CN117560938A - Amorphous nickel oxide for perovskite solar cell device - Google Patents
Amorphous nickel oxide for perovskite solar cell device Download PDFInfo
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- CN117560938A CN117560938A CN202311651295.4A CN202311651295A CN117560938A CN 117560938 A CN117560938 A CN 117560938A CN 202311651295 A CN202311651295 A CN 202311651295A CN 117560938 A CN117560938 A CN 117560938A
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- 229910000480 nickel oxide Inorganic materials 0.000 title claims abstract description 81
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000010410 layer Substances 0.000 claims abstract description 235
- 238000005566 electron beam evaporation Methods 0.000 claims abstract description 82
- 230000005525 hole transport Effects 0.000 claims abstract description 70
- 239000000758 substrate Substances 0.000 claims abstract description 69
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 31
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 8
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 50
- 229910052709 silver Inorganic materials 0.000 claims description 50
- 239000004332 silver Substances 0.000 claims description 50
- 239000011521 glass Substances 0.000 claims description 38
- 239000010453 quartz Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000004528 spin coating Methods 0.000 claims description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- -1 polyethylene terephthalate Polymers 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000011358 absorbing material Substances 0.000 claims description 5
- 230000000903 blocking effect Effects 0.000 claims description 4
- 239000002356 single layer Substances 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 229910000851 Alloy steel Inorganic materials 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000956 alloy Substances 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
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 238000003618 dip coating Methods 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 2
- 238000007641 inkjet printing Methods 0.000 claims description 2
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 2
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims description 2
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 238000007761 roller coating Methods 0.000 claims description 2
- 238000010020 roller printing Methods 0.000 claims description 2
- 239000010980 sapphire Substances 0.000 claims description 2
- 229910052594 sapphire Inorganic materials 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 238000010345 tape casting Methods 0.000 claims description 2
- 238000002207 thermal evaporation Methods 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 33
- 239000004065 semiconductor Substances 0.000 abstract description 14
- 239000002346 layers by function Substances 0.000 abstract description 13
- 239000010955 niobium Substances 0.000 abstract description 13
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 abstract description 13
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 abstract description 13
- 230000031700 light absorption Effects 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 4
- 238000000137 annealing Methods 0.000 abstract description 3
- 238000001704 evaporation Methods 0.000 description 47
- 230000008020 evaporation Effects 0.000 description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 24
- 230000005540 biological transmission Effects 0.000 description 24
- 239000010408 film Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 239000013078 crystal Substances 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 239000003599 detergent Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 238000011056 performance test Methods 0.000 description 12
- 238000004506 ultrasonic cleaning Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- 235000010678 Paulownia tomentosa Nutrition 0.000 description 1
- 240000002834 Paulownia tomentosa Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910001411 inorganic cation Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- 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
- H10K30/40—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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- 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)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention belongs to the technical field of photovoltaic devices, and discloses a perovskite solar cell device using amorphous nickel oxide as a hole transport layer and a preparation method thereof. The amorphous nickel oxide used as a hole transport layer for a perovskite solar cell device comprises a substrate, an anode (ITO), and an electron beam evaporation hole transport layer (NiO) which are sequentially stacked x ) A perovskite light absorption layer, an electron beam evaporation electron transport layer (Nb) 2 O 5 ) And electron beam evaporation cathodes (Ag). Each corresponding functional layer is made of a metal oxide semiconductor material capable of functioning as the corresponding function. The amorphous nickel oxide is used as a hole transport layer for a perovskite solar cell device and the preparation method thereof obtains higher energy conversion efficiency, and the hole transport layer nickel oxide and the electron transport layer niobium pentoxide are both at normal temperatureThe electron beam evaporation is realized without any high-temperature processing procedures such as annealing treatment, so that the method has lower processing cost and can realize large-area flexible processing, and has good application prospect in the field of solar cells.
Description
Technical Field
The invention belongs to the technical field of photovoltaic devices, and particularly relates to an amorphous nickel oxide for a perovskite device and a method thereof.
Background
The Miyasaka professor task group, university of Japanese tung shadow shore, early 2006 tried to use perovskite materials as light absorbing materials in dye-sensitized solar cells, they reported for the first time dye-sensitized perovskite solar cells with solar conversion efficiencies of 3-4% in 2009 (J.Am. Chem. Soc.,2009,131,6050). Next, the Nam-Gyu Park professor group of university of Korea improved energy conversion efficiency by nearly doubling (nanoscales, 2011,3,4088) by optimizing precursor solution concentration and annealing temperature, and perovskite solar cells really paid attention to their use of perovskite materials in all solid state structures like organic thin film solar cells, and improved energy conversion efficiency and stability (Sci.Rep., 2012,2,591). Because perovskite solar cells have significant advantages such as low raw material and manufacturing costs, and with the great investment in research efforts in related fields, the energy conversion efficiency of perovskite solar cells has been rapidly improved in recent years.
Such perovskite materials generally have ABX 3 Wherein A is a basic chemical formula + Typically organic cations (most commonly methylamine ions, CH 3 NH 3 + ，MA + )，B 2+ Is an inorganic cation (typically Pb 2+ )，X - As halogen anions (generally I - 、Cl - Or Br (Br) - :MAPb(I，Br，Cl) 3 ). The band gap of the perovskite material can be continuously regulated within 1.6 to 3.2 electron volts according to the types of halogen elements used. Using formamidine ion (CH (NH) 2 ) 2 + ，FA + ) Replacement MA + Or using Sn 2+ To replace Pb 2+ Or the band gap of the perovskite material can be further regulated by adopting methods such as mixed ions and the like, so that the sunlight absorption in a wider range is realized. Mesoporous structures are common because perovskite solar cells were originally evolved from dye sensitized solar cells. In this structure, in dense TiO 2 The selective electron transport layer is also provided with a layer made of TiO 2 A mesoporous layer composed of nano particles. The mesoporous layer is used as a framework for depositing the perovskite film, and can reduce the distance of electron diffusion so as to improve the electron collection efficiency. At the mostThe mesoporous thickness used in the initial research was about 500-600 nm, and the perovskite light absorbing material was completely infiltrated into the mesoporous framework. However, as research proceeds, it has been found that thinner mesoporous layers, on the order of 150-200 nanometers, can be used, while forming a continuous dense perovskite light absorbing layer thereon, resulting in better device performance. Because the diffusion length of electrons and holes in the perovskite material is long, the perovskite solar cell with higher efficiency can be obtained by using a planar structure after the mesoporous layer is completely removed, and compared with the mesoporous perovskite solar cell, the planar perovskite solar cell with simpler structure has obvious advantages in preparation structure, so that the planar perovskite solar cell is easier to realize commercialization finally.
The perovskite solar cell device structures commonly found today include mesoporous, planar (n-i-p) and planar inversion (p-i-n). The n-type electron transport materials used in the current planar structures are typically metal oxide semiconductor materials, the p-type hole transport materials are typically organic hole transport materials, and the organic hole transport materials used often need to be doped with other substances due to their low mobility to obtain high energy conversion efficiency, which limits further commercial applications. The n-type electron transport materials used in the planar inversion structure at present are generally fullerenes and derivatives thereof, and the materials have the defects of high production cost, difficult purification and the like which restrict the mass production of the materials. Thus, development of a low-cost large-area stable planar perovskite solar cell device and a structure thereof is urgent.
Disclosure of Invention
In order to solve the above drawbacks and disadvantages of the prior art, a primary object of the present invention is to provide a hole transport layer using amorphous nickel oxide as a perovskite solar cell device.
Another object of the present invention is to provide a method for preparing a hole transport layer using amorphous nickel oxide as a perovskite solar cell device.
Another object of the present invention is to provide a method for preparing a hole transport layer of a perovskite solar cell device by introducing different oxygen contents during the preparation of a nickel oxide film.
The invention aims at realizing the following technical scheme:
a hole transport layer of a perovskite solar cell device using amorphous nickel oxide comprises a substrate, an anode, an electron beam evaporation hole transport layer, a perovskite light absorption layer, an electron beam evaporation electron transport layer and an electron beam evaporation cathode which are sequentially stacked, wherein the structure schematic diagram of the hole transport layer is shown in figure 1.
The substrate is a hard substrate such as glass, quartz, sapphire, etc., and a flexible substrate such as polyimide, polyethylene terephthalate, polyethylene naphthalate or other polyester-based materials, metal, alloy or stainless steel films, etc.
The anode and the cathode are metal or metal oxide or poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT: PSS) and modified products thereof; the metal is preferably aluminum, silver-magnesium alloy, silver, gold, titanium and copper; the metal oxide is preferably one or a combination of more than two of Indium Tin Oxide (ITO), fluorine-doped tin dioxide (FTO), zinc oxide (ZnO) and Indium Gallium Zinc Oxide (IGZO).
The hole transport layer may be a single transport layer or a multilayer comprising electron and exciton blocking layers.
The perovskite light absorbing material is prepared from a blended or unblended perovskite light absorbing material; the perovskite material light absorption layer can be a single-layer or a multi-layer modification layer.
The electron transport layer may be a single transport layer or a multilayer comprising hole and exciton blocking layers.
An anode buffer layer (also called anode interface layer) can be added between the anode and the hole transport layer; a cathode buffer layer (also called a cathode interface layer) can be added between the cathode and the electron transport layer.
The method for preparing the perovskite solar cell device comprises the following steps of:
and taking a substrate material with an anode layer, and then sequentially preparing a hole transport layer, a perovskite light absorption layer, an electron transport layer and a cathode on the anode layer to obtain the perovskite solar cell device.
The preparation method comprises one or more of electron beam evaporation, thermal evaporation, knife coating, spin coating, brush coating, spray coating, dip coating, roller coating, printing or ink-jet printing.
The preparation method of the invention and the obtained device have the following advantages and beneficial effects:
(1) The device can be prepared in a large area at room temperature, which is beneficial to reducing the cost of preparing the device;
(2) The device provided by the invention uses electron beam evaporation nickel oxide as a hole transport layer, does not need any heat treatment and the like, and provides a feasible implementation scheme for realizing large-area low-cost preparation of perovskite solar cell devices;
(3) The electron transport layer of the device is prepared at room temperature without any heat treatment and the like, and provides a feasible implementation scheme for realizing the perovskite solar cell device.
(4) The metal oxide used for the hole transport layer and the electron transport layer of the perovskite battery of the device does not need any annealing treatment, thermal processing and the like, which is a device which is reported to be prepared in an amorphous state for the first time, and provides a feasible implementation scheme for obtaining low cost and high stability for a photovoltaic device.
(5) The perovskite battery of the device can be prepared at room temperature, and has high energy conversion efficiency, thereby providing a feasible implementation scheme for the application of the perovskite battery to commercialization.
Drawings
FIG. 1 is a schematic view of a transmission layer by electron beam evaporation and a schematic view of a layered structure of a perovskite solar cell device, which are ITO/NiO in sequence x (amorphous)/Active layer/Nb 2 O 5 /Ag；
Fig. 2 is a graph showing the current density-voltage characteristics of the perovskite solar cell device obtained in example 1;
fig. 3 is a graph of current density vs. voltage characteristics of the perovskite solar cell device obtained in example 2;
fig. 4 is a graph showing the current density-voltage characteristics of the perovskite solar cell device obtained in example 3;
fig. 5 is a graph of current density vs. voltage characteristics of the perovskite solar cell device obtained in example 4;
fig. 6 is a graph of current density vs. voltage characteristics of the perovskite solar cell device obtained in example 5;
fig. 7 is a graph showing the current density-voltage characteristics of the perovskite solar cell device obtained in example 6;
fig. 8 is a graph of current density vs. voltage characteristics of the perovskite solar cell device obtained in example 7;
fig. 9 is a graph of current density vs. voltage characteristics of the perovskite solar cell device obtained in example 8;
fig. 10 is a graph of current density vs. voltage characteristics of the perovskite solar cell device obtained in example 9;
fig. 11 is a graph showing the current density-voltage characteristics of the perovskite solar cell device obtained in example 10;
fig. 12 is a graph of current density vs. voltage characteristics of the perovskite solar cell device obtained in example 11;
fig. 13 is a graph showing the current density-voltage characteristics of the perovskite solar cell device obtained in example 12.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto.
Example 1
Several ITO conductive glass substrates of the same batch number are taken, the thickness of the ITO is about 200 nanometers, and the square resistance is about 20 ohms/square. Sequentially ultrasonic cleaning with special-purpose micron-sized semiconductor detergent, deionized water, acetone and isopropanol for 15 minutes to remove dirt on the surface of the substrate. And then placing the mixture into an incubator to be dried at 80 ℃. Then at normal temperature using electronsBeam evaporation method for evaporating nickel oxide (NiO) on ITO substrate x ) As a hole transport layer, the energy conversion efficiency of the perovskite battery device was optimized by adjusting the thickness of the hole transport layer to 20-50 nm, and then transferred into a glove box filled with high-purity nitrogen without water and oxygen. In the glove box, the component Cs is prepared by one-step spin coating 0.05 MA 0.15 FA 0.8 Pb(I 0.85 Br 0.15 ) 3 The mixed perovskite photoactive layer of (2) is then heated at 110 ℃ for 60 minutes on a heated platen, and the device is then loaded into an electron beam evaporation apparatus when the vacuum in the evaporation chamber is less than 5 x 10 -4 And starting electron beam evaporation of the film after Pa. Sequentially evaporating niobium pentoxide (Nb) on electron transport layer by using specific mask 2 O 5 ) The energy conversion efficiency of the perovskite battery device can be optimized by adjusting the thickness of the electron transport layer to 50-70 nanometers, and the electron transport layer and the hole transport layer are prepared at room temperature by using electron beam evaporation equipment and can be large in area, so that the battery device with large-area flexibility and different shapes can be prepared by using different masks; and using electron beam evaporation of metallic silver as a cathode of the device. The evaporation rate and thickness of each evaporated functional layer are monitored in real time by a quartz crystal diaphragm thickness detector, and the thickness of the hole transmission layer is controlled to be 30 nanometers, the thickness of the electron transmission layer is controlled to be 60 nanometers, and the thickness of the cathode layer material metallic silver is controlled to be not less than 80 nanometers. The structure of the obtained perovskite solar cell device and the thickness of each layer are as follows: ITO glass substrate/NiO x (30 nm)/perovskite layer (550-600 nm)/Nb 2 O 5 (60 nm)/silver (100 nm).
The perovskite solar cell device obtained in this example performs a photoelectric performance test:
and after the device is prepared, the device is taken out of the evaporation cavity. Testing was then performed in air with a SAN-ELECTRIC (XES-40S 2-CE) solar simulator lamp, and device current voltage information was determined by 2400 power meter manufactured by Ginkilli corporation (Keithley). The current density, the filling factor and the power conversion efficiency of the device can be respectively calculated through the information such as current, voltage, light intensity and the like.
Perovskite solar cell device obtained by the implementation: ITO glass substrate/NiO x (30 nm)/perovskite layer (550-600 nm)/Nb 2 O 5 The current density vs. voltage characteristic graph of (60 nm)/silver (100 nm) is shown in fig. 2.
The present example results in a highly efficient perovskite solar cell device. The perovskite battery device structure prepared by using metal oxide for both the hole transport layer and the electron transport layer without any heat treatment is reported for the first time, and has higher energy conversion efficiency.
Example 2
The procedure was as in example 1, except that a number of ITO conductive glass substrates of the same lot were used, the ITO thickness was about 200 nm, and the sheet resistance was about 20 ohm/square. Sequentially ultrasonic cleaning with special-purpose micron-sized semiconductor detergent, deionized water, acetone and isopropanol for 15 minutes to remove dirt on the surface of the substrate. And then placing the mixture into an incubator to be dried at 80 ℃. Then nickel oxide (NiO) is evaporated on the ITO substrate by an electron beam evaporation method at normal temperature x ) As a hole transport layer, oxygen with the purity of more than 99.999% of 5sccm is introduced into an electron beam evaporation chamber in the process of evaporating nickel oxide, the energy conversion efficiency of a perovskite battery device is optimized by adjusting the thickness of the hole transport layer to 20-50 nanometers, and then the perovskite battery device is transferred into a glove box which is anhydrous, anaerobic and full of high-purity nitrogen. In the glove box, the component Cs is prepared by one-step spin coating 0.05 MA 0.15 FA 0.8 Pb(I 0.85 Br 0.15 ) 3 The mixed perovskite photoactive layer of (2) is then heated at 110 ℃ for 60 minutes on a heated platen, and the device is then loaded into an electron beam evaporation apparatus when the vacuum in the evaporation chamber is less than 5 x 10 -4 And starting electron beam evaporation of the film after Pa. Sequentially evaporating niobium pentoxide (Nb) on electron transport layer by using specific mask 2 O 5 ) The energy conversion efficiency of the perovskite battery device can be optimized by adjusting the thickness of the electron transport layer to 50-70 nanometers, and the electron transport layer and the electron can be prepared by using electron beam evaporation equipmentThe transmission layers are prepared at room temperature and can realize a large area, so that the battery devices with large area flexibility and different shapes can be prepared by using different masks; and using electron beam evaporation of metallic silver as a cathode of the device. The evaporation rate and thickness of each evaporated functional layer are monitored in real time by a quartz crystal diaphragm thickness detector, and the thickness of the hole transmission layer is controlled to be 30 nanometers, the thickness of the electron transmission layer is controlled to be 60 nanometers, and the thickness of the cathode layer material metallic silver is controlled to be not less than 80 nanometers. The structure of the obtained perovskite solar cell device and the thickness of each layer are as follows: ITO glass substrate/NiO x (30 nm)/perovskite layer (550-600 nm)/Nb 2 O 5 (60 nm)/silver (100 nm).
The perovskite solar cell device obtained in this example performs a photoelectric performance test:
perovskite solar cell device obtained by the implementation: ITO glass substrate/NiO x (30 nm)/perovskite layer (550-600 nm)/Nb 2 O 5 The current density vs. voltage characteristic graph of (60 nm)/silver (100 nm) is shown in fig. 3.
Example 3
The procedure was as in example 1, except that a number of ITO conductive glass substrates of the same lot were used, the ITO thickness was about 200 nm, and the sheet resistance was about 20 ohm/square. Sequentially ultrasonic cleaning with special-purpose micron-sized semiconductor detergent, deionized water, acetone and isopropanol for 15 minutes to remove dirt on the surface of the substrate. And then placing the mixture into an incubator to be dried at 80 ℃. Then nickel oxide (NiO) is evaporated on the ITO substrate by an electron beam evaporation method at normal temperature x ) As a hole transport layer, 10sccm of oxygen with purity of more than 99.999% is introduced into an electron beam evaporation chamber in the process of evaporating nickel oxide, the energy conversion efficiency of a perovskite battery device is optimized by adjusting the thickness of the hole transport layer to 20-50 nanometers, and then the perovskite battery device is transferred into a glove box which is anhydrous, anaerobic and full of high-purity nitrogen. In the glove box, the component Cs is prepared by one-step spin coating 0.05 MA 0.15 FA 0.8 Pb(I 0.85 Br 0.15 ) 3 And then heated at 110 c for 60 minutes on a heated platen,the device is then loaded into an electron beam evaporation apparatus when the vacuum in the evaporation chamber is less than 5 x 10 -4 And starting electron beam evaporation of the film after Pa. Sequentially evaporating niobium pentoxide (Nb) on electron transport layer by using specific mask 2 O 5 ) The energy conversion efficiency of the perovskite battery device can be optimized by adjusting the thickness of the electron transport layer to 50-70 nanometers, and the electron transport layer and the hole transport layer are prepared at room temperature by using electron beam evaporation equipment and can be large in area, so that the battery device with large-area flexibility and different shapes can be prepared by using different masks; and using electron beam evaporation of metallic silver as a cathode of the device. The evaporation rate and thickness of each evaporated functional layer are monitored in real time by a quartz crystal diaphragm thickness detector, and the thickness of the hole transmission layer is controlled to be 30 nanometers, the thickness of the electron transmission layer is controlled to be 60 nanometers, and the thickness of the cathode layer material metallic silver is controlled to be not less than 80 nanometers. The structure of the obtained perovskite solar cell device and the thickness of each layer are as follows: ITO glass substrate/NiO x (30 nm)/perovskite layer (550-600 nm)/Nb 2 O 5 (60 nm)/silver (100 nm).
The perovskite solar cell device obtained in this example performs a photoelectric performance test:
perovskite solar cell device obtained by the implementation: ITO glass substrate/NiO x (30 nm)/perovskite layer (550-600 nm)/Nb 2 O 5 The current density vs. voltage characteristic graph of (60 nm)/silver (100 nm) is shown in fig. 4.
Example 4
The procedure was as in example 1, except that a number of ITO conductive glass substrates of the same lot were used, the ITO thickness was about 200 nm, and the sheet resistance was about 20 ohm/square. Sequentially ultrasonic cleaning with special-purpose micron-sized semiconductor detergent, deionized water, acetone and isopropanol for 15 minutes to remove dirt on the surface of the substrate. And then placing the mixture into an incubator to be dried at 80 ℃. Then nickel oxide (NiO) is evaporated on the ITO substrate by an electron beam evaporation method at normal temperature x ) As a hole transport layer, 15sccm of oxygen with purity of 99.999% or more is introduced into an electron beam evaporation chamber during nickel oxide evaporation, and the mixture is adjustedThe thickness of the hole-saving transport layer is 20-50 nanometers so as to optimize the energy conversion efficiency of the perovskite battery device, and then the perovskite battery device is transferred into a glove box which is anhydrous, anaerobic and full of high-purity nitrogen. In the glove box, the component Cs is prepared by one-step spin coating 0.05 MA 0.15 FA 0.8 Pb(I 0.85 Br 0.15 ) 3 The mixed perovskite photoactive layer of (2) is then heated at 110 ℃ for 60 minutes on a heated platen, and the device is then loaded into an electron beam evaporation apparatus when the vacuum in the evaporation chamber is less than 5 x 10 -4 And starting electron beam evaporation of the film after Pa. Sequentially evaporating niobium pentoxide (Nb) on electron transport layer by using specific mask 2 O 5 ) The energy conversion efficiency of the perovskite battery device can be optimized by adjusting the thickness of the electron transport layer to 50-70 nanometers, and the electron transport layer and the hole transport layer are prepared at room temperature by using electron beam evaporation equipment and can be large in area, so that the battery device with large-area flexibility and different shapes can be prepared by using different masks; and using electron beam evaporation of metallic silver as a cathode of the device. The evaporation rate and thickness of each evaporated functional layer are monitored in real time by a quartz crystal diaphragm thickness detector, and the thickness of the hole transmission layer is controlled to be 30 nanometers, the thickness of the electron transmission layer is controlled to be 60 nanometers, and the thickness of the cathode layer material metallic silver is controlled to be not less than 80 nanometers. The structure of the obtained perovskite solar cell device and the thickness of each layer are as follows: ITO glass substrate/NiO x (30 nm)/perovskite layer (550-600 nm)/Nb 2 O 5 (60 nm)/silver (100 nm).
The perovskite solar cell device obtained in this example performs a photoelectric performance test:
perovskite solar cell device obtained by the implementation: ITO glass substrate/NiO x (30 nm)/perovskite layer (550-600 nm)/Nb 2 O 5 The current density vs. voltage characteristic graph of (60 nm)/silver (100 nm) is shown in fig. 5.
Example 5
The procedure was as in example 1, except that a number of ITO conductive glass substrates of the same lot were used, the ITO thickness was about 200 nm, and the sheet resistance was about 20 ohm/square. In turnUltrasonic cleaning with micron-sized semiconductor special-purpose detergent, deionized water, acetone and isopropanol for 15 min to remove dirt on the surface of the substrate. And then placing the mixture into an incubator to be dried at 80 ℃. Then nickel oxide (NiO) is evaporated on the ITO substrate by an electron beam evaporation method at normal temperature x ) As a hole transport layer, the energy conversion efficiency of the perovskite battery device was optimized by adjusting the thickness of the hole transport layer to 20-50 nm, and then transferred into a glove box filled with high-purity nitrogen without water and oxygen. In the glove box, the component Cs is prepared by one-step spin coating 0.05 MA 0.15 FA 0.8 Pb(I 0.75 Br 0.25 ) 3 The mixed perovskite photoactive layer of (2) is then heated at 110 ℃ for 60 minutes on a heated platen, and the device is then loaded into an electron beam evaporation apparatus when the vacuum in the evaporation chamber is less than 5 x 10 -4 And starting electron beam evaporation of the film after Pa. Sequentially evaporating niobium pentoxide (Nb) on electron transport layer by using specific mask 2 O 5 ) The energy conversion efficiency of the perovskite battery device can be optimized by adjusting the thickness of the electron transport layer to 50-70 nanometers, and the electron transport layer and the hole transport layer are prepared at room temperature by using electron beam evaporation equipment and can be large in area, so that the battery device with large-area flexibility and different shapes can be prepared by using different masks; and using electron beam evaporation of metallic silver as a cathode of the device. The evaporation rate and thickness of each evaporated functional layer are monitored in real time by a quartz crystal diaphragm thickness detector, and the thickness of the hole transmission layer is controlled to be 30 nanometers, the thickness of the electron transmission layer is controlled to be 60 nanometers, and the thickness of the cathode layer material metallic silver is controlled to be not less than 80 nanometers. The structure of the obtained perovskite solar cell device and the thickness of each layer are as follows: ITO glass substrate/NiO x (30 nm)/perovskite layer (550-600 nm)/Nb 2 O 5 (60 nm)/silver (100 nm).
The perovskite solar cell device obtained in this example performs a photoelectric performance test:
perovskite solar cell device obtained by the implementation: ITO glass substrate/NiO x (30 nm)/perovskite layer (550-600 nm)/Nb 2 O 5 (60 nm)) The current density vs. voltage characteristic of silver (100 nm) is shown in FIG. 6.
Example 6
The procedure was as in example 1, except that a number of ITO conductive glass substrates of the same lot were used, the ITO thickness was about 200 nm, and the sheet resistance was about 20 ohm/square. Sequentially ultrasonic cleaning with special-purpose micron-sized semiconductor detergent, deionized water, acetone and isopropanol for 15 minutes to remove dirt on the surface of the substrate. And then placing the mixture into an incubator to be dried at 80 ℃. Then nickel oxide (NiO) is evaporated on the ITO substrate by an electron beam evaporation method at normal temperature x ) As a hole transport layer, oxygen with the purity of more than 99.999% of 5sccm is introduced into an electron beam evaporation chamber in the process of evaporating nickel oxide, the energy conversion efficiency of a perovskite battery device is optimized by adjusting the thickness of the hole transport layer to 20-50 nanometers, and then the perovskite battery device is transferred into a glove box which is anhydrous, anaerobic and full of high-purity nitrogen. In the glove box, the component Cs is prepared by one-step spin coating 0.05 MA 0.15 FA 0.8 Pb(I 0.75 Br 0.25 ) 3 The mixed perovskite photoactive layer of (2) is then heated at 110 ℃ for 60 minutes on a heated platen, and the device is then loaded into an electron beam evaporation apparatus when the vacuum in the evaporation chamber is less than 5 x 10 -4 And starting electron beam evaporation of the film after Pa. Sequentially evaporating niobium pentoxide (Nb) on electron transport layer by using specific mask 2 O 5 ) The energy conversion efficiency of the perovskite battery device can be optimized by adjusting the thickness of the electron transport layer to 50-70 nanometers, and the electron transport layer and the hole transport layer are prepared at room temperature by using electron beam evaporation equipment and can be large in area, so that the battery device with large-area flexibility and different shapes can be prepared by using different masks; and using electron beam evaporation of metallic silver as a cathode of the device. The evaporation rate and thickness of each evaporated functional layer are monitored in real time by a quartz crystal diaphragm thickness detector, and the thickness of the hole transmission layer is controlled to be 30 nanometers, the thickness of the electron transmission layer is controlled to be 60 nanometers, and the thickness of the cathode layer material metallic silver is controlled to be not less than 80 nanometers. The structure of the obtained perovskite solar cell device and the thickness of each layer are as follows: ITO glass substrate/NiO x (30 nm)/perovskite layer (550-600 nm)/Nb 2 O 5 (60 nm)/silver (100 nm).
The perovskite solar cell device obtained in this example performs a photoelectric performance test:
perovskite solar cell device obtained by the implementation: ITO glass substrate/NiO x (30 nm)/perovskite layer (550-600 nm)/Nb 2 O 5 The current density vs. voltage characteristic graph of (60 nm)/silver (100 nm) is shown in fig. 7.
Example 7
The procedure was as in example 1, except that a number of ITO conductive glass substrates of the same lot were used, the ITO thickness was about 200 nm, and the sheet resistance was about 20 ohm/square. Sequentially ultrasonic cleaning with special-purpose micron-sized semiconductor detergent, deionized water, acetone and isopropanol for 15 minutes to remove dirt on the surface of the substrate. And then placing the mixture into an incubator to be dried at 80 ℃. Then nickel oxide (NiO) is evaporated on the ITO substrate by an electron beam evaporation method at normal temperature x ) As a hole transport layer, 10sccm of oxygen with purity of more than 99.999% is introduced into an electron beam evaporation chamber in the process of evaporating nickel oxide, the energy conversion efficiency of a perovskite battery device is optimized by adjusting the thickness of the hole transport layer to 20-50 nanometers, and then the perovskite battery device is transferred into a glove box which is anhydrous, anaerobic and full of high-purity nitrogen. In the glove box, the component Cs is prepared by one-step spin coating 0.05 MA 0.15 FA 0.8 Pb(I 0.75 Br 0.25 ) 3 The mixed perovskite photoactive layer of (2) is then heated at 110 ℃ for 60 minutes on a heated platen, and the device is then loaded into an electron beam evaporation apparatus when the vacuum in the evaporation chamber is less than 5 x 10 -4 And starting electron beam evaporation of the film after Pa. Sequentially evaporating niobium pentoxide (Nb) on electron transport layer by using specific mask 2 O 5 ) The energy conversion efficiency of the perovskite battery device can be optimized by adjusting the thickness of the electron transport layer to 50-70 nanometers, and the electron transport layer and the hole transport layer are prepared at room temperature by using electron beam evaporation equipment and can realize large area, so that large-area flexibility and different shapes can be prepared by using different masksA battery device; and using electron beam evaporation of metallic silver as a cathode of the device. The evaporation rate and thickness of each evaporated functional layer are monitored in real time by a quartz crystal diaphragm thickness detector, and the thickness of the hole transmission layer is controlled to be 30 nanometers, the thickness of the electron transmission layer is controlled to be 60 nanometers, and the thickness of the cathode layer material metallic silver is controlled to be not less than 80 nanometers. The structure of the obtained perovskite solar cell device and the thickness of each layer are as follows: ITO glass substrate/NiO x (30 nm)/perovskite layer (550-600 nm)/Nb 2 O 5 (60 nm)/silver (100 nm).
The perovskite solar cell device obtained in this example performs a photoelectric performance test:
perovskite solar cell device obtained by the implementation: ITO glass substrate/NiO x (30 nm)/perovskite layer (550-600 nm)/Nb 2 O 5 The current density vs. voltage characteristic graph of (60 nm)/silver (100 nm) is shown in fig. 8.
Example 8
The procedure was as in example 1, except that a number of ITO conductive glass substrates of the same lot were used, the ITO thickness was about 200 nm, and the sheet resistance was about 20 ohm/square. Sequentially ultrasonic cleaning with special-purpose micron-sized semiconductor detergent, deionized water, acetone and isopropanol for 15 minutes to remove dirt on the surface of the substrate. And then placing the mixture into an incubator to be dried at 80 ℃. Then nickel oxide (NiO) is evaporated on the ITO substrate by an electron beam evaporation method at normal temperature x ) As a hole transport layer, oxygen with the purity of more than 99.999% is introduced into an electron beam evaporation chamber in the process of evaporating nickel oxide, the energy conversion efficiency of the perovskite battery device is optimized by adjusting the thickness of the hole transport layer to 20-50 nanometers, and then the perovskite battery device is transferred into a glove box which is anhydrous, anaerobic and full of high-purity nitrogen. In the glove box, the component Cs is prepared by one-step spin coating 0.05 MA 0.15 FA 0.8 Pb(I 0.75 Br 0.25 ) 3 The mixed perovskite photoactive layer of (2) is then heated at 110 ℃ for 60 minutes on a heated platen, and the device is then loaded into an electron beam evaporation apparatus when the vacuum in the evaporation chamber is less than 5 x 10 -4 And starting electron beam evaporation of the film after Pa. By means of specific featuresSequentially evaporating an electron transport layer of niobium pentoxide (Nb) 2 O 5 ) The energy conversion efficiency of the perovskite battery device can be optimized by adjusting the thickness of the electron transport layer to 50-70 nanometers, and the electron transport layer and the hole transport layer are prepared at room temperature by using electron beam evaporation equipment and can be large in area, so that the battery device with large-area flexibility and different shapes can be prepared by using different masks; and using electron beam evaporation of metallic silver as a cathode of the device. The evaporation rate and thickness of each evaporated functional layer are monitored in real time by a quartz crystal diaphragm thickness detector, and the thickness of the hole transmission layer is controlled to be 30 nanometers, the thickness of the electron transmission layer is controlled to be 60 nanometers, and the thickness of the cathode layer material metallic silver is controlled to be not less than 80 nanometers. The structure of the obtained perovskite solar cell device and the thickness of each layer are as follows: ITO glass substrate/NiO x (30 nm)/perovskite layer (550-600 nm)/Nb 2 O 5 (60 nm)/silver (100 nm).
The perovskite solar cell device obtained in this example performs a photoelectric performance test:
perovskite solar cell device obtained by the implementation: ITO glass substrate/NiO x (30 nm)/perovskite layer (550-600 nm)/Nb 2 O 5 The current density vs. voltage characteristic graph of (60 nm)/silver (100 nm) is shown in fig. 9.
Example 9
The procedure was as in example 1, except that a number of ITO conductive glass substrates of the same lot were used, the ITO thickness was about 200 nm, and the sheet resistance was about 20 ohm/square. Sequentially ultrasonic cleaning with special-purpose micron-sized semiconductor detergent, deionized water, acetone and isopropanol for 15 minutes to remove dirt on the surface of the substrate. And then placing the mixture into an incubator to be dried at 80 ℃. Then nickel oxide (NiO) is evaporated on the ITO substrate by an electron beam evaporation method at normal temperature x ) As a hole transport layer, the energy conversion efficiency of the perovskite battery device was optimized by adjusting the thickness of the hole transport layer to 20-50 nm, and then transferred into a glove box filled with high-purity nitrogen without water and oxygen. In the glove box, the component for preparing the MA by spin coating in one step 0.2 FA 0.8 Pb(I 0.85 Br 0.15 ) 3 The mixed perovskite photoactive layer of (2) is then heated at 110 ℃ for 60 minutes on a heated platen, and the device is then loaded into an electron beam evaporation apparatus when the vacuum in the evaporation chamber is less than 5 x 10 -4 And starting electron beam evaporation of the film after Pa. Sequentially evaporating niobium pentoxide (Nb) on electron transport layer by using specific mask 2 O 5 ) The energy conversion efficiency of the perovskite battery device can be optimized by adjusting the thickness of the electron transport layer to 50-70 nanometers, and the electron transport layer and the hole transport layer are prepared at room temperature by using electron beam evaporation equipment and can be large in area, so that the battery device with large-area flexibility and different shapes can be prepared by using different masks; and using electron beam evaporation of metallic silver as a cathode of the device. The evaporation rate and thickness of each evaporated functional layer are monitored in real time by a quartz crystal diaphragm thickness detector, and the thickness of the hole transmission layer is controlled to be 30 nanometers, the thickness of the electron transmission layer is controlled to be 60 nanometers, and the thickness of the cathode layer material metallic silver is controlled to be not less than 80 nanometers. The structure of the obtained perovskite solar cell device and the thickness of each layer are as follows: ITO glass substrate/NiO x (30 nm)/perovskite layer (550-600 nm)/Nb 2 O 5 (60 nm)/silver (100 nm).
The perovskite solar cell device obtained in this example performs a photoelectric performance test:
perovskite solar cell device obtained by the implementation: ITO glass substrate/NiO x (30 nm)/perovskite layer (550-600 nm)/Nb 2 O 5 The current density vs. voltage characteristic graph of (60 nm)/silver (100 nm) is shown in fig. 10.
Example 10
The procedure was as in example 1, except that a number of ITO conductive glass substrates of the same lot were used, the ITO thickness was about 200 nm, and the sheet resistance was about 20 ohm/square. Sequentially ultrasonic cleaning with special-purpose micron-sized semiconductor detergent, deionized water, acetone and isopropanol for 15 minutes to remove dirt on the surface of the substrate. And then placing the mixture into an incubator to be dried at 80 ℃. Then nickel oxide (NiO) is evaporated on the ITO substrate by an electron beam evaporation method at normal temperature x ) As a hole transport layer, oxygen with the purity of more than 99.999% of 5sccm is introduced into an electron beam evaporation chamber in the process of evaporating nickel oxide, the energy conversion efficiency of a perovskite battery device is optimized by adjusting the thickness of the hole transport layer to 20-50 nanometers, and then the perovskite battery device is transferred into a glove box which is anhydrous, anaerobic and full of high-purity nitrogen. In the glove box, the component for preparing the MA by spin coating in one step 0.2 FA 0.8 Pb(I 0.85 Br 0.15 ) 3 The mixed perovskite photoactive layer of (2) is then heated at 110 ℃ for 60 minutes on a heated platen, and the device is then loaded into an electron beam evaporation apparatus when the vacuum in the evaporation chamber is less than 5 x 10 -4 And starting electron beam evaporation of the film after Pa. Sequentially evaporating niobium pentoxide (Nb) on electron transport layer by using specific mask 2 O 5 ) The energy conversion efficiency of the perovskite battery device can be optimized by adjusting the thickness of the electron transport layer to 50-70 nanometers, and the electron transport layer and the hole transport layer are prepared at room temperature by using electron beam evaporation equipment and can be large in area, so that the battery device with large-area flexibility and different shapes can be prepared by using different masks; and using electron beam evaporation of metallic silver as a cathode of the device. The evaporation rate and thickness of each evaporated functional layer are monitored in real time by a quartz crystal diaphragm thickness detector, and the thickness of the hole transmission layer is controlled to be 30 nanometers, the thickness of the electron transmission layer is controlled to be 60 nanometers, and the thickness of the cathode layer material metallic silver is controlled to be not less than 80 nanometers. The structure of the obtained perovskite solar cell device and the thickness of each layer are as follows: ITO glass substrate/NiO x (30 nm)/perovskite layer (550-600 nm)/Nb 2 O 5 (60 nm)/silver (100 nm).
The perovskite solar cell device obtained in this example performs a photoelectric performance test:
perovskite solar cell device obtained by the implementation: ITO glass substrate/NiO x (30 nm)/perovskite layer (550-600 nm)/Nb 2 O 5 The current density vs. voltage characteristic graph of (60 nm)/silver (100 nm) is shown in fig. 11.
Example 11
The preparation process is as followsIn example 1, a number of ITO conductive glass substrates of the same lot were used, the ITO thickness was about 200 nm, and the sheet resistance was about 20 ohm/square. Sequentially ultrasonic cleaning with special-purpose micron-sized semiconductor detergent, deionized water, acetone and isopropanol for 15 minutes to remove dirt on the surface of the substrate. And then placing the mixture into an incubator to be dried at 80 ℃. Then nickel oxide (NiO) is evaporated on the ITO substrate by an electron beam evaporation method at normal temperature x ) As a hole transport layer, 10sccm of oxygen with purity of more than 99.999% is introduced into an electron beam evaporation chamber in the process of evaporating nickel oxide, the energy conversion efficiency of a perovskite battery device is optimized by adjusting the thickness of the hole transport layer to 20-50 nanometers, and then the perovskite battery device is transferred into a glove box which is anhydrous, anaerobic and full of high-purity nitrogen. In the glove box, the component for preparing the MA by spin coating in one step 0.2 FA 0.8 Pb(I 0.85 Br 0.15 ) 3 The mixed perovskite photoactive layer of (2) is then heated at 110 ℃ for 60 minutes on a heated platen, and the device is then loaded into an electron beam evaporation apparatus when the vacuum in the evaporation chamber is less than 5 x 10 -4 And starting electron beam evaporation of the film after Pa. Sequentially evaporating niobium pentoxide (Nb) on electron transport layer by using specific mask 2 O 5 ) The energy conversion efficiency of the perovskite battery device can be optimized by adjusting the thickness of the electron transport layer to 50-70 nanometers, and the electron transport layer and the hole transport layer are prepared at room temperature by using electron beam evaporation equipment and can be large in area, so that the battery device with large-area flexibility and different shapes can be prepared by using different masks; and using electron beam evaporation of metallic silver as a cathode of the device. The evaporation rate and thickness of each evaporated functional layer are monitored in real time by a quartz crystal diaphragm thickness detector, and the thickness of the hole transmission layer is controlled to be 30 nanometers, the thickness of the electron transmission layer is controlled to be 60 nanometers, and the thickness of the cathode layer material metallic silver is controlled to be not less than 80 nanometers. The structure of the obtained perovskite solar cell device and the thickness of each layer are as follows: ITO glass substrate/NiO x (30 nm)/perovskite layer (550-600 nm)/Nb 2 O 5 (60 nm)/silver (100 nm).
The perovskite solar cell device obtained in this example performs a photoelectric performance test:
perovskite solar cell device obtained by the implementation: ITO glass substrate/NiO x (30 nm)/perovskite layer (550-600 nm)/Nb 2 O 5 The current density vs. voltage characteristic graph of (60 nm)/silver (100 nm) is shown in fig. 12.
Example 12
The procedure was as in example 1, except that a number of ITO conductive glass substrates of the same lot were used, the ITO thickness was about 200 nm, and the sheet resistance was about 20 ohm/square. Sequentially ultrasonic cleaning with special-purpose micron-sized semiconductor detergent, deionized water, acetone and isopropanol for 15 minutes to remove dirt on the surface of the substrate. And then placing the mixture into an incubator to be dried at 80 ℃. Then nickel oxide (NiO) is evaporated on the ITO substrate by an electron beam evaporation method at normal temperature x ) As a hole transport layer, oxygen with the purity of more than 99.999% is introduced into an electron beam evaporation chamber in the process of evaporating nickel oxide, the energy conversion efficiency of the perovskite battery device is optimized by adjusting the thickness of the hole transport layer to 20-50 nanometers, and then the perovskite battery device is transferred into a glove box which is anhydrous, anaerobic and full of high-purity nitrogen. In the glove box, the component for preparing the MA by spin coating in one step 0.2 FA 0.8 Pb(I 0.85 Br 0.15 ) 3 The mixed perovskite photoactive layer of (2) is then heated at 110 ℃ for 60 minutes on a heated platen, and the device is then loaded into an electron beam evaporation apparatus when the vacuum in the evaporation chamber is less than 5 x 10 -4 And starting electron beam evaporation of the film after Pa. Sequentially evaporating niobium pentoxide (Nb) on electron transport layer by using specific mask 2 O 5 ) The energy conversion efficiency of the perovskite battery device can be optimized by adjusting the thickness of the electron transport layer to 50-70 nanometers, and the electron transport layer and the hole transport layer are prepared at room temperature by using electron beam evaporation equipment and can be large in area, so that the battery device with large-area flexibility and different shapes can be prepared by using different masks; and using electron beam evaporation of metallic silver as a cathode of the device. The vapor deposition rate and thickness of each functional layer of vapor deposition are monitored in real time by a quartz crystal diaphragm thickness detector, and the thickness of the hole transport layer is controlled to be 30 nanometers respectivelyThe thickness of the electron transport layer is 60 nanometers, and the thickness of the cathode layer material silver is not less than 80 nanometers. The structure of the obtained perovskite solar cell device and the thickness of each layer are as follows: ITO glass substrate/NiO x (30 nm)/perovskite layer (550-600 nm)/Nb 2 O 5 (60 nm)/silver (100 nm).
The perovskite solar cell device obtained in this example performs a photoelectric performance test:
perovskite solar cell device obtained by the implementation: ITO glass substrate/NiO x (30 nm)/perovskite layer (550-600 nm)/Nb 2 O 5 The current density vs. voltage characteristic graph of (60 nm)/silver (100 nm) is shown in fig. 13.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (9)
1. An amorphous nickel oxide as a hole transport layer for a perovskite solar cell device, characterized in that: the amorphous nickel oxide serving as a hole transport layer of the perovskite battery device structurally comprises a substrate, an anode ITO and an electron beam evaporation hole transport layer NiO which are sequentially laminated x Perovskite photoactive layer, electron beam evaporation electron transport layer Nb 2 O 5 And electron beam evaporation cathode Ag.
2. An amorphous nickel oxide as claimed in claim 1 as a hole transport layer for perovskite solar cell devices and a method of making the same, wherein: the substrate is a glass, quartz, sapphire, polyimide, polyethylene terephthalate, polyethylene naphthalate, metal, alloy or stainless steel film; the anode and the cathode are metal, metal oxide, poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) or modified products thereof.
3. An amorphous nickel oxide as claimed in claim 1 as a hole transport layer for perovskite solar cell devices and a method of making the same, wherein: the metal refers to aluminum, silver, gold or silver magnesium alloy, titanium, copper and the like which can be used as electrodes; the metal oxide refers to one or a combination of more than two of indium tin oxide, fluorine-doped tin dioxide, zinc oxide, indium gallium zinc oxide and the like which can serve as electrodes.
4. An amorphous nickel oxide as claimed in claim 1 as a hole transport layer for perovskite solar cell devices and a method of making the same, wherein: the hole transport layer is not limited to a single layer, but includes a multilayer case where electron and exciton blocking layers are added.
5. An amorphous nickel oxide as claimed in claim 1 as a hole transport layer for a perovskite solar cell device, wherein: the perovskite photoactive layer is prepared from perovskite light absorbing materials with different components, which are blended or unblended; the light absorbing layer is a single layer or multiple layers.
6. An amorphous nickel oxide as claimed in claim 1 as a hole transport layer for perovskite solar cell devices, wherein the electron transport layer is not limited to a single layer, including the multilayer case of added hole, exciton blocking layers.
7. An amorphous nickel oxide as claimed in claim 1 as a hole transport layer for a perovskite solar cell device, wherein: an anode buffer layer can be added between the anode and the hole transport layer; a cathode buffer layer can be added between the cathode and the electron transport layer.
8. An amorphous nickel oxide as claimed in any one of claims 1 to 7 as a hole transport layer for a perovskite solar cell device and a method for manufacturing the same, comprising the steps of: and taking a substrate material with an anode layer, and then sequentially preparing a hole transport layer, a perovskite photoactive layer, an electron transport layer and a cathode on the anode layer to obtain the perovskite battery device taking the amorphous nickel oxide as the hole transport layer.
9. The use of amorphous nickel oxide as a hole transport layer for perovskite solar cell devices and methods of making same as defined in claim 8, wherein: the preparation method comprises one or more of electron beam evaporation, thermal evaporation, spin coating, knife coating, brush coating, spray coating, dip coating, roller coating, printing or ink-jet printing.
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