Perovskite solar cell with modified hole transport layer and preparation method thereof
By introducing 3MTPAI to modify the hole transport layer in perovskite solar cells, the problem of difficult-to-control buried interface is solved, energy level matching is optimized, and device efficiency and stability are improved.
Patent Information
- Application Number
- CN202510280738.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-11
- Publication Date
- 2026-01-06
- Estimated Expiration
- 2045-03-11
AI Technical Summary
In existing technologies, the buried interface of perovskite solar cells is difficult to control effectively, leading to defect enrichment and carrier transport barriers, which affects device performance.
The hole transport layer was modified with the ionic compound 3MTPAI. Through interaction with the SAM material MeO-2PACz, the dipole moment was enhanced, the energy level matching between the hole transport layer and the perovskite layer was optimized, the buried interface defects were passivated, and hole extraction was promoted.
It improves the efficiency and stability of perovskite solar cells, enhances hole transport performance, and reduces interfacial nonradiative recombination.
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Figure CN120112059B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of perovskite solar cell technology, specifically a perovskite solar cell with a modified hole transport layer and its fabrication method. Background Technology
[0002] In recent years, the power conversion efficiency (PCE) of perovskite solar cells (PSCs) has significantly improved, rapidly increasing from 3.8% in 2009 to over 26% today, highlighting PSCs' position as a focal point in the future photovoltaic field. Interfacial carrier recombination loss is a crucial factor affecting efficiency improvement; therefore, interface engineering strategies are considered an effective method to achieve higher PCE. To date, researchers have gained a deep understanding of top interface optimization, but top interface post-processing has become an indispensable technique for efficient PSC fabrication. However, compared to the top interface, the optimization of the buried interface, which directly affects perovskite crystallization and interfacial charge transport, has a more critical impact on solar cell performance.
[0003] The buried interface of perovskite thin films, due to its unique location and difficulty in direct manipulation, often becomes a source of defect enrichment and carrier transport barriers. Introducing self-assembled monolayers (SAMs) as passivation layers to passivate defects and suppress nonradiative recombination has become an effective method. The dipole moment of SAMs can increase the work function of the hole transport layer (HTL) and reduce the interface barrier, thereby optimizing hole transport performance. However, how to further enhance the dipole moment of SAMs while simultaneously passivating perovskite defects to more effectively improve the properties of the buried interface remains an important research direction. Summary of the Invention
[0004] To address the shortcomings of existing technologies, this invention provides a perovskite solar cell with a modified hole transport layer and its fabrication method. The method employs an ionic compound-modified hole transport layer strategy, introducing 3MTPAI between the SAM material MeO-2PACz and the perovskite layer as the hole transport layer to fabricate an inverted perovskite device. The introduction of 3MTPAI can improve the work function of the SAM, optimize the energy level matching between the hole transport layer and the perovskite layer, and passivate defects at the perovskite buried interface, thereby promoting hole extraction and reducing non-radiative recombination at the interface. This dual-effect 3MTPAI molecular buried modification strategy provides an effective way to improve the efficiency and stability of photovoltaic cells.
[0005] To achieve the above objectives, the present invention employs the following technical solution:
[0006] A perovskite solar cell with a modified hole transport layer includes an ITO substrate layer, a hole transport layer, a 3MTPAI layer, a perovskite layer, an electron transport layer, and an electrode layer arranged sequentially, wherein the hole transport layer is a MeO-2PACz SAM layer.
[0007] The electron transport layer is a C layer with a thickness of 20–30 nm. 60 The electrode layer is a silver thin film with a thickness of 90–110 nm.
[0008] An interface modification layer is provided between the electron transport layer and the electrode layer, and the interface modification layer is a BCP thin film with a thickness of 4 to 10 nm.
[0009] The C 60 The thickness of the layer is 24 nm, the thickness of the BCP film is 6 nm, and the thickness of the silver film is 100 nm.
[0010] A method for fabricating a perovskite solar cell with a modified hole transport layer includes the following steps:
[0011] (1) The glass / ITO substrate was ultrasonically cleaned with deionized water, acetone and isopropanol in sequence, dried with nitrogen, and then subjected to ultraviolet ozone treatment. The glass / ITO substrate after ultraviolet ozone treatment was transferred to a glove box filled with nitrogen for subsequent preparation.
[0012] (2) A MeO-2PACz solution dissolved in ethanol was coated onto a glass / ITO substrate and annealed at 100°C to obtain a glass / ITO / MeO-2PACz substrate.
[0013] (3) A 3MTPAI solution dissolved in isopropanol was coated onto a glass / ITO / MeO-2PACz substrate and annealed at 100°C to obtain a glass / ITO / MeO-2PACz / 3MTPAI substrate.
[0014] (4) A perovskite solution was coated onto a glass / ITO / MeO-2PACz / 3MTPAI substrate to prepare a perovskite film. After annealing the perovskite film at 100°C, C was sequentially thermally evaporated under high vacuum. 60 Layer, BCP film, silver film.
[0015] Furthermore, the mass concentration of the MeO-2PACz solution in step (2) is 3-4 mg / ml; the mass concentration of the 3MTPAI solution in step (3) is 0.5-2 mg / ml; and the mass concentration of the C in step (4) is... 60 The thickness of the layer is 20-30 nm, the thickness of the BCP film is 4-10 nm, and the thickness of the silver film is 90-110 nm.
[0016] Furthermore, the mass concentration of the MeO-2PACz solution in step (2) is 3.3 mg / ml; the mass concentration of the 3MTPAI solution in step (3) is 1 mg / ml; and the mass concentration of the C solution in step (4) is... 60 The thickness of the layer is 24 nm, the thickness of the BCP film is 6 nm, and the thickness of the silver film is 100 nm.
[0017] Furthermore, the perovskite solution prepared in step (4) is prepared by dissolving CsI, FAI, MABr, PbI2, and PbBr2 in a DMF-DMSO mixed solvent to obtain a perovskite precursor solution. The chemical formula of the perovskite precursor solution is: (FA 0.98 MA 0.02 ) 0.95 Cs 0.05 Pb(I 0.95 Br 0.05 )3, wherein the amount of PbI2 added is excessive; a perovskite solution is prepared by adding MACl to the perovskite precursor solution.
[0018] Furthermore, the volume ratio of DMF to DMSO in the DMF-DMSO mixed solvent is 4:1; and the perovskite precursor solution contains an excess of 10 mol% PbI₂.
[0019] Furthermore, in step (1), the glass / ITO substrate is ultrasonically cleaned with deionized water, acetone and isopropanol in sequence for 10 to 20 minutes, and the glass / ITO substrate is treated with ultraviolet ozone for 10 to 20 minutes; the annealing temperature in steps (2), (3) and (4) is 90 to 100°C, and the annealing time is 5 to 40 minutes.
[0020] Furthermore, in step (1), the glass / ITO substrate is ultrasonically cleaned with deionized water, acetone, and isopropanol for 15 minutes in sequence, and the glass / ITO substrate is treated with ultraviolet ozone for 15 minutes; in step (2), the annealing temperature is 100℃ and the annealing time is 10 minutes; in step (3), the annealing temperature is 100℃ and the annealing time is 5 minutes; in step (4), the annealing temperature is 100℃ and the annealing time is 30 minutes.
[0021] Furthermore, the method of coating the MeO-2PACz solution onto the glass / ITO substrate in step (2) is spin coating, with a spin coating speed of 2500-3500 rpm and a time of 20-40 s; the method of coating the 3MTPAI solution onto the glass / ITO / MeO-2PACz substrate in step (3) is spin coating, with a spin coating speed of 4000-6000 rpm and a time of 20-40 s; the method of coating the perovskite solution onto the glass / ITO / MeO-2PACz / 3MTPAI substrate in step (4) is spin coating, and the spin coating steps are as follows: first spin coating at a speed of 1000-2000 rpm for 8-15 s, then spin coating at a speed of 4000-6000 rpm for 30-50 s, and CB solution is dropped into the center of the film 10-20 s before the end of spin coating.
[0022] Furthermore, in step (2), the spin coating speed of the MeO-2PACz solution coated on the glass / ITO substrate is 3000 rpm and the time is 30 s; in step (3), the spin coating speed of the 3MTPAI solution coated on the glass / ITO / MeO-2PACz substrate is 5000 rpm and the time is 30 s; in step (4), the spin coating steps of the perovskite solution coated on the glass / ITO / MeO-2PACz / 3MTPAI substrate are as follows: first spin coating at 1000 rpm for 10 s, then spin coating at 5000 rpm for 40 s, and CB is dropped into the center of the film 10 s before the end of spin coating.
[0023] Compared with the prior art, the advantages of this invention are as follows:
[0024] 1. The method for preparing a perovskite solar cell with a modified hole transport layer provided by the present invention requires mature raw material preparation processes that are commercially available. It does not require laboratory design and synthesis of molecules, nor does it require mixing of SAM layers or passivation layers. A single component can be selected for modification.
[0025] 2. In this invention, MeO-2PACz serves as the SAM layer, and 3MTPAI modifies the SAM layer. Iodide ions in the 3MTPAI molecule increase the dipole moment of the SAM layer through interaction with MeO-2PACz, thereby increasing the atomic basin volume of the SAM molecule. This characteristic makes the 3MTPAI-modified MeO-2PACz molecule exhibit a higher advantage in filling iodine vacancies in perovskites. Since ion-dipole interactions dominate in intermolecular interactions, this leads to the decoration of the MeO-2PACz molecule by iodide ions in 3MTPAI. The decoration of the MeO-2PACz molecule by iodide ions results in an increase in the dipole moment of the modified MeO-2PACz, and thus an increase in the atomic basin. This characteristic makes the 3MTPAI-modified MeO-2PACz molecule exhibit a higher advantage in filling iodine vacancies. The molecules can modify Pb, I, and N in the buried interface of the perovskite to form active sites to fill defects; the synergistic effect of 3MTPAI between the SAM layer and the perovskite leads to the improvement of the perovskite crystal quality, thereby increasing the device efficiency of perovskite solar cells. Attached Figure Description
[0026] Appendix Figure 1 This is a schematic diagram of the perovskite solar cell structure of the present invention.
[0027] Appendix Figure 2 This is the dipole moment contribution diagram of MeO-2PACz after 3MTPAI modification.
[0028] Appendix Figure 3 This is a schematic diagram of the unmodified MeO-2PACz molecular structure.
[0029] Appendix Figure 4 This is a schematic diagram of the 3MTPAI-modified MeO-2PACz molecule structure.
[0030] Appendix Figure 5 This is the spectrum of the tested UPS.
[0031] Appendix Figure 6 This is the energy level diagram from the test.
[0032] Appendix Figure 7 This is the JV curve from the test. Detailed Implementation
[0033] To make the objectives, technical solutions, and advantages of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. The same reference numerals in the drawings represent the same components. It should be noted that the described embodiments are only some, not all, of the embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the described embodiments of the present invention without creative effort are within the scope of protection of the present invention.
[0034] like Figure 1 As shown, the present invention provides a perovskite solar cell with a modified hole transport layer, comprising an ITO substrate layer, a hole transport layer, a 3MTPAI layer, a perovskite layer, an electron transport layer, and an electrode layer arranged sequentially, wherein the hole transport layer is a MeO-2PACz SAM layer.
[0035] In one embodiment, the electron transport layer (ETL) is a C layer with a thickness of 20–30 nm. 60 The electrode layer is a silver thin film with a thickness of 90–110 nm.
[0036] In one embodiment, an interface modification layer is provided between the electron transport layer and the electrode layer, and the interface modification layer is a BCP thin film with a thickness of 4 to 10 nm.
[0037] In one embodiment, the C 60 The thickness of the layer is 24 nm, the thickness of the BCP film is 6 nm, and the thickness of the silver film is 100 nm.
[0038] MeO-2PACz is a SAM material. In this invention, MeO-2PACz is used as a hole transport layer, and 3MTPAI is introduced between MeO-2PACz and the perovskite layer to fabricate an inverted perovskite device as a hole transport layer. The introduction of 3MTPAI can improve the work function of the SAM, optimize the energy level matching between the hole transport layer and the perovskite layer, passivate the defects at the perovskite buried interface, thereby promoting hole extraction and reducing nonradiative recombination at the interface.
[0039] A method for fabricating a perovskite solar cell with a modified hole transport layer includes the following steps:
[0040] Step (1): The glass / ITO substrate was ultrasonically cleaned sequentially with deionized water, acetone and isopropanol, dried with nitrogen, and then subjected to ultraviolet ozone treatment. The glass / ITO substrate after ultraviolet ozone treatment was transferred to a glove box filled with nitrogen for subsequent preparation.
[0041] In step (1), the glass / ITO substrate is ultrasonically cleaned with deionized water, acetone, and isopropanol in sequence for 10 to 20 minutes. For example, the ultrasonic cleaning time for the glass / ITO substrate with deionized water, acetone, and isopropanol is 15 minutes. Ultrasonic cleaning is used to remove contaminants (such as dust and organic matter) from the surface of the glass / ITO substrate.
[0042] The UV ozone treatment time for the glass / ITO substrate is 10–20 minutes, exemplarily 15 minutes. UV ozone treatment can improve the hydrophilicity of the glass / ITO substrate surface, remove organic residues, increase surface oxygen vacancies, and improve hole extraction performance.
[0043] Step (2): A solution of [2-(3,6-dimethoxy-9H-carbazole-9-yl)ethyl]phosphonic acid MeO-2PACz dissolved in ethanol was coated onto a glass / ITO substrate and annealed at 100°C to obtain a glass / ITO / MeO-2PACz substrate. The SAM material MeO-2PACz acts as a hole transport layer (HTL), improving the interfacial contact between ITO and the perovskite layer. The HOMO energy level of MeO-2PACz matches the valence band of the perovskite, promoting hole extraction and blocking electrons.
[0044] The mass concentration of the MeO-2PACz solution is 3 to 4 mg / ml, for example, the mass concentration of the MeO-2PACz solution is 3.3 mg / ml.
[0045] The method for coating the MeO-2PACz solution onto the glass / ITO substrate is spin coating, with a spin coating speed of 2500-3500 rpm and a time of 20-40 s; for example, the spin coating speed of the MeO-2PACz solution onto the glass / ITO substrate is 3000 rpm and the time is 30 s.
[0046] The annealing temperature in step (2) is 90–100°C, and the annealing time is 5–40 minutes; for example, the annealing temperature in step (2) is 100°C, and the annealing time is 10 minutes. Annealing can remove the solvent and enhance the ordered arrangement of molecules on the surface.
[0047] Step (3): The solution of [3-(3,6-dimethoxy-9H-carbazole-9-yl)propyl]phosphonic acid 3MTPAI dissolved in isopropanol was coated on a glass / ITO / MeO-2PACz substrate and annealed at 100°C to obtain a glass / ITO / MeO-2PACz / 3MTPAI substrate.
[0048] The mass concentration of the 3MTPAI solution is 0.5 to 2 mg / ml, and for example, the mass concentration of the 3MTPAI solution is 1 mg / ml.
[0049] The method for coating the 3MTPAI solution onto the glass / ITO / MeO-2PACz substrate is spin coating, with a spin coating speed of 4000-6000 rpm and a time of 20-40 s; for example, the spin coating speed of the 3MTPAI solution onto the glass / ITO / MeO-2PACz substrate is 5000 rpm and the time is 30 s.
[0050] The annealing temperature in step (3) is 90-100°C and the annealing time is 5-40 minutes; for example, the annealing temperature in step (2) is 100°C and the annealing time is 5 minutes.
[0051] Step (4): The perovskite solution was coated onto a glass / ITO / MeO-2PACz / 3MTPAI substrate to obtain a perovskite film. After annealing at 100°C, the perovskite film was subjected to high vacuum (<2×10⁻⁶). -4 Under Torr), C is sequentially thermally evaporated. 60 Layer, BCP film, silver film.
[0052] The C 60 The thickness of the layer is 20–30 nm, the thickness of the BCP film is 4–10 nm, and the thickness of the silver film is 90–110 nm; exemplarily, the C… 60 The thickness of the layer is 24 nm, the thickness of the BCP film is 6 nm, and the thickness of the silver film is 100 nm. The BCP film, as an interface modification layer, can improve C... 60 The interface between the perovskite layer and the silver electrode prevents holes from being directly transported from the perovskite layer to the silver electrode.
[0053] The perovskite solution is prepared by dissolving CsI, FAI, MABr, PbI2, and PbBr2 in a mixed solvent of N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) to obtain a perovskite precursor solution. The chemical formula of the perovskite precursor solution is: (FA... 0.98 MA 0.02 ) 0.95 Cs 0.05 Pb(I 0.95 Br 0.05 )3, wherein the amount of PbI2 added is in excess; a perovskite solution is prepared by adding methylammonium chloride (MACl) to the perovskite precursor solution. The volume ratio of DMF to DMSO in the DMF-DMSO mixed solvent is 4:1; the amount of PbI2 in the perovskite precursor solution is 10 mol% in excess.
[0054] The method for coating the perovskite solution onto the glass / ITO / MeO-2PACz / 3MTPAI substrate is spin coating. The spin coating steps are as follows: first, spin coating at 1000-2000 rpm for 8-15 seconds, then spin coating at 4000-6000 rpm for 30-50 seconds; 10-20 seconds before the end of the spin coating, a CB solution is dropped into the center of the film. For example, the spin coating steps for coating the perovskite solution onto the glass / ITO / MeO-2PACz / 3MTPAI substrate are as follows: first, spin coating at 1000 rpm for 10 seconds, then spin coating at 5000 rpm for 40 seconds; 10 seconds before the end of the spin coating, a chlorobenzene CB solution is dropped into the center of the film.
[0055] The annealing temperature in step (4) is 90-100°C and the annealing time is 5-15 minutes; for example, the annealing temperature in step (4) is 100°C and the annealing time is 30 minutes.
[0056] The raw material preparation process required by the method of this invention is mature and commercially available, requiring no laboratory design or synthesis of molecules. The preparation steps are simple, requiring no mixing of SAM layers or passivation layers, and single components can be selected for modification. Iodide ions in the 3MTPAI molecule increase the dipole moment of the SAM layer through interaction with SAM, thereby increasing the atomic basin volume of the SAM molecule. This characteristic gives 3MTPAI-modified MeO-2PACz molecules a greater advantage in filling iodine vacancies in perovskites. Ion-dipole interactions dominate in intermolecular interactions, leading to the decoration of MeO-2PACz molecules by iodide ions in 3MTPAI. The decoration of MeO-2PACz by I ions results in an increased dipole moment and consequently, an increased atomic basin volume. This characteristic further enhances the advantage of 3MTPAI-modified MeO-2PACz molecules in filling iodine vacancies. Furthermore, the molecule can be modified to form interaction sites for Pb, I, and N at the buried interface of the perovskite to fill defects. The synergistic effect of 3MTPAI between the SAM layer and the perovskite leads to an improvement in the quality of the perovskite crystals, thereby increasing the device efficiency of perovskite solar cells.
[0057] Example 1
[0058] A method for fabricating a perovskite solar cell with a modified hole transport layer includes the following steps:
[0059] (1) The glass / ITO substrate was ultrasonically cleaned with deionized water, acetone and isopropanol for 15 minutes in sequence. Then, the glass / ITO substrate was dried with nitrogen and treated with ultraviolet ozone for 15 minutes. Then the substrate was transferred to a glove box filled with nitrogen.
[0060] (2) Dissolve MeO-2PACz in ethanol solvent at a concentration of 3.3 mg / ml; coat the prepared 40 μL MeO-2PACz solution onto glass / ITO at a speed of 3000 rpm for 30 s, and then anneal at 100 °C for 10 min to obtain glass / ITO / MeO-2PACz substrate.
[0061] (3) Dissolve 3MTPAI in IPA to a concentration of 1 mg / ml; spin-coat 40 μL of the prepared 3MTPAI solution onto a glass / ITO / MeO-2PACz substrate at 5000 rpm for 30 s, and then anneal at 100 °C for 5 min to obtain glass / ITO / MeO-2PACz / 3MTPAI.
[0062] (4) A 1.73 M perovskite precursor solution was prepared by mixing CsI, FAI, MABr, PbI2, and PbBr2 in 1 ml of DMF:DMSO (4:1 / v:v) mixed solvent. The chemical formula of the perovskite precursor solution was (FA... 0.98 MA 0.02 ) 0.95 Cs 0.05 Pb(I 0.95 Br 0.05 3. 10 mol% PbI2 excess was added to improve device performance; then 15 mol% MACl was added to the perovskite precursor solution and stirred for 3 h to obtain a perovskite solution; the perovskite solution was spin-deposited on a glass / ITO / MeO-2PACz / 3MTPAI substrate at 1000 rpm for 10 s, then spin-deposited at 5000 rpm for 40 s. 10 s before the end of the spin-deposit, 180 μL of CB was slowly dropped into the center of the film; the prepared perovskite film was annealed on a hot plate at 100 °C for 30 min, and then subjected to high vacuum (<2 × 10⁻⁶). - 4 Torr) sequentially thermally evaporates 24nm C 60 6nm BCP and 100nm silver.
[0063] The device fabricated in Example 1 has an area of 0.0625 cm². 2 We will test it.
[0064] Iodine ions in the 3MTPAI molecule increase the dipole moment of the SAM layer by interacting with SAM, thereby increasing the atomic basin volume of the SAM molecule. This property makes the 3MTPAI-modified MeO-2PACz molecule more advantageous in filling iodine vacancies in perovskite.
[0065] like Figure 2As shown, the dipole moment contribution of MeO-2PACz after 3MTPAI modification is illustrated. The yellow arrows represent the contribution of MeO-2PACz itself, the red arrows indicate the contribution of iodide ions, and the green arrows comprehensively reflect the direction and magnitude of the overall dipole moment. The dipole contribution of iodide ions is aligned with the overall direction of MeO-2PACz, thus significantly enhancing the total dipole moment of the molecule. This enhanced dipole moment effect makes the 3MTPAI-modified MeO-2PACz molecule (such as...)... Figure 4 As shown, Compared to unmodified MeO-2PACz molecules (such as...) Figure 3 As shown, With a larger atomic basin volume, the 3MTPAI-modified MeO-2PACz molecule exhibits a greater advantage in filling iodine vacancies, thereby effectively strengthening the PbI2 octahedral configuration of the buried surface.
[0066] The introduction of 3MTPAI alters the work function of MeO-2PACz, optimizing the energy levels of MeO-2PACz and perovskite, making their energy levels more well-matched.
[0067] like Figure 5 The image shown is the UPS spectrum of the test sample. Figure 6 The diagram shows the energy level plots of the test samples, where Control is the glass / ITO / MeO-2PACz sample and Target is the glass / ITO / MeO-2PACz / 3MTPAI sample. The energy levels on the surface of the glass / ITO / MeO-2PACz and glass / ITO / MeO-2PACz / 3MTPAI samples, as well as the corresponding perovskite energy levels, were measured. The work function (W) of the hole transport layer was also measured. F The valence band energy difference (ΔE) between the hole transport layer and the perovskite layer increased from 4.34 eV to 4.69 eV. VBM The voltage decreased from 0.86 eV to 0.36 eV, with a decrease in ΔE. VBM and the improvement of W F It is beneficial for hole transport layer transmission.
[0068] like Figure 7 As shown, 0.0625cm 2 The JV curve of the device shows that the efficiency increased from 23.9% to 25.3% after modifying MeO-2PACz with 3MTPAI; with an active area of 0.0625 cm². 2 The strategy has been validated in perovskite solar cells, demonstrating its effectiveness in improving device efficiency.
[0069] Those skilled in the art should understand that the specific embodiments described above are merely examples and not limitations. Various modifications, combinations, partial combinations, and substitutions can be made to the embodiments of the present invention according to design requirements and other factors, as long as they are within the scope of the appended claims or their equivalents, and thus fall within the scope of the rights to be protected by the present invention.
Claims
1. A perovskite solar cell modifying a hole transport layer, characterized in that, It comprises ITO substrate layer, hole transport layer, 3MTPAI layer, perovskite layer, electron transport layer and electrode layer arranged in sequence, wherein the hole transport layer is a SAM layer of MeO-2PACz.
2. The method for preparing a perovskite solar cell modified hole transport layer according to claim 1, characterized in that, It comprises the following steps: (1) ultrasonic cleaning the glass / ITO substrate with deionized water, acetone and isopropanol in sequence, drying with nitrogen and then performing ultraviolet ozone treatment; (2) coating MeO-2PACz solution dissolved in ethanol on the glass / ITO substrate and annealing at 100℃ to obtain glass / ITO / MeO-2PACz substrate; (3) coating 3MTPAI solution dissolved in isopropanol on the glass / ITO / MeO-2PACz substrate and annealing at 100℃ to obtain glass / ITO / MeO-2PACz / 3MTPAI substrate; (4) The perovskite solution is coated on the glass / ITO / MeO-2PACz / 3MTPAI substrate to obtain a perovskite film. After annealing treatment at 100℃, C 60 layer, BCP film and silver film are sequentially evaporated under high vacuum.
3. The preparation method of the perovskite solar cell with modified hole transport layer according to claim 2, wherein the mass concentration of the MeO-2PACz solution in step (2) is 3-4 mg / ml; the mass concentration of the 3MTPAI solution in step (3) is 0.5-2 mg / ml; 4. The preparation method of the perovskite solar cell with modified hole transport layer according to claim 3, wherein the mass concentration of the MeO-2PACz solution in step (2) is 3.3 mg / ml; The C 60 The thickness of the layer is 20-30 nm, the thickness of the BCP film is 4-10 nm, and the thickness of the silver film is 90-110 nm. the mass concentration of the 3MTPAI solution in step (3) is 1 mg / ml; the preparation method of the perovskite solution in step (4) is: adding MACl into the perovskite precursor solution to obtain the perovskite solution. The C 60 The thickness of the layer was 24 nm, the thickness of the BCP film was 6 nm, and the thickness of the silver film was 100 nm.
5. The method for preparing a perovskite solar cell modified hole transport layer according to claim 2, characterized in that, the volume ratio of DMF to DMSO in the DMF-DMSO mixed solvent is 4:1; PbI2 is in excess of 10 mol% in the perovskite precursor solution. A perovskite precursor solution is prepared by dissolving CsI, FAI, MABr, PbI2, PbBr2 in a DMF-DMSO mixed solvent, and the chemical formula of the perovskite precursor solution is: (FA 0.98 MA 0.02 ) 0.95 Cs 0.05 Pb(I 0.95 Br 0.05 )3, wherein the amount of PbI2 added is excessive; 7. The preparation method of the perovskite solar cell with modified hole transport layer according to claim 2, wherein the glass / ITO substrate is ultrasonic cleaned with deionized water, acetone and isopropanol in sequence for 10-20 minutes in step (1), and the glass / ITO substrate is ultraviolet ozone treated for 10-20 minutes; 6. The method for preparing a perovskite solar cell modified hole transport layer according to claim 5, characterized in that, the annealing temperature in steps (2), (3) and (4) is 90-100℃, and the annealing time is 5-40 minutes.
8. The preparation method of the perovskite solar cell with modified hole transport layer according to claim 7, wherein the glass / ITO substrate is ultrasonic cleaned with deionized water, acetone and isopropanol in sequence for 15 minutes in step (1), and the glass / ITO substrate is ultraviolet ozone treated for 15 minutes; the annealing temperature in step (2) is 100℃, and the annealing time is 10 minutes; the annealing temperature in step (3) is 100℃, and the annealing time is 5 minutes; the annealing temperature in step (4) is 100℃, and the annealing time is 30 minutes.
9. The preparation method of the perovskite solar cell with modified hole transport layer according to claim 2, wherein The method for coating the MeO-2PACz solution on the glass / ITO substrate in step (2) is spin coating, the spin coating speed is 2500-3500 rpm, and the time is 20-40 s; The method for coating the 3MTPAI solution on the glass / ITO / MeO-2PACz substrate in step (3) is spin coating, the spin coating speed is 4000-6000 rpm, and the time is 20-40 s; The method for coating the perovskite solution on the glass / ITO / MeO-2PACz / 3MTPAI substrate in step (4) is spin coating, the spin coating steps are: first spin coating at a speed of 1000-2000 rpm for 8-15 s, then spin coating at a speed of 4000-6000 rpm for 30-50 s, and 10-20 s before the end of spin coating, the CB solution is dropped into the center of the film.
10. The preparation method of the perovskite solar cell for modifying the hole transport layer according to claim 9, characterized in that, The spin coating speed of the MeO-2PACz solution on the glass / ITO substrate in step (2) is 3000 rpm, and the time is 30 s; The spin coating speed of the 3MTPAI solution on the glass / ITO / MeO-2PACz substrate in step (3) is 5000 rpm, and the time is 30 s; The spin coating steps of the perovskite solution on the glass / ITO / MeO-2PACz / 3MTPAI substrate in step (4) are: first spin coating at a speed of 1000 rpm for 10 s, then spin coating at a speed of 5000 rpm for 40 s, and 10 s before the end of spin coating, chlorobenzene is dropped into the center of the film.