Perovskite solar cell with N-dodecyl mercaptan-copper clusters cooperatively implanted into perovskite layer and hole transport layer

Abstract

The invention belongs to the technical field of solar cells, and particularly relates to a perovskite solar cell with N-dodecyl mercaptan-copper clusters cooperatively implanted into a perovskite layer and a hole transport layer, and the perovskite solar cell is characterized in that an N-dodecyl mercaptan-copper cluster colloidal solution is prepared by adopting a liquid-phase pulse laser irradiation technology; the passivated perovskite solar cell is prepared through the steps of preparing a perovskite substrate, taking n-dodecyl mercaptan-copper clusters as a co-doped additive, simultaneously implanting a perovskite layer and a hole transport layer, sequentially depositing an electron transport layer, spin-coating the perovskite layer and the hole transport layer, and finally, evaporating a metal electrode to obtain the passivated perovskite solar cell. The n-dodecyl mercaptan-copper cluster is implanted into the perovskite layer and the hole transport layer at the same time, a defect passivation and charge transfer channel is constructed, the energy levels of the perovskite layer and the hole transport layer are improved, the hole mobility is effectively improved, extraction and transport of hole carriers are promoted, and the high-efficiency passivated perovskite solar cell is obtained. The implantation mode is convenient, and the preparation process is simple.

Description

Technical Field

[0001] The present invention belongs to the technical field of solar cell preparation, and in particular relates to a perovskite solar cell in which n-dodecyl mercaptan-copper clusters are collaboratively implanted into a perovskite layer and a hole transport layer. Background Art

[0002] Organic-inorganic hybrid perovskite solar cells (PSCs) are widely used in the field of PSCs due to their excellent physical properties, including low cost, high absorption coefficient, long charge carrier diffusion length, low exciton binding energy, and tunable band gap. Currently, the photoelectric conversion efficiency has jumped from 3.8% in 2009 to 26.9% today, surpassing the decades-long development of crystalline silicon cells. These PSCs are considered the most promising third-generation photovoltaic devices and are expected to advance commercialization.

[0003] Despite progress in organic-inorganic hybrid perovskite solar cells, record efficiencies remain below the Shockley-Queisser theoretical efficiency limit (~31%) for single-junction perovskite solar cells. To effectively overcome these bottlenecks, two potential factors need to be addressed. On the one hand, due to the polycrystalline nature of perovskite films, a large number of dangling bonds are primarily located at the grain boundaries and upper surface of the perovskite film, significantly contributing to non-radiative recombination losses and thus degrading device performance. On the other hand, a severe imbalance exists between the carrier extraction and transport rates at the hole and interface, leading to the formation and accumulation of excessive interfacial space charge, which significantly affects device stability. Unfortunately, considerable effort has been devoted to developing novel hole transport layers with high hole mobility or adding interfacial layers to compensate for interface passivation, resulting in a gap between the actual efficiency of perovskite solar cells and their theoretical values.

[0004] In addition, the poor conductivity of organic molecules in most organic-inorganic hybrid perovskite solar cells affects the transport of photogenerated carriers. Highly conductive metal nanocrystals offer unique advantages in regulating perovskite carrier dynamics, but they are more rigid than organic molecules, which can easily lead to localized stress changes and affect the stability of the thin film in organic-inorganic hybrid perovskite solar cells. Furthermore, most metal nanocrystals are synthesized via wet chemical methods, which suffer from long cycles, complex processes, high costs, and uneven size. Summary of the Invention

[0005] In response to the deficiencies in the above-mentioned prior art, the present invention provides a perovskite solar cell in which n-dodecyl mercaptan-copper clusters are synergistically implanted into a perovskite layer and a hole transport layer. The present invention adopts liquid-phase laser irradiation technology to obtain a colloidal solution of n-dodecyl mercaptan-copper clusters with uniform particle size and uniform dispersion in a solvent, and uses n-dodecyl mercaptan-copper clusters as co-doping additives, which are simultaneously implanted into the perovskite layer and the hole transport layer, thereby overcoming the two problems existing in the prior art organic-inorganic hybrid perovskite solar cells, further improving the photoelectric conversion efficiency of the perovskite solar cell, and developing a new additive that is simple to prepare and can passivate perovskite defects and balance carrier transport.

[0006] Compared with the prior art, the technical solution of the present invention is: The present invention provides a method for preparing a n-dodecyl mercaptan-copper cluster colloidal solution, comprising the following steps: In an anhydrous and oxygen-free environment, n-dodecyl mercaptan is used as the organic ligand molecule, and n-dodecyl mercaptan and a copper target are placed together in a solvent. Then, they are irradiated using liquid-phase pulsed laser irradiation technology, and then the copper target is removed to obtain a precursor solution.

[0007] After the precursor solution was frozen with liquid nitrogen, it was irradiated with pulsed laser again to obtain a 0.1 mg / mL~0.2 mg / mL n-dodecyl mercaptan-copper cluster colloidal solution.

[0008] Preferably, the conditions for the two pulsed laser irradiation treatments are: irradiation is carried out under the conditions of laser emission wavelength of 1064nm, laser irradiation range of 1.3cm, pulse frequency of 6Hz~10Hz, pulse width of 6ns~8ns, spot size of 8mm~13mm, laser energy of 0.4J~0.6J, and irradiation time is 1min~5min.

[0009] Preferably, the pulse laser irradiation treatment is performed simultaneously with ultrasound and cryogenic assisted treatment, the ultrasound frequency is 80 Hz to 100 Hz, and the temperature of the cryogenic assisted treatment is -10°C to 0°C.

[0010] Preferably, the volume ratio of the solvent to n-dodecyl mercaptan is 200-500:1, and the solvent is N,N-dimethylformamide.

[0011] The present invention also protects an n-dodecyl mercaptan-copper cluster colloid solution, which is prepared by the above preparation method. The solute in the n-dodecyl mercaptan-copper cluster colloid solution is n-dodecyl mercaptan-copper clusters with an average particle size of 1.2 nm.

[0012] The present invention also protects a passivated perovskite solar cell, which is composed of a conductive substrate, an electron transport layer, a perovskite layer, a hole transport layer and a metal electrode stacked in sequence from bottom to top, and both the perovskite layer and the hole transport layer are doped with n-dodecyl mercaptan-copper clusters.

[0013] Preferably, the thickness of the perovskite layer is 500 nm to 600 nm, and the thickness of the hole transport layer is 150 nm to 200 nm.

[0014] The present invention also provides a method for preparing a passivated perovskite solar cell, comprising the following steps: A tin dioxide layer is deposited on a conductive substrate to obtain an electron transport layer.

[0015] First, a colloidal solution of n-dodecyl mercaptan-copper clusters is implanted into a perovskite layer solution and dropped onto the electron transport layer. Then, an antisolvent is added under rotating conditions, and the solution is heat treated to embed the n-dodecyl mercaptan-copper clusters into the composite layer at the perovskite grain boundary, thereby obtaining a perovskite layer. The volume ratio of the colloidal solution of n-dodecyl mercaptan-copper clusters to the solvent in the perovskite layer solution is 0.5-1.0:100.

[0016] The n-dodecyl mercaptan-copper cluster colloidal solution is implanted into a hole transport layer solution and spin-coated on the perovskite layer to obtain a hole transport layer; the volume ratio of the n-dodecyl mercaptan-copper cluster colloidal solution to the solvent in the hole transport layer solution is 0.1~0.5:100.

[0017] A metal electrode is evaporated on the hole transport layer, where the metal electrode layer is a gold electrode layer or a silver electrode layer, to produce a passivated perovskite solar cell.

[0018] Preferably, the perovskite layer is an ABX3 type compound, wherein A is CH3NH3 + 、HC(=NH)NH2 + or Cs + , B is Pb 2+ , X is a halogen ion, and the concentration of the perovskite layer solution is 1.40mol / L~1.60mol / L; Specifically, the perovskite layer solution is selected from cationic (FAPbI3 abbreviated as FA), double cationic (FA 0.95 MA 0.05 Pb(I 0.95 Br 0.05 )3 abbreviated as FAMA) or triple positive (Cs 0.05 FA 0.85 MA 0.10 Pb(I 0.97 Br 0.03 )3abbreviated as CsFAMA) ion solution.

[0019] Preferably, the hole transport layer solution is selected from 2,2',7,7'-tetrakis[N,N-bis(4-methoxyphenyl)amino]-9,9'-spirobifluorene (Spiro-OMeTAD) solution or poly(bis(4-phenyl)(2,4,6-trimethylphenyl)amine) solution; the 2,2',7,7'-tetrakis[N,N-bis(4-methoxyphenyl)amino]-9,9'-spirobifluorene (Spiro-OMeTAD) solution is 60~80 mg / mL, and the poly(bis(4-phenyl)(2,4,6-trimethylphenyl)amine) solution is 10 mg / mL~15 mg / mL.

[0020] Compared with the prior art, the present invention has the following beneficial effects: 1. The present invention uses a liquid-phase laser irradiation method to quickly and easily prepare size-controlled, monodisperse, and stable n-dodecylmercaptan-copper clusters, which can be directly put into use without going through complex processes such as solvent / ligand exchange and centrifugal drying. In n-dodecylmercaptan, one end of the thiol group is connected to a carbon chain and the other end is grafted to copper. At this time, the long-chain alkyl group prevents the copper clusters from growing (copper clusters tend to agglomerate when placed together), thereby improving the service life.

[0021] The principle of the preparation method of the present invention is that after the copper target is irradiated for the first time, a nanocrystalline colloidal solution is obtained, which is then quickly frozen with liquid nitrogen to fix the position of the dispersed nanocrystals. In this way, when laser irradiation is performed again, the size of the n-dodecyl mercaptan-copper clusters is completely reduced to a smaller size.

[0022] 2. The present invention provides a passivated perovskite solar cell comprising a conductive substrate, an electron transport layer, a perovskite layer, a hole transport layer, and a metal electrode, stacked sequentially from bottom to top. The perovskite layer and hole transport layer are composite layers formed by embedding n-dodecylmercaptan-copper clusters (organometallic clusters) at the perovskite grain boundaries and implanting a hole transport material. The present invention utilizes liquid-phase pulsed laser irradiation technology to prepare a colloidal solution of organometallic clusters. The organometallic clusters are then co-doped into the perovskite layer and the hole transport layer. The electron transport layer is then deposited, followed by spin coating of the perovskite layer and the hole transport layer. Finally, the metal electrode is evaporated to produce the perovskite solar cell. The simultaneous implantation of the organometallic clusters into the perovskite layer and the hole transport layer creates defect passivation and charge transfer channels, improves the energy levels of the perovskite layer and the hole transport layer, effectively increases hole mobility, and facilitates the extraction and transport of hole carriers. This results in a highly efficient perovskite solar cell with a convenient implantation method and a simple preparation process. The simultaneous implantation of organic metal clusters into the perovskite layer and the hole transport layer improves the current density of the organic metal cluster-passivated perovskite solar cells, thereby achieving an improvement in the stability and photoelectric conversion efficiency of the perovskite solar cells, which has extremely high application value.

[0023] In addition, the organometallic clusters of the present invention are simultaneously implanted into the perovskite layer and the hole transport layer, utilizing the high conductivity of the organometallic clusters and the strong bonding ability of the ligand molecules, as well as the localized surface plasmon coupling of the organometallic clusters to produce an enhanced light absorption effect, thereby simultaneously achieving the passivation of perovskite grain boundary defects and the rapid extraction and transmission of photogenerated carriers, thereby being able to obtain a highly efficient and stable perovskite solar cell in one step.

[0024] Furthermore, the present invention provides a strategy for the coordinated implantation of hydrophobic n-dodecylthiol-copper clusters (thiol copper clusters) into the perovskite layer and hole transport layer for efficient and stable perovskite solar cells. The thiol copper clusters with p-type semiconductor properties prepared by pulsed laser irradiation technology effectively combine the properties of organic molecules (strong passivation ability) and metal properties (high conductivity). Therefore, the thiol copper clusters in the perovskite layer can passivate grain boundary defects (such as Pb 2+ The copper thiol clusters in the hole transport layer improve interfacial contact and enhance hole mobility. The copper thiol clusters form an ideal charge transfer semiconductor heterostructure with the perovskite / hole transport layer, promoting exciton separation and increasing the extraction rate of photogenerated holes. This reduces the interfacial barrier between the perovskite layer and the hole transport layer. This dual improvement in both the bulk and interface creates an invisible green transfer bridge effect.

[0025] 3. The present invention uses organic metal clusters to simultaneously implant the perovskite layer and the hole transport layer, which is simple to operate and can effectively improve the conductivity and hole mobility of the hole transport layer, improve the energy levels of the perovskite layer and the hole transport layer, and promote the extraction and transport of hole carriers.

[0026] 4. The present invention simultaneously implants organic metal clusters into the perovskite layer and the hole transport layer, greatly improving the efficiency of perovskite solar cells. The photoelectric conversion efficiency is increased from the basic 23% to 25.2%, which promotes the development of perovskite solar cells and has extremely high application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 Schematic diagram of the structure of the perovskite solar cell of Examples 1 to 6.

[0028] Figure 2 These are characterization images of the n-dodecyl mercaptan-copper cluster (SCuNCs) colloidal solution of Example 1; Figure a is a TEM image of n-dodecyl mercaptan-copper clusters, the inset in Figure a is an optical photograph of the n-dodecyl mercaptan-copper cluster colloidal solution; and Figure b is the full XPS spectrum of n-dodecyl mercaptan-copper clusters.

[0029] Figure 3are SEM images; wherein, Figure a is an SEM image of the FA perovskite film without implantation of n-dodecyl mercaptan-copper clusters in Comparative Example 1, and Figure b is an SEM image of the FA perovskite film with implantation of n-dodecyl mercaptan-copper clusters in Example 1.

[0030] Figure 4 are SEM images; wherein, Figure a is an SEM image of the FAMA perovskite film without n-dodecyl mercaptan-copper cluster implantation in Comparative Example 2, and Figure b is an SEM image of the FAMA perovskite film with n-dodecyl mercaptan-copper cluster implantation in Example 2.

[0031] Figure 5 are SEM images; wherein, Figure a is an SEM image of the CsFAMA perovskite film without implantation of n-dodecyl mercaptan-copper clusters in Comparative Example 3, and Figure b is an SEM image of the CsFAMA perovskite film with implantation of n-dodecyl mercaptan-copper clusters in Example 3.

[0032] Figure 6 In the figure, Figure a is a hole mobility diagram with / without the implantation of n-dodecyl mercaptan-copper clusters into the Spiro-OMeTAD hole transport layer in Example 1 and Comparative Example 1, and Figure b is a hole mobility diagram with / without the implantation of n-dodecyl mercaptan-copper clusters into the PTAA hole transport layer in Example 4 and Comparative Example 4.

[0033] Figure 7 In the figure, Figure a is a conductivity diagram of the Spiro-OMeTAD hole transport layer with / without the implantation of n-dodecyl mercaptan-copper clusters in Example 1 and Comparative Example 1, and Figure b is a conductivity diagram of the PTAA hole transport layer with / without the implantation of n-dodecyl mercaptan-copper clusters in Example 4 and Comparative Example 4.

[0034] Figure 8 In the figure, Figure a is a current-voltage curve of a perovskite solar cell prepared in Comparative Example 1 without the implantation of n-dodecyl mercaptan-copper clusters into a FA perovskite film and a Spiro-OMeTAD hole transport layer; Figure b is a current-voltage curve of a passivated perovskite solar cell prepared in Example 1 with the collaborative implantation of n-dodecyl mercaptan-copper clusters into a FA perovskite film and a Spiro-OMeTAD hole transport layer.

[0035] Figure 9 In the figure, Figure a is a current-voltage curve of a perovskite solar cell prepared in Comparative Example 2 without the implantation of n-dodecyl mercaptan-copper clusters into a FAMA perovskite film and a Spiro-OMeTAD hole transport layer; Figure b is a current-voltage curve of a passivated perovskite solar cell prepared in Example 2 with the collaborative implantation of n-dodecyl mercaptan-copper clusters into a FAMA perovskite film and a Spiro-OMeTAD hole transport layer.

[0036] Figure 10 In the figure, Figure a is a current-voltage curve of a perovskite solar cell prepared in Comparative Example 3 without the implantation of n-dodecyl mercaptan-copper clusters into the CsFAMA perovskite film and the Spiro-OMeTAD hole transport layer; Figure b is a current-voltage curve of a passivated perovskite solar cell prepared in Example 3 with the synergistic implantation of n-dodecyl mercaptan-copper clusters into the CsFAMA perovskite film and the Spiro-OMeTAD hole transport layer.

[0037] Figure 11 In the figure, Figure a is a current-voltage curve of a perovskite solar cell prepared in Comparative Example 4 without the implantation of n-dodecyl mercaptan-copper clusters into a FA perovskite film and a PTAA hole transport layer; Figure b is a current-voltage curve of a passivated perovskite solar cell prepared in Example 4 with the collaborative implantation of n-dodecyl mercaptan-copper clusters into a FA perovskite film and a PTAA hole transport layer.

[0038] Figure 12 In the figure, Figure a is a current-voltage curve of a perovskite solar cell prepared in Comparative Example 5 without the implantation of n-dodecyl mercaptan-copper clusters into a FAMA perovskite film and a PTAA hole transport layer; Figure b is a current-voltage curve of a passivated perovskite solar cell prepared in Example 5 with the collaborative implantation of n-dodecyl mercaptan-copper clusters into a FAMA perovskite film and a PTAA hole transport layer.

[0039] Figure 13 In the figure, Figure a is a current-voltage curve of a perovskite solar cell prepared in Comparative Example 6 without the implantation of n-dodecyl mercaptan-copper clusters into the CsFAMA perovskite film and the PTAA hole transport layer; Figure b is a current-voltage curve of a passivated perovskite solar cell prepared in Example 6 with the collaborative implantation of n-dodecyl mercaptan-copper clusters into the CsFAMA perovskite film and the PTAA hole transport layer.

[0040] Figure 1 Description of the reference numerals: 1. Conductive substrate; 2. Electron transport layer; 3. Perovskite layer; 4. Hole transport layer; 5. Metal electrode layer. DETAILED DESCRIPTION

[0041] The specific embodiments of the present invention are described in detail below, but it should be understood that the scope of protection of the present invention is not limited by the specific embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention. The experimental methods described in the embodiments of the present invention are all conventional methods unless otherwise specified.

[0042] The technical solution of the present invention is further explained below using embodiments, which are specifically as follows: Example 1 A method for preparing a passivated perovskite solar cell. In this embodiment, n-dodecyl mercaptan-copper clusters are synergistically implanted into a FA perovskite layer and a Spiro-OMeTAD hole transport layer to passivate the perovskite solar cell. The specific preparation method is as follows: S1. In an anhydrous and oxygen-free environment, place 10 μL of n-dodecyl mercaptan and a copper block in 5 mL of N,N-dimethylformamide and mix well to obtain a mixed solution. Under the assistance of ultrasound and low temperature, use an Nd:YAG pulse laser (wavelength 1064 nm, irradiation range 1.3 cm, pulse frequency 10 Hz, pulse width 8 ns, spot size 13 mm, laser energy 0.6 J) to irradiate the mixed solution for 2 min at a low temperature of -10°C. After irradiation, remove the copper block to obtain a precursor solution.

[0043] S2. The precursor solution of step S1 was frozen with liquid nitrogen for 1 minute, and then the precursor solution of step S1 was irradiated again with a pulsed laser under the same conditions as step S1 for 1 minute. After the irradiation was completed, a 0.1 mg / mL organic metal cluster colloidal solution was obtained. In the organic metal cluster colloidal solution, the organic metal clusters were well-dispersed n-dodecyl mercaptan-copper clusters with a size of about 1.2 nm.

[0044] S3. Preparation of SnO2 electron transport layer: 10 μL of thioglycolic acid, 0.5 mL of hydrochloric acid, 110 mg of SnCl2·2H2O and 500 mg of urea were added in sequence to a Shuniu bottle filled with 40 mL of ice ultrapure water. After the ice was completely melted, the SnO2 electron transport layer precursor solution was obtained. The SnO2 electron transport layer precursor solution was poured into a culture dish filled with FTO conductive substrate, and then placed in a 90°C oven for hydrothermal treatment for 3 h. After the hydrothermal treatment, the FTO conductive substrate was taken out, ultrasonically cleaned with ultrapure water and isopropanol, and then blown dry with nitrogen. It was then placed on a hot plate at 170°C for heat treatment for 1 h to obtain a dense SnO2 layer with a thickness of 20 nm to 30 nm, which is the SnO2 electron transport layer.

[0045] S4. A FA perovskite precursor solution with a concentration of 1.4 mol / L was prepared in a nitrogen glove box. The preparation method was as follows: 240.75 mg of HC(=NH)NH3I, 703.50 mg of PbI2 and 32.77 mg of CH3NH3Cl were mixed in a small reagent bottle, and 800 μL of the n-dodecyl mercaptan-copper cluster colloidal solution of step S2 and 200 μL of dimethyl sulfoxide solvent were added to obtain a mixed solution. The mixed solution consisted of the n-dodecyl mercaptan-copper cluster colloidal solution and the FA perovskite precursor solution. The mixed solution was stirred at 50°C for 2 h and filtered through a 0.22 μm organic filter head to obtain 1 mL of 1.4 mol / L n-dodecyl mercaptan-copper cluster-implanted FA perovskite precursor solution for the experiment. The solvent volume ratio of the n-dodecyl mercaptan-copper cluster colloidal solution to the FA perovskite precursor solution was 8:100.

[0046] S5. Preparation of FA perovskite layer: Take 30 μL of the FA perovskite precursor solution implanted with n-dodecyl mercaptan-copper clusters in step S4, and spin-coat it onto the SnO2 electron transport layer in step S3. First, spin-coat it at a low speed (2000 rpm) for 10 seconds, then spin-coat it at a high speed (5000 rpm) for 30 seconds, and when there are 10 seconds left in the high-speed spin coating, immediately add 100 μL of ethyl acetate solution. After the addition is completed, heat treat it at 100°C for 40 minutes to prepare a perovskite film with a thickness of 500 nm and n-dodecyl mercaptan-copper clusters embedded in the perovskite grain boundaries.

[0047] S6. Prepare a Spiro-OMeTAD hole transport layer solution with a concentration of 73 mg / mL in a nitrogen glove box. The preparation method is as follows: place 73 mg of Spiro-OMeTAD powder in a small reagent bottle, add 1 mL of chlorobenzene solvent and shake until the Spiro-OMeTAD powder is fully dissolved, then use a pipette to add 30 μL of 4-tert-butylpyridine solution, 18 μL of lithium bis(trifluoromethanesulfonyl)imide solution and 20 μL of n-dodecyl mercaptan-copper cluster colloid solution in sequence, add a rotor and stir for 3 hours, and then filter using a 0.22 μm organic filter head to prepare a Spiro-OMeTAD hole transport layer solution implanted with n-dodecyl mercaptan-copper clusters. The solvent volume ratio of the n-dodecyl mercaptan-copper cluster colloid solution to the Spiro-OMeTAD hole transport layer solution is 0.2:100.

[0048] S7. Preparation of Spiro-OMeTAD hole transport layer: Take 30 μL of the Spiro-OMeTAD hole transport layer solution implanted with n-dodecyl mercaptan-copper clusters in step S6 and spin-coat it onto the perovskite film in step S5. Spin-coat at 4000 rpm for 30 seconds to prepare a Spiro-OMeTAD film with a uniform and flat surface and a thickness of 160 nm. Then oxidize it in a drying cabinet for 12 hours to obtain a hole transport layer.

[0049] S8, evaporating a layer with an effective area of ​​0.05 cm on the hole transport layer in step S7 2 , a gold electrode with a thickness of 80 nm, and a FA perovskite solar cell with synergistic passivation of n-dodecyl mercaptan-copper clusters were obtained.

[0050] Example 2 A method for preparing a passivated perovskite solar cell. In this embodiment, n-dodecyl mercaptan-copper clusters are synergistically implanted into a FAMA perovskite layer and a Spiro-OMeTAD hole transport layer to passivate the perovskite solar cell. Steps S1 to S3 and S6 are the same as those in Example 1, except that: S4. Prepare a 1.5 mol / L FAMA perovskite precursor solution in a nitrogen glove box by mixing 245.05 mg of HC(=NH)NH3I, 35.92 mg of CH3NH3PbBr3, 753.75 mg of PbI2, and 34.35 mg of CH3NH3Cl in a small reagent bottle, and add 800 μL of n-dodecyl mercaptan-copper cluster colloidal solution and 200 μL of dimethyl sulfoxide solvent. A mixed solution was obtained, which consisted of a n-dodecyl mercaptan-copper cluster colloidal solution and a FAMA perovskite precursor solution. The mixed solution was stirred at 50°C for 2 hours and filtered through a 0.22 μm organic filter head to obtain 1 mL of a 1.5 mol / L n-dodecyl mercaptan-copper cluster-implanted FAMA perovskite precursor solution for the experiment. The solvent volume ratio of the n-dodecyl mercaptan-copper cluster colloidal solution to the FAMA perovskite precursor solution was 8:100.

[0051] S5. Preparation of FAMA perovskite layer: Take 30 μL of the FAMA perovskite precursor solution implanted with n-dodecyl mercaptan-copper clusters in step S4, and spin-coat it onto the SnO2 electron transport layer. First, spin-coat it at a low speed (1000 rpm) for 10 seconds, then spin-coat it at a high speed (5000 rpm) for 30 seconds. When there are 10 seconds left in the high-speed spin coating, immediately add 150 μL of ethyl acetate solution. After the addition is completed, heat treat it at 100°C for 30 minutes to prepare a perovskite film with a thickness of 530 nm and n-dodecyl mercaptan-copper clusters embedded in the perovskite grain boundaries.

[0052] S7. Preparation of Spiro-OMeTAD hole transport layer: Take 30 μL of the Spiro-OMeTAD hole transport layer solution implanted with n-dodecyl mercaptan-copper clusters and spin-coat it onto the perovskite film. Spin-coat at 4000 rpm for 30 seconds to prepare a Spiro-OMeTAD film with a uniform and flat surface and a thickness of 160 nm. Then oxidize it in a drying cabinet for 12 hours to obtain the hole transport layer.

[0053] S8, evaporating a layer with an effective area of ​​0.05 cm on the hole transport layer in step S7 2 , a gold electrode with a thickness of 80 nm, and a FAMA perovskite solar cell with synergistic passivation of n-dodecyl mercaptan-copper clusters were obtained.

[0054] Example 3 A method for preparing a passivated perovskite solar cell. In this embodiment, n-dodecyl mercaptan-copper clusters are synergistically implanted into a CsFAMA perovskite layer and a Spiro-OMeTAD hole transport layer to passivate the perovskite solar cell. Steps S1 to S3 and S6 are the same as those in Example 1, except that: S4. Prepare a 1.55 mol / L CsFAMA perovskite precursor solution in a nitrogen glove box by mixing 226.57 mg of HC(=NH)NH3I, 16.79 mg of CH3NH3Br, 751.44 mg of PbI2, 36.62 mg of CH3NH3Cl, and 20.71 mg of CsI in a small reagent bottle, and add 800 μL of n-dodecyl mercaptan-copper cluster colloid solution and 200 μL of dimethyl Sulfoxide solvent was added to obtain a mixed solution, which consisted of a n-dodecyl mercaptan-copper cluster colloidal solution and a CsFAMA perovskite precursor solution. The mixed solution was stirred at 50°C for 2h and filtered through a 0.22μm organic filter head to obtain 1mL of 1.55mol / L n-dodecyl mercaptan-copper cluster-implanted CsFAMA perovskite precursor solution for the experiment. The solvent volume ratio of the n-dodecyl mercaptan-copper cluster colloidal solution to the perovskite precursor solution was 8:100.

[0055] S5. Preparation of CsFAMA perovskite layer: Take 30 μL of CsFAMA perovskite precursor solution implanted with n-dodecyl mercaptan-copper clusters and spin-coat it onto the SnO2 electron transport layer at 4000 rpm for 30 seconds. When there are 10 seconds left in the high-speed spin coating, immediately add 250 μL of ethyl acetate solution. After the addition is complete, heat treat at 130°C for 20 minutes to prepare a perovskite film with a thickness of 600 nm and n-dodecyl mercaptan-copper clusters embedded in the perovskite grain boundaries.

[0056] S7. Preparation of Spiro-OMeTAD hole transport layer: Take 30 μL of the Spiro-OMeTAD hole transport layer solution implanted with n-dodecyl mercaptan-copper clusters and spin-coat it onto the perovskite film. Spin-coat at 4000 rpm for 30 seconds to prepare a Spiro-OMeTAD film with a uniform and flat surface and a thickness of 160 nm. Then oxidize it in a drying cabinet for 12 hours to obtain the hole transport layer.

[0057] S8, evaporating a layer with an effective area of ​​0.05 cm on the hole transport layer in step S7 2 , a gold electrode with a thickness of 80 nm, and obtained a CsFAMA perovskite solar cell with synergistic passivation of n-dodecyl mercaptan-copper clusters.

[0058] Example 4 A method for preparing a passivated perovskite solar cell. In this embodiment, n-dodecyl mercaptan-copper clusters are synergistically implanted into a FA perovskite layer and a PTAA hole transport layer to passivate the perovskite solar cell. Steps S1 to S5 are the same as those in Example 1, except that: S6. Prepare a PTAA hole transport layer solution with a concentration of 12 mg / mL in a nitrogen glove box. The preparation method is as follows: place 12 mg of PTAA powder in a small reagent bottle, add 1 mL of toluene solvent and shake until the PTAA powder is fully dissolved, then use a pipette to add 4 μL of 4-tert-butylpyridine solution, 7.5 μL of lithium bis(trifluoromethanesulfonyl)imide solution and 20 μL of n-dodecyl mercaptan-copper cluster colloid solution in sequence, add a rotor and stir for 3 hours, and then filter using a 0.22 μm organic filter head to prepare a PTAA hole transport layer solution implanted with n-dodecyl mercaptan-copper clusters. The solvent volume ratio of the n-dodecyl mercaptan-copper cluster colloid solution to the PTAA hole transport layer solution is 0.2:100.

[0059] S7. Preparation of PTAA hole transport layer: Take 30 μL of the PTAA hole transport layer solution implanted with n-dodecyl mercaptan-copper clusters in step S6 and spin-coat it onto the perovskite film at a high speed of 3000 rpm for 30 seconds to prepare a PTAA film with a uniform and flat surface and a thickness of 150 nm. Then oxidize it in a drying cabinet for 12 hours to obtain a hole transport layer.

[0060] S8, evaporating a layer with an effective area of ​​0.05 cm on the hole transport layer in step S7 2 , a gold electrode with a thickness of 80 nm, and a FA perovskite solar cell with synergistic passivation of n-dodecyl mercaptan-copper clusters were obtained.

[0061] Example 5 A method for preparing a passivated perovskite solar cell. In this embodiment, n-dodecyl mercaptan-copper clusters are synergistically implanted into a FAMA perovskite layer and a PTAA hole transport layer to passivate the perovskite solar cell. Steps S1 to S6 are the same as those in Example 1, except that: S7. Preparation of PTAA hole transport layer: Take 30 μL of PTAA hole transport layer solution implanted with n-dodecyl mercaptan-copper clusters and spin-coat it onto the perovskite film at a high speed of 3000 rpm for 30 seconds to prepare a PTAA film with a uniform and flat surface and a thickness of 150 nm. Then oxidize it in a drying cabinet for 12 hours to obtain a hole transport layer.

[0062] S8, evaporating a layer with an effective area of ​​0.05 cm on the hole transport layer in step S7 2 , a gold electrode with a thickness of 80 nm, and a FAMA perovskite solar cell with synergistic passivation of n-dodecyl mercaptan-copper clusters were obtained.

[0063] Example 6 A method for preparing a passivated perovskite solar cell. In this embodiment, n-dodecyl mercaptan-copper clusters are synergistically implanted into a CsFAMA perovskite layer and a PTAA hole transport layer to passivate the perovskite solar cell. Steps S1 to S6 are the same as those in Example 1, except that: S7. Preparation of PTAA hole transport layer: Take 30 μL of PTAA hole transport layer solution implanted with n-dodecyl mercaptan-copper clusters and spin-coat it onto the perovskite film at a high speed of 3000 rpm for 30 seconds to prepare a PTAA film with a uniform and flat surface and a thickness of 150 nm. Then oxidize it in a drying cabinet for 12 hours to obtain a hole transport layer.

[0064] S8, evaporating a layer with an effective area of ​​0.05 cm on the hole transport layer in step S7 2 , a gold electrode with a thickness of 80 nm, and obtained a CsFAMA perovskite solar cell with synergistic passivation of n-dodecyl mercaptan-copper clusters.

[0065] Comparative Example 1 A method for preparing a perovskite solar cell is the same as the preparation steps of Example 1, except that no n-dodecylmercaptan-copper clusters are implanted into the FA perovskite layer and the Spiro-OMeTAD hole transport layer. The specific preparation method is as follows: S1. Preparation of SnO2 electron transport layer: 10 μL of thioglycolic acid, 0.5 mL of hydrochloric acid, 110 mg of SnCl2·2H2O and 500 mg of urea were added in sequence to a Shuniu bottle containing 40 mL of ice ultrapure water. After the ice was completely melted, the SnO2 electron transport layer precursor solution was obtained. The SnO2 electron transport layer precursor solution was poured into a culture dish filled with FTO conductive substrate, and then placed in a 90°C oven for hydrothermal treatment for 3 h. After the hydrothermal treatment, the FTO conductive substrate was taken out, ultrasonically cleaned with ultrapure water and isopropanol, and then blown dry with nitrogen. It was then placed on a hot plate at 170°C for heat treatment for 1 h to obtain a dense SnO2 layer with a thickness of 20 nm to 30 nm, which is the SnO2 electron transport layer.

[0066] S2. Prepare a 1.4 mol / L FA perovskite precursor solution in a nitrogen glove box by mixing 240.75 mg of HC(=NH)NH3I, 703.50 mg of PbI2, and 32.77 mg of CH3NH3Cl in a small reagent bottle, and add 800 μL of N,N-dimethylformamide and 200 μL of dimethyl sulfoxide solvent to obtain a mixed solution. Stir the mixed solution at 50°C for 2 h, and filter it with a 0.22 μm organic filter head to obtain 1 mL of 1.4 mol / L FA perovskite precursor solution for the experiment.

[0067] S3. Preparation of FA perovskite layer: Take 30 μL of the FA perovskite precursor solution in step S2 and spin-coat it onto the SnO2 electron transport layer in step S1. First, spin-coat it at a low speed (2000 rpm) for 10 seconds, then spin-coat it at a high speed (5000 rpm) for 30 seconds. When there are 10 seconds left in the high-speed spin-coating, immediately add 100 μL of ethyl acetate solution. After the addition is completed, heat treat it at 100°C for 40 minutes to prepare a FA perovskite film with a thickness of 500 nm.

[0068] S4. Prepare a Spiro-OMeTAD hole transport layer solution with a concentration of 73 mg / mL in a nitrogen glove box. The preparation method is as follows: place 73 mg of Spiro-OMeTAD powder in a small reagent bottle, add 1 mL of chlorobenzene solvent and shake until the Spiro-OMeTAD powder is fully dissolved, then use a pipette to add 30 μL of 4-tert-butylpyridine solution and 18 μL of lithium bis(trifluoromethanesulfonyl)imide solution in sequence, add a rotor and stir for 3 hours, and then filter using a 0.22 μm organic filter head to prepare a Spiro-OMeTAD hole transport layer solution.

[0069] S5. Preparation of Spiro-OMeTAD hole transport layer: Take 30 μL of the Spiro-OMeTAD hole transport layer solution from step S4 and spin-coat it on the FA perovskite film from step S3. Spin-coat at 4000 rpm for 30 seconds to prepare a Spiro-OMeTAD film with a uniform and flat surface and a thickness of 160 nm. Then oxidize it in a drying cabinet for 12 hours to obtain a hole transport layer.

[0070] S6: Deposit a layer with an effective area of ​​0.05 cm on the hole transport layer in step S5. 2 , a gold electrode with a thickness of 80nm, and a FA perovskite solar cell is obtained.

[0071] Comparative Example 2 A method for preparing a perovskite solar cell is the same as the preparation steps of Example 2, except that no n-dodecyl mercaptan-copper clusters are synergistically implanted into the FAMA perovskite layer and the Spiro-OMeTAD hole transport layer. The specific preparation method is as follows: S1. Preparation of SnO2 electron transport layer: 10 μL of thioglycolic acid, 0.5 mL of hydrochloric acid, 110 mg of SnCl2·2H2O and 500 mg of urea were added in sequence to a Shuniu bottle containing 40 mL of ice ultrapure water. After the ice was completely melted, the SnO2 electron transport layer precursor solution was obtained. The SnO2 electron transport layer precursor solution was poured into a culture dish filled with FTO conductive substrate, and then placed in a 90°C oven for hydrothermal treatment for 3 h. After the hydrothermal treatment, the FTO conductive substrate was taken out, ultrasonically cleaned with ultrapure water and isopropanol, and then blown dry with nitrogen. It was then placed on a hot plate at 170°C for heat treatment for 1 h to obtain a dense SnO2 layer with a thickness of 20 nm to 30 nm, which is the SnO2 electron transport layer.

[0072] S2. Prepare a 1.5 mol / L FAMA perovskite precursor solution in a nitrogen glove box. The preparation method is as follows: mix 245.05 mg of HC(=NH)NH3I, 35.92 mg of CH3NH3PbBr3, 753.75 mg of PbI2 and 34.35 mg of CH3NH3Cl in a small reagent bottle, and add 800 μL of N,N-dimethylformamide and 200 μL of dimethyl sulfoxide solvent to obtain a mixed solution. Stir the mixed solution at 50°C for 2 h and filter it with a 0.22 μm organic filter head to obtain 1 mL of 1.5 mol / L FAMA perovskite precursor solution for the experiment.

[0073] S3. Preparation of FAMA perovskite layer: Take 30 μL of the FAMA perovskite precursor solution in step S2 and spin-coat it onto the SnO2 electron transport layer in step S1. First, spin-coat it at a low speed (1000 rpm) for 10 seconds, then spin-coat it at a high speed (5000 rpm) for 30 seconds. When there are 10 seconds left in the high-speed spin-coating, immediately add 150 μL of ethyl acetate solution. After the addition is completed, heat treat it at 100°C for 30 minutes to prepare a FAMA perovskite film with a thickness of 530 nm.

[0074] S4. Prepare a Spiro-OMeTAD hole transport layer solution with a concentration of 73 mg / mL in a nitrogen glove box. The preparation method is as follows: place 73 mg of Spiro-OMeTAD powder in a small reagent bottle, add 1 mL of chlorobenzene solvent and shake until the Spiro-OMeTAD powder is fully dissolved, then use a pipette to add 30 μL of 4-tert-butylpyridine solution and 18 μL of lithium bis(trifluoromethanesulfonyl)imide solution in sequence, add a rotor and stir for 3 hours, and then filter using a 0.22 μm organic filter head to prepare a Spiro-OMeTAD hole transport layer solution.

[0075] S5. Preparation of Spiro-OMeTAD hole transport layer: Take 30 μL of the Spiro-OMeTAD hole transport layer solution from step S4 and spin-coat it on the FAMA perovskite film from step S3. Spin-coat at 4000 rpm for 30 seconds to prepare a Spiro-OMeTAD film with a uniform and flat surface and a thickness of 160 nm. Then oxidize it in a drying cabinet for 12 hours to obtain a hole transport layer.

[0076] S6: Deposit a layer with an effective area of ​​0.05 cm on the hole transport layer in step S5. 2 , a gold electrode with a thickness of 80nm, and a FAMA perovskite solar cell is obtained.

[0077] Comparative Example 3 A method for preparing a perovskite solar cell is the same as the preparation steps of Example 3, except that no n-dodecyl mercaptan-copper clusters are synergistically implanted into the CsFAMA perovskite layer and the Spiro-OMeTAD hole transport layer. The specific preparation method is as follows: S1. Preparation of SnO2 electron transport layer: 10 μL of thioglycolic acid, 0.5 mL of hydrochloric acid, 110 mg of SnCl2·2H2O and 500 mg of urea were added in sequence to a Shuniu bottle containing 40 mL of ice ultrapure water. After the ice was completely melted, the SnO2 electron transport layer precursor solution was obtained. The SnO2 electron transport layer precursor solution was poured into a culture dish filled with FTO conductive substrate, and then placed in a 90°C oven for hydrothermal treatment for 3 h. After the hydrothermal treatment, the FTO conductive substrate was taken out, ultrasonically cleaned with ultrapure water and isopropanol, and then blown dry with nitrogen. It was then placed on a hot plate at 170°C for heat treatment for 1 h to obtain a dense SnO2 layer with a thickness of 20 nm to 30 nm, which is the SnO2 electron transport layer.

[0078] S2. Prepare a CsFAMA perovskite precursor solution with a concentration of 1.55 mol / L in a nitrogen glove box. The preparation method is as follows: mix 226.57 mg of HC(=NH)NH3I, 16.79 mg of CH3NH3Br, 751.44 mg of PbI2, 36.62 mg of CH3NH3Cl and 20.71 mg of CsI in a small reagent bottle, and add 800 μL of N,N-dimethylformamide and 200 μL of dimethyl sulfoxide solvent to obtain a mixed solution. Stir the mixed solution at 50°C for 2 h and filter it with a 0.22 μm organic filter head to obtain 1 mL of 1.5 mol / L FAMA perovskite precursor solution for the experiment.

[0079] S3. Preparation of CsFAMA perovskite layer: Take 30 μL of the FAMA perovskite precursor solution in step S2 and spin-coat it onto the SnO2 electron transport layer in step S1. Spin-coat it at 4000 rpm for 30 seconds. When there are 10 seconds left in the high-speed spin-coating, immediately add 250 μL of ethyl acetate solution. After the addition is complete, heat treat it at 130°C for 20 minutes to prepare a CsFAMA perovskite film with a thickness of 600 nm.

[0080] S4. Prepare a Spiro-OMeTAD hole transport layer solution with a concentration of 73 mg / mL in a nitrogen glove box. The preparation method is as follows: place 73 mg of Spiro-OMeTAD powder in a small reagent bottle, add 1 mL of chlorobenzene solvent and shake until the Spiro-OMeTAD powder is fully dissolved, then use a pipette to add 30 μL of 4-tert-butylpyridine solution and 18 μL of lithium bis(trifluoromethanesulfonyl)imide solution in sequence, add a rotor and stir for 3 hours, and then filter using a 0.22 μm organic filter head to prepare a Spiro-OMeTAD hole transport layer solution.

[0081] S5. Preparation of Spiro-OMeTAD hole transport layer: Take 30 μL of the Spiro-OMeTAD hole transport layer solution in step S4 and spin-coat it on the CsFAMA perovskite film in step S4. Spin-coat at 4000 rpm for 30 seconds to prepare a Spiro-OMeTAD film with a uniform and flat surface and a thickness of 160 nm. Then oxidize it in a drying cabinet for 12 hours to obtain a hole transport layer.

[0082] S6: Deposit a layer with an effective area of ​​0.05 cm on the hole transport layer in step S5. 2 , and a gold electrode with a thickness of 80 nm to obtain a CsFAMA perovskite solar cell.

[0083] Comparative Example 4 A method for preparing a perovskite solar cell is the same as the preparation steps of Example 4, except that no n-dodecyl mercaptan-copper clusters are co-implanted into the FA perovskite layer and the PTAA hole transport layer. The specific preparation method is as follows: S1. Preparation of SnO2 electron transport layer: 10 μL of thioglycolic acid, 0.5 mL of hydrochloric acid, 110 mg of SnCl2·2H2O and 500 mg of urea were added in sequence to a Shuniu bottle containing 40 mL of ice ultrapure water. After the ice was completely melted, the SnO2 electron transport layer precursor solution was obtained. The SnO2 electron transport layer precursor solution was poured into a culture dish filled with FTO conductive substrate, and then placed in a 90°C oven for hydrothermal treatment for 3 h. After the hydrothermal treatment, the FTO conductive substrate was taken out, ultrasonically cleaned with ultrapure water and isopropanol, and then blown dry with nitrogen. It was then placed on a hot plate at 170°C for heat treatment for 1 h to obtain a dense SnO2 layer with a thickness of 20 nm to 30 nm, which is the SnO2 electron transport layer.

[0084] S2. Prepare a 1.4 mol / L FA perovskite precursor solution in a nitrogen glove box by mixing 240.75 mg of HC(=NH)NH3I, 703.50 mg of PbI2, and 32.77 mg of CH3NH3Cl in a small reagent bottle, and add 800 μL of N,N-dimethylformamide and 200 μL of dimethyl sulfoxide solvent to obtain a mixed solution. Stir the mixed solution at 50°C for 2 h, and filter it with a 0.22 μm organic filter head to obtain 1 mL of 1.4 mol / L FA perovskite precursor solution for the experiment.

[0085] S3. Preparation of FA perovskite layer: Take 30 μL of the FA perovskite precursor solution in step S2 and spin-coat it onto the SnO2 electron transport layer in step S1. First, spin-coat it at a low speed (2000 rpm) for 10 seconds, then spin-coat it at a high speed (5000 rpm) for 30 seconds. When there are 10 seconds left in the high-speed spin-coating, immediately add 100 μL of ethyl acetate solution. After the addition is completed, heat treat it at 100°C for 40 minutes to prepare a FA perovskite film with a thickness of 500 nm.

[0086] S4. Prepare a PTAA hole transport layer solution with a concentration of 12 mg / mL in a nitrogen glove box. The preparation method is as follows: place 12 mg of PTAA powder in a small reagent bottle, add 1 mL of toluene solvent and shake until the PTAA powder is fully dissolved, then use a pipette to add 4 μL of 4-tert-butylpyridine solution and 7.5 μL of lithium bis(trifluoromethanesulfonyl)imide solution in sequence, add a rotor and stir for 3 hours, and then filter using a 0.22 μm organic filter head to prepare a PTAA hole transport layer solution.

[0087] S5. Preparation of PTAA hole transport layer: Take 30 μL of the PTAA hole transport layer solution in step S4 and spin-coat it on the FA perovskite film in step S3. Spin-coat at 3000 rpm for 30 seconds to prepare a PTAA film with a uniform and flat surface and a thickness of 150 nm. Then oxidize it in a drying cabinet for 12 hours to obtain a hole transport layer.

[0088] S6: Deposit a layer with an effective area of ​​0.05 cm on the hole transport layer in step S5. 2 , a gold electrode with a thickness of 80nm, and a FA perovskite solar cell is obtained.

[0089] Comparative Example 5 A method for preparing a perovskite solar cell is the same as the preparation steps of Example 5, except that no n-dodecyl mercaptan-copper clusters are co-implanted into the FAMA perovskite layer and the PTAA hole transport layer. The specific preparation method is as follows: S1. Preparation of SnO2 electron transport layer: 10 μL of thioglycolic acid, 0.5 mL of hydrochloric acid, 110 mg of SnCl2·2H2O and 500 mg of urea were added in sequence to a Shuniu bottle containing 40 mL of ice ultrapure water. After the ice was completely melted, the SnO2 electron transport layer precursor solution was obtained. The SnO2 electron transport layer precursor solution was poured into a culture dish filled with FTO conductive substrate, and then placed in a 90°C oven for hydrothermal treatment for 3 h. After the hydrothermal treatment, the FTO conductive substrate was taken out, ultrasonically cleaned with ultrapure water and isopropanol, and then blown dry with nitrogen. It was then placed on a hot plate at 170°C for heat treatment for 1 h to obtain a dense SnO2 layer with a thickness of 20 nm to 30 nm, which is the SnO2 electron transport layer.

[0090] S2. Prepare a 1.5 mol / L FAMA perovskite precursor solution in a nitrogen glove box. The preparation method is as follows: mix 245.05 mg of HC(=NH)NH3I, 35.92 mg of CH3NH3PbBr3, 753.75 mg of PbI2 and 34.35 mg of CH3NH3Cl in a small reagent bottle, and add 800 μL of N,N-dimethylformamide and 200 μL of dimethyl sulfoxide solvent to obtain a mixed solution. Stir the mixed solution at 50°C for 2 h and filter it with a 0.22 μm organic filter head to obtain 1 mL of 1.5 mol / L FAMA perovskite precursor solution for the experiment.

[0091] S3. Preparation of FAMA perovskite layer: Take 30 μL of the FAMA perovskite precursor solution in step S2 and spin-coat it onto the SnO2 electron transport layer in step S1. First, spin-coat it at a low speed (1000 rpm) for 10 seconds, then spin-coat it at a high speed (5000 rpm) for 30 seconds. When there are 10 seconds left in the high-speed spin-coating, immediately add 150 μL of ethyl acetate solution. After the addition is completed, heat treat it at 100°C for 30 minutes to prepare a FAMA perovskite film with a thickness of 530 nm.

[0092] S4. Prepare a PTAA hole transport layer solution with a concentration of 12 mg / mL in a nitrogen glove box. The preparation method is as follows: place 12 mg of PTAA powder in a small reagent bottle, add 1 mL of toluene solvent and shake until the PTAA powder is fully dissolved, then use a pipette to add 4 μL of 4-tert-butylpyridine solution and 7.5 μL of lithium bis(trifluoromethanesulfonyl)imide solution in sequence, add a rotor and stir for 3 hours, and then filter using a 0.22 μm organic filter head to prepare a PTAA hole transport layer solution.

[0093] S5. Preparation of PTAA hole transport layer: Take 30 μL of the PTAA hole transport layer solution in step S4 and spin-coat it on the FAMA perovskite film in step S3. Spin-coat at 3000 rpm for 30 seconds to prepare a PTAA film with a uniform and flat surface and a thickness of 150 nm. Then oxidize it in a drying cabinet for 12 hours to obtain a hole transport layer.

[0094] S6: Deposit a layer with an effective area of ​​0.05 cm on the hole transport layer in step S5. 2 , a gold electrode with a thickness of 80nm, and a FAMA perovskite solar cell is obtained.

[0095] Comparative Example 6 A method for preparing a perovskite solar cell is the same as the preparation steps of Example 6, except that no n-dodecyl mercaptan-copper clusters are synergistically implanted into the CsFAMA perovskite layer and the PTAA hole transport layer. The specific preparation method is as follows: S1. Preparation of SnO2 electron transport layer: 10 μL of thioglycolic acid, 0.5 mL of hydrochloric acid, 110 mg of SnCl2·2H2O and 500 mg of urea were added in sequence to a Shuniu bottle containing 40 mL of ice ultrapure water. After the ice was completely melted, the SnO2 electron transport layer precursor solution was obtained. The SnO2 electron transport layer precursor solution was poured into a culture dish filled with FTO conductive substrate, and then placed in a 90°C oven for hydrothermal treatment for 3 h. After the hydrothermal treatment, the FTO conductive substrate was taken out, ultrasonically cleaned with ultrapure water and isopropanol, and then blown dry with nitrogen. It was then placed on a hot plate at 170°C for heat treatment for 1 h to obtain a dense SnO2 layer with a thickness of 20 nm to 30 nm, which is the SnO2 electron transport layer.

[0096] S2. Prepare a FAMA perovskite precursor solution with a concentration of 1.55 mol / L in a nitrogen glove box. The preparation method is as follows: mix 226.57 mg of HC(=NH)NH3I, 16.79 mg of CH3NH3Br, 751.44 mg of PbI2, 36.62 mg of CH3NH3Cl and 20.71 mg of CsI in a small reagent bottle, and add 800 μL of N,N-dimethylformamide and 200 μL of dimethyl sulfoxide solvent to obtain a mixed solution. Stir the mixed solution at 50°C for 2 h and filter it with a 0.22 μm organic filter head to obtain 1 mL of 1.55 mol / L CsFAMA perovskite precursor solution for the experiment.

[0097] S3. Preparation of CsFAMA perovskite layer: Take 30 μL of the CsFAMA perovskite precursor solution in step S2 and spin-coat it onto the SnO2 electron transport layer in step S1. Spin-coat it at 4000 rpm for 30 seconds. When there are 10 seconds left in the high-speed spin-coating, immediately add 250 μL of ethyl acetate solution. After the addition is complete, heat treat it at 130°C for 20 minutes to prepare a CsFAMA perovskite film with a thickness of 600 nm.

[0098] S4. Prepare a PTAA hole transport layer solution with a concentration of 12 mg / mL in a nitrogen glove box. The preparation method is as follows: place 12 mg of PTAA powder in a small reagent bottle, add 1 mL of toluene solvent and shake until the PTAA powder is fully dissolved, then use a pipette to add 4 μL of 4-tert-butylpyridine solution and 7.5 μL of lithium bis(trifluoromethanesulfonyl)imide solution in sequence, add a rotor and stir for 3 hours, and then filter using a 0.22 μm organic filter head to prepare a PTAA hole transport layer solution.

[0099] S5. Preparation of PTAA hole transport layer: Take 30 μL of the PTAA hole transport layer solution in step S4 and spin-coat it on the CsFAMA perovskite film in step S3. Spin-coat at 3000 rpm for 30 seconds to prepare a PTAA film with a uniform and flat surface and a thickness of 150 nm. Then oxidize it in a drying cabinet for 12 hours to obtain a hole transport layer.

[0100] S6: Deposit a layer with an effective area of ​​0.05 cm on the hole transport layer in step S5. 2 , and a gold electrode with a thickness of 80 nm to obtain a CsFAMA perovskite solar cell.

[0101] Figure 1 Schematic diagram of the structure of the passivated perovskite solar cell of Examples 1 to 6 of the present invention; in order to verify the performance of the perovskite solar cell with the n-dodecyl mercaptan-copper clusters synergistically implanted into the perovskite layer and the hole transport layer passivated prepared by the present invention, the perovskite solar cells passivated in Examples 1 to 6 and the perovskite solar cells of Comparative Examples 1 to 6 are studied as examples, and the specific research methods and results are shown below: from Figure 2 As shown in Figure a, after pulsed laser treatment, the n-dodecylmercaptan-copper cluster colloidal solution exhibits a pronounced Tyndall effect, with a distinct optical path visible under laser illumination. TEM images reveal that the n-dodecylmercaptan-copper clusters in the colloidal solution are well-dispersed and have an average size of 1.2 nm. Figure 2 The XPS pattern in b shows C, S, and Cu elements, providing further evidence for the successful preparation of n-dodecylmercaptan-copper clusters.

[0102] from Figure 3 a and Figure 3 The SEM image of the single-cation FA perovskite film in b shows that the FA perovskite film with n-dodecylmercaptan-copper clusters implanted has a larger grain size and a smoother film than the perovskite film without n-dodecylmercaptan-copper clusters implanted.

[0103] The method of the present invention has been verified to be universal by similar experiments. When n-dodecylthiol-copper clusters were implanted into dicationic FAMA perovskite films and tricationic CsFAMA perovskite films, similar film lifting phenomena were observed. Figure 4 and Figure 5 The SEM images show that the perovskite film with n-dodecylmercaptan-copper clusters has larger grains and is smoother than the perovskite film without n-dodecylmercaptan-copper clusters, indicating that n-dodecylmercaptan-copper clusters can regulate the growth of perovskite films.

[0104] from Figure 6 and Figure 7 It can be seen that the hole mobility and conductivity of the Spiro-OMeTAD hole transport layer and the PTAA hole transport layer implanted with n-dodecyl mercaptan-copper clusters are significantly improved.

[0105] from Figures 8 to 10 It can be seen that the photoelectric conversion efficiency of the passivated perovskite solar cells prepared by synergistically implanting n-dodecyl mercaptan-copper clusters into FA perovskite film, FAMA perovskite film, CsFAMA perovskite film and Spiro-OMeTAD hole transport layer is improved compared with the efficiency without implanting n-dodecyl mercaptan-copper clusters. After the synergistic implantation of n-dodecyl mercaptan-copper clusters, the highest efficiencies achieved by FA, ​​FAMA and CsFMA passivated perovskite solar cells are 25.09%, 25.20% and 24.97%, respectively; the efficiencies of FA, FAMA and CsFAMA perovskite solar cells without implanting n-dodecyl mercaptan-copper clusters are 23.49%, 22.76% and 22.59%, respectively.

[0106] Similarly, from Figures 11 to 13 It can be seen that the photoelectric conversion efficiency of the passivated perovskite solar cells prepared by synergistically implanting n-dodecyl mercaptan-copper clusters into FA perovskite film, FAMA perovskite film, CsFAMA perovskite film and PTAA hole transport layer is improved compared with the efficiency without implanting n-dodecyl mercaptan-copper clusters. After the synergistic implantation of n-dodecyl mercaptan-copper clusters, the highest efficiencies achieved by FA, ​​FAMA and CsFMA passivated perovskite solar cells are 20.50%, 21.12% and 20.87%, respectively; the efficiencies of FA, FAMA and CsFAMA perovskite solar cells without implanting n-dodecyl mercaptan-copper clusters are 19.64%, 20.01% and 19.87%, respectively.

[0107] In summary, the present invention simultaneously introduces n-dodecyl mercaptan-copper clusters into the perovskite layer and the hole transport layer, passivates different perovskite grain boundary defects, facilitates the growth of perovskite films, and improves the extraction and transmission rate of photogenerated carriers. Compared with perovskite solar cells without the introduction of n-dodecyl mercaptan-copper clusters, the photoelectric conversion efficiency is higher.

[0108] The above description is merely a list of preferred embodiments for purposes of illustration only, and the scope of protection of the present invention is not limited thereto. Anyone skilled in the art, once understanding the basic inventive concepts, can readily make additional changes and modifications to these embodiments. Therefore, the appended claims are intended to fall within the scope of protection of the present invention.

Claims

1. A method for preparing a n-dodecyl mercaptan-copper cluster colloidal solution, characterized in that: The steps include: In an anhydrous and oxygen-free environment, n-dodecyl mercaptan is used as an organic ligand molecule, n-dodecyl mercaptan and a copper target are placed together in a solvent, and then irradiated using liquid-phase pulsed laser irradiation technology, and then the copper target is removed to obtain a precursor solution; After the precursor solution is frozen with liquid nitrogen, it is irradiated with pulsed laser again to obtain a n-dodecyl mercaptan-copper cluster colloidal solution.

2. The method for preparing the n-dodecyl mercaptan-copper cluster colloidal solution according to claim 1, wherein The conditions for the two pulsed laser irradiation treatments were: laser emission wavelength of 1064 nm, laser irradiation range of 1.3 cm, pulse frequency of 6 Hz to 10 Hz, pulse width of 6 ns to 8 ns, spot size of 8 mm to 13 mm, laser energy of 0.4 J to 0.6 J, and irradiation time of 1 min to 5 min.

3. The method for preparing the n-dodecyl mercaptan-copper cluster colloidal solution according to claim 2, wherein The pulse laser irradiation treatment is performed simultaneously with ultrasonic and cryogenic assisted treatment, the ultrasonic frequency is 80 Hz to 100 Hz, and the temperature of the cryogenic assisted treatment is -10°C to 0°C.

4. The method for preparing the n-dodecyl mercaptan-copper cluster colloidal solution according to claim 1, wherein The volume ratio of the solvent to n-dodecyl mercaptan is 200-500:

1.

5. A n-dodecyl mercaptan-copper cluster colloidal solution, characterized in that: The colloid solution of n-dodecyl mercaptan-copper clusters is prepared by the preparation method according to any one of claims 1 to 4, wherein the solute in the colloid solution is n-dodecyl mercaptan-copper clusters with an average particle size of 1.2 nm.

6. A passivated perovskite solar cell, comprising a conductive substrate (1), an electron transport layer (2), a perovskite layer (3), a hole transport layer (4) and a metal electrode (5) stacked in sequence from bottom to top, characterized in that: The perovskite layer (3) and the hole transport layer (4) are both doped with the n-dodecyl mercaptan-copper cluster according to claim 5.

7. The passivated perovskite solar cell according to claim 6, characterized in that The thickness of the perovskite layer (3) is 500 nm to 600 nm, and the thickness of the hole transport layer (4) is 150 nm to 200 nm.

8. A method for preparing a passivated perovskite solar cell according to claim 6, characterized in that: The steps include: Depositing a tin dioxide layer on the conductive substrate (1) to obtain the electron transport layer (2); First, a colloidal solution of n-dodecyl mercaptan-copper clusters is implanted into a perovskite layer solution and dripped onto the electron transport layer (2), and then an anti-solvent is dripped under a rotating condition, and then subjected to heat treatment, so that the n-dodecyl mercaptan-copper clusters are embedded in the composite layer of the perovskite grain boundary, thereby obtaining a perovskite layer (3); implanting a n-dodecyl mercaptan-copper cluster colloidal solution into a hole transport layer solution, and spin coating the solution on the perovskite layer (3) to obtain the hole transport layer (4); A metal electrode is evaporated on the hole transport layer (4) to produce a passivated perovskite solar cell.

9. The method for preparing a passivated perovskite solar cell according to claim 8, wherein: The volume ratio of the n-dodecyl mercaptan-copper cluster colloidal solution to the solvent in the perovskite layer solution is 0.5~1.0:

100.

10. The method for preparing a passivated perovskite solar cell according to claim 8, characterized in that: The volume ratio of the n-dodecyl mercaptan-copper cluster colloidal solution to the solvent in the hole transport layer solution is 0.1~0.5:100.

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