CN113540357A - Flexible organic solar cell and preparation method thereof - Google Patents
Flexible organic solar cell and preparation method thereof Download PDFInfo
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- CN113540357A CN113540357A CN202110686160.6A CN202110686160A CN113540357A CN 113540357 A CN113540357 A CN 113540357A CN 202110686160 A CN202110686160 A CN 202110686160A CN 113540357 A CN113540357 A CN 113540357A
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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
-
- 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
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- Photovoltaic Devices (AREA)
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 transport layer, an active layer, an electron transport 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. According to the flexible organic solar cell and the preparation method thereof, the good flexibility of the solar cell can be realized, and the photoelectric conversion efficiency of the solar cell can be improved.
Description
Technical Field
The invention relates to a flexible organic solar cell and a preparation method thereof, belonging to the technical field of photovoltaic power generation.
Background
Organic solar cells attract a wide range of 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 wearable devices, the requirements on lightness, flexibility, small size and the like of a battery are more and more urgent, and the flexible solar battery is undoubtedly the best choice and brings the development and the revolution of power-assisted electronic products. How to achieve good flexibility of the 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 evaporating or sublimating a substance to be formed into a film in vacuum so as to precipitate the substance on the surface of a substrate. When an organic solar cell is prepared, vacuum evaporation has certain defects, for example, the vacuum evaporation needs expensive equipment and has long preparation time, and an evaporated top electrode is light-proof and has no flexibility, so that the requirements of a flexible electronic device cannot be met.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a flexible organic solar cell which can realize good flexibility of the solar cell and can improve the photoelectric conversion efficiency of the solar cell and a preparation method thereof.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
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 transport layer, an active layer, an electron transport 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 polyethylene, polymethyl methacrylate, polycarbonate, polyurethane, polyphthalamide and polyacrylic acid.
The top electrode and the bottom electrode are made of one or a mixture of metal nanoparticles, metal nanowires, conductive polymers and metal grids.
The material of the hole transport layer material comprises one or a mixture of a plurality 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 the upper flexible transparent substrate and the lower flexible transparent substrate, and drying the substrates by using nitrogen for later use;
s02, carrying out ultraviolet ozone treatment on the cleaned and blow-dried upper flexible transparent substrate and the cleaned and blow-dried lower flexible transparent substrate, and respectively carrying out spin coating on the surfaces of the upper flexible transparent substrate and the lower flexible transparent substrate to prepare a top electrode and a bottom electrode;
s03, spin-coating a hole transport layer on the bottom electrode, and carrying out thermal annealing treatment;
s04, spin-coating an active layer on the hole transport layer, and carrying out thermal annealing treatment;
s05, preparing an electron transport layer by spin coating on the active layer;
s06, the top electrode is imprinted onto the electron transport layer by a lamination technique.
In S01, the specific cleaning method comprises the steps of sequentially cleaning in a cleaning agent, deionized water, acetone and absolute ethyl alcohol for 15min respectively; in S02, the ultraviolet ozone treatment time was 15 min.
In S03, the annealing temperature is 120 ℃, and the annealing time is 10 min; in S04, the annealing temperature is 120 ℃ and the annealing time is 20 min.
S06, the laminating technique includes two steps of a laminating process and a heating process, wherein the laminating process adopts a punching forming machine to form a flexible transparent substrateAnd a lower flexible transparent substrate under a clamping pressure of 2ton/cm2(ii) a The heating temperature in the heating process 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 a laminating method, double-sided light absorption can be realized by using the upper flexible transparent substrate and the lower flexible transparent substrate, the photon utilization rate is improved, the photoelectric conversion efficiency and flexibility of the solar cell are further improved, and meanwhile, the interface of the flexible organic solar cell prepared by the laminating method is in tight contact, and the stability of a 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 all-solution method, so that the device manufacturing process is simplified, the manufacturing cost is reduced, and the industrial production is facilitated; the electron transmission layer is an amphiphilic n-type organic interface material, and the amphiphilic n-type organic interface material can improve the carrier mobility and further improve the short-circuit current, so that the photoelectric conversion efficiency of the device is improved.
Drawings
Fig. 1 is a schematic structural diagram of a flexible organic solar cell according to the present invention;
FIG. 2 is a chemical structural formula of a material used in an example of the present invention;
fig. 3 is a schematic diagram of a hot rolling press for manufacturing a flexible organic solar cell according to the present invention;
fig. 4 is a graph of peel strength test data for organic solar cells prepared according to various embodiments of the present invention.
Detailed Description
The present invention is further described with reference to the accompanying drawings, and the following examples are only for clearly illustrating the technical solutions of the present invention, and should not be taken as limiting the scope of the present invention.
Detailed description of the preferred embodiment 1
As shown in fig. 1, the present invention discloses a flexible organic solar cell, which comprises an upper flexible transparent substrate and a lower flexible transparent substrate arranged from top to bottom, wherein a bottom electrode, a hole transport layer, an active layer, an electron transport 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. And the top electrode is pressed on the electron transport layer by a laminating 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 both 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 100 nm.
The flexible transparent substrate needs to simultaneously meet the 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 polyethylene 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, blade coating and ink-jet printing. In this embodiment, the top electrode and the bottom electrode are selected from conductive polymers, specifically PEDOT: PSS (PH 1000).
In the active layer, the electron donor and the electron acceptor are blended according to a certain weight ratio.
The electron transport layer is an organic small molecule having electron transport ability, and in this embodiment, 3'- (1,3,8, 10-tetraanthraenono [2,1,9-def:6,5,10-d' e 'f' ] bisisoquinoline-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. Preferred in this example is poly 3,4 ethylenedioxythiophene/polystyrene sulfonate (PEDOT: PSS (4083)).
The invention also discloses a preparation method of the flexible solar cell, which comprises the following steps:
step one, respectively cleaning an upper flexible transparent substrate and a lower flexible transparent substrate (a 14 x 14mm Polyester (PET) substrate) in a cleaning agent, deionized water, acetone and absolute ethyl alcohol for 15min, and carrying out ultraviolet ozone treatment for 15min after nitrogen blow drying.
And step two, preparing a PEDOT PSS electrode on PET. Firstly filtering a PEDOT/PSS solution by using a 0.45-micron filter, then spin-coating the solution on a PET substrate at the speed of 2500rpm for 60s, then soaking the PET substrate in a trifluoroethanol solution for 3min, then taking out the PET substrate, carrying out thermal annealing in the air at the annealing temperature of 120 ℃ for 10min, and finally obtaining the PEDOT/PSS top electrode and the PEDOT/PSS bottom electrode.
And step three, spin-coating PEDOT: PSS (4083) as a hole transport layer on a PEDOT: PSS electrode, wherein the film thickness is 30nm, and then annealing the film for 20min at 120 ℃ in air.
And step four, spin-coating an organic active layer on the hole transport layer. PBDB-T and PC71BM is dissolved in chlorobenzene and the chemical structure is shown in FIG. 2. PBDB-T and PC71BM concentration is 20mg/mL and 30mg/mL respectively, then blending according to the volume ratio of 1:1, spin-coating the mixed solution on the hole transport layer to form a film with the thickness of about 100nm, and then annealing at 100 ℃ for 10 min.
And fifthly, spin-coating a PDINO electron transport layer on the organic active layer. PDINO is dissolved in methanol to prepare a solution of 0.5mg/mL, and then the solution is spin-coated on an organic active layer to form a thin film of about 10 nm.
Step six, aligning the top electrode and the electron transport layer to perform a lamination process, and preparing the flexible organic solar cell by using a hot rolling and stamping machine as shown in fig. 3. The lamination process is to laminate the top electrode on the electron transport layer to form the flexible solar cell, and no adhesive is used between the electron transport layer and the top electrode. Specifically, they were held by a press-forming machine and applied at 2ton/cm from the bottom electrode and the top electrode2Then, 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 process can make the electron transmission layer and the top electrode tightly contact, so that the flexible organic solar cell device can be prepared.
Specific example 2
This example is the same as embodiment 1 except that the pressing temperature in step six is 30 ℃.
Specific example 3
This example is the same as embodiment 1 except that the pressing temperature in step six is 60 ℃.
Specific example 4
This example is the same as embodiment 1 except that the pressing temperature in step six is 100 ℃.
Specific example 5
This example is the same as embodiment 1 except that the pressing temperature in step six is 120 ℃.
Specific example 6
This example is the same as embodiment 1 except that the pressing temperature in step six is 200 ℃.
The peel strength of the flexible organic solar cell obtained in the specific examples 1 to 6 of the present invention was measured. Specifically, double-sided adhesive tapes of Φ 8mm were attached to the PET substrates on both ends of the bottom/top electrodes, and the peel strength was measured by a tensile strength tester, and the results are shown in fig. 4. As seen from the figure, the peel strength of the flexible organic solar cell is highest at a stamping temperature of 150 ℃.
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 flexible organic solar cell, characterized by: 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 transport layer, an active layer, an electron transport 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.
2. The flexible organic solar cell of claim 1, wherein: the upper flexible transparent substrate and the lower flexible transparent substrate are made of one or a mixture of polyethylene, polymethyl methacrylate, polycarbonate, polyurethane, polyphthalamide and polyacrylic acid.
3. The flexible organic solar cell of claim 1, wherein: the top electrode and the bottom electrode are made of one or a mixture of metal nanoparticles, metal nanowires, conductive polymers and metal grids.
4. The flexible organic solar cell of claim 1, wherein: the material of the hole transport layer material comprises one or a mixture of a plurality of poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid, nickel oxide, molybdenum oxide and copper oxide.
5. The flexible organic solar cell of claim 1, wherein: the electron transport layer is an amphiphilic n-type organic interface material.
6. The flexible organic solar cell of claim 1, wherein: the active layer is formed by blending an electron donor and an electron acceptor according to a certain weight ratio.
7. A preparation method of a flexible organic solar cell is characterized by comprising the following steps: the method comprises the following steps:
s01, cleaning the upper flexible transparent substrate and the lower flexible transparent substrate, and drying the substrates by using nitrogen for later use;
s02, carrying out ultraviolet ozone treatment on the cleaned and blow-dried upper flexible transparent substrate and the cleaned and blow-dried lower flexible transparent substrate, and respectively carrying out spin coating on the surfaces of the upper flexible transparent substrate and the lower flexible transparent substrate to prepare a top electrode and a bottom electrode;
s03, spin-coating a hole transport layer on the bottom electrode, and carrying out thermal annealing treatment;
s04, spin-coating an active layer on the hole transport layer, and carrying out thermal annealing treatment;
s05, preparing an electron transport layer by spin coating on the active layer;
s06, the top electrode is imprinted onto the electron transport layer by a lamination technique.
8. The method for preparing a flexible organic solar cell according to claim 7, wherein: in S01, the specific cleaning method comprises the steps of sequentially cleaning in a cleaning agent, deionized water, acetone and absolute ethyl alcohol for 15min respectively; in S02, the ultraviolet ozone treatment time was 15 min.
9. The method for preparing a flexible organic solar cell according to claim 7, wherein: in S03, the annealing temperature is 120 ℃, and the annealing time is 10 min; in S04, the annealing temperature is 120 ℃ and the annealing time is 20 min.
10. The method for preparing a flexible organic solar cell according to claim 7, wherein: s06, the laminating technique includes two steps of a laminating step and a heating step, wherein the laminating step uses a press-forming machine to clamp the upper and lower flexible transparent substrates at a clamping pressure of 2ton/cm2(ii) a The heating temperature in the heating process is 30-200 ℃.
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