CN107533924A - Gel, its forming method, photovoltaic device and forming method thereof - Google Patents
Gel, its forming method, photovoltaic device and forming method thereof Download PDFInfo
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- CN107533924A CN107533924A CN201680019545.4A CN201680019545A CN107533924A CN 107533924 A CN107533924 A CN 107533924A CN 201680019545 A CN201680019545 A CN 201680019545A CN 107533924 A CN107533924 A CN 107533924A
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- China
- Prior art keywords
- gel
- clay
- perovskite material
- halide perovskite
- perovskite
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- 238000000034 method Methods 0.000 title claims abstract description 62
- 239000004927 clay Substances 0.000 claims abstract description 78
- 239000000463 material Substances 0.000 claims abstract description 65
- 239000002105 nanoparticle Substances 0.000 claims abstract description 17
- -1 halide anion Chemical class 0.000 claims abstract description 9
- 150000004820 halides Chemical class 0.000 claims description 60
- 239000002243 precursor Substances 0.000 claims description 34
- 239000000758 substrate Substances 0.000 claims description 28
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 12
- 150000002892 organic cations Chemical class 0.000 claims description 11
- 125000000129 anionic group Chemical group 0.000 claims description 9
- 125000002091 cationic group Chemical group 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 abstract description 16
- 229910052751 metal Inorganic materials 0.000 abstract description 15
- 239000002184 metal Substances 0.000 abstract description 15
- 229910001410 inorganic ion Inorganic materials 0.000 abstract description 2
- LLWRXQXPJMPHLR-UHFFFAOYSA-N methylazanium;iodide Chemical compound [I-].[NH3+]C LLWRXQXPJMPHLR-UHFFFAOYSA-N 0.000 abstract description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 42
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- 229910044991 metal oxide Inorganic materials 0.000 description 12
- 150000004706 metal oxides Chemical class 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 239000010408 film Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 150000001450 anions Chemical class 0.000 description 7
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Inorganic materials [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 3
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 230000002045 lasting effect Effects 0.000 description 3
- 229910001507 metal halide Inorganic materials 0.000 description 3
- 150000005309 metal halides Chemical class 0.000 description 3
- 239000012802 nanoclay Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 241000370738 Chlorion Species 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- AJRXEXGVDMEBCT-UHFFFAOYSA-M [NH4+].[I-].C[N+]1=CC=CC=C1.[I-] Chemical compound [NH4+].[I-].C[N+]1=CC=CC=C1.[I-] AJRXEXGVDMEBCT-UHFFFAOYSA-M 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229940006460 bromide ion Drugs 0.000 description 2
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 229940006461 iodide ion Drugs 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- RQQRAHKHDFPBMC-UHFFFAOYSA-L lead(ii) iodide Chemical compound I[Pb]I RQQRAHKHDFPBMC-UHFFFAOYSA-L 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- ZSUXOVNWDZTCFN-UHFFFAOYSA-L tin(ii) bromide Chemical compound Br[Sn]Br ZSUXOVNWDZTCFN-UHFFFAOYSA-L 0.000 description 2
- JTDNNCYXCFHBGG-UHFFFAOYSA-L tin(ii) iodide Chemical compound I[Sn]I JTDNNCYXCFHBGG-UHFFFAOYSA-L 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- BFHRMYJJIMKAFV-UHFFFAOYSA-N 2-iodoguanidine Chemical compound NC(N)=NI BFHRMYJJIMKAFV-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 208000000058 Anaplasia Diseases 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910006111 GeCl2 Inorganic materials 0.000 description 1
- 229910006162 GeI2 Inorganic materials 0.000 description 1
- 229910021600 Germanium(II) bromide Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- LSHFIWNMHGCYRS-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[OH4+2] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[OH4+2] LSHFIWNMHGCYRS-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- XUEANQNEWYFMKT-UHFFFAOYSA-N azane;iodomethane Chemical compound N.IC XUEANQNEWYFMKT-UHFFFAOYSA-N 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- DUVPPTXIBVUIKL-UHFFFAOYSA-N dibromogermanium Chemical compound Br[Ge]Br DUVPPTXIBVUIKL-UHFFFAOYSA-N 0.000 description 1
- IAGYEMVJHPEPGE-UHFFFAOYSA-N diiodogermanium Chemical compound I[Ge]I IAGYEMVJHPEPGE-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- QHGIKMVOLGCZIP-UHFFFAOYSA-N germanium dichloride Chemical compound Cl[Ge]Cl QHGIKMVOLGCZIP-UHFFFAOYSA-N 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 229910001502 inorganic halide Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- CZMAIROVPAYCMU-UHFFFAOYSA-N lanthanum(3+) Chemical compound [La+3] CZMAIROVPAYCMU-UHFFFAOYSA-N 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910001419 rubidium ion Inorganic materials 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- WRTMQOHKMFDUKX-UHFFFAOYSA-N triiodide Chemical compound I[I-]I WRTMQOHKMFDUKX-UHFFFAOYSA-N 0.000 description 1
- 229940006158 triiodide ion Drugs 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
- C01B33/40—Clays
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
- H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Photovoltaic Devices (AREA)
Abstract
According to an embodiment of the invention, there is provided a kind of gel.The gel have include clay nanoparticle and formula AMX3Halide perovskite material component, wherein A can be organic or inorganic ion, and M can be metal cation or element, and X can be halide anion or element, such as lead iodide methylamine (CH3NH3Pbl2).According to other embodiments of the invention, a kind of method for forming gel, a kind of photovoltaic device and a kind of method for forming photovoltaic device are additionally provided.
Description
The cross reference of related application
This application claims on 2 6th, the 2015 Singapore patent application number 10201500940Q submitted benefit of priority,
Disclosure of which is fully incorporated herein by reference for all purposes.
Technical field
Various embodiments are related to a kind of gel, a kind of method for forming gel, a kind of photovoltaic device and a kind of formation photovoltaic
The method of device.
Background technology
Due to its good electrical and optical properties and the handlability of its solution, the lead halide calcium titanium of inorganic-organic
Ore deposit has obtained great concern as photovoltaic device material.It is reported that more than 17% high power conversion efficiency (η), its phase
When in the conversion efficiency that solar cell is commercialized made of silicon, CIGS (CIGS) or cadmium telluride (CdTe).
Generally, the MX that perovskite structure is connected by angle-angle6Octahedral three-dimensional network composition, wherein M (metal) cation
Positioned at octahedral center, and X (C1, Br, I) is located at the corner around M.The formula of inorganic-organic mixing perovskite is
AMX3, wherein A can be organic or inorganic ion, and M can be metal cation or element, and X can be halide anion or element.
Perovskite is as the sensitizer in the solar cell device based on perovskite.
In general, the medium-sized solar device of inorganic-organic hetero-junctions is generally by as the compact of hole blocking layer (bl.)
Metal oxide layer is (for example, titanium dioxide TiO2), as light anode nanocrystalline metal dioxide (for example, mesoporous
TiO2), as absorber of light organic metal halide perovskite (for example, CH3NH3PbI2), as hole mobile material
(HTM) p-type material (for example, loop coil) and noble metal film (for example, Au) composition as counterelectrode (CE).It is quick based on perovskite
The example of the solar cell device 180 of agent figure 1 illustrates.Solar cell device 180 includes substrate (for example, glass)
Stacked structure 181, fluorine-doped tin oxide (FTO) layer 182, titanium dioxide (TiO2) layer 184 is (for example, as hole blocking layer
(bl)), perovskite is (for example, CH3NH3PbI2Or CH3NH3Pbl3-xClx) layer 186, hole mobile material (HTM) (not shown) and
Noble metal film (for example, Au) 188 as counterelectrode (CE).Device architecture be FTO/bl/ metal oxide layers/perovskite/
HTM/ noble metal films.
As manufacturing technology, calcium titanium ore bed is deposited using single stage or double-step sediment method.Single stage deposition process
It is related to and perovskite sensitizer is directly spun on mesopore metal oxide layer (for example, TiO2) on.Double step process are related to metal
Halide layer is (for example, lead iodide (II), PbI2) spin coating, contain PbI2TiO2The infiltration of mesoporous layer, and be then impregnated in
CH3NH3In I (methylpyridinium iodide ammonium), this causes original position to be converted into CH3NH3PbI3(lead iodide methylamine).
However, for large area production, major obstacle is still suffered from.So far, using process described above,
The high efficiency perovskite solar cell shown is with small-scale (at most 0.2cm2) manufacture.Spin coating process is in research and development (R＆
D the technology in) extremely generally to use.However, when the materials'use in view of large area and coating, spin coating proceeding has reached it
The limit.The fast development in the field becomes solwution method solar cell maximally effective so far.Calcium titanium is based on to improve
The solar battery technology of ore deposit, it need to develop and use mass production process, such as print.
The content of the invention
According to an embodiment, there is provided a kind of gel.The gel has the group for including halide perovskite material and clay
Point.
According to an embodiment, there is provided a kind of method for forming gel.This method includes providing halide perovskite material,
Clay is provided, and halide perovskite material and clay are mixed to form gel.
According to an embodiment, there is provided a kind of photovoltaic device.The photovoltaic device includes the calcium titanium ore bed on substrate and substrate,
Wherein calcium titanium ore bed is made up of gel described herein, the gel is heat-treated to form calcium titanium ore bed.
According to an embodiment, there is provided a kind of method for forming photovoltaic device.This method includes will be described herein solidifying
Glue is put on substrate, and performs heat treatment to gel to form calcium titanium ore bed on substrate.
Brief description
In the accompanying drawings, identical reference is often referred to the same section in all different views.Accompanying drawing not necessarily press than
Example is drawn, but typically focuses on the principle of the explanation present invention.Hereinafter, various embodiments of the present invention refer to following accompanying drawings
It is described, wherein：
Fig. 1 shows the structure of the solar cell device based on perovskite sensitizer.
Fig. 2A is according to the various schematic plans for implementing to be illustrated gel.
Fig. 2 B are according to the various flow charts for implementing to be illustrated the method to form gel.
Fig. 2 C are according to the various schematic cross sectional views for implementing to be illustrated photovoltaic device.
Fig. 2 D are according to the various flow charts for implementing to be illustrated the method to form photovoltaic device.
Fig. 3 A are illustrated the method to form perovskite precursor solution according to various implementations.
Fig. 3 B are illustrated the method to form perovskite gel according to various implementations.
Fig. 4 A and Fig. 4 B respectively illustrate cationic clay and the structure of anionic clay.
Fig. 5 A show the photo of the inversion sample bottle of the perovskite gel including various embodiments.
Fig. 5 B and Fig. 5 C are respectively illustrated utilizes the perovskite gel precursors of various embodiments to apply before sintering and afterwards
The image for the perovskite film being distributed on glass substrate.
Fig. 6 A and Fig. 6 B show the representative current density vs. voltage (J-V) of the solar cell device of various embodiments,
With incident photon and the characteristic response curve figure of electric current conversion ratio (IPCE).
Fig. 7 shows the section Flied emission scanning of the perovskite device manufactured by the perovskite gel using various embodiments
Electronic Speculum (FESEM) image.
The method that Fig. 8 shows the perovskite gel-forming using various metal oxide nanoparticles.
Embodiment
Following detailed descriptions are related to accompanying drawing, and these accompanying drawings show that wherein the present invention can be put into practice specific by way of explanation
Details and embodiment.These embodiments fully describe in detail to enable those skilled in the art to put into practice this hair
It is bright.Using other embodiments and structure, the change of logical sum electricity can be made, without departing from the scope of the present invention.Various realities
Apply that example is not necessarily mutually exclusive, because some embodiments can be combined with one or more of the other embodiment to form new implementation
Example.
For other method or apparatus, the embodiment described in the context of one of method or apparatus approx has
Effect.Similarly, for device, the embodiment described in the context of method is approx effective, and vice versa.
Feature described in the context of embodiment can be accordingly same or similar suitable for other embodiments
Feature.Feature described in the context of embodiment can accordingly be applied to other embodiments, other even in these
It is not explicitly described in embodiment.In addition, for the addition described by the feature in the context of embodiment and/or combination and/
Or alternative form can accordingly suitable for other embodiments same or analogous feature.
In the context of various embodiments, as used in for feature or element article " one (a) ", " one (an) " and
" (the) " includes the reference to one or more of feature or element.
In the context of various embodiments, phrase " at least generally " may include " accurately " and reasonable difference.
In the context of various embodiments, the term " about (about) " or " about applied to numerical value
(approximately) exact value and reasonable difference " are included.
As used herein, term "and/or" includes any or all combination of one or more of related list items.
Various embodiments can relate to adding for large area technique (for example, silk-screen printing/coating) in photovoltaic device
(processable) perovskite gel preparation of work, for example, various embodiments, which can provide for large area, can print solar energy
Machinable perovskite gel preparation of volt.
Various embodiments can provide one of following or more persons：(i) as the material for can print perovskite photovoltaic device
The composite perofskite gel of material；(ii) formation of the perovskite gel with nanoclay particle (particle diameter ＜ 50nm) precursor；
(iii) low temperature perovskite gel-forming method；(iv) using nanoclay can silk-screen printing/can be coated with perovskite preparation；
Or the application of perovskite gel in photovoltaic of (v) based on nanoclay.
Fig. 2A is according to the various schematic plans for implementing to be illustrated gel 200.Gel 200 have include halide calcium
The component of titanium ore material 202 and clay 204.
In other words, it is possible to provide gel 200.Gel 200 can be made up of halide perovskite material 202 and clay 204, example
Such as, gel 200 may include the mixture of halide perovskite material 202 and clay 204.It means that gel 200 can be calcium
Titanium ore gel or composite perofskite gel.
Clay 204 may include that clay nanoparticle 204a, clay nanoparticle 204a have and be less than 50nm (that is, ＜
50nm), such as ＜ 40nm, ＜ 30nm, ＜ 20nm, ＜ 10nm size (for example, diameter), it is greater than 1nm and is less than 50nm,
Between e.g., from about 1nm and about 45nm, between about 1nm and about 30nm, between about 1nm and about 20nm, between about 1nm and about 10nm,
Between about 1nm and about 5nm, between about 10nm and about 45nm or the size between about 20nm and about 45nm.It is it means that each viscous
Native nano-particle 204a can have the size (for example, diameter) less than 50nm.Therefore, gel 200 can be glued based on nanometer
The perovskite gel of soil.
In various embodiments, the weight of clay 204 can be the weight of halide perovskite material 202 about 1% to
About 3%, between e.g., from about 1% and about 2%, or between about 2% and about 3%.It means that halide perovskite material 202 with
The weight ratio of clay 204 can be about 100:1 and about 100:Between 3.
In various embodiments, halide perovskite material 202 can be the form of halide perovskite precursor solution, its
Middle clay 204 is added in halide perovskite precursor solution.
In various embodiments, gel 200 may include solvent.The solvent may include but be not limited to dimethylformamide
(DMF), dimethyl sulfoxide (DMSO) (DMSO), gamma-butyrolacton (GBL), acetonitrile etc., or the mixture of the solvent of various volumes (ml) ratio
(such as DMF:DMSO：0.9:0.1、0.8:0.2、0.7:0.3、0.6:0.4、0.5:0.5, vice versa).
In various embodiments, clay 204 can include cationic clay or anionic clay or can be glued for cation
Soil or anionic clay.Cationic clay may include montmorillonite (montmorillonite), vermiculite, illite, kaolin etc..Based on hydrotalcite
Anionic clay may include, such as NO3 -、C1-、Br-、I-、SO4 2-、CO3 2-Deng anion.
In various embodiments, halide perovskite material 202 may include organic cation.Organic cation may include have
Machine ammonium cation.As non-limiting examples, organic cation may include CH3NH3 +、C2H5NH3+、CH(NH2)3、C(NH3)3、Cs、
RNH3, wherein R=(CH3(CH2) n), wherein n=1,2,3,4 etc., or the mixed-cation of different stoichiometric proportions.However, should
Work as understanding, can also use other organic cations.
In various embodiments, halide perovskite material 202 may include metal cation.Metal cation can correspond to
In the metal selected from the group being made up of lead (Pb), tin (Sn), cobalt (Co), nickel (Ni), zinc (Zn), gallium (Ga) and (germanium Ge).However,
It should be appreciated that it can also use other metal cations.
In various embodiments, halide perovskite material 202 may include to be selected from by F-(fluorine ion), I-(iodide ion),
Cl-(chlorion) and Br-One or more halide anions of the group of (bromide ion) composition.It means that halide perovskite material
Material 202 may include to be selected from one or more halogens by F, I, Cl and Br group formed.
In various embodiments, halide perovskite material 202 can be by formula AMX3Represent, wherein " A " represents organic sun
Ion, " M " represents metal and " X " represents halide or mixture of halides.
In the context of various embodiments, gel 200 can provide precursor (perovskite) material or component for manufacturing,
For example, photovoltaic device.
In the context of various embodiments, gel 200 can be used for the printable photovoltaic device of large area, for example, gel
200 can be machinable perovskite gel system of the large area technique (for example, silk-screen printing/coating) for photovoltaic device
Agent.
Fig. 2 B are according to the various flow charts 220 for implementing to be illustrated the method to form gel (for example, 200, Fig. 2A).
222, there is provided halide perovskite material.
224, there is provided clay.For example, the clay provided can be the form of clay powders.
226, halide perovskite material and clay are mixed to form gel.
In various embodiments, 224, there is provided be less than 50nm (that is, ＜ 50nm) clay nanoparticle comprising size
Clay.For example, the clay provided can be the form of clay nanoparticle powder (or nanoclay powder).
In various embodiments, halide perovskite material and clay may be provided in so that the weight of clay is halide
About the 1% to about 3% of the weight of perovskite material.
In various embodiments, one or more precursor materials in 222, halide perovskite material can be in a solvent
Mix to form halide perovskite material.By this way, halide perovskite material can be halide perovskite (precursor)
Solution.Then, 226, clay is added in halide perovskite solution for mix with halide perovskite material
Form gel.
One or more precursor materials can include metal halide, such as lead iodide (PbI2), lead bromide (PbBr2), chlorine
Change lead (PbCl2), one or more tin halides are (for example, SnI2、SnBr2、SnCl2), one or more germanium halide (for example,
GeI2、GeBr2、GeCl2) etc.；With organic or inorganic halide, for example, ammonium methyl iodide/bromide/chloride (CH3NH3I、
CH3NH3Br、CH3NH3C1), carbonamidine hydriodide/bromide/chloride (CH (NH2)2I、CH(NH2)2Br、CH(NH2)2C1)、
Caesium iodide/bromide/chloride (CsI, CsBr, CsCl), guanidine iodide/bromide/chloride (C (NH2)3I、C(NH2)3Br、C(NH2)3C1) etc..One or more precursor materials can provide in the form of a powder.
Solvent may include but be not limited to dimethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), gamma-butyrolacton (GBL),
Acetonitrile etc., or the mixture of the solvent of various volumes (ml) ratio, such as DMF:DMSO：0.9:0.1、0.8:0.2、0.7:0.3、
0.6:0.4、0.5:0.5, vice versa.
In various embodiments, 226, one or more precursor materials can be stirred to mix in a solvent in a solvent
Close one or more precursor materials.
In various embodiments, the mixture of one or more precursor materials and solvent can be subjected to heating.
Heating can be between about 40 DEG C and about 120 DEG C, between e.g., from about 40 DEG C and about 100 DEG C, about 40 DEG C and about 70
Between DEG C, between about 70 DEG C and about 120 DEG C, or carried out under predetermined temperature between about 60 DEG C and about 100 DEG C.As non-limiting
Example, heating can be carried out at about 70 DEG C -100 DEG C.
Heating can carry out about 0.5 hour to about 24 hours, for example, between about 0.5 hour and about 18 hours, about 0.5
Hour and between about 12 hours, about 0.5 hour and between about 2 hours, about 2 hours and between about 24 hours, about 12 hours peace treaties
Between 24 hours, or the predetermined lasting time between about 2 hours and about 12 hours.As non-limiting examples, heating can
Carry out about 12 hours.
In various embodiments, 226, halide perovskite material and clay are subjected to being ultrasonically treated with mixed halide calcium
Titanium ore material and clay.Supersound process can carry out about 0.5 hour to 12 hours, for example, between about 0.5 hour and about 8 hours, about
Between 0.5 hour and about 4 hours, about 0.5 hour and between about 1 hour, about 1 hour and between about 4 hours, or about 1 hour and
Predetermined lasting time between about 2 hours.As non-limiting examples, supersound process can be carried out about 1 hour.Being ultrasonically treated can be
Carry out at room temperature.
In various embodiments, 226, halide perovskite material and clay can be stirred before supersound process.
Whipping process can be carried out about 0.5 hour to about 24 hours, for example, between about 0.5 hour and about 18 hours, about 0.5 hour peace treaty
Between 12 hours, about 0.5 hour and between about 2 hours, about 2 hours and between about 24 hours, about 12 hours and about 24 hours it
Between, or the predetermined lasting time between about 2 hours and about 12 hours.As non-limiting examples, it is small that whipping process can carry out about 1
When.Whipping process can be carried out at room temperature.
In various embodiments, 224, it is possible to provide cationic clay or anionic clay.
In various embodiments, halide perovskite material can include organic cation.The organic cation can be with
Including organoammonium cations.As non-limiting example, organic cation can include CH3NH3 +、C2H5NH3+、CH(NH2)3、C
(NH3)3、Cs、RNH3, wherein R=(CH3(CH2) n), wherein n=1,2,3,4 etc., or different stoichiometric proportions mixing sun from
Son.It will be appreciated, however, that it can also use other organic cations.
In various embodiments, halide perovskite material can include metal cation.The metal cation can be with
Corresponding to the metal selected from the group being made up of lead (Pb), tin (Sn), cobalt (Co), nickel (Ni), zinc (Zn), gallium (Ga) and (germanium Ge).
It will be appreciated, however, that it can also use other metal cations.
In various embodiments, halide perovskite material can include being selected from by F-(fluorine ion), I-(iodide ion), Cl-
(chlorion) and Br-One or more halide anions of the group of (bromide ion) composition.
In various embodiments, halide perovskite material can be by formula AMX3Represent, wherein " A " represent it is organic sun from
Son, " M " represents metal and " X " represents halide or mixture of halides.
Fig. 2 C are according to the various schematic cross sectional views for implementing to be illustrated photovoltaic device 230.Photovoltaic device 230 includes substrate
232 and substrate 232 on calcium titanium ore bed 234, wherein calcium titanium ore bed 234 is by gel described herein (for example, 200, Fig. 2A)
It is made, gel is heat-treated to form calcium titanium ore bed 234.
In other words, photovoltaic device (for example, solar cell) 230 can be provided.Photovoltaic device 230 can include substrate
(or carrier) 230 and gel (for example, 200, Fig. 2A), the gel can put on substrate 232 and undergo heat treatment with
Calcium titanium ore bed 234 is formed on substrate 232.By this way, calcium titanium ore bed 234 can have the component at least generally with gel
Similar component.Gel can be put on substrate 232 by printing or being coated with.
In various embodiments, calcium titanium ore bed 234 can be used as absorber of light.
In various embodiments, heat treatment can between about 40 DEG C and about 120 DEG C, for example, about 40 DEG C and about 100 DEG C it
Between, between about 40 DEG C and about 70 DEG C, between about 70 DEG C and about 120 DEG C, or enter under predetermined temperature between about 60 DEG C and about 100 DEG C
OK.As non-limiting examples, heat treatment can be carried out at about 70 DEG C.
In various embodiments, heat treatment can carry out about 0.1 hour to about 24 hours, about 0.1 hour and about 10 hours it
Between, about 0.1 hour and between about 5 hours, about 0.1 hour and between about 1 hour, about 0.1 hour and between about 0.5 hour, about
Between 0.5 hour and about 10 hours, about 0.5 hour and between about 1 hour, or predetermined between about 10 hours and about 24 hours hold
The continuous time.As non-limiting examples, heat treatment can be carried out about 30 minutes (0.5 hour).
In various embodiments, heat treatment can include sintering process.
In the context of various embodiments, substrate 232 can include glass substrate.
In various embodiments, the thickness of calcium titanium ore bed 234 can be between about 100nm and about 2 μm (2000nm), example
Such as, between about 100nm and about 1000nm, between about 100nm and about 500nm, between about 100nm and about 200nm, about 500nm and
Between about 2000nm, between about 1000nm and about 2000nm, or between about 500nm and about 1000nm.
Photovoltaic device 230 can include a pair of electrodes, and wherein calcium titanium ore bed 234 can be folded in this between electrode.
Photovoltaic device 230 can include one or more of the other layer, for example, the metal oxide as hole blocking layer
Layer, hole mobile material etc..One or more of the other layer can be folded in this between electrode.
In various embodiments, calcium titanium ore bed 234 can include meso-porous titanium oxide (TiO2).As non-limiting examples,
Mesoporous TiO2Can use gel penetrate into or permeate, and be then heat-treated with formed there is mesoporous TiO2Calcium titanium ore bed
234。
In the context of various embodiments, photovoltaic device 230 can be perovskite photovoltaic device or perovskite solar energy
Battery component.
Fig. 2 D are according to the various flow charts 240 for implementing to be illustrated the method to form photovoltaic device.
242, gel as described herein is put on substrate.Substrate can be, for example, glass substrate.
244, gel is heat-treated to form calcium titanium ore bed on substrate.By this way, calcium titanium ore bed can be with
It is made up of gel, and there can be component at least generally similar to the component of gel.
In various embodiments, 242, by the way that gel to be printed to (for example, silk-screen printing) on substrate, gel can be applied
It is added on substrate.It will be appreciated, however, that other techniques can be used for applying gel to substrate, such as pass through coating.
In various embodiments, heat treatment can between about 40 DEG C and about 120 DEG C, for example, about 40 DEG C and about 100 DEG C it
Between, between about 40 DEG C and about 70 DEG C, between about 70 DEG C and about 120 DEG C, or enter under predetermined temperature between about 60 DEG C and about 100 DEG C
OK.As non-limiting examples, heat treatment can be carried out at about 70 DEG C.
In various embodiments, heat treatment can be carried out about 0.1 hour to about 24 hours, about 0.1 hour and about 10 hours
Between, about 0.1 hour and between about 5 hours, about 0.1 hour and between about 1 hour, about 0.1 hour and between about 0.5 hour,
Between about 0.5 hour and about 10 hours, about 0.5 hour and between about 1 hour, it is or predetermined between about 10 hours and about 24 hours
Duration.As non-limiting examples, heat treatment can be carried out about 30 minutes (0.5 hour).
In various embodiments, 244, heat treatment can include sintering process.
Although method as described above is shown and described as a series of step or event, but it is to be understood that such
Any order of step or event is not explained in a limiting sense.For example, some steps can occur in different order and/or with
Other steps or event outside those illustrated herein and/or described occur simultaneously.Furthermore, it is possible to shown in not requiring all
Step implements one or more aspects described herein or embodiment.In addition, one of step described herein or more
Person can one or more self contained functions and/or stage progress.
It should be appreciated that the description in the context of gel 200 and photovoltaic device 230 correspondingly can be applicable each other, and also
The method that the method for gel can be correspondingly applied to be formed and form photovoltaic device, vice versa.
Various embodiments can use the clay nanoparticle powder with suitable dimension (being, for example, less than 50nm (＜ 50nm))
To form perovskite gel.
In general, in various embodiments, gel-forming can be by (molten by clay powders and halide perovskite precursor
Liquid) mixed in dimethylformamide (DMF) to carry out.The ratio of clay and perovskite can be fixed to about 1-3% (for example,
Weight % or weight ratio), for example, about 10-30mg clay/ml (about 1g) perovskite (precursor) solution.Clay and perovskite
Mixture can be 1 hour with stir about, then be ultrasonically treated about 1 hour with formed with controllable-viscosity desired perovskite
Gel.The specific double-decker of clay and appropriate size (for example, being less than about 50nm) can be advantageous to gel-forming.
As the non-limiting examples of gel-forming, Fig. 3 A show the method to form (halide) perovskite precursor solution
350a and Fig. 3 B show to form the method 350b of (halide) perovskite gel, so as to elaborate perovskite+clay nano
The formation of particle.
With reference to figure 3A, in order to form perovskite precursor solution (MAPbX3), perovskite precursor powder is (for example, lead iodide PBI2
352 (weight is about 461mg) and methylpyridinium iodide ammonium CH3NH3I 354 (weight is about 158mg)) can be with, such as in bottle 359
About 1ml dimethylformamide (DMF) in mix.PBI2 352、CH3NH3I 354 and DMF 356 solution is mixed
Compound can at about 70 DEG C stir about 12 hours.Therefore, perovskite precursor solution 358 can be obtained.
With reference to figure 3B, using prepared perovskite precursor solution 358, the perovskite precursor solution of the about 1ml in DMF
358b can be prepared in sample bottle 359b.Can be by about 3wt% (for example, 30mg) clay powders 360 (particle diameter ＜ 50nm)
Added in perovskite precursor solution 358b.Then, can at room temperature, by perovskite precursor solution 358b and clay powders
360 solution or mixture stir about 1 hour, are then ultrasonically treated about 1 hour to be formed in sample bottle 359b at room temperature
The halide perovskite gel 362a of homogeneous, as shown in image 364a.The formation of perovskite gel can be by the way that sample bottle 359 be fallen
Put to test, and test whether gel 362a rests on top, can be observed in image 364b.
As described above, gel 362a components can include the perovskite solution (~42%)+3% of the about 1ml in DMF
The clay nanoparticle powder (particle diameter ＜ 50nm) of (for example, 30mg).
In various embodiments, as described herein, before the perovskite using clay nanoparticle and based on halide
Body, gel-forming are rational.In general, formula MAPbX3Perovskite, MA=organic cations, such as CH3NH3 +、
C2H5NH3+Deng, and X=halide or mixture of halides.In various embodiments, Pb (lead) can be by metal substitute, such as
Tin (Sn), cobalt (Co), nickel (Ni), zinc (Zn), gallium (Ga) etc..
Clay is the neutral material with layer structure, and it is mainly made up of phyllosilicate.For example, clay can include
The layer structure of tetrahedron and octahedra specification.
With reference to figure 4A, it illustrates the structure of cationic clay, cation (such as Li that can be embedded between argillic horizon+
(lithium ion), Na+(sodium ion), Ca+(calcium ion), Mg+(magnesium ion), Ba+(barium ions), La+(lanthanum ion), Ce+(cerium from
Son), Ru+(rubidium ion) etc.) it can be easy to be substituted by other cations.These other cations of alternative embedded cation take
Certainly in the electric charge of embedded cation, size and affinity.
Similarly, with reference to figure 4B, it illustrates the structure of anionic clay, in the commutative clay of anion (for example, neatly
Stone) in, anion can be embedded between argillic horizon, such as CO3 2-(carbonate), NO3 2-(three oxygen nitrate ion (.2-))、I3 -
(Triiodide ion) etc., wherein these charge balancing anions can be easy to swap (referring to Fig. 4 B) with various anion.It is based on
Electric charge, size and the affinity of the anion embedded, the replacement of existing anion is possible in anionic clay.
The clay (that is, cationic clay and anionic clay) of both types can be used as gel together with perovskite precursor
Forming agent.Clay with particular size (for example, being less than 50nm) is suitable to gel-forming.
Fig. 5 A show the photo of the inversion sample bottle 559 including perovskite gel 562.As being observed that, stop
Or perovskite (precursor) gel 562 being maintained at the top of inverted sample bottle 559 confirms the formation of gel.
Fig. 5 B and Fig. 5 C are respectively illustrated, and before and after about 30 minutes are sintered at about 70 DEG C, utilize various embodiments
Perovskite gel precursors (for example, 362a, Fig. 3 B；562, Fig. 5 A) it is coated on perovskite film 566a, 566b on glass substrate
Image.
In various embodiments, after formation of the gel, gel can be with, such as puts on substrate for preparing device
Part.Upon application, gel can be sintered about 30 minutes at about 70 DEG C, to prepare or obtain crystal film from the gel.Burn
The time of knot process and temperature can be with for example, between about 10 minutes and about 2 hours and in about 40 DEG C and about 120 DEG C of anaplasia
Change.
Solar cell device (or photovoltaic device) can be manufactured using the film of perovskite gel coating, wherein applying
After on device, film can then be sintered about 30 minutes at about 70 DEG C.The time of sintering process and temperature can be with examples
Such as, changed at 10 minutes between 2 hours and 40 DEG C -120 DEG C.Fig. 6 A and Fig. 6 B show the solar cell of various embodiments
The representative current density vs. voltage (J-V) of device, and incident photon and electric current conversion ratio (IPCE) characteristic response curve
Figure 67 0,678, show the characteristic J-V curves (song of the perovskite device manufactured by the perovskite gel using various embodiments
Line chart 670) and corresponding IPCE (curve map 678) under the conditions of being shined upon at 1.J-V curves in curve map 670 are in standard
Solar energy full sun test condition is (for example, 1000W/m2, AM 1.5) under under (curve 672) and dark condition (curve 674) obtain
.
Obtained J-V performance parameters are shown in table 1.As can be seen, the gel coating film based on various embodiments
Photovoltaic device can realize be up to about 9% conversion efficiency.
Table 1:Utilize the J-V characterisitic parameters of the photovoltaic device manufactured by perovskite gel
Wherein Jsc refers to short-circuit current density, and Voc refers to open-circuit voltage, and FF refers to fill factor.
Fig. 7 shows the section field hair of (gel) perovskite device manufactured by the perovskite gel using various embodiments
Penetrate ESEM (FESEM) image.Perovskite device includes having perovskite gel and TiO2(for example, mesoporous TiO2) layer 780
The structure of (sintering gel at about 70 DEG C about 30 minutes), layer 780 are interposed in the layer 782 and Fluorin doped of loop coil (spiro)
Between the layer 784 of tin oxide (FTO).Perovskite gel layer thicknesses can become according to the amount of gel precursors used in manufacturing step
Change.Device performance depends on the thickness of perovskite gel layer, wherein relatively thin film thickness provides more best performance.
Various metal oxide nanoparticles powder (such as, aluminum oxide (A1 are used in a certain method2O3), titanium oxide
(TiO2) and tin oxide (SnO2) etc.) to form perovskite gel.Fig. 8, which is shown, utilizes various metal oxide nanoparticles (examples
Such as A12O3、TiO2、SnO2) formed perovskite gel method 890.For example, metal oxide nanoparticles powder 894 can be
With different weight part (or weight ratio) (for example, 10mg metal oxide powder in DMF (solution 892, such as prepared according to Fig. 3 A)
Last 894/1g perovskite precursor solution 892 (equivalent to 1% weight ratio), 20mg/1g (2% weight ratio), 30mg/1g (2% weights
Measure ratio) etc.) and with perovskite precursor (for example, MAPbX3, X Cl, Br and I) and mixing, then it is ultrasonically treated about 1 hour and is coagulated with being formed
Glue.It is found, however, that metal oxide nanoparticles powder does not mix well with perovskite precursor.As that can be seen in Fig. 8
Observe, it can be clearly seen that perovskite precursor (top layers 896 in bottle 893) and metal oxide nanoparticles powder (bottom
Portion's layer 897) layering.Therefore, metal oxide nanoparticles are not the suitable alternatives items that gel is formed with perovskite precursor.
Various embodiments can provide the commercialized huge advantage of perovskite solar components.Various embodiments can be in order to
The mass production process of calcium titanium ore bed is deposited, this is the key fabrication steps of the solar cell of the type.
Although the present invention is specifically illustrated in and described by reference to specific embodiment, those skilled in the art should manage
Solution, can in the case of the spirit and scope of the present invention limited without departing from appended claims, to form and
Details makes various changes.Therefore, the scope of the present invention is represented by appended claims, and is fallen into it is intended that covering
All changes in the implication and scope of the equivalents of the claims.
Claims (20)
1. a kind of gel, the gel has the component for including halide perovskite material and clay.
2. gel according to claim 1, wherein the clay includes the clay nanoparticle that size is less than 50nm.
3. gel according to claim 1, wherein the weight of the clay is the weight of the halide perovskite material
About 1% to about 3%.
4. gel according to claim 1, wherein the gel includes solvent.
5. gel according to claim 1, wherein the clay includes cationic clay or anionic clay.
6. gel according to claim 1, wherein the halide perovskite material includes organic cation.
7. gel according to claim 1, wherein the halide perovskite material includes being selected from by F-、I-、C1-And Br-
One or more halide anions of the group of composition.
8. a kind of method for forming gel, including：
Halide perovskite material is provided；
Clay is provided；With
The halide perovskite material and the clay are mixed to form the gel.
9. according to the method for claim 8, wherein providing clay includes providing the clay nano for being less than 50nm comprising size
The clay of particle.
10. according to the method for claim 8, wherein the weight of the clay is the weight of the halide perovskite material
About 1% to about 3%.
11. according to the method for claim 8, wherein providing halide perovskite material includes mixing the halogen in a solvent
One or more precursor materials of compound perovskite material are to form the halide perovskite material.
12. according to the method for claim 11, include making mixing for one or more precursor materials and the solvent
Compound is subjected to a heating process.
13. according to the method for claim 8, wherein mixing the halide perovskite material and the clay includes making institute
State halide perovskite material and the clay is subjected to being ultrasonically treated.
14. according to the method for claim 13, wherein mixing the halide perovskite material and the clay also includes
The halide perovskite material and the clay are stirred before the supersound process.
15. according to the method for claim 8, wherein providing clay includes providing cationic clay or anionic clay.
16. according to the method for claim 8, wherein the halide perovskite material includes organic cation.
17. according to the method for claim 8, wherein the halide perovskite material includes being selected from by F-、I-、C1-And Br-
One or more halide anions of the group of composition.
18. a kind of photovoltaic device, including：
Substrate；With
Calcium titanium ore bed on the substrate, wherein the calcium titanium ore bed is made up of gel according to claim 1, by described in
Gel is heat-treated to form the calcium titanium ore bed.
19. a kind of method for forming photovoltaic device, methods described include：
Gel according to claim 1 is put on substrate；With
The gel is heat-treated to form calcium titanium ore bed on the substrate.
20. according to the method for claim 19, wherein applying gel includes the gel being printed on the substrate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SG10201500940Q | 2015-02-06 | ||
| SG10201500940Q | 2015-02-06 | ||
| PCT/SG2016/050060 WO2016126211A1 (en) | 2015-02-06 | 2016-02-04 | Gel, method of forming the same, photovoltaic device and method of forming the same |
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| Publication Number | Publication Date |
|---|---|
| CN107533924A true CN107533924A (en) | 2018-01-02 |
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| CN (1) | CN107533924A (en) |
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| CN115231618A (en) * | 2022-08-11 | 2022-10-25 | 桂林理工大学 | Method for preparing nano photovoltaic material and product prepared by method |
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| TR201608131A2 (en) * | 2016-06-15 | 2016-08-22 | Yenel Esma | NEW PEROVSKYTE SENSITIVE SOLAR CELL BUILT ON MEERSERSITE COMPONENTS |
| US10796901B2 (en) | 2016-09-29 | 2020-10-06 | Nanoco Technologies Ltd. | Shelling of halide perovskite nanoparticles for the prevention of anion exchange |
| TR201714384A2 (en) * | 2017-09-27 | 2018-07-23 | Yenel Esma | NEW PEROVSKYTE SENSITIVE SOLAR CELL CONTAINING MEERSERSITE COMPONENTS AS SKELETAL STRUCTURE IN INVERTED AND FLAT GEOMETRY |
| GB201808461D0 (en) * | 2018-05-23 | 2018-07-11 | Univ Manchester | Porous Perovskite films |
| CN110564402B (en) * | 2019-09-16 | 2022-11-29 | 哈尔滨工业大学 | Perovskite-like intermediate gel, preparation method thereof and method for preparing electronic skin by using perovskite-like intermediate gel |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1136014A (en) * | 1994-12-20 | 1996-11-20 | 丰顺矿业株式会社 | Method of activation of clay and activated clay |
| CN103346018A (en) * | 2013-06-26 | 2013-10-09 | 中国科学院青岛生物能源与过程研究所 | Iodide solar cell prepared through solid-liquid reactions and provided with perovskite structures |
-
2016
- 2016-02-04 CN CN201680019545.4A patent/CN107533924A/en active Pending
- 2016-02-04 WO PCT/SG2016/050060 patent/WO2016126211A1/en active Application Filing
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1136014A (en) * | 1994-12-20 | 1996-11-20 | 丰顺矿业株式会社 | Method of activation of clay and activated clay |
| CN103346018A (en) * | 2013-06-26 | 2013-10-09 | 中国科学院青岛生物能源与过程研究所 | Iodide solar cell prepared through solid-liquid reactions and provided with perovskite structures |
Non-Patent Citations (2)
| Title |
|---|
| LUCIANA C. SCHMIDT等: ""Nontemplate Synthesis of CH3NH3PbBr3 Perovskite Nanoparticles"", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| WENQIANG LIU等: ""Electrical characterization of TiO2/CH3NH3PbI3 heterojunction solar cells"", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115231618A (en) * | 2022-08-11 | 2022-10-25 | 桂林理工大学 | Method for preparing nano photovoltaic material and product prepared by method |
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| WO2016126211A1 (en) | 2016-08-11 |
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