of the PEI modifications under 4000 turns Line；Curve three be hydroxylating processing after, revolution be 5000 turns under PEI modification solar cell photocurrent curve.From figure In we can clearly compare, the solar cell for preparing of the present invention, the effect of device is most when PEI revolutions are 4000 turns It is good.
As shown in figure 5, curve one, two, three represents TiO respectively2The untreated lower progress PEI modifications of electron transfer layer, TiO2Electricity PEI modifications and TiO are carried out under the sub- ultraviolet processing of transport layer2The lower device for carrying out PEI modifications of electron transfer layer hydroxylating processing Photocurrent curve.It will be seen that in TiO from figure2In the case that electron transfer layer is not handled, PEI modifications can be produced Raw good device effect, the energy conversion efficiency of device can be made by carrying out PEI modifications again after the processing of ultraviolet and hydroxylating Further increase.
Embodiment
Embodiment 1：
(1) 15mm × 20mm ITO electro-conductive glass is put into beaker, surpassed successively with acetone, absolute ethyl alcohol, deionized water Sound cleans 15min, and the substrate after cleaning is dried up with nitrogen gun, is put into stand-by in culture dish；
(2) by 10mL Ti (OC at 25 DEG C of room temperature4H9)4It is added drop-wise in 90mL absolute ethyl alcohol, then 10mL ice second is added dropwise Acid, magnetic agitation 40min obtains the yellow solution of homogeneous transparent；Then 10mL acetylacetone,2,4-pentanedione is added, 30min is stirred, then 10mL deionized waters are slowly dropped in above-mentioned solution with 3mL/min speed, continues to stir 1h, obtains the light of homogeneous transparent Yellow sol, still aging 7h, obtained TiO2Colloidal sol；
By TiO2Colloidal sol is spin-coated on clean ito glass surface, and spin speed is 3000rpm；Then TiO will be carried2Colloidal sol ITO electro-conductive glass be put into Muffle furnace, be calcined 2h under the conditions of 450 DEG C, be then turned off power supply by Temperature fall 12h in stove, TiO can be made on ITO electro-conductive glass2Electron transfer layer；
(3) in TiO2Direct spin coating 2mg/mL PEI solution on electron transfer layer, revolution is 4000rmp, obtains PEI and repaiies Adorn layer；
(4) under room temperature condition, by PCDTBT and PCBM according to mass ratio 1：4 are dissolved in 1mL dichloro-benzenes organic solvents, configuration Into 7mg/mL solution, 20 μ L, 1mg/mL oil-soluble CdSe inorganic-quantum-dots solution is added, then stirs and obtained after 48h To PCDTBT:PCBM：CdSe active layer solution；
(5) the spin coating PCDTBT on PEI decorative layers:PCBM：CdSe active layer solution, rotating speed is 2000rpm；Then, will The good sample of spin coating is put into the glove box full of ar gas environment, 70 DEG C of annealing 20min in thermal station, you can in PEI decorative layers Upper obtained PCDTBT:PCBM：CdSe active layers, thickness is about 100nm；
(6) at 25 DEG C of room temperature, in the deionized water that 39.2mg ammonium molybdate is dissolved in 20mL, form 0.01mol/L's Solution, then 2mol/L aqueous hydrochloric acid solution is added dropwise in above-mentioned solution, until the pH value of mixed solution is 1.5, finally stir Mix 2 hours and obtain the molybdenum trioxide aqueous solution.Jenner's grain of rice that 10mL adds 0.58mg is taken out in the molybdenum trioxide aqueous solution prepared Ultrasonically treated 30min after son.
In PCDTBT:PCBM：Water-soluble molybdenum trioxide gold doping solution made from spin coating on CdSe active layers, rotating speed is 3000rpm；Then sample is put into the glove box full of argon gas, with 160 DEG C of annealing 10min in thermal station, so that PCDTBT:PCBM：The Molybdenum Oxide Thin Films by Sol-Gel thickness that gold doping is made on CdSe active layers is 6nm；
(7) sample is taken out, is put into SD400B type multi-source temperature control organic vapors molecule deposition systems, pressure be 5 × 10-4Under Pa, Ag electrodes are deposited with the Molybdenum Oxide Thin Films by Sol-Gel of gold doping, thickness is 100nm, and the speed of growth is
Embodiment 2：
(1) 15mm × 20mm ITO electro-conductive glass is put into beaker, surpassed successively with acetone, absolute ethyl alcohol, deionized water Sound cleans 15min, and the substrate after cleaning is dried up with nitrogen gun, is put into stand-by in culture dish；
(2) by 10mL Ti (OC at 25 DEG C of room temperature4H9)4It is added drop-wise in 90mL absolute ethyl alcohol, then 10mL ice second is added dropwise Acid, magnetic agitation 40min obtains the yellow solution of homogeneous transparent；Then 10mL acetylacetone,2,4-pentanedione is added, 30min is stirred, then 10mL deionized waters are slowly dropped in above-mentioned solution with 3mL/min speed, continues to stir 1h, obtains the light of homogeneous transparent Yellow sol, still aging 7h, obtained TiO2Colloidal sol；
By TiO2Colloidal sol is spin-coated on clean ito glass surface, and spin speed is 3000rpm；Then TiO will be carried2Colloidal sol ITO electro-conductive glass be put into Muffle furnace, be calcined 2h under the conditions of 450 DEG C, be then turned off power supply by Temperature fall 12h in stove, TiO can be made on ITO electro-conductive glass2Electron transfer layer；
(3) by TiO2Electron transfer layer 250nm ultraviolet lights 10min.Again by 2mg/mL PEI solution with 4000rmp is spun to the TiO after ultraviolet processing2On electron transfer layer, PEI decorative layers are obtained；
(4) under room temperature condition, by PCDTBT and PCBM according to mass ratio 1:4 are dissolved in organic solvent 1mL dichloro-benzenes, match somebody with somebody 7mg/mL solution is set to, 20 μ L 1mg/mL CdSe inorganic-quantum-dot solution is added, obtained after then stirring 48h PCDTBT:PCBM：CdSe active layer solution；
(5) the spin coating PCDTBT on PEI decorative layers:PCBM：CdSe active layer solution, rotating speed is 2000rpm；Then, will The good sample of spin coating is put into the glove box full of ar gas environment, 70 DEG C of annealing 20min in thermal station, you can in PEI decorative layers Upper obtained PCDTBT:PCBM：CdSe active layers, thickness is about 100nm；
(6) at 25 DEG C of room temperature, in the deionized water that 39.2mg ammonium molybdate is dissolved in 20mL, form 0.01mol/L's Solution, then 2mol/L aqueous hydrochloric acid solution is added dropwise in above-mentioned solution, until the pH value of mixed solution is 1.5.Finally stir Mix that to obtain the molybdenum trioxide aqueous solution within 2 hours standby.The gold nano that 10mL adds 0.58mg is taken out in the molybdenum trioxide solution prepared Ultrasonically treated 30min after particle.
In PCDTBT:PCBM：Water-soluble molybdenum trioxide gold doping solution made from spin coating on CdSe active layers, rotating speed is 3000rpm；Then sample is put into the glove box full of argon gas, with 160 DEG C of annealing 10min in thermal station, so that PCDTBT:PCBM：The Molybdenum Oxide Thin Films by Sol-Gel of gold doping is made on CdSe active layers, thickness is 6nm；
(7) sample is taken out, is put into SD400B type multi-source temperature control organic vapors molecule deposition systems, pressure be 5 × 10-4Under Pa, Ag electrodes are deposited with the Molybdenum Oxide Thin Films by Sol-Gel of gold doping, thickness is 100nm, and the speed of growth is
Embodiment 3：
(1) 15mm × 20mm ITO electro-conductive glass is put into beaker, surpassed successively with acetone, absolute ethyl alcohol, deionized water Sound cleans 15min, and the substrate after cleaning is dried up with nitrogen gun, is put into stand-by in culture dish；
(2) by 10mL Ti (OC at 25 DEG C of room temperature4H9)4It is added drop-wise in 90mL absolute ethyl alcohol, then 10mL ice second is added dropwise Acid, magnetic agitation 40min obtains the yellow solution of homogeneous transparent；Then 10mL acetylacetone,2,4-pentanedione is added, 30min is stirred, then 10mL deionized waters are slowly dropped in above-mentioned solution with 3mL/min speed, continues to stir 1h, obtains the light of homogeneous transparent Yellow sol, still aging 7h, obtained TiO2Colloidal sol；
By TiO2Colloidal sol is spin-coated on clean ito glass surface, and spin speed is 3000rpm；Then TiO will be carried2Colloidal sol ITO electro-conductive glass be put into Muffle furnace, be calcined 2h under the conditions of 450 DEG C, be then turned off power supply by Temperature fall 12h in stove, TiO can be made on ITO electro-conductive glass2Electron transfer layer；
(3) TiO to spin above2Electron transfer layer is matrix material, with non-conjugated electrolyte polyethyleneimine (PEI) It is used as interface-modifying layer.The electron transfer layer prepared is subjected to hydroxylating processing, hydroxylacion method is the TiO that will be prepared2 Electron transfer layer is immersed in 20h in 1mg/mL KOH ethylene glycol solution.Then, then by 2mg/mL PEI solution with revolution 4000rmp is spin-coated on the TiO after hydroxylating processing2On electron transfer layer.Due to containing the amine of substantial amounts of protonation in PEI solution Base energy and TiO2Electrostatic self-assembled process occurs for the hydroxyl on surface, forms a thin layer of interface dipole sublayer.
(4) under room temperature condition, by PCDTBT and PCBM according to mass ratio 1:4 are dissolved in organic solvent 1mL dichloro-benzenes, match somebody with somebody 7mg/mL solution is set to, 20 μ L 1mg/mL CdSe inorganic-quantum-dot solution is added, obtained after then stirring 48h PCDTBT:PCBM：CdSe active layer solution；
(5) the spin coating PCDTBT on PEI decorative layers:PCBM：CdSe active layer solution, rotating speed is 2000rpm；Then, will The good sample of spin coating is put into the glove box full of ar gas environment, 70 DEG C of annealing 20min in thermal station, you can in PEI decorative layers Upper obtained PCDTBT:PCBM：CdSe active layers, thickness is about 100nm；
(6) at 25 DEG C of room temperature, in the deionized water that 39.2mg ammonium molybdate is dissolved in 20mL, form 0.01mol/L's Solution, then 2mol/L aqueous hydrochloric acid solution is added dropwise in above-mentioned solution, until the pH value of mixed solution is 1.5.Finally stir Mix that to obtain the molybdenum trioxide aqueous solution within 2 hours standby.The gold nano that 10mL adds 0.58mg is taken out in the molybdenum trioxide solution prepared Ultrasonically treated 30min after particle.
In PCDTBT:PCBM：Water-soluble molybdenum trioxide gold doping solution made from spin coating on CdSe active layers, rotating speed is 3000rpm；Then sample is put into the glove box full of argon gas, with 160 DEG C of annealing 10min in thermal station, so that PCDTBT:PCBM：The Molybdenum Oxide Thin Films by Sol-Gel of gold doping is made on CdSe active layers, thickness is 6nm；
(7) sample is taken out, is put into SD400B type multi-source temperature control organic vapors molecule deposition systems, pressure be 5 × 10-4Under Pa, Ag electrodes are deposited with the Molybdenum Oxide Thin Films by Sol-Gel of gold doping, thickness is 100nm, and the speed of growth is

Claims (8)

1. a kind of transoid polymer solar battery modified based on active layer and transport layer, it is characterised in that：From bottom to up, according to Secondary ITO electro-conductive glass by as substrate and negative electrode, TiO2Electron transfer layer, polyethyleneimine PEI decorative layers, PCDTBT: PCBM active layers, MoO3Hole transmission layer and Ag anodes composition, incorporation and PCDTBT in active layer:PCBM mass ratioes are 0.0286%~0.114% inorganic-quantum-dot；Incorporation and MoO in hole transmission layer3Mass ratio is 3.0%~5.0% Au nano-particles.
2. a kind of transoid polymer solar battery modified based on active layer and transport layer as claimed in claim 1, it is special Levy and be：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, it is special Levy and be：TiO2The thickness of electron transfer layer is 20~40nm, and the thickness of PEI decorative layers is 4~10nm, mixes inorganic-quantum-dot PCDTBT:The thickness of PCBM active layers is 80~150nm, mixes the MoO of Au nano-particles3The thickness of hole transmission layer is 4 The thickness of~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, it is special Levy and be：TiO2Electron transfer layer carries out ultraviolet light processing.
5. a kind of transoid polymer solar battery modified based on active layer and transport layer as claimed in claim 1, it is special Levy and be：TiO2Electron transfer layer carries out hydroxylating processing.
6. a kind of 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, is cleaned by ultrasonic 10~20min with acetone, absolute ethyl alcohol, deionized water respectively, Dried up after cleaning with nitrogen；
2) by TiO2Colloidal sol is spin-coated on step 1) obtained ITO conductive glass surfaces, spin speed is 3000~5000rpm；Then TiO will be carried2The ITO electro-conductive glass of colloidal sol is calcined 2~3h, 10~12h of Temperature fall under the conditions of 450~600 DEG C, you can TiO is made on ITO electro-conductive glass2Electron transfer layer, the thickness of electron transfer layer is 20~40nm；
3) using one of following three kinds of method to TiO2Electron transfer layer is surface-treated,
Method one is TiO2Electric transmission layer surface is without any processing, directly with 3000~4000rmp spin coatings, 1~5mg/mL's PEI solution, obtains the PEI decorative layers that thickness is 4~10nm；
Method two is by step 2) in spin coating have TiO2The ITO electro-conductive glass wavelength of electron transfer layer is 200~400nm purple Outer 10~20min of light irradiation, then 1~5mg/mL PEI solution is spun to after ultraviolet processing with 3000~4000rmp revolution TiO2On electron transfer layer, the PEI decorative layers that thickness is 4~10nm are obtained；
Method three is by step 2 first) obtained TiO2Electron transfer layer is immersed in the ethylene glycol for the KOH that concentration is 1~3mg/mL 10~20h carries out hydroxylating processing in solution；Then, then by 1~5mg/mL PEI solution with 3000~4000rmp revolution It is spin-coated on the TiO after hydroxylating processing2On electron transfer layer, the PEI decorative layers that thickness is 4~10nm are obtained；
4) under room temperature condition, by donor material PCDTBT and acceptor material PCBM according to mass ratio 1：4 are dissolved in organic solvent dichloro In benzene, 5~10mg/mL active layer solution is configured to, 10~40 μ L, 1~5mg/mL are added in above-mentioned active layer solution Inorganic-quantum-dot solution, then stirs 24~48h, you can be configured to doped with inorganic quantum under 600~800rpm speed The PCDTBT of point:PCBM mixed solution；
5) PCDTBT of the spin coating doped with inorganic-quantum-dot on PEI decorative layers:PCBM active layer solution, rotating speed be 2000~ 3000rpm；Then, it is put into the glove box full of inert gas, with 50~100 DEG C of 10~20min of annealing in thermal station, so that In TiO2The PCDTBT doped with inorganic-quantum-dot is made on electron transfer layer:PCBM active layers, thickness is 80~150nm；
6) in the PCDTBT doped with inorganic-quantum-dot:The molybdenum trioxide aqueous solution of gold doping made from spin coating on PCBM active layers, Rotating speed is 3000~5000rpm；It is then placed in the glove box full of inert atmosphere, with 80~120 DEG C of annealing 10 in thermal station ~20min, so that molybdenum trioxide hole transmission layer be made on active layer, thickness is 4~10nm；
7) device is taken out, in pressure 1 × 10-4~5 × 10-4Under the conditions of Pa, Ag electricity is deposited with molybdenum trioxide hole transmission layer Pole, thickness is 80~120nm, and the speed of growth isSo as to prepare based on active layer and transport layer modify it is anti- Type polymer solar battery.
7. a kind of preparation of transoid polymer solar battery modified based on active layer and transport layer as claimed in claim 6 Method, it is characterised in that：Step 2) described in TiO2The preparation of colloidal sol is at ambient temperature by 10~20mL metatitanic acid four Butyl ester is added drop-wise in 90~100mL absolute ethyl alcohol, then 10~20mL glacial acetic acid is added dropwise, and 30~40min of magnetic agitation is obtained The yellow solution of homogeneous transparent；Then 10~20mL acetylacetone,2,4-pentanedione is added, 20~30min is stirred, then 10~20mL is gone Ionized water is slowly dropped in above-mentioned solution with 2~4mL/min speed, is continued to stir 1~2h, is obtained the yellowish of homogeneous transparent Color colloidal sol, places ageing 6~8h, obtained TiO2Colloidal sol.
8. a kind of preparation of transoid polymer solar battery modified based on active layer and transport layer as claimed in claim 6 Method, it is characterised in that：Step 6) described in the preparation of the molybdenum trioxide aqueous solution of gold doping be at room temperature by certain mass Ammonium molybdate dissolve in water, form 0.01~0.1mol/L solution, then 2mol/L aqueous hydrochloric acid solution is added into above-mentioned solution In, until the pH value of mixed solution is between 1~1.5, gained is water-soluble molybdenum trioxide solution；Take that 5~10mL's is above-mentioned Solution, adds 0.5~1.0mg golden nanometer particle, and ultrasonically treated 20~40min obtains the molybdenum trioxide aqueous solution of gold doping.
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