CN113299838B - Method for stabilizing interface of perovskite thin film and hole transport layer - Google Patents

Method for stabilizing interface of perovskite thin film and hole transport layer Download PDF

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CN113299838B
CN113299838B CN202110402386.9A CN202110402386A CN113299838B CN 113299838 B CN113299838 B CN 113299838B CN 202110402386 A CN202110402386 A CN 202110402386A CN 113299838 B CN113299838 B CN 113299838B
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hole transport
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CN113299838A (en
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李燕
张家旭
刘泽承
弓斌
王宇鹏
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Xian Shiyou University
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Abstract

The invention relates to a method for stabilizing an interface of a perovskite thin film and a hole transport layer, which comprises the following steps: step S1: cleaning the fluorine-doped tin oxide substrate, and spin-coating TiO on the fluorine-doped tin oxide substrate 2 The precursor solution is sintered after spin coating; step S2: s21: preparing a 1, 4-dibromobenzene precursor; s22: configuration CH 3 NH 3 PbI 3 A precursor; s23: preparing a hole transport layer precursor solution; and step S3: CH configured in step S22 3 NH 3 PbI 3 The precursor solution is subjected to three steps of dropwise adding, spin coating and drying to prepare CH 3 NH 3 PbI 3 A film; and step S4: spin coating 1, 4-dibromobenzene precursor solution to CH 3 NH 3 PbI 3 Carrying out heat treatment on the film; step S5: and coating the hole transport layer material on the surface of the perovskite thin film in a spinning way to obtain a stable interface of the perovskite thin film and the hole transport layer. The 1, 4-dibromobenzene hole transport material can prevent the perovskite thin film from being dissolved by a precursor solution, and avoid the mutual permeation between the perovskite thin film and the hole transport layer in the later battery power generation process.

Description

Method for stabilizing interface of perovskite thin film and hole transport layer
Technical Field
The invention belongs to the technical field of solar cells, and particularly relates to a method for stabilizing an interface between a perovskite thin film and a hole transport layer.
Background
The exhaustion of energy and environmental pollution make people pay more and more attention to sustainable development, and the development of novel clean energy to relieve the current environmental and energy problems is an important connotation of sustainable development. The characteristic that solar energy is inexhaustible as the source of all energy is that the conversion and utilization from light energy to electric energy become a reliable and powerful energy supply mode.
In recent decades, scientific research results have shown that photovoltaic devices, such as silicon solar cells, have great potential for low cost, ease of manufacture and high conversion efficiency, and after silicon solar cells, researchers have never stopped exploring cheaper, more efficient photovoltaic conversion devices, such as perovskite solar cells, and through the development of 10 years, the photoelectric conversion efficiency has reached 25.5% by 2020, and the maximum area of the cell assembly can reach 808cm 2 . In contrast, the stability problem of perovskite solar cells is considered to be a significant obstacle to their commercialization, with the laboratory reported maximum stable output of perovskite solar cells being only 1 year, which is far from the 20-25 years required for outdoor applications of the cells.
One of the reasons for poor stability of the perovskite solar cell is instability between the perovskite thin film and the hole transport layer thin film, which is caused by the problem of dissolution of the perovskite thin film by a precursor solution of the hole transport material in the preparation process and the problem of mutual permeation between the perovskite thin film and the hole transport layer in the later battery power generation process.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a method for stabilizing the interface between the perovskite thin film and the hole transport layer, which prevents the dissolution of the precursor solution of the hole transport material to the perovskite thin film during the preparation process, and avoids the mutual permeation between the perovskite thin film and the hole transport layer during the later battery power generation process, in view of the above-mentioned deficiencies in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for stabilizing the interface of a perovskite thin film and a hole transport layer comprises the following steps:
step S1: cleaning the fluorine-doped tin oxide substrate, and spin-coating TiO on the cleaned fluorine-doped tin oxide substrate 2 Sintering the precursor solution after the spin coating is finished;
step S2: the step S2 comprises the following steps,
s21: preparing a 1, 4-dibromobenzene precursor solution;
s22: configuration CH 3 NH 3 PbI 3 Precursor solution;
s23: preparing a hole transport layer precursor solution;
and step S3: CH configured in step S22 3 NH 3 PbI 3 The precursor solution is prepared into CH on the fluorine-doped tin oxide matrix prepared in the step S1 through three steps of dropwise adding, spin coating and drying 3 NH 3 PbI 3 A film;
and step S4: spin-coating the 1, 4-dibromobenzene precursor solution prepared in the step S21 on the CH prepared in the step S3 3 NH 3 PbI 3 Carrying out heat treatment on the film;
step S5: the hole transport layer precursor solution prepared in the step S23 is spin-coated on CH containing 1, 4-dibromobenzene by adopting a process of rotating speed of 3000rpm for 30S 3 NH 3 PbI 3 And preparing a stable interface of the perovskite film and the hole transport layer on the surface of the film.
Preferably, the cleaning in the step S1 is ultrasonic cleaning of the fluorine-doped tin oxide substrate with deionized water, acetone and ethanol for 30min, respectively, and spin coating: the rotation speed is 3000rpm, the time is 20s, the sintering temperature is 510 ℃, and the time is 30min.
Preferably, tiO in the step S1 2 The precursor solution is prepared by dissolving tetraisopropyl titanate in ethanol, acetylacetone and weakly acidic aqueous solvent, and standing and aging for 48h before use.
Preferably, in the step S21, the solute of the 1, 4-dibromobenzene precursor solution is 1, 4-dibromobenzene powder, the solvent is isopropanol, and the concentration of the prepared precursor solution is 0.2-2 mg/ml.
Preferably, CH in the step S22 3 NH 3 PbI 3 CH 3 NH 3 I and PbI 2 And CH 3 NH 3 I and PbI 2 Equimolar amount, the solvent was N, N-dimethylformamide.
Preferably, the cavity transport layer precursor solution in step S23 is prepared by uniformly mixing 72.3mg of Spiro-ome tad powder, 28.8 μ ltBP, and 17.5 μ l of lithium bis (trifluoromethanesulfonylimide) stock solution prepared by dissolving 520mg of lithium bis (trifluoromethanesulfonimide) in 1ml of acetonitrile in 1ml of chlorobenzene and stirring at room temperature for 2 hours.
Preferably, CH in the step S22 3 NH 3 I and PbI 2 The mixed solution with N, N-dimethylformamide was magnetically stirred at 70 ℃ for 5 hours and filtered through a 200nm filter head.
Preferably, the spin coating in step S3 is performed at 4000rpm for 10S at a drying pressure of 40Pa to 2000Pa.
Preferably, the spin coating in step S4 is performed at 3000rpm for 30S, and the heat treatment process is annealing at 150 ℃ for 2min.
Compared with the prior art, the invention has the beneficial effects that:
the invention relates to a method for stabilizing an interface of a perovskite film and a hole transport layer, which is characterized in that 1, 4-dibromobenzene molecules are added and absorbed on the interface of the perovskite film and the hole transport layer, the 1, 4-dibromobenzene molecules consist of benzene rings and two bromine groups at two sides and are deposited on the surface of the perovskite film, wherein the bromine group at one side can passivate the surface defect of the film and inhibit the recombination of photogenerated charges in the film, the middle benzene ring can play a role in blocking the diffusion of substances between the perovskite film and the hole transport layer, and the bromine group at the other side also increases the wettability between a precursor solution of the hole transport layer and the perovskite film passivated by the 1, 4-dibromobenzene layer.
Therefore, 1, 4-dibromobenzene molecules are added and absorbed on the interface of the perovskite thin film and the hole transport layer, so that the perovskite thin film is prevented from being dissolved by a precursor solution of the hole transport layer in the preparation process, the mutual permeation between the perovskite thin film and the hole transport layer in the later battery power generation process is avoided, and the prepared perovskite-1, 4-dibromobenzene modified layer-perovskite interface has high charge separation and transmission performance.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
In the drawings:
FIG. 1 is an SEM image of a perovskite thin film absorbed with 1, 4-dibromobenzene of example 1.
FIG. 2 is an SEM image of a perovskite thin film of example 2 imbibed with 1, 4-dibromobenzene.
FIG. 3 is an SEM image of a perovskite thin film of example 3 with 1, 4-dibromobenzene absorbed.
FIG. 4 is an SEM image of a perovskite thin film of example 4 with 1, 4-dibromobenzene absorbed.
Fig. 5 is a graph showing the efficiency decay of the perovskite solar cell before and after the interface between the perovskite thin film and the hole transport layer is stabilized.
Fig. 6 is a graph of open circuit voltage/short circuit current density for an unpassivated perovskite solar cell.
FIG. 7 is a graph of open circuit voltage/short circuit current density in example 1.
FIG. 8 is a graph of open circuit voltage/short circuit current density for example 2.
FIG. 9 is a graph of open circuit voltage/short circuit current density for example 3.
FIG. 10 is a graph of open circuit voltage/short circuit current density for example 4.
Detailed Description
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it should be understood that they are presented herein only to illustrate and explain the present invention and not to limit the present invention.
A method for stabilizing the interface of a perovskite thin film and a hole transport layer is characterized by comprising the following steps: the preparation method comprises the following steps:
step S1: ultrasonic cleaning fluorine-doped tin oxide matrix with deionized water, acetone and ethanol for 30min, respectively, dissolving tetraisopropyl titanate in ethanol, acetylacetone and weakly acidic aqueous solvent to prepare TiO 2 The precursor solution is placed and aged for 48 hours before use, and TiO is spin-coated on the cleaned fluorine-doped tin oxide substrate at 3000rpm 2 And (5) sintering the precursor solution for 20s in a muffle furnace at 510 ℃ for 30min after the spin coating is finished.
Step S2: the step S2 comprises the following steps,
s21: preparing 1, 4-dibromobenzene precursor solution, wherein the solute of the 1, 4-dibromobenzene precursor solution is 1, 4-dibromobenzene powder, the solvent is isopropanol, and the concentration of the prepared solution is 0.2-2 mg/ml.
S22: configuring CH 3 NH 3 PbI 3 Precursor solution, CH 3 NH 3 PbI 3 The solute of the precursor solution is CH 3 NH 3 I and PbI 2 And CH 3 NH 3 I and PbI 2 Equimolar amount, N-dimethylformamide as solvent, magnetically stirring the mixed solution at 70 deg.C for 5 hr, and filtering with 200nm filter head to obtain CH 3 NH 3 PbI 3 And (3) precursor solution.
S23: preparing a hole transport layer precursor solution, wherein the hole transport layer precursor solution is prepared by uniformly mixing 72.3mg of Spiro-OMeTAD powder, 28.8 mu l of tBP and 17.5 mu l of lithium bis (trifluoromethanesulfonyl) imide stock solution in 1ml of chlorobenzene and stirring at room temperature for 2h, wherein the lithium bis (trifluoromethanesulfonyl) imide stock solution is prepared by dissolving 520mg of lithium bis (trifluoromethanesulfonyl) imide in 1ml of acetonitrile.
And step S3: CH configured in step S22 3 NH 3 PbI 3 The precursor solution is prepared into CH on the fluorine-doped tin oxide matrix prepared in the step S1 through three steps of dripping, spin coating and drying 3 NH 3 PbI 3 And the spin coating of the film is carried out at the rotation speed of 4000rpm for 10s and at the drying pressure of 40-2000 Pa.
And step S4: spin-coating the 1, 4-dibromobenzene precursor solution prepared in the step S21 on the CH prepared in the step S3 3 NH 3 PbI 3 The film was spin-coated at 3000rpm for 30s and then annealed at 150 ℃ for 2min.
Step S5: the hole transport layer precursor solution prepared in the step S23 is spin-coated on CH containing 1, 4-dibromobenzene by adopting a process of rotating speed of 3000rpm for 30S 3 NH 3 PbI 3 And preparing a stable interface of the perovskite thin film and the hole transport layer on the surface of the thin film.
For a better understanding of the invention, the technical solution of the invention is further illustrated and described below with reference to examples 1 to 4 and figures 1 to 10.
Example 1
A method for stabilizing the interface of a perovskite thin film and a hole transport layer comprises the following steps:
step S1: ultrasonic cleaning fluorine-doped tin oxide matrix with deionized water, acetone and ethanol for 30min, respectively, dissolving tetraisopropyl titanate in ethanol, acetylacetone and weakly acidic aqueous solvent to prepare TiO 2 The precursor solution is placed and aged for 48 hours before use, and TiO is spin-coated on the cleaned fluorine-doped tin oxide substrate at 3000rpm 2 And (5) sintering the precursor solution for 20s in a muffle furnace at 510 ℃ for 30min after the spin coating is finished.
Step S2: the step S2 comprises the following steps,
s21: preparing a 1, 4-dibromobenzene precursor solution, wherein the solute of the 1, 4-dibromobenzene precursor solution is 1, 4-dibromobenzene powder, the solvent is isopropanol, and the concentration of the prepared solution is 0.2mg/ml.
S22: configuration CH 3 NH 3 PbI 3 Precursor solution, CH 3 NH 3 PbI 3 The solute of the precursor solution is CH 3 NH 3 I and PbI 2 And CH 3 NH 3 I and PbI 2 Equimolar amount, N-dimethylformamide as solvent, magnetically stirring the mixed solution at 70 deg.C for 5 hr, and filtering with 200nm filter head to obtain CH 3 NH 3 PbI 3 And (3) precursor solution.
S23: preparing a hole transport layer precursor solution, wherein the hole transport layer precursor solution is prepared by uniformly mixing 72.3mg of Spiro-OMeTAD powder, 28.8 mu l of tBP and 17.5 mu l of lithium bis (trifluoromethanesulfonyl) imide stock solution in 1ml of chlorobenzene and stirring at room temperature for 2h, wherein the lithium bis (trifluoromethanesulfonyl) imide stock solution is prepared by dissolving 520mg of lithium bis (trifluoromethanesulfonyl) imide in 1ml of acetonitrile.
And step S3: CH configured in step S22 3 NH 3 PbI 3 The precursor solution is prepared into CH on the fluorine-doped tin oxide matrix prepared in the step S1 through three steps of dropwise adding, spin coating and drying 3 NH 3 PbI 3 And the spin coating of the film is carried out at the rotation speed of 4000rpm for 10s and at the drying pressure of 40-2000 Pa.
And step S4: spin-coating the 1, 4-dibromobenzene precursor solution prepared in the step S21 on the CH prepared in the step S3 3 NH 3 PbI 3 The film was spin coated at 3000rpm for 30s and then annealed at 150 ℃ for 2min.
Step S5: the hole transport layer precursor solution prepared in the step S23 is spin-coated on CH containing 1, 4-dibromobenzene by adopting a process of rotating speed of 3000rpm for 30S 3 NH 3 PbI 3 And preparing a stable interface of the perovskite thin film and the hole transport layer on the surface of the thin film.
And finally, placing the prepared perovskite thin film and the hole transport layer in dry air for about 24 hours, and depositing an Ag electrode to obtain the perovskite solar cell.
FIG. 1 is an SEM image of this example, because the passivation layer is extremely thin, the 1, 4-dibromobenzene passivation layer can not be seen, and only the morphology of the perovskite thin film can be seen.
FIG. 7 is a graph showing the open-circuit voltage/short-circuit current density of the present embodiment, wherein the open-circuit voltage is 0.91V and the short-circuit current is 16.78mA/cm 2 The fill factor was calculated to be 73.01% and the photoelectric conversion efficiency was calculated to be 11.15%.
Example 2
A method for stabilizing the interface of a perovskite thin film and a hole transport layer comprises the following steps:
step S1: ultrasonic cleaning of fluorine-doped tin oxide substrate 3 with deionized water, acetone and ethanol respectivelyDissolving tetraisopropyl titanate in ethanol, acetylacetone and weakly acidic aqueous solvent for 0min to obtain TiO 2 The precursor solution is placed and aged for 48 hours before use, and TiO is spin-coated on the cleaned fluorine-doped tin oxide substrate at 3000rpm 2 And (5) sintering the precursor solution for 20s in a muffle furnace at 510 ℃ for 30min after the spin coating is finished.
Step S2: the step S2 comprises the following steps,
s21: preparing a 1, 4-dibromobenzene precursor solution, wherein the solute of the 1, 4-dibromobenzene precursor solution is 1, 4-dibromobenzene powder, the solvent is isopropanol, and the concentration of the prepared solution is 0.6mg/ml.
S22: configuration CH 3 NH 3 PbI 3 Precursor solution, CH 3 NH 3 PbI 3 The solute of the precursor solution is CH 3 NH 3 I and PbI 2 And CH 3 NH 3 I and PbI 2 Equimolar amount, solvent is N, N-dimethyl formamide, the mixed solution is magnetically stirred for 5h at 70 ℃, and is filtered by a filter head with the diameter of 200nm to obtain CH 3 NH 3 PbI 3 And (3) precursor solution.
S23: preparing a hole transport layer precursor solution, wherein the hole transport layer precursor solution is prepared by uniformly mixing 72.3mg of Spiro-OMeTAD powder, 28.8 mu l of tBP and 17.5 mu l of lithium bis (trifluoromethanesulfonyl) imide stock solution in 1ml of chlorobenzene and stirring at room temperature for 2h, wherein the lithium bis (trifluoromethanesulfonyl) imide stock solution is prepared by dissolving 520mg of lithium bis (trifluoromethanesulfonyl) imide in 1ml of acetonitrile.
And step S3: CH configured in step S22 3 NH 3 PbI 3 The precursor solution is prepared into CH on the fluorine-doped tin oxide matrix prepared in the step S1 through three steps of dropwise adding, spin coating and drying 3 NH 3 PbI 3 And the spin coating of the film is carried out at the rotation speed of 4000rpm for 10s and at the drying pressure of 40-2000 Pa.
And step S4: spin-coating the 1, 4-dibromobenzene precursor solution prepared in the step S21 on the CH prepared in the step S3 3 NH 3 PbI 3 The film was spin-coated at 3000rpm for 30s and then annealed at 150 ℃ for 2min.
Step S5: spin-coating the hole transport layer precursor solution prepared in the step S23 on CH containing 1, 4-dibromobenzene by adopting a process of rotating speed of 3000rpm for 30S 3 NH 3 PbI 3 And preparing a stable interface of the perovskite thin film and the hole transport layer on the surface of the thin film.
And finally, placing the prepared perovskite thin film and the hole transport layer in dry air for about 24 hours, and depositing an Ag electrode to prepare the perovskite solar cell.
FIG. 2 is an SEM image of this example showing no 1, 4-dibromobenzene passivation layer.
FIG. 8 is a graph showing the open-circuit voltage/short-circuit current density of the present example, wherein the open-circuit voltage is 0.92V and the short-circuit current is 16.90mA/cm 2 The fill factor was calculated to be 75.32% and the photoelectric conversion efficiency was calculated to be 11.77%.
Example 3
A method for stabilizing the interface of a perovskite thin film and a hole transport layer comprises the following steps:
step S1: ultrasonic cleaning fluorine-doped tin oxide matrix with deionized water, acetone and ethanol for 30min, dissolving tetraisopropyl titanate in ethanol, acetylacetone and weakly acidic aqueous solvent to prepare TiO 2 The precursor solution is placed and aged for 48 hours before use, and TiO is spin-coated on the cleaned fluorine-doped tin oxide substrate at 3000rpm 2 And (5) sintering the precursor solution for 20s in a muffle furnace at 510 ℃ for 30min after the spin coating is finished.
Step S2: the step S2 comprises the following steps,
s21: preparing a 1, 4-dibromobenzene precursor solution, wherein the solute of the 1, 4-dibromobenzene precursor solution is 1, 4-dibromobenzene powder, the solvent is isopropanol, and the concentration of the prepared solution is 0.2mg/ml.
S22: configuring CH 3 NH 3 PbI 3 Precursor solution, CH 3 NH 3 PbI 3 The solute of the precursor solution is CH 3 NH 3 I and PbI 2 And CH 3 NH 3 I and PbI 2 Equimolar amount, solvent is N, N-dimethyl formamide, the mixed solution is magnetically stirred for 5 hours at 70 ℃,filtering with 200nm filter head to obtain CH 3 NH 3 PbI 3 And (3) precursor solution.
S23: preparing a hole transport layer precursor solution, wherein the hole transport layer precursor solution is prepared by uniformly mixing 72.3mg of Spiro-OMeTAD powder, 28.8 mu l of tBP and 17.5 mu l of lithium bis (trifluoromethanesulfonylimide) stock solution in 1ml of chlorobenzene and stirring at room temperature for 2h, and the lithium bis (trifluoromethanesulfonylimide) stock solution is prepared by dissolving 520mg of lithium bis (trifluoromethanesulfonimide) in 1ml of acetonitrile.
And step S3: CH configured in step S22 3 NH 3 PbI 3 The precursor solution is prepared into CH on the fluorine-doped tin oxide matrix prepared in the step S1 through three steps of dripping, spin coating and drying 3 NH 3 PbI 3 The spin coating speed is 4000rpm, the time is 10s, and the drying pressure is 40 Pa-2000 Pa.
And step S4: spin-coating the 1, 4-dibromobenzene precursor solution prepared in the step S21 on the CH prepared in the step S3 3 NH 3 PbI 3 Spin coating on the film at 5000rpm for 30s, and annealing at 150 deg.C for 2min.
Step S5: spin-coating the hole transport layer precursor solution prepared in the step S23 on CH containing 1, 4-dibromobenzene by adopting a process of rotating speed of 3000rpm for 30S 3 NH 3 PbI 3 And preparing a stable interface of the perovskite film and the hole transport layer on the surface of the film.
And finally, placing the prepared perovskite thin film and the hole transport layer in dry air for about 24 hours, and depositing an Ag electrode to prepare the perovskite solar cell.
FIG. 3 is an SEM image of this example, which shows a thicker 1, 4-dibromobenzene passivation layer in the black mottled area, and the thicker 1, 4-dibromobenzene passivation layer can be clearly shown in the local area because the thickness of the 1, 4-dibromobenzene passivation layer is already very thick under the parameters.
FIG. 7 is a graph showing the open-circuit voltage/short-circuit current density of the present example, wherein the open-circuit voltage is 1.01V and the short-circuit current is 17.02mA/cm 2 Fill factor was calculated to be 78.14% lightThe electrical conversion efficiency was 13.50%.
Example 4
A method for stabilizing the interface of a perovskite thin film and a hole transport layer comprises the following steps:
step S1: ultrasonic cleaning fluorine-doped tin oxide matrix with deionized water, acetone and ethanol for 30min, dissolving tetraisopropyl titanate in ethanol, acetylacetone and weakly acidic aqueous solvent to prepare TiO 2 The precursor solution is placed and aged for 48 hours before use, and TiO is spin-coated on the cleaned fluorine-doped tin oxide substrate at 3000rpm 2 And (5) sintering the precursor solution for 20s in a muffle furnace at 510 ℃ for 30min after the spin coating is finished.
Step S2: the step S2 comprises the following steps,
s21: preparing a 1, 4-dibromobenzene precursor solution, wherein the solute of the 1, 4-dibromobenzene precursor solution is 1, 4-dibromobenzene powder, the solvent is isopropanol, and the concentration of the prepared solution is 0.2mg/ml.
S22: configuring CH 3 NH 3 PbI 3 Precursor solution, CH 3 NH 3 PbI 3 The solute of the precursor solution is CH 3 NH 3 I and PbI 2 And CH 3 NH 3 I and PbI 2 Equimolar amount, solvent is N, N-dimethyl formamide, the mixed solution is magnetically stirred for 5h at 70 ℃, and is filtered by a filter head with the diameter of 200nm to obtain CH 3 NH 3 PbI 3 And (3) precursor solution.
S23: preparing a hole transport layer precursor solution, wherein the hole transport layer precursor solution is prepared by uniformly mixing 72.3mg of Spiro-OMeTAD powder, 28.8 mu l of tBP and 17.5 mu l of lithium bis (trifluoromethanesulfonylimide) stock solution in 1ml of chlorobenzene and stirring at room temperature for 2h, and the lithium bis (trifluoromethanesulfonylimide) stock solution is prepared by dissolving 520mg of lithium bis (trifluoromethanesulfonimide) in 1ml of acetonitrile.
And step S3: CH configured in step S22 3 NH 3 PbI 3 The precursor solution is prepared into CH on the fluorine-doped tin oxide matrix prepared in the step S1 through three steps of dropwise adding, spin coating and drying 3 NH 3 PbI 3 Film, spin coating at a rotation speed of 4000rpm for 10s and a drying pressure of 40-2000 Pa.
And step S4: spin-coating the 1, 4-dibromobenzene precursor solution prepared in the step S21 on the CH prepared in the step S3 3 NH 3 PbI 3 Spin coating on the film at 5000rpm for 50s, and annealing at 150 deg.C for 2min.
Step S5: the hole transport layer precursor solution prepared in the step S23 is spin-coated on CH containing 1, 4-dibromobenzene by adopting a process of rotating speed of 3000rpm for 30S 3 NH 3 PbI 3 And preparing a stable interface of the perovskite film and the hole transport layer on the surface of the film.
And finally, placing the prepared perovskite thin film and the hole transport layer in dry air for about 24 hours, and depositing an Ag electrode to prepare the perovskite solar cell.
FIG. 4 is an SEM image of this example showing no 1, 4-dibromobenzene passivation layer.
FIG. 7 is a graph of open-circuit voltage/short-circuit current density of the present embodiment, wherein the open-circuit voltage is 1.00V and the short-circuit current is 16.85mA/cm 2 The fill factor was calculated to be 76.69%, and the photoelectric conversion efficiency was calculated to be 12.91%.
1. The output performance of the assembled perovskite solar cell is measured by adopting a Keithley 2400 digital source meter solar cell analyzer under simulated standard sunlight, as shown in FIG. 5, the solar energy conversion efficiency of the passivated interface added with 1, 4-dibromobenzene is obviously improved, and the conversion efficiency is more slowly reduced relative to the unpassivated interface without 1, 4-dibromobenzene along with the increase of time.
2. An open-circuit voltage/short-circuit current density test is carried out on an unpassivated interface without 1, 4-dibromobenzene, so that the open-circuit voltage is 0.91V, and the short-circuit current is 15.09mA/cm 2 The fill factor was calculated to be 68.89%, and the photoelectric conversion efficiency was calculated to be 9.46%.
3. A summary of the experiments for examples 1-4 and the unpassivated interface without the addition of 1, 4-dibromobenzene is shown in Table 1 below. It can be seen that:
(1) After the 1, 4-dibromobenzene is added, the open-circuit voltage of the perovskite thin film and the hole transport layer is improved. The direct contact between the perovskite thin film and the hole transport layer is blocked in a local area by the 1, 4-dibromobenzene passivation, so that the leakage current of the working area of the battery is further reduced, and the open-circuit voltage of the battery is improved.
(2) After the 1, 4-dibromobenzene is added, the short-circuit current of the perovskite thin film and the hole transport layer is improved. Bromine groups in the 1, 4-dibromobenzene can passivate defects on the surface of the perovskite thin film, and reverse recombination of photo-generated charges in the transmission process is inhibited, so that forward transmission is promoted, and short-circuit current is improved.
(3) After the 1, 4-dibromobenzene is added, the filling factor of the perovskite film and the hole transport layer is improved. Recombination inside the battery is suppressed, so that the fill factor is improved.
(4) After 1, 4-dibromobenzene is added, the photoelectric conversion efficiency of the perovskite thin film and the hole transport layer is improved.
In conclusion, with the precursor concentration increased from 0mg/ml to 0.2mg/ml and then to 0.6mg/ml, the conversion efficiency of the cell is increased and then decreased, and when the precursor concentration is 0.2mg/ml, the cell efficiency is optimal; when the concentration of the precursor is 0.2mg/ml, the battery efficiency is further increased as the spin-coating speed is increased from 3000rpm to 5000rpm, but the loading of the precursor is sharply reduced by further increasing the spin-coating speed, so that the battery efficiency is optimal when the spin-coating speed is 5000 rpm. When the precursor concentration is 0.2mg/ml and the spin speed is 5000rpm, the cell efficiency is slightly decreased if the spin time is increased from 30s to 50s, and thus the cell efficiency is optimal when the spin time is 30 s.
The optimal passivation effect is determined by the thickness of the passivation layer of the 1, 4-dibromobenzene, the thickness of the 1, 4-dibromobenzene layer is controlled mainly by the concentration of the precursor, the spin-coating speed and the spin-coating time, and from the result of battery efficiency, the current concentration of the 1, 4-dibromobenzene is 0.2mg/ml, the spin-coating speed is 5000rpm, and the spin-coating time is 30s, so that the battery performance is best.
The result shows that the method of the invention obviously improves the interface stability of the perovskite thin film and the hole transport layer.
TABLE 1 test results for unpassivated interfaces and examples 1-4
Figure BDA0003020813520000141
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (8)

1. A method for stabilizing the interface of a perovskite thin film and a hole transport layer is characterized in that: the method comprises the following steps:
step S1: cleaning the fluorine-doped tin oxide substrate, and spin-coating TiO on the cleaned fluorine-doped tin oxide substrate 2 Sintering the precursor solution after the spin coating is finished;
step S2: comprises the following steps of (a) carrying out,
s21: preparing a 1, 4-dibromobenzene precursor solution, preparing a solute of 1, 4-dibromobenzene powder from the 1, 4-dibromobenzene precursor solution, and a solvent of isopropanol, wherein the concentration of the prepared precursor solution is 0.2 to 2mg/ml;
s22: configuration CH 3 NH 3 PbI 3 Precursor solution;
s23: preparing a hole transport layer precursor solution;
and step S3: CH configured in step S22 3 NH 3 PbI 3 The precursor solution is prepared into CH on the fluorine-doped tin oxide matrix prepared in the step S1 through three steps of dripping, spin coating and drying 3 NH 3 PbI 3 A film;
and step S4: spin-coating the 1, 4-dibromobenzene precursor solution prepared in the step S21 on the CH prepared in the step S3 3 NH 3 PbI 3 Carrying out heat treatment on the film;
step S5: spin-coating the hole transport layer precursor solution prepared in the step S23 on CH containing 1, 4-dibromobenzene by adopting a process of rotating speed of 3000rpm for 30S 3 NH 3 PbI 3 And preparing a stable interface of the perovskite thin film and the hole transport layer on the surface of the thin film.
2. The method of stabilizing an interface between a perovskite thin film and a hole transport layer according to claim 1, wherein: the cleaning in the step S1 is that deionized water, acetone and ethanol are respectively subjected to ultrasonic cleaning on the fluorine-doped tin oxide substrate for 30min, and spin coating is carried out: the rotation speed is 3000rpm, the time is 20s, the sintering temperature is 510 ℃, and the time is 30min.
3. The method of stabilizing an interface between a perovskite thin film and a hole transport layer according to claim 1, wherein: tiO in the step S1 2 The precursor solution is prepared by dissolving tetraisopropyl titanate in ethanol, acetylacetone and a weak acid aqueous solvent, and standing and aging for 48h before use.
4. The method of stabilizing an interface between a perovskite thin film and a hole transport layer according to claim 1, wherein: CH in the step S22 3 NH 3 PbI 3 The solute of the precursor solution is CH 3 NH 3 I and PbI 2 And CH 3 NH 3 And PbI 3 Equimolar amount, the solvent was N, N-dimethylformamide.
5. The method of stabilizing an interface between a perovskite thin film and a hole transport layer according to claim 1, wherein: the cavity transport layer precursor solution in the step S23 is prepared by uniformly mixing 72.3mg of 2,2', 7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9' -spirobifluorene powder, 28.8 μ l of 4-tert-butylpyridine and 17.5 μ l of a lithium bis (trifluoromethanesulfonylimide) stock solution in 1ml of chlorobenzene and stirring at room temperature for 2 hours, wherein the lithium bis (trifluoromethanesulfonylimide) stock solution is prepared by dissolving 520mg of lithium bis (trifluoromethanesulfonylimide) in 1ml of acetonitrile.
6. A method of stabilizing the interface of a perovskite thin film and a hole transport layer according to claim 3, wherein: CH in the step S22 3 NH 3 I and PbI 2 The mixed solution with N, N-dimethylformamide was magnetically stirred at 70 ℃ for 5 hours and filtered through a 200nm filter head.
7. The method of stabilizing an interface between a perovskite thin film and a hole transport layer according to claim 1, wherein: the rotation speed of the spin coating in the step S3 is 4000rpm, the time is 10S, and the drying pressure is 40-2000 Pa.
8. The method of stabilizing an interface between a perovskite thin film and a hole transport layer according to claim 1, wherein: the rotation speed of the spin coating in the step S4 is 3000rpm, the time is 30S, the heat treatment process is annealing, the temperature is 150 ℃, and the time is 2min.
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