CN118102828A - Preparation method of organic electronic transmission layer and perovskite solar cell - Google Patents
Preparation method of organic electronic transmission layer and perovskite solar cell Download PDFInfo
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- 239000002243 precursor Substances 0.000 claims description 27
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Abstract
The invention provides a preparation method of an organic electronic transmission layer and a perovskite solar cell. The organic n-type micro-molecular AQF solution is dissolved in PCBM solution according to a certain proportion, the dissolution solvents are Chlorobenzene (CB) solution, the solution is stirred and then spin-coated on a perovskite layer to form a high-quality organic electronic transmission layer film, and the photoelectric conversion efficiency of the final device is measured to be 18.61%. After doping AQF, a series of characterization is carried out, so that the electron extraction capability between layers is improved, and the carrier recombination is inhibited; meanwhile, the roughness of the PCBM film is reduced, the formed organic electronic transmission layer film is more uniformly covered on the perovskite layer, and finally the efficiency and the environmental stability of the battery are greatly improved.
Description
Technical Field
The invention belongs to the technical field of semiconductor devices, and particularly relates to a preparation method of an organic electronic transmission layer and a preparation method of a perovskite solar cell.
Background
The electron transport layer in perovskite solar devices is used to extract and transport electrons in carriers and is one of the key factors affecting device efficiency and stability. The most commonly used material for the electron transport layer is fullerene derivative [6,6] -phenyl C 61 -methyl butyrate (PCBM), which has high electron mobility and low-temperature solution processing performance, but because of low viscosity and solubility of PCBM in organic solvents, a compact film is difficult to form on a perovskite film, so that the perovskite film cannot be completely covered by PCBM, and is in direct contact with an Ag electrode, thereby causing charge recombination and accelerating degradation of an interface layer.
Additive engineering is one of the promising ways to solve this problem. The conductivity of PCBM can be improved by adding certain additives, thereby reducing the carrier recombination at the ETL/perovskite interface. The introduction of the additive into the PCBM can change the energy level of the device to a certain extent, thereby effectively inducing proper energy level arrangement, enabling the PCBM to be better matched with the conduction band of the adjacent perovskite layer, and improving the photovoltaic performance of the device. Therefore, finding a dopant which can improve the performance and stability of the device and is low in cost and easy to obtain is particularly important for preparing a high-performance low-cost planar perovskite solar cell.
Accordingly, there is a need to provide an improved solution to the above-mentioned deficiencies of the prior art.
Disclosure of Invention
The invention aims to provide a preparation method of an organic electronic transmission layer and a perovskite solar cell, which improves the photoelectric conversion efficiency of a cell device by optimizing the electronic transmission layer.
In order to achieve the above object, the present invention provides the following technical solutions:
in a first aspect, there is provided a method of preparing an organic electronic transport layer, the method comprising the steps of:
Step 1, firstly dissolving an AQF material in chlorobenzene to prepare a solution, then doping the AQF solution into a PCBM solution according to a certain proportion to form a mixed solution, and stirring and filtering the mixed solution to form the PCBM;
and 2, spin-coating the PCBM-AQF solution on a spin coater at 2000-2500rpm for 20-40s, and curing to form an organic electronic transmission layer.
In one embodiment, the doping concentration of AQF in PCBM in the mixed solution is 1mg/mL;
In the step 1, the stirring time is 12h.
In one embodiment, the concentration of the PCBM to AQF solution is from 0.01 to 0.04mg/mL.
In a second aspect, there is also provided an organic electron transport layer prepared by the method for preparing an organic electron transport layer as described above.
In a third aspect, there is also provided the use of an organic electron transport layer for the preparation of a photovoltaic device.
In a fourth aspect, there is also provided a method of manufacturing a perovskite solar cell, the method comprising the steps of:
step S1, cleaning a glass substrate plated with an anode material according to steps, drying, and then treating with ultraviolet light to obtain a pretreated substrate;
S2, depositing PTAA on the pretreated substrate, heating at 100 ℃ for 10min for annealing treatment, and naturally cooling to room temperature to obtain a hole transport layer;
Step S3, spin-coating perovskite precursor solution on the hole transport layer by using a one-step anti-solvent method, and heating at 100 ℃ for 10min for annealing treatment to obtain a perovskite layer, namely an active layer;
s4, depositing PCBM (polycrystalline silicon wafer) AQF (AQF) solution on the perovskite layer to obtain an organic electron transport layer;
S5, plating silver on the organic electronic transmission layer through thermal evaporation under vacuum to obtain an inverted perovskite solar cell device;
wherein the organic electronic transmission layer adopts the organic electronic transmission layer.
In one embodiment, in the step S3, the perovskite precursor solution is prepared as follows:
Dissolving a donor A and a donor B in an organic solvent, and uniformly stirring to obtain a perovskite precursor solution;
Wherein the donor A is amine iodide (MAI), the donor B is lead iodide (PbI 2), and the organic solvent is N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO).
In one embodiment, the mass ratio of donor A to donor B is 1 (2-4).
In one embodiment, the total mass percent of the donor a and the donor B in the perovskite precursor solution is 35-50wt%.
In a fifth aspect, there is also provided a perovskite solar cell prepared by the method for preparing a perovskite solar cell as described above.
According to the invention, the novel n-type organic micro-molecular AQF is doped in the traditional electron transport layer PCBM, and the electron transport layer is optimized to prepare the efficient inverted perovskite solar cell, so that the novel n-type organic micro-molecular AQF has the following excellent effects:
1. The photoelectric performance of the inverted perovskite solar cell is improved. According to the invention, a novel doping agent AQF micromolecule is doped in a traditional electron transport layer to serve as an electron transport layer of the perovskite solar cell, a uniform and compact electron transport layer film structure is formed by optimizing the electron transport layer, the LUMO energy level is regulated to be more matched with the energy level of perovskite, the electron transport layer can well transport electrons and effectively block holes from the perovskite layer, carrier recombination is reduced, thus the open-circuit voltage, short-circuit current density and filling factor of the perovskite solar cell are improved, and finally the improvement of the photoelectric performance of the perovskite solar cell is realized, and the energy conversion efficiency of the inverted perovskite solar cell prepared by the preparation method disclosed by the invention reaches 18.61%.
2. The preparation method of the organic electronic transmission layer is simple. The novel doping agent AQF is used for doping the traditional electron transport layer, the obtained mixed solution is directly spin-coated on the perovskite layer, the operation is simple, the performance and the stability of the device are improved, the cost is low and the device is easy to obtain, and the preparation of a large-area film can be realized.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. Wherein:
fig. 1 is a schematic structural diagram of a perovskite solar cell according to an embodiment of the invention;
FIG. 2 is a diagram of the molecular structure of a dopant AQF of the present invention;
FIG. 3 is 1 H NMR of dopant AQF;
FIG. 4 is 13 C NMR of dopant AQF;
FIG. 5 is a fluorescence spectrum of the organic electron transport layer prepared in example 1 of the present invention and comparative example 1;
FIG. 6 is an ultraviolet absorption spectrum of the organic electron transport layer prepared in example 1 and comparative example 1 of the present invention;
FIG. 7 is a scanning electron micrograph of a top view and cross section of perovskite solar cell as prepared by example 1 and comparative example 1 of the invention;
FIG. 8 is a graph showing the current density vs. voltage characteristics of perovskite solar cell as prepared in example 1 and comparative example 1 of the invention;
FIG. 9 shows contact angles of PCBM AQF films prepared in example 1 and comparative example 1 of the present invention.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which are derived by a person skilled in the art based on the embodiments of the invention, fall within the scope of protection of the invention.
The present invention will be described in detail with reference to examples. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The perovskite solar cell doped with the organic electronic transmission layer provided by the invention aims at the defect that an electron transmission layer material [6,6] -phenyl-C61-methyl butyrate (PCBM) is commonly used in the existing inverted perovskite solar cell, and provides a preparation method of the inverted perovskite solar cell doped with n-type organic micromolecule AQF to the organic electronic transmission layer, so that the photoelectric property of the cell is improved, the operation is simple, the cost is low, and the large-area preparation can be realized.
As shown in fig. 1, the perovskite solar cell device structure of the present invention comprises, from bottom to top: a substrate (glass), an anode (ITO), a hole transport layer (PTAA), a perovskite layer (MAPbI 3), an electron transport layer (PCBM), a cathode (Ag); wherein the AQF is homogeneously doped in the electron transport layer (PCBM). As shown in fig. 2, the structural formula of the dopant AQF used in the organic electron transport layer of the present invention is shown, and is used in a photovoltaic device, so as to improve the performance of the device. Fig. 3 to 4 show 1H NMR、13 C NMR of the dopant AQF, respectively.
The electron transport layer is formed by dissolving the doping agent AQF and the traditional electron transport material PCBM in an organic solvent to form an electron transport layer solution PCBM: AQF, and spin-coating the electron transport layer solution on a spin coater to be solidified, wherein the spin-coating speed is 2000-2500rpm, so that the electron transport layer is more uniformly covered on the active layer, and meanwhile, the tight contact between a cathode and the active layer is reduced, and the electron transport layer is used for transporting electrons to block holes, thereby reducing the carrier recombination loss at an interface and improving the performance of a device. And when the organic electron transport layer is prepared, high-temperature annealing treatment is not needed, the operation is simple, and the preparation can be performed in a large area.
The organic electron transport layer of the present invention may also be used in other photovoltaic devices, such as organic solar cells.
The invention provides a preparation method of a perovskite solar cell, which comprises the following steps:
and S1, cleaning the glass substrate plated with the anode material, drying, and treating with ultraviolet light to obtain a pretreated substrate. The use of ultraviolet light treatment enables further cleaning of the substrate.
In an embodiment of the invention, the anode material is Indium Tin Oxide (ITO) for collecting holes.
And S2, depositing PTAA on the pretreated substrate, heating at 100 ℃ for 10min for annealing treatment, and naturally cooling to room temperature to obtain the hole transport layer. Preferably, the PTAA solution is spin coated on the pretreated substrate using a spin coater at a spin rate of 3000-4000rpm.
And S3, moving the substrate with the hole transport layer into a glove box, spin-coating a perovskite precursor solution (MAPbI 3) on the hole transport layer by adopting a one-step anti-solvent method, rapidly dripping chlorobenzene in the spin-coating process, continuing spin-coating, and carrying out annealing treatment at 100 ℃ for 10min to obtain a perovskite layer, namely an active layer.
In a specific embodiment of the invention, the perovskite precursor solution is prepared by the following method:
Dissolving a donor A and a donor B in an organic solvent, and uniformly stirring to obtain a perovskite precursor solution;
wherein donor A is amine iodide (MAI) and donor B is lead iodide (PbI 2). Preferably, the organic solvents are N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO).
In a specific embodiment of the invention, the mass ratio of donor A to donor B is 1:3.
And S4, preparing an organic electron transport layer on the perovskite layer.
In a specific embodiment of the present invention, a method for preparing an organic electronic transmission layer includes the steps of:
and step S41, mixing the AQF solution into the PCBM solution according to a proportion to form a mixed solution, and stirring for 12 hours to form the PCBM/AQF solution.
In the specific embodiment of the invention, the doping concentration of the AQF in the PCBM in the mixed solution is 1mg/mL; PCBM AQF solution concentration is 0.01-0.04mg/mL (such as 0.01mg/mL, 0.02mg/mL, 0.03mg/mL, 0.04 mg/mL).
Step S42, spin-coating the PCBM-AQF solution on a spin coater for 20-40S (such as 20S, 25S, 30S, 35S and 40S), and curing to form the organic electronic transmission layer. Preferably, spin coating is performed on the spin coater at a rotational speed of 2000-2500rpm (e.g., 2000rpm, 2200rpm, 2400rpm, 2500 rpm). In the step of the invention, the rotating speed is reduced when the PCBM and AQF solution are spin-coated, and the rotating speed is reduced so as to increase the thickness of the electron transport layer and better and completely cover the perovskite active layer.
And S5, plating a cathode material on the organic electronic transmission layer through thermal evaporation under vacuum to obtain the inverted perovskite solar cell.
In an embodiment of the invention, the cathode material is metallic silver (Ag).
The invention also provides a perovskite solar cell prepared by the preparation method of the perovskite solar cell and an organic electronic transmission layer prepared by the preparation method of the organic electronic transmission layer.
According to the preparation method of the organic electronic transmission layer, the n-type organic micromolecule AQF is dissolved in a chlorobenzene solution of PCBM, and then spin-coated on a perovskite absorption layer to form a high-quality organic electronic transmission layer film, wherein the high-quality organic electronic transmission layer film is used for electronic transmission, and the photoelectric conversion efficiency is 18.61%. The doping of the AQF can passivate the defect of perovskite interface, improve the electron transmission capability between layers, reduce carrier recombination and greatly improve the efficiency and photoelectric performance of the battery. And the operation is simple, the cost is low, and the commercial production can be carried out.
The materials, reagents, and the like used in the present example and the comparative example are commercially available products.
Example 1
The preparation method of the perovskite solar cell doped with the organic electron transport layer provided by the embodiment comprises the following steps:
Step S1, sequentially washing the anode glass substrate plated with Indium Tin Oxide (ITO) with detergent, distilled water, acetone and ethanol for 3 times in an ultrasonic mode for 15 minutes each time, drying the glass substrate after washing, and putting the glass substrate into ultraviolet cleaning surface treatment equipment for 15 minutes to obtain a pretreated substrate.
And S2, spin-coating PTAA on the pretreated glass substrate, heating at 100 ℃ for 10min for annealing treatment, and naturally cooling to room temperature to form the hole transport layer.
Step S3, MAI and PbI 2 are carried out according to the mass ratio of 1:3 was dissolved in N, N-Dimethylformamide (DMF) and Dimethylsulfoxide (DMSO) solution and stirred at room temperature for 12h to prepare perovskite precursor solution (MAPbI 3). And spin-coating perovskite precursor solution on the hole transport layer at a rotation speed of 5000rpm, then rapidly dripping anti-solvent chlorobenzene solution when the perovskite precursor solution is rotated to 5s, and after finishing dripping in 2s, promoting rapid crystallization of the perovskite layer, and carrying out annealing treatment at 100 ℃ for 10 minutes to obtain a black perovskite layer with a thickness of 300nm, namely the active layer.
Step S4, spin-coating an electron transport layer solution on the active layer to form an organic electron transport layer, wherein the spin-coating speed of the electron transport layer is 2000rpm, and the specific steps comprise:
Step S41, mixing 1mg/mL of AQF solution into PCBM solution according to a certain proportion, stirring for 12 hours, and filtering by a filter head before use to form PCBM; PCBM AQF solution concentration is 0.01mg/mL.
Step S42, spin-coating the PCBM and AQF solution on a spin coater for 30 seconds, and forming an organic electronic transmission layer after curing; PCBM AQF film.
And S5, plating a cathode material Ag on the organic electronic transmission layer through thermal evaporation under vacuum to obtain the inverted perovskite solar cell.
The device structure obtained in the embodiment 1 of the invention is ITO/PTAA/MAPbl 3/PCBM: AQF/Al, the device is tested for performance, under the optimal condition, the open-circuit voltage is 1.05V under the irradiation of 100mW/cm 2 of simulated sunlight, the short-circuit current is 22.24mA/cm 2, the filling factor is 79.68%, and the photoelectric conversion efficiency is 18.61%.
Example 2
The preparation of the perovskite solar cell doped with the organic electronic transmission layer comprises the following steps:
Step S1, sequentially washing the anode glass substrate plated with Indium Tin Oxide (ITO) with detergent, distilled water, acetone and ethanol for 3 times in an ultrasonic mode for 15 minutes each time, drying the glass substrate after washing, and putting the glass substrate into ultraviolet cleaning surface treatment equipment for 15 minutes to obtain a pretreated substrate.
And S2, spin-coating PTAA on the pretreated glass substrate, heating at 100 ℃ for 10min for annealing treatment, and naturally cooling to room temperature to form the hole transport layer.
Step S3, MAPbI 3 and PbI 2 are dissolved in N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) according to a mass ratio of 1:3, and stirred at room temperature to prepare a perovskite precursor solution (MAPbI 3). And spin-coating a perovskite precursor solution on the hole transport layer at a rotation speed of 5000rpm, then rapidly dripping an anti-solvent chlorobenzene solution when the perovskite precursor solution is rotated to a 5 th s to promote rapid crystallization of the perovskite layer, and carrying out annealing treatment at 95 ℃ for 10 minutes to obtain a black perovskite layer with a thickness of 300nm, namely an active layer.
Step S4, spin-coating an electron transport layer precursor solution on the active layer to form an organic electron transport layer, wherein the spin-coating speed of the electron transport layer is 2200rpm, and the specific steps comprise:
Step S41, mixing 1mg/mL of AQF into PCBM solution according to a certain proportion, stirring for 12h, and filtering by a filter head before use to form PCBM AQF solution; PCBM AQF solution concentration is 0.02mg/mL.
Step S42, spin-coating the PCBM AQF precursor liquid on a spin coater for 30 seconds, and forming an organic electronic transmission layer after curing; PCBM AQF film.
And S5, plating a cathode material Ag on the organic electronic transmission layer through thermal evaporation under vacuum to obtain the inverted perovskite solar cell.
The device structure obtained by the embodiment of the invention is ITO/PTAA/MAPbl 3/PCBM: AQF/Ag, the performance of the device is tested, under the optimal condition, the open-circuit voltage is 1.03V under the irradiation of 100mW/cm 2 of simulated sunlight, the short-circuit current is 21.89mA/cm 2, the filling factor is 78.34%, and the photoelectric conversion efficiency is 17.66%.
Example 3
The preparation of the perovskite solar cell doped with the organic electronic transmission layer comprises the following steps:
Step S1, sequentially washing the anode glass substrate plated with Indium Tin Oxide (ITO) with detergent, distilled water, acetone and ethanol for 3 times in an ultrasonic mode for 15 minutes each time, and putting the dried ITO glass substrate into ultraviolet cleaning surface treatment equipment for 15 minutes after washing, so that the pretreated substrate is obtained.
And S2, spin-coating PTAA on the pretreated glass substrate, heating at 100 ℃ for 10min for annealing treatment, and naturally cooling to room temperature to form the hole transport layer.
Step S3, MAPbI 3 and PbI 2 are dissolved in N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) according to a mass ratio of 1:3, and stirred at room temperature to prepare a perovskite precursor solution (MAPbI 3). And spin-coating a perovskite precursor solution on the hole transport layer at a rotation speed of 5000rpm, then rapidly dripping anti-solvent chlorobenzene when the perovskite precursor solution is rotated to a 5 th s, promoting rapid crystallization of the perovskite layer, and carrying out annealing treatment at 100 ℃ for 10 minutes to obtain a black perovskite layer with a thickness of 300nm, namely an active layer.
Step S4, spin-coating an electron transport layer precursor solution on the active layer to form an organic electron transport layer, wherein the spin-coating speed of the electron transport layer is 2500rpm, and the specific steps comprise:
step S41, mixing 1mg/mL of AQF solution into PCBM solution according to a certain proportion, stirring for 12h, and filtering by a filter head before use to form PCBM; PCBM AQF solution concentration is 0.03mg/mL.
Step S42, spin-coating the PCBM and AQF solution on a spin coater for 30 seconds, and forming an organic electronic transmission layer after curing; PCBM AQF film.
And S5, plating a cathode material Ag on the organic electronic transmission layer through thermal evaporation under vacuum to obtain the inverted perovskite solar cell.
The device structure obtained by the embodiment of the invention is ITO/PTAA/MAPbl 3/PCBM: AQF/Ag, the performance of the device is tested, under the optimal condition, the open-circuit voltage is 1.02V under the irradiation of 100mW/cm 2 of simulated sunlight, the short-circuit current is 21.36mA/cm 2, the filling factor is 78.36%, and the photoelectric conversion efficiency is 17.07%.
Example 4
The preparation of the perovskite solar cell doped with the organic electronic transmission layer comprises the following steps:
Step S1, sequentially washing the anode glass substrate plated with Indium Tin Oxide (ITO) with detergent, distilled water, acetone and ethanol for 3 times in an ultrasonic mode for 15 minutes each time, and putting the dried ITO glass substrate into ultraviolet cleaning surface treatment equipment for 15 minutes after washing, so that the pretreated substrate is obtained.
And S2, spin-coating PTAA on the pretreated glass substrate, heating at 100 ℃ for 10min for annealing treatment, and naturally cooling to room temperature to form the hole transport layer.
Step S3, MAPbI 3 and PbI 2 are dissolved in N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) according to a mass ratio of 1:3, and stirred at room temperature to prepare a perovskite precursor solution (MAPbI 3). And spin-coating a perovskite precursor solution on the hole transport layer at a rotation speed of 5000rpm, then rapidly dripping an anti-solvent chlorobenzene solvent when the perovskite precursor solution is rotated to a 5 th s, promoting rapid crystallization of the perovskite layer, and carrying out annealing treatment at 100 ℃ for 15 minutes to obtain a black perovskite layer with a thickness of 300nm, namely an active layer.
Step S4, spin-coating an electron transport layer precursor solution on the active layer to form an organic electron transport layer, wherein the spin-coating speed of the electron transport layer is 2000rpm, and the specific steps comprise:
Step S41, mixing 1mg/mL of AQF solution into PCBM solution according to a certain proportion, stirring for 12h, and filtering by a filter head before use to form PCBM; PCBM AQF solution concentration is 0.04mg/mL.
Step S42, spin-coating the PCBM and AQF solution on a spin coater for 30 seconds, and forming an organic electronic transmission layer after curing; PCBM AQF film.
And S5, plating a cathode material Ag on the organic electronic transmission layer through thermal evaporation under vacuum to obtain the inverted perovskite solar cell.
The device structure obtained by the embodiment of the invention is ITO/PTAA/MAPbl 3/PCBM: AQF/Ag, the performance of the device is tested, under the optimal condition, the open-circuit voltage is 1.03V under the irradiation of 100mW/cm 2 of simulated sunlight, the short-circuit current is 21.59mA/cm 2, the filling factor is 76.38%, and the photoelectric conversion efficiency is 16.98%.
Comparative example 1
The difference between this comparative example and example 1 is that in step S4, a single PCBM solution is used for the organic electronic transmission layer, and other steps and methods are the same as those in example 1, and are not described here again.
The perovskite solar cell prepared in the comparative example has the structure of ITO/PTAA/MAPbl 3/PCBM/Ag, performance test is carried out on the perovskite solar cell in the comparative example, the open-circuit voltage is 1.0V under the irradiation of 100mW/cm 2 of simulated sunlight, the short-circuit current is 20.15mA/cm 2, the filling factor is 71.56%, and the photoelectric conversion efficiency is 14.42%.
The perovskite solar cell has low photoelectric conversion efficiency because the organic electronic transmission layer has defects, the defects provide channels for the water oxygen to erode the active layer, and the PCBM is easy to gather due to the property of the PCBM, so that the photoelectric conversion efficiency of the cell is reduced due to poor coverage with the perovskite layer.
FIG. 5 is a fluorescence spectrum of the perovskite layer thin film+electron transporting layer thin film as prepared in example 1 of the present invention and comparative example 1. The fluorescence spectrum of the perovskite layer thin film+electron transport layer thin film (PCBM: AQF) prepared in example 1 is a dotted line in FIG. 5, and the fluorescence spectrum of the perovskite layer thin film+electron transport layer thin film (PCBM) prepared in comparative example 1 is a solid line in FIG. 5.
The ultraviolet absorption spectra of the organic electron transport layer films prepared in example 1 of the present invention and comparative example 1 are shown in fig. 6. Wherein the ultraviolet absorption spectrum of the organic electron transport layer film prepared in example 1 is a dotted line in fig. 6, and the ultraviolet absorption spectrum of the organic electron transport layer film prepared in comparative example 1 is a solid line in fig. 6.
It can be seen from the figure that neither the organic electron transport layer film of example 1 nor the organic electron transport layer film of comparative example 1 affected the light absorption of the perovskite layer, and that the spectral intensity was slightly higher at an AQF doping concentration of 0.01mg/mL than the samples prepared in the remaining examples, so that the best photovoltaic parameters and performance were obtained at an AQF doping concentration of 0.01 mg/mL.
Fig. 7 is a scanning electron micrograph of a cross-section of a perovskite thin film and perovskite solar cell prepared as per example 1 of the invention. Wherein, the left drawing in fig. 7 is a scanning electron microscopic image of the surface of the perovskite thin film, and the right drawing in fig. 7 is a scanning electron microscopic image of the cross section of the perovskite solar cell.
Fig. 8 is a current density-voltage characteristic curve of the perovskite solar cell prepared in example 1 and comparative example 1 of the present invention. Wherein the current density-voltage characteristic curve of the perovskite solar cell prepared in example 1 is the triangular dot line in fig. 8, and the current density-voltage characteristic curve of the perovskite solar cell prepared in comparative example 1 is the circular dot line in fig. 8.
FIG. 9 shows contact angles of PCBM AQF films prepared in example 1 and comparative example 1 of the present invention. Wherein, the left drawing in FIG. 9 is a schematic drawing of the contact angle of the PCBM film prepared in comparative example 1, and the right drawing is a schematic drawing of the contact angle of the PCBM: AQF film prepared in example 1. From the graph, the contact angle of the AQF doped organic electron transport layer film is larger than that of the pure PCBM film, so that the doping of the AQF can improve the hydrophobic property of the organic electron transport layer, and after the AQF is doped, the contact angle is the largest, which indicates that the hydrophobic property is the best, and the calcium titanium ore layer can be well prevented from being corroded by external moisture, thereby improving the photoelectric conversion efficiency of the device.
Example 5
The difference between this example and example 1 is that in step S4, the electron transport layer was formed, the spin-coating speed of the electron transport layer was 2000rpm, and the concentration of PCBM: AQF solution was 0.05mg/mL. Other steps and methods were the same as in example 1.
The device structure obtained by the embodiment of the invention is ITO/PTAA/MAPbl 3/PCBM: AQF/Ag, the performance of the device is tested, under the optimal condition, the open-circuit voltage is 1.02V under the irradiation of 100mW/cm 2 of simulated sunlight, the short-circuit current is 21.42mA/cm 2, the filling factor is 77.24%, and the photoelectric conversion efficiency is 16.88%.6.88%.
Example 6
The difference between this example and example 1 is that in step S3, an electron transport layer was formed, the spin-coating speed of the electron transport layer was 2000rpm, and the concentration of PCBM: AQF solution was 0.06mg/mL. Other steps and methods were the same as in example 1.
The device structure obtained by the embodiment of the invention is ITO/PTAA/MAPbl 3/PCBM: AQF/Ag, the performance of the device is tested, under the optimal condition, the open-circuit voltage is 1.01V under the irradiation of 100mW/cm 2 of simulated sunlight, the short-circuit current is 20.74mA/cm 2, the filling factor is 72.37%, and the photoelectric conversion efficiency is 15.17%.
To sum up: the perovskite solar cell doped with the organic electronic transmission layer comprises the following components from bottom to top: an anode, a hole transport layer, a perovskite layer, an organic electron transport layer, and a cathode. The organic electron transport layer is prepared by doping AQF serving as a doping agent into PCBM chlorobenzene solution. The organic electron transport layer can well reduce carrier recombination, improve the electron extraction capacity between layers, and the photoelectric conversion efficiency of the inverted perovskite battery prepared by the method reaches 18.61%, so that the performance of the perovskite solar cell is improved, and the inverted perovskite solar cell can be used for photoelectric conversion.
Meanwhile, the novel doping agent AQF is used for doping the traditional electron transport layer, the obtained solution can be directly spin-coated on the perovskite layer, annealing treatment is not needed, the operation is simple, the performance and the stability of the device are improved, the cost is low and the preparation of a large-area film can be realized.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method of preparing an organic electron transport layer, the method comprising the steps of:
step 1, doping an AQF solution into a PCBM solution according to a certain proportion, wherein the dissolution solvents are Chlorobenzene (CB) to form a mixed solution, and stirring and filtering to form the PCBM;
and 2, spin-coating the PCBM-AQF solution on a spin coater at 2000-2500rpm for 20-40s, and curing to form an organic electronic transmission layer.
2. The method of claim 1, wherein the doping concentration of AQF in PCBM in the mixed solution is 1mg/mL;
In the step 1, the stirring time is 12h.
3. The method of claim 1, wherein the concentration of the PCBM AQF solution is between 0.01 mg/mL and 0.04mg/mL.
4. An organic electron transport layer prepared by the method for preparing an organic electron transport layer according to any one of claims 1 to 3.
5. The organic electronic transmission layer according to claim 4, wherein the organic electronic transmission layer is used in the preparation of photovoltaic devices.
6. A method of manufacturing a perovskite solar cell, the method comprising the steps of:
step S1, cleaning a glass substrate plated with an anode material according to steps, drying, and then treating with ultraviolet light to obtain a pretreated substrate;
S2, depositing PTAA on the pretreated substrate, heating at 100 ℃ for 10min for annealing treatment, and naturally cooling to room temperature to obtain a hole transport layer;
step S3, spin-coating perovskite precursor solution on the hole transport layer by using a one-step anti-solvent method, and heating at 100 ℃ for 10min for annealing treatment to obtain a perovskite layer, namely an active layer;
s4, depositing PCBM (polycrystalline silicon wafer) AQF (AQF) solution on the perovskite layer to obtain an organic electron transport layer;
S5, plating silver on the organic electronic transmission layer through thermal evaporation under vacuum to obtain an inverted perovskite solar cell;
Wherein the organic electron transport layer is as claimed in claim 4.
7. The method of manufacturing a perovskite solar cell according to claim 6, wherein in the step S3, the perovskite precursor solution is prepared by the following method:
Dissolving a donor A and a donor B in an organic solvent, and uniformly stirring to obtain a perovskite precursor solution;
Wherein the donor A is amine iodide, the donor B is lead iodide, and the organic solvent is N, N-dimethylformamide and dimethyl sulfoxide.
8. The method of producing a perovskite solar cell as claimed in claim 7, wherein the mass ratio of the donor A to the donor B is 1 (2-4).
9. The method of claim 7, wherein the total mass percent of the donor a and the donor B in the perovskite precursor solution is 35-50wt%.
10. A perovskite solar cell prepared by the method for preparing a perovskite solar cell according to any one of claims 6 to 9.
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| CN114899321A (en) * | 2022-03-09 | 2022-08-12 | 河南理工大学 | Organic electron transport layer, perovskite solar cell, and preparation method and application thereof |
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| CN114899321A (en) * | 2022-03-09 | 2022-08-12 | 河南理工大学 | Organic electron transport layer, perovskite solar cell, and preparation method and application thereof |
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| SHILONG HE: "Interfacial defects passivation and energy level alignment with small molecule pyridine material for efficient and stable inverted perovskite solar cells", 《SURFACES AND INTERFACES》, vol. 46, no. 104031, 4 February 2024 (2024-02-04) * |
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