CN117042482A - Perovskite solar cell and preparation method thereof - Google Patents
Perovskite solar cell and preparation method thereof Download PDFInfo
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- CN117042482A CN117042482A CN202311125905.7A CN202311125905A CN117042482A CN 117042482 A CN117042482 A CN 117042482A CN 202311125905 A CN202311125905 A CN 202311125905A CN 117042482 A CN117042482 A CN 117042482A
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Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K39/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic radiation-sensitive element covered by group H10K30/00
- H10K39/10—Organic photovoltaic [PV] modules; Arrays of single organic PV cells
- H10K39/15—Organic photovoltaic [PV] modules; Arrays of single organic PV cells comprising both organic PV cells and inorganic PV cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
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Abstract
The application discloses a perovskite solar cell and a preparation method thereof, wherein the preparation method comprises the following steps: providing a first substrate; forming a first electrode on the surface of a first substrate; forming a perovskite photoelectric conversion layer on one side of the first electrode away from the first substrate; forming a second electrode on a side of the perovskite photoelectric conversion layer away from the first electrode; a second substrate is arranged on one side of the second electrode, which is away from the perovskite photoelectric conversion layer; forming a third electrode on one side of the second substrate away from the second electrode; forming a photoelectric conversion functional layer on one side of the third electrode away from the second substrate; forming a fourth electrode on one side of the photoelectric conversion functional layer away from the third electrode; wherein the absorption spectra of the perovskite photoelectric conversion layer and the photoelectric conversion functional layer are different. The perovskite solar cell prepared based on the method can absorb light waves with different spectrums in the photoelectric conversion process, so that the photoelectric conversion efficiency of the perovskite solar cell is higher.
Description
Technical Field
The application relates to the technical field of semiconductors, in particular to a perovskite solar cell and a preparation method thereof.
Background
In recent years, perovskite-based stacked cells have attracted considerable attention from researchers due to higher theoretical ultimate efficiencies. Currently, researchers have successfully produced solar cells including perovskite-crystalline silicon tandem solar cells, perovskite-perovskite tandem solar cells and perovskite-copper indium gallium diselenide (CIGS) tandem solar cells, and in the current research, solar cells based on such bandgap combinations of perovskite-crystalline silicon tandem solar cells are relatively thorough in research, but because crystalline silicon is an indirect bandgap semiconductor, crystalline silicon materials require a thickness of the order of hundred microns to effectively absorb sunlight, crystalline silicon cell materials as bottom cells are costly and energy consuming in the production process are large.
Disclosure of Invention
In view of this, the present application provides a perovskite solar cell and a method of manufacturing the same, the method of manufacturing comprising:
providing a first substrate;
forming a first electrode on the surface of the first substrate;
forming a perovskite photoelectric conversion layer on one side of the first electrode away from the first substrate;
forming a second electrode on one side of the perovskite photoelectric conversion layer away from the first electrode;
a second substrate is arranged on one side of the second electrode, which is away from the perovskite photoelectric conversion layer;
forming a third electrode on one side of the second substrate away from the second electrode;
forming a photoelectric conversion functional layer on one side of the third electrode away from the second substrate;
forming a fourth electrode on one side of the photoelectric conversion functional layer away from the third electrode;
wherein the absorption spectra of the perovskite photoelectric conversion layer and the photoelectric conversion functional layer are different.
Preferably, in the above preparation method, the method for forming the photoelectric conversion functional layer includes:
and forming a black phosphorus layer on one side of the third electrode, which is away from the second substrate, as the photoelectric conversion functional layer.
Preferably, in the above preparation method, the thickness of the black phosphorus layer ranges from 20 to 40nm.
Preferably, in the above preparation method, the method for forming the black phosphorus layer includes:
forming at least one thin film laminated structure on one side of the third electrode, which is far away from the second substrate, as the black phosphorus layer, wherein the thin film laminated structure comprises two laminated two-dimensional black phosphorus thin films;
when a plurality of the thin film laminated structures are formed as the black phosphorus layer on a side of the third electrode facing away from the second substrate, a barrier layer is formed between adjacent thin film laminated structures in a direction perpendicular to the second substrate.
Preferably, in the above preparation method, the thickness of the barrier layer is less than 10nm.
Preferably, in the above preparation method, the method for forming the thin film laminated structure includes:
obtaining a blocky black phosphorus single crystal;
stripping flaky black phosphorus single crystals from the bulk black phosphorus single crystals;
stripping a first black phosphorus layer from the flaky black phosphorus single crystal by adopting a first adhesive tape;
using a second adhesive tape to adhere and peel a second black phosphorus layer from the first black phosphorus layer adhered and fixed on the first adhesive tape; wherein the tackiness of the first tape is less than the tackiness of the second tape;
selecting a target second adhesive tape, wherein a second black phosphorus layer adhered on the target second adhesive tape is of the film laminated structure;
and transferring the thin film laminated structure to one side of the third electrode, which is away from the second substrate.
The perovskite solar cell provided by the application comprises:
a first substrate;
a first electrode located on the surface of the first substrate;
a perovskite photoelectric conversion layer positioned on one side of the first electrode away from the first substrate;
the second electrode is positioned on one side of the perovskite photoelectric conversion layer, which is away from the first electrode;
a second substrate positioned on one side of the second electrode away from the perovskite photoelectric conversion layer;
a third electrode positioned on a side of the second substrate facing away from the second electrode;
a photoelectric conversion functional layer positioned on one side of the third electrode away from the second substrate;
a fourth electrode positioned on one side of the photoelectric conversion functional layer away from the third electrode;
wherein the absorption spectra of the perovskite photoelectric conversion layer and the photoelectric conversion functional layer are different.
Preferably, in the above battery, the photoelectric conversion functional layer includes: black phosphorus layer.
Preferably, in the above battery, the black phosphorus layer includes:
at least one thin film laminated structure comprising two layers of two-dimensional black phosphorus thin films laminated;
when the black phosphorus layer includes a plurality of thin film laminated structures, there is a barrier layer between adjacent thin film laminated structures in a direction perpendicular to the second substrate.
Preferably, the battery further includes:
a first hole transport layer located between the first electrode and the perovskite photoelectric conversion layer;
a first electron transport layer located between the perovskite photoelectric conversion layer and the second electrode;
a second hole transport layer located between the third electrode and the photoelectric conversion functional layer;
and a second electron transport layer located between the photoelectric conversion functional layer and the fourth electrode.
Based on the above, the present application provides a perovskite solar cell and a preparation method thereof, wherein the preparation method comprises: providing a first substrate; forming a first electrode on the surface of the first substrate; forming a perovskite photoelectric conversion layer on one side of the first electrode away from the first substrate; forming a second electrode on one side of the perovskite photoelectric conversion layer away from the first electrode; a second substrate is arranged on one side of the second electrode, which is away from the perovskite photoelectric conversion layer; forming a third electrode on one side of the second substrate away from the second electrode; forming a photoelectric conversion functional layer on one side of the third electrode away from the second substrate; forming a fourth electrode on one side of the photoelectric conversion functional layer away from the third electrode; wherein the absorption spectra of the perovskite photoelectric conversion layer and the photoelectric conversion functional layer are different. In the photoelectric conversion process of the perovskite solar cell prepared based on the preparation method, the perovskite solar cell can absorb light waves with different spectrums due to the fact that the photoelectric conversion function layer in the perovskite solar cell and the absorption spectrum of the perovskite photoelectric conversion function layer are different, and therefore the photoelectric conversion efficiency of the perovskite solar cell is higher.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the related art, the drawings required for the description of the embodiments or the prior art will be briefly described below, and it is apparent that the drawings in the following description are only embodiments of the present application, and other drawings may be obtained according to the provided drawings without inventive effort to those skilled in the art.
The structures, proportions, sizes, etc. shown in the drawings are shown only in connection with the present disclosure, and therefore should not be construed as limiting the application, but rather as limiting the scope of the application, so that any structural modifications, proportional changes, or dimensional adjustments should fall within the scope of the application without affecting the efficacy or achievement thereof.
Fig. 1 to 8 are product structure diagrams of a perovskite solar cell manufacturing method provided by the embodiment of the application at different process stages;
fig. 9 is a schematic structural diagram of a perovskite solar cell according to an embodiment of the present application;
fig. 10 is a schematic structural diagram of another perovskite solar cell according to an embodiment of the application;
FIG. 11 is a schematic diagram of a perovskite solar cell according to an embodiment of the application;
fig. 12 is a flowchart of a method for forming a thin film stacked structure in a method for manufacturing a perovskite solar cell according to an embodiment of the application;
FIG. 13 is a schematic diagram of a perovskite solar cell according to an embodiment of the application;
FIG. 14 is a graph of the photovoltaic properties of a top cell of a perovskite solar cell according to embodiments of the application;
fig. 15 is a graph of the photovoltaic properties of a perovskite solar cell midsole cell provided in the examples of the application.
Detailed Description
Embodiments of the present application will now be described more fully hereinafter with reference to the accompanying drawings, in which it is shown, however, in which some, but not all embodiments of the application are shown. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
Currently, researchers have successfully produced a variety of stacked solar cells. However, the band gap of the light absorbing material of the low cell of the conventional laminate cell causes many problems for the production of the conventional laminate cell. According to theoretical calculation and prediction, scientific researchers find that for a four-terminal laminated cell, when the band gap of the light absorption layer material of the top cell is 1.7eV and the band gap of the light absorption layer material of the bottom cell is 1.1eV, the theoretical limit efficiency of the laminated cell can reach 46% at most, which is far higher than the theoretical limit efficiency of the existing silicon-based single-junction solar cell and perovskite single-junction solar cell, so that the photoelectric conversion efficiency of the laminated cell needs to be improved by searching materials with proper band gaps.
Based on the problems, the application provides a perovskite solar cell and a preparation method thereof, and in the photoelectric conversion process of the perovskite solar cell prepared based on the preparation method, the perovskite solar cell can absorb light waves with different light spectrums due to different absorption spectrums of a photoelectric conversion functional layer and a perovskite photoelectric conversion functional layer in the perovskite solar cell, so that the photoelectric conversion efficiency of the perovskite solar cell is higher.
In order that the above-recited objects, features and advantages of the present application will become more readily apparent, a more particular description of the application will be rendered by reference to the appended drawings and appended detailed description.
Referring to fig. 1 to 8, fig. 1 to 8 are product structure diagrams of a perovskite solar cell manufacturing method provided by an embodiment of the application at different process stages, and the manufacturing method includes:
step S1: as shown in fig. 1, a first substrate 1 is provided;
step S2: as shown in fig. 2, a first electrode 2 is formed on the surface of a first substrate 1;
step S3: as shown in fig. 3, a perovskite photoelectric conversion layer 3 is formed on a side of the first electrode 2 facing away from the first substrate 1;
step S4: as shown in fig. 4, a second electrode 4 is formed on a side of the perovskite photoelectric conversion layer 3 facing away from the first electrode 2;
step S5: as shown in fig. 5, a second substrate 5 is provided on the side of the second electrode 4 facing away from the perovskite photoelectric conversion layer 3;
step S6: as shown in fig. 6, a third electrode 6 is formed on a side of the second substrate 5 facing away from the second electrode 4;
step S7: as shown in fig. 7, a photoelectric conversion functional layer 7 is formed on a side of the third electrode 6 facing away from the second substrate 5;
step S7: as shown in fig. 8, a fourth electrode 8 is formed on the side of the photoelectric conversion functional layer 7 facing away from the third electrode 6;
wherein the absorption spectra of the perovskite photoelectric conversion layer 3 and the photoelectric conversion functional layer 7 are different.
In the present embodiment, the first electrode 2, the perovskite photoelectric conversion layer 3, the second electrode 4, the second substrate 5, the third electrode 6, the photoelectric conversion functional layer 7, and the fourth electrode 8 are sequentially formed on the surface of the first substrate 1; in the photoelectric conversion process of the perovskite solar cell prepared based on the preparation method, the perovskite solar cell can absorb light waves with different spectrums due to the fact that the absorption spectrums of the photoelectric conversion functional layer 7 and the perovskite photoelectric conversion functional layer 3 in the perovskite solar cell are different, and therefore the photoelectric conversion efficiency of the perovskite solar cell is higher.
The perovskite solar cell prepared by the preparation method according to the present embodiment is a four-terminal stacked cell, and the perovskite solar cell includes a top cell and a bottom cell, and the preparation of the top cell and the bottom cell of the perovskite solar cell is only taken as an example in this embodiment, but the preparation process of the cell includes, but is not limited to, the preparation method described above, and the cell may also be formed by stacking after the top cell and the bottom cell are respectively prepared. In the perovskite solar cell of the present embodiment, the top cell includes: a first substrate 1, a first electrode 2, a perovskite photoelectric conversion layer 3, and a second electrode 4, wherein the perovskite photoelectric conversion layer 3 is a light absorption conversion layer of a top cell; the bottom cell includes: a second substrate 5, a third electrode 6, a photoelectric conversion functional layer 7 and a fourth electrode 8, wherein the photoelectric conversion functional layer 7 is a light absorption conversion layer of a bottom cell.
In the present embodiment, the first substrate 1 and the second substrate 5 are both transparent glass substrates; the first electrode 2 and the third electrode 6 are transparent electrodes, and the transparent electrodes are fluorine doped tin oxide layers (FTO); the second electrode 4 is also a transparent electrode, which is an indium tin oxide layer (ITO); the fourth electrode 8 is one of gold, silver, copper, graphite and amorphous carbon, preferably Au, and has a thickness in the range of 50-200 nm; forming three-dimensional CsPbBr on the surface of the first electrode 2 x I 3-x The perovskite thin film layer is used as the perovskite photoelectric conversion layer 3, and the thickness of the perovskite photoelectric conversion layer 3 ranges from 300 nm to 500nm. In this embodiment, a tin oxide layer is plated on the surface of the first substrate 1 as the first electrode 2; a tin oxide layer is plated on the surface of the second substrate 5 to serve as a third electrode 6; preparing a second electrode 4 on the surface of the perovskite photoelectric conversion layer 3 by a vacuum evaporation method; a fourth electrode 8 is prepared on the surface of the photoelectric conversion functional layer 7 through a vacuum evaporation method; the specific method of forming the perovskite photoelectric conversion layer 3 includes: sequentially weighing a certain amount of formamidine hydroiodidate (FAI), thallium-doped cesium iodide (CsI) and lead iodide (PbI) 2 ) Placing in glass bottle, wherein FAI, csI and PbI 2 The molar ratio of (2) is 0.1:0.9:1, a step of; adding a certain amount of solvent N, N-Dimethylformamide (DMF) into a glass bottle, placing the glass bottle into an ultrasonic container, and performing ultrasonic treatment until the solid is completely dissolved to form perovskite precursor solution with the concentration of 1 mol/L; spin-coating perovskite precursor solution on one side of the first electrode 2, which is far away from the first substrate 1, wherein the rotating speed of a spin-coating device is set to 3000-5000 revolutions, the spin-coating time is 30-60 s, and then annealing the obtained product on a heating table to form a perovskite photoelectric conversion layer 3, wherein the annealing temperature is as followsBased on the above steps, the perovskite photoelectric conversion layer 3 with the thickness of 6nm can be prepared at the temperature of 80-120 ℃. Among them, the materials and thicknesses of the first substrate 1, the second substrate 5, the first electrode 2, the third electrode 6, the second electrode 4, the fourth electrode 8, and the perovskite photoelectric conversion layer 3 include, but are not limited to, those described above, and the method for specifically preparing a film layer includes, but is not limited to, those described above.
Referring to fig. 9, fig. 9 is a schematic structural diagram of a perovskite solar cell according to an embodiment of the present application, and in the preparation method of the embodiment, a method for forming a photoelectric conversion functional layer 7 includes:
a black phosphor layer 71 is formed as the photoelectric conversion functional layer 7 on the side of the third electrode 6 facing away from the second substrate 5.
Referring to fig. 9, black phosphorus is a layered two-dimensional material, and is a direct band gap semiconductor, the band gap of which can be regulated and controlled by thickness, and the band gap of the material from a single layer to a bulk material is reduced from 1.7eV to 0.4eV, so that the band gap requirement of the perovskite solar cell light absorption material can be better met. In the present embodiment, the black phosphorus layer 71 is used as the photoelectric conversion functional layer 7, and the absorption spectrum of the black phosphorus layer 71 is different from that of the perovskite photoelectric conversion layer 3 because the band gap of the black phosphorus layer 71 is different from that of the perovskite photoelectric conversion layer 3; when the band gap of the perovskite photoelectric conversion layer 3 in the perovskite solar cell is 1.7eV, and the band gap of the black phosphorus layer 71 is 1.1eV, the perovskite solar cell has higher photoelectric conversion efficiency, and the preparation process of the cell using the black phosphorus layer 71 as the photoelectric conversion functional layer 7 is simple, and the energy consumption is smaller.
In the above embodiment, the thickness of the black phosphorus layer 71 ranges from 20 to 40nm.
In the above embodiment, the black phosphorus layer 71 is formed on the surface of the third electrode 6 as the photoelectric conversion functional layer 7, and the band gap of the black phosphorus layer 71 is a fixed band gap in this embodiment, the light absorption capacity of the black phosphorus layer 71 can be improved based on changing the thickness of the black phosphorus layer 71, and the thickness of the black phosphorus layer 71 is positively correlated with the light absorption capacity of the black phosphorus layer 71, that is, when the thickness of the black phosphorus layer 71 is larger, the light absorption capacity of the black phosphorus layer 71 is stronger; in this embodiment, in order to ensure that the absorption value of the black phosphorus layer is 95% or more, the thickness of the black phosphorus layer 71 is required to be in the range of 20 to 40nm.
Referring to fig. 10 and 11, fig. 10 is a schematic structural diagram of another perovskite solar cell provided in an embodiment of the application, and fig. 11 is a schematic structural diagram of another perovskite solar cell provided in an embodiment of the application, a method for forming a black phosphorus layer 71 includes:
referring to fig. 10, at least one thin film stack structure 711 is formed as a black phosphor layer 71 on a side of the third electrode 6 facing away from the second substrate 5, the thin film stack structure 711 including two-dimensional black phosphor thin films stacked;
referring to fig. 11, when a plurality of thin film stack structures 711 are formed as the black phosphorus layer 71 on a side of the third electrode 6 facing away from the second substrate 5, barrier layers 712 are formed between adjacent thin film stack structures 711 in a direction perpendicular to the second substrate 5.
In the structure shown in fig. 10, the black phosphorus layer 71 is a thin film stack structure 711, and the thin film stack structure 711 is a two-dimensional thin film black phosphorus layer stacked. Wherein the two-dimensional black phosphorus thin film layer is a monoatomic layer of black phosphorus. In this embodiment, the light absorption conversion layer of the top cell in the perovskite solar cell is the perovskite photoelectric conversion layer 3, and the band gap of the material for preparing the perovskite photoelectric conversion layer 3 is about 1.7eV, in order to make the light absorption conversion efficiency of the perovskite cell higher, it is required that the band gap of the material for preparing the light absorption conversion function layer 7 in the bottom cell is small, and when the band gap of the material for preparing the light absorption conversion function layer 7 in the bottom cell is about 1.1eV, the light absorption conversion efficiency of the perovskite solar cell can reach about 46% at the highest. The band gap of the black phosphorus material can be regulated and controlled based on the thickness, when two-dimensional thin film black phosphorus layers are overlapped, the band gap of the two-dimensional thin film black phosphorus layers is about 1.1eV, so that the light absorption conversion efficiency of the perovskite solar cell can be effectively improved when the two-dimensional thin film black phosphorus layers are taken as the light absorption conversion functional layer 7 of the bottom cell.
In the structure shown in fig. 11, the black phosphorus layer 71 includes a plurality of thin film laminated structures 711, and a barrier layer 712 is disposed between adjacent thin film laminated structures 711 in a direction perpendicular to the second substrate 5, and the barrier layer 712 is used to block adjacent two thin film laminated structures 711, and when the adjacent two thin film laminated structures 711 are directly laminated, the band gap of the black phosphorus layer 71 is increased, so that the band gap of the black phosphorus layer 71 is increased, and the band gap requirement of the bottom cell is not satisfied. Specific methods of forming the barrier layer 712 between adjacent thin film stack structures 711 include: a chlorobenzene solution of polymethyl methacrylate (PMMA) with a mass fraction of 0.5% was prepared, 50 μl was dropped on the substrate having the thin film laminated structure 711 formed based on the above steps, and a spin coating device was set at a rotation speed of 3000r, and spin coating was performed for 30s, so that the barrier layer 712 was obtained by spin coating on the thin film laminated structure 711 based on the spin coating device, wherein the barrier layer 712 was a transparent barrier layer.
In the above embodiment, the thickness of the barrier layer 712 is less than 10nm.
In the above embodiment, the barrier layer 712 is provided between the adjacent thin film laminated structures 711 in the direction perpendicular to the second substrate 5, and the thickness of the barrier layer 712 is required to be less than 10nm, when the barrier layer 712 is formed on the thin film laminated structures 711, the barrier layer 712 is formed extremely thin, not more than 10nm, because the concentration of the solution forming the barrier layer 712 is thin, and when the thickness of the barrier layer 712 is less than 10nm, the influence of the barrier layer 712 on the charge transfer efficiency is also small.
Referring to fig. 12, fig. 12 is a flowchart of a method for forming a thin film stack structure in a method for manufacturing a perovskite solar cell according to an embodiment of the application, in the method for manufacturing a perovskite solar cell according to the embodiment, the method for forming a thin film stack structure 711 includes:
step S51: obtaining a blocky black phosphorus single crystal;
step S52: stripping the flaky black phosphorus single crystal from the massive black phosphorus single crystal;
step S53: stripping the first black phosphorus layer from the flaky black phosphorus single crystal by adopting a first adhesive tape;
step S54: adopting a second adhesive tape to adhere and peel the second black phosphorus layer from the first black phosphorus layer adhered and fixed on the first adhesive tape; wherein the tackiness of the first tape is less than the tackiness of the second tape;
step S55: selecting a target second adhesive tape, wherein a second black phosphorus layer adhered on the target second adhesive tape is a film laminated structure 711;
step S56: the thin-film stack structure 711 is transferred to the side of the third electrode 6 facing away from the second substrate 5.
Referring to fig. 12, in this embodiment, a specific method for preparing the thin film stack structure 711 is described by taking the black phosphorus layer 71 with a thickness of 30nm as an example, which includes: after obtaining a bulk black phosphorus single crystal, the bulk black phosphorus single crystal was peeled off with clean tweezers to obtain a film of about 0.1cm 2 Placing the flaky black phosphorus single crystal on a blue tape (1 cm is 4 cm), then placing the blue tape with the same size in alignment with the area covered with the flaky black phosphorus single crystal (forming an included angle of 90 degrees with the lower layer of blue tape), pressing the upper layer of blue tape to correspond to the area covered with the flaky black phosphorus single crystal, and then slowly uncovering the upper layer of blue tape, wherein the two layers of blue tape are covered with a first black phosphorus layer and have stronger adsorption between the blue tape and the first black phosphorus layer; cutting a plurality of polydimethylsiloxane films with the thickness of 1cm respectively, removing a protective layer of the polydimethylsiloxane films, placing and pressing the sticky side of the polydimethylsiloxane films in alignment with a region covered with a first black phosphorus layer, enabling the polydimethylsiloxane films to have stronger adsorptivity with the first black phosphorus layer, then rapidly removing the polydimethylsiloxane films from the edges of the polydimethylsiloxane films by using tweezers, adsorbing part of black phosphorus single crystals of the first black phosphorus layer with the polydimethylsiloxane films by using tweezers, removing part of the area on the removed polydimethylsiloxane films, carrying out absorption spectrum measurement on the second black phosphorus layer obtained by stripping from the original first black phosphorus layer, detecting the obtained second black phosphorus layer, obtaining a contrast parameter of the film laminated structure 711 by observing based on an optical microscope, selecting a plurality of polydimethylsiloxane films with the film laminated structure 711, removing the second electrode 711 with the film laminated structure by using a linear displacement table and the aid of a microscope, and gradually placing the obtained polydimethylsiloxane film with the film laminated structure 711 away from the second electrode 6 of the second electrode of the second substrate 711, and gradually covering the second electrode of the second substrate 711 for 20 minutes, thus obtaining the second film laminated structure of the second substrate 711. Wherein, when the black phosphorus layer 71 includes a plurality of thin film stack structures 711,after forming a thin film stack structure 711 on the side of the third electrode 6 facing away from the second substrate 5, forming a barrier layer 712 on the thin film stack structure 711, and repeating the above steps until the thickness of the black phosphorus layer 71 formed reaches about 30nm after forming the thin film stack structure 711 on the barrier layer 712; after the black phosphorus layer 71 is prepared, the second substrate 5 covered with the black phosphorus layer 71 on the surface is annealed at 100 ℃ for 2 hours to enhance the spatial contact between the black phosphorus layer 71 and the film layer on the side of the third electrode 6 facing away from the second substrate 5. Wherein the top layer of the black phosphorus layer 71 must be a thin film laminate 711 and the blue tape has a lower tackiness than the polydimethylsiloxane film.
Referring to fig. 8, a perovskite solar cell provided in this embodiment includes:
a first substrate 1;
a first electrode 2 located on the surface of the first substrate 1;
a perovskite photoelectric conversion layer 3 located on a side of the first electrode 2 facing away from the first substrate 1;
a second electrode 4 located on a side of the perovskite photoelectric conversion layer 3 facing away from the first electrode 2;
a second substrate 5 located on a side of the second electrode 4 facing away from the perovskite photoelectric conversion layer 3;
a third electrode 6 located on a side of the second substrate 5 facing away from the second electrode 4;
a photoelectric conversion functional layer 7 located on a side of the third electrode 6 facing away from the second substrate 5;
a fourth electrode 8 located on a side of the photoelectric conversion functional layer 7 facing away from the third electrode 6;
wherein the absorption spectra of the perovskite photoelectric conversion layer 3 and the photoelectric conversion functional layer 7 are different.
In the perovskite solar cell structure shown in fig. 8, the perovskite solar cell includes: the first substrate 1, the first electrode 2, the perovskite photoelectric conversion layer 3, the second electrode 4, the second substrate 5, the third electrode 6, the photoelectric conversion functional layer 7 and the fourth electrode 8 have different band gaps, so that the absorption spectra of the perovskite photoelectric conversion layer 3 and the photoelectric conversion functional layer 7 are different, the perovskite solar cell can absorb light waves with different spectra, and the photoelectric conversion efficiency of the perovskite cell is higher.
Referring to fig. 9, the photoelectric conversion functional layer 7 includes: black phosphorus layer 71.
In the perovskite solar cell structure shown in fig. 9, the photoelectric conversion functional layer 7 is the black phosphorus layer 71, the band gap of the black phosphorus material can be controlled by thickness, in this embodiment, the band gap of the black phosphorus layer 71 is set to be 1.1eV, and the band gap of the perovskite photoelectric conversion layer 3 is set to be 1.7eV, so that the photoelectric conversion efficiency of the perovskite solar cell can be effectively improved.
Referring to fig. 10 and 11, the black phosphor layer 71 includes:
at least one thin film lamination structure 711, the thin film lamination structure 711 including two-dimensional black phosphorus thin films laminated;
when the black phosphorus layer 71 includes a plurality of thin film stack structures 711, there is a barrier layer 712 between adjacent thin film stack structures 711 in a direction perpendicular to the second substrate 5.
In the perovskite solar cell structure shown in fig. 10, one thin film stacked structure 711 is used as the photoelectric conversion functional layer 7.
In the perovskite solar cell structure shown in fig. 11, a plurality of thin film stacked structures 711 are used as the photoelectric conversion functional layer 7, and a barrier layer 712 is provided between adjacent thin film stacked structures 711. The band gap of the black phosphorus material can be controlled by the thickness, if a plurality of thin film laminated structures 711 are directly stacked to form the black phosphorus layer 71, the band gap of the black phosphorus layer 71 is increased, so that a barrier layer 712 is arranged between adjacent thin film laminated structures 711 for blocking two adjacent thin film laminated structures 711, thereby preventing the band gap of the black phosphorus layer 71 from being increased and affecting the photoelectric conversion efficiency of the perovskite battery.
Referring to fig. 13, fig. 13 is a schematic structural diagram of another perovskite solar cell according to an embodiment of the application, where the cell further includes:
a first hole transport layer 9 located between the first electrode 2 and the perovskite photoelectric conversion layer 3;
a first electron transport layer 10 located between the perovskite photoelectric conversion layer 3 and the second electrode 4;
a second hole transport layer 11 located between the third electrode 6 and the photoelectric conversion functional layer 7;
a second electron transport layer 12 located between the photoelectric conversion functional layer 7 and the fourth electrode 8.
The perovskite solar cell structure shown in fig. 13 includes: a first hole transport layer 9, a first electron transport layer 10, a second hole transport layer 11 and a second electron transport layer 12. In the process of forming the perovskite solar cell, before forming the perovskite photoelectric conversion layer 3, preparing a first hole transport layer 9 on the surface of the first electrode 2 by magnetron sputtering; before forming the photoelectric conversion functional layer 7, preparing a second hole transport layer 11 on the surface of the third electrode 6 by magnetron sputtering; wherein the materials for preparing the first hole transport layer 9 and the second hole transport layer 11 include: niO x 、CuSCN、CuO x And CuI, preferably NiO x And the thickness of the first hole transport layer 9 and the second hole transport layer 11 ranges from 20 to 60nm. In this embodiment, the first hole transport layer 9 and the second hole transport layer 11 are NiO x The hole transport layer (x is 1 to 1.5) is exemplified by NiO formed to cover the first electrode 2 or the third electrode 6 x After the hole transport layer, the material has NiO x The first substrate 1 or the second substrate 5 of the hole transport layer is annealed at a temperature ranging from 200 to 400 ℃.
In the perovskite solar cell structure shown in fig. 13, a first electron transport layer 10 is prepared on the surface of the perovskite photoelectric conversion layer 3 before the second electrode 4 is formed, and a second electron transport layer 12 is prepared on the surface of the photoelectric conversion functional layer 7 before the fourth electrode 8 is formed; wherein the materials for preparing the first electron transport layer 10 and the second electron transport layer 12 include: tiO (titanium dioxide) 2 、SnO 2 Or one of fullerene and fullerene derivative, the first electron transport layer 10 is preferably C 60 The second electron transport layer 12 is preferably phenyl C 61 The thickness of the first electron transport layer 10 and the second electron transport layer 12 ranges from 20 to 60nm.
The perovskite solar cell structure shown in fig. 13 uses the first electron transport layer 10 as C 60 Electronic deviceA transport layer, a second electron transport layer 12 being phenyl C 61 By way of example, the production of C on perovskite photoelectric conversion layer 3 by vacuum evaporation method is described as an example of an isopropyl butyrate electron transport layer 60 An electron transport layer; preparation of phenyl C 61 The method for the methyl butyrate electron transport layer comprises the following steps: configuration of 20mg/mL phenyl C 61 50 microliter of chlorobenzene solution of methyl butyrate is dripped on the surface of the photoelectric conversion functional layer 7, the rotating speed of a spin coating device is 3000r, the spin coating time is 30s, and phenyl C can be formed on the surface of the photoelectric conversion functional layer 7 61 An isopropyl butyrate electron transport layer, the phenyl C 61 The thickness of the methyl butyrate electron transport layer was 30nm. The materials and thicknesses of the first hole transport layer 9, the first electron transport layer 10, the second hole transport layer 11, and the second electron transport layer 12 include, but are not limited to, the above materials and thicknesses.
Referring to fig. 14 and 15, fig. 14 is a graph of the photovoltaic properties of a top cell in a perovskite solar cell provided by an embodiment of the present application, fig. 15 is a graph of the photovoltaic properties of a bottom cell in a perovskite solar cell provided by an application embodiment, fig. 14 and 15 correspond to the photovoltaic properties of the top cell and the bottom cell in the perovskite solar cell of the same embodiment, respectively, and fig. 1 and 2 are the photovoltaic properties of the top cell and the bottom cell in the perovskite solar cell of the embodiment, respectively, at 100mW/cm using a 3A solar simulator at room temperature 2 Testing the obtained parameters under light intensity, wherein the effective area of the perovskite solar cell in the embodiment is 0.084cm 2 。
Table 1: the embodiment of the application provides a detection result of a top cell in a perovskite solar cell
| Open circuit voltage Voc | Short-circuit current Isc | Fill factor FF | Efficiency PCE |
| 1.074V | 2.060mA | 79.68％ | 21.16％ |
Table 2: the detection result of the perovskite solar cell midsole cell provided by the embodiment of the application
| Open circuit voltage Voc | Short-circuit current Isc | Fill factor FF | Efficiency PCE |
| 0.923V | 1.276mA | 73.81％ | 10.35％ |
The open circuit voltage of the top cell, the short circuit current, and the fill factor of the perovskite solar cell were 1.074V, 2.060mA, and 79.68% and the photoelectric conversion efficiency of the top cell was 21.16%, respectively, the open circuit voltage of the bottom cell, the short circuit current, and the fill factor of the perovskite solar cell were 0.923V, 1.276mA, and 73.81%, respectively, and the photoelectric conversion efficiency of the top cell was 10.35%, respectively, based on table 1, and thus the photoelectric conversion efficiency of the perovskite solar cell was 31.51%, respectively. The abscissas of fig. 14 and 15 are open circuit voltages, and the ordinates are short circuit current densities, wherein the photoelectric conversion efficiency of the perovskite solar cell is the sum of the photoelectric conversion efficiency of the top cell and the photoelectric conversion efficiency of the bottom cell, and the short circuit current densities are equal to the ratio of the short circuit current to the effective area of the perovskite solar cell.
Based on the above, the present application provides a perovskite solar cell and a method for manufacturing the same, in the perovskite solar cell, the light absorption conversion layer in the top cell is the perovskite photoelectric conversion layer 3, the band gap of the perovskite photoelectric conversion layer 3 is 1.7eV, the photoelectric conversion function layer 7 of the bottom cell is the black phosphorus layer 71, the band gap of the black phosphorus layer 71 is set to be 1.1eV, the band gap of the perovskite photoelectric conversion layer 3 is different from the band gap of the black phosphorus layer 71, so that the absorption spectra of the perovskite photoelectric conversion layer 3 and the black phosphorus layer 71 are different, thereby improving the photoelectric conversion efficiency of the perovskite solar cell, and further, when the band gap of the black phosphorus layer 71 is 1.1eV, the photoelectric conversion efficiency of the perovskite solar cell can be further improved.
In the present specification, each embodiment is described in a progressive manner, or a parallel manner, or a combination of progressive and parallel manners, and each embodiment is mainly described as a difference from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other. For the perovskite solar cell disclosed in the examples, since it corresponds to the preparation method of the perovskite solar cell disclosed in the examples, the description is relatively simple, and the relevant points are only referred to the description of the method section.
It is to be noted, however, that the description of the drawings and embodiments are illustrative and not restrictive. Like reference numerals refer to like structures throughout the embodiments of the specification. In addition, the drawings may exaggerate the thicknesses of some layers, films, panels, regions, etc. for understanding and ease of description. It will also be understood that when an element such as a layer, film, region or substrate is referred to as being "on" another element, it can be directly on the other element or intervening elements may be present. In addition, "on …" refers to positioning an element on or under another element, but not essentially on the upper side of the other element according to the direction of gravity.
The terms "upper," "lower," "top," "bottom," "inner," "outer," and the like are used for convenience in describing and simplifying the description based on the orientation or positional relationship shown in the drawings, and do not denote or imply that the devices or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore should not be construed as limiting the application. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present.
It is further noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that an article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such article or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in an article or apparatus that comprises such element.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A method of manufacturing a perovskite solar cell, the method comprising:
providing a first substrate;
forming a first electrode on the surface of the first substrate;
forming a perovskite photoelectric conversion layer on one side of the first electrode away from the first substrate;
forming a second electrode on one side of the perovskite photoelectric conversion layer away from the first electrode;
a second substrate is arranged on one side of the second electrode, which is away from the perovskite photoelectric conversion layer;
forming a third electrode on one side of the second substrate away from the second electrode;
forming a photoelectric conversion functional layer on one side of the third electrode away from the second substrate;
forming a fourth electrode on one side of the photoelectric conversion functional layer away from the third electrode;
wherein the absorption spectra of the perovskite photoelectric conversion layer and the photoelectric conversion functional layer are different.
2. The method of manufacturing according to claim 1, wherein the method of forming the photoelectric conversion functional layer includes:
and forming a black phosphorus layer on one side of the third electrode, which is away from the second substrate, as the photoelectric conversion functional layer.
3. The method of claim 2, wherein the black phosphorus layer has a thickness in the range of 20 to 40nm.
4. The method of manufacturing according to claim 2, wherein the method of forming the black phosphorus layer comprises:
forming at least one thin film laminated structure on one side of the third electrode, which is far away from the second substrate, as the black phosphorus layer, wherein the thin film laminated structure comprises two laminated two-dimensional black phosphorus thin films;
when a plurality of the thin film laminated structures are formed as the black phosphorus layer on a side of the third electrode facing away from the second substrate, a barrier layer is formed between adjacent thin film laminated structures in a direction perpendicular to the second substrate.
5. The method of claim 4, wherein the barrier layer has a thickness of less than 10nm.
6. The method of manufacturing according to claim 4, wherein the method of forming the thin film stack structure comprises:
obtaining a blocky black phosphorus single crystal;
stripping flaky black phosphorus single crystals from the bulk black phosphorus single crystals;
stripping a first black phosphorus layer from the flaky black phosphorus single crystal by adopting a first adhesive tape;
using a second adhesive tape to adhere and peel a second black phosphorus layer from the first black phosphorus layer adhered and fixed on the first adhesive tape; wherein the tackiness of the first tape is less than the tackiness of the second tape;
selecting a target second adhesive tape, wherein a second black phosphorus layer adhered on the target second adhesive tape is of the film laminated structure;
and transferring the thin film laminated structure to one side of the third electrode, which is away from the second substrate.
7. A perovskite solar cell, the cell comprising:
a first substrate;
a first electrode located on the surface of the first substrate;
a perovskite photoelectric conversion layer positioned on one side of the first electrode away from the first substrate;
the second electrode is positioned on one side of the perovskite photoelectric conversion layer, which is away from the first electrode;
a second substrate positioned on one side of the second electrode away from the perovskite photoelectric conversion layer;
a third electrode positioned on a side of the second substrate facing away from the second electrode;
a photoelectric conversion functional layer positioned on one side of the third electrode away from the second substrate;
a fourth electrode positioned on one side of the photoelectric conversion functional layer away from the third electrode;
wherein the absorption spectra of the perovskite photoelectric conversion layer and the photoelectric conversion functional layer are different.
8. The battery according to claim 7, wherein the photoelectric conversion functional layer includes: black phosphorus layer.
9. The battery of claim 8, wherein the black phosphorus layer comprises:
at least one thin film laminated structure comprising two layers of two-dimensional black phosphorus thin films laminated;
when the black phosphorus layer includes a plurality of thin film laminated structures, there is a barrier layer between adjacent thin film laminated structures in a direction perpendicular to the second substrate.
10. The battery of claim 8, wherein the battery further comprises:
a first hole transport layer located between the first electrode and the perovskite photoelectric conversion layer;
a first electron transport layer located between the perovskite photoelectric conversion layer and the second electrode;
a second hole transport layer located between the third electrode and the photoelectric conversion functional layer;
and a second electron transport layer located between the photoelectric conversion functional layer and the fourth electrode.
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