CN116669449A - Perovskite solar cell, preparation method thereof and electric equipment - Google Patents

Perovskite solar cell, preparation method thereof and electric equipment Download PDF

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Publication number
CN116669449A
CN116669449A CN202310965029.2A CN202310965029A CN116669449A CN 116669449 A CN116669449 A CN 116669449A CN 202310965029 A CN202310965029 A CN 202310965029A CN 116669449 A CN116669449 A CN 116669449A
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layer
barrier layer
solar cell
hole transport
perovskite solar
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张帆
苏硕剑
刘泽政
林翔玲
李晗芳
郭永胜
陈国栋
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Contemporary Amperex Technology Co Ltd
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Contemporary Amperex Technology Co Ltd
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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
    • 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
    • H10K30/40—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising a p-i-n structure, e.g. having a perovskite absorber between p-type and n-type charge transport 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
    • H10K30/50—Photovoltaic [PV] devices
    • 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
    • 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 application discloses a perovskite solar cell, a preparation method thereof and electric equipment, wherein the perovskite solar cell comprises the following components: and a barrier layer provided on a side of the hole transport layer remote from the substrate, wherein the barrier layer is made of at least one of polystyrene, polymethyl methacrylate, polyethylenimine, polyethylene glycol diacrylate, [2- (9H-carbazole-9-yl) ethyl ] phosphonic acid, [2- (3, 6-dimethoxy-9H-carbazole-9-yl) ethyl ] phosphonic acid, [2- (3, 6-diphenyl-9H-carbazole-9-yl) ethyl ] phosphonic acid, [4- (9H-carbazole-9-yl) butyl ] phosphonic acid, [4- (3, 6-dimethoxy-9H-carbazole-9-yl) butyl ] phosphonic acid, [4- (3, 6-dimethyl-9H-carbazole-9-yl) butyl ] phosphonic acid, 2- (3, 4-dihydroxyphenyl) ethylamine, pyridine propane sulfonate, 4- (diphenylamino) butyric acid, 1,3, 5-tris (4-carboxyphenyl) benzene, p-toluenesulfonyl hydrazine, p-cyanobenzoic acid or perylene.

Description

Perovskite solar cell, preparation method thereof and electric equipment
Technical Field
The application relates to the field of batteries, in particular to a perovskite solar cell, a preparation method thereof and electric equipment.
Background
Perovskite solar cells have received much attention for their excellent photovoltaic properties such as tunable band gap, higher light absorption coefficient, longer carrier lifetime and diffusion length, higher defect tolerance, low-cost low-temperature liquid phase preparation method, etc. Within a short decade, the efficiency of perovskite solar cells has increased from 3.8% to over 25%, showing great potential. However, the hole transport layer of the perovskite solar cell is distributed with high-valence cations, which can cause degradation of the perovskite layer, reducing the long-term stability of the perovskite solar cell.
Disclosure of Invention
In view of the technical problems existing in the background art, the perovskite solar cell provided by the application can reduce the probability of direct contact between the hole transport layer and the perovskite layer and improve the long-term stability of the perovskite solar cell.
A first aspect of the application provides a perovskite solar cell comprising: a substrate; a hole transport layer provided on one side of the substrate; a barrier layer disposed on a side of the hole transport layer remote from the substrate, the material of the barrier layer comprising at least one of polystyrene, polymethyl methacrylate, polyethylenimine, polyethylene glycol diacrylate, [2- (9H-carbazol-9-yl) ethyl ] phosphonic acid, [2- (3, 6-dimethoxy-9H-carbazol-9-yl) ethyl ] phosphonic acid, [2- (3, 6-diphenyl-9H-carbazol-9-yl) ethyl ] phosphonic acid, [4- (9H-carbazol-9-yl) butyl ] phosphonic acid, [4- (3, 6-dimethoxy-9H-carbazol-9-yl) butyl ] phosphonic acid, [4- (3, 6-dimethyl-9H-carbazol-9-yl) butyl ] phosphonic acid, 2- (3, 4-dihydroxyphenyl) ethylamine, pyridinium propane sulfonate, 4- (diphenylamino) butyric acid, 1,3, 5-tris (4-carboxyphenyl) benzene, p-toluenesulfonyl, p-cyanobenzoic acid, or perylene hydrazine; the perovskite layer is arranged on one side of the barrier layer away from the hole transport layer; and the electrode layer is arranged on one side of the perovskite layer, which is away from the barrier layer.
According to the perovskite solar cell provided by the application, the blocking layer is arranged between the hole transmission layer and the perovskite layer, and the blocking layer comprises the materials, so that the probability of reaction caused by contact between the materials of the perovskite layer and high-valence cations distributed on the surface of the hole transmission layer, which is close to the perovskite layer, is reduced, the risk of degradation of the perovskite layer is reduced, the long-term stability of the perovskite layer is improved, the service life of the perovskite solar cell is prolonged, and meanwhile, the transmission capacity of holes can be improved by the materials of the blocking layer, so that the energy conversion efficiency of the perovskite solar cell is improved.
According to some embodiments of the application, the barrier layer further comprises: at least one of polythiophene and its derivatives, polyaniline and its derivatives, or polypyrrole and its derivatives. Thereby, the hole transport capacity of the barrier layer is improved, and the energy conversion rate of the perovskite solar cell is improved.
According to some embodiments of the application, the material of the barrier layer comprises polythiophene and its derivatives, including at least one of poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid), poly 3-hexylthiophene, poly (3-octylthiophene-2, 5-diyl), poly-diketopyrrolopyrrole-thiophene, or poly-thiophene-pyrrolopyrrole-dione.
According to some embodiments of the application, the material of the barrier layer comprises polyaniline and derivatives thereof, including poly [ bis (4-phenyl) (4-butylphenyl) amine.
According to some embodiments of the application, the material of the barrier layer comprises polypyrrole and its derivatives, including mercapto-polypyrrole.
Therefore, when the material of the barrier layer comprises the material, the probability that the material of the perovskite layer reacts due to contact with high-valence cations distributed on the surface of the hole transport layer, which is close to the perovskite layer, can be reduced, and meanwhile, the hole transport capacity of the barrier layer is improved, and the energy conversion rate of the perovskite solar cell is improved.
According to some embodiments of the application, the barrier layer comprises-c=o, -NH in the material 2 At least one of =nh, -s=o, -c≡n, -p=o, -SH, -Cl, -Br, -I, or-F. Therefore, the end groups are distributed on the surface of the barrier layer, which is close to the perovskite layer, and have lone pair electrons, so that defects existing in the perovskite layer can be passivated, and the efficiency of the perovskite solar cell is improved.
According to some embodiments of the application, the barrier layer has a thickness of 1nm to 1000nm.
According to some embodiments of the application, the barrier layer has a thickness of 1nm to 100nm.
According to some embodiments of the application, the barrier layer has a thickness of 1nm to 50nm.
According to some embodiments of the application, the barrier layer has a thickness of 1nm to 30nm.
Therefore, when the thickness of the barrier layer is in the range, the uniformity of the barrier layer can be improved, the probability that the material of the perovskite layer contacts with high-valence cations distributed on the surface of the hole transport layer, which is close to the perovskite layer, to react is further reduced, and the service life of the perovskite solar cell is prolonged.
According to some embodiments of the application, the hole transport layer material comprises nickel oxide. Therefore, the blocking layer can reduce the probability of deprotonation reaction between the material of the perovskite layer and nickel ions on the surface of the hole transport layer, and the service life of the perovskite solar cell is prolonged.
According to some embodiments of the application, the nickel oxide includes a doping cation therein. This improves the mobility of carriers in the hole transport layer and improves the energy conversion rate of the perovskite solar cell.
According to some embodiments of the applicationThe doping cation comprises Li + 、Cs + 、Ag + 、Mg 2+ 、Ca 2+ 、Zn 2+ 、Sr 2+ 、Ba 2+ 、Fe 2+ 、Fe 3+ 、Co 2+ 、Co 3+ 、Cu + Or Cu 2+ At least one of them.
According to some embodiments of the application, the ratio of the molar ratio of the doping cations to the nickel ions is between 0.01 and 0.2. Therefore, the conductivity of the hole transport layer is improved, the hole transport layer can be well matched with the valence band top of the perovskite layer, and the capability of extracting carriers from the perovskite layer by the hole transport layer is improved.
According to some embodiments of the application, the ratio of the molar ratio of the doping cations to the nickel ions is between 0.01 and 0.05.
In a second aspect, the application provides a method of making a perovskite solar cell comprising: forming a hole transport layer on one side of the substrate; forming a blocking layer on a side of the hole transport layer away from the substrate, wherein the blocking layer comprises at least one of polystyrene, polymethyl methacrylate, polyethylenimine, polyethylene glycol diacrylate, [2- (9H-carbazole-9-yl) ethyl ] phosphonic acid, [2- (3, 6-dimethoxy-9H-carbazole-9-yl) ethyl ] phosphonic acid, [2- (3, 6-diphenyl-9H-carbazole-9-yl) ethyl ] phosphonic acid, [4- (9H-carbazole-9-yl) butyl ] phosphonic acid, [4- (3, 6-dimethoxy-9H-carbazole-9-yl) butyl ] phosphonic acid, [4- (3, 6-dimethyl-9H-carbazole-9-yl) butyl ] phosphonic acid, [2- (3, 4-dihydroxyphenyl) ethylamine, pyridinium propane sulfonate, 4- (diphenylamino) butyric acid, 1,3, 5-tris (4-carboxyphenyl) benzene, p-toluenesulfonyl hydrazine, p-cyanobenzoic acid or perylene; forming a perovskite layer on one side of the barrier layer away from the hole transport layer; an electrode layer is formed on a side of the perovskite layer remote from the barrier layer. Therefore, the prepared perovskite solar cell is provided with the barrier layer between the hole transmission layer and the perovskite layer, and the barrier layer comprises the materials, so that the probability of reaction caused by contact between the materials of the perovskite layer and high-valence cations distributed on the surface of the hole transmission layer, which is close to the perovskite layer, can be reduced, the risk of degradation of the perovskite layer is reduced, the long-term stability of the perovskite layer is improved, and the service life of the perovskite solar cell is prolonged. Meanwhile, the material of the blocking layer can also improve the hole transmission capability so as to improve the energy conversion efficiency of the perovskite solar cell.
According to some embodiments of the application, the method of forming the barrier layer on a side of the hole transport layer remote from the substrate comprises: and cleaning and drying the surface of the hole transport layer, which is far away from the substrate, by adopting a self-assembly solution, wherein the self-assembly solution comprises the material of the barrier layer so as to obtain the barrier layer. Therefore, a blocking layer is formed in the process of cleaning the cavity transmission layer, so that the preparation process of the perovskite solar cell is simplified, and the production cost is reduced.
According to some embodiments of the application, the mass concentration of the material of the barrier layer in the self-assembling solution is 0.1mg/mL to 100mg/mL. Thus, the series resistance of the perovskite solar cell is reduced, and a uniform barrier layer is formed between the hole transport layer and the perovskite layer.
According to some embodiments of the application, the mass concentration of the material of the barrier layer in the self-assembling solution is 0.1mg/mL to 10mg/mL.
According to some embodiments of the application, the time of the washing is 10s-3600s. Therefore, the uniformity of the barrier layer is improved, the probability of reaction caused by contact between the material of the perovskite layer and high-valence cations distributed on the surface of the hole transport layer, which is close to the perovskite layer, is further reduced, and the service life of the perovskite solar cell is prolonged.
According to some embodiments of the application, the self-assembling solution further comprises a solvent comprising at least one of deionized water, diethyl ether, pentane, methylene chloride, acetone, chloroform, methanol, hexane, benzene, toluene, o-xylene, p-xylene, aniline, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, 1,2, 4-trifluorobenzene, benzotrifluoride, iodobenzene, acetic acid, ethyl acetate, cyclohexane, ethanol, isopropanol, N-propanol, 2-methoxyethanol, acetonitrile, N-butanol, azobisisobutyronitrile, tetrahydrofuran, N-dimethylformamide, dimethylsulfoxide, or N-methylpyrrolidone.
According to some embodiments of the application, the method of preparing the perovskite solar cell further comprises: after the surface of the hole transport layer remote from the substrate is rinsed with the self-assembly solution, the surface of the hole transport layer remote from the substrate is rinsed with an anti-solvent. Therefore, the solvent of the self-assembled solution is extracted, and a barrier layer can be formed after the solvent is dried, so that the uniformity of the barrier layer is further improved, the probability that the material of the perovskite layer contacts with high-valence cations distributed on the surface of the hole transport layer, which is close to the perovskite layer, to react is reduced, and the service life of the perovskite solar cell is prolonged.
According to some embodiments of the application, the antisolvent comprises at least one of deionized water, diethyl ether, pentane, dichloromethane, acetone, chloroform, methanol, hexane, benzene, toluene, o-xylene, p-xylene, aniline, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, 1,2, 4-trifluorobenzene, benzotrifluoride, iodobenzene, acetic acid, ethyl acetate, cyclohexane, ethanol, isopropanol, N-propanol, 2-methoxyethanol, acetonitrile, N-butanol, azobisisobutyronitrile, tetrahydrofuran, N-dimethylformamide, dimethyl sulfoxide, or N-methylpyrrolidone.
According to some embodiments of the application, the hole transport layer material comprises nickel oxide. Therefore, the blocking layer can reduce the probability of deprotonation reaction between the material of the perovskite layer and nickel ions of the hole transport layer, and the service life of the perovskite solar cell is prolonged.
The third aspect of the application provides electric equipment, which comprises the perovskite solar cell provided by the first aspect of the application or the perovskite solar cell prepared by the method provided by the second aspect of the application. Therefore, the electric equipment has good long-term stability and long service life.
Additional aspects and advantages of the application will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the application.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the application. Also, like reference numerals are used to designate like parts throughout the accompanying drawings. In the drawings:
FIG. 1 is a schematic structural view of a perovskite solar cell according to one embodiment of the application;
fig. 2 is a schematic flow chart of a perovskite solar cell preparation according to one embodiment of the application.
Reference numerals illustrate:
1: perovskite solar cell; 11: a substrate; 12: a hole transport layer; 13: a barrier layer; 14: a perovskite layer; 15: an electrode layer.
Detailed Description
Embodiments of the technical scheme of the present application are described in detail below. The following examples are only for more clearly illustrating the technical aspects of the present application, and thus are merely examples, and are not intended to limit the scope of the present application.
Reference herein to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment may be included in at least one embodiment of the application. The appearances of such phrases in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. Those of skill in the art will explicitly and implicitly appreciate that the embodiments described herein may be combined with other embodiments.
For simplicity, only a few numerical ranges are specifically disclosed herein. However, any lower limit may be combined with any upper limit to form a range not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and any upper limit may be combined with any other upper limit to form a range not explicitly recited. Furthermore, each separately disclosed point or individual value may itself be combined as a lower limit or upper limit with any other point or individual value or with other lower limit or upper limit to form a range not explicitly recited.
In the description of the embodiments of the present application, the term "and/or" is merely an association relationship describing an association object, and indicates that three relationships may exist, for example, a and/or B may indicate: a exists alone, A and B exist together, and B exists alone. In addition, the character "/" herein generally indicates that the front and rear associated objects are an "or" relationship.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs; the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application; the terms "comprising" and "having" and any variations thereof in the description of the application and the claims and the description of the drawings above are intended to cover a non-exclusive inclusion.
With the increasing severity of global ecological environment and energy shortage problems, solar photovoltaic power generation is receiving a great deal of attention. Perovskite solar cells are used as third-generation novel solar cells, and become a new star which is raised in the field of solar cells by virtue of the advantages of low cost, simple preparation process, high efficiency and the like. However, in the preparation process of the perovskite solar cell, high-valence cations are distributed on the surface of the formed hole transport layer, the high-valence cations are equivalent to a Bronsted base, and deprotonation reaction occurs when the high-valence cations are contacted with the perovskite layer, so that degradation of the perovskite layer is caused, the long-term stability of the perovskite layer is influenced, and the service life of the perovskite solar cell is influenced.
According to the perovskite solar cell, the blocking layer is arranged between the hole transmission layer and the perovskite layer, and the material of the perovskite layer is designed, so that the probability of reaction caused by contact of the material of the perovskite layer and high-valence cations distributed on the surface of the hole transmission layer, which is close to the perovskite layer, can be reduced, the risk of degradation of the perovskite layer is reduced, the long-term stability of the perovskite layer is improved, and the service life of the perovskite solar cell is prolonged. Meanwhile, through screening the blocking layer material, the blocking layer can play a role in blocking, and meanwhile, the hole transmission capacity can be improved, so that the energy conversion efficiency of the perovskite solar cell is improved.
The perovskite solar cell disclosed by the embodiment of the application belongs to a photovoltaic cell, and can be used as a power supply of electric equipment, and can also be assembled into a photovoltaic power generation system and store electric energy in an energy storage system formed by energy storage batteries. The electric equipment may include street lamps, signal indicator lamps, deinsectization lamps, electric fans, electric toys, electric tools, battery cars, electric automobiles, ships, spacecrafts and the like, wherein the electric toys may include fixed or mobile electric toys, such as game machines, electric automobile toys, electric ship toys, electric plane toys and the like, and the spacecrafts may include planes, rockets, space planes, space ships and the like; the photovoltaic power generation system can comprise a large ground photovoltaic power generation system, a distributed photovoltaic power generation and building integrated photovoltaic power generation system and the like.
A first aspect of the application provides a perovskite solar cell 1, referring to fig. 1, comprising: a substrate 11; a hole transport layer 12, the hole transport layer 12 being provided on one side of the substrate 11; a blocking layer 13, the blocking layer 13 being disposed on a side of the hole transport layer 12 remote from the substrate 11, the blocking layer 13 material including Polystyrene (PS), polymethyl methacrylate (PMMA), polyethylenimine (PEI), polyethylene glycol (PEG), polyethylene glycol diacrylate (PEGDA), [2- (9H-carbazol-9-yl) ethyl ] phosphonic acid, [2- (3, 6-dimethoxy-9H-carbazol-9-yl) ethyl ] phosphonic acid, [2- (3, 6-diphenyl-9H-carbazol-9-yl) ethyl ] phosphonic acid, [4- (9H-carbazol-9-yl) butyl ] phosphonic acid, [4- (3, 6-dimethoxy-9H-carbazol-9-yl) butyl ] phosphonic acid, [4- (3, 6-dimethyl-9H-carbazol-9-yl) butyl ] phosphonic acid, [2- (3, 4-dihydroxyphenyl) ethylamine, propane pyridinium sulfonate, 4- (diphenylamino) butyric acid, 1,3, 5-tris (4-carboxyphenyl) benzenesulfonyl) p-toluenesulfonyl, or p-toluenesulfonyl; a perovskite layer 14, the perovskite layer 14 being provided on a side of the barrier layer 13 remote from the hole transport layer 12; an electrode layer 15, said electrode layer 15 being arranged on the side of said perovskite layer 14 remote from said barrier layer 13.
According to the perovskite solar cell 1 provided by the application, the blocking layer 13 is arranged between the hole transmission layer 12 and the perovskite layer 14, and the blocking layer 13 comprises the materials, so that the probability of reaction caused by contact between the materials of the perovskite layer 14 and high-valence cations distributed on the surface of the hole transmission layer 12 close to the perovskite layer 14 can be reduced, the risk of degradation of the perovskite layer 14 is reduced, the long-term stability of the perovskite layer 14 is improved, and the service life of the perovskite solar cell 1 is prolonged. At the same time, the material of the blocking layer 13 may also improve the hole transporting ability to improve the energy conversion efficiency of the perovskite solar cell 1.
According to some embodiments of the application, the material of the barrier layer 13 may further comprise: at least one of polythiophene and its derivatives, polyaniline and its derivatives, or polypyrrole and its derivatives. According to some embodiments of the present application, the material of the hole transport layer 12 may also include at least one of polythiophene and its derivatives, polyaniline and its derivatives, or polypyrrole and its derivatives. Thus, the material forming the hole transport layer 12 can also form the barrier layer 13, thereby improving the hole transport ability of the barrier layer 13 and the energy conversion rate of the perovskite solar cell 1. According to some embodiments of the application, the polythiophene and its derivatives include at least one of poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid)) (PEDOT: PSS), poly 3-hexylthiophene (P3 HT), poly (3-octylthiophene-2, 5-diyl), poly-bithiophene pyrrolopyrrolidinone-thiophene, or poly-thiophene-pyrrolopyrrolidinone. According to some embodiments of the application, the polyaniline and its derivatives include at least one of Poly [ bis (4-phenyl) (4-butylphenyl) amine (Poly-TPD) or Poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ]. According to some embodiments of the application, the polypyrrole and its derivatives include sulfhydryl-polypyrrole.
According to some embodiments of the application, the barrier layer 13 may comprise-C=O, -NH in its material 2 At least one of =nh, -s=o, -c≡n, -p=o, -SH, -Cl, -Br, -I, or-F. For example, 2- (9H-carbazol-9-yl) ethyl) phosphonic acid, [2- (3, 6-dimethoxy-9H-carbazol-9-yl) ethyl ]]Phosphonic acid, [2- (3, 6-diphenyl-9H-carbazol-9-yl) ethyl ]]Phosphonic acid, [4- (9H-carbazol-9-yl) butyl ]]Phosphonic acid, [4- (3, 6-dimethoxy-9H-carbazole-9)-yl) butyl]Phosphonic acid, [4- (3, 6-dimethyl-9H-carbazol-9-yl) butyl ]]Phosphonic acid includes-p=o, propane sulfonic acid pyridinium includes-s=o, 2- (3, 4-dihydroxyphenyl) ethylamine includes-NH 2 4- (diphenylamino) butyric acid, 1,3, 5-tris (4-carboxyphenyl) benzene include-c=o, p-toluenesulfonyl hydrazide include=nh, and p-cyanobenzoic acid include-c≡n. Thereby, the end group with lone pair electrons is exposed on the surface of the barrier layer 13 close to the perovskite layer 14, so that defects existing in the area of the perovskite layer 14 close to the barrier layer 13 are passivated, and the efficiency of the perovskite solar cell 1 is improved.
According to some embodiments of the application, the thickness of the barrier layer 13 is 1nm-1000nm, for example, may be 1nm, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm or 1000nm, or may be in the range of any of the values mentioned above.
The thickness test method in the application comprises the following steps: testing by a step instrument or an ellipsometer: according to the thickness of the barrier layer 13, in order to improve the accuracy of the test, a step meter is used for testing when the thickness of the barrier layer 13 is 100nm-1000nm, and an ellipsometer is used for testing when the thickness of the barrier layer 13 is 1nm-100 nm.
According to some embodiments of the present application, when the material of the barrier layer 13 includes at least one of polythiophene and its derivatives, polyaniline and its derivatives, or polypyrrole and its derivatives, the thickness of the barrier layer 13 may be 1nm to 100nm, for example, may be 1nm, 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, etc., or may be in a range of any of the numerical compositions mentioned above.
According to further embodiments of the present application, when the material of the barrier layer 13 comprises at least one of [2- (9H-carbazol-9-yl) ethyl ] phosphonic acid, [2- (3, 6-dimethoxy-9H-carbazol-9-yl) ethyl ] phosphonic acid, [2- (3, 6-diphenyl-9H-carbazol-9-yl) ethyl ] phosphonic acid, [4- (9H-carbazol-9-yl) butyl ] phosphonic acid, [4- (3, 6-dimethoxy-9H-carbazol-9-yl) butyl ] phosphonic acid, [4- (3, 6-dimethyl-9H-carbazol-9-yl) butyl ] phosphonic acid, 2- (3, 4-dihydroxyphenyl) ethylamine, pyridinium propane sulfonate, 4- (diphenylamino) butyric acid, 1,3, 5-tris (4-carboxyphenyl) benzene, p-toluenesulfonyl hydrazine, p-cyanobenzoic acid or perylene, the thickness of the barrier layer 13 may be 1nm to 50nm, for example, may be 1nm, 5nm, 10nm, 15nm, 25nm, 30nm, or any of the above, or other values.
According to other embodiments of the present application, when the material of the barrier layer 13 includes at least one of polystyrene or polymethyl methacrylate, the thickness of the barrier layer 13 may be 1nm to 30nm, for example, may be 1nm, 5nm, 10nm, 15nm, 20nm, 25nm, 30nm, or the like, or may be in a range of any of the above values.
Therefore, the blocking layer with the thickness can improve the uniformity of the blocking layer 13, further reduce the probability of the material of the perovskite layer 14 to react due to contact with high-valence cations distributed on the surface of the hole transport layer 12 close to the perovskite layer 14, improve the long-term stability of the perovskite layer 14 and prolong the service life of the perovskite solar cell 1.
According to some embodiments of the application, the material of the hole transport layer 12 may comprise nickel oxide. Thus, the hole transporting ability can be improved. In addition, when high-valence nickel ions are distributed on the surface of the hole transmission layer 12, which is close to the barrier layer 13, the barrier layer 13 in the perovskite solar cell 1 provided by the application can reduce the probability of reaction caused by contact between the material of the perovskite layer 14 and the high-valence nickel ions distributed on the surface of the hole transmission layer 12, which is close to the perovskite layer 14, reduce the risk of degradation of the perovskite layer 14, improve the long-term stability of the perovskite layer 14 and prolong the service life of the perovskite solar cell 1.
According to some embodiments of the present application, the hole transport layer 12 may further include doped cations to increase the mobility of carriers within the hole transport layer 12 and to increase the energy conversion rate of the perovskite solar cell 1. According to some embodiments of the application, the doping cations include Li + 、Cs + 、Ag + 、Mg 2+ 、Ca 2+ 、Zn 2+ 、Sr 2+ 、Ba 2+ 、Fe 2+ 、Fe 3+ 、Co 2+ 、Co 3 + 、Cu + Or Cu 2+ At least one of them.
According to some embodiments of the application, the ratio of the molar ratio of the doping cation to the nickel ion in the nickel oxide may be 0.01-0.2, for example, may be 0.01, 0.04, 0.07, 0.1, 0.13, 0.16, 0.18, or 0.2, etc., or may be a range of any of the numerical compositions mentioned above. Thereby, the conductivity of the hole transport layer 12 is improved, the hole transport layer 12 can be better matched with the valence band top of the perovskite layer 14, and the capability of the hole transport layer 12 to extract carriers from the perovskite layer 14 is improved. According to some embodiments of the application, the ratio of the molar ratio of the doping cations to the nickel ions may be between 0.01 and 0.05.
According to some embodiments of the present application, the material of the electrode layer 15 may include at least one of silver, copper, carbon, gold, aluminum, indium tin oxide, tungsten doped indium oxide, aluminum doped zinc oxide, boron doped zinc oxide, or indium zinc oxide.
According to some embodiments of the application, the material of the perovskite layer 14 may include a PBX 3 Or P 2 CDX 6 Wherein P comprises an organic cation, li + 、Na + 、K + 、Rb + Or Cs + At least one of (a) and (b); b includes Pb 2+ 、Sn 2+ 、Be 2+ 、Mg 2+ 、Ca 2+ 、Sr 2+ 、Ba 2+ 、Zn 2+ 、Ge 2+ 、Fe 2+ 、Co 2+ 、Cu 2+ And Ni 2+ At least one of (a) and (b); c includes Cs + 、Ag + 、K + Or Ru (Rust) + At least one of (a) and (b); d comprises Bi 3+ 、Ni 3+ 、Fe 3+ 、Cu 3+ 、Sb 3+ Or In 3+ At least one of (a) and (b); x includes Br - Or I - At least one of them. For example, the material of the perovskite layer 14 may be CH 3 NH 3 PbI 3 ，CH 3 NH 3 SnI 3 ，CH 3 NH 3 PbI 2 Br，CH 3 NH 3 Pb（I 1- x Br x ） 3 (wherein 0<x<1). According to the present applicationIn some embodiments of the application, B may include Pb 2+ Or Sn (Sn) 2+ At least one of them. According to some embodiments of the application, C may comprise Ag + 。
The second aspect of the present application provides a method of producing a perovskite solar cell 1, comprising: providing a substrate 11; forming a hole transport layer 12 on one side of the substrate 11; forming a blocking layer 13 on a side of the hole transport layer 12 remote from the substrate 11, wherein a material of the blocking layer 13 includes at least one of polystyrene, polymethyl methacrylate, polyethyleneimine, polyethylene glycol diacrylate, [2- (9H-carbazol-9-yl) ethyl ] phosphonic acid, [2- (3, 6-dimethoxy-9H-carbazol-9-yl) ethyl ] phosphonic acid, [2- (3, 6-diphenyl-9H-carbazol-9-yl) ethyl ] phosphonic acid, [4- (9H-carbazol-9-yl) butyl ] phosphonic acid, [4- (3, 6-dimethoxy-9H-carbazol-9-yl) butyl ] phosphonic acid, [4- (3, 6-dimethyl-9H-carbazol-9-yl) butyl ] phosphonic acid, 2- (3, 4-dihydroxyphenyl) ethylamine, pyridinium propane sulfonate, 4- (diphenylamino) butyric acid, 1,3, 5-tris (4-carboxyphenyl) benzene, p-toluenesulfonyl, p-cyanobenzoic acid, or perylene hydrazine; a perovskite layer 14 is formed on the side of the barrier layer 13 remote from the hole transport layer 12. The perovskite solar cell 1 prepared by the method is provided with the barrier layer 13 between the hole transport layer 12 and the perovskite layer 14, so that the probability of reaction caused by contact of the material of the perovskite layer 14 and high-valence cations distributed on the surface of the hole transport layer 12 close to the perovskite layer 14 can be reduced, the risk of degradation of the perovskite layer 14 is reduced, the long-term stability of the perovskite layer 14 is improved, and the service life of the perovskite solar cell 1 is prolonged. At the same time, the material of the blocking layer 13 may also improve the hole transporting ability to improve the energy conversion efficiency of the perovskite solar cell 1.
The steps of the method are described in detail below, with reference to fig. 2, the method comprising:
s100: forming a hole transport layer on a substrate
According to some embodiments of the present application, the substrate 11 may include transparent conductive glass including at least one of fluorine doped tin dioxide (FTO), indium Tin Oxide (ITO), tungsten doped indium oxide (IWO), aluminum doped zinc oxide (AZO), boron doped zinc oxide (BZO), or Indium Zinc Oxide (IZO).
According to some embodiments of the application, the hole transport layer 12 may be formed by magnetron sputtering.
According to some embodiments of the application, the material of the hole transport layer 12 may also include nickel oxide. Specifically, the hole transport layer 12 may be formed on the substrate 11 by magnetron sputtering.
S200: forming a barrier layer on the side of the hole transport layer away from the substrate
According to some embodiments of the present application, the method of forming the blocking layer 13 on the side of the hole transport layer 12 remote from the substrate 11 includes: the surface of the hole transport layer 12 remote from the substrate 11 is cleaned and dried with a self-assembling solution comprising a material of the barrier layer 13 and a solvent to obtain the barrier layer 13. Specifically, when the self-assembly solution cleans the substrate on which the hole transport layer 12 is formed, the material forming the barrier layer 13 in the self-assembly solution forms the barrier layer 13 by self-assembly. Thereby, the barrier layer 13 is formed in the process of cleaning the hole transport layer 12, simplifying the manufacturing process of the perovskite solar cell 1, and reducing the production cost.
According to some embodiments of the present application, before the substrate 11 on which the hole transport layer 12 is formed is washed with the self-assembly solution, a pre-washing process of the substrate 11 on which the hole transport layer 12 is formed, which may include pure water washing and two fluid spraying, may be further included, and after the pre-washing is completed, the substrate 11 is placed in a self-assembly solution tank of an ultrasonic washing apparatus, and the substrate 11 is washed with the self-assembly solution to form the barrier layer 13 by self-assembly.
According to some embodiments of the application, the mass concentration of the material of the barrier layer 13 in the self-assembled solution is 0.1mg/mL to 100mg/mL, for example, may be 0.1mg/mL, 1mg/mL, 10mg/mL, 20mg/mL, 30mg/mL, 40mg/mL, 50mg/mL, 60mg/mL, 70mg/mL, 80mg/mL, 90mg/mL or 100mg/mL, etc., or may be in the range of any of the above numerical compositions. This reduces the series resistance of the perovskite solar cell 1, and forms a uniform barrier layer 13 between the hole transport layer 12 and the perovskite layer 14. According to some embodiments of the application, the mass concentration of the material of the barrier layer 13 in the self-assembly solution is 0.1mg/mL to 10mg/mL.
According to some embodiments of the present application, the time for cleaning the substrate 11 on which the hole transport layer 12 is formed using the self-assembly solution is 10s-3600s, for example, may be 10s, 100s, 500s, 1000s, 1500s, 2000s, 2500s, 3000s, 3500s, 3600s, or the like, or may be a range of any of the above-mentioned numerical values. Thereby, the adhesion rate of the material of the barrier layer 13 in the self-assembly solution to the hole transport layer 12 is improved to form a dense and uniform barrier layer 13.
According to some embodiments of the application, the thickness of the barrier layer 13 is 1nm-1000nm, for example, may be 1nm, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm or 1000nm, or may be in the range of any of the values mentioned above.
According to some embodiments of the present application, when the material of the barrier layer 13 in the self-assembly solution includes at least one of polythiophene and its derivatives, polyaniline and its derivatives, or polypyrrole and its derivatives, the thickness of the barrier layer 13 formed by self-assembly may be 1nm to 100nm, for example, may be 1nm, 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, etc., or may be in a range of any of the above values by controlling the time of the cleaning.
According to further embodiments of the present application, when the material of the barrier layer 13 in the self-assembled solution comprises at least one of [2- (9H-carbazol-9-yl) ethyl ] phosphonic acid, [2- (3, 6-dimethoxy-9H-carbazol-9-yl) ethyl ] phosphonic acid, [2- (3, 6-diphenyl-9H-carbazol-9-yl) ethyl ] phosphonic acid, [4- (9H-carbazol-9-yl) butyl ] phosphonic acid, [4- (3, 6-dimethoxy-9H-carbazol-9-yl) butyl ] phosphonic acid, [4- (3, 6-dimethyl-9H-carbazol-9-yl) butyl ] phosphonic acid, 2- (3, 4-dihydroxyphenyl) ethylamine, pyridinium propane sulfonate, 4- (diphenylamino) butyric acid, 1,3, 5-tris (4-carboxyphenyl) benzene, p-toluenesulfonyl hydrazine, p-cyanobenzoic acid or perylene, the thickness of the barrier layer 13 may be made to be, for example, 50nm, 25nm, 50nm, 25nm, 30nm, or the like, by controlling the time of the cleaning.
According to other embodiments of the present application, when the material of the barrier layer 13 in the self-assembly solution includes at least one of polystyrene or polymethyl methacrylate, the thickness of the barrier layer 13 may be 1nm to 30nm, for example, may be 1nm, 5nm, 10nm, 15nm, 20nm, 25nm or 30nm, etc., or may be in a range of any of the above values by controlling the time of the cleaning.
Therefore, the cleaning time can be adjusted according to the material of the barrier layer 13 in the self-assembly solution, and the thickness of the barrier layer 13 formed by self-assembly can be adjusted to improve the uniformity of the barrier layer 13, further reduce the probability of the material of the perovskite layer 14 reacting with the high-valence cations distributed on the surface of the hole transport layer 12 close to the perovskite layer 14, and improve the service life of the perovskite solar cell 1.
According to some embodiments of the application, the solvent in the self-assembled solution may include at least one of deionized water, diethyl ether, pentane, methylene chloride, acetone, chloroform, methanol, hexane, benzene, toluene, o-xylene, p-xylene, aniline, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, 1,2, 4-trifluorobenzene, benzotrifluoride, iodobenzene, acetic acid, ethyl acetate, cyclohexane, ethanol, isopropanol, N-propanol, 2-methoxyethanol, acetonitrile, N-butanol, azobisisobutyronitrile, tetrahydrofuran, N-dimethylformamide, dimethyl sulfoxide, or N-methylpyrrolidone to form a uniformly dispersed self-assembled solution.
According to some embodiments of the present application, in order to further improve the uniformity of the barrier layer 13, the method for forming the barrier layer 13 on the side of the hole transport layer 12 away from the substrate 11 may further include: after the surface of the hole transport layer 12 remote from the substrate 11 is washed with the self-assembly solution, the surface of the hole transport layer 12 remote from the substrate 11 is rinsed with an anti-solvent. As used herein, "antisolvent" refers to a solvent that is miscible with the solvent in the self-assembled solution, while the solubility of the solute is lower. For example, when the solute and solvent in the self-assembled solution are [2- (9H-carbazol-9-yl) ethyl ] phosphonic acid and ethanol, respectively, the antisolvent may be toluene; when the solute and the solvent in the self-assembled solution are PEDOT PSS and dimethyl sulfoxide respectively, the antisolvent can be isopropanol; when the solute and solvent in the self-assembled solution are 1,3, 5-tris (4-carboxyphenyl) benzene and tetrahydrofuran, respectively, the antisolvent may be deionized water. Specifically, after the surface of the hole transport layer 12 far away from the substrate 11 is cleaned by the self-assembly solution, the redundant self-assembly solution on the surface of the hole transport layer 12 far away from the substrate 11 is rinsed by using the anti-solvent, and the solute in the self-assembly solution can be separated out in the rinsing process due to the low solubility of the solute in the self-assembly solution in the anti-solvent, so that the self-assembly solution forms the barrier layer 13 through self-assembly.
According to some embodiments of the application, the type of antisolvent may be selected according to the system of solvents in the self-assembled solution, e.g., the antisolvent may comprise at least one of deionized water, diethyl ether, pentane, dichloromethane, acetone, chloroform, methanol, hexane, benzene, toluene, o-xylene, p-xylene, aniline, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, 1,2, 4-trifluorobenzene, trifluorotoluene, iodobenzene, acetic acid, ethyl acetate, cyclohexane, ethanol, isopropanol, N-propanol, 2-methoxyethanol, acetonitrile, N-butanol, azobisisobutyronitrile, tetrahydrofuran, N-dimethylformamide, dimethyl sulfoxide, or N-methylpyrrolidone.
According to some embodiments of the present application, the method of preparing the hole transport layer 12 in the perovskite solar cell 1 is not particularly limited, and for example, when preparing a large-area hole transport layer 12, the hole transport layer 12 may be formed by magnetron sputtering to improve the uniformity of the hole transport layer 12.
According to some embodiments of the application, the material of the hole transport layer 12 may comprise nickel oxide. When the hole transport layer 12 is formed by magnetron sputtering, high-valence nickel ions are distributed on the top of the magnetron sputtered nickel oxide film, and the barrier layer 13 can reduce the probability of protonation reaction caused by contact of the high-valence nickel ions with the perovskite layer 14, reduce the risk of decomposition of the perovskite layer 14, and improve the long-term stability of the perovskite solar cell 1.
In accordance with some embodiments of the present application, cations may also be doped into the hole transport layer 12 during formation of the hole transport layer 12, thereby increasing the mobility of carriers within the hole transport layer 12 and increasing the energy conversion rate of the perovskite solar cell 1.
According to some embodiments of the application, the doping cations may include Li + 、Cs + 、Ag + 、Mg 2+ 、Ca 2+ 、Zn 2+ 、Sr 2+ 、Ba 2+ 、Fe 2+ 、Fe 3+ 、Co 2+ 、Co 3+ 、Cu + Or Cu 2+ At least one of them.
S300: forming a perovskite layer on one side of the barrier layer away from the hole transport layer
According to some embodiments of the application, the perovskite layer 14 may be formed from a perovskite precursor solution, and the material of the perovskite layer 14 may include a PBX 3 Or P 2 CDX 6 Wherein P comprises an organic cation, li + 、Na + 、K + 、Rb + Or Cs + At least one of (a) and (b); b includes Pb 2+ 、Sn 2+ 、Be 2+ 、Mg 2+ 、Ca 2+ 、Sr 2+ 、Ba 2+ 、Zn 2+ 、Ge 2+ 、Fe 2+ 、Co 2+ 、Cu 2 + And Ni 2+ One or more of the following; c includes Cs + 、Ag + 、K + And Ru (Rust) + One or more of the following; d comprises Bi 3+ 、Ni 3+ 、Fe 3+ 、Cu 3+ 、Sb 3+ Or In 3+ At least one of (a) and (b); x includes Br - Or I - At least one of them. For example, the material of the perovskite layer 14 may be CH 3 NH 3 PbI 3 ，CH 3 NH 3 SnI 3 ，CH 3 NH 3 PbI 2 Br，CH 3 NH 3 Pb（I 1-x Br x ） 3 (wherein 0<x<1). According to some embodiments of the application, B may include Pb 2+ Or Sn (Sn) 2+ At least one of them. According to some embodiments of the application, C may comprise Ag + 。
S400: forming an electrode layer on one side of the perovskite layer away from the barrier layer
According to some embodiments of the present application, the electrode layer 15 may be formed by vacuum evaporation, and a material of the electrode layer 15 may include at least one of silver, copper, carbon, gold, aluminum, indium tin oxide, tungsten doped indium oxide, aluminum doped zinc oxide, boron doped zinc oxide, or indium zinc oxide.
A third aspect of the application provides an electrical consumer comprising a perovskite solar cell 1 according to the first aspect of the application or a perovskite solar cell 1 prepared by a method according to the second aspect of the application. The electric equipment can comprise a lighting element, a display element, a mobile device and the like, and can particularly comprise a street lamp, a signal indicator lamp, an insect-killing lamp, an electric fan, an electric toy, an electric tool, an electric vehicle, an electric automobile, a ship, a spacecraft and the like, wherein the electric toy can comprise fixed or mobile electric toys, such as a game console, an electric automobile toy, an electric ship toy, an electric aircraft toy and the like, and the spacecraft can comprise an aircraft, a rocket, a space aircraft, a spacecraft and the like; the photovoltaic power generation system can comprise a large ground photovoltaic power generation system, a distributed photovoltaic power generation and building integrated photovoltaic power generation system and the like. Therefore, the electric equipment has good long-term stability and long service life.
In order to make the technical problems, technical schemes and beneficial effects solved by the embodiments of the present application more clear, the following will be described in further detail with reference to the embodiments and the accompanying drawings. It will be apparent that the described embodiments are only some, but not all, embodiments of the application. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the application, its application, or uses. All other embodiments, which can be made by a person skilled in the art based on the embodiments of the application without any inventive effort, are intended to fall within the scope of the application.
Example 1
1. Taking a group of specifications of 10 x 10 cm 2 Etching the regions with the opposite sides of 0.5 and cm by a laser marking machine, cleaning the regions by a cleaning agent, sequentially ultrasonically treating the FTO conductive glass in deionized water, ethanol and acetone for 10 minutes, and drying the FTO conductive glass by nitrogen after ultrasonic treatment;
2. preparing self-assembly solution according to the concentration of 1 mg/mL, wherein the solute in the self-assembly solution is ethanol, and placing the self-assembly solution into a self-assembly solution tank of an ultrasonic cleaning device;
3. taking a piece of FTO conductive glass, preparing a lithium doped nickel oxide layer with the thickness of 10 nm by using a magnetron sputtering method, scribing P1 by using laser, and then placing the lithium doped nickel oxide layer into an ultrasonic cleaning device;
4. In the process of cleaning the doped nickel oxide layer subjected to laser scribing, placing the substrate into a self-assembly solution for cleaning for 30 seconds;
5. after the substrate is taken out, using chlorobenzene anti-solvent to wash redundant self-assembly solution on the top of the substrate;
6. drying at 100deg.C for 10 min to form a barrier layer;
7. coating a FA layer with the thickness of about 500nm on the surface of the doped nickel oxide layer 0.9 Cs 0.1 PbI 3 Continuously blowing the perovskite film for 30 seconds by an air knife, transferring the perovskite film to a heating table, and annealing for 10 minutes at 100 ℃;
8. vacuum thermal evaporation coating process is adopted, the temperature is 1 x 10 -6 Sequentially evaporating 50nm C under Torr 60 The 20nm BCP and the 80nm Cu electrode are subjected to laser scribing P2 and then the 100nm Cu electrode is continuously evaporated;
9. and (3) laser scribing P3 and P4 is used for enabling the large-area perovskite device to form a serial structure, so that the preparation of the perovskite solar cell is completed.
The perovskite solar cell preparation methods of example 2-example 38 and comparative example 1-comparative example 3 are the same as example 1, and the differences are shown in Table 1.
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Performance test:
1. carrier mobility
The carrier mobility is calculated by a Hall constant method, wherein the sample glass is placed in an external magnetic field, a transverse electric field E is applied to enable the sample glass to be in a Hall equilibrium state, and the carrier mobility is calculated as follows:
μ=|R H |σ
=|V H d/(I S B)|σ
Wherein R is H 、V H 、I S Each of B, d and σ is a Hall coefficient (m 3 /C), hall voltage (V), amperage (A), external magnetic field strength (T), sample thickness (m), and sample conductivity (S/m).
2. Barrier layer thickness and uniformity test
Thickness test: according to different thicknesses of the barrier layers, a step meter is used for testing when the thickness of the barrier layers is 100-1000 nm, and an ellipsometer is used for testing when the thickness of the barrier layers is 1-100 nm, so as to improve the accuracy of testing results. Uniformity test: and uniformly selecting 9 points on the 100mm sample film, and respectively testing the film thickness of the corresponding points, wherein the uniformity (%) = (film thickness maximum value-film thickness minimum value)/(film thickness maximum value + film thickness minimum value).
3. Efficiency testing method of perovskite solar cell
At 100 mW/cm 2 The battery performance was tested and the photoelectric conversion efficiency was calculated as follows:
PCE = P OUT /P OPT
= V OC ×J SC ×(V MPP ×J MPP )/(V OC ×J SC )
= V OC ×J SC ×FF
wherein P is OUT 、P OPT 、V MPP (V)、J MPP (mA/cm 2 )、V OC (V) and J SC (mA/cm 2 ) The power supply is respectively a battery working output power, an incident light power, a battery maximum power point voltage, a battery maximum power point current, an open circuit voltage and a short circuit current.
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It can be seen from table 2 that the carrier mobility in examples 1-38 is higher than that in comparative examples 1-3, which means that doping the hole transport layer with cations can improve the carrier mobility, and that the initial photoelectric conversion efficiency of the cells in examples 1-38 is higher than that in comparative examples 1-3, and that the decrease in the photoelectric conversion efficiency of the cells in examples 1-38 after 30 days of storage is lower than that in comparative examples 1-3, which means that the material of the barrier layer has excellent hole transport ability, can improve the photoelectric conversion efficiency of the cells, and can improve the stability of the cells.
Example 39
1. Taking a group of specifications of 10 x 10 cm 2 Etching the regions with the opposite sides of 0.5 and cm by a laser marking machine, cleaning the regions by a cleaning agent, sequentially ultrasonically treating the FTO conductive glass in deionized water, ethanol and acetone for 10 minutes, and drying the FTO conductive glass by nitrogen after ultrasonic treatment;
2. preparing self-assembly solution according to the concentration of 1 mg/mL, wherein the solute in the self-assembly solution is PTAA, and placing the self-assembly solution into a self-assembly solution tank of an ultrasonic cleaning device;
3. taking a piece of FTO conductive glass, preparing a lithium doped nickel oxide layer with the thickness of 10 nm by using a magnetron sputtering method, scribing P1 by using laser, and then placing the lithium doped nickel oxide layer into an ultrasonic cleaning device;
4. in the process of cleaning the doped nickel oxide layer subjected to laser scribing, placing the substrate into a self-assembly solution for cleaning for 30 seconds;
5. after the substrate is taken out, using chlorobenzene anti-solvent to wash redundant self-assembly solution on the top of the substrate;
6. drying at 100deg.C for 10 min to form a barrier layer;
7. coating a FA layer with the thickness of about 500nm on the surface of the doped nickel oxide layer 0.9 Cs 0.1 PbI 3 Continuously blowing the perovskite film for 30 seconds by an air knife, transferring the perovskite film to a heating table, and annealing for 10 minutes at 100 ℃;
8. vacuum thermal evaporation coating process is adopted, the temperature is 1 x 10 -6 Sequentially evaporating 50nm C under Torr 60 The 20nm BCP and the 80nm Cu electrode are subjected to laser scribing P2 and then the 100nm Cu electrode is continuously evaporated;
9. and (3) laser scribing P3 and P4 is used for enabling the large-area perovskite device to form a serial structure, so that the preparation of the perovskite solar cell is completed.
The perovskite solar cell of example 40-example 53 was prepared in the same manner as in example 39, with the details given in Table 3.
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The thickness and uniformity of the barrier layer and the mobility of the hole transport layer carriers of the perovskite solar cell in example 39-example 53 were tested and the results are shown in table 4.
TABLE 4 Table 4
Conclusion: as can be seen from table 4, the thickness and uniformity of the barrier layer can be improved by adjusting the concentration of the self-assembly solution and the cleaning time.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the application, and are intended to be included within the scope of the appended claims and description. In particular, the technical features mentioned in the respective embodiments may be combined in any manner as long as there is no structural conflict. The present application is not limited to the specific embodiments disclosed herein, but encompasses all technical solutions falling within the scope of the claims.

Claims (22)

1. A perovskite solar cell, comprising:
a substrate;
a hole transport layer provided on one side of the substrate;
a barrier layer disposed on a side of the hole transport layer remote from the substrate, the material of the barrier layer comprising at least one of polystyrene, polymethyl methacrylate, polyethylenimine, polyethylene glycol diacrylate, [2- (9H-carbazol-9-yl) ethyl ] phosphonic acid, [2- (3, 6-dimethoxy-9H-carbazol-9-yl) ethyl ] phosphonic acid, [2- (3, 6-diphenyl-9H-carbazol-9-yl) ethyl ] phosphonic acid, [4- (9H-carbazol-9-yl) butyl ] phosphonic acid, [4- (3, 6-dimethoxy-9H-carbazol-9-yl) butyl ] phosphonic acid, [4- (3, 6-dimethyl-9H-carbazol-9-yl) butyl ] phosphonic acid, 2- (3, 4-dihydroxyphenyl) ethylamine, pyridinium propane sulfonate, 4- (diphenylamino) butyric acid, 1,3, 5-tris (4-carboxyphenyl) benzene, p-toluenesulfonyl, p-cyanobenzoic acid, or perylene hydrazine;
the perovskite layer is arranged on one side of the barrier layer away from the hole transport layer;
and the electrode layer is arranged on one side of the perovskite layer away from the barrier layer.
2. The perovskite solar cell of claim 1, wherein the material of the barrier layer further comprises: at least one of polythiophene and its derivatives, polyaniline and its derivatives, or polypyrrole and its derivatives.
3. The perovskite solar cell according to claim 2, wherein at least one of the following conditions is satisfied:
(1) The material of the barrier layer comprises polythiophene and derivatives thereof, wherein the polythiophene and derivatives thereof comprise at least one of poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid), poly (3-hexylthiophene), poly (3-octylthiophene-2, 5-diyl), poly (thiodithiophene) pyrrolopyrrole dione-thiophene or poly (thiofuran-pyrrolopyrrole dione);
(2) The material of the barrier layer comprises polyaniline and derivatives thereof, wherein the polyaniline and derivatives thereof comprise at least one of poly [ bis (4-phenyl) (4-butylphenyl) amine ] or poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ];
(3) The material of the barrier layer comprises polypyrrole and derivatives thereof, wherein the polypyrrole and derivatives thereof comprise sulfhydryl-polypyrrole.
4. A perovskite solar cell according to any one of claims 1 to 3, wherein the barrier layer comprises-c=o, -NH in its material 2 At least one of =nh, -s=o, -c≡n, -p=o, -SH, -Cl, -Br, -I, or-F.
5. The perovskite solar cell of claim 4, wherein the thickness of the barrier layer is 1nm to 1000nm.
6. The perovskite solar cell of claim 5, wherein the thickness of the barrier layer is 1nm-100nm.
7. The perovskite solar cell of claim 5, wherein the thickness of the barrier layer is 1nm to 50nm.
8. The perovskite solar cell of claim 5, wherein the thickness of the barrier layer is 1nm-30nm.
9. The perovskite solar cell of claim 1, wherein the material of the hole transport layer comprises nickel oxide.
10. The perovskite solar cell of claim 9, wherein the nickel oxide comprises doped cations therein.
11. The perovskite solar cell of claim 10, wherein the doped cations comprise Li + 、Cs + 、Ag + 、Mg 2+ 、Ca 2+ 、Zn 2+ 、Sr 2+ 、Ba 2+ 、Fe 2+ 、Fe 3+ 、Co 2+ 、Co 3+ 、Cu + Or Cu 2+ At least one of them.
12. The perovskite solar cell of claim 10 or 11, wherein the ratio of the molar ratio of the doping cations to nickel ions in the nickel oxide is 0.01-0.2.
13. The perovskite solar cell of claim 12, wherein the ratio of the molar ratio of doping cations to nickel ions is 0.01-0.05.
14. A method of making a perovskite solar cell comprising:
forming a hole transport layer on one side of the substrate;
forming a blocking layer on a side of the hole transport layer away from the substrate, wherein the blocking layer comprises at least one of polystyrene, polymethyl methacrylate, polyethylenimine, polyethylene glycol diacrylate, [2- (9H-carbazole-9-yl) ethyl ] phosphonic acid, [2- (3, 6-dimethoxy-9H-carbazole-9-yl) ethyl ] phosphonic acid, [2- (3, 6-diphenyl-9H-carbazole-9-yl) ethyl ] phosphonic acid, [4- (9H-carbazole-9-yl) butyl ] phosphonic acid, [4- (3, 6-dimethoxy-9H-carbazole-9-yl) butyl ] phosphonic acid, [4- (3, 6-dimethyl-9H-carbazole-9-yl) butyl ] phosphonic acid, [2- (3, 4-dihydroxyphenyl) ethylamine, pyridinium propane sulfonate, 4- (diphenylamino) butyric acid, 1,3, 5-tris (4-carboxyphenyl) benzene, p-toluenesulfonyl hydrazine, p-cyanobenzoic acid or perylene;
forming a perovskite layer on one side of the barrier layer away from the hole transport layer;
an electrode layer is formed on a side of the perovskite layer remote from the barrier layer.
15. The method of claim 14, wherein forming the barrier layer on a side of the hole transport layer remote from the substrate comprises:
And cleaning and drying the surface of the hole transport layer, which is far away from the substrate, by adopting a self-assembly solution, wherein the self-assembly solution comprises the material of the barrier layer so as to obtain the barrier layer.
16. The method of claim 15, wherein the self-assembling solution further comprises a solvent comprising at least one of deionized water, diethyl ether, pentane, methylene chloride, acetone, chloroform, methanol, hexane, benzene, toluene, o-xylene, p-xylene, aniline, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, 1,2, 4-trifluorobenzene, benzotrifluoride, iodobenzene, acetic acid, ethyl acetate, cyclohexane, ethanol, isopropanol, N-propanol, 2-methoxyethanol, acetonitrile, N-butanol, azobisisobutyronitrile, tetrahydrofuran, N-dimethylformamide, dimethylsulfoxide, or N-methylpyrrolidone.
17. The method of claim 16, wherein at least one of the following conditions is satisfied:
(1) The mass concentration of the material of the barrier layer in the self-assembly solution is 0.1mg/mL-100mg/mL;
(2) The cleaning time is 10s-3600s.
18. The method of claim 17, wherein the mass concentration of the material of the barrier layer in the self-assembling solution is 0.1mg/mL to 10mg/mL.
19. The method according to any one of claims 15-18, further comprising: after the surface of the hole transport layer remote from the substrate is rinsed with the self-assembly solution, the surface of the hole transport layer remote from the substrate is rinsed with an anti-solvent.
20. The method of claim 19, wherein the antisolvent comprises at least one of deionized water, diethyl ether, pentane, methylene chloride, acetone, chloroform, methanol, hexane, benzene, toluene, o-xylene, p-xylene, aniline, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, 1,2, 4-trifluorobenzene, benzotrifluoride, iodobenzene, acetic acid, ethyl acetate, cyclohexane, ethanol, isopropanol, N-propanol, 2-methoxyethanol, acetonitrile, N-butanol, azobisisobutyronitrile, tetrahydrofuran, N-dimethylformamide, dimethyl sulfoxide, or N-methylpyrrolidone.
21. The method of claim 14, wherein the material of the hole transport layer comprises nickel oxide.
22. A powered device comprising a perovskite solar cell as claimed in any one of claims 1 to 13 or a perovskite solar cell produced by a method as claimed in any one of claims 14 to 21.
CN202310965029.2A 2023-08-02 2023-08-02 Perovskite solar cell, preparation method thereof and electric equipment Pending CN116669449A (en)

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