CN111211224A

CN111211224A - Method for quickly preparing commercial perovskite film at low cost

Info

Publication number: CN111211224A
Application number: CN202010022553.2A
Authority: CN
Inventors: 萨德克·阿伯思; 王杨润乾; 沈文忠
Original assignee: Shanghai Jiao Tong University
Current assignee: Shanghai Jiao Tong University
Priority date: 2020-01-09
Filing date: 2020-01-09
Publication date: 2020-05-29

Abstract

The invention discloses a method for quickly preparing a commercial perovskite thin film at low cost, which relates to the field of perovskite solar cells and comprises the following steps: cleaning FTO glass; preparing a metal lead layer on the cleaned FTO glass surface; immersing the FTO glass containing the metallic lead layer into a methyl ammonium iodide/isopropanol solution to prepare the perovskite thin film. Through the implementation of the invention, the transformation from the metallic lead layer to the perovskite film can be rapidly and controllably realized, the crystal size of the perovskite film is easy to control, and the perovskite film can be easily prepared on a flexible, large-size and rough substrate.

Description

Method for quickly preparing commercial perovskite film at low cost

Technical Field

The invention relates to the field of perovskite solar cells, in particular to a method for quickly preparing a commercial perovskite thin film at low cost.

Background

In modern solar cell research, Perovskite Solar Cells (PSCs) are a unique class, considered as emerging photovoltaic power generation materials. The key layer in the perovskite solar cell, namely the organic metal halide perovskite light absorption layer, enables the solar cell to have higher energy conversion efficiency and lower material cost. In recent years, people have increasingly concentrated interest in organic lead halogenated perovskite solar cells, and research is becoming deeperAnd the Power Conversion Efficiency (PCE) is improved to more than 25%. Methyl ammonium lead iodide MAPbI₃(MA＝CH₃NH₃ ⁺) The material is a promising photovoltaic material, and has good band gap, high absorption coefficient, long hole-electron diffusion length and excellent carrier transport performance. Preparation of MAPbI₃There are many methods for perovskite thin films, such as one-step or two-step spin coating, thermal evaporation, electrochemical deposition, and the like. Spin coating is only suitable for small area deposition on planar substrates, which would limit commercialization of PSCs. Thermal evaporation processes require high vacuum and high temperatures, which limits cost-effectiveness and large-scale production. Whereas for electrochemical deposition methods, the metallic lead layer is electrochemically converted to MAPbI₃The perovskite thin film takes a long time.

Accordingly, those skilled in the art have been devoted to developing a method for controllably and rapidly preparing large-scale, high-quality perovskite thin films for efficient PSCs through a low-cost manufacturing process.

Disclosure of Invention

In view of the above-mentioned drawbacks of the prior art, the technical problem to be solved by the present invention is how to prepare perovskite thin films at low cost, controllably and rapidly, and can be applied to flexible, large-sized, rough substrates.

To achieve the above object, the present invention provides a method for rapidly preparing a commercial perovskite thin film at low cost, comprising the steps of:

step 1, cleaning FTO glass;

step 2, preparing a metal lead layer on the cleaned FTO glass surface;

and 3, immersing the FTO glass containing the metal lead layer into a methyl ammonium iodide/isopropanol solution to prepare the perovskite thin film.

Further, the step 1 further comprises:

step 1.1, firstly, placing the FTO glass in an ultrasonic cleaning machine, and sequentially cleaning the FTO glass by using deionized water, acetone, isopropanol and ethanol for 15 minutes respectively;

and 1.2, irradiating the FTO glass under ultraviolet rays to remove organic pollution and improve the hydrophilicity.

Further, the step 2 further comprises:

step 2.1, dissolving every 37.5 grams of sodium iodide (NaI, 99.99%) and every 15ml of methylene glycol tert-butyl ether (ETB, 99%) in 150ml of isopropanol (2-propanol, 99.9%), stirring and then filtering to obtain 150ml of a clear solution;

step 2.2, every 1.383 grams of lead iodide (PbI)₂99.99%) was added to 150ml of the clear solution and stirred until clear;

2.3, depositing the metal lead layer on the FTO glass by a constant current method in an electrochemical workstation;

and 2.4, taking out the prepared FTO glass with the metal lead layer, washing with isopropanol (2-propanol, 99.9%) and drying.

Further, in the step 2.1, the stirring temperature is 45 ℃ and the stirring time is 3 hours.

Further, the constant current method in step 2.3 uses a current of-3 mA (relative open circuit) and a power-on time of 300 s.

Further, the step 3 further comprises:

step 3.1, mixing every 1 g of methyl ammonium iodide (MAI, 99.9%) with 100ml of isopropanol (2-propanol, 99.9%), and stirring at room temperature until the mixture is clear to prepare the methyl ammonium iodide/isopropanol solution;

and 3.2, soaking the FTO glass with the metal lead layer in the methyl ammonium iodide/isopropanol solution to obtain the perovskite thin film.

Further, the time for soaking the FTO glass in the methyl ammonium iodide/isopropyl alcohol solution in step 3.2 is 1 minute.

The invention also provides a method for rapidly converting the flexible metal lead foil into the perovskite thin film by immersing the flexible metal lead foil into a methyl ammonium iodide/isopropanol solution.

Further, the methyl ammonium iodide/isopropanol solution was proportioned to correspond to 100ml of isopropanol (2-propanol, 99.9%) per 1 g of methyl ammonium iodide (MAI, 99.9%) and stirred at room temperature until clear.

Further, the flexible metal lead foil was soaked in the methyl ammonium iodide/isopropyl alcohol solution for 1 minute.

Compared with a one-step or two-step spin coating method, the method can be used for large-area, flexible and rough substrates; compared with thermal evaporation, the method does not need high vacuum and high temperature conditions; compared with electrochemical deposition, the method can more quickly realize the conversion of metallic lead into MAPbI₃Perovskite.

The conception, the specific structure and the technical effects of the present invention will be further described with reference to the accompanying drawings to fully understand the objects, the features and the effects of the present invention.

Drawings

FIG. 1 is a flow chart of a preferred embodiment of the present invention;

FIG. 2 is an X-ray diffraction (XRD) pattern of a preferred embodiment of the present invention;

FIG. 3 is a Scanning Electron Microscope (SEM) picture of a preferred embodiment of the present invention;

FIG. 4 is a Scanning Electron Microscope (SEM) picture of another preferred embodiment of the present invention.

Detailed Description

The technical contents of the preferred embodiments of the present invention will be more clearly and easily understood by referring to the drawings attached to the specification. The present invention may be embodied in many different forms of embodiments and the scope of the invention is not limited to the embodiments set forth herein.

As shown in FIG. 1, a preferred embodiment of the present invention uses a dipping method to achieve direct and rapid direct conversion of a metal lead layer into MAPbI₃Perovskite thin film:

step 1, cleaning FTO glass:

step 1.1, placing the FTO glass into an ultrasonic cleaning machine, and respectively cleaning the FTO glass for 15 minutes by using deionized water, acetone, isopropanol and ethanol;

step 1.2, finally, placing the substrate under ultraviolet radiation to remove organic pollution and improve hydrophilicity;

step 2, preparing a metal lead layer on the surface of the FTO glass:

step 2.1, preparation of sodium iodide solution: 33.75 g of sodium iodide (NaI, Aladdin reagent, 99.99%) and 15ml of methylene glycol tert-butyl ether (ETB, Aladdin reagent, 99%) were dissolved in 150ml of isopropanol (2-propanol, national reagent, 99.9%), stirred at 45 ℃ for 3 hours and then filtered to obtain 150ml of a clear solution;

step 2.2, preparation of lead iodide solution: 1.383 g of lead iodide (PbI)₂Sigma-Aldrich, 99.99%) was added to the above 150ml clear solution and stirred until clear;

step 2.3, preparing a metal lead layer: placing the FTO glass in an electrochemical workstation filled with the clarifying solution, and depositing a metal lead layer on the FTO glass by a constant current method, wherein the current is-3 mA (relative open circuit), and the electrifying time is 300 s;

step 2.4, taking out the prepared FTO glass with the metal lead layer, washing with isopropanol (2-propanol, a traditional Chinese medicine reagent, 99.9 percent) and drying;

step 3, immersing FTO glass containing a metal lead layer into a methyl ammonium iodide/isopropanol solution to prepare the perovskite thin film:

step 3.1, preparing a methyl ammonium iodide solution: 1 g of methyl ammonium iodide (MAI, Ci' an Baolaite, 99.9%) was dissolved in 100ml of isopropanol (2-propanol, national reagent, 99.9%) and stirred at room temperature until clear.

And 3.2, immediately soaking the prepared FTO glass with the metal lead layer into the methyl ammonium iodide/isopropanol solution for 1 minute. Rapid conversion of metallic lead layer to MAPbI₃A perovskite thin film.

As shown in FIG. 2, MAPbI obtained in a preferred embodiment of the invention₃The XRD pattern of the perovskite thin film, the asterisk corresponds to the peak position of the perovskite thin film. As shown in FIG. 3, MAPbI obtained in a preferred embodiment of the invention₃Scanning Electron Microscope (SEM) pictures of perovskite thin films. The result shows that MAPbI can be obtained by soaking the prepared metal lead layer in methyl ammonium iodide/isopropanol solution₃PerovskiteA film. This indicates that this approach is feasible.

As shown in FIG. 4, MAPbI obtained in another preferred embodiment of the present invention₃Scanning Electron Microscope (SEM) pictures of perovskite thin films. In this example, the perovskite thin film can be obtained by immersing the metal lead foil in a methyl ammonium iodide/isopropanol solution for 1 minute. Also illustrates the feasibility of this approach.

The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.

Claims

1. a method for preparing commercial perovskite thin film at low cost, characterized in that, the method comprises the following steps:

Step 1. FTO glass cleaning;

Step 2, preparing a metal lead layer on the cleaned surface of the FTO glass;

Step 3, immersing the FTO glass containing the metal lead layer in a methyl ammonium iodide/isopropanol solution to prepare the perovskite thin film.

2. a kind of method for preparing commercial perovskite thin film rapidly and low cost as claimed in claim 1, is characterized in that, described step 1 also comprises:

Step 1.1. First, place the FTO glass in an ultrasonic cleaning machine, and wash with deionized water, acetone, isopropanol, and ethanol for 15 minutes each in turn;

Step 1.2, the FTO glass is then irradiated under ultraviolet light to remove organic pollution and improve hydrophilicity.

3. a kind of method for preparing commercial perovskite thin film rapidly and low cost as claimed in claim 1, is characterized in that, described step 2 also comprises:

Step 2.1, dissolve every 37.5 grams of sodium iodide and every 15ml of methylene glycol tert-butyl ether in 150ml of isopropanol, stir and then filter to get 150ml of clear solution;

Step 2.2, adding every 1.383 grams of lead iodide to 150ml of the clear solution and stirring until clear;

Step 2.3, depositing the metal lead layer on the FTO glass by galvanostatic method in an electrochemical workstation;

Step 2.4, take out the prepared FTO glass with the metal lead layer, rinse with isopropanol and dry.

4 . The method for preparing a commercial perovskite thin film quickly and at low cost according to claim 3 , wherein the stirring temperature in the step 2.1 is 45° C. and the stirring time is 3 hours. 5 .

5. a kind of method for preparing commercial perovskite thin film rapidly and low cost as claimed in claim 3, it is characterized in that, the electric current that the constant current method described in described step 2.3 uses is-3mA (relative open circuit), energization time for 300s.

6. a kind of method for preparing commercial perovskite thin film fast and low cost as claimed in claim 1, is characterized in that, described step 3 also comprises:

Step 3.1, prepare the methyl ammonium iodide/isopropanol solution according to the ratio of 100ml of isopropanol corresponding to 1 gram of methyl ammonium iodide, and stir to clarify at room temperature;

Step 3.2, soak the FTO glass with the metal lead layer in the methyl ammonium iodide/isopropanol solution to prepare the perovskite thin film.

7. The method for preparing a commercial perovskite film at low cost and fast as claimed in claim 6, wherein the FTO glass described in the step 3.2 is soaked in the methyl ammonium iodide/isopropanol solution The time in is 1 minute.

8. A method for preparing a commercial perovskite thin film quickly and at low cost, characterized in that the method is to immerse the flexible metal lead foil in a methylammonium iodide/isopropanol solution to make the flexible metal lead foil rapidly. into the perovskite film.

9. a kind of method for preparing commercial perovskite film at low cost quickly as claimed in claim 8, is characterized in that, described methyl ammonium iodide/isopropanol solution ratio is every 1 gram of methyl ammonium iodide Corresponding to 100 ml of isopropanol, and stirred at room temperature until clear.

10. The method for preparing a commercial perovskite film rapidly and at low cost as claimed in claim 8, wherein the immersion time of the flexible metal lead foil in the methylammonium iodide/isopropanol solution is 1 minute.