CN112993169B - NIP heterojunction solar cell and manufacturing method thereof - Google Patents
NIP heterojunction solar cell and manufacturing method thereof Download PDFInfo
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- CN112993169B CN112993169B CN202110235747.5A CN202110235747A CN112993169B CN 112993169 B CN112993169 B CN 112993169B CN 202110235747 A CN202110235747 A CN 202110235747A CN 112993169 B CN112993169 B CN 112993169B
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- HVMJUDPAXRRVQO-UHFFFAOYSA-N copper indium Chemical compound [Cu].[In] HVMJUDPAXRRVQO-UHFFFAOYSA-N 0.000 claims abstract description 50
- QNWMNMIVDYETIG-UHFFFAOYSA-N gallium(ii) selenide Chemical compound [Se]=[Ga] QNWMNMIVDYETIG-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 40
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000758 substrate Substances 0.000 claims abstract description 24
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 18
- 239000011733 molybdenum Substances 0.000 claims abstract description 18
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 17
- 239000011787 zinc oxide Substances 0.000 claims abstract description 16
- 238000004528 spin coating Methods 0.000 claims abstract description 11
- 239000012046 mixed solvent Substances 0.000 claims abstract description 10
- 238000000151 deposition Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 230000005540 biological transmission Effects 0.000 claims abstract description 7
- 238000010549 co-Evaporation Methods 0.000 claims abstract description 6
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 claims description 20
- 239000010949 copper Substances 0.000 claims description 17
- 239000000463 material Substances 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
- 239000011669 selenium Substances 0.000 claims description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 5
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- 239000004642 Polyimide Substances 0.000 claims description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 230000006798 recombination Effects 0.000 description 7
- 238000005215 recombination Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000031700 light absorption Effects 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- ZZEMEJKDTZOXOI-UHFFFAOYSA-N digallium;selenium(2-) Chemical compound [Ga+3].[Ga+3].[Se-2].[Se-2].[Se-2] ZZEMEJKDTZOXOI-UHFFFAOYSA-N 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
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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
- H10K30/40—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising a p-i-n structure, e.g. having a perovskite absorber between p-type and n-type charge transport layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/10—Deposition of organic active material
- H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
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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
- H10K85/30—Coordination compounds
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
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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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides an NIP heterojunction solar cell and a manufacturing method thereof. The NIP heterojunction solar cell comprises: the method sequentially comprises the following steps from top to bottom: the solar cell comprises a transparent front electrode, an electron transmission layer, an N-type perovskite layer, an I-type copper indium gallium selenium layer, a P-type copper indium gallium selenium layer, a molybdenum electrode layer and a cell substrate. The manufacturing method comprises the following steps: preparing a molybdenum electrode layer on a battery substrate by adopting a direct current magnetron sputtering method; sequentially depositing a P-type copper indium gallium selenium layer and an I-type copper indium gallium selenium layer on the molybdenum electrode layer by adopting a three-step co-evaporation method; spin-coating the mixed solvent on the copper indium gallium selenium layer by using a spin-coating mode, and heating to obtain a perovskite layer; preparing a zinc oxide layer with the thickness of 70 nanometers on the N-type perovskite layer by adopting a direct current magnetron sputtering method; and preparing an AZO layer with the thickness of 500 nanometers on the electron transport layer by adopting a direct current magnetron sputtering method. The invention can improve the collection efficiency of electrons, thereby improving the photoelectric conversion efficiency of the solar cell.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to an NIP heterojunction solar cell and a manufacturing method thereof.
Background
The solar cell is an element for directly converting light energy into electric energy, and because the solar radiation spectrum range (0-4 eV) is very wide, according to the photovoltaic effect principle, a single junction solar cell formed by a single semiconductor material can only convert a part of light energy in the solar radiation spectrum into electric energy, and the solar energy has low effective utilization rate and low output voltage.
In the prior art, a laminated cell is adopted to realize the response of the response wavelength of the solar cell. Perovskite solar cells employing a stacked structure have attracted considerable attention in the photovoltaic world in recent years. The photoelectric conversion efficiency of the perovskite solar cell is improved very rapidly, the initial conversion efficiency in 2009 is only 3.8%, the conversion efficiency in 2012 is improved to 10.9%, and the conversion efficiency of the perovskite solar cell reaches 25.5% nowadays. The perovskite layer is used as an absorption layer, has the advantages of high carrier mobility, high light absorption coefficient and the like, and the band gap can be adjusted through halogen types and doping proportion, so that the perovskite layer plays a vital role in a battery. Copper indium gallium diselenide (CIGS) is a quaternary compound semiconductor material, and the forbidden band width of the CIGS is changed from 1.04eV to 1.69eV along with the change of a gallium component X from 0 to 1, so that the CIGS can absorb the visible spectrum range in sunlight and the solar spectrum of 700-1200 nm. In the perovskite and copper indium gallium selenide laminated battery structure, the top perovskite is used for absorbing short wavelength sunlight, and the bottom narrow band gap copper indium gallium selenide material is used for absorbing long wavelength light, so that the high-efficiency utilization of a wide wavelength range of sunlight can be realized.
However, on the one hand, the laminate battery has a disadvantage in that the cost is high. On the other hand, the copper indium gallium diselenide semiconductor material has more electron recombination, so that the collection efficiency of photo-generated electrons and the short-circuit current density are limited, and the problem of low photoelectric conversion efficiency is caused.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an NIP heterojunction solar cell and a manufacturing method thereof, which can improve the photoelectric conversion efficiency of the solar cell.
In order to solve the technical problems, the invention provides the following technical scheme:
in a first aspect, the present invention provides an NIP heterojunction solar cell comprising:
the method sequentially comprises the following steps from top to bottom: the solar cell comprises a transparent front electrode, an electron transmission layer, an N-type perovskite layer, an I-type copper indium gallium selenium layer, a P-type copper indium gallium selenium layer, a molybdenum electrode layer and a cell substrate.
Wherein the battery substrate is made of any one of glass, stainless steel or polyimide.
Wherein the thickness of the molybdenum electrode layer is 200-1000 nanometers.
Wherein the thickness of the P-type copper indium gallium selenium layer or the I-type copper indium gallium selenium layer is 1-3 micrometers.
Wherein the material of the N-type perovskite layer is lead halogen perovskite;
the lead halogen perovskite has a chemical formula of APbX 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein A is an organic ion or an inorganic alkali metal ion, and X is halogen.
Wherein, the material of electron transport layer is: titanium dioxide, zinc oxide or an organic electron transport material.
The transparent front electrode is made of indium tin oxide or AZO, and the thickness of the transparent front electrode is 150-1000 nanometers.
In a second aspect, the present invention provides a method for manufacturing an NIP heterojunction solar cell, comprising:
preparing a molybdenum electrode layer with the thickness of 500 nanometers on a battery substrate by adopting a direct current magnetron sputtering method;
sequentially depositing a P-type copper indium gallium selenium layer and an I-type copper indium gallium selenium layer on the molybdenum electrode layer by adopting a three-step co-evaporation method;
spin-coating the mixed solvent on the copper indium gallium selenium layer by using a spin-coating mode, and heating for 10-60 min at 80-150 ℃ to obtain a perovskite layer; wherein, the mixed solvent is obtained by dissolving methyl amine bromide and lead bromide in dimethylformamide and dimethyl sulfoxide solvent according to a preset proportion;
preparing a zinc oxide layer with the thickness of 70 nanometers on the N-type perovskite layer by adopting a direct current magnetron sputtering method; wherein the zinc oxide layer is an electron transport layer;
preparing an AZO layer with the thickness of 500 nanometers on the electron transport layer by adopting a direct current magnetron sputtering method; wherein the AZO layer is a transparent front electrode.
Further, the method for sequentially depositing a P-type copper indium gallium selenide layer and an I-type copper indium gallium selenide layer on the molybdenum electrode layer by adopting a three-step co-evaporation method comprises the following steps:
heating the battery substrate to 300 ℃ and then co-evaporating In-Ga-Se to prepare an IGS layer;
closing an In source and a Ga source, increasing the temperature of a battery substrate to 550 ℃, and opening a Cu source to prepare a copper-rich CIGS layer;
preparing In-Ga-Se on the surface of the copper-rich CIGS layer to obtain a P-type copper indium gallium selenium layer;
and opening a Cu source, an In source, a Ga source and a Se source on the P-type copper indium gallium selenium layer to continuously deposit so as to obtain the I-type copper indium gallium selenium layer.
Wherein, the material of battery substrate is glass, and thickness is 3 millimeters.
According to the NIP heterojunction solar cell and the manufacturing method thereof, the perovskite film with excellent absorption performance can be used for supplementing and absorbing with the copper indium gallium selenide film, so that more sufficient light absorption can be realized under the condition of thinner copper indium gallium selenide thickness; perovskite has excellent bipolar carrier transmission characteristics, and can effectively transmit electrons and holes, so that the electron collection efficiency is improved.
In addition, the P-type copper indium gallium selenide layer has higher recombination rate on electrons, and the I-type copper indium gallium selenide layer can reduce carrier recombination, thereby being beneficial to improving the battery filling factor, the short-circuit current and the open-circuit voltage and further improving the photoelectric conversion efficiency of the solar battery. Compared with the traditional copper indium gallium selenium battery, the cadmium sulfide buffer layer is not provided, and the cadmium pollution in the production process is reduced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic structural diagram of an NIP heterojunction solar cell according to the present embodiment;
fig. 2 is a flow chart of a method for manufacturing an NIP heterojunction solar cell according to the present embodiment.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The present invention provides an NIP heterojunction solar cell, see fig. 1, specifically comprising:
the method sequentially comprises the following steps from top to bottom: the solar cell comprises a transparent front electrode, an electron transmission layer, an N-type perovskite layer, an I-type copper indium gallium selenium layer, a P-type copper indium gallium selenium layer, a molybdenum electrode layer and a cell substrate.
In this embodiment, the battery substrate is any one of glass, stainless steel, and polyimide, and the material of the electron transport layer is any one of titanium dioxide, zinc oxide, and an electron transport material.
Preparing a molybdenum electrode layer with the thickness of 200nm-1000nm on a battery substrate, growing a copper indium gallium selenium layer on the molybdenum electrode layer to serve as a P-type copper indium gallium selenium layer of the heterojunction solar battery, and then growing an intrinsic copper indium gallium selenium layer on the P-type copper indium gallium selenium layer to serve as an I-type copper indium gallium selenium layer of the heterojunction solar battery;
wherein the thickness of the P-type copper indium gallium selenium layer or the I-type copper indium gallium selenium layer is 1-3 micrometers.
Preparing an N-type perovskite layer on the I-type copper indium gallium selenium layer, wherein the material of the N-type perovskite layer is lead halogen perovskite, and the chemical formula is APbX 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein A is an organic ion or an inorganic alkali metal ion, and X is halogen.
The N-type perovskite layer serves as an N-type layer of the battery, i.e., a light absorbing layer. The N-type perovskite layer, the P-type copper indium gallium selenide layer and the I-type copper indium gallium selenide layer form an NIP heterojunction.
In this embodiment, the transparent front electrode is made of indium tin oxide or AZO. The thickness of the transparent front electrode is 150-1000 nanometers.
It can be understood that AZO is aluminum-doped zinc oxide, which is simply called aluminum-doped zinc oxide (ZnO) transparent conductive glass.
From the above description, it can be seen that, in the NIP heterojunction solar cell provided by the embodiment of the present invention, the perovskite thin film with excellent absorption performance can be used to supplement absorption with the copper indium gallium selenide thin film, so that more sufficient light absorption can be achieved under the condition of thinner copper indium gallium selenide thickness; perovskite has excellent bipolar carrier transmission characteristics, and can effectively transmit electrons and holes, so that the electron collection efficiency is improved.
In addition, the P-type copper indium gallium selenide layer has higher recombination rate on electrons, and the I-type copper indium gallium selenide layer can reduce carrier recombination, thereby being beneficial to improving the battery filling factor, the short-circuit current and the open-circuit voltage and further improving the photoelectric conversion efficiency of the solar battery. Compared with the traditional copper indium gallium selenium battery, the cadmium sulfide buffer layer is not provided, and the cadmium pollution in the production process is reduced.
The invention provides a manufacturing method of an NIP heterojunction solar cell, referring to FIG. 2, the manufacturing method of the heterojunction solar cell specifically comprises the following steps:
s101: preparing a molybdenum electrode layer with the thickness of 500 nanometers on a battery substrate by adopting a direct current magnetron sputtering method;
in this step, the battery substrate was 3mm glass.
S102: sequentially depositing a P-type copper indium gallium selenium layer and an I-type copper indium gallium selenium layer on the molybdenum electrode layer by adopting a three-step co-evaporation method;
in this step, the temperature of the battery substrate was raised to 300℃and then In-Ga-Se was co-evaporated to obtain (In, ga) 2 Se 3 Layer (IGS layer); then closing an In source and a Ga source, raising the temperature of a battery substrate to 550 ℃, opening a Cu source to prepare a copper-rich CIGS layer, and preparing In-Ga-Se on the surface of the copper-rich CIGS layer to enable the CIGS to be copper-depleted, so as to obtain a P-type copper-indium-gallium-selenium layer with the thickness of 1 micron; and finally, on the P-type copper indium gallium selenium layer, opening a Cu source, an In source, a Ga source and a Se source for continuous deposition to obtain an I-type copper indium gallium selenium layer, wherein the thickness of the I-type copper indium gallium selenium layer is 1 micrometer.
S103: spin-coating the mixed solvent on the copper indium gallium selenium layer by using a spin-coating mode, and heating for 10-60 min at 80-150 ℃ to obtain a perovskite layer; wherein, the mixed solvent is obtained by dissolving methyl amine bromide and lead bromide in dimethylformamide and dimethyl sulfoxide solvent according to a preset proportion;
the step is the preparation of the perovskite layer, adopts MAPbBr 3 Perovskite material is prepared by mixing methyl amine bromide (MABr) and lead bromide (PbBr) 2 ) According to the proportion of 1 (0.95-1.1), the components are dissolved in a mixed solvent of N-N Dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), spin-coated on a CIGS layer by a spin-coating method, and heated for 10 min-60 min at 80-150 ℃ to obtain a perovskite layer.
S104: preparing a zinc oxide layer with the thickness of 70 nanometers on the N-type perovskite layer by adopting a direct current magnetron sputtering method; wherein the zinc oxide layer is an electron transport layer;
in the step, the electron transport layer adopts zinc oxide, and a zinc oxide layer with the thickness of 70 nanometers is prepared on the N-type perovskite layer by adopting a magnetron sputtering method.
S105: preparing an AZO layer with the thickness of 500 nanometers on the electron transport layer by adopting a direct current magnetron sputtering method; wherein the AZO layer is a transparent front electrode.
In this step, the transparent front electrode adopts AZO (aluminum doped zinc oxide), and a magnetron sputtering method is adopted to prepare an AZO layer with a thickness of 500 nm on the electron transport layer.
As can be seen from the above description, according to the manufacturing method of the NIP heterojunction solar cell provided by the embodiment of the present invention, the perovskite thin film with excellent absorption performance can be used to supplement and absorb with the copper indium gallium selenide thin film, so that more sufficient light absorption can be realized under the condition of thinner copper indium gallium selenide thickness; perovskite has excellent bipolar carrier transmission characteristics, and can effectively transmit electrons and holes, so that the electron collection efficiency is improved.
In addition, the P-type copper indium gallium selenide layer has higher recombination rate on electrons, and the I-type copper indium gallium selenide layer can reduce carrier recombination, thereby being beneficial to improving the battery filling factor, the short-circuit current and the open-circuit voltage and further improving the photoelectric conversion efficiency of the solar battery. Compared with the traditional copper indium gallium selenium battery, the cadmium sulfide buffer layer is not provided, and the cadmium pollution in the production process is reduced.
In this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, 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 process, method, article, or apparatus. The orientation or positional relationship indicated by the terms "upper", "lower", etc. are based on the orientation or positional relationship shown in the drawings, are merely for convenience of description and to simplify the description, and are not indicative or implying that the apparatus or elements in question must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be construed as limiting the present invention. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other. The present invention is not limited to any single aspect, nor to any single embodiment, nor to any combination and/or permutation of these aspects and/or embodiments. Moreover, each aspect and/or embodiment of the invention may be used alone or in combination with one or more other aspects and/or embodiments.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention, and are intended to be included within the scope of the appended claims and description.
Claims (7)
1. An NIP heterojunction solar cell, comprising:
the method sequentially comprises the following steps from top to bottom: the device comprises a transparent front electrode, an electron transmission layer, an N-type perovskite layer, an I-type copper indium gallium selenium layer, a P-type copper indium gallium selenium layer, a molybdenum electrode layer and a battery substrate;
the NIP heterojunction solar cell is manufactured by the following method:
preparing a molybdenum electrode layer with the thickness of 500 nanometers on a battery substrate by adopting a direct current magnetron sputtering method;
sequentially depositing a P-type copper indium gallium selenium layer and an I-type copper indium gallium selenium layer on the molybdenum electrode layer by adopting a three-step co-evaporation method; the method specifically comprises the following steps:
heating the battery substrate to 300 ℃ and then co-evaporating In-Ga-Se to prepare an IGS layer;
closing an In source and a Ga source, increasing the temperature of a battery substrate to 550 ℃, and opening a Cu source to prepare a copper-rich CIGS layer;
preparing In-Ga-Se on the surface of the copper-rich CIGS layer to obtain a P-type copper indium gallium selenium layer;
opening a Cu source, an In source, a Ga source and a Se source on the P-type copper indium gallium selenium layer to continue depositing to obtain an I-type copper indium gallium selenium layer;
spin-coating the mixed solvent on the copper indium gallium selenium layer by using a spin-coating mode, and heating for 10-60 min at 80-150 ℃ to obtain a perovskite layer; wherein, the mixed solvent is obtained by dissolving methyl amine bromide and lead bromide in dimethylformamide and dimethyl sulfoxide solvent according to a preset proportion;
preparing a zinc oxide layer with the thickness of 70 nanometers on the N-type perovskite layer by adopting a direct current magnetron sputtering method; wherein the zinc oxide layer is an electron transport layer;
preparing an AZO layer with the thickness of 500 nanometers on the electron transport layer by adopting a direct current magnetron sputtering method; wherein the AZO layer is a transparent front electrode.
2. The NIP heterojunction solar cell of claim 1, wherein the material of the cell substrate is any one of glass, stainless steel or polyimide.
3. The NIP heterojunction solar cell of claim 1, wherein the thickness of the P-type copper indium gallium selenide layer or the I-type copper indium gallium selenide layer is 1-3 micrometers.
4. The NIP heterojunction solar cell of claim 1, wherein the material of the N-type perovskite layer is lead halogen perovskite;
the lead halogen perovskite has a chemical formula of APbX 3 ；
Wherein A is an organic ion or an inorganic alkali metal ion, and X is halogen.
5. The NIP heterojunction solar cell of claim 1, wherein the electron transport layer is made of: titanium dioxide, zinc oxide or an organic electron transport material.
6. A method of manufacturing an NIP heterojunction solar cell, comprising:
preparing a molybdenum electrode layer with the thickness of 500 nanometers on a battery substrate by adopting a direct current magnetron sputtering method;
sequentially depositing a P-type copper indium gallium selenium layer and an I-type copper indium gallium selenium layer on the molybdenum electrode layer by adopting a three-step co-evaporation method; the method specifically comprises the following steps:
heating the battery substrate to 300 ℃ and then co-evaporating In-Ga-Se to prepare an IGS layer;
closing an In source and a Ga source, increasing the temperature of a battery substrate to 550 ℃, and opening a Cu source to prepare a copper-rich CIGS layer;
preparing In-Ga-Se on the surface of the copper-rich CIGS layer to obtain a P-type copper indium gallium selenium layer;
opening a Cu source, an In source, a Ga source and a Se source on the P-type copper indium gallium selenium layer to continue depositing to obtain an I-type copper indium gallium selenium layer;
spin-coating the mixed solvent on the copper indium gallium selenium layer by using a spin-coating mode, and heating for 10-60 min at 80-150 ℃ to obtain a perovskite layer; wherein, the mixed solvent is obtained by dissolving methyl amine bromide and lead bromide in dimethylformamide and dimethyl sulfoxide solvent according to a preset proportion;
preparing a zinc oxide layer with the thickness of 70 nanometers on the N-type perovskite layer by adopting a direct current magnetron sputtering method; wherein the zinc oxide layer is an electron transport layer;
preparing an AZO layer with the thickness of 500 nanometers on the electron transport layer by adopting a direct current magnetron sputtering method; wherein the AZO layer is a transparent front electrode.
7. The method of fabricating a NIP heterojunction solar cell as claimed in claim 6, wherein the material of the cell substrate is glass and the thickness is 3 mm.
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