CN113540357B - Flexible organic solar cell and preparation method thereof - Google Patents
Flexible organic solar cell and preparation method thereof Download PDFInfo
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Classifications
-
- 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
-
- 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
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/50—Forming devices by joining two substrates together, e.g. lamination techniques
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a flexible organic solar cell, which comprises an upper flexible transparent substrate and a lower flexible transparent substrate which are arranged up and down, wherein a bottom electrode, a hole transmission layer, an active layer, an electron transmission layer and a top electrode are sequentially connected between the upper flexible transparent substrate and the lower flexible transparent substrate from bottom to top, the upper surface of the top electrode is connected with the lower surface of the upper flexible transparent substrate, and the lower surface of the bottom electrode is connected with the upper surface of the lower flexible transparent substrate. The invention also provides a preparation method of the flexible organic solar cell. The flexible organic solar cell and the preparation method thereof provided by the invention can realize good flexibility of the solar cell and improve the photoelectric conversion efficiency of the solar cell.
Description
Technical Field
The invention relates to a flexible organic solar cell and a preparation method thereof, and belongs to the technical field of photovoltaic power generation.
Background
Organic solar cells have attracted considerable attention due to their potential advantages, such as tunable light absorption range, light weight, mechanical flexibility, and low cost mass production based on roll-to-roll printing. Along with the development of intellectualization, miniaturization and portability of electronic products, household appliances, precise instruments and meters and wearable devices, the requirements on light batteries, flexibility, small volume and the like are more and more urgent, the flexible solar battery is definitely the best choice, and the development and the revolution of power-assisted electronic products are improved. How to realize good flexibility performance of a solar cell and further improve the photoelectric conversion efficiency of the solar cell has become a hot spot of current research.
In the prior art, the top electrode of the organic solar cell is generally formed by vacuum evaporation technology. The vacuum evaporation technology is a process of putting a substance to be formed into a film in vacuum for evaporation or sublimation so as to separate the substance out of the surface of a substrate. In the preparation of organic solar cells, vacuum evaporation has certain defects, such as expensive equipment required by vacuum evaporation, long preparation time, and the evaporated top electrode is opaque and has no flexibility, and cannot meet the requirements of flexible electronic devices.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the flexible organic solar cell capable of realizing good flexibility of the solar cell and improving the photoelectric conversion efficiency of the solar cell and the preparation method of the flexible organic solar cell.
In order to solve the technical problems, the invention adopts the following technical scheme:
the flexible organic solar cell comprises an upper flexible transparent substrate and a lower flexible transparent substrate which are arranged up and down, wherein a bottom electrode, a hole transmission layer, an active layer, an electron transmission layer and a top electrode are sequentially connected between the upper flexible transparent substrate and the lower flexible transparent substrate from bottom to top, the upper surface of the top electrode is connected with the lower surface of the upper flexible transparent substrate, and the lower surface of the bottom electrode is connected with the upper surface of the lower flexible transparent substrate.
The upper flexible transparent substrate and the lower flexible transparent substrate are made of one or a mixture of more of polyethylene, polymethyl methacrylate, polycarbonate, polyurethane, polyimide and polyacrylic acid.
The materials of the top electrode and the bottom electrode comprise one or a mixture of a plurality of metal nano particles, metal nano wires, conductive polymers and metal grids.
The material of the hole transport layer material comprises one or a mixture of more of poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid, nickel oxide, molybdenum oxide and copper oxide.
The electron transport layer is an amphiphilic n-type organic interface material.
The active layer is formed by blending an electron donor and an electron acceptor according to a certain weight ratio.
A preparation method of a flexible organic solar cell comprises the following steps:
s01, cleaning an upper flexible transparent substrate and a lower flexible transparent substrate, and drying the upper flexible transparent substrate and the lower flexible transparent substrate with nitrogen for later use after cleaning;
s02, carrying out ultraviolet ozone treatment on the upper flexible transparent substrate and the lower flexible transparent substrate after cleaning and blow-drying, and respectively spin-coating the surfaces of the upper flexible transparent substrate and the lower flexible transparent substrate to prepare a top electrode and a bottom electrode;
s03, preparing a hole transport layer on the bottom electrode by spin coating, and performing thermal annealing treatment;
s04, preparing an active layer on the hole transport layer by spin coating, and performing thermal annealing treatment;
s05, preparing an electron transport layer on the active layer by spin coating;
s06, the top electrode is embossed onto the electron transport layer by lamination technique.
S01, cleaning the substrate for 15min in each of a cleaning agent, deionized water, acetone and absolute ethyl alcohol in sequence; in S02, the treatment time of ultraviolet ozone treatment is 15min.
S03, annealing at 120 ℃ for 10min; in S04, the annealing temperature is 120 ℃, and the annealing time is 20min.
In S06, the lamination technique comprises two steps of a lamination process and a heating process, wherein the lamination process uses a punch forming machine to clamp the upper flexible transparent substrate and the lower flexible transparent substrate with a clamping pressure of 2ton/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The heating temperature in the heating step is 30-200 ℃.
The invention has the beneficial effects that: according to the flexible organic solar cell and the preparation method thereof, the flexible organic solar cell is prepared by adopting the lamination method, the upper flexible transparent substrate and the lower flexible transparent substrate are used for realizing double-sided light absorption, so that the photon utilization rate is improved, the photoelectric conversion efficiency and flexibility of the solar cell are further improved, meanwhile, the interface contact of the flexible organic solar cell prepared by adopting the lamination method is tight, and the stability of the device is high; the bottom electrode, the hole transport layer, the active layer, the electron transport layer and the top electrode are respectively prepared into the flexible organic solar cell by adopting a spin-coating full-solution method, so that the manufacturing process of the device is simplified, the manufacturing cost is reduced, and the industrial production is facilitated; the electron transport layer is an amphiphilic n-type organic interface material, and the amphiphilic n-type organic interface material can improve carrier mobility and further improve short circuit current, so that photoelectric conversion efficiency of the device is improved.
Drawings
FIG. 1 is a schematic view of a flexible organic solar cell according to the present invention;
FIG. 2 is a chemical structural formula of a material used in the embodiment of the present invention;
FIG. 3 is a schematic diagram of a hot roll stamping machine for producing flexible organic solar cells according to the present invention;
fig. 4 is a graph showing peel strength test data of the sexual organic solar cell prepared in various embodiments of the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings, and the following examples are only for more clearly illustrating the technical aspects of the present invention, and are not to be construed as limiting the scope of the present invention.
Example 1
As shown in fig. 1, the invention discloses a flexible organic solar cell, which comprises an upper flexible transparent substrate and a lower flexible transparent substrate which are arranged up and down, wherein a bottom electrode, a hole transmission layer, an active layer, an electron transmission layer and a top electrode are sequentially connected between the upper flexible transparent substrate and the lower flexible transparent substrate from bottom to top, the upper surface of the top electrode is connected with the lower surface of the upper flexible transparent substrate, and the lower surface of the bottom electrode is connected with the upper surface of the lower flexible transparent substrate. The top electrode is stamped on the electron transport layer through a lamination method to prepare the flexible organic solar cell. The thickness of each layer is respectively as follows: the upper flexible transparent substrate and the lower flexible transparent substrate are 1mm, the top electrode is 70nm, the hole transport layer is 30nm, the organic active layer is 100nm, the electron transport layer is 10nm, and the bottom electrode is 100nm.
The flexible transparent substrate needs to satisfy three points of easy bending, high light transmittance and small surface roughness, and is preferably selected from one or more of polyethylene terephthalate (PET) film, polyimide (PEI) film and polyvinyl pyrrolidone (PVP) film. Polyethylene terephthalate (PET) is preferred in this embodiment.
The top electrode and the bottom electrode are one or more of metal nano particles, metal nano wires, conductive polymers and metal grids, and are prepared by one or more methods of spin coating, brush coating, knife coating and ink jet printing. In this embodiment, the top electrode and the bottom electrode are selected to be conductive polymers, specifically PEDOT: PSS (PH 1000).
In the active layer, electron donors and electron acceptors are blended at a certain weight ratio.
The electron transport layer is a small organic molecule with electron transport capability, and in this embodiment, 3'- (1,3,8,10-tetranthrone [2,1,9-def:6,5,10-d' e 'f' ] diisoquinoline-2, 9 (1H, 3H,8H, 10H) -diyl) bis (N, N-dimethylpropane-1-amine oxide) (PDINO) is preferred, and the chemical structure of PDINO is shown in FIG. 2.
The hole transport layer is one of poly 3,4 ethylene dioxythiophene/polystyrene sulfonate, nickel oxide, molybdenum oxide and copper oxide. Poly (3, 4-ethylenedioxythiophene)/polystyrene sulfonate (PEDOT: PSS (4083)) is preferred in this example.
The invention also discloses a preparation method of the flexible solar cell, which comprises the following steps:
step one, cleaning the upper flexible transparent substrate and the lower flexible transparent substrate (polyester (PET) substrate with the thickness of 14 x 14 mm) in cleaning agent, deionized water, acetone and absolute ethyl alcohol for 15min respectively, and carrying out ultraviolet ozone treatment for 15min after nitrogen blow-drying.
And secondly, preparing PEDOT-PSS electrode on PET. Filtering the PEDOT PSS solution by using a 0.45 mu m filter, spin-coating the PEDOT PSS solution on a PET substrate at a speed of 2500rpm for 60s, soaking the PEDOT PSS solution in a trifluoroethanol solution for 3min, taking out the PEDOT PSS solution, and thermally annealing the PEDOT PSS solution in air at 120 ℃ for 10min to obtain the PEDOT PSS top electrode and the PEDOT PSS bottom electrode.
And thirdly, spin-coating PEDOT PSS (4083) serving as a hole transport layer on the PEDOT PSS electrode, wherein the thickness of the film is 30nm, and then annealing at 120 ℃ for 20min in air.
And step four, spin-coating an organic active layer on the hole transport layer. PBDB-T and PC 71 BM is dissolved in chlorobenzene and the chemical structure is shown in FIG. 2. PBDB-T and PC 71 BM concentrations were 20mg/mL and 30mg/mL, respectively, and then blended at a volume ratio of 1:1, the mixed solution was spin-coated on the hole transport layer to form a film of about 100nm, and then annealed at 100℃for 10min.
And fifthly, spin coating a PDINO electron transport layer on the organic active layer. PDINO was dissolved in methanol to prepare a solution of 0.5mg/mL, and then spin-coated on the organic active layer to form a thin film of about 10 nm.
And step six, aligning the top electrode and the electron transport layer for lamination, and preparing the flexible organic solar cell by a hot roll punching machine, wherein a schematic diagram of the flexible organic solar cell is shown in fig. 3. The lamination step is to laminate the top electrode on the electron transport layer to form a flexible solar cell, and the electron transport layer and the top electrode do not use an adhesive. In particular they are held by a press forming machine, applying 2ton/cm from the bottom and top electrodes 2 Then, in order to make the stamping temperature reach 150 ℃, the stamping forming machine is heated by an electric furnace and kept for 20min, and the heating procedure can make the electron transport layer and the top electrode closely contact, thus obtaining the flexible organic solar cell device.
Example 2
This example is identical to example 1, except that the stamping temperature in step six is 30 ℃.
Example 3
This example is identical to example 1, except that the stamping temperature in step six is 60 ℃.
Example 4
This example is identical to example 1, except that the stamping temperature in step six is 100 ℃.
Example 5
This example is identical to example 1, except that the stamping temperature in step six is 120 ℃.
Example 6
This example is identical to example 1, except that the stamping temperature in step six is 200 ℃.
The flexible organic solar cells obtained in examples 1 to 6 of the present invention were subjected to peel strength measurement. Specifically, a double-sided adhesive tape of Φ8mm was stuck to a PET substrate at both ends of the bottom electrode/top electrode, and the peel strength was measured by a tensile strength tester, and the result is shown in fig. 4. As can be seen from the figure, the flexible organic solar cell has the highest peel strength at a pressing temperature of 150 ℃.
The foregoing is only a preferred embodiment of the invention, it being 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 present invention, and such modifications and adaptations are intended to be comprehended within the scope of the invention.
Claims (9)
1. A preparation method of a flexible organic solar cell is characterized by comprising the following steps: the method comprises the following steps:
s01, cleaning an upper flexible transparent substrate and a lower flexible transparent substrate, and drying the upper flexible transparent substrate and the lower flexible transparent substrate with nitrogen for later use after cleaning;
s02, carrying out ultraviolet ozone treatment on the upper flexible transparent substrate and the lower flexible transparent substrate after cleaning and blow-drying, and respectively spin-coating the surfaces of the upper flexible transparent substrate and the lower flexible transparent substrate to prepare a top electrode and a bottom electrode;
s03, preparing a hole transport layer on the bottom electrode by spin coating, and performing thermal annealing treatment;
s04, preparing an active layer on the hole transport layer by spin coating, and performing thermal annealing treatment;
s05, preparing an electron transport layer on the active layer by spin coating;
s06, embossing the top electrode on the electron transport layer by lamination technology, wherein the lamination technology comprises two steps of lamination process and heating process, and the lamination process adopts punchingThe press forming machine clamps the upper flexible transparent substrate and the lower flexible transparent substrate with clamping pressure of 2ton/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The heating temperature in the heating step is 150 ℃.
2. The method for preparing a flexible organic solar cell according to claim 1, wherein: s01, cleaning the substrate for 15min in each of a cleaning agent, deionized water, acetone and absolute ethyl alcohol in sequence; in S02, the treatment time of ultraviolet ozone treatment is 15min.
3. The method for preparing a flexible organic solar cell according to claim 1, wherein: s03, annealing at 120 ℃ for 10min; in S04, the annealing temperature is 120 ℃, and the annealing time is 20min.
4. A flexible organic solar cell produced by the production method according to claim 1, characterized in that: the device comprises an upper flexible transparent substrate and a lower flexible transparent substrate which are arranged up and down, wherein a bottom electrode, a hole transmission layer, an active layer, an electron transmission layer and a top electrode are sequentially connected between the upper flexible transparent substrate and the lower flexible transparent substrate from bottom to top, the upper surface of the top electrode is connected with the lower surface of the upper flexible transparent substrate, and the lower surface of the bottom electrode is connected with the upper surface of the lower flexible transparent substrate.
5. A flexible organic solar cell as claimed in claim 4, wherein: the upper flexible transparent substrate and the lower flexible transparent substrate are made of one or a mixture of more of polyethylene, polymethyl methacrylate, polycarbonate, polyurethane, polyimide and polyacrylic acid.
6. A flexible organic solar cell as claimed in claim 4, wherein: the materials of the top electrode and the bottom electrode comprise one or a mixture of a plurality of metal nano particles, metal nano wires, conductive polymers and metal grids.
7. A flexible organic solar cell as claimed in claim 4, wherein: the material of the hole transport layer material comprises one or a mixture of more of poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid, nickel oxide, molybdenum oxide and copper oxide.
8. A flexible organic solar cell as claimed in claim 4, wherein: the electron transport layer is an amphiphilic n-type organic interface material.
9. A flexible organic solar cell as claimed in claim 4, wherein: the active layer is formed by blending an electron donor and an electron acceptor according to a certain weight ratio.
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