High-efficiency perovskite photovoltaic devices modified with aromatic weak boronic acid and preparation method thereof

Abstract

The present invention discloses a highly efficient perovskite photovoltaic device based on aromatic weak boric acid modification and a preparation method thereof, belonging to the field of solar cells. The highly efficient perovskite photovoltaic device has a p-i-n structure and includes a conductive glass substrate, a hole transport layer, an aromatic weak boric acid modification layer, a perovskite light absorption layer, an electron transport layer, a buffer layer, and a metal electrode. The modification method is as follows: dynamically spin-coating an aromatic weak boric acid mixed solution on the hole transport layer; statically spin-coating a perovskite precursor solution. In the present invention, the hole transport layer is a self-assembled monolayer film. The adverse multi-layer structure of the hole transport layer can be reduced by the weak boric acid modification method, and the holes formed due to local aggregation in the hole transport layer can be filled, the substrate work function can be improved, the energy band is more matched with the perovskite, and the interfacial charge transport can be promoted. In addition, the hole transport layer modified by aromatic weak boric acid improves the film quality of the perovskite absorption layer, reduces the interfacial non-radiative recombination, increases the open-circuit photocurrent voltage, and ultimately improves the photovoltaic performance.

Description

Technical Field

[0001] The present invention belongs to the field of solar cells, and particularly relates to a highly efficient perovskite photovoltaic device based on aromatic weak boric acid modification and a preparation method thereof. Background Art

[0002] The emerging semiconductor material - halide perovskite with ABX3 structure has been the research focus in the photovoltaic field for nearly a decade due to its excellent optoelectronic properties such as adjustable bandgap, high extinction absorption coefficient, long carrier diffusion length, and high defect tolerance. The perovskite solar cells fabricated therefrom have the advantages of high efficiency, low cost, solution processability, etc., and have achieved a certified photoelectric conversion efficiency of >26%, comparable to silicon solar cells. To realize the practical application of perovskite photovoltaics, researchers need to pursue both higher efficiency and excellent long-term stability.

[0003] In particular, the efficiency of the inverted (p-i-n) perovskite photovoltaic device has increased rapidly, and the certified efficiency can be as high as 26.7%, mainly due to the use of an advanced self-assembled monolayer (SAM) film as the hole transport layer. However, this SAM film prepared by simple solution spin-coating is extremely prone to forming holes due to local molecular aggregation or forming an unfavorable multi-layer structure. These defects not only quench the charge carriers generated by perovskite light and cause non-radiative recombination, but also affect the interfacial charge transport, accelerate device aging, and thus limit the open-circuit voltage and overall performance of the photovoltaic device.

[0004] Therefore, there is an urgent need for a method to improve the quality of the existing SAM film and simultaneously achieve highly efficient inverted perovskite photovoltaic devices. Summary of the Invention

[0005] The purpose of the present invention is to provide a highly efficient perovskite photovoltaic device based on aromatic weak boric acid modification and a preparation method thereof in view of the deficiencies of the prior art.

[0006] The purpose of the present invention is achieved by the following technical solutions:

[0007] In the first aspect, the present invention provides a preparation method of a highly efficient perovskite photovoltaic device based on aromatic weak boric acid modification, comprising the following steps:

[0008] (1) Etch and cut the conductive glass to a size of 20 mm * 20 mm, then sequentially place it in deionized water, acetone, and absolute ethanol for ultrasonic treatment respectively, and finally perform ozone treatment to obtain a conductive glass substrate;

[0009] (2) Deposit a hole transport layer on the conductive glass substrate;

[0010] (3) Dynamically spin-coat an aromatic weak boric acid mixed solution on the hole transport layer, and perform annealing treatment to form an aromatic weak boric acid modified layer;

[0011] (4) Spin-coat the perovskite precursor solution statically on the aromatic weak boronic acid modified layer, and perform annealing treatment to form a perovskite light-absorbing layer;

[0012] (5) Deposit an electron transport layer and a buffer layer sequentially on the perovskite light-absorbing layer;

[0013] (6) Vacuum deposit metal on the buffer layer to form a metal electrode, and obtain a high-efficiency perovskite photovoltaic device based on aromatic weak boronic acid modification.

[0014] Further, the step (2) is specifically: statically spin-coat a nickel oxide nanoparticle aqueous dispersion with a concentration of 5-30 mg mL -1 on the conductive glass substrate, wherein the spin-coating time is 15-60 s and the rotation speed is 1000-6000 rpm s -1 ; then anneal on a hot plate at 100-150 °C for 5-30 min to form a nickel oxide layer; then statically spin-coat an ethanol solution containing SAM with a concentration of 0.05-2 mg mL -1 on the nickel oxide layer, wherein the spin-coating time is 15-60 s and the rotation speed is 1000-6000 rpm s -1 , and then anneal on a hot plate at 70-120 °C for 5-30 min to form a nickel oxide layer with a deposited SAM layer as a hole transport layer;

[0015] Or statically spin-coat an ethanol solution containing SAM with a concentration of 0.05-2 mg mL -1 on the conductive glass substrate, wherein the spin-coating time is 15-60 s and the rotation speed is 1000-6000 rpm s -1 , and then anneal on a hot plate at 70-120 °C for 5-30 min to form a SAM layer as a hole transport layer.

[0016] Further, the ethanol solution containing SAM is prepared by any one of MeO-2PACz and Me-4PACz, Ph-2PACz, TPA-2PA, 4PABCz, MeO-TPA-3PA, 2Br-4PACz, 2Br-4PAPT, 2Br-4PAPXZ, 2Br-4PADCB, 2Br-4PADMAc and ethanol in a ratio of 0.025-1 mg:0.025-1 mg:1 mL.

[0017] Further, the step (3) is specifically: dynamically spin-coat an aromatic weak boronic acid mixed solution with a concentration of 0.05-2 mg mL -1 on the hole transport layer, wherein the spin-coating time is 15-60 s and the rotation speed is 1500-6000 rpm s -1, and then anneal on a hot stage at 70-120 °C for 5-30 min to form an aromatic weak borate modification layer; the aromatic weak borate mixed solution is prepared by mixing aromatic weak borate OA-BA, ethanol, and DMF in a ratio of 0.05-2 mg:0.75 mL:0.25 mL.

[0018] Further, the aromatic weak borate is R3-R2-R1, where R1 is one or more boric acid groups; R2 is a carbon-free chain or an alkyl group with 1 to 6 carbon chains; R3 is any one, two, or a combination of two or more of benzene, naphthalene, anthracene, biphenyl, triphenylbenzene, dibenzofuran, dibenzothiophene, and carbazole.

[0019] Further, step (4) is specifically: dropping a perovskite precursor solution with a concentration of 1.5-2.2 mol mL -1 onto the aromatic weak borate modification layer, standing for 5 s and then statically spin-coating, where the spin-coating time is 30-60 s and the rotation speed is 1000-6000 rpm s -1 , and continuously dropping 100-500 μL of chlorobenzene antisolvent at 20-50 s after the start of static spin-coating. After the static spin-coating is completed, anneal on a hot stage at 70-150 °C for 20-60 min to form a perovskite light-absorbing layer; the perovskite precursor solution is prepared by mixing FA 0.95 Cs 0.05 PbI3, DMF, and DMSO in a ratio of 1.5-2.2 mol:0.8 mL:0.2 mL.

[0020] Further, step (5) specifically includes the following sub-steps:

[0021] (5.1) Static spin-coat a 15-40 nm electron transport layer formed by a PC -1 BM solution with a concentration of 10-30 mg mL 61 onto the perovskite light-absorbing layer, where the spin-coating time is 20-60 s and the rotation speed is 1000-3000 rpm s -1 ; the PC 61 BM solution is prepared by mixing PC 61 BM and chlorobenzene in a ratio of 10-50 mg:1 mL;

[0022] Or evaporate and deposit a C 60 film onto the perovskite light-absorbing layer to form an electron transport layer with a thickness of 15-40 nm;

[0023] (5.2) Subsequently, evaporate and deposit BCP onto the electron transport layer to form a buffer layer with a thickness of 4-10 nm.

[0024] Further, the metal is gold, silver, copper or aluminum.

[0025] Further, the thickness of the metal electrode is 80 - 150 nm.

[0026] In a second aspect, the present invention provides a highly efficient perovskite photovoltaic device modified by aromatic weak boric acid. The highly efficient perovskite photovoltaic device modified by aromatic weak boric acid includes, from bottom to top, a glass substrate, a hole transport layer, an aromatic weak boric acid modification layer, a perovskite light absorption layer, an electron transport layer, a buffer layer, and a metal electrode.

[0027] The beneficial effects of the present invention are as follows:

[0028] 1) The present invention modifies the SAM film with aromatic weak boric acid OA - BA, fills the holes formed by the aggregation of the SAM film, improves the substrate work function, and makes the SAM film more suitable as the hole - selective contact layer of the inverted perovskite photovoltaic device.

[0029] 2) The present invention modifies the SAM film with aromatic weak boric acid OA - BA, reduces the interfacial non - radiative recombination, and further improves the open - circuit photo - voltage and the final photoelectric conversion efficiency of the photovoltaic device.

[0030] 3) The present invention modifies the SAM film with aromatic weak boric acid OA - BA, reduces the multi - layer structure of the SAM film, enhances the interfacial charge transport, and further improves the fill factor and the final photoelectric conversion efficiency of the photovoltaic device. Description of the Drawings

[0031] Figure 1 It is a schematic structural diagram of the highly efficient perovskite photovoltaic device modified by aromatic weak boric acid prepared in Example 1;

[0032] Figure 2 It is a photocurrent density - voltage curve graph of the highly efficient perovskite photovoltaic device modified by aromatic weak boric acid prepared in Example 1 and the perovskite photovoltaic device prepared in Comparative Example 1;

[0033] Figure 3 It is a photocurrent density - voltage curve graph of the highly efficient perovskite photovoltaic device modified by aromatic weak boric acid prepared in Example 2 and the perovskite photovoltaic device prepared in Comparative Example 1;

[0034] Figure 4 It is a photocurrent density - voltage curve graph of the highly efficient perovskite photovoltaic device modified by aromatic weak boric acid prepared in Example 3 and the perovskite photovoltaic device prepared in Comparative Example 1;

[0035] Figure 5Photocurrent density-voltage curve graphs of the highly efficient perovskite photovoltaic device prepared in Example 4 and the perovskite photovoltaic device prepared in Comparative Example 1;

[0036] Figure 6 Photocurrent density-voltage curve graphs of the highly efficient perovskite photovoltaic device prepared in Example 5 and the perovskite photovoltaic device prepared in Comparative Example 1;

[0037] Figure 7 Schematic structural diagram of the highly efficient perovskite photovoltaic device prepared in Example 6 and modified with aromatic weak boronic acid;

[0038] Figure 8 Photocurrent density-voltage curve graphs of the highly efficient perovskite photovoltaic device prepared in Example 6 and modified with aromatic weak boronic acid and the perovskite photovoltaic device prepared in Comparative Example 2;

[0039] Figure 9 Contact angle test diagram, where, Figure 9 A in is the contact angle test diagram of the conductive glass substrate and the hole transport layer in the perovskite photovoltaic device prepared in Comparative Example 2, Figure 9 B in is the contact angle test diagram of the conductive glass substrate, the hole transport layer and the aromatic weak boronic acid modified layer in the highly efficient perovskite photovoltaic device prepared in Example 6 and modified with aromatic weak boronic acid;

[0040] Figure 10 Atomic force microscope image of the hole transport layer, where, Figure 10 A in is the atomic force microscope image of the conductive glass substrate and the hole transport layer in the perovskite photovoltaic device prepared in Comparative Example 2, Figure 10 B in is the atomic force microscope image of the conductive glass substrate, the hole transport layer and the aromatic weak boronic acid modified layer in the highly efficient perovskite photovoltaic device prepared in Example 6 and modified with aromatic weak boronic acid;

[0041] Figure 11 Atomic force microscope image of the perovskite light-absorbing layer, where, Figure 11 A in is the atomic force microscope image of the conductive glass substrate, the hole transport layer and the perovskite light-absorbing layer in the perovskite photovoltaic device prepared in Comparative Example 2, Figure 11 B in is the atomic force microscope image of the conductive glass substrate, the hole transport layer, the aromatic weak boronic acid modified layer and the perovskite light-absorbing layer in the highly efficient perovskite photovoltaic device prepared in Example 6 and modified with aromatic weak boronic acid;

[0042] Figure 12UV-visible absorption spectra of the conductive glass substrate, hole transport layer, and perovskite light-absorbing layer in the perovskite photovoltaic device prepared in Comparative Example 2, and the conductive glass substrate, hole transport layer, aromatic weak boronic acid modification layer, and perovskite light-absorbing layer in the highly efficient perovskite photovoltaic device based on aromatic weak boronic acid modification prepared in Example 6;

[0043] Figure 13 X-ray diffraction patterns of the conductive glass substrate, hole transport layer, and perovskite light-absorbing layer in the perovskite photovoltaic device prepared in Comparative Example 2, and the conductive glass substrate, hole transport layer, aromatic weak boronic acid modification layer, and perovskite light-absorbing layer in the highly efficient perovskite photovoltaic device based on aromatic weak boronic acid modification prepared in Example 6;

[0044] Figure 14 Photoluminescence spectra of the conductive glass substrate, hole transport layer, and perovskite light-absorbing layer in the perovskite photovoltaic device prepared in Comparative Example 2, and the conductive glass substrate, hole transport layer, aromatic weak boronic acid modification layer, and perovskite light-absorbing layer in the highly efficient perovskite photovoltaic device based on aromatic weak boronic acid modification prepared in Example 6;

[0045] Figure 15 Transient PL kinetic curves of the conductive glass substrate, hole transport layer, and perovskite light-absorbing layer in the perovskite photovoltaic device prepared in Comparative Example 2, and the conductive glass substrate, hole transport layer, aromatic weak boronic acid modification layer, and perovskite light-absorbing layer in the highly efficient perovskite photovoltaic device based on aromatic weak boronic acid modification prepared in Example 6. Detailed Description of the Invention

[0046] In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, rather than all embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts are within the protection scope of the present invention.

[0047] The present invention provides a preparation method for a highly efficient perovskite photovoltaic device based on aromatic weak boronic acid modification, comprising the following steps:

[0048] (1) Etch and cut the conductive glass to a size of 20 mm * 20 mm, then sequentially place it in deionized water, acetone, and absolute ethanol for ultrasonic treatment respectively, and finally perform ozone treatment to obtain a conductive glass substrate.

[0049] (2) Deposit a hole transport layer on the conductive glass substrate.

[0050] The specific step (2) is as follows:

[0051] A nickel oxide nano aqueous dispersion with a concentration of 5 - 30 mg / mL is statically spin-coated on the conductive glass substrate, where the spin-coating time is 15 - 60 s and the rotation speed is 1000 - 6000 rpm s -1 ; Subsequently, annealing is performed on a hot plate at 100 - 150 °C for 5 - 30 min to form a nickel oxide layer; Then, an ethanol solution containing SAM with a concentration of 0.05 - 2 mg / mL is statically spin-coated on the nickel oxide layer, where the spin-coating time is 15 - 60 s and the rotation speed is 1000 - 6000 rpm s -1 ; Subsequently, annealing is performed on a hot plate at 70 - 120 °C for 5 - 30 min to form a nickel oxide layer with a deposited SAM layer as the hole transport layer. -1 The ethanol solution containing SAM is prepared by mixing any one of MeO - 2PACz, Me - 4PACz, Ph - 2PACz, TPA - 2PA, 4PABCz, MeO - TPA - 3PA, 2Br - 4PACz, 2Br - 4PAPT, 2Br - 4PAPXZ, 2Br - 4PADCB, 2Br - 4PADMAc and ethanol in a ratio of 0.025 - 1 mg:0.025 - 1 mg:1 mL. -1 Or step (2) is specifically: An ethanol solution containing SAM with a concentration of 0.05 - 2 mg / mL is statically spin-coated on the conductive glass substrate, where the spin-coating time is 15 - 60 s and the rotation speed is 1000 - 6000 rpm s

[0052] ; Subsequently, annealing is performed on a hot plate at 70 - 120 °C for 5 - 30 min to form a SAM layer as the hole transport layer. -1 The ethanol solution containing SAM is prepared by mixing any one of MeO - 2PACz, Me - 4PACz, Ph - 2PACz, TPA - 2PA, 4PABCz, MeO - TPA - 3PA, 2Br - 4PACz, 2Br - 4PAPT, 2Br - 4PAPXZ, 2Br - 4PADCB, 2Br - 4PADMAc and ethanol in a ratio of 0.025 - 1 mg:0.025 - 1 mg:1 mL. -1 Or step (2) is specifically: An ethanol solution containing SAM with a concentration of 0.05 - 2 mg / mL is statically spin-coated on the conductive glass substrate, where the spin-coating time is 15 - 60 s and the rotation speed is 1000 - 6000 rpm s

[0053] The ethanol solution containing SAM is prepared by mixing any one of MeO - 2PACz, Me - 4PACz, Ph - 2PACz, TPA - 2PA, 4PABCz, MeO - TPA - 3PA, 2Br - 4PACz, 2Br - 4PAPT, 2Br - 4PAPXZ, 2Br - 4PADCB, 2Br - 4PADMAc and ethanol in a ratio of 0.025 - 1 mg:0.025 - 1 mg:1 mL.

[0054] (3) Aromatic weak boric acid mixed solution is dynamically spin-coated on the hole transport layer and annealed to form an aromatic weak boric acid modified layer.

[0055] Step (3) is specifically: An aromatic weak boric acid mixed solution with a concentration of 0.05 - 2 mg / mL is dynamically spin-coated on the hole transport layer, where the spin-coating time is 15 - 60 s and the rotation speed is 1500 - 6000 rpm s -1 ; Subsequently, annealing is performed on a hot plate at 70 - 120 °C for 5 - 30 min to form an aromatic weak boric acid modified layer; The aromatic weak boric acid mixed solution is prepared by mixing aromatic weak boric acid OA - BA, ethanol and DMF in a ratio of 0.05 - 2 mg:0.75 mL:0.25 mL. -1 The ethanol solution containing SAM is prepared by mixing any one of MeO - 2PACz, Me - 4PACz, Ph - 2PACz, TPA - 2PA, 4PABCz, MeO - TPA - 3PA, 2Br - 4PACz, 2Br - 4PAPT, 2Br - 4PAPXZ, 2Br - 4PADCB, 2Br - 4PADMAc and ethanol in a ratio of 0.025 - 1 mg:0.025 - 1 mg:1 mL.

[0056] The aromatic weak boronic acid OA-BA is R3-R2-R1, where R1 is one or more boronic acid groups; R2 is a carbon-free chain or an alkyl group with 1 to 6 carbon chains; R3 is any one, two or a combination of two or more of benzene, naphthalene, anthracene, biphenyl, triphenylbenzene, dibenzofuran, dibenzothiophene, carbazole.

[0057] (4) Spin-coat the perovskite precursor solution statically on the aromatic weak boronic acid modified layer, and perform annealing treatment to form a perovskite light-absorbing layer.

[0058] The specific operation of step (4) is as follows: Drop the perovskite precursor solution with a concentration of 1.5~2.2mol mL -1 onto the aromatic weak boronic acid modified layer, let it stand for 5 s and then spin-coat statically, where the spin-coating time is 30~60 s and the rotation speed is 1000~6000rpm s -1 , and continuously drop 100~500 μL of chlorobenzene antisolvent at 20~50 s after the start of static spin-coating. After the static spin-coating is completed, anneal on a hot plate at 70~150 °C for 20~60 min to form a perovskite light-absorbing layer; the perovskite precursor solution is prepared from FA 0.95 Cs 0.05 PbI3, DMF and DMSO in a ratio of 1.5~2.2mol:0.8mL:0.2mL.

[0059] (5) Deposit an electron transport layer and a buffer layer sequentially on the perovskite light-absorbing layer.

[0060] The specific operation of step (5) includes the following sub-steps:

[0061] (5.1) Spin-coat a 15~40 nm electron transport layer formed by a PC -1 BM solution with a concentration of 10~30mg mL 61 on the perovskite light-absorbing layer, where the spin-coating time is 20~60 s and the rotation speed is 1000~3000rpm s -1 ; the PC 61 BM solution is prepared from PC 61 BM and chlorobenzene in a ratio of 10~50mg:1mL;

[0062] Or deposit a C 60 thin film by evaporation on the perovskite light-absorbing layer to form a 15~40 nm electron transport layer.

[0063] (5.2) Then deposit BCP by evaporation on the electron transport layer to form a 4~10 nm buffer layer.

[0064] (6) Vacuum deposit a metal on the buffer layer to form a metal electrode with a thickness of 80 - 150 nm, thereby obtaining a highly efficient perovskite photovoltaic device modified with an aromatic weak boronic acid. The metal is gold, silver, copper or aluminum.

[0065] Example 1: In this example, the aromatic weak boronic acid OA - BA used is dibenzofuran - 4 - boronic acid, with the molecular formula C 12 H9BO3, simply abbreviated as DF - BA, and is produced by TCI Corporation. The structural formula of DF - BA is shown as follows:

[0066] .

[0067] A preparation method of a highly efficient perovskite photovoltaic device modified with an aromatic weak boronic acid, comprising the following steps:

[0068] (1) Prepare a conductive glass substrate: Etch and cut an ITO conductive glass to a size of 20 mm * 20 mm, then sequentially place it in deionized water, acetone, and absolute ethanol for ultrasonic treatment for 10 min each, and finally perform ozone treatment for 0.5 h to obtain a conductive glass substrate.

[0069] (2) Prepare a hole - transporting layer: Spin - coat 100 μL of a nickel oxide nanoparticle aqueous dispersion with a concentration of 10 mg mL -1 statically on the conductive glass substrate, where the spin - coating time is 20 s and the rotation speed is 2000 rpm s -1 ; then anneal on a hot stage at 150 °C for 10 min to form a nickel oxide layer; then spin - coat 100 μL of an ethanol solution containing SAM with a concentration of 0.5 mg mL -1 statically on the nickel oxide layer, where the spin - coating time is 30 s and the rotation speed is 3000 rpm s -1 ; then anneal on a hot stage at 100 °C for 10 min to form a nickel oxide layer with a deposited SAM layer as the hole - transporting layer; in this example, the ethanol solution containing SAM is prepared by mixing MeO - 2PACz, 2Br - 4PADMAc, and ethanol in a ratio of 0.25 mg:0.25 mg:1 mL.

[0070] (3) Prepare an aromatic weak boronic acid modified layer: Spin - coat 100 μL of an aromatic weak boronic acid mixed solution with a concentration of 0.5 mgmL -1 dynamically on the hole - transporting layer, where the spin - coating time is 30 s and the rotation speed is 3000 rpm s -1; Subsequently, it was annealed on a hot stage at 100 °C for 5 min to form an aromatic weak boric acid modified layer. In this example, the aromatic weak boric acid mixed solution was prepared by dibenzofuran-4-boric acid DF-BA, ethanol, and DMF in a ratio of 0.5 mg:0.75 mL:0.25 mL.

[0071] (4) Preparation of the perovskite light-absorbing layer: 100 μL of a perovskite precursor solution with a concentration of 1.5 mol mL -1 was dropped onto the aromatic weak boric acid modified layer, and after standing for 5 s, it was spin-coated statically. Among them, the spin-coating time was 50 s, and the rotation speed was 2000 rpm s -1 , and 200 μL of chlorobenzene antisolvent was continuously dropped at 38 s after the start of static spin-coating. After the static spin-coating was completed, it was annealed on a hot stage at 100 °C for 0.5 h to form a perovskite light-absorbing layer. In this example, the perovskite precursor solution was prepared by FA 0.95 Cs 0.05 PbI3, DMF, and DMSO in a ratio of 1.5 mol:0.8 mL:0.2 mL.

[0072] (5) Preparation of the electron transport layer and the buffer layer: First, 100 μL of a PC -1 BM solution with a concentration of 20 mg mL 61 was spin-coated statically on the perovskite light-absorbing layer to form an electron transport layer, where the spin-coating time was 35 s and the rotation speed was 1500 rpm s -1 ; Subsequently, BCP was deposited by evaporation on the electron transport layer to form a buffer layer with a thickness of 6 nm.

[0073] (6) Silver was vacuum-evaporated on the buffer layer to form a metal electrode with a thickness of 100 nm, and a highly efficient perovskite photovoltaic device based on aromatic weak boric acid modification was obtained.

[0074] The structure of the highly efficient perovskite photovoltaic device based on aromatic weak boric acid modification prepared in this example is ITO / NiO x / SAM / DF-BA / FA 0.95 Cs 0.05 PbI3 / PC 61 BM / BCP / Ag, as Figure 1 shown. As Figure 1 can be seen, the highly efficient perovskite photovoltaic device based on aromatic weak boric acid modification is, from bottom to top, a conductive glass substrate, a hole transport layer, an aromatic weak boric acid modified layer, a perovskite light-absorbing layer, an electron transport layer, a buffer layer, and a metal electrode.

[0075] Comparative Example 1: A perovskite photovoltaic device was prepared, which from bottom to top was a conductive glass substrate, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, a buffer layer, and a metal electrode, as Comparative Example 1; compared with the highly efficient perovskite photovoltaic device based on aromatic weak boronic acid modification prepared in Example 1, the perovskite light-absorbing layer was directly formed on the hole transport layer, and the other preparation processes were the same.

[0076] Under standard AM1.5G simulated sunlight, the photocurrent density-voltage ( J — V )characteristics of the highly efficient perovskite photovoltaic device based on aromatic weak boronic acid modification prepared in Example 1 and the perovskite photovoltaic device prepared in Comparative Example 1 were measured, as Figure 2 shown. From the Figure 2 shown J — V curves, the photovoltaic parameters are shown in Table 1. The short-circuit photocurrent density ( J SC )of the perovskite photovoltaic device prepared in Comparative Example 1 was 25.17 mA cm -2 , the open-circuit voltage ( V OC )was 1.165 V, the fill factor (FF) was 83.6%, and the final power conversion efficiency (PCE) was 24.51%. In contrast, for the highly efficient perovskite photovoltaic device based on aromatic weak boronic acid modification prepared in Example 1, after the hole transport layer was modified with dibenzofuran-4-boronic acid PC-BA, the photovoltaic parameters were significantly improved. J SC The slight increase was to 25.41 mA cm -2 , V OC the increase was 10 mV to 1.175 V, and the FF increased by about 1% to 84.7%, resulting in a significant increase in the final PCE to 25.25%. V OC The significant increase in

[0077] and FF indicates that modifying the hole transport layer with dibenzofuran-4-boronic acid PC-BA can reduce the interfacial non-radiative recombination between the hole transport layer and the perovskite light-absorbing layer, enhance the interfacial charge transport between the hole transport layer and the perovskite light-absorbing layer, and effectively improve the performance of the photovoltaic device.

[0078]

[0079] Example 2: In this example, the aromatic weak boronic acid OA-BA used is 9-phenylcarbazole-2-boronic acid ((9-Phenyl-9H-carbazol-2-yl)boronic acid), with the molecular formula C 18 H 14 BNO2, abbreviated as PC-BA, produced by TCI. The structural formula of PC-BA is as follows:

[0080] 。

[0081] A preparation method of an efficient perovskite photovoltaic device based on aromatic weak boronic acid modification, comprising the following steps:

[0082] (1) Prepare a conductive glass substrate: Etch and cut the ITO conductive glass to a size of 20 mm * 20 mm, then sequentially place it in deionized water, acetone, and absolute ethanol for ultrasonic treatment for 10 min each, and finally perform ozone treatment for 0.5 h to obtain a conductive glass substrate.

[0083] (2)Prepare a hole transport layer: Spin-coat 100 μL of a nickel oxide nanoparticle aqueous dispersion with a concentration of 10 mg mL -1 statically on the conductive glass substrate, where the spin-coating time is 20 s and the rotation speed is 2000 rpm s -1 ; Then anneal on a hot plate at 150 °C for 10 min to form a nickel oxide layer; Then spin-coat 100 μL of an ethanol solution containing SAM with a concentration of 0.5 mg mL -1 statically on the nickel oxide layer, where the spin-coating time is 30 s and the rotation speed is 3000 rpm s -1 ; Then anneal on a hot plate at 100 °C for 10 min to form a nickel oxide layer with a deposited SAM layer as the hole transport layer; In this example, the ethanol solution containing SAM is prepared by mixing MeO-2PACz, 2Br-4PADMAc, and ethanol in a ratio of 0.25 mg:0.25 mg:1 mL.

[0084] (3)Prepare an aromatic weak boronic acid modification layer: Spin-coat 100 μL of an aromatic weak boronic acid mixed solution with a concentration of 0.5 mg mL -1 dynamically on the hole transport layer, where the spin-coating time is 30 s and the rotation speed is 3000 rpm s -1 ; Then anneal on a hot plate at 100 °C for 5 min to form an aromatic weak boronic acid modification layer; In this example, the aromatic weak boronic acid mixed solution is prepared by mixing 9-phenylcarbazole-2-boronic acid PC-BA, ethanol, and DMF in a ratio of 0.5 mg:0.75 mL:0.25 mL.

[0085] (4)Fabricating the perovskite light-absorbing layer: 100 μL of the perovskite precursor solution with a concentration of 1.5 mol mL -1 was dropped onto the aromatic weak boronic acid modified layer, and after standing for 5 s, static spin coating was performed. Among them, the spin coating time was 50 s, and the rotation speed was 2000 rpm s -1 , and 200 μL of chlorobenzene antisolvent was continuously dropped at 38 s after the start of static spin coating. After the static spin coating was completed, annealing was performed on a hot plate at 100 °C for 0.5 h to form the perovskite light-absorbing layer; in this example, the perovskite precursor solution was prepared from FA 0.95 Cs 0.05 PbI3, DMF, and DMSO in a ratio of 1.5 mol:0.8 mL:0.2 mL.

[0086] (5)Fabricating the electron transport layer and the buffer layer: First, 100 μL of a PC -1 BM solution with a concentration of 20 mg mL 61 was statically spin coated on the perovskite light-absorbing layer to form the electron transport layer, where the spin coating time was 35 s and the rotation speed was 1500 rpm s -1 ; subsequently, BCP was deposited by evaporation on the electron transport layer to form a buffer layer with a thickness of 6 nm.

[0087] (6)Silver was vacuum evaporated on the buffer layer to form a metal electrode with a thickness of 100 nm, obtaining a highly efficient perovskite photovoltaic device based on aromatic weak boronic acid modification.

[0088] The structure of the highly efficient perovskite photovoltaic device prepared in this example is ITO / NiO x / SAM / PC-BA / FA 0.95 Cs 0.05 PbI3 / PC 61 BM / BCP / Ag.

[0089] Under standard AM1.5G simulated sunlight, the photocurrent density-voltage ( J — V ) characteristics of the highly efficient perovskite photovoltaic device prepared in Example 2 and the perovskite photovoltaic device prepared in Comparative Example 1 were measured, as shown in Figure 3 . As shown in Figure 3 , the photovoltaic parameters obtained from the J — V curve graph are shown in Table 2. The short-circuit photocurrent density ( J SC ) of the perovskite photovoltaic device prepared in Comparative Example 1 was 25.17 mA cm -2 , and the open-circuit voltage ( V OC) was 1.165 V, the fill factor (FF) was 83.6%, and the final power conversion efficiency (PCE) was 24.51%. In contrast, for the high-efficiency perovskite photovoltaic device prepared in Example 2 and modified with aromatic weak boronic acid, after using 9-phenylcarbazole-2-boronic acid PC-BA to modify the hole transport layer, the photovoltaic parameters were significantly improved. J SC The slight increase was 25.32 mA cm -2 , V OC increased to 1.170 V, the FF increased by 2.4% to 86.0%, and the final PCE was significantly increased to 25.47%. V OC The significant increase in Jsc and FF indicates that using 9-phenylcarbazole-2-boronic acid PC-BA to modify the hole transport layer can reduce the interfacial non-radiative recombination between the hole transport layer and the perovskite light-absorbing layer, enhance the interfacial charge transport between the hole transport layer and the perovskite light-absorbing layer, and effectively improve the performance of the photovoltaic device.

[0090] Table 2: Photovoltaic parameters of the high-efficiency perovskite photovoltaic device prepared in Example 2 and modified with aromatic weak boronic acid and the perovskite photovoltaic device prepared in Comparative Example 1

[0091]

[0092] Example 3: In this example, the aromatic weak boronic acid OA-BA was 3-(9H-carbazol-9-yl)phenylboronic acid, with the molecular formula C 18 H 14 BNO2, abbreviated as HCP-BA, which was an isomer of PC-BA in Example 2 and was produced by TCI Corporation. The structural formula of HCP-BA is shown as follows:

[0093] .

[0094] A preparation method of a high-efficiency perovskite photovoltaic device modified with aromatic weak boronic acid, comprising the following steps:

[0095] (1) Prepare a conductive glass substrate: Etch and cut the ITO conductive glass to a size of 20 mm * 20 mm, then place it in deionized water, acetone, and absolute ethanol in sequence and ultrasonically treat it for 10 min each, and finally ozone treat it for 0.5 h to obtain a conductive glass substrate.

[0096] (2) Prepare a hole transport layer: Spin-coat 100 μL of a solution with a concentration of 10 mg mL -1The nickel oxide nano-dispersion liquid, where the spin-coating time is 20 s and the rotation speed is 2000 rpm s -1 ; Subsequently, it was annealed on a hot plate at 150 °C for 10 min to form a nickel oxide layer; Then, 100 μL of an ethanol solution containing SAM with a concentration of 0.5 mg mL -1 was spin-coated statically on the nickel oxide layer, where the spin-coating time is 30 s and the rotation speed is 3000 rpm s -1 ; Subsequently, it was annealed on a hot plate at 100 °C for 10 min to form a nickel oxide layer with a deposited SAM layer as a hole transport layer; In this embodiment, the ethanol solution containing SAM was prepared by mixing MeO-2PACz, 2Br-4PADMAc, and ethanol in a ratio of 0.25 mg:0.25 mg:1 mL.

[0097] (3)Preparation of the aromatic weak boronic acid modified layer: 100 μL of an aromatic weak boronic acid mixed solution with a concentration of 0.5 mg mL -1 was spin-coated dynamically on the hole transport layer, where the spin-coating time is 30 s and the rotation speed is 3000 rpm s -1 ; Subsequently, it was annealed on a hot plate at 100 °C for 5 min to form an aromatic weak boronic acid modified layer; In this embodiment, the aromatic weak boronic acid mixed solution was prepared by mixing 3-(9H-carbazol-9-yl)phenyl-boronic acid HCP-BA, ethanol, and DMF in a ratio of 0.5 mg:0.75 mL:0.25 mL.

[0098] (4)Preparation of the perovskite light-absorbing layer: 100 μL of a perovskite precursor liquid with a concentration of 1.5 mol mL -1 was dropped onto the aromatic weak boronic acid modified layer, and after standing for 5 s, it was spin-coated statically, where the spin-coating time is 50 s and the rotation speed is 2000 rpm s -1 , and 200 μL of chlorobenzene antisolvent was continuously dropped at 38 s after the start of static spin-coating. After the static spin-coating was completed, it was annealed on a hot plate at 100 °C for 0.5 h to form a perovskite light-absorbing layer; In this embodiment, the perovskite precursor liquid was prepared by mixing FA 0.95 Cs 0.05 PbI3, DMF, and DMSO in a ratio of 1.5 mol:0.8 mL:0.2 mL.

[0099] (5)Preparation of the electron transport layer and the buffer layer: First, 100 μL of a PC -1 BM solution with a concentration of 20 mg mL 61 was spin-coated statically on the perovskite light-absorbing layer to form an electron transport layer, where the spin-coating time is 35 s and the rotation speed is 1500 rpm s -1 ; Subsequently, BCP was deposited by evaporation on the electron transport layer to form a buffer layer with a thickness of 6 nm.

[0100] (6) Vacuum deposit silver on the buffer layer to form a metal electrode with a thickness of 100 nm, obtaining a highly efficient perovskite photovoltaic device modified by aromatic weak boric acid.

[0101] The structure prepared in this example is ITO / NiO x / SAM / HCP - BA / FA 0.95 Cs 0.05 PbI3 / PC 61 BM / BCP / Ag highly efficient perovskite photovoltaic device modified by aromatic weak boric acid.

[0102] Under standard AM1.5G simulated sunlight, measure the photocurrent density - voltage ( J — V ) characteristics of the highly efficient perovskite photovoltaic device modified by aromatic weak boric acid prepared in Example 3 and the perovskite photovoltaic device prepared in Comparative Example 1, as Figure 4 shown. The photovoltaic parameters obtained from the Figure 4 shown J — V curve graph are shown in Table 3. The short - circuit photocurrent density ( J SC ) of the perovskite photovoltaic device prepared in Comparative Example 1 is 25.17 mA cm -2 , the open - circuit voltage ( V OC ) is 1.165 V, the fill factor (FF) is 83.6%, and the final power conversion efficiency (PCE) is 24.51%. In contrast, for the highly efficient perovskite photovoltaic device modified by aromatic weak boric acid prepared in Example 3, after using 3 - (9H - carbazol - 9 - yl)phenyl - boric acid HCP - BA to modify the hole - transporting layer, the photovoltaic parameters have been significantly improved. J SC The short - circuit photocurrent density has slightly increased to 25.40 mA cm -2 , V OC the open - circuit voltage has significantly increased by 13 mV to 1.178 V, and the FF has increased to 84.1%, resulting in a significant increase in the final PCE to 25.16%. V OC The significant increase in and FF indicates that using 3 - (9H - carbazol - 9 - yl)phenyl - boric acid HCP - BA to modify the hole - transporting layer can reduce the interfacial non - radiative recombination between the hole - transporting layer and the perovskite light - absorbing layer, enhance the interfacial charge transport between the hole - transporting layer and the perovskite light - absorbing layer, and effectively improve the performance of the photovoltaic device.

[0103] Table 3: Photovoltaic parameters of the highly efficient perovskite photovoltaic device modified by aromatic weak boric acid prepared in Example 3 and the perovskite photovoltaic device prepared in Comparative Example 1

[0104]

[0105] Example 4: In this example, the aromatic weak boronic acid OA-BA used is [4′-(carbazol-9-yl)-4-biphenyl]boronic acid (abbreviated as BC-BA), with the molecular formula C 24 H 18 BNO2, and it is produced by TCI Company. The structural formula of BC-BA is as follows: 。

[0106] A preparation method of an efficient perovskite photovoltaic device modified with aromatic weak boronic acid, comprising the following steps:

[0107] (1) Prepare a conductive glass substrate: Etch and cut the ITO conductive glass to a size of 20 mm * 20 mm, then place it in deionized water, acetone, and absolute ethanol in sequence and ultrasonically treat it for 10 min each, and finally ozone treat it for 0.5 h to obtain the conductive glass substrate.

[0108] (2) Prepare a hole transport layer: Spin-coat 100 μL of a nickel oxide nanoparticle aqueous dispersion with a concentration of 10 mg mL -1 statically on the conductive glass substrate, where the spin-coating time is 20 s and the rotation speed is 2000 rpm s -1 ; then anneal it on a hot plate at 150 °C for 10 min to form a nickel oxide layer; then spin-coat 100 μL of an ethanol solution containing SAM with a concentration of 0.5 mg mL -1 statically on the nickel oxide layer, where the spin-coating time is 30 s and the rotation speed is 3000 rpm s -1 ; then anneal it on a hot plate at 100 °C for 10 min to form a nickel oxide layer with a deposited SAM layer as the hole transport layer; in this example, the ethanol solution containing SAM is prepared by mixing MeO-2PACz, 2Br-4PADMAc, and ethanol in a ratio of 0.25 mg:0.25 mg:1 mL.

[0109] (3) Prepare an aromatic weak boronic acid modified layer: Spin-coat 100 μL of an aromatic weak boronic acid mixed solution with a concentration of 0.5 mgmL -1 dynamically on the hole transport layer, where the spin-coating time is 30 s and the rotation speed is 3000 rpm s -1; Subsequently, it was annealed on a hot stage at 100 °C for 5 min to form an aromatic weak borate modification layer; in this example, the aromatic weak borate mixed solution was prepared from [4′-(carbazol-9-yl)-4-biphenyl]boronic acid BC-BA, ethanol, and DMF in a ratio of 0.5 mg:0.75 mL:0.25 mL.

[0110] (4) Preparation of the perovskite light-absorbing layer: 100 μL of a perovskite precursor solution with a concentration of 1.5 mol mL -1 was dropped onto the aromatic weak borate modification layer, and after standing for 5 s, it was spin-coated statically. Among them, the spin-coating time was 50 s, and the rotation speed was 2000 rpm s -1 , and 200 μL of chlorobenzene antisolvent was continuously dropped at 38 s after the start of static spin-coating. After the static spin-coating was completed, it was annealed on a hot stage at 100 °C for 0.5 h to form a perovskite light-absorbing layer; in this example, the perovskite precursor solution was prepared from FA 0.95 Cs 0.05 PbI3, DMF, and DMSO in a ratio of 1.5 mol:0.8 mL:0.2 mL.

[0111] (5) Preparation of the electron transport layer and the buffer layer: First, 100 μL of a PC -1 BM solution with a concentration of 20 mg mL 61 was spin-coated statically on the perovskite light-absorbing layer to form an electron transport layer, where the spin-coating time was 35 s and the rotation speed was 1500 rpm s -1 ; Subsequently, BCP was deposited by evaporation on the electron transport layer to form a buffer layer with a thickness of 6 nm.

[0112] (6) Silver was vacuum-evaporated on the buffer layer to form a metal electrode with a thickness of 100 nm, obtaining a highly efficient perovskite photovoltaic device based on aromatic weak borate modification.

[0113] The structure of the highly efficient perovskite photovoltaic device based on aromatic weak borate modification prepared in this example is ITO / NiO x / SAM / BC-BA / FA 0.95 Cs 0.05 PbI3 / PC 61 BM / BCP / Ag.

[0114] Under standard AM1.5G simulated sunlight, the photocurrent density–voltage ( J — V ) characteristics of the highly efficient perovskite photovoltaic device based on aromatic weak borate modification prepared in Example 4 and the perovskite photovoltaic device prepared in Comparative Example 1 were measured, as Figure 5 shown. From Figure 5 shown in J — VThe photovoltaic parameters obtained from the curve are shown in Table 4. The short-circuit photocurrent density ( J SC ) of the perovskite photovoltaic device prepared in Comparative Example 1 is 25.17 mA cm -2 , the open-circuit voltage ( V OC ) is 1.165 V, the fill factor (FF) is 83.6%, and the final power conversion efficiency (PCE) is 24.51%. In contrast, for the highly efficient perovskite photovoltaic device based on aromatic weak boronic acid modification prepared in Example 4, after using [4′-(carbazol-9-yl)-4-biphenyl]boronic acid BC-BA to modify the hole transport layer, the photovoltaic parameters have been significantly improved. J SC The slight increase is 25.45 mA cm -2 , V OC the obvious increase is 15 mV to 1.18 V, and the FF is increased to 84.2%, resulting in the final PCE being significantly increased to 25.29%. V OC The obvious increase in V

[0115] oc and FF indicates that using [4′-(carbazol-9-yl)-4-biphenyl]boronic acid BC-BA to modify the hole transport layer can reduce the interfacial non-radiative recombination between the hole transport layer and the perovskite light-absorbing layer, enhance the interfacial charge transport between the hole transport layer and the perovskite light-absorbing layer, and effectively improve the performance of the photovoltaic device.

[0116]

[0117] Example 5: In this example, the aromatic weak boronic acid OA-BA used is 1,3,5-tris(4-phenylboronic acid)benzene (1,3,5-Tris[(4-phenylboronic acid)]benzene), with the molecular formula C 24 H 21 3O6, abbreviated as TPB-BA, and is produced by TCI Company. The structural formula of TPB-BA is shown as follows: .

[0118] A preparation method of a highly efficient perovskite photovoltaic device based on aromatic weak boronic acid modification includes the following steps:

[0119] (1) Preparation of conductive glass substrate: The ITO conductive glass was etched and cut into a size of 20 mm * 20 mm, and then successively placed in deionized water, acetone, and absolute ethanol for ultrasonic treatment for 10 min each. Finally, it was treated with ozone for 0.5 h to obtain the conductive glass substrate.

[0120] (2) Preparation of hole transport layer: 100 μL of a nickel oxide nanowater dispersion with a concentration of 10 mg mL -1 was spin-coated statically on the conductive glass substrate, where the spin-coating time was 20 s and the rotation speed was 2000 rpm s -1 ; then it was annealed on a hot plate at 150 °C for 10 min to form a nickel oxide layer; then 100 μL of an ethanol solution containing SAM with a concentration of 0.5 mg mL -1 was spin-coated statically on the nickel oxide layer, where the spin-coating time was 30 s and the rotation speed was 3000 rpm s -1 ; then it was annealed on a hot plate at 100 °C for 10 min to form a nickel oxide layer with a deposited SAM layer as the hole transport layer; in this example, the ethanol solution containing SAM was prepared by mixing MeO-2PACz, 2Br-4PADMAc, and ethanol in a ratio of 0.25 mg:0.25 mg:1 mL.

[0121] (3) Preparation of aromatic weak boronic acid modified layer: 100 μL of an aromatic weak boronic acid mixed solution with a concentration of 0.5 mg mL -1 was spin-coated dynamically on the hole transport layer, where the spin-coating time was 30 s and the rotation speed was 3000 rpm s -1 ; then it was annealed on a hot plate at 100 °C for 5 min to form the aromatic weak boronic acid modified layer; in this example, the aromatic weak boronic acid mixed solution was prepared by mixing 1,3,5-tris(4-phenylboronic acid)benzene (TPB-BA), ethanol, and DMF in a ratio of 0.5 mg:0.75 mL:0.25 mL.

[0122] (4) Preparation of perovskite light-absorbing layer: 100 μL of a perovskite precursor solution with a concentration of 1.5 mol mL -1 was dropped onto the aromatic weak boronic acid modified layer, and after standing for 5 s, it was spin-coated statically, where the spin-coating time was 50 s and the rotation speed was 2000 rpm s -1 , and 200 μL of chlorobenzene antisolvent was continuously dropped at 38 s after the start of static spin-coating. After the static spin-coating was completed, it was annealed on a hot plate at 100 °C for 0.5 h to form the perovskite light-absorbing layer; in this example, the perovskite precursor solution was prepared by mixing FA 0.95 Cs 0.05 PbI3, DMF, and DMSO in a ratio of 1.5 mol:0.8 mL:0.2 mL.

[0123] (5) Preparation of the electron transport layer and the buffer layer: First, 100 μL of a PC -1 BM solution with a concentration of 20 mg mL 61 was spin-coated statically on the perovskite light-absorbing layer to form the electron transport layer, where the spin-coating time was 35 s and the rotation speed was 1500 rpm s -1 ; subsequently, BCP was deposited by evaporation on the electron transport layer to form a buffer layer with a thickness of 6 nm.

[0124] (6) Silver was vacuum-evaporated on the buffer layer to form a metal electrode with a thickness of 100 nm, obtaining a highly efficient perovskite photovoltaic device modified by aromatic weak boronic acid.

[0125] The structure of the highly efficient perovskite photovoltaic device modified by aromatic weak boronic acid prepared in this example is ITO / NiO x / SAM / TPB-BA / FA 0.95 Cs 0.05 PbI3 / PC 61 BM / BCP / Ag.

[0126] Under standard AM1.5G simulated sunlight, the photocurrent density-voltage ( J — V ) characteristics of the highly efficient perovskite photovoltaic device modified by aromatic weak boronic acid prepared in Example 5 and the perovskite photovoltaic device prepared in Comparative Example 1 were measured, as Figure 6 shown. The photovoltaic parameters obtained from the Figure 6 shown J — V curve are shown in Table 5. The short-circuit photocurrent density ( J SC ) of the perovskite photovoltaic device prepared in Comparative Example 1 was 25.17 mA cm -2 , the open-circuit voltage ( V OC ) was 1.165 V, the fill factor (FF) was 83.6%, and the final power conversion efficiency (PCE) was 24.51%. In contrast, for the highly efficient perovskite photovoltaic device modified by aromatic weak boronic acid prepared in Example 5, after using 1,3,5-tris(4-phenylboronic acid)benzene TPB-BA to modify the hole transport layer, the photovoltaic parameters were significantly improved. J SC The short-circuit photocurrent density was slightly increased to 25.60 mA cm -2 , V OC the open-circuit voltage was significantly increased by 27 mV to 1.192 V, and the FF was significantly increased by 1.4% to 85.0%, resulting in a significant increase in the final PCE to 25.94%. V OCThe obvious improvement in FF indicates that modifying the hole transport layer with 1,3,5-tris(4-phenylboronic acid)phenyl (TPB-BA) can reduce the non-radiative recombination at the interface between the hole transport layer and the perovskite light-absorbing layer, enhance the interfacial charge transport between the hole transport layer and the perovskite light-absorbing layer, and effectively improve the performance of the photovoltaic device.

[0127] Table 5: Photovoltaic parameters of the highly efficient perovskite photovoltaic device prepared in Example 5 based on aromatic weak boronic acid modification and the perovskite photovoltaic device prepared in Comparative Example 1

[0128]

[0129] Example 6: A preparation method of a highly efficient perovskite photovoltaic device based on aromatic weak boronic acid modification, comprising the following steps:

[0130] (1) Prepare a conductive glass substrate: Etch and cut the ITO conductive glass to a size of 20 mm * 20 mm, then sequentially place it in deionized water, acetone, and absolute ethanol for ultrasonic treatment for 10 min each, and finally perform ozone treatment for 0.5 h to obtain a conductive glass substrate.

[0131] (2) Prepare a hole transport layer: Spin-coat 100 μL of an ethanol solution containing SAM with a concentration of 0.5 mg mL -1 statically on the conductive glass substrate, where the spin-coating time is 30 s and the rotation speed is 3000 rpm s -1 ; then anneal on a hot plate at 100 °C for 10 min to form a nickel oxide layer deposited with the SAM layer as the hole transport layer; in this example, the ethanol solution containing SAM is prepared by mixing MeO-2PACz, 2Br-4PADMAc, and ethanol in a ratio of 0.25 mg:0.25 mg:1 mL.

[0132] (3) Prepare an aromatic weak boronic acid modification layer: Spin-coat 100 μL of an aromatic weak boronic acid mixed solution with a concentration of 0.5 mg mL -1 dynamically on the hole transport layer, where the spin-coating time is 30 s and the rotation speed is 3000 rpm s -1 ; then anneal on a hot plate at 100 °C for 5 min to form an aromatic weak boronic acid modification layer; in this example, the aromatic weak boronic acid mixed solution is prepared by mixing 1,3,5-tris(4-phenylboronic acid)phenyl (TPB-BA), ethanol, and DMF in a ratio of 0.5 mg:0.75 mL:0.25 mL.

[0133] (4) Prepare a perovskite light-absorbing layer: Drop 100 μL of a perovskite precursor solution with a concentration of 1.5 mol mL -1 onto the aromatic weak boronic acid modification layer, let it stand for 5 s and then spin-coat statically, where the spin-coating time is 50 s and the rotation speed is 2000 rpm s-1 , and 200 μL of chlorobenzene antisolvent was continuously dropped at 38 s after the start of static spin coating. After the static spin coating was completed, it was annealed on a hot plate at 100 °C for 0.5 h to form a perovskite light-absorbing layer; in this example, the perovskite precursor solution was prepared from FA 0.95 Cs 0.05 PbI3, DMF, and DMSO were prepared in a ratio of 1.5 mol: 0.8 mL: 0.2 mL.

[0134] (5) Preparation of the electron transport layer and the buffer layer: First, 100 μL of a PC -1 solution with a concentration of 20 mg mL 61 was statically spin-coated on the perovskite light-absorbing layer to form an electron transport layer, where the spin coating time was 35 s and the rotation speed was 1500 rpm s -1 ; subsequently, BCP was deposited by evaporation on the electron transport layer to form a buffer layer with a thickness of 6 nm.

[0135] (6) Silver was vacuum-evaporated on the buffer layer to form a metal electrode with a thickness of 100 nm, and a highly efficient perovskite photovoltaic device modified by aromatic weak boric acid was obtained.

[0136] The structure of the highly efficient perovskite photovoltaic device prepared in this example is ITO / SAM / TPB-BA / FA 0.95 Cs 0.05 PbI3 / PC 61 BM / BCP / Ag, as shown in Figure 7 .

[0137] Comparative Example 2: A perovskite photovoltaic device with a conductive glass substrate, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, a buffer layer, and a metal electrode from bottom to top was prepared as Comparative Example 2; the perovskite photovoltaic device prepared in Comparative Example 2 was compared with the highly efficient perovskite photovoltaic device modified by aromatic weak boric acid prepared in Example 6. The perovskite light-absorbing layer was directly formed on the hole transport layer, and the other preparation processes were the same.

[0138] Under standard AM1.5G simulated sunlight, the photocurrent density-voltage ( J — V ) characteristics of the highly efficient perovskite photovoltaic device modified by aromatic weak boric acid prepared in Example 6 and the perovskite photovoltaic device prepared in Comparative Example 1 were measured, as shown in Figure 8 . The photovoltaic parameters obtained from the Figure 8 — J — V curve graph are shown in Table 6. The short-circuit photocurrent density ( J SCis 25.20 mA cm -2 , the open-circuit voltage ( V OC ) is 1.165 V, the fill factor (FF) is 83.50%, and the final power conversion efficiency (PCE) is 24.51%. In contrast, for the highly efficient perovskite photovoltaic device prepared in Example 6 and modified with aromatic weak boronic acid, after modifying the hole transport layer with 1,3,5-tris(4-phenylboronic acid)benzene (TPB-BA), the photovoltaic parameters have been significantly improved. J SC The slight improvement is 25.50 mA cm -2 , V OC it has increased significantly by 35 mV to 1.20 V, and the FF has increased significantly by 2.1% to 85.6%, resulting in a significant increase in the final PCE to 26.20%. V OC The significant increase in Jsc and FF indicates that modifying the hole transport layer with 1,3,5-tris(4-phenylboronic acid)benzene (TPB-BA) can reduce the non-radiative recombination at the interface between the hole transport layer and the perovskite light-absorbing layer, enhance the interfacial charge transport between the hole transport layer and the perovskite light-absorbing layer, and effectively improve the performance of the photovoltaic device.

[0139] Table 6: Photovoltaic parameters of the highly efficient perovskite photovoltaic device prepared in Example 6 and modified with aromatic weak boronic acid and the perovskite photovoltaic device prepared in Comparative Example 2

[0140]

[0141] To investigate the effect of trisboronic acid benzene (TPB-BA) on the wettability of the perovskite precursor solution, the contact angles of the conductive glass substrate and the hole transport layer in the perovskite photovoltaic device prepared in Comparative Example 2 and the conductive glass substrate, the hole transport layer, and the aromatic weak boronic acid modified layer in the highly efficient perovskite photovoltaic device prepared in Example 6 were measured. The contact angle test diagrams are as shown in Figure 9 shown, where Figure 9 A in Figure 9 is the contact angle test diagram of the conductive glass substrate and the hole transport layer in the perovskite photovoltaic device prepared in Comparative Example 2, and

[0142] As Figure 9 shown in A in Figure 9As shown in B of , the contact angle between the conductive glass substrate, the hole transport layer, and the aromatic weak boronic acid modification layer in the highly efficient perovskite photovoltaic device prepared in Example 6 increased to approximately 29.63°. The increased hydrophobicity indicates that after modifying the hole transport layer with 1,3,5-tris(4-phenylboronic acid)benzene, the compactness of the hole transport layer increased, thereby reducing some multilayer structures on the hole transport layer that were not anchored to the ITO conductive glass.

[0143] Atomic force microscopy tests were also performed on the conductive glass substrate and the hole transport layer in the perovskite photovoltaic device prepared in Comparative Example 2, as well as on the conductive glass substrate, the hole transport layer, and the aromatic weak boronic acid modification layer in the highly efficient perovskite photovoltaic device prepared in Example 6, and atomic force microscopy images were obtained, as Figure 10 shown, where Figure 10 A in is the atomic force microscopy image of the conductive glass substrate and the hole transport layer in the perovskite photovoltaic device prepared in Comparative Example 2, Figure 10 and B in is the atomic force microscopy image of the conductive glass substrate, the hole transport layer, and the aromatic weak boronic acid modification layer in the highly efficient perovskite photovoltaic device prepared in Example 6. Measuring the surface morphology and roughness through the atomic force microscopy images (AFM images) indicates that modifying the hole transport layer with 1,3,5-tris(4-phenylboronic acid)benzene hardly affects the surface morphology and roughness of the hole transport layer. Since the molecular scales of MeO-2PACz, 2Br-4PADMAc, and 1,3,5-tris(4-phenylboronic acid)benzene are all approximately 1 nm, Figure 10 A in and Figure 10 the morphology shown in B in is mainly information of the conductive glass substrate.

[0144] Atomic force microscopy tests were also performed on the conductive glass substrate, the hole transport layer, and the perovskite light-absorbing layer in the perovskite photovoltaic device prepared in Comparative Example 2, as well as on the conductive glass substrate, the hole transport layer, the aromatic weak boronic acid modification layer, and the perovskite light-absorbing layer in the highly efficient perovskite photovoltaic device prepared in Example 6, and atomic force microscopy images of the perovskite light-absorbing layer were obtained, as Figure 11 shown, where Figure 11 A in is the atomic force microscopy image of the conductive glass substrate, the hole transport layer, and the perovskite light-absorbing layer in the perovskite photovoltaic device prepared in Comparative Example 2, Figure 11In [Example 6], B is the atomic force microscope image of the conductive glass substrate, hole transport layer, aromatic weak boric acid modified layer, and perovskite light-absorbing layer in the highly efficient perovskite photovoltaic device prepared by Example 6. The roughness of the perovskite light-absorbing layer in the perovskite photovoltaic device prepared by Comparative Example 2 is about 33.0 nm, while the roughness of the perovskite light-absorbing layer in the highly efficient perovskite photovoltaic device based on aromatic weak boric acid modification prepared by Example 6 is significantly reduced to 20.9 nm. The reason may be that the pores in the latter film are reduced and the perovskite grain boundaries become denser, making the morphology of the perovskite light-absorbing layer smoother.

[0145] At the same time, ultraviolet-visible absorption tests, X-ray diffraction tests, steady-state and transient photoluminescence tests were respectively carried out on the conductive glass substrate, hole transport layer, and perovskite light-absorbing layer in the perovskite photovoltaic device prepared by Comparative Example 2, and on the conductive glass substrate, hole transport layer, aromatic weak boric acid modified layer, and perovskite light-absorbing layer in the highly efficient perovskite photovoltaic device based on aromatic weak boric acid modification prepared by Example 6.

[0146] Figure 12 Figure [is] the ultraviolet-visible absorption spectra of the conductive glass substrate, hole transport layer, and perovskite light-absorbing layer in the perovskite photovoltaic device prepared by Comparative Example 2, and of the conductive glass substrate, hole transport layer, aromatic weak boric acid modified layer, and perovskite light-absorbing layer in the highly efficient perovskite photovoltaic device based on aromatic weak boric acid modification prepared by Example 6. The absorbance of the perovskite light-absorbing layer in the highly efficient perovskite photovoltaic device based on aromatic weak boric acid modification prepared by Example 6 increases slightly relative to Comparative Example 2, which may be related to the increased thickness or improved crystallinity. In addition, it can be clearly seen from Figure 12 that the edge absorption of the perovskite light-absorbing layer in the highly efficient perovskite photovoltaic device based on aromatic weak boric acid modification prepared by Example 6 is enhanced and the edge is red-shifted by about 4 nm, all of which are beneficial to enhancing and broadening the light trapping efficiency of the device.

[0147] Figure 13 Figure [is] the X-ray diffraction patterns of the conductive glass substrate, hole transport layer, and perovskite light-absorbing layer in the perovskite photovoltaic device prepared by Comparative Example 2, and of the conductive glass substrate, hole transport layer, aromatic weak boric acid modified layer, and perovskite light-absorbing layer in the highly efficient perovskite photovoltaic device based on aromatic weak boric acid modification prepared by Example 6. The diffraction angle The diffraction peak at 12.6° is the signal of excessive lead iodide, and the diffraction angle The diffraction peak at 14° is the signal of the (100) crystal plane of perovskite. Compared with the perovskite light-absorbing layer in the perovskite photovoltaic device prepared in Comparative Example 2, the perovskite signal in the perovskite light-absorbing layer of the highly efficient perovskite photovoltaic device based on aromatic weak boronic acid modification prepared in Example 6 is enhanced, and the lead iodide signal is weakened, indicating that the crystallinity of the perovskite light-absorbing layer in the highly efficient perovskite photovoltaic device based on aromatic weak boronic acid modification prepared in Example 6 is improved.

[0148] Figure 14 It is the photoluminescence spectra of the conductive glass substrate, hole transport layer and perovskite light-absorbing layer in the perovskite photovoltaic device prepared in Comparative Example 2, and the conductive glass substrate, hole transport layer, aromatic weak boronic acid modification layer and perovskite light-absorbing layer in the highly efficient perovskite photovoltaic device based on aromatic weak boronic acid modification prepared in Example 6. When the surface of the perovskite film is irradiated with an excitation light with a wavelength of 450 nm and the same intensity, it can be observed that the photoluminescence intensity emitted by the perovskite light-absorbing layer in the highly efficient perovskite photovoltaic device based on aromatic weak boronic acid modification prepared in Example 6 is stronger, which means that the radiative recombination is enhanced after modifying the hole transport layer with 1,3,5-tris(4-phenylboronic acid)benzene.

[0149] Figure 15 It is the transient PL kinetic curve of the conductive glass substrate, hole transport layer and perovskite light-absorbing layer in the perovskite photovoltaic device prepared in Comparative Example 2, and the conductive glass substrate, hole transport layer, aromatic weak boronic acid modification layer and perovskite light-absorbing layer in the highly efficient perovskite photovoltaic device based on aromatic weak boronic acid modification prepared in Example 6. Using the time-correlated single photon technique, the time-resolved PL decay kinetics under low-intensity pulsed excitation was measured. By fitting with an exponential function, the charge carrier lifetime can be obtained. The lifetime (5608 ns) of the perovskite light-absorbing layer in the highly efficient perovskite photovoltaic device based on aromatic weak boronic acid modification prepared in Example 6 is significantly longer than that (4357 ns) of the perovskite light-absorbing layer in the perovskite photovoltaic device prepared in Comparative Example 2, indicating that the defect-assisted non-radiative recombination kinetics is inhibited after modifying the hole transport layer with 1,3,5-tris(4-phenylboronic acid)benzene.

[0150] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the scope of protection of the present invention.

Claims

1. A method for preparing a high-efficiency perovskite photovoltaic device based on aromatic weak boric acid modification, characterized in that: The following steps are involved: (1) The conductive glass was etched and cut into a size of 20 mm*20 mm, and then ultrasonically treated in deionized water, acetone and anhydrous ethanol respectively, and finally ozone treated to obtain a conductive glass substrate; (2) depositing a hole transport layer on the conductive glass substrate; The step (2) is specifically as follows: statically spin coating the conductive glass substrate at a concentration of 5 to 30 mg mL -1 The nano nickel oxide aqueous dispersion is prepared by spinning for 15 to 60 seconds at a speed of 1000 to 6000 rpm. -1 ; Then, a nickel oxide layer is formed after annealing on a hot plate at 100-150°C for 5-30 min; Then, a concentration of 0.05-2 mg mL -1 The ethanol solution containing SAM is prepared by spinning for 15 to 60 seconds at a speed of 1000 to 6000 rpm. -1 , then annealed on a hot plate at 70-120°C for 5-30 min to form a nickel oxide layer of the deposited SAM layer as a hole transport layer; Or static spin coating concentration on the conductive glass substrate is 0.05~2mg mL -1 The ethanol solution containing SAM is prepared by spinning for 15 to 60 seconds at a speed of 1000 to 6000 rpm. -1 , and then annealed on a hot stage at 70-120°C for 5-30 min to form a SAM layer as a hole transport layer; The SAM-containing ethanol solution is prepared by mixing MeO-2PACz with any one of Me-4PACz, Ph-2PACz, TPA-2PA, 4PABCz, MeO-TPA-3PA, 2Br-4PACz, 2Br-4PAPT, 2Br-4PAPXZ, 2Br-4PADCB, and 2Br-4PADMAc and ethanol in a ratio of 0.025-1 mg: 0.025-1 mg: 1 mL; (3) dynamically spin coating an aromatic weak boric acid mixed solution on the hole transport layer, and performing annealing treatment to form an aromatic weak boric acid modified layer; The step (3) is specifically as follows: dynamically spin-coating the hole transport layer at a concentration of 0.05-2 mg mL -1 Aromatic weak boric acid mixed solution, wherein the spin coating time is 15~60s, and the rotation speed is 1500~6000rpm s -1 , and then annealing on a hot plate at 70-120° C. for 5-30 min to form an aromatic weak boric acid modified layer; the aromatic weak boric acid mixed solution is prepared by using aromatic weak boric acid OA-BA, ethanol and DMF in a ratio of 0.05-2 mg: 0.75 mL: 0.25 mL; The aromatic weak boronic acid OA-BA is R3-R2-R1, wherein R1 is one or more boronic acid groups; R2 is a carbon-free chain or an alkyl group with 1 to 6 carbon chains; R3 is any one of benzene, naphthalene, anthracene, biphenyl, triphenylbenzene, dibenzofuran, dibenzothiophene, and carbazole, or a combination of two or more thereof; (4) statically spin coating a perovskite precursor solution on the aromatic weak boric acid modified layer, and performing annealing treatment to form a perovskite light absorbing layer; The step (4) is specifically as follows: adding a concentration of 1.5-2.2 mol mL -1 The perovskite precursor solution is dropped onto the aromatic weak boric acid modified layer, and then statically spin-coated after standing for 5 seconds, wherein the spin-coating time is 30-60 seconds and the rotation speed is 1000-6000 rpm s -1 , and continuously add 100-500 μL of chlorobenzene antisolvent 20-50 seconds after the static spin coating begins. After the static spin coating is completed, anneal on a hot plate at 70-150° C. for 20-60 minutes to form a perovskite light-absorbing layer; the perovskite precursor solution is heated by FA 0.95 Cs 0.05 PbI3, DMF and DMSO were prepared in the ratio of 1.5~2.2mol:0.8mL:0.2mL; (5) sequentially depositing an electron transport layer and a buffer layer on the perovskite light absorbing layer; (6) Vacuum evaporating metal on the buffer layer to form a metal electrode, thereby obtaining a high-efficiency perovskite photovoltaic device based on aromatic weak boric acid modification.

2. The method for preparing a high-efficiency perovskite photovoltaic device based on aromatic weak boric acid modification according to claim 1, characterized in that: The step (5) specifically includes the following sub-steps: (5.1) Static spin coating concentration on the perovskite light absorbing layer is 10~30mg mL -1 PC 61 The BM solution forms an electron transport layer of 15-40 nm, wherein the spin coating time is 20-60 s and the rotation speed is 1000-3000 rpm s -1 ; The PC 61 BM solution through PC 61 BM and chlorobenzene were prepared in a ratio of 10-50 mg:1 mL; Or C evaporated and deposited on the perovskite light absorbing layer 60 Thin film, forming an electron transport layer with a thickness of 15~40nm; (5.2) Then, BCP is deposited on the electron transport layer by evaporation to form a buffer layer with a thickness of 4 to 10 nm.

3. The method for preparing a high-efficiency perovskite photovoltaic device based on aromatic weak boric acid modification according to claim 1, characterized in that: The metal is gold, silver, copper or aluminum.

4. The method for preparing a high-efficiency perovskite photovoltaic device based on aromatic weak boric acid modification according to claim 1, characterized in that: The thickness of the metal electrode is 80-150 nm.

5. A high-efficiency perovskite photovoltaic device based on aromatic weak boric acid modification prepared by any method of claims 1-4, characterized in that: The high-efficiency perovskite photovoltaic device based on aromatic weak boric acid modification comprises, from bottom to top, a conductive glass substrate, a hole transport layer, an aromatic weak boric acid modified layer, a perovskite light absorption layer, an electron transport layer, a buffer layer and a metal electrode.

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