CN117812922A - Perovskite laminated solar cell structure and preparation method thereof - Google Patents
Perovskite laminated solar cell structure and preparation method thereof Download PDFInfo
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- 229910006404 SnO 2 Inorganic materials 0.000 description 1
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- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/84—Layers having high charge carrier mobility
- H10K30/85—Layers having high electron mobility, e.g. electron-transporting layers or hole-blocking layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/88—Passivation; Containers; Encapsulations
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Electromagnetism (AREA)
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention relates to the technical field of solar cells and discloses a perovskite laminated solar cell structure and a preparation method thereof. The composite electron transport layer and the composite packaging film layer are used for cooperatively inhibiting water and oxygen corrosion, enhancing the stability of the perovskite laminated solar cell structure, prolonging the service life, ensuring the migration of carriers in the cell body, improving the photoelectric conversion efficiency and the power generation efficiency, and being beneficial to industrialized development.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to a perovskite laminated solar cell structure and a preparation method thereof.
Background
The perovskite solar cell gradually goes to industrialization due to the advantages of high efficiency, adjustable band gap, simple process and the like, wherein the power generation efficiency of the perovskite laminated solar cell matched with the silicon-based cell is 33.9%, which is far higher than that of the existing crystalline silicon cell technology, and the perovskite solar cell is a photovoltaic type with the most potential in the future photovoltaic market due to the market characteristics of low cost of perovskite materials and low manufacturing equipment.
However, the greatest problem faced by the perovskite solar cell is that the instability, the external conditions such as water, oxygen and the like can accelerate the decomposition and failure of the material and cause the performance of other structural layers to be weakened, so that the service life of the perovskite solar cell is greatly reduced. At present, the main body with the largest proportion in the photovoltaic industry is still a crystalline silicon battery, and the sensitivity of a crystalline silicon material to water and oxygen is far lower than that of a perovskite material, so that a packaging structure and a packaging method applied to the crystalline silicon battery are not applicable to a perovskite type solar battery, and the industrialization of the perovskite type solar battery brings higher requirements to the existing battery structure and packaging technology.
Disclosure of Invention
In view of the above, the invention provides a perovskite laminated solar cell structure and a preparation method thereof, which are used for solving the problems that the conventional perovskite solar cell is easily corroded by water, oxygen and the like, the service life is greatly reduced, the stability and the power generation efficiency cannot be considered, and the industrialization is affected.
In a first aspect, the present invention provides a perovskite stacked solar cell structure comprising: the battery body comprises a basal layer, a first electrode layer arranged on one side surface of the basal layer, and a tunneling interconnection layer, a hole transmission layer, a perovskite layer, a composite electron transmission layer, a transparent conductive layer and a second electrode layer which are sequentially laminated on the other side surface of the basal layer, wherein the second electrode layer is provided with a hollowed-out area so that light rays are incident to the perovskite layer, the composite packaging film layer is coated on the outer surface of the battery body, and the composite packaging film layer is a parylene composite layer.
The beneficial effects are that: the perovskite laminated solar cell structure plays an internal blocking role through the composite electron transport layer in the perovskite laminated solar cell structure, and halogen ions, lead ions, silver ions and the like in the perovskite layer are blocked from moving in the cell, so that electrode corrosion and interface loss caused by internal ion migration are reduced; the composite packaging film layer is used as an external packaging structure, so that the internal materials of the perovskite laminated solar cell structure and the acceleration effect on ion migration are prevented from being corroded and decomposed by external water oxygen molecules, the overflow of iodine vapor and the like generated by decomposition of a perovskite phase is reduced, and the consumption of iodine is reduced. The method can cooperatively inhibit the water oxygen corrosion of the battery body, enhance the stability of the perovskite laminated solar cell structure and prolong the service life; in addition, the multi-layer composite electron transport layer can also improve the electron carrier migration performance of the battery body, further improve the photoelectric conversion efficiency and the power generation efficiency of the perovskite laminated solar cell structure, and is beneficial to industrialized development.
In an alternative embodiment, the composite encapsulation film layer comprises a type C parylene layer and a type F parylene layer; the C-type parylene layer is coated on the outer surface of the battery body, and the F-type parylene layer is coated on the outer surface of the C-type parylene layer, which is relatively far away from the battery body.
In the invention, the Parylene C has very low transmittance of water molecules and corrosive gases and higher light transmittance; the Parylene F has high dielectric strength and good thermal stability, the formed film is continuous, compact and pinhole-free, the short-term temperature resistance can reach 450 ℃, the long-term temperature resistance can reach 350 ℃, and the radiation resistance and the high temperature resistance are excellent, so that the composite packaging film layer formed by coating the Parylene F outside the Parylene C has high water resistance, high light transmittance, good ultraviolet aging resistance and high temperature resistance, and the composite electron transport layer inside the composite packaging film layer is beneficial to enhancing the stability of the perovskite laminated solar cell structure, prolonging the service life and providing reliability for long-term industrialized development.
In an alternative embodiment, the thickness of the type C parylene layer ranges from 10um to 1000um; the thickness of the F-type parylene layer ranges from 10um to 1000um.
In the invention, the composite packaging film layer formed in the thickness range can not only ensure good barrier performance, but also avoid the influence of the perovskite laminated solar cell structure on industrialization due to overlarge whole volume.
In an alternative embodiment, the composite electron transport layer includes, in a direction from the base layer toward the second electrode layer: the carbon 60 layer, the interface modification layer and the compact tin oxide layer are sequentially stacked.
In the invention, the interface modification layer made of the BCP material is inserted between the carbon 60 layer and the compact tin oxide layer, so that not only can the electron migration performance be remarkably improved, but also the photovoltaic performance of the perovskite laminated solar cell structure can be effectively improved. The compact tin oxide layer has good electron transmission performance, and can inhibit substances decomposed by perovskite phases from precipitating to damage the transparent conductive layer, so that the barrier performance is excellent. The composite electron transport layer formed by the carbon 60 layer, the interface modification layer and the dense tin oxide layer has excellent electron transport performance and barrier performance.
In an alternative embodiment, the thickness of the carbon 60 layer ranges from 2nm to 20nm; the thickness range of the interface modification layer is 2nm-20nm; the thickness of the compact tin oxide layer ranges from 10nm to 100nm.
In the invention, the overall thickness of the composite electron transport layer in the range can not influence the large-scale application of the perovskite laminated solar cell structure at the component end on the premise of ensuring the electron transport performance and the barrier performance.
In an alternative embodiment, the second electrode layer includes a gold electrode layer disposed on a portion of the transparent conductive layer and a silver electrode layer disposed on a side of the gold electrode layer relatively remote from the transparent conductive layer.
In the invention, the whole second electrode layer is arranged in a grid line structure, and the gap part is exposed out of the transparent conductive layer so as to ensure that external light can enter the perovskite layer. The second electrode layer is also provided with a composite structure, wherein the gold electrode layer has a conductive effect, and simultaneously has a blocking effect similar to a dense tin oxide layer for blocking ion migration due to a dense structure, so that the silver electrode layer is prevented from being corroded by a perovskite layer decomposition substance by serving as a barrier, and the stability of the battery structure is improved. In addition, the gold electrode layer can also be used as a seed layer for forming a silver electrode layer on the gold electrode layer, so that the excellent silver electrode layer is formed, the silver electrode layer is convenient for collecting current, and the current transmission and derivation performance of the second electrode layer are ensured.
In an alternative embodiment, the gold electrode layer has a thickness in the range of 1nm to 10nm; the thickness of the silver electrode layer ranges from 100nm to 1000nm.
In the invention, the thickness of the gold electrode layer is far smaller than that of the silver electrode layer, so that the cost is saved, and the method is beneficial to industrialized application and development.
In a second aspect, the present invention provides a method for preparing a perovskite stacked solar cell structure, which is used for preparing the perovskite stacked solar cell structure, and includes the following steps:
providing a base layer;
forming a first electrode layer on one side surface of the base layer;
forming a tunneling interconnection layer on the other side surface of the substrate layer;
forming a hole transport layer on a surface of the tunneling interconnection layer on a side facing away from the substrate layer;
forming a perovskite layer on a surface of the hole transport layer on a side facing away from the base layer;
forming a composite electron transport layer on a surface of the perovskite layer on a side facing away from the substrate layer;
forming a transparent conductive layer on a surface of the side of the composite electron transport layer facing away from the substrate layer;
forming a second electrode layer on the surface of one side of the transparent conductive layer, which is far away from the substrate layer, wherein the second electrode layer is provided with a hollowed-out area so that light rays are incident to the perovskite layer, and a battery body is formed;
and coating the outer surface of the battery body to form a composite packaging film layer, wherein the composite packaging film layer is a parylene composite layer.
The beneficial effects are that: preparing a composite electron transport layer in the battery body to prevent halogen ions, lead ions, silver ions and the like in the perovskite layer from moving in the battery, so that electrode corrosion and interface loss caused by internal ion migration are reduced; the composite packaging film layer is covered on the outer surface of the battery body to serve as an outer packaging structure, so that the internal materials of the perovskite laminated solar cell structure and the acceleration effect on ion migration are prevented from being corroded and decomposed by external water oxygen molecules, the overflow of iodine vapor and the like generated by the decomposition of the perovskite phase is reduced, and the consumption of iodine is reduced. The inside and outside cooperation inhibits the water oxygen corrosion, enhances the stability of the perovskite laminated solar cell structure and prolongs the service life; in addition, the multi-layer composite electron transport layer can also improve the electron carrier migration performance of the battery body, further improve the photoelectric conversion efficiency and the power generation efficiency of the perovskite laminated solar cell structure, and is beneficial to industrialized development.
In an alternative embodiment, the coating of the outer surface of the battery body to form a composite packaging film layer comprises:
coating the outer surface of the battery body to form a C-type parylene layer;
and the outer surface of the C-shaped parylene layer, which is far away from the battery body, is coated with the F-shaped parylene layer.
In an alternative embodiment, forming the second electrode layer on a side surface of the transparent conductive layer facing away from the base layer includes:
forming a gold electrode layer on a part of the surface of the transparent conductive layer on the side facing away from the substrate layer;
a silver electrode layer is formed on a surface of the gold electrode layer facing away from the base layer.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic structural view of a perovskite stacked solar cell structure according to an embodiment of the invention;
FIG. 2 is a schematic structural view of a perovskite stacked solar cell module according to an embodiment of the invention;
FIG. 3 is a schematic flow chart of a method for fabricating a perovskite stacked solar cell structure according to an embodiment of the invention;
fig. 4 is a schematic flow chart of a method for fabricating a perovskite stacked solar cell structure according to an embodiment of the invention.
Reference numerals illustrate:
11. a base layer; 12. a first electrode layer; 13. tunneling the interconnect layer; 14. a hole transport layer; 15. a perovskite layer; 16. a composite electron transport layer; 161. a carbon 60 layer; 162. an interface modification layer; 163. a dense tin oxide layer; 17. a transparent conductive layer; 18. a second electrode layer; 181. a gold electrode layer; 182. a silver electrode layer;
20. a composite packaging film layer; 21. c-parylene layer; 22. f-parylene layer;
30. and (5) packaging the cover plate.
Detailed Description
The invention is described in further detail below with reference to the drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the invention and are not limiting thereof. It should be further noted that, for convenience of description, only some, but not all of the structures related to the present invention are shown in the drawings. In the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the concepts of the present invention. Various structural schematic diagrams according to embodiments of the present invention are shown in the accompanying drawings. The figures are not drawn to scale, wherein certain details are exaggerated for clarity of presentation and may have been omitted. The shapes of the various regions, layers and relative sizes, positional relationships between them shown in the drawings are merely exemplary, may in practice deviate due to manufacturing tolerances or technical limitations, and one skilled in the art may additionally design regions/layers having different shapes, sizes, relative positions as actually required. In the context of the present invention, when a layer/element is referred to as being "on" another layer/element, it can be directly on the other layer/element or intervening layers/elements may be present therebetween. In addition, if one layer/element is located "on" another layer/element in one orientation, that layer/element may be located "under" the other layer/element when the orientation is turned.
Due to the excellent performance and economic benefits of the perovskite material, the perovskite laminated solar cell structure formed by matching with the silicon-based cell in the perovskite solar cell is the most potential photovoltaic cell type in the future photovoltaic market due to the excellent photoelectric conversion efficiency. However, the perovskite type solar cell has a biggest problem in that the perovskite phase is unstable, and organic materials in the perovskite type solar cell are easily decomposed by reacting with moisture and oxygen in the atmosphere, thereby resulting in a decrease in stability and service life of the cell.
In the related art, a single mode of adding a barrier layer or an external protective film in a battery structure is generally adopted to isolate external influences such as water vapor, but the mode is often accompanied with the reduction of efficiency while improving the stability, so that the industrialization of the perovskite type solar cell is not facilitated.
Therefore, the embodiment of the invention provides a perovskite laminated solar cell structure and a preparation method thereof, wherein the composite electron transport layer 16 is arranged inside the cell body, and the composite packaging film layer 20 is arranged on the outer surface of the cell body so as to achieve the effect of cooperatively inhibiting water oxygen corrosion inside and outside, alleviate cell degradation at multiple angles, enhance cell stability, ensure cell photoelectric conversion efficiency and improve the industrialization level of the perovskite laminated solar cell structure.
The perovskite stacked solar cell structure provided in this embodiment, as shown in fig. 1, includes: the battery body comprises a substrate layer 11, a first electrode layer 12 arranged on one side surface of the substrate layer 11, and a tunneling interconnection layer 13, a hole transmission layer 14, a perovskite layer 15, a composite electron transmission layer 16, a transparent conductive layer 17 and a second electrode layer 18 which are sequentially laminated on the other side surface of the substrate layer 11, wherein the second electrode layer 18 is provided with a hollowed-out area so that light rays are incident on the perovskite layer 15, the composite packaging film layer 20 is coated on the outer surface of the battery body, and the composite packaging film layer 20 is a parylene composite layer.
In this embodiment, the light receiving side is the side of the battery body where the second electrode layer 18 is located.
The base layer 11 of the battery body in this embodiment is a narrow bandgap silicon-based heterojunction battery as a bottom battery, and may be a copper indium gallium selenide battery, a PERC (Passivated Emitter and Rear Cell, passivation emitter and back) battery, a TOPCON (Tunnel Oxide Passivated Contact, tunneling oxide passivation contact) battery, a glass substrate, or the like.
The first electrode layer 12 may be a metal electrode layer, for example, made of a metal material having superior conductivity such as gold, silver, etc., to serve as a cathode of the battery body.
The tunneling interconnection layer 13 may be a transparent conductive oxide (Transparent Conductive Oxide, hereinafter referred to as TCO) coated on the upper surface of the base layer 11, and the TCO may be Indium Tin Oxide (ITO), zinc oxide (ZnO), tin oxide (SnO) 2 ) The tunneling interconnection layer 13 of the embodiment is a TCO film layer with a thickness of 10nm-1000nm, and the tunneling interconnection layer 13 plays a role of connecting a lower bottom cell and an upper perovskite cell, so that the tunneling interconnection layer 13 has good contact performance.
The hole transport layer 14 is a self-assembled monolayer (hereinafter referred to as SAM), specifically a non-conjugated SAM (MeO-2 PACz), and has a chemical formula: (2- (3, 6-dimethoxy-9H-carbazol-9-yl) ethyl) phosphonic acid, SAM has molecular designability, excellent mechanical flexibility, no need of dopant, negligible light transmittance loss, large-area scalability and conformal and lossless electrical contact as hole transport layer 14, thus has good hole carrier transport performance, and the SAM layer thickness of this example is 5nm-50nm.
The perovskite layer 15 is made of a wide-bandgap perovskite material, the bandgap is approximately equal to 1.60 ev, and the wide-bandgap perovskite material of various corresponding ABX3 structures in the current mainstream can be selected, wherein the a-site ions comprise cesium ions, methylamine ions and formamidine ions, the B-site ions are lead ions, and the C-site ions are mixed components of I ions and Br ions. The perovskite layer 15 of the present embodiment has a thickness of 100nm to 1000nm.
The composite electron transport layer 16 may be an inorganic metal oxide material such as a layer including titanium oxide, zinc oxide, tin oxide, or the like, or a C60 layer. The composite electron transport layer 16 is disposed inside the cell structure, for example, when the composite electron input layer is made of a material including a dense electron input layer, the multilayer structure can block the movement of halogen ions, lead ions, silver ions, etc. in the perovskite layer 15 inside the cell, thereby reducing electrode corrosion and interface loss due to internal ion migration; in addition, it is very important that the multi-layered composite electron transport layer 16 can ensure good electron transfer performance, and further ensure photoelectric conversion efficiency and power generation efficiency of the perovskite stacked solar cell structure.
The transparent conductive layer 17 is a TCO film layer, and may be any one of Indium Tin Oxide (ITO), zinc Oxide (ZnO), tin Oxide (SnO 2), indium Zinc Oxide (IZO), and is used for collecting lateral current, and has the functions of isolating air and protecting the underlying film layer, and in this embodiment, the thickness of the transparent conductive layer 17 is 100nm-1000nm.
The second electrode layer 18 may be a metal electrode layer made of a metal material having superior conductivity such as gold and silver, so as to collect and transmit current. The second electrode layer 18 of the present embodiment is disposed on the transparent conductive layer 17 in a line-shaped structure, i.e., a grid line, at intervals to serve as an anode of the battery body.
The composite packaging film layer 20 is a composite layer of Parylene (Parylene) series materials, the Parylene materials are thin, the property is stable, a uniform and conformal film is easy to form, good isolation and protection performance and transmittance are considered, and the Parylene polymer film has good ultraviolet ageing resistance and high temperature performance. The composite packaging film layer 20 is coated on the battery body in a film form, so that the whole outer surface of the battery body is covered in a surrounding manner, and the internal materials of the battery body and the acceleration effect on ion migration of the perovskite laminated solar cell structure are prevented from being corroded and decomposed by external water oxygen molecules.
Therefore, the perovskite laminated solar cell structure of the embodiment plays an internal blocking role through the composite electron transport layer 16 in the perovskite laminated solar cell structure, and the halogen ions, lead ions, silver ions and the like in the perovskite layer 15 are blocked from moving in the cell, so that electrode corrosion and interface loss caused by internal ion migration are reduced; by using the composite packaging film layer 20 as an external packaging structure, the internal materials of the perovskite stacked solar cell structure and the acceleration effect on ion migration are prevented from being corroded and decomposed by external water oxygen molecules, the overflow of iodine vapor and the like generated by the decomposition of the perovskite phase is reduced, and the consumption of iodine is reduced. The inside and outside cooperation inhibits the water oxygen corrosion, enhances the stability of the perovskite laminated solar cell structure and prolongs the service life; in addition, the multi-layer composite electron transport layer 16 can also improve the electron carrier mobility of the battery body, further improve the photoelectric conversion efficiency and the power generation efficiency of the perovskite stacked solar cell structure, and is beneficial to the industrialized development.
In this embodiment, the composite packaging film layer 20 includes a Parylene layer 21 (Parylene C) and a Parylene layer 22 (Parylene efs); the C-type parylene layer 21 (parylene C) is coated on the outer surface of the battery body, and the F-type parylene layer 22 (parylene F) is coated on the outer surface of the C-type parylene layer 21 (parylene C).
Parylene c has very low water molecule and corrosive gas transmission rates and high light transmission rates; the parylene-F has high dielectric strength and good thermal stability, the formed film is continuous, compact and pinhole-free, the short-term temperature resistance can reach 450 ℃, the long-term temperature resistance can reach 350 ℃, and the radiation resistance and the high temperature resistance are excellent, so that the composite packaging film layer 20 formed by coating the parylene-F outside the parylene-E has high water resistance, high light transmittance, good ultraviolet aging resistance and high temperature resistance, and the composite electron transport layer 16 inside the composite packaging film layer is beneficial to enhancing the stability of the perovskite laminated solar cell structure, prolonging the service life and providing reliability for long-term industrialized development.
Specifically, the thickness of the C-type parylene layer 21 ranges from 10um to 1000um; the thickness of the F-type parylene layer 22 ranges from 10um to 1000um, and the composite packaging film layer 20 formed in the thickness range can not only ensure good barrier performance, but also avoid the influence of the perovskite laminated solar cell structure on industrialization due to overlarge whole volume.
In one embodiment, the composite electron transport layer 16 includes a carbon 60 layer 161, an interface modification layer 162, and a dense tin oxide layer 163 sequentially laminated in a direction from the base layer 11 toward the second electrode layer 18, i.e., from bottom to top.
The interface modification layer 162 is made of an organic material BCP, the Chinese name is 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline, and the interface modification layer 162 made of the BCP material is inserted between the carbon 60 layer 161 and the compact tin oxide layer 163, so that not only can the electron migration performance be remarkably improved, but also the photovoltaic performance of the perovskite laminated solar cell structure can be effectively improved. The carbon 60 layer 161 (abbreviated as C60 layer) is a common electron transport layer material, and will not be described in detail in this embodiment. The dense tin oxide layer 163 is prepared by an ALD atomic layer deposition method, has good electron transport performance, can inhibit substances decomposed by perovskite phases from precipitating and damaging the transparent conductive layer 17, and has excellent barrier performance.
The composite electron transport layer 16 formed by the combination of the carbon 60 layer 161, the interface modification layer 162 and the dense tin oxide layer 163 has excellent electron transport properties and barrier properties.
Specifically, the thickness of the carbon 60 layer 161 ranges from 2nm to 20nm; the thickness of the interface modification layer 162 ranges from 2nm to 20nm; the dense tin oxide layer 163 has a thickness in the range of 10nm to 100nm. Within this range, the overall thickness of the composite electron transport layer 16, while guaranteeing electron transport and barrier properties, does not affect the large-scale application of the perovskite stacked solar cell structure at the module end.
As a preferred embodiment, the second electrode layer 18 includes a gold electrode layer 181 and a silver electrode layer 182, the gold electrode layer 181 being disposed on a portion of the transparent conductive layer 17, the silver electrode layer 182 being disposed on a side surface of the gold electrode layer 181 relatively distant from the transparent conductive layer 17.
The second electrode layer 18 is integrally provided in a grid line structure, and the gap portion exposes the transparent conductive layer 17 to ensure that external light can enter the perovskite layer 15. The second electrode layer 18 is also provided as a metal composite structure, wherein the gold electrode layer 181 has a conductive effect, and also has a blocking effect similar to the dense tin oxide layer 163 for blocking ion migration, and acts as a barrier to prevent the decomposed substances of the perovskite layer 15 from corroding the silver electrode layer 182, thereby improving the stability of the cell structure. In addition, the gold electrode layer 181 may also be used as a seed layer on which the silver electrode layer 182 is formed, which facilitates the formation of an excellent silver electrode layer 182, facilitates the collection of current by the silver electrode layer 182, and ensures the current transmission and derivation performance of the second electrode layer 18.
Specifically, the thickness of the gold electrode layer 181 ranges from 1nm to 10nm; the silver electrode layer 182 has a thickness in the range of 100nm to 1000nm. The thickness of the gold electrode layer 181 is far smaller than that of the silver electrode layer 182, so that the cost is saved, and the industrialized application and development are facilitated.
When the perovskite stacked solar cell structures are interconnected and applied at the module end, the external composite packaging film layer 20 can be coated on the outer surface of the whole connected plurality of cell bodies, as shown in fig. 2, and a packaging cover plate 30 and other structures can be arranged outside the composite packaging film layer 20 to form the perovskite stacked solar cell module.
The embodiment also provides a method for preparing a perovskite stacked solar cell structure, which is used for preparing the perovskite stacked solar cell structure, and fig. 3 is a flowchart of a method for preparing a perovskite stacked solar cell structure according to an embodiment of the invention, as shown in fig. 3, and the flowchart includes the following steps:
in step S301, the base layer 11 is provided.
The substrate layer 11 is a narrow bandgap silicon-based heterojunction cell, and the fabrication method is a conventional heterojunction cell process, which is not described in this embodiment.
In step S302, the first electrode layer 12 is formed on one surface of the base layer 11.
The first electrode layer 12 in the form of a grid is formed on the lower surface of the base layer 11 by vapor deposition, and the first electrode layer 12 may be a metal electrode layer made of a metal material having excellent conductivity such as gold or silver, and may serve as a cathode of the battery body.
In step S303, the tunnel interconnection layer 13 is formed on the other side surface of the base layer 11.
The tunneling interconnection layer 13 is prepared on the upper surface of the substrate layer 11, and the tunneling interconnection layer 13 is a TCO metal oxide film layer, typically prepared by Physical Vapor Deposition (PVD) or Atomic Layer Deposition (ALD). The tunneling interconnect layer 13 in this embodiment is a TCO film layer with a thickness between 10nm and 1000nm deposited on the silicon-based heterojunction bottom cell by PVD magnetron sputtering technique.
In step S304, a hole transport layer 14 is formed on a surface of the tunnel interconnect layer 13 facing away from the base layer 11.
And coating and preparing a hole transport layer 14 on the upper surface of the tunneling interconnection layer 13, wherein the hole transport layer 14 is a self-assembled monolayer SAM with the thickness ranging from 5nm to 50nm prepared by adopting a wet chemical coating method.
In step S305, the perovskite layer 15 is formed on the surface of the hole transport layer 14 on the side facing away from the base layer 11.
The perovskite layer 15 is prepared on the upper surface of the hole transport layer 14, and the perovskite layer 15 is prepared by adopting a coating or vapor deposition mode, and the thickness range of the perovskite layer 15 is 100nm-1000nm.
In step S306, a composite electron transport layer 16 is formed on a surface of the perovskite layer 15 facing away from the base layer 11.
The composite electron transport layer 16 is prepared on the upper surface of the perovskite layer 15, the composite electron transport layer 16 can comprise a carbon 60 layer 161, an interface modification layer 162 and a compact tin oxide layer 163, and the multilayer composite electron transport layer 16 can ensure good electron migration performance, further has good barrier effect, ensures the stability and efficiency of the titanium-ore laminated solar cell, and prolongs the service life.
In step S307, the transparent conductive layer 17 is formed on the surface of the side of the composite electron transport layer 16 facing away from the base layer 11.
And preparing a transparent conductive layer 17 on the upper surface of the composite electronic layer, wherein the transparent conductive layer 17 is a TCO film layer with the thickness of 100-1000 nm prepared by utilizing a magnetron sputtering technology.
In step S308, a metal electrode layer is formed on a surface of the transparent conductive layer 17 facing away from the substrate layer 11, wherein the metal electrode layer has a hollowed-out area so that light is incident on the perovskite layer 15.
A second electrode layer 18 is formed on a part of the upper surface of the transparent conductive layer 17, and the second electrode layer 18 may be a metal electrode layer formed in a shape similar to a grid line which is arranged at intervals, so as to form a hollowed-out area for light incidence. The second electrode layer 18 may be, for example, a silver electrode layer 182, and the silver electrode layer 182 may be prepared by a thermal evaporation method.
The preparation of the battery body is completed, and then the packaging layer is prepared outside the battery body.
Step S309, the outer surface of the battery body is coated with a composite packaging film layer 20, and the composite packaging film layer 20 is a parylene composite layer.
The composite packaging film layer 20 is a composite layer of Parylene (Parylene) series materials, and is coated on the outer surface of the battery body in a film mode by chemical vapor deposition at room temperature.
The perovskite laminated solar cell structure is prepared by the method, and the composite electron transport layer 16 is prepared in the cell to prevent halogen ions, lead ions, silver ions and the like in the perovskite layer 15 from moving in the cell, so that electrode corrosion and interface loss caused by internal ion migration are reduced; the composite packaging film layer 20 is covered on the outer upper surface of the battery structure as an outer packaging structure, so that the internal materials of the perovskite laminated solar cell structure and the acceleration effect on ion migration are prevented from being corroded and decomposed by external water oxygen molecules, the overflow of iodine vapor and the like generated by decomposition of the perovskite phase is reduced, and the consumption of iodine is reduced. The inside and outside cooperation inhibits the water oxygen corrosion, enhances the stability of the perovskite laminated solar cell structure and prolongs the service life; in addition, the multi-layer composite electron transport layer 16 can also improve the electron carrier mobility in the battery, further improve the photoelectric conversion efficiency and the power generation efficiency of the perovskite stacked solar cell structure, and is beneficial to the industrialized development.
On the basis of the above scheme, as shown in fig. 4, this embodiment also provides a complete preparation method of a perovskite stacked solar cell structure, in which:
the step S306 includes:
in step S3061, the carbon 60 layer 161 is formed on a surface of the perovskite layer 15 facing away from the base layer 11.
A carbon 60 layer 161 having a thickness of 2nm to 20nm is prepared on the upper surface of the perovskite layer 15 by a thermal evaporation method for realizing electron transport.
In step S3062, an interface modification layer 162 is formed on the side of the carbon 60 layer 161 facing away from the base layer 11.
The interface modification layer 162 is an organic material BCP, and the Chinese name is 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline. An interface modification layer 162 having a thickness of 2nm to 20nm is prepared on the upper surface of the carbon 60 layer 161 by a thermal evaporation method to achieve efficient electron transport between the carbon 60 layer 161 and the dense tin oxide layer 163.
In step S3063, a dense tin oxide layer 163 is formed on the interface modification layer 162 on the side facing away from the base layer 11.
The dense tin oxide layer 163 is prepared on the upper surface of the interface modification layer 162 by an atomic layer deposition (Atomic Layer Deposition, abbreviated as ALD) method, the thickness and the composition of the film are precisely controlled, a dense film structure on the nanometer scale is formed, the thickness range of the dense tin oxide layer 163 formed in the embodiment is 10nm-100nm, and the transparent conductive layer 17 can be prevented from being damaged by precipitation of substances decomposed by perovskite phases while the electron transport performance is good.
The step S308 includes:
in step S3081, a gold electrode layer 181 is formed on a portion of the surface of the transparent conductive layer 17 on the side facing away from the base layer 11.
A gate-line-shaped gold electrode layer 181 having a thickness ranging from 1nm to 10nm was prepared on the upper surface of the transparent conductive layer 17 by a thermal evaporation method. The gold electrode layer 181 has a conductive effect and a dense structure, and also has a similar barrier effect to the dense tin oxide layer 163 for blocking ion migration, and serves as a barrier to prevent the decomposed substances of the perovskite layer 15 from corroding the silver electrode layer 182, thereby improving the stability of the battery. Further, the gold electrode layer 181 may also serve as a seed layer on which the silver electrode layer 182 is formed, contributing to the formation of an excellent silver electrode layer 182.
In step S3082, a silver electrode layer 182 is formed on a surface of the gold electrode layer 181 facing away from the base layer 11.
Silver electrode layer 182 with thickness ranging from 100nm to 1000nm is prepared on the upper surface of gold electrode layer 181 by thermal evaporation method, so that silver electrode layer 182 is convenient for collecting current, and current transmission and export performance of the metal electrode layer are ensured.
The thickness of the gold electrode layer 181 is far smaller than that of the silver electrode layer 182, for example, the gold electrode layer 181 with the thickness of 1nm and the silver electrode layer 182 with the thickness of 100nm are prepared, so that the cost is saved, and the industrialized application and development are facilitated.
The step S309 includes:
in step S3091, the outer surface of the battery body is coated with the C-type parylene layer 21.
The C-type parylene layer 21 having a thickness of 10um to 1000um is prepared on the outer surface of the battery body at room temperature by chemical vapor deposition.
In step S2082, an F-type parylene layer 22 is formed by wrapping the outer surface of the C-type parylene layer 21 facing away from the battery body.
And preparing an F-type parylene layer 22 with the thickness of 10-1000 um on the outer surface of the C-type parylene layer 21 by adopting a chemical vapor deposition method at room temperature.
The composite packaging film layer 20 formed by coating the Parylene F on the outer layer of the Parylene C has high water resistance, high light transmittance, good ultraviolet aging resistance and high temperature performance, and the composite electron transmission layer 16 inside the composite packaging film layer is beneficial to enhancing the stability of the perovskite laminated solar cell structure, prolonging the service life and providing reliability for long-term industrialized development.
The rest of the steps are detailed in the embodiment shown in fig. 3, and will not be described in detail herein.
In the above description, technical details of patterning, etching, and the like of each layer are not described in detail. Those skilled in the art will appreciate that layers, regions, etc. of the desired shape may be formed by a variety of techniques. In addition, to form the same structure, those skilled in the art can also devise methods that are not exactly the same as those described above. In addition, although the embodiments are described above separately, this does not mean that the measures in the embodiments cannot be used advantageously in combination.
Although embodiments of the present invention have been described in connection with the accompanying drawings, various modifications and variations may be made by those skilled in the art without departing from the spirit and scope of the invention, and such modifications and variations fall within the scope of the invention as defined by the appended claims.
Claims (10)
1. A perovskite stacked solar cell structure comprising:
the battery body comprises a basal layer (11), a first electrode layer (12) arranged on one side surface of the basal layer (11), and a tunneling interconnection layer (13), a hole transmission layer (14), a perovskite layer (15), a composite electron transmission layer (16), a transparent conductive layer (17) and a second electrode layer (18) which are sequentially laminated on the other side surface of the basal layer (11), wherein the second electrode layer (18) is provided with a hollowed-out area so that light rays are incident on the perovskite layer (15);
the composite packaging film layer (20), the composite packaging film layer (20) is coated on the outer surface of the battery body, and the composite packaging film layer (20) is a parylene composite layer.
2. The perovskite-stacked solar cell structure according to claim 1, wherein the composite encapsulation film layer (20) comprises a C-type parylene layer (21) and an F-type parylene layer (22);
the C-type parylene layer (21) is coated on the outer surface of the battery body, and the F-type parylene layer (22) is coated on the outer surface, relatively far away from the battery body, of the C-type parylene layer (21).
3. The perovskite-stacked solar cell structure according to claim 2, characterized in that the thickness of the C-type parylene layer (21) ranges from 10um to 1000um; the thickness of the F-type parylene layer (22) ranges from 10um to 1000um.
4. The perovskite-stacked solar cell structure according to claim 1, characterized in that the composite electron transport layer (16) comprises, in a direction from the base layer (11) towards the second electrode layer (18): the carbon 60 layer (161), the interface modification layer (162) and the dense tin oxide layer (163) are laminated in this order.
5. The perovskite-stacked solar cell structure according to claim 4, characterized in that the thickness of the carbon 60 layer (161) ranges from 2nm to 20nm; the thickness of the interface modification layer (162) ranges from 2nm to 20nm; the dense tin oxide layer (163) has a thickness in the range of 10nm to 100nm.
6. The perovskite-stacked solar cell structure according to any one of claims 1-5, wherein the second electrode layer (18) comprises a gold electrode layer (181) and a silver electrode layer (182), the gold electrode layer (181) being disposed on a portion of the transparent conductive layer (17), the silver electrode layer (182) being disposed on a side of the gold electrode layer (181) that is opposite from the transparent conductive layer (17).
7. The perovskite-stacked solar cell structure according to claim 6, characterized in that the thickness of the gold electrode layer (181) ranges from 1nm to 10nm; the thickness of the silver electrode layer (182) ranges from 100nm to 1000nm.
8. A method for producing a perovskite stacked solar cell structure as claimed in any one of claims 1 to 7, comprising:
providing a substrate layer (11);
forming a first electrode layer (12) on one side surface of the base layer (11);
forming a tunneling interconnection layer (13) on the other side surface of the base layer (11);
forming a hole transport layer (14) on a surface of the tunneling interconnection layer (13) on a side facing away from the base layer (11);
forming a perovskite layer (15) on a surface of the hole transport layer (14) on a side facing away from the substrate layer (11);
-forming a composite electron transport layer (16) on a surface of the perovskite layer (15) facing away from the substrate layer (11);
forming a transparent conductive layer (17) on a surface of the composite electron transport layer (16) on a side facing away from the base layer (11);
forming a second electrode layer (18) on the surface of one side of the transparent conductive layer (17) facing away from the substrate layer (11), wherein the second electrode layer (18) is provided with a hollowed-out area so that light rays are incident to the perovskite layer (15) to form a battery body;
and the outer surface of the battery body is coated with a composite packaging film layer (20), and the composite packaging film layer (20) is a parylene composite layer.
9. The method for manufacturing a perovskite stacked solar cell structure according to claim 8, wherein the coating of the outer surface of the cell body to form a composite encapsulation film layer (20) comprises:
coating the outer surface of the battery body to form a C-type parylene layer (21);
and the outer surface of the C-shaped parylene layer (21) deviating from the battery body is coated with an F-shaped parylene layer (22).
10. A method of manufacturing a perovskite-stack solar cell structure according to claim 8 or 9, characterized in that the forming of the second electrode layer (18) on a side surface of the transparent conductive layer (17) facing away from the substrate layer (11) comprises:
forming a gold electrode layer (181) on a part of the surface of the transparent conductive layer (17) on the side facing away from the base layer (11);
a silver electrode layer (182) is formed on a surface of the gold electrode layer (181) on a side facing away from the base layer (11).
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| CN121001548A (en) * | 2025-10-23 | 2025-11-21 | 浙江大学 | Perovskite photovoltaic devices and their fabrication methods |
| WO2026002269A1 (en) * | 2024-06-28 | 2026-01-02 | 安徽华晟新能源科技股份有限公司 | Zoned down-conversion composite adhesive film and preparation method therefor, and perovskite heterojunction tandem cell |
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| WO2026002269A1 (en) * | 2024-06-28 | 2026-01-02 | 安徽华晟新能源科技股份有限公司 | Zoned down-conversion composite adhesive film and preparation method therefor, and perovskite heterojunction tandem cell |
| CN121001548A (en) * | 2025-10-23 | 2025-11-21 | 浙江大学 | Perovskite photovoltaic devices and their fabrication methods |
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