CN113054108A - Organic solar cell and preparation method thereof - Google Patents

Organic solar cell and preparation method thereof Download PDF

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Publication number
CN113054108A
CN113054108A CN202110253022.9A CN202110253022A CN113054108A CN 113054108 A CN113054108 A CN 113054108A CN 202110253022 A CN202110253022 A CN 202110253022A CN 113054108 A CN113054108 A CN 113054108A
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acceptor
solar cell
organic solar
donor
active layer
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杨诚
刘孔
李其聪
詹松霖
吴玉林
王智杰
曲胜春
王占国
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Institute of Semiconductors of CAS
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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
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • 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
    • 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
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
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Abstract

An organic solar cell and a method for fabricating the same, the organic solar cell comprising: the active layer comprises a donor, a first acceptor and a second acceptor, wherein the donor, the first acceptor and the second acceptor form a cascade energy level arrangement structure, the donor is a polymer donor, and the first acceptor and the second acceptor are both non-fullerene acceptors. The charge transmission path of the organic solar cell is expanded, which is beneficial to improving the charge transmission efficiency, thereby improving the photoelectric conversion efficiency of the device. In addition, due to the fact that the non-fullerene acceptor is doped, the hydrophobic performance of the active layer is improved, permeation of water molecules to the active layer is slowed down, and therefore the photoelectric conversion stability of the organic solar cell is improved.

Description

Organic solar cell and preparation method thereof
Technical Field
The disclosure relates to the field of solar cells, and in particular relates to an organic solar cell and a preparation method thereof.
Background
The burning of a large amount of fossil energy brings serious environmental pollution, and as the reserves of fossil fuels are increasingly reduced, the search for green and pollution-free alternative energy is urgent. Solar energy is a natural green sustainable energy, and if the solar energy can be effectively utilized, the energy requirements of human society can be met to a great extent. Solar cells can directly convert solar energy into electrical energy, and are an effective way to utilize solar energy. Among solar cell systems, organic solar cells are receiving wide attention because of their unique advantages of being lightweight, flexible, capable of being printed and prepared in large areas, and the like. However, the energy conversion efficiency of the organic solar cell depends on the absorption degree of the active layer to sunlight, and the intrinsic absorption spectrum of the organic material is narrow, which hinders the efficiency development of the organic solar cell.
Disclosure of Invention
Technical problem to be solved
In view of the prior art problems, the present disclosure provides an organic solar cell and a method for manufacturing the same, which are used to at least partially solve the above technical problems.
(II) technical scheme
An aspect of the present disclosure is an organic solar cell including: the active layer comprises a donor, a first acceptor and a second acceptor, wherein the donor, the first acceptor and the second acceptor form a cascade energy level arrangement structure, the donor is a polymer donor, and the first acceptor and the second acceptor are both non-fullerene acceptors.
Optionally, the donor is PTB7-Th, the first acceptor is COi8DFIC, and the second acceptor is ITIC-4F.
Optionally, the ratio of the amount of donor to the sum of the amount of first acceptor and the amount of second acceptor is 1: 1.2 to 1: 1.6, wherein the doping ratio of the second acceptor is 5 to 20 wt%.
Optionally, the total concentration of the donor, the first acceptor, and the second acceptor is 10-30 mg/mL.
Optionally, the active layer has a thickness in the range of 90-100 nm.
Optionally, the organic solar cell further comprises: the electron transport layer, the active layer, the hole transport layer and the metal electrode are sequentially stacked on the surface of the transparent conductive substrate.
Optionally, the transparent conductive substrate is an ITO glass substrate, the electron transport layer is a ZnO layer, and the hole transport layer is MoO3And the electrode is a metal electrode.
In another aspect of the present disclosure, a method for manufacturing an organic solar cell includes: mixing and dissolving a polymer donor and two non-fullerene receptors to obtain a mixed solution; heating and stirring the mixed solution at a preset temperature, adding a DIO additive, and continuously stirring to obtain an active layer solution; and spin-coating the active layer solution on an electron transport layer to enable the polymer donor and two non-fullerene receptors to form a cascade energy level arrangement structure, so as to obtain the active layer.
In one aspect of the disclosure, the mixed liquid is stirred in an inert gas atmosphere.
In one aspect of the present disclosure, before the spin coating the active layer solution on the electron transport layer, the method further includes: preparing an electron transport layer on a transparent conductive substrate; after the solution spin coating the active layer on the electron transport layer, the method further comprises: and sequentially preparing a hole transport layer and an electrode on the active layer.
(III) advantageous effects
The present disclosure provides an organic solar cell and a method for manufacturing the same, which at least have the following beneficial effects:
the active layer of the solar cell is a cascade energy level arrangement structure formed by the polymer donor and the two non-fullerene receptors, so that the charge transmission path of the solar cell can be expanded, the charge transmission efficiency can be improved, and the photoelectric conversion efficiency of the device can be improved. In addition, due to the fact that the non-fullerene acceptor is doped, the hydrophobic performance of the active layer is improved, permeation of water molecules to the active layer is slowed down, and therefore the photoelectric conversion stability of the device is improved.
Drawings
Fig. 1 schematically illustrates an energy level diagram of an organic solar cell provided by an embodiment of the present disclosure;
fig. 2 schematically illustrates a structural view of an organic solar cell provided by an embodiment of the present disclosure;
fig. 3 schematically shows a current density versus voltage graph of the ternary organic solar cell in the above embodiment and the undoped acceptor organic solar cell in the comparative example;
fig. 4 schematically shows a water contact angle test chart of an undoped organic solar cell in a comparative example;
fig. 5 schematically shows a water contact angle test chart of a ternary organic solar cell in an embodiment of the present invention;
fig. 6 schematically shows a graph of normalized efficiency versus time for a ternary organic solar cell in an embodiment of the present invention and an undoped organic solar cell in a comparative example.
Detailed Description
For the purpose of promoting a better understanding of the objects, aspects and advantages of the present disclosure, reference is made to the following detailed description taken in conjunction with the accompanying drawings.
In the process of implementing the present disclosure, the applicant researches and discovers that the problems of large exciton binding energy and short exciton diffusion distance of organic materials can be solved and efficient dissociation of excitons can be realized by preparing a nano-scale phase-separated donor/acceptor interpenetrating network structure by blending a donor material and an acceptor material. Therefore, the applicant further thinks that the active layer of the solar cell prepared by blending the donor material and the acceptor material can expand the charge transmission path of the original system, and is beneficial to improving the charge transmission efficiency, thereby improving the photoelectric conversion efficiency of the device. The applicant has also found that in order to improve the stability of the solar cell, it is important to reduce the impact of environmental factors on the device. Since the influence of light and heat cannot be avoided, improvement of stability requires adjustment of the active layer itself, such as improvement of crystallinity of the donor material and increase of glass transition temperature of the polymer. For reducing the influence of water and oxygen, besides the adjustment of the active layer, reducing the penetration of water and oxygen in the active layer is an effective solution.
Based on the above research, the present disclosure provides an organic solar cell, which includes an active layer, where the active layer includes a donor, a first acceptor and a second acceptor, and the donor, the first acceptor and the second acceptor form a cascade energy level arrangement structure, where the donor is a polymer donor, and the first acceptor and the second acceptor are both non-fullerene acceptors.
According to embodiments of the present disclosure, the donor may be, for example, PTB7-Th, the first acceptor may be, for example, COi8DFIC, and the second acceptor may be, for example, ITIC-4F.
Based on this type of donor and acceptor, a cascade energy level arrangement structure is formed. Typically, the donor has an energy level higher than the first acceptor, which is higher than the second acceptor, to enable spontaneous transitions.
As shown in fig. 1, the HOMO level 51 of the donor is higher than the HOMO level 52 of the first acceptor, and the HOMO level 52 of the first acceptor is higher than the HOMO level 53 of the second acceptor. The donor has a LUMO level 61 that is higher than the LUMO level 62 of the first acceptor, and the first acceptor has a LUMO level 62 that is higher than the LUMO level 63 of the second acceptor. For example, in one particular example, the donor PTB7-Th has a LUMO level of-3.34 eV and a HOMO level of-4.98 eV; the LUMO level of the first acceptor COi8DFIC is-4.20 eV, and the HOMO level is-5.52 eV; the LUMO level of the second receptor ITIC-4F is-4.32 eV, and the HOMO level is-5.90 eV; the three materials form a cascade energy level arrangement structure. At this time, the charge transfer paths in the active layer include three kinds of PTB7-Th → COi8DFIC, PTB7-Th → ITIC-4F, COi8DFIC → ITIC-4F.
Further, in a specific example, the donor PTB7-Th had an absorption spectrum in the range of 550-750 nm. The absorption spectrum of the first acceptor COi8DFIC was in the range of 700-950 nm. The second receptor ITIC-4F has an absorption spectrum in the range of 600-800 nm. The incorporation of the second acceptor does not broaden the absorption spectrum.
According to embodiments of the present disclosure, the ratio of the amount of donor to the sum of the amount of first acceptor and the amount of second acceptor may be 1: 1.2 to 1: 1.6, preferably 1: 1.5, wherein the doping ratio of the second acceptor may be 5 to 20 wt%, preferably 10 wt%. Further, the total concentration of the donor, the first acceptor and the second acceptor may be 10-30mg/mL, preferably 25 mg/mL.
According to an embodiment of the present disclosure, the thickness of the active layer 3 may range from 90 to 100 nm.
According to the embodiment of the present disclosure, as shown in fig. 2, the organic solar cell further includes a transparent conductive substrate 1, an electron transport layer 21, a hole transport layer 22, and an electrode 4, wherein the electron transport layer 21, the active layer 3, the hole transport layer 22, and the metal electrode 4 are sequentially stacked on the surface of the transparent conductive substrate 1. The transparent conductive substrate 1 may be an ITO glass substrate, the electron transport layer 21 may be a ZnO layer, and the hole transport layer 22 may be MoO3The layer, electrode 4, may be a metal electrode, such as Ag. At this time, the organic solar cell is an inverted structure device, and the structure thereof is as follows: ITO/ZnO/PTB 7-Th: COi8 DFIC: ITIC-4F/MoO3and/Ag. In a specific example, the thickness of the hole transport layer MoO3 was 4nm, and the thickness of the metal electrode Ag was 100 nm.
Based on the same inventive concept, the present disclosure also provides a method for manufacturing the organic solar cell, which may include:
s301, mixing and dissolving the polymer donor and the two non-fullerene receptors to obtain a mixed solution.
According to the embodiment of the disclosure, a polymer donor and a non-fullerene acceptor can be dissolved in a high-purity chlorobenzene solution, so that the polymer donor and the two non-fullerene acceptors are fully dissolved to obtain a mixed solution.
And S302, heating and stirring the mixed solution at a preset temperature, adding a DIO additive, and continuously stirring to obtain an active layer solution.
According to an embodiment of the present disclosure, first, heating and stirring are performed at a temperature of 40 to 50 ℃ for at least 2 hours. Then, 1% by volume of DIO additive was added and stirring was continued for at least 0.5 hour. Further, the heating stirring process and the stirring process for adding the DIO additive are all in the inert gas atmosphere.
And S303, spin-coating the active layer solution on the electron transport layer to enable the polymer donor and the two non-fullerene receptors to form a cascade energy level arrangement structure, so as to obtain the active layer.
According to embodiments of the present disclosure, the active layer may be annealed by solution spin coating the active layer onto the electron transport layer. In a specific example, the annealing atmosphere may be a nitrogen atmosphere, the annealing temperature may be 100 ℃, and the annealing time may be 10 minutes.
Further, before step S301, the method further comprises:
s300, preparing an electron transport layer on the transparent conductive substrate.
In a specific example, first, an ITO glass substrate is cleaned and subjected to surface treatment: and ultrasonic cleaning with liquid detergent, deionized water, acetone and isopropanol for 20 min. And then, treating the dried ITO glass substrate for 15 minutes by using an ultraviolet ozone cleaning machine, wherein the organic matter residue on the ITO surface can be cleaned by the treatment method, and the surface wettability is improved. And finally, spin-coating a ZnO precursor solution on the surface of the ITO glass substrate, and annealing at 200 ℃ for 10 minutes to prepare the electron transport layer.
After step S302, the method further comprises:
and S304, sequentially preparing a hole transport layer and an electrode on the active layer.
In a specific example, a hole transport layer MoO3 and a metal electrode Ag are sequentially evaporated on the active layer.
It should be noted that portions of the method embodiments that are not described in detail are similar to portions of the product embodiments, and please refer to the portions of the product embodiments, which are not described herein again.
To further illustrate the advantages of the organic solar cell provided by embodiments of the present disclosure, embodiments of the present disclosure provide a solution to the above-described ITO/ZnO/PTB 7-Th: COi8 DFIC:ITIC-4F/MoO3the organic solar cell with the structure of/Ag is subjected to performance test. The stability test parameters of the organic solar cell comprise open-circuit voltage, short-circuit current density, filling factor and photoelectric conversion efficiency. The storage conditions of the organic solar cell for stability test are room temperature illumination, air atmosphere and relative humidity range of 20-30%.
Fig. 3 schematically shows a current density versus voltage graph of the ternary organic solar cell in the above embodiment and the undoped acceptor organic solar cell in the comparative example. Wherein, curve 1 is the current density and voltage curve of the undoped organic solar cell in the comparative example, and curve 2 is the current density and voltage curve of the ternary organic solar cell in the embodiment.
As can be seen from FIG. 3, the short-circuit current density of the comparative example was 23.86mAcm-2The fill factor was 68.8%, and the short-circuit current density of the example was 26.75mAcm-2The fill factor was 71.5%. Due to the overlapping of absorption spectra, the range of the absorption spectrum of the active layer is not widened by the incorporation of the ITIC-4F, but the short-circuit current density and the filling factor of the device are improved. This indicates that the charge transport path increased in the active layer after incorporation of ITIC-4F can effectively enhance exciton separation efficiency and reduce recombination loss in the active layer, thereby improving photoelectric conversion efficiency.
Fig. 4 schematically shows a water contact angle test chart of an undoped organic solar cell in a comparative example, and fig. 5 schematically shows a water contact angle test chart of a ternary organic solar cell in the above-described example. As can be seen from fig. 4 and 5, the water contact angle of the comparative example was 97.3 °, and the water contact angle of the example was 102.3 °. This shows that incorporation of ITIC-4F is effective in improving the hydrophobic properties of the film.
Fig. 6 schematically shows normalized efficiency versus time curves of the ternary organic solar cell in the above embodiment and the undoped organic solar cell in the comparative example, where curve 1 is the normalized efficiency versus time curve of the undoped organic solar cell in the comparative example, and curve 2 is the normalized efficiency versus time curve of the ternary organic solar cell in the embodiment.
As can be seen from fig. 6, the efficiency of the device gradually decreases with time. Wherein the efficiency of the example is reduced by a lower extent than that of the comparative example. This shows that the improvement of the hydrophobic property of the active layer film after the incorporation of the ITIC-4F can slow down the permeation of water molecules to the active layer, thereby improving the stability.
The above-mentioned embodiments are intended to illustrate the objects, aspects and advantages of the present disclosure in further detail, and it should be understood that the above-mentioned embodiments are only illustrative of the present disclosure and are not intended to limit the present disclosure, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present disclosure should be included in the scope of the present disclosure.

Claims (10)

1. An organic solar cell, comprising:
the active layer (3) comprises a donor, a first acceptor and a second acceptor, wherein the donor, the first acceptor and the second acceptor form a cascade energy level arrangement structure, the donor is a polymer donor, and the first acceptor and the second acceptor are both non-fullerene acceptors.
2. The organic solar cell according to claim 1, wherein the donor is PTB7-Th, the first acceptor is COi8DFIC, and the second acceptor is ITIC-4F.
3. The organic solar cell of claim 1, wherein the ratio of the amount of donor to the sum of the amount of first acceptor and the amount of second acceptor is 1: 1.2 to 1: 1.6, wherein the doping ratio of the second acceptor is 5 to 20 wt%.
4. The organic solar cell of claim 1, wherein the total concentration of the donor, the first acceptor, and the second acceptor is 10-30 mg/mL.
5. The organic solar cell according to claim 1, wherein the active layer (3) has a thickness in the range of 90-100 nm.
6. The organic solar cell of claim 1, further comprising:
the light-emitting diode comprises a transparent conductive substrate (1), an electron transport layer (21), a hole transport layer (22) and an electrode (4), wherein the electron transport layer (21), an active layer (3), the hole transport layer (22) and the metal electrode (4) are sequentially stacked on the surface of the transparent conductive substrate (1).
7. The organic solar cell according to claim 6, wherein the transparent conductive substrate (1) is an ITO glass substrate, the electron transport layer (21) is a ZnO layer, and the hole transport layer (22) is MoO3And the electrode (4) is a metal electrode.
8. A method of fabricating an organic solar cell, comprising:
mixing and dissolving a polymer donor and two non-fullerene receptors to obtain a mixed solution;
heating and stirring the mixed solution at a preset temperature, adding a DIO additive, and continuously stirring to obtain an active layer solution;
and spin-coating the active layer solution on an electron transport layer to enable the polymer donor and two non-fullerene receptors to form a cascade energy level arrangement structure, so as to obtain the active layer.
9. The method according to claim 8, wherein the mixed solution is stirred in an inert gas atmosphere.
10. A method of making as defined in claim 8, prior to said solution spin coating the active layer onto an electron transport layer, the method further comprising:
preparing an electron transport layer on a transparent conductive substrate;
after the solution spin coating the active layer on the electron transport layer, the method further comprises:
and sequentially preparing a hole transport layer and an electrode on the active layer.
CN202110253022.9A 2021-03-08 2021-03-08 Organic solar cell and preparation method thereof Pending CN113054108A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106025073A (en) * 2016-06-14 2016-10-12 苏州大学 Organic solar cell employing ternary component as active layer
CN108912140A (en) * 2018-06-11 2018-11-30 武汉大学 A kind of asymmetry A-D-A type conjugation small molecule and its intermediate and application
CN109265656A (en) * 2018-09-05 2019-01-25 苏州大学 The conjugated polymer and its preparation and application that double alkane sulphur chains replace
CN109326716A (en) * 2018-08-20 2019-02-12 电子科技大学 Non- fullerene organic solar batteries and preparation method thereof
CN109524549A (en) * 2018-11-02 2019-03-26 中国科学院重庆绿色智能技术研究院 The non-fullerene system organic solar batteries of the full small molecule of bifunctional layer

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106025073A (en) * 2016-06-14 2016-10-12 苏州大学 Organic solar cell employing ternary component as active layer
CN108912140A (en) * 2018-06-11 2018-11-30 武汉大学 A kind of asymmetry A-D-A type conjugation small molecule and its intermediate and application
CN109326716A (en) * 2018-08-20 2019-02-12 电子科技大学 Non- fullerene organic solar batteries and preparation method thereof
CN109265656A (en) * 2018-09-05 2019-01-25 苏州大学 The conjugated polymer and its preparation and application that double alkane sulphur chains replace
CN109524549A (en) * 2018-11-02 2019-03-26 中国科学院重庆绿色智能技术研究院 The non-fullerene system organic solar batteries of the full small molecule of bifunctional layer

Non-Patent Citations (1)

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Title
CHENG YANG等: "Nonfullerene Ternary Organic Solar Cell with Effective Charge Transfer between Two Acceptors", 《THE JOURNAL OF PHYSICAL CHEMISTRY LETTERS》, vol. 11, 18 January 2020 (2020-01-18), pages 927 - 928 *

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Application publication date: 20210629