CN117979714B - Having NiOxPerovskite solar cell with buffer layer and preparation method thereof - Google Patents
Having NiOxPerovskite solar cell with buffer layer and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 32
- 239000000758 substrate Substances 0.000 claims abstract description 77
- 230000005525 hole transport Effects 0.000 claims abstract description 47
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 44
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 41
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 37
- 238000000151 deposition Methods 0.000 claims abstract description 33
- 230000000903 blocking effect Effects 0.000 claims abstract description 18
- 238000004528 spin coating Methods 0.000 claims abstract description 18
- 230000031700 light absorption Effects 0.000 claims abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 83
- 229910052759 nickel Inorganic materials 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 239000002243 precursor Substances 0.000 claims description 24
- 239000011261 inert gas Substances 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 14
- 238000000137 annealing Methods 0.000 claims description 13
- 239000000084 colloidal system Substances 0.000 claims description 12
- 230000008021 deposition Effects 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 238000010926 purge Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910001868 water Inorganic materials 0.000 claims description 8
- 238000007781 pre-processing Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000006479 redox reaction Methods 0.000 claims description 5
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 5
- 239000012498 ultrapure water Substances 0.000 claims description 5
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 4
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 claims description 4
- NQMRYBIKMRVZLB-UHFFFAOYSA-N methylamine hydrochloride Chemical compound [Cl-].[NH3+]C NQMRYBIKMRVZLB-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical compound O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- KYVXIDYFPYFKTM-UHFFFAOYSA-N n-methylmethanamine;propan-2-ol Chemical compound CNC.CC(C)O KYVXIDYFPYFKTM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- IQSUNBLELDRPEY-UHFFFAOYSA-N 1-ethylcyclopenta-1,3-diene Chemical compound CCC1=CC=CC1 IQSUNBLELDRPEY-UHFFFAOYSA-N 0.000 claims description 2
- IGRLELOKIQLMHM-UHFFFAOYSA-N 2,2,5-trimethyloctane-3,4-dione Chemical compound CCCC(C)C(=O)C(=O)C(C)(C)C IGRLELOKIQLMHM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- QHJPGANWSLEMTI-UHFFFAOYSA-N aminomethylideneazanium;iodide Chemical class I.NC=N QHJPGANWSLEMTI-UHFFFAOYSA-N 0.000 claims description 2
- GUOAPVPPPVLIQQ-UHFFFAOYSA-N dimethyldicyclopentadiene Chemical compound C1=CC2CC1C1C2C(C)C(C)=C1 GUOAPVPPPVLIQQ-UHFFFAOYSA-N 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 11
- 230000003746 surface roughness Effects 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 200
- 239000010408 film Substances 0.000 description 31
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 16
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 9
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000007738 vacuum evaporation Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- -1 nickel bis (tetramethyl heptanedione) Chemical compound 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000013545 self-assembled monolayer Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229920001167 Poly(triaryl amine) Polymers 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- CNUVEAGSJLUJCX-UHFFFAOYSA-L disodium;4-[2,9-dimethyl-7-(4-sulfonatophenyl)-1,10-phenanthrolin-4-yl]benzenesulfonate Chemical class [Na+].[Na+].C=12C=CC3=C(C=4C=CC(=CC=4)S([O-])(=O)=O)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=C(S([O-])(=O)=O)C=C1 CNUVEAGSJLUJCX-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical compound NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000000707 layer-by-layer assembly Methods 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000013082 photovoltaic technology Methods 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
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- 239000007858 starting material Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- 239000002699 waste material Substances 0.000 description 1
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Classifications
-
- 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
- H10K30/50—Photovoltaic [PV] devices
-
- 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
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
-
- 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
-
- 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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- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention relates to the technical field of perovskite solar cells, in particular to a perovskite solar cell with a NiO x buffer layer and a preparation method thereof, wherein the preparation method comprises the following steps: depositing a NiO x buffer layer on the pretreated TCO substrate by utilizing an atomic layer deposition method; depositing a nickel oxide hole transport layer on the NiO x buffer layer by using a spin coating method; and sequentially preparing a perovskite light absorption layer, an electron transport layer, a charge blocking layer and an electrode layer on the nickel oxide hole transport layer to obtain the perovskite solar cell with the NiO x buffer layer. The buffer layer effectively solves the problem that the NiO x hole transport layer is not matched with the TCO substrate in lattice, and the preparation of the ultrathin NiO x buffer layer by an atomic layer deposition technology reduces the surface roughness, improves the surface wettability and promotes the film forming quality of the subsequent hole transport layer.
Description
Technical Field
The invention relates to the technical field of perovskite solar cells, in particular to a perovskite solar cell with a NiO x buffer layer and a preparation method thereof.
Background
The current mainstream preparation method of the hole transport layer NiO x has certain problems; the solution method is characterized in that the operation method is simple, but the quality of the film is easily influenced by the environment and the process; the spraying method has the defect that the thickness of the film cannot be accurately mastered; magnetron sputtering may cause holes in the film due to high energy particle bombardment. Both of the above methods result in the hole transport layer NiO x not matching well with the transparent conductive electrode (TCO) substrate.
The mainstream method mainly utilizes ultraviolet ozone-oxygen plasma (UV-O 3) or monomolecular self-assembled layer (SAM) chemical agent passivation treatment to improve the surface wettability and change the roughness so as to improve the surface coverage rate; however, TCO surface activation is sensitive to UV-O 3 treatment time, which does not improve surface wettability well, whereas long UV-O 3 results in degradation of NiO x electrochemical performance and thus affects device efficiency; SAM has the disadvantages of high cost, poor material stability and the like, and is not beneficial to the improvement of the stability of perovskite solar cells and the large-area commercialization process.
Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a perovskite solar cell with a NiO x buffer layer and a preparation method thereof, and aims to solve the problems of lattice mismatch, poor film coverage rate, poor film forming quality and the like of the conventional hole transport layer NiO x and a TCO substrate.
The technical scheme of the invention is as follows:
A method for preparing a perovskite solar cell with a NiO x buffer layer, comprising the steps of:
providing a TCO substrate and preprocessing to obtain a preprocessed TCO substrate;
Depositing a NiO x buffer layer on the pretreated TCO substrate by utilizing an atomic layer deposition method;
Depositing a nickel oxide hole transport layer on one side of the NiO x buffer layer away from the TCO substrate by using a spin coating method;
And sequentially preparing a perovskite light absorption layer, an electron transport layer, a charge blocking layer and an electrode layer on one side of the nickel oxide hole transport layer, which is away from the NiO x buffer layer, so as to obtain the perovskite solar cell with the NiO x buffer layer.
The preparation method of the perovskite solar cell with the NiO x buffer layer comprises the following steps of depositing the NiO x buffer layer on the pretreated TCO substrate by utilizing an atomic layer deposition method:
placing an organic nickel source in a reaction cavity of atomic layer deposition equipment, and setting a deposition temperature and a nickel source heating temperature;
A pulse oxide precursor is utilized to enter a reaction cavity, and then a pulse inert gas is used for purging the reaction cavity;
the pulse organic nickel source enters the cavity and performs oxidation-reduction reaction with the pretreated TCO substrate to generate a NiO x film;
And (5) purging the reaction cavity by using pulse inert gas again to prepare the NiO x buffer layer.
The preparation method of the perovskite solar cell with the NiO x buffer layer comprises the steps that the organic nickel source comprises one or more of nickel dichloride, nickel bis (methylcyclopentadiene), nickel bis (ethylcyclopentadiene), nickel bis (dimethylamine-2-propanol), nickel bis (tetramethyl heptanedione), nickel N, N '-diisopropylacetamido, and nickel N, N' -di-tert-butylacetamido; and/or, the oxidizing precursor comprises one or more of O 3、H2O、H2O2; and/or the inert gas comprises one or more of nitrogen, helium, argon and neon.
The preparation method of the perovskite solar cell with the NiO x buffer layer comprises the steps that the pulse time of the pulse oxide precursor is 0.1s-9999s; the pulse time of the pulse inert gas is 0.1s-9999s; the pulse time of the pulse organic nickel source is 0.1s-9999s.
The preparation method of the perovskite solar cell with the NiO x buffer layer comprises the steps of depositing at 150-250 ℃; the heating temperature of the nickel source is 50-100 ℃.
The preparation method of the perovskite solar cell with the NiO x buffer layer comprises the following steps of depositing a nickel oxide hole transport layer on one side of the NiO x buffer layer, which is away from the TCO substrate, by using a spin coating method, wherein the steps comprise:
carrying out ultrasonic mixing on nickel oxide powder and ultrapure water to obtain nickel oxide nano colloid solution;
And spin-coating and depositing the nickel oxide nano colloid solution on one side of the NiO x buffer layer, which is away from the TCO substrate, and carrying out annealing treatment to obtain the nickel oxide hole transport layer.
The perovskite solar cell with the NiO x buffer layer is prepared by spin coating and annealing treatment of a precursor solution of (FA 0.83MA0.17)0.95Cs0.05Pb(I0.9Br0.1)3) and/or the precursor solution of (FA 0.83MA0.17)0.95Cs0.05Pb(I0.9Br0.1)3) is composed of cesium iodide, formamidine hydroiodic acid salt, methyl amine bromide, lead iodide, lead bromide, methyl ammonium chloride, N-dimethylformamide and dimethyl sulfoxide.
The preparation method of the perovskite solar cell with the NiO x buffer layer comprises the steps that the material of the electron transport layer comprises one of [6,6] -phenyl-C61-methyl butyrate, tin dioxide, titanium dioxide, aluminum-doped zinc oxide and C60; and/or the material of the charge blocking layer comprises one of disodium salt of bath ketoamine disulfonate, aluminum oxide and tin dioxide.
A perovskite solar cell with a NiO x buffer layer, which is characterized in that the perovskite solar cell with the NiO x buffer layer is prepared by a preparation method; and/or the substrate comprises a TCO substrate, a NiO x buffer layer, a nickel oxide hole transport layer, a perovskite light absorption layer, an electron transport layer, a charge blocking layer and an electrode layer which are sequentially stacked from bottom to top.
The perovskite solar cell with the NiO x buffer layer, wherein the thickness of the NiO x buffer layer is 1nm-10nm.
The beneficial effects are that: the invention provides a perovskite solar cell with a NiO x buffer layer and a preparation method thereof, wherein the preparation method comprises the following steps: providing a TCO substrate and preprocessing to obtain a preprocessed TCO substrate; depositing a NiO x buffer layer on the pretreated TCO substrate by utilizing an atomic layer deposition method; depositing a nickel oxide hole transport layer on one side of the NiO x buffer layer away from the TCO substrate by using a spin coating method; and sequentially preparing a perovskite light absorption layer, an electron transport layer, a charge blocking layer and an electrode layer on one side of the nickel oxide hole transport layer, which is away from the NiO x buffer layer, so as to obtain the perovskite solar cell with the NiO x buffer layer. According to the invention, a layer of NiO x film is prepared on the TCO substrate by utilizing an atomic layer deposition technology and is used as a buffer layer of the hole transport layer of the perovskite solar cell, the buffer layer effectively solves the problem that the hole transport layer of NiO x is not matched with the crystal lattice of the TCO substrate, and the preparation of the ultrathin NiO x buffer layer by utilizing the atomic layer deposition technology reduces the surface roughness, improves the surface wettability and promotes the film forming quality of the subsequent hole transport layer; the buffer layer is applied to the hole transport layer of the perovskite solar cell with the inverted structure, so that the perovskite solar cell shows excellent photoelectric conversion efficiency and stability.
Drawings
FIG. 1 is a schematic flow chart of a method for fabricating a perovskite solar cell having a buffer layer of NiO x according to the present invention;
FIG. 2 is a schematic diagram of an atomic layer deposition technique;
FIG. 3 is a schematic structural diagram of a perovskite solar cell with a buffer layer of NiO x;
FIG. 4 is a graph comparing the conversion efficiency, fill factor, open circuit voltage and short circuit current of perovskite solar cell devices with different thicknesses of NiO x buffer layers with control groups;
FIG. 5 is a graph of cell efficiency decay for perovskite solar cell devices with different thickness NiO x buffer layers versus control;
FIG. 6 is a graph comparing the surface wettability of a TCO substrate with the wettability of the TCO substrate after modification of the ALD ultra-thin NiO x buffer layer.
Detailed Description
The invention provides a perovskite solar cell with a NiO x buffer layer and a preparation method thereof, and the invention is further described in detail below in order to make the purposes, technical schemes and effects of the invention clearer and more definite. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
It will be understood by those skilled in the art that all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs unless defined otherwise. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Perovskite solar cells are an emerging high efficiency photovoltaic technology that has received great attention due to its tunable energy band, long carrier diffusion length and high absorption coefficient. In the last decade, perovskite solar cell efficiency has increased rapidly from 3.8% to 26.1%, and its rapid efficiency breakthrough was unprecedented in the history of photovoltaic development. In the technical field of photovoltaics, the cost, the efficiency and the service life are gold triangle elements for judging the commercial feasibility of the solar cell, and the leveling cost of the perovskite photovoltaic module is lower than that of the silicon-based photovoltaic module through calculation, however, the stability is an urgent problem to be overcome in large-scale commercialization of the perovskite solar cell.
Perovskite advances in the photovoltaic field are due to optimization of absorber layer composition and engineering of suitable hole/electron transport layers (HTL/ETL). Although perovskite photovoltaics have achieved excellent work, to date, there has been limited investigation into the interfacial coverage of the upper surface of a transparent conductive electrode (TCO) with a contact layer. The conventional techniques for preparing the hole transport layer of the perovskite photovoltaic device are a solution method, a knife coating method, a spraying method, a magnetron sputtering method and the like, but the surface of the TCO is not absolutely flat, the rough surface of the TCO can lead to the reduction of the coverage degree of the charge transport layer, uncovered areas can lead to low open circuit voltage and high series resistance, thus reducing the device efficiency, and poor coverage can lead to the direct contact of the perovskite film with the TCO layer, thus reducing the stability.
The current inverted perovskite solar cell hole transport layer materials are mainly poly [ bis (4-phenyl) (2, 4, 6-trimethylphenyl) amine ] (PTAA), niO x, polystyrene sulfonate (PEDOT: PSS) or self-assembled monolayers (SAM). PTAA can be prepared well at low temperature, but has poor wettability to perovskite solutions and a price of about 50 times that of gold, which is unfavorable for large-area commercialization. PEDOT PSS has the advantage of high permeation and high conductivity, but the hygroscopicity of PSS can lead to poor PSC stability. Aiming at the problems, niO x which is relatively stable and moderate in cost is often selected as a perovskite solar cell hole transport layer material, but the NiO x film prepared by a spin coating method cannot solve the problems of lattice mismatch between NiO x and a TCO substrate, poor film coverage rate, poor film forming quality and the like.
Based on this, as shown in fig. 1, the present invention provides a method for preparing a perovskite solar cell having a NiO x buffer layer, comprising the steps of:
Step S10: providing a TCO substrate and preprocessing to obtain a preprocessed TCO substrate;
Step S20: depositing a NiO x buffer layer on the pretreated TCO substrate by utilizing an atomic layer deposition method;
step S30: depositing a nickel oxide hole transport layer on one side of the NiO x buffer layer away from the TCO substrate by using a spin coating method;
Step S40: and sequentially preparing a perovskite light absorption layer, an electron transport layer, a charge blocking layer and an electrode layer on one side of the nickel oxide hole transport layer, which is away from the NiO x buffer layer, so as to obtain the perovskite solar cell with the NiO x buffer layer.
In this embodiment, an ultrathin NiO x thin film is prepared on a TCO substrate by using an Atomic Layer Deposition (ALD) technology to serve as a buffer layer of a hole transport layer of a perovskite solar cell, and the buffer layer effectively solves the problem that the NiO x hole transport layer is not lattice matched with the TCO substrate, and the preparation of the ultrathin NiO x buffer layer on the TCO substrate by ALD can reduce the surface roughness of the TCO substrate, improve the surface wettability, and promote the film formation quality of the subsequent hole transport layer.
Specifically, the invention aims to prepare an ultrathin NiO x buffer layer by utilizing the characteristic that atomic layer deposition can prepare a high-quality, large-area and uniform oxide film on an atomic level through self-limiting half reaction, and the buffer layer also changes the potential and wettability of the surface of a TCO substrate by focusing on interface roughness on the combination between interfaces. ALD technology is highly conformal and capable of producing high quality pinhole-free thin films; the NiO x buffer layer effectively avoids device short circuit and light absorption layer decomposition caused by direct contact of the hole transport layer with the TCO substrate, and improves the efficiency and device stability of the inverted perovskite solar cell from the perspective of improving short circuit current and reducing series resistance. And the NiO x buffer layer is prepared in the perovskite solar cell by an ALD technology, so that the damage of water and oxygen to the light absorption layer of the perovskite solar cell is effectively prevented, the open-circuit voltage (Voc), the short-circuit current (Jsc), the Filling Factor (FF) and the conversion efficiency (PEC) of the cell device are improved, and the efficient and stable perovskite solar cell device is realized.
In some embodiments, in the step S10, the preprocessing includes the steps of: and respectively carrying out ultrasonic cleaning on the TCO substrate for 15 minutes by using acetone, isopropanol and ethanol, blow-drying the surface of the TCO substrate by using an argon gun, and treating the TCO substrate by using UV ozone for 15 minutes to obtain the pretreated TCO substrate. And (3) preprocessing the TCO substrate to remove impurities on the surface of the TCO substrate, thereby obtaining the clean TCO substrate.
In some embodiments, the TCO substrate includes, but is not limited to, one of fluorine doped tin dioxide (FTO), indium Tin Oxide (ITO).
In some embodiments, in the step S20, the step of depositing the NiO x buffer layer on the pretreated TCO substrate by using an atomic layer deposition method includes:
Step S21: placing an organic nickel source in a reaction cavity of atomic layer deposition equipment, and setting a deposition temperature and a nickel source heating temperature;
Step S22: a pulse oxide precursor is utilized to enter a reaction cavity, and then a pulse inert gas is used for purging the reaction cavity;
step S23: the pulse organic nickel source enters the cavity and performs oxidation-reduction reaction with the pretreated TCO substrate to generate a NiO x film;
Step S24: and (5) purging the reaction cavity by using pulse inert gas again to prepare the NiO x buffer layer.
Atomic Layer Deposition (ALD) is a vapor deposition technique that produces high quality, uniform oxide films at the atomic level by two self-limiting half reactions. The thickness at the atomic level is controlled by controlling the number of reaction cycles, so that fine tuning of the optical, chemical and electrical properties of the film can be realized. The atomic layer deposition has the characteristics of conformality, repeatability, industrial feasibility and the like, and the technology is beneficial to the industrialized mass production of perovskite.
Specifically, atomic layer deposition is to alternately enter a reaction cavity through a pulse airflow mode and another oxide reaction source through a gas path control mode, perform surface chemical adsorption on a substrate reaching a certain chemical reaction temperature, and finally prepare a compact metal oxide film after alternating layer-by-layer adsorption saturation reaction. As shown in fig. 2, an oxide precursor (for example, O 3) is first pulsed into the reaction chamber, chemisorbed on the TCO substrate, and then an inert gas (for example, N 2) is purged from the chamber to purge the excess oxide precursor out of the chamber; next, pulsing an organonickel source that will undergo an oxidation-reduction reaction with the oxide precursor on the substrate surface to produce metal oxide NiO x and byproducts (H 2O、CO2); and then, the inert gas (for example, N 2) is pulsed again to purge the cavity to remove redundant organic nickel sources and reaction byproducts, so that atomic layer deposition is completed once, and only a layer of single atomic layer film material is deposited in each growth period, so that the thickness is controlled at the atomic layer level.
In some embodiments, the thickness of the NiO x buffer layer is controlled by controlling the number of ALD cycles, which is 5-20 times; too thick a buffer layer of NiO x would reduce light transmittance and affect light absorption by the perovskite light absorbing layer, too thin a buffer layer of NiO x would not adequately isolate water oxygen and would be detrimental to charge transport. Preferably, when the number of cycles is 10, the stability of the resulting perovskite solar cell device is optimal, and too thin or too thick buffer layers can affect the efficiency and stability of the device.
In some embodiments, the organonickel source comprises one or more of nickel dicyclopentadienyl, nickel bis (methylcyclopentadienyl), nickel bis (ethylcyclopentadienyl), nickel bis (dimethylamine-2-propanol), nickel bis (tetramethylheptanedione), nickel N, N '-diisopropylacetamidinate, nickel N, N' -di-tert-butylacetamidinate; and/or, the oxidizing precursor comprises one or more of O 3、H2O、H2O2; and/or the inert gas comprises one or more of nitrogen, helium, argon and neon.
In some embodiments, the pulse time of the pulse oxide precursor is 0.1s-9999s; the pulse time of the pulse inert gas is 0.1s-9999s; the pulse time of the pulse organic nickel source is 0.1s-9999s. Too little pulse time cannot fully react and purge the clean chamber of excess raw materials and reaction byproducts, too much pulse time can lead to waste of materials and contamination of the chamber.
The atomic layer deposition equipment produced by different manufacturers has different raw materials, inert gases and pulse time, and the pulse time is influenced by factors such as the size of a reaction cavity, the size of pulse air pressure, deposition temperature and the like.
In some embodiments, the deposition temperature is 150 ℃ to 250 ℃; the heating temperature of the nickel source is 50-100 ℃. Too low a deposition temperature may result in a precursor not being surface reacted with the substrate; when the deposition temperature is too high, the precursor is thermally decomposed on the substrate to be converted into an unlimited growth CVD mode, the growth rate is increased in a nonlinear manner, and on the other hand, the substrate desorption effect is caused by high temperature, and the growth rate is reduced. In addition, the saturated vapor pressure and good volatility promote efficient transport of the gas within the cavity. The heating of the nickel source is to give extra heat compensation outside the organic nickel source bottle, so as to better gasify the organic nickel source to pulse into the reaction cavity.
In some embodiments, the atomic layer deposition apparatus has a vacuum level of 2Pa (2X 10 -2 Torr).
In some embodiments, in the step S30, the step of depositing a nickel oxide hole transport layer on a side of the NiO x buffer layer facing away from the TCO substrate by spin coating includes:
Step S31: carrying out ultrasonic mixing on nickel oxide powder and ultrapure water to obtain nickel oxide nano colloid solution;
Step S32: and spin-coating and depositing the nickel oxide nano colloid solution on one side of the NiO x buffer layer, which is away from the TCO substrate, and carrying out annealing treatment to obtain the nickel oxide hole transport layer.
In the embodiment, the agglomeration of NiO nano particles is prevented by ultrasonic mixing, and the annealing treatment effectively promotes the film forming quality of the film, so that a compact and uniform nickel oxide hole transport layer is prepared.
In some embodiments, the nickel oxide powder is ultrasonically stirred with ultrapure water for 20-40 minutes to uniformly disperse the nanoparticles, resulting in a nickel oxide nano-colloid solution having a concentration of between 15-20 mg/ml. Sufficient ultrasonic time can prevent NiO nano particles from agglomerating, and the agglomeration of the particles can lead to poor charge transmission performance of the prepared nickel oxide film.
In some embodiments, in the step S32, the annealing treatment is annealing at 120 ℃ to 150 ℃ for 20 minutes to 40 minutes in an air environment; the film forming quality of the film can be effectively promoted by the sufficient annealing temperature and the annealing time, and the moisture in the film can be sufficiently volatilized by the proper temperature, so that the preparation of the subsequent functional layer is facilitated.
In some embodiments, the perovskite light absorbing layer is formed by spin coating and annealing (FA 0.83MA0.17)0.95Cs0.05Pb(I0.9Br0.1)3 precursor solution; and/or the (FA 0.83MA0.17)0.95Cs0.05Pb(I0.9Br0.1)3 precursor solution is formed by cesium iodide (CsI), formamidine hydroiodidate (FAI), methyl amine bromide (MABr), lead iodide (PbI 2), lead bromide (PbBr 2), methyl ammonium chloride (MACl), N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO)), wherein the annealing is performed at 100 ℃ for 60 minutes in a glove box.
The perovskite precursor solution may be used to adjust the band gap of the perovskite light absorbing layer according to different needs. (the band gap of FA 0.83MA0.17)0.95Cs0.05Pb(I0.9Br0.1)3 is about 1.54eV.
In some embodiments, the (FA 0.83MA0.17)0.95Cs0.05Pb(I0.9Br0.1)3 precursor solution concentration is 1.4M. The volume ratio of N, N-dimethylformamide to dimethylsulfoxide is 4:1.
In some embodiments, the electron transport layer comprises one of [6,6] -phenyl-C61-butyric acid isopropyl ester (PCBM), tin dioxide (SnO 2), titanium dioxide (TiO 2), aluminum doped zinc oxide (AZO), C60, and the preparation process is chemical vapor deposition, vacuum evaporation, electron beam evaporation, spin coating, etc.
Specifically, taking [6,6] -phenyl-C61-butyric acid isopropyl ester (PCBM) as an example, an electron transport layer was prepared comprising the steps of: a certain amount of [6,6] -phenyl-C61-methyl butyrate (PCBM) is added into Chlorobenzene (CB), a magnetic stirrer is added to stir a solvent on a magnetic stirrer to prepare 15-20mg/ml PCBM colloid solution, and then 80 μl of PCBM colloid solution is spin-coated and deposited on a perovskite light absorption layer to obtain an electron transport layer. Preferably, the concentration of the PCBM colloidal solution is 20mg/ml.
In some embodiments, the material of the charge blocking layer includes one of bathocuproinedisulfonic acid disodium salt (BCP), aluminum oxide (AlO x), and tin dioxide (SnO 2).
Specifically, taking bathocuproinedisulfonic acid disodium salt (BCP) as an example, the preparation of the charge blocking layer comprises the steps of: a certain amount of disodium salt of bath ketoamine disulfonate (BCP) is added into isopropyl alcohol (IPA), a magnetic stirrer is added to stir a solvent on a magnetic stirrer to prepare 0.3-0.5mg/ml BCP solution, and then 100 mu l of BPC solution is spin-coated and deposited on the electron transport layer to obtain a charge blocking layer. Preferably, the concentration of the BCP solution is 0.5mg/ml.
In some embodiments, the electrode layer is, but is not limited to, a silver electrode.
Specifically, transferring the device with the prepared charge blocking layer into a vacuum evaporation bin, and evaporating a silver electrode; the vacuum degree in the vacuum evaporation process is recommended to be lower than 10 -5 Pa, the deposition rate is 0.1-0.8 A.S -1, and the 80-100nm Ag electrode is obtained. Preferably, the thickness of the electrode layer is 100nm.
In addition, the invention also provides a perovskite solar cell with the NiO x buffer layer, which is prepared by the preparation method of the perovskite solar cell with the NiO x buffer layer; and/or, as shown in fig. 3, the TCO substrate 10, niO x buffer layer 20, nickel oxide hole transport layer 30, perovskite light absorbing layer 40, electron transport layer 50, charge blocking layer 60, and electrode layer 70 are stacked in this order from bottom to top.
In the embodiment, the ultra-thin NiO x buffer layer is prepared by utilizing the characteristic that atomic layer deposition can prepare a high-quality, large-area and uniform oxide film on an atomic level through self-limiting half reaction, and the buffer layer also changes the potential and the wettability of the surface of the TCO substrate by focusing on the interface roughness on the combination between interfaces. ALD technology is highly conformal and capable of producing high quality pinhole-free thin films; the NiO x buffer layer effectively avoids device short circuit and light absorption layer decomposition caused by direct contact of the hole transport layer with the TCO substrate, and improves the efficiency and device stability of the inverted perovskite solar cell from the perspective of improving short circuit current and reducing series resistance. And the NiO x buffer layer is prepared in the perovskite solar cell by an ALD technology, so that the damage of water and oxygen to the light absorption layer of the perovskite solar cell is effectively prevented, the open-circuit voltage (Voc), the short-circuit current (Jsc), the Filling Factor (FF) and the conversion efficiency (PEC) of the cell device are improved, and the efficient and stable perovskite solar cell device is realized.
In some embodiments, the NiO x buffer layer has a thickness of 1nm to 10nm; too thick a buffer layer of NiO x will reduce light transmittance to affect light absorption by the perovskite light absorbing layer. Too thin a buffer layer of NiO x does not adequately insulate water from oxygen and does not facilitate charge transport.
In some embodiments, the nickel oxide hole transport layer has a thickness of 30-50nm; the thickness of the perovskite light absorption layer is 500-600nm; the thickness of the electron transport layer is 40-60nm; the thickness of the charge blocking layer is 20-30nm.
The following examples are further given to illustrate the invention in detail. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure.
Example 1
The embodiment provides a perovskite solar cell device with NiO x buffer layers with different thicknesses, which comprises the following steps:
1) TCO substrate pretreatment
And respectively carrying out ultrasonic cleaning on the TCO substrate for 15 minutes by using acetone, isopropanol and ethanol, drying the surface by using an argon gun, and carrying out UV ozone treatment for 15 minutes to obtain the pretreated TCO substrate.
2) Preparation of ALD ultra-thin NiO x buffer layer
And placing the pretreated TCO substrate into ALD deposition equipment, wherein an organic nickel source is nickel-dicyano (Ni (Cp) 2), the deposition temperature is set to 250 ℃, and the heating temperature of the nickel source is set to 90 ℃.
One complete ALD cycle includes: first, pulse 0.5s O 3 into the reaction chamber to make O 3 fully adsorb on the surface of TCO substrate. Pulse N 2 then purges the chamber 10s to remove excess O 3. Then pulse 1s Ni (Cp) 2 enters the cavity and O 3 adsorbed on the surface of the TCO substrate to carry out oxidation-reduction reaction to generate the NiO film. Finally, the chamber was purged again with pulse N 2 for 15s to remove excess Ni (Cp) 2 and reaction byproducts from the chamber. Briefly, O 3 was exposed (0.5 s) -N 2 purged (10 s) -Ni (Cp) 2 exposed (1 s) -N 2 purged (15 s).
In the embodiment, the thickness of the ultrathin NiO x buffer layer is controlled by controlling ALD cycle times; in this example, three NiO x buffer layers with different thicknesses were obtained for 5, 10, and 20 cycles.
3) Preparation of Nickel oxide hole transport layer
Weighing a certain amount of nickel oxide powder in ultrapure water, and stirring by ultrasonic for 20 minutes to uniformly disperse nano particles to obtain a nickel oxide nano colloid solution of 20 mg/ml. And then, spin-coating and depositing 100ul of nickel oxide nano colloid solution on the ALD ultrathin NiO x buffer layers with different thicknesses in the step 2), and annealing at 150 ℃ for 30 minutes in an air environment to obtain the nickel oxide hole transport layer with the thickness of 50 nm.
4) Preparation of perovskite light absorbing layer
The stoichiometrically required starting materials are weighed out and dissolved in DMF (N, N-dimethylformamide): DMSO (dimethyl sulfoxide) =4: 1, (FA 0.83MA0.17)0.95Cs0.05Pb(I0.9Br0.1)3 precursor solution of 1.4M. 100ul of perovskite solution was spin-coated onto the nickel oxide hole transport layer of step 3), the precursor perovskite film was transferred onto a hot plate, and annealed at 100 ℃ for 60 minutes in a glove box to give a perovskite light absorbing layer having a thickness of 600 nm.
5) Preparation of electron transport layer
A certain amount of [6,6] -phenyl-C61-methyl butyrate (PCBM) is weighed into Chlorobenzene (CB), and a magnetic stirrer is added to stir the solvent on a magnetic stirrer to prepare a PCBM colloid solution of 20 mg/ml. Then, 80ul of PCBM colloidal solution was spin-deposited on the perovskite light absorbing layer of step 4), resulting in an electron transport layer having a thickness of 60 nm.
6) Preparation of a Charge blocking layer
An amount of disodium salt of bath ketoamine disulfonate (BCP) was weighed into isopropyl alcohol (IPA), and a magnetic stirrer was added to stir the solvent on a magnetic stirrer to prepare a 0.5mg/ml BCP solution. Then 100ul of BCP solution was spin-deposited on the electron transport layer of step 5), resulting in a charge blocking layer with a thickness of 30 nm.
7) Preparation of electrode layer
Transferring the prepared device into a vacuum evaporation bin, and evaporating a silver (Ag) electrode. The vacuum degree in the vacuum evaporation process is recommended to be lower than 10 < -5 > Pa, and the deposition rate is 0.1-0.8 A.S < -1 >, so that the 100nm Ag electrode is obtained.
Perovskite solar cell devices with NiO x buffer layers with different thicknesses are prepared through the steps 1) to 7), and are respectively marked as ALD-5, ALD-10 and ALD-20. In addition, a perovskite solar cell device without the NiO x buffer layer was used as a Control group, and was designated as Control.
Specifically, a comparison graph of the conversion efficiency (a), the fill factor (b), the open circuit voltage (c) and the short circuit current (d) of the perovskite solar cell device with NiO x buffer layers of different thicknesses with the comparison group is shown in fig. 4; the figure shows that the addition of the ALD ultrathin NiO x buffer layer effectively improves the photoelectric conversion efficiency, the filling factor, the open-circuit voltage and the short-circuit current of the device. The photoelectric conversion efficiency is improved from 16% to 18%, the filling factor is improved from 72% to 76%, the open circuit voltage is improved from 1.08V to 1.10V, the short circuit current is improved from 20 mA/cm 2 to 22 mA/cm 2, and the performance repeatability of the battery device is improved well.
The cell efficiency attenuation diagrams of perovskite solar cell devices with NiO x buffer layers with different thicknesses and the control group are shown in FIG. 5; from the figure, the addition of the ALD ultrathin NiO x buffer layer effectively improves the stability of the perovskite solar cell device. The data obtained by testing in an air environment with relative humidity of 20-30% at 25 ℃ for 220 hours shows that the efficiency of the device of the control group is attenuated to 65.25% of the initial efficiency, while the device added with the ALD ultrathin NiO x buffer layer is attenuated along with the sample, but the attenuation degree is greatly reduced, and the optimal stability is that the perovskite solar cell device prepared by 10 times of ALD cycle is 98.86% of the initial efficiency.
A comparison of the surface wettability (a) of the TCO substrate and the wettability (b) of the TCO substrate after modification of the ALD ultra-thin NiO x buffer layer is shown in fig. 6, from which it can be seen that the wettability of the surface of the TCO substrate after insertion of an ultra-thin NiO x buffer layer having a layer thickness of about 2nm has changed significantly from hydrophilic to hydrophobic. The hydrophobic film layer can effectively isolate water and oxygen to improve the stability of the device, and the experimental characterization result is corresponding to the result of fig. 5.
In summary, the perovskite solar cell with the NiO x buffer layer and the preparation method thereof provided by the invention comprise the following steps: providing a TCO substrate and preprocessing to obtain a preprocessed TCO substrate; depositing NiO x on the pretreated TCO substrate by utilizing an atomic layer deposition method to obtain a NiO x buffer layer; depositing a nickel oxide hole transport layer on one side of the NiO x buffer layer away from the TCO substrate by using a spin coating method; and sequentially preparing a perovskite light absorption layer, an electron transport layer, a charge blocking layer and an electrode layer on one side of the nickel oxide hole transport layer, which is away from the NiO x buffer layer, so as to obtain the perovskite solar cell with the NiO x buffer layer. According to the invention, a layer of NiO x film is prepared on the TCO substrate by utilizing an atomic layer deposition technology and is used as a buffer layer of the hole transport layer of the perovskite solar cell, the buffer layer effectively solves the problem that the hole transport layer of NiO x is not matched with the crystal lattice of the TCO substrate, and the preparation of the ultrathin NiO x buffer layer by utilizing the atomic layer deposition technology reduces the surface roughness, improves the surface wettability and promotes the film forming quality of the subsequent hole transport layer; the buffer layer is applied to the hole transport layer of the perovskite solar cell with the inverted structure, so that the perovskite solar cell shows excellent photoelectric conversion efficiency and stability.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (9)
1. A method for preparing a perovskite solar cell with a NiO x buffer layer, comprising the steps of:
providing a TCO substrate and preprocessing to obtain a preprocessed TCO substrate;
placing an organic nickel source in a reaction cavity of atomic layer deposition equipment, and setting a deposition temperature and a nickel source heating temperature;
A pulse oxide precursor is utilized to enter a reaction cavity, and then a pulse inert gas is used for purging the reaction cavity;
the pulse organic nickel source enters the cavity and performs oxidation-reduction reaction with the pretreated TCO substrate to generate a NiO x film;
purging the reaction cavity by using pulse inert gas again to prepare a NiO x buffer layer;
Depositing a nickel oxide hole transport layer on one side of the NiO x buffer layer away from the TCO substrate by using a spin coating method;
And sequentially preparing a perovskite light absorption layer, an electron transport layer, a charge blocking layer and an electrode layer on one side of the nickel oxide hole transport layer, which is away from the NiO x buffer layer, so as to obtain the perovskite solar cell with the NiO x buffer layer.
2. The method of claim 1, wherein the organonickel source comprises one or more of nickel dichloride, nickel bis (methylcyclopentadiene), nickel bis (ethylcyclopentadiene), nickel bis (dimethylamine-2-propanol), nickel bis (tetramethylheptanedione), nickel N, N '-diisopropylacetamido, nickel N, N' -di-tert-butylacetamido; and/or, the oxide precursor comprises one or more of O 3、H2O、H2O2; and/or the inert gas comprises one or more of nitrogen, helium, argon and neon.
3. The method of claim 1, wherein the pulse time of the pulsed oxide precursor is 0.1s-9999s; the pulse time of the pulse inert gas is 0.1s-9999s; the pulse time of the pulse organic nickel source is 0.1s-9999s.
4. The method of fabricating a perovskite solar cell having a NiO x buffer layer according to claim 1, wherein the deposition temperature is 150 ℃ to 250 ℃; the heating temperature of the nickel source is 50-100 ℃.
5. The method of claim 1, wherein the step of depositing a nickel oxide hole transport layer on the side of the NiO x buffer layer facing away from the TCO substrate by spin coating comprises:
carrying out ultrasonic mixing on nickel oxide powder and ultrapure water to obtain nickel oxide nano colloid solution;
And spin-coating and depositing the nickel oxide nano colloid solution on one side of the NiO x buffer layer, which is away from the TCO substrate, and carrying out annealing treatment to obtain the nickel oxide hole transport layer.
6. The method according to claim 1, wherein the perovskite light absorbing layer is formed by spin coating and annealing of a FA 0.83MA0.17)0.95Cs0.05Pb(I0.9Br0.1)3 precursor solution, and/or the FA 0.83MA0.17)0.95Cs0.05Pb(I0.9Br0.1)3 precursor solution is formed by cesium iodide, formamidine hydroiodides, methyl amine bromide, lead iodide, lead bromide, methyl ammonium chloride, N-dimethylformamide, dimethyl sulfoxide.
7. The method for preparing a perovskite solar cell with a NiO x buffer layer according to claim 1, wherein the material of the electron transport layer comprises one of [6,6] -phenyl-C61-butyric acid isopropyl ester, tin dioxide, titanium dioxide, aluminum doped zinc oxide and C60; and/or the material of the charge blocking layer comprises one of disodium salt of bath ketoamine disulfonate, aluminum oxide and tin dioxide.
8. A perovskite solar cell with a NiO x buffer layer, characterized by being produced by a method for producing a perovskite solar cell with a NiO x buffer layer according to any one of claims 1-7; and/or the substrate comprises a TCO substrate, a NiO x buffer layer, a nickel oxide hole transport layer, a perovskite light absorption layer, an electron transport layer, a charge blocking layer and an electrode layer which are sequentially stacked from bottom to top.
9. The perovskite solar cell with NiO x buffer layer of claim 8, wherein the NiO x buffer layer has a thickness of 1nm to 10nm.
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| CN116156979A (en) * | 2022-12-30 | 2023-05-23 | 武汉大学 | Photovoltaic device based on FTO conductive substrate and preparation method thereof |
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