CN115172593A - Organic solar cell based on inorganic/organic double-layer composite hole transport material and preparation method and application thereof - Google Patents
Organic solar cell based on inorganic/organic double-layer composite hole transport material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an organic solar cell based on an inorganic/organic double-layer composite hole transport material, a preparation method and application thereof, and belongs to the field of energy photoelectric materials and devices. The double-layer composite p-type hole transport material comprises a multi-element oxide inorganic material film and an organic p-type hole transport material film; the multi-element oxide inorganic material film and the organic p-type hole transport material film are mutually attached; the film of the multi-element oxide inorganic material comprises an alkaline earth metal element and NiO; the alkaline earth metal element is doped into NiO. The material has the advantages of high light transmittance, excellent hole transmission capability, adjustable energy level structure, controllable thickness, high stability and the like; the double-layer composite p-type hole transport material can realize that the photoelectric conversion efficiency of the organic solar cell reaches more than 14%, and also realizes that the efficiency reaches more than 12% and the average visible light transmittance exceeds 25% in a semitransparent device, thereby being expected to explore practical application.
Description
Technical Field
The application relates to an organic solar cell based on an inorganic/organic double-layer composite hole transport material, a preparation method and application thereof, and belongs to the field of energy photoelectric materials and devices.
Background
The solar cell can directly convert solar energy into electric energy, and is an important clean energy power generation technology. With the rapid development of the field, the photovoltaic technology has been developed from commercial silicon-based solar cells and inorganic thin-film solar cells to third-generation new solar cells, including dye-sensitized solar cells, perovskite solar cells, quantum dot solar cells, and the like. These devices can achieve high energy conversion efficiency (PCE), but their widespread use is limited by high cost, poor stability, presence of harmful components, and the like. As one of the important representatives of the new solar cell, an Organic Solar Cell (OSC), also known as an Organic Photovoltaic (OPV) device, also has a good application prospect. They are easy to implement low-cost, large-area solution processing, and can be made into semi-transparent or flexible devices, but their relatively low photoelectric conversion efficiency and poor stability are major challenges that limit the practical application of OSC devices.
To solve these problems, researchers have proposed strategies such as development of new organic photovoltaic materials, design of device structures, and interface engineering to improve the efficiency and stability of OSC. Wherein the electrode interface layer is positioned between the organic photovoltaic active layer and the electrode, and the electrode interface layer play an important role in reducing interface potential barrier, promoting the capture and transmission of charge carriers and the like, so the interface engineering is an effective method for improving the performance of the device. The electrode interface layer mainly comprises a hole-transporting anode interface layer and an electron-transporting cathode interface layer. The electrode interface layer in an OSC often needs to meet the following requirements: (1) The organic photovoltaic active layer has good interface compatibility; (2) Has high optical transmittance, allows more light to reach the organic photovoltaic active layer; (3) The work function of the cathode interface layer is matched to the lowest unoccupied molecular orbital of the acceptor material to facilitate electron capture and transport, while the work function of the anode interface layer should be close to the highest occupied molecular orbital of the donor material to facilitate hole capture and transport.
In organic photovoltaics, conventional anode interface layers often use p-type organic materials such as poly (3,4-ethylenedioxythiophene): polystyrene sulfonate (PEDOT: PSS) or binary oxide inorganic materials as hole transport layers. However, the properties of binary oxide materials such as band gap, energy level and the like are fixed, and more intrinsic thin film defects and external defects exist, so that charge recombination is serious, and the stability of the organic solar cell is not facilitated due to the acidity and hygroscopicity of the pure organic PEDOT (PSS) material, so that the improvement of the device performance is restricted. Therefore, development of a new hole transport material to improve the performance of OSC is required.
Disclosure of Invention
According to one aspect of the application, a double-layer composite p-type hole transport material is provided, and the material has the advantages of high light transmittance, excellent hole transport capability, adjustable energy level structure, controllable thickness and high stability; the organic hole transport material and the inorganic hole transport material are compounded, so that the interface compatibility of a hole transport film and an organic photovoltaic active layer can be effectively improved, meanwhile, the double-layer composite hole transport film can utilize the high stability of a multi-element oxide, the defect that the organic hole transport material such as PEDOT (PEDOT-PSS) is easily damaged by air, water and oxygen is effectively overcome, finally, the high-efficiency and stable organic solar cell is realized, the photoelectric conversion efficiency of the organic hole transport film reaches more than 14%, the efficiency of the organic hole transport film reaches more than 12% and the average visible light transmittance of more than 25% in a semitransparent device, and the practical application is expected to be explored.
A double-layer composite p-type hole transport material comprises a multi-element oxide inorganic material film and an organic p-type hole transport material film;
the multi-element oxide inorganic material film and the organic p-type hole transport material film are mutually attached;
the film of the multi-element oxide inorganic material comprises an alkaline earth metal element and NiO;
the alkaline earth metal element is doped into NiO.
Optionally, the surface of the film of the multi-element oxide inorganic material is flat and dense.
Optionally, the root-mean-square roughness of the surface of the multi-element oxide inorganic material film is 0.5 nm-10 nm;
preferably, the root-mean-square roughness of the surface of the multi-element oxide inorganic material film is 1nm to 5nm.
Optionally, the root mean square roughness of the surface of the multi-component oxide inorganic material thin film 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, 5.5nm, 6.0nm, 6.5nm, 7.0nm, 7.5nm, 8.0nm, 8.5nm, 9.0nm, 9.5nm, 10nm or a range between any two of them.
Optionally, the thickness of the multi-element oxide inorganic material film is 5nm to 100nm;
preferably, the thickness of the multi-component oxide inorganic material film is 10nm to 50nm.
Optionally, the thickness of the multi-component oxide inorganic material thin film is independently selected from any value of 5nm, 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm or a range value between any two.
Optionally, the surface of the organic p-type hole transport material film is flat and dense.
Optionally, the root mean square roughness of the surface of the organic p-type hole transport material film is 0.5 nm-5 nm;
preferably, the root mean square roughness of the surface of the organic p-type hole transport material thin film is 1 nm-2 nm.
Optionally, the root mean square roughness of the surface of the organic p-type hole transport material thin film is independently selected from any value 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 organic p-type hole transport film is 5nm to 200nm;
preferably, the thickness of the organic p-type hole transport thin film is 20nm to 100nm.
Optionally, the thickness of the organic p-type hole transport thin film is independently selected from any of 5nm, 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 150nm, 200nm, or a range between any two.
Optionally, in the film of the multi-element oxide inorganic material, the molar content of the alkaline earth metal element accounts for 5 to 50 percent of the total metal element;
optionally, the molar content of the alkaline earth metal element in the multi-component oxide inorganic material thin film is independently selected from any value of 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50% or a range value between any two.
Preferably, in the film of the multi-element oxide inorganic material, the molar content of the alkaline earth metal element accounts for 10 to 40 percent of the total metal element.
The above-mentioned integral metal elements mean: alkaline earth metal elements and Ni elements in the film of the multi-element oxide inorganic material.
Optionally, in the film of the multi-element oxide inorganic material, the alkaline earth metal element is at least one selected from beryllium, magnesium, calcium, strontium and barium.
Optionally, the organic p-type hole transport material is selected from poly (3,4-ethylenedioxythiophene): polystyrene sulfonate, polyaniline, polypyrrole, poly [ bis (4-phenyl) (2,4,6-trimethylphenyl) amine ], 2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene.
The average light transmittance of the double-layer composite p-type hole transport material film in a visible light region of 380-780nm is more than 80%.
According to the second aspect of the application, a preparation method of the double-layer composite p-type hole transport material is provided, and the method is low in cost, simple and convenient in process and capable of being popularized universally.
The preparation method of the double-layer composite p-type hole transport material comprises the following steps:
(S1) mixing a mixed solution containing soluble alkaline earth metal salt, soluble nickel salt, a stabilizer and a solvent I to obtain a precursor solution of the multi-element oxide inorganic material film;
(S2) adding a solvent II into the dispersion liquid of the organic p-type hole transport material to obtain a diluted dispersion liquid;
(S3) forming a film on or under the film formed by the diluted dispersion by using a solution processing film-forming method.
Optionally, the soluble alkaline earth metal salt is selected from at least one of magnesium acetate, calcium acetate, barium chloride.
Optionally, in the step (S1), the soluble nickel salt is selected from at least one of nickel acetate, nickel chloride and nickel nitrate.
Optionally, in the step (S1), the stabilizer is at least one selected from the group consisting of ethanolamine, diethanolamine, and isopropanolamine.
Optionally, in step (S1), the solvent i is at least one selected from water, methanol, ethanol, 2-methoxyethanol, and isopropanol.
Optionally, the molar ratios of the soluble alkaline earth metal salt, the soluble nickel salt, the stabilizer and the whole metal element are respectively 5% to 50%, 50% to 95%, and 50% to 200%.
The soluble alkaline earth metal salt is metered in terms of the amount of its species of alkaline earth metal element; the soluble nickel salt is measured as the amount of the species of nickel element.
Optionally, in the step (S1), the concentration of the precursor solution is 0.05mol/L to 0.5mol/L.
Alternatively, in the step (S1), the concentration of the precursor solution is independently selected from any of 0.05mol/L, 0.10mol/L, 0.15mol/L, 0.20mol/L, 0.25mol/L, 0.30mol/L, 0.35mol/L, 0.40mol/L, 0.45mol/L, 0.50mol/L, or a range between any two.
Optionally, in the 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 alcoholic solvents;
preferably, in step (S2), the solvent ii is selected from methanol;
preferably, in step (S2), the solvent ii is selected from ethanol;
preferably, in step (S2), the solvent ii is selected from isopropanol.
Optionally, in the step (S2), the mass of the solvent ii is 20% to 50% of the mass of the diluted dispersion liquid.
Optionally, in the step (S2), the mass percentage of the solvent ii is independently selected from any value of 20%, 25%, 33%, 40%, 45%, 50% or a range value between any two.
Optionally, in step (S3), the solution processing film-forming method includes solution spin coating and then low-temperature annealing.
Alternatively, in the step (S3), the conditions of the solution spin coating are as follows:
the spin coating parameter is 500 rpm-5000 rpm;
the glue homogenizing time is 10-120 s.
Alternatively, in step (S3), the conditions of the low temperature annealing are as follows:
the temperature is 50-350 ℃;
the time is 10min to 200min.
According to a third aspect of the present application, there is provided a use of a two-layer composite p-type hole transport material.
The double-layer composite p-type hole transport material and/or the double-layer composite p-type hole transport material prepared by the preparation method are/is applied to an organic solar cell.
According to a fourth aspect of the present application, there is provided an organic solar cell having high efficiency and stability, and having a photoelectric conversion efficiency of 14% or more.
An organic solar cell comprises a substrate, a bottom electrode, a hole transport layer, an organic photovoltaic active layer, an electron transport layer and a top electrode;
the hole transport layer is selected from the double-layer composite p-type hole transport material and/or the double-layer composite p-type hole transport material obtained by the preparation method.
According to a fifth aspect of the present application, there is provided a method of fabricating an organic solar cell.
A preparation method of an organic solar cell comprises the following steps:
(A1) Depositing the bottom electrode on the substrate to obtain a bottom electrode/substrate assembly;
(A2) Spin-coating the hole transport layer on the surface of the bottom electrode/substrate assembly, and annealing at low temperature to obtain the hole transport layer/bottom electrode/substrate assembly;
(A3) Spin-coating the organic photovoltaic active layer to the surface of the hole transport layer/bottom electrode/substrate assembly, and annealing at low temperature to obtain the organic photovoltaic active layer/hole transport layer/bottom electrode/substrate assembly;
(A4) Spin-coating the electron transport layer on the surface of the organic photovoltaic active layer/hole transport layer/bottom electrode/substrate assembly, and annealing at low temperature to obtain the electron transport layer/organic photovoltaic active layer/hole transport layer/bottom electrode/substrate assembly;
(A5) And depositing the top electrode on the surface of the electron transport layer/organic photovoltaic active layer/hole transport layer/bottom electrode/substrate assembly to obtain the organic solar cell.
Optionally, the substrate is selected from at least one of glass, polyimide, polyethylene terephthalate, polydimethylsiloxane, polyethylene naphthalate, polycarbonate, polyvinyl alcohol.
Optionally, the bottom electrode and the top electrode are independently selected from at least one of indium tin oxide, zinc aluminum oxide, fluorine doped tin oxide, conductive polymer, and metal.
Optionally, the organic photovoltaically active layer includes a donor material and an acceptor material.
Optionally, the donor material is selected from at least one of an organic polymeric semiconductor donor material and an organic small molecule semiconductor donor material.
Optionally, the acceptor material is selected from at least one of an organic polymer semiconductor acceptor material, an organic small molecule semiconductor acceptor material, 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, and composite material.
More preferably, the substrate material is glass.
More preferably, the bottom electrode is indium tin oxide or fluorine-doped tin oxide.
More preferably, the organic photovoltaic active layer material is selected from a blend material of an organic polymer semiconductor donor and an organic small molecule semiconductor acceptor.
More preferably, the organic photovoltaic active layer material is selected from two blending materials of an organic wide-bandgap conjugated polymer semiconductor donor material PM6 and an A-D-A type non-fullerene organic small molecule acceptor material M36 containing a benzodithiophene fused 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 organic small molecule materials: n, N' -bis [3- (dimethylamino) propyl ] perylene-3,4,9,10-tetracarboxylic acid diimide (abbreviated as PDIN).
More preferably, the top electrode material is selected from metallic electrode materials.
More preferably, the top electrode material is silver or aluminum.
Alternatively, in steps (A2) to (A4), the conditions for solution spin coating are as follows:
the spin coating parameter is 500 rpm-5000 rpm;
the glue homogenizing time is 10-120 s.
Alternatively, in steps (A2) to (A4), the conditions of the low-temperature annealing are as follows:
the temperature is 50-350 ℃;
the time is 10min to 200min.
According to a sixth aspect of the present application, there is provided a use of an organic solar cell.
The organic solar cell and/or the organic solar cell prepared by the preparation method are applied to the fields of energy and photoelectricity.
The beneficial effects that this application can produce include:
1) The double-layer composite p-type hole transport material has the advantages of high light transmittance, excellent hole transport capability, adjustable energy level structure, controllable thickness and high stability; the material combines an organic hole transport material and an inorganic hole transport material, can effectively improve the interface compatibility of a hole transport film and an organic photovoltaic active layer, and can effectively overcome the defect that an organic hole transport material PEDOT (Poly ethylene glycol ether ketone), namely PSS (Poly ethylene glycol ether ketone), is easily damaged by air water and oxygen by utilizing the high stability of a multi-element oxide. Finally, the organic solar cell realized by the invention is stable and efficient, the efficiency is up to more than 12% in a semitransparent device, the average visible light transmittance is up to more than 25%, and the practical application is expected to be promoted.
2) The preparation method of the double-layer composite p-type hole transport material has the advantages of low cost, simple and convenient process and universality popularization.
3) The organic solar cell provided by the application is efficient and stable, the photoelectric conversion efficiency of the organic solar cell reaches more than 14%, and the organic solar cell is expected to be commercially applied and has high performance.
Drawings
FIG. 1 is a schematic diagram of an OSC structure based on a NiMgO/PEDOT/PSS double-layer composite p-type hole transport material in example 1 of the present invention.
Fig. 2 is a graph of current density-voltage (J-V) characteristics of the OSC prepared in example 2 of the present invention.
FIG. 3 is a graph of the External Quantum Efficiency (EQE) spectrum of an OSC prepared in example 2 of the present invention.
FIG. 4 is a graph of the visible transmission spectrum of a translucent OSC prepared according to examples 3-5 of the present invention.
Detailed Description
The present application will be described in detail 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 all purchased commercially, wherein:
nickel acetate tetrahydrate (Ni (CH) 3 COO) 2 ·4H 2 O, 99.0%), magnesium acetate tetrahydrate (Mg (CH) 3 COO) 2 ·4H 2 O, 99.5%), 2-methoxyethanol (99.8%), and ethanolamine (99.5%) were purchased from Sigma-Aldrich;
poly (3,4-ethylenedioxythiophene): polystyrene sulfonate was purchased from alatin reagent ltd;
PBDB-T-2F was purchased from Solarmer Energy;
indium tin oxide was purchased from Shenzhen south China Hunan science and technology Limited;
n, N' -bis [3- (dimethylamino) propyl ] perylene-3,4,9,10-tetracarboxylic diimide was purchased from Suzhou nakai 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 invention, indium tin oxide is abbreviated as ITO;
the organic solar cell is abbreviated as OSC;
ternary nickel magnesium oxide is abbreviated as NiMgO;
the A-D-A type non-fullerene organic micromolecule acceptor material containing benzodithiophene condensed ring is abbreviated as M36;
PBDB-T-2F is abbreviated as PM6;
poly (3,4-ethylenedioxythiophene): polystyrene sulfonate is abbreviated PEDOT: PSS;
PSS is abbreviated as D-PEDOT;
n, N' -bis [3- (dimethylamino) propyl ] perylene-3,4,9,10-tetracarboxylic diimide is abbreviated as PDIN.
The analytical methods in the examples of the present application are as follows:
using AM 1.5G (100 mW cm) -2 ) Photo-irradiation conditions, photovoltaic performance analysis of the OSC was performed by Oriel Sol3A solar simulator (Newport) and Keithley 2400 source tables.
The light transmission performance of the translucent OSC was analyzed using a Lambda35 spectrophotometer.
The inorganic oxide or organic polymer semiconductor is divided according to the size of carrier transport capacity, the electron transport capacity of the semiconductor is obviously better than the hole transport capacity, and the semiconductor is defined as an n-type semiconductor, otherwise, the semiconductor is a p-type semiconductor.
Example 1
1. By adopting a positive device structure, the preparation process of the corresponding OSC is as follows:
(1) Preparing an organic modified inorganic double-layer composite p-type hole transport layer by adopting a solution spin coating method and a low-temperature annealing process:
step 1: selecting commercially available ITO glass (sheet resistance about 15 omega/□) as a substrate, and treating for 15min by adopting ultraviolet ozone before use;
step 2: weighing appropriate amount of Ni (CH) 3 COO) 2 ·4H 2 O and Mg (CH) 3 COO) 2 ·4H 2 Dissolving O in 2-methoxy ethanol, adding ethanolamine with the molar ratio of 1:1 to metal elements as a stabilizer, stirring for 8 hours until the solution is completely dissolved to form transparent clear liquid, and preparing to obtain 0.1mol/L ternary oxide NiMgO precursor solution; simultaneously, mixing methanol and a purchased undiluted PEDOT/PSS aqueous solution according to a mass ratio of 1:4, and stirring for 15min until the mixture is uniform to form a D-PEDOT/PSS solution;
and step 3: spin-coating the ternary oxide NiMgO precursor solution prepared in the step 2 on the ITO glass subjected to ultraviolet ozone treatment, wherein the spin-coating parameters are 3500rpm, and the spin-coating time is 50 s; after spin coating, placing the sample on a heating table at 120 ℃ for preheating treatment; then, annealing the sample in a 290 ℃ oven for 60min, and cooling the sample to room temperature to obtain a NiMgO film; then, the D-PEDOT, PSS solution is coated on the NiMgO film which is treated by ultraviolet ozone for 15min in a spinning way, the spinning parameters are 3500rpm, and the spin-coating time is 30s; after spin coating, annealing the sample in a baking oven at 140 ℃ for 30min to obtain a NiMgO/D-PEDOT/PSS double-layer composite film, thereby finally obtaining a hole transport layer/bottom electrode/substrate assembly;
(2) Preparing an organic photovoltaic active layer by adopting a solution spin coating technology:
step 1: weighing 3.2mg of each of an organic polymer semiconductor donor material PM6 and an organic small molecule semiconductor acceptor material M36, dissolving in 0.4mL of chloroform, and stirring in a nitrogen atmosphere glove box for 8 hours to obtain a uniformly mixed PM6: M36 organic photovoltaic active layer solution;
and 2, step: spin-coating the PM6: M36 blending solution obtained in the step 1 on the surface of an organic modified inorganic double-layer composite p-type hole transport film sample in a nitrogen atmosphere glove box, setting the spin-coating parameters to be 3500rpm, and setting the glue homogenizing time to be 45s; after the spin coating is finished, putting the spin-coated sample on a heating table at 90 ℃ for annealing for 5min to obtain an organic photovoltaic active layer/hole transport layer/bottom electrode/substrate assembly;
(3) Preparing an electron transport layer by adopting a solution spin coating technology:
step 1: weighing 5mg of PDIN, dissolving the PDIN in 2.5mL of methanol, and dissolving the PDIN in a glove box in a nitrogen atmosphere to obtain a clear and uniform solution of the electron transport layer material;
step 2: spin-coating the PDIN methanol solution obtained in the step 1 on the surface of the organic photovoltaic active layer film in a nitrogen atmosphere glove box, setting the spin-coating parameters to be 3300rpm, and setting the spin-coating time to be 30s to obtain an electron transport layer/organic photovoltaic active layer/hole transport layer/bottom electrode/substrate assembly;
(4) Preparing a metal top electrode by adopting a vacuum thermal evaporation method:
preparing metal electrode on the electron transmission layer by conventional vacuum thermal evaporation method and prefabricated structure mask plate with thermal evaporation vacuum degree of about 1 × 10 -4 Pa, current of 30-50A, speed of
The prepared top electrode is an Ag electrode, and the thickness of the electrode is 100nm, so that the organic solar cell is prepared.
2. The schematic diagram of the prepared OSC device with the structure of glass/ITO/NiMgO/D-PEDOT: PSS/PM6: M36/PDIN/Ag is shown in figure 1.
Example 2
(1) The difference to the preparation scheme of the OSC of example 1 is that the organic p-type hole transport material was prepared using undiluted PEDOT: PSS aqueous solution.
(2) Performance testing of OSC devices:
in AM 1.5GUnder irradiation conditions, the photovoltaic performance of the organic solar cell is tested by an Oriel Sol3A solar simulator (Newport) and a Keithley 2400 semiconductor tester, the J-V characteristic curve of a device sample is shown in figure 2, and the EQE spectrum of the device is shown in figure 3. Wherein the effective area of the device is 4mm 2 The test starting voltage was-0.2V and the termination voltage was 1.0V. As can be seen from FIG. 2, the open-circuit voltage of the device to be tested was 0.90V, and the short-circuit current density was 21.98mA cm -2 The fill factor was 67.47% and the PCE of the final device was 13.24%. As can be seen from fig. 3, the device has a higher EQE value in the visible region, indicating that there is an efficient photo-to-electrical conversion process in the OSC operation. These test results show that OSC based on a NiMgO/PEDOT: PSS double layer composite p-type hole transport layer have good photovoltaic performance.
Examples 3 to 5
(1) The difference from the preparation procedure of the OSC in example 1 is that the top electrode Ag film thickness is 10nm, 15nm and 20nm, respectively.
(2) Testing the light transmission performance of the OSC device:
samples of the prepared OSC device were tested for light transmission using a Lambda35 spectrophotometer, and the corresponding visible light transmission spectra curves for the series of semi-transparent devices are shown in fig. 4, where the spectral test range is 380-780nm. It can be seen that the average visible light transmittance of the devices for the OSC prepared using three different top electrode Ag film thicknesses of 10nm, 15nm and 20nm is 9.39%, 12.81% and 14.44%, respectively. PSS organic modified inorganic double-layer composite p-type hole transport layer OSC based on NiMgO/PEDOT shows good potential as a high-performance organic photovoltaic semitransparent device.
Examples 6 to 14
The OSC preparation processes of examples 6 to 14 and example 1 are shown in table 1, and the portions not described are the same as example 1.
TABLE 1
a) The translucent OSC uses 15nm Ag and 20nm MoO vapor deposited 3 Together as a top electrode (Ag/MoO) 3 )；
b) The average visible light transmittance of the translucent OSC in the wavelength range of 380 to 780nm is 25.84%.
Performance tests were performed on the OSC devices obtained in examples 6 to 14, and the test conditions were consistent with those of examples 1 and 2, and it was found that the obtained OSCs each obtained high photoelectric conversion efficiency, having good photovoltaic performance similar to those of examples 1 and 2.
Although the present invention has been described with reference to a few preferred embodiments, it should be understood that various changes and modifications can be made without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A double-layer composite p-type hole transport material is characterized in that the double-layer composite p-type hole transport material comprises a multi-element oxide inorganic material film and an organic p-type hole transport material film;
the multi-element oxide inorganic material film and the organic p-type hole transport material film are mutually attached;
the multi-element oxide inorganic material film comprises an alkaline earth metal element and NiO;
the alkaline earth metal element is doped into NiO.
2. The double-layer composite p-type hole transport material according to claim 1, wherein the surface of the multi-element oxide inorganic material thin film is flat and dense;
preferably, the root-mean-square roughness of the surface of the multi-element oxide inorganic material film is 0.5 nm-10 nm;
preferably, the root-mean-square roughness of the surface of the multi-element oxide inorganic material film is 1 nm-5 nm;
preferably, the thickness of the multi-element oxide inorganic material film is 5nm to 100nm;
preferably, the thickness of the multi-element oxide inorganic material film is 10 nm-50 nm;
preferably, the surface of the organic p-type hole transport material film is flat and dense;
preferably, the root-mean-square roughness of the surface of the organic p-type hole transport material film is 0.5 nm-5 nm;
preferably, the root-mean-square roughness of the surface of the organic p-type hole transport material film is 1 nm-2 nm;
preferably, the thickness of the organic p-type hole transport material film is 5nm to 200nm,
preferably, the thickness of the organic p-type hole transport material thin film is 20nm to 100nm.
3. The double-layer composite p-type hole transport material according to claim 1, wherein the molar content of the alkaline earth metal element in the multi-element oxide inorganic material thin film accounts for 5-50% of the total metal element;
preferably, in the film of the multi-element oxide inorganic material, the molar content of the alkaline earth metal element accounts for 10 to 40 percent of the total metal element.
4. The double-layer composite p-type hole transport material according to claim 1, wherein in the multi-element oxide inorganic material thin film, the alkaline earth metal element is at least one selected from beryllium, magnesium, calcium, strontium and barium;
preferably, the organic p-type hole transport material is selected from poly (3,4-ethylenedioxythiophene): polystyrene sulfonate, polyaniline, polypyrrole, poly [ bis (4-phenyl) (2,4,6-trimethylphenyl) amine ], 2,2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene.
5. The method for preparing a double-layer composite p-type hole transport material according to any one of claims 1 to 4, comprising the steps of:
(S1) mixing a mixed solution containing soluble alkaline earth metal salt, soluble nickel salt, a stabilizer and a solvent I to obtain a precursor solution of the multi-element oxide inorganic material film;
(S2) adding a solvent II into the dispersion liquid of the organic p-type hole transport material to obtain a diluted dispersion liquid;
(S3) forming a film on or under the film formed by the diluted dispersion by using a solution processing film-forming method.
6. The method according to claim 5, wherein in the step (S1), the soluble alkaline earth metal salt is at least one selected from the group consisting of magnesium acetate, calcium acetate and barium chloride;
preferably, in the step (S1), the soluble nickel salt is selected from at least one of nickel acetate, nickel chloride and nickel nitrate;
preferably, in the step (S1), the stabilizer is at least one selected from the group consisting of ethanolamine, diethanolamine, isopropanolamine;
preferably, in the step (S1), the solvent i is at least one selected from water, methanol, ethanol, 2-methoxyethanol, and isopropanol;
preferably, in the step (S1), the molar ratios of the soluble alkaline earth metal salt, the soluble nickel salt, the stabilizer and the entire metal element are 5% to 50%, 50% to 95%, and 50% to 200%, respectively;
the soluble alkaline earth metal salt is metered in terms of the amount of its species of alkaline earth metal element; the soluble nickel salt is measured as the amount of the material of the nickel element;
preferably, in the step (S1), the concentration of the precursor solution is 0.05 mol/L-0.5 mol/L;
preferably, in the step (S2), the mass of the solvent ii is 20% to 50% of the mass of the diluted dispersion liquid;
preferably, in the 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 alcoholic solvents;
preferably, in the step (S3), the solution processing film-forming method includes solution spin coating and then low-temperature annealing;
preferably, in the step (S3), the conditions of the solution spin coating are as follows:
the spin coating parameter is 500 rpm-5000 rpm;
the glue homogenizing time is 10-120 s;
preferably, in the step (S3), the conditions of the low temperature annealing are as follows:
the temperature is 50-350 ℃;
the time is 10min to 200min.
7. Use of the double-layer composite p-type hole transport material according to any one of claims 1 to 4 and/or the double-layer composite p-type hole transport material obtained by the preparation method according to any one of claims 5 to 6 in an organic solar cell.
8. An organic solar cell is characterized by comprising a substrate, a bottom electrode, a hole transport layer, an organic photovoltaic active layer, an electron transport layer and a top electrode;
the hole transport layer is selected from the double-layer composite p-type hole transport material according to any one of claims 1 to 4 and/or the double-layer composite p-type hole transport material obtained by the preparation method according to any one of claims 5 to 6.
9. A preparation method of an organic solar cell is characterized by comprising the following steps:
(A1) Depositing the bottom electrode on the substrate to obtain a bottom electrode/substrate assembly;
(A2) Spin-coating the hole transport layer on the surface of the bottom electrode/substrate assembly, and annealing at low temperature to obtain the hole transport layer/bottom electrode/substrate assembly;
(A3) Spin-coating the organic photovoltaic active layer to the surface of the hole transport layer/bottom electrode/substrate assembly, and annealing at low temperature to obtain the organic photovoltaic active layer/hole transport layer/bottom electrode/substrate assembly;
(A4) Spin-coating the electron transport layer on the surface of the organic photovoltaic active layer/hole transport layer/bottom electrode/substrate assembly, and annealing at low temperature to obtain the electron transport layer/organic photovoltaic active layer/hole transport layer/bottom electrode/substrate assembly;
(A5) Depositing the top electrode on the surface of the electron transport layer/organic photovoltaic active layer/hole transport layer/bottom electrode/substrate assembly to obtain the organic solar cell;
preferably, the substrate is selected from at least one of glass, polyimide, polyethylene terephthalate, polydimethylsiloxane, polyethylene naphthalate, polycarbonate, polyvinyl alcohol;
preferably, the bottom electrode and the top electrode are independently selected from at least one of indium tin oxide, zinc aluminum oxide, fluorine-doped tin oxide, conductive polymer and metal;
preferably, the organic photovoltaically active layer comprises a donor material and an acceptor material;
preferably, the donor material is selected from at least one of an organic polymeric semiconductor donor material and an organic small molecule semiconductor donor material;
preferably, the acceptor material is selected from at least one of an organic polymer semiconductor acceptor material, an organic small molecule semiconductor acceptor material, 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 and composite material;
preferably, in steps (A2) to (A4), the conditions for solution spin coating are as follows:
the spin coating parameter is 500 rpm-5000 rpm;
the glue homogenizing time is 10-120 s;
preferably, in steps (A2) to (A4), the conditions of the low-temperature annealing are as follows:
the temperature is 50-350 ℃;
the time is 10min to 200min.
10. Use of the organic solar cell according to claim 8 and/or the organic solar cell obtained by the method according to claim 9 in the fields of energy and photovoltaics.
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