Perovskite solar cell and preparation method and application thereof
By constructing a tenon-and-mortise three-dimensional passivation layer in perovskite solar cells, the problem of weak interfacial bonding between the substrate and the perovskite layer is solved, improving carrier transport and cell stability, and promoting the high efficiency and commercial application of perovskite solar cells.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- RENSHUO SOLAR ENERGY (SUZHOU) CO LTD
- Filing Date
- 2026-03-04
- Publication Date
- 2026-07-24
AI Technical Summary
In existing perovskite solar cells, the interfacial bonding between the substrate and the perovskite layer is weak, with porosity and interfacial defects affecting carrier transport and cell stability, thus limiting cell efficiency and commercial applications.
A three-dimensional passivation layer with a mortise and tenon structure is constructed by using a three-dimensional passivation material formed by organic passivation material and metal oxide nanoparticles coated on its surface. This enhances the interfacial adhesion, reduces defects, and improves the carrier transport rate.
It significantly improved interfacial adhesion, reduced charge recombination and energy loss, enhanced interfacial bonding, and improved the performance and stability of perovskite solar cells, laying the foundation for commercial applications.
Smart Images
Figure CN121772479B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of photovoltaic technology, specifically relating to a perovskite solar cell, its preparation method, and its application. Background Technology
[0002] Since 2012, perovskite solar cells have rapidly emerged and achieved numerous significant breakthroughs under laboratory conditions, becoming an important development direction in the field of solar energy research. Perovskite materials occupy an indispensable position in solar cell technology due to their excellent energy conversion efficiency and low-cost manufacturing potential. Typically, the growth of excellent perovskite crystals requires a specific substrate. The morphology and physicochemical properties of the substrate play a crucial role in the spreading of the perovskite precursor solution, the formation of crystal nuclei, and the grain growth process. Under the same precursor solution and preparation method, the properties of the substrate often determine the quality of the perovskite crystals, which is crucial for the fabrication of high-performance modules. Therefore, selecting suitable substrate materials and structures is a necessary condition for improving the efficiency and stability of perovskite solar cells. Furthermore, in the commercialization of perovskite solar cells, the substrate structure commonly used for high-performance modules is glass / FTO (ITO) / NiO. x In this structure, the organic-inorganic hybrid perovskite layer and NiO x The bonding force between the substrate and the perovskite layer is relatively weak, and porosity is easily introduced during the fabrication process. This not only affects the effective transport of charge carriers but may also lead to a decrease in the long-term stability of the cell, thus significantly impacting the overall performance of the module. Therefore, optimizing the interface characteristics between the substrate and the perovskite layer and reducing porosity and interface defects has become one of the key technical challenges in improving the efficiency and stability of perovskite solar cells.
[0003] Industry experts have conducted numerous studies, such as introducing an ultrathin organic molecular passivation layer to modify the interface. This passivation layer can reduce interface defects and improve interface properties by covering the substrate surface. However, although this method can improve the electrical properties and stability of the interface to some extent, ultrathin two-dimensional passivation layers often cannot fundamentally solve the interface problem. The main reason is that such passivating agents usually only act on the perovskite layer or NiO. x The surface of the layer cannot effectively form a stable passivation film across the entire interface, resulting in limited effectiveness in enhancing interfacial adhesion and bonding. Furthermore, the presence of an ultrathin two-dimensional passivation layer may restrict its comprehensive repair of interfacial defects, particularly hindering charge transport and carrier migration at the interface.
[0004] Therefore, how to achieve an efficient and stable hole transport layer / perovskite absorber layer interface to further optimize the electrochemical performance of perovskite solar cells and enhance their commercial application potential is a technical challenge that urgently needs to be solved. Summary of the Invention
[0005] To address the shortcomings of existing technologies, the present invention aims to provide a perovskite solar cell, its fabrication method, and its applications. This invention proposes a three-dimensional passivation strategy. A three-dimensional passivation material, composed of an organic passivation material and metal oxide nanoparticles coated on the surface of the organic passivation material, is interlocked with the extension of the perovskite absorber layer to form a mortise-and-tenon three-dimensional passivation layer with a mortise-and-tenon three-dimensional concave-convex structure, achieving an interface passivation effect. This structure effectively enhances the interfacial adhesion between the hole transport layer and the perovskite absorber layer, significantly reduces interface defects, lowers charge recombination and energy loss at the interface, and simultaneously improves the interfacial carrier transport rate. Furthermore, this mortise-and-tenon three-dimensional passivation layer, through the synergistic effect between the organic passivation material and the metal oxide nanoparticles, constructs a more stable and efficient interface structure, strengthens the bonding force between interfaces, and helps to slow down performance degradation. In summary, this strategy not only provides a new solution for the high-efficiency performance of perovskite solar cells but also lays a solid foundation for their commercialization and large-scale application, providing important technical support for the future industrial development of solar cells, with broad application prospects.
[0006] To achieve this objective, the present invention adopts the following technical solution:
[0007] In a first aspect, the present invention provides a perovskite solar cell, the perovskite solar cell comprising a conductive substrate, a hole transport layer, a tenon-and-mortise three-dimensional passivation layer, a perovskite absorption layer, an electron transport layer, and electrodes stacked together.
[0008] The mortise and tenon three-dimensional passivation layer has a mortise and tenon three-dimensional concave-convex structure, including a protruding unit made of a three-dimensional passivation material and a concave unit made of an extension of the perovskite absorption layer, wherein the protruding unit and the concave unit are mortised and tenoned together; the three-dimensional passivation material includes an organic passivation material and metal oxide nanoparticles coated on the surface of the organic passivation material.
[0009] This invention proposes a three-dimensional passivation strategy. A three-dimensional passivation material, composed of an organic passivation material and metal oxide nanoparticles coated on its surface, is interlocked with an extension of the perovskite absorber layer to form a tenon-and-mortise three-dimensional passivation layer with a tenon-and-mortise three-dimensional uneven structure, achieving an interface passivation effect. This structure effectively enhances the interfacial adhesion between the hole transport layer and the perovskite absorber layer, significantly reduces interface defects, lowers charge recombination and energy loss at the interface, and simultaneously increases the interfacial carrier transport rate. Furthermore, this tenon-and-mortise three-dimensional passivation layer, through the synergistic effect between the organic passivation material and the metal oxide nanoparticles, constructs a more stable and efficient interface structure, strengthens the bonding force between interfaces, and helps to slow down performance degradation. In summary, this strategy not only provides a new solution for the high-efficiency performance of perovskite solar cells but also lays a solid foundation for their commercialization and large-scale application, providing important technical support for the future industrial development of solar cells, with broad application prospects.
[0010] The tenon-and-mortise three-dimensional passivation layer provided by this invention not only effectively improves the grain growth environment of the perovskite absorber layer, but also enhances the structural stability and performance of the perovskite absorber layer, providing an important foundation for further improving the efficiency and long-term stability of perovskite-based devices.
[0011] The tenon-and-mortise three-dimensional passivation layer provided by this invention can effectively reduce the defect state density of the perovskite absorption layer and improve the photoelectric performance and stability of the perovskite material, which also lays the foundation for further optimization of perovskite optoelectronic devices.
[0012] Preferably, the protruding units are discretely distributed in the tenon-and-mortise three-dimensional passivation layer.
[0013] In this invention, the discrete distribution provides space for the embedding of the perovskite absorber layer material, thereby forming a stable tenon-and-mortise structure. Therefore, this distribution pattern can increase the effective contact area of the interface and provide more channels for charge extraction. At the same time, the discrete protrusion units can passivate perovskite interface defects and can form two-dimensional perovskite passivation materials (such as (PEA)2PbI4 type) with lead iodide (PbI2), thereby improving the interface quality of perovskite solar cells, reducing non-radiative recombination, and enhancing device stability.
[0014] Preferably, in the tenon-and-mortise type three-dimensional passivation layer, the distribution density of the protrusion units is 50%-80%, for example, it can be 50%, 60%, 70% or 80%, etc.
[0015] Preferably, the thickness of the tenon-and-mortise three-dimensional passivation layer is 5-30nm, for example, it can be 5nm, 10nm, 15nm, 20nm, 25nm or 30nm, etc.
[0016] In this invention, the suitable thickness of the tenon-and-mortise type three-dimensional passivation layer is 5-30 nm.
[0017] Preferably, the average height of the protrusion unit is 5-30nm, for example, it can be 5nm, 10nm, 15nm, 20nm, 25nm or 30nm, etc.
[0018] Preferably, the organic passivating material is an organic compound containing positively charged amino groups and negatively charged halogen functional groups.
[0019] In this invention, an organic compound containing positively charged amino and negatively charged halogen functional groups is used as an organic passivation material. The amino group can bind with uncoordinated halide ions in the perovskite, while the halide anion can interact with uncoordinated organic cations, thereby achieving dual-site passivation of the perovskite layer surface and interface, effectively reducing the defect state density and improving device stability and photoelectric performance.
[0020] Preferably, the particle size D50 of the metal oxide nanoparticles is 5-30 nm, for example, it can be 5 nm, 10 nm, 15 nm, 20 nm, 25 nm or 30 nm.
[0021] Preferably, based on the mass of the three-dimensional passivation material, the mass content of the metal oxide nanoparticles is 40wt%-60wt%, for example, it can be 40wt%, 50wt% or 60wt%.
[0022] In this invention, an appropriate mass content ensures that the metal oxide nanoparticles form a continuous and stable coating network in the three-dimensional passivation material. This fully leverages the mechanical reinforcement and interface stabilization effects while maintaining good compatibility and flexible fit between the organic passivation material and the perovskite absorber layer, thereby synergistically improving the photoelectric conversion efficiency and long-term environmental stability of the battery.
[0023] Preferably, the organic compound includes any one or a combination of at least two of phenylethyl iodide, phenylethyl ammonium chloride, 4-fluorophenylethylamine hydrochloride, ethylenediamine dihydroiodide, or guanidine chloride.
[0024] Preferably, the metal oxide nanoparticles include any one or a combination of at least two of aluminum oxide, tin oxide, silicon oxide, or titanium oxide.
[0025] Preferably, the chemical formula of the perovskite absorber layer is ABX3, wherein A includes any one or a combination of at least two of formamidinium ions, methylamine ions, or cesium ions; B includes lead ions and / or tin ions; and X includes any one or a combination of at least two of chloride ions, bromide ions, or iodide ions.
[0026] Preferably, the thickness of the perovskite absorber layer is 350-450 nm, for example, it can be 350 nm, 400 nm or 450 nm.
[0027] Preferably, the grain size in the perovskite absorber layer is 400-1200 nm, for example, it can be 400 nm, 600 nm, 800 nm, 1000 nm or 1200 nm.
[0028] The present invention utilizes a tenon-and-mortise three-dimensional passivation layer to make the perovskite absorber layer grains more uniform and larger, significantly improving the overall crystal quality and exhibiting superior crystal quality, fewer grain boundary defects, and more complete grain growth.
[0029] Preferably, in the perovskite absorber layer, the crystal orientation is... <001> With crystal orientation <011> The ratio is 2-12, for example, it can be 2, 4, 6, 8, 10 or 12, etc.
[0030] This invention utilizes a tenon-and-mortise type three-dimensional passivation layer to enable the perovskite absorber layer to exhibit superior performance. <001> Crystal orientation, crystal direction <001> With crystal orientation <011> The significantly improved ratio demonstrates that the crystal quality of the perovskite absorber layer has been significantly improved, particularly in terms of crystal orientation and grain order, which helps to improve the optoelectronic performance of the device and provides support for the efficiency improvement of perovskite-based devices.
[0031] Preferably, the conductive substrate is a transparent conductive glass. Examples include ITO (indium tin oxide) conductive glass or FTO (fluorine-doped tin oxide) conductive glass.
[0032] Preferably, the hole transport layer comprises any one or a combination of at least two of the following: a nickel oxide layer, a poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) layer, or a self-assembled monomolecular (SAM) layer.
[0033] In this invention, in the three-dimensional passivation material, metal oxide nanoparticles can be physically adsorbed with nickel oxide through van der Waals forces or hydrogen bonds, and at the same time, they can form relatively strong chemical bonds under heating conditions. This interaction can greatly enhance the adhesion between the two.
[0034] Preferably, the thickness of the hole transport layer is 5-20 nm, for example, it can be 5 nm, 10 nm, 15 nm or 20 nm.
[0035] Preferably, the electron transport layer includes C 60 Any one or at least a combination of two of the following: a SnO2 layer or a SnO2 layer.
[0036] Preferably, the thickness of the electron transport layer is 10-30 nm, for example, it can be 10 nm, 20 nm or 30 nm.
[0037] Preferably, the electrode comprises a metal electrode. For example, it may be a Cu electrode, an Ag electrode, or an Au electrode.
[0038] Preferably, a hole-blocking layer is further disposed between the electron transport layer and the electrode. For example, this could be a tin dioxide layer.
[0039] In a second aspect, the present invention provides a method for preparing a perovskite solar cell as described in the first aspect, the method comprising the following steps:
[0040] A hole transport layer is fabricated on a conductive substrate.
[0041] An initial three-dimensional passivation layer of three-dimensional passivation material is prepared on the hole transport layer. The three-dimensional passivation material includes an organic passivation material and metal oxide nanoparticles coated on the surface of the organic passivation material.
[0042] A perovskite absorption layer is prepared on the initial three-dimensional passivation layer; wherein the perovskite absorption layer partially fills the initial passivation layer and is tenon-and-mortise connected to the three-dimensional passivation material, thereby obtaining a tenon-and-mortise three-dimensional passivation layer with a tenon-and-mortise three-dimensional concave-convex structure.
[0043] An electron transport layer and an electrode are sequentially fabricated on the perovskite absorber layer to obtain the perovskite solar cell.
[0044] This invention achieves precise and controllable construction of a tenon-and-mortise three-dimensional concave-convex structure by first constructing an initial three-dimensional passivation layer, and then naturally forming a concave structure that complements and interlocks with the protrusion units of the passivation layer during the filling process of the perovskite precursor. This process not only optimizes the crystal quality and interface contact of the perovskite, but also effectively suppresses ion migration and interface defects, significantly improving the performance and long-term stability of the device.
[0045] Preferably, the method for preparing the initial three-dimensional passivation layer includes:
[0046] (a) Disperse metal oxide nanoparticles in a solvent and then add an organic passivation material to obtain a three-dimensional passivation precursor solution.
[0047] (b) The three-dimensional passivation precursor liquid is coated onto the hole transport layer and dried.
[0048] The dispersion method includes any one of ultrasonic dispersion, oscillation dispersion, or stirring dispersion. For example, the ultrasonic dispersion time is 1-10 min, such as 1 min, 3 min, 5 min, 7 min, 9 min, or 10 min.
[0049] In this invention, the method for preparing the initial three-dimensional passivation layer helps to induce the formation of a regular and stable tenon-and-mortise interlocking interface during the subsequent perovskite crystallization process, providing a reliable process basis for improving the passivation effect and device performance.
[0050] Preferably, the preparation method includes the following steps:
[0051] (1) Provide transparent conductive glass.
[0052] A hole transport layer is prepared on the transparent conductive glass.
[0053] (2) Preparation of the initial three-dimensional passivation layer, including the following steps:
[0054] (a) Disperse metal oxide nanoparticles in an alcohol solvent (exemplary, such as isopropanol, ethanol, or n-butanol), and then add an organic passivation material to disperse and dissolve, thereby obtaining a three-dimensional passivation precursor solution; wherein the dispersion method includes any one of ultrasonic dispersion, oscillation dispersion, or stirring dispersion; and the dispersion and dissolution method includes any one of ultrasonic dissolution, oscillation dissolution, or stirring dissolution.
[0055] (b) The three-dimensional passivation precursor liquid is coated onto the hole transport layer and dried to obtain the initial three-dimensional passivation layer; wherein the coating method includes slot coating.
[0056] (3) The perovskite precursor solution is coated and deposited on the initial three-dimensional passivation layer to obtain a perovskite wet film.
[0057] The perovskite wet film is subjected to vacuum concentration, drying, and annealing crystallization to obtain a perovskite absorber layer.
[0058] The perovskite absorption layer is partially filled in the initial passivation layer and is tenon-and-mortise connected to the three-dimensional passivation material in the initial three-dimensional passivation layer, thereby obtaining a tenon-and-mortise three-dimensional passivation layer with a tenon-and-mortise three-dimensional concave-convex structure.
[0059] (4) An electron transport layer, a hole blocking layer and a metal electrode are sequentially prepared on the perovskite absorber layer to obtain a perovskite solar cell.
[0060] Thirdly, the present invention provides an application of perovskite solar cells as described in the first aspect in the photovoltaic field.
[0061] The numerical range described in this invention includes not only the point values listed above, but also any point values within the numerical ranges not listed above. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific point values included in the range.
[0062] Compared with the prior art, the present invention has the following beneficial effects:
[0063] (1) This invention proposes a three-dimensional passivation strategy. A three-dimensional passivation material, composed of an organic passivation material and metal oxide nanoparticles coated on the surface of the organic passivation material, is used to form a mortise-and-tenon three-dimensional passivation layer with a mortise-and-tenon three-dimensional concave-convex structure, achieving an interface passivation effect. This structure effectively enhances the interfacial adhesion between the hole transport layer and the perovskite absorber layer, significantly reduces interface defects, lowers charge recombination and energy loss at the interface, and simultaneously improves the interfacial carrier transport rate. Furthermore, this mortise-and-tenon three-dimensional passivation layer, through the synergistic effect between the organic passivation material and the metal oxide nanoparticles, constructs a more stable and efficient interface structure, strengthens the bonding force between interfaces, and helps to slow down performance degradation. In summary, this strategy not only provides a new solution for the high-efficiency performance of perovskite solar cells but also lays a solid foundation for their commercialization and large-scale application, providing important technical support for the future industrial development of solar cells, with broad application prospects.
[0064] (2) The tenon-and-mortise three-dimensional passivation layer provided by the present invention not only effectively improves the grain growth environment of the perovskite absorption layer, but also enhances the structural stability and performance of the perovskite absorption layer, providing an important foundation for further improving the efficiency and long-term stability of perovskite-based devices.
[0065] (3) The tenon-and-mortise three-dimensional passivation layer provided by the present invention can effectively reduce the defect state density of the perovskite absorption layer and improve the photoelectric performance and stability of the perovskite material, which also lays the foundation for further optimization of perovskite optoelectronic devices. Attached Figure Description
[0066] Figure 1 This is a partial structural schematic diagram of the perovskite solar cell provided in Embodiment 1 of the present invention.
[0067] Figure 2 This is a surface SEM image of the perovskite absorber layer provided in Example 1 of the present invention.
[0068] Figure 3 This is a fluorescence lifetime distribution diagram of the perovskite absorber layer provided in Example 1 of the present invention.
[0069] Figure 4 This is a surface SEM image of the perovskite absorber layer provided in Comparative Example 1 of this invention.
[0070] Figure 5 This is a fluorescence lifetime distribution diagram of the perovskite absorption layer provided in Comparative Example 1 of this invention.
[0071] Figure 6The images show a comparison of the XRD diffraction patterns of the perovskite absorption layers provided in Example 1 and Comparative Example 1 of this invention.
[0072] Figure 7 This is a stability comparison curve of the perovskite solar cells provided in Example 1 and Comparative Example 1 of the present invention.
[0073] Among them, 1-substrate; 2-mortise and tenon three-dimensional passivation layer; 21-three-dimensional passivation material; 3-perovskite absorption layer. Detailed Implementation
[0074] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.
[0075] It should be understood that in the description of this invention, the terms "center," "longitudinal," "lateral," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," and "outer," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. These terms are used only for the convenience of describing the invention and for simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on the invention. Furthermore, the terms "first," "second," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Thus, a feature defined with "first," "second," etc., may explicitly or implicitly include one or more of that feature. In the description of this invention, unless otherwise stated, "a plurality of" means two or more.
[0076] It should be noted that, in the description of this invention, unless otherwise explicitly specified and limited, the terms "set," "connected," and "linked" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components. Those skilled in the art can understand the specific meaning of the above terms in this invention based on the specific circumstances.
[0077] Example 1
[0078] This embodiment provides a perovskite solar cell, which includes a stacked FTO transparent conductive glass, a nickel oxide layer, a tenon-and-mortise three-dimensional passivation layer, a perovskite absorber layer, and a C... 60 Layer, tin dioxide layer and Cu electrode.
[0079] See Figure 1FTO transparent conductive glass and nickel oxide layer serve as the substrate 1 of the tenon-and-mortise three-dimensional passivation layer 2; the tenon-and-mortise three-dimensional passivation layer 2 has a tenon-and-mortise three-dimensional concave-convex structure, including protruding units composed of three-dimensional passivation material 21 and concave units composed of the extension portion of perovskite absorption layer 3, the protruding units and concave units are tenon-and-mortise connected; the protruding units are discretely distributed in the tenon-and-mortise three-dimensional passivation layer 2.
[0080] In the mortise and tenon three-dimensional passivation layer 2, the distribution density of the protrusion units is 65%; the thickness of the mortise and tenon three-dimensional passivation layer 2 is 18nm; and the average height of the protrusion units is 18nm.
[0081] The three-dimensional passivation material 21 includes an organic passivation material and metal oxide nanoparticles coated on the surface of the organic passivation material. The organic passivation material is phenylethyl iodide amine; the metal oxide nanoparticles are alumina nanoparticles with a particle size D50 of 18 nm; based on the mass of the three-dimensional passivation material 21, the mass content of the metal oxide nanoparticles is 50 wt%.
[0082] The chemical formula of the perovskite absorber layer 3 is Cs. 0.05 FA 0.95 The PbI3 layer has a thickness of 400 nm; the perovskite absorber layer 3 has a grain size of 800-1000 nm; the perovskite absorber layer 3 has a crystal orientation... <001> With crystal orientation <011> The ratio is 12; the thickness of the nickel oxide layer is 12 nm, C 60 The thickness of the layer is 20nm.
[0083] This embodiment also provides a method for preparing the above-mentioned perovskite solar cell, the method comprising the following steps:
[0084] (1) Provide FTO transparent conductive glass and clean it in sequence with detergent, deionized water and ethanol.
[0085] A nickel oxide layer was prepared on the FTO transparent conductive glass using magnetron sputtering.
[0086] (2) Preparation of the initial three-dimensional passivation layer, including the following steps:
[0087] (a) Alumina was ultrasonically dispersed in isopropanol for 5 min, and then phenylethyl iodide powder was added to disperse and dissolve it to obtain a three-dimensional passivation precursor solution; the dispersion and dissolution method was ultrasonic dissolution.
[0088] (b) The three-dimensional passivation precursor liquid is coated onto the nickel oxide layer using the slit coating method and dried to obtain the initial three-dimensional passivation layer.
[0089] (3) Provide Cs at a concentration of 0.6 mol / L 0.05 FA0.95 PbI3 precursor solution (solvent composed of DMF and DMSO in a volume ratio of 9:1, with a volume of 50 mL).
[0090] The Cs were coated using a slot coating method. 0.05 FA 0.95 PbI3 precursor solution was deposited on the initial three-dimensional passivation layer to obtain a perovskite wet film.
[0091] The perovskite wet film was vacuum concentrated and dried, and then placed on a hot plate at 135°C for annealing and crystallization for 20 minutes to obtain a perovskite absorber layer.
[0092] The perovskite absorption layer is partially filled in the initial passivation layer and is tenon-and-mortise connected to the three-dimensional passivation material in the initial three-dimensional passivation layer, thereby obtaining a tenon-and-mortise three-dimensional passivation layer with a tenon-and-mortise three-dimensional concave-convex structure.
[0093] (4) Using a thermal evaporation method, C is prepared on the perovskite absorber layer. 60 Layer, and then use the ALD method, in the C 60 A 20nm thick tin dioxide layer is deposited on the layer as a hole blocking layer.
[0094] A 120 nm thick Cu electrode was deposited on the hole blocking layer using magnetron sputtering to obtain a perovskite solar cell.
[0095] Example 2
[0096] This embodiment provides a perovskite solar cell, which includes a stacked FTO transparent conductive glass, a nickel oxide layer, a tenon-and-mortise three-dimensional passivation layer, a perovskite absorber layer, and a C... 60 Layer, tin dioxide layer and Cu electrode.
[0097] Among them, FTO transparent conductive glass and nickel oxide layer serve as the base of the tenon-and-mortise three-dimensional passivation layer; the tenon-and-mortise three-dimensional passivation layer has a tenon-and-mortise three-dimensional concave-convex structure, including protruding units composed of three-dimensional passivation material and concave units composed of the extension of the perovskite absorption layer, the protruding units and concave units are connected by tenon and mortise; the protruding units are discretely distributed in the tenon-and-mortise three-dimensional passivation layer.
[0098] In the mortise and tenon three-dimensional passivation layer, the distribution density of the protrusion units is 70%; the thickness of the mortise and tenon three-dimensional passivation layer is 22nm; and the average height of the protrusion units is 22nm.
[0099] The three-dimensional passivation material includes an organic passivation material and metal oxide nanoparticles coated on the surface of the organic passivation material. The organic passivation material is phenylethyl iodide amine; the metal oxide nanoparticles are alumina nanoparticles with a particle size D50 of 22 nm; based on the mass of the three-dimensional passivation material, the mass content of the metal oxide nanoparticles is 55 wt%.
[0100] The chemical formula of the perovskite absorber layer is Cs. 0.05 FA 0.95 The PbI3 layer has a thickness of 420 nm; the grain size in the perovskite absorber layer is 900 nm-1100 nm; the crystal orientation in the perovskite absorber layer is... <001> With crystal orientation <011> The ratio is 11.7; the thickness of the nickel oxide layer is 15 nm, C 60 The thickness of the layer is 25nm.
[0101] This embodiment also provides a method for preparing the above-mentioned perovskite solar cell, the method comprising the following steps:
[0102] (1) Provide FTO transparent conductive glass and clean it in sequence with detergent, deionized water and ethanol.
[0103] A nickel oxide layer was prepared on the FTO transparent conductive glass using magnetron sputtering.
[0104] (2) Preparation of the initial three-dimensional passivation layer, including the following steps:
[0105] (a) Tin oxide was ultrasonically dispersed in isopropanol for 5 min, and then 4-fluorophenylethylamine hydrochloride powder was added to disperse and dissolve it to obtain a three-dimensional passivation precursor solution; the dispersion and dissolution method was ultrasonic dissolution.
[0106] (b) The three-dimensional passivation precursor liquid is coated onto the nickel oxide layer using the slit coating method and dried to obtain the initial three-dimensional passivation layer.
[0107] (3) Provide Cs at a concentration of 0.6 mol / L 0.05 FA 0.95 PbI3 precursor solution (solvent composed of DMF and DMSO in a volume ratio of 9:1, with a volume of 50 mL).
[0108] The Cs were coated using a slot coating method. 0.05 FA 0.95 PbI3 precursor solution was deposited on the initial three-dimensional passivation layer to obtain a perovskite wet film.
[0109] The perovskite wet film was vacuum concentrated and dried, and then placed on a hot plate at 120°C for annealing and crystallization for 30 minutes to obtain a perovskite absorber layer.
[0110] The perovskite absorption layer is partially filled in the initial passivation layer and is tenon-and-mortise connected to the three-dimensional passivation material in the initial three-dimensional passivation layer, thereby obtaining a tenon-and-mortise three-dimensional passivation layer with a tenon-and-mortise three-dimensional concave-convex structure.
[0111] (4) Using a thermal evaporation method, C is prepared on the perovskite absorber layer. 60 Layer, and then use the ALD method, in the C 60 A 10 nm thick tin dioxide layer is deposited on the layer as a hole blocking layer.
[0112] A 100 nm thick Cu electrode was deposited on the hole blocking layer using magnetron sputtering to obtain a perovskite solar cell.
[0113] Example 3
[0114] This embodiment provides a perovskite solar cell, which includes a stacked FTO transparent conductive glass, a nickel oxide layer, a tenon-and-mortise three-dimensional passivation layer, a perovskite absorber layer, and a C... 60 Layer, tin dioxide layer and Cu electrode.
[0115] Among them, FTO transparent conductive glass and nickel oxide layer serve as the base of the tenon-and-mortise three-dimensional passivation layer; the tenon-and-mortise three-dimensional passivation layer has a tenon-and-mortise three-dimensional concave-convex structure, including protruding units composed of three-dimensional passivation material and concave units composed of the extension of the perovskite absorption layer, the protruding units and concave units are connected by tenon and mortise; the protruding units are discretely distributed in the tenon-and-mortise three-dimensional passivation layer.
[0116] In the mortise and tenon three-dimensional passivation layer, the distribution density of the protrusion units is 65%; the thickness of the mortise and tenon three-dimensional passivation layer is 15nm; and the average height of the protrusion units is 15nm.
[0117] The three-dimensional passivation material includes an organic passivation material and metal oxide nanoparticles coated on the surface of the organic passivation material. The organic passivation material is phenylethyl iodide amine; the metal oxide nanoparticles are alumina nanoparticles with a particle size D50 of 15 nm; based on the mass of the three-dimensional passivation material, the mass content of the metal oxide nanoparticles is 45 wt%.
[0118] The chemical formula of the perovskite absorber layer is Cs. 0.05 FA 0.95 The PbI3 layer has a thickness of 380 nm; the grain size in the perovskite absorber layer is 900 nm-1100 nm; the crystal orientation in the perovskite absorber layer is... <001> With crystal orientation <011> The ratio is 11.4; the thickness of the nickel oxide layer is 10 nm, C 60 The thickness of the layer is 17nm.
[0119] This embodiment also provides a method for preparing the above-mentioned perovskite solar cell, the method comprising the following steps:
[0120] (1) Provide FTO transparent conductive glass and clean it in sequence with detergent, deionized water and ethanol.
[0121] A nickel oxide layer was prepared on the FTO transparent conductive glass using magnetron sputtering.
[0122] (2) Preparation of the initial three-dimensional passivation layer, including the following steps:
[0123] (a) Silica was ultrasonically dispersed in isopropanol for 5 min, and then guanidine chloride powder was added to disperse and dissolve it to obtain a three-dimensional passivation precursor solution; the dispersion and dissolution method was ultrasonic dissolution.
[0124] (b) The three-dimensional passivation precursor liquid is coated onto the nickel oxide layer using the slit coating method and dried to obtain the initial three-dimensional passivation layer.
[0125] (3) Provide Cs at a concentration of 0.6 mol / L 0.05 FA 0.95 PbI3 precursor solution (solvent composed of DMF and DMSO in a volume ratio of 9:1, with a volume of 50 mL).
[0126] The Cs were coated using a slot coating method. 0.05 FA 0.95 PbI3 precursor solution was deposited on the initial three-dimensional passivation layer to obtain a perovskite wet film.
[0127] The perovskite wet film was vacuum concentrated and dried, and then placed on a hot plate at 150°C for annealing and crystallization for 10 minutes to obtain a perovskite absorber layer.
[0128] The perovskite absorption layer is partially filled in the initial passivation layer and is tenon-and-mortise connected to the three-dimensional passivation material in the initial three-dimensional passivation layer, thereby obtaining a tenon-and-mortise three-dimensional passivation layer with a tenon-and-mortise three-dimensional concave-convex structure.
[0129] (4) Using a thermal evaporation method, C is prepared on the perovskite absorber layer. 60 Layer, and then use the ALD method, in the C 60 A 20nm thick tin dioxide layer is deposited on the layer as a hole blocking layer.
[0130] A Cu electrode with a thickness of 150 nm was deposited on the hole blocking layer using magnetron sputtering to obtain a perovskite solar cell.
[0131] Example 4
[0132] The difference between this embodiment and Embodiment 1 is that the distribution density of the protrusion units in the tenon-and-mortise three-dimensional passivation layer is 45%.
[0133] The remaining preparation methods and parameters are consistent with those in Example 1.
[0134] Example 5
[0135] The difference between this embodiment and Embodiment 1 is that the distribution density of the protrusion units in the tenon-and-mortise three-dimensional passivation layer is 85%.
[0136] The remaining preparation methods and parameters are consistent with those in Example 1.
[0137] Example 6
[0138] The difference between this embodiment and Embodiment 1 is that the thickness of the tenon-and-mortise three-dimensional passivation layer is 3nm.
[0139] The remaining preparation methods and parameters are consistent with those in Example 1.
[0140] Example 7
[0141] The difference between this embodiment and Embodiment 1 is that the thickness of the tenon-and-mortise three-dimensional passivation layer is 35 nm.
[0142] The remaining preparation methods and parameters are consistent with those in Example 1.
[0143] Example 8
[0144] The difference between this embodiment and Embodiment 1 is that, based on the mass of the three-dimensional passivation material, the mass content of the metal oxide nanoparticles is 35wt%.
[0145] The remaining preparation methods and parameters are consistent with those in Example 1.
[0146] Example 9
[0147] The difference between this embodiment and Embodiment 1 is that, based on the mass of the three-dimensional passivation material, the mass content of the metal oxide nanoparticles is 65 wt%.
[0148] The remaining preparation methods and parameters are consistent with those in Example 1.
[0149] Comparative Example 1
[0150] The difference between this comparative example and Example 1 is that no tenon-and-mortise type three-dimensional passivation layer is provided.
[0151] The remaining preparation methods and parameters are consistent with those in Example 1.
[0152] The results were obtained using scanning electron microscopy (SEM). Figure 2 and Figure 4 The surface SEM images shown demonstrate that, as can be seen from the comparison, after interface modification with the tenon-and-mortise three-dimensional passivation layer, the grain size of the perovskite absorber layer significantly increases, the grains become more uniform and larger, and the overall crystallinity quality is significantly improved. Compared with the unmodified perovskite absorber layer, the perovskite absorber layer modified with the tenon-and-mortise three-dimensional passivation layer exhibits superior crystallinity quality, fewer grain boundary defects, and more complete grain growth. This indicates that the tenon-and-mortise three-dimensional passivation layer not only effectively improves the grain growth environment but also promotes the structural stability and performance of the perovskite thin film, providing an important foundation for further improving the efficiency and long-term stability of perovskite-based devices.
[0153] Using laser confocal microscopy, the following were obtained: Figure 3 and Figure 5 The fluorescence lifetime distribution diagram shown in the figure reveals that, after the interface modification of the tenon-and-mortise three-dimensional passivation layer, the perovskite absorption layer exhibits a significantly extended carrier lifetime. This indicates that the recombination rate of photogenerated carriers within the material is slowed down. This phenomenon suggests that the tenon-and-mortise three-dimensional passivation layer effectively reduces the defect state density in the perovskite, thereby improving the photoelectric performance and stability of the material. This also provides experimental evidence for further optimization of perovskite optoelectronic devices.
[0154] Figure 6 The XRD diffraction comparison images of the perovskite absorber layers provided in Example 1 and Comparative Example 1 are shown. As can be seen from the figures, the perovskite absorber layer modified with the tenon-and-mortise three-dimensional passivation layer interface exhibits superior performance. <001> Planar crystal orientation, and its <001> / <011> The significantly improved crystal orientation ratio indicates that the tenon-and-mortise three-dimensional passivation layer significantly improves the crystallinity of the perovskite absorber layer, particularly in terms of crystal orientation and grain order. This improved crystallinity strongly supports the efficiency enhancement of perovskite-based devices. In summary, the tenon-and-mortise three-dimensional passivation layer plays a crucial role in optimizing the crystal structure of the perovskite absorber layer and is expected to further drive the performance improvement of perovskite solar cells and other optoelectronic devices.
[0155] Figure 7 The stability comparison curves of the perovskite solar cells provided in Example 1 and Comparative Example 1 are shown. As can be seen from the figure, after 1000 hours of continuous aging under the double 85 test environment (85% RH and 85°C), the perovskite solar cell provided in Example 1 still maintains an efficiency of up to 92%, while Comparative Example 1 only maintains 71% of the initial photoelectric conversion efficiency. This result shows that the tenon-and-mortise three-dimensional passivation layer not only improves the crystal quality of the perovskite absorption layer, but also reduces the defect state density in the material, thereby significantly enhancing the durability of the device under high temperature and high humidity environment.
[0156] Comparative Example 2
[0157] The difference between this comparative example and Example 1 is that no metal oxide nanoparticles are introduced.
[0158] The remaining preparation methods and parameters are consistent with those in Example 1.
[0159] Comparative Example 3
[0160] The difference between this comparative example and Example 1 is that no organic passivating material is introduced.
[0161] The remaining preparation methods and parameters are consistent with those in Example 1.
[0162] Performance testing
[0163] The photoelectric performance of the perovskite solar cells provided in the above embodiments and comparative examples was tested, with a cell area of 810 cm². 2 Test conditions included: AM1.5, 1000W / m 2 , 25±2℃.
[0164] The perovskite solar cells provided in the above embodiments and comparative examples were continuously aged for 1000 hours in a dual 85 environment (85% RH humidity, 85°C temperature), and the retention rate of their photoelectric conversion efficiency after 1000 hours was recorded.
[0165] The results are shown in Table 1.
[0166] Table 1
[0167]
[0168] analyze:
[0169] As shown in Table 1, this invention proposes a three-dimensional passivation strategy. By employing a three-dimensional passivation material composed of an organic passivation material and metal oxide nanoparticles coated on the surface of the organic passivation material, a tenon-and-mortise three-dimensional passivation layer with a tenon-and-mortise three-dimensional concave-convex structure is formed by mortise-and-mortise connection with the extended portion of the perovskite absorber layer, achieving an interface passivation effect. This structure effectively enhances the interfacial adhesion between the hole transport layer and the perovskite absorber layer, significantly reduces interface defects, lowers charge recombination and energy loss at the interface, and simultaneously improves the interfacial carrier transport rate. Furthermore, this tenon-and-mortise three-dimensional passivation layer, through the synergistic effect between the organic passivation material and the metal oxide nanoparticles, constructs a more stable and efficient interface structure, strengthens the bonding force between interfaces, and helps to slow down performance degradation. The efficiency and long-term stability of the perovskite-based device prepared based on this strategy are significantly improved, with a photoelectric conversion efficiency of 23.54%. After 1000 hours of continuous aging under dual 85°C conditions, its efficiency retention rate remains as high as 92%.
[0170] As can be seen from the comparison between Example 1 and Examples 4-5, if the distribution density of the protruding units in the tenon-and-mortise three-dimensional passivation layer is too small, the interface recombination center will not be sufficiently passivated; if the distribution density of the protruding units in the tenon-and-mortise three-dimensional passivation layer is too large, the carrier transport will be hindered.
[0171] As can be seen from the comparison between Example 1 and Examples 6-7, if the thickness of the tenon-and-mortise three-dimensional passivation layer is too small, the interface recombination center will not be sufficiently passivated; if the thickness of the tenon-and-mortise three-dimensional passivation layer is too large, the carrier transport will be hindered.
[0172] As can be seen from the comparison between Example 1 and Examples 8-9, if the mass content of metal oxide nanoparticles in the three-dimensional passivation material is too low, the coverage will be insufficient; if the mass content of metal oxide nanoparticles in the three-dimensional passivation material is too high, the interfacial conductivity will be poor.
[0173] As can be seen from the comparison between Example 1 and Comparative Example 1, if the tenon-and-mortise three-dimensional passivation layer is not provided, the interface defects cannot be passivated, the interface connection is weak, and the carrier transport is hindered.
[0174] As can be seen from the comparison between Example 1 and Comparative Example 2, if metal oxide nanoparticles are not introduced, and only organic passivation materials are used to form the passivation layer, it is impossible to achieve full passivation of the interface, and the interface is fragile.
[0175] As can be seen from the comparison between Example 1 and Comparative Example 3, without the introduction of organic passivation materials, it is impossible to achieve better defect passivation and carrier transport.
[0176] It should be noted that the present invention is illustrated through the above embodiments, but the present invention is not limited to the above process steps, that is, it does not mean that the present invention must rely on the above process steps to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials used in the present invention, additions of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.
Claims
1. A perovskite solar cell, characterized in that, The perovskite solar cell includes a conductive substrate, a hole transport layer, a tenon-and-mortise three-dimensional passivation layer, a perovskite absorption layer, an electron transport layer, and electrodes stacked together. The mortise and tenon three-dimensional passivation layer has a mortise and tenon three-dimensional concave-convex structure, including a protruding unit made of a three-dimensional passivation material and a concave unit made of an extension of the perovskite absorption layer, wherein the protruding unit and the concave unit are mortised and tenoned; the three-dimensional passivation material includes an organic passivation material and metal oxide nanoparticles coated on the surface of the organic passivation material. The organic passivation material is an organic compound containing positively charged amino and negatively charged halogen functional groups; based on the mass of the three-dimensional passivation material, the mass content of the metal oxide nanoparticles is 40wt%-60wt%.
2. The perovskite solar cell according to claim 1, characterized in that, The protruding units are discretely distributed in the tenon-and-mortise three-dimensional passivation layer; And / or, in the tenon-and-mortise type three-dimensional passivation layer, the distribution density of the protrusion units is 50%-80%; And / or, the thickness of the tenon-and-mortise three-dimensional passivation layer is 5-30 nm; And / or, the average height of the protrusion unit is 5-30 nm.
3. The perovskite solar cell according to claim 1, characterized in that, The particle size D50 of the metal oxide nanoparticles is 5-30 nm.
4. The perovskite solar cell according to claim 3, characterized in that, The organic compound includes any one or a combination of at least two of the following: phenylethyl ammonium iodide, phenylethyl ammonium chloride, 4-fluorophenylethylammonium hydrochloride, ethylenediammonium dihydroiodide, or guanidine chloride. And / or, the metal oxide nanoparticles include any one or a combination of at least two of aluminum oxide, tin oxide, silicon oxide, or titanium oxide.
5. The perovskite solar cell according to claim 1, characterized in that, The chemical formula of the perovskite absorber layer is ABX3, wherein A includes any one or a combination of at least two of formamidinium ions, methylamine ions, or cesium ions; B includes lead ions and / or tin ions; and X includes any one or a combination of at least two of chloride ions, bromide ions, or iodide ions. And / or, the thickness of the perovskite absorber layer is 350-450 nm; And / or, in the perovskite absorber layer, the grain size is 400-1200 nm; And / or, in the perovskite absorber layer, the crystal orientation <001> With crystal orientation <011> The ratio is 5-12.
6. The perovskite solar cell according to claim 1, characterized in that, The conductive substrate is transparent conductive glass; And / or, the hole transport layer comprises any one or a combination of at least two of the following: a nickel oxide layer, a poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] layer, or a self-assembled monolayer; And / or, the thickness of the hole transport layer is 5-20 nm; And / or, the electron transport layer includes C 60 Any one or at least a combination of two of the following: a SnO2 layer or a SnO2 layer. And / or, the thickness of the electron transport layer is 10-30 nm; And / or, the electrode comprises a metal electrode; And / or, a hole blocking layer is further provided between the electron transport layer and the electrode.
7. A method for preparing a perovskite solar cell according to any one of claims 1-6, characterized in that, The preparation method includes the following steps: A hole transport layer is fabricated on a conductive substrate; An initial three-dimensional passivation layer of three-dimensional passivation material is prepared on the hole transport layer, wherein the three-dimensional passivation material includes an organic passivation material and metal oxide nanoparticles coated on the surface of the organic passivation material; A perovskite absorption layer is prepared on the initial three-dimensional passivation layer; wherein the perovskite absorption layer partially fills the initial passivation layer and is tenon-and-mortise connected to the three-dimensional passivation material, thereby obtaining a tenon-and-mortise three-dimensional passivation layer with a tenon-and-mortise three-dimensional concave-convex structure. An electron transport layer and an electrode are sequentially fabricated on the perovskite absorber layer to obtain the perovskite solar cell.
8. The preparation method according to claim 7, characterized in that, The method for preparing the initial three-dimensional passivation layer includes: (a) Disperse metal oxide nanoparticles in a solvent and then add an organic passivation material to obtain a three-dimensional passivation precursor solution; (b) The three-dimensional passivation precursor solution is coated onto the hole transport layer and dried; The dispersion method includes any one of ultrasonic dispersion, oscillation dispersion, or stirring dispersion.
9. The preparation method according to claim 7, characterized in that, The preparation method includes the following steps: (1) Provide transparent conductive glass; A hole transport layer is prepared on the transparent conductive glass; (2) Preparation of the initial three-dimensional passivation layer, including the following steps: (a) Dispersing metal oxide nanoparticles in an alcohol solvent, and then adding an organic passivation material to disperse and dissolve them to obtain a three-dimensional passivation precursor solution; wherein the dispersion method includes any one of ultrasonic dispersion, oscillation dispersion or stirring dispersion; and the dispersion and dissolution method includes any one of ultrasonic dissolution, oscillation dissolution or stirring dissolution. (b) The three-dimensional passivation precursor liquid is coated onto the hole transport layer and dried to obtain the initial three-dimensional passivation layer; wherein the coating method includes slot coating. (3) The perovskite precursor solution is coated and deposited on the initial three-dimensional passivation layer to obtain a perovskite wet film; The perovskite wet film is subjected to vacuum concentration, drying, annealing, and crystallization to obtain a perovskite absorber layer; The perovskite absorption layer is partially filled in the initial passivation layer and is tenon-and-mortise connected to the three-dimensional passivation material in the initial three-dimensional passivation layer, thereby obtaining a tenon-and-mortise three-dimensional passivation layer with a tenon-and-mortise three-dimensional concave-convex structure. (4) An electron transport layer, a hole blocking layer and a metal electrode are sequentially prepared on the perovskite absorber layer to obtain a perovskite solar cell.
10. An application of a perovskite solar cell as described in any one of claims 1-6 in the photovoltaic field.