WO2023103650A1 - 钙钛矿太阳能电池和光伏组件 - Google Patents

钙钛矿太阳能电池和光伏组件 Download PDF

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WO2023103650A1
WO2023103650A1 PCT/CN2022/128778 CN2022128778W WO2023103650A1 WO 2023103650 A1 WO2023103650 A1 WO 2023103650A1 CN 2022128778 W CN2022128778 W CN 2022128778W WO 2023103650 A1 WO2023103650 A1 WO 2023103650A1
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layer
perovskite
sublayer
solar cell
transport layer
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French (fr)
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陈长松
郭永胜
陈国栋
欧阳楚英
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Contemporary Amperex Technology Co Ltd
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Priority to KR1020247018634A priority patent/KR20240097915A/ko
Publication of WO2023103650A1 publication Critical patent/WO2023103650A1/zh
Priority to US18/734,442 priority patent/US20240324253A1/en
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    • 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
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
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    • H10K30/84—Layers having high charge carrier mobility
    • H10K30/85—Layers having high electron mobility, e.g. electron-transporting layers or hole-blocking layers
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
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    • H10K2101/40—Interrelation of parameters between multiple constituent active layers or sublayers, e.g. HOMO values in adjacent layers
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    • H10K30/84—Layers having high charge carrier mobility
    • H10K30/86—Layers having high hole mobility, e.g. hole-transporting layers or electron-blocking layers
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    • 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

Definitions

  • the present application relates to the technical field of solar cells, in particular to a perovskite solar cell and a photovoltaic module.
  • Perovskite solar cells are solar cells that use organometallic halide perovskite materials as light-absorbing layers. They have excellent photoelectric properties and simple preparation methods, bringing new space and hope for photovoltaic power generation.
  • Embodiments of the present application provide a perovskite solar cell and a photovoltaic module, which can improve the photoelectric conversion efficiency of the perovskite solar cell.
  • An embodiment of the first aspect of the present application provides a perovskite solar cell, and the perovskite solar cell includes a perovskite layer, a hole transport layer and an electron transport layer.
  • the perovskite layer includes first and second surfaces facing each other in a thickness direction thereof.
  • the hole transport layer is disposed on the first surface.
  • the electron transport layer is arranged on the second surface, the electron transport layer includes at least two sublayers, the electron transport layer includes a doping material, and the conduction band bottom energy level of each sublayer is smaller than the conduction band bottom energy level of the hole transport layer; each The valence band top energy level of the sublayer is smaller than the valence band top energy level of the hole transport layer.
  • the energy level structure is adjusted by doping the electron transport layer with a doping material, which can ensure the formation of the built-in electric field of the perovskite solar cell and ensure the efficient transport of carriers.
  • the energy level difference at the bottom of the conduction band can ensure the one-way transmission of electrons
  • the energy level difference at the top of the valence band can ensure the one-way transmission of holes, which can effectively improve the photoelectric conversion efficiency of perovskite solar cells.
  • the perovskite solar cell of the present application can suppress the migration of halogen in the perovskite layer, improve the structural stability of the perovskite solar cell, thereby further improving the photoelectric conversion efficiency of the perovskite solar cell.
  • the difference between the conduction band bottom energy level of the sublayer of the electron transport layer close to the second surface and the perovskite layer is -1.0eV ⁇ 1.0eV.
  • the conductance of the sublayer and the perovskite layer is -0.3eV ⁇ 0.3eV; the above numerical range can improve the electron transmission efficiency.
  • the valence band top energy level of the sublayer of the electron transport layer close to the second surface is smaller than the valence band top energy level of the perovskite layer, which can avoid the recombination of holes and electrons to a certain extent, and reduce the current of the solar cell.
  • the difference between the Fermi level of the sub-layer of the electron transport layer close to the second surface and the perovskite layer is ⁇ 1.5eV, and the range of the above difference can ensure that the electron transport layer is of electronic conductivity type, and improve the electron transport efficiency.
  • the difference between the conduction band bottom energy level and the Fermi level of the sublayer of the electron transport layer close to the second surface is ⁇ 1.5eV, and the above range of difference can reduce the gap between the electron transport layer and the perovskite layer. Unnecessary energy band bending increases the carrier transport rate, thereby improving the photoelectric conversion efficiency of perovskite solar cells.
  • the difference between the bottom energy level of the conduction band and the top energy level of the valence band of the sublayer of the electron transport layer close to the second surface is ⁇ 1.5eV, and the sublayer satisfying the above numerical range has a larger band gap, which can The ultraviolet light is filtered to avoid the damage of the ultraviolet light to the perovskite layer.
  • the electron transport layer includes a first sub-layer, a second sub-layer and a third sub-layer that are sequentially stacked in a direction away from the second surface, wherein the first sub-layer is an oxide layer comprising a first dopant material.
  • the first dopant material includes alkali metal, alkaline earth metal, transition metal, poor metal, metalloid, non-metal element, ionic liquid, carboxylic acid, phosphoric acid, carbon derivative, self-assembled single molecule or organic polymer ;
  • the electron transport layer comprising three sublayers can flexibly adjust the energy level of each layer, which is beneficial to improve the extraction efficiency of carriers and the transfer efficiency of carriers.
  • the alkali metal includes at least one of Li, K, Na, Rb, and Cs.
  • the alkaline earth metal includes at least one of Be, Sr and Ba.
  • the transition metal includes at least one of Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Ta, Pt and Au.
  • the poor metal includes at least one of Al, Ga, In, Sn, Tl, Pb, and Bi.
  • the metalloid includes at least one of B, Si, Ge, As, Sb and Te.
  • the non-metal elements include at least one of F, Cl, Br, I, P, S and Se.
  • the ionic liquid includes at least one of 1-butyl-3-methylimidazolium tetrafluoroborate, ammonium chloride, ammonium sulfide, tetramethylammonium hydroxide and 2,2,2-trifluoroethanol.
  • the carboxylic acid includes at least one of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 4-imidazoleacetic acid hydrochloride and acetic acid.
  • the carbon derivatives include at least one of carbon quantum dots, carbon nanotubes, graphene, carbon 60, carbon 60 derivatives, graphite-phase carbon nitride, and carbon 9.
  • the self-assembled single molecule includes at least one of 4-pyridinecarboxylic acid, dopamine, 3-aminopropyltriethoxysilane and glycine.
  • the organic macromolecular polymer includes at least one of polystyrene, polyethoxyethyleneimine, polyethylene oxide and triphenylphosphine oxide.
  • the above-mentioned first doping material can effectively improve the energy level of the electron transport layer and adjust the energy level structure of the perovskite battery.
  • the second sublayer includes an imide compound layer, a quinone compound layer, a fullerene layer, a perovskite oxide layer, a fluoride layer, or an oxide layer.
  • the first sublayer and the second sublayer cooperate with each other to effectively improve the energy level structure of the electron transport layer.
  • the imide compound layer includes an imide compound or a derivative of an imide compound, and the imide compound includes: phthalimide, succinimide, N-bromosuccinyl imine, glutarimide or maleimide.
  • the quinone compound layer includes quinone compounds or derivatives of quinone compounds, and the quinone compounds include benzoquinone, naphthoquinone, phenanthrenequinone or anthraquinone.
  • the perovskite oxide layer includes strontium titanate, calcium titanate, barium titanate, lithium titanate, ferrous titanate, nickel titanate, or cobalt titanate.
  • the fluoride layer includes lithium fluoride or calcium fluoride.
  • the oxide layer includes oxide layers of the following elements: Ce, Mg, Si, Cd, Zn, In, Pb, Mo, W, Sb, Bi, Cu, Hg, Ti, Ag, Mn, Fe, V, Sn, Zr , Sr, Ga or Cr.
  • the second sublayer of the above material can effectively improve the energy level structure of the electron transport layer.
  • the third sublayer comprises a metal oxide layer or a metal oxide layer comprising a second dopant material, the metal oxide layer comprising a SnO2 layer, an In2O3 layer, a ZnO layer, a CdO layer, a NiO layer, CdIn 2 O 4 layer, Cd 2 SnO 4 layer, Zn 2 SnO 4 layer, MgIn 2 O 4 layer, ZnIn 2 O 4 layer, CoIn 3 O 6 layer, ZnV 2 O 6 layer, CuAlO 2 layer or CuGaO 2 layer.
  • the first sublayer, the second sublayer and the third sublayer cooperate with each other to effectively improve the energy level structure of the electron transport layer.
  • the SnO 2 layer includes a second dopant material whose elements include at least one of F, Sb, P, As, Te, and Cl.
  • the In 2 O 3 layer includes a second doping material, and elements of the second doping material include at least one of W, Mn, Zr, Ti, Sb, F, and Ag.
  • the ZnO layer includes a second doping material, and elements of the second doping material include at least one of Ga, In, F, N, B and Al.
  • the third sublayer comprising the above-mentioned second doping material can effectively improve the energy level structure of the electron transport layer.
  • the second aspect of the present application provides a photovoltaic module, including the perovskite solar cell according to any embodiment of the first aspect of the present application.
  • FIG. 1 is a schematic structural view of a perovskite solar cell provided by some embodiments of the present application
  • Fig. 2 is a schematic structural view of a perovskite solar cell provided by other embodiments of the present application;
  • Fig. 3 is a schematic structural diagram of a perovskite solar cell provided by some other embodiments of the present application.
  • Perovskite layer 10a, first surface; 10b, second surface;
  • Electron transport layer 31. The first sublayer; 32. The second sublayer; 33. The third sublayer;
  • ranges disclosed herein are defined in terms of lower and upper limits, and a given range is defined by selecting a lower limit and an upper limit that define the boundaries of the particular range. Ranges defined in this manner may be inclusive or exclusive and may be combined arbitrarily, ie any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are contemplated. Additionally, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, the following ranges are all expected: 1-3, 1-4, 1-5, 2- 3, 2-4 and 2-5.
  • the numerical range "a-b” represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers.
  • the numerical range "0-5" indicates that all real numbers between "0-5" have been listed in this article, and "0-5" is only an abbreviated representation of the combination of these values.
  • a certain parameter is an integer ⁇ 2
  • a method comprising steps (a) and (b) means that the method may comprise steps (a) and (b) performed sequentially, and may also comprise steps (b) and (a) performed sequentially.
  • the method may also include step (c) means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), and may also include step (a) , (c) and (b), may also include steps (c), (a) and (b) and the like.
  • the term "or” is inclusive unless otherwise stated.
  • the phrase "A or B” means “A, B, or both A and B.” More specifically, the condition "A or B” is satisfied by either of the following: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists) ; or both A and B are true (or exist).
  • a perovskite solar cell includes a perovskite layer, a hole-transport layer and an electron-transport layer, and electrodes.
  • the working process of perovskite batteries mainly includes: the generation and separation of excitons, the transport of free carriers, the collection of carriers and the generation of current.
  • the specific process is as follows: In a perovskite solar cell, sunlight is absorbed by the perovskite layer, and the perovskite layer absorbs photons to generate excitons, which are then separated into free electrons and hole. The separated free carriers are transported in the perovskite layer and transported out through the transport layer.
  • the electron transport layer plays the role of transporting electrons and blocking holes, and the hole transport layer plays the role of transporting holes and blocking electrons. The electrons and holes transported through the transport layer are collected by the electrodes to form current and voltage respectively.
  • the inventors improved the perovskite solar cells by adjusting the energy level structure of the bulk phase doping method. Adjusting the energy level structure can reduce the recombination of photogenerated carriers to a certain extent and improve The extraction and transmission efficiency of electrons is improved, thereby increasing the opening voltage and current.
  • Embodiments of the first aspect of the present application provide a perovskite solar cell.
  • FIG. 1 shows a schematic structural view of a perovskite solar cell provided by some embodiments of the present application.
  • the perovskite solar cell includes a perovskite layer 10 , a hole transport layer 20 and an electron transport layer 30 .
  • the perovskite layer 10 includes a first surface 10a and a second surface 10b facing each other in a thickness direction X thereof.
  • the hole transport layer 20 is disposed on the first surface 10a.
  • the electron transport layer 30 is arranged on the second surface 10b, the electron transport layer 30 includes at least two sublayers 30a, the electron transport layer 30 includes a doping material, and the conduction band bottom energy level of each sublayer 30a is smaller than the conductance of the hole transport layer 20.
  • Band bottom energy level, the conduction band bottom energy level of each sublayer 30 a is smaller than the valence band top energy level of the hole transport layer 20 .
  • the energy level structure is adjusted by doping the electron transport layer 30 with a dopant material, so that the conduction band bottom energy level of each sub-layer 30a in the electron transport layer 30 is less than
  • the top energy level of the valence band of each sublayer 30a is less than the top energy level of the valence band of the hole transport layer 20
  • the energy level of each sublayer 30a is the same as the energy level of the hole transport layer 20
  • There is an energy level difference and the existence of the energy level difference can ensure the formation of the built-in electric field of the perovskite solar cell and ensure the efficient transport of carriers.
  • the energy level difference at the bottom of the conduction band can ensure the one-way transmission of electrons
  • the energy level difference at the top of the valence band can ensure the one-way transmission of holes, which can effectively improve the photoelectric conversion efficiency of perovskite solar cells.
  • the embodiment of the present application can suppress the migration of halogen in the perovskite layer 10 and improve the structural stability of the perovskite solar cell.
  • the large energy level difference between each sublayer 30a and the hole transport layer 20 can further ensure the formation of the built-in electric field of the perovskite solar cell and ensure the efficient transport of carriers.
  • the difference between the conduction band bottom energy level of the sub-layer 30a of the electron transport layer 30 near the second surface 10b and the perovskite layer 10 is -1.0eV ⁇ 1.0eV.
  • the difference between the conduction band bottom energy level of the sublayer 30a of the electron transport layer 30 near the second surface 10b and the perovskite layer 10 is -0.3eV ⁇ .3eV.
  • the energy level difference between the sub-layer 30a of the electron transport layer 30 near the second surface 10b and the perovskite layer 10 satisfies the above numerical range, which can improve the electron transport efficiency.
  • the energy level difference at the bottom of the conduction band in the above-mentioned range can reduce the recombination of photogenerated carriers and increase the opening voltage and current.
  • the top valence level of the sublayer 30 a of the electron transport layer 30 near the second surface 10 b is smaller than the top valence level of the perovskite layer 10 .
  • the valence band top energy level of the sublayer 30a of the electron transport layer 30 close to the second surface 10b can more effectively block the holes from the perovskite layer 10, and can avoid the recombination of holes and electrons to a certain extent, reducing the perovskite current of the solar cell.
  • the difference between the Fermi level of the sublayer 30a of the electron transport layer 30 near the second surface 10b and the perovskite layer 10 is ⁇ 1.5eV, and the above range of difference can ensure that the electron transport layer 30 is electronically conductive type, improving electron transport efficiency.
  • the severe energy band bending can form barriers on the carrier transport channel, which affects the performance of perovskite solar cells.
  • the difference between the conduction band bottom energy level and the Fermi level of the sublayer 30a of the electron transport layer 30 close to the second surface 10b is ⁇ 1.5eV, and the above range of difference can reduce the interaction between the electron transport layer 30 and the calcium Unnecessary energy band bending between the titanite layers 10 increases the carrier transport rate, thereby improving the photoelectric conversion efficiency of the perovskite solar cell.
  • the difference between the bottom energy level of the conduction band and the top energy level of the valence band of the sublayer 30a of the electron transport layer 30 close to the second surface 10b is ⁇ 1.5eV, and the sublayer satisfying the above numerical range has a larger band
  • the gap can filter ultraviolet light and avoid damage to the perovskite layer 10 by ultraviolet light.
  • the electron transport layer 30 can effectively transport electrons, reduce carrier recombination at the interface between the perovskite layer 10 and the electron transport layer 30, and improve the photoelectric conversion efficiency of the perovskite solar cell.
  • the electron transport layer 30 includes at least two sublayers 30a.
  • the electron transport layer 30 includes two sublayers 30a, respectively the first sublayer 31 and the second sublayer 32; or the electron transport layer 30 includes three sublayers 30a, respectively the first sublayer 31, the second sublayer 32 The second sublayer 32 and the third sublayer 33; or the electron transport layer 30 includes four sublayers, which are respectively the first sublayer 31, the second sublayer 32, the third sublayer 33 and the fourth sublayer and so on.
  • the above description of the electron transport layer 30 is only an exemplary illustration, and is not intended to limit the specific number of layers of the electron transport layer 30 .
  • Fig. 2 shows a schematic structural diagram of a perovskite solar cell provided by some embodiments of the present application.
  • the electron transport layer 30 includes three sublayers, namely a first sublayer 31 , a second sublayer 32 and a third sublayer 33 .
  • the first sub-layer 31 , the second sub-layer 32 and the third sub-layer 33 are sequentially stacked from the direction away from the second surface 10 b.
  • the first sublayer 31 is disposed close to the perovskite layer 10
  • the third sublayer 33 is disposed away from the perovskite layer 10
  • the second sublayer 32 is located between the first sublayer 31 and the third sublayer 33 .
  • the electron transport layer 30 comprising three sublayers can flexibly adjust the energy levels of each layer, which is beneficial to improve the extraction efficiency of carriers and the transfer efficiency of carriers.
  • the first sub-layer 31 is a tin oxide layer containing a first dopant material.
  • the first dopant material includes alkali metal, alkaline earth metal, transition metal, poor metal, metalloid, non-metal element, ionic liquid, carboxylic acid, phosphoric acid, carbon derivative, self-assembled single molecule or organic polymer.
  • the tin oxide layer has good energy level alignment and high mobility, which can realize efficient electron extraction and transport. By doping the first dopant material in the first sublayer 31, the first dopant material can regulate the energy level of the first sublayer 31, and can passivate the material bulk phase defect, improve the carrier concentration and mobility, Thereby improving the photoelectric conversion efficiency of perovskite solar cells.
  • the energy level of the electron transport layer 30 can be effectively improved, and the energy level structure of the perovskite battery can be adjusted.
  • specific examples of the first doping material will be described.
  • the alkali metal includes at least one of Li, K, Na, Rb, and Cs.
  • the alkaline earth metals include at least one of Be, Sr, and Ba.
  • transition metals include at least one of Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Ta, Pt, and Au. A sort of.
  • the poor metal includes at least one of Al, Ga, In, Sn, Tl, Pb, and Bi.
  • the metalloid includes at least one of B, Si, Ge, As, Sb, and Te.
  • the non-metal elements include at least one of F, Cl, Br, I, P, S, and Se.
  • ionic liquids include 1-butyl-3-methylimidazolium tetrafluoroborate, ammonium chloride, ammonium sulfide, tetramethylammonium hydroxide, and 2,2,2-trifluoroethanol at least one of .
  • the carboxylic acid includes at least one of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 4-imidazoleacetic acid hydrochloride, and acetic acid.
  • the carbon derivatives include at least one of carbon quantum dots, carbon nanotubes, graphene, carbon 60, carbon 60 derivatives, carbon nitride of graphite phase, and carbon 9.
  • the self-assembled monomolecule includes at least one of 4-pyridinecarboxylic acid, dopamine, 3-aminopropyltriethoxysilane, and glycine.
  • the organic high molecular polymer includes at least one of polystyrene, polyethoxyethyleneimine, polyethylene oxide, and triphenylphosphine oxide.
  • the second sublayer 32 includes an imide compound layer, a quinone compound layer, a fullerene layer, a perovskite oxide layer, a fluoride layer, or an oxide layer.
  • the first sublayer 31 and the second sublayer 32 cooperate with each other to effectively improve the energy level structure of the electron transport layer 30 .
  • the imide compound layer includes an imide compound or a derivative of an imide compound, and the imide compound includes: phthalimide, succinimide, N- Bromosuccinimide, glutarimide, or maleimide.
  • the quinone compound layer includes quinone compounds or derivatives of quinone compounds, and the quinone compounds include: benzoquinone, naphthoquinone, phenanthrenequinone or anthraquinone.
  • the perovskite-type oxide layer includes strontium titanate, calcium titanate, barium titanate, lithium titanate, ferrous titanate, nickel titanate, or cobalt titanate.
  • the fluoride layer includes lithium fluoride or calcium fluoride.
  • oxide layers include oxide layers of the following elements: Ce, Mg, Si, Cd, Zn, In, Pb, Mo, W, Sb, Bi, Cu, Hg, Ti, Ag, Mn , Fe, V, Sn, Zr, Sr, Ga or Cr.
  • the third sub-layer 33 comprises a metal oxide layer or a metal oxide layer comprising a second dopant material, the metal oxide layer comprising a SnO2 layer, an In2O3 layer, a ZnO layer, a CdO layer, a NiO layer, a CdIn2O 4 layers, Cd 2 SnO 4 layers, Zn 2 SnO 4 layers, MgIn 2 O 4 layers, ZnIn 2 O 4 layers, CoIn 3 O 6 layers, ZnV 2 O 6 layers, CuAlO 2 layers, or CuGaO 2 layers.
  • the first sublayer 31 , the second sublayer 32 and the third sublayer 33 cooperate with each other to effectively improve the energy level structure of the electron transport layer 30 .
  • the SnO 2 layer includes a second doping material whose elements include at least one of F, Sb, P, As, Te, and Cl.
  • the In 2 O 3 layer includes a second doping material whose elements include at least one of W, Mn, Zr, Ti, Sb, F and Ag.
  • the ZnO layer includes a second doping material whose elements include at least one of Ga, In, F, N, B, and Al.
  • the hole transport layer 20 can effectively transport holes, reduce carrier recombination at the interface between the perovskite layer 10 and the hole transport layer 20, and improve the photoelectric conversion efficiency of the perovskite solar cell.
  • the material of the hole transport layer 20 can be selected from conventional materials in the art, and is not limited here.
  • the perovskite layer 10 acts as a light absorbing layer and can convert photons into holes and electrons.
  • the material of the perovskite layer 10 can be selected from conventional materials in the field, and is not limited here.
  • the perovskite solar cell of the embodiment of the present application further includes a first electrode and a second electrode. At least one of the first electrode and the second electrode is a transparent electrode.
  • the transparent electrodes are FTO conductive glass electrodes.
  • Fig. 3 shows a schematic structural view of a perovskite solar cell provided by some embodiments of the present application.
  • the perovskite solar cell includes a first electrode 40, a hole transport layer arranged in sequence along its thickness direction X 20.
  • the second aspect of the present application provides a method for preparing a perovskite solar cell, which is used to prepare the perovskite solar cell of the first aspect of the present application, and each sublayer of the electron transport layer of the prepared perovskite solar cell
  • the bottom energy level of the conduction band is lower than the bottom energy level of the conduction band of the hole transport layer; the top energy level of the valence band of each sublayer is smaller than the top energy level of the valence band of the hole transport layer.
  • the third aspect of the present application also provides a photovoltaic module, including the perovskite solar cell according to any embodiment of the first aspect of the present application, or the perovskite solar cell prepared by the method of the second aspect of the present application.
  • Perovskite solar cells can be used as a power source for photovoltaic modules and also as an energy storage unit for photovoltaic modules.
  • An electron transport layer is prepared, and the electron transport layer includes a first sublayer and a second sublayer.
  • the second mixture is spin-coated on the FTO conductive glass electrode at a speed of 4000rpm-6500rpm, heated at a constant temperature on a constant-temperature heating platform, and the coating thickness is 10-30nm.
  • the first mixture is spin-coated on the second sub-layer at a speed of 4000rpm-6500rpm, heated on a constant-temperature heating platform at a constant temperature, and the coating thickness is 10-30nm.
  • the aforementioned samples were placed in a vacuum coating machine, and an Ag electrode was vapor-deposited on the surface of the obtained hole transport layer under a vacuum condition of 5 ⁇ 10 ⁇ 4 Pa, and the thickness of the Ag electrode was 80 nm.
  • the SnO 2 nano-colloid aqueous solution refers to that SnO 2 particles are distributed in the aqueous solution with a particle diameter of 10-50 nm.
  • Perylene imide is Perylene tetracarboxylic acid diimide, abbreviated as PDI.
  • FAMAPbI 3 is formamidine methylamino lead iodide perovskite.
  • MAPbI 3 is a methylamino lead iodide perovskite.
  • MAPbI 2 Br is methylamino lead iodide bromide perovskite.
  • FA 0.85 Cs 0.15 PbI 3 is formamidine cesium lead iodide perovskite.
  • FA 0.9 Cs 0.1 PbI 3 is formamidine cesium lead iodide perovskite.
  • FA 0.9 MA 0.1 PbI 3 is formamidine methylamino lead iodide perovskite.
  • MAPbBr3 is a methylamino lead bromide perovskite.
  • DMF refers to N,N-dimethylformamide, and its English name is N,N-Dimethylformamide.
  • the preparation includes the first sublayer and the second sublayer and the third sublayer
  • the third mixture (target) is magnetron sputtered on the FTO conductive glass electrode.
  • the sputtering power is 1000W
  • the ratio of argon/oxygen is 1:1
  • the pressure is 0.25Pa
  • the sputtering thickness is 10-30nm
  • it is heated at 150°C for 20min.
  • the second mixture is spin-coated on the FTO conductive glass electrode at a speed of 4000rpm-6500rpm, heated at a constant temperature on a constant-temperature heating platform, and the coating thickness is 10-30nm.
  • the first mixture is spin-coated on the second sub-layer at a speed of 4000rpm-6500rpm, heated on a constant-temperature heating platform at a constant temperature, and the coating thickness is 10-30nm.
  • the aforementioned samples were placed in a vacuum coating machine, and an Ag electrode was evaporated on the surface of the obtained hole transport layer under a vacuum condition of 5 ⁇ 10 ⁇ 4 Pa, and the thickness of the Ag electrode was 80 nm.
  • the electron transport layer includes the first sublayer and the second sublayer
  • H101 in Table 3 represents triphenylamine with triptycene as the core
  • CzPAF-SBF represents N-(4-aniline) carbazole-spirobifluorene
  • Z101 represents 4-((E)-4-(bis(4 -((E)-4-(Dibutylamino)styryl)-phenyl)amino)styryl)-N-(4-((E)((E)-4-(Dibutylamino) Styryl)phenyl)amino)styryl)phenyl)-N-phenylaniline.
  • the aforementioned samples were placed in a vacuum coating machine, and an Ag electrode was evaporated on the surface of the obtained hole transport layer under a vacuum condition of 5 ⁇ 10 ⁇ 4 Pa, and the thickness of the Ag electrode was 80 nm.
  • Ultraviolet photoelectron spectroscopy UPS
  • XPS X-ray photoelectron spectroscopy
  • the test conditions are normal temperature, normal pressure and atmospheric environment, using He I lamp (21.2eV) as the laser source.
  • the UPS and XPS equipment models are Escalab 250Xi (Thermo Scientific).
  • the energy conversion efficiency is obtained through the voltage-current characteristic test, the intensity of the simulated solar light source is standard AM1.5G, and the test conditions are normal temperature, normal pressure and atmospheric environment.
  • the test equipment model is Guangyan IVS-KA5000.
  • CBM in the following description represents the bottom energy level of the conduction band
  • VBM represents the top energy level of the valence band
  • FLP represents the Fermi level difference
  • CBM1 represents the bottom energy level of the conduction band of the first sublayer
  • CBM2 represents the energy level of the first sublayer
  • the bottom energy level of the conduction band of the second sublayer CBM3 represents the bottom energy level of the conduction band of the third sublayer
  • CBM4 represents the bottom energy level of the conduction band of the hole transport layer
  • CBM5 represents the bottom energy level of the conduction band of the perovskite layer.
  • Example 9 to Example 14 and Comparative Example 5 to Comparative Example 7 are shown in Table 5 and Table 6.
  • the valence band top energy level of the first sublayer of the perovskite solar cells of Examples 9 to 14 is smaller than the valence band top energy level of the perovskite layer, and the first sublayer
  • the electron transport efficiency can be further improved, which is further conducive to improving the power conversion efficiency of perovskite solar cells.
  • Example 11 The performance test results of Example 11, Example 13 to Example 21 are shown in Table 7 and Table 8.
  • Example 20 Compared with Example 20, the difference between the conduction band bottom energy level and the Fermi level of the first sublayer of the perovskite solar cells of Example 11, Example 13 to Example 18 CBM1-FLP1 ⁇ 1.5eV, Its power conversion efficiency is higher.
  • Example 21 Compared with Example 21, the difference CBM-VBM between the bottom energy level of the conduction band and the top energy level of the valence band of the first sublayer of the perovskite solar cells of Examples 13 to 18 ⁇ 1.5eV, the power conversion higher efficiency.
  • the electron transport layer of the perovskite solar cell of Example 22 to Example 40 includes three sublayers, which is beneficial to improve the power conversion efficiency of the perovskite solar cell.

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Abstract

本申请提供了一种钙钛矿太阳能电池和光伏组件，钙钛矿太阳能电池包括：钙钛矿层，包括沿其厚度方向彼此相对的第一表面和第二表面；空穴传输层，设置于所述第一表面；以及电子传输层，设置于所述第二表面，所述电子传输层包括至少两层子层，所述电子传输层包括掺杂材料，各所述子层的导带底能级小于所述空穴传输层的导带底能级；各所述子层的价带顶能级小于所述空穴传输层的价带顶能级。本申请实施例的钙钛矿太阳能电池的能级结构，能够保证载流子的高效传输，提高钙钛矿太阳能电池的光电转换效率。

Description

钙钛矿太阳能电池和光伏组件
相关申请的交叉引用
本申请要求享有于2021年12月08日提交的名称为“钙钛矿太阳能电池和光伏组件”的中国专利申请202111494365.0的优先权，该申请的全部内容通过引用并入本文中。
技术领域
本申请涉及太阳能电池技术领域，尤其涉及一种钙钛矿太阳能电池和光伏组件。
背景技术
钙钛矿太阳能电池是利用有机金属卤化物钙钛矿材料作为吸光层的太阳能电池，具有优异的光电性质和简单的制备方法，为光伏发电带来了新的空间和希望。
在钙钛矿太阳能电池的生产过程中，如何进一步提高其光电转换效率是亟待解决的问题。
发明内容
本申请实施例提供一种钙钛矿太阳能电池和光伏组件，能够提高钙钛矿太阳能电池的光电转换效率。
本申请第一方面的实施例提供一种钙钛矿太阳能电池，钙钛矿太阳能电池包括钙钛矿层、空穴传输层和电子传输层。钙钛矿层包括沿其厚度方向彼此相对的第一表面和第二表面。空穴传输层设置于第一表面。电子传输层，设置于第二表面，电子传输层包括至少两层子层，电子传输层包括掺杂材料，各子层的导带底能级小于空穴传输层的导带底能级；各子层的价带顶能级小于空穴传输层的价带顶能级。
在本申请的钙钛矿太阳能电池，通过在电子传输层中掺杂有掺杂材料来调控能级结构，能够保证钙钛矿太阳能电池内建电场的形成，保证载流子的高效传输。同时，导带底能级差值能够保证电子的单向传输，价带顶能级差值能够保证空穴的单向传输，能够有效提高钙钛矿太阳能电池的光电转换效率。同时本申请的钙钛矿太阳能电池能够抑制钙钛矿层中的卤素迁移，提高钙钛矿太阳能电池的结构稳定性，从而进一步提高钙钛矿太阳能电池的光电转换效率。
在任意实施方式中，靠近第二表面的电子传输层的子层与钙钛矿层的导带底能级的差值为-1.0eV～1.0eV，可选地，子层与钙钛矿层的导带底能级的差值为-0.3eV～0.3eV；上述数值范围，能够提高电子的传输效率。
在任意实施方式中，靠近第二表面的电子传输层的子层的价带顶能级小于钙钛矿层的价带顶能级，能够在一定程度上避免空穴和电子复合，降低钙钛矿太阳能电池的电流。
在任意实施方式中，靠近第二表面的电子传输层的子层与钙钛矿层的费米能级的差值≤1.5eV，上述差值范围能够保证电子传输层为电子导电类型，提高电子传输效率。
在任意实施方式中，靠近第二表面的电子传输层的子层的导带底能级与费米能级的差值≤1.5eV，上述差值范围能够减少电子传输层与钙钛矿层之间不必要的能带弯曲，提高载流子传输速率，进而提高钙钛矿太阳能电池的光电转换效率。
在任意实施方式中，靠近第二表面的电子传输层的子层的导带底能级与价带顶能级的差值≥1.5eV，满足上述数值范围的子层具有较大带隙，能够过滤紫外光，避免了紫外光对钙钛矿层的损伤。
在任意实施方式中，电子传输层包括离开第二表面的方向依次层叠设置的第一子层、第二子层和第三子层，其中，第一子层为包括第一掺杂材料的氧化锡层，第一掺杂材料包括碱金属、碱土金属、过渡金属、贫金属、类金属、非金属元素、离子液体、羧酸、磷酸、碳衍生物、自组装单分子或有机高分子聚合物；包含三层子层的电子传输层能够灵活调控各层的能级，有利于提高载流子的提取效率和载流子的传输效率。
在任意实施方式中，碱金属包括Li、K、Na、Rb和Cs中的至少一种。
碱土金属包括Be、Sr和Ba中的至少一种。
过渡金属包括Ti、Cr、Mn、Fe、Co、Ni、Cu、Zn、Zr、Nb、Mo、Ru、Rh、Pd、Ag、Cd、Ta、Pt和Au中的至少一种。
贫金属包括Al、Ga、In、Sn、Tl、Pb和Bi中的至少一种。
类金属包括B、Si、Ge、As、Sb和Te中的至少一种。
非金属元素包括F、Cl、Br、I、P、S和Se中的至少一种。
离子液体包括1-丁基-3-甲基咪唑四氟硼酸盐、氯化铵、硫化铵、四甲基氢氧化铵和2,2,2-三氟乙醇中的至少一种。
羧酸包括乙二胺四乙酸、二乙烯三胺五乙酸、4-咪唑乙酸盐酸盐和醋酸中的至少一种。
碳衍生物包括碳量子点、碳纳米管、石墨烯、碳60、碳60衍生物、石墨相的氮化碳和碳9中的至少一种。
自组装单分子包括4-吡啶羧酸、多巴胺、3-氨丙基三乙氧基硅烷和甘氨酸中的至少一种。
有机高分子聚合物包括聚苯乙烯、聚乙氧基乙烯亚胺、聚氧化乙烯和氧化三苯基膦中的至少一种。
上述第一掺杂材料能够有效改善电子传输层的能级，并调节钙钛矿电池的能级结构。
在任意实施方式中，第二子层包括酰亚胺化合物层、醌类化合物层、富勒烯层、钙钛矿型氧化物层、氟化物层或氧化物层。第一子层和第二子层相互协同，能够有效改善电子传输层的能级结构。
在一些实施例中，酰亚胺化合物层包括酰亚胺化合物或酰亚胺化合物的衍生物，酰亚胺化合物包括：邻苯二甲酰亚胺、琥珀酰亚胺、N-溴代琥珀酰亚胺、戊二酰亚胺或马来酰亚胺。
醌类化合物层包括醌类化合物或醌类化合物的衍生物，醌类化合物包括苯醌、萘醌、菲醌或蒽醌。
钙钛矿型氧化物层包括钛酸锶、钛酸钙、钛酸钡、钛酸锂、钛酸亚铁、钛酸镍或钛酸钴。
氟化物层包括氟化锂或氟化钙。
氧化物层包括以下元素的氧化物层：Ce、Mg、Si、Cd、Zn、In、Pb、Mo、W、Sb、Bi、Cu、Hg、Ti、Ag、Mn、Fe、V、Sn、Zr、Sr、Ga或Cr。
上述材质的第二子层能够有效改善电子传输层的能级结构。
在任意实施方式中，第三子层包括金属氧化物层或包含第二掺杂材料的金属氧化物层，金属氧化物层包括SnO 2层、In 2O 3层、ZnO层、CdO层、NiO层、CdIn 2O 4层、Cd 2SnO 4层、Zn 2SnO 4层、MgIn 2O 4层、ZnIn 2O 4层、CoIn 3O 6层、ZnV 2O 6层、CuAlO 2层或CuGaO 2层。第一子层和第二子层以及第三子层相互协同，能够有效改善电子传输层的能级结构。
在任意实施方式中，SnO 2层包括第二掺杂材料，第二掺杂材料的元素包括F、Sb、P、As、Te和Cl中的至少一种。
In 2O 3层包括第二掺杂材料，第二掺杂材料的元素包括W、Mn、Zr、Ti、Sb、F和Ag中的至少一种。
ZnO层包括第二掺杂材料，第二掺杂材料的元素包括Ga、In、F、N、B和Al中的至少一种。包含上述第二掺杂材料的第三子层能够有效改善电子传输层的能级结构。
本申请第二方面提供一种光伏组件，包括如本申请第一方面任一实施例的钙钛矿太阳能电池。
附图说明
为了更清楚地说明本申请实施例的技术方案，下面将对本申请实施例中所需要使用的附图作简单地介绍，显而易见地，下面所描述的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据附图获得其他的附图。
图1为本申请一些实施例提供的钙钛矿太阳能电池的结构示意图；
图2是本申请另一些实施例提供的钙钛矿太阳能电池的结构示意图；
图3是本申请又一些实施例提供的钙钛矿太阳能电池的结构示意图。
在附图中，附图未必按照实际的比例绘制。
其中，图中各附图标记：
X、厚度方向；
10、钙钛矿层；10a、第一表面；10b、第二表面；
20、空穴传输层；
30、电子传输层；31、第一子层；32、第二子层；33、第三子层；
40、第一电极；50、第二电极。
具体实施方式
以下，适当地参照附图详细说明具体公开了本申请的钙钛矿太阳能电池、光伏组件的实施方式。但是会有省略不必要的详细说明的情况。例如，有省略对已众所周知的事项的详细说明、实际相同结构的重复说明的情况。这是为了避免以下的说明不必要地变得冗长，便于本领域技术人员的理解。此外，附图及以下说明是为了本领域技术人员充分理解本申请而提供的，并不旨在限定权利要求书所记载的主题。
本申请所公开的“范围”以下限和上限的形式来限定，给定范围是通过选定一个下限和一个上限进行限定的，选定的下限和上限限定了特别范围的边界。这种方式进行限定的范围可以是包括端值或不包括端值的，并且可以进行任意地组合，即任何下限可以与任何上限组合形成一个范围。例如，如果针对特定参数列出了60-120和80-110的范围，理解为60-110和80-120的范围也是预料到的。此外，如果列出的最小范围值1和2，和如果列出了最大范围值3，4和5，则下面的范围可全部预料到：1-3、1-4、1-5、2-3、2-4和2-5。在本申请中，除非有其他说明，数值范围“a-b”表示a到b之间的任意实数组合的缩略表示，其中a和b都是实数。例如数值范围“0-5”表示本文中已经全部列出了“0-5”之间的全部实数，“0-5”只是这些数值组合的缩略表示。另外，当表述某个参数为≥2的整数，则相当于公开了该参数为例如整数2、3、4、5、6、7、8、9、10、11、12等。
如果没有特别的说明，本申请的所有实施方式以及可选实施方式可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有技术特征以及可选技术特征可以相互组合形成新的技术方案。
如果没有特别的说明，本申请的所有步骤可以顺序进行，也可以随机进行，优选是顺序进行的。例如，方法包括步骤(a)和(b)，表示方法可包括顺序进行的步骤(a)和(b)，也可以包括顺序进行的步骤(b)和(a)。例如，提到方法还可包括步骤(c)，表示步骤(c)可以任意顺序加入到方法，例如，方法可以包括步骤(a)、(b)和(c)，也可包括步骤(a)、(c)和(b)，也可以包括步骤(c)、(a)和(b)等。
如果没有特别的说明，本申请所提到的“包括”和“包含”表示开放式，也可以是封闭式。例如，“包括”和“包含”可以表示还可以包括或包含没有列出的其他组分，也可以仅包括或包含列出的组分。
如果没有特别的说明，在本申请中，术语“或”是包括性的。举例来说，短语“A或B”表示“A，B，或A和B两者”。更具体地，以下任一条件均满足条件“A或B”：A为真(或存在)并且B为假(或不存在)；A为假(或不存在)而B为真(或存在)；或A和B都为真(或存在)。
钙钛矿太阳能电池包括钙钛矿层、空穴传输层和电子传输层以及电极。钙钛矿电池的工作过程主要包括：激子的产生及分离、自由载流子的传输、载流子的收集及电流的产生。具体过程如下：在钙钛矿太阳能电池中，太阳光被钙钛矿层吸收，钙钛矿层吸收光子产生激子，由于钙钛矿层具有较低的库仑力束缚，激子随后分离为自由的电子和空穴。分离后的自由载流子在钙钛矿层中传输，并通过传输层传输出去。电子传输层起到传输电子阻挡空穴的作用，空穴传输层起到传输空穴阻挡电子的作用。通过传输层传输出的电子和空穴分别被电极收集形成电流以及电压。
另外，在钙钛矿电池的工作过程中，载流子会在钙钛矿层与传输层的界面处发生复合，载流子的复合会严重影响钙钛矿太阳能电池的效率。
为了提高钙钛矿太阳能电池的光电转换效率，发明人通过体相掺杂方法调控能级结构对钙钛矿太阳能电池进行改进，调控能级结构能在一定程度上减少光生载流子复合，提高电子的提取和传输效率，进而提高开压及电流。
[钙钛矿太阳能电池]
本申请第一方面的实施例提供了一种钙钛矿太阳能电池。
图1示出了本申请一些实施例提供的钙钛矿太阳能电池的结构示意图，如图1所示，钙钛矿太阳能电池包括钙钛矿层10、空穴传输层20和电子传输层30。钙钛矿层10包括沿其厚度方向X彼此相对的第一表面10a和第二表面10b。空穴传输层20设置于第一表面10a。电子传输层30设置于第二表面10b，电子传输层30包括至少两层子层30a，电子传输层30包括掺杂材料，各子层30a的导带底能级小于空穴传输层20的导带底能级，各子层30a的导带底能级小于空穴传输层20的价带顶能级。
根据本申请实施例的钙钛矿太阳能电池，通过在电子传输层30中掺杂有掺杂材料来调控能级结构，以使电子传输层30中的各子层30a的导带底能级小于空穴传输层20的导带底能级，各子层30a的价带顶能级小于空穴传输层20的价带顶能级，各子层30a的能级与空穴传输层20能级存在能级差值，能级差值的存在能够保证钙钛矿太阳能电池内建电场的形成，保证载流子的高效传输。同时，导带底能级差值能够保证电子的单向传输，价带顶能级差值能够保证空穴的单向传输，能够有效提高钙钛矿太阳能电池的光电转换效率。同时本申请实施例能够抑制钙钛矿层10中的卤素迁移，提高钙钛矿太阳能电池的结构稳定性。
各子层30a和空穴传输层20之间的较大能级差值能够进一步保证钙钛矿太阳能电池内建电场的形成，保证载流子的高效传输。
在一些实施例中，靠近第二表面10b的电子传输层30的子层30a与钙钛矿层 10的导带底能级的差值为-1.0eV～1.0eV。可选地，靠近第二表面10b的电子传输层30的子层30a与钙钛矿层10的导带底能级的差值为-0.3eV～.3eV。靠近第二表面10b的电子传输层30的子层30a与钙钛矿层10的能级差满足上述数值范围，能够提高电子的传输效率。并且上述范围的导带底能级差值能够减少光生载流子的复合，提高开压及电流。
在一些实施例中，靠近第二表面10b的电子传输层30的子层30a的价带顶能级小于钙钛矿层10的价带顶能级。靠近第二表面10b的电子传输层30的子层30a的价带顶能级能够更有效地阻挡来自钙钛矿层10的空穴，能够在一定程度上避免空穴和电子复合，降低钙钛矿太阳能电池的电流。
在一些实施例中，靠近第二表面10b的电子传输层30的子层30a与钙钛矿层10的费米能级的差值≤1.5eV，上述差值范围能够保证电子传输层30为电子导电类型，提高电子传输效率。
由于剧烈的能带弯曲能够形成载流子传输通道上的壁垒，影响钙钛矿太阳能电池的性能。在一些实施例中，靠近第二表面10b的电子传输层30的子层30a的导带底能级与费米能级的差值≤1.5eV，上述差值范围能够减少电子传输层30与钙钛矿层10之间不必要的能带弯曲，提高载流子传输速率，进而提高钙钛矿太阳能电池的光电转换效率。
在一些实施例中，靠近第二表面10b的电子传输层30的子层30a的导带底能级与价带顶能级的差值≥1.5eV，满足上述数值范围的子层具有较大带隙，能够过滤紫外光，避免了紫外光对钙钛矿层10的损伤。
[电子传输层]
电子传输层30作为一种传输层，能够有效传输电子，减少钙钛矿层10和电子传输层30界面处的载流子复合，提高钙钛矿太阳能电池光电转换效率。
在本申请实施例中，电子传输层30包括至少两层子层30a。
示例性地，电子传输层30包括两层子层30a，分别为第一子层31和第二子层32；或者电子传输层30包括三层子层30a，分别为第一子层31、第二子层32和第三子层33；又或者电子传输层30包括四层子层，分别为第一子层31、第二子层32、第三子层33和第四子层等等。上述对电子传输层30的说明仅为示例性说明，并不用于限定电子传输层30的具体层数。
图2示出了本申请一些实施例提供的钙钛矿太阳能电池的结构示意图。如图2所示，在一些实施例中，电子传输层30包括三层子层，分别为第一子层31、第二子层32和第三子层33。第一子层31、第二子层32和第三子层33由离开第二表面10b的方向依次层叠设置。第一子层31靠近钙钛矿层10设置，第三子层33背离钙钛矿层10设置，第二子层32位于第一子层31和第三子层33之间。包含三层子层的电子传输层30能够灵活调控各层的能级，有利于提高载流子的提取效率和载流子的传输效率。
第一子层31为包含第一掺杂材料的氧化锡层。第一掺杂材料包括碱金属、碱土金属、过渡金属、贫金属、类金属、非金属元素、离子液体、羧酸、磷酸、碳衍生物、自组装单分子或有机高分子聚合物。氧化锡层具有较好的能级对准的同时自身的 迁移率较高，能够实现高效的电子提取和输运。通过在第一子层31中掺杂第一掺杂材料，第一掺杂材料能够调控第一子层31的能级，并能够钝化材料体相缺陷，提高载流子浓度及迁移率，从而提高钙钛矿太阳能电池的光电转换效率。
通过对第一掺杂材料进行选取，能够有效改善电子传输层30的能级，并调节钙钛矿电池的能级结构，接下来对第一掺杂材料进行具体举例说明。
作为碱金属的一些示例，碱金属包括Li、K、Na、Rb和Cs中的至少一种。
作为碱土金属的一些示例，碱土金属包括Be、Sr和Ba中的至少一种。
作为过渡金属的一些示例，过渡金属包括Ti、Cr、Mn、Fe、Co、Ni、Cu、Zn、Zr、Nb、Mo、Ru、Rh、Pd、Ag、Cd、Ta、Pt和Au中的至少一种。
作为贫金属的一些示例，贫金属包括包括Al、Ga、In、Sn、Tl、Pb和Bi中的至少一种。
作为类金属的一些示例，类金属包括B、Si、Ge、As、Sb和Te中的至少一种。
作为非金属元素的一些示例，非金属元素包括F、Cl、Br、I、P、S和Se中的至少一种。
作为离子液体的一些示例，离子液体包括1-丁基-3-甲基咪唑四氟硼酸盐、氯化铵、硫化铵、四甲基氢氧化铵和2,2,2-三氟乙醇中的至少一种。
作为羧酸的一些示例，羧酸包括乙二胺四乙酸、二乙烯三胺五乙酸、4-咪唑乙酸盐酸盐和醋酸中的至少一种。
作为碳衍生物的一些示例，碳衍生物包括碳量子点、碳纳米管、石墨烯、碳60、碳60衍生物、石墨相的氮化碳和碳9中的至少一种。
作为自组装单分子的一些示例，自组装单分子包括4-吡啶羧酸、多巴胺、3-氨丙基三乙氧基硅烷和甘氨酸中的至少一种。
作为有机高分子聚合物的一些示例，有机高分子聚合物包括聚苯乙烯、聚乙氧基乙烯亚胺、聚氧化乙烯和氧化三苯基膦中的至少一种。
第二子层32包括酰亚胺化合物层、醌类化合物层、富勒烯层、钙钛矿型氧化物层、氟化物层或氧化物层。第一子层31和第二子层32相互协同，能够有效改善电子传输层30的能级结构。
作为酰亚胺化合物层的一些示例，酰亚胺化合物层包括酰亚胺化合物或酰亚胺化合物的衍生物，酰亚胺化合物包括：邻苯二甲酰亚胺、琥珀酰亚胺、N-溴代琥珀酰亚胺、戊二酰亚胺或马来酰亚胺。
作为醌类化合物的一些示例，醌类化合物层包括醌类化合物或醌类化合物的衍生物，醌类化合物包括：苯醌、萘醌、菲醌或蒽醌。
作为钙钛矿型氧化物层的一些示例，钙钛矿型氧化物层包括钛酸锶、钛酸钙、钛酸钡、钛酸锂、钛酸亚铁、钛酸镍或钛酸钴。
作为氟化物层的一些示例，氟化物层包括氟化锂或氟化钙。
作为氧化物层的一些示例，氧化物层包括以下元素的氧化物层：Ce、Mg、Si、Cd、Zn、In、Pb、Mo、W、Sb、Bi、Cu、Hg、Ti、Ag、Mn、Fe、V、Sn、Zr、 Sr、Ga或Cr。
第三子层33包括金属氧化物层或包含第二掺杂材料的金属氧化物层，金属氧化物层包括SnO 2层、In 2O 3层、ZnO层、CdO层、NiO层、CdIn 2O 4层、Cd 2SnO 4层、Zn 2SnO 4层、MgIn 2O 4层、ZnIn 2O 4层、CoIn 3O 6层、ZnV 2O 6层、CuAlO 2层或CuGaO 2层。第一子层31和第二子层32以及第三子层33相互协同，能够有效改善电子传输层30的能级结构。
作为SnO 2层的一些示例，SnO 2层包括第二掺杂材料，第二掺杂材料的元素包括F、Sb、P、As、Te和Cl中的至少一种。
作为In 2O 3层的一些示例，In 2O 3层包括第二掺杂材料，第二掺杂材料的元素包括W、Mn、Zr、Ti、Sb、F和Ag中的至少一种。
作为ZnO层的一些示例，ZnO层包括第二掺杂材料，第二掺杂材料的元素包括Ga、In、F、N、B和Al中的至少一种。
[空穴传输层]
空穴传输层20作为一种传输层，能够有效传输空穴，减少钙钛矿层10和空穴传输层20界面处的载流子复合，提高钙钛矿太阳能电池光电转换效率。空穴传输层20的材质可以选取本领域常规的材质，在此不作限定。
[钙钛矿层]
钙钛矿层10作为光的吸收层，能够将光子转变为空穴和电子，其材质可以选取本领域常规的材质，在此不作限定。
本申请实施例的钙钛矿太阳能电池还包括第一电极和第二电极。第一电极、第二电极中至少有一个为透明电极。作为示例，透明电极为FTO导电玻璃电极。
图3示出了本申请一些实施例提供的钙钛矿太阳能电池的结构示意图，如图3所示，钙钛矿太阳能电池包括沿其厚度方向X依次设置的第一电极40、空穴传输层20、钙钛矿层10、电子传输层30和第二电极50，其中，电子传输层30包括第一子层31和第二子层32以及第三子层33。
[钙钛矿太阳能电池的制备方法]
本申请第二方面提供了一种钙钛矿太阳能电池的制备方法，用于制备本申请第一方面的钙钛矿太阳能电池，所制备的钙钛矿太阳能电池的电子传输层的各子层的导带底能级小于空穴传输层的导带底能级；各子层的价带顶能级小于空穴传输层的价带顶能级。
[光伏组件]
本申请第三方面还提供了一种光伏组件，包括本申请第一方面任一实施例的钙钛矿太阳能电池、或者本申请第二方面的方法所制备的钙钛矿太阳能电池。钙钛矿太阳能电池可以用作光伏组件的电源，也可以用作光伏组件的能量存储单元。
实施例
下述实施例更具体地描述了本申请公开的内容，这些实施例仅仅用于阐述性说明，因为在本申请公开内容的范围内进行各种修改和变化对本领域技术人员来说是明显的。除非另有声明，以下实施例中所报道的所有份、百分比、和比值都是基于重 量计，而且实施例中使用的所有试剂都可商购获得或是按照常规方法进行合成获得，并且可直接使用而无需进一步处理，以及实施例中使用的仪器均可商购获得。
实施例1-实施例21
制备FTO导电玻璃电极
取一组规格为2.0cm×2.0cm的FTO导电玻璃，FTO导电玻璃表面依次用丙酮和异丙醇清洗2次，浸入去离子水中超声处理10min，再在鼓风干燥箱中干燥后，放置在手套箱中(N2氛围)。
制备电子传输层，电子传输层包括第一子层和第二子层。
制备第二子层
在第二主体材料中加入第二掺杂材料以形成第二混合物，
以4000rpm～6500rpm的速度在FTO导电玻璃电极上旋涂第二混合物，在恒温热台上恒温加热，涂覆厚度为10～30nm。
制备第一子层
在第一主体材料中加入第一掺杂材料以形成第一混合物，
以4000rpm～6500rpm的速度在第二子层上旋涂第一混合物，在恒温热台上恒温加热，涂覆厚度为10～30nm。
制备钙钛矿层
以3000rpm～4500rpm的速度在所得到的第一子层上旋涂浓度为1.5mol/L的M溶液，之后将所得产物移至恒温热台上，以100℃加热30min，冷却至室温后，形成钙钛矿层，厚度为500nm。
制备空穴传输层
以4500rpm～6000rpm的速度在钙钛矿层上继续旋涂浓度为0.1mol/L的氧化铜的乙酸乙酯溶液，以100℃加热60min，厚度为30～60nm。
制备Ag电极
将前述样品放入真空镀膜机，在5×10 -4Pa的真空条件下，在所得到的空穴传输层表面蒸镀Ag电极，Ag电极厚度为80nm。
实施例1至实施例21中的相关物质种类如表1所示：
表1
Figure PCTCN2022128778-appb-000001
Figure PCTCN2022128778-appb-000002
Figure PCTCN2022128778-appb-000003
表1中，
SnO 2纳米胶体水溶液是指SnO 2颗粒以10～50nm粒径分布于水溶液中。苝酰亚胺为Perylene tetracarboxylic acid diimide，缩写PDI。FAMAPbI 3为甲脒甲胺基铅碘钙钛矿。MAPbI 3为甲胺基铅碘钙钛矿。MAPbI 2Br为甲胺基铅碘溴钙钛矿。FA 0.85Cs 0.15PbI 3为甲脒铯基铅碘钙钛矿。FA 0.9Cs 0.1PbI 3为甲脒铯基铅碘钙钛矿。FA 0.9MA 0.1PbI 3为甲脒甲胺基铅碘钙钛矿。MAPbBr 3为甲胺基铅溴钙钛矿。DMF是指N,N-二甲基甲酰胺，英文名称为N,N-Dimethylformamide。
实施例22-实施例40
制备FTO导电玻璃电极
取一组规格为2.0cm×2.0cm的FTO导电玻璃，FTO导电玻璃表面依次用丙酮和异丙醇清洗2次，浸入去离子水中超声处理10min，再在鼓风干燥箱中干燥后，放置在手套箱中(N 2氛围)。
制备包括第一子层和第二子层以及第三子层
制备第三子层
在第三主体材料中掺杂第三掺杂材料以形成第三混合物；
在FTO导电玻璃电极上磁控溅射第三混合物(靶材)。其中，溅射功率1000W，氩气/氧气比例1：1，压强0.25Pa，溅射厚度10～30nm，以150℃加热20min。
制备第二子层
在第二主体材料中加入第二掺杂材料以形成第二混合物，
以4000rpm～6500rpm的速度在FTO导电玻璃电极上旋涂第二混合物，在恒温热台上恒温加热，涂覆厚度为10～30nm。
制备第一子层
在第一主体材料中加入第一掺杂材料以形成第一混合物，
以4000rpm～6500rpm的速度在第二子层上旋涂第一混合物，在恒温热台上恒温加热，涂覆厚度为10～30nm。
制备钙钛矿层
以3000rpm～4500rpm的速度在所得到的电子传输层上旋涂浓度为1.5mol/L的FA 0.9MA 0.1PbI 3的DMF溶液，之后移至恒温热台上，以100℃加热30min，冷却至室温后，形成钙钛矿层，厚度为500nm。
制备空穴传输层
以4500rpm～6000rpm的速度继续在钙钛矿层上旋涂浓度为0.1mol/L的氧化铜的乙酸乙酯溶液，以100℃加热60min，厚度为30～60nm。
制备Ag电极
将前述样品放入真空镀膜机，在5×10 -4Pa的真空条件下所得到的空穴传输层表面蒸镀Ag电极，Ag电极厚度为80nm。
实施例22至实施例40中的相关物质种类如表2所示：
表2
Figure PCTCN2022128778-appb-000004
Figure PCTCN2022128778-appb-000005
Figure PCTCN2022128778-appb-000006
对比例1-对比例7
制备FTO导电玻璃电极
取一组规格为2.0cm×2.0cm的FTO导电玻璃，FTO导电玻璃表面依次用丙酮和异丙醇清洗2次，浸入去离子水中超声处理10min，再在鼓风干燥箱中干燥后，放置在手套箱中(N 2氛围)。
制备电子传输层，电子传输层包括第一子层和第二子层
制备第二子层
以4000rpm～6500rpm的速度在FTO导电玻璃电极上旋涂浓度为F溶液，以100℃加热10min，厚度为10～30nm。F溶液的具体种类如表5所示。
制备第一子层
以4000rpm～6500rpm在第二子层上旋涂3wt.％SnO 2纳米胶体水溶液，之后在恒温热台上以150℃加热15min，厚度为30～60nm。
制备钙钛矿层
以3000rpm～4500rpm的速度在第一子层上旋涂浓度为1.5mol/L的M溶液，之后移至恒温热台上，以100℃加热30min，冷却至室温后，形成钙钛矿层，厚度为500nm。M溶液的具体种类如表5所示。
制备空穴传输层
以4500rpm～6000rpm的速度在钙钛矿层上旋涂浓度为0.1mol/L的S溶液溶液，以100℃加热60min，厚度为30～60nm。S溶液的具体种类如表3所示。
表3
Figure PCTCN2022128778-appb-000007
Figure PCTCN2022128778-appb-000008
其中，表3中的H101表示三蝶烯为核的三苯胺，CzPAF-SBF表示N-(4-苯胺)咔唑-螺双芴，Z101表示4-((E)-4-(双(4-((E)-4-(二丁基氨基)苯乙烯基)苯基)氨基)苯乙烯基)-N-(4-((E)((E)-4-(二丁基氨基)苯乙烯基)苯基)氨基)苯乙烯基)苯基)-N-苯基苯胺。
制备Ag电极
将前述样品放入真空镀膜机，在5×10 -4Pa的真空条件下所得到的空穴传输层表面蒸镀Ag电极，Ag电极厚度为80nm。
钙钛矿太阳能电池的性能测试方法
1、能带分布测试方法
使用紫外光电子能谱仪(UPS)及X射线光电子能谱仪(XPS)测试所得到的电子传输层中各子层、空穴传输层和钙钛矿吸收层的能带分布。测试条件为常温、常压、大气环境，使用He I灯(21.2eV)为激光源。示例性地，UPS及XPS设备型号为Escalab 250Xi(Thermo Scientific)。
2、功率转换效率测试方法
能量转换效率通过电压-电流特性测试得到，模拟太阳光源强度为标准AM1.5G，测试条件为常温、常压、大气环境。示例性地，测试设备型号为光焱IVS-KA5000。
钙钛矿太阳能电池的性能测试结果
需要说明的是，以下描述中的CBM代表导带底能级，VBM代表价带顶能级，FLP代表费米能级差，其中，CBM1表示第一子层的导带底能级，CBM2表示第二子层的导带底能级，CBM3表示第三子层的导带底能级，CBM4表示空穴传输层的导带底能级，CBM5表示钙钛矿层的导带底能级。
1、实施例1至实施例8、对比例1至对比例4的性能测试结果如表4所示。
表4
Figure PCTCN2022128778-appb-000009
Figure PCTCN2022128778-appb-000010
由表4可知，相较于对比例1至4，实施例1至实施例8的钙钛矿太阳能电池的各子层的导带底能级小于空穴传输层的导带底能级，第一子层的电子传输效率较高，各子层的价带顶能级小于空穴传输层的价带顶能级，电子传输层的电子传输效率较高，有利于提升钙钛矿太阳能电池的功率转换效率。
2、实施例9至实施例14、对比例5至对比例7的性能测试结果如表5和表6所示。
表5
Figure PCTCN2022128778-appb-000011
表6
Figure PCTCN2022128778-appb-000012
由表5和表6可知，相较于对比例5至7，实施例9至实施例14的钙钛矿太阳能电池的第一子层与钙钛矿层的导带底能级的差值为-1.0eV～1.0eV，尤其是第一子层与钙钛矿层的导带底能级的差值为-0.3eV～0.3eV时，第一子层的电子传输效率较 高，有利于提升钙钛矿太阳能电池的功率转换效率。
相较于对比例5和对比例6，实施例9至实施例14的钙钛矿太阳能电池的第一子层的价带顶能级小于钙钛矿层的价带顶能级，第一子层的电子传输效率能够进一步提高，进一步有利于提升钙钛矿太阳能电池的功率转换效率。
3、实施例11、实施例13至实施例21的性能测试结果如表7和表8所示。
表7
Figure PCTCN2022128778-appb-000013
表8
Figure PCTCN2022128778-appb-000014
由表7和表8可知，相较于实施例19，实施例11、实施例13至实施例18的钙钛矿太阳能电池的第一子层与钙钛矿层的费米能级的差值FLP1-FLP5≤1.5eV，第一子层的电子传输效率较高，有利于提升钙钛矿太阳能电池的功率转换效率。
相较于实施例20，实施例11、实施例13至实施例18的钙钛矿太阳能电池的第一子层的导带底能级与费米能级的差值CBM1-FLP1≤1.5eV，其功率转换效率更高。
相较于实施例21，实施例13至实施例18的钙钛矿太阳能电池的第一子层的导带底能级与价带顶能级的差值CBM-VBM≥1.5eV，其功率转换效率更高。
4、实施例22至实施例40的性能测试结果如表9所示。
表9
Figure PCTCN2022128778-appb-000015
由表9可知，相较于实施例1，实施例22至实施例40的钙钛矿太阳能电池的电子传输层包括三层子层，有利于提升钙钛矿太阳能电池的功率转换效率。
虽然已经参考优选实施例对本申请进行了描述，但在不脱离本申请的范围的情况下，可以对其进行各种改进并且可以用等效物替换其中的部件，尤其是，只要不存在结构冲突，各个实施例中所提到的各项技术特征均可以任意方式组合起来。本申请并不局限于文中公开的特定实施例，而是包括落入权利要求的范围内的所有技术方案。

Claims (13)

  1. 一种钙钛矿太阳能电池，包括：
    钙钛矿层，包括沿其厚度方向彼此相对的第一表面和第二表面；
    空穴传输层，设置于所述第一表面；以及
    电子传输层，设置于所述第二表面，所述电子传输层包括掺杂材料，所述电子传输层包括至少两层子层，各所述子层的导带底能级小于所述空穴传输层的导带底能级；各所述子层的价带顶能级小于所述空穴传输层的价带顶能级。
  2. 根据权利要求1所述的钙钛矿太阳能电池，其中，
    靠近所述第二表面的所述电子传输层的子层与所述钙钛矿层的导带底能级的差值为-1.0eV～1.0eV，可选地，所述子层与所述钙钛矿层的导带底能级的差值为-0.3eV～0.3eV。
  3. 根据权利要求1或2所述的钙钛矿太阳能电池，其中，
    靠近所述第二表面的所述电子传输层的所述子层的价带顶能级小于所述钙钛矿层的价带顶能级。
  4. 根据权利要求1至3中任一项所述的钙钛矿太阳能电池，其中，
    靠近所述第二表面的所述电子传输层的子层与所述钙钛矿层的费米能级的差值≤1.5eV。
  5. 根据权利要求1至4中任一项所述的钙钛矿太阳能电池，其中，
    靠近所述第二表面的所述电子传输层的子层的导带底能级与费米能级的差值≤1.5eV。
  6. 根据权利要求1至5中任一项所述的钙钛矿太阳能电池，其中，
    靠近所述第二表面的所述电子传输层的子层的导带底能级与价带顶能级的差值≥1.5eV。
  7. 根据权利要求1至6中任一项所述的钙钛矿太阳能电池，其中，所述电子传输层包括离开所述第二表面的方向依次层叠设置的第一子层、第二子层和第三子层，其中，所述第一子层为包括第一掺杂材料的氧化锡层，所述第一掺杂材料包括碱金属、碱土金属、过渡金属、贫金属、类金属、非金属元素、离子液体、羧酸、磷酸、碳衍生物、自组装单分子或有机高分子聚合物。
  8. 根据权利要求7所述的钙钛矿太阳能电池，其中，
    所述碱金属包括Li、K、Na、Rb和Cs中的至少一种；
    所述碱土金属包括Be、Sr和Ba中的至少一种；
    所述过渡金属包括Ti、Cr、Mn、Fe、Co、Ni、Cu、Zn、Zr、Nb、Mo、Ru、Rh、Pd、Ag、Cd、Ta、Pt和Au中的至少一种；
    所述贫金属包括Al、Ga、In、Sn、Tl、Pb和Bi中的至少一种；
    所述类金属包括B、Si、Ge、As、Sb和Te中的至少一种；
    所述非金属元素包括F、Cl、Br、I、P、S和Se中的至少一种；
    所述离子液体包括1-丁基-3-甲基咪唑四氟硼酸盐、氯化铵、硫化铵、四甲基氢氧化铵和2,2,2-三氟乙醇中的至少一种；
    所述羧酸包括乙二胺四乙酸、二乙烯三胺五乙酸、4-咪唑乙酸盐酸盐和醋酸中的至少一种；
    所述碳衍生物包括碳量子点、碳纳米管、石墨烯、碳60、碳60衍生物、石墨相的氮化碳和碳9中的至少一种；
    所述自组装单分子包括4-吡啶羧酸、多巴胺、3-氨丙基三乙氧基硅烷和甘氨酸中的至少一种；
    所述有机高分子聚合物包括聚苯乙烯、聚乙氧基乙烯亚胺、聚氧化乙烯和氧化三苯基膦中的至少一种。
  9. 根据权利要求7或8所述的钙钛矿太阳能电池，其中，
    所述第二子层包括酰亚胺化合物层、醌类化合物层、富勒烯层、钙钛矿型氧化物层、氟化物层或氧化物层。
  10. 根据权利要求9所述的钙钛矿太阳能电池，其中，
    所述酰亚胺化合物层包括酰亚胺化合物或所述酰亚胺化合物的衍生物，所述酰亚胺化合物包括邻苯二甲酰亚胺、琥珀酰亚胺、N-溴代琥珀酰亚胺、戊二酰亚胺或马来酰亚胺；
    所述醌类化合物层包括醌类化合物或所述醌类化合物的衍生物，所述醌类化合物包括苯醌、萘醌、菲醌或蒽醌；
    所述钙钛矿型氧化物层包括钛酸锶、钛酸钙、钛酸钡、钛酸锂、钛酸亚铁、钛酸镍或钛酸钴；
    所述氟化物层包括氟化锂或氟化钙；
    所述氧化物层包括以下元素的氧化物层：Ce、Mg、Si、Cd、Zn、In、Pb、Mo、W、Sb、Bi、Cu、Hg、Ti、Ag、Mn、Fe、V、Sn、Zr、Sr、Ga或Cr。
  11. 根据权利要求7至10中任一项所述的钙钛矿太阳能电池，其中，所述第三子层包括金属氧化物层或包含第二掺杂材料的金属氧化物层，所述金属氧化物层包括SnO 2层、In 2O 3层、ZnO层、CdO层、NiO层、CdIn 2O 4层、Cd 2SnO 4层、Zn 2SnO 4层、 MgIn 2O 4层、ZnIn 2O 4层、CoIn 3O 6层、ZnV 2O 6层、CuAlO 2层或CuGaO 2层。
  12. 根据权利要求11所述的钙钛矿太阳能电池，其中，
    所述SnO 2层包括第二掺杂材料，所述第二掺杂材料的元素包括F、Sb、P、As、Te和Cl中的至少一种；
    所述In 2O 3层包括第二掺杂材料，所述第二掺杂材料的元素包括W、Mn、Zr、Ti、Sb、F和Ag中的至少一种；
    所述ZnO层包括第二掺杂材料，所述第二掺杂材料的元素包括Ga、In、F、N、B和Al中的至少一种。
  13. 一种光伏组件，包括如权利要求1至12任一项所述的钙钛矿太阳能电池。
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