Asymmetric perylene organic matter, preparation method and application

Abstract

The application provides an asymmetric perylene organic matter, a preparation method and application. The asymmetric perylene organic matter has a structure of formula (I), n is 1-5, and m is 1-10. After the asymmetric perylene organic matter with the structure is applied to a passivated perovskite thin film, the phosphate group and the trifluoromethyl group can passivate the grain boundary and the surface defect in the perovskite thin film, the charge transport of the grain boundary and the surface is improved, the F atom can improve the hydrophobicity of the perovskite thin film surface, the perovskite thin film can form a hydrogen bond with N to inhibit the migration of methylamine and formamidinium ions, and P=O and C=O are coordinated with Pb ions to inhibit the migration of Pb ions. Through the superposition of the multiple effects, the efficiency and stability of the perovskite device can be improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of solar cell preparation, in particular to an asymmetric perylene organic matter, a preparation method and application. BACKGROUND

[0002] In the process of grain growth of perovskite thin film, grain boundaries and surface defects are serious, which causes a large number of carriers to be non-radiative recombination, resulting in the decrease of device efficiency. In addition, perovskite thin film is easily eroded by water and oxygen, causing degradation and aging, which affects the long-term stability of perovskite devices. At present, the main solution is to passivate the grain boundary defects in the perovskite thin film through additive engineering, and to passivate the surface defects of the perovskite thin film through the preparation of mixed-dimensional thin film, so as to improve the stability of the device.

[0003] In view of the above problems, it is necessary to provide a method which can passivate the grain boundaries and surface defects in the perovskite thin film at the same time, and improve the charge transport of the grain boundaries and surface. SUMMARY

[0004] The main purpose of the present application is to provide an asymmetric perylene organic matter, a preparation method and application, so as to solve the problem that the existing process needs multiple processes to improve the grain boundary defects and surface defects in the perovskite thin film, resulting in a long process flow, high cost and poor stability of the prepared perovskite device.

[0005] In order to achieve the above purpose, the present application provides an asymmetric perylene organic matter in one aspect, which has the structure of formula (I):

[0006]

[0007] Wherein, n is 1-5, and m is 1-10.

[0008] The second aspect of the present application also provides a preparation method of the above asymmetric perylene organic matter, which comprises: under the action of a catalyst, perylene tetracarboxylic dianhydride, halogenated alcohol and fluorinated alkane are subjected to acid anhydride esterification reaction and substitution reaction in sequence to obtain a first intermediate, the first intermediate has the structure shown in formula (II); the first intermediate is subjected to partial ring formation reaction in the presence of p-toluenesulfonic acid and C5-C10 alkane to obtain a second intermediate, the second intermediate has the structure shown in formula (III); the second intermediate is subjected to amidation reaction with ammonia water to obtain a third intermediate, the third intermediate has the structure shown in formula (IV); the third intermediate is subjected to substitution reaction with dihalogenated hydrocarbon to obtain a fourth intermediate, the fourth intermediate has the structure shown in formula (V); and the fourth intermediate is subjected to phosphonate ester synthesis reaction with trialkyl phosphite to obtain the asymmetric perylene organic matter.

[0009]

[0010] Further, the temperature of the synthesis reaction of the first intermediate is 60-90 °C, the reaction time is 30-120 min, and the molar ratio of the perylene tetracarboxylic dianhydride, the halogenated alcohol, the fluorinated alkane, and the catalyst is 1:(2-4):(2-4):(4-5); in the synthesis process of the first intermediate, the catalyst is 1,8-diazabicyclo[5.4.0]undec-7-ene, the halogenated alcohol is trifluoroethanol, and the fluorinated alkane is trihaloethane.

[0011] Further, in the ester hydrolysis reaction, the molar ratio of the first intermediate, p-toluenesulfonic acid, and C5-C10 alkane is 1:(1.0-1.5):(0.02-0.03), the temperature of the ester hydrolysis reaction is 80-100 °C, and the reaction time is 300-600 min.

[0012] Further, the amidation reaction includes refluxing the second intermediate and ammonia at 50-70 °C for 120-180 min; preferably, in the amidation reaction, the molar ratio of the second intermediate to ammonia is 1:(10-15).

[0013] Further, the substitution reaction includes: under the catalysis of sodium hydride, reacting the third intermediate with a dihaloalkane to obtain a fourth intermediate; preferably, the molar ratio of the third intermediate, sodium hydride, and the dihaloalkane is 1:(1.5-3):(2-10), the reaction temperature is 80-90 °C, and the reaction time is 10-12 h; preferably, the dihaloalkane is one or more selected from the group consisting of dibromoethane, dibromopropane, dibromobutane, dibromopentane, and dibromohexane.

[0014] Further, in the phosphonate synthesis reaction, the molar ratio of the fourth intermediate to trialkyl phosphite is 1:15-20, the reaction temperature is 130-150 °C, and the reaction time is 10-12 h.

[0015] The third aspect of the present application also provides a perovskite additive, which comprises the asymmetric perylene organic matter or the asymmetric perylene organic matter prepared by the preparation method.

[0016] The fourth aspect of the present application also provides a perovskite film, which comprises the asymmetric perylene perovskite additive.

[0017] The fifth aspect of the present application also provides a solar cell, which comprises the perovskite film.

[0018] By using the technical solution of the present application, the asymmetric perylene organic matter with the above structure is applied to the passivated perovskite film, the phosphate group and the trifluoromethyl group can passivate the grain boundaries and surface defects in the perovskite film, improve the charge transport of the grain boundaries and the surface, the F atom can improve the hydrophobicity of the surface of the perovskite film, the perovskite film can form hydrogen bonds with N to inhibit the migration of methylamine and formamidinium ions, and P=O and C=O can coordinate with Pb ions to inhibit the migration of Pb ions. Through the superposition of the above multiple effects, the efficiency and stability of the perovskite device can be improved. BRIEF DESCRIPTION OF DRAWINGS

[0019] The accompanying drawings, which form a part of the specification, are included to provide a further understanding of the application and are incorporated herein for explanation by referring to the embodiments of the present application. In the drawings:

[0020] Figure 1 SEM images of the active layer of the experimental example device at different magnifications (50.0K).

[0021] Figure 2 SEM images of the active layer of the experimental example device at different magnifications (20.0K).

[0022] Figure 3 SEM images of the active layer of the comparative example device at different magnifications (50.0K).

[0023] Figure 4 SEM images of the active layer of the comparative example device at different magnifications (20.0K). DETAILED DESCRIPTION

[0024] It should be noted that the embodiments in the present application and the features in the embodiments can be combined with each other without conflict. The present application will be described in detail below with reference to the embodiments.

[0025] As described in the background, the existing process needs multiple processes to improve the grain boundary defects and surface defects in the perovskite film, resulting in a long process flow, high cost and poor stability of the prepared perovskite device. In order to solve the above technical problems, the present application provides an asymmetric perylene organic matter, which has the structure of formula (I):

[0026]

[0027] wherein n is 1-5, and m is 1-10.

[0028] The asymmetric perylene organic matter with the above structure is applied to the passivated perovskite thin film, the phosphate group and the trifluoromethyl group can passivate the grain boundaries and surface defects in the perovskite thin film, improve the charge transport of the grain boundaries and the surface, the F atom can improve the hydrophobicity of the perovskite thin film surface, the perovskite thin film can form a hydrogen bond with -N to inhibit the migration of methylamine and formamidinium ions, P=O and C=O are coordinated with Pb ions to inhibit the migration of Pb ions. Through the superposition of the above multiple effects, the efficiency and stability of the perovskite device can be improved. The above asymmetric perylene organic matter can be dissolved in polar organic solvents such as ethanol, isopropanol, N,N-dimethylformamide, dimethyl sulfoxide, etc.

[0029] The second aspect of the present application also provides a preparation method of the above asymmetric perylene organic matter, comprising: under the action of a catalyst, perylene tetracarboxylic dianhydride, halogenated alcohol and fluorinated alkane are sequentially subjected to acid anhydride esterification and substitution reaction to obtain a first intermediate, the first intermediate has a structure shown in formula (II); under the action of p-toluenesulfonic acid and C5-C 10 C5-C12alkane, the first intermediate is subjected to partial ring formation reaction to obtain a second intermediate, the second intermediate has a structure shown in formula (III); the second intermediate and ammonia are subjected to amidation reaction to obtain a third intermediate, the third intermediate has a structure shown in formula (IV); the third intermediate and dihalogenated hydrocarbon are subjected to substitution reaction to obtain a fourth intermediate, the fourth intermediate has a structure shown in formula (V); the fourth intermediate and trialkyl phosphite are subjected to phosphonate synthesis reaction to obtain the asymmetric perylene organic matter;

[0030]

[0031] The above method can prepare a perylene organic matter containing phosphate groups, trifluoromethyl groups, F atoms, N atoms, -O-(PO)-O- and -CO- at the same time, and the multiple effects of the above groups can improve the efficiency and stability of the perovskite device. At the same time, the above method has the advantages of high yield and good selectivity.

[0032] The specific synthesis steps of the first intermediate are as follows: perylene tetracarboxylic dianhydride and halogenated alcohol are subjected to acid anhydride esterification to obtain perylene tetracarboxylic diester; then under the action of a catalyst, the perylene tetracarboxylic diester and fluorinated alkane are subjected to reaction to obtain the first intermediate.

[0033] In order to improve the yield and selectivity of the first intermediate, in a preferred embodiment, the synthesis reaction temperature of the first intermediate is 60-90°C, the reaction time is 30-120 min, and the molar ratio of perylene tetracarboxylic dianhydride, halogenated alcohol, fluorinated alkane and catalyst is 1:(2-4):(2-4):(4-5).

[0034] To make the above-mentioned raw materials more fully reacted, preferably, the preparation process of the first intermediate is carried out in a first organic solvent. The type of the first organic solvent is not specifically limited as long as the above-mentioned effect can be achieved. More preferably, the first organic solvent includes but is not limited to DMF.

[0035] Preferably, in the synthesis process of the first intermediate, the catalyst includes but is not limited to 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). Compared with other catalysts, the use of the above-mentioned catalyst is conducive to further improving the reaction rate and improving the selectivity.

[0036] The types of the halogenated alcohol and the fluoroalkane can be selected from those commonly used in the art. Specifically, the halogenated alcohol includes but is not limited to trifluoroethanol; the fluoroalkane includes but is not limited to trihaloethane.

[0037] The synthesis principle of the second intermediate is to make half of the ester groups in the first intermediate cyclize with p-toluenesulfonic acid as a catalyst. Since the second intermediate has a smaller solubility in the C5-C 10 The solubility of the alkane solvent (the second solvent) is smaller, so that the second intermediate can be automatically precipitated after being generated, thereby improving the selectivity and yield of the second intermediate.

[0038] To improve the yield and selectivity of the second intermediate, preferably, in the ester hydrolysis reaction, the molar ratio of the first intermediate, p-toluenesulfonic acid and C5-C 10 The molar ratio of the alkane is 1: (1.0-1.5): (0.02-0.03), the temperature of the ester hydrolysis reaction is 80-100°C, and the reaction time is 300-600 min.

[0039] In a preferred embodiment, the amidation reaction includes refluxing the second intermediate and ammonia at 50-70°C for 120-180 min to obtain the third intermediate. Preferably, in the amidation reaction, the molar ratio of the second intermediate to ammonia is 1: (10-15). The molar ratio of the second intermediate to ammonia includes but is not limited to the above-mentioned range, and being limited in the above-mentioned range is conducive to further improving the yield of the third intermediate.

[0040] To make the above-mentioned raw materials more fully reacted, preferably, the preparation process of the first intermediate is carried out in a first organic solvent. The type of the first organic solvent is not specifically limited as long as the above-mentioned effect can be achieved. More preferably, the first organic solvent includes but is not limited to DMF.

[0041] In a preferred embodiment, the substitution reaction comprises: reacting the third intermediate and a dihalogenated hydrocarbon under catalysis of sodium hydride to obtain a fourth intermediate. In order to further improve the yield and selectivity of the fourth intermediate, the reaction parameters thereof can be optimized. Preferably, the molar ratio of the third intermediate and the dihalogenated hydrocarbon is 1:(2-10), the reaction temperature is 70-90°C, and the reaction time is 10-12h. More preferably, the dihalogenated hydrocarbon comprises one or more selected from the group consisting of dibromoethane, dibromopropane, dibromobutane, dibromopentane, and dibromohexane.

[0042] In a preferred embodiment, the molar ratio of the fourth intermediate and trialkyl phosphite in the phosphonate synthesis reaction is 1:15-20, the reaction temperature is 130-150°C, and the reaction time is 10-12h. By limiting the reaction raw materials, reaction temperature, and reaction time within the above ranges, the yield of the target product can be further improved.

[0043] The third aspect of the present application also provides a perovskite additive, which comprises the above asymmetric perylene organic matter or the asymmetric perylene organic matter prepared by the above preparation method.

[0044] Since the above asymmetric perylene organic matter can significantly improve the efficiency and stability of the perovskite device in the application process, the perovskite additive containing the above asymmetric perylene organic matter can also achieve the above effects.

[0045] The fourth aspect of the present application also provides a perovskite film, which comprises the above asymmetric perylene perovskite additive. After the asymmetric perylene organic matter with the above structure is applied to the passivated perovskite thin film, the phosphate group and the trifluoromethyl group can passivate the grain boundaries and surface defects in the perovskite thin film, improve the charge transport of the grain boundaries and the surface, the F atom can improve the hydrophobicity of the perovskite thin film surface, the perovskite thin film can form a hydrogen bond with -N to inhibit the migration of methylamine and formamidinium ions, and P=O and C=O coordinate with Pb ions to inhibit the migration of Pb ions.

[0046] The fifth aspect of the present application also provides a solar cell, which comprises the perovskite film provided by the present application. Compared with the prior art, by adding the multifunctional asymmetric perylene perovskite additive to prepare the perovskite thin film, the grain boundaries and surface defects can be effectively passivated, the charge transport can be improved, the ion migration can be inhibited, and the efficiency and stability of the perovskite thin film cell can be improved.

[0047] The present application will be further described in detail below in combination with specific embodiments, which cannot be understood as limiting the scope of the present application.

[0048] Example 1

[0049] (1) Preparation of monomer M11 (first intermediate):

[0050]

[0051] Perylene tetra carboxylic dianhydride (1.0 eq, 100 mg), trifluoroethanol (4.0 eq, 102.0 mg), DBU (4.0 eq, 15.2 mg) in DMF solvent 50 ml was taken in a flask and heated at 60 °C for 30 min.

[0052] Trifluoroiodoethane (4.0 eq, 214.05 mg) in DMF solvent 30 ml was added to the above reaction and heated at 60 °C for 90 min. After cooling the reaction, the mixture solution was poured into ice water and stirred for 5 min. After the orange red solid was precipitated, the crude product was obtained by suction filtration. The crude product was recrystallized to obtain the target product M11 (166 mg, yield 86.09 wt%).

[0053] 1H NMR (500 MHz, CDC13): δ = 8.14 (d, 4H), 8.10 (d, 4H), 4.80-4.70 (d, 8H).

[0054] (2) Preparation of monomer M21 (second intermediate):

[0055]

[0056] Monomer M11 (1.0 eq, 100 mg), p-toluenesulfonic acid (1.1 eq, 25.0 mg), heptane 10 mL was taken in a flask and heated at 90 °C for 6 h. After the reaction was completed, it was cooled to room temperature and the crude product (orange precipitate) was filtered. The orange precipitate was washed with methanol and water and dried. Subsequently, the dried orange precipitate was taken in 100 mL of methanol and refluxed for 2 h. It was cooled to room temperature and filtered to obtain the residue. Finally, the dried residue was dissolved in dichloromethane and the filtrate was filtered. The solvent was removed by rotary evaporation to obtain the target product M21 (63 mg, yield 83.2 wt%).

[0057] 1H NMR (500 MHz, CDC13): δ = 8.30 (d, 2H), 8.14 (d, 2H), 8.10-8.04 (d, 4H), 4.80-4.70 (d, 8H).

[0058] (3) Preparation of monomer M31 (third intermediate):

[0059]

[0060] Monomer M21 (1.0 eq, 100 mg), 35% ammonia (10 mL), butanol (10 mL) were weighed and the reaction was refluxed at 80 °C for 12 h. After completion of the reaction, the solvent was removed using a rotary evaporator and the crude product was purified using column chromatography to obtain monomer M31 (60.2 mg, yield 60.3 wt%).

[0061] 1H NMR (500 MHz, CDC13): δ = 8.20 (d, 2H), 8.10-8.04 (d, 4H), 7.9 (d, 2H), 4.80-4.70 (d, 8H).

[0062] (4) Preparation of monomer M41 (fourth intermediate):

[0063]

[0064] Monomer M31 (1.0 eq, 100 mg) and 1,2-dibromoethane (20 eq, 655 mg) were dissolved in 20 mL of DMF solvent, followed by the addition of sodium hydride (2 eq, 8.37 mg). The reaction was stirred at 80 °C overnight. After completion of the reaction, extraction was carried out with dichloromethane and the organic layer was retained. The organic layer was dried with anhydrous Na2S04. The residue was distilled under reduced pressure. The crude product was purified using column chromatography to obtain M41 (102 mg, yield 86 wt%).

[0065] 1H NMR (500 MHz, CDC13): δ = 8.20 (d, 2H), 8.10-8.04 (d, 4H), 7.9 (d, 2H), 4.80-4.70 (d, 8H), 3.80-3.70 (t, 4H).

[0066] (5) Preparation of monomer M51 (asymmetric perylene):

[0067]

[0068] Monomer M41 (1.0 eq, 100 mg) was dissolved in triethyl phosphite (20 eq, 488 mg) and the reaction mixture was heated at 140 °C overnight. After completion of the reaction, the solvent was distilled out under reduced pressure. The crude product was purified using column chromatography to obtain M51 (90 mg, yield 83%).

[0069] 1H NMR (500 MHz, CDC13): δ = 8.20 (d, 2H), 8.10-8.04 (d, 4H), 7.9 (d, 2H), 4.80-4.70 (d, 8H), 4.20 (t, 4H), 3.70 (t, 2H), 2.10 (t, 2H), 1.36 (s, 6H).

[0070] Example 2

[0071] The difference from Example 1 is that the temperature of the synthesis reaction of the first intermediate is 60°C, and the molar ratio of perylene tetracarboxylic dianhydride, halogenated alcohol, fluorinated alkane and catalyst is 1:2:2:4. The yield of M11 is 84.20wt%, and the yield of M51 is 81.3wt%.

[0072] Example 3

[0073] The difference from Example 1 is that the temperature of the synthesis reaction of the first intermediate is 90°C, and the molar ratio of perylene tetracarboxylic dianhydride, halogenated alcohol, fluorinated alkane and catalyst is 1:4:4:5. The yield of M11 is 88.2wt%, and the yield of M51 is 83.6wt%.

[0074] Example 4

[0075] The difference from Example 1 is that the temperature of the synthesis reaction of the first intermediate is 50°C, and the molar ratio of perylene tetracarboxylic dianhydride, halogenated alcohol, fluorinated alkane and catalyst is 1:1.5:1.5:3. The yield of M11 is 60.26wt%, and the yield of M51 is 58wt%.

[0076] Example 6

[0077] The difference from Example 1 is that in the preparation process of the second intermediate, the molar ratio of the first intermediate, p-toluenesulfonic acid and C5-C 10 alkane is 1:1:0.02, and the temperature of the ester hydrolysis reaction is 80°C. The yield of M21 is 82.1wt%, and the yield of M51 is 82.0wt%.

[0078] Example 7

[0079] The difference from Example 1 is that in the preparation process of the second intermediate, the molar ratio of the first intermediate, p-toluenesulfonic acid and C5-C 10 alkane is 1:1.5:0.03, and the temperature of the ester hydrolysis reaction is 100°C. The yield of M21 is 84.2wt%, and the yield of M51 is 83.4wt%.

[0080] Example 8

[0081] The difference from Example 1 is that in the preparation process of the second intermediate, the molar ratio of the first intermediate, p-toluenesulfonic acid and C5-C 10 alkane is 1:0.8:0.01, and the temperature of the ester hydrolysis reaction is 60°C. The yield of M21 is 37wt%, and the yield of M51 is 36.95wt%.

[0082] Example 9

[0083] The difference from Example 1 is that the molar ratio of the second intermediate to ammonia in the preparation of the third intermediate is 1:10. The yield of M31 is 60.2wt%, and the yield of M51 is 83wt%.

[0084] Example 10

[0085] The difference from Example 1 is that the molar ratio of the second intermediate to ammonia in the preparation of the third intermediate is 1:15. The yield of M31 is 64.5wt%, and the yield of M51 is 83.3wt%.

[0086] Example 11

[0087] The difference from Example 1 is that the molar ratio of the second intermediate to ammonia in the preparation of the third intermediate is 1:5. The yield of M31 is 47.5wt%, and the yield of M51 is 65.5wt%.

[0088] Example 12

[0089] The difference from Example 1 is that the molar ratio of the third intermediate, sodium hydride and dihalogenated hydrocarbon in the preparation of the fourth intermediate is 1:1.5:2. The yield of M41 is 85wt%, and the yield of M51 is 83wt%.

[0090] Example 13

[0091] The difference from Example 1 is that the molar ratio of the third intermediate, sodium hydride and dihalogenated hydrocarbon in the preparation of the fourth intermediate is 1:3:10. The yield of M41 is 89wt%, and the yield of M51 is 83.7wt%.

[0092] Example 14

[0093] The difference from Example 1 is that the molar ratio of the third intermediate, sodium hydride and dihalogenated hydrocarbon in the preparation of the fourth intermediate is 1:1:1. The yield of M41 is 62wt%, and the yield of M51 is 60wt%.

[0094] Example 15

[0095] The difference from Example 1 is that the molar ratio of the fourth intermediate to trialkyl phosphite in the phosphonate synthesis reaction is 1:15, and the reaction temperature is 130℃. The yield of M51 is 83wt%.

[0096] Example 16

[0097] The difference from Example 1 is that the molar ratio of the fourth intermediate to trialkyl phosphite in the phosphonate synthesis reaction is 1:20, and the reaction temperature is 150℃. The yield of M51 is 84wt%.

[0098] Example 17

[0099] The difference from Example 1 is that the molar ratio of the fourth intermediate to trialkyl phosphite is 1:10, and the reaction temperature is 100°C during the phosphonate synthesis reaction. The yield of M51 is 42wt%.

[0100] Device preparation:

[0101] The ITO glass was cleaned with detergent water, deionized water, acetone, and isopropanol solution respectively, and then ultrasonically cleaned for 15 min. After drying, it was ready for use.

[0102] The cleaned ITO glass was plasma treated for 10-15 min.

[0103] The hole transport layer was prepared on the treated ITO glass. A 1 mg / mL solution of (2-(9H-carbazol-9-yl)ethyl)phosphonic acid (2PACz) in ethanol was spin-coated on the ITO glass at 5000 rpm for 30 s, and then dried at 100°C for 10 min.

[0104] Preparation of the active layer of the experimental device: The perovskite active layer was prepared on the hole transport layer. A 1.5M perovskite precursor solution was prepared using cesium bromide (CsBr), lead iodide (PbI)2, lead bromide (PbBr2), formamidinium hydriodide (FAI), methylamine hydrobromide (MABr), and methylamine hydrochloride (MACl) as the raw materials, and DMF and DMSO mixed at a volume ratio of 4:1 as the solvent. 5wt% of the additive material M51 was added to the above solution and mixed uniformly. The perovskite active layer was then prepared using the spin-coating method at 2000 rpm for 40 s, followed by 5000 rpm for 20 s. 200μL of chlorobenzene was dropped into the center of the substrate 15 s before the end of the spin-coating process. After the rotation stopped, the substrate was immediately transferred to a heating plate at 100°C and annealed for 15 min. The SEM image of the active layer of the experimental device is shown in Figure 1 and 2 .

[0105] ​Preparation of the active layer for the comparative device: A perovskite active layer was prepared on the hole transport layer using a 1.5 M perovskite precursor solution prepared with cesium bromide (CsBr), lead methylide (PbI)₂, lead bromide (PbBr₂), formamidinium hydroiodide (FAI), methylamine hydrobromide (MABr), and methylamine hydrochloride (MACl). A mixed solvent of DMF and DMSO in a 4:1 volume ratio was used. After thorough mixing, the perovskite active layer was prepared by spin coating at 2000 rpm for 40 s, followed by 5000 rpm for 20 s. 15 s before the end of the spin coating process, 200 μL of chlorobenzene was dropped into the center of the substrate. Immediately after the spin coating stopped, the substrate was transferred to a 100°C heating plate and annealed for 15 min. The SEM image of the active layer of the comparative device is shown below. Figure 3 and 4 .

[0106] An electron transport layer was spin-coated onto the active layer prepared above. Using a spin-coating process, a 15 mg / mL chlorobenzene solution of PCBM was deposited onto the perovskite active layer at 2500 rpm for 30 s.

[0107] An interface layer was prepared on the PCBM film prepared above. A thin BCP layer was deposited on the PCBM using a spin coating process, and then annealed at 100°C for 10 min.

[0108] Finally, a 100 nm Ag electrode was deposited on the surface of the BCP thin film using a vacuum thermal deposition method.

[0109] The effective area of ​​the device is 4mm. 2 .

[0110] Battery performance testing

[0111] The obtained solar cell device was subjected to photovoltaic performance testing; the effective area of ​​the device was 4 mm². 2 The test conditions were: spectral distribution AM1.5G, light intensity 100mW / cm². 2 The AAA solar simulator (Keithley Instruments, Inc.) was used, and the JV curve was measured using a Keithly 2400 digital source meter. All components were simply encapsulated with UV adhesive, and measurements were taken in an atmospheric environment. The test results are shown in Table 1.

[0112] Table 1

[0113]

[0114] From the above description, it can be seen that the above-mentioned embodiments of the present application achieve the following technical effects: compared with the prior art, the present application can effectively passivate grain boundaries and surface defects, improve charge transport, inhibit ion migration, and improve the efficiency and stability of the perovskite thin film battery by adding a multifunctional asymmetric perylene perovskite additive to prepare the perovskite thin film.

[0115] It should be noted that the terms "first", "second", and the like in the specification and claims of the present application are used to distinguish similar objects, and do not necessarily have to describe a specific order or sequence. It should be understood that the terms thus used can be interchanged under appropriate circumstances, so that the embodiments of the present application described herein can be implemented in an order other than that described herein.

[0116] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. For those skilled in the art, the present application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. An asymmetric perylene-based organic compound, characterized in that, The asymmetric perylene organic compound has the structure of formula (Ⅰ): Wherein, n is 1 to 5, and m is 1 to 10.

2. A method for preparing the asymmetric perylene-based organic compound according to claim 1, characterized in that, The method for preparing the asymmetric perylene organic compound includes: Under the action of a catalyst, perylene tetracarboxylic anhydride, haloalcohol and fluoroalkanes undergo an anhydride esterification reaction and a substitution reaction in sequence to obtain a first intermediate, which has the structure shown in formula (II). In p-toluenesulfonic acid and C5-C 10 In the presence of alkanes, the first intermediate undergoes a partial cyclization reaction to give a second intermediate, which has the structure shown in formula (III); The second intermediate undergoes an amidation reaction with ammonia to obtain a third intermediate, which has the structure shown in formula (Ⅳ). The third intermediate undergoes a substitution reaction with a dihalohydrocarbon to obtain a fourth intermediate, which has the structure shown in formula (V). The fourth intermediate and trialkylphosphite are reacted to form a phosphonate to obtain the asymmetric perylene-based organic compound; 3. The method for preparing asymmetric perylene-based organic compounds according to claim 2, characterized in that, The synthesis reaction of the first intermediate is carried out at a temperature of 60-90°C and a reaction time of 30-120 min. The molar ratio of the perylene tetracarboxylic dianhydride, the haloalcohol, the fluoroalkane and the catalyst is 1:(2-4):(2-4):(4-5). In the synthesis of the first intermediate, the catalyst is 1,8-diazabicyclo[5.4.0]undec-7-ene, the haloalcohol is trifluoroethanol, and the fluoroalkane is trihaloethane.

4. The method for preparing asymmetric perylene-based organic compounds according to claim 2, characterized in that, In the ester hydrolysis reaction, the first intermediate, the p-toluenesulfonic acid, and the C5-C6 bonds are involved. 10 The molar ratio of alkanes is 1:(1.0~1.5):(0.02~0.03), and the temperature of the ester hydrolysis reaction is 80~100℃, and the reaction time is 300~600min.

5. The method for preparing asymmetric perylene-based organic compounds according to claim 2, characterized in that, The amidation reaction includes refluxing the second intermediate and the ammonia solution at 50–70°C for 120–180 min; Preferably, in the amidation reaction, the molar ratio of the second intermediate to the ammonia is 1:(10-15).

6. The method for preparing asymmetric perylene-based organic compounds according to claim 2, characterized in that, The substitution reaction includes reacting the third intermediate and the dihalohydrocarbon under sodium hydride catalysis to obtain the fourth intermediate; Preferably, the molar ratio of the third intermediate, the sodium hydride, and the dihalohydrocarbon is 1:(1.5-3):(2-10), the reaction temperature is 80-90°C, and the reaction time is 10-12 h. Preferably, the dihalohydrocarbon is selected from one or more of the group consisting of dibromoethane, dibromopropane, dibromobutane, dibromopentane, and dibromohexane.

7. The method for preparing asymmetric perylene-based organic compounds according to claim 2, characterized in that, In the phosphonate synthesis reaction, the molar ratio of the fourth intermediate to the trialkylphosphorous acid is 1:15-20, the reaction temperature is 130-150℃, and the reaction time is 10-12h.

8. A perovskite additive, characterized in that, The perovskite additive includes the asymmetric perylene organic compound as described in claim 1 or the asymmetric perylene organic compound prepared by any one of claims 2 to 7.

9. A perovskite film, characterized in that, The perovskite film contains the asymmetric perovskite additive as described in claim 8.

10. A solar cell, characterized in that, The solar cell includes the perovskite film as described in claim 9.

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