Mesoscopic perovskite solar cell preparation method and mesoscopic perovskite solar cell
By fabricating passivation and electron blocking layers in mesoscopic perovskite solar cells, the problems of carrier recombination and scattering centers in mesoscopic perovskite solar cells are solved, thereby improving carrier transport lifetime and cell efficiency.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- 旗滨新能源发展(深圳)有限责任公司
- Filing Date
- 2025-12-31
- Publication Date
- 2026-05-01
AI Technical Summary
In mesoscopic perovskite solar cells, carrier recombination occurs at the interface between the perovskite active layer, the electron transport layer, and the back electrode layer. Furthermore, carrier scattering centers exist at the interface between the mesoscopic spacer layer and the perovskite, leading to a decline in carrier transport lifetime and limiting the improvement of cell efficiency.
In the fabrication of mesoscopic perovskite solar cells, passivation layers are prepared on the surface of the mesoporous spacer layer and the inner wall of the pores. Materials such as tri(triethylmethyl)ammonium phosphate are used to form passivation layers to suppress carrier recombination. An electron blocking layer is also formed at the interface between the perovskite active layer and the back electrode layer to reduce carrier scattering centers.
It effectively reduces carrier recombination, improves carrier transport lifetime, and increases battery efficiency.
Smart Images
Figure CN121968971A_ABST
Abstract
Description
Fabrication methods of mesoscopic perovskite solar cells and mesoscopic perovskite solar cells Technical Field
[0001] This invention relates to the field of mesoscopic perovskite solar cell technology, and more particularly to a method for preparing a mesoscopic perovskite solar cell and the mesoscopic perovskite solar cell itself. Background Technology
[0002] Mesoscopic perovskite solar cells are a type of solar cell based on an electron transport layer, a mesoporous spacer layer, and a perovskite active layer. In mesoscopic perovskite solar cells, the perovskite material fills the mesoporous framework, acting as both a light-absorbing material to absorb sunlight and a charge-carrying material to transport charge carriers. Because the perovskite material is confined within the mesoporous framework, it exhibits excellent stability. Furthermore, the perovskite material possesses a long carrier diffusion length, resulting in a high theoretical conversion efficiency. The large contact area between the mesoporous spacer layer and the perovskite material is beneficial for efficient collection of photogenerated electrons. However, significant carrier recombination occurs at the interfaces between the electron transport layer and the perovskite, and between the back electrode layer and the perovskite. Additionally, carrier scattering centers exist at the interface between the mesoscopic spacer layer and the perovskite, which are detrimental to improving the carrier transport lifetime and limit further improvements in cell efficiency. Summary of the Invention
[0003] The main objective of this invention is to provide a method for preparing a mesoscopic perovskite solar cell and a mesoscopic perovskite solar cell, thereby solving the technical problems of carrier recombination at the interface between the perovskite active layer, the electron transport layer, and the back electrode layer, which easily leads to carrier recombination, and the presence of carrier scattering centers at the interface between the mesoscopic spacer layer and the perovskite active layer, which causes carrier transport lifetime decay.
[0004] To achieve the above objectives, the present invention provides a method for fabricating a mesoscopic perovskite solar cell, characterized by comprising the following steps: preparing a mesoporous spacer layer; preparing a passivation layer: dissolving a passivation material to obtain a passivation material solution, coating the passivation material solution onto the surface of the mesoporous spacer layer and allowing it to penetrate into the pores of the mesoporous spacer layer to form a passivation layer; preparing a perovskite active layer: allowing a perovskite precursor solution to penetrate into the pores of the mesoporous spacer layer and crystallize to obtain the perovskite active layer, wherein the passivation layer is located between the perovskite active layer and the mesoporous spacer layer; and preparing a back electrode layer.
[0005] In some embodiments of the present invention, the passivation material includes at least one of tri(triethylmethyl)ammonium phosphate, tetraethylammonium phosphate, benzyltriethylammonium phosphate, benzyltrimethylammonium phosphate, adamantyltrimethylammonium phosphate, (cyanomethyl)trimethylammonium phosphate, and N-type self-assembly material; and / or, the N-type self-assembly material includes at least one of sulfone-carbazole ethyl phosphate, thienylcarbazole ethyl phosphate, fullerene carboxylic acid, and fullerene phosphate; and / or, the mesoporous spacer layer includes at least one of zirconium dioxide and alumina.
[0006] In some embodiments of the present invention, the mass concentration of the passivating material in the passivating material solution is 0.2 mg / mL to 5 mg / mL; and / or, the thickness of the passivation layer is 0.4 nm to 2 nm; and / or, the method for preparing the passivation layer includes solution method or vapor deposition method; and / or, after the passivating material solution is coated onto the surface of the mesoporous spacer layer and penetrates into the surface of the pores of the mesoporous spacer layer, it is further subjected to annealing treatment at a temperature of 90°C to 110°C for a time of 8 min to 12 min.
[0007] In some embodiments of the present invention, the method for fabricating the mesoscopic perovskite solar cell includes the following steps: fabricating an electron transport layer on the surface of a conductive substrate; fabricating a mesoporous spacer layer on the surface of the electron transport layer away from the conductive substrate; fabricating the passivation layer; and then performing either Scheme 1 or Scheme 2: Scheme 1: fabricating a back electrode layer: fabricating the back electrode layer on the surface of the passivation layer away from the mesoporous spacer layer, the back electrode layer having a mesoporous structure; fabricating the perovskite active layer: coating the perovskite precursor solution onto the surface of the back electrode layer away from the passivation layer, and allowing the perovskite precursor solution to penetrate into the pores of the mesoporous spacer layer and crystallize to obtain the perovskite active layer.
[0008] Option 2: Preparation of the perovskite active layer: The perovskite precursor solution is coated onto the surface of the passivation layer away from the mesoporous spacer layer, and the perovskite precursor solution is allowed to penetrate into the pores of the mesoporous spacer layer and crystallize to obtain the perovskite active layer; Preparation of the back electrode layer: The back electrode layer is prepared on the surface of the perovskite active layer away from the mesoporous spacer layer.
[0009] In some embodiments of the present invention, the electron transport layer comprises a dense layer and a mesoporous layer stacked sequentially; and / or, the electron transport layer comprises titanium dioxide.
[0010] In some embodiments of the present invention, in Scheme 1: the back electrode layer includes at least one of carbon material and conductive oxide; and / or, after the preparation of the perovskite active layer is completed, an electron blocking layer precursor solution is permeated into the interface between the perovskite active layer and the back electrode layer to form an electron blocking layer.
[0011] In some embodiments of the present invention, in the second embodiment: the back electrode layer includes at least one of carbon material and conductive oxide; and / or, after the perovskite active layer is prepared, an electron blocking layer precursor solution is coated on the surface of the perovskite active layer away from the mesoporous spacer layer to prepare an electron blocking layer, and then the back electrode layer is prepared on the surface of the electron blocking layer away from the perovskite active layer.
[0012] In some embodiments of the present invention, the electron blocking layer precursor solution in Scheme 1 or Scheme 2 includes an electron blocking material, wherein the electron blocking material includes at least one of hexamethylene diisocyanate, malondiamide, phenyl diisocyanate, and phenyl diisothiocyanate.
[0013] The present invention also provides a mesoscopic perovskite solar cell, which is prepared by the method described above for preparing a mesoscopic perovskite solar cell.
[0014] In some embodiments of the present invention, the mesoscopic perovskite solar cell includes a conductive substrate, an electron transport layer, a mesoscopic support layer, a passivation layer covering the surface of the mesoscopic support layer and the inner wall surface of the pores, a perovskite active layer on the surface of the passivation layer and penetrating into the pores of the mesoscopic support layer, an electron blocking layer, and a back electrode layer, which are stacked sequentially.
[0015] The beneficial effects achievable by this invention are as follows: This invention prepares a passivation layer on the surface of the mesoporous spacer layer and the surface of the pore inner wall of the mesoporous solar cell. On the one hand, it can effectively reduce oxygen vacancies on the surface of the mesoporous spacer layer and suppress carrier recombination. On the other hand, it passivates the interface of the perovskite crystal, suppressing carrier recombination at the interface between the mesoporous spacer layer and the perovskite active layer, the interface between the perovskite active layer and the back electrode, and the interface between the perovskite active layer and the electron transport layer. Furthermore, it reduces the presence of carrier scattering centers at the interface between the mesoporous spacer layer and the perovskite active layer, thereby improving carrier transport lifetime, accelerating electron transport, and thus improving cell efficiency. Attached Figure Description
[0016] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art are briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the structures shown in these drawings without creative effort.
[0017] Figure 1 is a schematic diagram of the fabrication process of a mesoscopic perovskite solar cell according to an embodiment of the present invention.
[0018] The realization of the objective, functional features and advantages of the present invention will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation
[0019] It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
[0020] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.
[0021] In this invention, descriptions involving "first," "second," etc., are for descriptive purposes only and should not be construed as indicating or implying their relative importance or implicitly specifying the number of technical features indicated. Therefore, a feature defined as "first" or "second" may explicitly or implicitly include at least one of that feature. Furthermore, the technical solutions of the various embodiments can be combined with each other, but only on the basis of being achievable by those skilled in the art. If the combination of technical solutions is contradictory or impossible to implement, such a combination should be considered non-existent and not within the scope of protection claimed by this invention.
[0022] This invention provides a mesoscopic perovskite solar cell and its fabrication method. Referring to Figure 1, the fabrication method includes the following steps: S10, fabricating a mesoporous spacer layer; S20, fabricating a passivation layer: dissolving a passivation material to obtain a passivation material solution, coating the passivation material solution onto the surface of the mesoporous spacer layer and allowing it to penetrate into the pores of the mesoporous spacer layer to form a passivation layer; S30, fabricating a perovskite active layer: allowing a perovskite precursor solution to penetrate into the pores of the mesoporous spacer layer and crystallize to obtain a perovskite active layer, with the passivation layer located between the perovskite active layer and the mesoporous spacer layer; S40, fabricating a back electrode layer.
[0023] In this invention, a mesoscopic perovskite solar cell refers to a hybrid photovoltaic device that combines a mesoscopic scaffold material with a perovskite active layer. The mesoscopic perovskite solar cell achieves efficient photoelectric conversion by forming a composite structure in close contact between the insulating scaffold with a nanoporous structure and the perovskite material.
[0024] In this invention, the core function of the mesoporous spacer layer is to provide a framework structure to support the crystallization and permeation of the perovskite active layer.
[0025] In some embodiments, the mesoporous spacer layer includes an insulating material, which includes at least one of zirconium dioxide and alumina.
[0026] In some embodiments, the thickness of the mesoporous spacer layer is 400 nm to 5000 nm.
[0027] In some embodiments, the mesoporous spacer layer contains a mesoporous structure with an average pore size of 20 nm to 60 nm, which can provide a uniform filling space for the perovskite precursor solution, promote the directional growth of perovskite crystals, and reduce pores and defects.
[0028] This invention prepares a passivation layer on the surface of the mesoporous spacer layer and the surface of the pore inner wall of a mesoscopic perovskite solar cell. On the one hand, it can effectively reduce oxygen vacancies on the surface of the mesoporous spacer layer and suppress carrier recombination. On the other hand, it passivates the interface of the perovskite crystal, suppressing carrier recombination at the interface between the mesoporous spacer layer and the perovskite active layer, the interface between the perovskite active layer and the back electrode, and the interface between the perovskite active layer and the electron transport layer. Furthermore, it reduces the presence of carrier scattering centers at the interface between the mesoporous spacer layer and the perovskite active layer, thereby improving carrier transport lifetime, accelerating electron transport, and thus improving cell efficiency.
[0029] It should be noted that in this invention, after coating the surface of the mesoporous spacer layer with a passivation material solution, the passivation material solution will penetrate into the internal pores of the mesoporous spacer layer to form a passivation layer. The passivation layer covers the surface of the mesoporous support and the surface of the inner wall of the pores. Then, a perovskite active layer is prepared. The passivation layer can effectively passivate the perovskite crystal.
[0030] In some embodiments, the passivation material includes at least one of tri(triethylmethyl)ammonium phosphate, tetraethylammonium phosphate, benzyltriethylammonium phosphate, benzyltrimethylammonium phosphate, adamantyltrimethylammonium phosphate, (cyanomethyl)trimethylammonium phosphate, phenyltrimethylammonium phosphate, and an N-type self-assembly material, wherein the N-type self-assembly material includes at least one of sulfone-carbazole ethyl phosphate, thienylcarbazole ethyl phosphate, fullerene carboxylic acid, and fullerene phosphate. These passivation materials can effectively reduce oxygen vacancies in oxides on the surface of functional layers such as mesoporous spacers, reducing sites for carrier recombination, while simultaneously passivating the perovskite crystal and suppressing carrier recombination at the perovskite active layer interface.
[0031] In some embodiments, the mass concentration of the passivating material in the passivating material solution is 0.2 mg / mL to 5 mg / mL, and may be 0.5, 3 mg / mL, etc.
[0032] In some embodiments, the thickness of the passivation layer is 0.4 nm to 2 nm, and can be 1 nm, 2 nm, etc.
[0033] In some embodiments, the method for preparing the passivation layer includes a solution method or a vapor deposition method.
[0034] The solution method can be understood as dissolving the passivation material in a polar solvent, coating it onto the surface of the mesoporous spacer layer through liquid phase, and penetrating into the pores of the mesoporous spacer layer and the mesoporous layer below it.
[0035] In some embodiments, the coating method is a solution method, which includes spin coating, dip coating, inkjet printing, and screen printing.
[0036] In some embodiments, a passivation material solution is coated onto the surface of the mesoporous spacer layer away from the conductive substrate using a solution method, and the passivation material solution penetrates into the inner wall surface of the pores of the mesoporous spacer layer, followed by annealing to form a passivation layer.
[0037] Vapor deposition can be understood as the process of vaporizing a passivation material solution through physical or chemical means and depositing it onto the surface of the mesoporous spacer layer and the surface of the pore inner wall in a vacuum or carrier gas environment.
[0038] In some embodiments, vapor deposition methods include thermal evaporation, atomic layer deposition, or chemical vapor deposition.
[0039] In some embodiments, after the passivating material solution is coated onto the surface of the mesoporous spacer layer and penetrates into the pores of the mesoporous spacer layer, it is further subjected to an annealing treatment. The annealing treatment promotes the crystallization of the perovskite material. The annealing temperature is 90°C to 110°C, or it can be 100°C, and the annealing time is 8 min to 12 min, or it can be 10 min.
[0040] In some embodiments, the perovskite precursor solution comprises a perovskite material, which includes at least one of ABX3, MAPbI3, and FAPbI3, wherein the A in ABX3 includes MA. + FA + Cs + At least one of them.
[0041] In some embodiments, the solvent for dissolving perovskite materials to prepare perovskite precursor solutions includes at least one of isopropanone, dimethyl sulfoxide, and N,N-dimethylformamide.
[0042] In some embodiments, the method for fabricating a mesoscopic perovskite solar cell includes the following steps: fabricating an electron transport layer on the surface of a conductive substrate; fabricating a mesoporous spacer layer on the surface of the electron transport layer away from the conductive substrate; fabricating a passivation layer; and then performing either Scheme 1 or Scheme 2: Scheme 1: Fabricating a back electrode layer: fabricating a back electrode layer on the surface of the passivation layer away from the mesoporous spacer layer, the back electrode layer having a mesoporous structure; fabricating a perovskite active layer: coating a perovskite precursor solution onto the surface of the back electrode layer away from the passivation layer, and allowing the perovskite precursor solution to penetrate into the pores of the mesoporous spacer layer and crystallize to obtain the perovskite active layer.
[0043] Option 2: Preparation of perovskite active layer: Coating the perovskite precursor solution onto the surface of the passivation layer away from the mesoporous spacer layer, and allowing the perovskite precursor solution to penetrate into the pores of the mesoporous spacer layer and crystallize to obtain the perovskite active layer; Preparation of back electrode layer: Preparing a back electrode layer on the surface of the perovskite active layer away from the mesoporous spacer layer.
[0044] Option 1 involves first preparing a back electrode layer and then preparing a perovskite active layer. Therefore, the back electrode layer has a mesoporous structure. A perovskite precursor solution is coated on the surface of the back electrode layer away from the passivation layer. Then, the solution permeates through the mesopores of the back electrode layer into the pores of the mesoporous spacer layer and crystallizes to obtain the perovskite active layer.
[0045] Option 2 involves first preparing the perovskite active layer and then preparing the back electrode layer. Therefore, the back electrode layer does not need to contain a mesoporous structure.
[0046] In some embodiments, in Scheme 1: the back electrode layer includes at least one of carbon material and conductive oxide.
[0047] In some embodiments, in Scheme 1: after the perovskite active layer is prepared, an electron blocking layer precursor solution is infiltrated into the interface between the perovskite active layer and the back electrode layer to form an electron blocking layer. The electron blocking layer precursor solution infiltrates into the interface between the perovskite active layer and the back electrode layer and reacts with the surface of the perovskite crystal to form an electron blocking layer, which can further suppress carrier recombination at the interface between the perovskite active layer and the back electrode layer, thereby further improving the battery efficiency.
[0048] In some embodiments, the electron blocking layer precursor solution in Scheme 1 includes an electron blocking material, which includes hexamethylene diisocyanate.
[0049] In some embodiments, the mass concentration of the electron blocking layer precursor solution in Scheme 1 is 0.5 mg / mL to 1.0 mg / mL.
[0050] In some embodiments, in Scheme 2: the back electrode layer includes at least one of carbon material and conductive oxide.
[0051] In some embodiments, in Scheme 2: after the perovskite active layer is prepared, an electron blocking layer precursor solution is coated on the surface of the perovskite active layer away from the mesoporous spacer layer. The electron blocking material reacts with the surface of the perovskite active layer to obtain the electron blocking material. Then, a back electrode layer is prepared on the surface of the electron blocking layer away from the perovskite active layer. The electron blocking material can react with the surface of the perovskite active layer to form an electron blocking layer, thereby suppressing carrier recombination at the interface between the perovskite active layer and the back electrode layer.
[0052] In the step of preparing a mesoporous carbon electrode layer on the surface of the passivation layer, carbon material is deposited onto the surface of the passivation layer and then annealed at a temperature of 100℃~400℃.
[0053] In some embodiments, after the perovskite active layer is prepared, an electron blocking layer precursor solution is coated onto the surface of the mesoporous carbon electrode layer, penetrating into the perovskite active layer to obtain an electron blocking layer. In this embodiment, the penetrating electron blocking material can form a blocking layer between the particle surface of the carbon conductive network and the perovskite crystal.
[0054] In some embodiments, the electron blocking layer precursor solution includes an electron blocking material, which includes hexamethylene diisocyanate.
[0055] In some embodiments, the conductive substrate includes a transparent conductive oxide, which includes at least one of fluorine-doped tin oxide (FTO), indium-doped tin oxide (ITO), and aluminum-doped zinc oxide (AZO).
[0056] In some embodiments, the electron transport layer comprises a dense layer and a mesoporous layer stacked sequentially. The dense layer refers to a continuous, non-porous electron transport film with a density close to that of the bulk material, while the mesoporous layer refers to an electron transport film with a mesoporous structure. The dense layer achieves better electron transport properties, while the mesoporous layer can significantly increase the contact area with the perovskite active crystal, expand the charge transport interface, and improve electron extraction efficiency. Moreover, the nanopores of the mesoporous layer can serve as templates to promote the formation of oriented crystals in the perovskite, reduce grain boundary defects, and provide a flat substrate for the upper mesoporous spacer layer and the perovskite active layer.
[0057] In some embodiments, the thickness of the dense layer is 50±10 nm.
[0058] In some embodiments, the thickness of the mesoporous layer is 100 nm to 3 μm.
[0059] In some embodiments, the electron transport layer includes at least one of titanium dioxide and lanthanum-doped strontium stannate.
[0060] The present invention also provides a mesoscopic perovskite solar cell prepared by any of the above preparation methods.
[0061] In some embodiments, referring to FIG1, a mesoscopic perovskite solar cell includes a conductive substrate, an electron transport layer, a mesoscopic support layer, a passivation layer covering the surface of the mesoscopic support layer and the inner wall surface of the pores, a perovskite active layer on the surface of the passivation layer and penetrating into the pores of the mesoscopic support layer, an electron blocking layer, and a back electrode layer, which are stacked sequentially.
[0062] In some embodiments, the electron transport layer comprises a dense layer and a mesoporous layer stacked sequentially.
[0063] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following specific embodiments are only used to explain the present invention and are not intended to limit the present invention.
[0064] Example 1: Preparation of electron transport layer: A dense titanium dioxide layer with a thickness of 50 nm was deposited by spray pyrolysis on FTO conductive glass at 450 °C. Then, a mesoporous titanium dioxide layer with a thickness of 100 nm was deposited by screen printing and annealed at 500 °C to obtain a mesoporous carbon dioxide layer.
[0065] Preparation of mesoporous spacer layer: A 2.5 μm thick layer of mesoporous zirconium dioxide was screen-printed and deposited, sintered at 400 °C to obtain a mesoporous zirconium dioxide layer, and then cooled to room temperature.
[0066] Preparation of passivation layer: A sulfone-carbazole ethyl phosphate solution with a mass concentration of 1 mg / mL was deposited on the surface of the mesoporous zirconium dioxide layer. The sulfone-carbazole ethyl phosphate solution penetrated into the pores of the mesoporous zirconium dioxide layer. The passivation layer was obtained by annealing at 100 °C for 10 min.
[0067] Preparation of back electrode layer: A 25 μm thick mesoporous carbon material was deposited on the surface of the passivation layer away from the mesoporous spacer layer by screen printing. The material was then annealed at 150 °C for 30 min to obtain a back electrode layer with a mesoporous structure and cooled to room temperature.
[0068] Preparation of perovskite active layer: A perovskite precursor solution is coated on the surface of the back electrode layer, allowing the perovskite precursor solution to penetrate into the pores of the mesoporous zirconium dioxide layer. The perovskite precursor solution is then heated at 57°C for 20 hours to crystallize and obtain the perovskite active layer.
[0069] Preparation of electron blocking layer: Hexamethylene diisocyanate was dissolved in isopropanol to obtain a hexamethylene diisocyanate solution with a concentration of 0.5 mg / mL. The hexamethylene diisocyanate solution was deposited on the surface of the back electrode layer. The hexamethylene diisocyanate solution penetrated into the interface between the perovskite active layer and the back electrode layer to form an electron blocking layer, thereby preparing a mesoscopic perovskite solar cell.
[0070] Example 2: Preparation of electron transport layer: A dense titanium dioxide layer with a thickness of 50 nm was deposited on FTO conductive glass by spray pyrolysis at 450 °C. Then, a mesoporous titanium dioxide layer with a thickness of 800 nm was deposited by screen printing and annealed at 500 °C to obtain a mesoporous carbon dioxide layer. Preparation of mesoporous spacer layer: A mesoporous zirconium dioxide layer with a thickness of 2.5 μm was deposited by screen printing and sintered at 400 °C to obtain a mesoporous zirconium dioxide layer. The layer was then cooled to room temperature.
[0071] Preparation of passivation layer: A tetraethylammonium phosphate solution with a mass concentration of 1.5 mg / mL was deposited on the surface of the mesoporous zirconium dioxide layer. The sulfone carbazole ethyl phosphate solution penetrated into the pores of the mesoporous zirconium dioxide layer. The passivation layer was obtained by annealing at 100 °C for 30 min.
[0072] Preparation of back electrode layer: A 25 μm thick mesoporous carbon material was deposited by screen printing, and annealed at 200 °C for 30 min to obtain a back electrode layer with a mesoporous structure, and then cooled to room temperature.
[0073] Preparation of perovskite active layer: A perovskite precursor solution is coated on the surface of the back electrode layer, allowing the perovskite precursor solution to penetrate into the pores of the mesoporous zirconium dioxide layer. The perovskite precursor solution is then heated at 57°C for 20 hours to crystallize and obtain the perovskite active layer.
[0074] Preparation of electron blocking layer: malondiamine is dissolved in isopropanol to obtain a malondiamine solution with a concentration of 0.5 mg / mL. The malondiamine solution is deposited on the surface of the mesoporous carbon electrode. The malondiamine solution penetrates into the interface between the perovskite active layer and the mesoporous carbon particles to form an electron blocking layer, thereby preparing a mesoscopic perovskite solar cell.
[0075] Example 3: Preparation of electron transport layer: A dense titanium dioxide layer with a thickness of 50 nm was deposited on FTO conductive glass by spray pyrolysis at 400 °C. Then, a mesoporous titanium dioxide layer with a thickness of 1000 nm was deposited by screen printing and annealed at 500 °C to obtain a mesoporous carbon dioxide layer.
[0076] Preparation of mesoporous spacer layer: A 2.5 μm thick layer of mesoporous zirconium dioxide was screen-printed and deposited, sintered at 400 °C to obtain a mesoporous zirconium dioxide layer, and then cooled to room temperature.
[0077] Preparation of passivation layer: A fullerene carboxylic acid solution with a mass concentration of 0.5 mg / mL was deposited on the surface of the mesoporous zirconia layer. The fullerene carboxylic acid solution penetrated into the pores of the mesoporous zirconia layer. The passivation layer was obtained by annealing at 100 °C for 10 min and then cooled to room temperature.
[0078] Preparation of back electrode layer: A 25 μm thick mesoporous carbon material was deposited by screen printing, and annealed at 150 °C for 30 min to obtain a back electrode layer with a mesoporous structure, and then cooled to room temperature.
[0079] Preparation of perovskite active layer: A perovskite precursor solution is coated on the surface of the back electrode layer. The perovskite precursor solution penetrates into the pores of the mesoporous zirconium dioxide layer. The perovskite precursor solution is heated at 57°C for 20 h to crystallize and obtain the perovskite active layer.
[0080] Preparation of electron blocking layer: Benzene diisocyanate is dissolved in isopropanol to obtain a Benzene diisocyanate solution with a concentration of 2 mg / mL. The Benzene diisocyanate solution is deposited on the surface of the mesoporous carbon electrode layer. The Benzene diisocyanate solution penetrates into the interface between the perovskite active layer and the back electrode layer to form an electron blocking layer, thereby preparing a perovskite solar cell.
[0081] Example 4: Preparation of electron transport layer: A dense titanium dioxide layer with a thickness of 50 nm was deposited on FTO conductive glass by spray pyrolysis at 450 °C. Then, a mesoporous titanium dioxide layer with a thickness of 1000 nm was deposited by screen printing and annealed at 500 °C to obtain a mesoporous carbon dioxide layer.
[0082] Preparation of mesoporous spacer layer: A 2.5 μm thick layer of mesoporous zirconium dioxide was screen-printed and deposited, sintered at 400 °C to obtain a mesoporous zirconium dioxide layer, and then cooled to room temperature.
[0083] Preparation of passivation layer: A fullerene phosphate solution with a mass concentration of 1.5 mg / mL was deposited on the surface of the mesoporous zirconia layer by solution method. The fullerene phosphate solution penetrated into the pores of the mesoporous zirconia layer. The passivation layer was obtained by annealing at 100 °C for 10 min.
[0084] Preparation of back electrode layer: A layer of mesoporous carbon material with a surface thickness of 25 μm on the passivation layer away from the mesoporous spacer layer was deposited by screen printing, and then annealed at 400℃ for 30 min to obtain a back electrode layer with a mesoporous structure, and then cooled to room temperature.
[0085] Preparation of perovskite active layer: A perovskite precursor solution is coated on the surface of the back electrode layer, allowing the perovskite precursor solution to penetrate into the pores of the mesoporous zirconium dioxide layer. The perovskite precursor solution is then heated at 57°C for 20 hours to crystallize and obtain the perovskite active layer.
[0086] Preparation of electron blocking layer: Benzene diisothiocyanate is dissolved in isopropanol to obtain a Benzene diisothiocyanate solution with a concentration of 3 mg / mL. The Benzene diisothiocyanate solution is deposited on the surface of the back electrode layer. The Benzene diisothiocyanate solution penetrates into the interface between the perovskite active layer and the back electrode layer to form an electron blocking layer, thereby preparing a perovskite solar cell.
[0087] Example 5: In Example 5, an electron transport layer, a mesoporous spacer layer, and a passivation layer are prepared according to the method of Example 1. Then, a perovskite active layer is prepared. An electron blocking layer is prepared on the surface of the perovskite active layer away from the passivation layer. Then, a back electrode layer is prepared on the surface of the electron blocking layer away from the perovskite active layer. This back electrode layer has no mesoporous structure.
[0088] Comparative Example 1: A mesoscopic perovskite solar cell was prepared according to the preparation method of Example 1, except that no passivation layer was prepared in Comparative Example 1.
[0089] The performance of the mesoscopic perovskite solar cells in the test examples and comparative examples was recorded in Table 1.
[0090] Table 1
[0091] The above are merely preferred embodiments of the present invention and do not limit the scope of the patent. Any equivalent structural or procedural transformations made based on the description and drawings of the present invention, or direct or indirect applications in other related technical fields, are similarly included within the scope of patent protection of the present invention.
Claims
1. A method for fabricating a mesoscopic perovskite solar cell, characterized in that, Includes the following steps: Preparation of mesoporous spacer layers; Preparation of passivation layer: Dissolve the passivation material to obtain a passivation material solution, coat the passivation material solution onto the surface of the mesoporous spacer layer and allow it to penetrate into the pores of the mesoporous spacer layer to form a passivation layer; Preparation of perovskite active layer: Perovskite precursor solution is permeated into the pores of the mesoporous spacer layer and crystallized to obtain the perovskite active layer, and the passivation layer is between the perovskite active layer and the mesoporous spacer layer; Prepare the back electrode layer.
2. The method for preparing a mesoscopic perovskite solar cell according to claim 1, characterized in that, The passivation material includes at least one of tri(triethylmethyl)ammonium phosphate, tetraethylammonium phosphate, benzyltriethylammonium phosphate, benzyltrimethylammonium phosphate, adamantyltrimethylammonium phosphate, (cyanomethyl)trimethylammonium phosphate, and N-type self-assembly materials; and / or, the N-type self-assembly materials include at least one of sulfone-carbazole ethyl phosphate, thienylcarbazole ethyl phosphate, fullerene carboxylic acid, and fullerene phosphate; and / or, the mesoporous spacer layer includes at least one of zirconium dioxide and alumina.
3. The method for preparing a mesoscopic perovskite solar cell according to claim 1, characterized in that, The passivating material concentration in the passivating material solution is 0.2 mg / mL to 5 mg / mL; and / or, the thickness of the passivation layer is 0.4 nm to 2 nm; and / or, the method for preparing the passivation layer includes solution method or vapor deposition method; and / or, after the passivating material solution is coated onto the surface of the mesoporous spacer layer and penetrates into the surface of the pores of the mesoporous spacer layer, it is further subjected to annealing treatment at a temperature of 90°C to 110°C for a time of 8 min to 12 min.
4. The method for preparing a mesoscopic perovskite solar cell according to any one of claims 1 to 3, characterized in that, The method for fabricating the mesoscopic perovskite solar cell includes the following steps: fabricating an electron transport layer on the surface of a conductive substrate; fabricating a mesoporous spacer layer on the surface of the electron transport layer away from the conductive substrate; fabricating a passivation layer; and then performing either Scheme 1 or Scheme 2: Scheme 1: Fabricating a back electrode layer: fabricating a back electrode layer on the surface of the passivation layer away from the mesoporous spacer layer, the back electrode layer having a mesoporous structure; Fabricating the perovskite active layer: coating the perovskite precursor solution onto the surface of the back electrode layer away from the passivation layer, and allowing the perovskite precursor solution to penetrate into the pores of the mesoporous spacer layer and crystallize to obtain the perovskite active layer; Scheme 2: Fabricating the perovskite active layer: coating the perovskite precursor solution onto the surface of the passivation layer away from the mesoporous spacer layer, and allowing the perovskite precursor solution to penetrate into the pores of the mesoporous spacer layer and crystallize to obtain the perovskite active layer; Fabricating a back electrode layer: fabricating a back electrode layer on the surface of the perovskite active layer away from the mesoporous spacer layer.
5. The method for preparing a mesoscopic perovskite solar cell according to claim 4, characterized in that, The electron transport layer comprises a dense layer and a mesoporous layer stacked sequentially; and / or, the electron transport layer comprises titanium dioxide.
6. The method for preparing a mesoscopic perovskite solar cell according to claim 4, characterized in that, In the first embodiment: the back electrode layer includes at least one of carbon material and conductive oxide; and / or, after the perovskite active layer is prepared, an electron blocking layer precursor solution is infiltrated into the interface between the perovskite active layer and the back electrode layer to form an electron blocking layer.
7. The method for preparing a mesoscopic perovskite solar cell according to claim 4, characterized in that, In the second embodiment: the back electrode layer includes at least one of carbon material and conductive oxide; and / or, after the perovskite active layer is prepared, an electron blocking layer precursor solution is coated on the surface of the perovskite active layer away from the mesoporous spacer layer to prepare an electron blocking layer, and then the back electrode layer is prepared on the surface of the electron blocking layer away from the perovskite active layer.
8. The method for preparing a mesoscopic perovskite solar cell according to claim 6 or 7, characterized in that, The electron blocking layer precursor solution in Scheme 1 or Scheme 2 includes an electron blocking material, which includes at least one of hexamethylene diisocyanate, malondiamide, phenyl diisocyanate, and phenyl diisothiocyanate.
9. A mesoscopic perovskite solar cell, characterized in that, The mesoscopic perovskite solar cell is prepared by any of the methods described in claims 4 to 8.
10. The mesoscopic perovskite solar cell according to claim 9, characterized in that, The mesoscopic perovskite solar cell comprises, in sequence, a conductive substrate, an electron transport layer, a mesoscopic support layer, a passivation layer covering the surface of the mesoscopic support layer and the inner wall surface of the pores, a perovskite active layer on the surface of the passivation layer and penetrating into the pores of the mesoscopic support layer, an electron blocking layer, and a back electrode layer.