A thienyl carbinol derivative material, preparation method and application thereof

Abstract

The present application relates to the technical field of organic optoelectronic materials, in particular to a thiophene secondary amine ester derivative material, a preparation method and application thereof.The molecular structure of the thiophene secondary amine ester derivative material is shown in the general formula; wherein R1-R5 are independently selected from hydrogen or halogen; L1 is methyl, ethyl or isopropyl.In the thiophene secondary amine ester derivative material, the sulfur atom in the thiophene ring can form a strong coordination bond with the uncoordinated Pb 2+ of the perovskite surface, the N-H bond in the secondary amino group can form a hydrogen bond with the iodine vacancy in the peroviskite, and the ester group can improve the solubility of the molecule in the organic solvent, ensuring the formation of a uniform passivation layer, thereby achieving efficient and comprehensive passivation of the surface and grain boundary defects of the peroviskite thin film, significantly reducing the probability of non-radiative recombination of carriers, and solving the problems of weak interfacial interaction, limited passivation effect and poor long-term stability of the existing organic small molecule passivation agent.

Description

Technical Field

[0001] This invention relates to the field of organic optoelectronic materials technology, specifically to a thiophene secondary urethane derivative material, its preparation method, and its application. Background Technology

[0002] Perovskite solar cells have become a research hotspot in the photovoltaic field due to their outstanding advantages such as high photoelectric conversion efficiency, low fabrication cost, and good solution processability, and have great potential for industrial application. However, perovskite thin films are prone to generating a large number of surface defects during the fabrication process, such as uncoordinated Pb. 2+ Defects such as iodine vacancies and grain boundary defects lead to severe nonradiative recombination of charge carriers, significantly reducing the open-circuit voltage and fill factor of the cell, thus limiting the improvement of photoelectric conversion efficiency. Simultaneously, the presence of these defects accelerates the photodegradation, thermal degradation, and water-oxygen degradation of perovskite materials, severely affecting the long-term stability of the cell. This is a critical issue that urgently needs to be addressed in the industrialization of perovskite solar cells.

[0003] To address these issues, researchers have developed various defect passivation strategies. Among them, organic small-molecule passivators have attracted widespread attention due to their strong structural tunability, low preparation cost, and good compatibility with perovskites. Currently reported organic small-molecule passivators mainly include compounds such as amines, carboxylic acids, thiols, and ureas. These compounds achieve passivation effects by forming coordination or hydrogen bonding interactions between their functional groups and perovskite surface defects. However, existing passivators generally suffer from several drawbacks: some have insufficient interaction strength with perovskites, resulting in limited passivation effects; some have poor solubility, making it difficult to form a uniform passivation layer; and some have poor inherent stability, easily decomposing or migrating during long-term use, leading to insignificant improvements in battery stability. Summary of the Invention

[0004] To address the technical problems of limited passivation effect and poor long-term device stability caused by the weak interfacial strength, poor solubility, and insufficient chemical stability of existing organic small molecule passivators, this invention provides a thiophene secondary urethane derivative material, its preparation method, and its application.

[0005] Thiophene secondary amine derivatives are a class of multifunctional organic molecules containing multiple functional groups, including a thiophene ring, a secondary amino group, and an ester group. The π electrons of the thiophene ring can form π-π interactions with the perovskite lattice; the NH bonds of the secondary amino group can form hydrogen bonds or coordination bonds with perovskite surface defects; and the ester group can regulate the solubility of the molecule and its interfacial compatibility with perovskite films. Given the excellent conjugated electronic effect and strong coordinating ability of sulfur atoms in thiophene compounds, this invention aims to utilize thiophene secondary amine derivatives as interfacial passivating agents for perovskite films in perovskite solar cells.

[0006] To achieve the above objectives, the technical solution of the present invention is as follows.

[0007] The first aspect of this invention provides a thiophene secondary amine derivative material, the general molecular structure of which is shown below: ; R1 to R5 are each independently selected from hydrogen or halogen; L1 is methyl, ethyl or isopropyl.

[0008] Preferably, R1 to R5 are each independently selected from hydrogen or F; and R1 to R5 are not all H at the same time.

[0009] Preferably, the thiophene secondary amino ester derivative material is any one of the following compounds: .

[0010] A second aspect of the present invention provides a method for preparing a thiophene secondary amino ester derivative material, comprising the following steps: Using compounds shown in Formula 1 and Formula 2 as starting materials, a coupling reaction was carried out under the action of a first catalyst, a ligand, a first base, and a first solvent to obtain the compound shown in Formula 3; using compounds shown in Formula 3 and Formula 4 as starting materials, a coupling reaction was carried out under the action of a second catalyst, a second base, and a second solvent to obtain the thiophene secondary amine derivative material shown in Formula 5; the synthetic route of the thiophene secondary amine derivative material is as follows: .

[0011] In this invention, the preparation process of the thiophene secondary amine derivative material is simple and inexpensive, and it is suitable for solution processing. It is compatible with existing perovskite solar cell fabrication processes, requiring no additional equipment and possessing promising prospects for large-scale industrial application. The thiophene secondary amine derivative material is prepared by obtaining a high-purity product through an organic synthesis reaction. In application, it is coated onto the perovskite surface using a spin-coating process, followed by the deposition of an electron transport layer and an Ag electrode.

[0012] Preferably, the molar ratio of the compound shown in Formula 1 to the compound shown in Formula 2 is 1:1 to 5; and the molar ratio of the compound shown in Formula 3 to the compound shown in Formula 4 is 1:1 to 5.

[0013] Preferably, the first catalyst and the second catalyst are independently selected from tris(dibenzylacetone)palladium or tetra(triphenylphosphine)palladium; the ligand is 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl; the first base and the second base are independently selected from cesium carbonate or potassium carbonate; the first solvent is toluene; and the second solvent is a mixture of tetrahydrofuran and water.

[0014] Preferably, the amount of the first catalyst is 3.1% to 3.2% of the molar percentage of the compound shown in Formula 1; the amount of the ligand is 5.3% to 5.4% of the molar percentage of the compound shown in Formula 1; the molar ratio of the compound shown in Formula 1 to the first base is 1:2 to 2.2; the amount of the second catalyst is 4.9% to 5% of the molar percentage of the compound shown in Formula 3; and the molar ratio of the compound shown in Formula 3 to the second base is 1:2 to 2.2.

[0015] Preferably, the coupling reaction process of the compound shown in Formula 3 and the thiophene secondary amino ester derivative material shown in Formula 5 is carried out under reflux conditions.

[0016] Preferably, the ratio of the compound shown in Formula 1 to the first solvent is 1 mmol: 2 mL to 3 mL; and the ratio of the compound shown in Formula 3 to the second solvent is 1 mmol: 4 mL to 5 mL.

[0017] The third aspect of this invention provides the application of a thiophene secondary urethane derivative material as an interface passivator for perovskite thin films in the preparation of perovskite solar cells.

[0018] A perovskite solar cell comprises a transparent conductive substrate and a self-assembled monolayer deposited on the substrate. The self-assembled monolayer consists of a hole transport layer, a perovskite light-absorbing layer, an interface passivation layer, an electron transport layer, and a metal electrode sequentially deposited on the transparent conductive substrate. The interface passivation layer is a thiophene secondary urethane derivative material as described in the first aspect. The interface passivation layer is located between the perovskite light-absorbing layer and the electron transport layer. The perovskite thin film serves as the perovskite light-absorbing layer.

[0019] The beneficial effects of this invention are: 1. The thiophene secondary urethane derivative material of the present invention has a unique synergistic effect of multiple functional groups: the sulfur atom in the thiophene ring can interact with the uncoordinated Pb on the perovskite surface. 2+ By forming strong coordination bonds, the NH bond in the secondary amino group can form hydrogen bonds with the iodine vacancy in the perovskite, while the ester group can enhance the solubility of the molecule in organic solvents, ensuring the formation of a uniform passivation layer. This achieves efficient and all-round passivation of perovskite film surface and grain boundary defects, significantly reducing the probability of nonradiative recombination of charge carriers.

[0020] 2. The thiophene secondary amine derivative material of the present invention can serve as an interface passivator for perovskite thin films. This interface passivator has a core structure of nitrogen-containing heterocycles (pyridine / amidinyl) and sulfur / oxygen functional groups, which can specifically modify the in-interface (between the perovskite light-absorbing layer and the n-type electron transport layer) of inverted perovskite solar cells. The present invention achieves efficient passivation of perovskite thin film defects through the synergistic effect of multiple functional groups in the thiophene secondary amine derivative material, simultaneously improving the photoelectric conversion efficiency and long-term stability of the solar cell.

[0021] 3. The thiophene secondary urethane derivative material of the present invention serves as an interface passivating agent, through the interaction of heterocyclic nitrogen atoms with uncoordinated Pb on the perovskite surface. 2+ Stable coordination bonds are formed, while sulfur / oxygen functional groups fill iodine vacancies, providing dual passivation of interface defects, accelerating electron extraction, and suppressing nonradiative recombination. Devices based on this interface passivator achieve a photoelectric conversion efficiency (PCE) of 21.37%, significantly better than those using traditional passivators. This invention optimizes the problems of high interface defect density, severe carrier recombination, and poor stability in existing in-interface systems, and its fabrication process is simple, low-cost, and suitable for large-scale production. Attached Figure Description

[0022] Figure 1 This is a schematic diagram of the structure of an inverse perovskite solar cell based on a thiophene secondary urethane derivative material according to an embodiment of the present invention. Wherein, 1 is a transparent conductive substrate; 2 is a hole transport layer; 3 is a perovskite light-absorbing layer; 4 is an interface passivation layer; 5 is a C60 thin film; 6 is a BCP thin film; and 7 is an Ag electrode.

[0023] Figure 2 This is a comparison chart of the JV characteristic curves of inverted perovskite solar cells from Application Examples 1 to 6 and Comparative Examples 1 to 2.

[0024] Figure 3 These are electron microscope (EM) images of the perovskite light-absorbing layer surfaces of Comparative Example 1, Application Example 1, and Application Example 5. Specifically, (a) is an EEM image of the perovskite light-absorbing layer surface of Comparative Example 1; (b) is an EEM image of the perovskite light-absorbing layer surface of Application Example 1; and (c) is an EEM image of the perovskite light-absorbing layer surface of Application Example 5.

[0025] Figure 4 This is the 1H NMR spectrum of compound 1.

[0026] Figure 5 This is the 1H NMR spectrum of compound 2.

[0027] Figure 6 This is the hydrogen NMR spectrum of compound 3.

[0028] Figure 7 This is the hydrogen NMR spectrum of compound 4.

[0029] Figure 8 This is the hydrogen NMR spectrum of compound 5.

[0030] Figure 9 This is the hydrogen NMR spectrum of compound 6. Detailed Implementation

[0031] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0032] Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0033] Figure 1 This is a schematic diagram of the structure of an inverted perovskite solar cell based on a thiophene secondary amino ester derivative material in an embodiment of the present invention.

[0034] like Figure 1 The perovskite solar cell comprises a transparent conductive substrate 1 and a self-assembled monolayer deposited on the transparent conductive substrate 1. The self-assembled monolayer is formed by sequentially depositing a hole transport layer 2, a perovskite light-absorbing layer 3, an interface passivation layer 4, an electron transport layer, and an Ag electrode 7 on the transparent conductive substrate 1. The interface passivation layer 4 is a thiophene secondary urethane derivative material as described in this invention. The interface passivation layer 4 is located between the perovskite light-absorbing layer 4 and the electron transport layer. A perovskite thin film serves as the perovskite light-absorbing layer. The electron transport layer includes a C60 thin film 5 and a BCP thin film 6, which are formed by evaporating the C60 thin film 5 and the BCP thin film 6 onto the surface of the interface passivation layer 4.

[0035] Preferably, the perovskite solar cell is an inverted perovskite solar cell; the method for preparing the perovskite solar cell includes the following steps: Preparation of perovskite precursor solution: The FA was prepared by dissolving FAI (formamidinium iodide, CH(NH2)2I), CsI, and PbI2 in a DMF / DMSO mixed solvent with a volume ratio of 4:1 according to a mass ratio of 12.55:1:35.46 (228.4 mg FAI, 18.2 mg CsI, 645.4 mg PbI2). The solution was shaken and dissolved for 2 hours. 0.95 Cs 0.05 PbI3 perovskite precursor solution. The perovskite precursor solution was obtained by filtration through a 0.22 μm polytetrafluoroethylene filter membrane before spin coating.

[0036] Preparation of perovskite thin films: Substrate pretreatment: A clean conductive substrate was treated with a UV ozone cleaner for 15 minutes to remove surface organic impurities. NiO was then prepared. xLayer: High-purity H2O was used to dissolve nano-nickel oxide to prepare a nano-nickel oxide solution with a concentration of 2.5 mg / mL to 20 mg / mL. The solution was sonicated for 5 min, filtered through a 0.22 μm hydrophilic filter (PES), and the nano-nickel oxide solution was spin-coated at 3000 rpm for 20 s. Annealing was then performed at 100℃ to 150℃ for 10 min to prepare NiO on the surface of a transparent conductive substrate. x layer.

[0037] Then, [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (MeO-2PACz) was used as the material for the hole transport layer. The compound [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (MeO-2PACz) was mixed with anhydrous ethanol to obtain a hole transport layer solution with a concentration of 0.5 mg / mL. 100 μL of the coating solution was pipetted onto the bottom electrode and spin-coated at 3000 rpm for 30 s. After spin-coating, the solution was annealed on a hot plate at 100 °C for 10 min and then allowed to cool naturally to obtain the hole transport layer.

[0038] The perovskite precursor solution was uniformly drop-coated onto the pretreated substrate surface using a two-step spin-coating process: first, spin-coating at 1000-2000 rpm for 10 seconds (ensuring uniform solution coverage of the substrate), followed by spin-coating at 3000-5000 rpm for 30 seconds; 8 seconds before the end of spin-coating, 100-200 μL of chlorobenzene was dropped onto the substrate edge as an anti-solvent to promote rapid perovskite crystallization. The spin-coated substrate was immediately placed on a hot plate at 100-130℃ for annealing for 10-20 minutes, and then naturally cooled to room temperature to obtain a dense, pinhole-free, and highly crystalline perovskite film; that is, a perovskite light-absorbing layer was formed on the hole transport layer.

[0039] The thiophene secondary urethane derivative material was used as an interface passivating agent and dissolved in ethanol to prepare a passivation solution of the corresponding concentration. The solution was dynamically spin-coated at 3000 r for 30 s and then immediately placed on a heating table for annealing at 100 °C for 10 min to form an interface passivation layer on the surface of the perovskite light-absorbing layer.

[0040] Inverse cell assembly (ITO / hole transport layer / perovskite / electron transport layer / electron): An electron transport layer (C) is deposited on the surface of the interface passivation layer. 60 (and BCP); then Ag electrode (thickness 100nm~120nm) is deposited by vapor deposition. Device encapsulation: the prepared battery device is encapsulated with UV-curable adhesive to avoid external water vapor and oxygen corrosion, thus obtaining an inverted perovskite solar cell.

[0041] The technical solution of the present invention will be further described below through specific embodiments.

[0042] In the following embodiments, unless otherwise specified, the methods described are conventional methods; and unless otherwise specified, the reagents and materials described are commercially available.

[0043] 2-Dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl, abbreviated as x-phos, has the following molecular structure: .

[0044] Formamidinium iodide, with the chemical formula CH(NH2)2I, is abbreviated as FAI.

[0045] Cesium iodide has the chemical formula CsI; lead iodide has the chemical formula PbI2.

[0046] Indium tin oxide, abbreviated as ITO, is a type of conductive glass substrate.

[0047] Photoelectric conversion efficiency, abbreviated as PCE. Open-circuit voltage, abbreviated as V. OC Short-circuit current density, known in English as J of Short Circuit, is abbreviated as J. SC The fill factor, abbreviated as FF, is the English name for the fill factor.

[0048] Example 1 A thiophene secondary amino ester derivative material, the molecular structural formula of which is: .

[0049] The preparation method of thiophene secondary amino ester derivative materials includes the following steps: Synthesis of S1 and Intermediate 1: 62.0 mmol of 2,5-dibromothiophene, 58.90 mmol of methyl anthranilate, 124 mmol of cesium carbonate, 1.86 mmol of tris(dibenzylacetone)dipalladium, 3.72 mmol of x-phos, and 150 mL of toluene solvent were added to a reaction flask. The mixture was heated to reflux for 7 h. After the reaction was complete, the reaction mixture was extracted with water and ethyl acetate, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The product was then separated by column chromatography using hexane and ethyl acetate in a volume ratio of 20:1 to obtain Intermediate 1. The product yield was 77.1%. The synthetic route for Intermediate 1 is as follows: .

[0050] Synthesis of S2 and Compound 1: Intermediate 1 (19.22 mmol), 4-fluorophenylboronic acid (24.99 mmol), potassium carbonate (38.44 mmol), tetra(triphenylphosphine)palladium (0.96 mmol), tetrahydrofuran (70 mL), and deionized water (18 mL) were added to a reaction flask. The gas was purged with nitrogen, and the mixture was heated to 60 °C for 18 h. After the reaction, the solvent was concentrated to dryness, and the mixture was extracted with ethyl acetate and water. The extract was dried over anhydrous sodium sulfate, and the solvent was concentrated under reduced pressure. The reaction product was then separated by column chromatography using hexane and ethyl acetate in a volume ratio of 20:1 to obtain Compound 1, which is the thiophene secondary amino ester derivative. The product yield was 69.6%. The synthetic route for Compound 1 is as follows:

[0051] .

[0052] The detection results of the proton NMR spectrum of compound 1 are as follows: Figure 4 As shown.

[0053] Example 2 A thiophene secondary amino ester derivative material, the molecular structural formula of which is: .

[0054] The preparation method of thiophene secondary amino ester derivative materials includes the following steps: Synthesis of S1 and Intermediate 2: 49.60 mmol of 2,5-dibromothiophene, 47.12 mmol of ethyl 2-aminobenzoate, 99.20 mmol of cesium carbonate, 1.49 mmol of tris(dibenzylacetone)dipalladium, and 2.98 mmol of x-phos were added to a reaction flask along with 120 mL of toluene. The mixture was heated to reflux for 7 h. After the reaction was complete, the reaction mixture was extracted with water and ethyl acetate, dried over anhydrous sodium sulfate, and the solvent was concentrated under reduced pressure. The product was then separated by column chromatography using hexane and ethyl acetate in a volume ratio of 20:1 to obtain intermediate 2. The product yield was 72.5%. The synthetic route for intermediate 2 is as follows: .

[0055] Synthesis of S2 and Compound 2: 15.33 mmol of intermediate 2, 18.39 mmol of 4-fluorophenylboronic acid, 30.66 mmol of potassium carbonate, 0.46 mmol of tetra(triphenylphosphine)palladium, 40 mL of tetrahydrofuran, and 10 mL of deionized water were added to a reaction flask. The atmosphere was purged with nitrogen, and the mixture was heated to 60 °C for 18 h. After the reaction, the solvent was concentrated to dryness, extracted with ethyl acetate and water, dried over anhydrous sodium sulfate, and the solvent was concentrated under reduced pressure. The reaction product was then separated by column chromatography using hexane and ethyl acetate in a volume ratio of 20:1 to obtain compound 2, which is the thiophene secondary amino ester derivative. The product yield was 71.8%. The synthetic route for compound 2 is as follows:

[0056] The detection results of the proton NMR spectrum of compound 2 are as follows: Figure 5 As shown.

[0057] Example 3 A thiophene secondary amino ester derivative material, the molecular structural formula of which is: .

[0058] The preparation method of thiophene secondary amino ester derivative materials includes the following steps: Synthesis of S1 and Intermediate 3: 53.73 mmol of 2,5-dibromothiophene, 51.05 mmol of isopropyl anthranilate, 107.4 mmol of cesium carbonate, 1.61 mmol of tris(dibenzylacetone)dipalladium, and 3.22 mmol of x-phos were added to a reaction flask along with 130 mL of toluene. The mixture was heated to reflux for 7 h. After the reaction was complete, the reaction mixture was extracted with water and ethyl acetate, dried over anhydrous sodium sulfate, and the solvent was concentrated under reduced pressure. The product was then separated by column chromatography using hexane and ethyl acetate in a volume ratio of 20:1 to obtain intermediate 3. The product yield was 67.3%. The synthetic route for intermediate 3 is as follows: .

[0059] Synthesis of S2 and Compound 3: Intermediate 3 (14.7 mmol), 4-fluorophenylboronic acid (17.63 mmol), potassium carbonate (29.39 mmol), tetra(triphenylphosphine)palladium (0.44 mmol), tetrahydrofuran (40 mL), and deionized water (10 mL) were added to a reaction flask. The atmosphere was purged with nitrogen, and the mixture was heated to 60 °C for 18 h. After the reaction, the solvent was concentrated to dryness, extracted with ethyl acetate and water, dried over anhydrous sodium sulfate, and the solvent was concentrated under reduced pressure. The reaction product was then separated by column chromatography using hexane and ethyl acetate in a volume ratio of 20:1 to obtain compound 3, which is the thiophene secondary amino ester derivative. The product yield was 53.6%. The synthetic route for compound 3 is as follows:

[0060] The detection results of the proton NMR spectrum of compound 3 are as follows: Figure 6 As shown.

[0061] Example 4 A thiophene secondary amino ester derivative material, the molecular structural formula of which is: .

[0062] The preparation method of thiophene secondary amino ester derivative materials includes the following steps: Synthesis of Intermediate 1 (S1): The method of Example 1 was followed. 62.0 mmol of 2,5-dibromothiophene, 58.90 mmol of methyl anthranilate, 124 mmol of cesium carbonate, 1.86 mmol of tris(dibenzylacetone)dipalladium, 3.72 mmol of x-phos, and 150 mL of toluene were added to the reaction flask. The mixture was heated to reflux for 7 h. After the reaction, the reaction mixture was extracted with water and ethyl acetate, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The product was then separated by column chromatography using hexane and ethyl acetate in a volume ratio of 20:1 to obtain Intermediate 1. The product yield was 77.1%. The synthetic route for Intermediate 1 is as follows:

[0063] .

[0064] Synthesis of S2 and Compound 4: Intermediate 1 (22.42 mmol), 2,3,4,5,6-pentafluorophenylboronic acid (26.91 mmol), potassium carbonate (44.85 mmol), tetra(triphenylphosphine)palladium (1.12 mmol), tetrahydrofuran (70 mL), and deionized water (15 mL) were added to a reaction flask. The atmosphere was purged with nitrogen, and the mixture was heated to 60 °C for 18 h. After the reaction, the solvent was concentrated to dryness, extracted with ethyl acetate and water, dried over anhydrous sodium sulfate, and the solvent was concentrated under reduced pressure. The reaction product was then separated by column chromatography using hexane and ethyl acetate in a volume ratio of 20:1 to obtain compound 4, which is the thiophene secondary amino ester derivative. The product yield was 58.7%. The synthetic route for compound 4 is as follows:

[0065] The detection results of the proton NMR spectrum of compound 4 are as follows: Figure 7 As shown.

[0066] Example 5 A thiophene secondary amino ester derivative material, the molecular structural formula of which is: .

[0067] The preparation method of thiophene secondary amino ester derivative materials includes the following steps: Synthesis of S1 and Intermediate 2: The method of Example 2 was followed. 49.60 mmol of 2,5-dibromothiophene, 47.12 mmol of ethyl 2-aminobenzoate, 99.20 mmol of cesium carbonate, 1.49 mmol of tris(dibenzylacetone)dipalladium, and 2.98 mmol of x-phos were added to a reaction flask along with 120 mL of toluene. The mixture was heated to reflux for 7 h. After the reaction was complete, the reaction mixture was extracted with water and ethyl acetate, dried over anhydrous sodium sulfate, and the solvent was concentrated under reduced pressure. The product was then separated by column chromatography using hexane and ethyl acetate in a volume ratio of 20:1 to obtain intermediate 2. The product yield was 72.5%. The synthetic route for intermediate 2 is as follows:

[0068] .

[0069] Synthesis of S2 and Compound 5: Intermediate 2 (18.39 mmol), 2,3,4,5,6-pentafluorophenylboronic acid (23.91 mmol), potassium carbonate (36.79 mmol), tetra(triphenylphosphine)palladium (0.55 mmol), tetrahydrofuran (48 mL), and deionized water (12 mL) were added to a reaction flask. The atmosphere was purged with nitrogen, and the mixture was heated to 60 °C for 18 h. After the reaction, the solvent was concentrated to dryness, extracted with ethyl acetate and water, dried over anhydrous sodium sulfate, and the solvent was concentrated under reduced pressure. The reaction product was then separated by column chromatography using hexane and ethyl acetate in a volume ratio of 20:1 to obtain compound 5, which is the thiophene secondary amino ester derivative. The product yield was 58.7%. The synthetic route for compound 5 is as follows:

[0070] The detection results of the proton NMR spectrum of compound 5 are as follows: Figure 8 As shown.

[0071] Example 6 A thiophene secondary amino ester derivative material, the molecular structural formula of which is: .

[0072] The preparation method of thiophene secondary amino ester derivative materials includes the following steps: Synthesis of S1 and Intermediate 3: The method of Example 3 was followed. 53.73 mmol of 2,5-dibromothiophene, 51.05 mmol of isopropyl anthranilate, 107.4 mmol of cesium carbonate, 1.61 mmol of tris(dibenzylacetone)dipalladium, 3.22 mmol of x-phos, and 130 mL of toluene solvent were added to the reaction flask. The mixture was heated to reflux for 7 h. After the reaction, the reaction mixture was extracted with water and ethyl acetate, dried over anhydrous sodium sulfate, and the solvent was concentrated under reduced pressure. The product was then separated by column chromatography using hexane and ethyl acetate in a volume ratio of 20:1 to obtain intermediate 3. The product yield was 67.3%. The synthetic route of intermediate 3 is as follows:

[0073] .

[0074] Synthesis of S2 and Compound 6: Intermediate 3 (17.63 mmol), 2,3,4,5,6-pentafluorophenylboronic acid (22.93 mmol), potassium carbonate (35.27 mmol), tetra(triphenylphosphine)palladium (0.88 mmol), tetrahydrofuran (48 mL), and deionized water (12 mL) were added to a reaction flask. The atmosphere was purged with nitrogen, and the mixture was heated to 60 °C for 18 h. After the reaction, the solvent was concentrated to dryness, extracted with ethyl acetate and water, dried over anhydrous sodium sulfate, and the solvent was concentrated under reduced pressure. The reaction product was then separated by column chromatography using hexane and ethyl acetate in a volume ratio of 20:1 to obtain compound 6, which is the thiophene secondary amino ester derivative. The product yield was 59.1% (4.45 g). The synthetic route for compound 6 is as follows:

[0075] The detection results of the proton NMR spectrum of compound 6 are as follows: Figure 9 As shown.

[0076] Application Example 1 The method for fabricating an inverted perovskite solar cell based on Example 1 includes the following steps: S1. Dissolve 228.4 mg FAI, 18.2 mg CsI, and 645.4 mg PbI2 in a DMF / DMSO mixed solvent with a volume ratio of 4:1, and shake to dissolve for 2 hours to prepare FA. 0.95 Cs 0.05 PbI3 perovskite precursor solution.

[0077] S2. Take a 2cm×2cm ITO substrate, clean it with UV ozone for 15min, spin coat it with a 10mg / mL nano nickel oxide solution at 3000rpm for 30s, then immediately place it on a heating table to anneal at 150℃ for 15min, and then remove it and let it sit at room temperature for later use.

[0078] S3. [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid (MeO-2PACz) was mixed with ultra-dry ethanol to obtain a hole transport material solution with a concentration of 1 mmol / L. The obtained hole transport layer solution was spin-coated onto the surface of a prepared ITO transparent conductive substrate and annealed at 100°C for 10 min to obtain a hole transport layer.

[0079] S4, FA in S1 0.95 Cs 0.05 50 μL of PbI3 perovskite precursor solution was drop-coated onto the hole transport layer of an ITO transparent conductive substrate using a two-step spin-coating process: spin-coating at 1500 rpm for 10 s and spin-coating at 4000 rpm for 25 s. 150 μL of chlorobenzene was added 5 s before the end of spin-coating. The spin-coated substrate was immediately placed on a hot plate at 120℃ for annealing for 15 min. After cooling, a perovskite film was obtained, which is a perovskite light-absorbing layer formed on the hole transport layer.

[0080] S5. Dissolve the thiophene secondary amino ester derivative material from Example 1 in ethanol to prepare a passivation solution with a concentration of 0.5 mg / mL. Spin-coat the solution onto the substrate surface at 3000 rpm for 30 seconds, and immediately place it on a heating table to anneal at 100°C for 10 minutes to form an interface passivation layer on the surface of the perovskite light-absorbing layer.

[0081] S6. Transfer to the vacuum evaporation chamber, under a vacuum degree of 5×10 -4 Evaporation under Pa C 60 The thin film is 25 nm thick, the BCP thin film is 6 nm thick, and the evaporation rate is 0.1 nm / s, forming C on the surface of the interface passivation layer. 60 / BCP electron transport layer; then in C 60 An Ag electrode with a thickness of 110 nm is deposited on the surface of the BCP electron transport layer at a deposition rate of 0.1 nm / s, and the Ag electrode area is 0.09 cm². 2 .

[0082] S7. Encapsulate the device with UV-curable adhesive to obtain an inverted perovskite solar cell.

[0083] S8. Performance Testing: Under AM 1.5G simulated sunlight (100mW / cm²), the JV curve of the device was tested using a Keithley 2400 source meter at a scan rate of 0.1 V / s. The test results are as follows: Figure 2 As shown. The results show: PCE 21.12%, V OC 1.118V, J SC 24.11 mA / cm 2 , FF 78.34%.

[0084] Application Example 2 The preparation method of the inverted perovskite solar cell based on Example 2 is carried out according to the method of Application Example 1, except that in S5, the thiophene secondary urethane derivative material of Example 2 is dissolved in ethanol to prepare a passivation solution with a concentration of 0.5 mg / mL, which is dynamically spin-coated onto the substrate surface at a speed of 3000 rpm for 30 s, and then immediately placed on a heating stage for annealing at 100°C for 10 min to form an interface passivation layer on the surface of the perovskite light-absorbing layer.

[0085] The JV curve results of the inverted perovskite solar cell prepared using Example 2 are as follows: Figure 2 As shown, the initial PCE of the device is 21.79%, V OC 1.139V, J SC 24.95 mA / cm 2 , FF 76.65%.

[0086] Application Example 3 The preparation method of the inverted perovskite solar cell based on Example 3 is carried out according to the method of Application Example 1, except that in S5, the thiophene secondary urethane derivative material of Example 3 is dissolved in ethanol to prepare a passivation solution with a concentration of 0.5 mg / mL, which is dynamically spin-coated onto the substrate surface at a speed of 3000 rpm for 30 s, and then immediately placed on a heating stage to anneal at 100°C for 10 min to form an interface passivation layer on the surface of the perovskite light-absorbing layer.

[0087] The JV curve results of the inverted perovskite solar cell prepared using Example 3 are as follows: Figure 2 As shown, the initial PCE of the device is 21.76%, V OC 1.144V, J SC 24.96 mA / cm 2 , FF 76.24%.

[0088] Application Example 4 The preparation method of the inverted perovskite solar cell based on Example 4 is carried out according to the method of Application Example 1, except that in S5, the thiophene secondary urethane derivative material of Example 4 is dissolved in ethanol to prepare a passivation solution with a concentration of 0.5 mg / mL, which is dynamically spin-coated onto the substrate surface at a speed of 3000 rpm for 30 s, and then immediately placed on a heating stage for annealing at 100°C for 10 min to form an interface passivation layer on the surface of the perovskite light-absorbing layer.

[0089] The JV curve results of the inverted perovskite solar cell prepared using Example 4 are as follows: Figure 2 As shown, the initial PCE of the device is 21.98%, V OC 1.136V, J SC 24.86 mA / cm 2, FF 77.85%.

[0090] Application Example 5 The preparation method of the inverted perovskite solar cell based on Example 5 is carried out according to the method of Application Example 1, except that in S5, the thiophene secondary urethane derivative material of Example 5 is dissolved in ethanol to prepare a passivation solution with a concentration of 0.5 mg / mL, which is dynamically spin-coated onto the substrate surface at a speed of 3000 rpm for 30 s, and then immediately placed on a heating stage for annealing at 100°C for 10 min to form an interface passivation layer on the surface of the perovskite light-absorbing layer.

[0091] The JV curve results of the inverted perovskite solar cell prepared using Example 5 show that the initial PCE of the device is 21.37%, and V0... OC 1.115V, J SC 24.19 mA / cm 2 , FF 79.21%.

[0092] Application Example 6 The preparation method of the inverted perovskite solar cell based on Example 6 is carried out according to the method of Application Example 1, except that in S5, the thiophene secondary urethane derivative material of Example 6 is dissolved in ethanol to prepare a passivation solution with a concentration of 0.5 mg / mL, which is dynamically spin-coated onto the substrate surface at a speed of 3000 rpm for 30 s, and then immediately placed on a heating stage for annealing at 100°C for 10 min to form an interface passivation layer on the surface of the perovskite light-absorbing layer.

[0093] The JV curve results of the inverted perovskite solar cell prepared using Example 6 show that the initial PCE of the device is 21.25%, and V0... OC 1.112V, J SC 24.12 mA / cm 2 , FF 79.28%.

[0094] Comparative Example 1 Inverted perovskite solar cells without passivation agents: Except for not spin-coating the thiophene secondary urethane derivative material of Example 1 of this invention onto the surface of the perovskite light-absorbing layer, the other preparation steps are exactly the same as in Application Example 1.

[0095] The JV curve results of the inverted perovskite solar cell device prepared in Comparative Example 1 without passivation agent show that the initial PCE is 18.68%, and V0... OC 1.095 V, J SC 24.5mA / cm 2 , FF 69.63%.

[0096] Comparative Example 2 Trans-perovskite solar cells prepared by replacing the thiophene secondary urethane derivative material in Example 1 of the present invention with phenylethylamine iodide (PEAI): The thiophene secondary urethane derivative material in Application Example 1 was replaced with phenylethylamine iodide (PEAI), and the remaining preparation steps were exactly the same as in Application Example 1. The device JV curve results of the inverted perovskite solar cell prepared in Comparative Example 2 show that the initial PCE is 19.93%, and V0... OC 1.100 V, J SC 24.15 mA / cm², FF 75.04%.

[0097] Table 1 Performance test results of inverted perovskite solar cells Figure 2 This is a comparison chart of the JV characteristic curves of inverted perovskite solar cells from Application Examples 1 to 6 and Comparative Examples 1 to 2.

[0098] Depend on Figure 2 As shown in Table 1, the thiophene secondary urethane derivative material of the present invention, as an interface passivator for inverted perovskite solar cells, has significantly better performance than devices modified with traditional phenylethylamine iodide (PEAI) without passivator, and can achieve a simultaneous and substantial improvement in photoelectric conversion efficiency and environmental stability.

[0099] Figure 3 These are electron microscope (EM) images of the perovskite light-absorbing layer surfaces of Comparative Example 1, Application Example 1, and Application Example 5. Specifically, (a) is an EEM image of the perovskite light-absorbing layer surface of Comparative Example 1; (b) is an EEM image of the perovskite light-absorbing layer surface of Application Example 1; and (c) is an EEM image of the perovskite light-absorbing layer surface of Application Example 5.

[0100] Depend on Figure 3 As can be seen from the electron microscope images, the thiophene secondary urethane derivative material of the present invention, as an interface passivator for inverted perovskite solar cells, increases the grain size and reduces the roughness of the perovskite light-absorbing layer surface after the addition of the interface passivator, which is beneficial to enhancing carrier transport and reducing non-radiative recombination, resulting in significant overall performance advantages.

[0101] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A thiophene secondary urethane derivative material, characterized in that, The general molecular structural formula of the thiophene secondary amino ester derivative material is shown below: ； R1 to R5 are each independently selected from hydrogen or F; and R1 to R5 are not all H at the same time; L1 is methyl, ethyl or isopropyl.

2. The thiophene secondary urethane derivative material according to claim 1, characterized in that, The thiophene secondary amino ester derivative material is any one of the following compounds: 。 3. A method for preparing a thiophene secondary amine derivative material according to any one of claims 1 to 2, characterized in that, Includes the following steps: Using the compounds shown in Formula 1 and Formula 2 as raw materials, a coupling reaction was carried out under the action of a first catalyst, a ligand, a first base and a first solvent to obtain the compound shown in Formula 3. Using the compounds shown in Formula 3 and Formula 4 as raw materials, a coupling reaction was carried out under the action of a second catalyst, a second base, and a second solvent to obtain the thiophene secondary amino ester derivative material shown in Formula 5. The synthetic route for thiophene secondary amino ester derivative materials is as follows: 。 4. The method for preparing the thiophene secondary urethane derivative material according to claim 3, characterized in that, The molar ratio of the compound shown in Formula 1 to the compound shown in Formula 2 is 1:1 to 5; The molar ratio of the compound shown in Formula 3 to the compound shown in Formula 4 is 1:1 to 5.

5. The method for preparing the thiophene secondary urethane derivative material according to claim 3, characterized in that, The first catalyst and the second catalyst are each independently selected from tris(dibenzylacetone)palladium or tetra(triphenylphosphine)palladium; The ligand is 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl; The first and second bases are independently selected from cesium carbonate or potassium carbonate, respectively. The first solvent is toluene; the second solvent is a mixture of tetrahydrofuran and water.

6. The method for preparing the thiophene secondary urethane derivative material according to claim 3, characterized in that, The amount of the first catalyst is 3.1% to 3.2% of the molar percentage of the compound shown in Formula 1; The amount of ligand used is 5.3% to 5.4% of the molar percentage of the compound shown in Formula 1; The molar ratio of the compound shown in Formula 1 to the first base is 1:2 to 2.2; The amount of the second catalyst is 4.9% to 5% of the molar percentage of the compound shown in Formula 3; The molar ratio of the compound shown in Formula 3 to the second base is 1:2 to 2.

2.

7. The method for preparing the thiophene secondary urethane derivative material according to claim 3, characterized in that, The coupling reaction between the compound shown in Formula 3 and the thiophene secondary urethane derivative material shown in Formula 5 was carried out under reflux conditions.

8. The application of a thiophene secondary urethane derivative material as described in any one of claims 1 to 2 as an interface passivator for perovskite thin films in the preparation of perovskite solar cells.

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