CN111883659B - Efficient ternary organic solar cell prepared based on gradual deposition method - Google Patents

Efficient ternary organic solar cell prepared based on gradual deposition method Download PDF

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CN111883659B
CN111883659B CN202010785164.5A CN202010785164A CN111883659B CN 111883659 B CN111883659 B CN 111883659B CN 202010785164 A CN202010785164 A CN 202010785164A CN 111883659 B CN111883659 B CN 111883659B
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solar cell
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CN111883659A (en
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陈红征
占玲玲
李水兴
施敏敏
李寒莹
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Zhejiang University ZJU
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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    • 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
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    • 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
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Abstract

The invention discloses a high-efficiency ternary organic solar cell prepared based on a step-by-step deposition method, which comprises a substrate, an anode modification layer, an active layer, a cathode modification layer and a cathode from bottom to top, wherein the active layer is formed by sequentially depositing a layer of wide-bandgap polymer donor (PM 6) film and a layer of non-fullerene acceptor compound (mixture of BO-4Cl and BTP-S2) film on the anode modification layer by adopting a spin coating process. The active layer has an ideal P-i-N morphology structure by utilizing poor compatibility between BTP-S2 and PM6 and large shearing force during film formation by a spin coating process, namely a donor rich phase is formed at the interface of the anode modification layer, a receptor rich phase is formed at the interface of the cathode modification layer, and a bulk heterojunction thick film with a donor and a receptor uniformly mixed is arranged in the middle. Therefore, the ternary organic solar cell obtained by the method realizes the efficient generation and efficient collection of photocurrent, and the PCE is higher than that of a corresponding bulk heterojunction ternary cell, so that the highest efficiency (18.50%) of the organic solar cell is obtained.

Description

Efficient ternary organic solar cell prepared based on gradual deposition method
Technical Field
The invention relates to the technical field of solar cells, in particular to a high-efficiency ternary organic solar cell prepared based on a step-by-step deposition method.
Background
Organic solar cells have gained rapid improvement in energy conversion efficiency in recent years, benefiting from the advent of Y-series electron acceptors. The energy conversion efficiency of current single junction batteries has broken through 18% (Science Bulletin 2020,65,272).
In addition to the development of new materials, control of the morphology of the active layer is also a critical factor in determining device performance. The purpose of the topography control is to enable photocurrent to be efficiently generated in the active layer and efficiently collected by the electrodes. At present, a spin coating process is generally adopted to obtain the morphology structure of an active layer of a Bulk Heterojunction (BHJ), namely, an electron donor and an electron acceptor are simultaneously dissolved in a solvent, and a mixed solution is spin-coated to obtain the active layer. The high shearing force is generated by the intense centrifugal action during spin coating film forming, and the donor and the acceptor in the active layer can be fully mixed and uniformly distributed, so that a huge donor/acceptor interface (bulk heterojunction) is provided, and the efficient generation of charges is facilitated. But such a topographical structure is detrimental to efficient collection of charges: when holes move along the transport channels constructed by the donor phase towards the anode and electrons move along the transport channels constructed by the acceptor phase towards the cathode, the large donor/acceptor interface increases the risk of recombination of the two photo-generated charges (electrons and holes) during transport. Therefore, along the charge transmission direction, a concentration gradient of the donor/acceptor is formed in the active layer, namely, the concentration of the donor gradually increases from the interface of the cathode modification layer to the interface of the anode modification layer, and the concentration of the acceptor gradually decreases, so that the vertical phase distribution can greatly inhibit charge recombination, greatly improve the collection efficiency of the electrode on the generated charge, and further improve the photovoltaic performance of the device (Journal of the American Chemical Society 2018,140,7159;Energy&Environmental Science 2019,12,384).
For this reason, a stepwise deposition method (Layer-by-Layer, lbL) has been developed to sequentially film a donor material and a acceptor material, thereby achieving effective vertical phase distribution control. The usual stepwise deposition processes are: 1) Orthogonal solvent process (ADVANCED MATERIALS 2019,31,1808153), the upper layer solvent must be swellable but not dissolve the lower layer material. Therefore, the method has great limitation, has high selection requirements on a material system and a solvent, and has no universality; 2) The film forming process (Joule 2020,4,407) includes the steps of successively scraping the donor and the receptor to form film, and utilizing the shearing force which is smaller than that of the spin coating process in film forming to reduce the mutual diffusion degree between the upper film and the lower film. However, this method requires a lot of time to debug the blade coating parameters, and the process operation is complicated and the film is not uniform. Based on the above limiting factors, the research on the organic solar cell related to the step-by-step deposition method is not so much carried out, and the highest efficiency of the organic solar cell prepared by adopting the step-by-step deposition method is 16.5% (Nat Commun 2020,11,2855) and is far no more than 18.22% of that of the organic solar cell with the upper bulk heterojunction structure (Science Bulletin 2020,65,272). Therefore, a simple and universal gradual deposition process is obtained to realize effective regulation and control of the longitudinal component gradient in the active layer, and the method has important research and application values for expanding the application range of the gradual deposition method and further improving the efficiency of the organic solar cell device.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an effective strategy for gradually depositing an active layer by a simple spin-coating process so as to realize a ternary organic solar cell with ideal longitudinal composition gradient and high efficiency in the active layer.
The high-efficiency ternary organic solar cell comprises a substrate, an anode modification layer, an active layer, a cathode modification layer and a cathode from top to bottom, wherein the active layer is formed by sequentially depositing a layer of electron donor film and a layer of electron acceptor compound film on the anode modification layer by adopting a spin coating process.
The electron donor is a wide-bandgap polymer donor PM6, the electron acceptor compound is formed by mixing two non-fullerene acceptors BO-4Cl and BTP-S2 according to different proportions, and the chemical structural formula of the polymer donor and the non-fullerene acceptors is as follows:
The electron donor film is formed by spin coating PM6 solution with the concentration of 6-10mg/mL, the electron acceptor compound film is formed by spin coating non-fullerene acceptor mixture (BO-4 Cl and BTP-S2) solution with the total concentration of 6-10mg/mL, and the total thickness of the active layer is 50-200 nm. The effect of the ternary organic solar cell produced is very excellent when the proportion of BTP-S2 in the total weight of the acceptor mixture is 15% -75%, especially when the mass ratio of BTP-S2 in the acceptor mixture is 25%.
The electron acceptor compound film is added with an additive during film forming, wherein the additive is 1, 8-Diiodooctane (DIO), and the volume of the additive is 0.2-1% of the volume of the non-fullerene acceptor mixture solution.
The active layer is annealed at 80-200 deg.c for 5-60 min.
Typically, the substrate is glass; the anode is ITO; the anode modification layer is PEDOT: PSS; the cathode modification layer is PFN-Br; the cathode is Ag.
The innovation point of the invention is that a ternary strategy is adopted, namely, a mixture of two non-fullerene receptors BO-4Cl and BTP-S2 is used for replacing the traditional non-fullerene receptor BO-4Cl, so that the following advantages are brought: 1. because the acceptor BTP-S2 has poor compatibility with the donor PM6, even under the condition that a donor film and an acceptor film are sequentially deposited by adopting the same solvent and a simple spin coating process, the interdiffusion between the upper and lower donor/acceptor films is limited, so that an active layer can have an ideal P-i-N morphology structure, namely a donor rich phase (P) is formed at an anode modification layer interface, a acceptor rich phase (N) is formed at a cathode modification layer interface, and a bulk heterojunction thick film (i) with good mixing and uniform distribution of the donor and the acceptor is arranged in the middle. Therefore, the obtained ternary organic solar cell greatly inhibits charge recombination, and simultaneously realizes high-efficiency generation and high-efficiency collection of photocurrent. 2. The introduction of the second acceptor BTP-S2 optimizes the energy level structure of the active layer and improves the crystallinity of the material, thereby improving the photovoltage of the battery and further improving the charge collection efficiency. Because of the above advantages, the ternary organic solar cell (PM 6/BO-4Cl: BTP-S2) prepared by the method of the invention achieves the highest energy conversion efficiency (PCE=18.50%) of the organic solar cell so far, which is significantly better than the binary organic solar cell (PM 6/BO-4Cl, 16.66%) prepared by the corresponding step-by-step deposition method, and the ternary organic solar cell (PM 6: BO-4Cl: BTP-S2, 18.07%) based on the bulk heterojunction structure.
Drawings
FIG. 1LbL method preparation and EQE spectra of conventional BHJ type organic solar cells.
Fig. 2 is a current-voltage curve of a BHJ type organic solar cell under light. The active layer thickness of the cell was about 115nm, 1, 8-Diiodooctane (DIO) was added in an amount of 0.25% by volume of the active layer solution, the total weight ratio of PM6 to non-fullerene acceptor mixture (BO-4 Cl and BTP-S2) in the active layer was 1:1.2, the proportion of BTP-S2 in the non-fullerene acceptor mixture was varied from 0% to 100%, and the cell was annealed at 100℃for 10 min.
Fig. 3 is a current-voltage curve of an LbL-type organic solar cell under illumination. The active layer of the battery is about 115nm thick, 1, 8-Diiodooctane (DIO) accounting for 0.25% of the volume of the solution is added into an acceptor mixture during preparation, PM6 in the active layer is firstly spin-coated to form a film, the acceptor mixture is spin-coated to form a film, the proportion of BTP-S2 in a non-fullerene acceptor mixture is changed from 0% to 100%, and annealing treatment is carried out at 100 ℃ for 10 min.
Detailed Description
Example 1
Sequentially ultrasonically oscillating and cleaning transparent conductive glass with strip-shaped ITO (anode) etched on the surface by using a cleaning agent, deionized water, acetone and isopropanol, drying, and treating for 15 minutes by using ultraviolet ozone; a20 nm thick layer of PEDOT PSS was then spin coated onto the surface of the conductive glass at 4500rpm, followed by an annealing treatment at 170℃for 20 minutes, followed by transfer of the flakes into a glove box. Preparation of BHJ-type organic solar cell: a mixed solution of PM6:BO-4Cl (weight ratio: 1:1.2) added with 0.25% by volume of 1, 8-Diiodooctane (DIO) and a total concentration of 17.6mg/mL in chloroform was spin-coated at 3500rpm for 30 seconds to obtain a 115nm thick active layer. The active layer was annealed at 100 ℃ for 10min. A5 nm thick PFN-Br modification layer was then spin coated onto the active layer with 0.5mg/mL PFN-Br in methanol. Finally, an Ag electrode (cathode) with the thickness of 100nm is evaporated by an evaporator, so that an organic solar cell with the effective area of 4mm 2 is obtained.
The current-voltage curve of the device was tested under an AM1.5 simulated solar light with an illumination intensity of 100mW/cm 2, from which an open circuit voltage of 0.854V, a short circuit current density of 26.64mA/cm 2, a fill factor of 73.43% and a PCE of 16.75% was obtained.
FIG. 1 shows the external quantum efficiency curve of the device under the irradiation of AM1.5 simulated sunlight with the illumination intensity of 100mW/cm 2.
FIG. 2 shows the current-voltage curve of the device under an AM1.5 simulated solar light with an illumination intensity of 100mW/cm 2.
Example 2
Sequentially ultrasonically oscillating and cleaning transparent conductive glass with strip-shaped ITO (anode) etched on the surface by using a cleaning agent, deionized water, acetone and isopropanol, drying, and treating for 15 minutes by using ultraviolet ozone; a20 nm thick layer of PEDOT PSS was then spin coated onto the surface of the conductive glass at 4500rpm, followed by an annealing treatment at 170℃for 20 minutes, followed by transfer of the flakes into a glove box. Preparation of BHJ-type organic solar cell: a mixed solution of 1, 8-Diiodooctane (DIO) added with a volume ratio of 0.25% and PM6:BO-4Cl:BTP-S2 (wherein the total weight ratio of the donor and the acceptor is 1:1.2, and the mass ratio of BTP-S2 in the acceptor is 15%) in chloroform was spin-coated for 30 seconds at 3500rpm to obtain a 115nm thick active layer. The active layer was annealed at 100 ℃ for 10min. A5 nm thick PFN-Br modification layer was then spin coated onto the active layer with 0.5mg/mL PFN-Br in methanol. Finally, an Ag electrode (cathode) with the thickness of 100nm is evaporated by an evaporator, so that an organic solar cell with the effective area of 4mm 2 is obtained.
The current-voltage curve of the device was tested under an AM1.5 simulated solar light with an illumination intensity of 100mW/cm 2, from which an open circuit voltage of 0.870V, a short circuit current density of 26.93mA/cm 2, a fill factor of 75.33% and a PCE of 17.71% was obtained.
Example 3
Sequentially ultrasonically oscillating and cleaning transparent conductive glass with strip-shaped ITO (anode) etched on the surface by using a cleaning agent, deionized water, acetone and isopropanol, drying, and treating for 15 minutes by using ultraviolet ozone; a20 nm thick layer of PEDOT PSS was then spin coated onto the surface of the conductive glass at 4500rpm, followed by an annealing treatment at 170℃for 20 minutes, followed by transfer of the flakes into a glove box. Preparation of BHJ-type organic solar cell: a mixed solution of 0.25% 1, 8-Diiodooctane (DIO) and 17.6mg/mL total PM6:BO-4Cl: BTP-S2 (wherein the total weight ratio of donor to acceptor is 1:1.2, and the mass ratio of BTP-S2 in acceptor is 25%) in chloroform was spin-coated at 3500rpm for 30 seconds to obtain a 115nm thick active layer. The active layer was annealed at 100 ℃ for 10min. A5 nm thick PFN-Br modification layer was then spin coated onto the active layer with 0.5mg/mL PFN-Br in methanol. Finally, an Ag electrode (cathode) with the thickness of 100nm is evaporated by an evaporator, so that an organic solar cell with the effective area of 4mm 2 is obtained.
The current-voltage curve of the device was tested under an AM1.5 simulated solar light with an illumination intensity of 100mW/cm 2, from which an open circuit voltage of 0.886V, a short circuit current density of 26.86mA/cm 2, a fill factor of 75.98% and a PCE of 18.07% was obtained.
FIG. 1 shows the external quantum efficiency curve of the device under the irradiation of AM1.5 simulated sunlight with the illumination intensity of 100mW/cm 2.
FIG. 2 shows the current-voltage curve of the device under an AM1.5 simulated solar light with an illumination intensity of 100mW/cm 2.
Example 4
Sequentially ultrasonically oscillating and cleaning transparent conductive glass with strip-shaped ITO (anode) etched on the surface by using a cleaning agent, deionized water, acetone and isopropanol, drying, and treating for 15 minutes by using ultraviolet ozone; a20 nm thick layer of PEDOT PSS was then spin coated onto the surface of the conductive glass at 4500rpm, followed by an annealing treatment at 170℃for 20 minutes, followed by transfer of the flakes into a glove box. Preparation of BHJ-type organic solar cell: a mixed solution of 1, 8-Diiodooctane (DIO) added with a volume ratio of 0.25% and PM6:BO-4Cl:BTP-S2 (wherein the total weight ratio of the donor and the acceptor is 1:1.2, and the mass ratio of BTP-S2 in the acceptor is 35%) in chloroform was spin-coated for 30 seconds at 3500rpm to obtain a 115nm thick active layer. The active layer was annealed at 100 ℃ for 10min. A5 nm thick PFN-Br modification layer was then spin coated onto the active layer with 0.5mg/mL PFN-Br in methanol. Finally, an Ag electrode (cathode) with the thickness of 100nm is evaporated by an evaporator, so that an organic solar cell with the effective area of 4mm 2 is obtained.
The current-voltage curve of the device was tested under an AM1.5 simulated solar light with an illumination intensity of 100mW/cm 2, from which an open circuit voltage of 0.890V, a short circuit current density of 26.86mA/cm 2, a fill factor of 74.79% and a PCE of 17.81% was obtained.
Example 5
Sequentially ultrasonically oscillating and cleaning transparent conductive glass with strip-shaped ITO (anode) etched on the surface by using a cleaning agent, deionized water, acetone and isopropanol, drying, and treating for 15 minutes by using ultraviolet ozone; a20 nm thick layer of PEDOT PSS was then spin coated onto the surface of the conductive glass at 4500rpm, followed by an annealing treatment at 170℃for 20 minutes, followed by transfer of the flakes into a glove box. Preparation of BHJ-type organic solar cell: a mixed solution of 1, 8-Diiodooctane (DIO) added with a volume ratio of 0.25% and PM6:BO-4Cl:BTP-S2 (wherein the total weight ratio of the donor and the acceptor is 1:1.2, and the mass ratio of BTP-S2 in the acceptor is 50%) in chloroform was spin-coated for 30 seconds at 3500rpm to obtain a 115nm thick active layer. The active layer was annealed at 100 ℃ for 10min. A5 nm thick PFN-Br modification layer was then spin coated onto the active layer with 0.5mg/mL PFN-Br in methanol. Finally, an Ag electrode (cathode) with the thickness of 100nm is evaporated by an evaporator, so that an organic solar cell with the effective area of 4mm 2 is obtained.
The current-voltage curve of the device was tested under an AM1.5 simulated solar light with an illumination intensity of 100mW/cm 2, from which an open circuit voltage of 0.897V, a short circuit current density of 26.13mA/cm 2, a fill factor of 74.12% and a PCE of 17.32% was obtained.
Example 6
Sequentially ultrasonically oscillating and cleaning transparent conductive glass with strip-shaped ITO (anode) etched on the surface by using a cleaning agent, deionized water, acetone and isopropanol, drying, and treating for 15 minutes by using ultraviolet ozone; a20 nm thick layer of PEDOT PSS was then spin coated onto the surface of the conductive glass at 4500rpm, followed by an annealing treatment at 170℃for 20 minutes, followed by transfer of the flakes into a glove box. Preparation of BHJ-type organic solar cell: 1, 8-Diiodooctane (DIO) was added at a volume ratio of 0.25% and PM6 at a total concentration of 17.6 mg/mL: a mixed solution of BTP-S2 (weight ratio of 1:1.2) in chloroform was spin-coated at 3500rpm for 30 seconds to obtain a 115nm thick active layer. The active layer was annealed at 100 ℃ for 10min. A5 nm thick PFN-Br modification layer was then spin coated onto the active layer with 0.5mg/mL PFN-Br in methanol. Finally, an Ag electrode (cathode) with the thickness of 100nm is evaporated by an evaporator, so that an organic solar cell with the effective area of 4mm 2 is obtained.
The current-voltage curve of the device was tested under an AM1.5 simulated solar light with an illumination intensity of 100mW/cm 2, from which an open circuit voltage of 0.950V, a short circuit current density of 22.00mA/cm 2, a fill factor of 70.35% and a PCE of 14.74% was obtained.
FIG. 1 shows the external quantum efficiency curve of the device under the irradiation of AM1.5 simulated sunlight with the illumination intensity of 100mW/cm 2.
FIG. 2 shows the current-voltage curve of the device under an AM1.5 simulated solar light with an illumination intensity of 100mW/cm 2.
Example 7
Sequentially ultrasonically oscillating and cleaning transparent conductive glass with strip-shaped ITO (anode) etched on the surface by using a cleaning agent, deionized water, acetone and isopropanol, drying, and treating for 15 minutes by using ultraviolet ozone; a20 nm thick layer of PEDOT PSS was then spin coated onto the surface of the conductive glass at 4500rpm, followed by an annealing treatment at 170℃for 20 minutes, followed by transfer of the flakes into a glove box. Preparation of an LbL-type organic solar cell: a solution of PM6 in chloroform at a concentration of 8mg/mL was spin-coated at 2000rpm for 30 seconds to give a 60nm thick donor layer. Next, a solution of BO-4Cl in chloroform, added with 0.25% by volume of 1, 8-Diiodooctane (DIO), at a concentration of 8mg/mL, was spin-coated at 2000rpm for 30 seconds to give an active layer having a total thickness of 115 nm. The active layer was annealed at 100 ℃ for 10min. A5 nm thick PFN-Br modification layer was then spin coated onto the active layer with 0.5mg/mL PFN-Br in methanol. Finally, an Ag electrode (cathode) with the thickness of 100nm is evaporated by an evaporator, so that an organic solar cell with the effective area of 4mm 2 is obtained.
The current-voltage curve of the device was tested under an AM1.5 simulated solar light with an illumination intensity of 100mW/cm 2, from which an open circuit voltage of 0.854V, a short circuit current density of 26.68mA/cm 2, a fill factor of 75.85% and a PCE of 17.28% was obtained.
FIG. 1 shows the external quantum efficiency curve of the device under the irradiation of AM1.5 simulated sunlight with the illumination intensity of 100mW/cm 2.
FIG. 3 shows the current-voltage curve of the device under an AM1.5 simulated solar light with an illumination intensity of 100mW/cm 2.
Example 8
Sequentially ultrasonically oscillating and cleaning transparent conductive glass with strip-shaped ITO (anode) etched on the surface by using a cleaning agent, deionized water, acetone and isopropanol, drying, and treating for 15 minutes by using ultraviolet ozone; a20 nm thick layer of PEDOT PSS was then spin coated onto the surface of the conductive glass at 4500rpm, followed by an annealing treatment at 170℃for 20 minutes, followed by transfer of the flakes into a glove box. Preparation of an LbL-type organic solar cell: a solution of PM6 in chloroform at a concentration of 8mg/mL was spin-coated at 2000rpm for 30 seconds to give a 60nm thick donor layer. 1, 8-Diiodooctane (DIO) was then added at a volume ratio of 0.25% and a total concentration of 8mg/mL BO-4Cl: a solution of BTP-S2 (wherein BTP-S2 represents 15% by mass) in chloroform was spin-coated at 2000rpm for 30 seconds to give an active layer having a total thickness of 115 nm. The active layer was annealed at 100 ℃ for 10min. A5 nm thick PFN-Br modification layer was then spin coated onto the active layer with 0.5mg/mL PFN-Br in methanol. Finally, an Ag electrode (cathode) with the thickness of 100nm is evaporated by an evaporator, so that an organic solar cell with the effective area of 4mm 2 is obtained.
The current-voltage curve of the device was tested under an AM1.5 simulated solar light with an illumination intensity of 100mW/cm 2, from which an open circuit voltage of 0.869V, a short circuit current density of 27.03mA/cm 2, a fill factor of 76.58% and a PCE of 18.00% was obtained.
Example 9
Sequentially ultrasonically oscillating and cleaning transparent conductive glass with strip-shaped ITO (anode) etched on the surface by using a cleaning agent, deionized water, acetone and isopropanol, drying, and treating for 15 minutes by using ultraviolet ozone; a20 nm thick layer of PEDOT PSS was then spin coated onto the surface of the conductive glass at 4500rpm, followed by an annealing treatment at 170℃for 20 minutes, followed by transfer of the flakes into a glove box. Preparation of an LbL-type organic solar cell: a solution of PM6 in chloroform at a concentration of 8mg/mL was spin-coated at 2000rpm for 30 seconds to give a 60nm thick donor layer. 1, 8-Diiodooctane (DIO) was then added at a volume ratio of 0.25% and a total concentration of 8mg/mL BO-4Cl: a solution of BTP-S2 (wherein BTP-S2 represents 25% by mass) in chloroform was spin-coated at 2000rpm for 30 seconds to give an active layer having a total thickness of 115 nm. The active layer was annealed at 100 ℃ for 10min. A5 nm thick PFN-Br modification layer was then spin coated onto the active layer with 0.5mg/mL PFN-Br in methanol. Finally, an Ag electrode (cathode) with the thickness of 100nm is evaporated by an evaporator, so that an organic solar cell with the effective area of 4mm 2 is obtained.
The current-voltage curve of the device was tested under an AM1.5 simulated solar light with an illumination intensity of 100mW/cm 2, from which an open circuit voltage of 0.886V, a short circuit current density of 27.15mA/cm 2, a fill factor of 77.21% and a PCE of 18.50% was obtained.
FIG. 1 shows the external quantum efficiency curve of the device under the irradiation of AM1.5 simulated sunlight with the illumination intensity of 100mW/cm 2.
FIG. 3 shows the current-voltage curve of the device under an AM1.5 simulated solar light with an illumination intensity of 100mW/cm 2.
Example 10
Sequentially ultrasonically oscillating and cleaning transparent conductive glass with strip-shaped ITO (anode) etched on the surface by using a cleaning agent, deionized water, acetone and isopropanol, drying, and treating for 15 minutes by using ultraviolet ozone; a20 nm thick layer of PEDOT PSS was then spin coated onto the surface of the conductive glass at 4500rpm, followed by an annealing treatment at 170℃for 20 minutes, followed by transfer of the flakes into a glove box. Preparation of an LbL-type organic solar cell: a solution of PM6 in chloroform at a concentration of 8mg/mL was spin-coated at 2000rpm for 30 seconds to give a 60nm thick donor layer. 1, 8-Diiodooctane (DIO) was then added at a volume ratio of 0.25% and a total concentration of 8mg/mL BO-4Cl: a solution of BTP-S2 (wherein the BTP-S2 accounts for 35% by mass) in chloroform was spin-coated at 2000rpm for 30 seconds to obtain an active layer having a total thickness of 115 nm. The active layer was annealed at 100 ℃ for 10min. A5 nm thick PFN-Br modification layer was then spin coated onto the active layer with 0.5mg/mL PFN-Br in methanol. Finally, an Ag electrode (cathode) with the thickness of 100nm is evaporated by an evaporator, so that an organic solar cell with the effective area of 4mm 2 is obtained.
The current-voltage curve of the device was tested under an AM1.5 simulated solar light with an illumination intensity of 100mW/cm 2, from which an open circuit voltage of 0.886V, a short circuit current density of 26.60mA/cm 2, a fill factor of 76.64%, and a PCE of 17.99% was obtained.
Example 11
Sequentially ultrasonically oscillating and cleaning transparent conductive glass with strip-shaped ITO (anode) etched on the surface by using a cleaning agent, deionized water, acetone and isopropanol, drying, and treating for 15 minutes by using ultraviolet ozone; a20 nm thick layer of PEDOT PSS was then spin coated onto the surface of the conductive glass at 4500rpm, followed by an annealing treatment at 170℃for 20 minutes, followed by transfer of the flakes into a glove box. Preparation of an LbL-type organic solar cell: a solution of PM6 in chloroform at a concentration of 8mg/mL was spin-coated at 2000rpm for 30 seconds to give a 60nm thick donor layer. 1, 8-Diiodooctane (DIO) was then added at a volume ratio of 0.25% and a total concentration of 8mg/mL BO-4Cl: a solution of BTP-S2 (wherein BTP-S2 represents 50% by mass) in chloroform was spin-coated at 2000rpm for 30 seconds to give an active layer having a total thickness of 115 nm. The active layer was annealed at 100 ℃ for 10min. A5 nm thick PFN-Br modification layer was then spin coated onto the active layer with 0.5mg/mL PFN-Br in methanol. Finally, an Ag electrode (cathode) with the thickness of 100nm is evaporated by an evaporator, so that an organic solar cell with the effective area of 4mm 2 is obtained.
The current-voltage curve of the device was tested under an AM1.5 simulated solar light with an illumination intensity of 100mW/cm 2, from which an open circuit voltage of 0.899V, a short circuit current density of 25.64mA/cm 2, a fill factor of 76.76%, and a PCE of 17.63% was obtained.
Example 12
Sequentially ultrasonically oscillating and cleaning transparent conductive glass with strip-shaped ITO (anode) etched on the surface by using a cleaning agent, deionized water, acetone and isopropanol, drying, and treating for 15 minutes by using ultraviolet ozone; a20 nm thick layer of PEDOT PSS was then spin coated onto the surface of the conductive glass at 4500rpm, followed by an annealing treatment at 170℃for 20 minutes, followed by transfer of the flakes into a glove box. Preparation of an LbL-type organic solar cell: a solution of PM6 in chloroform at a concentration of 8mg/mL was spin-coated at 2000rpm for 30 seconds to give a 60nm thick donor layer. Next, a solution of BTP-S2 in chloroform, to which 1, 8-Diiodooctane (DIO) was added at a volume ratio of 0.25%, at a concentration of 8mg/mL was spin-coated at 2000rpm for 30 seconds to obtain an active layer having a total thickness of 115 nm. The active layer was annealed at 100 ℃ for 10min. A5 nm thick PFN-Br modification layer was then spin coated onto the active layer with 0.5mg/mL PFN-Br in methanol. Finally, an Ag electrode (cathode) with the thickness of 100nm is evaporated by an evaporator, so that an organic solar cell with the effective area of 4mm 2 is obtained.
The current-voltage curve of the device was tested under an AM1.5 simulated solar light with an illumination intensity of 100mW/cm 2, from which an open circuit voltage of 0.956V, a short circuit current density of 22.68mA/cm 2, a fill factor of 71.29% and a PCE of 15.51% was obtained.
FIG. 1 shows the external quantum efficiency curve of the device under the irradiation of AM1.5 simulated sunlight with the illumination intensity of 100mW/cm 2.
FIG. 3 shows the current-voltage curve of the device under an AM1.5 simulated solar light with an illumination intensity of 100mW/cm 2.

Claims (5)

1. The high-efficiency ternary organic solar cell prepared based on a step-by-step deposition method comprises a substrate, an anode modification layer, an active layer, a cathode modification layer and a cathode from bottom to top, and is characterized in that the active layer is formed by sequentially depositing a layer of electron donor film and a layer of electron acceptor compound film on the anode modification layer by adopting a spin coating process;
The electron donor is a wide-bandgap polymer donor PM6, the electron acceptor compound is formed by mixing two non-fullerene acceptors BO-4Cl and BTP-S2, and the chemical structural formula of the polymer donor and the non-fullerene acceptors is as follows:
。
2. The efficient ternary organic solar cell prepared based on the step-by-step deposition method according to claim 1, wherein the electron donor film is formed by spin-coating a PM6 solution with a concentration of 6-10 mg/mL, the electron acceptor composite film is formed by spin-coating a mixture solution of non-fullerene acceptor BO-4Cl and BTP-S2 with a total concentration of 6-10 mg/mL, and the total thickness of the active layer is 50-200 nm.
3. The efficient ternary organic solar cell prepared on the basis of a step-by-step deposition method according to claim 1 or 2, wherein an additive is added during film formation, and the additive is 1, 8-Diiodooctane (DIO), and the volume of the additive is 0.2-1% of the volume of the solution of the non-fullerene acceptor mixture.
4. The efficient ternary organic solar cell prepared based on the step-by-step deposition method according to claim 1, wherein the active layer is annealed at 80-200 ℃ for 5-60 min.
5. The efficient ternary organic solar cell prepared based on the step-by-step deposition method according to claim 1, wherein the efficient ternary organic solar cell is characterized in that: the substrate is glass; the anode is ITO; the anode modification layer is PEDOT: PSS; the cathode modification layer is PFN-Br; the cathode is Ag.
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