Multifunctional conjugated interface modification material as well as preparation method and application thereof

Abstract

The invention relates to the field of perovskite solar cells, and discloses a multifunctional conjugated interface modification material with one of the following structural formulas as well as a preparation method and application thereof. A trans-perovskite solar cell obtained by taking the conjugated interface modification material as a buried interface modification layer has a high-quality perovskite thin film with a low defect state; the solar cell prepared by the method has the advantages of low energy loss of a buried interface, obviously enhanced carrier extraction and transmission, improved photoelectric conversion efficiency to 25.48%-26.61%, and excellent long-term stability.

Description

Technical Field

[0001] This invention belongs to the field of perovskite solar cells, specifically relating to a multifunctional conjugated interface modification material, its preparation method, and its application. Background Technology

[0002] Perovskite solar cells (PSCs) have attracted much attention due to their excellent photoelectric properties, including high absorption coefficient, long carrier diffusion length, and tunable bandgap. In just over a decade, their photoelectric conversion efficiency has increased from the initial 3.8% to the current certified efficiency of over 26% (J. Am. Chem. Soc. 2009, 131, 6050-6051; Nature, 2024, 632, 536-542), approaching the theoretical limit of crystalline silicon cells, while also possessing lower production costs and more flexible fabrication processes. PSCs can be divided into nip structures and pin structures. Compared with nip structures, pin structures have better stability, can be processed at low temperatures, are more suitable for fabricating large-area, transparent, and flexible devices, and can be fabricated into stacked devices with crystalline silicon, organic solar cells, etc., showing significant advantages in terms of commercialization potential (Nature, 2023, 624, 289–294). The structure of pi-nPSCs mainly includes: a transparent indium tin oxide (ITO) conductive glass substrate, a hole transport layer, a perovskite layer, an electron transport layer, and a metal electrode. The hole transport material (HTM) is a key functional layer for achieving high efficiency in PSCs, playing a decisive role in hole extraction and transport, interface optimization, perovskite crystallization, and device stability (Nature, 2001, 414, 338-344; Joule, 2024, 8, 737-750).

[0003] To date, self-assembled monolayers (SAMs) have advantages such as low material consumption, low parasitic absorption, suitability for large-area manufacturing, green solvent processing, simple fabrication, high reproducibility, and good film formation on textured or rough surfaces (Adv. Mater. 2024, 36, 2405630; Adv. Energy Mater. 2025, 15, 2400205). SAMs are widely used as the high-molecular-weight metamaterials (HTMs) of pin PSCs. However, the inventors discovered at least the following problems in the existing technology during their research. Commonly used SAMs, such as [4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid (Me-4PACz), have poor surface wettability, making it difficult for the subsequently deposited perovskite precursor solution to spread uniformly. Furthermore, Me-4PACz lacks passivating groups that strongly interact with perovskite, resulting in uncontrolled perovskite crystallization and the formation of poor-quality perovskite films. The bottom interface of these films is prone to generating numerous nanopores and defects. These unavoidable defects act as non-radiative recombination centers, accelerating perovskite layer degradation and reducing the photoelectric conversion efficiency of the battery (Joule, 2023, 6, 1879-1893). The interface between SAMs and the perovskite layer is called the buried interface. Optimizing the buried interface may be the most promising approach to further pursuing high-efficiency pin PSCs (Adv. Funct. Mater, 2024, 34, 2314039). Therefore, the development of corresponding interface modification materials is urgently needed. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a multifunctional conjugated interface modification material, its preparation method and application, in order to address the shortcomings of the prior art. The multifunctional conjugated interface modification material is based on thiadiazole or thiazothiazolium, and the perovskite solar cell with the multifunctional conjugated interface modification material as the buried interface modification layer has a photoelectric conversion efficiency of up to 26.61%, which is significantly higher than that of perovskite solar cells without the buried interface modification layer.

[0005] Compared with the prior art, the present invention has the following advantages:

[0006] 1. This invention provides a multifunctional conjugated interface modification material with thiadiazole or thiazothiazolium as the core, which can be used as a buried interface modification layer to improve the photoelectric performance and storage stability of inverted perovskite solar cells. The photoelectric conversion efficiency of perovskite solar cells containing the above-mentioned buried interface modification layer is as high as 26.61%, and the efficiency degradation rate of storage devices is less than 15% after more than 2000 hours.

[0007] 2. The multifunctional conjugated interface modification material TDZI or TzTzI of the present invention has the effect of promoting the spreading of perovskite precursor solution, effectively controlling the crystallization process of perovskite, obtaining high-quality perovskite films with low defect states, and effectively reducing the surface porosity of the post-deposited perovskite active layer after being used as a buried interface modification layer, thereby improving the uniformity and density of the active layer.

[0008] 3. The present invention also provides a method for preparing a multifunctional conjugated interface modification material, which has a high synthesis yield, readily available raw materials, and low cost. Attached Figure Description

[0009] Figure 1 This is a schematic diagram of the TDZI or TzTzI synthesis process in Example 1;

[0010] Figure 2 These are schematic diagrams of the perovskite solar cell structure with a buried interface modification layer in Example 2 and the perovskite solar cell structure in Comparative Example 1.

[0011] Figure 3 The UV-Vis absorption spectrum of TDZI or TzTzI in Example 1;

[0012] Figure 4 ITO / NiO as described in Example 2 x / Me-4PACz / TDZI substrate, ITO / NiO of Example 3 x / Me-4PACz / TzTzI substrate and ITO / NiO of Comparative Example 1 x Schematic diagram of water contact angle test results for the / Me-4PACz substrate;

[0013] Figure 5 Scanning electron microscope images of the films with perovskite active layers in Example 2, Example 3, and Comparative Example 1;

[0014] Figure 6 The current-voltage (JV) curves of the perovskite solar cells of Examples 2, 3 and Comparative Example 1 are shown.

[0015] Figure 7 This is a schematic diagram showing the long-term stability test results of perovskite solar cells in Examples 2, 3, and Comparative Example 1 under environmental conditions. Detailed Implementation

[0016] The technical solution will now be clearly and completely described with reference to the embodiments of this application. Obviously, the described embodiments are only a part of the embodiments of this application, not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this application without creative effort are within the scope of protection of this application.

[0017] In the following description, the term "and / or" is used to describe the relationship between related objects, indicating that there can be three relationships. For example, A and / or B can mean: A exists alone, B exists alone, and A and B exist simultaneously. A and B can be singular or plural.

[0018] In the following description, the terms “including,” “containing,” “having,” and “containing” are open-ended terms, meaning that they include but are not limited to.

[0019] Those skilled in the art should understand that, in the following description of the embodiments of this application, the sequence of numbers does not imply the order of execution. Some or all steps may be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of this application.

[0020] Those skilled in the art will understand that the numerical ranges in the embodiments of this application should be understood to specifically disclose each intermediate value between the upper and lower limits of the range. Each smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this application. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0021] Unless otherwise stated, the technical / scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains. While this application describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this application. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0022] On the one hand, a multifunctional conjugated interface modification material is provided, which is the compound TDZI or TzTzI, with the following structural formula:

[0023]

[0024] On the other hand, a method for preparing the above-mentioned multifunctional conjugated interface modified material is provided, comprising:

[0025] Step 1: At room temperature, 3-methylthiophene-2-carboxylic acid and oxalyl chloride are reacted via acylation to obtain compound TCl. The structural formula of compound TCl is as follows:

[0026] The molar ratio of 3-methylthiophene-2-carboxylic acid to oxalyl chloride is 1:(1-100);

[0027] Step 2: Under nitrogen protection and a low temperature environment of -10 to -5°C, compound TCl, triethylamine, and hydrazine hydrate were subjected to an acylation reaction to obtain compound DTN. The structural formula of compound DTN is as follows:

[0028] The molar ratio of the compound TCl, triethylamine, and hydrazine hydrate is 1:(1-2):(0.4-0.6).

[0029] Step 3: Under nitrogen protection and heating at 115–125°C, compound DTN and Lawson's reagent were subjected to a ring-closure reaction to obtain compound TDZ. The structural formula of compound TDZ is as follows:

[0030] The molar ratio of the compound DTN to Lawson's reagent is 1:(1-1.5);

[0031] Step 4: Under heating conditions of 40–60°C, compound TDZ and N-bromosuccinimide are subjected to a bromination reaction to obtain compound TDZ-Br. The structural formula of compound TDZ-Br is as follows:

[0032] The molar ratio of the compound TDZ to N-bromosuccinimide is 1:(1-1.2);

[0033] Step 5: Under nitrogen protection and heating at 150–170°C, 3-methylthiophenealdehyde and dithiooxalylamine are reacted via a ring-closure reaction to obtain compound TzTz. The structural formula of compound TzTz is as follows:

[0034] The molar ratio of 3-methylthiophenealdehyde to dithiooxalylamine is 1:(0.47-0.53);

[0035] Step 6: Under heating conditions of 55–65°C, compound TzTz and N-bromosuccinimide are subjected to a bromination reaction to obtain compound TzTz-Br. The structural formula of compound TzTz-Br is as follows:

[0036] The molar ratio of the compound TzTz to N-bromosuccinimide is 1:(1-1.2);

[0037] Step 7: Under nitrogen protection and heating at 45–55°C, 2-thiopheneethylamine is reacted with triethylamine and di-tert-butyl dicarbonate via a Boc protection reaction to obtain compound TNBoc. The structural formula of compound TNBoc is as follows:

[0038] The molar ratio of 2-thiopheneethylamine, triethylamine, and ditert-butyl dicarbonate is 1:(1-1.5):(1-1.5).

[0039] Step 8: Under nitrogen protection and a low temperature environment of -30 to -78°C, compound TNBoc and n-butyllithium undergo a lithium-hydrogen exchange reaction to obtain a lithium-substituted compound. Tributyltin chloride is added to the reaction system, and the reaction is first carried out at a low temperature of -30 to -78°C for 0.5 to 1 hour. Then, the temperature is raised to 20 to 30°C and maintained for 2 to 8 hours to obtain compound TNBoc-Sn. The structural formula of compound TNBoc-Sn is as follows: The molar ratio of the compound TNBoc, n-butyllithium, and tributyltin chloride is 1:(2-2.5):(2-2.5).

[0040] Step 9: Under nitrogen protection and heating at 90–120°C, compound TNBoc-Sn and compound TDZ-Br undergo a Still coupling reaction catalyzed by tris[dibenzylacetone]dipalladium and tris(o-methylphenyl)phosphine to obtain compound TDZ-Boc; or, under nitrogen protection and heating at 100–110°C, compound TNBoc-Sn and compound TzTz-Br undergo a Still coupling reaction catalyzed by tris[dibenzylacetone]dipalladium and tris(o-methylphenyl)phosphine to obtain compound TzTz-Boc; the structural formula of compound TDZ-Boc or compound TzTz-Boc is as follows:

[0041]

[0042] The molar ratio of the compounds TDZ-Br or TzTz-Br, TNBoc-Sn, tris[dibenzylideneacetone]palladium and tris(o-methylphenyl)phosphine is 1:(1-2):0.04:0.16;

[0043] Step 10: Under nitrogen protection and heating at 78–85°C, compound TDZ-Boc is reacted with hydroiodic acid via deBoc and salt formation to obtain compound TDZI; or, under nitrogen protection and heating at 78–85°C, compound TzTz-Boc is reacted with hydroiodic acid via deBoc and salt formation to obtain compound TzTzI; the molar ratio of TDZ-Boc or TzTz-Boc to hydroiodic acid is 1:(2–10).

[0044] On another aspect, a method for applying the aforementioned multifunctional conjugated interface modification material is provided, comprising using the multifunctional conjugated interface modification material as a buried interface modification layer for a perovskite solar cell; in some preferred embodiments, the perovskite solar cell is an inverted perovskite solar cell, which includes an indium tin oxide transparent conductive substrate, a hole transport layer, a perovskite active layer, a top interface modification layer, an electron transport layer, a hole blocking layer, and a metal electrode, wherein the buried interface modification layer is located between the hole transport layer and the perovskite active layer; the hole transport layer has a thickness of 2-5 nm; the buried interface modification layer has a thickness of 3 nm; the perovskite active layer has a thickness of 800 nm; the top interface modification layer has a thickness of 2 nm; the electron transport layer has a thickness of 20 nm; the hole blocking layer has a thickness of 7 nm; and the metal electrode has a thickness of 100 nm; in some specific embodiments, the method for preparing the perovskite solar cell containing the buried interface modification layer includes:

[0045] Step 1: Spin-coat a nickel oxide-containing slurry onto an indium tin oxide transparent conductive substrate, anneal, then spin-coat a 4-(3,6-dimethyl-9H-carbazole-9-yl)butylphosphonic acid ethanol solution, anneal, to obtain a hole transport layer; in some specific embodiments, the nickel oxide concentration in the nickel oxide-containing slurry is 10 mg / mL, and the nickel oxide-containing slurry is obtained by dispersing nickel oxide in deionized water; the spin-coating speed of the nickel oxide-containing slurry is 2000 rpm / s, the spin-coating time is 30 s, the annealing temperature is 150℃, and the annealing time is 30 min; 4-(3,6-dimethyl-9H-carbazole-9-yl)butylphosphonic acid ethanol solution is ... The ethanol solution of 4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid contained 0.5 mg / mL of 4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid, which was prepared by dissolving 4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid in anhydrous ethanol. The spin-coating speed of the 4-(3,6-dimethyl-9H-carbazole-9-yl)butyl]phosphonic acid ethanol solution was 4000 rpm / s, the spin-coating time was 30 s, the annealing temperature was 100℃, and the annealing time was 10 min.

[0046] Step 2: Spin-coat the hole transport layer with a solution containing the multifunctional conjugated interface modifier, and anneal to obtain a buried interface modifier layer; in some specific embodiments, the concentration of the multifunctional conjugated interface modifier in the solution is 0.5 mg / mL, and the solution is obtained by dissolving the multifunctional conjugated interface modifier in dimethylformamide; the spin-coating speed is 4000 rpm / s, the spin-coating time is 30 s, the annealing temperature is 100℃, and the annealing time is 10 min;

[0047] Step 3: A perovskite precursor solution is spin-coated onto the subsurface interface modification layer in two steps, followed by annealing to obtain the perovskite active layer. In some specific embodiments, the perovskite precursor solution is prepared by dissolving 19.8 mg cesium iodide, 15.2 mg methylammonium chloride, 23.8 mg methylammonium iodide, 219.3 mg formamidinium hydroiodate, and 760.7 mg lead iodide in 1 mL. It is obtained in a mixed solvent of DMF and DMSO; the volume ratio of DMF to DMSO in the mixed solvent of DMF and DMSO is 4:1; the first spin coating speed is 1000 rpm / s and the time is 10s, the second spin coating speed is 5000 rpm / s and the time is 40s; it also includes adding 200μL of chlorobenzene as an anti-solvent 15s before the end of the second spin coating; the annealing temperature is 100℃ and the annealing time is 30min; through the two-step spin coating of slow speed followed by fast speed, the perovskite precursor solution is first fully spread on the buried interface modification layer, and then rapidly forms a film;

[0048] Step 4: Spin-coat an isopropanol solution of 1,3-diaminopropane dihydroiodate onto the perovskite active layer, and anneal to obtain a top interface modified layer; in some specific embodiments, the concentration of 1,3-diaminopropane dihydroiodate in the isopropanol solution of 1,3-diaminopropane dihydroiodate is 1 mg / mL; in Step 4, the spin-coating speed is 5000 rpm / s, the spin-coating time is 30 s, the annealing temperature is 100℃, and the annealing time is 5 min;

[0049] Step 5: Sequentially deposit C on the top interface modification layer. 60 BCP and Ag were used to obtain perovskite solar cells with a buried interface modification layer.

[0050] Prior to the application for this invention, a series of experiments were conducted. Some of the experimental results are listed below to provide a more detailed description of the invention. The following is a detailed description in conjunction with the embodiments.

[0051] Example 1

[0052] This embodiment provides a method for preparing a multifunctional conjugated interface modification material, the process of which is as follows: Figure 1 As shown, it specifically includes:

[0053] The multifunctional conjugated interface modification material is the compound TDZI or TzTzI, with the following structural formula:

[0054]

[0055] The preparation methods of the above two multifunctional conjugated organic interface passivation materials include:

[0056] Step 1 involves reacting 3-methylthiophene-2-carboxylic acid and oxalyl chloride via an acylation reaction to obtain compound TCl. Specifically, at room temperature, 30 mL of oxalyl chloride is added dropwise to commercially available 3-methylthiophene-2-carboxylic acid (5 g, 35.2 mmol), and the mixture is stirred for 4 h. The system after stirring is then concentrated under reduced pressure to remove excess oxalyl chloride, yielding an orange liquid compound TCl with a mass of 5.2 g and a yield of 92.9%. The structure of TCl is shown below.

[0057]

[0058] Step two involves the acylation reaction of compound TCl, triethylamine, and hydrazine hydrate to obtain compound DTN. Specifically, under nitrogen protection and at -5°C, triethylamine (5.7 mL, 40.6 mmol) and hydrazine hydrate (80%, 1.2 mL, 19.5 mmol) are slowly added to an anhydrous tetrahydrofuran (THF, 100 mL) solution containing compound TCl (5.2 g, 32.5 mmol), resulting in a turbid reaction solution. The mixture is stirred for 0.5 h, then the reaction is continued at room temperature for 6 h. The THF is removed by concentration under reduced pressure, and the mixture is recrystallized from chloroform (CHCl3) and petroleum ether (PE) to obtain a white flocculent solid compound DTN. The mass of DTN is 3.0 g, with a yield of 66.7%. The structural formula of DTN is as follows:

[0059]

[0060] The DTN NMR spectrum of the product is as follows: 1 H NMR (400MHz, CDCl3) δ: 10.56 (s, 2H), 7.37 (d, J = 4.9Hz, 2H), 6.96 (d, J = 4.7Hz, 2H), 2.55 (s, 6H);

[0061] Step 3 involves a ring-closure reaction of compound DTN and Lawson's reagent to obtain compound TDZ. Specifically, under nitrogen protection and at 120°C, compound DTN (1.5 g, 5.4 mmol) and Lawson's reagent (2.6 g, 6.5 mmol) were dissolved in o-xylene (OX, 50 mL), and the reaction was stirred for 8 h. The OX was removed by concentration under reduced pressure, and the mixture was recrystallized from CHCl3 and anhydrous ethanol (EtOH) to obtain yellow crystalline compound TDZ. The mass of TDZ was 1.4 g, with a yield of 93.3%. The structural formula of TDZ is as follows:

[0062]

[0063] The TDZ NMR spectrum is as follows: 1H NMR (400MHz, CDCl3) δ: 7.37 (d, J = 5.0 Hz, 2H), 6.97 (d, J = 5.0 Hz, 2H), 2.57 (s, 6H);

[0064] Step four involves a bromination reaction of compound TDZ and N-bromosuccinimide to obtain compound TDZ-Br. This includes: slowly adding N-bromosuccinimide (NBS, 0.98 g, 5.5 mmol) to an anhydrous N,N-dimethylformamide (DMF, 80 mL) solution containing compound TDZ (1.4 g, 5.0 mmol) at 50 °C under light-protected conditions; stirring for 8 h; quenching the reaction with water; extraction with dichloromethane (CH2Cl2); drying with anhydrous MgSO4; filtration and concentration; recrystallization of the crude product with CHCl3 / EtOH to obtain a yellow solid compound TDZ-Br. The mass of TDZ-Br is 0.92 g, with a yield of 51.6%. The structural formula of TDZ-Br is as follows:

[0065]

[0066] The TDZ-Br NMR spectrum is as follows: 1 H NMR (400MHz, CDCl3) δ: 7.40 (d, J = 5.0Hz, 1H), 6.98 (d, J = 8.0Hz, 1H), 6.95 (s, 1H), 2.58 (d, J = 3.3Hz, 3H), 2.51 (d, J = 3.3Hz, 3H);

[0067] Step 5 involves a cyclization reaction of 3-methylthiophenealdehyde with dithiooxalamide to obtain compound TzTz. Specifically, under nitrogen protection and at 160°C, commercially available 3-methylthiophenealdehyde (6.7 g, 52.5 mmol) and dithiooxalamide (3 g, 25.0 mmol) are dissolved in nitrobenzene (PhNO2, 100 mL) by heating. The mixture is stirred for 40 h, cooled to room temperature, and EtOH is added to precipitate a large amount of solid. The solid is filtered to obtain a black residue, which is washed with a large amount of EtOH. The residue is purified by column chromatography using PE:CH2Cl2 = 2:1 as the eluent. The crude product is then recrystallized from CHCl3 / EtOH to obtain an orange-yellow solid compound TzTz. The mass of TzTz is 2.5 g, with a yield of 29.9%. The structural formula of TzTz is as follows:

[0068]

[0069] The TzTz NMR spectrum is as follows: 1 H NMR (400MHz, CDCl3) δ: 7.34 (d, J = 5.0 Hz, 2H), 6.96 (d, J = 5.0 Hz, 2H), 2.58 (s, 6H);

[0070] Step six involves brominating compound TzTz and N-bromosuccinimide to obtain compound TzTz-Br. This includes: slowly adding N-bromosuccinimide (NBS, 0.58 g, 3.3 mmol) to an 80 mL CHCl3 solution containing compound TzTz (1.0 g, 3.0 mmol) at 60 °C under light-protected conditions, stirring for 8 h, and recrystallizing the product using CHCl3 / EtOH to obtain a yellow solid compound TzTz-Br. The mass of TzTz-Br is 1.0 g, with a yield of 83.1%. The structural formula of TzTz-Br is as follows:

[0071]

[0072] Step 7: 2-Thiopheneethylamine was reacted with triethylamine and di-tert-butyl dicarbonate via a Boc protection reaction to obtain compound TNBoc. Specifically, under nitrogen protection and at 50°C, commercially available 2-thiopheneethylamine (9.4 g, 93.0 mmol), triethylamine (9.4 g, 93.0 mL), and di-tert-butyl dicarbonate (20.3 g, 93.0 mmol) were dissolved in CH2Cl2 (150 mL), stirred for 6 h, cooled to room temperature, quenched with water, extracted with DCM, dried over anhydrous MgSO4, filtered, and concentrated to obtain a yellow liquid compound TNBoc. The mass of TNBoc was 18.4 g, with a yield of 87.2%. The structural formula of TNBoc is as follows:

[0073]

[0074] The TNBoc NMR spectrum is as follows: 1 H NMR (400MHz, CDCl3) δ: 7.15 (dd, J=5.1, 1.1Hz, 1H), 6.94 (dd, J=5.1, 3.5Hz, 1H), 6. 83(d,J=2.6Hz,1H),4.66(s,1H),3.39(s,2H),3.01(t,J=6.7Hz,2H),1.44(s,9H);

[0075] Step 8, Synthesis of compound TNBoc-Sn: Under nitrogen atmosphere and at -78°C, n-butyllithium (1.6M, 18.3mL, 29.2mmol) was slowly added dropwise to an anhydrous THF (100mL) solution containing compound TNBoc (3g, 13.17mmol). The reaction was stirred for 1 hour, then tributyltin chloride (8.1mL, 29.5mmol) was added dropwise, and the reaction was stirred for 30 minutes. The reaction mixture was then brought to room temperature and stirred overnight. The reaction was quenched with water, extracted with CH2Cl2, dried over anhydrous MgSO4, filtered and concentrated, and dried under vacuum to obtain compound TNBoc-Sn, with the following structural formula:

[0076]

[0077] Step 9, Synthesis of compound TDZ-Bo: Under nitrogen atmosphere and at 110℃, compound TDZ-Br (0.8 g), compound TNBoc-Sn (2 molar equivalents), tris[dibenzylacetone]palladium (0.04 molar equivalents), and tris(o-methylphenyl)phosphine (0.16 molar equivalents) were dissolved in anhydrous toluene (50 mL), stirred for 8 h to allow Still coupling, cooled to room temperature, quenched with water, extracted with DCM, dried over anhydrous MgSO4, filtered and concentrated, and the crude product was purified by column chromatography using PE:CH2Cl2 = 1:2 as eluent to obtain a yellow solid compound TDZ-Boc with a mass of 0.83 g and a yield of 75.5%. The structural formula of TDZ-Boc is as follows:

[0078]

[0079] The TDZ-Boc NMR spectrum is as follows: 1 H NMR (400MHz, CDCl3) δ: 7.38 (d, J = 4.9 Hz, 1H), 7.10 (d, J = 3.5 Hz, 1H), 6.98 (s, 2H), 6.77 (d, J = 3. 3Hz,1H),4.70(s,1H),3.41(s,2H),3.01(t,J=6.2Hz,2H),2.56(d,J=15.5Hz,6H),1.46(s,9H);

[0080] Synthesis of compound TzTz-Boc: Under nitrogen atmosphere and at 110 °C, compound TzTz-Br (0.8 g), compound TNBoc-Sn (2 molar equivalents), tris[dibenzylacetone]palladium (0.04 molar equivalents), and tris(o-methylphenyl)phosphine (0.16 molar equivalents) were dissolved in anhydrous toluene (50 mL), stirred for 8 h to allow Still coupling, cooled to room temperature, quenched with water, extracted with DCM, dried over anhydrous MgSO4, filtered and concentrated, and the crude product was purified by column chromatography using PE:CH2Cl2 = 1:2 as eluent to give a yellow solid compound TzTz-Boc with a mass of 0.84 g and a yield of 80.7%. The structural formula of TzTz-Boc is as follows:

[0081]

[0082] The TzTz-Boc NMR spectrum is as follows: 1 H NMR (400MHz, CDCl3) δ: 7.34 (d, J = 2.3 Hz, 2H), 7.07 (d, J = 3.6 Hz, 1H), 6.94 (d, J = 5.0 Hz, 1H), 6.82 (d, J = 3. 5Hz,1H),4.73(s,1H),3.52–3.30(m,2H),3.03(t,J=6.4Hz,2H),2.56(s,3H),2.40(s,3H),1.45(s,9H);

[0083] Step 10, Synthesis of compound TDZI: Under nitrogen atmosphere and at 80°C, hydroiodic acid (55%, 0.3 mL) was slowly added to an anhydrous EtOH (20 mL) solution of compound TDZI-Boc (0.3 g). The mixture was stirred for 6 h to remove Boc and form a salt. The solid first dissolved and then precipitated. The mixture was cooled to room temperature, filtered, and the residue was washed with EtOH. The residue was dissolved in a small amount of methanol and precipitated in a large amount of anhydrous diethyl ether. The mixture was filtered again to obtain a yellow solid compound TDZI with a mass of 0.27 g and a yield of 87.1%.

[0084] The TDZI NMR spectrum is as follows: 1 H NMR(400MHz, DMSO-d6)δ:7.80(s,3H),7.73(d,J=5.0Hz,1H),7.33(d,J=3.6Hz,1H), 7.27(s,1H),7.12(d,J=5.0Hz,1H),6.98(d,J=3.6Hz,1H),3.09(s,4H),2.48(s,6H). 13C NMR(400MHz,DMSO-d6)δ:160.27,159.66,141.14,140.61,140.12,138.85,134.54,1 32.66,129.69,128.49,128.21,126.59,126.07,125.03,27.93,16.52,16.39.LC-TOF MS(C 18 H 18 N3S4I)[MI) + Theoretical value: 404.0384, measured value: 404.0388;

[0085] Synthesis of compound TzTzI: Under nitrogen atmosphere and 80°C, hydroiodic acid (55%, 0.3 mL) was slowly added to an anhydrous EtOH (20 mL) solution of compound TzTzI-Boc (0.3 g). The mixture was stirred for 6 h to remove Boc and form a salt. The solid first dissolved and then precipitated. After cooling to room temperature, the mixture was filtered and the residue was washed with EtOH. The residue was dissolved in a small amount of methanol and precipitated in a large amount of anhydrous diethyl ether. The mixture was filtered again to obtain a yellow solid compound TzTzI with a mass of 0.28 g and a yield of 90.3%.

[0086] The NMR spectrum of TzTzI is as follows: 1 H NMR (400MHz, DMSO-d6) δ: 7.82 (s, 3H), 7.75–7.63 (m, 2H), 7.26 (d, J = 3.7Hz, 1H), 7. 12(d,J=5.0Hz,1H),7.06(d,J=3.7Hz,1H),3.13(s,4H),2.53(s,3H),2.38(s,3H). 13 C NMR(400MHz,DMSO-d6)δ:140.85,138.72,135.16,134.43,133.99,133.32,132. 99,132.45,131.60,129.22,127.83,127.15,99.99,27.84,16.53,15.73.LC-TOF MS(C 20 H 18 N3S4I)[MI) + Theoretical value: 460.0104, measured value: 460.0048.

[0087] Example 2

[0088] This embodiment provides a method for applying the multifunctional conjugated interface modification material of Embodiment 1, including using the multifunctional conjugated interface modification material as a buried interface modification layer for a perovskite solar cell. The perovskite solar cell is an inverted perovskite solar cell, which includes an indium tin oxide transparent conductive substrate, a hole transport layer, a perovskite active layer, a top interface modification layer, an electron transport layer, a hole blocking layer, and a metal electrode. The buried interface modification layer is located between the hole transport layer and the perovskite active layer. The structure of the perovskite solar cell containing the buried interface modification layer is as follows: Figure 2 As shown in 'a', the specific preparation steps are as follows:

[0089] Step 1: The indium tin oxide transparent conductive substrate (ITO) was ultrasonically cleaned sequentially with detergent, deionized water, acetone, and isopropanol. The solvent was dried with nitrogen gas, and the substrate was then cleaned in ultraviolet ozone for 15 minutes to obtain pretreated ITO. The ITO was purchased from South China Xiangcheng Technology Co., Ltd., with an effective area of ​​0.04 cm². 2 ;

[0090] Step 2: Set a hole transport layer on the pretreated ITO, specifically including: applying NiO... x Dispersed in deionized water, it was prepared into a 10 mg / mL solution containing NiO. x The slurry was filtered through a 0.45 μm polytetrafluoroethylene filter and spin-coated onto ITO at 2000 rpm / s for 30 seconds in air. It was then annealed at 150°C for 30 minutes, cooled to room temperature, and transferred to a nitrogen glove box. A 0.5 mg / mL Me-4PACz ethanol solution was then spin-coated onto NiO at 4000 rpm / s. x The layer is spin-coated for 30 seconds, annealed at 100°C for 10 minutes, and cooled to room temperature to obtain a hole transport layer with a thickness of approximately 2-5 nm. The Me-4PACz ethanol solution is obtained by stirring 4-(3,6-dimethyl-9H-carbazole-9-yl)butylphosphonic acid in anhydrous ethanol at room temperature for 2 hours.

[0091] Step 3: A buried interface modification layer is formed on the hole transport layer, comprising: dissolving TDZI from Example 1 in DMF to obtain a solution containing a multifunctional conjugated interface modification material at a concentration of 0.5 mg / mL; spin-coating the solution onto the hole transport layer at a rate of 4000 rpm / s for 30 seconds; annealing at 100°C for 10 minutes; and cooling to room temperature to obtain a buried interface modification layer with a thickness of approximately 3 nm, which is named ITO / NiO as the substrate. x / Me-4PACz / TDZI substrate;

[0092] Step 4: Set a perovskite active layer on the subsurface interface modification layer, including: dissolving 19.8 mg cesium iodide (CsI), 15.2 mg methylammonium chloride (MACl), 23.8 mg methylammonium iodide (MAI), 219.3 mg formamidinium hydroiodate (FAI), and 760.7 mg lead iodide (PbI2) in 1 mL A perovskite active layer source solution was obtained in a mixed solvent of DMF and DMSO, wherein the volume ratio of DMF to DMSO in the mixed solvent was 4:1. The perovskite active layer source solution was stirred overnight at 75°C and filtered through a 0.45 μm polytetrafluoroethylene filter. The filtered perovskite active layer source solution was first spin-coated at a rate of 1000 rpm / s for 10 s, and then spin-coated at 5000 rpm / s for 40 s. 15 s before the end of the spin-coating at 5000 rpm / s, 200 μL of chlorobenzene was added dropwise as an anti-solvent. The solution was annealed at 100°C for 30 min and cooled to room temperature to obtain a perovskite active layer with a thickness of approximately 800 nm.

[0093] Step 5: Set a top interface modification layer on the perovskite active layer, including: filtering a 1 mg / mL PDAI isopropanol solution through a 0.45 μm polytetrafluoroethylene filter, spin-coating it onto the perovskite active layer at 5000 rpm / s for 30 seconds, annealing at 100℃ for 5 minutes, and cooling to room temperature to obtain a top interface modification layer with a thickness of approximately 2 nm; the PDAI isopropanol solution is obtained by stirring 1,3-diaminopropane dihydroiodate in isopropanol at room temperature overnight.

[0094] Step 6: Evaporate C onto the top interface modification layer. 60 An electron transport layer with a thickness of 20 nm was obtained. BCP was deposited on the electron transport layer to obtain a hole blocking layer with a thickness of 7 nm. Ag was deposited on the hole blocking layer to obtain a metal electrode with a thickness of 100 nm.

[0095] Example 3

[0096] This embodiment provides an application method of the multifunctional conjugate interface modification material of Embodiment 1, which is the same as that of Embodiment 2, except that in step three, it is TzTzI of Embodiment 1.

[0097] Comparative Example 1

[0098] This comparative study examines the effect of the buried interface modification layer on the performance of perovskite solar cells. The preparation method is the same as in Example 2, except that step three is omitted, i.e., the buried interface is not modified. The resulting perovskite solar cell structure is as follows. Figure 2 As shown in b in the figure.

[0099] Performance Evaluation

[0100] The UV-Vis absorption spectra of compounds TDZI and TzTzI in Example 1 are as follows: Figure 3 As shown, the absorption peaks of the two materials are between 300 and 500 nm. Compared with TDZI, the ultraviolet absorption of TzTzI shows a red shift, which may be due to the presence of π conjugation extension in TzTzI.

[0101] ITO / NiO in Example 2 x / Me-4PACz / TDZI substrate, ITO / NiO of Example 3 x / Me-4PACz / TzTzI substrate and ITO / NiO of Comparative Example 1 x Water contact angle test of the / Me-4PACz substrate, as shown in... Figure 4 As shown, the substrate surface modified with TDZI or TzTzI has a smaller water contact angle and better wettability. The substrate of the present invention is more conducive to the uniform spreading of perovskite precursor solution.

[0102] Scanning electron microscopy (SEM) results of the films with perovskite active layers in Examples 2, 3, and 1 (Comparative Example 1) are shown below. Figure 5 As shown in the comparison, after setting the buried interface modification layer of TDZI or TzTzI, the porosity of the perovskite active layer surface is greatly reduced, and the uniformity and density are significantly increased.

[0103] The JV characteristics of the perovskite solar cells of Examples 2, 3, and Comparative Example 1 were tested using a Keithley 2400. The tests were conducted under standard sunlight, and the curves are shown below. Figure 6 As shown, according to Figure 6 As can be seen, the open-circuit voltage of the device modified with TDZI or TzTzI is significantly improved, and the photoelectric conversion efficiency increases from 24.21% in the comparative example to 25.48% and 26.61%, respectively.

[0104] The long-term stability test results of the perovskite solar cells of Examples 2, 3, and Comparative Example 1 under environmental conditions (humidity 40%-50%, temperature 25±5℃) are as follows: Figure 7 As shown, the standard efficiency of the device modified with TDZI or TzTzI decreases by less than 15%, which significantly improves the storage stability compared to the comparative example.

Claims

1. A multifunctional conjugated interface modification material, characterized in that, The compound is TDZI or TzTzI, with the following structural formula:

2. A method for preparing the multifunctional conjugated interface modification material as described in claim 1, characterized in that, include: The compound TCl was obtained by acyl chlorination of 3-methylthiophene-2-carboxylic acid and oxalyl chloride. The structural formula of the compound TCl is as follows: The compound DTN was obtained by acylation of compound TCl, triethylamine, and hydrazine hydrate. The structural formula of compound DTN is as follows: Compound DTN and Lawson's reagent were reacted via a ring-closure reaction to yield compound TDZ, the structural formula of which is as follows: The compound TDZ and N-bromosuccinimide were subjected to a bromination reaction to obtain the compound TDZ-Br, the structural formula of which is as follows: The compound TzTz was obtained by cyclization reaction of 3-methylthiophenaldehyde with dithiooxalylamine. The structural formula of the compound TzTz is as follows: The compound TzTz and N-bromosuccinimide were subjected to a bromination reaction to yield the compound TzTz-Br, the structural formula of which is as follows: 2-Thiopheneethylamine was reacted with triethylamine and di-tert-butyl dicarbonate via a Boc protection reaction to yield compound TNBoc, the structural formula of which is as follows: Compound TNBoc and n-butyllithium were subjected to a lithium-hydrogen exchange reaction to obtain a lithium-substituted compound. Tributyltin chloride was added to the post-reaction system, and after a two-stage temperature-controlled reaction, compound TNBoc-Sn was obtained. The structural formula of compound TNBoc-Sn is as follows: In the presence of tris[dibenzylacetone]dipalladium and tris(o-methylphenyl)phosphine as catalysts, TNBoc-Sn was coupled with compound TDZ-Br or TzTz-Br via a Still coupling reaction to yield compound TDZ-Boc or TzTz-Boc; the structural formulas of compound TDZ-Boc or compound TzTz-Boc are as follows: The compound TDZ-Boc or the compound TzTz-Boc is reacted with hydroiodic acid via a Boc removal and salt formation reaction to obtain the compound TDZI or the compound TzTzI.

3. The method according to claim 2, characterized in that, The acyl chloride reaction was carried out at room temperature, with a molar ratio of 3-methylthiophene-2-carboxylic acid and oxalyl chloride of 1:(1-100); the hydrazideation reaction was carried out under nitrogen protection and at a low temperature of -10 to -5°C, with a molar ratio of compound TCl, triethylamine, and hydrazine hydrate of 1:(1-2):(0.4-0.6); the cyclization reaction of compound DTN and Lawson's reagent was carried out under nitrogen protection and at a heating temperature of 115-125°C, with a molar ratio of compound DTN and Lawson's reagent of 1:(1-1.5); the bromination reaction of compound TDZ and N-bromosuccinimide was carried out at a temperature of 40°C. The molar ratio of compound TDZ to N-bromosuccinimide is 1:(1-1.2) at ~60℃; the cyclization reaction of 3-methylthiophenealdehyde with dithiooxalylamine is carried out under nitrogen protection and heating at 150-170℃, with the molar ratio of 3-methylthiophenealdehyde to dithiooxalylamine being 1:(0.47-0.53); the bromination reaction of compound TzTz with N-bromosuccinimide is carried out under heating at 55-65℃, with the molar ratio of compound TzTz to N-bromosuccinimide being 1:(1-1.2); the Boc protection reaction is carried out under nitrogen protection and heating at 45-55℃. The molar ratio of 2-thiopheneethylamine, triethylamine, and ditert-butyl dicarbonate is 1:(1-1.5):(1-1.5); the lithium-hydrogen exchange reaction, under nitrogen protection and a low temperature environment of -30 to -78°C, yields compound TNBoc-Sn through a two-stage temperature-controlled reaction comprising: adding tributyltin chloride and reacting at a low temperature environment of -30 to -78°C for 0.5 to 1 hour, then heating to 20 to 30°C and stirring overnight, wherein the molar ratio of compound TNBoc, n-butyllithium, and tributyltin chloride is 1:(2-2.5):(2-2.5); the Stil of compound TDZ-Boc is then obtained. The coupling reaction was carried out under nitrogen protection and heating at 90–120 °C to obtain compound TzTz-Boc. The Still coupling reaction was carried out under nitrogen protection and heating at 100–110 °C. The molar ratio of compound TDZ-Br or TzTz-Br, TNBoc-Sn, tris[dibenzylideneacetone]palladium and tris(o-methylphenyl)phosphine was 1:(1–2):0.04:0.

16. The de-Boc and salt formation reactions were carried out under nitrogen protection and heating at 78–85 °C. The molar ratio of TDZ-Boc or TzTz-Boc to hydroiodic acid was 1:(2–10).

4. A method for applying the multifunctional conjugated interface modification material as described in claim 1, characterized in that, This includes using the aforementioned multifunctional conjugated interface modification material as the buried interface modification layer for perovskite solar cells.

5. The application according to claim 4, characterized in that, The perovskite solar cell is an inverted perovskite solar cell, comprising an indium tin oxide transparent conductive substrate, a hole transport layer, a perovskite active layer, a top interface modification layer, an electron transport layer, a hole blocking layer, and a metal electrode. The buried interface modification layer is located between the hole transport layer and the perovskite active layer. The hole transport layer has a thickness of 2–5 nm; the buried interface modification layer has a thickness of 3 nm; the perovskite active layer has a thickness of 800 nm; the top interface modification layer has a thickness of 2 nm; the electron transport layer has a thickness of 20 nm; the hole blocking layer has a thickness of 7 nm; and the metal electrode has a thickness of 100 nm.

6. The application according to claim 4, characterized in that, The method for preparing the perovskite solar cell containing the buried interface modification layer includes: Step 1: Spin-coat a nickel oxide-containing paste onto an indium tin oxide transparent conductive substrate, anneal, then spin-coat a 4-(3,6-dimethyl-9H-carbazole-9-yl)butylphosphonic acid ethanol solution, anneal, to obtain a hole transport layer; Step 2: Spin-coat the hole transport layer with a liquid containing the multifunctional conjugate interface modification material, and anneal to obtain the buried interface modification layer; Step 3: Spin-coating the perovskite precursor solution onto the buried interface modification layer in two steps, followed by annealing to obtain the perovskite active layer. Step 4: Spin-coat an isopropanol solution of 1,3-diaminopropane dihydroiodate onto the perovskite active layer, and anneal to obtain a top interface modification layer. Step 5: Sequentially deposit C on the top interface modification layer. 60 BCP and Ag were used to obtain perovskite solar cells with a buried interface modification layer.

7. The application according to claim 6, characterized in that, In step one, the nickel oxide concentration in the nickel oxide-containing slurry is 10 mg / mL, and the nickel oxide-containing slurry is obtained by dispersing nickel oxide in deionized water; in step one, the spin-coating speed of the nickel oxide-containing slurry is 2000 rpm / s, the spin-coating time is 30 s, the annealing temperature is 150℃, and the annealing time is 30 min; in step one, the 4-(3,6-dimethyl-9H-carbazole-9-yl)butylphosphonic acid ethanol solution contains 4-(3,6-dimethyl-9H-carbazole-9-yl) The concentration of butylphosphonic acid was 0.5 mg / mL. The ethanol solution of 4-(3,6-dimethyl-9H-carbazole-9-yl)butylphosphonic acid was obtained by dissolving 4-(3,6-dimethyl-9H-carbazole-9-yl)butylphosphonic acid in anhydrous ethanol. In step one, the spin coating speed of the ethanol solution of 4-(3,6-dimethyl-9H-carbazole-9-yl)butylphosphonic acid was 4000 rpm / s, the spin coating time was 30 s, the annealing temperature was 100℃, and the annealing time was 10 min.

8. The application according to claim 6, characterized in that, In step two, the concentration of the multifunctional conjugated interface modifier in the solution containing the multifunctional conjugated interface modifier is 0.5 mg / mL, and the solution containing the multifunctional conjugated interface modifier is obtained by dissolving the multifunctional conjugated interface modifier in dimethylformamide; in step two, the spin coating speed is 4000 rpm / s, the spin coating time is 30 s, the annealing temperature is 100℃, and the annealing time is 10 min.

9. The application according to claim 6, characterized in that, In step three, the perovskite precursor solution is obtained by dissolving 19.8 mg cesium iodide, 15.2 mg methylammonium chloride, 23.8 mg methylammonium iodide, 219.3 mg formamidinium hydroiodate, and 760.7 mg lead iodide in a mixed solvent of 1 mL DMF and DMSO; the volume ratio of DMF to DMSO in the mixed solvent is 4:1; in step three, the spin coating speed in the first step is 1000 rpm / s for 10 s, and the spin coating speed in the second step is 5000 rpm / s for 40 s; in step three, 200 μL of chlorobenzene is added dropwise as an antisolvent 15 s before the end of the second spin coating; in step three, the annealing temperature is 100℃ and the annealing time is 30 min.

10. The application according to claim 6, characterized in that, In step four, the concentration of 1,3-diaminopropane dihydroiodate in the isopropanol solution of 1,3-diaminopropane dihydroiodate is 1 mg / mL; in step four, the spin coating speed is 5000 rpm / s, the spin coating time is 30 s, the annealing temperature is 100℃, and the annealing time is 5 min.

Images