Modification methods and applications for improving energy level matching at the interface of vapor-deposited copper phthalocyanine / perovskite

Abstract

This invention belongs to the field of photovoltaic technology and discloses a modification method and its application for improving the energy level matching of the evaporated copper phthalocyanine / perovskite interface. The method includes: laser etching a conductive glass substrate of a predetermined size; after laser etching, ultrasonically cleaning the conductive glass substrate sequentially with glass cleaning solution, copper propylene, and isopropanol; drying and storing for later use; subjecting the dried conductive glass substrate to ultraviolet-ozone treatment, followed by evaporation to obtain a copper phthalocyanine film; spreading a pre-prepared silane-modified nano-dispersion onto the copper phthalocyanine film, and then annealing to obtain the modified film. This invention utilizes the dehydration condensation reaction between silane hydroxyl groups and surface hydroxyl groups to improve the dispersibility and stability of nanoparticles, resulting in a dense, uniform, and highly covered modification layer on the surface of copper phthalocyanine with a wide bandgap.

Description

Technical Field

[0001] This invention relates to the field of photovoltaic technology, and in particular to a modification method and application for improving the energy level matching of the vapor-deposited copper phthalocyanine / perovskite interface, which is used to improve the photoelectric conversion efficiency and long-term stability of inverted perovskite solar cells with vapor-deposited copper phthalocyanine as the hole transport layer. Background Technology

[0002] Photovoltaics is a key pillar of renewable energy and a strategic emerging industry that the country is focusing on developing. However, traditional crystalline silicon solar cells suffer from high energy consumption in fabrication, limited improvement in photoelectric conversion efficiency, and restricted application scenarios, hindering their further development. Perovskite solar cells, with their advantages of simple fabrication processes, low material costs, high theoretical limit efficiency, and flexible device structures, have become one of the most promising emerging technologies in the photovoltaic field. In recent years, the photoelectric conversion efficiency of single-junction inverted perovskite solar cells has exceeded 27%, and the efficiency of perovskite / silicon tandem solar cells has reached 34.85%, with the industrialization process continuing to accelerate.

[0003] However, the long-term stability of perovskite solar cells is still far lower than that of traditional silicon solar cells, and this stability issue has become a key factor restricting the commercialization of perovskite photovoltaic technology. Copper phthalocyanine (PTC), as a P-type semiconductor material, possesses advantages such as strong weather resistance, low cost, good film formation properties, and suitability for large-area evaporation, and is considered a potential material for achieving stable and efficient perovskite photovoltaic devices. However, the low lowest unoccupied molecular orbital energy level of the hole transport layer in PTC results in insufficient blocking ability against electron reverse injection, easily leading to severe non-radiative recombination losses at the PTC / perovskite interface, significantly reducing the open-circuit voltage of the device. This results in the efficiency of current inverse perovskite solar cells based on evaporated PTC generally being below 22%. Improving the interfacial charge transfer efficiency of the PTC / perovskite heterojunction has become a crucial problem that urgently needs to be solved to improve the performance of PTC-based perovskite solar cells.

[0004] Therefore, how to provide modification methods and applications to improve the energy level matching of the vapor-deposited copper phthalocyanine / perovskite interface is an urgent problem to be solved. Summary of the Invention

[0005] The present invention provides a modification method and application for improving the energy level matching of the vapor-deposited copper phthalocyanine / perovskite interface, in order to solve the problems of the above-mentioned technologies in the prior art.

[0006] According to a first aspect of the present invention, a modification method is provided to improve the energy level matching of the vapor-deposited copper phthalocyanine / perovskite interface.

[0007] In one embodiment, the modification method for improving the energy level matching of the vapor-deposited copper phthalocyanine / perovskite interface includes: Laser etching is performed on a conductive glass substrate of a preset size. After laser etching is completed, the conductive glass substrate is ultrasonically cleaned with glass cleaning fluid, copper propylene, and isopropanol in sequence, and then dried and stored for later use. After the conductive glass substrate was dried, it was subjected to ultraviolet-ozone treatment to obtain a copper phthalocyanine film by vapor deposition. Pre-prepared silane-modified The nano-dispersion was spread on a copper phthalocyanine film and then annealed to obtain... Modified thin films.

[0008] Preferably, the pre-prepared silane-modified... The nano-dispersion was spread on a copper phthalocyanine film and then annealed to obtain... Modified films include: Will After diluting the nanoparticles with isopropanol, the following was obtained: Isopropanol solution; exist Silane and deionized water are added to an isopropanol solution and mixed thoroughly by ultrasonic vibration to obtain... Nano-dispersion; Using spin coating method The nano-dispersion was spin-coated onto a copper phthalocyanine film, and then annealed on a hot plate to obtain... Modified thin films.

[0009] Preferably, the silane is any one of 3-aminopropyltriethoxysilane, trimethylchlorosilane, and triisopropylchlorosilane.

[0010] Preferably, the spin coating speed is 3000~8000 rpm and the spin coating time is 10~50 min.

[0011] Preferably, the annealing temperature during the annealing process on the hot plate is 50~120℃, and the spin coating time is 5~20min.

[0012] According to a second aspect of the present invention, a modification method for improving the energy level matching of the vapor-deposited copper phthalocyanine / perovskite interface is provided for use in a vapor-deposited copper phthalocyanine-based inverted perovskite solar cell. The steps of the vapor-deposited copper phthalocyanine-based inverted perovskite solar cell include: Laser etching is performed on a conductive glass substrate of a preset size. After laser etching is completed, the conductive glass substrate is ultrasonically cleaned with glass cleaning fluid, copper propylene, and isopropanol in sequence, and then dried and stored for later use. After the conductive glass substrate was dried, it was subjected to ultraviolet-ozone treatment to obtain a copper phthalocyanine film by vapor deposition. Pre-prepared silane-modified The nano-dispersion was spread on a copper phthalocyanine film and then annealed to obtain... Modified thin film; After filtering, the perovskite precursor solution was spin-coated onto... A perovskite wet film was obtained by modifying the film. The antisolvent ethyl acetate and 1,3-propanediamine hydroiodide passivating agent were then added dropwise to the perovskite wet film. After annealing, a perovskite absorber film was obtained. The perovskite absorber film was placed in a vacuum thermal evaporation apparatus to obtain C. 60 Thin film, in C 60 A copper hydroxide solution was added dropwise onto the thin film to obtain C. 60 Electron transport thin films; C 60 An electron transport thin film is placed in a vacuum thermal evaporation apparatus to deposit a silver electrode with a high work function.

[0013] Preferably, the perovskite precursor solution is filtered and then spin-coated onto... A perovskite wet film was obtained by modifying the film. Ethyl acetate (an antisolvent) and 1,3-propanediamine hydroiodate (a passivating agent) were then sequentially added to the perovskite wet film. After annealing, a perovskite absorber film was obtained, comprising: Prepare the perovskite precursor solution. Take the perovskite precursor solution in a glove box, filter it, and then spin-coat it in two steps onto... A perovskite wet film was obtained by modifying the film; After adding ethyl acetate as the antisolvent to the perovskite wet film, the perovskite wet film was removed from the glove box and annealed in air. After natural cooling, the perovskite composition was obtained as FA. 0.9 Cs 0.07 MA 0.03 PbI 2.76 Br 0.24 Perovskite thin films; The perovskite film was placed in a glove box, and 1,3-propanediamine hydroiodate was spin-coated as a passivating agent. After annealing on a hot plate, the perovskite absorber film was obtained.

[0014] Preferably, the UV-ozone treatment time is 10-30 minutes and the temperature is 20-30°C; the vacuum degree of the phthalocyanine copper thin film obtained by vapor deposition is 2-10×10⁻⁶. -4 Torr, with a temperature of 300~500℃ and a speed of 0.02~0.1Å / s; the copper phthalocyanine film has a thickness of 5~15nm.

[0015] Preferably, the perovskite precursor solution is taken from the glove box, filtered, and then spin-coated in two steps onto... The first spin coating speed on the modified film is 500~3000 rpm and the spin coating time is 5~20s. The second spin coating speed is 1000~5000 rpm and the spin coating time is 10~50s. The annealing temperature in the air annealing process is 80~120℃, and the annealing time is 20~50min; the annealing temperature in the perovskite absorber film obtained after the hot annealing process is 80~120℃, and the annealing time is 1~10min.

[0016] Preferably, the perovskite absorber film is placed in a vacuum thermal evaporation apparatus to deposit C. 60 The vacuum degree of vapor deposition in thin films is 2~8×10 -4 Torr, with a evaporation rate of 0.1~0.4 Å / s and a temperature of 300~600℃; the C 60 The film thickness is 10~30nm; The above in C 60 A copper hydroxide solution was added dropwise onto the thin film to obtain C. 60 The spin coating speed of the copper bath solution in the electron transport thin film is 2000~8000 rpm, and the spin coating time is 20~50 min.

[0017] The technical solutions provided by the embodiments of the present invention may include the following beneficial effects: This invention utilizes silane hydroxyl groups and The dehydration condensation reaction between surface hydroxyl groups enhances The dispersibility and stability of nanoparticles enable a wide bandgap. A dense, uniform, and highly covered modification layer is formed on the surface of copper phthalocyanine, effectively suppressing electron reverse injection and thus improving hole extraction and transport efficiency. Furthermore, this modification layer effectively enhances the wettability of the substrate surface, and its electron-rich amino groups can react with Pb. 2+ The interaction improves the crystallization kinetics of perovskite, thereby enhancing the film quality of perovskite and effectively solving the problem of interfacial energy level mismatch between evaporated copper phthalocyanine films and perovskite, ultimately resulting in high-efficiency copper phthalocyanine-based inverse perovskite photovoltaic devices.

[0018] It should be understood that the above general description and the following detailed description are exemplary and explanatory only, and are not intended to limit the invention. Attached Figure Description

[0019] The accompanying drawings, which are incorporated in and form part of this specification, illustrate embodiments consistent with the invention and, together with the description, serve to explain the principles of the invention.

[0020] Figure 1 This is a silane coupling illustrated according to an exemplary embodiment. A schematic diagram of the fabrication process of modified copper phthalocyanine perovskite solar cells; Figure 2 This is a schematic diagram illustrating the effect of APTES on the dispersibility of alumina nanoparticles according to an exemplary embodiment. and Dynamic light scattering diagram of @APTES dispersion; Figure 3 The images are scanning electron microscope (SEM) images of three thin films, CuPc, CuPc / Al2O3, and CuPc / Al2O3@APTES, as shown in an exemplary embodiment. Figure 4 This is a scanning electron microscope image of perovskite thin films on three substrates: CuPc, CuPc / Al2O3, and CuPc / Al2O3@APTES, according to an exemplary embodiment. Figure 5 The photoluminescence spectra of three thin films (a) and three thin films (b) of ITO / perovskite, ITO / Al2O3 / perovskite, and ITO / Al2O3@APTES / perovskite are shown according to an exemplary embodiment. Figure 6 This is a current-voltage curve of a perovskite solar cell with CuPc, CuPc / Al2O3, or CuPc / Al2O3@APTES as the hole transport layer, according to an exemplary embodiment.

[0021] The English annotations in the attached figures are as follows: APTES is 3-aminopropyltriethoxysilane; CuPc is copper phthalocyanine; BCP is copper bath solution; perovskite is perovskite; hydrolyze is hydrolysis; intensity is absorbance; wavelength is wavelength; excitation is excitation; control is the reference group (copper phthalocyanine surface without any modification layer); current intensity is current density; voltage is voltage; Voc is open circuit voltage; Jsc is circuit current; FF is fill factor; PCE is photoelectric conversion efficiency. Detailed Implementation

[0022] The following description and accompanying drawings fully illustrate specific embodiments described herein to enable those skilled in the art to practice them. Some portions and features of certain embodiments may be included in or replace portions and features of other embodiments. The scope of the embodiments herein includes the entire scope of the claims and all available equivalents thereof. The various embodiments described herein are presented in a progressive manner, with each embodiment focusing on its differences from other embodiments; similar or identical parts between embodiments can be referred to interchangeably.

[0023] Where there is no conflict, the embodiments and features in the embodiments of the present invention can be combined with each other.

[0024] Figure 1 An embodiment of the modification method of the present invention for improving the energy level matching of the vapor-deposited copper phthalocyanine / perovskite interface is shown.

[0025] In this optional embodiment, the modification method for improving the energy level matching of the vapor-deposited copper phthalocyanine / perovskite interface includes: Laser etching is performed on a conductive glass substrate of a preset size. After laser etching is completed, the conductive glass substrate is ultrasonically cleaned with glass cleaning fluid, copper propylene, and isopropanol in sequence, and then dried and stored for later use. After the conductive glass substrate was dried, it was subjected to ultraviolet-ozone treatment to obtain a copper phthalocyanine film by vapor deposition. Pre-prepared silane-modified The nano-dispersion was spread on a copper phthalocyanine film and then annealed to obtain... Modified thin films.

[0026] In this optional embodiment, the pre-prepared silane-modified... The nano-dispersion was spread on a copper phthalocyanine film and then annealed to obtain... Modified films include: Will After diluting the nanoparticles with isopropanol, the following was obtained: Isopropanol solution; exist Silane and deionized water are added to an isopropanol solution and mixed thoroughly by ultrasonic vibration to obtain... Nanodispersion.

[0027] Specifically, in 1 mL Add 5-20 μL of silane and 1-3 μL of deionized water to the isopropanol solution, and sonicate at room temperature for 5-10 min to thoroughly mix the mixture using ultrasonic vibration. Nano-dispersion; The concentration of the dispersion is 0.2~0.5wt%, and the solvent is isopropanol.

[0028] Using spin coating method The nano-dispersion was spin-coated onto a copper phthalocyanine film, and then annealed on a hot plate to obtain... Modified thin films.

[0029] In this optional embodiment, the silane is any one of 3-aminopropyltriethoxysilane, trimethylchlorosilane, and triisopropylchlorosilane.

[0030] In this optional embodiment, the spin coating speed is 3000~8000 rpm and the spin coating time is 10~5 min.

[0031] In this optional embodiment, the annealing temperature during the annealing process on the hot table is 50~120℃, and the spin coating time is 5~20min.

[0032] It should be noted that this invention prepares a copper phthalocyanine hole transport layer, and then uses silane modification... Nano-dispersion treatment of copper phthalocyanine films; the treatment method is spin coating followed by annealing, specifically including: Cleaning conductive glass: Select a size of 2*2cm 2 Shear resistance is 5~20Ω / cm 2 Using ITO (indium tin oxide) or FTO (fluorine-doped tin oxide) as the conductive substrate, laser etching is performed on the substrate, followed by ultrasonic cleaning with glass cleaning solution, copper propylene, and isopropanol for 20 minutes in sequence. After drying, the substrate is stored for later use.

[0033] Preparation of copper phthalocyanine hole transport layer: Conductive glass was dried by UV-ozone treatment, and then copper phthalocyanine thin film was deposited by vapor deposition.

[0034] preparation Modification layer: Preparation of silane-modified... Nano-dispersion, spin-coated onto the obtained copper phthalocyanine film Modification layer ( Modified thin film).

[0035] Figures 1-2 An embodiment of the modification method of the present invention for improving the energy level matching of the vapor-deposited copper phthalocyanine / perovskite interface is shown in a vapor-deposited copper phthalocyanine-based inverse perovskite solar cell.

[0036] In this optional embodiment, the modification method for improving the energy level matching of the evaporated copper phthalocyanine / perovskite interface is applied in a evaporated copper phthalocyanine-based inverted perovskite solar cell. The steps of the evaporated copper phthalocyanine-based inverted perovskite solar cell include: Laser etching is performed on a conductive glass substrate of a preset size. After laser etching, the conductive glass substrate is ultrasonically cleaned with glass cleaning solution, copper propylene, and isopropanol in sequence. After drying, it is stored for later use. After the conductive glass substrate was dried, it was subjected to ultraviolet-ozone treatment to obtain a copper phthalocyanine film by vapor deposition. Pre-prepared silane-modified The nano-dispersion was spread on a copper phthalocyanine film and then annealed to obtain... Modified thin film; After filtering, the perovskite precursor solution was spin-coated onto... A perovskite wet film was obtained by modifying the film. The antisolvent ethyl acetate and 1,3-propanediamine hydroiodide passivating agent were then added dropwise to the perovskite wet film. After annealing, a perovskite absorber film was obtained. The perovskite absorber film was placed in a vacuum thermal evaporation apparatus to obtain C. 60 Thin film, in C 60 A copper hydroxide solution was added dropwise onto the thin film to obtain C. 60 Electron transport thin films; C 60 An electron transport thin film is placed in a vacuum thermal evaporation apparatus to deposit a silver electrode with a high work function.

[0037] In this optional embodiment, the perovskite precursor solution is filtered and then spin-coated onto... A perovskite wet film was obtained by modifying the film. Ethyl acetate (an antisolvent) and 1,3-propanediamine hydroiodate (a passivating agent) were then sequentially added to the perovskite wet film. After annealing, a perovskite absorber film was obtained, comprising: Prepare the perovskite precursor solution. Take the perovskite precursor solution in a glove box, filter it, and then spin-coat it in two steps onto... A perovskite wet film was obtained by modifying the film; After adding ethyl acetate as the antisolvent to the perovskite wet film, the perovskite wet film was removed from the glove box and annealed in air. After natural cooling, the perovskite composition was obtained as FA. 0.9 Cs 0.07 MA 0.03 PbI 2.76 Br 0.24 Perovskite thin films; The perovskite film was placed in a glove box, and 1,3-propanediamine hydroiodate was spin-coated as a passivating agent. After annealing on a hot plate, the perovskite absorber film was obtained.

[0038] In this optional embodiment, the UV-ozone treatment time is 10-30 min, and the temperature is 20-30°C; the vacuum degree of the evaporated copper phthalocyanine film is 2-10×10⁻⁶. -4 Torr, with a temperature of 300~500℃ and a rate of 0.02~0.1Å / s; and a copper phthalocyanine film thickness of 5~15nm.

[0039] In this optional embodiment, the perovskite precursor solution is taken from the glove box, filtered, and then spin-coated in two steps onto... The first spin coating speed on the modified film is 500~3000 rpm and the spin coating time is 5~20s. The second spin coating speed is 1000~5000 rpm and the spin coating time is 10~50s. The annealing temperature in the air atmosphere annealing process is 80~120℃, and the annealing time is 20~50min; the annealing temperature for the perovskite absorber film obtained after annealing on a hot plate is 80~120℃, and the annealing time is 1~10min.

[0040] In this optional embodiment, the perovskite absorber film is placed in a vacuum thermal evaporation apparatus to obtain C. 60 The vacuum degree of vapor deposition in thin films is 2~8×10 -4 Torr, with a evaporation rate of 0.1~0.4 Å / s and a temperature of 300~600℃; C 60 The film thickness is 10~30nm; In C 60 A copper hydroxide solution was added dropwise onto the thin film to obtain C. 60 The spin coating speed of copper hydroxide solution in electron transport thin films is 2000~8000 rpm, and the spin coating time is 20~50 min.

[0041] It should be noted that this invention uses silane molecules such as 3-aminopropyltriethoxysilane (APTES), trimethylchlorosilane, and triisopropylchlorosilane with... The interaction between them enhances Particle dispersibility and stability, especially after APTES treatment. The dispersibility and solution stability were significantly improved. The nano-dispersion can form a dense and uniform modification layer on the surface of copper phthalocyanine, while improving the wettability of the film surface and enhancing the energy level matching and interfacial contact between copper phthalocyanine and perovskite, thereby reducing interfacial nonradiative recombination losses. This invention is based on silane coupling. The fabrication process of modified copper phthalocyanine-based inverse perovskite solar cells is as follows: Figure 1 As shown, the specific steps are as follows: 1) Cleaning conductive glass: Select glass with a size of 2*2cm. 2 Shear resistance is 5~20Ω / cm 2 Using ITO or FTO as a conductive substrate, laser etching is performed on it, followed by ultrasonic cleaning with glass cleaning solution, copper propylene, and isopropanol for 20 minutes in sequence. After drying, it is stored for later use.

[0042] 2) Preparation of copper phthalocyanine hole transport layer: The conductive glass obtained in step 1) was treated with ultraviolet-ozone, and then a copper phthalocyanine thin film was deposited by vapor deposition.

[0043] It should be noted that in step 2), the UV-ozone treatment time is 10~30 min, the temperature is 20~30℃, and the vacuum degree of the vapor deposition is 2~10×10 -4 Torr, with a temperature of 300~500℃ and a rate of 0.02~0.1Å / s; and a copper phthalocyanine film thickness of 5~15nm.

[0044] 3) Preparation Modification layer: Preparation of silane-modified... Nano-dispersion, spin-coated onto the film obtained in step 2). Modification layer.

[0045] It should be noted that in step 3), the silane molecule is any one of 3-aminopropyltriethoxysilane, trimethylchlorosilane, or triisopropylchlorosilane; the modification method is to use 1 mL of... Add 5-20 μL of silane and 1-3 μL of deionized water to the isopropanol solution and sonicate at room temperature for 5-10 min; spin coating speed is 3000-8000 rpm for 10-50 s; annealing temperature is 50-120℃ for 5-20 min.

[0046] 4) Preparation of the perovskite absorber layer: Prepare a perovskite precursor solution, spin-coat the perovskite film obtained in step 3) in two steps, add the antisolvent ethyl acetate, and then anneal. Spin-coat and layer with 1,3-propanediamine hydroiodate passivating agent (1 mg / mL isopropanol solution), and anneal again.

[0047] It should be noted that in step 4), the perovskite component is FA. 0.9 Cs 0.07 MA 0.03 PbI 2.76 Br 0.24 The precursor solution concentration was 1~1.5 mol / L, and the solvent was a mixture of dimethyl sulfoxide and N,N-dimethylformamide in a volume ratio of 8~5:1. The spin coating speed in the first step was 500~3000 rpm for 5~20 s, and the spin coating speed in the second step was 1000~5000 rpm for 10~50 s. The ethyl acetate was added by dropping 100~300 μL of antisolvent onto the perovskite wet film when there were 10 s left in the second spin coating. The annealing temperature was 80~120℃ for 20~50 min. The passivation molecule was spin coated at a speed of 1000~5000 rpm for 20~50 min and annealed at a temperature of 80~120℃ for 1~10 min.

[0048] 5) Preparation of C 60 Electron transport layer: C is deposited on the thin film obtained in step 4). 60An electron transport layer was formed, and a copper bath (0.5 mg / mL isopropanol solution) modification layer was spin-coated.

[0049] It should be noted that in step 5), the vacuum degree of vapor deposition is 2~8×10⁻⁶. -4 Torr, with a velocity of 0.1~0.4 Å / s and a temperature of 300~600℃; C 60 The film thickness is 10~30nm; the copper bath spin coating speed is 2000~8000rpm and the time is 20~50min.

[0050] 6) Preparation of silver counter electrode: A high work function silver counter electrode is deposited on the thin film obtained in step 5).

[0051] It should be noted that in step 6), the vacuum degree of the vapor deposition apparatus is 2~8×10⁻⁶. -4 Torr, with a velocity of 0.5~2 nm / s; Ag electrode thickness of 50~150 nm. Example 1

[0052] This embodiment prepares APTES coupling. The process flow for modified copper phthalocyanine-based inverse perovskite solar cells is as follows: Figure 1 As shown, the specific steps are as follows: (1) Cleaning conductive glass: Select glass with a size of 2*2cm 2 Sheet resistance is 15Ω / cm 2 ITO was used as a conductive substrate. It was laser etched, and then ultrasonically cleaned with glass cleaning solution, copper propylene and isopropanol for 15 minutes each. After drying, it was stored for later use.

[0053] (2) Preparation of copper phthalocyanine hole transport layer: The glass obtained in step (1) was treated with ultraviolet-ozone for 15 min and then placed in a vacuum thermal evaporation apparatus. The vacuum level inside the cavity was evacuated to 5 × 10⁻⁶. -4 Torr deposited copper phthalocyanine at a vapor deposition temperature of 420 °C and a deposition rate of 0.05 Å / s, with a film thickness of 10 nm.

[0054] (3) Preparation Modification layer: First, apply The nano-dispersion (concentration of 20 wt% before dilution) was diluted with isopropanol (concentration of 0.4 wt% after dilution). Take 1 mL of the above solution, add 10 μL of APTES and 1-2 μL of deionized water, and then sonicate for 5 min to mix thoroughly. Take 60 μL of the above dispersion and spread it on the copper phthalocyanine film obtained in step (2), spin-coat at 5000 rpm for 30 s, and then anneal at 100 °C for 10 min on a hot plate.

[0055] (4) Preparation of the perovskite light-absorbing layer: First, prepare a perovskite precursor solution. Dissolve 0.0128 g of MAI, 0.0270 g of FABr, 0.0492 g of CsI, 0.0792 g of PbBr2, 0.3208 g of FAI, and 1.1824 g of PbI2 in 1.6 mL of dimethyl sulfoxide and 0.4 mL of N,N-dimethylformamide and stir for 4 h. The total component concentration is 1.35 mol / L. Take 50 μL of the perovskite precursor solution in a glove box, filter it, and spread it on the film obtained in step (3). Spin coat it at 1000 rpm for 10 s, then spin coat it at 4000 rpm for 30 s. In the remaining 10 s, drop 260 μL of ethyl acetate antisolvent onto the perovskite wet film. Then remove the wet film from the glove box and anneal it at 100 °C for 40 min in an air atmosphere. After natural cooling, obtain FABr2. 0.9 Cs 0.07 MA 0.03 PbI 2.76 Br 0.24 Perovskite thin film. The above film was placed in a glove box and spin-coated at 4000 rpm for 30 s, while 60 μL of 1,3-propanediamine hydroiodate (1 mg / mL in isopropanol) was added dropwise as a passivating agent. Finally, it was annealed on a hot plate at 100 °C for 5 min.

[0056] (5) Preparation of C 60 Electron transport layer: The thin film obtained in step (4) is placed in a vacuum thermal evaporation apparatus, and the vacuum level inside the cavity is evacuated to 5×10⁻⁶. -4 Torr deposited C at an evaporation temperature of 540 °C and a deposition rate of 0.2 Å / s. 60 The film thickness is 20 nm. Then in C... 60 A modified layer was prepared by adding 60 μL of copper bath solution (0.5 mg / mL isopropanol) to the thin film and spin-coating at 5000 rpm for 30 s.

[0057] (6) Preparation of silver counter electrode: The thin film obtained in step (5) is placed in a vacuum thermal evaporation apparatus, and the vacuum degree in the cavity is evacuated to 5×10 -4 Torr deposited a silver counter electrode at a rate of 1 Å / s with an electrode thickness of 100 nm. Example 2

[0058] This embodiment differs from Embodiment 1 in that, in this embodiment... The nanoparticles are not coupled with silane molecules. The method for preparing the Al2O3 modified layer in step (3) is as follows: first, ... The nano-dispersion (concentration of 20 wt% before dilution) was diluted with isopropanol (concentration of 0.4 wt% after dilution) and then ultrasonically vibrated for 5 min. 60 μL of the above dispersion was spread on a copper phthalocyanine film, spin-coated at 5000 rpm for 30 s, and then annealed on a hot plate at 100 °C for 10 min.

[0059] The other specific steps are the same as in Example 1, and will not be repeated here. Comparative Example 1

[0060] The specific steps for preparing a copper phthalocyanine-based inverse perovskite solar cell in this embodiment are as follows: (1) Cleaning conductive glass: Select glass with a size of 2*2cm 2 Sheet resistance is 15Ω / cm 2 ITO was used as a conductive substrate. It was laser etched, and then ultrasonically cleaned with glass cleaning solution, copper propylene and isopropanol for 15 minutes each. After drying, it was stored for later use.

[0061] (2) Preparation of copper phthalocyanine hole transport layer: The glass obtained in step (1) was treated with ultraviolet-ozone for 15 min and then placed in a vacuum thermal evaporation apparatus. The vacuum level inside the cavity was evacuated to 5 × 10⁻⁶. -4 Torr deposited copper phthalocyanine at a vapor deposition temperature of 420 °C and a deposition rate of 0.05 Å / s, with a film thickness of 10 nm.

[0062] (3) Preparation of the perovskite light-absorbing layer: First, prepare a perovskite precursor solution. Dissolve 0.0128 g of MAI, 0.0270 g of FABr, 0.0492 g of CsI, 0.0792 g of PbBr2, 0.3208 g of FAI, and 1.1824 g of PbI2 in 1.6 mL of dimethyl sulfoxide and 0.4 mL of N,N-dimethylformamide and stir for 4 h. The total component concentration is 1.35 mol / L. Take 50 μL of the perovskite precursor solution in a glove box, filter it, and spread it on the film obtained in step (2). Spin coat it at 1000 rpm for 10 s, then spin coat it at 4000 rpm for 30 s. In the remaining 10 s, drop 260 μL of ethyl acetate antisolvent onto the perovskite wet film. Then remove the wet film from the glove box and anneal it at 100 °C for 40 min in an air atmosphere. After natural cooling, obtain FABr2. 0.9 Cs 0.07 MA 0.03 PbI 2.76 Br 0.24 Perovskite thin film. The above film was placed in a glove box and spin-coated at 4000 rpm for 30 s, while 60 μL of 1,3-propanediamine hydroiodate (1 mg / mL in isopropanol) was added dropwise as a passivating agent. Finally, it was annealed on a hot plate at 100 °C for 5 min.

[0063] (4) Preparation of C 60 Electron transport layer: The thin film obtained in step (3) is placed in a vacuum thermal evaporation apparatus, and the vacuum level inside the cavity is evacuated to 5×10⁻⁶. -4 Torr deposited C at an evaporation temperature of 540 °C and a deposition rate of 0.2 Å / s. 60 A thin film with a thickness of 20 nm was then applied to C. 60 A modified layer was prepared by adding 60 μL of copper bath solution (0.5 mg / mL isopropanol) to the thin film and spin-coating at 5000 rpm for 30 s.

[0064] (5) Preparation of silver counter electrode: The thin film obtained in step (4) is placed in a vacuum thermal evaporation apparatus, and the vacuum degree in the cavity is evacuated to 5×10 -4 Torr deposited a silver counter electrode at a rate of 1 Å / s with an electrode thickness of 100 nm.

[0065] Based on the above analysis, it can be concluded that the hydroxyl groups produced by the hydrolysis of APTES can interact with... The hydroxyl groups on the particle surface undergo a dehydration condensation reaction, forming an electric double layer structure on the particle surface, increasing the surface charge of the particles, thereby improving... The dispersibility and solution stability of nanoparticles, specifically as follows: Figure 2 As shown. This makes the coupled... It can form a more uniform and dense modification layer on the surface of copper phthalocyanine without APTES coupling. The particles exhibit poor dispersibility, forming uneven island-like aggregates on the copper phthalocyanine film, with noticeable large-sized clusters also visible. Furthermore, no... Modified copper phthalocyanine films exhibit numerous trench-like structural defects and poor density, easily leading to direct contact between perovskite and ITO, thereby reducing interfacial charge transport efficiency. Specifically, for example... Figure 3 As shown.

[0066] At the same time, such as Figure 4 As shown, APTES can effectively improve the wettability of the film surface and promote the spreading of the perovskite precursor solution. The electron-rich amino groups on the uniformly distributed APTES molecules can react with Pb in the perovskite component. 2+ The interaction results in more uniform and denser perovskite nucleation, leading to perovskite films with high crystallinity and low defects, effectively enhancing the photogenerated carrier capacity of the perovskite layer. Figure 5 a). Simultaneously, dense wide bandwidth The modification layer can form an effective barrier on the surface of copper phthalocyanine, inhibiting the reverse injection of electrons into the copper phthalocyanine layer, reducing interfacial nonradiative recombination, accelerating the fluorescence quenching process, and greatly improving the extraction and transport efficiency of holes. Figure 5b). Based on the synergistic improvement in perovskite film quality and copper phthalocyanine interface properties, the open-circuit voltage of the evaporated copper phthalocyanine-based inverse perovskite solar cell increased from 1.064V in Comparative Example 1 to 1.149V in Example 1, and the photoelectric conversion efficiency also significantly increased from 20.7% to 23.037%, as detailed below. Figure 6 As shown.

[0067] This invention is not limited to the structures described above and shown in the accompanying drawings, and various modifications and changes can be made without departing from its scope. The scope of this invention is limited only by the appended claims.

Claims

1. A modification method for improving the energy level matching of the vapor-deposited copper phthalocyanine / perovskite interface, characterized in that, The method includes: Laser etching is performed on a conductive glass substrate of a preset size. After laser etching is completed, the conductive glass substrate is ultrasonically cleaned with glass cleaning fluid, copper propylene, and isopropanol in sequence, and then dried and stored for later use. After the conductive glass substrate was dried, it was subjected to ultraviolet-ozone treatment to obtain a copper phthalocyanine film by vapor deposition. Pre-prepared silane-modified The nano-dispersion was spread on a copper phthalocyanine film and then annealed to obtain... Modified thin films.

2. The modification method for improving the energy level matching of the vapor-deposited copper phthalocyanine / perovskite interface according to claim 1, characterized in that, The pre-prepared silane-modified The nano-dispersion was spread on a copper phthalocyanine film and then annealed to obtain... Modified films include: Will After diluting the nanoparticles with isopropanol, the following was obtained: Isopropanol solution; exist Silane and deionized water are added to an isopropanol solution and mixed thoroughly by ultrasonic vibration to obtain... Nano-dispersion; Using spin coating method The nano-dispersion was spin-coated onto a copper phthalocyanine film, and then annealed on a hot plate to obtain... Modified thin films.

3. The modification method for improving the energy level matching of the vapor-deposited copper phthalocyanine / perovskite interface according to claim 2, characterized in that, The silane is any one of 3-aminopropyltriethoxysilane, trimethylchlorosilane, and triisopropylchlorosilane.

4. The modification method for improving the energy level matching of the vapor-deposited copper phthalocyanine / perovskite interface according to claim 2, characterized in that, The spin coating method is described with a spin coating speed of 3000~8000 rpm and a spin coating time of 10~50 min.

5. The modification method for improving the energy level matching of the vapor-deposited copper phthalocyanine / perovskite interface according to claim 2, characterized in that, The annealing temperature during the annealing process on the hot plate is 50~120℃, and the spin coating time is 5~20min.

6. The application of a modification method for improving the energy level matching of the evaporated copper phthalocyanine / perovskite interface in evaporated copper phthalocyanine-based inverse perovskite solar cells, characterized in that, The steps for depositing the copper phthalocyanine-based inverse perovskite solar cell include: Laser etching is performed on a conductive glass substrate of a preset size. After laser etching is completed, the conductive glass substrate is ultrasonically cleaned with glass cleaning fluid, copper propylene, and isopropanol in sequence, and then dried and stored for later use. After the conductive glass substrate was dried, it was subjected to ultraviolet-ozone treatment to obtain a copper phthalocyanine film by vapor deposition. Pre-prepared silane-modified The nano-dispersion was spread on a copper phthalocyanine film and then annealed to obtain... Modified thin film; After filtering, the perovskite precursor solution was spin-coated onto... A perovskite wet film was obtained by modifying the film. The antisolvent ethyl acetate and 1,3-propanediamine hydroiodide passivating agent were then added dropwise to the perovskite wet film. After annealing, a perovskite absorber film was obtained. The perovskite absorber film was placed in a vacuum thermal evaporation apparatus to obtain C. 60 Thin film, in C 60 A copper hydroxide solution was added dropwise onto the thin film to obtain C. 60 Electron transport thin films; C 60 An electron transport thin film is placed in a vacuum thermal evaporation apparatus to deposit a silver electrode with a high work function.

7. The application of the modification method for improving the energy level matching of the vapor-deposited copper phthalocyanine / perovskite interface according to claim 6 in vapor-deposited copper phthalocyanine-based inverse perovskite solar cells, characterized in that, The perovskite precursor solution was filtered and then spin-coated onto... A perovskite wet film was obtained by modifying the film. Ethyl acetate (an antisolvent) and 1,3-propanediamine hydroiodate (a passivating agent) were then sequentially added to the perovskite wet film. After annealing, a perovskite absorber film was obtained, comprising: Prepare the perovskite precursor solution. Take the perovskite precursor solution in a glove box, filter it, and then spin-coat it in two steps onto... A perovskite wet film was obtained by modifying the film; After adding ethyl acetate as the antisolvent to the perovskite wet film, the perovskite wet film was removed from the glove box and annealed in air. After natural cooling, the perovskite composition was obtained as FA. 0.9 Cs 0.07 MA 0.03 PbI 2.76 Br 0.24 Perovskite thin films; The perovskite film was placed in a glove box, and 1,3-propanediamine hydroiodate was spin-coated as a passivating agent. After annealing on a hot plate, the perovskite absorber film was obtained.

8. The application of the modification method for improving the energy level matching of the vapor-deposited copper phthalocyanine / perovskite interface according to claim 6 in vapor-deposited copper phthalocyanine-based inverse perovskite solar cells, characterized in that, The ultraviolet-ozone treatment lasts for 10-30 minutes at a temperature of 20-30°C; the vacuum degree of the copper phthalocyanine film obtained by vapor deposition is 2-10×10⁻⁶. -4 Torr, with a temperature of 300~500℃ and a speed of 0.02~0.1Å / s; the copper phthalocyanine film has a thickness of 5~15nm.

9. The application of the modification method for improving the energy level matching of the vapor-deposited copper phthalocyanine / perovskite interface according to claim 6 in vapor-deposited copper phthalocyanine-based inverse perovskite solar cells, characterized in that, The perovskite precursor solution was taken from the glove box, filtered, and then spin-coated in two steps onto... The first spin coating speed on the modified film is 500~3000 rpm and the spin coating time is 5~20s. The second spin coating speed is 1000~5000 rpm and the spin coating time is 10~50s. The annealing temperature in the air annealing process is 80~120℃, and the annealing time is 20~50min; the annealing temperature in the perovskite absorber film obtained after the hot annealing process is 80~120℃, and the annealing time is 1~10min.

10. The application of the modification method for improving the energy level matching of the vapor-deposited copper phthalocyanine / perovskite interface according to claim 6 in vapor-deposited copper phthalocyanine-based inverse perovskite solar cells, characterized in that, The perovskite absorber film is placed in a vacuum thermal evaporation apparatus to deposit C. 60 The vacuum degree of vapor deposition in thin films is 2~8×10 -4 Torr, with a evaporation rate of 0.1~0.4 Å / s and a temperature of 300~600℃; the C 60 The film thickness is 10~30nm; The above in C 60 A copper hydroxide solution was added dropwise onto the thin film to obtain C. 60 The spin coating speed of the copper bath solution in the electron transport thin film is 2000~8000 rpm, and the spin coating time is 20~50 min.

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