Application of organic sulfonate molecules in perovskite solar cells and a normal perovskite solar cell and a method of manufacturing the same
By doping organic sulfonate molecules into the hole transport layer of perovskite solar cells, the diffusion of Li+ and tBP and the migration of halide ions were solved, thus achieving high efficiency, stability and long-term operational stability of perovskite solar cells.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- CHONGQING UNIV
- Filing Date
- 2023-11-21
- Publication Date
- 2026-08-04
AI Technical Summary
The diffusion of Li+ and tBP and the migration of halide ions in existing perovskite solar cells cause device instability problems. There is a lack of effective dopants to fix these materials, which affects long-term operational stability.
In perovskite solar cells, organic sulfonate molecules are doped into the hole transport layer. By forming chemical bonds or hydrogen bonds with Li+, tBP and halide ions, Li+ and tBP are fixed, interface defects are passivated and their migration is suppressed.
This improves the power conversion efficiency and stability of perovskite solar cells. The doped solar cells maintain high efficiency during aging, thus enhancing the long-term operational stability of the devices.
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Figure CN117529206B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of perovskite solar cell fabrication technology, and relates to the application of organic sulfonate molecules in perovskite solar cells and an upright perovskite solar cell and its fabrication method. Background Technology
[0002] Perovskite solar cells (PSCs) have become one of the most commercially promising new types of solar cells due to their advantages such as low cost, high efficiency, and solution-processability, and are currently the fastest-growing photovoltaic technology. At present, perovskite solar cells have achieved certified power conversion efficiencies (PCE) exceeding 26%. However, long-term operational stability remains a major obstacle to their large-scale commercial application. Intrinsic instabilities caused by ion migration and diffusion, as well as deep-level traps, are the biggest challenges to achieving long-term stable operation of these devices.
[0003] Highly efficient positive-position perovskite solar cells (PSCs) typically rely on 2,2',7,7'-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene (Spiro-OMeTAD) doped with lithium bis(trifluoromethanesulfonyl)imide (Li-TFSI) and 4-tert-butylpyridine (tBP) as an organic hole transport layer (HTL). The diffusion of Li+ and the volatilization of tBP severely limit the long-term operational stability of PSCs. Furthermore, halide ions in the perovskite migrate into the HTL and interact with Spiro-OMeTAD•+TFSI- radicals, then further diffuse to and react with the metal electrode layer, severely degrading the performance and stability of both the HTL and the electrode. In fact, numerous halide ion vacancy defects exist at grain boundaries and interfaces of perovskite films, providing pathways for halide ion migration. Therefore, suppressing or blocking halide ion migration by repairing defects at grain boundaries and interfaces is an effective method.
[0004] However, there are currently no reports of simultaneously fixing Li. + tBP and I - Therefore, it is necessary to develop effective dopants to stabilize the hole transport layer in order to further improve the long-term operational stability of perovskite solar cells. Summary of the Invention
[0005] In view of this, one objective of the present invention is to provide the application of organic sulfonate molecules in perovskite solar cells; a second objective of the present invention is to provide an upright perovskite solar cell; and a third objective of the present invention is to provide a method for preparing an upright perovskite solar cell.
[0006] To achieve the above objectives, the present invention provides the following technical solution: 1. The application of organic sulfonate molecules in perovskite solar cells, wherein the application specifically refers to: using organic sulfonate molecules to prepare the hole transport layer of perovskite solar cells; The structural formula of the organic sulfonate molecule is as follows: .
[0007] 2. An upright perovskite solar cell, wherein the hole transport layer of the perovskite solar cell is doped with organic sulfonate molecules; The structural formula of the organic sulfonate molecule is as follows: .
[0008] Preferably, the perovskite solar cell is composed of a conductive substrate layer, an electron transport layer, a perovskite light-absorbing layer, a hole transport layer, and a metal back electrode layer stacked from bottom to top.
[0009] 3. The method for preparing the above-mentioned solar cell, wherein the method comprises the following steps: (1) Spin-coating the electron transport layer solution onto the pretreated conductive substrate, annealing at 100~180℃ and then subjecting it to ultraviolet ozone irradiation or Plasma plasma treatment for 20~80min to form an electron transport layer on the conductive substrate. (2) Spin-coat the perovskite precursor solution onto the electron transport layer described in step (1), add antisolvent, and anneal to form a perovskite light-absorbing layer on the electron transport layer; (3) Spin-coat the hole transport layer solution containing organic sulfonate molecules onto the perovskite light-absorbing layer described in step (2) to form a hole transport layer on the perovskite light-absorbing layer; (4) Prepare a metal back electrode on the hole transport layer described in step (3).
[0010] Preferably, in step (1), the material of the conductive substrate layer is either ITO or FTO; The pretreatment specifically involves: ultrasonically cleaning the conductive substrate material sequentially with detergent, deionized water, acetone, and anhydrous ethanol, then drying it with nitrogen, treating it with ultraviolet ozone for 10-30 minutes, and cooling it for later use.
[0011] Preferably, in step (1), the electron transport layer material in the electron transport layer solution is any one or more of SnO2, TiO2, ZnO, BaSnO3 or CeO2.
[0012] Preferably, in step (2), the perovskite precursor material in the perovskite precursor solution is ABX3, where A is CH3NH3. + CH(NH2)2+ Cs + or Rb + B is any one or more of the following, where B is Pb. 2+ Sn 2+ Or Ge 2+ Any one or more of them, X is Cl - ,Br - Or I - Any one or more of them.
[0013] Preferably, in step (3), the hole transport layer material in the hole transport layer solution containing the mixed organic sulfonate molecules is a mixture of organic sulfonate molecules and 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene (Spiro OMeTAD) in a molar ratio of 1:97 to 1:102, wherein the concentration of the organic sulfonate molecules in the hole transport layer solution containing the mixed organic sulfonate molecules is 0.01 to 5.0 mg / mL; The hole transport layer material in the hole transport layer solution containing the mixed organic sulfonate molecules further includes 4-tert-butylpyridine (tBP) and lithium bis(trifluoromethanesulfonyl)imide (Li-TFSI), wherein the mass-to-volume ratio of 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene (Spiro OMeTAD), 4-tert-butylpyridine (tBP), and lithium bis(trifluoromethanesulfonyl)imide (Li-TFSI) is 72.3:29:18, mg:μL:μL; The antisolvent is any one or more of chlorobenzene, dichloromethane, dichlorobenzene, toluene, ethyl acetate, chloroform, or diethyl ether.
[0014] Preferably, in step (4), the metal back electrode is Au or Ag.
[0015] Preferably, the spin coating speed is 2500-6500 rpm and the time is 25-50 s.
[0016] The beneficial effects of this invention are as follows: (1) This invention discloses the application of organic sulfonate molecules in perovskite solar cells. The main method involves using organic sulfonate molecules to prepare the hole transport layer of a perovskite solar cell. By simultaneously controlling the hole transport layer (HTL) and the perovskite / hole transport layer (HTL) interface, Li is fixed. + , tBP and halide ions, along with passivation of interfacial defects, stabilize the hole transport layer (HTL) and minimize interfacial energy loss (taking 2,2',7,7'-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene (Spiro OMeTAD) as an example, during aging, Spiro-OMeTAD forms Spiro-OMeTAD). ·+ TFSI - Subsequently, the organic sulfonate reacts with Li via the p-toluenesulfonate anion. + The ionic bond interactions prevent Li + The diffusion of ions, and the cations of organic sulfonates -NH3 + and t BP forms hydrogen bonds, inhibiting t (BP volatilization); In addition, organic sulfonate molecules can also suppress halide ion migration and interface trap-induced nonradiative recombination by regulating interface defects.
[0017] (2) This invention also discloses a positive perovskite solar cell, in which the hole transport layer is doped with organic sulfonate molecules, achieving a power conversion efficiency of 23.83% from 21.43% to over 23.58%, maintaining an initial efficiency of over 93.76% after aging for 3000 h under relative humidity of 35-45%, and maintaining an initial efficiency of over 90.99% after aging at 65 ℃ in a nitrogen glove box for 2000 h. In addition, the HTL doping method based on organic sulfonate molecules in this invention is simple and has good reproducibility, which is of great significance in promoting the industrialization of perovskite solar cells.
[0018] Other advantages, objectives, and features of the invention will be set forth in part in the description which follows, and in part will be apparent to those skilled in the art from the following examination, or may be learned from practice of the invention. The objectives and other advantages of the invention can be realized and obtained through the following description. Attached Figure Description
[0019] To make the objectives, technical solutions, and advantages of the present invention clearer, the preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings, wherein: Figure 1 ESR spectra of the hole transport layer (HTL) (Spiro) without organic sulfonate (M1) in the comparative examples and the hole transport layer (HTL) (Spiro-M1) doped with organic sulfonate molecule (M1) in Example 1; Figure 2 The NMR spectrum of the interaction between the organic sulfonate molecule (M1) and LiTFSI in Example 1 is shown.7 Li NMR; Figure 3 The organic sulfonate molecule (M1) and 4-tert-butylpyridine (M1) in Example 1 t NMR spectrum of BP effect 1 HNMR, where a is t Before and after mixing BP with organic sulfonate molecules (M1) 1 The H NMR spectrum and b represent a mixture of organic sulfonate molecules (M1). t Before and after BP 1 H NMR spectrum; Figure 4 This is a schematic diagram of the HTL stabilization mechanism after doping with organic sulfonate molecule (M1) in Example 1; Figure 5 The graph shows the relationship between open-circuit voltage and light intensity for the HTL undoped organic sulfonate solar cell (Spiro) in the comparative example and the HTL doped organic sulfonate molecule (M1) solar cell (Spiro-M1) in Example 1. Figure 6 In the image, a and b are the TOF-SIMS spectra of the HTL of the undoped organic sulfonate in Comparative Example 1 and the HTL-M1 of the doped organic sulfonate molecule (M1) in Example 1, respectively. Figure 7 To compare the current density-voltage curves of the perovskite solar cells in Example 1 and Example 2; Figure 8 To compare the humidity stability test results of the unencapsulated perovskite solar cells in Example 1 and Example 2; Figure 9 To compare the thermal stability test results of the unencapsulated perovskite solar cells in Example 1 and Example 2; Figure 10 The current density-voltage curve of the perovskite solar cell in Example 2; Figure 11 To compare the humidity stability test results of the unencapsulated perovskite solar cells in Example 1 and Example 2; Figure 12 To compare the thermal stability test results of the unencapsulated perovskite solar cells in Example 1 and Example 2; Figure 13 The current density-voltage curve of the perovskite solar cell in Example 3; Figure 14 To compare the humidity stability test results of the unencapsulated perovskite solar cells in Example 1 and Example 3; Figure 15 The thermal stability test results of the unencapsulated perovskite solar cells in the comparative examples and Example 3 are presented here. Detailed Implementation
[0020] The following specific examples illustrate the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and various details in this specification can be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention. It should be noted that the illustrations provided in the following embodiments are only schematic representations of the basic concept of the present invention. Unless otherwise specified, the following embodiments and features can be combined with each other.
[0021] The structural formula of the organic sulfonate molecule used in the following examples is as follows: .
[0022] Example 1 An upright perovskite solar cell doped with organic sulfonate molecules (M1) in the hole transport layer is specifically fabricated using the following steps: (1) The ITO conductive substrate was ultrasonically cleaned in sequence with detergent, deionized water, acetone and anhydrous ethanol, then dried with nitrogen, treated with ultraviolet ozone for 15 min, and cooled for later use. (2) Add 750 μL of deionized water to 250 μL of SnO2 nanoparticle dispersion with a mass fraction of 15%, filter through 0.22 μm PVDF, take 40 μL and drop it onto the ITO conductive substrate pretreated in step (1), spin coat at 3000 rpm for 30 s, then anneal at 150℃ for 30 min, and then perform ultraviolet ozone irradiation treatment for 15 min to form an electron transport layer on the ITO conductive substrate. (3) Dissolve FAI (248.16 mg), CsI (19.73 mg), RbI (6.58 mg), PbI2 (682.73 mg), PbBr2 (8.53 mg), PbCl2 (12.74 mg) and MACl (35 mg) in a mixed solvent of DMF and DMSO (the volume ratio of DMF to DMSO is 4:1). After shaking for 10 min, a perovskite precursor solution with a concentration of 1.55 mol / L is obtained. After filtering through 0.22 μm PTFE, 40 μL is added to the electron transport layer in step (2). Spin coat at 4000 rpm for 30 s. 80 μL of chlorobenzene is added as an antisolvent 15-16 s before the end of spin coating. Then anneal at 130℃ for 30 min to form a perovskite light-absorbing layer on the electron transport layer. (4) Dissolve 72.3 mg of 2,2',7,7'-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene (Spiro-OMeTAD) in 1 mL of chlorobenzene, add organic sulfonate molecules (M1) to make the concentration 0.2 mg / mL, add 29 μL of 4-tert-butylpyridine (tBP) and 18 μL of lithium bis(trifluoromethanesulfonylimide) (concentration 520 mg / mL, solvent is anhydrous acetonitrile), mix well, take 30 μL and drop it onto the perovskite light-absorbing layer in step (4), spin coat at 3000 rpm for 30 s to form a hole transport layer on the perovskite light-absorbing layer; (5) In high vacuum (10 -4 Under the condition of Pa), an Au electrode with a thickness of 80 nm can be deposited on the hole transport layer in step (5) by thermal evaporation, and an upright perovskite solar cell doped with organic sulfonate molecules (M1) can be obtained.
[0023] Example 2 An upright perovskite solar cell doped with organic sulfonate molecules (M2) in the hole transport layer is prepared according to Example 1, except that "organic sulfonate molecules (M1)" in Example 1 is replaced with "organic sulfonate molecules (M2)" while the other conditions remain unchanged.
[0024] Example 3 An upright perovskite solar cell doped with organic sulfonate molecules (M3) in the hole transport layer is prepared according to Example 1, except that "organic sulfonate molecules (M1)" in Example 1 is replaced with "organic sulfonate molecules (M3)", and the other conditions remain unchanged.
[0025] Example 4 An upright perovskite solar cell doped with organic sulfonate molecules (M3) in the hole transport layer is prepared according to Example 1, except that the concentration of organic sulfonate molecules (M1) in Example 1 is replaced with "0.01 mg / mL" or "5.0 mg / mL" respectively, to obtain upright perovskite solar cells doped with different concentrations of organic sulfonate molecules (M3) in the hole transport layer.
[0026] Comparative Examples An upright perovskite solar cell is prepared according to Example 1, except that the "organic sulfonate molecule (M1)" in Example 1 is not added, and all other conditions remain unchanged.
[0027] Performance testing Figure 1The ESR spectra of the hole transport layer (HTL) (Spiro) without organic sulfonate (M1) in the comparative examples and the hole transport layer (HTL) (Spiro-M1) doped with organic sulfonate molecules (M1) in Example 1 are shown below. Figure 1 It can be seen that after the hole transport layer (HTL) is doped with organic sulfonate molecules, the hole transport layer (Spiro-M1) doped with organic sulfonate molecules (M1) has a higher ESR signal intensity under a magnetic field of ~3510 G, indicating that more Spiro-OMeTAD exists in the HTL after doping with organic sulfonate molecules (M1). •+ The presence of free radical cations indicates that the organic sulfonate molecule (M1) promotes the oxidation of neutral Spiro-OMeTAD.
[0028] Figure 2 The NMR spectrum of the interaction between the organic sulfonate molecule (M1) and LiTFSI in Example 1 is shown. 7 Li NMR. From Figure 2 It can be seen that after the organic sulfonate molecule (M1) is mixed with LiTFSI, the peak position of the Li element in the LiTFSI molecule shifts significantly, indicating that the organic sulfonate molecule (M1) can chemically react with the LiTFSI molecule to form a mixture containing organic sulfonate molecule (M1) and Li. + The chelate of the ions prevents Li from + The aggregation and diffusion of these molecules stabilize the hole transport layer in perovskite solar cells.
[0029] Figure 3 The organic sulfonate molecule (M1) and 4-tert-butylpyridine (M1) in Example 1 t NMR spectrum of BP effect 1 HNMR, where a is t Before and after mixing BP with organic sulfonate molecules (M1) 1 ¹H NMR spectrum, b represents a mixture of organic sulfonate molecules (M1). t Before and after BP 1 H NMR spectrum. From Figure 3 It can be seen that the organic sulfonate molecule (M1) and t After BP is mixed, the organic sulfonate molecules (M1) and t The hydrogen ions in BP all underwent significant shifts, indicating that the organic sulfonate molecule (M1) can further interact with... t BP molecules undergo chemical reactions, forming a more stable organic mixture through hydrogen bonds, thus inhibiting... t BP volatilization, to avoid due to t The volatilization of BP leads to the formation of pores.
[0030] Figure 4This is a schematic diagram of the HTL stabilization mechanism after doping with the organic sulfonate molecule (M1) in Example 1. From... Figure 4 It can be seen that Spiro-OMeTAD is oxidized to Spiro-OMeTAD in the presence of O2. •+ and with TFSI - Combined to form Spiro-OMeTAD •+ TFSI - , and Li + The electrostatic interaction between the organic sulfonate molecule (M1) and the organic sulfonate molecule forms M1-Li. + Therefore, it is possible to fix Li + Finally, M1-Li + and t BP further interacts to generate M1-Li + - t BP, inhibition t BP volatilization.
[0031] Figure 5 This is a graph showing the relationship between open-circuit voltage and light intensity for the HTL undoped organic sulfonate solar cell (Spiro) in Example 1 and the HTL-doped organic sulfonate molecule solar cell (Spiro-M1) in Example 1. From... Figure 5 It can be seen that the ideal factor for the relationship between the open-circuit voltage and light intensity of the solar cell device formed after HTL doping with organic sulfonate molecules (M1) is... m A value closer to 1 indicates that the organic sulfonate molecule (M1) reduces the nonradiative recombination loss at the interface by effectively passivating defects at the perovskite / HTL interface.
[0032] Figure 6 In Figure a and b, respectively, are the TOF-SIMS spectra of the HTL of undoped organic sulfonate in Comparative Example 1 and the HTL-M1 of doped organic sulfonate molecule (M1) in Example 1. Figure 6 As can be seen from this, in the HTL without organic sulfonate (M1), Li + Diffusion and accumulation occur at the perovskite / HTL interface. Additionally, halide ions from the perovskite also migrate from the perovskite layer to the HTL. However, due to the chemical interaction between the organic sulfonate (M1) and the HTL, and the defect passivation effect of the organic sulfonate (M1) on the perovskite, Li is immobilized. + And halide ions, therefore in HTL-M1 doped with organic sulfonates (M1), Li + There was no migration between the ions and the halide ions.
[0033] Figure 7 To compare the current density-voltage curves of the perovskite solar cells prepared in Example 1 and Example 2, according to... Figure 7 The photovoltaic parameters of the perovskite solar cells prepared in the comparative example and example 1 were obtained, and the results are shown in Table 1.
[0034] Table 1. Photovoltaic parameters of perovskite solar cells in the comparative examples and Example 1.
[0035] from Figure 7 As can be seen from Table 1, compared with the solar cell formed by the hole transport layer without organic sulfonate (M1) in the comparative example, the perovskite solar cell formed by the hole transport layer doped with organic sulfonate (M1) in Example 1 has significantly improved short-circuit current density, open-circuit voltage and fill factor, and the power conversion efficiency has increased from 21.43% in the comparative example to 23.83%, which is a significant improvement over the solar cell in the comparative example.
[0036] Figure 8 To compare the humidity stability test results of the unencapsulated perovskite solar cells prepared in Example 1 and Example 2. Figure 8 It can be seen that the unencapsulated perovskite solar cell in Example 1 maintained 94.19% of its initial efficiency after aging for 3000 hours under a relative humidity of 35-45%, which is a significant improvement compared to the solar cell in the comparative example.
[0037] Figure 9 The graph shows the thermal stability test results of the unencapsulated perovskite solar cells in the comparative examples and Example 1. Figure 9 It can be seen that the unencapsulated perovskite solar cell in Example 1 maintained 92.21% of its initial efficiency after being heated and aged at 65°C for 2000 h, which is a significant improvement compared to the solar cell in the comparative example.
[0038] Figure 10 The current density-voltage curve of the perovskite solar cell prepared in Example 2 is shown, and according to... Figure 10 The photovoltaic parameters of the battery were obtained, and the results are shown in Table 2.
[0039] Table 2 Photovoltaic parameters of perovskite solar cells in Example 2
[0040] Depend on Figure 10 As shown in Table 2, the open-circuit voltage of the perovskite solar cell in Example 2 was improved, and the power conversion efficiency increased from 21.43% in the comparative example to 23.66%.
[0041] Figure 11To compare the humidity stability test results of the unencapsulated perovskite solar cells in Example 1 and Example 2. Figure 11 It can be seen that the unencapsulated perovskite solar cell in Example 2 maintained 94.11% of its initial efficiency after aging for 3000 hours under a relative humidity of 35-45%, which is a significant improvement compared to the solar cell in the comparative example.
[0042] Figure 12 To compare the light stability test results of the unencapsulated perovskite solar cells in Example 1 and Example 2. Figure 12 It can be seen that the unencapsulated perovskite solar cell in Example 2 maintained 92.09% of its initial efficiency after being heated and aged at 65°C for 2000 h, which is a significant improvement compared to the solar cell in the comparative example.
[0043] Figure 13 The current density-voltage curve of the perovskite solar cell in Example 3 is shown, and based on... Figure 13 The photovoltaic parameters of the battery were obtained, and the results are shown in Table 3.
[0044] Table 3. Photovoltaic parameters of the perovskite solar cells in Example 3.
[0045] Depend on Figure 13 As shown in Table 3, the open-circuit voltage and fill factor of the perovskite solar cell in Example 3 are improved, and the power conversion efficiency is increased from 21.43% in the comparative example to 23.58%, which is a significant improvement compared to the solar cell in the comparative example.
[0046] Figure 14 To compare the humidity stability test results of the unencapsulated perovskite solar cells in Example 1 and Example 3. Figure 14 It can be seen that the unencapsulated perovskite solar cell in Example 3 maintained 93.76% of its initial efficiency after aging for 3000 hours under a relative humidity of 35-45%, which is a significant improvement compared to the solar cell in the comparative example.
[0047] Figure 15 To compare the light stability test results of the unencapsulated perovskite solar cells in Example 1 and Example 3. Figure 15 It can be seen that the unencapsulated perovskite solar cell in Example 3 maintained 90.99% of its initial efficiency after being heated and aged at 65°C for 2000 h, which is a significant improvement compared to the solar cell in the comparative example.
[0048] Similarly, analysis revealed that the interaction mechanism between organic sulfonate molecules (M2) and (M3) and 2,2',7,7'-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene (Spiro OMeTAD), 4-tert-butylpyridine (tBP), and lithium bis(trifluoromethanesulfonyl)imide (Li-TFSI) in the hole transport layer is the same as that of organic sulfonate molecule (M1) in Example 1. Therefore, doping these three organic sulfonate molecules, M1, M2, and M3, into the hole transport layer of perovskite can modify its properties.
[0049] Furthermore, during the fabrication of solar cells using the organic sulfonate molecules prepared above, the spin coating speed can be between 2500 and 6500 rpm, and the spin coating time can be between 25 and 50 s. The annealing process specifically involves annealing at 80 to 150 °C for 5 to 30 min. The antisolvent used is one or more of chlorobenzene, dichloromethane, dichlorobenzene, toluene, ethyl acetate, chloroform, or diethyl ether. The concentration of the organic sulfonate molecule solution is 0.01 to 5.0 mg / mL. The electron transport layer material in the electron transport layer solution is any one or more of SnO2, TiO2, ZnO, BaSnO3, or CeO2. Since the interaction between the organic sulfonate molecules doped in the hole transport layer and 2',7,7'-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene (SpiroOMeTAD), LiTFSI, and tBP is not affected, changes in the above parameters do not affect the performance of the prepared solar cell.
[0050] In summary, this invention immobilizes Li by adding organic sulfonate molecules to the hole transport layer. + , t BP and halide ions passivate interface defects and stabilize the hole transport layer using Spiro-OMeTAD as the hole material, minimizing nonradiative recombination losses of interfacial carriers. This simultaneously improves the power conversion efficiency and stability of the device, enabling the controllable fabrication of high-efficiency and stable perovskite solar cells. The process of doping HTL with organic sulfonate molecules in this invention is simple and reproducible, and is of great significance in promoting the industrialization of perovskite solar cells.
[0051] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the present invention, and all such modifications or substitutions should be covered within the scope of the claims of the present invention.
Claims
1. Use of an organic sulfonate salt molecule in a perovskite solar cell, characterized in that, The specific application is: using organic sulfonate molecules to prepare the hole transport layer of perovskite solar cells; The hole transport layer is a mixture of organic sulfonate molecules and 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene in a molar ratio of 1:97 to 1:102; The hole transport layer material also includes 4-tert-butylpyridine and lithium bis(trifluoromethanesulfonyl)imide, wherein the mass-to-volume ratio of 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene, 4-tert-butylpyridine and lithium bis(trifluoromethanesulfonyl)imide is 72.3:29:18, mg:μL:μL; The structural formula of the organic sulfonate molecule is as follows: 。 2. A normal perovskite solar cell, characterized by, The hole transport layer of the perovskite solar cell is doped with organic sulfonate molecules; The hole transport layer is a mixture of organic sulfonate molecules and 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene in a molar ratio of 1:97 to 1:102; The hole transport layer material also includes 4-tert-butylpyridine and lithium bis(trifluoromethanesulfonyl)imide, wherein the mass-to-volume ratio of 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene, 4-tert-butylpyridine and lithium bis(trifluoromethanesulfonyl)imide is 72.3:29:18, mg:μL:μL; The structural formula of the organic sulfonate molecule is as follows: 。 3. The solar cell according to claim 2, characterized in that, The perovskite solar cell is composed of, from bottom to top, a conductive substrate layer, an electron transport layer, a perovskite light-absorbing layer, a hole transport layer, and a metal back electrode layer stacked together.
4. The method of producing a solar cell according to any one of claims 2 to 3, characterized by, The preparation method includes the following steps: (1) Spin-coating the electron transport layer solution onto the pretreated conductive substrate, annealing at 100~180℃ and then subjecting it to ultraviolet ozone irradiation or Plasma plasma treatment for 20~80min to form an electron transport layer on the conductive substrate. (2) Spin-coat the perovskite precursor solution onto the electron transport layer described in step (1), add antisolvent, and anneal to form a perovskite light-absorbing layer on the electron transport layer; (3) Spin-coat the hole transport layer solution containing organic sulfonate molecules onto the perovskite light-absorbing layer described in step (2) to form a hole transport layer on the perovskite light-absorbing layer; (4) Prepare a metal back electrode on the hole transport layer described in step (3).
5. The production method according to claim 4, characterized by, In step (1), the material of the conductive substrate layer is either ITO or FTO; The pretreatment specifically involves: ultrasonically cleaning the conductive substrate material sequentially with detergent, deionized water, acetone, and anhydrous ethanol, then drying it with nitrogen, treating it with ultraviolet ozone for 10-30 minutes, and cooling it for later use.
6. The preparation method according to claim 4, characterized in that, In step (1), the electron transport layer material in the electron transport layer solution is any one or more of SnO2, TiO2, ZnO, BaSnO3 or CeO2.
7. The preparation method according to claim 4, characterized in that, In step (2), the perovskite precursor material in the perovskite precursor solution is ABX3, where A is CH3NH3. + CH(NH2)2 + Cs + or Rb + B is any one or more of the following, where B is Pb. 2+ Sn 2+ Or Ge 2+ Any one or more of them, X is Cl - ,Br - Or I - Any one or more of them.
8. The preparation method according to claim 4, characterized in that, In step (3), the hole transport layer material in the hole transport layer solution containing organic sulfonate molecules is a mixture of organic sulfonate molecules and 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene in a molar ratio of 1:97 to 1:102, wherein the concentration of organic sulfonate molecules in the hole transport layer solution containing organic sulfonate molecules is 0.01 to 5.0 mg / mL; The hole transport layer material in the hole transport layer solution containing the mixed organic sulfonate molecules further includes 4-tert-butylpyridine and lithium bis(trifluoromethanesulfonyl)imide, wherein the mass-to-volume ratio of 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene, 4-tert-butylpyridine and lithium bis(trifluoromethanesulfonyl)imide is 72.3:29:18, mg:μL:μL; The antisolvent is any one or more of chlorobenzene, dichloromethane, dichlorobenzene, toluene, ethyl acetate, chloroform, or diethyl ether.
9. The preparation method according to claim 4, characterized in that, In step (4), the metal back electrode is Au or Ag.
10. The method of claim 4, wherein, The spin coating is performed at a speed of 2500–6500 rpm for a time of 25–50 s.