CN105552233A - Bulk heterojunction organic solar cell with dual-anode buffer layer and preparation method of bulk heterojunction organic solar cell - Google Patents
Bulk heterojunction organic solar cell with dual-anode buffer layer and preparation method of bulk heterojunction organic solar cell Download PDFInfo
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Abstract
The invention relates to a bulk heterojunction organic solar cell with a dual-anode buffer layer. The cell adopts a positive structure and sequentially comprises a transparent substrate, a transparent conductive positive electrode, an anode buffer layer, an organic active layer, a cathode buffer layer and a metal positive electrode from bottom to top, wherein the anode buffer layer is the dual-anode buffer layer composed of a polytetrafluoroethylene (PTFE) anode buffer layer and a MoO3 anode buffer layer, the PTFE anode buffer layer is prepared on the transparent conductive positive electrode, the thickness of the PTFE anode buffer layer is 0.3 to 2 nanometers, the MoO3 anode buffer layer is prepared between the PTFE anode buffer layer and the organic active layer, and the thickness of the MoO3 anode buffer layer is 4 to 10 nanometers. By introducing the dual-anode buffer layer between the positive electrode and the active layer, the surface work function of the positive electrode is increased, the interface energy level difference is favorably modified, the electron blocking capability is improved as well as ensuring hole transmission, the combination of electrons and holes is greatly reduced, and thus, the energy conversion efficiency of the solar cell is improved.
Description
Technical field
The invention belongs to organic photovoltaic devices technical field, be specifically related to bulk heterojunction organic solar batteries of a kind of double anode resilient coating and preparation method thereof.
Background technology
Nowadays, traditional energy is day by day exhausted, and environmental pollution is day by day serious, and facing mankind the dual test of energy crisis and environmental pollution.Therefore, find the green energy resource of low energy consumption, low stain, low emission, as solar energy, wind energy, water energy, geothermal energy, tidal energy etc. become the needs of development low-carbon economy.Wherein the feature such as solar energy, rich reserves renewable, clean with it, becomes the research emphasis and focus that solve energy and environment problem.
Solar cell is the device transform light energy of solar radiation being become electric energy, is to utilize one of most important mode of solar energy.At present, conventional inorganic solar cell, as silicon, gallium arsenide solar cell etc., although put goods on the market, the cost of its costliness, limits further developing of it to shortcomings such as the requirement of inorganic semiconductor are high.Organic solar batteries is the novel solar battery that recent two decades grows up, because it has, material source is extensive, cost is low, preparation technology is simple, can be made into the advantages such as large area flexible device, have more advantage and development space compared to conventional solar cell, obtain increasing attention.The energy conversion efficiency of the organic solar batteries of current report reaches more than 10%, however this numeral be far from reaching can the requirement of large-scale production.Therefore, how by optimised devices structure, improve the methods such as preparation technology to improve the energy conversion efficiency of organic solar batteries, become the emphasis of research organic solar batteries.
Determine that the key factor of organic solar batteries device performance has a lot, one of them is exactly effective transferring charge in organic active layer, and this depends on interface performance good between active layer and anode.Therefore researchers introduce an interfacial layer between active layer and anode, namely anode buffer layer.Anode buffer layer conventional at present has the metal oxide of PEDOT:PSS and high work function as MoO
3.But the acidity of PEDOT:PSS and moisture absorption reduce the overall performance of device.In addition, although MoO
3can effective transporting holes, but it can not stop the electric transmission of active layer to anode effectively, and therefore device has higher Carrier recombination.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of double anode resilient coating bulk heterojunction organic solar batteries and preparation method thereof.This solar cell introduces double anode resilient coating, has well modified the interface between active layer and anode ITO, reduces the potential barrier between active layer and anode.Double anode resilient coating is conducive to the separation of exciton and the transmission of charge carrier in addition, decreases the probability of Carrier recombination, therefore, it is possible to the effective energy conversion efficiency improving device.
In order to solve the problems of the technologies described above, double anode resilient coating bulk heterojunction organic solar batteries of the present invention adopts eurymeric structure, is followed successively by from bottom to top: transparent substrates, transparent conductive anode, anode buffer layer, organic active layer, cathode buffer layer, metallic cathode; It is characterized in that described anode buffer layer is PTFE anode buffer layer and MoO
3the double anode resilient coating that anode buffer layer is formed; PTFE anode buffer layer is prepared on transparent conductive anode; MoO
3anode buffer layer is prepared between PTFE anode buffer layer and organic active layer; PTFE anode buffer layer thickness is 0.3 ~ 2nm, MoO
3anode buffer layer thickness is 4 ~ 10nm.
The preferred 1.5nm of described PTFE anode buffer layer thickness.
Described transparent substrates is clear glass or transparent flexible polymer, transparent flexible polymer is the one in polyethylene, poly terephthalic acid second two fat, polymethyl methacrylate, Merlon, polyurethanes, polyimides or polyacrylic acid, or be mixed by wherein two or more material, or be prepared from from level to level in order by wherein two or more material.
Described transparent conductive anode, its material is tin indium oxide (ITO), is deposited in transparent substrates;
Described transparent conductive anode thickness is 150nm, and square resistance is 15 Ω/.
Described organic active layer is by electron donor material PCDTBT and electron acceptor material PC
71bM presses the mixture of the mass ratio configuration of 1:4, or by electron donor material P3HT and electron acceptor material PC
61bM presses the mixture of the mass ratio configuration of 1:1.
Described cathode buffer layer, its material is the one in Alq3, LiF, porphyrin Small molecular, Bphen or BCP, or is prepared from from level to level in order by wherein two or more material, and thickness is 1 ~ 10nm.
Described metallic cathode, its material is the one in Al, Ca, Ag or Au, or is prepared from from level to level in order by wherein two or more material, and thickness is 100nm ~ 200nm.
The preparation method of double anode resilient coating bulk heterojunction organic solar batteries of the present invention, comprises the following steps:
1. use toluene, acetone, washing agent, deionized water, isopropyl alcohol to carry out ultrasonic cleaning to the substrate that transparent conductive anode and transparent substrates are formed successively, the substrate after cleaned is kept in isopropyl alcohol for subsequent use;
2. the substrate nitrogen after cleaning dries up, and moves in drying box and dries, then carry out plasma treatment with Plasma cleaning machine;
3. the substrate handled well is moved in vacuum coating equipment, evaporation PTFE anode buffer layer on transparent conductive anode, then evaporation MoO on PTFE anode buffer layer
3anode buffer layer; Wherein the evaporation rate of PTFE is
thickness is 0.3 ~ 2nm, MoO
3evaporation rate be
thickness is 4 ~ 10nm;
4. the substrate of double anode resilient coating moves into Plasma cleaning machine by above-mentioned evaporation, carries out plasma treatment;
5. at MoO
3anode buffer layer prepares organic active layer;
6. substrate step 5. obtained moves in vacuum coating equipment, evaporation cathode buffer layer and metallic cathode on organic active layer successively.
Described step is 5. middle adopts the method for spin coating in nitrogen atmosphere by electron donor material PCDTBT and electron acceptor material PC
71the mixed solution that BM configures by the mass ratio of 1:4 is spin-coated on MoO
3on anode buffer layer, sol evenning machine rotating speed is 1500rpm/s, and spin-coating time is 40s; The solvent of described mixed solution is o-dichlorohenzene, and the concentration of solution is PCDTBT:PC
71bM=8mg/ml:32mg/ml; Then to anneal under the condition of 70 DEG C 30min solvent evaporated, obtain organic active layer.
Described step 5. in, adopt the method for spin coating in nitrogen atmosphere by electron donor material P3HT and electron acceptor material PC
61the mixed solution that BM configures by the mass ratio of 1:1 is spin-coated on MoO
3on anode buffer layer, sol evenning machine rotating speed is 700rpm/s, and spin-coating time is 36s; The solvent of described mixed solution is o-dichlorohenzene, and the concentration of solution is P3HT:PC
61bM=17mg/ml:17mg/ml; Then annealing at room temperature 3h solvent evaporated, obtains organic active layer.
In described 6. step, evaporating Al q3 cathode buffer layer on organic active layer, evaporation rate is
alq3 thickness is 1nm; Evaporating Al metal electrode on Alq3 cathode buffer layer, evaporation rate is about
al thickness is 100nm-200nm.
The invention provides a kind of bulk heterojunction organic solar batteries of double anode resilient coating, make the performance of organic solar batteries, especially factor of influence and energy conversion efficiency all have significant improvement, and have that preparation technology is simple, cost is low, efficiency advantages of higher.
Compared with prior art, the invention has the advantages that:
One, double anode resilient coating bulk heterojunction organic solar batteries provided by the invention, with PTFE and MoO
3be combined into double anode resilient coating, improve anode surface work function, the fabulous interface energy modified between anode ITO and active layer is differential, ensure that good interface performance.
Two, double anode resilient coating bulk heterojunction organic solar batteries provided by the invention, with PTFE and MoO
3be combined into double anode resilient coating, relative to single layer anode resilient coating MoO
3, improve the blocking capability to electronics, greatly reduce the recombination probability in electronics and hole, thus improve the energy conversion efficiency of solar cell.
Three, double anode resilient coating bulk heterojunction organic solar batteries provided by the invention, with PTFE and MoO
3be combined into double anode resilient coating, compared to traditional anode buffer layer PEDOT:PSS, the chemical property of PTFE and physical property are all very stable, have moisture-proof, and can not corrode anode ITO, and therefore device has better stability.
Four, double anode resilient coating bulk heterojunction organic solar batteries provided by the invention, with PTFE and MoO
3be combined into double anode resilient coating, material source is extensive, and cost is low, and preparation technology is simple.
Accompanying drawing explanation
Below in conjunction with the drawings and the specific embodiments, the present invention is further illustrated.
Fig. 1 is the structural representation of double anode resilient coating bulk heterojunction organic solar batteries of the present invention;
Fig. 2 is the J-V curve that the embodiment 1 of double anode resilient coating bulk heterojunction organic solar batteries of the present invention records under intensity of illumination is AM1.5G with comparative device;
Fig. 3 is the schematic diagram that the performance of double anode resilient coating bulk heterojunction organic solar batteries of the present invention changes with the thickness change of PTFE anode buffer layer.
Fig. 4 is the J-V curve that the embodiment 2 of double anode resilient coating bulk heterojunction organic solar batteries of the present invention records under intensity of illumination is AM1.5G with comparative device.
Fig. 5 is performance and the MoO of double anode resilient coating bulk heterojunction organic solar batteries of the present invention
3the relation schematic diagram of anode buffer layer thickness.
Embodiment
As shown in Figure 1, double anode resilient coating bulk heterojunction organic solar batteries of the present invention adopts eurymeric structure, is followed successively by from bottom to top: transparent substrates, transparent conductive anode, double anode resilient coating, organic active layer, cathode buffer layer, metal anode.The ground floor of double anode resilient coating is PTFE anode buffer layer, is prepared on transparent conductive anode, and its thickness range is 0.3 ~ 2nm; The second layer is MoO
3anode buffer layer, is prepared on PTFE anode buffer layer, and its thickness range is 4 ~ 10nm; Organic active layer is mixed by electron donor material and electron acceptor material, is prepared in MoO
3on anode buffer layer.
Wherein in embodiment 1 organic active layer by donor material PCDTBT and acceptor material PC
71bM is mixed with and forms, described PCDTBT:PC
71the mass percent of BM mixed solution is 1:4, and solvent is o-dichlorohenzene, and solution concentration is PCDTBT:PC
71bM=8mg/ml:32mg/ml, mixed solution adds thermal agitation 12h with 60 DEG C.In embodiment 5, active layer is by donor material P3HT and acceptor material PC
61bM is mixed with and forms, described P3HT:PC
61the mass percent of BM mixed solution is 1:1, and solvent is o-dichlorohenzene, and solution concentration is P3HT:PC
61bM=17mg/ml:17mg/ml, mixed solution at room temperature stirs 14h.
Embodiment 1:
Preparation method is as follows for double anode resilient coating bulk heterojunction organic solar batteries: use toluene, acetone, washing agent, deionized water, isopropyl alcohol to carry out ultrasonic cleaning to the substrate that transparent substrates and tin indium oxide (ITO) transparent conductive anode form first successively, often walk each 20min.After the substrate after cleaning being dried up with nitrogen, move in drying box and dry 20min.Then Plasma cleaning machine treatment substrate 5min is used.Double anode resilient coating adopts the method preparation of vacuum evaporation, and first the substrate handled well to be moved in vacuum coating equipment evaporation PTFE anode buffer layer on transparent conductive anode, the evaporation rate of PTFE is
then evaporation MoO on PTFE anode buffer layer
3anode buffer layer, MoO
3evaporation rate be
after evaporation completes, the thickness of PTFE anode buffer layer is 1.5nm, MoO
3the thickness of anode buffer layer is 5nm.By evaporation, the substrate of double anode resilient coating moves into Plasma cleaning machine, process 2min.By electron donor material PCDTBT and electron acceptor material PC
71bM is dissolved in o-dichlorohenzene for 1:4 by mass percentage, and obtaining concentration is PCDTBT:PC
71the mixed solution of BM=8mg/ml:32mg/ml, mixed solution adds thermal agitation 12h with 60 DEG C; Then substrate is moved in glove box (nitrogen atmosphere), adopt spin-coating method at MoO
3anode buffer layer prepares PCDTBT:PCB
71m organic active layer, rotating speed is 1500rpm/s, and the time is 40s, and thickness is about 90nm.After spin-coating film, substrate is placed on heating plate and carries out thermal annealing (70 DEG C, 30min), to evaporate unnecessary solvent, make organic active layer form good phase separation structure.After annealing, substrate is moved into vacuum coating equipment, on organic active layer successively evaporation cathode buffer layer Alq3 (thickness is 1nm, and evaporation rate is
) and metallic cathode Al (thickness is 120nm, and evaporation rate is
).After metallic cathode Al evaporation completes, 15min to be stopped in glove box, to make substrate cool, prevent Al electrode oxidized in atmosphere.The device effective area prepared is 0.05cm
2.Device is all at 100mw/cm
2aM1.5 illumination simulation under test, Current density-voltage (J-V) curve is recorded by Keithley2400 digital sourcemeter, and test process all carries out under atmospheric environment.Device architecture of the present invention is: transparent substrates/ITO/PTFE (thickness 1.5nm)/MoO
3(thickness 5nm)/PCDTBT:PC
71bM/Alq3 (thickness 1nm)/Al (thickness 120nm).Device of the present invention and the J-V curve measured by comparative device are as shown in Figure 2.Comparative example 1:
The substrate nitrogen that cleaned transparent substrates and ITO transparent conductive anode form is dried up, dries 20min and with after Plasma cleaning machine treatment substrate 5min, move into evaporation anode buffer layer MoO in vacuum coating equipment
3(thickness is 5nm, and evaporation rate is
).The anode buffer layer MoO by evaporation
3substrate move into Plasma cleaning machine, process 2min.Then substrate is moved in glove box (nitrogen atmosphere), adopt spin-coating method to prepare organic active layer on anode buffer layer.Organic active layer is by electron donor material PCDTBT and electron acceptor material PC
71bM is mixed with and forms, PCDTBT:PC
71the mass percent of BM mixed solution is 1:4, and solvent is o-dichlorohenzene, organic active layer PCDTBT:PC
71bM adopts spin-coating method preparation, and rotating speed is 1500rpm/s, and the time is 40s, and thickness is about 90nm.Then thermal annealing (70 DEG C, 30min) is carried out.On organic active layer successively evaporation cathode buffer layer Alq3 (thickness is 1nm, and evaporation rate is
) and metallic cathode Al (thickness is 120nm, and evaporation rate is
).The device prepared (AM1.5,100mw/cm at the standard conditions
2) measure, use Keithley2400 digital sourcemeter to collect J-V curve data.Comparative device structure is: transparent substrates/ITO/MoO
3(thickness 5nm)/PCDTBT:PC
71bM/Alq3 (thickness 1nm)/Al (thickness 120nm).
Comparative example 2:
The substrate nitrogen that cleaned transparent substrates and ITO transparent conductive anode form is dried up, dry 20min also with after Plasma cleaning machine treatment substrate 5min, on anode, (rotating speed is 3000rpm/s to spin coating anode buffer layer Polyglycolic acid fibre (PEDOT:PSS), time is 60s), under the condition of 120 DEG C, heat 10min.Then substrate is moved in glove box (nitrogen atmosphere), adopt spin-coating method to prepare organic active layer on anode buffer layer; Organic active layer is by electron donor material PCDTBT and electron acceptor material PC
71bM is mixed with and forms, PCDTBT:PC
71the mass percent of BM mixed solution is 1:4, and solvent is o-dichlorohenzene, organic active layer PCDTBT:PC
71bM adopts spin-coating method preparation, and rotating speed is 1500rpm/s, and the time is 40s, and thickness is about 90nm; Then thermal annealing (70 DEG C, 30min) is carried out.On active layer successively evaporation cathode buffer layer Alq3 (thickness is 1nm, and evaporation rate is
) and metallic cathode Al (thickness is 120nm, and evaporation rate is
).The device prepared (AM1.5,100mw/cm at the standard conditions
2) measure, use Keithley2400 digital sourcemeter to collect J-V curve data.Comparative device structure is: transparent substrates/ITO/PEDOT:PSS/PCDTBT:PC
71bM/Alq3 (thickness 1nm)/Al (thickness 120nm).
Table 1 is that embodiment 1 contrasts with the data result of comparative example 1 and comparative example 2, and result shows, with PTFE anode buffer layer and MoO
3anode buffer layer is combined into double anode resilient coating, relative to single layer anode resilient coating MoO
3, the short circuit current of device improves 9.3%, and fill factor, curve factor improves 9.8%, and energy conversion efficiency improves 25%; In contrast to traditional anode buffer layer PEDOT:PSS, short circuit current improves 14.3%, and fill factor, curve factor improves 8.83%, and energy conversion efficiency improves 26.3%.
Table 1 is the invention structure devices of embodiment 1 and the Comparative result of comparative device performance test
| Jsc(mA/cm 2) | Voc(V) | FF(％) | PCE(％) | |
| Embodiment 1 device | 12.926 | 0.896 | 63.12 | 7.311 |
| Comparative example 1 device | 11.823 | 0.861 | 57.48 | 5.850 |
| Comparative example 2 device | 11.310 | 0.882 | 58.00 | 5.787 |
Embodiment 2
Preparation method is as follows for double anode resilient coating bulk heterojunction organic solar batteries: use toluene, acetone, washing agent, deionized water, isopropyl alcohol to carry out ultrasonic cleaning to the substrate that transparent substrates and tin indium oxide (ITO) transparent conductive anode form first successively, often walk each 20min.The substrate nitrogen that cleaned transparent substrates and ITO transparent conductive anode form is dried up, dry 20min also with after Plasma cleaning machine treatment substrate 5min, (thickness is 0.3nm, and evaporation rate is to move in vacuum coating equipment evaporation PTFE anode buffer layer successively
) and MoO
3anode buffer layer (thickness is 5nm), evaporation rate is
).Substrate is moved into Plasma cleaning machine, after process 2min, adopt the method identical with embodiment 1 at MoO
3organic active layer PCDTBT:PCB prepared by anode buffer layer
71m.Afterwards substrate is moved into vacuum coating equipment, on organic active layer successively evaporation cathode buffer layer Alq3 (thickness is 1nm, and evaporation rate is
) and metallic cathode Al (thickness is 120nm, and evaporation rate is
).The device prepared (AM1.5,100mw/cm at the standard conditions
2) measure, use Keithley2400 digital sourcemeter to collect J-V curve data.Device architecture is: transparent substrates/ITO/PTFE (thickness 0.3nm)/MoO
3(thickness 5nm)/PCDTBT:PC
71bM/Alq3 (thickness 1nm)/Al (thickness 120nm).J-V curve measured by the device of embodiment 2 as shown in Figure 3.
Embodiment 3
Preparation method is as follows for double anode resilient coating bulk heterojunction organic solar batteries: use toluene, acetone, washing agent, deionized water, isopropyl alcohol to carry out ultrasonic cleaning to the substrate that transparent substrates and tin indium oxide (ITO) transparent conductive anode form first successively, often walk each 20min.The substrate nitrogen that cleaned transparent substrates and ITO transparent conductive anode form is dried up, dry 20min also with after Plasma cleaning machine treatment substrate 5min, (thickness is 1.0nm, and evaporation rate is to move in vacuum coating equipment evaporation PTFE anode buffer layer successively
) and MoO
3(thickness is 5nm to anode buffer layer, and evaporation rate is
).Substrate is moved into Plasma cleaning machine, after process 2min, adopt the method identical with embodiment 1 at MoO
3organic active layer PCDTBT:PC prepared by anode buffer layer
71bM.On organic active layer successively evaporation cathode buffer layer Alq3 (thickness is 1nm, and evaporation rate is
) and metallic cathode Al (thickness is 120nm, and evaporation rate is
).The device prepared (AM1.5,100mw/cm at the standard conditions
2) measure, use Keithley2400 digital sourcemeter to collect J-V curve data.Device architecture is: transparent substrates/ITO/PTFE (thickness 1.0nm)/MoO
3(thickness 5nm)/PCDTBT:PC
71bM/Alq3 (thickness 1nm)/Al (thickness 120nm).J-V curve measured by the device of embodiment 3 as shown in Figure 3.
Embodiment 4
Preparation method is as follows for double anode resilient coating bulk heterojunction organic solar batteries: use toluene, acetone, washing agent, deionized water, isopropyl alcohol to carry out ultrasonic cleaning to the substrate that transparent substrates and tin indium oxide (ITO) transparent conductive anode form first successively, often walk each 20min.The substrate nitrogen that cleaned transparent substrates and ITO transparent conductive anode form is dried up, dry 20min also with after Plasma cleaning machine treatment substrate 5min, (thickness is 2.0nm, and evaporation rate is to move in vacuum coating equipment evaporation PTFE anode buffer layer successively
) and MoO
3(thickness 5nm, evaporation rate is anode buffer layer
).Substrate is moved into Plasma cleaning machine, after process 2min, adopt the method identical with embodiment 1 at MoO
3organic active layer PCDTBT:PC prepared by anode buffer layer
71bM.On organic active layer successively evaporation cathode buffer layer Alq3 (thickness is 1nm, and evaporation rate is
) and metallic cathode Al (thickness is 120nm, and evaporation rate is
).The device prepared (AM1.5,100mw/cm at the standard conditions
2) measure, use Keithley2400 digital sourcemeter to collect J-V curve data.Device architecture is: transparent substrates/ITO/PTFE (thickness 2.0nm)/MoO
3(thickness 5nm)/PCDTBT:PC
71bM/Alq3 (thickness 1nm)/Al (thickness 120nm).J-V curve measured by the device of embodiment 4 as shown in Figure 3.
Table 2 is the Comparative result of the invention structure devices performance test of embodiment 1 ~ 4
| Jsc(mA/cm 2) | Voc(V) | FF(％) | PCE(％) | |
| Embodiment 1 device | 12.926 | 0.896 | 63.12 | 7.311 |
| Embodiment 2 device | 11.935 | 0.867 | 60.56 | 6.268 |
| Embodiment 3 device | 12.304 | 0.886 | 63.89 | 6.967 |
| Embodiment 4 device | 11.649 | 0.882 | 61.26 | 6.294 |
Embodiment 5
Preparation method is as follows for double anode resilient coating bulk heterojunction organic solar batteries: use toluene, acetone, washing agent, deionized water, isopropyl alcohol to carry out ultrasonic cleaning to the substrate that transparent substrates and tin indium oxide (ITO) transparent conductive anode form first successively, often walk each 20min.The substrate nitrogen that cleaned transparent substrates and ITO transparent conductive anode form is dried up, dry 20min, after Plasma cleaning machine treatment substrate 5min, (thickness is 1.5nm, and evaporation rate is to move in vacuum coating equipment evaporation PTFE anode buffer layer successively
) and MoO
3(thickness is 5nm to anode buffer layer, and evaporation rate is
).By evaporation, the substrate of double anode resilient coating moves into Plasma cleaning machine, process 2min.By electron donor material P3HT and electron acceptor material PC
61bM is dissolved in o-dichlorohenzene for 1:1 by mass percentage, and obtaining concentration is P3HT:PC
61the mixed solution of BM=17mg/ml:17mg/ml, mixed solution stirring at room temperature 14h; Then substrate is moved in glove box (nitrogen atmosphere), adopt spin-coating method at MoO
3anode buffer layer prepares P3HT:PC
61bM organic active layer, rotating speed is 700rpm/s, and the time is 36s, and thickness is about 230nm; After spin-coating film, in glove box, place 3h to make solvent evaporates.On organic active layer successively evaporation cathode buffer layer Alq3 (thickness is 1nm, and evaporation rate is
) and metallic cathode Al (thickness is 120nm, and evaporation rate is
).The device prepared is at reference condition (AM1.5,100mw/cm
2) under measure, use Keithley2400 digital sourcemeter to collect J-V curve data.Device architecture of the present invention is: transparent substrates/ITO/PTFE (thickness 1.5nm)/MoO
3(thickness 5nm)/P3HT:PC
61bM/Alq3 (thickness 1nm)/Al (thickness 120nm).Device of the present invention and the J-V curve measured by comparative device are as shown in Figure 4.
Comparative example 3
The substrate nitrogen that cleaned transparent substrates and transparent conductive anode ITO form is dried up, dries 20min and with after Plasma cleaning machine treatment substrate 5min, move into evaporation anode buffer layer MoO in vacuum coating equipment
3(thickness is 5nm, and evaporation rate is
).The anode buffer layer MoO by evaporation
3substrate move into Plasma cleaning machine, process 2min.By electron donor material P3HT and electron acceptor material PC
61bM is dissolved in o-dichlorohenzene for 1:1 by mass percentage, and obtaining concentration is P3HT:PC
61the mixed solution of BM=17mg/ml:17mg/ml, mixed solution stirring at room temperature 14h; Then substrate is moved in glove box (nitrogen atmosphere), adopt spin-coating method at MoO
3anode buffer layer prepares P3HT:PC
61bM organic active layer, rotating speed is 700rpm/s, and the time is 36s, and thickness is about 230nm; Then in glove box, 3h is placed to make solvent evaporates.On organic active layer successively evaporation cathode buffer layer Alq3 (thickness is 1nm, and evaporation rate is
) and metallic cathode Al (thickness is 120nm, and evaporation rate is
).The device prepared is at reference condition (AM1.5,100mw/cm
2) under measure, use Keithley2400 digital sourcemeter to collect J-V curve data.Comparative device structure is: transparent substrates/ITO/MoO
3(thickness 5nm)/P3HT:PC
61bM/Alq3 (thickness 1nm)/Al (thickness 120nm).
Table 3 is that embodiment 5 contrasts with the data result of comparative example 3, and result shows, for organic active layer material P3HT:PC
61bM, with PTFE anode buffer layer and MoO
3anode buffer layer is combined into double anode resilient coating, and compared to single layer anode resilient coating, the short circuit current of device improves 17.6%, and fill factor, curve factor improves 6.47%, and energy conversion efficiency improves 26.6%.
Table 3 is the invention structure devices of embodiment 5 and the Comparative result of comparative device performance test
Embodiment 6
Preparation method is as follows for double anode resilient coating bulk heterojunction organic solar batteries: dried up by the substrate nitrogen that cleaned transparent substrates and ITO transparent conductive anode form, dry 20min also with after Plasma cleaning machine treatment substrate 5min, (thickness is 0.8nm, and evaporation rate is to move in vacuum coating equipment evaporation PTFE anode buffer layer successively
) and MoO
3(thickness is 4nm to anode buffer layer, and evaporation rate is
).The method identical with embodiment 1 is at MoO
3organic active layer PCDTBT:PC prepared by anode buffer layer
71bM.On organic active layer successively evaporation cathode buffer layer Alq3 (thickness is 1nm, and evaporation rate is
) and metallic cathode Al (thickness is 120nm, and evaporation rate is
).The device prepared (AM1.5,100mw/cm at the standard conditions
2) measure, use Keithley2400 digital sourcemeter to collect J-V curve data.Device architecture is: transparent substrates/ITO/PTFE (thickness 0.8nm)/MoO
3(thickness 4nm)/PCDTBT:PC
71bM/Alq3 (thickness 1nm)/Al (thickness 120nm).J-V curve measured by the device of embodiment 6 as shown in Figure 5.
Embodiment 7
Preparation method is as follows for double anode resilient coating bulk heterojunction organic solar batteries: dried up by the substrate nitrogen that cleaned transparent substrates and ITO transparent conductive anode form, dry 20min also with after Plasma cleaning machine treatment substrate 5min, (thickness is 0.8nm, and evaporation rate is to move in vacuum coating equipment evaporation PTFE anode buffer layer successively
) and MoO
3(thickness is 5nm to anode buffer layer, and evaporation rate is
).The method identical with embodiment 1 is at MoO
3organic active layer PCDTBT:PC prepared by anode buffer layer
71bM.On organic active layer successively evaporation cathode buffer layer Alq3 (thickness is 1nm, and evaporation rate is
) and metallic cathode Al (thickness is 120nm, and evaporation rate is
).The device prepared (AM1.5,100mw/cm at the standard conditions
2) measure, use Keithley2400 digital sourcemeter to collect J-V curve data.Device architecture is: transparent substrates/ITO/PTFE (thickness 0.8m)/MoO
3(thickness 5nm)/PCDTBT:PC
71bM/Alq3 (thickness 1nm)/Al (thickness 120nm).J-V curve measured by the device of embodiment 7 as shown in Figure 5.
Embodiment 8
Preparation method is as follows for double anode resilient coating bulk heterojunction organic solar batteries: dried up by the substrate nitrogen that cleaned transparent substrates and ITO transparent conductive anode form, dry 20min also with after Plasma cleaning machine treatment substrate 5min, (thickness is 0.8nm, and evaporation rate is to move in vacuum coating equipment evaporation PTFE anode buffer layer successively
) and MoO
3(thickness is 10nm to anode buffer layer, and evaporation rate is
).The method identical with embodiment 1 is at MoO
3organic active layer PCDTBT:PC prepared by anode buffer layer
71bM.On organic active layer successively evaporation cathode buffer layer Alq3 (thickness is 1nm, and evaporation rate is
) and metallic cathode Al (thickness is 120nm, and evaporation rate is
).The device prepared (AM1.5,100mw/cm at the standard conditions
2) measure, use Keithley2400 digital sourcemeter to collect J-V curve data.Device architecture is: transparent substrates/ITO/PTFE (thickness 0.8m)/MoO
3(thickness 10nm)/PCDTBT:PC
71bM/Alq3 (thickness 1nm)/Al (thickness 120nm).J-V curve measured by the device of embodiment 8 as shown in Figure 5.
The result display of embodiment 6 ~ 8, changes MoO in allowed band
3the thickness of anode buffer layer is not very large to the performance impact of device.
Table 4 is the Comparative result of the invention structure devices performance test of embodiment 6 ~ 8
| Jsc(mA/cm 2) | Voc(V) | FF(％) | PCE(％) | |
| Embodiment 6 device | 11.750 | 0.877 | 63.69 | 6.566 |
| Embodiment 7 device | 11.643 | 0.871 | 65.89 | 6.681 |
| Embodiment 8 device | 11.899 | 0.879 | 63.50 | 6.640 |
The invention is not restricted to above-described embodiment, described cathode cushioning layer material can also be the one in LiF, porphyrin Small molecular, Bphen, BCP, or is prepared from from level to level in order by wherein two or more material.Described metallic cathode material can also be the one in Al, Ca, Ag, Au, or is prepared from from level to level in order by wherein two or more material.Described transparent substrates can also be transparent flexible polymer substrate, transparent flexible polymeric material comprises the one in polyethylene, poly terephthalic acid second two fat, polymethyl methacrylate, Merlon, polyurethanes, polyimides or polyacrylic acid, or be mixed by wherein two or more material, or be prepared from from level to level in order by wherein two or more material.
The present invention is described the present invention by above-described embodiment.It should be noted that embodiment is just for citing of the present invention and explanation, is not limited to above-mentioned example.Within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a double anode resilient coating bulk heterojunction organic solar batteries, adopts eurymeric structure, is followed successively by from bottom to top: transparent substrates, transparent conductive anode, anode buffer layer, organic active layer, cathode buffer layer, metallic cathode; It is characterized in that described anode buffer layer is PTFE anode buffer layer and MoO
3the double anode resilient coating that anode buffer layer is formed; PTFE anode buffer layer is prepared on transparent conductive anode; MoO
3anode buffer layer is prepared between PTFE anode buffer layer and organic active layer; PTFE anode buffer layer thickness is 0.3 ~ 2nm, MoO
3anode buffer layer thickness is 4 ~ 10nm.
2. double anode resilient coating bulk heterojunction organic solar batteries according to claim 1, is characterized in that the preferred 1.5nm of described PTFE anode buffer layer thickness.
3. double anode resilient coating bulk heterojunction organic solar batteries according to claim 1, is characterized in that described transparent substrates is clear glass or transparent flexible polymer.
4. double anode resilient coating bulk heterojunction organic solar batteries according to claim 3, it is characterized in that transparent flexible polymer is the one in polyethylene, poly terephthalic acid second two fat, polymethyl methacrylate, Merlon, polyurethanes, polyimides or polyacrylic acid, or be mixed by wherein two or more material, or be prepared from from level to level in order by wherein two or more material.
5. double anode resilient coating bulk heterojunction organic solar batteries according to claim 1, it is characterized in that described transparent conductive anode, its material is tin indium oxide, is deposited in transparent substrates.
6. double anode resilient coating bulk heterojunction organic solar batteries according to claim 1, is characterized in that described organic active layer is by electron donor material PCDTBT and electron acceptor material PC
71bM presses the mixture of the mass ratio configuration of 1:4, or by electron donor material P3HT and electron acceptor material PC
61bM presses the mixture of the mass ratio configuration of 1:1.
7. double anode resilient coating bulk heterojunction organic solar batteries according to claim 1, it is characterized in that described cathode buffer layer, its material is the one in Alq3, LiF, porphyrin Small molecular, Bphen or BCP, or be prepared from from level to level in order by wherein two or more material, thickness is 1 ~ 10nm; Described metallic cathode, its material is the one in Al, Ca, Ag or Au, or is prepared from from level to level in order by wherein two or more material, and thickness is 100nm ~ 200nm.
8. a preparation method for double anode resilient coating bulk heterojunction organic solar batteries as claimed in claim 1, comprises the following steps:
1. use toluene, acetone, washing agent, deionized water, isopropyl alcohol to carry out ultrasonic cleaning to the substrate that transparent conductive anode and transparent substrates are formed successively, the substrate after cleaned is kept in isopropyl alcohol for subsequent use;
2. the substrate nitrogen after cleaning dries up, and moves in drying box and dries, then carry out plasma treatment with Plasma cleaning machine;
3. the substrate handled well is moved in vacuum coating equipment, evaporation PTFE anode buffer layer on transparent conductive anode, then evaporation MoO on PTFE anode buffer layer
3anode buffer layer; Wherein the evaporation rate of PTFE is
thickness is 0.3 ~ 2nm, MoO
3evaporation rate be
thickness is 4 ~ 10nm;
4. the substrate of double anode resilient coating moves into Plasma cleaning machine by above-mentioned evaporation, carries out plasma treatment;
5. at MoO
3anode buffer layer prepares organic active layer;
6. substrate step 5. obtained moves in vacuum coating equipment, evaporation cathode buffer layer and metallic cathode on organic active layer successively.
9. the preparation method of double anode resilient coating bulk heterojunction organic solar batteries according to claim 8, is characterized in that adopting the method for spin coating in nitrogen atmosphere by electron donor material PCDTBT and electron acceptor material PC during described step 5.
71the mixed solution that BM configures by the mass ratio of 1:4 is spin-coated on MoO
3on anode buffer layer, sol evenning machine rotating speed is 1500rpm/s, and spin-coating time is 40s; The solvent of described mixed solution is o-dichlorohenzene, and the concentration of solution is PCDTBT:PC
71bM=8mg/ml:32mg/ml; Then to anneal under the condition of 70 DEG C 30min solvent evaporated, obtain organic active layer.
10. the preparation method of double anode resilient coating bulk heterojunction organic solar batteries according to claim 8, in it is characterized in that described step 5., adopts the method for spin coating in nitrogen atmosphere by electron donor material P3HT and electron acceptor material PC
61the mixed solution that BM configures by the mass ratio of 1:1 is spin-coated on MoO
3on anode buffer layer, sol evenning machine rotating speed is 700rpm/s, and spin-coating time is 36s; The solvent of described mixed solution is o-dichlorohenzene, and the concentration of solution is P3HT:PC
61bM=17mg/ml:17mg/ml; Then annealing at room temperature 3h solvent evaporated, obtains organic active layer.
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