Asymmetric perylene organic matter, preparation method and application

Abstract

The invention provides an asymmetric perylene organic matter as well as a preparation method and application thereof. The asymmetric perylene organic matter has a structure shown in a 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, a phosphate group and a trifluoromethyl group can passivate grain boundary and surface defects in the perovskite thin film and improve grain boundary and surface charge transfer, F atoms can improve the hydrophobicity of the surface of the perovskite thin film, and therefore the perovskite thin film can be used for passivating the perovskite thin film. The perovskite thin film can form a hydrogen bond with N to inhibit methylamine and formamidine ion migration, and P = O and C = O are coordinated with Pb ions to inhibit Pb ion migration. The efficiency and the stability of the perovskite device can be improved through superposition of the multiple effects. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to the field of solar cell preparation, and in particular to an asymmetric perylene organic compound, a preparation method and application thereof. Background Art

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

[0003] In view of the above problems, it is necessary to provide a method that can simultaneously passivate the grain boundaries and surface defects in the perovskite film and improve the charge transport at the grain boundaries and the surface. Summary of the invention

[0004] The main purpose of the present invention is to provide an asymmetric perylene organic compound, a preparation method and an application thereof, so as to solve the problem that the existing process requires 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 perovskite device obtained.

[0005] In order to achieve the above object, the present invention provides an asymmetric perylene organic compound having a structure of formula (I):

[0006]

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

[0008] The second aspect of the present application also provides a method for preparing the above-mentioned asymmetric perylene organic compound, which comprises: in the presence of a catalyst, subjecting perylene tetracarboxylic acid dianhydride, a halogenated alcohol and a fluoroalkane to an anhydride esterification reaction and a substitution reaction in sequence to obtain a first intermediate, the first intermediate having a structure shown in formula (II); in the presence of p-toluenesulfonic acid and a C5-C10 alkane, subjecting the first intermediate to a partial cyclization reaction to obtain a second intermediate, the second intermediate having a structure shown in formula (III); subjecting the second intermediate to an amidation reaction with ammonia water to obtain a third intermediate, the third intermediate having a structure shown in formula (IV); subjecting the third intermediate to a substitution reaction with a dihalogenated hydrocarbon to obtain a fourth intermediate, the fourth intermediate having a structure shown in formula (V); subjecting the fourth intermediate to a phosphonate synthesis reaction with trialkylphosphite to obtain an asymmetric perylene organic compound;

[0009]

[0010] Furthermore, the temperature of the synthesis reaction of the first intermediate is 60-90°C, the reaction time is 30-120min, and the molar ratio of perylenetetracarboxylic dianhydride, halohydrin, fluoroalkane and 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 halohydrin is trifluoroethanol, and the fluoroalkane is trihaloethane.

[0011] Furthermore, 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] Furthermore, the amidation reaction comprises subjecting the second intermediate and aqueous ammonia to a reflux reaction at 50-70° C. for 120-180 min; preferably, in the amidation reaction, the molar ratio of the second intermediate to aqueous ammonia is 1:(10-15).

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

[0014] Furthermore, during the phosphonate synthesis reaction, the molar ratio of the fourth intermediate to trialkylphosphorous acid 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 further provides a perovskite additive, which includes the asymmetric perylene organic compound mentioned above or the asymmetric perylene organic compound prepared by the above preparation method.

[0016] The fourth aspect of the present application further provides a perovskite film, wherein the perovskite film comprises the above-mentioned asymmetric perylene perovskite additive.

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

[0018] By applying the technical solution of the present invention, after applying the asymmetric perylene organic matter having the above structure to the passivated perovskite film, the phosphate group and the trifluoromethyl group can passivate the grain boundary and surface defects in the perovskite film, improve the charge transfer at the grain boundary and the surface, the F atom can improve the hydrophobicity of the surface of the perovskite film, the perovskite film can form a hydrogen bond with N to inhibit the migration of methylamine and formamidine ions, and P=O and C=O coordinate with Pb ions to inhibit the migration of Pb ions. The superposition of the above multiple effects can achieve the improvement of the efficiency and stability of the perovskite device. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] The drawings constituting a part of the present application are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. 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 The SEM images of the active layer of the comparative device at different magnifications (50.0K) are shown.

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

[0024] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be described in detail below in conjunction with the embodiments.

[0025] As described in the background art, the existing process requires 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 obtained perovskite device. In order to solve the above technical problems, the present application provides an asymmetric perylene organic compound, which has a structure of formula (I):

[0026]

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

[0028] After applying the asymmetric perylene organic matter with the above structure to the passivated perovskite film, the phosphate group and the trifluoromethyl group can passivate the grain boundary and surface defects in the perovskite film, improve the charge transfer at the grain boundary and the surface, the F atom can improve the hydrophobicity of the surface of the perovskite film, the perovskite film can form a hydrogen bond with -N to inhibit the migration of methylamine and formamidine ions, and P=O and C=O coordinate with Pb ions to inhibit the migration of Pb ions. The superposition of the above multiple effects can achieve the improvement of the efficiency and stability of the perovskite device. The above asymmetric perylene organic matter can be dissolved in organic polar solvents such as ethanol, isopropanol, N,N-dimethylformamide, dimethyl sulfoxide, etc.

[0029] The second aspect of the present application also provides a method for preparing the above-mentioned asymmetric perylene organic compound, comprising: in the presence of a catalyst, subjecting perylene tetracarboxylic acid dianhydride, a halogenated alcohol and a fluoroalkane to an acid anhydride esterification reaction and a substitution reaction in sequence to obtain a first intermediate having a structure shown in formula (II); reacting p-toluenesulfonic acid and C5-C 10 In the presence of an alkane, the first intermediate undergoes a partial ring-forming reaction to obtain a second intermediate, the second intermediate having a structure shown in formula (III); the second intermediate undergoes an amidation reaction with aqueous ammonia to obtain a third intermediate, the third intermediate having a structure shown in formula (IV); the third intermediate undergoes a substitution reaction with a dihalogenated hydrocarbon to obtain a fourth intermediate, the fourth intermediate having a structure shown in formula (V); the fourth intermediate undergoes a phosphonate synthesis reaction with trialkylphosphite to obtain an asymmetric perylene organic compound;

[0030]

[0031] The above method can be used to prepare perylene organic compounds containing phosphate groups, trifluoromethyl groups, F atoms, N atoms, -O-(PO)-O- and -CO- at the same time, and the efficiency and stability of perovskite devices can be improved under the multiple effects of the above groups. 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: perylenetetracarboxylic acid dianhydride and halogenated alcohol are subjected to anhydride esterification to obtain perylenetetracarboxylic acid diester; then, under the action of a catalyst, the perylenetetracarboxylic acid diester is reacted with a fluoroalkane to obtain the first intermediate.

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

[0034] In order to make the above raw materials react more fully, preferably, the preparation process of the above first intermediate is carried out in a first organic solvent. As long as the above effect can be achieved, the type of the first organic solvent is not specifically limited. More preferably, the above 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 above catalyst is conducive to further improving the reaction rate and the selectivity.

[0036] The types of halohydrins and fluoroalkanes can be selected from those commonly used in the art. Specifically, halohydrins include but are not limited to trifluoroethanol; fluoroalkanes include but are not limited to trihaloethane.

[0037] The synthesis principle of the second intermediate is: p-toluenesulfonic acid is used as a catalyst to make half of the ester groups in the first intermediate form a ring. 10 The solubility in the alkane solvent (the second solvent) is relatively small, so the second intermediate can automatically precipitate after being generated, thereby improving the selectivity and yield of the second intermediate.

[0038] In order to improve the yield and selectivity of the second intermediate, preferably, in the esterification reaction, the first intermediate, p-toluenesulfonic acid and C5-C 10 The molar ratio of alkanes 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 comprises subjecting the second intermediate and aqueous ammonia to a reflux reaction at 50-70° C. for 120-180 min to obtain a third intermediate. Preferably, in the amidation reaction, the molar ratio of the second intermediate to aqueous ammonia is 1:(10-15). The molar ratio of the second intermediate to aqueous ammonia includes but is not limited to the above range, and limiting it within the above range is conducive to further improving the yield of the third intermediate.

[0040] In order to make the above raw materials react more fully, preferably, the preparation process of the above third intermediate is carried out in a third organic solvent. As long as the above effect can be achieved, the type of the third organic solvent is not specifically limited. More preferably, the above third organic solvent includes but is not limited to butanol.

[0041] In a preferred embodiment, the substitution reaction comprises: reacting the third intermediate with a dihalogenated hydrocarbon under the 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 can be optimized. Preferably, the amount of substance ratio of the third intermediate to the dihalogenated hydrocarbon is 1: (2 to 10), the reaction temperature is 70 to 90 ° C, and the reaction time is 10 to 12 hours. More preferably, the dihalogenated hydrocarbon includes but is not limited to one or more of the group consisting of dibromoethane, dibromopropane, dibromobutane, dibromopentane and dibromohexane.

[0042] In a preferred embodiment, during the phosphonate synthesis reaction, the molar ratio of the fourth intermediate to trialkylphosphite 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, it is beneficial to further improve the yield of the target product.

[0043] The third aspect of the present application further provides a perovskite additive, which includes the asymmetric perylene organic compound or the asymmetric perylene organic compound prepared by the above-mentioned preparation method.

[0044] Since the above-mentioned asymmetric perylene organics can significantly improve the efficiency and stability of perovskite devices during application, the perovskite additives containing the above-mentioned asymmetric perylene organics can also achieve the above-mentioned effects.

[0045] The fourth aspect of the present application also provides a perovskite film, which contains the above-mentioned asymmetric perylene perovskite additive. After the asymmetric perylene organic matter having the above-mentioned structure is applied to the passivated perovskite film, the phosphate group and the trifluoromethyl group can passivate the grain boundary and surface defects in the perovskite film, improve the charge transfer at the grain boundary and the surface, the F atom can improve the hydrophobicity of the surface of the perovskite film, the perovskite film can form a hydrogen bond with -N to inhibit the migration of methylamine and formamidine 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 includes the perovskite film provided by the present application. Compared with the prior art, the present invention can effectively passivate grain boundaries and surface defects, improve charge transfer, inhibit ion migration, and improve the efficiency and stability of perovskite thin film batteries by adding multifunctional asymmetric perylene perovskite additives to prepare perovskite films.

[0047] The present application is further described in detail below in conjunction with specific embodiments. These embodiments should not be construed as limiting the scope of protection claimed in the present application.

[0048] Example 1

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

[0050]

[0051] Perylenetetracarboxylic dianhydride (1.0 eq, 100 mg), trifluoroethanol (4.0 eq, 102.0 mg), and DBU (4.0 eq, 15.2 mg) were weighed and added to 50 ml of DMF solvent and heated at 60° C. for reaction for 30 min.

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

[0053] 1H NMR (500MHz, CDCl3): 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] Weigh monomer M11 (1.0eq, 100mg), p-toluenesulfonic acid (1.1eq, 25.0mg), and 10mL of heptane and react at 90°C for 6h. After the reaction is completed, cool to room temperature and filter to obtain a crude product (orange precipitate). Wash the above orange precipitate with methanol and water and dry it. Subsequently, reflux the dried orange precipitate in 100mL of methanol for 2h. Cool to room temperature and filter to obtain a residue. Finally, dissolve the dried residue in dichloromethane, filter to obtain the filtrate, and remove the solvent by rotary evaporation to obtain the target product M21 (63mg, yield 83.2wt%).

[0057] 1H NMR (500MHz, CDCl3): 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 water (10 mL), and butanol (10 mL) were weighed and refluxed at 80° C. for 12 h. After the reaction, the solvent was removed by a rotary evaporator, and the crude product was separated and purified by column chromatography to obtain monomer M31 (60.2 mg, yield 60.3 wt%).

[0061] 1H NMR (500MHz, CDCl3): 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 weighed and 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 the reaction was completed, dichloromethane was used for extraction, and the organic layer was retained. The organic layer was dried over anhydrous Na2SO4. The raffinate was distilled under reduced pressure. The crude product was purified by column chromatography to obtain M41 (102 mg, yield 86 wt%).

[0065] 1H NMR (500MHz, CDCl3): 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 weighed and dissolved in triethyl phosphite (20 eq, 488 mg), and the reaction mixture was heated at 140°C overnight. After the reaction was completed, the solvent was distilled off under reduced pressure. The crude product was purified by column chromatography to obtain M51 (90 mg, yield 83%).

[0069] 1H NMR (500MHz, CDCl3): 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 perylenetetracarboxylic dianhydride, halohydrin, fluoroalkane 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 perylenetetracarboxylic dianhydride, halogenated alcohol, fluoroalkane 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 perylenetetracarboxylic dianhydride, halogenated alcohol, fluoroalkane and catalyst is 1:1.5:1.5:3. The yield of M11 is 60.26 wt %, and the yield of M51 is 58 wt %.

[0076] Example 6

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

[0078] Example 7

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

[0080] Example 8

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

[0082] Example 9

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

[0084] Example 10

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

[0086] Embodiment 11

[0087] The difference from Example 1 is that in the preparation process of the third intermediate, the molar ratio of the second intermediate to ammonia water 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 in the preparation process of the fourth intermediate, the molar ratio of the third intermediate, sodium hydride and dihalogenated hydrocarbon is 1:1.5:2. The yield of M41 is 85wt%, and the yield of M51 is 83wt%.

[0090] Embodiment 13

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

[0092] Embodiment 14

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

[0094] Embodiment 15

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

[0096] Example 16

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

[0098] Embodiment 17

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

[0100] Device preparation:

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

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

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

[0104] Preparation of the active layer of the experimental example device: A 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), formamidine hydroiodide (FAI), methylamine hydrobromide (MABr), and methylamine hydrochloride (MACl). The solvent used was a mixed solvent of DMF and DMSO with a volume ratio of 4:1. 5wt% of the additive material M51 was added to the above solution. After mixing evenly, the perovskite active layer was prepared by spin coating. The spin coating conditions were 2000rpm, 40s, and then 5000rpm, 20s. 15s before the end of the spin coating process, 200μL of chlorobenzene was dropped into the center of the substrate. After the rotation stopped, the substrate was immediately transferred to a heating plate at 100°C and annealed for 15min. The SEM electron microscope image of the active layer of the experimental example device is shown in Figure 1 and 2 .

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

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

[0107] An interface layer was prepared on the PCBM film prepared above, and a thin BCP layer was deposited on the PCBM by spin coating, followed by annealing at 100° C. for 10 min.

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

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

[0110] Battery performance test

[0111] The obtained solar cell device was tested for photovoltaic performance, and the effective area of ​​the device was 4mm 2 ; Test conditions: spectral distribution AM1.5G, light intensity 100mW / cm 2 AAA solar simulator (Keithley Instruments, USA). JV curve was measured by Keithly 2400 digital source meter. All devices were simply packaged with UV glue and measured in the atmosphere. 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 invention achieve the following technical effects: compared with the prior art, the present invention prepares perovskite thin films by adding multifunctional asymmetric perylene perovskite additives, which can effectively passivate grain boundaries and surface defects, improve charge transfer, inhibit ion migration, and improve the efficiency and stability of perovskite thin film batteries.

[0115] It should be noted that the terms "first", "second", etc. in the specification and claims of the present application are used to distinguish similar objects, and are not necessarily used to describe a specific order or sequence. It should be understood that the terms used in this way can be interchangeable where appropriate, so that the embodiments of the present application described herein can be implemented in an order other than those described herein, for example.

[0116] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

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

2. A method for preparing an asymmetric perylene organic compound according to claim 1, characterized in that: The preparation method of the asymmetric perylene organic compound comprises: Under the action of a catalyst, perylenetetracarboxylic dianhydride, a halogenated alcohol and a fluoroalkane are sequentially subjected to anhydride esterification reaction and a substitution reaction to obtain a first intermediate having a structure shown in formula (II); In p-toluenesulfonic acid and C5~C 10 In the presence of an alkane, the first intermediate undergoes a partial cyclization reaction to obtain a second intermediate, wherein the second intermediate has a structure represented by formula (III); The second intermediate and aqueous ammonia react to form a third intermediate, wherein the third intermediate has a structure shown in formula (IV); The third intermediate and dihalogenated hydrocarbon undergo a substitution reaction to obtain a fourth intermediate, wherein the fourth intermediate has a structure shown in formula (V); The fourth intermediate and trialkylphosphorous acid undergo a phosphonate synthesis reaction to obtain the asymmetric perylene organic compound; 3. The method for preparing asymmetric perylene organic compounds according to claim 2, characterized in that: 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 perylenetetracarboxylic dianhydride, the halogenated alcohol, the fluoroalkane 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.

4. The method for preparing asymmetric perylene organic compounds according to claim 2, characterized in that: In the ester hydrolysis reaction, the first intermediate, the p-toluenesulfonic acid and the C5-C 10 The molar ratio of the alkanes 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.

5. The method for preparing asymmetric perylene organic compounds according to claim 2, characterized in that: The amidation reaction comprises subjecting the second intermediate and the aqueous ammonia to a reflux reaction at 50 to 70° C. for 120 to 180 minutes; Preferably, in the amidation reaction, the molar ratio of the second intermediate to the aqueous ammonia is 1:(10-15).

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

7. The method for preparing asymmetric perylene organic compounds according to claim 2, characterized in that: During 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° C., and the reaction time is 10-12 hours.

8. A perovskite additive, characterized in that: The perovskite additive comprises the asymmetric perylene organic compound according to claim 1 or the asymmetric perylene organic compound prepared by the preparation method according to any one of claims 2 to 7.

9. A perovskite film, characterized in that: The perovskite film comprises the asymmetric perylene perovskite additive according to claim 8.

10. A solar cell, characterized in that: The solar cell comprises the perovskite film according to claim 9.

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