Preparation method and application of thiophene [2, 3-d] pyrimidine-4 (3h) ketone modified organic-inorganic hybrid perovskite MAPbI3

Abstract

The application discloses a preparation method and application of a thieno[2,3-D]pyrimidin-4(3H)one modified organic-inorganic hybrid perovskite MAPbI3. The thieno[2,3-D]pyrimidin-4(3H)one is used as an additive to modify the MAPbI3. The thieno[2,3-D]pyrimidin-4(3H)one can improve the quality of the MAPbI3 powder and thin film due to a unique structure, increase the grain size, enhance the light absorption, enhance the hydrophobicity and enhance the stability.

Description

Technical Field

[0001] This invention belongs to the field of solar cells (light-absorbing layer of perovskite solar cells), specifically relating to a method for preparing organic-inorganic hybrid perovskite MAPbI3 modified with thiophene[2,3-D]pyrimidine-4(3H)one and its application. Background Technology

[0002] Environment and energy have become two important issues affecting the sustainable development of human society. Therefore, as the most important environmentally friendly renewable energy source, solar energy is receiving increasing attention from society. The rational and efficient use of solar energy is the key to solving the above problems.

[0003] Perovskite solar cells (PSCs) are gradually becoming strong competitors for third-generation high-efficiency solar cells due to their low cost, low power consumption, simple process, and high theoretical efficiency. Among them, organic-inorganic hybrid perovskite solar cells are favored for their high light absorption capacity and adjustable bandgap capability, but their poor stability has greatly hindered their commercialization. Therefore, obtaining stable organic-inorganic perovskite materials is of great significance for the development of perovskite solar cells. MAPbI3 has been proven to be a mature light-absorbing material with the advantages of simple process and mature technology. Thiophene[2,3-D]pyrimidin-4(3H)one's unique structure can assist in the crystallization process of perovskite materials, obtaining larger grains, and can passivate defects at grain boundaries. Its hydrophobicity can also prevent moisture from eroding and damaging the material, enhancing its stability. Summary of the Invention

[0004] This invention aims to provide a method for preparing thiophene[2,3-D]pyrimidine-4(3H)one-modified organic-inorganic hybrid perovskite MAPbI3 and its applications. In this invention, thiophene[2,3-D]pyrimidine-4(3H)one, due to its unique structure, can improve the quality of MAPbI3 powder and thin films, increasing its grain size, enhancing its light absorption, improving its hydrophobicity, and enhancing its stability.

[0005] The present invention discloses a method for preparing thiophene[2,3-D]pyrimidin-4(3H)one-modified organic-inorganic hybrid perovskite MAPbI3, using thiophene[2,3-D]pyrimidin-4(3H)one as an additive to improve the stability and light absorption capacity of MAPbI3, comprising the following steps:

[0006] 1a: Weigh 461 mg of lead iodide (PbI2) and 159 mg of methyl ammonium iodide (MAI), mix them, add them to 1 mL of ethylene glycol methyl ether (2-Me), and add 1-3 mg / mL of thiophene[2,3-D]pyrimidine-4(3H) one. Shake vigorously for 10 min until completely dissolved to obtain a clear and transparent yellow MAPbI3 solution.

[0007] 1b: The solution obtained in step 1a was filtered through a 0.22 μm filter and divided into two equal portions, which were then transferred to centrifuge tubes. 4.5 mL of ethyl acetate was added, and the mixture was vigorously shaken to ensure complete precipitation. The mixture was centrifuged at 12000 rpm for 2 min to obtain a black precipitate. Ethyl acetate was added again, and the mixture was vigorously shaken to completely disperse the precipitate. The mixture was centrifuged again to obtain another black precipitate. This process was repeated three times. The precipitate was then dried in a vacuum drying oven at 60 °C for 8 h to obtain MAPbI3 powder modified with thiophene[2,3-D]pyrimidin-4(3H)one.

[0008] The above method prepares MAPbI3 modified with thiophene[2,3-D]pyrimidin-4(3H)one in powder form.

[0009] The present invention can also directly prepare MAPbI3 modified with thiophene[2,3-D]pyrimidin-4(3H)one in thin film form by the following method:

[0010] 2a: 1290.8 mg PbI2, 445.1 mg MAI, 1.6 mL N,N-dimethylformamide (DMF), 0.4 mL dimethyl sulfoxide (DMSO), and 1-3 mg / mL thiophene[2,3-D]pyrimidine-4(3H)one were added to a three-necked flask and heated to 60 °C under a N2 atmosphere with stirring for 30 min. After natural cooling, the mixture was filtered through a 0.22 μm filter to obtain the MAPbI3 perovskite precursor solution.

[0011] 2b: Substrate cleaning. First, ultrasonically clean the glass substrate or FTO substrate with deionized water, acetone, and ethanol for 15 minutes each. After drying, place it in a UV ozone cleaner for 15 minutes.

[0012] 2c: Place the glass substrate obtained in step 2b on a spin coater, and add 30 μL of the MAPbI3 perovskite precursor solution obtained in step 2a. Start the spin coater when the solution has covered the substrate. Spin coat at 1500 rpm for 8 s, then at 4000 rpm for 20 s, and add 500 μL of ethyl acetate as an antisolvent at the 15th second of the total time. After spin coating, immediately place the substrate on a hot plate at 110°C for annealing for 10 min to obtain an organic-inorganic hybrid perovskite MAPbI3 film modified with thiophene[2,3-D]pyrimidine-4(3H)one.

[0013] The present invention relates to the application of thiophene[2,3-D]pyrimidine-4(3H)one-modified organic-inorganic hybrid perovskite MAPbI3 in the preparation of perovskite solar cells.

[0014] Specifically, the light-absorbing layer of a solar cell is prepared using organic-inorganic hybrid perovskite MAPbI3 modified with the thiophene[2,3-D]pyrimidine-4(3H)one.

[0015] For example, the MAPbI3 powder modified with thiophene[2,3-D]pyrimidine-4(3H)one can be used as a raw material for preparing a perovskite precursor solution; and the MAPbI3 film modified with thiophene[2,3-D]pyrimidine-4(3H)one can be used as a light-absorbing layer for a perovskite solar cell.

[0016] The grain size and stability of MAPbI3 powder modified with thiophene[2,3-D]pyrimidine-4(3H)one were improved; the grain size and stability of MAPbI3 film modified with thiophene[2,3-D]pyrimidine-4(3H)one were also improved.

[0017] The MAPbI3 powder prepared by adding thiophene[2,3-D]pyrimidine-4(3H)one at a concentration of 2 mg / mL showed an increase in grain size from 400 nm to 480 nm. After being placed in air for 7 days, the powder diffraction pattern showed almost no change, while the unmodified powder showed obvious PbI2 diffraction peaks. The MAPbI3 film prepared by adding thiophene[2,3-D]pyrimidine-4(3H)one at a concentration of 2 mg / mL showed an increase in grain size from 228 nm to 331 nm, and the water contact angle changed from 50.7° to 55.5°. After aging in air for one month, the diffraction peaks showed very little change, while the unmodified film showed obvious PbI2 diffraction peaks.

[0018] In this invention, the unique structure of thiophene[2,3-D]pyrimidine-4(3H)one can assist in the crystallization process of perovskite materials, resulting in larger grains. It can also passivate defects at grain boundaries, improve the absorbance of the material, and its hydrophobicity can also prevent moisture from eroding and damaging the material, thus enhancing the stability of the material. Attached Figure Description

[0019] Figure 1 Scanning electron microscope (SEM) images of the thiophene[2,3-D]pyrimidine-4(3H)one-modified organic-inorganic hybrid perovskite MAPbI3 powder of the present invention. (a) is an image of the powder without additive modification, and (b) is an image of the powder after additive modification.

[0020] Figure 2 The X-ray diffraction pattern of the organic-inorganic hybrid perovskite MAPbI3 powder modified with thiophene[2,3-D]pyrimidine-4(3H)one of this invention is shown in the aging test.

[0021] Figure 3 Scanning electron microscope (SEM) images of the thiophene[2,3-D]pyrimidine-4(3H)one-modified organic-inorganic hybrid perovskite MAPbI3 thin films of the present invention. (a) is an image of the unmodified film, and (b) is an image of the modified film.

[0022] Figure 4 The absorption spectrum of the organic-inorganic hybrid perovskite MAPbI3 thin film modified with thiophene[2,3-D]pyrimidine-4(3H)one of the present invention is shown in the 550-850 nm light absorption spectrum.

[0023] Figure 5 The X-ray photoelectron spectra of the organic-inorganic hybrid perovskite MAPbI3 thin films modified with thiophene[2,3-D]pyrimidine-4(3H)one according to the present invention are shown. (a) is a comparison of the I 3d energy level before and after modification, and (b) is a comparison of the Pb 4f energy level before and after modification.

[0024] Figure 6 The figures show the water contact angle measurements of the organic-inorganic hybrid perovskite MAPbI3 thin films modified with thiophene[2,3-D]pyrimidine-4(3H)one according to the present invention. (a) is the water contact angle measurement of the unmodified film, and (b) is the water contact angle measurement of the modified film.

[0025] Figure 7 X-ray diffraction (XRD) patterns of the organic-inorganic hybrid perovskite MAPbI3 thin films modified with thiophene[2,3-D]pyrimidine-4(3H)one according to the present invention were obtained during aging tests. (a) shows the XRD patterns of fresh films at different additive concentrations, and (b) shows the XRD patterns of the film in (a) after aging in ambient air for 30 days. Detailed Implementation

[0026] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0027] Example 1: Preparation and characterization of thiophene[2,3-D]pyrimidin-4(3H)one-modified organic-inorganic hybrid perovskite MAPbI3 powder

[0028] The preparation of thiophene[2,3-D]pyrimidine-4(3H)one-modified organic-inorganic hybrid perovskite MAPbI3 powder includes the following steps: First, 461 mg of lead iodide (PbI2) and 159 mg of methyl ammonium iodide (MAI) were weighed and mixed, then added to 1 mL of ethylene glycol methyl ether (2-Me), and 2 mg of thiophene[2,3-D]pyrimidine-4(3H)one was added. The mixture was vigorously shaken for 10 min until completely dissolved, yielding a clear and transparent yellow MAPbI3 solution. The solution was then filtered through a 0.22 μm filter and divided into two equal portions, transferred to centrifuge tubes. 4.5 mL of ethyl acetate was added, and the mixture was vigorously shaken to completely precipitate the precipitate. The mixture was centrifuged at 12000 rpm for 2 min to obtain a black precipitate. Ethyl acetate was added again, and the mixture was vigorously shaken to completely disperse the precipitate. The mixture was centrifuged again to obtain another black precipitate, and this process was repeated three times. Finally, the mixture was placed in a vacuum drying oven and dried at 60 °C for 8 h to obtain thiophene[2,3-D]pyrimidine-4(3H)one-modified MAPbI3 powder.

[0029] Figure 1 These are scanning electron microscope (SEM) images of the organic-inorganic hybrid perovskite MAPbI3 powder modified with thiophene[2,3-D]pyrimidine-4(3H)one according to this invention. (a) is an image of the powder without additive modification, and (b) is an image of the powder modified with additive. The comparison reveals that the powder modified with additive has a larger average grain size, increasing from approximately 400 nm to approximately 480 nm, and the grains are more regular and uniform. This indicates that thiophene[2,3-D]pyrimidine-4(3H)one promotes the crystallization of perovskite MAPbI3.

[0030] Figure 2 This is the X-ray diffraction pattern of the thiophene[2,3-D]pyrimidine-4(3H)one-modified organic-inorganic hybrid perovskite MAPbI3 powder after natural aging in air for 7 days. As can be seen from the figure, the unmodified MAPbI3 powder exhibits a distinct PbI2 diffraction peak at 12.7° after 7 days of natural aging; however, the modified MAPbI3 powder does not show this peak after 7 days of natural aging. This indicates that thiophene[2,3-D]pyrimidine-4(3H)one can enhance the stability of MAPbI3 powder.

[0031] Example 2: Preparation and characterization of thiophene[2,3-D]pyrimidin-4(3H)one-modified organic-inorganic hybrid perovskite MAPbI3 thin films

[0032] The preparation of thiophene[2,3-D]pyrimidin-4(3H)one-modified organic-inorganic hybrid perovskite MAPbI3 thin films includes the following steps: First, 1290.8 mg PbI2, 445.1 mg MAI, 1.6 mL N,N-dimethylformamide (DMF), 0.4 mL dimethyl sulfoxide (DMSO), and 4 mg thiophene[2,3-D]pyrimidin-4(3H)one are added to a three-necked flask and heated to 60 °C under a N2 atmosphere with stirring for 30 min. After natural cooling, the solution is filtered through a 0.22 μm filter to obtain the MAPbI3 perovskite precursor solution. Then, the substrate is cleaned by ultrasonically cleaning the glass substrate or FTO substrate with deionized water, acetone, and ethanol for 15 min each, drying it, and then cleaning it in a UV ozone cleaner for 15 min to obtain a clean substrate with good surface wettability. The cleaned substrate was placed on a spin coater, and 30 μL of MAPbI3 perovskite precursor solution was added dropwise. The spin coater was started when the solution covered the substrate. The spin coater was operated at 1500 rpm for 8 seconds, then at 4000 rpm for 20 seconds, with 500 μL of ethyl acetate added dropwise as an antisolvent at the 15th second of the total time. After spin coating, the substrate was immediately placed on a hot plate at 110°C for annealing for 10 minutes to obtain an organic-inorganic hybrid perovskite MAPbI3 film modified with thiophene[2,3-D]pyrimidine-4(3H)one.

[0033] Figure 3 These are scanning electron microscope (SEM) images of the organic-inorganic hybrid perovskite MAPbI3 thin films modified with thiophene[2,3-D]pyrimidine-4(3H)one according to this invention. Image (a) shows the unmodified film, and image (b) shows the modified film. The addition concentration was 2 mg / mL. As can be seen from the images, the grain size in the film significantly increased after modification, from 228 nm in the control group to 331 nm. This indicates that thiophene[2,3-D]pyrimidine-4(3H)one can effectively promote the crystallization of MAPbI3 films.

[0034] Figure 4 This is the light absorption spectrum of the organic-inorganic hybrid perovskite MAPbI3 thin film modified with thiophene[2,3-D]pyrimidin-4(3H)one in the 550-850 nm range. As can be seen from the figure, when the additive concentration is 3 mg / mL, the light absorption intensity of the MAPbI3 thin film in the visible light range is significantly improved.

[0035] Figure 5 This is the X-ray photoelectron spectrum of the organic-inorganic hybrid perovskite MAPbI3 thin film modified with thiophene[2,3-D]pyrimidin-4(3H)one according to the present invention. Figure (a) is a comparison of the I 3d energy level before and after modification, and Figure (b) is a comparison of the Pb 4f energy level before and after modification. It can be seen from Figure (a) that the Pb 4f... 5 / 2 and Pb 4f7 / 2 The characteristic peaks of the energy levels were located at 143.18 eV and 138.33 eV, respectively. After the addition of the additive, the characteristic peaks shifted to 143.14 eV and 138.27 eV, respectively. Meanwhile, in figure (b), I 3d... 3 / 2 and I3d 5 / 2 The characteristic peaks also shifted from 630.77 eV and 619.26 eV to 630.73 eV and 619.21 eV, respectively. This indicates that thiophene[2,3-D]pyrimidin-4(3H)one can react with Pb in the MAPbI3 film. 2+ and I - It has an effect and passesivates related defects.

[0036] Figure 6 These are water contact angle measurements of the organic-inorganic hybrid perovskite MAPbI3 thin film modified with thiophene[2,3-D]pyrimidine-4(3H)one according to the present invention. Figure (a) shows the water contact angle measurement of the unmodified film, and Figure (b) shows the water contact angle measurement of the modified film. As can be seen from the figures, after the addition of thiophene[2,3-D]pyrimidine-4(3H)one modification, the water contact angles on the left and right sides of the MAPbI3 film increased from 50.7° and 49.6° in Figure (a) to 55.5° and 53.7° in Figure (b), respectively, indicating that thiophene[2,3-D]pyrimidine-4(3H)one can enhance the water resistance of the MAPbI3 film.

[0037] Figure 7 This is an X-ray diffraction pattern of the organic-inorganic hybrid perovskite MAPbI3 thin film modified with thiophene[2,3-D]pyrimidine-4(3H)one according to the present invention, showing the aging test results. (a) shows the X-ray diffraction pattern of the fresh film at different additive concentrations, and (b) shows the X-ray diffraction pattern of the film in (a) after aging in ambient air for 30 days. As can be seen from the figure, after 30 days of aging in ambient air, the diffraction peaks of the MAPbI3 thin film modified with thiophene[2,3-D]pyrimidine-4(3H)one hardly changed, while the unmodified film showed a significant PbI2 diffraction peak at 12.7°, indicating that thiophene[2,3-D]pyrimidine-4(3H)one can effectively enhance the stability of the MAPbI3 thin film.

Claims

1. A method for preparing thiophene[2,3-D]pyrimidin-4(3H)one-modified organic-inorganic hybrid perovskite MAPbI3, characterized in that: Thiophene[2,3-D]pyrimidin-4(3H)one was used as an additive to improve the stability and light absorption capacity of MAPbI3.

2. The preparation method according to claim 1, characterized in that... Includes the following steps: 1a: Weigh 461 mg lead iodide and 159 mg ammonium methyl iodide, mix them, add them to 1 mL ethylene glycol methyl ether, add thiophene[2,3-D]pyrimidine-4(3H) one, shake until completely dissolved, and obtain a clear and transparent yellow MAPbI3 solution; 1b: The solution obtained in step 1a was filtered through a 0.22 μm filter and transferred to a centrifuge tube. Antisolvent was added to completely precipitate the solution. The solution was centrifuged to obtain a black precipitate. The antisolvent was added repeatedly to precipitate the solution and centrifuged multiple times. The solution was then dried under vacuum to obtain MAPbI3 powder material modified with thiophene[2,3-D]pyrimidine-4(3H)one.

3. The preparation method according to claim 2, characterized in that: The amount of thiophene[2,3-D]pyrimidine-4(3H)one added is 1-3 mg / mL.

4. The preparation method according to claim 2, characterized in that: The antisolvent is ethyl acetate.

5. The preparation method according to claim 1, characterized in that... Includes the following steps: 2a: 1290.8 mg lead iodide, 445.1 mg ammonium methyl iodide, 1.6 mL N,N-dimethylformamide, 0.4 mL dimethyl sulfoxide and thiophene[2,3-D]pyrimidine-4(3H)one were added to a three-necked flask, heated to 60 °C under N2 atmosphere and stirred for 30 min. After natural cooling, the mixture was filtered through a 0.22 μm filter to obtain the MAPbI3 perovskite precursor solution. 2b: Clean the glass substrate or FTO substrate with deionized water, acetone and ethanol for 15 minutes each, blow dry and then place it in a UV ozone cleaner for 15 minutes. 2c: Place the substrate material obtained in step 2b on a spin coater, add 30 μL of the MAPbI3 perovskite precursor solution obtained in step 2a, and start the spin coater when the solution covers the substrate. Spin coat at 1500 rpm for 8 s and 4000 rpm for 20 s, and add the antisolvent at the 15th second of the total time. After spin coating, anneal the substrate to obtain MAPbI3 thin film material modified with thiophene[2,3-D]pyrimidine-4(3H)one.

6. The preparation method according to claim 5, characterized in that: The amount of thiophene[2,3-D]pyrimidine-4(3H)one added is 1-3 mg / mL.

7. The preparation method according to claim 5, characterized in that: The antisolvent is ethyl acetate.

8. The preparation method according to claim 5, characterized in that: The annealing temperature was 110℃ and the annealing time was 10 minutes.

9. The application of thiophene[2,3-D]pyrimidin-4(3H)one-modified organic-inorganic hybrid perovskite MAPbI3 prepared by any one of the preparation methods in claims 1-8 in the preparation of perovskite solar cells.

10. The application according to claim 9, characterized in that: The light-absorbing layer of a solar cell was prepared using the thiophene[2,3-D]pyrimidine-4(3H)one-modified organic-inorganic hybrid perovskite MAPbI3.

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