CN111584718B - Efficient organic solar cell and preparation method thereof - Google Patents

Efficient organic solar cell and preparation method thereof Download PDF

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CN111584718B
CN111584718B CN202010533221.0A CN202010533221A CN111584718B CN 111584718 B CN111584718 B CN 111584718B CN 202010533221 A CN202010533221 A CN 202010533221A CN 111584718 B CN111584718 B CN 111584718B
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solar cell
organic solar
layer
buffer layer
high efficiency
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CN111584718A (en
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赖文勇
杜斌
刘晨
汪洋
耿海港
牛坚
黄维
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Nanjing University of Posts and Telecommunications
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Nanjing University of Posts and Telecommunications
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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
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • 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
    • 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
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/211—Fullerenes, e.g. C60
    • H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
    • 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

The invention discloses a high-efficiency organic solar cell and a preparation method thereof, wherein the organic solar cell is of an inverted structure and sequentially comprises the following components from bottom to top: the device comprises a substrate layer, a transparent conductive cathode, a cathode buffer layer, an optical activity layer, an anode buffer layer and a metal anode; wherein the photoactive layer consists of a polymer electron donor, an electron acceptor and an amphiphilic small molecule additive. The invention adopts a novel amphiphilic micromolecule additive which is added into an active layer of an organic solar cell according to a certain weight ratio to assist in improving the photoelectric conversion performance of the organic solar cell. The amphiphilic micromolecule additive is used for regulating and controlling the micro morphology of the active layer, so that the active layer is orderly crystallized, pi-pi stacking of the donor and acceptor is promoted, a network interpenetrating microstructure is formed, exciton separation and charge transmission are facilitated, and meanwhile, the stability of the device is effectively improved. The photoelectric conversion efficiency of the organic solar cell prepared by the method is improved by about 7-22%.

Description

Efficient organic solar cell and preparation method thereof
Technical Field
The invention relates to an organic solar cell and a preparation method thereof, in particular to a method for applying an amphiphilic micromolecule additive to a photoactive layer, and belongs to the technical field of photovoltaics.
Background
Bulk Heterojunction (BHJ) Polymer Solar Cells (PSCs) are a promising green renewable energy technology, and have gradually become a hotspot of research because of their advantages of light weight, low cost, simple preparation, large-area preparation of flexible solar cells, and the like. Currently, the highest photoelectric Power Conversion Efficiency (PCE) of single junction cells has exceeded 17%. However, compared with inorganic solar cells, the disadvantages of low energy conversion efficiency, short lifetime, and poor stability become major factors that restrict commercialization thereof. The morphology of the active layer plays an important role in the BHJ organic solar cell, and how to accurately regulate and control the heterojunction phase separation and the microscopic film crystal size become important factors limiting the efficiency and stability of the device for the receptor molecular orientation.
In order to overcome these problems and realize a high-efficiency organic solar cell, an effective method is to introduce an additive into the active layer to effectively control the morphology of the thin film. In general, solvent additives, solid additives are included to manipulate the active layer micro-topography to enhance cell performance. Solvent additives can improve device efficiency, but are poor in repeatability and stability; the solid additive only has a positive effect on a part of active layer materials and has no universality. Therefore, how to select the efficient additive is the key to improve the photoelectric conversion efficiency of the organic solar cell.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a high-efficiency organic solar cell and a preparation method thereof, so as to solve the problems of poor stability and low efficiency of the organic solar cell.
In order to achieve the purpose, the invention adopts the technical scheme that:
the utility model provides a high-efficient organic solar cell, this organic solar cell is the inversion structure, and from the bottom up is in proper order: the device comprises a substrate layer, a transparent conductive cathode, a cathode buffer layer, an optical activity layer, an anode buffer layer and a metal anode; wherein the photoactive layer consists of a polymer electron donor, an electron acceptor and an amphiphilic small molecule additive.
Preferably, the amphiphilic small molecule additive is a non-ionic surfactant, preferably dodecyl glyceryl acetate DGI.
Preferably, the weight ratio of the polymer electron donor to the electron acceptor to the amphiphilic small molecule additive in the photoactive layer is 1:1: (0-0.2).
Preferably, the electron donor material is a narrow-band polymer electron donor, and is preferably a polythiophene derivative.
Preferably, the electron acceptor material is a fullerene derivative or a small molecule acceptor.
Preferably, the anode buffer layer is made of a materialIs an organic compound or metal oxide with hole transport capability or electron blocking capability, preferably molybdenum oxide MoO 3 Aluminum-doped zinc oxide AZO, zinc oxide ZnO and titanium dioxide TiO 2 One or more of (a); the thickness of the anode buffer layer is 1-200 nm.
Preferably, the cathode buffer layer material is an organic compound or a metal oxide with electron transport capability or hole blocking capability, such as zinc oxide (ZnO), and the thickness of the cathode buffer layer is 1-200 nm.
Preferably, the substrate layer material is glass or a transparent polymer, and the transparent polymer material is one or more of polyethylene, polymethyl methacrylate, polycarbonate, polyurethane, polyphthalamide, vinyl chloride-vinyl acetate resin or polyacrylic acid.
Preferably, the transparent conductive cathode is a conductive material transparent or semitransparent in a visible light region, and has a light transmittance of more than 50%.
Preferably, the metal anode material is one of gold, silver, platinum, copper and aluminum.
A preparation method of a high-efficiency organic solar cell comprises the following steps: cleaning a substrate with the surface roughness less than 1nm and consisting of a substrate layer and a transparent conductive cathode, and drying by using nitrogen after cleaning; rotationally coating a cathode buffer layer on the surface of the transparent conductive cathode, and carrying out thermal annealing; preparing an optical active layer on the cathode buffer layer by adopting spin coating; evaporating an anode buffer layer on the surface of the optical active layer; and evaporating a metal anode on the anode buffer layer.
Has the beneficial effects that: according to the invention, the amphiphilic micromolecular additive is added into the active layer to regulate and control the shape of the active layer micro-film, so that the performance of the device is improved. The device prepared by the method has good active layer appearance, and can realize the preparation of high-efficiency photovoltaic devices.
Compared with the prior art, the stable and efficient organic solar cell provided by the invention has the following advantages:
1) the amphiphilic micromolecular additive self-assembled network laminated structure induces the micromolecular receptor to crystallize, strengthens pi-pi accumulation among molecules of the donor receptor, induces the molecules of the receptor to be biased to face-to-face orientation, and the series of actions promote the molecular mobility together, reduces the carrier recombination among molecules and in molecules, obviously improves the short-circuit current and further improves the efficiency of a device;
2) the self-assembly time of the amphiphilic micromolecule additive is short, so that the amphiphilic micromolecule additive is limited and plasticized to a receptor phase to separate in a short time, the shape stability of an active layer is improved, and the stability of a device is improved;
3) the amphiphilic small molecule additive has universality. The network layered self-assembly structure not only can obviously regulate and control non-fullerene receptors, but also has good regulation and control effect on fullerene receptors.
Drawings
FIGS. 1a to 1f show the polymer electron donor materials PBDB-TF and PBDB-T selected for the active layer in examples 2-7; electron acceptor material IT-4F, PC 71 BM, ITIC; and the molecular structure of the amphiphilic micromolecular additive DGI;
FIG. 2 is a schematic structural diagram of a high efficiency organic solar cell device of example 1;
FIG. 3 shows AM1.5 (intensity 100 mW/cm) for the devices described in examples 2-7 2 ) Current density-voltage characteristic curve under irradiation.
Detailed Description
The invention is further described with reference to the following figures and examples. The present invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the specific material ratios, process conditions and results thereof described in the examples are illustrative only and should not be taken as limiting the invention as detailed in the claims.
Example 1
A high-efficiency organic solar cell, as shown in FIG. 2, adopts an inversion structure, which is from bottom to top: the device comprises a substrate layer, a transparent conductive cathode, a cathode buffer layer, an optical active layer, an anode buffer layer and a metal anode; wherein, amphiphilic micromolecular additive is introduced into the photoactive layer, and the photoactive layer comprises the following components in percentage by weight: 40.5-50% of a polymer electron donor, 40.5-50% of an electron acceptor, and 0-15.5% of an amphiphilic micromolecule additive.
The amphiphilic small molecule additive is DGI, and the structure is shown in figure 1 f. The polymer electron donor materials in the photoactive layer are PBDB-TF and PBDB-T, and the structures of the polymer electron donor materials are shown in figures 1a to 1 b. The electron acceptor material in the photoactive layer is IT-4F, PC 71 BM and ITIC are shown in FIGS. 1c to 1 e.
The anode buffer layer is made of molybdenum oxide (MoO) 3 ) The thickness of the anode buffer layer is 8 nm. The cathode buffer layer is made of zinc oxide (ZnO), and the thickness range of the cathode buffer layer is 35 nm. The substrate layer is made of glass substrate, and the transparent electrode material is Indium Tin Oxide (ITO). The metal anode is silver (Ag).
Example 2
This example served as a control group.
Cleaning a substrate with the surface roughness less than 1nm and composed of a transparent substrate layer and a transparent conductive cathode ITO, and drying the substrate by using nitrogen after cleaning; rotationally coating ZnO (4500rpm, 40s and 25nm) on the surface of the transparent conductive cathode ITO to prepare a cathode buffer layer, and thermally annealing the formed film (200 ℃, 60 min); preparing a photoactive layer (2500rpm, 60s and 95nm) on the cathode buffer layer by adopting spin coating, wherein the mass ratio of PBDB-TF to IT-4F in the photoactive layer is 1: 1; evaporating MoO on the surface of the optical active layer 3 (8 nm); and evaporating metal anode Ag (80nm) on the anode buffer layer. Under standard test conditions (AM1.5, 100 mW/cm) 2 ) Measuring the open circuit voltage (V) of the device OC ) 0.86V, short-circuit current (J) SC )＝20.60mA/cm 2 The Fill Factor (FF) is 0.74, and the Photoelectric Conversion Efficiency (PCE) is 13.10%.
Example 3
This example is essentially the same as example 2 except that in the photoactive layer, the PBDB-TF: IT-4F: DGI mass ratio is 1:1: 0.15. Under standard test conditions (AM1.5, 100 mW/cm) 2 ) The open circuit voltage (V) of the device is measured OC ) 0.84V, short-circuit current (J) SC )＝22.80mA/cm 2 The Fill Factor (FF) is 0.75, and the Photoelectric Conversion Efficiency (PCE) is 14.50%. Compared with a control group, the short-circuit current of the device is obviously improved, and the photoelectric conversion efficiency is improved by 10.7%.
Example 4
This example served as a control group.
This example is substantially the same as example 2 except that a photoactive layer (2300rpm, 60s, 95nm) in which PBDB-T: ITIC mass ratio was 1:1 was prepared by spin coating. Under standard test conditions (AM1.5, 100 mW/cm) 2 ) Measuring the open circuit voltage (V) of the device OC ) 0.88V, short-circuit current (J) SC )＝16.30mA/cm 2 The Fill Factor (FF) is 0.64, and the Photoelectric Conversion Efficiency (PCE) is 9.25%.
Example 5
This example is substantially the same as example 2 except that a photoactive layer (2300rpm, 60s, 95nm) was prepared by spin coating, and the mass ratio of PBDB-T: ITIC: DGI in the photoactive layer was 1:1: 0.15. Under standard test conditions (AM1.5,100 mW/cm) 2 ) Measuring the open circuit voltage (V) of the device OC ) 0.90V, short-circuit current (J) SC )＝18.20mA/cm 2 The Fill Factor (FF) is 0.69, and the Photoelectric Conversion Efficiency (PCE) is 11.30%. Compared with a control group, the short-circuit current and the fill factor of the device are obviously improved, and the photoelectric conversion efficiency is improved by 22.1%.
Example 6
This example served as a control group.
This example is essentially the same as example 2 except that a photoactive layer (2000rpm, 60s, 95nm) in which PBDB-T is PC was prepared by spin coating 71 BM mass ratio is 1: 1.5. Under standard test conditions (AM1.5, 100 mW/cm) 2 ) Measuring the open circuit voltage (V) of the device OC ) 0.82V, short-circuit current (J) SC )＝14.91mA/cm 2 The Fill Factor (FF) is 0.71, and the Photoelectric Conversion Efficiency (PCE) is 8.70%.
Example 7
This example is essentially the same as example 2, except that a photoactive layer (2000rpm, 60s, 95nm) in which PBDB-T is PC was prepared by spin coating 71 The mass ratio of BM to DGI is 1:1.5: 0.15. Under standard test conditions (AM1.5, 100 mW/cm) 2 ) Measuring the open circuit voltage (V) of the device OC ) 0.83V, short-circuit current (J) SC )＝15.40mA/cm 2 The Fill Factor (FF) is 0.72, and the Photoelectric Conversion Efficiency (PCE) is 9.30%. Compared with a control group, the short-circuit current of the device is obviously improved, and the photoelectric conversion efficiency is improved by 6.9%.
FIG. 3 shows AM1.5 (intensity 100 mW/cm) for the devices described in examples 2-7 2 ) Current density-voltage characteristic under irradiation, illustrated in the polymer donor: small molecule acceptors and polymer donors: in a fullerene receptor system, the amphiphilic micromolecular additive DGI can effectively improve short-circuit current and a filling factor, and finally, the efficiency of a device is improved. The photoelectric conversion efficiency is improved by about 7-22%.
By adding amphiphilic micromolecules as additives into the photoactive layer, the microstructure of the thin film can be optimized, phase separation is improved, molecular orientation and crystal size are adjusted, bimolecular charge recombination can be inhibited, more effective charge generation and transmission are caused, the short-circuit current density of the device is improved, and the photoelectric conversion performance of the device is finally improved.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.

Claims (10)

1. A high efficiency organic solar cell, characterized by: this organic solar cell is the inversion structure, and from the bottom up is in proper order: the device comprises a substrate layer, a transparent conductive cathode, a cathode buffer layer, an optical activity layer, an anode buffer layer and a metal anode; the photoactive layer consists of a polymer electron donor, an electron acceptor and an amphiphilic small molecule additive, wherein the amphiphilic small molecule additive is dodecyl glyceryl acetate.
2. A high efficiency organic solar cell as claimed in claim 1, wherein: the amphiphilic small molecule additive is a nonionic surfactant.
3. A high efficiency organic solar cell as claimed in claim 1, wherein: in the photoactive layer, the weight ratio of the polymer electron donor to the electron acceptor to the amphiphilic micromolecule additive is 1:1: (0-0.2).
4. A high efficiency organic solar cell as claimed in claim 1, wherein: the material of the polymer electron donor is a narrow-band polymer electron donor; the electron acceptor material is a fullerene derivative or a small molecule acceptor.
5. A high efficiency organic solar cell as claimed in claim 1, wherein: the anode buffer layer is made of organic compounds or metal oxides with hole transmission capacity or electron blocking capacity, and the thickness of the anode buffer layer is 1-200 nm.
6. A high efficiency organic solar cell as claimed in claim 1, wherein: the cathode buffer layer is made of organic compounds or metal oxides with electron transmission capacity or hole blocking capacity, and the thickness of the cathode buffer layer is 1-200 nm.
7. A high efficiency organic solar cell as claimed in claim 1, wherein: the substrate layer is made of glass or transparent polymer, and the transparent polymer material is one or more of polyethylene, polymethyl methacrylate, polycarbonate, polyurethane, polyphthalamide, vinyl chloride-vinyl acetate copolymer or polyacrylic acid.
8. A high efficiency organic solar cell as claimed in claim 1, wherein: the transparent conductive cathode is made of a transparent or semitransparent conductive material in a visible light area, and the light transmittance is greater than 50%.
9. A high efficiency organic solar cell as claimed in claim 1, wherein: the metal anode material is one of gold, silver, platinum, copper and aluminum.
10. A method of fabricating a high efficiency organic solar cell as claimed in claim 1, wherein: the method comprises the following steps: cleaning a substrate with the surface roughness less than 1nm and consisting of a substrate layer and a transparent conductive cathode, and drying by using nitrogen after cleaning; rotationally coating a cathode buffer layer on the surface of the transparent conductive cathode, and carrying out thermal annealing; preparing an optical active layer on the cathode buffer layer by adopting spin coating; evaporating an anode buffer layer on the surface of the optical active layer; and evaporating a metal anode on the anode buffer layer.
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