WO2019080594A1 - 一种铁电增强型的太阳能电池及其制备方法 - Google Patents

一种铁电增强型的太阳能电池及其制备方法

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WO2019080594A1
WO2019080594A1 PCT/CN2018/099518 CN2018099518W WO2019080594A1 WO 2019080594 A1 WO2019080594 A1 WO 2019080594A1 CN 2018099518 W CN2018099518 W CN 2018099518W WO 2019080594 A1 WO2019080594 A1 WO 2019080594A1
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mesoporous
layer
ferroelectric
solar cell
nanocrystalline
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PCT/CN2018/099518
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English (en)
French (fr)
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韩宏伟
梅安意
刘爽
李小磊
张德义
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华中科技大学
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Priority to EP18871336.6A priority Critical patent/EP3553830B1/en
Priority to JP2019536975A priority patent/JP7012282B2/ja
Publication of WO2019080594A1 publication Critical patent/WO2019080594A1/zh
Priority to US16/655,271 priority patent/US11127535B2/en

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Definitions

  • the invention belongs to the technical field of solar cells, and more particularly to a ferroelectric enhanced solar cell and a preparation method thereof.
  • Solar energy has been extensively studied for its inexhaustible, inexhaustible, clean and pollution-free features.
  • Solar cells directly convert light energy into electrical energy and can be directly used in production and life. Therefore, it is important to prepare efficient, stable and low-cost solar cells to solve the current energy crisis.
  • Solar cells face charge injection and recombination losses during operation, which greatly limits the ultimate efficiency of solar cells.
  • ferroelectric materials In the unit cell structure of ferroelectric materials, the positive and negative charge centers do not coincide and the electric dipole moment occurs, resulting in an electrodeization intensity not equal to zero, so that the crystal has spontaneous polarization. Under the applied electric field, the direction of the electric dipole moment will follow. The electric field changes to exhibit an oriented electric field inside the crystal. This property of the crystal is called ferroelectricity. Ferroelectric materials, with their unique spontaneous polarization characteristics, can form a built-in electric field different from the PN junction of solar cells, and apply ferroelectric materials in solar cells, using ferroelectric materials to spontaneously polarize electric fields and PN junctions to build electric fields. Synergism is expected to greatly promote the separation and transmission of charge and inhibit recombination, thereby improving the efficiency of solar cells.
  • polymer ferroelectric materials have long been used in polymer solar cells, and Yuan et al. use LB film method to polymerize polyvinylidene fluoride-trifluoroethylene (P(VDF-TrFE)).
  • the material is used in a polymer solar cell, and the positive electrode of the ferroelectric layer is directed to the blended layer by artificial polarization, and the electric field effectively promotes the separation of excitons in the blended layer and reduces the recombination of electron holes.
  • the charge collection efficiency is increased, and the photoelectric conversion efficiency of the battery is nearly doubled (see Reference: [1] Yuan Y, Reece T J, Sharma P, et al.
  • organic ferroelectric materials have been successfully applied in polymer solar cells, there are also many problems.
  • the insulating properties of ferroelectric materials affect the transport of carriers inside the solar cells on the one hand, and it is difficult to obtain crystallinity on the other hand.
  • the organic ferroelectric material greatly reduces the residual polarization. These aspects have limited the application of organic ferroelectric materials in solar cells.
  • an object of the present invention is to provide a ferroelectric-enhanced solar cell and a method for fabricating the same, wherein a common thin film is replaced by a ferroelectric nano material having good crystallinity, such as nanoparticles.
  • the aspect has high residual polarization, on the other hand, it does not affect the transmission of carriers inside the solar cell.
  • the inorganic ferroelectric material treated by the specific artificial polarization process can effectively promote the carrier.
  • the present invention also utilizes materials used in each layer structure of the ferroelectric-enhanced solar cell (including specific The overall fit of the material type and particle size requirements, the shape parameters of each layer structure, and the like, particularly effectively control the mesoporous morphology of each mesoporous layer, so that the ferroelectric enhanced solar cell as a whole has a good photoelectric conversion effect.
  • a ferroelectric-enhanced solar cell characterized in that the solar cell comprises a conductive substrate (1) and an empty layer deposited on the conductive substrate (1) in sequence a hole blocking layer (2), a mesoporous nanocrystalline layer (3), a mesoporous spacer layer (4) and a mesoporous back electrode layer (5), wherein the mesoporous nanocrystalline layer (3), the mesoporous spacing At least one of the layer (4) and the mesoporous back electrode layer (5) is further filled with a photoactive material in the mesopores;
  • At least one of the hole blocking layer (2), the mesoporous nanocrystalline layer (3), and the mesoporous spacer layer (4) comprises a ferroelectric material or a ferroelectric nanocomposite.
  • the thickness of the hole blocking layer (2) does not exceed 100 nm;
  • the mesoporous nanocrystalline layer (3) comprises the ferroelectric material or the ferroelectric nanocomposite, the mesoporous nanocrystalline layer (3) has a thickness of 100 nm to 5000 nm;
  • the mesoporous spacer layer (4) When the ferroelectric material or the ferroelectric nanocomposite is included, the mesoporous spacer layer (4) has a thickness of 100 nm to 5000 nm.
  • the ferroelectric material is a dielectric material having a ferroelectric effect; preferably, the hole blocking layer (2) and the iron in the mesoporous nanocrystalline layer (3) dielectric material is BaSnO 3, the spacer layer of the mesoporous ferroelectric material (4) is from CaTiO 3, BaTiO 3, PbZrO 3 , PbTiO 3, PbZrO 3, ZnTiO 3, BaZrO 3, Pb (Zr 1-x Ti x )O 3 , (La y Pb 1-y )(Zr 1-x Ti x )O 3 , (1-x)[Pb(Mg 1/3 Nb 2/3 )O 3 ].
  • x in x[PbTiO 3 ] satisfies 0 ⁇ x ⁇ 1; x in the (La y Pb 1-y )(Zr 1-x Ti x )O 3 satisfies 0 ⁇ x ⁇ 1; y satisfies 0 ⁇ y ⁇ 1; x in the Pb(Sr x Ta 1-x )O 3 satisfies 0 ⁇ x ⁇ 1; x in the Ba x Sr 1-x TiO 3 satisfies 0 ⁇ x ⁇ 1;
  • the ferroelectric material in the mesoporous nanocrystalline layer (3) or the mesoporous spacer layer (4) has a particle diameter of 5 nm to 200 nm.
  • the ferroelectric nanocomposite is a composite material having a core-shell structure with a ferroelectric material nanoparticle as a core and an insulating material as a shell; preferably, the insulating material is ZrO 2 At least one of Al 2 O 3 and SiO 2 ; the ferroelectric material corresponding to the hole blocking layer (2) and the mesoporous nanocrystalline layer (3) is BaSnO 3 , corresponding to the mesoporous spacer layer
  • the ferroelectric material of (4) is CaTiO 3 , BaTiO 3 , PbZrO 3 , PbTiO 3 , PbZrO 3 , ZnTiO 3 , BaZrO 3 , Pb(Zr 1-x Ti x )O 3 , (La y Pb 1-y ) (Zr 1-x Ti x )O 3 , (1-x)[Pb(Mg 1/3 Nb 2/3 )O 3 ].
  • x in x[PbTiO 3 ] satisfies 0 ⁇ x ⁇ 1;
  • x in the (La y Pb 1-y )(Zr 1-x Ti x )O 3 satisfies 0 ⁇ x ⁇ 1, and y satisfies 0 ⁇ y ⁇ 1;
  • x in the Pb(Sr x Ta 1-x )O 3 satisfies 0 ⁇ x ⁇ 1;
  • x in the Ba x Sr 1-x TiO 3 satisfies 0 ⁇ x ⁇ 1;
  • the ferroelectric nanocomposite in the mesoporous nanocrystalline layer (3) or the mesoporous spacer layer (4) has a particle diameter of 5 to 200 nm.
  • the hole blocking layer (2) is a dense inorganic oxide semiconductor material film or a dense ferroelectric material film; wherein the inorganic oxide semiconductor material is TiO 2 , ZnO or SnO 2 .
  • the mesoporous nanocrystalline layer (3) is a mesoporous TiO 2 nanocrystalline layer, a mesoporous ZnO nanocrystalline layer, a mesoporous SnO 2 nanocrystalline layer, a mesoporous ferroelectric nanocrystal layer, Or a mesoporous ferroelectric nanocomposite nanocrystalline layer; preferably, the mesoporous nanocrystalline layer (3) is a mesoporous BaSnO 3 nanocrystalline layer.
  • the mesoporous spacer layer (4) is a mesoporous ZrO 2 layer, a mesoporous SiO 2 layer, a mesoporous Al 2 O 3 layer, a mesoporous ferroelectric material layer, or a mesoporous ferroelectric nanometer. Composite layer.
  • the photoactive material is a perovskite semiconductor material or a semiconductor material having a band gap of not more than 2 eV;
  • the perovskite semiconductor material has a chemical formula of ABX 3 , wherein A is A At least one of an amine, a formazan, and an alkali metal element, B is at least one of lead and tin, and X is at least one of iodine, bromine, and chlorine;
  • the narrow band gap semiconductor material is Se or SbSe. At least one of CdSe.
  • the ferroelectric-enhanced solar cell device is obtained by drying and removing the solvent in the precursor liquid.
  • the mesoporous back electrode layer is a mesoporous carbon electrode layer.
  • the invention adopts a ferroelectric material having ferroelectric properties or a core-shell structure nanocomposite composed of ferroelectric materials to form one or several layers in the hole blocking layer, the mesoporous nanocrystalline layer and the mesoporous spacer layer.
  • the ferroelectric material constitutes a hole blocking layer or a mesoporous nanocrystalline layer, taking BaSnO 3 as an example, the band position is matched with the light absorbing material (especially a perovskite light absorbing material), and has good electrical conductivity, and at the same time After artificial polarization, BaSnO 3 generates an oriented electric field inside it, which can further promote the separation and transport of charges.
  • ferroelectric materials are used as mesoporous spacers, such as BaTiO 3 and Pb (Zr 1-x Ti x ) O 3 and so on are good inorganic insulating ferroelectric materials. These materials have good insulating properties and can meet the requirements of the spacer layer in solar cells. At the same time, after artificial polarization, the electric field generated inside can promote the charge separation and back. The transmission of the electrodes.
  • the invention also controls the polarization step in the preparation process of the solar cell, controls the polarization environment temperature to be between 80 ° C and 150 ° C, and controls the magnitude and direction of the electric field strength of the applied electric field, and the applied electric field strength satisfies E. ⁇ 10kV/mm, the direction perpendicular to the plane of the conductive substrate and the applied electric field from the mesoporous nanocrystalline layer to the mesoporous back electrode layer ensures the polarization effect of the ferroelectric material.
  • a ferroelectric material or a core-shell nanocomposite composed of a ferroelectric material constitutes one or more layers of a hole blocking layer, a mesoporous nanocrystalline layer and a mesoporous spacer layer, it can block
  • the holes are directly transmitted to the conductive substrate or act as a photoactive material support, while an oriented polarized electric field exists in the mesoporous ferroelectric material layer after applying an applied electric field at a certain temperature, so that the light filled in the mesoporous layer is filled.
  • the separation and transport efficiency of the electron-hole pairs generated by the active material material after absorbing sunlight is greatly improved, thereby improving the photoelectric conversion efficiency of the solar cell.
  • a ferroelectric material (including a ferroelectric nanocomposite) is introduced into a mesoporous nanocrystalline layer or a mesoporous spacer layer, and a ferroelectric material can be used as a support for a photoactive material, and a unique iron can be utilized.
  • the electrical effect is to form an orientation electric field inside the ferroelectric material by polarization, which helps to promote charge separation and transmission in the photoactive layer, reduce recombination and transmission loss, thereby improving the photoelectric conversion efficiency of the solar cell.
  • the present invention utilizes the ferroelectric effect to promote the separation and transmission of electrons and holes in a solar cell, thereby achieving higher photoelectric conversion efficiency.
  • the preparation process of the invention is simple, and the ferroelectric material is utilized to improve the separation and transmission of electrons and holes in the entire solar cell.
  • FIG. 1 is a schematic view showing the structure of a battery of a ferroelectric-enhanced solar cell according to an embodiment of the present invention.
  • 1 is a conductive substrate
  • 2 is a hole blocking layer
  • 3 is a nanocrystalline layer
  • 4 is a mesoporous spacer layer
  • 5 is a mesoporous back electrode
  • a photoactive material is filled in all mesoporous layers.
  • Medium ie, nanocrystalline layer 3, mesoporous spacer layer 4 and mesoporous back electrode 5).
  • Perovskite solar cell based on Pb(Zr x Ti 1-x )O 3 as mesoporous spacer
  • the device uses conductive glass (such as transparent conductive glass, such as FTO, etc.) as the conductive substrate (1), deposits a thin layer of titanium dioxide (2) with a thickness of 50 nm, and sequentially prepares a titanium dioxide nanocrystalline layer by screen printing from bottom to top ( 3), mesoporous spacer layer (4), mesoporous back electrode (5), sequentially sintered at a high temperature, for example, 500 ° C, then the positive electrode is connected to the FTO conductive substrate, the negative electrode is connected to the back electrode of the mesoporous, and the field strength is, for example, 2.5 kV. /mm, the direction of the electric field can be directed to the mesoporous back electrode layer by the conductive substrate, and polarized for a period of time, for example 20 min, at a temperature of 80 °C.
  • conductive glass such as transparent conductive glass, such as FTO, etc.
  • the nano titanium dioxide grain size is, for example, 18 nm, and the thickness of the titanium dioxide layer is, for example, about 1 ⁇ m.
  • the titanium dioxide grain size is, for example, 20 nm, and the thickness is, for example, about 1 ⁇ m.
  • the mesoporous spacer layer is a Pb(Zr x Ti 1-x )O 3 mesoporous spacer layer (x may take any value in the range of 0 to 1) or a ZrO 2 mesoporous spacer layer, and a uniform stable particle size of, for example, 30 nm of Pb (Zr x Ti 1-x )O 3 nanoparticles or ZrO 2 nanoparticles having a particle size of, for example, 30 nm, and having a certain viscosity in a ratio of 1:1:5 by mass ratio of ethyl cellulose to terpineol
  • the slurry of the degree is further removed by high-temperature sintering (for example, 400 to 500 ° C) to form a film having a mesoporous porous structure, thereby obtaining a mesoporous spacer having a thickness of, for example, about 1 ⁇ m.
  • the mesoporous back electrode layer is a mesoporous conductive film made of graphite or carbon black, and has a thickness of, for example, about 10 ⁇ m.
  • a certain amount of, for example, 4 ⁇ L of lead iodide (CH 3 NH 3 Pbl 3 ) precursor solution (30 wt%) is added dropwise to the mesoporous back electrode, allowed to stand for 10 minutes, and then dried, for example, at 100 ° C. can.
  • the test shows that the photoelectric conversion efficiency of the unpolarized device is 9.77% when Pb(Zr x Ti 1-x )O 3 is used as the mesoporous spacer under 100mW*cm -2 simulated sunlight.
  • the conversion efficiency was 11.03%; the photoelectric conversion efficiencies before and after polarization were 3.54% and 8.51%, respectively, when ZrO 2 was used as the mesoporous spacer layer.
  • the device uses conductive glass as the conductive substrate (1), deposits a dense layer (2) of a thickness of, for example, 50 nm, and then deposits a nanocrystalline layer (3) in a screen printing manner from bottom to top, and the mesoporous spacer layer (4)
  • the mesoporous back electrode (5) is sequentially sintered at a high temperature, for example, 400 ° C, and then the positive electrode is connected to the FTO conductive substrate, and the negative electrode is connected to the back electrode of the mesopores.
  • the field strength is, for example, 1.5 kV/mm, and the temperature is 80 ° C.
  • the mesoporous nanocrystalline layer is a BaSnO 3 mesoporous nanocrystalline layer or a TiO 2 mesoporous nanocrystalline layer, and BaSnO 3 nanoparticles having a uniform stable particle size of, for example, 30 nm or TiO 2 nanoparticles and ethyl fibers having a particle size of, for example, 30 nm are used.
  • the pigment and terpineol are formulated into a slurry having a certain viscosity at a mass ratio of 1:2:7, and formed to have a thickness of, for example, about 800 nm after sintering.
  • the ZrO 2 grain size is, for example, 20 nm, and the thickness is, for example, about 2 ⁇ m.
  • the mesoporous back electrode layer is a mesoporous conductive film made of graphite or carbon black, and has a thickness of, for example, about 10 ⁇ m.
  • a certain amount of, for example, 4 ⁇ L of lead iodide (CH 3 NH 3 Pbl 3 ) precursor solution (30 wt%) is added dropwise to the mesoporous back electrode, allowed to stand for 10 minutes, and then dried, for example, at 100 ° C. can.
  • the test shows that the photoelectric conversion efficiency of the unpolarized device is 10.60% and the photoelectric conversion efficiency of the device after polarization is 11.34% when using BaSnO 3 mesoporous nanocrystalline layer under 100mW*cm -2 simulated sunlight.
  • the photoelectric conversion efficiencies of the 2 mesoporous nanocrystalline layers before and after polarization were 10.10% and 10.15%, respectively.
  • Perovskite solar cell based on BaSnO 3 as mesoporous nanocrystalline layer and Pb(Zr x Ti 1-x )O 3 as mesoporous spacer layer
  • the device uses conductive glass as the conductive substrate (1), deposits a dense layer (2) of a thickness of, for example, 30 nm, and then sequentially prepares a BaSnO 3 nanocrystalline layer (3), Pb (Zr x Ti) from bottom to top by screen printing.
  • mesoporous spacer layer (4) mesoporous back electrode layer (5), which is sequentially sintered at a high temperature, for example, 500 ° C, then the positive electrode is connected to the FTO conductive substrate, and the negative electrode is connected to the back electrode of the mesopores, and the field strength is For example, it is 4.5 kV/mm, and the polarization is performed at a temperature of 120 ° C for a period of time, for example, 20 min.
  • BaSnO 3 mesoporous nanocrystalline layer for example, a uniform and stable particle size of 30nm nanoparticles BaSnO 3 and ethyl cellulose, terpineol according to a mass ratio of 1: 2: 7 ratio formulated to have a certain viscosity
  • the slurry is then sintered to form a mesoporous BaSnO 3 nanocrystalline layer having a thickness of, for example, about 800 nm.
  • Pb(Zr x Ti 1-x )O 3 mesoporous spacer layer which has a uniform stable particle size of, for example, 30 nm of Pb(Zr x Ti 1-x )O 3 nanoparticles and ethyl cellulose, terpineol according to mass
  • the ratio of 1:1:5 is formulated into a slurry having a certain viscosity, and then sintered to form a mesoporous layer having a thickness of, for example, about 1 ⁇ m.
  • the mesoporous back electrode layer is a mesoporous conductive film made of graphite or carbon black, and has a thickness of, for example, about 10 ⁇ m.
  • a certain amount of, for example, 4 ⁇ L of lead iodide (CH 3 NH 3 Pbl 3 ) precursor solution (30 wt%) is added dropwise to the mesoporous back electrode, allowed to stand for 10 minutes, and then dried, for example, at 100 ° C. can.
  • Tests show that under 100mW*cm -2 simulated sunlight, the photoelectric conversion efficiency of the unpolarized device is 10.06%, and the photoelectric conversion efficiency of the device after polarization is 11.76%.
  • Perovskite solar cell based on ZrO 2 wrapped Pb(Zr x Ti 1-x )O 3 nanocomposite as mesoporous spacer
  • the device uses conductive glass as the conductive substrate (1), deposits a dense layer (2) of a thickness of 50 nm, for example, and then sequentially prepares a titanium dioxide nanocrystalline layer (3) by screen printing from bottom to top, and ZrO 2 encapsulates Pb (Zr).
  • the nano titanium dioxide grain size is, for example, 18 nm, and the thickness of the titanium dioxide layer is, for example, about 1 ⁇ m.
  • the titanium dioxide grain size is, for example, 20 nm and a thickness of, for example, 800 nm.
  • the mesoporous spacer layer is a ZrO 2 coated Pb(Zr x Ti 1-x )O 3 mesoporous spacer layer or a ZrO 2 mesoporous spacer layer, and a uniform stable particle size of, for example, 30 nm of ZrO 2 is wrapped with Pb (Zr x Ti 1- x )O 3 nanocomposite particles (ie, core-shell composite particles with ZrO 2 as the shell and Pb(Zr x Ti 1-x )O 3 as the core, the overall particle size of the core-shell composite particles is 30 nm Or ZrO 2 nanoparticles having a particle size of, for example, 30 nm, and a slurry having a
  • the mesoporous back electrode layer is a mesoporous conductive film made of graphite or carbon black, and has a thickness of, for example, about 10 ⁇ m.
  • a certain amount of, for example, 4 ⁇ L of lead iodide (CH 3 NH 3 Pbl 3 ) precursor solution (30 wt%) is added dropwise to the mesoporous back electrode, allowed to stand for 10 minutes, and then dried, for example, at 100 ° C. can.
  • the test shows that the photoelectric conversion efficiency of the unpolarized device is 9.56% when the ZrO 2 is coated with Pb(Zr x Ti 1-x )O 3 as a mesoporous spacer under 100mW*cm -2 simulated sunlight. After that, the photoelectric conversion efficiency of the device was 11.77%; when ZrO 2 was used as the mesoporous spacer layer, the photoelectric conversion efficiencies before and after polarization were 8.54% and 8.51%, respectively.
  • the conductive substrate may preferably be a conductive glass or a conductive plastic
  • the hole blocking layer (2) is an inorganic oxide film having good hole blocking ability, preferably a dense titanium oxide film and a tin oxide film, and the thickness is preferably 30 nm, but not limited to the above two films, the thickness can be adjusted as needed, for example, 10-50 nm.
  • the mesoporous nanocrystalline layer (3) is TiO 2 , ZnO, SnO 2 , BaSnO 3 , BaTiO 3 , (Na x Bi 1-x )TiO 3 , (K x Bi 1-x )TiO 3 and is involved in the above materials.
  • the grain size is not limited to 18 nm or 30 nm, and may be selected as needed, for example, 20 to 100 nm, and the thickness is not limited to the above embodiment, for example, 0.5 to 2 ⁇ m.
  • the mesoporous spacer layer is ZrO 2 , SiO 2 , Al 2 O 3 , CaTiO 3 , BaTiO 3 , PbZrO 3 , PbTiO 3 , PbZrO 3 , ZnTiO 3 , BaZrO 3 , Pb(Zr 1-x Ti x )O 3 , ( La y Pb 1-y )(Zr 1-x Ti x )O 3 , (1-x)[Pb(Mg 1/3 Nb 2/3 )O 3 ].
  • the particle size is not limited to the above embodiment, and may be adjusted as needed, for example, 10-100 nm, and the thickness may be adjustable at 1-4 ⁇ m.
  • the mesoporous back electrode 5 is preferably a high work function material such as a carbon electrode or indium tin oxide, but is not limited to the above two kinds of back electrodes.
  • the photoactive material is not limited to the iodized lead methylamine (CH 3 NH 3 Pbl 3 ) perovskite semiconductor material given in the examples, and all the perovskite photoactive materials of the chemical formula ABX 3 satisfy the condition, wherein A is A At least one of an amine, a formazan, and an alkali metal element, B is at least one of lead and tin, and X is at least one of iodine, bromine, and chlorine; and a narrow band gap is included in addition to the perovskite-based photoactive material. Photoactive materials such as Se, SbSe, CdSe, and the like.
  • the mesoporous material, the nanocrystalline material and the like in the present invention satisfy the conventional definition in the art, that is, the mesoporous material refers to a kind of porous material having a pore diameter of 2 to 100 nm, and the nanocrystalline material refers to a crystal structure having a size of 1 to 100 nm. Nanomaterials.
  • the sintering may be performed by one method of depositing one layer per deposition, or by depositing a plurality of layers (for example, two layers or more) and then sintering, for example, sintering once after depositing the mesoporous nanocrystalline layer.
  • the mesoporous spacer layer and the mesoporous back electrode layer are deposited and then sintered once.
  • the electric field strength satisfies E ⁇ 10 kV/mm, and the direction is perpendicular to the plane of the conductive substrate and is directed from the mesoporous nanocrystalline layer to the mesoporous back electrode layer.
  • the photoactive material in the present invention may be a light absorbing semiconductor material, in addition to a perovskite semiconductor material (corresponding to a perovskite solar cell), it may also be an organic material having photosensitive properties (corresponding to an organic solar cell), or photosensitive a dye (corresponding to a dye-sensitized solar cell) or the like; at the time of preparation, a photoactive material precursor droplet may be applied onto the polarized solar cell frame structure (ie, dispensed onto the polarized mesoporous back electrode layer) The precursor liquid is sequentially filled in the nanopore of the mesoporous back electrode, the mesoporous spacer layer, and the mesoporous nanocrystalline layer from top to bottom.
  • the dense hole blocking layer that is, the electron transport layer, may be, for example, a dense titanium oxide film, a dense tin oxide film, a dense zinc oxide film, or a dense ferroelectric material or a nano-ferroelectric composite film.
  • At least one of the hole blocking layer, the mesoporous nanocrystalline layer and the mesoporous layer may be composed of a ferroelectric material or a ferroelectric nanocomposite.
  • the layer thickness of each layer structure may be adjusted according to the needs of the battery; preferably, the ferroelectric material or the ferroelectric nanocomposite participates in the formation of the hole blocking layer having a thickness of not more than 100 nm ( Particularly preferably not more than 50 nm), the ferroelectric material or the ferroelectric nanocomposite participates in the mesoporous nanocrystalline layer having a thickness of 100 nm to 5000 nm (particularly preferably 500 nm to 1000 nm); the ferroelectric material or the ferroelectric nanocomposite participates in the composition.
  • the ferroelectric material or the ferroelectric nanocomposite participates in the formation of the hole blocking layer having a thickness of not more than 100 nm ( Particularly preferably not more than 50 nm)
  • the ferroelectric material or the ferroelectric nanocomposite participates in the mesoporous nanocrystalline layer having a thickness of 100 nm to 5000 nm (particularly preferably 500 nm to 1000 nm
  • the mesoporous spacer layer has a thickness of from 100 nm to 5000 nm (particularly preferably from 1 to 3 ⁇ m). It is possible to introduce a hole blocking layer, a mesoporous nanocrystalline layer or a mesoporous spacer layer of a ferroelectric material or a ferroelectric nanocomposite, and the preparation methods thereof can be referred to the prior art, and correspondingly, according to the thickness of each layer. Requirements, etc., flexible adjustment of the parameter conditions in the preparation method.
  • the overall energy band structure needs to meet the requirements of the prior art for the overall energy band of the solar cell.
  • the conduction band of the spacer material should be higher than the conduction band of the photoactive material (such as a perovskite photoactive material), and the ferroelectric material of the present invention, such as Pb(Zr 1-x Ti x )O 3 , (1 x) [Pb(Mg 1/3 Nb 2/3 )O 3 ].
  • x[PbTiO 3 ], etc., x satisfies 0 to 1 and can satisfy the energy band requirement of the corresponding ferroelectric material as the spacer layer.
  • a separate dense ferroelectric material film can be used as a hole blocking layer, and a photoactive material is a perovskite semiconductor material.
  • a ferroelectric material has a suitable energy band
  • the conduction band is lower than the perovskite light absorbing material.
  • the conduction band, the valence band is also lower than the valence band of the perovskite light absorbing material, and when it has good electrical conductivity, it can be used as a hole blocking layer and as an electron transport layer; for example, BaSnO 3 ferroelectric material can be deposited
  • a very thin dense film is used to serve as a hole blocking layer.
  • the ferroelectric material and the ferroelectric nanocomposite ie, a composite material having a core-shell structure using a ferroelectric material nanoparticle as a core and an insulating material as a shell
  • the ferroelectric material and the ferroelectric nanocomposite preferably have a particle diameter of 5 to 200 nm ( It is preferably 20 to 50 nm) in order to form a spacer layer or a nanocrystalline layer having a mesoporous structure.

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Abstract

本发明公开了一种铁电增强型的太阳能电池及其制备方法，其中该铁电增强型的太阳能电池包括导电基底(1)和依次沉积于该导电基底(1)上的空穴阻挡层(2)、介孔纳米晶层(3)、介孔间隔层(4)及介孔背电极层(5)，其中介孔纳米晶层(3)、介孔间隔层(4)和介孔背电极层(5)中的至少一层其介孔中还填充有光活性材料；并且，空穴阻挡层(2)、介孔纳米晶层(3)和介孔间隔层(4)中的至少一层包括铁电材料或铁电纳米复合材料。本发明利用结晶性良好的铁电纳米材料例如纳米颗粒代替普通薄膜，既具有较高的剩余极化强度，又不会对载流子的传输造成影响，经特定人工极化工艺处理后的无机铁电材料还能有效促进载流子的分离和传输。

Description

一种铁电增强型的太阳能电池及其制备方法 【技术领域】
本发明属于太阳能电池技术领域，更具体地，涉及一种铁电增强型的太阳能电池及其制备方法。
【背景技术】
太阳能以其取之不尽、用之不竭和清洁无污染等特点而受到广泛研究。太阳能电池直接将光能转化成电能可直接用于生产生活中，因此制备高效、稳定、低成本的太阳能电池对于解决当前面临的能源危机具有重要意义。太阳能电池在工作的过程中面临着电荷注入以及复合等损失，大幅度限制了太阳能电池的极限效率。
铁电材料的晶胞结构中正负电荷中心不重合而出现电偶极矩，产生不等于零的电极化强度，使晶体具有自发极化，在外加电场作用下，电偶极矩的方向会沿着电场改变，从而在晶体内部呈现出取向的电场，晶体的这种性质叫铁电性。铁电材料以其特有的自发极化特性，可以形成不同于太阳能电池PN结的内建电场，把铁电材料应用在太阳能电池中，利用铁电材料自发极化电场与PN结内建电场的协同作用有望大幅度促进电荷的分离与传输并抑制复合，从而提升太阳能电池的效率。
其中聚合物铁电材料在聚合物太阳能电池中早有应用，Yuan等人利用LB膜的方法将聚偏氟乙烯-三氟乙烯(P(VDF-TrFE))这种性能优异的聚合物铁电材料用于聚合物太阳能电池中，并通过人工极化的方式使铁电层正极指向共混层，该电场有效促进了共混层中的激子分离，并减小了电子空穴的复合，增加了电荷收集效率，最终使得电池的光电转换效率提高了近一倍(可参见参考文献：【1】Yuan Y,Reece T J,Sharma P,et al.Efficiency enhancement in organic solar cells with ferroelectric polymers[J].Nature  materials,2011,10(4):296-302.)；随后，该小组又成功的将P(VDF-TrFE)单分子层应用于给受体材料层之间，利用铁电层形成的内建电场有效降低了给受体材料间的能级差，减小了激子转移过程中产生的能量损耗，使器件的开路电压提高了25％。
虽然有机铁电材料已经成功应用于聚合物太阳能电池中，但是也存在诸多问题，铁电材料的绝缘性质一方面会影响载流子在太阳能电池内部的传输，另一方面难以得到结晶性良好的有机铁电材料使得剩余极化强度大大降低。这些方面都限制了有机铁电材料在太阳能电池中的应用。
【发明内容】
针对现有技术的以上缺陷或改进需求，本发明的目的在于提供一种铁电增强型的太阳能电池及其制备方法，其中通过利用结晶性良好的铁电纳米材料例如纳米颗粒代替普通薄膜，一方面既具有较高的剩余极化强度，另一方面又不会对太阳能电池内部载流子的传输造成影响，经特定人工极化工艺处理后的无机铁电材料还能有效促进载流子的分离和传输，能够有效解决现有技术中仅采用有机铁电材料、太阳能电池性能受限的问题，并且本发明还利用该铁电增强型太阳能电池内各个层结构所采用的材料(包括具体的材料种类及粒径要求等)、各个层结构的形状参数等的整体配合，尤其有效控制各个介孔层的介孔形貌，使该铁电增强型太阳能电池整体具有良好的光电转换效应。
为实现上述目的，按照本发明的一个方面，提供了一种铁电增强型的太阳能电池，其特征在于，该太阳能电池包括导电基底(1)和依次沉积于该导电基底(1)上的空穴阻挡层(2)、介孔纳米晶层(3)、介孔间隔层(4)及介孔背电极层(5)，其中所述介孔纳米晶层(3)、所述介孔间隔层(4)和所述介孔背电极层(5)中的至少一层其介孔中还填充有光活性材料；
并且，所述空穴阻挡层(2)、所述介孔纳米晶层(3)和所述介孔间隔层(4)中的至少一层包括铁电材料或铁电纳米复合材料。
作为本发明的进一步优选，当所述空穴阻挡层(2)包括所述铁电材料或所述铁电纳米复合材料时，该空穴阻挡层(2)的厚度不超过100nm；当所述介孔纳米晶层(3)包括所述铁电材料或所述铁电纳米复合材料时，该介孔纳米晶层(3)的厚度为100nm-5000nm；当所述介孔间隔层(4)包括所述铁电材料或所述铁电纳米复合材料时，该介孔间隔层(4)的厚度为100nm-5000nm。
作为本发明的进一步优选，所述铁电材料为具有铁电效应的介电材料；优选的，所述空穴阻挡层(2)和所述介孔纳米晶层(3)中的所述铁电材料为BaSnO 3，所述介孔间隔层(4)中的所述铁电材料为CaTiO 3，BaTiO 3、PbZrO 3、PbTiO 3、PbZrO 3、ZnTiO 3、BaZrO 3、Pb(Zr 1-xTi x)O 3、(La yPb 1-y)(Zr 1-xTi x)O 3、(1-x)[Pb(Mg 1/3Nb 2/3)O 3]﹒x[PbTiO 3]、BiFeO 3、Pb(Zn 1/3Nb 2/3)O 3、Pb(Mg 1/3Nb 2/3)O 3、(Na 1/2Bi 1/2)TiO 3、(K 1/2Bi 1/2)TiO 3、LiNbO 3、KNbO 3、KTaO 3、Pb(Sr xTa 1-x)O 3、Ba xSr 1-xTiO 3中的一种或多种；其中，所述Pb(Zr 1-xTi x)O 3和所述(1-x)[Pb(Mg 1/3Nb 2/3)O 3]﹒x[PbTiO 3]中的x满足0≤x≤1；所述(La yPb 1-y)(Zr 1-xTi x)O 3中的x满足0≤x≤1；y满足0≤y≤1；所述Pb(Sr xTa 1-x)O 3中的x满足0≤x≤1；所述Ba xSr 1-xTiO 3中的x满足0≤x≤1；
优选的，所述介孔纳米晶层(3)或所述介孔间隔层(4)中的铁电材料其粒径为5nm～200nm。
作为本发明的进一步优选，所述铁电纳米复合材料为以铁电材料纳米颗粒为核、且以绝缘材料为壳的具有核-壳结构的复合材料；优选的，所述绝缘材料为ZrO 2、Al 2O 3、SiO 2中的至少一种；对应所述空穴阻挡层(2)和所述介孔纳米晶层(3)的所述铁电材料为BaSnO 3，对应介孔间隔层(4)的所述铁电材料为CaTiO 3，BaTiO 3、PbZrO 3、PbTiO 3、PbZrO 3、ZnTiO 3、BaZrO 3、Pb(Zr 1-xTi x)O 3、(La yPb 1-y)(Zr 1-xTi x)O 3、(1-x)[Pb(Mg 1/3Nb 2/3)O 3]﹒x[PbTiO 3]、BiFeO 3、Pb(Zn 1/3Nb 2/3)O 3、Pb(Mg 1/3Nb 2/3)O 3、(Na 1/2Bi 1/2)TiO 3、(K 1/2Bi 1/2)TiO 3、LiNbO 3、KNbO 3、KTaO 3、Pb(Sr xTa 1-x)O 3、Ba xSr 1-xTiO 3中的一种或多种；其中，所述Pb(Zr 1-xTi x)O 3和所述(1-x)[Pb(Mg 1/3Nb 2/3)O 3]﹒x[PbTiO 3] 中的x满足0≤x≤1；所述(La yPb 1-y)(Zr 1-xTi x)O 3中的x满足0≤x≤1，y满足0≤y≤1；所述Pb(Sr xTa 1-x)O 3中的x满足0≤x≤1；所述Ba xSr 1-xTiO 3中的x满足0≤x≤1；
优选的，所述介孔纳米晶层(3)或所述介孔间隔层(4)中的铁电纳米复合材料其粒径为5～200nm。
作为本发明的进一步优选，所述空穴阻挡层(2)为致密无机氧化物半导体材料薄膜或致密铁电材料薄膜；其中，所述无机氧化物半导体材料为TiO 2、ZnO或SnO 2。
作为本发明的进一步优选，所述介孔纳米晶层(3)为介孔TiO 2纳米晶层、介孔ZnO纳米晶层、介孔SnO 2纳米晶层、介孔铁电材料纳米晶层、或介孔铁电纳米复合材料纳米晶层；优选的，所述介孔纳米晶层(3)为介孔BaSnO 3纳米晶层。
作为本发明的进一步优选，所述介孔间隔层(4)为介孔ZrO 2层、介孔SiO 2层、介孔Al 2O 3层、介孔铁电材料层、或介孔铁电纳米复合材料层。
作为本发明的进一步优选，所述光活性材料为钙钛矿类半导体材料或禁带宽度不超过2eV的半导体材料；所述钙钛矿类半导体材料其化学通式为ABX 3，其中A为甲胺、甲脒、碱金属元素中的至少一种，B为铅、锡中至少一种，X为碘、溴、氯中至少一种；优选的，所述窄禁带半导体材料为Se、SbSe、CdSe中的至少一种。
按照本发明的另一方面，本发明提供了制备上述铁电增强型太阳能电池的方法，其特征在于，包括以下步骤：
(1)在导电基底上制备一层空穴阻挡层；
(2)在所述空穴阻挡层上依次层叠介孔纳米晶层、介孔间隔层和介孔背电极层，烧结后得到太阳能电池框架结构；
(3)在80℃～150℃的温度下，对所述太阳能电池框架结构施加外加电场进行极化；所述外加电场的电场强度大小满足E≤10kV/mm，方向为垂 直于所述导电基底平面、并从所述介孔纳米晶层指向所述介孔背电极层；
(4)将光活性材料前驱液涂在所述步骤(3)得到的极化后的太阳能电池框架结构上，使所述光活性材料前驱液从上至下填充于所述介孔背电极、所述介孔间隔层及所述介孔纳米晶层的介孔中，烘干除去所述前驱液中的溶剂后即得到铁电增强型太阳能电池器件。
作为本发明的进一步优选，所述步骤(2)中，所述介孔背电极层为介孔碳电极层。
通过本发明所构思的以上技术方案，与现有技术相比，能够取得以下
有益效果：
本发明采用具有铁电性质的铁电材料或由铁电材料参与构成的核-壳结构纳米复合材料构成空穴阻挡层、介孔纳米晶层和介孔间隔层中的一层或几层。当铁电材料构成空穴阻挡层或介孔纳米晶层时，以BaSnO 3为例，能带位置与吸光材料(尤其是钙钛矿类吸光材料)相匹配，且具有良好的电导率，同时BaSnO 3经过人工极化之后，在其内部产生一个取向的电场，能够进一步促进电荷的分离和传输；当铁电材料作为介孔间隔层时，例如BaTiO 3、Pb(Zr 1-xTi x)O 3等都是良好的无机绝缘铁电材料，这类材料具有良好的绝缘性能，能够满足太阳能电池中间隔层的要求，同时经过人工极化之后，其内部产生的电场能够促进电荷分离和向背电极的传输。
本发明尤其还通过对太阳能电池制备过程中的极化步骤进行控制，将极化环境温度控制在80℃～150℃，并对外加电场的电场强度大小及方向进行控制，施加电场强度大小满足E≤10kV/mm，方向垂直于导电基底平面且从介孔纳米晶层指向介孔背电极层的外加电场，可确保铁电材料的极化效果。
综上所述，当铁电材料或由铁电材料参与构成的核-壳结构纳米复合材料构成空穴阻挡层、介孔纳米晶层和介孔间隔层中的一层或几层既能阻挡空穴直接向导电基底传输或作为光活性材料支架的作用，同时经过在一定 温度下施加外加电场后的介孔铁电材料层中存在取向的极化电场，使得填充在介孔层中的光活性材料材料在吸收太阳光后产生的电子-空穴对的分离及输运效率大大提高，从而提高太阳能电池的光电转换效率。以本发明中在介孔纳米晶层或介孔间隔层中引入铁电材料(包括铁电纳米复合材料)为例，既可用铁电材料作为光活性材料的支架，又能利用其特有的铁电效应，通过极化使铁电材料内部形成取向电场，该电场有助于促进光活性层中的电荷分离和传输，减小复合和传输损失，从而提高太阳能电池的光电转效率。
可见，本发明利用铁电效应促进太阳能电池中电子和空穴的分离和传输，从而实现更高的光电转换效率。本发明制备工艺简单，利用铁电材料来改善电子和空穴在整个太阳能电池中的分离与传输。
【附图说明】
图1是本发明实施例中的一种铁电增强型太阳能电池的电池结构示意图。
图中各附件标记的含义如下：1为导电基底，2为空穴阻挡层，3为纳米晶层，4为介孔间隔层，5为介孔背电极，光活性材料填充在所有介孔层中(即纳米晶层3、介孔间隔层4和介孔背电极5中)。
【具体实施方式】
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。此外，下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
实施例1
基于Pb(Zr xTi 1-x)O 3作介孔间隔层的钙钛矿太阳能电池
器件以导电玻璃(如透明导电玻璃，例如FTO等)为导电基板(1)， 沉积50nm厚度的二氧化钛致密层(2)后，自下而上以丝网印刷的方式依次制备二氧化钛纳米晶层(3)，介孔间隔层(4)，介孔背电极(5)，依次在高温下烧结例如500℃，然后正极接FTO导电基底，负极接介孔背电极，场强大小为例如为2.5kV/mm，电场方向可由导电基底指向介孔背电极层，温度为80℃条件下进行极化一段时间例如20min。
纳米二氧化钛晶粒大小例如为18nm，二氧化钛层厚度例如约为lμm。二氧化钛晶粒大小例如为20nm，厚度例如约为lμm。介孔间隔层为Pb(Zr xTi 1-x)O 3介孔间隔层(x可以取0～1范围内任意值)或ZrO 2介孔间隔层，将均一稳定颗粒大小例如为30nm的Pb(Zr xTi 1-x)O 3纳米颗粒或颗粒大小例如为30nm的ZrO 2纳米颗粒，与乙基纤维素、松油醇按照质量比为1:1:5的比例配制成具有一定粘稠度的浆料，再通过高温烧结(例如400～500℃)除去其中的乙基纤维素即可形成具有介孔多孔结构的薄膜，从而得到厚度例如约为1μm的介孔间隔层。介孔背电极层为石墨、炭黑制成的介孔导电薄膜，厚度例如约为10μm。将一定量例如4μL碘铅甲胺(CH 3NH 3Pbl 3)前驱液(30wt％)滴加在介孔背电极上，静置10分钟待其充分渗透后例如在100℃条件下烘干即可。测试表明在100mW*cm -2模拟太阳光下，采用Pb(Zr xTi 1-x)O 3作介孔间隔层时未经极化的器件光电转换效率为9.77％，极化之后的器件光电转换效率为11.03％；采用ZrO 2作介孔间隔层时极化前后光电转换效率分别为8.54％和8.51％。
实施例2
基于BaSnO 3用作介孔纳米晶层的钙钛矿太阳能电池
器件以导电玻璃为导电基板(1)，沉积一定厚度例如50nm二氧化钛致密层(2)后，自下而上以丝网印刷的方式依次沉积纳米晶层(3)，介孔间隔层(4)，介孔背电极(5)，依次在高温例如400℃下烧结，然后正极接FTO导电基底，负极接介孔背电极，场强大小为例如为1.5kV/mm，温度为80℃条件下进行极化一段时间例如20min(极化环境的温度越高， 所需要的极化场强越小)。
介孔纳米晶层为BaSnO 3介孔纳米晶层或者TiO 2介孔纳米晶层，将均一稳定颗粒大小例如为30nm的BaSnO 3纳米颗粒或颗粒大小例如为30nm的TiO 2纳米颗粒和乙基纤维素、松油醇按照质量比为1:2:7的比例配制成具有一定粘稠度的浆料，经烧结后形成厚度例如约为800nm。ZrO 2晶粒大小例如为20nm，厚度例如约为2μm。介孔背电极层为石墨、炭黑制成的介孔导电薄膜，厚度例如约为10μm。将一定量例如4μL碘铅甲胺(CH 3NH 3Pbl 3)前驱液(30wt％)滴加在介孔背电极上，静置10分钟待其充分渗透后例如在100℃条件下烘干即可。测试表明在100mW*cm -2模拟太阳光下，采用BaSnO 3介孔纳米晶层时，未经极化的器件光电转换效率为10.60％，极化之后的器件光电转换效率为11.34％；采用TiO 2介孔纳米晶层极化前后的光电转换效率分别为10.10％和10.15％。
实施例3
基于BaSnO 3用作介孔纳米晶层、Pb(Zr xTi 1-x)O 3作介孔间隔层的钙钛矿太阳能电池
器件以导电玻璃为导电基板(1)，沉积一定厚度例如30nm二氧化钛致密层(2)后，自下而上以丝网印刷的方式依次制备BaSnO 3纳米晶层(3)，Pb(Zr xTi 1-x)O 3介孔间隔层(4)，介孔背电极层(5)，依次在高温例如500℃下烧结，然后正极接FTO导电基底，负极接介孔背电极，场强大小为例如为4.5kV/mm，温度为120℃条件下进行极化一段时间例如20min。
介孔BaSnO 3纳米晶层，将均一稳定颗粒大小例如为30nm的的BaSnO 3纳米颗粒和乙基纤维素、松油醇按照按照质量比为1:2:7的比例配制成具有一定粘稠度的浆料，然后烧结形成厚度例如约为800nm的介孔BaSnO 3纳米晶层。Pb(Zr xTi 1-x)O 3介孔间隔层，将均一稳定颗粒大小例如为30nm的的Pb(Zr xTi 1-x)O 3纳米颗粒和乙基纤维素、松油醇按照质量比为1:1:5的比例配制成具有一定粘稠度的浆料，然后烧结形成厚度例如约为1μm的 介孔间隔层。介孔背电极层为石墨、炭黑制成的介孔导电薄膜，厚度例如约为10μm。将一定量例如4μL碘铅甲胺(CH 3NH 3Pbl 3)前驱液(30wt％)滴加在介孔背电极上，静置10分钟待其充分渗透后例如在100℃条件下烘干即可。测试表明在100mW*cm -2模拟太阳光下，未经极化的器件光电转换效率为10.06％，极化之后的器件光电转换效率为11.76％。
实施例4
基于ZrO 2包裹Pb(Zr xTi 1-x)O 3纳米复合材料作介孔间隔层的钙钛矿太阳能电池
器件以导电玻璃为导电基板(1)，沉积一定厚度例如50nm二氧化钛致密层(2)后，自下而上以丝网印刷的方式依次制备二氧化钛纳米晶层(3)，ZrO 2包裹Pb(Zr xTi 1-x)O 3介孔间隔层(4)，介孔背电极(5)，依次在高温下烧结例如500℃，然后正极接FTO导电基底，负极接介孔背电极，场强大小为例如为3.5kV/mm，温度为200℃条件下进行极化一段时间例如20min。
纳米二氧化钛晶粒大小例如为18nm，二氧化钛层厚度例如约为lμm。二氧化钛晶粒大小例如为20nm，厚度例如800nm。介孔间隔层为ZrO 2包裹Pb(Zr xTi 1-x)O 3介孔间隔层或者ZrO 2介孔间隔层，将均一稳定颗粒大小例如为30nm的ZrO 2包裹Pb(Zr xTi 1-x)O 3纳米复合颗粒(即，以ZrO 2为壳、Pb(Zr xTi 1-x)O 3为核的核-壳结构复合颗粒，该核-壳结构复合颗粒整体的粒径为30nm)或者颗粒大小例如为30nm的ZrO 2纳米颗粒，与乙基纤维素、松油醇按照质量比为1:1:5的比例配制具有一定粘稠度的浆料，然后烧结形成厚度例如约为2μm的介孔间隔层。介孔背电极层为石墨、炭黑制成的介孔导电薄膜，厚度例如约为10μm。将一定量例如4μL碘铅甲胺(CH 3NH 3Pbl 3)前驱液(30wt％)滴加在介孔背电极上，静置10分钟待其充分渗透后例如在100℃条件下烘干即可。测试表明在100mW*cm -2模拟太阳光下，采用ZrO 2包裹Pb(Zr xTi 1-x)O 3做介孔间隔层时，未经极化的器件 光电转换效率为9.56％，极化之后的器件光电转换效率为11.77％；采用ZrO 2作介孔间隔层时极化前后光电转换效率分别为8.54％和8.51％。
上述各个实施例中，导电基底可以优选为导电玻璃或导电塑料，空穴阻挡层(2)为具有良好空穴阻挡能力的无机氧化物薄膜，优选为致密二氧化钛薄膜和氧化锡薄膜，厚度优选为30nm，但不仅限于以上两种薄膜，厚度可根据需要调节，例如10-50nm。介孔纳米晶层(3)为TiO 2、ZnO、SnO 2、BaSnO 3、BaTiO 3、(Na xBi 1-x)TiO 3、(K xBi 1-x)TiO 3以及由上述材料参与的构成的纳米复合材料中的至少一种，晶粒大小并不仅限于18nm或30nm，可根据需要自行选择，例如20-100nm，厚度也不限于上述实施例，例如0.5-2μm。介孔间隔层为ZrO 2，SiO 2，Al 2O 3，CaTiO 3，BaTiO 3、PbZrO 3、PbTiO 3、PbZrO 3、ZnTiO 3、BaZrO 3、Pb(Zr 1-xTi x)O 3、(La yPb 1-y)(Zr 1-xTi x)O 3、(1-x)[Pb(Mg 1/3Nb 2/3)O 3]﹒x[PbTiO 3]、BiFeO 3、Pb(Zn 1/3Nb 2/3)O 3、Pb(Mg 1/3Nb 2/3)O 3、(Na 1/2Bi 1/2)TiO 3、(K 1/2Bi 1/2)TiO 3、LiNbO 3、KNbO 3、KTaO 3、Pb(Sr xTa 1-x)O 3、Ba xSr 1-xTiO 3或由上述材料参与构成的纳米复合材料中的一种或几种，颗粒大小不仅限于上述实施例，可根据需要自行调节，例如10-100nm，厚度也可在1-4μm可调。介孔背电极5优选为碳电极、氧化铟锡等高功函材料，但不仅限于以上两种背电极。光活性材料不仅限于实例中所给碘铅甲胺(CH 3NH 3Pbl 3)钙钛矿类半导体材料，所有化学通式为ABX 3的钙钛矿光活性材料均满足条件，其中A为甲胺、甲脒、碱金属元素中的至少一种，B为铅、锡中至少一种，X为碘、溴、氯中至少一种；除钙钛矿类光活性材料以外，还包括窄带隙光活性材料，如Se、SbSe、CdSe等。
本发明中的介孔材料、纳米晶材料等满足本领域的常规定义，即，介孔材料是指孔径在2-100nm的一类多孔材料，纳米晶材料是指尺寸在1-100nm具有晶体结构的纳米材料。
上述实施例中，烧结既可以采用每沉积一层烧结一次的方式，也可以 采用沉积多层(如两层或以上)之后再烧结的方式，例如，如沉积介孔纳米晶层之后烧结一次，沉积介孔间隔层和介孔背电极层之后再烧结一次。极化步骤所处的环境温度，施加的外加电场的电场强度大小及方向等均可根据实际情况(如铁电材料层的厚度以及种类等)灵活调整，只要环境温度为80℃～150℃，电场强度满足E≤10kV/mm，方向垂直于导电基底平面且从介孔纳米晶层指向介孔背电极层即可。
本发明中的光活性材料可以为吸光半导体材料，除了钙钛矿类半导体材料(对应于钙钛矿太阳能电池)外，还可以为具有光敏性质的有机材料(对应于有机太阳能电池)、或光敏染料(对应于染料敏化太阳能电池)等；在制备时，可将光活性材料前驱液滴涂在极化后的太阳能电池框架结构上(即滴涂在极化后的介孔背电极层上)，使该前驱液从上至下依次填充于介孔背电极、介孔间隔层及介孔纳米晶层的纳米孔中。以介孔纳米晶层填充光活性材料为例，在填充钙钛矿类半导体或窄禁带半导体材料等光活性材料之后，该介孔纳米晶层成为光活性层。致密的空穴阻挡层也即电子传输层，例如可以为致密二氧化钛薄膜、致密氧化锡薄膜、致密氧化锌薄膜，或致密铁电材料或纳米铁电复合材料薄膜。
本发明中的铁电增强型的太阳能电池，只要空穴阻挡层、介孔纳米晶层和介孔间隔层中的至少一层由铁电材料或铁电纳米复合材料构成即可。除了上述实施例中的具体设置外，各层结构的层厚度可根据电池的需要来进行调节；优选的，铁电材料或铁电纳米复合材料参与构成的空穴阻挡层其厚度不超过100nm(尤其优选不超过50nm)，铁电材料或铁电纳米复合材料参与构成的介孔纳米晶层其厚度为100nm-5000nm(尤其优选500nm-1000nm)；铁电材料或铁电纳米复合材料参与构成的介孔间隔层其厚度为100nm-5000nm(尤其优选1-3μm)。可能引入铁电材料或铁电纳米复合材料的空穴阻挡层、介孔纳米晶层或介孔间隔层，它们的制备方法均可参考现有技术，相应的，也可根据对各个层的厚度要求等，灵活调整制备 方法中的参数条件。本发明中的铁电增强型的太阳能电池，其整体能带结构需满足现有技术对太阳能电池整体能带的要求，以间隔层为例，间隔层的目的是阻止电子向介孔背电极传输，因此间隔层材料的导带应该高于光活性材料(如钙钛矿光活性材料)的导带，而本发明中的铁电材料，如Pb(Zr 1-xTi x)O 3、(1-x)[Pb(Mg 1/3Nb 2/3)O 3]﹒x[PbTiO 3]等，x满足0～1均能满足相应铁电材料作为间隔层的能带要求。单独的致密铁电材料薄膜可作为空穴阻挡层，以光活性材料为钙钛矿类半导体材料为例，当某种铁电材料的能带合适，其导带低于钙钛矿光吸收材料导带，价带也低于钙钛矿光吸收材料价带，且具有良好的电导率时，即可作为空穴阻挡层，同时作为电子传输层；如BaSnO 3铁电材料，可将其沉积成很薄的致密薄膜从而用作空穴阻挡层。本发明中铁电材料及铁电纳米复合材料(即以铁电材料纳米颗粒为核、且以绝缘材料为壳的具有核-壳结构的复合材料)，它们的粒径均优选为5～200nm(优选为20～50nm)，以便于形成具有介孔结构的间隔层或纳米晶层。
本领域的技术人员容易理解，以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种铁电增强型的太阳能电池，其特征在于，该太阳能电池包括导电基底(1)和依次沉积于该导电基底(1)上的空穴阻挡层(2)、介孔纳米晶层(3)、介孔间隔层(4)及介孔背电极层(5)，其中所述介孔纳米晶层(3)、所述介孔间隔层(4)和所述介孔背电极层(5)中的至少一层其介孔中还填充有光活性材料；
    并且，所述空穴阻挡层(2)、所述介孔纳米晶层(3)和所述介孔间隔层(4)中的至少一层包括铁电材料或铁电纳米复合材料。
  2. 如权利要求1所述铁电增强型的太阳能电池，其特征在于，当所述空穴阻挡层(2)包括所述铁电材料或所述铁电纳米复合材料时，该空穴阻挡层(2)的厚度不超过100nm；当所述介孔纳米晶层(3)包括所述铁电材料或所述铁电纳米复合材料时，该介孔纳米晶层(3)的厚度为100nm-5000nm；当所述介孔间隔层(4)包括所述铁电材料或所述铁电纳米复合材料时，该介孔间隔层(4)的厚度为100nm-5000nm。
  3. 如权利要求1所述铁电增强型的太阳能电池，其特征在于，所述铁电材料为具有铁电效应的介电材料；优选的，所述空穴阻挡层(2)和所述介孔纳米晶层(3)中的所述铁电材料为BaSnO 3，所述介孔间隔层(4)中的所述铁电材料为CaTiO 3，BaTiO 3、PbZrO 3、PbTiO 3、PbZrO 3、ZnTiO 3、BaZrO 3、Pb(Zr 1-xTi x)O 3、(La yPb 1-y)(Zr 1-xTi x)O 3、(1-x)[Pb(Mg 1/3Nb 2/3)O 3]·x[PbTiO 3]、BiFeO 3、Pb(Zn 1/3Nb 2/3)O 3、Pb(Mg 1/3Nb 2/3)O 3、(Na 1/2Bi 1/2)TiO 3、(K 1/2Bi 1/2)TiO 3、LiNbO 3、KNbO 3、KTaO 3、Pb(Sr xTa 1-x)O 3、Ba xSr 1-xTiO 3中的一种或多种；其中，所述Pb(Zr 1-xTi x)O 3和所述(1-x)[Pb(Mg 1/3Nb 2/3)O 3]·x[PbTiO 3]中的x满足0≤x≤1；所述(La yPb 1-y)(Zr 1-xTi x)O 3中的x满足0≤x≤1，y满足0≤y≤1；所述Pb(Sr xTa 1-x)O 3中的x满足0≤x≤1；所述Ba xSr 1-xTiO 3中的x满足0≤x≤1；
    优选的，所述介孔纳米晶层(3)或所述介孔间隔层(4)中的铁电材料其粒径为5～200nm。
  4. 如权利要求1所述铁电增强型的太阳能电池，其特征在于，所述铁电纳米复合材料为以铁电材料纳米颗粒为核、且以绝缘材料为壳的具有核-壳结构的复合材料；优选的，所述绝缘材料为ZrO 2、Al 2O 3、SiO 2中的至少一种；对应所述空穴阻挡层(2)和所述介孔纳米晶层(3)的所述铁电材料为BaSnO 3，对应介孔间隔层(4)的所述铁电材料为CaTiO 3，BaTiO 3、PbZrO 3、PbTiO 3、PbZrO 3、ZnTiO 3、BaZrO 3、Pb(Zr 1-xTi x)O 3、(La yPb 1-y)(Zr 1-xTi x)O 3、(1-x)[Pb(Mg 1/3Nb 2/3)O 3]·x[PbTiO 3]、BiFeO 3、Pb(Zn 1/3Nb 2/3)O 3、Pb(Mg 1/3Nb 2/3)O 3、(Na 1/2Bi 1/2)TiO 3、(K 1/2Bi 1/2)TiO 3、LiNbO 3、KNbO 3、KTaO 3、Pb(Sr xTa 1-x)O 3、Ba xSr 1-xTiO 3中的一种或多种；其中，所述Pb(Zr 1-xTi x)O 3和所述(1-x)[Pb(Mg 1/3Nb 2/3)O 3]·x[PbTiO 3]中的x满足0≤x≤1；所述(La yPb 1-y)(Zr 1-xTi x)O 3中的x满足0≤x≤1；y满足0≤y≤1；所述Pb(Sr xTa 1-x)O 3中的x满足0≤x≤1；所述Ba xSr 1-xTiO 3中的x满足0≤x≤1；
    优选的，所述介孔纳米晶层(3)或所述介孔间隔层(4)中的铁电纳米复合材料其粒径为5～200nm。
  5. 如权利要求1所述铁电增强型的太阳能电池，其特征在于，所述空穴阻挡层(2)为致密无机氧化物半导体材料薄膜或致密铁电材料薄膜；其中，所述无机氧化物半导体材料为TiO 2、ZnO或SnO 2。
  6. 如权利要求1所述铁电增强型的太阳能电池，其特征在于，所述介孔纳米晶层(3)为介孔TiO 2纳米晶层、介孔ZnO纳米晶层、介孔SnO 2纳米晶层、介孔铁电材料纳米晶层、或介孔铁电纳米复合材料纳米晶层；优选的，所述介孔纳米晶层(3)为介孔BaSnO 3纳米晶层。
  7. 如权利要求1所述铁电增强型的太阳能电池，其特征在于，所述介孔间隔层(4)为介孔ZrO 2层、介孔SiO 2层、介孔Al 2O 3层、介孔铁电材料层、或介孔铁电纳米复合材料层。
  8. 如权利要求1所述铁电增强型的太阳能电池，其特征在于，所述光活性材料为钙钛矿类半导体材料或禁带宽度不超过2eV的半导体材料；所述钙钛矿类半导体材料其化学通式为ABX 3，其中A为甲胺、甲脒、碱金属元素中的至少一种，B为铅、锡中至少一种，X为碘、溴、氯中至少一种；优选的，所述窄禁带半导体材料为Se、SbSe、CdSe中的至少一种。
  9. 制备如权利要求1－8任意一项所述铁电增强型太阳能电池的方法，其特征在于，包括以下步骤：
    (1)在导电基底上制备一层空穴阻挡层；
    (2)在所述空穴阻挡层上依次层叠介孔纳米晶层、介孔间隔层和介孔背电极层，烧结后得到太阳能电池框架结构；
    (3)在80℃～150℃的温度下，对所述太阳能电池框架结构施加外加电场进行极化；所述外加电场的电场强度大小满足E≤10kV/mm，方向为垂直于所述导电基底平面、并从所述介孔纳米晶层指向所述介孔背电极层；
    (4)将光活性材料前驱液涂在所述步骤(3)得到的极化后的太阳能电池框架结构上，使所述光活性材料前驱液从上至下填充于所述介孔背电极、所述介孔间隔层及所述介孔纳米晶层的介孔中，烘干除去所述前驱液中的溶剂后即得到铁电增强型太阳能电池器件。
  10. 如权利要求9所述制备方法，其特征在于，所述步骤(2)中，所述介孔背电极层为介孔碳电极层。
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JP7012282B2 (ja) 2022-01-28
EP3553830A1 (en) 2019-10-16

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