CN113571642A - Organic photovoltaic element - Google Patents
Organic photovoltaic element Download PDFInfo
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- CN113571642A CN113571642A CN202010354077.4A CN202010354077A CN113571642A CN 113571642 A CN113571642 A CN 113571642A CN 202010354077 A CN202010354077 A CN 202010354077A CN 113571642 A CN113571642 A CN 113571642A
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/451—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising a metal-semiconductor-metal [m-s-m] structure
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/81—Electrodes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
- H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
An organic photovoltaic element comprises a first electrode, an electron transport layer, a photoactive layer, a hole transport unit and a second electrode. The photoactive layer contains an electron donor material and an electron acceptor material. The hole transmission unit comprises a hole transmission layer and an electron blocking layer, the electron blocking layer contains an electron blocking material, and the energy of the lowest unoccupied molecular orbital region of the electron blocking material is higher than that of the electron acceptor material. The organic photovoltaic element can reduce recombination quenching of electrons at an electrode interface, and further can improve energy conversion efficiency.
Description
Technical Field
The present invention relates to an organic photovoltaic device, and more particularly, to an organic photovoltaic device including an electron blocking layer.
Background
The organic photovoltaic element (organic solar cell) has the advantages of light weight, low cost, flexibility, solution processing and the like, the element structure is easy to simplify and fast, the important application potential is shown, and great attention is paid to the academic world and the industrial world. Compared with the traditional inorganic photovoltaic element, the existing organic photovoltaic element has unique advantages and applied scenes. The material of the optical active layer of the organic photovoltaic element and the mass production technology thereof can be coated by solution at room temperature, so that the large-area process can be carried out, and the material can also be applied to flexible substrates.
Currently, the industry uses coating technology for large area processes to prepare organic photovoltaic devices, which mainly include substrate/Indium Tin Oxide (ITO) thin film/electron transport layer/photoactive layer/hole transport layer/silver. In terms of the substrate/ITO thin film/electron transport layer/photoactive layer/hole transport layer/silver element, the electron transport layer and the hole transport layer usually use metal oxide as material, for example, the electron transport layer uses zinc oxide by high temperature process, while the hole transport layer uses molybdenum trioxide by vacuum evaporation, however, the high temperature process is not suitable for large area process when mass production is performed; in addition, the vacuum vapor deposition is limited by cost, and is not suitable for mass production, and such a preparation method is a great challenge for mass production of organic photovoltaic devices in the industry. Currently, the industry usually uses polymer PEDOT: PSS (poly (3,4-ethylenedioxythiophene): poly (styrene sulfonate)) as hole transport material, which can be coated and is suitable for large-area process to solve the problem of mass production.
In the photoactive layer of the organic photovoltaic element, the electron donor material has a lower Highest Occupied Molecular Orbital (HOMO) domain, and can achieve a higher open-circuit voltage by matching with a suitable electron acceptor material. However, in the devices mainly comprising the substrate, the Indium Tin Oxide (ITO) film, the electron transport layer, the photoactive layer, the PEDOT: PSS, and the silver, the mismatch of the PEDOT: PSS energy levels causes the recombination quenching of electrons at the electrode interface, and further the device has a leakage, which results in the loss of open circuit voltage and fill factor, and finally affects the energy conversion efficiency of the organic photovoltaic device.
Therefore, how to improve the conventional organic photovoltaic device to reduce the recombination quenching of electrons at the electrode interface, and further improve the energy conversion efficiency of the organic photovoltaic device becomes a target of current research.
Disclosure of Invention
Therefore, an object of the present invention is to provide an organic photovoltaic device capable of reducing recombination quenching of electrons at an electrode interface, thereby improving energy conversion efficiency.
Therefore, the organic photovoltaic device of the present invention includes a first electrode, an electron transport layer, a photoactive layer, a hole transport unit, and a second electrode.
The electron transport layer is located on the first electrode.
The photoactive layer is located on a side of the electron transport layer opposite the first electrode and includes an electron donor material and an electron acceptor material.
The hole transmission unit is positioned on one side of the optical active layer opposite to the electron transmission layer and comprises a hole transmission layer and an electron blocking layer, the electron blocking layer contains an electron blocking material, and the energy of a Lowest Unoccupied Molecular Orbital (LUMO) of the electron blocking material is higher than that of the LUMO of the electron acceptor material.
The second electrode is located on a side of the hole transport unit opposite the photoactive layer.
The invention has the following effects: since the organic photovoltaic device of the present invention includes the electron blocking layer, and the energy of the Lowest Unoccupied Molecular Orbital (LUMO) of the electron blocking material is higher than the energy of the Lowest Unoccupied Molecular Orbital (LUMO) of the electron acceptor material, the organic photovoltaic device of the present invention can reduce recombination quenching of electrons at the electrode interface, thereby improving the energy conversion efficiency.
In addition, it is added that the material used for the hole transport unit of the organic photovoltaic element of the present invention can be applied by being formulated into a solution, and thus is also suitable for a process of large-area and roll-to-roll production.
The present invention will be described in detail below:
the invention relates to an organic photovoltaic element, which comprises a first electrode, an electron transport layer, a photoactive layer, a hole transport unit and a second electrode.
Preferably, the material of the first electrode is, for example, but not limited to, Indium Tin Oxide (ITO).
The electron transport layer is located on the first electrode.
Preferably, the material of the electron transport layer is, for example, but not limited to, Zwitterionic modified polyethylene imine (zwitterion Polyethyleneimine).
The photoactive layer is located on a side of the electron transport layer opposite the first electrode and includes an electron donor material and an electron acceptor material.
Preferably, the electron donor material has a structure such as, but not limited to, the following:
Preferably, the electron acceptor material is, for example, but not limited to
The hole transport unit is positioned on one side of the light active layer opposite to the electron transport layer and comprises a hole transport layer and an electron blocking layer.
Preferably, the hole transport layer is located on a side of the photoactive layer opposite the electron transport layer, and the electron blocking layer is located on a side of the hole transport layer opposite the photoactive layer.
Preferably, the electron blocking layer is located on a side of the photoactive layer opposite the electron transport layer, and the hole transport layer is located on a side of the electron blocking layer opposite the photoactive layer.
Preferably, the hole transport layer contains a hole transport material, and the hole transport material has an electrical conductivity higher than 0.01S/cm. More preferably, the hole transport material has a conductivity in the range of 0.1 to 300S/cm.
Still more preferably, the hole transport material comprises the polymer PEDOT PSS. PSS, such as but not limited to Al 4083, HTL Solar or PH1000 from Heraeus, Germany.
Still more preferably, the hole transport layer further comprises an additive selected from the group consisting of dimethylsulfoxide, ethylene glycol, or a combination thereof.
Still more preferably, the additive is present in an amount ranging from 0.01 to 8 wt% based on 100 wt% (wt%) of the total weight of the components contained in the hole transport layer.
Still more preferably, the hole transport layer further contains a surfactant. Such surfactants are, for example, but are not limited to, fluorosurfactants (e.g., DuPont model number FSO-100, FSN-100, FS-300), silicon-containing surfactants (e.g., BYK model number BYK-306, BYK-323, BYK-333), polyols (e.g., D-Glucose, D-Sucrose, D-Maltose), or combinations of the foregoing.
More preferably, the amount of the surfactant is 0.01 to 5 wt% based on 100 wt% of the total amount of the components contained in the hole transport layer.
Preferably, the hole transport layer comprises a hole transport material and the Highest Occupied Molecular Orbital (HOMO) of the hole transport material has a higher energy than the Highest Occupied Molecular Orbital (HOMO) of the electron donor material.
More preferably, the energy of the Highest Occupied Molecular Orbital (HOMO) of the hole transporting material is between the energy of the Highest Occupied Molecular Orbital (HOMO) of the electron donor material and the work function (work function) of the second electrode.
Preferably, the thickness of the hole transport layer is in the range of 5 to 200 nm. More preferably, the thickness of the hole transport layer is in the range of 20 to 100 nm.
The electron blocking layer contains an electron blocking material, and the electron blocking material has a higher energy of a Lowest Unoccupied Molecular Orbital (LUMO) than that of the electron acceptor material.
Preferably, the energy difference between the Lowest Unoccupied Molecular Orbital (LUMO) of the electron blocking material and the Lowest Unoccupied Molecular Orbital (LUMO) of the electron acceptor material is greater than 1.0 eV.
More preferably, the electron blocking material is a triarylamine derivative. The triarylamine derivative refers to a small molecule compound or a high molecule polymer having a triarylamine structure. Still more preferably, the electron blocking material is a triarylamine derivative having one of the following structures:
wherein n is an integer greater than 1.
Preferably, the thickness of the electron blocking layer is in the range of 2 to 100 nm. More preferably, the thickness of the electron blocking layer is 5 to 50 nm.
The second electrode is located on a side of the hole transport unit opposite the photoactive layer.
Preferably, the material of the second electrode is, for example, but not limited to, silver.
Preferably, the organic photovoltaic device of the present invention further comprises a substrate. The substrate is located on the side of the first electrode opposite to the electron transport layer.
More preferably, the substrate is made of a material such as, but not limited to, glass.
Drawings
Other features and effects of the present invention will be apparent from the embodiments with reference to the accompanying drawings, in which:
FIG. 1 is a schematic side view illustrating the structure of a first embodiment of the organic photovoltaic element of the present invention;
FIG. 2 is a schematic side view illustrating the structure of a second embodiment of the organic photovoltaic element of the present invention; and
FIG. 3 is a graph showing current density-voltage curves of the organic photovoltaic devices of comparative examples and examples 1 to 5.
Wherein the reference numerals are as follows:
11 first electrode
12 electron transport layer
13 photoactive layer
14 hole transport unit
141 hole transport layer
142 electron blocking layer
15 second electrode
16 base plate
Detailed Description
Referring to fig. 1, a structure of a first embodiment of the organic photovoltaic device of the present invention is shown. The organic photovoltaic device comprises a first electrode 11, an electron transport layer 12, a photoactive layer 13, a hole transport unit 14 and a second electrode 15.
The electron transport layer 12 is located on the first electrode 11.
The photoactive layer 13 is located on the side of the electron transport layer 12 opposite the first electrode 11.
The hole transporting unit 14 is located on the side of the photoactive layer 13 opposite to the electron transporting layer 12, and includes a hole transporting layer 141 and an electron blocking layer 142. The hole transport layer 141 is located on the side of the photoactive layer 13 opposite to the electron transport layer 12, and the electron blocking layer 142 is located on the side of the hole transport layer 141 opposite to the photoactive layer 13.
The second electrode 15 is located on the side of the hole transport unit 14 opposite to the photoactive layer 13.
The organic photovoltaic device of the present invention further comprises a substrate 16 disposed on a side of the first electrode 11 opposite to the electron transport layer 12.
It should be noted that the positions of the hole transport layer 141 and the electron blocking layer 142 of the hole transport unit 14 are not limited to those of the first embodiment, and referring to fig. 2, in the second embodiment, the electron blocking layer 142 is located on the side of the photoactive layer 13 opposite to the electron transport layer 12, and the hole transport layer 141 is located on the side of the electron blocking layer 142 opposite to the photoactive layer 13.
< examples 1 to 5>
Organic photovoltaic element
The organic photovoltaic devices of examples 1-5 are shown in FIG. 1, and are made from the electron donor material and the electron acceptor material in Table 1, the electron blocking material in Table 2, and the following methods:
the patterned Indium Tin Oxide (ITO) glass (12 Ω/□) was sequentially cleaned in an ultrasonic vibration bath for 15min with a cleaning agent, deionized water, acetone, and isopropyl alcohol, then cleaned by ultrasonic vibration, and then surface-treated in a UV-ozone cleaner for 20min to form the substrate 16 (glass) and the first electrode 11 (ITO).
The electron transport layer 12 is formed by coating Zwitterionic Polyethyleneimine (zwitterion Polyethyleneimine) on the first electrode 11, placing the coated first electrode on a heating plate, and baking the coated first electrode at 120 ℃ for 5min.
The electron donor material (10mg) and the electron acceptor material (12mg) listed in Table 1 were mixed with a solvent of o-xylene (1mL) to prepare a photoactive layer solution. The photoactive layer solution was coated on the electron transport layer 12 and placed on a hot plate, and after removing the solvent, a photoactive layer 13 having a thickness of about 100nm was formed.
Conducting polymers of the type Clevios from Heraeus, GermanyTMA solution of hole transport layer having a PH1000(HOMO about-4.90 eV, conductivity 850S/cm) was coated on the photoactive layer 13 and placed on a hot plate, and baked at 100 ℃ for 5min, to form the hole transport layer 141 having a thickness of about 30 nm.
An electron blocking material (1.5mg) having the chemical structure listed in table 2 was mixed with toluene (1mL), a solvent, to form an electron blocking layer solution. The electron blocking layer solution is coated on the hole transport layer 141 and baked at 100 ℃ for 2min to form the electron blocking layer 142 with a thickness of about 10 nm.
The above-obtained element was introduced into a vacuum chamber at 1.0X10-6this second electrode 15 was formed to a thickness of about 100nm by evaporating silver metal (work function-4.70 eV) under torr.
Finally, Epoxy resin of Epoxy Technology company model EPOTEKOG116-31 was coated on the element, a cover glass was covered on the element, and after laminating the element, the Epoxy resin was cured under a 365nm lamp source to obtain the organic photovoltaic elements of examples 1 to 5.
TABLE 1
The weight average molecular weight and the number average molecular weight were measured by gel permeation chromatography.
TABLE 2
PDI: polydispersity index, molecular weight distribution index, PDI ═ Mw/Mn
< comparative example >
Organic photovoltaic element
The organic photovoltaic element of the comparative example is similar to the organic photovoltaic elements of examples 1 to 5, except that the hole transport unit of the organic photovoltaic element of the comparative example does not include an electron blocking layer.
< organic photovoltaic element characteristics test >
The measurement region of the organic photovoltaic device is defined as 0.04cm by the metal mask2. Keithley 2400 as a power supply, controlled by a Lab-View program at a light intensity of 100mW/cm2The electrical property of the organic photovoltaic device was measured under irradiation of simulated am1.5g sunlight (SAN-EI XES-40S3), and recorded by a computer program to obtain a current-voltage curve (see fig. 3).
Table 3 shows the characteristics of the organic photovoltaic devices of comparative examples and examples 1 to 5, VocRepresents an open circuit voltage (J)scRepresents short-circuit current (short-circuit current), FF represents fill factor (fill factor), and PCE represents energy conversion efficiency (energy conversion efficiency). Referring also to FIG. 3, the short circuit current and the open circuit voltage are the intercepts of the current density-voltage curves on the Y-axis and the X-axis, respectively. In addition, the fill factor is a value obtained by dividing an area that can be plotted in a curve by a product of the short-circuit current and the open-circuit voltage, and when three values of the open-circuit voltage, the short-circuit current, the fill factor, and the like are divided by the irradiated light, the energy conversion efficiency can be obtained, and a higher value is preferable.
TABLE 3
From the results of Table 3, it was found that the open circuit voltage was 0.66V and the current density was 23.52mA/cm in the comparative example without the electron blocking layer2The fill factor was 57, and the energy conversion efficiency was 8.8%. Compared with the comparative examples, the organic photovoltaic devices of examples 1 to 5 (with the electron blocking layer) have higher open circuit voltage, fill factor and energy conversion efficiency.
As can be seen from the foregoing description, in the organic photovoltaic devices (examples 1 to 5) according to the present invention, since the organic photovoltaic device includes the electron blocking layer and the energy of the Lowest Unoccupied Molecular Orbital (LUMO) of the electron blocking material (examples 1 to 5 are respectively-2.13 eV, -2.32eV, -2.48eV, -2.66eV, -2.42eV) is higher than the energy of the Lowest Unoccupied Molecular Orbital (LUMO) of the electron acceptor material (-4.10eV), the open-circuit voltage can be increased, the recombination quenching of electrons at the electrode interface can be reduced, and the occurrence of the leakage current in the device can be avoided, and the fill factor can be increased, thereby increasing the energy conversion efficiency of the organic photovoltaic device. In addition, in examples 1 to 5, the energy difference between the lowest unoccupied molecular orbital of the electron blocking material and the lowest unoccupied molecular orbital of the electron acceptor material was 1.97eV (-2.13 eV-4.10 eV), 1.78eV, 1.62eV, 1.44eV, and 1.68eV, respectively, and the energy difference was greater than 1.0 eV. The hole-transporting layer contains a hole-transporting material, and the highest occupied molecular orbital energy of the hole-transporting material (pH 1000) (-4.90eV) is higher than the highest occupied molecular orbital energy of the electron-donor material (Table one) (-5.50 eV). The energy of the highest occupied molecular orbital of the hole-transporting material (pH 1000 (-4.90eV) was between the energy of the highest occupied molecular orbital of the electron donor material (Table one (-5.50eV) and the work function of the second electrode (silver (-4.70 eV)).
In summary, since the organic photovoltaic device of the present invention includes the electron blocking layer, and the energy of the Lowest Unoccupied Molecular Orbital (LUMO) of the electron blocking material is higher than the energy of the Lowest Unoccupied Molecular Orbital (LUMO) of the electron acceptor material, the organic photovoltaic device of the present invention can reduce recombination quenching of electrons at the electrode interface, and further can improve the energy conversion efficiency, thereby achieving the object of the present invention.
However, the above description is only an example of the present invention, and the scope of the present invention should not be limited thereby, and all simple equivalent changes and modifications made according to the claims and the contents of the patent specification are still included in the scope covered by the present invention.
Claims (10)
1. An organic photovoltaic element comprising:
a first electrode;
an electron transport layer on the first electrode;
a photoactive layer on a side of the electron transport layer opposite the first electrode and comprising an electron donor material and an electron acceptor material;
the hole transmission unit is positioned on one side of the optical active layer opposite to the electron transmission layer and comprises a hole transmission layer and an electron blocking layer, the electron blocking layer contains an electron blocking material, and the energy of the lowest unoccupied molecular orbital region of the electron blocking material is higher than that of the lowest unoccupied molecular orbital region of the electron acceptor material; and a second electrode located on the opposite side of the hole transport unit from the photoactive layer.
2. The organic photovoltaic element of claim 1, wherein the energy difference between the lowest unoccupied molecular orbital of the electron blocking material and the lowest unoccupied molecular orbital of the electron acceptor material is greater than 1.0 eV.
3. The organic photovoltaic device of claim 2, wherein the electron blocking material is a triarylamine derivative.
4. The organic photovoltaic device of claim 3, wherein the electron blocking material is a triarylamine derivative having one of the following structures:
5. The organic photovoltaic element according to claim 1, wherein the hole transport layer comprises a hole transport material and the hole transport material has an electrical conductivity higher than 0.01S/cm.
6. The organic photovoltaic device according to claim 5, wherein the hole transport material has an electrical conductivity ranging from 0.1 to 300S/cm.
7. The organic photovoltaic device according to claim 6, wherein the hole transport material comprises the polymer PEDOT PSS.
8. The organic photovoltaic element of claim 7, wherein the hole transport layer further comprises an additive selected from dimethylsulfoxide, ethylene glycol, or a combination thereof.
9. The organic photovoltaic element of claim 1, wherein the hole transport layer comprises a hole transport material and the energy of the highest occupied molecular orbital of the hole transport material is higher than the energy of the highest occupied molecular orbital of the electron donor material.
10. The organic photovoltaic element of claim 9, wherein the energy of the highest occupied molecular orbital of the hole transporting material is between the energy of the highest occupied molecular orbital of the electron donor material and the work function of the second electrode.
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