CN115621331A - Perovskite laminated solar cell and preparation method thereof - Google Patents
Perovskite laminated solar cell and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229910021417 amorphous silicon Inorganic materials 0.000 claims abstract description 70
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- 229910052710 silicon Inorganic materials 0.000 claims abstract description 67
- 239000010703 silicon Substances 0.000 claims abstract description 67
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 32
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 23
- 230000031700 light absorption Effects 0.000 claims abstract description 14
- 238000000151 deposition Methods 0.000 claims description 24
- 150000003839 salts Chemical class 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 6
- 229910001414 potassium ion Inorganic materials 0.000 claims description 5
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical group [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 4
- 230000005540 biological transmission Effects 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 239000000969 carrier Substances 0.000 abstract description 17
- 230000005641 tunneling Effects 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 12
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- 239000000126 substance Substances 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 17
- 239000010408 film Substances 0.000 description 17
- 230000000694 effects Effects 0.000 description 8
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- 230000005525 hole transport Effects 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000000231 atomic layer deposition Methods 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- 238000005240 physical vapour deposition Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 229910021424 microcrystalline silicon Inorganic materials 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- -1 diisopropyl titanate Chemical compound 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 238000011056 performance test Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
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- H—ELECTRICITY
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- 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
- H01L31/02—Details
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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- 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
- H01L31/0352—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 their shape or by the shapes, relative sizes or disposition of the semiconductor regions
- H01L31/035272—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 their shape or by the shapes, relative sizes or disposition of the semiconductor regions characterised by at least one potential jump barrier or surface barrier
- H01L31/03529—Shape of the potential jump barrier or surface barrier
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- 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
- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
- H01L31/06—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 adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
- H01L31/072—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 adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type
- H01L31/0745—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 adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells
- H01L31/0747—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 adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells comprising a heterojunction of crystalline and amorphous materials, e.g. heterojunction with intrinsic thin layer or HIT® solar cells; solar cells
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- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic System
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- 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
Abstract
The application relates to the field of solar cells, in particular to a perovskite laminated solar cell and a preparation method thereof. The perovskite tandem solar cell comprises a silicon bottom cell and a perovskite top cell, wherein a silicon oxide layer and a P-type doped amorphous silicon layer are sequentially stacked on the top surface of the silicon bottom cell, and the P-type doped amorphous silicon layer is positioned on the bottom surface of the perovskite top cell; the perovskite light absorption layer of the perovskite roof battery contains alkali metal ions. The P-type doped amorphous silicon layer is a disordered simple silicon substance, has a plurality of defects and is convenient for movement of current carriers, tunneling of the current carriers can be increased through cooperation of the silicon oxide layer and the P-type doped amorphous silicon layer, tunneling efficiency of the current carriers between the silicon bottom battery and the perovskite top battery is greatly increased, and open-circuit voltage and conversion efficiency of the silicon bottom battery and the perovskite top battery are effectively superposed.
Description
Technical Field
The application relates to the field of solar cells, in particular to a perovskite laminated solar cell and a preparation method thereof.
Background
The crystalline silicon-perovskite laminated cell takes a crystalline silicon cell as a bottom cell for absorbing solar energy of 700nm-1200nm, takes a perovskite cell as a top cell for absorbing solar energy of 300nm-800nm, and is connected with the perovskite cell through a composite layer, and the crystalline silicon cell and the perovskite cell are connected in series.
When the bottom battery and the top battery are stacked, the problem that lattice mismatching tunneling is not easy to happen easily, and therefore the open-circuit voltage and the conversion efficiency cannot be effectively superposed.
Disclosure of Invention
An object of the embodiment of the present application is to provide a perovskite tandem solar cell and a preparation method thereof, which aim to solve the problem that effective superposition of the open-circuit voltage and the conversion efficiency of the existing perovskite tandem solar cell cannot be achieved.
The perovskite laminated solar cell comprises a silicon bottom cell and a perovskite top cell, wherein a silicon oxide layer and a P-type doped amorphous silicon layer are sequentially laminated on the top surface of the silicon bottom cell, and a hole transmission layer of the perovskite top cell is positioned on the surface of the P-type doped amorphous silicon layer; the perovskite light absorption layer of the perovskite roof battery contains alkali metal ions.
The P-type doped amorphous silicon layer is a disordered simple silicon substance, has a plurality of defects and is convenient for movement of current carriers, tunneling of the current carriers can be increased through cooperation of the silicon oxide layer and the P-type doped amorphous silicon layer, tunneling efficiency of the current carriers between the silicon bottom battery and the perovskite top battery is greatly increased, and open-circuit voltage and conversion efficiency of the silicon bottom battery and the perovskite top battery are effectively superposed.
In some embodiments of the present application, the silicon oxide layer has a thickness of 0.5nm to 2nm; the thickness of the P-type doped amorphous silicon layer is 10-20 nm.
In some embodiments of the present application, the P-type doped amorphous silicon layer has a doping concentration of 10 18 cm -3 ～10 20 cm -3 。
In some embodiments of the present application, the alkali metal ion is a potassium ion.
The alkali metal ions can eliminate the hysteresis effect in the perovskite solar cell, and have important significance for accurately measuring the conversion efficiency of the cell. The alkali metal ions are doped to reduce the defect state density in the perovskite light absorption layer, and the method has important significance for prolonging the diffusion of carriers, improving the collection of the carriers and improving the conversion efficiency of the solar cell.
The application also provides a preparation method of the perovskite tandem solar cell, which comprises the following steps:
providing the silicon bottom cell;
depositing the silicon oxide layer on the top surface of the silicon bottom cell;
depositing the P-type doped amorphous silicon layer on the surface of the silicon oxide layer;
forming the perovskite top cell on the surface of the P-type doped amorphous silicon layer; wherein, the perovskite light absorption layer is prepared by adopting a raw material containing alkali metal ion salt.
In some embodiments of the present application, a PECVD magnetron sputtering apparatus is used to deposit the P-type doped amorphous silicon layer, and the deposition conditions are as follows: h 2 、SiH 4 、CO 2 And B 2 H 6 The flow ratio of (1-20) to (1-5), the air pressure range is (0.4-1.0) mbar, and the radio frequency power range is (300-1200) W.
In some embodiments of the present application, the alkali metal ion salt is a potassium salt.
In some embodiments of the present application, in the step of forming the perovskite top cell on the surface of the P-type doped amorphous silicon layer: preparation of light-absorbing layers of perovskitesThe raw materials comprise alkali metal ion salt and PbI 2 、PbBr 2 、CH 3 NH 3 Br、CH(NH 2 ) 2 I. Dimethylformamide and dimethylsulfoxide;
wherein, the PbI 2 The concentration of (A) is 1.0-1.5mol/L;
the PbBr is 2 The concentration of (A) is 0.20-0.25mol/L;
the CH 3 NH 3 The concentration of Br is 0.20-0.25mol/L;
the CH (NH) 2 ) 2 The concentration of I is 1.0-1.3mol/L;
the molar concentration of the alkali metal ion salt is PbI 2 、PbBr 2 、CH 3 NH 3 Br and CH (NH) 2 ) 2 5 to 7.5 percent of the sum of the I molar concentration.
In some embodiments of the present application, the alkali metal ion salt is a potassium salt.
In some embodiments of the present application, a method of manufacturing the silicon bottom cell includes: texturing an N-type doped silicon wafer; depositing intrinsic amorphous silicon layers with the thickness of 5nm to 10nm on the front surface and the back surface of the N-type doped silicon wafer respectively, and depositing an N-type doped amorphous silicon doping layer with the thickness of 10nm to 20nm on the front surface of the N-type doped silicon wafer; and depositing a 10-20 nm thick P-type doped amorphous silicon layer on the back of the N-type doped silicon wafer.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and those skilled in the art can also obtain other related drawings based on the drawings without inventive efforts.
Fig. 1 shows a schematic structural diagram of a perovskite tandem solar cell provided in an embodiment of the present application.
Icon: a 100-perovskite tandem solar cell; 101-a silicon oxide layer; 102-a first P-type doped amorphous silicon layer; 201-TO conductive film layer; 202-a second P-type doped amorphous silicon layer; 203-N type silicon chip; 204-intrinsic amorphous silicon layer; 205-N type doped amorphous silicon layer; 301-hole transport layer; 302-perovskite light absorbing layers; 303-electron transport layer; 304-C60 film layer; 305-SnO2 film layers; 306-ITO transparent conductive layer.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. The components of the embodiments of the present application, generally described and illustrated in the figures herein, can be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present application, presented in the accompanying drawings, is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
It should be noted that: like reference numbers and letters refer to like items in the following figures, and thus, once an item is defined in one figure, it need not be further defined or explained in subsequent figures.
In the description of the embodiments of the present application, it is to be understood that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", and the like, refer to the orientation or positional relationship as shown in the drawings, or as conventionally placed in use of the product of the application, or as conventionally understood by those skilled in the art, and are used merely for convenience of description and for simplicity of description, and do not indicate or imply that the referenced device or element must have a particular orientation, be constructed in a particular orientation, and be operated, and therefore should not be considered as limiting the present application.
Furthermore, the terms "first," "second," "third," and the like are used solely to distinguish one from another and are not to be construed as indicating or implying relative importance.
In the description of the embodiments of the present application, it should also be noted that, unless otherwise explicitly stated or limited, the terms "disposed," "mounted," "connected," and "connected" are to be construed broadly and may, for example, be fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meaning of the above terms in the present application can be understood in a specific case by those of ordinary skill in the art.
Examples
Fig. 1 shows a schematic structural diagram of a perovskite tandem solar cell 100 provided in an embodiment of the present application, and referring to fig. 1, the embodiment provides a perovskite tandem solar cell 100, where the perovskite tandem solar cell 100 mainly includes a silicon bottom cell and a perovskite top cell. Between the silicon bottom cell and the perovskite top cell there is a silicon oxide layer 101 and a first P-doped amorphous silicon layer 102. Specifically, the top surface of the silicon bottom cell is provided with a silicon oxide layer 101, a first P-type doped amorphous silicon layer 102 is arranged on the surface of the silicon oxide layer 101, and the first P-type doped amorphous silicon layer 102 is positioned on the bottom surface of the perovskite top cell. The hole transport layer of the perovskite top cell is located on the surface of the first P-type doped amorphous silicon layer 102.
In this embodiment, the silicon bottom cell includes an ITO conductive film layer 201, an intrinsic amorphous silicon layer 204, a second P-type doped amorphous silicon layer 202, an N-type silicon wafer 203, an intrinsic amorphous silicon layer 204, and an N-type doped amorphous silicon layer 205, which are stacked in sequence; the silicon oxide layer 101 is located on the surface of the N-type doped amorphous silicon layer 205.
The perovskite top cell comprises a hole transport layer 301, a perovskite light absorption layer 302, an electron transport layer 303, a C60 film layer 304 and SnO which are sequentially stacked 2 A film layer 305 and an ITO transparent conductive layer 306. The hole transport layer 301 is disposed on the surface of the first P-type doped amorphous silicon layer 102.
In the present application, alkali metal ions are contained within the perovskite light absorbing layer 302; alternatively, the alkali metal ion is a potassium ion; alternatively, in other embodiments, the alkali metal ion liquid may be sodium ions, lithium ions, or the like.
In other embodiments of the present application, the silicon bottom battery and the perovskite top battery may have other structures, and are not limited to the above structures, and the present application does not limit the structures.
Illustratively, the thickness of the silicon oxide layer 101 is 0.5nm to 2nm, and may be, for example, 0.5nm, 0.6nm, 0.9nm, 1.2nm, 1.5nm, 1.8nm, 2nm, or the like.
Illustratively, the thickness of the P-type doped amorphous silicon layer is 10 to 20nm. For example, 10nm, 12nm, 14nm, 17nm, 19nm, 20nm, etc. may be mentioned.
Illustratively, the doping concentration of the P-type doped amorphous silicon layer is 10 18 cm -3 ～10 20 cm -3 。
The perovskite tandem solar cell 100 provided by the embodiment of the application has at least the following advantages:
the first P-type doped amorphous silicon layer 102 is a disordered simple silicon substance, has a plurality of defects, and facilitates movement of current carriers, and the cooperation of the silicon oxide layer 101 and the first P-type doped amorphous silicon layer 102 can increase tunneling of the current carriers, so that tunneling efficiency of the current carriers between the silicon bottom battery and the perovskite top battery is increased to a great extent, and open-circuit voltage and conversion efficiency of the silicon bottom battery and the perovskite top battery are effectively superposed.
For the embodiment in which the perovskite light absorption layer 302 contains alkali metal ions, the alkali metal ions can eliminate the hysteresis effect in the perovskite solar cell, and have an important significance for accurately measuring the conversion efficiency of the cell. The alkali metal ions are doped to reduce the defect state density in the perovskite light absorption layer, and the method has important significance for prolonging the diffusion of carriers, improving the collection of the carriers and improving the conversion efficiency of the solar cell.
Some examples are made below of a method of fabricating the perovskite tandem solar cell 100, and in particular, the method of fabricating the perovskite tandem solar cell 100 includes:
firstly, an N-type silicon wafer with the resistivity of 1.0-7.0 and the thickness of 100-200 mu m is adopted, and the silicon wafer is subjected to texturing and cleaning treatment to form an N-type monocrystalline silicon-based substrate with a textured structure.
Secondly, depositing intrinsic amorphous silicon layers on the front side and the back side of the silicon-based substrate respectively by utilizing PECVD equipment; the thickness of the intrinsic amorphous silicon layer is 5-10nm, and may be, for example, 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, or the like.
Thirdly, depositing a phosphorus-doped N-type doped amorphous silicon layer on the front surface of the silicon substrate by utilizing PECVD equipment to form a front electric field structure; the thickness of the N-type doped amorphous silicon layer is 10-20 nm, and may be, for example, 10nm, 12nm, 16nm, 18nm, 20nm, or the like.
Fourthly, depositing a boron-doped P-type doped amorphous silicon layer on the back surface of the silicon substrate by utilizing PECVD equipment to form a back electric field structure; the thickness of the P-type doped amorphous silicon layer is 10-20 nm, and may be, for example, 10nm, 12nm, 16nm, 18nm, 20nm, or the like. Doping concentration of 10 18 cm -3 ～10 20 cm -3 。
Fifthly, adopting PECVD equipment to sequentially deposit SiO on the front surface of the silicon-based substrate x A silicon oxide layer and a boron doped P-type doped amorphous silicon layer, the thickness of the P-type doped amorphous silicon layer is 10-20 nm, for example, 10nm, 12nm, 16nm, 18nm, 20nm, etc. The doping concentration of the P-type doped amorphous silicon layer is 10 18 cm -3 ～10 20 cm -3 . The thickness of the silicon oxide layer is 0.5nm to 2nm, and may be, for example, 0.5nm, 0.6nm, 0.9nm, 1.2nm, 1.5nm, 1.8nm, 2nm, or the like.
Illustratively, the conditions for depositing the P-type doped amorphous silicon layer are: the flow ratio of H2, siH4, CO2 and B2H6 is (1-20) 1, (1-5) 1-5, the air pressure range is (0.4-1.0) mbar, and the radio frequency power range is (300-1200) W.
For example, the flow ratio of H2, siH4, CO2, B2H6 can be 1.
Sixthly, preparing an ITO transparent conductive layer on the back of the silicon-based substrate by adopting PVD magnetron sputtering equipment; the thickness of the ITO transparent conductive layer is 80 to 100nm, and may be, for example, 80nm, 85nm, 88nm, 90nm, 92nm, 96nm, 98nm, 100nm, or the like.
And step seven, preparing a hole transport layer on the front surface of the silicon substrate. For example, 0.2 to 0.6mL of bis (acetylacetonate) diisopropyl titanate (titanium diisopropoxy salts) is dissolved in 3 to 6mL of ethanol as a precursor solution, and the dense TiO with the thickness of 30 to 100nm is prepared by a spray thermal decomposition method at a high temperature of 400 to 550 DEG C 2 A film.
And eighth step, preparing a perovskite light absorption layer on the front surface of the silicon substrate, wherein the thickness of the perovskite light absorption layer is 800 nm-1200nm, such as 800nm, 900nm, 1000nm, 1100nm, 1200nm and the like.
In some embodiments, the perovskite light absorbing layer contains alkali metal ions, and the preparation method comprises the following steps:
will contain alkali metal ion salt, pbI 2 、PbBr 2 、CH 3 NH 3 Br、CH(NH 2 ) 2 I. Application of raw materials of dimethyl formamide and dimethyl sulfoxide to TiO 2 On the film layer, two-step rotation speed of 1000rpm (10 s) and 4000rpm (30 s) is adopted during spin coating, and chlorobenzene or toluene solution is dripped 20s before the rotation is finished. Heat treatment is carried out for 5-20 min at 160 ℃ to form the perovskite film.
Wherein, in the raw materials, pbI 2 The concentration of (B) is 1.0 to 1.5mol/L, and may be, for example, 1.0mol/L, 1.15mol/L, 1.2mol/L, 1.3mol/L, 1.4mol/L, 1.5mol/L, or the like.
PbBr in the above raw materials 2 The concentration of (B) is 0.20 to 0.25mol/L, and may be, for example, 0.20mol/L, 0.21mol/L, 0.22mol/L, 0.23mol/L, 0.24mol/L, 0.25mol/L, or the like.
CH in the above raw materials 3 NH 3 The concentration of Br is 0.20 to 0.25mol/L, and may be, for example, 0.20mol/L, 0.21mol/L, 0.22mol/L, 0.23mol/L, 0.24mol/L, 0.25mol/L or the like.
CH (NH) in the above raw materials 2 ) 2 The concentration of I is 1.0 to 1.3mol/L, and may be, for example, 1.0mol/L, 1.09mol/L, 1.2mol/L, 1.3mol/L, or the like.
The concentration of alkali metal ion salt is PbI 2 、PbBr 2 、CH 3 NH 3 Br and CH (NH) 2 ) 2 The sum of the I concentration is 5 to 7.5 percent. The concentration of alkali metal ion salt can be 5%, 6%, 7%, 7.5%, etc. of the sum of the latter concentrations; in some embodiments, the alkali metal ion is a potassium ion; alternatively, in other embodiments, the alkali metal ion liquid may be sodium ions, lithium ions, or the like.
Based on the above, the raw material of the perovskite light absorption layer contains alkali metal ion salt, and the alkali metal ion can eliminate the hysteresis effect in the perovskite solar cell, and has important significance for accurately measuring the conversion efficiency of the cell. The alkali metal ions are doped to reduce the defect state density in the perovskite light absorption layer, and the method has important significance for prolonging the diffusion of carriers, improving the collection of the carriers and improving the conversion efficiency of the solar cell.
Ninthly, preparing a LiF and C60 film layer 304 on the electron transport layer on the front surface of the silicon substrate; for example, a LiF thin film layer and a C60 thin film layer are formed on a perovskite absorption layer using a thermal evaporation process. The thickness of the LiF thin film layer is 10nm to 20nm, and may be, for example, 10nm, 11nm, 12nm, 15nm, 18nm, 19nm, 20nm, or the like. The thickness of the C60 film 304 is 10nm to 20nm, for example, 10nm, 11nm, 13nm, 15nm, 17nm, 19nm, 20nm, etc.
Tenth, preparing an electron transport layer on the front surface of the silicon substrate by adopting Atomic Layer Deposition (ALD), and specifically, preparing SnO on the front surface of the silicon substrate 2 Film layer, snO 2 The thickness of the film layer is 20 to 40nm, and may be, for example, 20nm, 25nm, 27nm, 29nm, 32nm, 35nm, 40nm, or the like.
And a tenth step of preparing an ITO transparent conductive layer on the front side of the silicon substrate by adopting PVD magnetron sputtering equipment, wherein the thickness of the ITO transparent conductive layer is 80-100 nm, such as 80nm, 85nm, 87nm, 89nm, 92nm, 95nm, 100nm and the like.
And step ten, preparing a copper electrode, wherein the copper electrode is prepared on the back surface of the silicon substrate by adopting a copper electroplating process.
It should be noted that the preparation method of the present application is only a few examples, and in other embodiments of the present application, the silicon bottom cell and the perovskite top cell may be prepared by other processes, and the thicknesses of the layers in the silicon bottom cell and the perovskite top cell may be selected according to performance requirements without referring to the thicknesses described above.
The features and properties of the present application are described in further detail below with reference to examples.
Example 1
The embodiment provides a perovskite tandem solar cell which is mainly prepared by the following steps:
firstly, an N-type silicon wafer with the resistivity of 2.0 and the thickness of 120 mu m is adopted, and texturing and cleaning treatment are carried out on the silicon wafer to form an N-type monocrystalline silicon-based substrate with a textured structure.
And secondly, depositing intrinsic amorphous silicon passivation layers with the thickness of 6nm on the front surface and the back surface of the silicon-based substrate respectively by utilizing PECVD equipment.
And thirdly, depositing a phosphorus-doped N-type doped amorphous silicon layer with the thickness of 12nm on the front surface of the silicon substrate by utilizing PECVD equipment to form a front electric field structure.
And fourthly, depositing a boron-doped P-type doped amorphous silicon layer with the thickness of 12nm on the back surface of the silicon substrate by utilizing PECVD equipment to form a back electric field structure.
And fifthly, sequentially depositing a SiOx silicon oxide layer with the thickness of 1nm and a boron-doped P-type doped amorphous silicon layer with the thickness of 12nm on the front surface of the silicon-based substrate by adopting PECVD equipment. The conditions for depositing the P-type doped amorphous silicon layer are as follows: h 2 、SiH 4 、CO 2 、B 2 H 6 Flow ratio of 10.
And sixthly, preparing an ITO transparent conducting layer with the thickness of 80nm on the back surface of the silicon substrate by adopting PVD magnetron sputtering equipment.
Seventhly, preparing a hole transport layer with the thickness of 30nm on the front surface of the silicon substrate, specifically, dissolving 0.2mL of bis (acetylacetonate) diisopropyl titanate (titanium diisopropoxy salts) in 6mL of ethanol as a precursor solution, and preparing dense TiO with the thickness of 30nm by a spray thermal decomposition method at the high temperature of 450 DEG C 2 A film.
And eighthly, preparing a perovskite light absorption layer with the thickness of 900nm on the front surface of the silicon substrate. In particular toEarth, mix PbI 2 、PbBr 2 、CH 3 NH 3 Br and CH (NH) 2 ) 2 Dissolving the compound I in a mixed solvent of dimethylformamide and dimethyl sulfoxide. Controlling PbI 2 、PbBr 2 、CH 3 NH 3 Br and CH (NH) 2 ) 2 The molar concentrations of I were 1.15M, 0.20M and 1.09M, respectively. The volume ratio of dimethylformamide to dimethyl sulfoxide is 4. Preparing 1.5M potassium iodide, adding the potassium iodide into the solution to enable the final concentration of K + to be 0.16M, spin-coating the prepared precursor solution on a TiO2 film layer, and dropping chlorobenzene or toluene solution 20s before the end of the rotation by adopting two-step rotation speed of 1000rpm (10 s) and 4000rpm (30 s) during the spin-coating. Heat treatment is carried out at 160 ℃ for 10min to form the perovskite thin film.
And ninthly, preparing a LiF thin film layer with the thickness of 10nm and a C60 film layer with the thickness of 12nm on the electron transport layer on the front surface of the silicon substrate.
Tenth step, adopting Atomic Layer Deposition (ALD) to manufacture SnO with the thickness of 30nm on the front surface of the silicon substrate 2 And (5) film layer.
And step eleven, preparing an ITO transparent conducting layer with the thickness of 80nm on the front side of the silicon substrate by adopting PVD magnetron sputtering equipment.
And step ten, preparing a copper electrode, wherein the copper electrode is prepared on the back surface of the silicon substrate by adopting a copper electroplating process.
Example 2
Referring to example 1, example 2 differs from example 1 in that in the eighth step, the precursor solution of the perovskite light absorbing layer does not contain potassium ions.
Comparative example 1
Referring to embodiment 1, comparative example 1 is different from embodiment 1 in that, in the fifth step, the conditions for depositing the P-type doped amorphous silicon layer are as follows: h 2 、SiH 4 、CO 2 、B 2 H 6 The flow ratio of 500; the result is a boron-doped P-type doped microcrystalline silicon layer.
Comparative example 2
Referring to embodiment 1, comparative example 1 is different from embodiment 1 in that, in the fifth step, the conditions for depositing the P-type doped amorphous silicon layer are as follows: h 2 、SiH 4 、CO 2 、B 2 H 6 The flow ratio of (1); the result is a boron-doped P-type doped microcrystalline silicon layer.
Comparative example 3
Referring to example 1, comparative example 3 differs from example 1 in that in the fifth step, siO is not deposited on the front side of the bottom cell x A layer of silicon oxide 101, a 12nm thick layer of boron doped P-type doped amorphous silicon is deposited directly on the front side of the bottom cell.
Comparative example 4
Referring to example 1, the difference between comparative example 4 and example 1 is that in the fifth step, the P-type doped amorphous silicon layer 102 is not deposited on the front surface of the silicon-based substrate, and a 2nm thick silicon dioxide layer is directly deposited on the front surface of the bottom cell.
The perovskite tandem solar cell 100 provided in example 1, comparative example 2, comparative example 3 and comparative example 4 was subjected to a performance test. Specifically, a BERGER online I-V test system is selected to test the electrical performance parameters of the silicon/perovskite tandem solar cell, such as conversion efficiency, open-circuit voltage, short-circuit current, filling factor and the like, under the conditions of 25 ℃, AM 1.5 and 1 standard sun.
TABLE 1 Performance of perovskite tandem solar cells 100
Comparative example 1 is a P-type doped microcrystalline silicon layer of high crystallinity, example 1 is a P-type doped amorphous silicon phase layer; as can be seen from a comparison of comparative example 1 with example 1, this illustrates that high crystallinity does not facilitate tunneling of carriers between the bottom and top cells.
From the aspect of electrical parameters, the difference between the two comparative examples is mainly FF; it is proved that the lower the crystallinity, the better the tunneling effect, i.e. when the P-type doped layer is completely in the amorphous silicon state, the easier the carrier tunneling is, so that there is no FF loss.
The example 1 has an intermediate silicon dioxide layer, the comparative example 3 does not have the intermediate silicon dioxide layer, and the FF performance of the two layers shows poor electrical parameters, which shows that the tunneling effect between the bottom cell and the top cell is poor without silicon dioxide, namely, carriers cannot pass from the lower layer to the upper layer or from the upper layer to the lower layer, so that the silicon dioxide layer plays an important role in the tunneling process, and the silicon dioxide layer has a good tunneling effect.
The embodiment 1 has middle P-type doped amorphous silicon, the comparative example 4 has no middle P-type poor amorphous silicon, the difference of the electrical parameters is firstly shown on FF, and the combination of the comparative example 3 shows that the tunneling effect of the silicon dioxide layer is better than that of the P-type doped amorphous silicon, and the two can be superposed to obtain the optimal tunneling effect.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. A perovskite tandem solar cell comprises a silicon bottom cell and a perovskite top cell and is characterized in that a silicon oxide layer and a P-type doped amorphous silicon layer are sequentially arranged on the top surface of the silicon bottom cell in a tandem mode, and a hole transmission layer of the perovskite top cell is located on the surface of the P-type doped amorphous silicon layer; the perovskite light absorption layer of the perovskite roof battery contains alkali metal ions.
2. The perovskite tandem solar cell according to claim 1, wherein the thickness of the silicon oxide layer is 0.5nm to 2nm; the thickness of the P-type doped amorphous silicon layer is 10-20 nm.
3. The perovskite tandem solar cell according to claim 1, wherein the P-type doped amorphous silicon layer has a doping concentration of 10 18 cm -3 ～10 20 cm -3 。
4. The perovskite tandem solar cell according to any one of claims 1 to 3, wherein the alkali metal ions are potassium ions.
5. A method of manufacturing a perovskite tandem solar cell as defined in any one of claims 1 to 4, comprising:
providing the silicon bottom cell;
depositing the silicon oxide layer on the top surface of the silicon bottom cell;
depositing the P-type doped amorphous silicon layer on the surface of the silicon oxide layer;
forming the perovskite top cell on the surface of the P-type doped amorphous silicon layer; wherein, the perovskite light absorption layer is prepared by adopting a raw material containing alkali metal ion salt.
6. The method of manufacturing a perovskite tandem solar cell according to claim 5,
and depositing the P-type doped amorphous silicon layer by adopting PECVD magnetron sputtering equipment, wherein the deposition conditions are as follows: h 2 、SiH 4 、CO 2 And B 2 H 6 The flow ratio of (1-20) to (1-5), the air pressure range of (0.4-1.0) mbar and the radio frequency power range of (300-1200) W.
7. The method for manufacturing a perovskite tandem solar cell according to claim 5 wherein the alkali metal ion salt is a potassium salt.
8. The method for fabricating a perovskite tandem solar cell according to claim 5, wherein in the step of forming the perovskite top cell on the surface of the P-type doped amorphous silicon layer: preparation of perovskiteThe light absorbing layer is prepared from alkali metal ion salt and PbI 2 、PbBr 2 、CH 3 NH 3 Br、CH(NH 2 ) 2 I. Dimethylformamide and dimethylsulfoxide;
wherein, the PbI 2 The concentration of (A) is 1.0-1.5mol/L;
the PbBr is 2 The concentration of (b) is 0.20-0.25mol/L;
the CH 3 NH 3 The concentration of Br is 0.20-0.25mol/L;
the CH (NH) 2 ) 2 The concentration of I is 1.0-1.3mol/L;
the molar concentration of the alkali metal ion salt is PbI 2 、PbBr 2 、CH 3 NH 3 Br and CH (NH) 2 ) 2 5 to 7.5 percent of the sum of the I molar concentration.
9. The method of fabricating a perovskite tandem solar cell according to claim 8,
the alkali metal ion salt is potassium salt.
10. The method for manufacturing a perovskite tandem solar cell according to any one of claims 5 to 9,
the preparation method of the silicon bottom battery comprises the following steps: texturing an N-type doped silicon wafer; depositing intrinsic amorphous silicon layers with the thickness of 5nm to 10nm on the front surface and the back surface of the N-type doped silicon wafer respectively, and depositing an N-type doped amorphous silicon doping layer with the thickness of 10nm to 20nm on the front surface of the N-type doped silicon wafer; and depositing a 10-20 nm thick P-type doped amorphous silicon layer on the back of the N-type doped silicon wafer.
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