CN116723714A - Modified perovskite film, efficient stable perovskite solar cell and preparation method thereof - Google Patents

Modified perovskite film, efficient stable perovskite solar cell and preparation method thereof Download PDF

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CN116723714A
CN116723714A CN202310606498.5A CN202310606498A CN116723714A CN 116723714 A CN116723714 A CN 116723714A CN 202310606498 A CN202310606498 A CN 202310606498A CN 116723714 A CN116723714 A CN 116723714A
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perovskite
solution
layer
transport layer
tert
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魏月琳
黄雍恒
黄昀防
吴季怀
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Huaqiao University
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/88—Passivation; Containers; Encapsulations
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E10/549—Organic PV cells

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Abstract

The application relates to the technical field of solar cell preparation, in particular to a modified perovskite thin film, a high-efficiency stable perovskite solar cell and a preparation method thereof. The perovskite film is used in a perovskite solar cell and comprises a perovskite layer and a passivation layer formed by spin-coating a tert-butyl guanidine hydrochloride solution on the upper surface of the perovskite layer. According to the application, the Tu Shu butyl guanidine hydrochloride solution is screwed on a perovskite layer to prepare a high-quality perovskite film, so that each photovoltaic property of the perovskite solar cell is improved, the photoelectric conversion efficiency of the finally obtained perovskite solar cell is up to 23.06%, the photoelectric conversion efficiency is improved by 14% compared with 20.18% of devices without modification, and the initial efficiency is still kept to be more than 90% after aging for 1000 hours.

Description

Modified perovskite film, efficient stable perovskite solar cell and preparation method thereof
Technical Field
The application relates to the technical field of solar cell preparation, in particular to a modified perovskite thin film, a high-efficiency stable perovskite solar cell and a preparation method thereof.
Background
With the recent increase of the conflict and crisis between the internationally, the main issues of the present society such as energy problems and sustainable development are severely challenged. The conventional energy supply is impacted, and the high price burden and environmental pollution are also increased. Therefore, the development of renewable energy sources is more urgent, and solar energy is one of the important directions of human beings in the development direction of energy sources as the main stream of new energy sources. At present, perovskite Solar Cells (PSCs) are used as the latest generation of photovoltaic cells, and the perovskite solar cells are expected to be a powerful substitute for silicon solar cells due to the advantages of excellent performance, wide material sources, rich and various types, low cost, simple and controllable preparation process, suitability for large-scale and flexible preparation and the like, and the great influence of the perovskite solar cells on the global renewable energy market. The key of the technology is to design and prepare the high-efficiency stable solar cell device.
PSCs are generally composed of a transparent conductive glass substrate, an Electron Transport Layer (ETL), a perovskite light absorbing layer, a Hole Transport Layer (HTL), and a metal electrode. Under illumination, the perovskite light-absorbing material can absorb the energy of photons in a certain wavelength range, dissociates electron hole pairs into free carriers, and meanwhile, the free carriers can be rapidly diffused to the interface between the perovskite light-absorbing layer and the charge transmission layer due to the small thickness of the perovskite light-absorbing layer. Electrons are collected by the ETL and directed to the conductive glass, holes move through the HTL to the metal electrode, and finally an electric current is generated through connection of an external circuit. The perovskite light absorbing material is the core of the solar cell, and has the characteristics of wide adjustable band gap, large light absorbing coefficient, long service life of carriers and the like. However, due to the perovskite structure of perovskite, distortion, defects and ion vacancies generated by oxidation reduction of elements often occur in the preparation process; in addition, in the charge transfer process, carrier recombination exists not only in the perovskite layer, but also frequently occurs at the interface of the related functional layer, thereby generating dark current, reducing the performance of the battery and stably reducing. Aiming at the problems, the perovskite crystal quality is improved by additive engineering and interface engineering, a uniform and compact perovskite film is prepared, the defect concentration is reduced, the recombination of photogenerated carriers is inhibited, the photoelectric property of the perovskite film is improved, and the energy level structure is regulated so as to obtain the high-efficiency and stable perovskite solar cell.
Tert-butylguanidine hydrochloride is an electron rich and electron poor domain multifunctional inactivating molecule. T-butylguanidine hydrochloride is composed of negatively charged amine and imine groups and positively charged ammonium head groups, when used for perovskite surface passivation, amine and imine groups of t-butylguanidine hydrochloride react with perovskite surface I/I - A stronger hydrogen bond is formed between the perovskite and the perovskite to coordinate Pb 2 + Promoting PbI 2 And the formation of pure perovskite nanocrystals. Simultaneously, the performance of the perovskite film is beneficially regulated through the participation of tert-butyl guanidine hydrochloride; finally, the perovskite film with better quality is obtained, and the photoelectric conversion efficiency of the perovskite solar cell is further improved.
Disclosure of Invention
The application aims to overcome the defects in the prior art and provide a modified perovskite thin film, a high-efficiency stable perovskite solar cell and a preparation method thereof.
In order to solve the technical problems, one of the technical schemes provided by the application is as follows:
the perovskite thin film is used in a perovskite solar cell and comprises a perovskite layer and a passivation layer formed on the upper surface of the perovskite layer by spin coating of a tert-butyl guanidine hydrochloride solution.
The second technical scheme provided by the application is as follows:
the application provides a high-efficiency stable perovskite solar cell, which comprises conductive glass, an electron transport layer, a perovskite film, a hole transport layer and a metal electrode which are sequentially stacked from bottom to top;
the perovskite film comprises a perovskite layer and a passivation layer formed by spin coating a tert-butyl guanidine hydrochloride solution on the upper surface of the perovskite layer.
The third technical scheme provided by the application is as follows:
the preparation method of the high-efficiency stable perovskite solar cell comprises the following steps of:
providing a conductive glass;
forming an electron transport layer on the conductive glass;
forming a perovskite layer on the electron transport layer;
forming a passivation layer on the perovskite layer, wherein the passivation layer is formed by spin-coating a tert-butyl guanidine hydrochloride solution on the upper surface of the perovskite layer and annealing;
forming a hole transport layer on the passivation layer;
and forming a metal electrode on the hole transport layer.
In a more preferred embodiment, the conductive glass is an ITO conductive glass.
In a more preferred embodiment, the electron transport layer is prepared by: snO at room temperature 2 The nano solution is spin-coated on ITO conductive glass and is prepared through annealing treatment.
In a more preferred embodiment, the perovskite layer is prepared by the steps of: spin-coating the solution A on the electron transport layer, annealing, cooling to room temperature, spin-coating the solution B on the film formed by the solution A, and annealing to obtain the product; the solution A is PbI 2 And the solution B is a solution formed by mixing formamidine hydroiodic acid salt, methyl iodized amine and methyl ammonium chloride in isopropanol.
In a more preferred embodiment, the hole transport layer is prepared by: spin-coating the solution E on the electron transport layer to obtain the electron transport layer; the solution E is formed by mixing a solution C and a solution D, wherein the solution C is acetonitrile solution of lithium bistrifluoro-methanesulfonimide, and the solution D is a mixed solution of chlorobenzene, spiro-OMeTAD and 4-tert-butylpyridine.
In a more preferred embodiment, the metal electrode is prepared by the following steps: and plating a silver electrode on the hole transport layer.
In a more preferred embodiment, the concentration of the t-butylguanidine hydrochloride solution is 0.3-1.0mg/ml.
In a more preferred embodiment, the spin-coating speed of the t-butylguanidine hydrochloride solution is 4000-5000rpm, the spin-coating time is 20-40 seconds, and annealing is performed at 100℃for 5 minutes.
In summary, the present application includes at least one of the following beneficial technical effects:
1. the application uses tert-butyl guanidine hydrochloride to uniformly coat on the surface of perovskite for passivation, amine and imine groups in tert-butyl guanidine hydrochloride molecules and the surface I/I of perovskite - A stronger hydrogen bond is formed between the perovskite and the perovskite to coordinate Pb 2+ Avoiding a large amount of redundant PbI 2 The generation reduces the defect density and inhibits the non-radiative recombination between interfaces;
2. compared with the prior art, the preparation method provided by the application has the advantages of low operation difficulty, strong feasibility, short preparation period, low cost and the like, and can be used for preparing a large amount of high-efficiency stable perovskite solar cells.
Additional features and advantages of the application will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the application. The objectives and other advantages of the application will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
For a clearer description of embodiments of the application or of the solutions of the prior art, the drawings that are needed in the description of the embodiments or of the prior art will be briefly described, it being obvious that the drawings in the description below are some embodiments of the application, and that other drawings can be obtained from them without inventive effort for a person skilled in the art; the positional relationships described in the drawings in the following description are based on the orientation of the elements shown in the drawings unless otherwise specified.
FIG. 1 is an X-ray diffraction pattern of a Pristine and t-butylguanidine hydrochloride (TBGaCl) modified perovskite cell according to example 1 of the present application;
FIG. 2 is a surface scanning electron micrograph of an original perovskite cell and a tert-butylguanidine hydrochloride modified perovskite cell according to example 1 of the application;
FIG. 3 is a cross-sectional scanning electron micrograph of an original perovskite cell and a tert-butylguanidine hydrochloride modified perovskite cell of example 1 of the application;
FIG. 4 is an X-ray photoelectron spectrum of an original perovskite cell and a tert-butylguanidine hydrochloride modified perovskite cell in example 1 of the application;
FIG. 5 is a graph showing the diffuse reflectance of ultraviolet and visible light of an original perovskite cell and a tert-butylguanidine hydrochloride modified perovskite cell according to example 1 of the present application;
FIG. 6 is a graph showing the ultraviolet electron energy spectra and energy level arrangements of the original perovskite cell and the tert-butylguanidine hydrochloride modified perovskite cell according to example 1 of the present application;
FIG. 7 is a steady state fluorescence spectrum of the original perovskite cell and the tert-butylguanidine hydrochloride modified perovskite cell of example 1 of the application;
FIG. 8 is a time resolved photoluminescence spectrum of an original perovskite cell and a tert-butylguanidine hydrochloride modified perovskite cell according to example 1 of the application;
FIG. 9 is a graph of photocurrent-voltage (J-V) curves of a pristine perovskite cell and a t-butylguanidine hydrochloride modified perovskite cell according to example 1 of the application;
FIG. 10 is a graph showing the quantum efficiency of the original perovskite cell and the tert-butylguanidine hydrochloride modified perovskite cell according to example 1 of the application;
FIG. 11 is a Mott-Schottky plot of the original perovskite cell and the t-butylguanidine hydrochloride modified perovskite cell of example 1 of the application;
FIG. 12 is a graph of the chemical impedance of the original perovskite cell and the t-butylguanidine hydrochloride modified perovskite cell of example 1 of the application;
fig. 13 is a graph of stability test performance versus time for the original perovskite cell and the t-butylguanidine hydrochloride modified perovskite cell of example 1 of the application.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions of the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments of the present application; the technical features designed in the different embodiments of the application described below can be combined with each other as long as they do not conflict with each other; all other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
In the description of the present application, it should be noted that all terms used in the present application (including technical terms and scientific terms) have the same meaning as commonly understood by one of ordinary skill in the art to which the present application belongs and are not to be construed as limiting the present application; it will be further understood that terms used herein should be interpreted as having a meaning that is consistent with their meaning in the context of this specification and the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
The application provides a modified perovskite film which is used in a perovskite solar cell and comprises a perovskite layer and a passivation layer formed on the upper surface of the perovskite layer by spin coating of a tert-butyl guanidine hydrochloride solution.
Specifically, the tert-butyl guanidine hydrochloride solution is spin-coated on a perovskite layer to prepare a high-quality perovskite film, so that each photovoltaic property of the perovskite solar cell is improved, the perovskite solar cell with the photoelectric conversion efficiency up to 23.06% is finally obtained, and 90% of the initial efficiency of the perovskite solar cell is still maintained after 1000 hours of aging experiments.
As shown in the right graph of FIG. 3, the application provides a high-efficiency stable perovskite solar cell, which comprises conductive glass (ITO) and an electron transport layer (SnO) which are stacked in sequence from bottom to top 2 ) Perovskite thin film (PVK for short), hole transport layer (Sprio-OMeTAD) and metal electrode (Ag);
the perovskite thin film comprises a perovskite layer and a passivation layer (TBGaCl) formed by spin coating a tert-butyl guanidine hydrochloride solution on the upper surface of the perovskite layer.
Specifically, the application provides a preparation method of a high-efficiency stable perovskite solar cell, which comprises the following steps:
providing conductive glass which is ITO conductive glass, wherein the conductive glass can be sequentially cleaned by distilled water, detergent, deionized water, toluene, acetone and absolute ethyl alcohol under the condition of ultrasound, and finally treated in an ultraviolet ozone cleaner and a plasma cleaner; preferably, the cleaning step is performed for at least 20 minutes or more, and in an ozone cleaning machine, at least 20 minutes or more, and in a plasma cleaning machine, at least 5 minutes or more.
Forming an electron transport layer on the conductive glass, wherein the electron transport layer is prepared by the following steps: snO at room temperature 2 The nano solution is spin-coated on ITO conductive glass, the ITO conductive glass is preferably cleaned, and the ITO/SnO is prepared by annealing treatment 2 A substrate of SnO 2 The nano solution can be prepared in advance and placed in a refrigerator for standby; preferably, snO in the step (2) 2 SnO is prepared with secondary deionized water in a ratio of 1:4 2 Nano solution, and ultrasonic oscillation for more than 30 minutes is needed before the use, the SnO 2 The spin-coating speed of the nano-solution was 3500rpm for 25 seconds, the acceleration was 2000rpm/s, and annealing was performed at 180℃for 30 minutes.
Forming a perovskite layer on the electron transport layer, wherein the preparation process of the perovskite layer comprises the following steps: spin coating solution A on electron transportCarrying out annealing treatment on the layer, cooling to room temperature, spin-coating the solution B on the film formed by the solution A, and carrying out annealing treatment to obtain the film; the solution A is PbI 2 A mixed solution of N, N-Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), wherein the solution B is a solution formed by mixing formamidine hydroiodidate (FAI), methyl iodized amine (MAI) and methyl ammonium chloride (MACl) in isopropanol; preferably, pbI 2 The dosages of DMF and DMSO are respectively 0.6915g,900 mu L and 100 mu L, and the mixture is heated and stirred for more than 4 hours at 70 ℃; the dosages of FAI, MAI, MACl and isopropanol are 135mg, 9.59mg, 13.5mg and 1.5mL respectively, and the mixture is stirred for more than 4 hours by using a polytetrafluoroethylene magnetic stirrer; the dosage of the solution A is 35 mu L, the spin coating speed is 1500rpm, the spin coating duration is 30 seconds, the acceleration is 1500rpm/s, the annealing temperature is 70 ℃, and the annealing duration is 1 minute; the solution B is used in an amount of 35 mu L and is dripped into the center of a substrate within 5 seconds, the spin coating speed is 2000rpm, the spin coating duration is 30 seconds, the acceleration is 2000rpm/s, the substrate is pre-annealed at 30 ℃ for 5 minutes, and then the substrate is transferred into air (the air humidity is 30% -40%) and annealed at 150 ℃ for 15 minutes.
Forming a passivation layer on the perovskite layer, wherein the passivation layer is formed by spin-coating a tert-butyl guanidine hydrochloride solution on the upper surface of the perovskite layer and annealing treatment, and the tert-butyl guanidine hydrochloride solution is formed by dissolving tert-butyl guanidine hydrochloride in isopropanol; the concentration of the tert-butyl guanidine hydrochloride solution is 0.3-1.0mg/ml, preferably 0.5mg/ml, and the solution is stirred for more than 1 hour by using a polytetrafluoroethylene magnetic stirrer and is subjected to ultrasonic oscillation for at least more than 30 minutes before being used; the t-butylguanidine hydrochloride solution is used in an amount of 100. Mu.L, and the spin-coating speed is 4000-5000rpm, at which speed the passivation layer formed by the material can be made thinner and uniform, preferably 5000rpm, for 20-40 seconds to keep the spin-coated film stable on the substrate, preferably 30 seconds, and the acceleration is 2000rpm/s, and annealing is performed at 100 ℃ for 5 minutes.
Forming a hole transport layer on the passivation layer, wherein the hole transport layer is prepared by the following steps: spin-coating the solution E on the electron transport layer to obtain the electron transport layer; the solution E is formed by mixing a solution C and a solution D, wherein the solution C is acetonitrile solution of lithium bis (trifluoromethanesulfonyl) imide (Li-TFSI), and the solution D is a mixed solution of chlorobenzene, spiro-OMeTAD and 4-tert-butylpyridine; preferably, the Li-TFSI and acetonitrile are used in an amount of 520mg and 1mL, respectively; the amounts of chlorobenzene, spiro-OMeTAD and 4-t-butylpyridine were 1mL, 75mg and 28.8. Mu.L, respectively. The amount of solution C was 17.5. Mu.L, and the mixture was stirred with a polytetrafluoroethylene magnetic stirrer for at least 1 hour. The dosage of the solution E is 35 mu L, the rotating speed of the one-step spin coating procedure is 3500rpm, the spin coating time is 25 seconds, and the acceleration is 2000rpm/s; this step was operated in a glove box filled with nitrogen and the final device was placed in an electronic moisture proof cabinet at 20% humidity for 12 hours of oxidation.
Forming a metal electrode on the hole transport layer, wherein the preparation process of the metal electrode comprises the following steps: plating silver electrode on the hole transport layer; the silver electroplating is carried out in a high vacuum coating instrument, wherein the vacuum degree is 6.4x10 -4 Pa, the vapor deposition speed was 0.2nm/s, and the thickness of the vapor deposition of the silver electrode was 150nm.
The technical scheme of the application is further illustrated and described through specific examples. The scope of the application is not limited in this respect.
Example 1
(1) Repeatedly cleaning conductive film glass (ITO) of conductive film glass for 20 minutes by adopting distilled water, detergent, deionized water, toluene, acetone and absolute ethyl alcohol in sequence under the condition of ultrasonic oscillation, and finally treating for 20 minutes in an ultraviolet ozone cleaner and 5 minutes in a plasma cleaner;
(2) SnO is prepared according to the proportion of 1:4 2 The nanoparticle aqueous solution is put in a refrigerator for standby after ultrasonic oscillation for 30 minutes, and ultrasonic oscillation is needed to be carried out again for 30 minutes before the nanoparticle aqueous solution is used;
(3) Preparing isopropanol solution of tert-butyl guanidine hydrochloride according to the concentration of 0.5mg/ml, and stirring for more than 1 hour by using a polytetrafluoroethylene magnetic stirrer;
(4) 0.6915gPbI 2 After mixing with 900. Mu.L of N, N-Dimethylformamide (DMF) and 100. Mu.L of dimethyl sulfoxide (DMSO), heating and stirring at 70℃for 4 hours, solution A was obtained. However, the method is thatThen 135mg of formamidine hydroiodidate, 9.59mg of methyl iodized amine and 13.5mg of methyl amine chloride are mixed in 1.5mL of isopropanol and stirred for more than 4 hours by using a polytetrafluoroethylene magnetic stirrer to obtain a solution B;
(5) 520mg of lithium bistrifluoromethylsulfonylimide (Li-TFSI) was dissolved in 1mL of acetonitrile to obtain solution C. To 1mL of chlorobenzene was added 75mg of spiro-OMeTAD, and after stirring was completed, 28.8. Mu.L of 4-t-butylpyridine was added thereto, and stirring was continued for 10 minutes to obtain a solution D. Then adding 17.5 mu L of the solution C into the solution D, and stirring for more than 1 hour by using a polytetrafluoroethylene magnetic stirrer to obtain a solution E for sealing for later use;
(6) SnO prepared in the step (2) is treated at room temperature 2 Spin-coating the nano-solution on the ITO conductive glass cleaned in the step (1) at 3500 revolutions per minute (rpm) for 25 seconds with an acceleration of 2000 revolutions per second (rpm/s), and annealing at 180 ℃ for 30 minutes to prepare ITO/SnO 2 A substrate.
(7) Spreading the ITO/SnO prepared in the step (6) with 35 mu L of the solution A prepared in the step (4) 2 Spin-coating the substrate at 1500rpm for 30 seconds with an acceleration of 1500rpm/s, and then annealing at 70 ℃ for 1 minute; cooling to room temperature, spin-coating 35 μl of the solution B prepared in step (4) onto a film, spin-coating at 2000rpm for 30 seconds with an acceleration of 2000rpm/s, rapidly dripping ammonium salt solution into the center of the substrate within 5 seconds, pre-annealing at 30deg.C for 5 minutes, and moving the substrate into air (air humidity of 30% -40%) after pre-annealing, and annealing at 150deg.C for 15 minutes 2 PVK device;
(8) Taking 100 mu L of the tert-butyl guanidine hydrochloride isopropanol solution prepared in the step (3), spin-coating at 5000rpm for 30 seconds, dispersing the solution on a prepared perovskite layer at an acceleration of 2000rpm/s, and annealing at 100 ℃ for 5 minutes to prepare ITO/SnO 2 PVK/TBGaCl devices;
(9) Taking 35 mu L of the solution E prepared in the step (5), and depositing the solution E on the ITO/SnO prepared in the step (8) by a one-step spin coating method (spin coating procedure: rotation speed 3500rpm, spin coating 25s, acceleration speed 2000 rpm/s) 2 On the PVK/TBGaCl substrate, ITO/SnO is prepared 2 PVK/TBGaCl/Spiro-OMeTAD substrate. This step was carried out in a glove box filled with nitrogenIs operated in the middle. After spin coating is finished, the prepared device is put into an electronic dampproof cabinet with 20 percent of humidity to be oxidized for about 12 hours;
(10) The vacuum degree should be reduced to 6.4X10 -4 After Pa, a layer of 150 nm-thick silver electrode is plated on ITO/SnO in a high vacuum coating apparatus at a vapor deposition speed of 0.2nm/s 2 On the PVK/TBGaCl/Spiro-OMeTAD substrate, ITO/SnO is prepared 2 The assembly of the PVK/TBGaCl/Spiro-OMeTAD/Ag device and the perovskite solar cell device is completed.
It should be noted that the specific parameters or some common reagents in the above embodiments are specific embodiments or preferred embodiments under the concept of the present application, and are not limited thereto; and can be adaptively adjusted by those skilled in the art within the concept and the protection scope of the application. In addition, unless otherwise specified, the starting materials employed may also be commercially available products conventionally used in the art or may be prepared by methods conventionally used in the art.
The X-ray diffraction of the original perovskite thin film (which was not subjected to the modification of tert-butylguanidine hydrochloride alone, and the rest of the procedure was identical to example 1) and the tert-butylguanidine hydrochloride modified perovskite thin film provided in example 1 of the present application is shown in fig. 1. After the perovskite film is modified by tert-butylguanidine hydrochloride, the perovskite peak characteristics have higher diffraction intensity, which shows that the perovskite film has better crystallinity and optimized film quality. While PbI 2 Characteristic peak intensity decrease, indicating t-butylguanidine hydrochloride and PbI 2 Has stronger interaction. Thus improving crystallinity and excessive PbI 2 The reduction of (c) has a positive effect on the dissociation and transport of charge.
The flat scanning electron microscope for preparing the original perovskite film and the tertiary butyl guanidine hydrochloride modified perovskite film is shown in fig. 2. The original perovskite film has irregular appearance, more pinholes, rough surface and unequal grain size from tens to hundreds of nanometers, and a large amount of PbI exists on the surface of the film 2 And (5) a crystal. While the attachment of the tert-butylguanidine hydrochloride to the perovskite surface and grain boundaries substantially eliminates surface pinholes, pbI 2 The number of crystals is greatly reduced, which is consistent with the test structure of X-ray diffraction. And the crystal grainThe size is more uniform and larger, the crystallinity is high, the grain boundary is reduced, the surface is compact and smooth, the carrier recombination loss caused by the defects is reduced, and the carrier transmission is also facilitated.
The cross-sectional electron microscope of the original perovskite thin film and the tertiary butyl guanidine hydrochloride modified perovskite thin film are prepared as shown in figure 3. In the cross section of the original perovskite device, the contact surface of the Sprio-OMeTAD and the perovskite layer is not regular, the crystal size is not uniform, the arrangement is not regular, and a large amount of redundant PbI exists 2 A crystal; the cross section of the perovskite battery device modified by the tert-butylguanidine hydrochloride has the advantages that the contact surface between Sprio-OMeTAD and a perovskite layer is neat, and PbI 2 The crystal is obviously reduced, and the perovskite crystal has uniform particle size and regular and compact arrangement, so that the internal resistance is reduced, the charge transmission capability of the film is improved, and the perovskite film with high quality is obtained.
XPS spectra of the original perovskite thin film and the t-butylguanidine hydrochloride modified perovskite thin film were prepared as shown in fig. 4. It can be found in XPS spectrum of Pb 4f that the modification of tert-butylguanidine hydrochloride is followed by the fact that the tert-butylguanidine hydrochloride molecule is not coordinated to Pb in perovskite 2+ Coordination is carried out, pb 2+ The density of the surrounding electron cloud is increased, so that two characteristic peaks of Pb 4f in the perovskite film are shifted to a position with lower binding energy; at the same time, the characteristic peak of I3 d modified by the tert-butyl guanidine hydrochloride also shifts in the same direction, which proves the interaction of the tert-butyl guanidine hydrochloride with Pb and I in the perovskite film.
The absorption intensity in the ultraviolet and visible region of the perovskite film was increased relative to the original perovskite film due to the addition of t-butylguanidine hydrochloride, as shown on the left in fig. 5. This shows that the modified device improves the light utilization rate, can absorb stronger light energy, and excites more carriers, thereby improving the output current of the device. It can also be seen that the curves almost coincide at 800 nm. The Tauc graph on the right of FIG. 5 is obtained through conversion, and shows that the modification of tert-butyl guanidine hydrochloride has almost no influence on the forbidden bandwidth of perovskite, and the forbidden bandwidth is 1.55eV, so that the Tauc graph is an ideal forbidden bandwidth for preparing a high-efficiency perovskite solar cell.
The UPS spectra of the perovskite thin film before and after preparation of t-butylguanidine hydrochloride modification are shown in fig. 6. And by combining the energy gap obtained by the diagram, and the depicted schematic diagram of the energy level arrangement, after the modification of the tert-butylguanidine hydrochloride, the perovskite energy level moves upwards to be more matched with the energy level of the Sprio-OMeTAD, thereby being beneficial to extracting holes and blocking electrons.
Steady state fluorescence tests were performed on perovskite thin films before and after modification with t-butylguanidine hydrochloride, and the results are shown in fig. 7. The modification of the tert-butyl guanidine hydrochloride causes the fluorescence intensity of the perovskite film to be increased, which indicates that the addition of the tert-butyl guanidine hydrochloride reduces the concentration of surface defects, inhibits the recombination of carriers and effectively improves the quality of the perovskite film.
Table 1 time resolved photoluminescence spectra data table for original perovskite cells and t-butylguanidine hydrochloride modified perovskite cells
τ 1 (ns) τ 2 (ns) τ avg (ns)
Pristine 25.01 35.51 156.30
TBGaCl 35.51 212.26 190.81
Meanwhile, the perovskite thin film before and after the modification of the tert-butylguanidine hydrochloride was subjected to time-resolved photoluminescence spectroscopy, and the results are shown in fig. 8, and the corresponding data are shown in table 1. The average fluorescence lifetime of the perovskite film before the modification of the tert-butylguanidine hydrochloride is only 156.30ns, and the average fluorescence lifetime of the perovskite film after the modification of the tert-butylguanidine hydrochloride reaches 190.81ns, thereby being prolonged by 22.07%. The longer carrier life can effectively improve carrier transmission efficiency and reduce defect recombination.
TABLE 2 Table of specific parameters of the photoelectric properties of the original perovskite cells and the t-butylguanidine hydrochloride modified perovskite cells
V OC (V) J SC (mA·cm -2 ) FF(％) PCE(％)
Pristine 1.09 24.33 76.08 20.18
TBGaCl 1.11 25.11 82.55 23.06
The J-V curves obtained from the perovskite cells before and after modification with t-butylguanidine hydrochloride are shown in FIG. 9, and the specific performance parameters are shown in Table 2. Compared with the original device, various indexes of the perovskite solar cell after the modification of the tert-butyl guanidine hydrochloride are improved, especially the photovoltage, the filling factor and the conversion efficiency are improved, the photoelectric conversion efficiency of the perovskite solar cell after the modification of the tert-butyl guanidine hydrochloride is up to 23.06%, and the photoelectric conversion efficiency is improved by 14.27% compared with 20.18% of the device without the modification.
The perovskite batteries before and after modification of the tert-butylguanidine hydrochloride are tested to obtain IPCE curves, the structure of the IPCE curves is shown in figure 10, and the JSC obtained after modification is 24.15mA cm -2 Is significantly higher than the original perovskite cell by 23.40mA cm -2 The contribution of interface modification of tert-butyl guanidine hydrochloride to the improvement of the photoelectric performance of the perovskite battery is proved according to the J-V curve.
Fig. 11 is a mote-schottky curve of perovskite cells before and after t-butylguanidine hydrochloride modification. As shown in the figure, the built-in electric field of the perovskite battery device modified by the tert-butylguanidine hydrochloride is 0.95V obviously higher than that of the original device, so that a driving force is provided for separation of carriers, and the open-circuit voltage is improved.
FIG. 12 is a graph of Electrochemical Impedance Spectroscopy (EIS) for perovskite cells before and after t-butylguanidine hydrochloride modification under dark conditions. The inset is a fitted resistance equivalent circuit diagram of the curve. As shown in the figure, the radius of the perovskite battery modified by the tert-butylguanidine hydrochloride is obviously smaller than that of the original device, which shows that the modified device has smaller charge transfer resistance, and the defect of the prepared high-quality perovskite film is reduced, so that the non-radiative recombination of carriers is inhibited.
Fig. 13 shows the stability of perovskite solar cell at room temperature and in air with a relative humidity of 20% before and after modification with t-butylguanidine hydrochloride. After 1000 hours of aging, the perovskite battery modified by the tert-butylguanidine hydrochloride can keep more than 90% of the original value, and the original device can only keep 76% of the original value. This fully demonstrates that devices modified and passivated with t-butylguanidine hydrochloride exhibit better stability.
In addition, it should be understood by those skilled in the art that although many problems exist in the prior art, each embodiment or technical solution of the present application may be modified in only one or several respects, without having to solve all technical problems listed in the prior art or the background art at the same time. Those skilled in the art will understand that nothing in one claim should be taken as a limitation on that claim.
Although terms such as perovskite thin film, conductive glass, electron transport layer, perovskite layer, passivation layer, hole transport layer, metal electrode, etc. are more used herein, the possibility of using other terms is not excluded. These terms are used merely for convenience in describing and explaining the nature of the application; they are to be interpreted as any additional limitation that is not inconsistent with the spirit of the present application.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the application.

Claims (10)

1. A modified perovskite thin film for use in a perovskite solar cell, characterized by: comprises a perovskite layer and a passivation layer formed by spin coating a tert-butyl guanidine hydrochloride solution on the upper surface of the perovskite layer.
2. The utility model provides a high-efficient stable perovskite solar cell which characterized in that: the device comprises conductive glass, an electron transport layer, a perovskite film, a hole transport layer and a metal electrode which are sequentially stacked from bottom to top;
the perovskite film comprises a perovskite layer and a passivation layer formed by spin coating a tert-butyl guanidine hydrochloride solution on the upper surface of the perovskite layer.
3. The preparation method of the high-efficiency stable perovskite solar cell is characterized by comprising the following steps of:
providing a conductive glass;
forming an electron transport layer on the conductive glass;
forming a perovskite layer on the electron transport layer;
forming a passivation layer on the perovskite layer, wherein the passivation layer is formed by spin-coating a tert-butyl guanidine hydrochloride solution on the upper surface of the perovskite layer and annealing;
forming a hole transport layer on the passivation layer;
and forming a metal electrode on the hole transport layer.
4. A method of preparation according to claim 3, characterized in that: the conductive glass is ITO conductive glass.
5. A method of preparation according to claim 3, characterized in that: the preparation process of the electron transport layer comprises the following steps: snO at room temperature 2 The nano solution is spin-coated on ITO conductive glass and is prepared through annealing treatment.
6. A method of preparation according to claim 3, characterized in that: the preparation process of the perovskite layer comprises the following steps: spin-coating the solution A on the electron transport layer, annealing, cooling to room temperature, spin-coating the solution B on the film formed by the solution A, and annealing to obtain the product; the solution A is PbI 2 Mixed solution of N, N-dimethylformamide and dimethyl sulfoxide, wherein the solution B is formamidine hydroiodic acid salt and formamidine hydroiodic acid saltA solution of the amine iodide and the amine methyl chloride mixed in isopropanol.
7. A method of preparation according to claim 3, characterized in that: the preparation process of the hole transport layer comprises the following steps: spin-coating the solution E on the electron transport layer to obtain the electron transport layer; the solution E is formed by mixing a solution C and a solution D, wherein the solution C is acetonitrile solution of lithium bistrifluoro-methanesulfonimide, and the solution D is a mixed solution of chlorobenzene, spiro-OMeTAD and 4-tert-butylpyridine.
8. A method of preparation according to claim 3, characterized in that: the preparation process of the metal electrode comprises the following steps: and plating a silver electrode on the hole transport layer.
9. A method of preparation according to claim 3, characterized in that: the concentration of the tert-butyl guanidine hydrochloride solution is 0.3-1.0mg/ml.
10. A method of preparation according to claim 3, characterized in that: the spin coating speed of the tert-butylguanidine hydrochloride solution is 4000-5000rpm, the spin coating time is 20-40 seconds, and the annealing is carried out at 100 ℃ for 5 minutes.
CN202310606498.5A 2023-05-26 2023-05-26 Modified perovskite film, efficient stable perovskite solar cell and preparation method thereof Pending CN116723714A (en)

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