Preparation method of thiophene-containing perovskite solar cell and perovskite cell thereof

Abstract

The invention relates to a preparation method of a thiophene-containing perovskite solar cell and a perovskite cell thereof, a thiophene compound is introduced into a preparation process of a perovskite thin film as a passivating agent, and the perovskite thin film is prepared by controlling the addition amount and the addition time of the passivating agent. And it is ensured that the passivating agent can uniformly and effectively cover the surface and the grain boundary of the perovskite thin film. The process not only reduces the obstruction of defects to charge transmission, but also improves the structural stability and photoelectric conversion efficiency of the perovskite thin film.

Description

Technical Field

[0001] The present application relates to the field of photovoltaic cells, and in particular to a method for preparing a thiophene-containing perovskite solar cell and a perovskite cell thereof. Background Art

[0002] Perovskite materials often have many defects at the grain boundaries and surfaces, which can lead to non-radiative recombination of carriers, thereby reducing the efficiency and stability of the device. Therefore, passivating the surface and grain boundary defects of perovskite materials is crucial to improving device performance.

[0003] In order to achieve the above passivation effect, various materials have been developed to passivate the surface and grain boundary defects of perovskites, including organic molecules, inorganic materials, and organic-inorganic hybrid materials. In actual devices, the compatibility of the passivation layer with the charge transport layer or electrode material is also an important factor affecting the performance of the device. Some passivation materials may affect the charge transport characteristics of the interface during the passivation process, or even introduce new interface defects, resulting in the passivation effect being counterproductive. Summary of the invention

[0004] In view of this, the present application proposes a method for preparing a thiophene-containing perovskite solar cell and a perovskite cell thereof, which can effectively passivate the surface and grain boundary defects of the perovskite film, thereby improving the performance of photovoltaic devices and photoelectric devices.

[0005] According to one aspect of the present application, a method for preparing a thiophene-containing perovskite solar cell is provided, comprising the following steps:

[0006] depositing a conductive substrate on a base, and preparing a hole transport layer on the conductive substrate;

[0007] Preparing a precursor solution, and depositing the precursor solution on the hole transport layer to form a perovskite film;

[0008] coating an ammonium salt compound solution on the perovskite film to form a passivation layer;

[0009] An electron transport layer is prepared on the passivation layer, and a back electrode is prepared on the electron transport layer.

[0010] In one possible implementation, the preparation of the precursor solution further includes: stirring a 1.5 M MAPbI3 precursor solution in a mixed solvent of DMF and DMSO.

[0011] In one possible implementation, the volume ratio of the DMF to the DMSO is 4:1.

[0012] In a possible implementation, the preparing of the precursor solution further includes: the solute of the precursor solution is a two-dimensional ammonium salt compound.

[0013] In a possible implementation, the precursor solution is deposited on the ITO glass substrate by spin coating, with a spin coating speed of 4000 rpm and a spin coating time of 30 s.

[0014] In a possible implementation, the two-dimensional ammonium salt compound includes 2-thiopheneethylamine and / or 3-(2-thiophene)-1-propylamine.

[0015] In one possible implementation, the two-dimensional ammonium salt compound has 1-20 carbon atoms.

[0016] In one possible implementation, coating the ammonium salt compound solution on the perovskite film further includes: coating the ammonium salt compound solution on the perovskite film by spin coating or dip coating; coating the ammonium salt compound solution on the perovskite film to form a passivation layer further includes: spin coating the ammonium salt compound solution on the annealed perovskite film at a spin coating speed of 3000 rpm for 20 seconds, and forming the passivation layer after drying.

[0017] In one possible implementation, an electron transport layer is prepared on the passivation layer, and preparing a back electrode on the electron transport layer further includes: depositing a PCBM electron transport layer and an Ag electrode on the passivated perovskite film by vacuum evaporation to complete the preparation of the solar cell, and conducting a photoelectric performance test.

[0018] According to another aspect of the present application, a perovskite solar cell is proposed, which is prepared by the preparation method of a thiophene-containing perovskite solar cell described in any of the above items, and includes: the conductive substrate, the hole transport layer, the perovskite film, the passivation layer, the electron transport layer and the back electrode arranged in sequence from bottom to top.

[0019] Beneficial effects of the present application: The present application provides a method for preparing a thiophene-containing perovskite solar cell and a perovskite cell thereof, which significantly improves the performance of photovoltaic devices and photoelectric devices by passivating the surface and grain boundary defects of the perovskite film. The composition of the present application is simple to prepare, has a significant passivation effect, and can effectively improve the performance of photovoltaic devices and photoelectric devices.

[0020] Other features and aspects of the present application will become apparent from the following detailed description of exemplary embodiments with reference to the attached drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate exemplary embodiments, features, and aspects of the present application and, together with the description, serve to explain the principles of the present application.

[0022] Figure 1 A schematic diagram showing the structure of the perovskite battery of the present application is shown;

[0023] Figure 2 A schematic diagram of photoluminescence spectrum without / with passivation using thiophene ammonium iodide salt is shown;

[0024] Figure 3 A schematic diagram of transient photoluminescence spectrum of no / some states passivated by thiophene ammonium iodide salt is shown;

[0025] Figure 4 A graph showing the energy conversion efficiency without / with passivation using thiophene ammonium iodide salt;

[0026] Figure 5 Shown is a stability test graph with and without passivation using thiophene ammonium iodide salt. DETAILED DESCRIPTION

[0027] Various exemplary embodiments, features and aspects of the present application will be described in detail below with reference to the accompanying drawings. The same reference numerals in the accompanying drawings represent elements with the same or similar functions. Although various aspects of the embodiments are shown in the accompanying drawings, the drawings are not necessarily drawn to scale unless otherwise specified.

[0028] Among them, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", "clockwise", "counterclockwise", "axial", "radial", "circumferential" and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present application or simplifying the description, and do not indicate or imply that the referred device or element must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as a limitation on the present application.

[0029] In addition, the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of the features. In the description of this application, the meaning of "plurality" is two or more, unless otherwise clearly and specifically defined.

[0030] The word “exemplary” is used exclusively herein to mean “serving as an example, example, or illustration.” Any embodiment described herein as “exemplary” is not necessarily to be construed as preferred or advantageous over other embodiments.

[0031] In addition, in order to better illustrate the present application, numerous specific details are given in the following specific embodiments. It should be understood by those skilled in the art that the present application can also be implemented without certain specific details. In some examples, methods, means, components and circuits well known to those skilled in the art are not described in detail in order to highlight the subject matter of the present application.

[0032] A method for preparing a thiophene-containing perovskite solar cell comprises the following steps;

[0033] Depositing a conductive substrate 100 on a substrate, and preparing a hole transport layer 200 on the conductive substrate 100;

[0034] Preparing a precursor solution, and depositing the precursor solution on the hole transport layer 200 to form a perovskite film 300;

[0035] Coating an ammonium salt compound solution on the perovskite film 300 to form a passivation layer 400;

[0036] The electron transport layer 500 is formed on the passivation layer 400 , and the back electrode 600 is formed on the electron transport layer 500 .

[0037] In one embodiment, a thiophene-based two-dimensional ammonium salt compound for surface passivation of perovskite materials and its application are provided. The composition can effectively passivate the surface and grain boundary defects of the perovskite film 300, thereby improving the performance of photovoltaic devices and photoelectric devices.

[0038] To achieve the above objectives, the present invention provides a class of thiophene two-dimensional ammonium salt compounds, including 2-thiopheneethylamine and 3-(2-thiophene)-1-propylamine, wherein the number of carbon atoms in the alkyl chain can be n=1, 2, 3, ... 20, etc. The compound can synergistically passivate different types of defects in the perovskite material and improve the quality and stability of the perovskite film 300.

[0039] Commercially purchased thiopheneamine organic compounds were synthesized by a one-step method to obtain thiopheneammonium halide salts, the chemical formula of which is as follows:

[0040]

[0041] Wherein, R is an alkyl chain, the length of the carbon chain is 1-20, and X is F, Cl, Br or I.

[0042] In one possible implementation, preparing the precursor solution further includes: stirring a 1.5 M MAPbI3 precursor solution uniformly in a mixed solvent of DMF (dimethylformamide) and DMSO (dimethyl sulfoxide).

[0043] In one possible implementation, the volume ratio of DMF to DMSO is 4:1.

[0044] In a possible implementation, preparing the precursor solution further includes: the solute of the precursor solution is a two-dimensional ammonium salt compound.

[0045] In one possible implementation, the precursor solution is deposited on an ITO (indium tin oxide) glass substrate by spin coating, with a spin coating speed of 4000 rpm and a spin coating time of 30 s.

[0046] In one possible implementation, the two-dimensional ammonium salt compound includes 2-thienylethylamine and / or 3-(2-thienyl)-1-propylamine.

[0047] In one possible implementation, the two-dimensional ammonium salt compound has 1-20 carbon atoms.

[0048] In a possible implementation, coating the ammonium salt compound solution on the perovskite film 300 further includes: coating the ammonium salt compound solution on the perovskite film 300 by spin coating or dip coating.

[0049] In one possible implementation, coating the perovskite film 300 with an ammonium salt compound solution to form the passivation layer 400 further includes: spin coating the ammonium salt compound solution on the annealed perovskite film 300 at a spin coating speed of 3000 rpm for 20 seconds, and forming the passivation layer 400 after drying.

[0050] In one possible implementation, an electron transport layer 500 is prepared on the passivation layer 400, and preparing a back electrode 600 on the electron transport layer 500 further includes: depositing a PCBM (fullerene derivative) electron transport layer 500 and an Ag electrode on the passivated perovskite film 300 by vacuum evaporation, completing the preparation of the solar cell, and conducting a photoelectric performance test.

[0051] According to another aspect of the present application, a perovskite solar cell is proposed, which is prepared by any of the above-mentioned methods for preparing a thiophene-containing perovskite solar cell, and includes: a conductive substrate 100, a hole transport layer 200, a perovskite film 300, a passivation layer 400, an electron transport layer 500 and a back electrode 600 arranged in sequence from bottom to top.

[0052] The advantage of the present application over the prior art is that the performance of the passivated perovskite film 300 is tested by photoelectric testing equipment, including photoluminescence spectrum and carrier lifetime measurement, etc. The results show that after passivation with the thiophene ammonium halide salt of the present invention, the photoelectric performance of the perovskite film 300 is significantly improved, and non-radiative recombination is significantly reduced.

[0053] Among them, Figure 2As shown in Figure 2, the photoluminescence intensity is enhanced after passivation by thiophene ammonium iodide salt, indicating that the non-radiative recombination is significantly reduced after passivation by thiophene ammonium iodide salt. Figure 3 As shown, it shows that the carrier lifetime increases from 180ns to 2080ns after passivation by thiophene ammonium iodide salt, which also shows that the passivation effect is significant. The ammonium salt can reduce the surface defects of perovskite and reduce non-radiative recombination; Figure 4 As shown, it is shown that the photoelectric performance of perovskite is significantly increased by passivation with thiophene ammonium iodide salt; Figure 5 As shown, it is shown that the stability of the perovskite is significantly increased by passivation with thiophene ammonium iodide salt.

[0054] Table 1. Detailed photovoltaic data before and after passivation, at a light intensity of 100mW / cm 2 The measured data below.

[0055]

[0056] Embodiment 1:

[0057] Preparation of precursor solution: 1.5 M MAPbI3 precursor solution was stirred evenly in a mixed solvent of DMF and DMSO (4:1, v / v);

[0058] Thin film deposition: The precursor solution was deposited on the ITO glass substrate by spin coating at a speed of 4000 rpm for 30 seconds.

[0059] Annealing treatment: annealing at 100°C for 10 minutes to obtain a uniform perovskite film 300;

[0060] Ammonium salt passivation: spin-coating an ammonium salt compound solution on the annealed perovskite film 300 at a spin-coating speed of 3000 rpm for 20 seconds, and forming a passivation layer 400 after drying;

[0061] Electrode preparation: A PCBM electron transport layer 500 and an Ag electrode are deposited on the passivated perovskite film 300 by vacuum evaporation to complete the preparation of a solar cell.

[0062] Through photoelectric performance testing, the results show that the photoelectric conversion efficiency of the passivated solar cells is significantly improved, and the short-circuit current density and open-circuit voltage are significantly improved.

[0063] It should be noted that although the present application introduces a method for preparing a thiophene-containing perovskite solar cell as an example, those skilled in the art will understand that the present application should not be limited thereto. In fact, users can flexibly set various parameters according to personal preferences and / or actual application scenarios, as long as the design is reasonable.

[0064] The present application proposes a method for preparing a perovskite solar cell containing thiophene substances and a perovskite cell thereof. The present application aims to efficiently passivate the defects existing on the surface and grain boundaries of the perovskite film 300 by passivation. This method not only solves the negative impact of internal defects of perovskite materials on photovoltaic performance, but also can utilize the chemical properties of thiophene compounds to achieve effective repair and passivation of defects, thereby significantly improving the overall performance of the prepared photovoltaic devices and optoelectronic devices.

[0065] Specifically, the preparation method of the present application involves introducing thiophene compounds as passivators into the preparation process of the perovskite film 300, and by precisely controlling the amount and timing of the passivator, ensuring that the passivator can be evenly and effectively covered on the surface and grain boundaries of the perovskite film 300. This process not only reduces the obstacles to charge transfer caused by defects, but also improves the structural stability and photoelectric conversion efficiency of the perovskite film 300.

[0066] It is worth mentioning that the preparation process of the composition of the present application is relatively simple, and large-scale production and application can be achieved without complex equipment and cumbersome steps. At the same time, due to the introduction of thiophene compounds, the passivation effect is significant, so that the performance of the prepared photovoltaic devices and optoelectronic devices has been significantly improved, including higher open circuit voltage, short circuit current and fill factor, as well as lower dark current and energy loss.

[0067] In summary, the preparation method of thiophene-containing perovskite solar cells and the perovskite cells provided in the present application not only solve the performance degradation problem caused by surface defects and grain boundary defects of the perovskite film 300, but also achieve a significant improvement in the performance of photovoltaic devices and photoelectric devices through a simple and effective preparation process, providing new ideas and methods for the development and application of perovskite solar cells.

[0068] The embodiments of the present application have been described above, and the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and changes will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments. The selection of terms used herein is intended to best explain the principles of the embodiments, practical applications, or improvements to the technology in the market, or to enable other persons of ordinary skill in the art to understand the embodiments disclosed herein.

Claims

1. A method for preparing a thiophene-containing perovskite solar cell, characterized in that: The method comprises the following steps: depositing a conductive substrate on a base, and preparing a hole transport layer on the conductive substrate; Preparing a precursor solution, and depositing the precursor solution on the hole transport layer to form a perovskite film; coating an ammonium salt compound solution on the perovskite film to form a passivation layer; An electron transport layer is prepared on the passivation layer, and a back electrode is prepared on the electron transport layer.

2. The method for preparing a thiophene-containing perovskite solar cell according to claim 1, characterized in that: The preparation of the precursor solution also includes: Stir the 1.5 M MAPbI3 precursor solution in a mixed solvent of DMF and DMSO.

3. The method for preparing a thiophene-containing perovskite solar cell according to claim 2, characterized in that: The volume ratio of the DMF to the DMSO is 4:

1.

4. The method for preparing a thiophene-containing perovskite solar cell according to claim 1 or 2, characterized in that: The preparation of the precursor solution also includes: The solute of the precursor solution is a two-dimensional ammonium salt compound.

5. The method for preparing a thiophene-containing perovskite solar cell according to claim 4, characterized in that: The precursor solution was deposited on the ITO glass substrate by spin coating, with a spin coating speed of 4000 rpm and a spin coating time of 30 s.

6. The method for preparing a thiophene-containing perovskite solar cell according to claim 4, characterized in that: The two-dimensional ammonium salt compound includes 2-thienylethylamine and / or 3-(2-thienyl)-1-propylamine.

7. The method for preparing a thiophene-containing perovskite solar cell according to claim 4, characterized in that: The two-dimensional ammonium salt compound has 1-20 carbon atoms.

8. The method for preparing a thiophene-containing perovskite solar cell according to claim 1, characterized in that: The step of coating the ammonium salt compound solution on the perovskite film further comprises: coating the ammonium salt compound solution on the perovskite film by spin coating or dip coating; Coating an ammonium salt compound solution on the perovskite film to form a passivation layer further comprises: spin coating the ammonium salt compound solution on the annealed perovskite film at a spin coating speed of 3000 rpm for 20 seconds, and forming the passivation layer after drying.

9. The method for preparing a thiophene-containing perovskite solar cell according to claim 1, characterized in that: The step of preparing an electron transport layer on the passivation layer and preparing a back electrode on the electron transport layer further comprises: The PCBM electron transport layer and Ag electrode were deposited on the passivated perovskite film by vacuum evaporation to prepare the solar cell, and the photoelectric performance was tested.

10. A perovskite solar cell, prepared by the method for preparing a thiophene-containing perovskite solar cell according to any one of claims 1 to 9, characterized in that: include: The conductive substrate, the hole transport layer, the perovskite film, the passivation layer, the electron transport layer and the back electrode are arranged in sequence from bottom to top.

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