CN117457762A - All-inorganic perovskite solar cell and preparation method thereof - Google Patents
All-inorganic perovskite solar cell and preparation method thereof Download PDFInfo
- Publication number
- CN117457762A CN117457762A CN202311649107.4A CN202311649107A CN117457762A CN 117457762 A CN117457762 A CN 117457762A CN 202311649107 A CN202311649107 A CN 202311649107A CN 117457762 A CN117457762 A CN 117457762A
- Authority
- CN
- China
- Prior art keywords
- inorganic
- layer
- inorganic perovskite
- solar cell
- transport layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000010410 layer Substances 0.000 claims abstract description 163
- 239000000758 substrate Substances 0.000 claims abstract description 64
- 238000005566 electron beam evaporation Methods 0.000 claims abstract description 52
- 230000005525 hole transport Effects 0.000 claims abstract description 49
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 34
- 229910052709 silver Inorganic materials 0.000 claims description 34
- 239000004332 silver Substances 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 32
- 239000011521 glass Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 18
- 239000010453 quartz Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000004528 spin coating Methods 0.000 claims description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 6
- 239000011358 absorbing material Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 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
- 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
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims description 2
- 238000007761 roller coating Methods 0.000 claims description 2
- 238000010020 roller printing Methods 0.000 claims description 2
- 229910052594 sapphire Inorganic materials 0.000 claims description 2
- 239000010980 sapphire Substances 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
- 229910000480 nickel oxide Inorganic materials 0.000 abstract description 51
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 abstract description 31
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 239000002346 layers by function Substances 0.000 abstract description 9
- 230000031700 light absorption Effects 0.000 abstract description 4
- 230000003287 optical effect Effects 0.000 abstract description 2
- 229910010272 inorganic material Inorganic materials 0.000 abstract 1
- 239000011147 inorganic material Substances 0.000 abstract 1
- 238000010025 steaming Methods 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 description 38
- 230000008020 evaporation Effects 0.000 description 21
- 238000010438 heat treatment Methods 0.000 description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 239000010408 film Substances 0.000 description 11
- 239000011777 magnesium Substances 0.000 description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 10
- 239000000395 magnesium oxide Substances 0.000 description 10
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 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 description 10
- 239000004065 semiconductor Substances 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000003599 detergent Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000010955 niobium Substances 0.000 description 8
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 238000011056 performance test Methods 0.000 description 8
- 238000004506 ultrasonic cleaning Methods 0.000 description 8
- 238000010894 electron beam technology Methods 0.000 description 6
- 230000009977 dual effect Effects 0.000 description 5
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000007740 vapor deposition Methods 0.000 description 5
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical compound NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- -1 methylamine ions Chemical class 0.000 description 3
- 150000002892 organic cations Chemical class 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 150000001767 cationic compounds Chemical class 0.000 description 2
- 238000010549 co-Evaporation Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910001411 inorganic cation Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000484 niobium oxide Inorganic materials 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 125000000962 organic group Chemical group 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
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
- H01L31/075—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PIN type, e.g. amorphous silicon PIN solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention belongs to the technical field of photovoltaic devices, and discloses an all-inorganic perovskite solar cell device and a preparation method thereof. The all-inorganic perovskite solar cell device and the preparation method thereof comprise a substrate, an anode (ITO) and an electron beam evaporation inorganic hole transport layer (NiO) which are sequentially laminated x ) An inorganic perovskite light absorption layer, an electron beam evaporation inorganic electron transport layer (Nb) 2 O 5 ) And electron beam evaporation cathodes (Ag). Each corresponding functional layer is made of an inorganic material capable of functioning as a respective function. The all-inorganic perovskite solar cell device and the preparation method thereof obtain higher energy conversion efficiency, and the nickel oxide of the hole transport layer can be shared by double-source electron beamsThe doping of different elements and different concentrations is achieved by steaming, so that the optical and electrical characteristics of the device are improved, and the all-inorganic perovskite battery device has lower processing cost and can realize large-area processing, so that the device 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 a perovskite solar cell with a hole transport layer, an electron transport layer and a perovskite layer which are all inorganic matters, and a preparation 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. On one hand, the mesoporous layer is used as a framework for depositing a perovskite filmOn the other hand, the electron diffusion distance can be reduced, and the electron collection efficiency is further improved. The mesoporous thickness used in the initial studies 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 organic group used in the organic-inorganic hybrid perovskite solar cell at present leads to poor thermal stability and humidity stability of the final device, so that the use of inorganic cations to replace organic cations such as Methyl Ammonia (MA) or Formamidine (FA) is one of the main ways to improve the stability to obtain high efficiency, the use of cationic cesium (Cs) to replace organic cations to obtain an all-inorganic perovskite device, and the all-inorganic component CsPbI 2 Br has proper energy band (about 1.8 electron volts), is favorable for being integrated with the existing silicon-based solar cell to prepare a series cell, and can further obtain a high-efficiency cell device. The planar perovskite solar cell device structure that is common when the following includes planar (n-i-p) and planar inversion (p-i-n). The n-type electron transport material used in the planar structure is typically a metal oxide semiconductor material, the p-type hole transport material is typically an organic hole transport material, and the organic hole transport material used often needs to be doped with other substances due to its 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 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 developing low-cost large-area stable all-inorganic calciumTitanium-ore solar cell devices and structures thereof are 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 inorganic nickel oxide as an inorganic perovskite solar cell device.
Another object of the present invention is to provide an electron transport layer using an inorganic niobium oxide as an all-inorganic perovskite solar cell device.
It is another object of the present invention to provide a method of making an all inorganic perovskite battery device.
The invention aims at realizing the following technical scheme:
a hole transport layer of an all-inorganic perovskite solar cell device using inorganic nickel oxide comprises a substrate, an anode, an electron beam evaporation inorganic hole transport layer, an inorganic perovskite light absorption layer, an electron beam evaporation inorganic 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 and the like, and a metal, alloy or stainless steel film and the like.
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 preparation material of the inorganic perovskite light absorbing material is an inorganic perovskite light absorbing material of blended or non-blended halogen; 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 all-inorganic perovskite solar cell device comprises the following steps of:
and taking a substrate material with an anode layer, and then sequentially preparing an inorganic hole transport layer, an inorganic perovskite light absorption layer, an inorganic electron transport layer and a cathode on the anode layer to obtain the all-inorganic 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 inorganic hole transport layer nickel oxide of the device can be doped by double-source electron beam evaporation, and the optical and electrical characteristics of the hole transport layer can be changed by doping metal elements with different valence states or different concentrations;
(2) The device provided by the invention uses electron beam evaporation inorganic nickel oxide as a hole transport layer, and provides a feasible implementation scheme for preparing the inorganic perovskite solar cell device in a large area and at low cost;
(3) The inorganic electron transport layer of the device can realize a large-area uniform film by utilizing electron beam evaporation of niobium oxide, and provides a feasible implementation scheme for preparing an inorganic perovskite solar cell device in a large area and at low cost.
(4) The all-inorganic perovskite battery device can be uniformly prepared in a large area, and has high energy conversion efficiency, so that a feasible implementation scheme is provided for the application of perovskite batteries to commercialization.
Drawings
FIG. 1 is a stacked junction of an all-inorganic perovskite solar cell device of the inventionSchematic diagram of ITO/NiO in turn x /CsPbI 2 Br/Nb 2 O 5 /Ag；
Fig. 2 is a graph showing the current density-voltage characteristics of the all-inorganic perovskite solar cell device obtained in example 1;
fig. 3 is a graph showing the current density-voltage characteristics of the all-inorganic perovskite solar cell device obtained in example 2;
fig. 4 is a graph showing the current density-voltage characteristics of the all-inorganic perovskite solar cell device obtained as example 3;
fig. 5 is a graph of current density vs. voltage characteristics of the all-inorganic perovskite solar cell device obtained as example 4;
fig. 6 is a graph of current density vs. voltage characteristics of the all-inorganic perovskite solar cell device obtained as example 5;
fig. 7 is a graph showing the current density-voltage characteristics of the all-inorganic perovskite solar cell device obtained as example 6;
fig. 8 is a graph of current density vs. voltage characteristics of the all-inorganic perovskite solar cell device obtained as example 7;
fig. 9 is a graph of current density vs. voltage characteristics of the all-inorganic perovskite solar cell device obtained as example 8;
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 evaporating inorganic nickel oxide (NiO) on ITO substrate by electron beam evaporation at normal temperature x ) As a hole transport layer, the energy conversion efficiency of the all-inorganic perovskite battery device is optimized by adjusting the thickness of the inorganic hole transport layer to be 20-50 nanometers, and the evaporation is carried outThe nickel oxide substrate was transferred without any treatment into a glove box filled with high purity nitrogen gas without water and oxygen. In this glove box, csPbI was the component prepared by spin coating 2 The Br mixed inorganic perovskite photoactive layer is heated by a two-step heating method, firstly heated for 4 minutes at 40 ℃ on a heating table, then heated for 10 minutes at 160 ℃, then the substrate is put into an electron beam evaporation device, and when the vacuum degree in an evaporation cavity is less than 5 multiplied by 10 -4 And starting electron beam evaporation of the film after Pa. Sequentially evaporating an inorganic electron transport layer of niobium pentoxide (Nb) by using a specific mask 2 O 5 ) The energy conversion efficiency of the all-inorganic perovskite battery device can be optimized by adjusting the thickness of the electron transport layer to 50-70 nanometers, and a large-area uniform film can be obtained by using the electron beam evaporation equipment to prepare the inorganic hole transport layer and the electron transport layer, so that the battery device with large area and various 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 inorganic hole transport layer is controlled to be 30 nanometers, the thickness of the inorganic electron transport 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 all-inorganic perovskite solar cell device and the thickness of each layer are as follows: ITO glass substrate/NiO x (30 nm)/inorganic perovskite layer (300-400 nm)/Nb 2 O 5 (60 nm)/silver (100 nm).
The photoelectric performance test is carried out on the all-inorganic perovskite solar cell device obtained in the embodiment:
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.
The full inorganic perovskite solar cell device obtained by the implementation: ITO glass substrate/NiO x (30 nm)) Inorganic perovskite layer (300-400 nm)/Nb 2 O 5 The current density vs. voltage characteristic graph of (60 nm)/silver (100 nm) is shown in fig. 2.
The embodiment is a high-efficiency all-inorganic perovskite solar cell device. The hole transport layer and the electron transport layer both use inorganic metal oxide, and the photoactive layer uses all inorganic components, which is the first report that the hole transport layer and the electron transport layer are all inorganic perovskite battery device structures of inorganic metal oxide and show 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 evaporating inorganic nickel oxide (NiO) on ITO substrate by electron beam evaporation at normal temperature x ) As a hole transport layer, the evaporated nickel oxide substrate was annealed in air at 200 degrees celsius for 1 hour, and then transferred into a glove box filled with high purity nitrogen gas without water and without oxygen. In this glove box, csPbI was the component prepared by spin coating 2 The Br mixed inorganic perovskite photoactive layer is heated by a two-step heating method, firstly heated for 4 minutes at 40 ℃ on a heating table, then heated for 10 minutes at 160 ℃, then the substrate is put into an electron beam evaporation device, and when the vacuum degree in an evaporation cavity is less than 5 multiplied by 10 -4 And starting electron beam evaporation of the film after Pa. Sequentially evaporating an inorganic electron transport layer of niobium pentoxide (Nb) by using a specific mask 2 O 5 ) Because the inorganic hole transport layer and the electron transport layer can be uniformly and widely prepared by using the electron beam evaporation equipment, battery devices with large areas 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 inorganic hole transport layer is controlled to be 30 nanometers and inorganic 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 all-inorganic perovskite solar cell device and the thickness of each layer are as follows: ITO glass substrate/NiO x (30 nm)/inorganic perovskite layer (300-400 nm)/Nb 2 O 5 (60 nm)/silver (100 nm).
The photoelectric performance test is carried out on the all-inorganic perovskite solar cell device obtained in the embodiment:
the full inorganic perovskite solar cell device obtained by the implementation: ITO glass substrate/NiO x (30 nm)/inorganic perovskite layer (300-400 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 evaporating inorganic nickel oxide (NiO) on ITO substrate by electron beam evaporation at normal temperature x ) As a hole transport layer, the evaporated nickel oxide substrate was annealed in air at 300 degrees celsius for 1 hour, and then transferred into a glove box filled with high purity nitrogen gas without water and without oxygen. In this glove box, csPbI was the component prepared by spin coating 2 The Br mixed inorganic perovskite photoactive layer is heated by a two-step heating method, firstly heated for 4 minutes at 40 ℃ on a heating table, then heated for 10 minutes at 160 ℃, then the substrate is put into an electron beam evaporation device, and when the vacuum degree in an evaporation cavity is less than 5 multiplied by 10 -4 And starting electron beam evaporation of the film after Pa. Sequentially evaporating an inorganic electron transport layer of niobium pentoxide (Nb) by using a specific mask 2 O 5 ) Because the inorganic hole transport layer and the electron transport layer can be uniformly and widely prepared by using the electron beam evaporation equipment, battery devices with large areas and different shapes can be prepared by using different masks; vapor deposition by electron beamMetallic silver acts as the 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 inorganic hole transport layer is controlled to be 30 nanometers, the thickness of the inorganic electron transport 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 all-inorganic perovskite solar cell device and the thickness of each layer are as follows: ITO glass substrate/NiO x (30 nm)/inorganic perovskite layer (300-400 nm)/Nb 2 O 5 (60 nm)/silver (100 nm).
The photoelectric performance test is carried out on the all-inorganic perovskite solar cell device obtained in the embodiment:
the full inorganic perovskite solar cell device obtained by the implementation: ITO glass substrate/NiO x (30 nm)/inorganic perovskite layer (300-400 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 evaporating inorganic nickel oxide (NiO) on ITO substrate by electron beam evaporation at normal temperature x ) As the hole transport layer, electron beam devices having dual sources are used, so that different materials can be co-evaporated to achieve doping of the hole transport layer nickel oxide, while nickel oxide (NiO x ) And magnesium oxide (MgO), the doping concentration of which is 2.5% in this example, by adjusting the evaporation rate, the evaporated nickel oxide substrate is annealed in air at 300 ℃ for 1 hour, and then transferred into a glove box filled with high-purity nitrogen without water and oxygen. In this glove box, csPbI was the component prepared by spin coating 2 The Br mixed inorganic perovskite photoactive layer is heated by a two-step heating method, firstly heated for 4 minutes at 40 ℃ on a heating table, and then photographed at 160 DEG CHeating at vacuum for 10 min, loading the substrate into electron beam evaporation equipment, and vacuum degree in evaporation cavity is less than 5×10 -4 And starting electron beam evaporation of the film after Pa. Sequentially evaporating an inorganic electron transport layer of niobium pentoxide (Nb) by using a specific mask 2 O 5 ) Because the inorganic hole transport layer and the electron transport layer can be uniformly and widely prepared by using the electron beam evaporation equipment, battery devices with large areas 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 inorganic hole transport layer is controlled to be 30 nanometers, the thickness of the inorganic electron transport 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 all-inorganic perovskite solar cell device and the thickness of each layer are as follows: ITO glass substrate/Mg 0.025 Ni 0.975 O x (30 nm)/inorganic perovskite layer (300-400 nm)/Nb 2 O 5 (60 nm)/silver (100 nm).
The photoelectric performance test is carried out on the all-inorganic perovskite solar cell device obtained in the embodiment:
the full inorganic perovskite solar cell device obtained by the implementation: ITO glass substrate/Mg 0.025 Ni 0.975 O x (30 nm)/inorganic perovskite layer (300-400 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. 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 evaporating inorganic nickel oxide (NiO) on ITO substrate by electron beam evaporation at normal temperature x ) As hole transport layer, electron beam devices are used which have dual sources, so that different materials can be co-evaporated to achieve hole transportDoping of the layer of nickel oxide while evaporating nickel oxide (NiO x ) And magnesium oxide (MgO), the doping concentration of which is 3% in this example, by adjusting the evaporation rate, the evaporated nickel oxide substrate is annealed in air at 300 ℃ for 1 hour, and then transferred into a glove box filled with high-purity nitrogen without water and oxygen. In this glove box, csPbI was the component prepared by spin coating 2 The Br mixed inorganic perovskite photoactive layer is heated by a two-step heating method, firstly heated for 4 minutes at 40 ℃ on a heating table, then heated for 10 minutes at 160 ℃, then the substrate is put into an electron beam evaporation device, and when the vacuum degree in an evaporation cavity is less than 5 multiplied by 10 -4 And starting electron beam evaporation of the film after Pa. Sequentially evaporating an inorganic electron transport layer of niobium pentoxide (Nb) by using a specific mask 2 O 5 ) Because the inorganic hole transport layer and the electron transport layer can be uniformly and widely prepared by using the electron beam evaporation equipment, battery devices with large areas 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 inorganic hole transport layer is controlled to be 30 nanometers, the thickness of the inorganic electron transport 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 all-inorganic perovskite solar cell device and the thickness of each layer are as follows: ITO glass substrate/Mg 0.03 Ni 0.97 O x (30 nm)/inorganic perovskite layer (300-400 nm)/Nb 2 O 5 (60 nm)/silver (100 nm).
The photoelectric performance test is carried out on the all-inorganic perovskite solar cell device obtained in the embodiment:
the full inorganic perovskite solar cell device obtained by the implementation: ITO glass substrate/Mg 0.03 Ni 0.97 O x (30 nm)/inorganic perovskite layer (300-400 nm)/Nb 2 O 5 The current density vs. voltage characteristic graph of (60 nm)/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 evaporating inorganic nickel oxide (NiO) on ITO substrate by electron beam evaporation at normal temperature x ) As the hole transport layer, electron beam devices having dual sources are used, so that different materials can be co-evaporated to achieve doping of the hole transport layer nickel oxide, while nickel oxide (NiO x ) And magnesium oxide (MgO), the doping concentration of which is 3.5% in this example, by adjusting the evaporation rate, the evaporated nickel oxide substrate is annealed in air at 300 ℃ for 1 hour, and then transferred into a glove box filled with high-purity nitrogen without water and oxygen. In this glove box, csPbI was the component prepared by spin coating 2 The Br mixed inorganic perovskite photoactive layer is heated by a two-step heating method, firstly heated for 4 minutes at 40 ℃ on a heating table, then heated for 10 minutes at 160 ℃, then the substrate is put into an electron beam evaporation device, and when the vacuum degree in an evaporation cavity is less than 5 multiplied by 10 -4 And starting electron beam evaporation of the film after Pa. Sequentially evaporating an inorganic electron transport layer of niobium pentoxide (Nb) by using a specific mask 2 O 5 ) Because the inorganic hole transport layer and the electron transport layer can be uniformly and widely prepared by using the electron beam evaporation equipment, battery devices with large areas 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 inorganic hole transport layer is controlled to be 30 nanometers, the thickness of the inorganic electron transport 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 all-inorganic perovskite solar cell device and the thickness of each layer are as follows: ITO glass substrate/Mg 0.035 Ni 0.965 O x (30 nm)/inorganic perovskite layer (300-400 nm)/Nb 2 O 5 (60 nm)/silver (100 nm).
The photoelectric performance test is carried out on the all-inorganic perovskite solar cell device obtained in the embodiment:
the full inorganic perovskite solar cell device obtained by the implementation: ITO glass substrate/Mg 0.035 Ni 0.965 O x (30 nm)/inorganic perovskite layer (300-400 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 evaporating inorganic nickel oxide (NiO) on ITO substrate by electron beam evaporation at normal temperature x ) As hole transport layer, electron beam device having dual sources is used, so that doping of nickel oxide layer can be achieved by co-evaporation of different materials, while nickel oxide (NiO x ) And magnesium oxide (MgO), the doping concentration of which is 5% in this example, by adjusting the evaporation rate, the evaporated nickel oxide substrate is annealed in air at 300 ℃ for 1 hour and then transferred into a glove box filled with high-purity nitrogen without water and oxygen. In this glove box, csPbI was the component prepared by spin coating 2 The Br mixed inorganic perovskite photoactive layer is heated by a two-step heating method, firstly heated for 4 minutes at 40 ℃ on a heating table, then heated for 10 minutes at 160 ℃, then the substrate is put into an electron beam evaporation device, and when the vacuum degree in an evaporation cavity is less than 5 multiplied by 10 -4 And starting electron beam evaporation of the film after Pa. Sequentially evaporating an inorganic electron transport layer of niobium pentoxide (Nb) by using a specific mask 2 O 5 ) Because the inorganic hole transport layer and the electron transport layer can be uniformly and widely prepared by using the electron beam evaporation equipment, large-area and differently shaped electricity can be prepared by using different masksA cell 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 inorganic hole transport layer is controlled to be 30 nanometers, the thickness of the inorganic electron transport 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 all-inorganic perovskite solar cell device and the thickness of each layer are as follows: ITO glass substrate/Mg 0.05 Ni 0.95 O x (30 nm)/inorganic perovskite layer (300-400 nm)/Nb 2 O 5 (60 nm)/silver (100 nm).
The photoelectric performance test is carried out on the all-inorganic perovskite solar cell device obtained in the embodiment:
the full inorganic perovskite solar cell device obtained by the implementation: ITO glass substrate/Mg 0.05 Ni 0.95 O x (30 nm)/inorganic perovskite layer (300-400 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 evaporating inorganic nickel oxide (NiO) on ITO substrate by electron beam evaporation at normal temperature x ) As hole transport layer, electron beam device having dual sources is used, so that doping of nickel oxide layer can be achieved by co-evaporation of different materials, while nickel oxide (NiO x ) And magnesium oxide (MgO), the doping concentration of which is 9% in this example, by adjusting the evaporation rate, the evaporated nickel oxide substrate is annealed in air at 300 ℃ for 1 hour, and then transferred into a glove box filled with high-purity nitrogen without water and oxygen. In this glove box, csPbI was the component prepared by spin coating 2 The Br mixed inorganic perovskite photoactive layer is added in two stepsHeating by thermal method, heating at 40deg.C for 4 min on a heating table, heating at 160deg.C for 10 min, and loading the substrate into electron beam vapor deposition equipment, when vacuum degree in vapor deposition cavity is less than 5×10 -4 And starting electron beam evaporation of the film after Pa. Sequentially evaporating an inorganic electron transport layer of niobium pentoxide (Nb) by using a specific mask 2 O 5 ) Because the inorganic hole transport layer and the electron transport layer can be uniformly and widely prepared by using the electron beam evaporation equipment, battery devices with large areas 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 inorganic hole transport layer is controlled to be 30 nanometers, the thickness of the inorganic electron transport 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 all-inorganic perovskite solar cell device and the thickness of each layer are as follows: ITO glass substrate/Mg 0.09 Ni 0.91 O x (30 nm)/inorganic perovskite layer (300-400 nm)/Nb 2 O 5 (60 nm)/silver (100 nm).
The photoelectric performance test is carried out on the all-inorganic perovskite solar cell device obtained in the embodiment:
the full inorganic perovskite solar cell device obtained by the implementation: ITO glass substrate/Mg 0.09 Ni 0.91 O x (30 nm)/inorganic perovskite layer (300-400 nm)/Nb 2 O 5 The current density vs. voltage characteristic graph of (60 nm)/silver (100 nm) is shown in fig. 9.
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. The preparation method of the all-inorganic perovskite solar cell device is characterized by comprising the following steps of: the all-inorganic perovskite battery deviceThe structure of the component comprises a substrate, an anode ITO and an inorganic hole transport layer NiO which are sequentially laminated by electron beam evaporation x Inorganic perovskite photoactive layer, electron beam evaporation inorganic electron transport layer Nb 2 O 5 And electron beam evaporation cathode Ag.
2. An all-inorganic perovskite solar cell device and a preparation method thereof as claimed in claim 1, wherein: the substrate is a glass, quartz, sapphire, 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 all-inorganic perovskite solar cell device and a preparation method thereof as claimed in claim 1, 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 all-inorganic perovskite solar cell device and a preparation method thereof as claimed in claim 1, 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 all-inorganic perovskite solar cell device and a preparation method thereof as claimed in claim 1, wherein: the preparation material of the inorganic perovskite photoactive layer is perovskite light absorbing material with different components which are blended or not blended; the light absorbing layer is a single layer or multiple layers.
6. An all-inorganic perovskite solar cell device and a preparation method thereof according to claim 1, wherein the electron transport layer is not limited to a single layer, and comprises a multilayer state of an added hole and exciton blocking layer.
7. An all-inorganic perovskite solar cell device and a preparation method thereof as claimed in claim 1, 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 all-inorganic perovskite solar cell device and a method for manufacturing the same as defined in any one of claims 1 to 7, characterized by comprising the steps of: and taking a substrate material with an anode layer, and then sequentially preparing an inorganic hole transport layer, an inorganic perovskite photoactive layer, an inorganic electron transport layer and a cathode on the anode layer to obtain the all-inorganic perovskite battery device.
9. An all-inorganic perovskite solar cell device and a preparation method thereof as claimed 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311649107.4A CN117457762A (en) | 2023-12-04 | 2023-12-04 | All-inorganic perovskite solar cell and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311649107.4A CN117457762A (en) | 2023-12-04 | 2023-12-04 | All-inorganic perovskite solar cell and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117457762A true CN117457762A (en) | 2024-01-26 |
Family
ID=89580097
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311649107.4A Pending CN117457762A (en) | 2023-12-04 | 2023-12-04 | All-inorganic perovskite solar cell and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117457762A (en) |
-
2023
- 2023-12-04 CN CN202311649107.4A patent/CN117457762A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yang et al. | Recent progress in electron transport layers for efficient perovskite solar cells | |
| Dagar et al. | Efficient fully laser-patterned flexible perovskite modules and solar cells based on low-temperature solution-processed SnO 2/mesoporous-TiO 2 electron transport layers | |
| Hamed et al. | Mixed halide perovskite solar cells: progress and challenges | |
| ES2787890T3 (en) | Solar cell and manufacturing method for it | |
| WO2017073472A1 (en) | Highly reliable perovskite solar cell | |
| Jiang et al. | Nano-mesoporous TiO2 vacancies modification for halide perovskite solar cells | |
| CN106025085A (en) | Perovskite solar cell based on Spiro-OMeTAD/CuxS composite hole transport layer and preparation method thereof | |
| US20200251289A1 (en) | Perovskite photovoltaic device | |
| CN110112258A (en) | Perovskite solar battery and its manufacturing method | |
| Zong et al. | Highly stable hole-conductor-free perovskite solar cells based upon ammonium chloride and a carbon electrode | |
| CN109326715A (en) | A kind of p-i-n type perovskite solar battery and its manufacturing method | |
| Chen et al. | Efficient planar perovskite solar cells with low-temperature atomic layer deposited TiO2 electron transport layer and interfacial modifier | |
| CN111446369B (en) | Perovskite photovoltaic cell device and manufacturing method thereof | |
| CN109378390A (en) | A method of manufacture p-i-n type perovskite solar battery | |
| Liu et al. | Ni nanobelts induced enhancement of hole transport and collection for high efficiency and ambient stable mesoscopic perovskite solar cells | |
| CN111446368B (en) | Perovskite photovoltaic device and manufacturing method thereof | |
| CN114678472A (en) | FAPBI3Perovskite thin film and method for efficient perovskite solar cell by using same | |
| Li et al. | TiO2 nanorod arrays modified with SnO2-Sb2O3 nanoparticles and application in perovskite solar cell | |
| CN110690351A (en) | Method for manufacturing perovskite solar cell | |
| Fang et al. | Sputtered SnO2 as an interlayer for efficient semitransparent perovskite solar cells | |
| CN117457762A (en) | All-inorganic perovskite solar cell and preparation method thereof | |
| CN114420853A (en) | Method for modifying self-assembled hole transport layer by alkali metal acetate | |
| CN117560938A (en) | Amorphous nickel oxide for perovskite solar cell device | |
| CN111446367A (en) | Perovskite photovoltaic device and preparation method thereof | |
| CN117637882A (en) | Method for improving performance of perovskite solar cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |