Multidimensional perovskite solar cell with a wide processing window and method for manufacturing the same

Abstract

The present invention provides a multidimensional perovskite solar cell with a wide processing window and a method for manufacturing the same. [Solution] The internal structure of the multidimensional perovskite solar cell includes, from bottom to top, a transparent conductive electrode layer, a hole transport layer, a 1D / 3D perovskite light absorption layer containing hydrophobic groups or waterproof material, an electron transport layer, and a metal electrode layer in that order. By adding 1D perovskite as a seed crystal to standard 3D perovskite, the preferential orientation of the 3D perovskite is effectively promoted, eliminating the need for specific annealing temperatures and times, expanding the processing window for the formation of optically active α-perovskite, and effectively improving the conversion efficiency of the perovskite solar cell module. In addition, the hydrophobic properties of the 1D perovskite effectively prevent erosion of the perovskite by moisture in the air, thereby improving the stability of the device.

Description

[Technical Field]

[0001] [Cross-reference of related applications] This disclosure claims priority to a Chinese patent application filed with the Chinese National Intellectual Property Office on 13 February 2025, application number CN202510162165.7, titled "Multidimensional perovskite solar cell with wide processing window and method for manufacturing the same," the entire contents of which are incorporated by reference into this disclosure.

[0002] This application relates to the technology of solar cells, and more particularly to a multidimensional perovskite solar cell having a wide processing window and a method for manufacturing the same. [Background technology]

[0003] In recent years, attention has been focused on the development and use of new energy sources to address increasingly serious energy and environmental problems. Solar energy, a clean energy source, is considered the best way to solve future energy problems, and solar cells, which convert solar energy into electrical energy, are currently the most urgently needed energy technology. Perovskite solar cells have become a hot spot in the global solar cell research field in recent years due to their significant advantages, such as low manufacturing costs and high efficiency.

[0004] For example, the patent document with publication number CN117560937A discloses "Perovskite solar cell based on 3-methoxyphenylethylamine passivation agent and method for manufacturing the same," in which this perovskite solar cell uses 3-methoxyphenylethylamine as a surface passivation agent. Passivation with 3-methoxyphenylethylamine can effectively reduce the defect density of states at the perovskite interface, and non-coordinating Pb 2+This solves the problem of reduced photoelectric conversion efficiency and stability in existing perovskite solar cells due to the presence of [unspecified element]. The perovskite solar cell is arranged from bottom to top in the following order: FTO glass as a conductive cathode, tin oxide deposited on the FTO layer by chemical bath as an electron transport layer, a perovskite layer spin-coated by a one-step method, 3-methoxyphenylethylamine spin-coated on the perovskite layer as a passivation layer, spiro-OMeTAD spin-coated as a hole transport layer, and a metal anode evaporated by vacuum heat.

[0005] Patent document CN118870929A discloses a "method for manufacturing a perovskite solar cell," which involves sequentially forming a hole transport layer, a lower interface passivation layer, a perovskite light absorption layer, an upper interface passivation layer, an electron transport layer, an electron buffer layer, and a metal electrode layer on the surface of a conductive glass substrate. This invention uses a combination of phenethylammonium iodide and a methylamine ethanol solution as passivation agents to passivate the upper interface of a perovskite solar cell. MA induces grain boundary migration and regrowth of perovskite crystal grains while promoting the penetration of the passivation molecule phenylethylamine into the embedded interface, thereby achieving deep passivation and reducing non-radiative recombination centers. Furthermore, its low production cost and ease of operation make it useful for actual production and provide important reference for the industrialization of perovskite solar cells.

[0006] Patent document No. CN110518128B discloses "ACI-type two-dimensional perovskite solar cell and method for manufacturing the same." In this solar cell, the perovskite absorption layer is a mixture of C(NH2)3I, CH3NH3I, and PbI2, with CH3NH3Cl added as an additive during the manufacturing process. Compared to conventional two-dimensional perovskite devices, the addition of CH3NH3Cl significantly improves the crystallization quality of the perovskite film, increases the crystal grain size, reduces carrier recombination losses due to grain boundary defects, extends carrier lifetime, increases the effective gradient distribution of different n values, improves charge transport efficiency, and ultimately improves the photoelectric conversion efficiency of the perovskite cell device, improves the series-parallel resistance of the device, and ultimately achieves a photoelectric conversion efficiency of 18.48%. The excellent photoelectric performance and device efficiency will facilitate the commercialization of perovskite solar cells.

[0007] As is well known, perovskite materials are easily decomposed by the effects of water vapor and oxygen, so achieving both high efficiency and stability in perovskite solar cells has always been a major challenge in this field. The structure of perovskites in conventional technology is mainly 3D perovskites. In recent years, conventional 3D perovskites have achieved continuous breakthroughs in power conversion efficiency (PCE), but their processing window is narrow, and depending on the thermal annealing temperature and time, the perovskite can form different optical phases, which can reduce the efficiency and stability of the device. 2D / 3D mixed-dimensional perovskites have excellent stability, but 2D perovskites have low charge conductivity, a wide band gap, and strong exciton coupling, which hinders carrier transport, resulting in relatively low power conversion efficiency for 2D / 3D perovskites. [Overview of the project] [Problems that the invention aims to solve]

[0008] The object of this application is to provide a multidimensional perovskite solar cell and a method for manufacturing the same, which has a wide processing window, in which the crystal orientation of the 3D perovskite can be induced by adding a 1D perovskite layer as a seed crystal to a conventional 3D perovskite solution, thereby effectively improving the conversion efficiency of the assembly, and in which the hydrophobicity of the 1D perovskite can effectively prevent erosion of the perovskite by water while considering the stability of the assembly. To achieve the above object, this application provides the following technical solutions. [Means for solving the problem]

[0009] The present invention provides a multidimensional perovskite solar cell having a wide processing window, wherein the internal structure of the multidimensional perovskite solar cell comprises, in order from bottom to top, a transparent conductive electrode layer, a hole transport layer, a 1D / 3D perovskite light absorption layer containing hydrophobic groups or waterproof material, an electron transport layer, and a metal electrode layer, thereby providing a multidimensional perovskite solar cell having a wide processing window.

[0010] Furthermore, the transparent conductive electrode layer is one of ITO, FTO, or AZO.

[0011] Furthermore, the hole transport layer is NiO x CuGaO3, CuAlO2, VO2, or Cu x It is one or more of O.

[0012] Furthermore, the 1D / 3D perovskite light absorption layer is obtained by spin-coating 1D / 3D perovskite nanoparticles onto the hole transport layer using a spin coating method. Specifically, first, a hydrophobic group R or a waterproof material is bonded to PbX2 to form 1D perovskite RPbX3, then the 1D perovskite RPbX3 is dispersed in a 3D perovskite precursor solution, and the 3D perovskite crystal is coated with 1D perovskite RPbX3 to form 1D / 3D perovskite nanoparticles. The waterproof material is one of tributylmethylphosphonium iodide, tributylethylphosphonium bromide, tetrabutylphosphonium iodide, or tetrabutylphosphonium bromide, The 3D perovskite is one of FAPbX3, CsPbX3, CsFAPbX3, MAFAPbX3, CsFAMAPbX3, CsPbX 3-x X’ x 、CsFAPbX 3-x X’ x 、MAFAPbX 3-x X’ x 、or CsFAMAPbX 3-x X’ x and, wherein X and X’ both represent halogen elements.

[0013] Furthermore, the electron transport layer is an inorganic material or an organic material, The inorganic material is one of SnO, ZnO, TiO2, ZnS, CdS, In2S3, MoS2, or SnS2, The organic material is one of PDI, NDI, PDIN, or PDINO.

[0014] Furthermore, the metal electrode layer is one of Au, Ag, Cu, or Al.

[0015] This application also relates to a method for manufacturing a multi-dimensional perovskite solar cell having a wide processing window, the method comprising: Pretreatment of the transparent conductive electrode layer: Step S1 of sequentially ultrasonic cleaning the transparent conductive electrode layer with deionized water, isopropyl alcohol, and acetone, then blow-drying the transparent conductive electrode layer with nitrogen gas, and performing UV-Ozone treatment for 10 to 30 minutes; Manufacture of the hole transport layer: Step S2 of manufacturing a hole transport layer on the pretreated transparent conductive electrode layer to obtain a transparent conductive electrode layer / hole transport layer sample; Fabrication of 1D / 3D perovskite light absorption layer: Step S3 involves fabricating a 1D / 3D perovskite light absorption layer containing hydrophobic groups or waterproof materials onto a hole transport layer by spin coating, and then annealing it to obtain a transparent conductive electrode layer / hole transport layer / 1D / 3D perovskite light absorption layer sample. Fabrication of electron transport layer: Step S4 involves fabricating an electron transport layer on a 1D / 3D perovskite light absorption layer, A manufacturing method is provided, comprising step S5 of manufacturing a metal electrode layer, wherein a metal material is deposited on an electron transport layer to obtain the desired product.

[0016] Furthermore, the method for manufacturing the hole transport layer is one or more of PVD, ALD, CVD, screen printing, and solution methods, and its thickness is 10 to 50 nm.

[0017] Furthermore, the annealing conditions include a temperature of 70-180°C and a time of 10-60 min.

[0018] Furthermore, the method for manufacturing the electron transport layer is one or more of PVD, ALD, CVD, screen printing, and solution methods, and its thickness is 10 to 100 nm.

[0019] Furthermore, the thickness of the metal electrode layer is 50 to 200 nm. [Effects of the Invention]

[0020] The technical effects and advantages of this invention are as follows:

[0021] Firstly, in this invention, a 1D perovskite is added to a conventional 3D perovskite as a seed crystal to aid in crystallization. The 1D perovskite is bonded to PbX2 through multiple hydrophobic groups (R) or waterproof materials to form 1D perovskite RPbX3. Next, the 1D perovskite RPbX3 is dispersed in a 3D perovskite precursor solution, and the 3D perovskite crystal FAPbX'3 is coated with these 1D perovskite RPbX3. Finally, a new structure of 1D / 3D perovskite with high stability and high power conversion efficiency is formed and applied to perovskite solar cells.

[0022] Secondly, compared to conventional 3D perovskites, adding 1D perovskite as a seed crystal to standard 3D perovskite effectively promotes the preferred orientation of the 3D perovskite, eliminating the need for specific annealing temperatures and times, expanding the processing window for the formation of optically active α-perovskite, and effectively improving the conversion efficiency of perovskite solar cell modules. Furthermore, the hydrophobic properties of 1D perovskite effectively prevent erosion of the perovskite by moisture in the air, thereby improving the stability of the device.

[0023] Other features and advantages of the present application are described in the following specification, some of which may become apparent from the specification or may be understood by practicing the present application. The purpose and other advantages of the present application are realized and obtained through the structures indicated in the specification and drawings. [Brief explanation of the drawing]

[0024] To more clearly explain the technical solutions in the embodiments of this application or related technologies, the drawings necessary for describing the embodiments or related technologies will be briefly described below. The drawings in the following description are of some embodiments of this application, and it will be obvious to those skilled in the art that other drawings can be obtained based on these drawings without any creative effort. [Figure 1] This is a structural diagram of a multidimensional perovskite solar cell having a wide processing window according to the present invention. [Figure 2] This is a structural diagram of the 1D perovskite according to the present invention. [Figure 3] This is a flowchart of the method for manufacturing a multidimensional perovskite solar cell having a wide processing window according to the present invention. [Figure 4] This is a comparison diagram of the conversion efficiencies of a 1D / 3D perovskite solar cell manufactured in Example 1 of this application and a standard 3D perovskite solar cell. [Figure 5] This is a comparative diagram of aging experiments between a 1D / 3D perovskite and a standard 3D perovskite solar cell manufactured in Example 1 of this application. [Modes for carrying out the invention]

[0025] The technical solutions in the embodiments of this application will be described clearly and completely below with reference to the drawings of the embodiments of this application, although it is clear that the embodiments described are only a part of the embodiments of this application and not all of them. All other embodiments that a person skilled in the art could obtain without creative effort based on the embodiments of this application are within the scope of protection of this application.

[0026] The flowchart shown in the diagram is for illustrative purposes only and does not necessarily include all steps. For example, some steps may be broken down, and some steps may be combined or partially combined, so the actual execution order may change depending on the actual situation.

[0027] The terms “First,” “Second,” etc., in the specification and claims of this application, as well as in the drawings above, are for distinguishing similar subjects and are not intended to indicate a specific order or priority. It should be understood that the data used in this manner are interchangeable where appropriate, and the embodiments of this application described herein may be carried out in an order other than that illustrated or described herein.

[0028] Furthermore, the terms “contains” and “have” and their variations are intended to cover exclusive inclusion. For example, a process, method, system, product, or device that includes a set of steps or submodules is not limited to the explicitly stated steps or submodules and may include other steps or submodules that are not explicitly stated or are specific to those processes, methods, products, or devices.

[0029] To overcome the shortcomings of the prior art, the present invention discloses a multidimensional perovskite solar cell having a wide fabrication window, and Figure 1 is a structural diagram of the multidimensional perovskite solar cell having a wide fabrication window according to the present invention, and as shown in Figure 1, the internal structure of the multidimensional perovskite solar cell includes, from bottom to top, a transparent conductive electrode layer 1, a hole transport layer 2, a 1D / 3D perovskite light absorption layer 3 containing hydrophobic groups or waterproof material, an electron transport layer 4, and a metal electrode layer 5 in that order. The transparent conductive electrode layer 1 includes, but is not limited to, one of the following materials: indium tin oxide (ITO), fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide (AZO), etc. The hole transport layer 2 is NiO x (Nickel oxide), CuAlO2 (copper metaaluminate), VO2 (vanadium oxide), Cu x This includes, but is not limited to, one or more of the O (copper oxide) materials. The 1D / 3D perovskite light absorption layer is obtained by spin-coating 1D / 3D perovskite nanoparticles onto a hole transport layer using a spin coating method. Specifically, first, a hydrophobic group R or a waterproof material is bonded to PbX2 to form 1D perovskite RPbX3, then the 1D perovskite is dispersed in a 3D perovskite precursor solution, and the 3D perovskite crystal is coated with 1D perovskite RPbX3 to form 1D / 3D perovskite nanoparticles. The aforementioned 3D perovskites include FAPbI3, CsPbI3, CsFAPbI3, MAFAPbI3, CsFAMAPbI3, and CsPbI 3-x Brx , CsFAPbI 3-x Br x MAFAPbI 3-x Br x , CsFAMAPbI 3-x Br x It includes, but is not limited to, one of the following materials.

[0030] Tributylmethylphosphonium iodide is given as an example of a waterproofing material in the 1D perovskite, but other halide materials that can react with PbX2 to produce RPbX2 may also be used. These materials include one of the following: tributylethylphosphonium bromide, tetrabutylphosphonium iodide, tetrabutylphosphonium bromide, etc.

[0031] The electron transport layer 4 may be an inorganic or organic material. The inorganic material includes, but is not limited to, one of the following: SnO (stannous oxide), ZnO (zinc oxide), TiO2 (titanium oxide), ZnS (zinc sulfide), CdS (cadmium sulfide), In2S3 (indium sulfide), MoS2 (molybdenum disulfide), SnS2 (tin sulfide). The organic material includes, but is not limited to, one of the following: PDI (perylenediimide), NDI (naphthalenetetracarboxylic acid diimide), PDIN (N,N'-bis[3-(dimethylamino)propyl]perylene-3,4,9,10-tetracarboxylic acid diimide), PDINO (3,3'-(1,3,8,10-tetrathrono[2,1,9-DEF:6,5,10-D'E'F']diisoquinoline-2,9(1H,3H,8H,10H)-diyl)bis(N,N-dimethylpropane-1-amine oxide)).

[0032] The metal electrode layer 5 contains, but is not limited to, one of the following materials: Au (gold), Ag (silver), Cu (copper), Al (aluminum), etc.

[0033] The present invention also discloses a method for manufacturing a multidimensional perovskite solar cell having a wide fabrication window, and Figure 3 is a flowchart of the method for manufacturing a multidimensional perovskite solar cell having a wide fabrication window according to the present invention, and as shown in Figure 3, the method includes the following steps.

[0034] Step S1: Pretreatment of transparent conductive electrode layer 1: After sequentially ultrasonically cleaning the transparent conductive electrode layer 1 with deionized water, isopropyl alcohol, and acetone, the transparent conductive electrode layer 1 is blow-dried with nitrogen gas and then subjected to UV-Ozone treatment for 10-30 minutes.

[0035] Step S2: Manufacturing of hole transport layer 2: A hole transport layer 2 is manufactured on the pre-treated transparent conductive electrode layer 1 to obtain a transparent conductive electrode layer / hole transport layer sample. The manufacturing method of the hole transport layer 2 is one or more of PVD (physical vapor deposition), ALD (atomic layer deposition), CVD (chemical vapor deposition), screen printing, and solution method, and its thickness is 10 to 50 nm.

[0036] Step S3: Fabrication of 1D / 3D perovskite light-absorbing layer 3: A 1D / 3D perovskite light-absorbing layer 3 containing hydrophobic groups or waterproof material is fabricated on the hole transport layer 2 by spin coating and annealed to obtain a transparent conductive electrode layer / hole transport layer / 1D / 3D perovskite light-absorbing layer sample. The annealing conditions include an annealing temperature of 70-180°C and a time of 10-60 min.

[0037] Step S4: Manufacturing of electron transport layer 4: An electron transport layer 4 is manufactured on the 1D / 3D perovskite light absorption layer 3. The method for manufacturing the electron transport layer 4 is one or more of PVD (physical vapor deposition), ALD (atomic layer deposition), CVD (chemical vapor deposition), screen printing, and solution method, and its thickness is 10 to 100 nm.

[0038] Step S5: Manufacturing of metal electrode layer 5: Materials such as Au, Ag, Cu, and Al are deposited on electron transport layer 4 to a thickness of 50-200 nm to obtain the desired product.

[0039] Although the specific solutions described above utilize an inverted (pin) perovskite solar cell structure, the method of this invention can also be applied to forward (nip) perovskite solar cells.

[0040] The solution of this application will be further described below with reference to specific embodiments. Example 1:

[0041] Embodiment 1 of the present invention provides a method for manufacturing a multidimensional perovskite solar cell having a wide processing window, the method comprising the following steps.

[0042] Step S1: Pretreatment of transparent conductive electrode layer 1: The ITO (indium tin oxide) substrate was ultrasonically cleaned sequentially with deionized water, isopropyl alcohol, and acetone for 15 minutes each. Then the ITO substrate was blow-dried with nitrogen gas and subjected to UV treatment for 30 minutes.

[0043] Step S2: Hole transport layer 2 was prepared by a solution process. Specifically, this included steps S21 and S22 below.

[0044] Step S21: NiO x Solution Preparation: 9 g of nickel(II) nitrate hexahydrate was dissolved in 120 mL of water and stirred at room temperature to obtain a clear green solution. Then, 1 M sodium hydroxide solution was added until the pH value was 10. After stirring for 10 minutes, the green precipitate was collected by centrifugation and washed three times each with deionized water and ethanol. The green powder was dried at 80°C for 12 hours and then sintered at 275°C for 2 hours. Finally, a dark gray powder was obtained. 20 mg of this powder was dissolved in 1 mL of ethanol to make a 20 mg / mL NiO solution. x A solution was obtained.

[0045] Step S22: Preparation of HTL layer (hole transport layer): 20 mg / mL NiO x The solution was filtered through a PVDF (polyvinylidene fluoride) filter, then spin-coated onto washed ITO at a speed of 3000 rpm for 30 seconds, and subsequently annealed at 250°C for 60 minutes to obtain the HTL layer.

[0046] Step S3: Fabrication of 1D / 3D perovskite light-absorbing layer 3: Specifically, this includes the following steps.

[0047] Step S31: Preparation of 1D perovskite layer: 521 mg of FAAc (formamidine acetate), 344 mg of tributylmethylphosphonium iodide, and 20 mL of OL (oleic acid) were mixed and heated at 150°C until completely dissolved to obtain FA / TP-OL solution. 2433 mg of PbI was added to a mixed solution of 2.5 mL of oleylamine, 2.5 mL of OL, and 25 mL of 1-octadecene and heated at 150°C until completely dissolved to obtain PbI2 solution. 6 mL of PbI2 solution was heated to 120°C, and while stirring at 1000 rpm, 2.5 mL of FA / TP-OL solution preheated to 120°C was added and the mixture was reacted for 30 seconds. The mixture was then cooled in ice water until the reaction stopped. 14 mL of acetone was added to precipitate the synthesized perovskite as a gel, which was centrifuged at 8000 rpm for 10 minutes, precipitated, and filtered to obtain 1D perovskite.

[0048] Step S32: Preparation of 3D perovskite solution: 18 mg of CsI (cesium iodide), 26.7 mg of MABr (methylamine hydrobromide), 199.8 mg of FAI (formamidinium iodide), 580.9 mg of PbI2 (lead iodide), and 87.4 mg of PbBr2 (lead bromide) were dissolved in a mixed solvent of 1 mL of DMF (N,N-dimethylformamide) and DMSO (dimethyl sulfoxide) in a ratio of 4:1 to obtain a 3D perovskite precursor solution.

[0049] Step S33: Preparation of 1D / 3D perovskite light absorption layer 3: A 1D perovskite dispersion was dispersed in a 3D perovskite precursor solution with a concentration of 20 mg / mL to obtain a 1D / 3D hybrid perovskite solution. The perovskite light absorption layer was prepared on the hole transport layer 2 by spin coating. Poor solvent CB (chlorobenzene) was added dropwise during spin coating, and the mixture was annealed at 120°C for 30 minutes to obtain the 1D / 3D perovskite light absorption layer 3.

[0050] Step S4: Manufacturing of the ETL layer (electron transport layer 4): 20 mg / mL of PC 61 30 μL of CB solution of BM (fullerene derivative [6,6]-phenyl-C61-methyl butyrate) was dropped onto 1D / 3D perovskite light absorption layer 3 and spin-coated at a speed of 2000 rpm for 30 seconds, and 70 μL of 0.5 mg / mL IPA (isopropyl alcohol) solution containing BCP (basocupproine) was applied to the PC 61 The material was dropped onto the BM layer and spin-coated at a speed of 5000 rpm for 30 seconds to obtain the ETL layer.

[0051] Step S5: Fabrication of metal electrode layer 5: Electrode Au was deposited on electron transport layer 4 to a thickness of 60 nm. Example 2:

[0052] Embodiment 2 of the present invention provides a method for manufacturing a multidimensional perovskite solar cell having a wide processing window, the method comprising the following steps.

[0053] Step S1: Pretreatment of transparent conductive electrode layer 1: The ITO substrate was ultrasonically cleaned sequentially with deionized water, isopropyl alcohol, and acetone for 15 minutes each. Then the ITO substrate was blow-dried with nitrogen gas and UV treatment was performed for 30 minutes.

[0054] Step S2: Manufacturing of hole transport layer 2: Specifically, this includes the following steps.

[0055] Step S21: NiO x Solution Preparation: 9 g of nickel(II) nitrate hexahydrate was dissolved in 120 mL of water and stirred at room temperature to obtain a clear green solution. Then, 1 M sodium hydroxide solution was added until the pH value was 10. After stirring for 10 minutes, the green precipitate was collected by centrifugation and washed three times each with deionized water and ethanol. The green powder was dried at 80°C for 12 hours and then sintered at 275°C for 2 hours. Finally, a dark gray powder was obtained. 20 mg of this powder was dissolved in 1 mL of ethanol to make a 20 mg / mL NiO solution. x A solution was obtained.

[0056] Step S22: Production of HTL layer: 20 mg / mL NiO x The solution was filtered through a PVDF (polyvinylidene fluoride) filter, then spin-coated onto washed ITO at a speed of 3000 rpm for 30 seconds, and subsequently annealed at 250°C for 60 minutes to obtain the HTL layer.

[0057] Step S3: Fabrication of 1D / 3D perovskite light-absorbing layer 3: Specifically, this includes the following steps.

[0058] Step S31: Preparation of 1D perovskite: 521 mg of formamidine acetate, 311 mg of tributylethylphosphonium bromide, and 20 mL of oleic acid were mixed and heated at 150°C until completely dissolved to obtain FA / EP-OL solution. 2433 mg of PbI was added to a mixed solution of 2.5 mL of oleylamine, 2.5 mL of oleic acid, and 25 mL of 1-octadecene and heated at 150°C until completely dissolved to obtain PbI2 solution. 6 mL of PbI2 solution was heated to 120°C, and while stirring at 1000 rpm, 2.5 mL of FA / EP-OL solution preheated to 120°C was added and the mixture was reacted for 30 seconds. The mixture was then cooled in ice water until the reaction stopped. 14 mL of acetone was added to precipitate the synthesized perovskite as a gel, which was centrifuged at 8000 rpm for 10 minutes, precipitated, and filtered to obtain 1D perovskite.

[0059] Step S32: Preparation of 3D perovskite solution: 18 mg of CsI, 26.7 mg of MABr, 199.8 mg of FAI, 2580.9 mg of PbI, and 287.4 mg of PbBr were dissolved in a mixed solvent of 1 mL of DMF and DMSO in a ratio of 4:1 to obtain a perovskite precursor solution.

[0060] Step S33: Preparation of 1D / 3D perovskite light absorption layer 3: A 1D perovskite dispersion was dispersed in a 3D perovskite precursor solution with a concentration of 20 mg / mL to obtain a 1D / 3D hybrid perovskite solution. The perovskite light absorption layer was prepared on hole transport layer 2 by spin coating, the poor solvent CB was reduced during spin coating, and the layer was annealed at 120°C for 30 min to obtain 1D / 3D perovskite light absorption layer 3.

[0061] Step S4: Manufacturing of electron transport layer 4: 20 mg / mL PC 61 30 μL of BM CB solution was dropped onto the perovskite light absorption layer 3 and spin-coated at a speed of 2000 rpm for 30 seconds, and 70 μL of 0.5 mg / mL BCP IPA solution was applied to the PC 61 The material was dropped onto the BM layer and spin-coated at a speed of 5000 rpm for 30 seconds to obtain the ETL layer.

[0062] Step S5: Fabrication of metal electrode layer 5: Electrode Au was deposited to a thickness of 60 nm. Example 3:

[0063] Embodiment 3 of the present invention provides a method for manufacturing a multidimensional perovskite solar cell having a wide processing window, the method comprising the following steps.

[0064] Step S1: Pretreatment of transparent conductive electrode layer 1: The ITO substrate was ultrasonically cleaned sequentially with deionized water, isopropyl alcohol, and acetone for 15 minutes each. Then the ITO substrate was blow-dried with nitrogen gas and UV treatment was performed for 30 minutes.

[0065] Step S2: Manufacturing of hole transport layer 2: Specifically, this includes the following steps.

[0066] Step S21: Preparation of NiOx solution: 9 g of nickel(II) nitrate hexahydrate was dissolved in 120 mL of water and stirred at room temperature to obtain a clear green solution. Then, 1 M sodium hydroxide solution was added until the pH value was 10. After stirring for 10 min, the green precipitate was collected by centrifugation and washed three times each with deionized water and ethanol. The green powder was dried at 80°C for 12 hours and then sintered at 275°C for 2 hours. Finally, a dark gray powder was obtained. 20 mg of this powder was dissolved in 1 mL of ethanol to make a 20 mg / mL NiOx solution. x A solution was obtained.

[0067] Step S22: Production of HTL layer: 20 mg / mL NiO xAfter filtering the solution through a PVDF filter, it was spin-coated onto washed ITO at a speed of 3000 rpm for 30 seconds, and then annealed at 250°C for 60 minutes to obtain the HTL layer.

[0068] Step S3: Fabrication of 1D / 3D perovskite light-absorbing layer: Specifically, this includes the following steps.

[0069] Step S31: Preparation of 1D perovskite: 137.7 mg of TPI and 1.659 g of PbI2 were added to 8 mL of 47% HI (hydrogen iodide) aqueous solution, heated to 110°C to completely dissolve, cooled in ice water to crystallize, precipitated, filtered, and freeze-dried at -60°C for 12 hours to obtain PbI2-TPI nanocrystals. The PbI2-TPI nanocrystals were dispersed in 1 mL of 1 M FAI solution, 1 mL of toluene solution was added, filtered, and dried to obtain 1D perovskite.

[0070] Step S32: Preparation of 3D perovskite solution: 18 mg of CsI, 26.7 mg of gMABr, 199.8 mg of FAI, 2580.9 mg of PbI, and 287.4 mg of PbBr were dissolved in a mixed solvent of 1 mL of DMF and DMSO in a ratio of 4:1 to obtain a perovskite precursor solution.

[0071] Step S33: Preparation of 1D / 3D perovskite light absorption layer 3: 1D perovskite was dispersed in a 3D perovskite precursor at a concentration of 20 mg / mL to obtain a 1D / 3D hybrid perovskite solution. The perovskite light absorption layer was prepared on hole transport layer 2 by spin coating, and the poor solvent CB was added dropwise during spin coating. The mixture was annealed at 120°C for 30 minutes to obtain 1D / 3D perovskite light absorption layer 3.

[0072] Step S4: Manufacturing of electron transport layer 4: 20 mg / mL PC 61 30 μL of BM's CB solution was dropped onto the perovskite layer and spin-coated at a speed of 2000 rpm for 30 seconds, and 70 μL of 0.5 mg / ml BCP's IPA solution was applied to the PC. 61 The material was dropped onto the BM layer and spin-coated at a speed of 5000 rpm for 30 seconds to obtain the ETL layer.

[0073] Step S5: Fabrication of metal electrode layer 5: Electrode Au was deposited on electron transport layer 4 to a thickness of 60 nm.

[0074] Figure 4 compares the conversion efficiency of a 1D / 3D perovskite solar cell manufactured in Example 1 of the present invention and a standard 3D perovskite solar cell. As shown in Figure 4, in the present invention, by adding 1D perovskite as a seed crystal to standard 3D perovskite, the preferred orientation of the 3D perovskite is effectively promoted, eliminating the need for specific annealing temperatures and times, expanding the processing window for the formation of optically active α-perovskite, and effectively improving the conversion efficiency of the perovskite solar cell module. In addition, the hydrophobic properties of 1D perovskite effectively prevent erosion of the perovskite by moisture in the air, thereby improving the stability of the device.

[0075] Figure 5 compares aging experiments of 1D / 3D perovskite and standard 3D perovskite solar cells manufactured in Example 1 of the present invention. As shown in Figure 5, the 1D perovskite of the present invention is a nanoparticle coated with RPbI3 on ​​FAPbI3, where the R group employs several larger alkyl groups. On the one hand, doping with these larger groups is advantageous for the mechanical stability of the perovskite crystal. On the other hand, these groups have excellent hydrophobicity, which helps to enhance the thermal stability of the perovskite component. In the present invention, 1D / 3D perovskite and standard perovskite were encapsulated and subjected to aging experiments for 2000 hours under conditions of 85°C, 85% RH, and 1 standard of sunlight irradiation. The PCE of the 1D / 3D perovskite ultimately decayed by 7%, while the PCE of the standard 3D perovskite ultimately decayed by 36%.

[0076] The above are merely preferred embodiments of the present application and do not limit it. While the present application has been described in detail with reference to the above embodiments, those skilled in the art can modify the technical solutions described in each of the above embodiments or replace some of their technical features with equivalents. Any modifications, equivalent replacements, improvements, etc., made within the spirit and principles of the present application should be included within the scope of protection. [Explanation of symbols]

[0077] 1 Transparent conductive electrode layer 2 Hole transport layer 3. 1D / 3D Perovskite Light-Absorbing Layer 4 Electron transport layer 5 Metal electrode layer

Claims

1. A multidimensional perovskite solar cell having a wide processing window, wherein the internal structure of the multidimensional perovskite solar cell comprises, from bottom to top, a transparent conductive electrode layer (1), a hole transport layer (2), a 1D / 3D perovskite light absorption layer (3) containing hydrophobic groups or waterproof material, an electron transport layer (4), and a metal electrode layer (5), in this order.

2. The multidimensional perovskite solar cell having a wide processing window according to claim 1, wherein the transparent conductive electrode layer (1) is one of ITO, FTO, or AZO.

3. The hole transport layer (2) is NiO ｘ ,CuGaO ３ CuAlO ２ , VO ２ , or Cu ｘ A multidimensional perovskite solar cell having a wide processing window according to claim 1, wherein one or more of O.

4. The 1D / 3D perovskite light absorption layer (3) is obtained by spin-coating 1D / 3D perovskite nanoparticles on the hole transport layer (2) by the spin-coating method. Specifically, first, a hydrophobic group R or a waterproof material is bonded to PbX ２ to form 1D perovskite RPbX ３ , and then 1D perovskite RPbX ３ is dispersed in a 3D perovskite precursor solution, and 3D perovskite crystals are coated with 1D perovskite RPbX ３ to form 1D / 3D perovskite nanoparticles. The waterproofing material is one of the following: tributylmethylphosphonium iodide, tributylethylphosphonium bromide, tetrabutylphosphonium iodide, or tetrabutylphosphonium bromide. The aforementioned 3D perovskite is FAPbX ３ , CsPbX ３ , CsFAPbX ３ MAFAPbX ３ , CsFAMAPbX ３ , CsPbX ３－ｘ X' ｘ , CsFAPbX ３－ｘ X' ｘ MAFAPbX ３－ｘ X' ｘ , or CsFAMAPbX ３－ｘ X' ｘ It is one of them, A multidimensional perovskite solar cell having a wide processing window according to claim 2, wherein X and X' both represent halogen elements.

5. The electron transport layer (4) is made of an inorganic or organic material. The inorganic materials mentioned above are SnO, ZnO, and TiO ２ , ZnS, CdS, In ２ S ３ MoS ２ , or SnS ２ It is one of them, The multidimensional perovskite solar cell having a wide processing window according to claim 1, wherein the organic material is one of PDI, NDI, PDIN, or PDINO.

6. The multidimensional perovskite solar cell having a wide processing window according to claim 1, wherein the metal electrode layer (5) is one of Au, Ag, Cu, or Al.

7. A method for manufacturing a multidimensional perovskite solar cell having a wide processing window according to any one of claims 1 to 6, The aforementioned method, Pretreatment of transparent conductive electrode layer (1): Step S1 involves sequentially ultrasonically cleaning the transparent conductive electrode layer (1) with deionized water, isopropyl alcohol, and acetone, then blow-drying the transparent conductive electrode layer (1) with nitrogen gas, and performing UV-Ozone treatment for 10 to 30 minutes. Manufacturing of hole transport layer (2): Step S2 involves manufacturing a hole transport layer (2) on the pre-treated transparent conductive electrode layer (1) to obtain a transparent conductive electrode layer / hole transport layer sample, Manufacturing of the 1D / 3D perovskite light-absorbing layer (3): Step S3 involves manufacturing a 1D / 3D perovskite light-absorbing layer (3) containing hydrophobic groups or waterproof materials on a hole transport layer (2) by spin coating, and annealing it to obtain a transparent conductive electrode layer / hole transport layer / 1D / 3D perovskite light-absorbing layer sample. Manufacturing of electron transport layer (4): Step S4 involves manufacturing an electron transport layer (4) on a 1D / 3D perovskite light absorption layer (3), A manufacturing method characterized by comprising the step S5 of manufacturing a metal electrode layer (5): depositing a metal material on an electron transport layer (4) to obtain the desired product.

8. A method for manufacturing a multidimensional perovskite solar cell having a wide processing window, according to claim 7, wherein the method for manufacturing the hole transport layer (2) is one or more of PVD, ALD, CVD, screen printing, and a solution method, and the thickness thereof is 10 to 50 nm.

9. A method for manufacturing a multidimensional perovskite solar cell having a wide processing window according to claim 7, wherein the annealing conditions include a temperature of 70 to 180°C and a time of 10 to 60 min.

10. A method for manufacturing a multidimensional perovskite solar cell having a wide processing window, according to claim 7, wherein the method for manufacturing the electron transport layer (4) is one or more of PVD, ALD, CVD, screen printing, and a solution method, and the thickness thereof is 10 to 100 nm.

11. A method for manufacturing a multidimensional perovskite solar cell having a wide processing window, wherein the thickness of the metal electrode layer (5) is 50 to 200 nm, as described in claim 7.

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