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

Abstract

The invention discloses a preparation method of organic-inorganic hybrid perovskite MAPbI3 modified by thiophene [2, 3-D] pyrimidine-4 (3H) ketone and an application of the organic-inorganic hybrid perovskite MAPbI3 modified by thiophene [2, 3-D] pyrimidine-4 (3H) ketone. The thiophene [2, 3-D] pyrimidine-4 (3H) ketone is used as an additive to modify MAPbI3, and due to the unique structure of the thiophene [2, 3-D] pyrimidine-4 (3H) ketone, the mass of MAPbI3 powder and a thin film can be improved, the grain size of the MAPbI3 powder and the thin film can be increased, and the light absorbance, the hydrophobicity and the stability of the MAPbI3 powder and the thin film can be enhanced.

Description

Technical Field

[0001] The present invention belongs to the field of solar cells (perovskite solar cell light absorption layer), and specifically relates to an organic-inorganic hybrid perovskite MAPbI modified with thiophene [2,3-D] pyrimidin-4 (3H) ketone 3 Preparation method and application thereof. Background Art

[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, solar energy has received more and more attention from society. Rational and efficient use of solar energy is the key to solving the above problems.

[0003] Perovskite solar cells (PSCs) have gradually become a strong competitor for the third generation of 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 due to their efficient light absorption ability and adjustable band gap ability, 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. MAPbI 3 It has been proven to be a mature light-absorbing material with simple process and mature technology. The unique structure of thiophene [2,3-D] pyrimidine-4 (3H) ketone can assist in the crystallization of perovskite materials, obtain larger grains, and passivate defects at grain boundaries. Its hydrophobicity can also prevent moisture from eroding and damaging the material, enhancing the stability of the material. Summary of the invention

[0004] The present invention aims to provide an organic-inorganic hybrid perovskite MAPbI modified with thiophene[2,3-D]pyrimidin-4(3H)one 3 Preparation method and application thereof. In the present invention, thiophene [2,3-D] pyrimidin-4 (3H) ketone can improve MAPbI due to its unique structure. 3 The quality of powder and film increases its grain size, enhances light absorption, enhances its hydrophobicity, and enhances its stability.

[0005] Thiophene [2,3-D] pyrimidin-4 (3H) ketone modified organic-inorganic hybrid perovskite MAPbI of the present invention 3 Preparation method, using thiophene [2,3-D] pyrimidin-4 (3H) ketone as an additive to improve MAPbI 3 The stability and light absorption ability of the catalyst include the following steps:

[0006] 1a: Weigh 461 mg of lead iodide (PbI 2), 159 mg methylammonium iodide (MAI) were mixed and added to 1 mL ethylene glycol methyl ether (2-Me), and 1-3 mg / mL thiophene [2,3-D] pyrimidin-4 (3H) ketone was added, and the mixture was shaken vigorously for 10 min until it was completely dissolved to obtain a clear and bright yellow MAPbI 3 Solution.

[0007] 1b: Filter the solution obtained in step 1a with a 0.22um filter and transfer it into two equal parts into a centrifuge tube. Add 4.5mL of ethyl acetate and shake vigorously to completely precipitate it. Centrifuge at 12000rpm for 2min to obtain a black precipitate. Add ethyl acetate again and shake vigorously to completely disperse the precipitate. Centrifuge again to obtain a black precipitate. Repeat three times. Place in a vacuum drying oven and dry at 60℃ for 8h to obtain MAPbI modified with thiophene[2,3-D]pyrimidine-4(3H) ketone 3 powder.

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

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

[0010] 2a: Take 1290.8 mg PbI 2 , 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] pyrimidin-4 (3H) one were added into a three-necked flask and heated under N 2 Heat to 60°C and stir for 30 min under ambient temperature. After cooling naturally, filter using a 0.22 μm filter to obtain MAPbI 3 Perovskite precursor solution.

[0011] 2b: Cleaning of the substrate: First, the glass substrate or FTO substrate was ultrasonically cleaned with deionized water, acetone, and ethanol for 15 minutes each, and then placed in a UV ozone cleaning machine for 15 minutes after drying.

[0012] 2c: Place the glass substrate obtained in step 2b on a spin coater and drop 30uL of MAPbI obtained in step 2a. 3Perovskite precursor solution, when the solution covers the substrate, start the spin coater. 1500 rpm for 8s, 4000 rpm for 20s, and add 500uL ethyl acetate as antisolvent at the 15th second of the total time. After the spin coating, immediately place it on a hot plate at 110℃ for annealing for 10min to obtain the organic-inorganic hybrid perovskite MAPbI modified with thiophene [2,3-D] pyrimidine-4 (3H) ketone 3 film.

[0013] Thiophene [2,3-D] pyrimidin-4 (3H) ketone modified organic-inorganic hybrid perovskite MAPbI of the present invention 3 Application in the preparation of perovskite solar cells.

[0014] Specifically, the organic-inorganic hybrid perovskite MAPbI modified with the thiophene [2,3-D] pyrimidin-4 (3H) ketone 3 Prepare the solar cell light absorption layer.

[0015] For example, the thiophene [2,3-D] pyrimidin-4 (3H) ketone modified MAPbI 3 Powder as raw material for the preparation of perovskite precursor solution; MAPbI modified with thiophene[2,3-D]pyrimidin-4(3H)one 3 The film serves as the light-absorbing layer of perovskite solar cells.

[0016] Thiopheno[2,3-D]pyrimidin-4(3H)one-modified MAPbI 3 The crystal size and stability of the powder are improved; MAPbI modified with thiophene[2,3-D]pyrimidin-4(3H)one 3 The grain size of the film is improved and the stability is also improved.

[0017] MAPbI prepared with thiophene[2,3-D]pyrimidin-4(3H)one at a concentration of 2 mg / mL 3 The crystal size of the powder increased from 400 nm to 480 nm. After being placed in air for 7 days, the powder diffraction pattern showed almost no change, and the unmodified powder showed obvious PbI 2 Diffraction peak: MAPbI prepared with thiophene[2,3-D]pyrimidin-4(3H)one at a concentration of 2 mg / mL 3 The grain size of the film increased from 228 nm to 331 nm, and the water contact angle changed from 50.7° to 55.5°. The film aged in air for one month, and the diffraction peak changed little. The unmodified film showed obvious PbI 2 Diffraction peak.

[0018] In the present invention, the unique structure of thiophene [2,3-D] pyrimidine-4 (3H) ketone can assist crystallization during the crystallization process of perovskite materials to obtain larger grains, and can passivate defects at the grain boundaries to improve the absorbance of the material. Its hydrophobicity can also prevent moisture from corroding and damaging the material, thereby enhancing the stability of the material. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 The organic-inorganic hybrid perovskite MAPbI modified by thiophene [2,3-D] pyrimidin-4 (3H) ketone of the present invention 3 Scanning electron micrographs of powders. (a) is a picture of powders without additive modification, and (b) is a picture of powders with additive modification.

[0020] Figure 2 The organic-inorganic hybrid perovskite MAPbI modified by thiophene [2,3-D] pyrimidin-4 (3H) ketone of the present invention 3 X-ray diffraction patterns of powder aging tests.

[0021] Figure 3 The organic-inorganic hybrid perovskite MAPbI modified by thiophene [2,3-D] pyrimidin-4 (3H) ketone of the present invention 3 Scanning electron microscopy images of the films. (a) is the image of the unmodified film, and (b) is the image of the modified film.

[0022] Figure 4 The organic-inorganic hybrid perovskite MAPbI modified by thiophene [2,3-D] pyrimidin-4 (3H) ketone of the present invention 3 The optical absorption diagram of the film at 550-850nm.

[0023] Figure 5 The organic-inorganic hybrid perovskite MAPbI modified by thiophene [2,3-D] pyrimidin-4 (3H) ketone of the present invention 3 X-ray photoelectron spectra of the film. (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 organic-inorganic hybrid perovskite MAPbI modified by thiophene [2,3-D] pyrimidin-4 (3H) ketone of the present invention 3 Water contact angle measurement diagram of the film. (a) is the water contact angle measurement diagram of the unmodified film, and (b) is the water contact angle measurement diagram of the modified film.

[0025] Figure 7 The organic-inorganic hybrid perovskite MAPbI modified by thiophene [2,3-D] pyrimidin-4 (3H) ketone of the present invention 3X-ray diffraction patterns of film aging test. (a) is the X-ray diffraction pattern of fresh film at different additive concentrations, and (b) is the X-ray diffraction pattern of the film in (a) after aging in ambient air for 30 days. DETAILED DESCRIPTION

[0026] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0027] Example 1: Thiophene [2,3-D] pyrimidin-4 (3H) one modified organic-inorganic hybrid perovskite MAPbI 3 Powder preparation and characterization

[0028] Thiopheno[2,3-D]pyrimidin-4(3H)one-modified organic-inorganic hybrid perovskite MAPbI 3 The preparation of the powder includes the following steps: first weigh 461 mg of lead iodide (PbI 2 ), 159 mg of methylammonium iodide (MAI) were mixed and added to 1 mL of ethylene glycol methyl ether (2-Me), and 2 mg of thiophene [2,3-D] pyrimidin-4 (3H) ketone was added. Vigorously shake for 10 minutes until completely dissolved to obtain a clear and bright yellow MAPbI 3 Solution. Then the solution was filtered with a 0.22um filter and divided into two equal parts and transferred to a centrifuge tube. 4.5mL of ethyl acetate was added and shaken vigorously to completely precipitate it. Centrifuge at 12000rpm for 2min to obtain a black precipitate. Ethyl acetate was added again and shaken vigorously to completely disperse the precipitate. Centrifuge again to obtain a black precipitate. Repeat three times. Finally, place it in a vacuum drying oven and dry it at 60℃ for 8h to obtain MAPbI modified with thiophene [2,3-D] pyrimidine-4 (3H) ketone. 3 powder.

[0029] Figure 1 The present invention is a thiophene [2,3-D] pyrimidin-4 (3H) ketone modified organic-inorganic hybrid perovskite MAPbI 3 Scanning electron microscope images of powders. (a) is a picture of powders without additive modification, and (b) is a picture of powders modified with additives. From the comparison between the two, it can be found that the average grain size of the powder modified with additives is larger, increasing from about 400nm to about 480nm, and the grains are more regular and neat. This shows that thiophene [2,3-D] pyrimidine-4 (3H) ketone has a great influence on the perovskite MAPbI 3 It plays a promoting role in crystallization.

[0030] Figure 2 The organic-inorganic hybrid perovskite MAPbI modified by thiophene [2,3-D] pyrimidin-4 (3H) ketone of the present invention 3 X-ray diffraction pattern of the powder after natural aging in air for 7 days. It can be seen from the figure that the unmodified MAPbI 3 After 7 days of natural aging, the powder showed obvious PbI 2 The diffraction peaks of the modified MAPbI 3 The powder did not show this peak after 7 days of natural aging. This indicates that thiophene[2,3-D]pyrimidin-4(3H)one can enhance the 3 Powder stability.

[0031] Example 2: Thiophene [2,3-D] pyrimidin-4 (3H) one modified organic-inorganic hybrid perovskite MAPbI 3 Thin film preparation and characterization

[0032] Thiopheno[2,3-D]pyrimidin-4(3H)one-modified organic-inorganic hybrid perovskite MAPbI 3 The preparation of the film includes the following steps: first, 1290.8 mg PbI 2 , 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 were added into a three-necked flask and heated under N 2 Heat to 60°C and stir for 30 min under ambient temperature. After cooling naturally, filter using a 0.22 μm filter to obtain MAPbI 3 Perovskite precursor solution. Then clean the substrate. Use deionized water, acetone, and ethanol to ultrasonically clean the glass substrate or FTO substrate for 15 minutes each. After drying, place it in a UV ozone light cleaner for 15 minutes to obtain a clean substrate with good surface wettability. Place the cleaned substrate on a spin coater and drop 30uL MAPbI 3 Perovskite precursor solution, when the solution covers the substrate, start the spin coater. 1500 rpm for 8s, 4000 rpm for 20s, and add 500uL ethyl acetate as antisolvent at the 15th second of the total time. After the spin coating, immediately place it on a hot plate at 110℃ for annealing for 10min to obtain the organic-inorganic hybrid perovskite MAPbI modified with thiophene [2,3-D] pyrimidine-4 (3H) ketone 3 film.

[0033] Figure 3 The present invention is a thiophene [2,3-D] pyrimidin-4 (3H) ketone modified organic-inorganic hybrid perovskite MAPbI3 Scanning electron microscopy images of the film, (a) is the unmodified film, (b) is the modified film, the added concentration is 2 mg / mL. It can be seen from the figure that after modification, the grain size in the film is significantly increased, from 228 nm in the control group to 331 nm. This shows that thiophene [2,3-D] pyrimidine-4 (3H) ketone can effectively promote MAPbI 3 Crystallization of thin films.

[0034] Figure 4 The present invention is a thiophene [2,3-D] pyrimidin-4 (3H) ketone modified organic-inorganic hybrid perovskite MAPbI 3 The film absorbs light at 550-850nm. It can be seen from the figure that when the additive concentration is 3mg / mL, MAPbI 3 The light absorption intensity of the film in the visible light range is significantly improved.

[0035] Figure 5 The present invention is a thiophene [2,3-D] pyrimidin-4 (3H) ketone modified organic-inorganic hybrid perovskite MAPbI 3 X-ray photoelectron spectrum of the film. (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. As can be seen from (a), Pb 4f 5 / 2 and Pb 4f 7 / 2 The characteristic peaks of the energy levels are located at 143.18 eV and 138.33 eV respectively. After adding the additives, the characteristic peaks shift to 143.14 eV and 138.27 eV respectively. 3 / 2 and I3d 5 / 2 The characteristic peaks of MAPbI 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 MAPbI 3 Pb in thin films 2+ and I - Take effect and passivate related defects.

[0036] Figure 6 The present invention is a thiophene [2,3-D] pyrimidin-4 (3H) ketone modified organic-inorganic hybrid perovskite MAPbI 3 Water contact angle measurement diagram of the film. (a) is the water contact angle measurement diagram of the unmodified film, and (b) is the water contact angle measurement diagram of the modified film. It can be seen from the figure that after adding thiophene [2,3-D] pyrimidine-4 (3H) ketone modification, MAPbI 3The water contact angles on the left and right sides of the film increased from 50.7° and 49.6° in (a) to 55.5° and 53.7° in (b), respectively, indicating that thiophene[2,3-D]pyrimidin-4(3H)one can enhance the MAPbI 3 The film's resistance to moisture.

[0037] Figure 7 The present invention is a thiophene [2,3-D] pyrimidin-4 (3H) ketone modified organic-inorganic hybrid perovskite MAPbI 3 X-ray diffraction patterns of film aging test. (a) is the X-ray diffraction pattern of fresh film at different additive concentrations, and (b) is the X-ray diffraction pattern of the film in (a) after aging in ambient air for 30 days. It can be seen from the figure that after aging in ambient air for 30 days, MAPbI modified with thiophene [2,3-D] pyrimidin-4 (3H) one 3 The diffraction peak of the film is almost unchanged, while the unmodified film shows an obvious PbI 2 The diffraction peaks indicate that thiophene[2,3-D]pyrimidin-4(3H)one can effectively enhance MAPbI 3 Stability of the film.

Claims

1. A method for preparing thiophene [2,3-D] pyrimidin-4 (3H) ketone-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 ability of MAPbI3.

2. The preparation method according to claim 1, characterized in that The steps include: 1a: Weigh 461 mg of lead iodide and 159 mg of methylammonium iodide, mix them and add them to 1 mL of ethylene glycol methyl ether, then add thiophene[2,3-D]pyrimidin-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 um filter and transferred to a centrifuge tube. An antisolvent was added to completely precipitate the solution. A black precipitate was obtained by centrifugation. The antisolvent was added repeatedly for precipitation and centrifugation. The solution was dried under vacuum to obtain a 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]pyrimidin-4(3H)one added was 1-3 mg / mL.

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

5. The preparation method according to claim 1, characterized in that The steps include: 2a: 1290.8 mg of lead iodide, 445.1 mg of methylammonium iodide, 1.6 mL of N,N-dimethylformamide, 0.4 mL of dimethyl sulfoxide and thiophene [2,3-D] pyrimidin-4 (3H) ketone 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 using a 0.22 um filter to obtain a MAPbI3 perovskite precursor solution; 2b: The glass substrate or FTO substrate was ultrasonically cleaned with deionized water, acetone, and ethanol for 15 minutes each, and then placed in a UV ozone cleaning machine for cleaning for 15 minutes after drying; 2c: Place the substrate material obtained in step 2b on a spin coater, add 30uL of the MAPbI3 perovskite precursor solution obtained in step 2a, start the spin coater when the solution covers the substrate, 1500 rpm for 8s, 4000 rpm for 20s, and add the anti-solvent at the 15th second of the total time; after the spin coating is completed, annealing treatment is performed 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]pyrimidin-4(3H)one added was 1-3 mg / mL.

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

8. The preparation method according to claim 5, characterized in that: The annealing temperature is 110°C and the annealing time is 10 min.

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

10. The use according to claim 9, characterized in that: The solar cell light absorption layer is prepared using the organic-inorganic hybrid perovskite MAPbI3 modified with the thiophene [2,3-D] pyrimidin-4 (3H) ketone.

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