CN116056470A - High-efficiency organic solar cell prepared by solid additive auxiliary step-by-step deposition method - Google Patents

High-efficiency organic solar cell prepared by solid additive auxiliary step-by-step deposition method Download PDF

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CN116056470A
CN116056470A CN202310051536.5A CN202310051536A CN116056470A CN 116056470 A CN116056470 A CN 116056470A CN 202310051536 A CN202310051536 A CN 202310051536A CN 116056470 A CN116056470 A CN 116056470A
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solar cell
organic solar
solid additive
active layer
electron acceptor
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陈红征
丁观宇
左立见
陈天一
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Zhejiang University ZJU
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Abstract

The invention discloses a high-efficiency organic solar cell prepared by a solid additive auxiliary gradual deposition method, which comprises a substrate, an anode modification layer, an active layer, a cathode modification layer and a cathode which are sequentially arranged from bottom to top; the active layer consists of an electron donor and solid additive compound film and an electron acceptor film which are sequentially deposited on the anode modification layer; the solid additive is solid fatty acid FA-C shown in the following formula n Wherein n is 9 to 17:
Figure DDA0004058266990000011
the invention can adopt a simple spin coating process to gradually deposit the active layer so as to realize the organic solar cell with controllable vertical phase separation structure and high efficiency in the active layer.

Description

High-efficiency organic solar cell prepared by solid additive auxiliary step-by-step deposition method
Technical Field
The invention relates to the field of organic solar cells, in particular to a high-efficiency organic solar cell prepared by a solid additive auxiliary gradual deposition method.
Background
Organic solar cells have attracted considerable attention because of their colorful, translucent, low cost, flexible and large-area fabrication. Recently, the energy conversion efficiency of single junction cells has broken through 19% and reached the standard of industrial mass production (Nat. Mater.21 (6), 656-663 (2022)).
In addition to developing new molecules with excellent photovoltaic properties, it is equally important to construct appropriate active layer morphologies and to develop materials in device fabrication. At present, the organic solar cells with the best performance are all based on bulk heterojunction prepared by a mixed deposition method, namely an electron donor and an electron acceptor are simultaneously dissolved in a solvent, and an active layer is obtained by spin coating, so that the phase separation of the acceptor in the process of spin coating film formation is extremely dependent on spontaneous thermodynamic and kinetic behaviors of the acceptor, the phase separation degree is not easy to regulate, and the improper morphology can lead to charge recombination. Holes are extracted by the anode along the donor phase transport channel and electrons are extracted by the cathode along the acceptor phase transport channel, so the degree of phase separation has an important effect on the generation and transport of charges: on the one hand, the limited exciton diffusion length of organic semiconductors dictates that there must be sufficient donor and acceptor interface area, i.e., less phase separation, to dissociate the excitons; on the other hand, large phase separation means a decrease in interface area and an increase in phase purity, which may slow down recombination of holes and electrons. Thus, proper phase separation is necessary for charge transport and collection without affecting exciton dissociation. However, precise control of the nano-sized structures and the degree of phase separation of the donor and acceptor is challenging, limiting the commercial production of organic solar cells.
Currently, the quasi-planar heterojunction of p-i-n structure prepared by the step-by-step deposition method is gradually considered to be a more ideal structure than the bulk heterojunction, in which the donor is enriched at the top and the acceptor is enriched at the bottom, which can effectively inhibit the recombination of charges during the transport to the anode and cathode (adv. Mater.33 (43), e2103091 (2021); na. Commun.12 (1), 468 (2021); adv. Mater.33 (12), e2007231 (2021)). In addition, during the stepwise deposition process, the acceptor permeates into the donor film and phase separation is formed, so that concentration gradient distribution is formed in the vertical direction, and charge transmission and extraction are facilitated. However, a significant disadvantage of the stepwise deposition method alone is that the diffusion of the receptor during deposition is not controllable. In addition, the degree of phase separation is also difficult to control due to the simultaneous solvation and interdiffusion effects. Therefore, controllable vertical phase separation is realized, and the degree of phase separation is regulated so that the exciton diffusion length and the charge transport distance are matched, thus having important scientific research and application value.
Disclosure of Invention
Aiming at the technical problems and the defects existing in the field, the invention provides a high-efficiency organic solar cell prepared by a solid additive auxiliary gradual deposition method, and an active layer can be gradually deposited by adopting a simple spin-coating process so as to realize the organic solar cell with a controllable vertical phase separation structure and high efficiency in the active layer.
The high-efficiency organic solar cell prepared by a solid additive auxiliary gradual deposition method comprises a substrate, an anode modification layer, an active layer, a cathode modification layer and a cathode which are sequentially arranged from bottom to top;
the active layer consists of an electron donor and solid additive composite film and an electron acceptor film which are sequentially deposited on the anode modification layer;
the solid additive is solid fatty acid FA-C shown in the following formula n Wherein n is 9 to 17:
Figure BDA0004058266970000021
the invention utilizes electron donor and FA-C n (n=9 to 17) phase separation constructed in advance, which allows the receptor to smoothly enter FA-C n (n=9-17) so that the active layer has a desirable vertical phase separation structure, i.e. an enriched phase of the donor is formed at the anode modification layer interface, an enriched phase of the acceptor is formed at the cathode modification layer interface, and a suitable intermediate donor and acceptor are formedIs a phase separation dimension of (c). Therefore, the binary organic solar cell obtained by the invention realizes the cooperative promotion of short-circuit current and filling factor, and the energy conversion efficiency exceeds that of the binary organic solar cell prepared by a mixed deposition method and a gradual deposition method, and the binary organic solar cell based on PM6:Y6 obtains the highest efficiency of 18.16%; the binary organic solar cell based on the PM6:L8-BO system achieves 19.02% efficiency, and is one of the highest efficiencies of the current binary organic solar cells.
The invention can adapt to various donor-acceptor systems by changing the carbon atom number and the addition amount of the solid additive. In a preferred embodiment, the mass ratio of the electron donor to the solid additive is 100:5-15, more preferably 100:5-10 and the solid additive is FA-C 12 . The binary organic solar cell produced is very excellent when the mass ratio of the solid additive to the electron donor is increased from 5:100 to 15:100, especially when the mass ratio of the solid additive to the electron donor is 10:100, the binary organic solar cell based on PM6:Y6 and PM6:L8-BO is optimal.
Preferably, the electron donor is a p-type semiconductor selected from wide band gap polymer donors, in particular PM6 or D18.
Figure BDA0004058266970000031
In the molecular structures of PM6 and D18, n represents the degree of polymerization, and in PM6, n=17 to 33; d18, n=31 to 47.
Preferably, the electron acceptor is an n-type semiconductor and is selected from organic small molecule condensed ring acceptors, in particular Y6 or L8-BO.
Figure BDA0004058266970000032
In a preferred embodiment, the electron donor and solid additive composite film is spin coated from a chloroform solution of a mixture of electron donor and solid additive having a total concentration of 7-13 mg/mL.
In a preferred embodiment, the electron acceptor film is spin-coated from a chloroform solution of electron acceptor at a concentration of 8-15 mg/mL.
Preferably, the total thickness of the active layer is 95-250nm, wherein the mass ratio of the electron donor to the electron acceptor is 1:1.1-1.3.
In a preferred example, 1-Chloronaphthalene (CN) is also added to the electron acceptor solution as an additive, wherein the addition volume of the 1-chloronaphthalene is 0.5% -0.7% of the volume of the electron acceptor solution.
Figure BDA0004058266970000033
In another preferred example, 1, 8-Diiodooctane (DIO) is further added as an additive to the electron acceptor solution, the addition volume of 1, 8-diiodooctane being 0.2% to 0.3% of the volume of the electron acceptor solution.
Figure BDA0004058266970000041
Preferably, after the electron donor and solid additive compound film and the electron acceptor film are sequentially deposited on the anode modification layer, annealing treatment is carried out, wherein the annealing temperature is 80-100 ℃, and the annealing time is 5-8 min.
In a preferred embodiment, the substrate is transparent glass; the anode is an Indium Tin Oxide (ITO); the anode modification layer is poly (3, 4-ethylidepoxithiophen): polystyrene sulfonate (PEDOT: PSS); the cathode modification layer is N, N' -Bis {3- [3- (dimethyl lamino) propyl ] propyl } perylene-3,4,9,10-tetraca rboxylic diimide (PDINN); the cathode is Ag.
The innovation point of the invention is that a solid additive assisted gradual deposition method is adopted, namely solid fatty acid FA-C is mixed into an electron donor solution n (n=9 to 17), thereby bringing about the following advantages:
1. due to FA-C n (n=9 to 17) has suitable compatibility with the polymer electron donor, and therefore inFA-C during deposition of the first layer electron donor and solid additive composite film n (n=9-17) and electron donor to form ideal phase separation morphology, and during depositing the second electron acceptor film, chloroform dissolves the solid additive and the electron acceptor can enter the film from FA-C n The channels constructed in the way of (n=9-17) enable the polymer electron donor and the organic micromolecule condensed ring electron acceptor to form an ideal phase separation structure, so that the polymer electron donor and the organic micromolecule condensed ring electron acceptor have enough interface area for the dissociation of excitons and enough phase purity to ensure the smooth transmission and collection of charges. Thus, the resulting organic solar cell achieves a simultaneous increase in short-circuit current and fill factor.
2. When the solution is spin-coated with organic micromolecule condensed ring electron acceptor, the solution is due to FA-C n (n=9 to 17) as small molecules can be dissolved rapidly by chloroform, while the polymer electron donor can only be swollen, furthermore FA-C n (n=9 to 17) as impurities disturb the regular packing of the polymer chains, so that the amorphous state of the chains increases, and thus FA-C n The introduction of (n=9 to 17) can promote the penetration and diffusion of the electron acceptor, so that the active layer has an ideal p-i-n morphology structure, i.e. an enriched phase (p) of the donor is formed at the interface of the anode modification layer, an enriched phase (n) of the acceptor is formed at the interface of the cathode modification layer, and a heterojunction (i) of the donor well mixed with the acceptor and having an ideal vertical phase separation structure is in the middle.
Due to the advantages, the binary organic solar cell PM6:Y6 prepared by the method obtains 18.16% of energy conversion efficiency which is higher than that of binary organic solar cells prepared by 17.52% of corresponding step-by-step deposition method and 16.80% of mixed deposition method. In the PM6:L8-BO system, the binary organic solar cell prepared by the method obtains 19.02% of energy conversion efficiency, which is one of the highest efficiencies of the binary organic solar cells so far, and is obviously superior to the binary organic solar cell (PM 6:L8-BO, 18.73%) prepared by the corresponding progressive deposition method and the binary organic solar cell (PM 6:L8-BO, 18.56%) prepared by the mixed deposition method.
In addition, the method of the invention has universality, and different donor-acceptor systems can reach the optimal phase separation degree by changing the carbon atom number and the addition amount of the solid additive.
Drawings
Fig. 1 is a schematic diagram of a hybrid deposition method, a step-by-step deposition method and a solid additive assisted step-by-step deposition method for preparing an active layer of an organic solar cell according to an embodiment of the present invention, where donor represents an electron donor and aceptor represents an electron acceptor.
Fig. 2 is a graph of current versus voltage for different processes of PM6:y6 organic solar cells under illumination. The thickness of the active layer prepared by adopting the mixed deposition method is about 100nm, 1-chloronaphthalene accounting for 0.5 percent of the volume of the active layer solution is added during the preparation, the total weight ratio of PM6 to Y6 in the active layer is 1:1.2, and the active layer is annealed at 80 ℃ for 8 min; the thickness of the active layer prepared by adopting a step-by-step deposition method is about 95nm, 1-chloronaphthalene accounting for 0.5% of the volume of the solution is added into a receptor during preparation, PM6 in the active layer is firstly spin-coated to form a film, Y6 is spin-coated to form a film, and the film is annealed at 80 ℃ for 8 min; the thickness of the active layer prepared by adopting a solid additive auxiliary step-by-step deposition method is about 95nm, 1-chloronaphthalene accounting for 0.5% of the volume of the solution is added into a receptor during preparation, a compound of a donor and the solid additive in the active layer is firstly spin-coated to form a film, and Y6 is then spin-coated to form a film, wherein the mass ratio of the solid additive to the donor is changed from 5:100 to 15:100, and the annealing treatment is carried out at 80 ℃ for 8min.
Detailed Description
The invention will be further elucidated with reference to the drawings and to specific embodiments. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The procedure not specified in the following examples is generally carried out in accordance with the usual conditions reported in the literature or in accordance with the conditions recommended by the manufacturer.
Example 1
Ultrasonically cleaning transparent conductive glass plated with ITO (anode) with a cleaning agent, deionized water, acetone, isopropanol and absolute ethyl alcohol for 15min, drying, and treating with ultraviolet ozone for 20min; a layer of 15nm thick PEDOT: PSS was then spin coated on the surface of the conductive glass at 4500rpm, followed by an annealing treatment at 150℃for 15 minutes, followed by transferring the flakes into a glove box. Hybrid deposition method: 1%Chloronaphthalene (CN) and PM6:Y6 (mass ratio 1:1.2) mixed solution with total concentration of 16mg/mL in chloroform were spin-coated at 3000rpm for 25s to obtain a 100nm thick active layer. The active layer was annealed at 80℃for 8min. Then spin-coating a PDINN modified layer with a thickness of 5nm on the active layer with 1mg/mL PDINN methanol solution, and finally evaporating a Ag electrode (cathode) with a thickness of 100nm by using an evaporator to obtain a cathode with an effective area of 6mm 2 Is provided.
At an illumination intensity of 100mW/cm 2 The current-voltage curve of the device was tested under the AM1.5 simulated sunlight, from which an open circuit voltage of 0.85V and a short circuit current density of 26.66mA/cm were obtained 2 The fill factor was 74.1% and the PCE was 16.80%.
FIG. 2 shows the device at an illumination intensity of 100mW/cm 2 AM1.5 of (c) simulates the current-voltage curve under solar irradiation.
Example 2
Ultrasonically cleaning transparent conductive glass plated with ITO (anode) with a cleaning agent, deionized water, acetone, isopropanol and absolute ethyl alcohol for 15min, drying, and treating with ultraviolet ozone for 20min; a layer of 15nm thick PEDOT: PSS was then spin coated on the surface of the conductive glass at 4500rpm, followed by an annealing treatment at 150℃for 15 minutes, followed by transferring the flakes into a glove box. Step-by-step deposition method: a solution of PM6 in chloroform at a concentration of 7mg/mL was spin-coated at 2500rpm for 25s to give a 55nm thick donor layer. Then, a solution of Y6 in chloroform was added at a total concentration of 8mg/mL with 1-Chloronaphthalene (CN) at a volume ratio of 0.5%, and spin-coated at a rotation speed of 2500rpm for 25 seconds to obtain an active layer having a total thickness of 95 nm. The active layer was annealed at 80℃for 8min. Then spin-coating a PDINN modified layer with a thickness of 5nm on the active layer with 1mg/mL PDINN methanol solution, and finally evaporating a Ag electrode (cathode) with a thickness of 100nm by using an evaporator to obtain a cathode with an effective area of 6mm 2 Is provided.
At an illumination intensity of 100mW/cm 2 The current-voltage curve of the device was tested under the AM1.5 simulated solar irradiation to obtain an open circuit voltage of 0.85V and a short circuit current density of 26.81mA/cm 2 The fill factor was 76.5% and the PCE 17.52%.
FIG. 2 shows the device at an illumination intensity of 100mW/cm 2 AM1.5 of (c) simulates the current-voltage curve under solar irradiation.
Example 3
Ultrasonically cleaning transparent conductive glass plated with ITO (anode) with a cleaning agent, deionized water, acetone, isopropanol and absolute ethyl alcohol for 15min, drying, and treating with ultraviolet ozone for 20min; a layer of 15nm thick PEDOT: PSS was then spin coated on the surface of the conductive glass at 4500rpm, followed by an annealing treatment at 150℃for 15 minutes, followed by transferring the flakes into a glove box. Solid additive assisted step-by-step deposition process: PM6:FA-C at a total concentration of 7mg/mL 12 (mass ratio 100:5) in chloroform, spin-coating at 2500rpm for 25s, to give a 55nm thick donor layer. Then, a solution of Y6 in chloroform was added at a total concentration of 8mg/mL with 1-Chloronaphthalene (CN) at a volume ratio of 0.5%, and spin-coated at a rotation speed of 2500rpm for 25 seconds to obtain an active layer having a total thickness of 95 nm. The active layer was annealed at 80℃for 8min. Then spin-coating a PDINN modified layer with a thickness of 5nm on the active layer with 1mg/mL PDINN methanol solution, and finally evaporating a Ag electrode (cathode) with a thickness of 100nm by using an evaporator to obtain a cathode with an effective area of 6mm 2 Is provided.
At an illumination intensity of 100mW/cm 2 The current-voltage curve of the device was tested under the AM1.5 simulated sunlight, from which an open circuit voltage of 0.85V and a short circuit current density of 26.78mA/cm were obtained 2 The fill factor was 77.3% and the PCE 17.65%.
FIG. 2 shows the device at an illumination intensity of 100mW/cm 2 AM1.5 of (c) simulates the current-voltage curve under solar irradiation.
Example 4
Ultrasonically cleaning transparent conductive glass plated with ITO (anode) with a cleaning agent, deionized water, acetone, isopropanol and absolute ethyl alcohol for 15min, drying, and treating with ultraviolet ozone for 20min; spin-coating a layer of 15nm thick PEDOT (PSS) on the surface of the conductive glass at 4500rpm, and annealing at 150deg.CThe pieces were then transferred to a glove box for 15 minutes. Solid additive assisted step-by-step deposition process: PM6:FA-C at a total concentration of 7mg/mL 12 (mass ratio 100:10) in chloroform, spin-coating at 2500rpm for 25s, to give a 55nm thick donor layer. Then, a solution of Y6 in chloroform was added at a total concentration of 8mg/mL with 1-Chloronaphthalene (CN) at a volume ratio of 0.5%, and spin-coated at a rotation speed of 2500rpm for 25 seconds to obtain an active layer having a total thickness of 95 nm. The active layer was annealed at 80℃for 8min. Then spin-coating a PDINN modified layer with a thickness of 5nm on the active layer with 1mg/mL PDINN methanol solution, and finally evaporating a Ag electrode (cathode) with a thickness of 100nm by using an evaporator to obtain a cathode with an effective area of 6mm 2 Is provided.
At an illumination intensity of 100mW/cm 2 The current-voltage curve of the device was tested under the AM1.5 simulated sunlight, from which an open circuit voltage of 0.85V and a short circuit current density of 27.74mA/cm were obtained 2 The fill factor was 76.7% and the PCE was 18.16%.
FIG. 2 shows the device at an illumination intensity of 100mW/cm 2 AM1.5 of (c) simulates the current-voltage curve under solar irradiation.
Example 5
Ultrasonically cleaning transparent conductive glass plated with ITO (anode) with a cleaning agent, deionized water, acetone, isopropanol and absolute ethyl alcohol for 15min, drying, and treating with ultraviolet ozone for 20min; a layer of 15nm thick PEDOT: PSS was then spin coated on the surface of the conductive glass at 4500rpm, followed by an annealing treatment at 150℃for 15 minutes, followed by transferring the flakes into a glove box. Solid additive assisted step-by-step deposition process: PM6:FA-C at a total concentration of 7mg/mL 12 (mass ratio 100:15) in chloroform, spin-coating at 2500rpm for 25s, to give a 55nm thick donor layer. Then, a solution of Y6 in chloroform was added at a total concentration of 8mg/mL with 1-Chloronaphthalene (CN) at a volume ratio of 0.5%, and spin-coated at a rotation speed of 2500rpm for 25 seconds to obtain an active layer having a total thickness of 95 nm. The active layer was annealed at 80℃for 8min. Then spin-coating a PDINN modified layer with thickness of 5nm on the active layer with 1mg/mL PDINN methanol solution, and finally steaming with a steam plating instrumentPlating a 100nm thick Ag electrode (cathode) to obtain a cathode with an effective area of 6mm 2 Is provided.
At an illumination intensity of 100mW/cm 2 The current-voltage curve of the device was tested under the AM1.5 simulated sunlight, from which an open circuit voltage of 0.85V and a short circuit current density of 26.66mA/cm were obtained 2 The fill factor was 76.6% and the PCE 17.36%.
FIG. 2 shows the device at an illumination intensity of 100mW/cm 2 AM1.5 of (c) simulates the current-voltage curve under solar irradiation.
Example 6
Ultrasonically cleaning transparent conductive glass plated with ITO (anode) with a cleaning agent, deionized water, acetone, isopropanol and absolute ethyl alcohol for 15min, drying, and treating with ultraviolet ozone for 20min; a layer of 15nm thick PEDOT: PSS was then spin coated on the surface of the conductive glass at 4500rpm, followed by an annealing treatment at 150℃for 15 minutes, followed by transferring the flakes into a glove box. Solid additive assisted step-by-step deposition process: PM6:FA-C at a total concentration of 7mg/mL 9 (mass ratio 100:10) in chloroform, spin-coating at 2500rpm for 25s, to give a 55nm thick donor layer. Then, a solution of Y6 in chloroform was added at a total concentration of 8mg/mL with 1-Chloronaphthalene (CN) at a volume ratio of 0.5%, and spin-coated at a rotation speed of 2500rpm for 25 seconds to obtain an active layer having a total thickness of 95 nm. The active layer was annealed at 80℃for 8min. Then spin-coating a PDINN modified layer with a thickness of 5nm on the active layer with 1mg/mL PDINN methanol solution, and finally evaporating a Ag electrode (cathode) with a thickness of 100nm by using an evaporator to obtain a cathode with an effective area of 6mm 2 Is provided.
At an illumination intensity of 100mW/cm 2 The current-voltage curve of the device was tested under the AM1.5 simulated sunlight, from which an open circuit voltage of 0.85V and a short circuit current density of 27.12mA/cm were obtained 2 The fill factor was 75.3% and the PCE 17.40%.
Example 7
Sequentially cleaning transparent conductive glass plated with ITO (anode) with cleaning agent, deionized water, acetone, isopropanol and absolute ethanolUltrasonic cleaning for 15min, oven drying, and treating with ultraviolet ozone for 20min; a layer of 15nm thick PEDOT: PSS was then spin coated on the surface of the conductive glass at 4500rpm, followed by an annealing treatment at 150℃for 15 minutes, followed by transferring the flakes into a glove box. Solid additive assisted step-by-step deposition process: PM6:FA-C at a total concentration of 7mg/mL 16 (mass ratio 100:10) in chloroform, spin-coating at 2500rpm for 25s, to give a 55nm thick donor layer. Then, a solution of Y6 in chloroform was added at a total concentration of 8mg/mL with 1-Chloronaphthalene (CN) at a volume ratio of 0.5%, and spin-coated at a rotation speed of 2500rpm for 25 seconds to obtain an active layer having a total thickness of 95 nm. The active layer was annealed at 80℃for 8min. Then spin-coating a PDINN modified layer with a thickness of 5nm on the active layer with 1mg/mL PDINN methanol solution, and finally evaporating a Ag electrode (cathode) with a thickness of 100nm by using an evaporator to obtain a cathode with an effective area of 6mm 2 Is provided.
At an illumination intensity of 100mW/cm 2 The current-voltage curve of the device was tested under the AM1.5 simulated sunlight, from which an open circuit voltage of 0.84V and a short circuit current density of 27.17mA/cm were obtained 2 The fill factor was 77.0% and the PCE 17.57%.
Example 8
Ultrasonically cleaning transparent conductive glass plated with ITO (anode) with a cleaning agent, deionized water, acetone, isopropanol and absolute ethyl alcohol for 15min, drying, and treating with ultraviolet ozone for 20min; a layer of 15nm thick PEDOT: PSS was then spin coated on the surface of the conductive glass at 4500rpm, followed by an annealing treatment at 150℃for 15 minutes, followed by transferring the flakes into a glove box. Step-by-step deposition method: a solution of PM6 in chloroform at a concentration of 7mg/mL was spin-coated at 2500rpm for 25s to give a 55nm thick donor layer. Then, a solution of L8-BO in chloroform, to which 1, 8-Diiodooctane (DIO) was added in an amount of 0.25% by volume, was spin-coated at a rotation speed of 2500rpm for 25 seconds to give an active layer having a total thickness of 95 nm. The active layer was annealed at 80℃for 8min. Then spin-coating a PDINN modified layer with a thickness of 5nm on the active layer with 1mg/mL PDINN methanol solution, and finally evaporating a 100nm thick Ag electrode (negative electrode) with an evaporatorPolar) to obtain an effective area of 6mm 2 Is provided.
At an illumination intensity of 100mW/cm 2 The current-voltage curve of the device was tested under the AM1.5 simulated sunlight, from which an open circuit voltage of 0.88V and a short circuit current density of 26.76mA/cm were obtained 2 The fill factor was 79.2% and the PCE was 18.73%.
Example 9
Ultrasonically cleaning transparent conductive glass plated with ITO (anode) with a cleaning agent, deionized water, acetone, isopropanol and absolute ethyl alcohol for 15min, drying, and treating with ultraviolet ozone for 20min; a layer of 15nm thick PEDOT: PSS was then spin coated on the surface of the conductive glass at 4500rpm, followed by an annealing treatment at 150℃for 15 minutes, followed by transferring the flakes into a glove box. Solid additive assisted step-by-step deposition process: PM6:FA-C at a total concentration of 7mg/mL 12 (mass ratio 100:10) in chloroform, spin-coating at 2500rpm for 25s, to give a 55nm thick donor layer. Then, a solution of L8-BO in chloroform, to which 1, 8-Diiodooctane (DIO) was added in an amount of 0.25% by volume, at a total concentration of 8mg/mL, was spin-coated at a rotation speed of 2500rpm for 25 seconds to obtain an active layer having a total thickness of 95 nm. The active layer was annealed at 80℃for 8min. Then spin-coating a PDINN modified layer with a thickness of 5nm on the active layer with 1mg/mL PDINN methanol solution, and finally evaporating a Ag electrode (cathode) with a thickness of 100nm by using an evaporator to obtain a cathode with an effective area of 6mm 2 Is provided.
At an illumination intensity of 100mW/cm 2 The current-voltage curve of the device was tested under the AM1.5 simulated sunlight, from which an open circuit voltage of 0.88V and a short circuit current density of 26.68mA/cm were obtained 2 The fill factor was 80.5% and the PCE was 19.02%.
Example 10
Ultrasonically cleaning transparent conductive glass plated with ITO (anode) with a cleaning agent, deionized water, acetone, isopropanol and absolute ethyl alcohol for 15min, drying, and treating with ultraviolet ozone for 20min; spin-coating a layer of 15nm thick PEDOT (PSS) on the surface of the conductive glass at 4500rpm, and annealing at 150deg.CThe pieces were then transferred to a glove box for 15 minutes. Solid additive assisted step-by-step deposition process: PM6:FA-C with a total concentration of 13mg/mL 12 (mass ratio of 100:10) in chloroform, spin-coating at 2800rpm for 25s, to give a 150nm thick donor layer. Next, a solution of L8-BO in chloroform, to which 1, 8-Diiodooctane (DIO) was added in an amount of 0.25% by volume, at a total concentration of 15mg/mL, was spin-coated at a rotation speed of 2500rpm for 25 seconds to obtain an active layer having a total thickness of 250 nm. The active layer was annealed at 80℃for 8min. Then spin-coating a PDINN modified layer with a thickness of 5nm on the active layer with 1mg/mL PDINN methanol solution, and finally evaporating a Ag electrode (cathode) with a thickness of 100nm by using an evaporator to obtain a cathode with an effective area of 6mm 2 Is provided.
At an illumination intensity of 100mW/cm 2 The current-voltage curve of the device was tested under the AM1.5 simulated sunlight, from which an open circuit voltage of 0.88V and a short circuit current density of 27.30mA/cm were obtained 2 The fill factor was 69.0% and the PCE 16.44%.
Further, it will be understood that various changes and modifications may be made by those skilled in the art after reading the foregoing description of the invention, and such equivalents are intended to fall within the scope of the claims appended hereto.

Claims (10)

1. The high-efficiency organic solar cell prepared by the solid additive auxiliary gradual deposition method is characterized by comprising a substrate, an anode modification layer, an active layer, a cathode modification layer and a cathode which are sequentially arranged from bottom to top;
the active layer consists of an electron donor and solid additive composite film and an electron acceptor film which are sequentially deposited on the anode modification layer;
the solid additive is solid fatty acid FA-C shown in the following formula n Wherein n is 9 to 17:
Figure FDA0004058266960000011
2. the efficient organic solar cell according to claim 1, wherein a mass ratio of the electron donor and the solid additive is 100:5-10.
3. The high efficiency organic solar cell according to claim 1, wherein the electron donor is a p-type semiconductor selected from wide band gap polymer donors, in particular PM6 or D18;
the electron acceptor is an n-type semiconductor and is selected from organic small molecule condensed ring acceptors, in particular Y6 or L8-BO.
4. The high efficiency organic solar cell of claim 1, wherein the electron donor and solid additive composite film is spin coated from a chloroform solution of a mixture of electron donor and solid additive having a total concentration of 7-13 mg/mL.
5. The efficient organic solar cell according to claim 1, wherein the electron acceptor film is spin-coated from a chloroform solution of the electron acceptor at a concentration of 8-15 mg/mL.
6. The efficient organic solar cell according to claim 1, wherein the total thickness of the active layer is 95-250nm, and wherein the mass ratio of electron donor to electron acceptor is 1:1.1-1.3.
7. The efficient organic solar cell according to claim 5, wherein 1-chloronaphthalene is further added to the electron acceptor solution as an additive, and the addition volume of 1-chloronaphthalene is 0.5% to 0.7% of the volume of the electron acceptor solution.
8. The efficient organic solar cell according to claim 5, wherein 1, 8-diiodooctane is further added as an additive to the electron acceptor solution, and the addition volume of 1, 8-diiodooctane is 0.2% to 0.3% of the volume of the electron acceptor solution.
9. The efficient organic solar cell according to claim 1, wherein after sequentially depositing an electron donor and solid additive composite film and an electron acceptor film on the anode modification layer, an annealing treatment is performed at 80-100 ℃ for 5-8 min.
10. The high efficiency organic solar cell of claim 1, wherein the substrate is transparent glass; the anode is ITO; the anode modification layer is PEDOT: PSS; the cathode modification layer is PDINN; the cathode is Ag.
CN202310051536.5A 2023-02-02 2023-02-02 High-efficiency organic solar cell prepared by solid additive auxiliary step-by-step deposition method Pending CN116056470A (en)

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