A kind of translucent perovskite solar cell containing sulfide functional group and its preparation method

Abstract

The present application relates to the field of perovskite solar cells, and particularly relates to a kind of semi-transparent perovskite solar cell containing sulfide functional group and preparation method thereof.The preparation method of the semi-transparent perovskite solar cell includes: sequentially assembling hole transport layer, perovskite functional layer, modification layer, electron transport layer on the surface of conductive glass substrate;The assembly of the perovskite functional layer: perovskite precursor solution is coated on the surface of hole transport layer, anti-solvent is added dropwise in the coating of perovskite precursor solution, and first annealing treatment is carried out;The perovskite precursor solution also includes 3-methylthio-1-propylamine hydroiodide.This application adds passivator 3-methylthio-1-propylamine hydroiodide to perovskite precursor.The bulk phase passivation method can sufficiently passivate perovskite bulk phase defects, reduce the non-radiative recombination loss on the surface of perovskite, and the efficiency and stability of perovskite solar cell are obviously improved, and energy conversion efficiency is improved.

Description

Technical Field

[0001] This invention relates to the field of perovskite solar cells, and more particularly to a semi-transparent perovskite solar cell containing sulfide functional groups and its preparation method. Background Technology

[0002] Perovskite solar cells (PSCs) have become a key candidate for the commercialization of next-generation photovoltaic technology due to their superior photoelectric conversion efficiency and low manufacturing cost. Particularly in the fields of building-integrated photovoltaics (BIPV) and tandem solar cells, semi-transparent perovskite solar cells (ST-PSCs) have shown great application potential.

[0003] However, in the solution-based preparation of perovskite thin films, the extremely rapid and difficult-to-control crystallization kinetics often lead to a large number of point defects (such as lead vacancies and iodine vacancies) and uncoordinated Pb within the film and at grain boundaries. 2+ For semi-transparent devices, in order to obtain a high average visible light transmittance (AVT), it is usually necessary to reduce the thickness of the light-absorbing layer or adjust the composition, which further amplifies the impact of defect state density on device performance.

[0004] These defect centers present in the bulk can induce severe nonradiative recombination, leading not only to the loss of photogenerated carriers and a decrease in open-circuit voltage (Voc), but also becoming channels for water and oxygen intrusion and ion migration, seriously threatening the long-term operational stability of the device. Furthermore, in semi-transparent devices, inhomogeneous crystallization can also increase film haze, affecting visual effects and light transmission uniformity.

[0005] While traditional interface modification strategies can improve surface defects, they struggle to eliminate defects within the perovskite layer (bulk phase). Therefore, developing a novel functionalized additive that can effectively regulate crystallization kinetics, achieve deep passivation of the bulk phase, and balance high efficiency with high transmittance is a key challenge for improving the performance of semi-transparent perovskite solar cells. Summary of the Invention

[0006] This invention provides a semi-transparent perovskite solar cell containing sulfide functional groups and its preparation method, thereby improving the overall performance of the perovskite solar cell by optimizing the perovskite light-absorbing layer.

[0007] To solve the above-mentioned technical problems, the present invention provides the following technical solution: This invention provides a method for preparing a semi-transparent perovskite solar cell containing sulfide functional groups, comprising the following steps: Assemble a hole transport layer on the surface of a conductive glass substrate; Assemble a perovskite functional layer on the surface of the hole transport layer; A modification layer is assembled on the surface of the perovskite functional layer; An electron transport layer is assembled on the surface of the modified layer; The assembly of the perovskite functional layer includes: The perovskite precursor solution was coated onto the surface of the hole transport layer, an antisolvent was added, and then a first annealing treatment was performed. The perovskite precursor solution also includes 3-methylthio-1-propylamine hydroiodate.

[0008] In some specific embodiments, the assembly of the hole transport layer includes: A hole transport material solution is applied to the surface of the conductive glass substrate, followed by a second annealing treatment.

[0009] In some specific embodiments, the concentration of hole transport material in the hole transport material solution is 1~1.5 mg / mL.

[0010] In some specific embodiments, the hole transport material in the hole transport material solution includes MeO-4PACz.

[0011] In some specific embodiments, the solvent in the hole transport material solution includes an ethanol solution.

[0012] In some specific embodiments, the temperature of the second annealing treatment is 100~120℃, and the time of the second annealing treatment is 10~20min.

[0013] In some specific embodiments, the concentration of the perovskite precursor in the perovskite precursor solution is 0.6~0.8M.

[0014] In some specific embodiments, the concentration of 3-methylthio-1-propylamine hydroiodate in the perovskite precursor solution is 0.4~0.5 mg / mL.

[0015] In some specific embodiments, the perovskite precursor solution contains FA as the perovskite precursor. 0.85 MA 0.1 Cs 0.05 Pb(I 0.77 Br 0.23 3.

[0016] In some specific embodiments, the solvent in the perovskite precursor solution includes N,N-dimethylformamide and / or dimethyl sulfoxide.

[0017] In some specific embodiments, the antisolvent includes chlorobenzene antisolvent.

[0018] In some specific embodiments, the temperature of the first annealing treatment is 100~120℃, and the time of the first annealing treatment is 30~40min.

[0019] In some specific embodiments, the assembly of the modification layer includes: The modification material solution is applied to the surface of the perovskite functional layer and then subjected to a third annealing treatment.

[0020] In some specific embodiments, the modifying material in the modifying material solution includes phenylethylamine iodide.

[0021] In some specific embodiments, the concentration of the modifying material in the modifying material solution is 0.2~0.6 mg / mL.

[0022] In some specific embodiments, the solvent in the modified material solution includes N,N-dimethylformamide and / or dimethyl sulfoxide.

[0023] In some specific embodiments, the temperature of the third annealing treatment is 100~120℃, and the time of the third annealing treatment is 5~10min.

[0024] In some specific embodiments, the assembly of the electron transport layer includes: Electron transport layer material C is sequentially vacuum-deposited onto the modification layer material. 60 SnO2 was deposited by ALD atomic layer deposition, followed by ITO deposition by magnetron sputtering.

[0025] In some specific embodiments, the C 60 The thickness is 18nm.

[0026] In some specific embodiments, the thickness of the SnO2 is 18 nm.

[0027] In some specific embodiments, the thickness of the ITO is 200 nm.

[0028] In some specific embodiments, the conductive glass substrate further includes, before use: The etched ITO conductive glass is subjected to ultrasonic treatment in deionized water, ethanol, and isopropanol in sequence, then dried with nitrogen gas, and finally treated with ultraviolet ozone.

[0029] A second aspect of the present invention also provides a semi-transparent perovskite solar cell containing sulfide functional groups prepared by the above-mentioned method for preparing a semi-transparent perovskite solar cell containing sulfide functional groups.

[0030] Compared with the prior art, the present invention has the following beneficial effects: This invention utilizes a passivating agent, 3-methylthio-1-propylamine hydroiodate, added to the perovskite precursor. This bulk passivation method effectively passivates bulk defects in the perovskite, reducing non-radiative recombination losses on the perovskite surface. Perovskite solar cells prepared based on this method show significantly improved efficiency and stability, with the power conversion efficiency increasing from 16.58% to 18.71%. Attached Figure Description

[0031] The above and other objects, features, and advantages of the invention will be apparent from the following description of preferred embodiments illustrating the gist of the invention and its use, and the accompanying drawings, in which: Figure 1 The images shown are SEM images of perovskite thin films from Example 1 and Comparative Example 1; where a is Comparative Example 1 and b is Example 1.

[0032] Figure 2 The images show the X-ray diffraction (XRD) patterns of the perovskite thin films of Example 1 and Comparative Example 1; where a is Comparative Example 1 and b is Example 1.

[0033] Figure 3 Photoluminescence (PL) images of perovskite thin films on ITO substrates, in Example 1 and Comparative Example 1.

[0034] Figure 4 The roughness (AFM) diagrams are for the perovskite films of Example 1 and Comparative Example 1.

[0035] Figure 5 This is a schematic diagram illustrating the battery performance characterization of the perovskite thin films of Example 1 and Comparative Example 1. Detailed Implementation

[0036] The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and embodiments. The embodiments of this application are only examples, and all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0037] Example 1

[0038] (1) Prepare various precursor solutions as follows: Hole transport material solution: MeO-4PACz was dissolved in ethanol at a concentration of 1 mg / mL and stirred at room temperature for 5 hours; Modification material solution: Phenethylamine iodide (PEAI) was dissolved at a concentration of 0.3 mg / mL in a mixed solution of N,N-dimethylformamide and dimethyl sulfoxide (v / v=1:1) to obtain a phenylethylamine iodide solution; Perovskite precursor solution: A mixture of 471.1 mg lead iodide, 192.6 mg formamidine iodoformide, 23.5 mg methyl bromide, 18.2 mg cesium iodide, 13.8 mg chloromethylamine, and 149.5 mg lead bromide was dissolved in 1600 μL of N,N-dimethylformamide (DMF) and 400 μL of dimethyl sulfoxide (DMSO). The solution was then stirred for 12 h at room temperature in a nitrogen-filled glove box. The solution was then added to a 0.6 M FA solution. 0.85 MA 0.1 Cs 0.05 Pb(I 0.77 Br 0.23 )3 Perovskite precursor solution, 0.4 mg of 3-methylthio-1-propylamine hydroiodate (3MTPAI) was dissolved in FA 0.85 MA 0.1 Cs 0.05 Pb(I 0.77 Br 0.23 In the perovskite precursor solution, the concentration of 3-methylthio-1-propylamine hydroiodate was 0.4 mg / mL. (2) The etched ITO conductive glass was ultrasonically treated in deionized water, ethanol and isopropanol for 20 minutes each, and then dried with nitrogen to obtain a clean ITO substrate.

[0039] (3) Clean ITO substrates were treated with ultraviolet ozone for 20 minutes; (4) In a nitrogen glove box, take 100 μL of MeO-4PACz solution and drop it onto the ITO substrate. Spin coat at 4000 rpm for 30 s and anneal at 100 °C for 10 min.

[0040] (5) Perovskite thin films were prepared on ITO substrates with deposited hole transport materials using a one-step spin-coating technique. 100 μL of perovskite precursor solution was dropped onto the substrate, and the film was spin-coated at 1000 rpm for 10 s, then at 5000 rpm for 30 s. In the last 10 s, 150 μL of chlorobenzene antisolvent was added, and the film was annealed at 100 °C for 30 min.

[0041] (6) Spin-coat the surface modification material onto the perovskite film. Take 70 μL of phenylethylamine iodide (PEAI) solution and quickly drop it onto the surface of the perovskite film at a speed of 4000 rpm. Spin-coat for 30 s and anneal at 100 °C for 5 min.

[0042] (7) Electron transport layer material C60 18nm was vacuum evaporated onto the modification layer material, ALD atomic layer 18nm SnO2 was deposited, and then 200nm ITO was deposited by magnetron sputtering.

[0043] Comparative Example 1 The difference from Example 1 is that 3-methylthio-1-propylamine hydroiodate was not added; otherwise, it is the same as Example 1.

[0044] This invention systematically optimized the concentration of the surface modification material, determining 0.4 mg / mL 3-methylthio-1-propylamine hydroiodate (3MTPAI) as the optimal condition. The surface morphology of the perovskite film was characterized using scanning electron microscopy. Figure 1 As shown, the unmodified pristine perovskite film (labeled Control) exhibits uneven grain size distribution and numerous grain boundaries, resulting in poor compactness. After modification with 3-methylthio-1-propylamine hydroiodate (3MTPAI), the grain size distribution of the film becomes more uniform, and its compactness is significantly improved. Figure 2 As shown, the roughness of the film was effectively reduced after modification with 3-methylthio-1-propylamine hydroiodide (3MTPAI). These results indicate that modification with 3-methylthio-1-propylamine hydroiodide (3MTPAI) can effectively improve the morphology of perovskite films. This may be because 3-methylthio-1-propylamine hydroiodide (3MTPAI) molecules fill the grain boundary interstices, thereby synergistically improving grain uniformity and film density.

[0045] To investigate the influence of surface modification materials on the perovskite crystal structure, this paper further conducted X-ray diffraction characterization analysis, and the results are as follows: Figure 3 As shown, Figure 3 In this text, Target represents Example 1, and Control represents Comparative Example 1. Figure 3 It can be seen that the characteristic diffraction peak positions of all films are basically consistent, indicating that the surface modification did not change the main crystal structure of the perovskite, nor did it introduce new crystal phases. Notably, the diffraction peak intensities of the modified films are generally enhanced, indicating an improvement in crystallinity. This may be because the modifier has a passivating effect on grain boundary defects, reducing the disorder within the crystal and making the lattice arrangement more regular, thereby enhancing the diffraction signal.

[0046] Regarding carrier dynamics characterization: To investigate the carrier dynamics behavior of perovskite thin films, steady-state photoluminescence (PL) spectroscopy was performed. For example... Figure 4 As shown, Figure 4 In this text, Target represents Example 1, and Control represents Comparative Example 1. Figure 4 It can be seen that all samples exhibit a emission peak at 760 nm, but the intensity of the PL peak in the latter is significantly enhanced. This indicates that the introduction of 3-methylthio-1-propylamine hydroiodate (3MTPAI) passivates deep-level defects and suppresses nonradiative recombination.

[0047] Battery performance characterization such as Figure 5(Target represents Example 1, Control represents Comparative Example 1) and as shown in Table 1, analysis of the performance data of perovskite solar cells with and without 3-methylthio-1-propylamine hydroiodate (3MTPAI) modification shows that bulk passivation can significantly improve cell performance. The PCE of the Control device is shown to be 16.58%, VOC to be 1.13 V, and JSC to be 18.83 mA / cm². 2 The FF was 77.78%. After modification with 3-methylthio-1-propylamine hydroiodate (3MTPAI), the PCE of the device was significantly improved to 18.71%, the VOC was 1.18 V, and the JSC was 19.25 mA / cm². 2 The PCE was 18.71%. AVT is the average transmittance of visible light. The AVT of the control device was 28.12%, and that of the target device was 28.15%, proving that the modification did not change the device transmittance. LUE is a comprehensive indicator of performance and transmittance, and LUE = PCE * AVT. The LUE of the control device was 4.66%, and that of the target device was 5.27%. The significant improvement in VOC and JSC is due to two factors: firstly, the 3-methylthio-1-propylamine hydroiodate (3MTPAI) modification effectively suppressed nonradiative recombination of carriers at the interface; secondly, the 3-methylthio-1-propylamine hydroiodate (3MTPAI) modification improved the morphology of the perovskite film, optimized the carrier transport path, and improved the carrier transport efficiency at the interface. The synergistic effect of these two mechanisms effectively promoted the overall improvement of device performance.

[0048] Table 1

[0049] Although preferred embodiments of the invention have been shown and described, it is conceivable that those skilled in the art can devise various modifications to the invention within the spirit and scope of the appended claims.

Claims

1. A method for preparing a translucent perovskite solar cell containing sulfide functional groups, characterized in that, Includes the following steps: Assemble a hole transport layer on the surface of a conductive glass substrate; Assemble a perovskite functional layer on the surface of the hole transport layer; A modification layer is assembled on the surface of the perovskite functional layer; An electron transport layer is assembled on the surface of the modified layer; The assembly of the perovskite functional layer includes: The perovskite precursor solution was coated onto the surface of the hole transport layer, an antisolvent was added, and then a first annealing treatment was performed. The perovskite precursor solution also includes 3-methylthio-1-propylamine hydroiodate.

2. The method for preparing a translucent perovskite solar cell containing sulfide functional groups according to claim 1, characterized in that, The assembly of the hole transport layer includes: A hole transport material solution is applied to the surface of the conductive glass substrate, followed by a second annealing treatment.

3. The method for preparing a translucent perovskite solar cell containing sulfide functional groups according to claim 2, characterized in that, The concentration of hole transport material in the hole transport material solution is 1~1.5 mg / mL; The hole transport material in the hole transport material solution includes MeO-4PACz; The solvent in the hole transport material solution includes ethanol; The temperature of the second annealing treatment is 100~120℃, and the time of the second annealing treatment is 10~20min.

4. The method for preparing a translucent perovskite solar cell containing sulfide functional groups according to claim 1, characterized in that, The concentration of the perovskite precursor in the perovskite precursor solution is 0.6~0.8M; The concentration of 3-methylthio-1-propylamine hydroiodate in the perovskite precursor solution is 0.4~0.5 mg / mL; The perovskite precursor solution contains FA as the perovskite precursor. 0.85 MA 0.1 Cs 0.05 Pb(I 0.77 Br 0.23 )3; The solvent in the perovskite precursor solution includes N,N-dimethylformamide and dimethyl sulfoxide; The antisolvent includes chlorobenzene antisolvent.

5. The method for preparing a translucent perovskite solar cell containing sulfide functional groups according to claim 1, characterized in that, The temperature of the first annealing treatment is 100~120℃, and the time of the first annealing treatment is 30~40min.

6. The method for preparing a translucent perovskite solar cell containing sulfide functional groups according to claim 1, characterized in that, The assembly of the modification layer includes: The modification material solution is applied to the surface of the perovskite functional layer and then subjected to a third annealing treatment.

7. The method for preparing a translucent perovskite solar cell containing sulfide functional groups according to claim 6, characterized in that, The modifying material in the modified material solution includes phenylethylamine iodide; The concentration of the modifying material in the modified material solution is 0.2-0.6 mg / mL; The solvent in the modified material solution includes N,N-dimethylformamide and / or dimethyl sulfoxide; The temperature of the third annealing treatment is 100~120℃, and the time of the third annealing treatment is 5~10min.

8. The method for preparing a translucent perovskite solar cell containing sulfide functional groups according to claim 1, characterized in that, The assembly of the electron transport layer includes: Electron transport layer material C is sequentially vacuum-deposited onto the modification layer material. 60 SnO2 was deposited by ALD atomic layer deposition, followed by ITO deposition by magnetron sputtering. The C 60 The thickness is 18nm; The thickness of the SnO2 is 18 nm; The thickness of the ITO is 200 nm.

9. The method for preparing a translucent perovskite solar cell containing sulfide functional groups according to claim 1, characterized in that, Before use, the conductive glass substrate also includes: The etched ITO conductive glass is subjected to ultrasonic treatment in deionized water, ethanol, and isopropanol in sequence, then dried with nitrogen gas, and finally treated with ultraviolet ozone.

10. A semi-transparent perovskite solar cell containing sulfide functional groups, prepared by the method of any one of claims 1 to 9.

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