CN106784331B - A kind of lamination cathode buffer layer organic polymer solar cell and preparation method thereof - Google Patents

A kind of lamination cathode buffer layer organic polymer solar cell and preparation method thereof Download PDF

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CN106784331B
CN106784331B CN201710028941.XA CN201710028941A CN106784331B CN 106784331 B CN106784331 B CN 106784331B CN 201710028941 A CN201710028941 A CN 201710028941A CN 106784331 B CN106784331 B CN 106784331B
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buffer layer
cathode buffer
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layer
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CN106784331A (en
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徐旭
申思
康博南
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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
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract

The present invention relates to a kind of lamination cathode buffer layer organic polymer solar cell, which uses eurymeric structure, is followed successively by from top to bottom：Transparent substrates, transparent conductive anode, anode buffer layer, photoactive layer, cathode buffer layer, metallic cathode；The photoactive layer is electron donor material PCDTBT and electron acceptor material PC71BM is according to 1:The composition of 4 mass ratio mixing；Polyvinylpyrrolidone cathode buffer layer is prepared on photoactive layer；Alq3Cathode buffer layer is prepared on polyvinylpyrrolidone cathode buffer layer, and thickness is 0.5~1.5nm；CaF2Cathode buffer layer is prepared in Alq3Between cathode buffer layer and metallic cathode, thickness is 0.6~1.2nm.Present invention reduces the series resistances of device, reduce Carrier recombination probability, and battery has more stability, effectively raises the photoelectric conversion efficiency of device.

Description

A kind of lamination cathode buffer layer organic polymer solar cell and preparation method thereof
Technical field
The invention belongs to organic polymer photovoltaic device technical fields, and in particular to a kind of lamination cathode buffer layer is organic poly- Close object solar cell and preparation method thereof.
Background technology
In recent years, the demand of fossil energy of the people to traditional energy including coal, oil, natural gas increases year by year Add, this also directly results in the getting worse of environmental pollution, is increased including water pollution, atmosphere pollution, acid rain, global temperatures The problems such as.Therefore, people are there is an urgent need to seek a kind of new clean energy resource to replace traditional energy, and solar energy is exactly a kind of point Cloth extensively, the regenerative resource of cleanliness without any pollution, become the research hotspot and emphasis of new energy field.
Solar cell can convert the solar into electric energy by photoelectric effect, be using solar energy important channel it One.Inorganic solar cell production cost is high, energy consumption is big, complex process, the requirement to material is harsh in manufacturing process, be not easy into Row large area produces, therefore organic polymer solar cell comes into being, it has at low cost, less energy consumption, light weight, material Derive from a wealth of sources, preparation process is simple, can large area the advantages that preparing flexible device, obtained extensive research in recent years and closed Note.However, compared with inorganic solar cell, the photoelectric conversion efficiency of organic solar batteries is relatively low, cannot be satisfied existing The demand grown directly from seeds in living, people improve the opto-electronic conversion effect of organic polymer solar cell there is an urgent need to seek new method Rate.
In organic polymer solar cell, electrons and holes pass through electron acceptor material and electron donor material respectively It is transferred to electrode, generates electric current.Therefore, electric current generation it is not only related with the transmission in electronics, hole, also with photoactive layer and electricity Interfacial property between pole is closely related.Studies have shown that being introduced between the photoactive layer and metal electrode of solar cell cloudy Pole buffer layer can promote the transmission of charge, be conducive to the collection of carrier at electrode, optimize energy level and interface performance, into And improve the photoelectric conversion efficiency of battery.Currently used cathode buffer layer has ZnO, TiO2, PFN, be mostly used in reciprocal form structure In, the autologous common cathode buffer layer of battery has LiF, CsCO3Although electronics can be transmitted effectively, it cannot Effectively for blocking active layer to the hole transport of cathode, the Carrier recombination probability of device is higher.
Invention content
Technical problem to be solved by the invention is to provide a kind of series resistance is low, open-circuit voltage, is filled out short-circuit current density Fill the factor and the high lamination cathode buffer layer organic polymer solar cell and preparation method thereof of photoelectric conversion efficiency.
In order to solve the above-mentioned technical problem, lamination cathode buffer layer organic polymer solar cell of the invention uses Eurymeric structure, is followed successively by from top to bottom：Transparent substrates, transparent conductive anode, anode buffer layer, photoactive layer, cathode buffer layer, Metallic cathode；It is characterized in that the photoactive layer is electron donor material PCDTBT and electron acceptor material PC71BM is according to 1:4 Mass ratio mixing composition；Cathode buffer layer is used by polyvinylpyrrolidone cathode buffer layer, Alq3Cathode buffer layer And CaF2The lamination cathode buffer layer that cathode buffer layer is constituted；Polyvinylpyrrolidone cathode buffer layer is prepared in photoactive layer On；Alq3Cathode buffer layer is prepared on polyvinylpyrrolidone cathode buffer layer, and thickness is 0.5~1.5nm；CaF2Cathode Buffer layer is prepared in Alq3Between cathode buffer layer and metallic cathode, thickness is 0.6~1.2nm.
The polyvinylpyrrolidone cathode buffer layer is prepared in by spin coating method on photoactive layer.
The polyvinylpyrrolidone cathode buffer layer can also be prepared in by self-assembling method on photoactive layer, be formed SAM polyvinylpyrrolidone cathode buffer layers.
The SAM polyvinylpyrrolidones cathode buffer layer preparation method is as follows：By electron donor material PCDTBT and electricity Sub- acceptor material PC71BM is according to 1:4 mass ratio, which is blended in solvent chlorobenzene, obtains photoactive layer material, then by polyvinyl pyrrole Alkanone is dissolved in the mixed solution for being configured to that polyvinylpyrrolidone mass fraction is 1~3wt% in photoactive layer material, then 50~80 DEG C of heating while 12~14h of stirring on magnetic stirring apparatus；In the glove box of nitrogen atmosphere, carried out using sol evenning machine The spin coating of photoactive layer material and polyvinylpyrrolidone mixed solution, rotating speed 1000rpm/s, time 60s；Spin coating is completed Later, 30~60min is stood in glove box, and polyvinylpyrrolidone is made to be moved to the upper of photoactive layer in self assembly effect Fang Chengwei polyvinylpyrrolidone cathode buffer layers；20~40min is finally made annealing treatment under the conditions of 60~80 DEG C.
Preferably, polyvinylpyrrolidone is dissolved in photoactive layer material, mass fraction 2wt%；Alq3It is cloudy Pole buffer layer and CaF2Cathode buffer layer thickness is 1.0nm.
The transparent substrates use glass substrate or transparent polymer substrate, and wherein transparent polymer includes poly- to benzene It is one or more in naphthalate, polystyrene, polyethylene, vinyl chloride-vinyl acetate resin or polyacrylic acid.
The transparent conductive anode material therefor is tin indium oxide (ITO), and tin indium oxide deposits on a transparent substrate, transparent Conductive anode thickness is 150nm, and square resistance is 15 Ω/.
The anode buffer layer material uses polytetrafluoroethylene (PTFE), PEDOT:PSS or p-type oxide M oO3、WO3、V2O5, One kind in high work function hole mobile material NiO or by two of which and it is two or more be prepared from level to level in order, it is thick Degree is 1~20nm.
The metallic cathode use Al, Ca, Mg or Li in one kind or by several alloys formed therein, thickness For 80nm~180nm.
The preparation method of above-mentioned lamination cathode buffer layer organic polymer solar cell, includes the following steps：
(1) substrate that cleaning is made of transparent substrates and transparent conductive anode；
(2) after substrate drying, anode buffer layer is deposited on transparent anode；
(3) after anode buffer layer vapor deposition is completed, photoactive layer and polyvinylpyrrolidone are prepared on anode buffer layer Cathode buffer layer, preparation method are as follows：By electron donor material PCDTBT and electron acceptor material PC71BM is according to 1:4 quality Photoactive layer material is obtained than being blended in solvent chlorobenzene, then polyvinylpyrrolidone is dissolved in photoactive layer material and is prepared In the mixed solution for being 1~3wt% at polyvinylpyrrolidone mass fraction, then 50~80 DEG C of heating on magnetic stirring apparatus 12~14h is stirred simultaneously；In the glove box of nitrogen atmosphere, photoactive layer material and polyvinylpyrrolidine are carried out using sol evenning machine The spin coating of ketone mixed solution, rotating speed 1000rpm/s, time 60s；Spin coating complete after, in glove box stand 30~ 60min makes the top that polyvinylpyrrolidone is moved to photoactive layer in self assembly effect become polyvinylpyrrolidone the moon Pole buffer layer；20~40min is finally made annealing treatment under the conditions of 60~80 DEG C；
(4) the evaporating Al q on polyvinylpyrrolidone cathode buffer layer3Cathode buffer layer, thickness are 0.5~1.5nm, Evaporation rate isNext in Alq3CaF is deposited on cathode buffer layer2Cathode buffer layer, thickness 0.6 ~1.2nm, evaporation rate are
(5) the evaporation metal cathode on cathode buffer layer.
The present invention has the following advantages compared with prior art：
One, lamination cathode buffer layer organic polymer solar cell provided by the invention, it is slow by introducing lamination cathode Layer is rushed, the series resistance of device is reduced, reduces the impedance of device, promotes biography of the electronics from photoactive layer to metallic cathode It is defeated, improve the transmission performance of electronics, while reducing contact resistance.
Two, lamination cathode buffer layer organic polymer solar cell provided by the invention, it is slow by introducing lamination cathode Layer is rushed, compared to the cathode buffer layer of single layer, work function is more matched with electron acceptor material, advantageously forms good Europe Nurse contacts.
Three, lamination cathode buffer layer organic polymer solar cell provided by the invention, it is slow by introducing lamination cathode Layer is rushed, electrons and holes are fully dissociated, electronics and the recombination probability in hole can be reduced, adjusts light field, solar energy is more filled The absorption divided prevents oxygen and hydrone from being permeated to photoactive layer.
Four, lamination cathode buffer layer organic polymer solar cell provided by the invention, it is slow by introducing lamination cathode Layer is rushed, cathode will not be corroded, and device has more stability.
Description of the drawings
Invention is further described in detail with reference to the accompanying drawings and detailed description.
Fig. 1 is the structural schematic diagram of the lamination cathode buffer layer organic polymer solar cell of the present invention.
Fig. 2 is the organic polymer solar cell of single cathode buffer layer with Alq3The J-V curves of thickness change.
Fig. 3 is the organic polymer solar cell of single cathode buffer layer with CaF2The J-V curves of thickness change.
Fig. 4 is that the lamination cathode buffer layer organic polymer solar cell of the present invention is slow with polyvinylpyrrolidone cathode Rush the J-V curves of layer mass fraction variation.
Specific implementation mode
The technical solution of the present invention is to provide a kind of lamination cathode buffer layer organic polymer solar cells, such as Fig. 1 institutes Show, device uses eurymeric structure, is followed successively by from top to bottom：Transparent substrates, transparent conductive anode, anode buffer layer, photoactive layer, Lamination cathode buffer layer, metallic cathode.The first layer of lamination cathode buffer layer is polyvinylpyrrolidone cathode buffer layer, is passed through Self-assembling method or spin coating method are prepared on photoactive layer；The second layer is Alq3Cathode buffer layer is prepared in polyvinyl pyrrole On alkanone cathode buffer layer, thickness is 0.5~1.5nm；Third layer is CaF2Cathode buffer layer is prepared in Alq3Cathode buffers On layer, thickness is 0.6~1.2nm；Photoactive layer is by electron donor material PCDTBT and electron acceptor material PC71BM is according to 1: 4 mass ratio mixes, and prepares on anode buffer layer.
Comparative example 1
Be cleaned by ultrasonic with tin indium oxide (ITO) transparent conductive anode glass transparent substrate (transparent conductive anode with thoroughly Bright substrate constitutes substrate), cleaning reagent is followed successively by toluene, acetone, deionized water, isopropanol, is respectively cleaned by ultrasonic using ultrasonic machine 20min.Use nitrogen (N2) dry up substrate, it is placed in baking oven and heats 10min, carried out at plasma with Plasma cleaning machines Manage 10min.Anode buffer layer uses polytetrafluoroethylene (PTFE) (PTFE), prepares film forming with the method for vapor deposition, the evaporation rate of PTFE isThickness is 2.0nm.After the completion of vapor deposition, corona treatment 5min is carried out with Plasma cleaning machines.It will steam The substrate for having plated anode buffer layer moves on to nitrogen (N2) atmosphere glove box in, using sol evenning machine carry out photoactive layer spin coating, Rotating speed is 1000rpm/s, and time 60s, thickness is about 100nm.Photoactive layer material is by electron donor material PCDTBT and electricity Sub- acceptor material PC71BM in mass ratio 1:4 configure.The PC of the PCDTBT and 32mg of 8mg are weighed respectively71BM is dissolved in 1ml's In chlorobenzene, a concentration of PCDTBT is obtained:PC71BM=8mg/ml:The mixed solution of 32mg/ml, mixed solution are stirred in magnetic force 60 DEG C of heating stirring 12h on device are mixed, photoactive layer material is obtained.After photoactive layer material spin coating is completed, put on hot plate Thermal anneal process, processing time 30min are carried out, temperature is 60 DEG C, so that excess of solvent is volatilized and improves appearance structure.At annealing The substrate with anode buffer layer and photoactive layer is moved on to from the junction of glove box and vacuum coater in plated film instrument after reason, Carry out the vapor deposition of cathode buffer layer.Using plated film instrument on photoactive layer evaporating Al q3Cathode buffer layer, evaporation rate areThickness is 0.5nm.Al metallic cathodes are equally prepared by the way of vapor deposition, and evaporation rate isThickness is 150nm.The device effective area prepared is 0.05cm2, in standard test condition：100mw/cm2, It is tested under the illumination simulation of AM1.5, Current density-voltage (J-V) curve is measured by Keithley2400 digital sourcemeters, is surveyed Examination process carries out under atmospheric environment.Device architecture is：Transparent substrates/ITO/PTFE (thickness 2.0nm)/PCDTBT: PC71BM/Alq3(thickness 0.5nm)/Al (thickness 150nm).J-V curves such as Fig. 2 institutes measured by the device of comparative example 1 Show.
Comparative example 2
The substrate that cleaning is made of transparent conductive anode and transparent substrates, transparent conductive anode material are tin indium oxide (ITO), transparent substrates are glass.Use N2Substrate is dried up, is placed in baking oven and heats 10min, is handled with Plasma cleaning machines 10min.PTFE anode buffer layers are deposited on substrate, evaporation rate isThickness is 2.0nm.Vapor deposition is completed Afterwards, 5min is handled with Plasma cleaning machines.It spin coating photoactive layer and is made annealing treatment on anode buffer layer, method and comparison Example 1 is identical.The substrate with anode buffer layer and photoactive layer is moved on in vacuum coater after annealing, it is slow to carry out cathode Rush the vapor deposition of layer.The evaporating Al q on photoactive layer3Cathode buffer layer, evaporation rate areThickness is 1.0nm. Evaporating Al metallic cathode, evaporation rate areThickness is 150nm.Current density-voltage (J-V) curve uses Keithley2400 digital sourcemeters are in 100mw/cm2, measure under conditions of AM1.5.Device architecture is：Transparent substrates ITO/PTFE (thickness 2.0nm)/PCDTBT:PC71BM/Alq3(thickness 1.0nm)/Al (thickness 150nm).The device institute of comparative example 2 The J-V curves measured are as shown in Figure 2.
Comparative example 3
The substrate that cleaning is made of transparent conductive anode and transparent substrates, transparent conductive anode material are tin indium oxide (ITO), transparent substrates are glass.Use N2Substrate is dried up, is placed in baking oven and heats 10min, is handled with Plasma cleaning machines 10min.PTFE anode buffer layers are deposited, evaporation rate isThickness is 2.0nm.After the completion of vapor deposition, substrate is used Plasma cleaning machines handle 5min.It spin coating photoactive layer and is made annealing treatment, method and 1 phase of comparative example on anode buffer layer Together.The substrate with anode buffer layer and photoactive layer is moved on in vacuum coater after annealing, carries out cathode buffer layer Vapor deposition, the evaporating Al q on photoactive layer3Cathode buffer layer, evaporation rate areThickness is 1.5nm.Vapor deposition Al metallic cathodes, evaporation rate areThickness is 150nm.Current density-voltage (J-V) curve uses Keithley2400 digital sourcemeters are in 100mw/cm2, measure under conditions of AM1.5.Device architecture is：Transparent substrates ITO/PTFE (thickness 2.0nm)/PCDTBT:PC71BM/Alq3(thickness 1.5nm)/Al (thickness 150nm).The device institute of comparative example 3 The J-V curves measured are as shown in Figure 2.
Table 1 is Alq3Single cathode buffer layer device is in different-thickness Alq3Under open-circuit voltage Voc (V), short-circuit current density Jsc(mA/cm2), fill factor FF (%), photoelectric conversion efficiency PCE (%), it can be seen that work as Alq3Thickness be 1.0nm when, Device performance is the most excellent.
Table 1
Voc(V) Jsc(mA/cm2) FF (%) PCE (%)
1 device of comparative example 0.876 10.019 56.80 4.985
2 device of comparative example 0.883 11.377 59.01 5.929
3 device of comparative example 0.870 11.044 56.72 5.451
Comparative example 4
The substrate that cleaning is made of transparent conductive anode and transparent substrates, transparent conductive anode material are tin indium oxide (ITO), transparent substrates are glass.Use N2Substrate is dried up, is placed in baking oven and heats 10min, is handled with Plasma cleaning machines 10min.PTFE anode buffer layers are deposited, evaporation rate isThickness is 2.0nm.After the completion of vapor deposition, use Plasma cleaning machines handle 5min.It spin coating photoactive layer and is made annealing treatment, method and 1 phase of comparative example on anode buffer layer Together.The substrate with anode buffer layer and photoactive layer is moved on in vacuum coater after annealing, carries out cathode buffer layer Vapor deposition, CaF is deposited on photoactive layer2Cathode buffer layer, evaporation rate areThickness is 0.6nm.Vapor deposition Al metallic cathodes, evaporation rate areThickness is 150nm.Current density-voltage (J-V) curve uses Keithley2400 digital sourcemeters are in 100mw/cm2, measure under conditions of AM1.5.Device architecture is：Transparent substrates ITO/PTFE (thickness 2.0nm)/PCDTBT:PC71BM/CaF2(thickness 0.6nm)/Al (thickness 150nm).The device institute of comparative example 4 The J-V curves measured are as shown in Figure 3.
Comparative example 5
The substrate that cleaning is made of transparent conductive anode and transparent substrates, transparent conductive anode material are tin indium oxide (ITO), transparent substrates are glass.Use N2Substrate is dried up, is placed in baking oven and heats 10min, is handled with Plasma cleaning machines 10min.PTFE anode buffer layers are deposited, evaporation rate isThickness is 2.0nm.After the completion of vapor deposition, use Plasma cleaning machines handle 5min.It spin coating photoactive layer and is made annealing treatment, method and 1 phase of comparative example on anode buffer layer Together.The substrate with anode buffer layer and photoactive layer is moved on in vacuum coater after annealing, carries out cathode buffer layer Vapor deposition, CaF is deposited on photoactive layer2Cathode buffer layer, evaporation rate areThickness is 0.8nm.Vapor deposition Al metallic cathodes, evaporation rate areThickness is 150nm.Current density-voltage (J-V) curve uses Keithley2400 digital sourcemeters are in 100mw/cm2, measure under conditions of AM1.5.Device architecture is：Transparent substrates ITO/PTFE (thickness 2.0nm)/PCDTBT:PC71BM/CaF2(thickness 0.8nm)/Al (thickness 150nm).The device institute of comparative example 5 The J-V curves measured are as shown in Figure 3.
Comparative example 6
The substrate that cleaning is made of transparent conductive anode and transparent substrates, transparent conductive anode material are tin indium oxide (ITO), transparent substrates are glass.Use N2Substrate is dried up, is placed in baking oven and heats 10min, is handled with Plasma cleaning machines 10min.PTFE anode buffer layers are deposited, evaporation rate isThickness is 2.0nm.After the completion of vapor deposition, use Plasma cleaning machines handle 5min.It spin coating photoactive layer and is made annealing treatment, method and 1 phase of comparative example on anode buffer layer Together.The substrate with anode buffer layer and cathode buffer layer is moved on in vacuum coater after annealing, carries out cathode buffering The vapor deposition of layer, is deposited CaF on photoactive layer2Cathode buffer layer, evaporation rate areThickness is 1.0nm. Evaporating Al metallic cathode, evaporation rate areThickness is 150nm.Current density-voltage (J-V) curve uses Keithley2400 digital sourcemeters are in 100mw/cm2, measure under conditions of AM1.5.Device architecture is：Transparent substrates ITO/PTFE (thickness 2.0nm)/PCDTBT:PC71BM/CaF2(thickness 1.0nm)/Al (thickness 150nm).The device institute of comparative example 6 The J-V curves measured are as shown in Figure 3.
Comparative example 7
The substrate that cleaning is made of transparent conductive anode and transparent substrates, transparent conductive anode material are tin indium oxide (ITO), transparent substrates are glass.Use N2Substrate is dried up, is placed in baking oven and heats 10min, is handled with Plasma cleaning machines 10min.PTFE anode buffer layers are deposited, evaporation rate isThickness is 2.0nm.After the completion of vapor deposition, use Plasma cleaning machines handle 5min.It spin coating photoactive layer and is made annealing treatment, method and 1 phase of comparative example on anode buffer layer Together.The substrate with anode buffer layer and photoactive layer is moved on in vacuum coater after annealing, carries out cathode buffer layer Vapor deposition, CaF is deposited on photoactive layer2Cathode buffer layer, evaporation rate areThickness is 1.2nm.Vapor deposition Al metallic cathodes, evaporation rate areThickness is 150nm.Current density-voltage (J-V) curve uses Keithley2400 digital sourcemeters are in 100mw/cm2, measure under conditions of AM1.5.Device architecture is：Transparent substrates ITO/PTFE (thickness 2.0nm)/PCDTBT:PC71BM/CaF2(thickness 1.2nm)/Al (thickness 150nm).The device institute of comparative example 7 The J-V curves measured are as shown in Figure 3.
Table 2 is CaF2Single cathode buffer layer device is in different-thickness CaF2Under open-circuit voltage Voc (V), short-circuit current density Jsc(mA/cm2), fill factor FF (%), photoelectric conversion efficiency PCE (%), when thickness be 0.6nm when, efficiency reaches 5.572%, work as CaF2Thickness when increasing to 1.0nm, device performance is optimal, and thickness continues growing efficiency reduction.
Table 2
Voc(V) Jsc(mA/cm2) FF (%) PCE (%)
4 device of comparative example 0.874 10.997 57.94 5.572
5 device of comparative example 0.874 11.477 59.40 5.961
6 device of comparative example 0.882 11.848 60.27 6.296
7 device of comparative example 0.870 11.260 58.91 5.769
Comparative example 8
The substrate that cleaning is made of transparent conductive anode and transparent substrates, transparent conductive anode material are tin indium oxide (ITO), transparent substrates are glass.Use N2Substrate is dried up, is placed in baking oven and heats 10min, is handled with Plasma cleaning machines 10min.PTFE anode buffer layers are deposited, evaporation rate isThickness is 2.0nm.After the completion of vapor deposition, use Plasma cleaning machines handle 5min.It spin coating photoactive layer and is made annealing treatment on PTFE anode buffer layers, method and comparison Example 1 is identical.The substrate with anode buffer layer and photoactive layer is moved on in vacuum coater after annealing, into row metal the moon The vapor deposition of pole, the evaporating Al metallic cathode on photoactive layer, evaporation rate areThickness is 150nm.Electric current is close Degree-voltage (J-V) curve is using Keithley2400 digital sourcemeters in 100mw/cm2, measure under conditions of AM1.5.Device junction Structure is：Transparent substrates/ITO/PTFE (thickness 2.0nm)/PCDTBT:PC71BM/Al (thickness 150nm).
Embodiment 1
The substrate that cleaning is made of transparent conductive anode and transparent substrates, transparent conductive anode material are tin indium oxide (ITO), transparent substrates are glass.Use N2Substrate is dried up, is placed in baking oven and heats 10min, is handled with Plasma cleaning machines 10min.PTFE anode buffer layers are deposited, evaporation rate isThickness is 2.0nm.After the completion of vapor deposition, use Plasma cleaning machines handle 5min.Substrate with anode buffer layer is moved on into N2In the glove box of atmosphere, using sol evenning machine into The spin coating of row photoactive layer material and polyvinylpyrrolidone mixed liquor, rotating speed 1000rpm/s, time 60s.Photoactive layer Material is by electron donor material PCDTBT and electron acceptor material PC71BM in mass ratio 1:4 configure.Weigh 8mg's respectively The PC of PCDTBT and 32mg71BM is dissolved in the chlorobenzene of 1ml, obtains a concentration of PCDTBT:PC71BM=8mg/ml:32mg/ml's Polyvinylpyrrolidone is dissolved in above-mentioned mixed solution by mixed solution, and it is 1wt% to obtain polyvinylpyrrolidone mass fraction Mixed solution, then 60 DEG C of heating stirring 12h on magnetic stirring apparatus.After spin coating is completed, stood in glove box 30min, since there is polyvinylpyrrolidone self assembly effect to be moved to the upper of photoactive layer by the slow growth of 30min Fang Chengwei polyvinylpyrrolidone cathode buffer layers, are then placed in heating plate and carry out thermal anneal process, and processing time is 30min, temperature are 60 DEG C, so that excess of solvent is volatilized and improve appearance structure.Above-mentioned substrate is moved on into Vacuum Deposition after annealing In film instrument, the vapor deposition of follow-up cathode buffer layer is carried out, the evaporating Al q on polyvinylpyrrolidone cathode buffer layer3Cathode buffers Layer, evaporation rate areThickness is 1.0nm；In Alq3CaF is deposited on cathode buffer layer2Cathode buffer layer steams Sending out rate isThickness is 1.0nm.Al metallic cathodes are equally prepared by the way of vapor deposition, evaporation speed Rate isThickness is 150nm.Current density-voltage (J-V) curve is existed using Keithley2400 digital sourcemeters 100mw/cm2, measure under conditions of AM1.5.Device architecture is：Transparent substrates/ITO/PTFE (thickness 2.0nm)/PCDTBT: PC71BM/SAM polyvinylpyrrolidones (solution quality ratio is 1wt%)/Alq3 (thickness 1.0nm)/CaF2(thickness is 1.0nm)/Al (thickness 150nm).J-V curves measured by the device of embodiment 1 are as shown in Figure 4.
Embodiment 2
The substrate that cleaning is made of transparent conductive anode and transparent substrates, transparent conductive anode material are tin indium oxide (ITO), transparent substrates are glass.Use N2Substrate is dried up, is placed in baking oven and heats 10min, is handled with Plasma cleaning machines 10min.PTFE anode buffer layers are deposited, evaporation rate isThickness is 2.0nm.After the completion of vapor deposition, use Plasma cleaning machines handle 5min.Substrate with anode buffer layer is moved on into N2In the glove box of atmosphere, using sol evenning machine into The spin coating of row photoactive layer material and polyvinylpyrrolidone mixed liquor, rotating speed 1000rpm/s, time 60s.Photoactive layer Material is by electron donor material PCDTBT and electron acceptor material PC71BM in mass ratio 1:4 configure, and weigh 8mg's respectively The PC of PCDTBT and 32mg71BM is dissolved in the chlorobenzene of 1ml, obtains a concentration of PCDTBT:PC71BM=8mg/ml:32mg/ml's Polyvinylpyrrolidone is dissolved in above-mentioned mixed solution by mixed solution, and it is 2wt% to obtain polyvinylpyrrolidone mass fraction Mixed solution, then 60 DEG C of heating stirring 12h on magnetic stirring apparatus.After spin coating is completed, stood in glove box 30min, since there is polyvinylpyrrolidone self assembly effect to be moved to the upper of photoactive layer by the slow growth of 30min Then Fang Chengwei cathode buffer layers are placed in heating plate and carry out thermal anneal process, processing time 30min, and temperature is 60 DEG C, is made Excess of solvent volatilizees and improves appearance structure.Above-mentioned substrate is moved on in vacuum coater after annealing, carries out follow-up cathode The vapor deposition of buffer layer, the evaporating Al q on polyvinylpyrrolidone cathode buffer layer3Cathode buffer layer, evaporation rate areThickness is 1.0nm；In Alq3CaF is deposited on cathode buffer layer2Cathode buffer layer, evaporation rate areThickness is 1.0nm.Al metallic cathodes are equally prepared by the way of vapor deposition, and evaporation rate isThickness is 150nm.Current density-voltage (J-V) curve is using Keithley2400 digital sourcemeters in 100mw/ cm2, measure under conditions of AM1.5.Device architecture is：Transparent substrates/ITO/PTFE (thickness 2.0nm)/PCDTBT:PC71BM/ Polyvinylpyrrolidone (solution quality ratio is 2wt%)/Alq3(thickness 1.0nm)/CaF2(thickness 1.0nm)/Al (thickness For 150nm).J-V curves measured by the device of embodiment 2 are as shown in Figure 4.
Embodiment 3
The substrate that cleaning is made of transparent conductive anode and transparent substrates, transparent conductive anode material are tin indium oxide (ITO), transparent substrates are glass.Use N2Substrate is dried up, is placed in baking oven and heats 10min, is handled with Plasma cleaning machines 10min.PTFE anode buffer layers are deposited, evaporation rate isThickness is 2.0nm.After the completion of vapor deposition, use Plasma cleaning machines handle 5min.Substrate with anode buffer layer is moved on into N2In the glove box of atmosphere, using sol evenning machine into The spin coating of row photoactive layer material and polyvinylpyrrolidone, rotating speed 1000rpm/s, time 60s.Photoactive layer material by Electron donor material PCDTBT and electron acceptor material PC71BM in mass ratio 1:4 configure, and weigh the PCDTBT of 8mg respectively With the PC of 32mg71BM is dissolved in the chlorobenzene of 1ml, obtains a concentration of PCDTBT:PC71BM=8mg/ml:The mixing of 32mg/ml is molten Polyvinylpyrrolidone is dissolved in mixed solution by liquid, obtains the solution that polyvinylpyrrolidone mass fraction is 3wt%, so 60 DEG C of heating stirring 12h on magnetic stirring apparatus afterwards.After spin coating is completed, 30min is stood in glove box, due to polyethylene pyrrole Pyrrolidone has self assembly effect, and by the slow growth of 30min, being moved to the top of photoactive layer becomes polyvinylpyrrolidine Then ketone cathode buffer layer is placed in heating plate and carries out thermal anneal process, processing time 30min, and temperature is 60 DEG C, and it is extra to make Solvent volatilizees and improves appearance structure.Above-mentioned substrate is moved on in vacuum coater after annealing, carries out follow-up cathode buffering The vapor deposition of layer, the evaporating Al q on polyvinylpyrrolidone cathode buffer layer3Cathode buffer layer, evaporation rate areThickness is 1.0nm；In Alq3CaF is deposited on cathode buffer layer2Cathode buffer layer, evaporation rate areThickness is 1.0nm.Metallic cathode Al is equally prepared by the way of vapor deposition, and evaporation rate isThickness is 150nm.Current density-voltage (J-V) curve is using Keithley2400 digital sourcemeters in 100mw/ cm2, measure under conditions of AM1.5.Device architecture is：Transparent substrates/ITO/PTFE (thickness 2.0nm)/PCDTBT:PC71BM/ SAM polyvinylpyrrolidones (solution quality ratio is 3wt%)/Alq3(thickness 1.0nm)/CaF2(thickness 1.0nm)/Al is (thick Degree is 150nm).J-V curves measured by the device of embodiment 3 are as shown in Figure 4.
Table 3 is the performance that the lamination cathode buffer layer device of the present invention changes with polyvinylpyrrolidonesolution solution mass fraction Parameter (Alq3Thickness be 1.0nm, CaF2Thickness be 1.0nm), the performance test of device is in 100mw/cm2, AM1.5's It is carried out under illumination simulation.When the mass fraction of polyvinylpyrrolidone is 2wt%, efficiency reaches 7.349%, and device performance reaches To optimal, polyvinylpyrrolidone mass fraction continues growing efficiency reduction.
Table 3
Voc(V) Jsc(mA/cm2) FF (%) PCE (%)
1 device of embodiment 0.891 12.154 61.98 6.711
2 device of embodiment 0.899 12.754 64.11 7.349
3 device of embodiment 0.898 12.266 63.22 6.961
Table 4 is 8 device of comparative example (no cathode buffer layer), single cathode buffer layer device (1.0nmAlq3、1.0nmCaF2) with The comparison of lamination cathode buffer layer organic polymer solar cell performance parameter of the present invention, the performance test of device exist 100mw/cm2, carry out under the illumination simulation of AM1.5.When using lamination cathode buffer layer, series resistance reduces, and efficiency reaches 7.349%, device performance is optimal, and the device performance of single cathode buffer layer is better than comparative device (no cathode buffer layer), string Join resistance and is less than comparative device.
Table 4
Voc(V) Jsc(mA/cm2) FF (%) PCE (%) Rs(Ω·cm2)
2 device of comparative example 0.883 11.377 59.01 5.929 10.477
6 device of comparative example 0.882 11.848 60.27 6.296 9.144
2 device of embodiment 0.899 12.754 64.11 7.349 7.276
8 device of comparative example 0.872 10.140 52.62 4.651 16.358
Table 5 is for structure：Transparent substrates/ITO/PTFE (thickness 2.0nm)/PCDTBT:PC71BM/ polyvinylpyrrolidines Ketone (polyvinylpyrrolidone mass fraction is 2wt%)/Alq3(thickness 1.0nm)/CaF2(thickness 1.0nm)/Al (thickness For 150nm), transparent substrates/ITO/PTFE (thickness 2.0nm)/PCDTBT:PC71BM/ polyvinylpyrrolidones (polyethylene pyrrole Pyrrolidone mass fraction is 2wt%)/CaF2(thickness 1.0nm)/Alq3(thickness 1.0nm)/Al's (thickness 150nm) is folded The comparison of layer cathode buffer layer organic polymer solar cell performance parameter, the performance test of device is in 100mw/cm2, It is carried out under the illumination simulation of AM1.5.It can be seen that when device architecture uses the cathode buffer layer of different order to device performance It has a certain impact, only the suitable sequence of selection, energy level could be enabled more to match, be conducive to transmission and extraction, the boundary of electronics Good Ohmic contact is formed between face.
Table 5
In addition to the implementation, polyvinylpyrrolidone cathode buffer layer of the invention can also be straight by the method for spin coating It connects and is prepared on photoactive layer.Wherein photoactive layer is prepared in by following methods on anode buffer layer：By electron donor material PCDTBT and electron acceptor material PC71BM is according to 1:4 mass ratio, which is blended in solvent chlorobenzene, obtains photoactive layer material, then It is spun on anode buffer layer.Polyvinylpyrrolidone is spun on photoactive layer after being dissolved in the solution for being made into 1mg/mL in isopropanol On.
Embodiment 4
The substrate that cleaning is made of transparent conductive anode and transparent substrates, transparent conductive anode material are tin indium oxide (ITO), transparent substrates are glass.Use N2Substrate is dried up, is placed in baking oven and heats 10min, is handled with Plasma cleaning machines 10min.PTFE anode buffer layers are deposited, evaporation rate isThickness is 2.0nm.After the completion of vapor deposition, use Plasma cleaning machines handle 5min.Substrate with anode buffer layer is moved on into N2In the glove box of atmosphere, sol evenning machine point is utilized Other spin coating photoactive layer material and polyvinylpyrrolidone cathode buffer layer are simultaneously made annealing treatment, the wherein spin coating of photoactive layer It is identical as comparative example 1.Polyvinylpyrrolidone is spin-coated on after being dissolved in the solution for being made into 1mg/mL in isopropanol on photoactive layer, is turned Speed is 3000rpm/s, time 45s.After the completion of spin coating, thermal anneal process, processing time 20min, temperature 120 are carried out ℃.Above-mentioned substrate is moved on in vacuum coater after annealing, the vapor deposition of follow-up cathode buffer layer is carried out, in polyvinyl pyrrole Evaporating Al q on alkanone cathode buffer layer3Cathode buffer layer, evaporation rate areThickness is 1.0nm；In Alq3 CaF is deposited on cathode buffer layer2Cathode buffer layer, evaporation rate areThickness is 1.0nm.Al metallic cathodes Same to be prepared by the way of vapor deposition, evaporation rate isThickness is 150nm.Current density-voltage (J- V) curve uses Keithley2400 digital sourcemeters in 100mw/cm2, measure under conditions of AM1.5.Device architecture is：Transparent lining Bottom/ITO/PTFE (thickness 2.0nm)/PCDTBT:PC71BM/SAM polyvinylpyrrolidones (rotating speed 3000rpm/s)/Alq3 (thickness 1.0nm)/CaF2(thickness 1.0nm)/Al (thickness 150nm).Embodiment 5
The substrate that cleaning is made of transparent conductive anode and transparent substrates, transparent conductive anode material are tin indium oxide (ITO), transparent substrates are glass.Use N2Substrate is dried up, is placed in baking oven and heats 10min, is handled with Plasma cleaning machines 10min.PTFE anode buffer layers are deposited, evaporation rate isThickness is 2.0nm.After the completion of vapor deposition, use Plasma cleaning machines handle 5min.Substrate with anode buffer layer is moved on into N2In the glove box of atmosphere, sol evenning machine point is utilized Other spin coating photoactive layer material and polyvinylpyrrolidone cathode buffer layer are simultaneously made annealing treatment, the wherein spin coating of photoactive layer It is identical as comparative example 1.Polyvinylpyrrolidone is spin-coated on after being dissolved in the solution for being made into 1mg/mL in isopropanol on photoactive layer, is turned Speed is 4000rpm/s, time 45s.After the completion of spin coating, thermal anneal process, processing time 20min, temperature 120 are carried out ℃.Above-mentioned substrate is moved on in vacuum coater after annealing, the vapor deposition of follow-up cathode buffer layer is carried out, in polyvinyl pyrrole Evaporating Al q on alkanone cathode buffer layer3Cathode buffer layer, evaporation rate areThickness is 1.0nm；In Alq3 CaF is deposited on cathode buffer layer2Cathode buffer layer, evaporation rate areThickness is 1.0nm.Al metallic cathodes Same to be prepared by the way of vapor deposition, evaporation rate isThickness is 150nm.Current density-voltage (J- V) curve uses Keithley2400 digital sourcemeters in 100mw/cm2, measure under conditions of AM1.5.Device architecture is：Transparent lining Bottom/ITO/PTFE (thickness 2.0nm)/PCDTBT:PC71BM/SAM polyvinylpyrrolidones (rotating speed 4000rpm/s)/Alq3 (thickness 1.0nm)/CaF2(thickness 1.0nm)/Al (thickness 150nm).Embodiment 6
The substrate that cleaning is made of transparent conductive anode and transparent substrates, transparent conductive anode material are tin indium oxide (ITO), transparent substrates are glass.Use N2Substrate is dried up, is placed in baking oven and heats 10min, is handled with Plasma cleaning machines 10min.PTFE anode buffer layers are deposited, evaporation rate isThickness is 2.0nm.After the completion of vapor deposition, use Plasma cleaning machines handle 5min.Substrate with anode buffer layer is moved on into N2In the glove box of atmosphere, sol evenning machine point is utilized Other spin coating photoactive layer material and polyvinylpyrrolidone cathode buffer layer are simultaneously made annealing treatment, the wherein spin coating of photoactive layer It is identical as comparative example 1.Polyvinylpyrrolidone is spin-coated on after being dissolved in the solution for being made into 1mg/mL in isopropanol on photoactive layer, is turned Speed is 5000rpm/s, time 45s.After the completion of spin coating, thermal anneal process, processing time 20min, temperature 120 are carried out ℃.Above-mentioned substrate is moved on in vacuum coater after annealing, the vapor deposition of follow-up cathode buffer layer is carried out, in polyvinyl pyrrole Evaporating Al q on alkanone cathode buffer layer3Cathode buffer layer, evaporation rate areThickness is 1.0nm；In Alq3 CaF is deposited on cathode buffer layer2Cathode buffer layer, evaporation rate areThickness is 1.0nm.Al metallic cathodes Same to be prepared by the way of vapor deposition, evaporation rate isThickness is 150nm.Current density-voltage (J- V) curve uses Keithley2400 digital sourcemeters in 100mw/cm2, measure under conditions of AM1.5.Device architecture is：Transparent lining Bottom/ITO/PTFE (thickness 2.0nm)/PCDTBT:PC71BM/SAM polyvinylpyrrolidones (rotating speed 5000rpm/s)/Alq3 (thickness 1.0nm)/CaF2(thickness 1.0nm)/Al (thickness 150nm).
Table 6 is the performance parameter that the lamination cathode buffer layer device of the present invention changes with polyvinylpyrrolidonesolution solution rotating speed (Alq3Thickness be 1.0nm, CaF2Thickness be 1.0nm), the performance test of device is in 100mw/cm2, the simulation of AM1.5 It is carried out under illumination.When the rotating speed of polyvinylpyrrolidonesolution solution is 4000rpm/s, efficiency reaches 7.000%, and device performance reaches To optimal, rotating speed continues growing, and causes thickness to increase, efficiency reduces.
Table 6
Voc(V) Jsc(mA/cm2) FF (%) PCE (%)
4 device of embodiment 0.885 11.699 61.70 6.387
5 device of embodiment 0.882 12.434 63.82 7.000
6 device of embodiment 0.875 12.387 61.37 6.611
The lamination cathode buffer layer organic polymer solar cell of the present invention, open-circuit voltage Voc (V), short circuit current Density Jsc (mA/cm2), fill factor FF (%), photoelectric conversion efficiency PCE (%) mainly with each cathode buffer layer material therefor, Sequence is related with thickness, thus the material of each layer choosing and preparation technology parameter are not limited to the above embodiments.For example, this field skill Art personnel can be with reasonable prediction, and when anode buffer layer selects other materials and different-thickness, the performance of device can also reach Essentially identical technique effect.
The present invention has modified the interface between photoactive layer and metallic cathode, has reduced by introducing lamination cathode buffer layer The series resistance of device, the transmission resistance for reducing impedance and then charge become smaller, and promote electronics from photoactive layer to metallic cathode Transmission, improve electronic transmission performance, reduce Carrier recombination probability, while contact resistance reduces.Lamination cathode buffer layer The corrosion of electrode, battery is prevented to have more stability.In addition the work function of lamination cathode buffer layer with from photoactive layer Electron acceptor material more matches, and is conducive to form good Ohmic contact between photoactive layer and cathode, further to promote The transmission and extraction of electronics, and then can effectively improve the photoelectric conversion efficiency of device.

Claims (10)

1. a kind of lamination cathode buffer layer organic polymer solar cell is followed successively by from top to bottom using eurymeric structure：It is transparent Substrate, transparent conductive anode, anode buffer layer, photoactive layer, cathode buffer layer, metallic cathode；It is characterized in that the light is lived Property layer be electron donor material PCDTBT and electron acceptor material PC71BM is according to 1:The composition of 4 mass ratio mixing；Cathode is slow Layer is rushed to use by polyvinylpyrrolidone cathode buffer layer, Alq3Cathode buffer layer and CaF2The lamination that cathode buffer layer is constituted is cloudy Pole buffer layer；Polyvinylpyrrolidone cathode buffer layer is prepared on photoactive layer；Alq3Cathode buffer layer is prepared in polyethylene On pyrrolidones cathode buffer layer, thickness is 0.5~1.5nm；CaF2Cathode buffer layer is prepared in Alq3Cathode buffer layer and gold Between belonging to cathode, thickness is 0.6~1.2nm.
2. lamination cathode buffer layer organic polymer solar cell according to claim 1, it is characterised in that described poly- Vinylpyrrolidone cathode buffer layer is prepared in by spin coating method on photoactive layer.
3. lamination cathode buffer layer organic polymer solar cell according to claim 1, it is characterised in that described poly- Vinylpyrrolidone cathode buffer layer is prepared in by self-assembling method on photoactive layer, and it is cloudy to form SAM polyvinylpyrrolidones Pole buffer layer.
4. lamination cathode buffer layer organic polymer solar cell according to claim 3, it is characterised in that the SAM Polyvinylpyrrolidone cathode buffer layer preparation method is as follows：By electron donor material PCDTBT and electron acceptor material PC71BM According to 1:4 mass ratio, which is blended in solvent chlorobenzene, obtains photoactive layer material, then polyvinylpyrrolidone is dissolved in light and is lived Property layer material in be configured to polyvinylpyrrolidone mass fraction be 1~3wt% mixed solution, then on magnetic stirring apparatus 50~80 DEG C of heating while 12~14h of stirring；In the glove box of nitrogen atmosphere, using sol evenning machine carry out photoactive layer material with The spin coating of polyvinylpyrrolidone mixed solution, rotating speed 1000rpm/s, time 60s；After spin coating is completed, in glove box 30~60min of middle standing makes the top that polyvinylpyrrolidone is moved to photoactive layer in self assembly effect become polyethylene Pyrrolidones cathode buffer layer；20~40min is finally made annealing treatment under the conditions of 60~80 DEG C.
5. lamination cathode buffer layer organic polymer solar cell according to claim 4, it is characterised in that described poly- Vinylpyrrolidone is dissolved in photoactive layer material, mass fraction 2wt%；Alq3Cathode buffer layer and CaF2Cathode is slow It is 1.0nm to rush layer thickness.
6. lamination cathode buffer layer organic polymer solar cell according to claim 1, it is characterised in that described Transparent substrates use glass substrate or transparent polymer substrate, and wherein transparent polymer includes polyethylene terephthalate It is one or more in ester, polystyrene, polyethylene, vinyl chloride-vinyl acetate resin or polyacrylic acid.
7. lamination cathode buffer layer organic polymer solar cell according to claim 1, it is characterised in that described Bright conductive anode material therefor is tin indium oxide (ITO), and tin indium oxide deposits on a transparent substrate, and transparent conductive anode thickness is 150nm, square resistance are 15 Ω/.
8. lamination cathode buffer layer organic polymer solar cell according to claim 1, it is characterised in that described Anode buffer layer material uses polytetrafluoroethylene (PTFE), PEDOT:PSS or p-type oxide M oO3、WO3、V2O5, high work function hole passes One kind in defeated material Ni O or by more than two of which being prepared from level to level in order, thickness is 1~20nm.
9. lamination cathode buffer layer organic polymer solar cell according to claim 1, it is characterised in that described Metallic cathode uses one kind in Al, Ca, Mg or Li or by several alloy formed therein, and thickness is 80nm~180nm.
10. a kind of preparation method of lamination cathode buffer layer organic polymer solar cell as described in claim 1, special Sign is to include the following steps：
(1) substrate that cleaning is made of transparent substrates and transparent conductive anode；
(2) after substrate drying, anode buffer layer is deposited on transparent anode；
(3) after anode buffer layer vapor deposition is completed, photoactive layer and polyvinylpyrrolidone cathode are prepared on anode buffer layer Buffer layer, preparation method are as follows：By electron donor material PCDTBT and electron acceptor material PC71BM is according to 1:4 mass ratio is mixed Conjunction obtains photoactive layer material in solvent chlorobenzene, then polyvinylpyrrolidone is dissolved in photoactive layer material and is configured to gather Vinylpyrrolidone mass fraction be 1~3wt% mixed solution, then on magnetic stirring apparatus 50~80 DEG C heating and meanwhile stir Mix 12~14h；In the glove box of nitrogen atmosphere, carries out photoactive layer material using sol evenning machine and mixed with polyvinylpyrrolidone The spin coating of solution, rotating speed 1000rpm/s, time 60s；After spin coating is completed, 30~60min is stood in glove box, is made The top that polyvinylpyrrolidone is moved to photoactive layer in self assembly effect becomes polyvinylpyrrolidone cathode buffer layer； 20~40min is finally made annealing treatment under the conditions of 60~80 DEG C；
(4) the evaporating Al q on polyvinylpyrrolidone cathode buffer layer3Cathode buffer layer, thickness are 0.5~1.5nm, evaporation Rate isNext in Alq3CaF is deposited on cathode buffer layer2Cathode buffer layer, thickness be 0.6~ 1.2nm, evaporation rate are
(5) the evaporation metal cathode on cathode buffer layer.
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