CN116648072A - Organic semiconductor hole transport interface composite material modified by conductive polymer film, and preparation method and application thereof - Google Patents

Organic semiconductor hole transport interface composite material modified by conductive polymer film, and preparation method and application thereof Download PDF

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CN116648072A
CN116648072A CN202310369664.4A CN202310369664A CN116648072A CN 116648072 A CN116648072 A CN 116648072A CN 202310369664 A CN202310369664 A CN 202310369664A CN 116648072 A CN116648072 A CN 116648072A
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hole transport
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conductive polymer
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尹志刚
郑庆东
陈汉生
马云龙
蔡东东
蔡丽娜
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Mindu Innovation Laboratory
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Abstract

The application discloses a conductive polymer film modified organic semiconductor hole transport interface composite material, a preparation method and application thereof, and belongs to the field of optoelectronic materials and devices. The organic semiconductor hole transport interface composite material comprises a poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] film and a conductive polymer material film; the poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] film and the conductive polymer material film are mutually adhered. The material has the advantages of good film forming quality, high light transmittance, excellent hole transmission capacity and the like; the energy conversion efficiency of the organic photovoltaic device prepared by the composite material reaches more than 14%, the device still keeps more than 80% of the initial efficiency after being stored for 3 months, the energy conversion efficiency reaches more than 12% when the organic photovoltaic device is applied to a semitransparent device, the average visible light transmittance exceeds 25%, and the organic photovoltaic device has wide prospect in energy photoelectron application.

Description

Organic semiconductor hole transport interface composite material modified by conductive polymer film, and preparation method and application thereof
Technical Field
The application relates to a conductive polymer film modified organic semiconductor hole transport interface composite material, a preparation method and application thereof, belonging to the field of optoelectronic materials and devices.
Background
Solar cells can utilize the photovoltaic effect to directly convert solar energy into electric energy, and are an important component of the current green clean power generation technology. The organic photovoltaic (Organic photovoltaic, OPV) device is used as a new generation solar cell, has the advantages of low cost, simple preparation process, capability of being made into a flexible or semitransparent device, easiness in large-area solution processing to realize a photovoltaic assembly module and the like, and has better commercial application potential. However, the energy conversion efficiency (PCE) of the current OPV device is relatively low, and the stability is poor, which is unfavorable for the subsequent application development.
The interface engineering is an effective strategy for improving the photovoltaic performance of the OPV device, and the selective transmission capacity of carriers can be effectively improved by using a proper electrode interface layer, so that the probability of carrier recombination is reduced, and the collection of charges by the electrode is promoted, thereby improving the performance of the device. According to the difference in function, the electrode interface layer mainly includes a Hole Transport Layer (HTL) and an Electron Transport Layer (ETL). The HTL is positioned between the active layer and the anode of the OPV device, and can promote hole carrier capture and transmission, optimize the energy level arrangement of the device interface and regulate the appearance of the active layer.
Poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] (PTAA) is an inherently stable organic semiconductor hole transport material, is widely used in perovskite solar cells, but has the problems of poor conductivity, difficult energy level matching with organic photovoltaic active layer molecular materials and the like. Therefore, there is a need to build new HTL materials by developing interface engineering strategies that improve device performance, providing an efficient way to achieve efficient and stable OPV devices and other optoelectronic devices.
Disclosure of Invention
According to one aspect of the present application, there is provided a conductive polymer film modified organic semiconductor hole transport interface composite. The material has high light transmittance, good film forming quality, excellent hole transmission capability and good stability.
The material combines the organic hole transport material PTAA film and the conductive polymer material film, so that the hole migration capability of the hole transport interface composite material film can be effectively improved. Meanwhile, the hole transport interface composite film can effectively overcome the defects of conductive polymer materials such as poly (3, 4-ethylenedioxythiophene) by utilizing the inherent high stability of PTAA materials: polystyrene sulfonate (PEDOT: PSS) is vulnerable to damage by air, water and oxygen, and to corrosion of ITO. Finally, the application realizes the high-efficiency stable organic photovoltaic device, the energy conversion efficiency of the device reaches more than 14 percent, and the device still maintains more than 80 percent of the initial efficiency after being stored in the air for 90 days. In addition, the PCE of the corresponding semitransparent OPV device reaches more than 12% by applying the organic semiconductor hole transport interface composite material modified by the conductive polymer film, and the average visible light transmittance exceeds 25%, so that the application is expected to be explored practically.
An organic semiconductor hole transport interface composite modified by a conductive polymer film, the organic semiconductor hole transport interface composite comprising a poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] film and a conductive polymer material film;
the poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] film and the conductive polymer material film are mutually adhered.
Optionally, the poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] film and the conductive polymer material film are mutually attached to form at least one of a double-layer structure, a sandwich structure or a multilayer structure with alternating two.
Optionally, the organic semiconductor hole transport interface composite material is a bilayer film structure in which the poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] film and the conductive polymer material film are attached to each other.
Optionally, the conductive polymer material film is formed by film formation of diluted conductive polymer material solution.
Optionally, the poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] film has a smooth and dense surface.
Optionally, the poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] film has a surface root mean square roughness of 0.5nm to 10nm.
Optionally, the poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] film has a surface root mean square roughness of 1nm to 5nm.
Alternatively, the surface root mean square roughness of the poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] film is independently selected from any value or range between any two of 0.5nm, 1.0nm, 1.5nm, 2.0nm, 2.5nm, 3.0nm, 3.5nm, 4.0nm, 4.5nm, 5.0nm, 5.5nm, 6.0nm, 6.5nm, 7.0nm, 7.5nm, 8.0nm, 8.5nm, 9.0nm, 9.5nm, 10nm.
Optionally, the poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] film has a thickness of 5nm to 100nm.
Optionally, the poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] film has a thickness of 10nm to 50nm.
Alternatively, the thickness of the poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] film is independently selected from any of 5nm, 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, or a range of values between any two.
Optionally, the surface of the conductive polymer material film is flat and compact.
Optionally, the surface root mean square roughness of the conductive polymer material film is 0.5 nm-5 nm.
Optionally, the surface root mean square roughness of the conductive polymer material film is 1 nm-2 nm.
Alternatively, the root mean square roughness of the surface of the thin film of conductive polymer material is independently selected from any of 0.5nm, 1.0nm, 1.5nm, 2.0nm, 2.5nm, 3.0nm, 3.5nm, 4.0nm, 4.5nm, 5.0nm, or a range between any two.
Optionally, the thickness of the conductive polymer material film is 5 nm-200 nm.
Optionally, the thickness of the conductive polymer material film is 20 nm-100 nm.
Alternatively, the thickness of the thin film of conductive polymer material is independently selected from any of 5nm, 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 150nm, 200nm, or a range of values between any two.
Optionally, the conductive polymer material is selected from poly (3, 4-ethylenedioxythiophene), poly (3, 4-ethylenedioxythiophene): at least one of polystyrene sulfonate, polyaniline, polypyrrole and derivatives thereof.
Optionally, the average transmittance of the organic semiconductor hole transport interface composite material film modified by the conductive polymer film in the visible light region of 380 nm-780 nm is more than 95%.
According to a second aspect of the present application, there is provided a method for preparing an organic semiconductor hole transport interface composite material. The method adopts a simple solution processing method and a low-temperature annealing process, has low cost and can be popularized universally.
The preparation method of the organic semiconductor hole transport interface composite material comprises the following steps:
s1, heating and mixing a material containing poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] and an organic solvent I to obtain a poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] solution;
s2, mixing materials containing conductive polymer materials and a solvent II to obtain diluted dispersion liquid;
s3, adopting a solution processing film forming method to form a poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] solution film on the upper surface or the lower surface of a film formed by the diluted dispersion liquid.
Optionally, in step S1, the organic solvent i is at least one selected from chloroform, tetrahydrofuran, acetonitrile, N-dimethylformamide, toluene, and chlorobenzene.
Optionally, in step S1, the temperature of the heating and mixing is 30 ℃ to 300 ℃.
Optionally, in step S1, the poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] solution has a concentration of 0.05mol/L to 0.5mol/L.
Optionally, in step S2, the mass of the solvent ii is 10% to 40% of the mass of the diluted dispersion.
Optionally, in step S2, the mass percentage of the solvent ii is independently selected from any value of 10%, 15%, 20%, 25%, 30%, 35%, 40%, or a range between any two.
Optionally, in step S2, the solvent ii is at least one selected from water and alcohol solvents.
Optionally, in step S2, the solvent ii is selected from alcohol solvents.
Optionally, in step S3, the solution processing film forming method includes solution spin coating and then low temperature annealing.
Alternatively, in step S3, the conditions for spin coating the solution are as follows:
spin coating parameters are 500 rpm-5000 rpm;
the spin time is 10 s-120 s.
Optionally, in step S3, the conditions of the low temperature annealing are as follows:
the temperature is 50-350 ℃;
the time is 10 min-200 min.
According to a third aspect of the present application there is provided the use of an organic semiconductor hole transport interface composite.
The organic semiconductor hole transport interface composite material and/or the organic semiconductor hole transport interface composite material obtained by the preparation method are applied to organic photovoltaic devices, transistors, photodetectors and sensors.
According to a fourth aspect of the present application, an organic photovoltaic device is provided. The organic photovoltaic device has the advantages of excellent stability, high photoelectric conversion efficiency, no toxicity, low cost and the like, the energy conversion efficiency reaches more than 14 percent, and the device still maintains more than 80 percent of the initial efficiency after being stored for 3 months. In addition, the energy conversion efficiency of the semitransparent organic photovoltaic device reaches more than 12%, the average visible light transmittance exceeds 25%, and the semitransparent organic photovoltaic device has wide application prospect in the field of photoelectricity.
An organic photovoltaic device comprises a substrate, an anode, a hole transport layer, an organic photovoltaic active layer, an electron transport layer and a cathode;
the hole transport layer is selected from the organic semiconductor hole transport interface composite material and/or the organic semiconductor hole transport interface composite material obtained by the preparation method;
wherein the poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] layer in the hole transport layer is attached to the anode.
Optionally, the substrate is selected from at least one of glass, polyimide, polyethylene terephthalate, polydimethylsiloxane, polyethylene naphthalate, polycarbonate, polyvinyl alcohol.
Optionally, the anode and the cathode are independently selected from at least one of indium tin oxide, zinc aluminum oxide, fluorine doped tin oxide, conductive polymers, metals.
Optionally, the organic photovoltaic active layer comprises a donor material and an acceptor material.
Optionally, the donor material is selected from at least one of an organic polymer semiconductor donor material and an organic small molecule semiconductor donor material having light absorption.
Optionally, the acceptor material is selected from at least one of an organic polymer semiconductor acceptor material, a small organic molecule semiconductor acceptor material, and a fullerene derivative acceptor material.
Optionally, the electron transport layer is selected from at least one of n-type metal oxide, polymer, small molecule, low work function metal, metal salt/complex, carbon-based material, composite material.
More preferably, the substrate material is glass.
More preferably, the anode is indium tin oxide or fluorine doped tin oxide.
More preferably, the organic photovoltaic active layer material is selected from the group consisting of organic polymer semiconductor donors and organic small molecule semiconductor acceptors having light absorption properties.
More preferably, the organic photovoltaic active layer material is selected from the two blend materials of an organic wide-bandgap conjugated polymer semiconductor donor material PM6 with light absorption and an A-D-A type non-fullerene small organic molecule acceptor material M36 containing a benzodithiophene condensed ring.
Preferably, the electron transport layer material is selected from at least one of n-type metal oxides, polymers and small molecules, low work function metals and metal salts/complexes, carbon-based materials, composite materials.
More preferably, the electron transport layer material is selected from organic small molecule materials.
More preferably, the electron transport layer material uses an organic small molecule material: n, N' -bis [3- (dimethylamino) propyl ] perylene-3, 4,9, 10-tetracarboxylic acid diimide.
More preferably, the cathode material is selected from metal electrode materials.
More preferably, the cathode material is silver or aluminum.
The film thickness of the cathode is 10 nm-200 nm.
According to a fifth aspect of the present application, there is provided a method of manufacturing an organic photovoltaic device. The method has the advantages of simple process, low cost and low energy consumption.
A method of making an organic photovoltaic device comprising the steps of:
a1, depositing the anode on the substrate to obtain an anode/substrate assembly;
a2, spin-coating the hole transport layer on the anode surface of the anode/substrate assembly, and annealing at a low temperature to obtain the hole transport layer/anode/substrate assembly;
a3, spin-coating the organic photovoltaic active layer on the surface of the hole transport layer/anode/substrate assembly, and annealing at a low temperature to obtain the organic photovoltaic active layer/hole transport layer/anode/substrate assembly;
a4, spin-coating the electron transport layer on the surface of the organic photovoltaic active layer/hole transport layer/anode/substrate assembly, and annealing at a low temperature to obtain the electron transport layer/organic photovoltaic active layer/hole transport layer/anode/substrate assembly;
and A5, depositing the cathode on the surface of the electron transport layer/organic photovoltaic active layer/hole transport layer/anode/substrate assembly, and performing low-temperature annealing to obtain the organic photovoltaic device.
Alternatively, in steps A2-A4, the conditions for spin coating the solution are as follows:
spin coating parameters are 500 rpm-5000 rpm;
the spin time is 10 s-120 s.
Optionally, in the steps A2 to A4, the conditions of the low temperature annealing are as follows:
the temperature is 50-350 ℃;
the time is 10 min-200 min.
According to a sixth aspect of the present application there is provided the use of an organic photovoltaic device.
The organic photovoltaic device and/or the organic photovoltaic device obtained by the preparation method are applied to the fields of energy and photoelectricity.
The application has the beneficial effects that:
1) The organic semiconductor hole transport interface composite material modified by the conductive polymer film has the advantages of high light transmittance, good film forming quality, controllable thickness, excellent hole transport capacity, good stability and the like. According to the application, the organic hole transport material PTAA film and the conductive polymer material film are compounded, so that the hole capturing and transporting capacity of the composite hole transport layer film can be effectively improved, and meanwhile, the composite hole transport layer film can effectively isolate the corrosion of the conductive polymer material such as PEDOT: PSS on ITO and overcome the defect that the PEDOT: PSS is easily damaged by air, water and oxygen by utilizing the high stability of the PTAA material. In addition, the D-PEDOT PSS solution is formed by diluting PEDOT PSS with a solvent, so that the surface morphology and film forming quality of the composite film can be improved, and finally, a stable and efficient organic photovoltaic device can be realized.
2) The organic semiconductor hole transport interface composite material provided by the application adopts a simple solution processing method and a low-temperature annealing process, has low cost, can be prepared in a large area, is suitable for rigid or flexible substrates, can be popularized in a universal way, and has good application prospects in the fields of organic photovoltaic devices and other optoelectronic devices such as transistors, detectors, sensors and the like.
3) The organic semiconductor hole transport interface composite material provided by the application has wide application prospect. The composite material has good photoelectric property and interface property, can greatly improve the performance of an organic photovoltaic device, and has the energy conversion efficiency reaching more than 14%. The semitransparent device can be prepared by adjusting the electrode structure, so that the energy conversion efficiency reaches more than 12 percent and the average visible light transmittance exceeds 25 percent.
4) According to the organic photovoltaic device provided by the application, the organic semiconductor hole transport interface composite material modified by the conductive polymer film effectively inhibits and blocks the erosion of the ITO electrode by the acidic conductive polymer material such as PEDOT: PSS, so that the efficiency and stability of the organic photovoltaic device are greatly improved. After the device is stored in the air for 3 months, the initial efficiency is still maintained to be more than 80%, which shows that the organic photovoltaic device provided by the application has excellent stability and is beneficial to the practical application of organic photovoltaics.
Drawings
FIG. 1 is an Atomic Force Microscope (AFM) height view of PTAA/D-PEDOT: PSS hole transport interface composite film according to example 1 of the present application.
FIG. 2 is a graph showing the transmission spectrum of PTAA/D-PEDOT: PSS hole transport interface composite film in example 1 of the present application.
Fig. 3 is a schematic structural diagram of an organic photovoltaic device based on PTAA/D-PEDOT: PSS hole transport interface composite according to example 1 of the present application.
Fig. 4 is a graph showing the short-circuit current density-voltage (J-V) characteristics of the organic photovoltaic device manufactured in example 2 of the present application.
FIG. 5 is a graph showing the External Quantum Efficiency (EQE) spectrum of the organic photovoltaic device according to example 2 of the present application.
FIG. 6 is a graph showing the visible light transmittance spectrum of the semitransparent organic photovoltaic device according to examples 3 to 5 of the present application.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the starting materials in the examples of the present application were purchased commercially, wherein:
poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] was purchased from sienna baolaet phototech limited;
poly (3, 4-ethylenedioxythiophene): polystyrene sulfonate was purchased from alaa Ding Shiji limited;
the organic wide band gap conjugated polymer material PBDB-T-2F is available from Solarmer Energy company;
indium tin oxide was purchased from Shenzhen Huanan Hunan City science and technology Co., ltd;
n, N ' -bis [3- (dimethylamino) propyl ] perylene-3, 4,9, 10-tetracarboxylic diimide and 12, 13-bis (2-ethylhexyl) -3, 9-bis-undecyl-12, 13-dihydro- [1,2,5] thiadiazolo [3,4-e ] thieno [2',3': 4',5' ] thieno [2',3':4,5] pyrrolo [3,2-g ] thieno [2',3':4,5] thieno [3,2-b ] indole-2, 10-bis (5, 6-difluoro-3- (dicyanomethylene) inden-1-one) available from Sunnoki technologies Co., ltd;
2,2', 7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene was purchased from the phylum howling technologies, inc;
the M36 material was self-made according to our previous literature report (Q.zheng, et al Natl. Sci. Rev.2020,7,1886).
In the application, indium tin oxide is abbreviated as ITO;
the organic photovoltaic is abbreviated as OPV;
poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] abbreviated PTAA;
the A-D-A type non-fullerene small organic molecule acceptor material containing benzodithiophene condensed rings is abbreviated as M36;
the organic wide band gap conjugated polymer donor material PBDB-T-2F polymer is abbreviated as PM6;
poly (3, 4-ethylenedioxythiophene): polystyrene sulfonate is abbreviated as PEDOT: PSS;
the PEDOT: PSS after solvent dilution is abbreviated as D-PEDOT: PSS;
n, N' -bis [3- (dimethylamino) propyl ] perylene-3, 4,9, 10-tetracarboxylic acid diimide abbreviated as PDIN;
12, 13-bis (2-ethylhexyl) -3, 9-bis-undecyl-12, 13-dihydro- [1,2,5] thiadiazolo [3,4-e ] thieno [2",3":4',5' ] thieno [2',3':4,5] pyrrolo [3,2-g ] thieno [2',3':4,5] thieno [3,2-b ] indole-2, 10-bis (5, 6-difluoro-3- (dicyanomethylene) inden-1-one) is abbreviated as Y6;
2,2', 7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene is abbreviated as Spiro-OMeTAD.
The analysis method in the embodiment of the application is as follows:
using AM 1.5G (100 mW cm -2 ) Photovoltaic performance testing of OPV devices was performed by Oriel Sol3A solar simulator (Newport) and Keithley 2400 source table under light irradiation conditions.
The light transmittance performance analysis of the translucent OPV device was performed using a Lambda35 spectrophotometer.
The organic polymer semiconductor is divided according to the carrier transport capacity, the electron transport capacity of the organic semiconductor is obviously better than the hole transport capacity, the semiconductor is defined as n-type, and the organic polymer semiconductor is p-type.
Example 1
1. The preparation process of the corresponding organic photovoltaic device adopts a positive device structure, and comprises the following steps:
(1) Preparing a conductive polymer film modified organic semiconductor hole transport interface composite material PTAA/D-PEDOT by adopting a solution spin coating method and a low-temperature annealing process, wherein the PTAA/D-PEDOT comprises a PSS film:
step 1: selecting commercially purchased ITO glass (square resistance is about 15 omega/≡) as a substrate, and treating the substrate for 12 minutes by adopting ultraviolet ozone before using the substrate;
step 2: weighing a proper amount of PTAA, dissolving in chloroform, and stirring in a glove box under nitrogen atmosphere at 50 ℃ for 15min until the PTAA is completely dissolved to form transparent clear liquid, wherein the concentration of the PTAA solution is 1mg/ml; meanwhile, isopropanol and the purchased undiluted PEDOT: PSS aqueous solution are mixed according to the mass ratio of 1:5, mixing, stirring for 15min to be uniform, and forming a D-PEDOT: PSS solution;
step 3: spin-coating the PTAA solution prepared in the step 2 on the ITO glass subjected to ultraviolet ozone treatment in a nitrogen atmosphere glove box, wherein spin-coating parameters are 3000rpm, and spin-coating time is 30s; after spin coating is finished, placing the spin-coated sample on a heating table at 100 ℃ for annealing for 10min to obtain a PTAA film; spin-coating the D-PEDOT PSS solution on the PTAA film, wherein spin-coating parameters are 3500rpm, and spin-coating time is 30s; after spin coating, annealing the sample in a 140 ℃ baking box for 15min to obtain PTAA/D-PEDOT: PSS composite film, thereby finally obtaining a hole transport layer/anode/substrate assembly;
(2) The organic photovoltaic active layer is prepared by adopting a solution spin coating technology:
step 1: 3.2mg of each of the organic polymer semiconductor donor material PM6 and the organic micromolecular semiconductor acceptor material M36 is weighed and dissolved in 0.4mL of chloroform, and the mixture is stirred for 6 hours in a glove box in a nitrogen atmosphere to obtain a uniformly mixed PM6:M36 organic photovoltaic active layer solution;
step 2: spin-coating the PM6:M36 blend liquid in the step 1 on the surface of a conductive polymer film modified organic semiconductor hole transport interface composite material film sample in a nitrogen atmosphere glove box, wherein spin-coating parameters are set to 3500rpm, and spin-coating time is 45s; after spin coating is finished, placing the spin-coated sample on a heating table at 90 ℃ for annealing for 5min to obtain an organic photovoltaic active layer/hole transport layer/anode/substrate assembly;
(3) The electron transport layer is prepared by adopting a solution spin coating technology:
step 1: weighing 5mg of PDIN and dissolving in 2.5mL of methanol, and dissolving in a glove box in a nitrogen atmosphere to obtain a clear and uniform electron transport layer solution;
step 2: spin-coating the PDIN methanol solution in the step 1 on the surface of the organic photovoltaic active layer film in a glove box in nitrogen atmosphere, wherein spin-coating parameters are set to 3300rpm, and spin-coating time is 30s, so as to obtain an electron transport layer/active layer/hole transport layer/anode/substrate assembly;
(4) The metal cathode is prepared by adopting a vacuum thermal evaporation method:
preparing metal electrode on electron transport layer by conventional vacuum thermal evaporation method and prefabricated mask plate, and vacuum degree of thermal evaporation is about 1×10 -4 Pa, current of 30A-50A, velocity of The prepared cathode is an Ag electrode, and the thickness of the electrode is 100nm, so that the organic photovoltaic device based on PTAA/D-PEDOT: PSS organic semiconductor hole transport interface composite material is prepared.
2. The surface morphology of the PTAA/D-PEDOT/PSS composite film prepared was measured under Bruker Nanoscale V mode by an atomic force microscope, as shown in FIG. 1; the transmission spectrum of PTAA/D-PEDOT: PSS composite film was measured by using a Lambda365 ultraviolet-visible spectrophotometer, as shown in FIG. 2.
3. The schematic diagram of the organic photovoltaic device with the structure of ITO/PTAA/D-PEDOT: PSS/PM6: M36/PDIN/Ag is shown in figure 3.
Example 2
1. The procedure for the preparation of organic photovoltaic devices was different from that of example 1 in that the D-PEDOT: PSS material was prepared using an aqueous solution of PEDOT: PSS diluted with methanol.
2. Performance test of organic photovoltaic device:
the photovoltaic performance of the organic photovoltaic device was tested by Oriel Sol3A solar simulator (Newport) and Keithley 2400 semiconductor tester under AM 1.5G irradiation conditions, the J-V characteristic curve of the device sample is shown in fig. 4, and the EQE spectrum of the device is shown in fig. 5. Wherein the effective area of the device is 5mm 2 The test initiation voltage was-0.2V and the termination voltage was 1.0V. From the following componentsAs can be seen in FIG. 4, the open circuit voltage of the device measured was 0.866V and the short circuit current density was 22.00mA cm -2 The fill factor was 70.14% and the PCE of the final device was 13.67%. As can be seen from fig. 5, the device has a higher EQE value in the visible region, indicating that there is an efficient photo-to-electrical conversion process for the organic photovoltaic device when operating. These test results show that organic photovoltaic devices based on PTAA/D-PEDOT: PSS bilayer structure organic semiconductor hole transport interface composite materials have excellent photovoltaic performance.
Examples 3 to 5
1. The process for preparing the OPV device in example 1 is different in that the thicknesses of the cathode Ag film are 12nm, 15nm and 18nm, respectively, and MoO of 20nm is evaporated on the upper layer of the Ag electrode 3 As an anti-reflection layer.
2. Light transmittance performance test of organic photovoltaic device:
the light transmittance of the prepared semitransparent OPV device samples was tested by using a Lambda35 spectrophotometer, and the corresponding visible light transmittance spectrum curves of the semitransparent devices are shown in FIG. 6, wherein the spectrum test range is 380 nm-780 nm. It can be seen that three different top electrodes Ag/MoO of 12nm/20nm, 15nm/20nm and 18nm/20nm were used 3 The semitransparent OPV devices prepared by the films have average visible light transmittance of 28.76%, 26.56% and 23.55%, respectively. It is shown that the semitransparent OPV device based on PTAA/D-PEDOT: PSS organic semiconductor hole transport interface composite exhibits good light transmission properties.
Examples 6 to 15
The organic photovoltaic devices of examples 6 to 15 were prepared in the same manner as in example 1 except that the differences in the preparation process of the organic photovoltaic devices of example 1 were shown in Table 1.
TABLE 1
Performance tests were performed on the organic photovoltaic devices obtained in examples 6 to 15 under the same test conditions as in examples 1 and 2, and it was found that the obtained organic photovoltaic devices each obtained higher energy conversion efficiency, and had good photovoltaic performance similar to examples 1 and 2.
Comparative example 1
Other steps are the same as in example 1, except that PTAA is replaced with other classical organic semiconductor materials such as spira-ome tad. And preparing the organic photovoltaic device based on the Spiro-OMeTAD/D-PEDOT: PSS double-layer structure organic semiconductor hole transport interface composite material, wherein the energy conversion efficiency of the device is only 4.52%.
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.

Claims (10)

1. An organic semiconductor hole transport interface composite material modified by a conductive polymer film, characterized in that the organic semiconductor hole transport interface composite material comprises a poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] film and a conductive polymer material film;
the poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] film and the conductive polymer material film are mutually adhered.
2. The organic semiconductor hole transport interface composite of claim 1, wherein the poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] film and the conductive polymer material film are bonded to each other to form at least one of a bilayer structure, a sandwich structure, or a multilayer structure in which the two are alternating;
preferably, the organic semiconductor hole transport interface composite material has a double-layer film structure that the poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] film and the conductive polymer material film are mutually attached;
preferably, the conductive polymer material film is formed by film formation of diluted conductive polymer material solution.
3. The organic semiconductor hole transport interface composite material according to claim 1 or 2, wherein the poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] film has a flat and dense surface;
preferably, the surface root mean square roughness of the poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] film is 0.5-10 nm;
preferably, the surface root mean square roughness of the poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] film is 1 nm-5 nm;
preferably, the poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] film has a thickness of 5nm to 100nm;
preferably, the poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] film has a thickness of 10nm to 50nm;
preferably, the surface of the conductive polymer material film is flat and compact;
preferably, the surface root mean square roughness of the conductive polymer material film is 0.5 nm-5 nm;
preferably, the surface root mean square roughness of the conductive polymer material film is 1 nm-2 nm;
preferably, the thickness of the conductive polymer material film is 5 nm-200 nm;
preferably, the thickness of the conductive polymer material film is 20 nm-100 nm.
4. An organic semiconductor hole transport interface composite according to claim 1 or 2, wherein the conductive polymer material is selected from the group consisting of poly (3, 4-ethylenedioxythiophene), poly (3, 4-ethylenedioxythiophene): at least one of polystyrene sulfonate, polyaniline, polypyrrole and derivatives thereof.
5. The method for preparing the organic semiconductor hole transport interface composite material according to claim 1 or 2, comprising the steps of:
s1, heating and mixing a material containing poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] and an organic solvent I to obtain a poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] solution;
s2, mixing materials containing conductive polymer materials and a solvent II to obtain diluted dispersion liquid;
s3, adopting a solution processing film forming method to form a poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] solution film on the upper surface or the lower surface of a film formed by the diluted dispersion liquid.
6. The process according to claim 5, wherein in step S1, the organic solvent I is at least one selected from the group consisting of chloroform, tetrahydrofuran, acetonitrile, N-dimethylformamide, toluene, and chlorobenzene;
preferably, in the step S1, the temperature of heating and mixing is 30-300 ℃;
preferably, in the step S1, the concentration of the poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] solution is 0.05mol/L to 0.5mol/L;
preferably, in the step S2, the mass of the solvent II is 10% -40% of the mass of the diluted dispersion liquid;
preferably, in step S2, the solvent ii is at least one selected from water and alcohol solvents;
preferably, in step S2, the solvent ii is selected from alcohol solvents;
preferably, in the step S3, the solution processing film forming method comprises solution spin coating and low-temperature DD230127I
Annealing;
preferably, in step S3, the conditions of the solution spin coating are as follows:
spin coating parameters are 500 rpm-5000 rpm;
the spin time is 10 s-120 s;
preferably, in step S3, the conditions of the low temperature annealing are as follows:
the temperature is 50-350 ℃;
the time is 10 min-200 min.
7. Use of the organic semiconductor hole transport interface composite material according to claim 1 or 2 and/or the organic semiconductor hole transport interface composite material obtained by the preparation method according to claim 5 in organic photovoltaic devices, transistors, photodetectors and sensors.
8. An organic photovoltaic device is characterized by comprising a substrate, an anode, a hole transport layer, an organic photovoltaic active layer, an electron transport layer and a cathode;
the hole transport layer is selected from the organic semiconductor hole transport interface composite material according to claim 1 or 2 and/or the organic semiconductor hole transport interface composite material obtained by the preparation method according to any one of claim 5;
wherein the poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] layer in the hole transport layer is bonded to the anode;
preferably, the substrate is selected from at least one of glass, polyimide, polyethylene terephthalate, polydimethylsiloxane, polyethylene naphthalate, polycarbonate, polyvinyl alcohol;
preferably, the anode and the cathode are independently selected from at least one of indium tin oxide, zinc aluminum oxide, fluorine doped tin oxide, conductive polymer, metal;
preferably, the organic photovoltaic active layer comprises a donor material and an acceptor material;
preferably, the donor material is selected from at least one of an organic polymer semiconductor donor material and an organic small molecule semiconductor donor material having light absorption properties;
preferably, the acceptor material is selected from at least one of an organic polymer semiconductor acceptor material, a small organic molecule semiconductor acceptor material, and a fullerene derivative acceptor material;
preferably, the electron transport layer is selected from at least one of n-type metal oxide, polymer, small molecule, low work function metal, metal salt/complex, carbon-based material, composite material.
9. A method of making an organic photovoltaic device comprising the steps of:
a1, depositing the anode on the substrate to obtain an anode/substrate assembly;
a2, spin-coating the hole transport layer on the anode surface of the anode/substrate assembly, and annealing at a low temperature to obtain the hole transport layer/anode/substrate assembly;
a3, spin-coating the organic photovoltaic active layer on the surface of the hole transport layer/anode/substrate assembly, and annealing at a low temperature to obtain the organic photovoltaic active layer/hole transport layer/anode/substrate assembly;
a4, spin-coating the electron transport layer on the surface of the organic photovoltaic active layer/hole transport layer/anode/substrate assembly, and annealing at a low temperature to obtain the electron transport layer/organic photovoltaic active layer/hole transport layer/anode/substrate assembly;
a5, depositing the cathode on the surface of the electron transport layer/organic photovoltaic active layer/hole transport layer/anode/substrate assembly, and performing low-temperature annealing to obtain the organic photovoltaic device; preferably, in steps A2 to A4, the conditions for spin coating the solution are as follows:
spin coating parameters are 500 rpm-5000 rpm;
the spin time is 10 s-120 s;
preferably, in steps A2-A4, the conditions for low temperature annealing are as follows:
the temperature is 50-350 ℃;
the time is 10 min-200 min.
10. Use of an organic photovoltaic device according to claim 8 and/or an organic photovoltaic device obtained according to the method of preparation according to claim 9 in the energy and photovoltaic fields.
CN202310369664.4A 2023-04-07 2023-04-07 Organic semiconductor hole transport interface composite material modified by conductive polymer film, and preparation method and application thereof Pending CN116648072A (en)

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