CN111081816B - Perovskite nanocrystalline with alkali metal ion passivated surface defect and preparation and application thereof - Google Patents
Perovskite nanocrystalline with alkali metal ion passivated surface defect and preparation and application thereof Download PDFInfo
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- CN111081816B CN111081816B CN201911317216.XA CN201911317216A CN111081816B CN 111081816 B CN111081816 B CN 111081816B CN 201911317216 A CN201911317216 A CN 201911317216A CN 111081816 B CN111081816 B CN 111081816B
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- 229910001413 alkali metal ion Inorganic materials 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 57
- 230000007547 defect Effects 0.000 title claims abstract description 43
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- 238000000034 method Methods 0.000 claims abstract description 34
- 239000011259 mixed solution Substances 0.000 claims abstract description 31
- 150000001768 cations Chemical class 0.000 claims abstract description 27
- 229910001507 metal halide Inorganic materials 0.000 claims abstract description 27
- 150000005309 metal halides Chemical class 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 239000013110 organic ligand Substances 0.000 claims abstract description 22
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 8
- 150000002367 halogens Chemical class 0.000 claims abstract description 8
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- 239000006184 cosolvent Substances 0.000 claims abstract description 6
- 239000002159 nanocrystal Substances 0.000 claims description 211
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- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 90
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- 238000003756 stirring Methods 0.000 claims description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 23
- 238000000926 separation method Methods 0.000 claims description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- XRWMGCFJVKDVMD-UHFFFAOYSA-M didodecyl(dimethyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCC XRWMGCFJVKDVMD-UHFFFAOYSA-M 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 15
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 14
- QBVXKDJEZKEASM-UHFFFAOYSA-M tetraoctylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QBVXKDJEZKEASM-UHFFFAOYSA-M 0.000 claims description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 11
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 11
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 9
- 238000000746 purification Methods 0.000 claims description 9
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- WLCFKPHMRNPAFZ-UHFFFAOYSA-M didodecyl(dimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCC WLCFKPHMRNPAFZ-UHFFFAOYSA-M 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- -1 alkali metal salt Chemical class 0.000 claims description 5
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000011736 potassium bicarbonate Substances 0.000 claims description 4
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- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- HHRIHEMWQAOMIC-UHFFFAOYSA-M didodecyl(dimethyl)azanium;iodide Chemical compound [I-].CCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCC HHRIHEMWQAOMIC-UHFFFAOYSA-M 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- 239000002798 polar solvent Substances 0.000 claims description 3
- 235000011056 potassium acetate Nutrition 0.000 claims description 3
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 claims description 3
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- 235000010289 potassium nitrite Nutrition 0.000 claims description 3
- 239000004304 potassium nitrite Substances 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- 235000019252 potassium sulphite Nutrition 0.000 claims description 3
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- 239000001632 sodium acetate Substances 0.000 claims description 3
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- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 235000010288 sodium nitrite Nutrition 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- SNNIPOQLGBPXPS-UHFFFAOYSA-M tetraoctylazanium;chloride Chemical compound [Cl-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC SNNIPOQLGBPXPS-UHFFFAOYSA-M 0.000 claims description 3
- KGPZZJZTFHCXNK-UHFFFAOYSA-M tetraoctylazanium;iodide Chemical compound [I-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC KGPZZJZTFHCXNK-UHFFFAOYSA-M 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
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- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
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- HMJCXVAXZCDOLV-UHFFFAOYSA-M potassium;hydroxy-oxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].OS([O-])(=O)=S HMJCXVAXZCDOLV-UHFFFAOYSA-M 0.000 claims 1
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- 239000000758 substrate Substances 0.000 description 6
- FJDQFPXHSGXQBY-UHFFFAOYSA-L Cs2CO3 Substances [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 5
- 229910000024 caesium carbonate Inorganic materials 0.000 description 5
- 239000002096 quantum dot Substances 0.000 description 5
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- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 description 2
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- CHYBTAZWINMGHA-UHFFFAOYSA-N tetraoctylazanium Chemical compound CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC CHYBTAZWINMGHA-UHFFFAOYSA-N 0.000 description 2
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
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- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
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- 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
- H01L31/036—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 their crystalline structure or particular orientation of the crystalline planes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/005—Processes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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Abstract
The invention belongs to the field of photoelectric materials, and discloses a perovskite nanocrystalline with surface defects passivated by alkali metal ions, and preparation and application thereof, wherein the preparation method comprises the steps of mixing a ligand solution containing alkali metal ions with a ligand solution of nanocrystalline A-site cations, and adding the mixture into a poor solution of divalent metal halide taking quaternary ammonium salt as a cosolvent to obtain a mixed solution; after the perovskite is formed, adding a poor solution of an organic ligand to obtain a crude perovskite nanocrystalline solution, and purifying to obtain the nanocrystalline colloid with passivated surface defects. The preparation method is improved, and in the process of preparing the nanocrystalline by adopting a ligand-assisted reprecipitation method, alkali metal ions such as potassium ions and sodium ions are introduced and serve as metal ion ligands to replace part of surface active organic ligands, so that the generation of halogen vacancies in the nanocrystalline can be inhibited, the surface defects of the perovskite nanocrystalline are effectively passivated, and the luminous efficiency and the conductivity of the material are effectively improved.
Description
Technical Field
The invention belongs to the field of photoelectric materials, and particularly relates to a perovskite nanocrystal with surface defects passivated by alkali metal ions, and preparation and application thereof.
Background
Perovskite light emitting diodes (PeLEDs) are a strong choice for next generation solid state lighting and high definition displays due to their high photoluminescence quantum yield (PLQY), tunable emission wavelength in the visible spectral band, and narrow emission linewidth. Over the last few years, red and green emitting pelds have been developed very rapidly, with corresponding external quantum efficiencies of over 20%. However, research on blue-emitting pelds has progressed far less than red and green light, mainly because it is difficult to obtain high-quality blue-emitting perovskite luminescent materials.
With all-inorganic cesium lead bromine chloride (CsPb (Br/Cl)3) Perovskite Nanocrystals (NCs) are exemplified as blue light emitting materials, which have high stability and narrow emission peaks, and are one of the commonly used blue light emitting materials. However, the introduction of chlorine element can cause the surface of the perovskite nanocrystal to have a plurality of halogen vacancies, and defect energy levels are generated in a conduction band and a valence band, so that an inherent non-radiative recombination channel is caused, and the PLQY is further reduced. Thus, to obtain high quality blue-emitting perovskite NCs, the passivation of surface defects by ligands appears to be of paramount importance. However, the ligands currently used are generally long-chain organic ligands, which, although they passivate NCs surface defects well and impart good stability to NCs inks, these insulating organic components severely impede charge transport in NCs Light Emitting Diodes (LEDs), thereby affecting the performance of the LEDs. In addition, these long-chain organic ligands are generally highly dynamic and unstable, and are highly susceptible to detachment from the surface during purification of NCs, resulting in the generation of defect states. Therefore, it is important to find a ligand that can simultaneously achieve the stability and electrical transport properties of NCs.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention aims to provide a perovskite nanocrystal with alkali metal ion passivated surface defects and a preparation method and an application thereof, wherein the preparation method is improved, alkali metal ions such as potassium ions and sodium ions are introduced into a perovskite precursor liquid in the process of preparing the nanocrystal by adopting a ligand-assisted reprecipitation method, the alkali metal ions such as potassium ions and sodium ions can be used as metal ion ligands and replace part of surface active organic ligands, the generation of halogen vacancies in the nanocrystal can be inhibited, the effective passivation of the perovskite nanocrystal surface defects is realized, the luminous efficiency and the conductivity of the material are effectively improved, and the perovskite nanocrystal with high-efficiency stability and charge transmission characteristics is obtained; the perovskite nanocrystalline prepared by the method provided by the invention is applied to an electroluminescent diode or a solar cell, and the efficiency of the device is greatly improved. Moreover, the method has the following advantages: 1. the operation is simple, and high temperature and protective gas are not needed; 2. the cost is low, and the alkali metal salt is a common industrial raw material and has low price.
To achieve the above object, according to one aspect of the present invention, there is provided a method for preparing alkali metal ion-passivated perovskite nanocrystal surface defects, characterized in that the method is performed by Li+、Na+、K+、Rb+One or more of the alkali metal ions are used as alkali metal ions, a ligand solution containing the alkali metal ions is mixed with a ligand solution of a monovalent cation at the A site of the perovskite nanocrystal, and a stirred poor solution of a divalent metal halide taking quaternary ammonium salt as a cosolvent is added within 2s to obtain a mixed solution; after the perovskite is formed, adding a poor solution of an organic ligand into the mixed solution within a certain time to obtain a crude perovskite nanocrystal solution; then, purifying the crude perovskite nanocrystal solution to obtain a perovskite nanocrystal colloidal solution with alkali metal ion passivated surface defects;
wherein, the halogen element in the divalent metal halide is one or more of F, Cl, Br and I; for the ligand solution containing the alkali metal ions, the alkali metal ions are derived from corresponding alkali metal inorganic salts.
In a further preferred embodiment of the present invention, the alkali metal ion is Na+、K+Wherein, in the step (A),
when the alkali metal ion is Na+When the alkali metal salt is sodium carbonate, sodium bicarbonate, sodium acetate, sodium sulfite, sodium bisulfite, sodium thiosulfate, sodium sulfate, sodium nitrate, and sodium nitrite;
when the alkali metal ion is K+When the corresponding alkali metal inorganic salt is potassium carbonate or hydrogen carbonatePotassium, potassium acetate, potassium sulfite, potassium bisulfite, potassium thiosulfate, potassium sulfate, potassium nitrate, potassium nitrite;
the perovskite nanocrystal A site univalent cation is selected from: cnH2n+1NH3 +、CH5N2 +、Cs+Wherein n is any positive integer; these a-site monovalent cations are derived from the corresponding carbonate; preferably, the perovskite nanocrystal a-site monovalent cation is selected from the group consisting of: CH (CH)3NH3 +、C2H5NH3 +、CH5N2 +、Cs+One or more of;
the divalent metal in the divalent metal halide is selected from Pb2+、Sn2+、Bi2+、Cu2+；
Preferably, the A-site univalent cation of the perovskite nanocrystal is Cs+The divalent metal in the divalent metal halide is Pb2+。
In a further preferred aspect of the present invention, the ligand solution containing the alkali metal ion is a solution containing the alkali metal ion and the perovskite nanocrystal a-site monovalent cation in a molar ratio of (0.001 to 0.5): 1, or a mixture of alkali metal ions and divalent metal ions contained in the divalent metal halide in a molar ratio of (0.001-0.16): 1 in admixture with a ligand solution of said monovalent cation in position a;
preferably, the ligand solution containing the alkali metal ion is a solution containing the alkali metal ion and the monovalent cation at the A position in a molar ratio of (0.001 to 0.33): 1, or a mixture of alkali metal ions and divalent metal ions contained in the divalent metal halide in a molar ratio of (0.001-0.08): 1 in admixture with a ligand solution of said monovalent cation in position a;
the certain time is not more than 60s, preferably 30 s;
the stirring speed of the stirred poor solution of the divalent metal halide taking the quaternary ammonium salt as the dissolution promoter is 500-3000r/min, preferably 1300-1700 r/min.
In a further preferred embodiment of the present invention, the ligand solution containing the alkali metal ion and the ligand solution containing the monovalent cation at the a-position are both fatty acid solutions selected from the group consisting of: one or more of caproic acid, caprylic acid (OTAc), oleic acid; preferably, the ligand solution is octanoic acid (OTAc);
in the poor solution of the organic ligand, the organic ligand is selected from one or more of didodecyl dimethyl ammonium iodide (DDAB), Didodecyl Dimethyl Ammonium Bromide (DDAB) and Didodecyl Dimethyl Ammonium Chloride (DDAC);
the quaternary ammonium salt is selected from one or more of tetraoctyl ammonium iodide, tetraoctyl ammonium bromide and tetraoctyl ammonium chloride;
preferably, the poor solution of the divalent metal halide using the quaternary ammonium salt as the dissolution promoter is the same as the poor solution of the organic ligand, and is selected from one or more of chloroform, dimethylacetamide, dimethylformamide, N-methylpyrrolidone, dioxane, carbon tetrachloride, toluene, xylene, propionitrile, acetone, ethyl acetate, alcohols and ethers; preferably, the poor solution is toluene or chloroform.
As a further preferred aspect of the present invention, the purification treatment specifically comprises the steps of:
(S1) mixing the crude perovskite nanocrystal solution with a first medium solvent, carrying out first centrifugal separation treatment to obtain a precipitate, and then adding a first dispersion liquid into the precipitate to obtain an intermediate solution;
(S2) mixing the intermediate solution obtained in the step (S1) with a second medium solvent, carrying out second centrifugal separation treatment to obtain a precipitate, adding a second dispersion liquid into the precipitate, carrying out third centrifugal separation treatment at a rotating speed of 3000-6000r/min for 3-8min, and collecting the stably dispersed supernatant to obtain the colloidal solution of the alkali metal ion passivated surface defect perovskite nanocrystal.
In a further preferred embodiment of the present invention, in the steps (S1) and (S2), the first centrifugal separation process and the second centrifugal separation process are both high-speed centrifugal separation, the rotation speed of the centrifugation satisfies 5000-30000r/min, and the centrifugation time satisfies 3-8 min; preferably, the rotating speed of the centrifugation meets 11000-13000r/min, and the centrifugation time is 5-8 min;
in the step (S2), the rotation speed of the third centrifugal separation treatment is preferably 4000-;
in the steps (S1) and (S2), the first medium solvent and the second medium solvent are both aprotic polar solvents, and each is independently selected from: ethyl acetate, methyl acetate, butanol and acetonitrile, dimethylformamide, acetone, acetonitrile; preferably, the first medium solvent and the second medium solvent are both ethyl acetate or acetonitrile;
in the step (S1), the volume ratio of the first medium solvent to the crude perovskite nanocrystal liquid is (1-5):1 or 1 (1-5); preferably, the volume ratio of the first medium solvent to the crude perovskite nanocrystal liquid is 2:1 or 1: 2;
in the steps (S1) and (S2), the first dispersion and the second dispersion are both aliphatic hydrocarbons selected from one or more of toluene, octane, and hexane;
in the step (S2), the collecting of the stably dispersed supernatant is performed by filtration separation.
According to another aspect of the present invention, there is provided a perovskite nanocrystal having surface defects passivated with alkali metal ions obtained by the above preparation method.
According to another aspect of the invention, the invention provides application of the alkali metal ion passivated surface defect perovskite nano crystal obtained by the preparation method as a light absorption layer in a solar cell or as a light emitting layer in an electroluminescent device.
According to still another aspect of the present invention, there is provided a solar cell characterized in that the light absorbing layer material of the device comprises perovskite nanocrystals having surface defects passivated with alkali metal ions obtained by the above-mentioned preparation method.
According to a final aspect of the present invention, there is provided an electroluminescent device, characterized in that the active layer material of the device comprises perovskite nanocrystals having alkali metal ions to passivate surface defects, obtained by the above-described preparation method.
In general, compared with the prior art, the above technical solution contemplated by the present invention can achieve the following beneficial effects:
(1) the invention provides a preparation method of a perovskite nanocrystalline with surface defects passivated by alkali metal ions. The introduced alkali metal ions such as sodium ions, potassium ions and the like can form bonds with halogen on the surface of the nanocrystal in the form of ionic bond formation, so that a metal ligand which is not easy to fall off is formed, the surface defects of the nanocrystal are effectively passivated, and meanwhile, the nanocrystal is endowed with high stability. Moreover, the addition of alkali metal ions such as sodium ions, potassium ions and the like reduces the density of organic ligands on the surface of the nanocrystal, and greatly improves the electrical transmission performance of the nanocrystal.
(2) The preparation method of the alkali metal ion passivated surface defect perovskite nanocrystalline adopted by the invention is a room temperature method, and compared with the traditional hot injection method, the method does not need high temperature and protective gas, and has simple operation and high yield. In addition, the added alkali metal salt is a common industrial raw material, and the cost is low.
(3) The perovskite nanocrystalline with alkali metal ions for passivating surface defects, which is obtained by the preparation method, can be particularly applied to solar cells and electroluminescent devices, and by taking the correspondingly obtained perovskite electroluminescent devices as an example, after the alkali metal ions such as sodium ions and potassium ions are introduced, the density of organic ligands on the surface of the perovskite nanocrystalline is reduced, the luminous life is prolonged, the fluorescence quantum yield is improved, the stability is enhanced, and the brightness and the external quantum efficiency of the device are obviously improved.
(4) The surface defects provided by the invention are passivatedThe preparation method of the metal halide perovskite nanocrystalline has certain universality and is suitable for passivating the surface defects of various perovskite nanocrystalline which can be synthesized by adopting a ligand-assisted reprecipitation method. Such as CsPbBr3 NCs、CsPb(Br/Cl)3 NCs、CsPbCl3 NCs、FAPbCl3NCs, and the like.
Drawings
FIG. 1 is CsPb (Br/Cl) synthesized in example 1 and comparative example 13Diffraction angle-intensity diagram of NCs.
FIG. 2 is CsPb (Br/Cl) synthesized in example 1 and comparative example 13Transmission electron micrographs of NCs; wherein (a) in fig. 2 corresponds to comparative example 1, and (b) in fig. 2 corresponds to example 1.
FIG. 3 is CsPb (Br/Cl) synthesized in example 1 and comparative example 13Ultraviolet absorption spectrum and photoluminescence spectrum of NCs n-hexane solution.
FIG. 4 is CsPb (Br/Cl) synthesized in example 1 and comparative example 13Fourier infrared transform spectrograms of NCs.
FIG. 5 is CsPb (Br/Cl) synthesized in example 1 and comparative example 13Time resolved spectra of NCs.
FIG. 6 is CsPb (Br/Cl) provided in example 1 and comparative example 13Atomic force microscopy of NCs spin-coated on ITO/PEDOT: PSS/ploy-TPD substrates; in fig. 6, (a) corresponds to comparative example 1, and (b) corresponds to example 1.
FIG. 7 is CsPb (Br/Cl) provided in example 1 and comparative example 13When NCs is used as a light emitting layer of a light emitting diode, the external quantum efficiency-brightness curve of the device is compared with that of the device.
Fig. 8 is a comparison of solutions after 24 hours of synthesis of perovskite quantum dots doped with different concentrations of potassium ions (where x is the molar ratio of potassium ions to lead ions).
Fig. 9 is a graph of the fluorescent quantum dot yield of perovskite quantum dot solutions at different doping amounts of potassium ions (where the percentage shown on the horizontal axis is the molar ratio of potassium ions to lead ions).
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Generally, the preparation method of the alkali metal ion passivated surface defect perovskite nanocrystal comprises the following steps: mixing a ligand solution of alkali metal ions and a ligand solution of univalent cations, quickly (within 2s) adding the mixed solution into a poor solution of divalent metal halide taking quaternary ammonium salt as a dissolving promoter, after perovskite is formed, adding the poor solution of organic ligands into the mixed solution to obtain a crude perovskite nanocrystal solution, and purifying the crude perovskite nanocrystal solution to obtain a colloidal solution of the perovskite nanocrystal with alkali metal ion passivation surface defects;
wherein, the halogen element in the halide is one or more of F, Cl, Br and I;
the alkali metal ion is selected from Li+、Na+、K+、Rb+One or more of them are derived from alkali metal inorganic salts.
In some embodiments, when the alkali metal ion is selected from Na+Inorganic salts corresponding to alkali metal ions include sodium carbonate, sodium bicarbonate, sodium acetate, sodium sulfite, sodium bisulfite, sodium thiosulfate, sodium sulfate, sodium nitrate, and sodium nitrite;
in some embodiments, when the alkali metal ion is selected from K+The inorganic salt corresponding to the alkali metal ions comprises potassium carbonate, potassium bicarbonate, potassium acetate, potassium sulfite, potassium bisulfite, potassium thiosulfate, potassium sulfate, potassium nitrate and potassium nitrite.
In some embodiments, the monovalent cation in the a position is selected from: cnH2n+1NH3 +(n is a positive integer such as 1,2,3 …), CH5N2 +、Cs+One or more of;
in some embodiments, the monovalent cation in the a position is selected from: CH (CH)3NH3 +(MA+Methyl ammonium), C2H5NH3 +(EA+Ethylammonium), CH5N2 +(FA+Formamidine), Cs+One or more of (a).
In some embodiments, the divalent metal is selected from Pb2+、Sn2+、Bi2+、Cu2+。
In some embodiments, the molar ratio of alkali metal ion to monovalent cation in the a-position is (0.001-0.5): 1.
in some embodiments, the molar ratio of alkali metal ion to monovalent cation in the a-position is (0.001-0.33): 1.
in some embodiments, the ligand solution is a fatty acid solution selected from the group consisting of: one or more of caproic acid, caprylic acid (OTAc), oleic acid.
In some embodiments, the solubilizing agent is a quaternary ammonium salt selected from one or more of tetraoctylammonium iodide, tetraoctylammonium bromide, tetraoctylammonium chloride;
in some embodiments, the poor solution is selected from one or more of chloroform, dimethylacetamide, dimethylformamide, N-methylpyrrolidone, dioxane, carbon tetrachloride, toluene, xylene, propionitrile, acetone, ethyl acetate, alcohols, ethers.
In some embodiments, the organic ligand is one or more of didodecyldimethylammonium iodide, didodecyldimethylammonium bromide, didodecyldimethylammonium chloride.
In some embodiments, the poor solution of the divalent metal halide with the quaternary ammonium salt as the cosolvent is added for a certain time, and the certain time is 0-60 s;
in some embodiments, the certain time is 30 s.
In some embodiments, the poor solution of divalent metal halide with quaternary ammonium salt as the dissolution promoter is stirred vigorously at a stirring speed of 500-3000 r/min.
In some embodiments, the poor solution stirring speed of the divalent metal halide using the quaternary ammonium salt as the cosolvent is 1300-1700 r/min.
In some embodiments, the poor solution stirring speed of the divalent metal halide with the quaternary ammonium salt as the cosolvent is 1500 r/min.
In some embodiments, the perovskite nanocrystal crude liquid purification treatment comprises the following steps: (1) mixing the perovskite nanocrystalline crude liquid with a first medium solvent, centrifuging at a high speed to obtain a precipitate, and adding a first dispersion liquid; (2) and (2) mixing the solution obtained in the step (1) with a second medium solvent, performing high-speed centrifugation again to obtain a precipitate, adding a second dispersion solution, performing low-speed centrifugation again, and collecting a stably dispersed supernatant to obtain the colloidal solution of the perovskite nanocrystal.
In some embodiments, in step (1) and/or step (2) of the purification process, the centrifugation speed for high-speed centrifugation is 5000-.
In some embodiments, in the step (1) and the step (2) of the purification treatment, the centrifugation rotation speed for high-speed centrifugation is 11000-13000r/min and the centrifugation time is 5-8 min.
In some embodiments, in the step (2) of the purification treatment, the centrifugation speed for the low-speed centrifugation is 3000-6000r/min, and the centrifugation time is 3-8 min.
In some embodiments, in the step (2) of the purification treatment, the low-speed centrifugation is performed at 4000-.
In some embodiments, the obtaining of the supernatant in step (2) of the purification treatment is achieved by filtration separation. For example, the stably dispersed supernatant is filtered through a filter to obtain a colloidal solution of the metal halide perovskite nanocrystals.
In some embodiments, the medium solvent is an aprotic polar solvent including ethyl acetate, methyl acetate, butanol and acetonitrile, dimethylformamide, acetone, acetonitrile, and the like.
In some embodiments, the medium solvent is ethyl acetate or acetonitrile.
In some embodiments, the ratio of the volume of the medium solvent to the volume of the crude liquid is (1-5):1 or 1 (1-5).
In some embodiments, the volume of the medium solvent to crude liquid volume ratio is 2:1 or 1: 2.
In some embodiments, the first and second dispersions are both aliphatic hydrocarbons selected from one or more of toluene, octane, and hexane.
The following are specific examples and corresponding proportions:
example 1
The embodiment provides a preparation method of a perovskite nanocrystal with potassium ion passivated surface defects, and the nanocrystal prepared by the method is applied to a light-emitting diode, and the preparation method specifically comprises the following steps:
1、CsPb(Br/Cl)3preparation of NCs solution: accurately weighing PbBr by electronic balance2(0.125mmol，0.046g)、PbCl2(0.125mmol, 0.035g) and tetra-n-octylammonium bromide (0.750mmol, 0.410mg), 5mL of toluene was added as a solvent, and the mixture was stirred on a magnetic stirrer until the starting material was sufficiently dissolved. Respectively preparing Cs with the concentration of 0.1mol/L2CO3With 0.1mol/L concentration of K2CO3Octanoic acid solution of (1). Pipette 300. mu.L of Cs with pipette2CO3Octanoic acid solution of 50. mu. L K2CO3The octanoic acid solution of (a) and 305. mu.L of the octanoic acid solution were thoroughly mixed in a bullet plastic tube. The mixed solution in the bullet plastic tube is quickly dripped into the toluene mixed solution which is vigorously stirred at one time, and blue-light perovskite NCs are formed immediately. After 30s, 1.66mL of a 12mg/mL DDAB toluene solution was added to the vigorously stirred NCs solution, and stirring was stopped after 2 minutes to obtain a crude NCs solution. To the crude solution was added 14mL of ethyl acetate, followed by centrifugation at 13000 r.p.m. for 5 minutes, the centrifuged supernatant was discarded, and the precipitate was redispersed in 2mL of toluene. Subsequently, 4mL of ethyl acetate was added, the mixture was centrifuged at 11000r.p.m for 5 minutes, the supernatant after centrifugation was discarded, and the precipitate was dispersed in 2.4mL of n-hexane. To obtain a uniform particle sizeFirst, the NCs solution dispersed in n-hexane was subjected to low-speed centrifugation at 4000 r.p.m., and after centrifugation, the supernatant was taken out by a syringe and filtered through a 0.22 μm filter to obtain the finally usable NCs solution.
2. Preparing the light-emitting diode: indium Tin Oxide (ITO) glass was ultrasonically cleaned in an ITO cleaner, deionized water, acetone, and isopropanol for 30 minutes in succession. The washed ITO glass was placed in a vacuum drying oven at a temperature of 120 ℃ for vacuum drying for 3 hours, followed by oxygen plasma treatment in a plasma reactor for 5 minutes. The PEDOT: PSS solution was spin-coated at an ITO glass rotation rate of 2000r.p.m. in air to form a PEDOT: PSS film, and annealed at 120 ℃ for 30 minutes, followed by being placed in a glove box under a nitrogen atmosphere. A solution of poly-TPD chlorobenzene at a concentration of 14mg/mL was spin-coated onto ITO/PEDOT: PSS substrates at a rotational speed of 2000r.p.m. in a glove box, followed by annealing for 20 minutes on a heating table at 140 ℃. And then the CsPb (Br/Cl) obtained in the step 1 is put at the rotating speed of 1000r.p.m3NCs n-hexane solution spin-coated poly-TPD surface, 70 ℃ annealing for 10 minutes. And finally, conveying the substrates into a high-vacuum cavity for evaporation coating of 30nm TPBi, 1nm LiF and 100nm Al respectively.
Comparative example 1
Compared with the embodiment 1, potassium carbonate is not introduced into the raw materials for synthesizing the perovskite NCs, and other preparation processes are not changed; the method comprises the following specific steps:
1、CsPb(Br/Cl)3preparation of NCs solution: accurately weighing PbBr by electronic balance2(0.125mmol，0.046g)、PbCl2(0.125mmol, 0.035g) and tetra-n-octylammonium bromide (0.750mmol, 0.410mg), 5mL of toluene was added as a solvent, and the mixture was stirred on a magnetic stirrer until the starting material was sufficiently dissolved. Preparing Cs with concentration of 0.1mol/L2CO3Octanoic acid solution of (1). Pipette 300. mu.L of Cs with pipette2CO3The octanoic acid solution of (a) and 355. mu.L of the octanoic acid solution were thoroughly mixed in a bullet plastic tube. The mixed solution in the bullet plastic tube is quickly dripped into the toluene mixed solution which is vigorously stirred at one time, and blue-light perovskite NCs are formed immediately. After 30s, 1.66mL of a 12mg/mL DDAB toluene solution was added to the NCs solution while vigorously stirring,after 2 minutes, the stirring was stopped to obtain crude NCs solution. To the crude solution was added 14mL of ethyl acetate, followed by centrifugation at 13000 r.p.m. for 5 minutes, the centrifuged supernatant was discarded, and the precipitate was redispersed in 2mL of toluene. Subsequently, 4mL of ethyl acetate was added, the mixture was centrifuged at 11000r.p.m for 5 minutes, the supernatant after centrifugation was discarded, and the precipitate was dispersed in 2.4mL of n-hexane. To obtain NCs having a uniform particle size, NCs solution dispersed in n-hexane was subjected to low-speed centrifugation at 4000 r.p.m., and after centrifugation, the supernatant was taken out by a syringe and filtered with a 0.22 μm filter to obtain NCs solution which was finally usable.
2. Preparing the light-emitting diode: indium Tin Oxide (ITO) glass was ultrasonically cleaned in an ITO cleaner, deionized water, acetone, and isopropanol for 30 minutes in succession. The washed ITO glass was placed in a vacuum drying oven at a temperature of 120 ℃ for vacuum drying for 3 hours, followed by oxygen plasma treatment in a plasma reactor for 5 minutes. The PEDOT: PSS solution was spin-coated at an ITO glass rotation rate of 2000r.p.m. in air to form a PEDOT: PSS film, and annealed at 120 ℃ for 30 minutes, followed by being placed in a glove box under a nitrogen atmosphere. A solution of poly-TPD chlorobenzene at a concentration of 14mg/mL was spin-coated onto ITO/PEDOT: PSS substrates at a rotational speed of 2000r.p.m. in a glove box, followed by annealing for 20 minutes on a heating table at 140 ℃. And then the CsPb (Br/Cl) obtained in the step 1 is put at the rotating speed of 1000r.p.m3NCs n-hexane solution spin-coated poly-TPD surface, 70 ℃ annealing for 10 minutes. And finally, conveying the substrates into a high-vacuum cavity for evaporation coating of 30nm TPBi, 1nm LiF and 100nm Al respectively.
The test results are shown in fig. 1 to 9, in which:
FIG. 1 is CsPb (Br/Cl) synthesized in example 1 and comparative example 13Diffraction angle-intensity pattern of NCs, the diffraction peaks before and after doping did not shift, indicating that potassium ions did not enter CsPb (Br/Cl)3The crystal lattice of NCs, but at its surface.
FIG. 2 is CsPb (Br/Cl) synthesized in example 1 and comparative example 13Transmission Electron microscopy of NCs shows that the NCs obtained in example 1 and comparative example 1 are monodisperse and nearly cubic, and that the addition of potassium ions results in CsPb (Br/Cl)3The NCs increase slightly in size.
FIG. 3 is CsPb (Br/Cl) synthesized in example 1 and comparative example 13UV absorption and photoluminescence spectra of NCs n-hexane solution, indicating that the addition of potassium ions results in CsPb (Br/Cl)3The UV absorption spectra of the NCs and the photoluminescence spectra are red-shifted.
FIG. 4 is CsPb (Br/Cl) synthesized in example 1 and comparative example 13Fourier transform infrared spectrogram of NCs, showing that the addition of potassium ions leads to CsPb (Br/Cl)3The surface organic ligand content of NCs is reduced.
FIG. 5 is CsPb (Br/Cl) synthesized in example 1 and comparative example 13The time resolved spectra of NCs, all fitting with double exponentials, indicate that the addition of potassium ions is beneficial to prolonging CsPb (Br/Cl)3The photoluminescence lifetime of NCs suppresses the generation of defect states.
FIG. 6 is CsPb (Br/Cl) provided in example 1 and comparative example 13Atomic force microscopy of NCs spin-coated on ITO/PEDOT: PSS/ploy-TPD substrates, indicating that the addition of potassium ions favors CsPb (Br/Cl)3Uniformity of film formation of the NCs thin film.
FIG. 7 is CsPb (Br/Cl) provided in example 1 and comparative example 13When NCs are used as the luminous layer of the light-emitting diode, the external quantum efficiency-brightness curve contrast graph of the device shows that the addition of potassium ions can greatly improve CsPb (Br/Cl)3External quantum efficiency and brightness of NCs blue light emitting diodes.
Fig. 8 is a comparison of the solutions after 24 hours of standing after synthesis of perovskite quantum dots doped with different concentrations of potassium ions, and it was found that the solution after doping with potassium ions maintained good dispersibility after 24 hours and remained clear, while the undoped solution became cloudy, which was associated with highly dynamic shedding of organic ligands.
FIG. 9 is the fluorescence quantum yield of perovskite quantum dot solutions doped with different concentrations of potassium ions (where x is the molar ratio of potassium ions to lead ions). By introducing potassium ions as ligands, high-quality nanocrystals can be obtained.
As can be seen from fig. 1 to 9, compared with the method for preparing perovskite nanocrystals in the prior art, the perovskite nanocrystals prepared by the preparation method of the present invention can simultaneously achieve both the stability and the electrical transmission performance of the nanocrystals. Namely, the introduced alkali metal ions such as potassium ions can form bonds with halogen on the surface of the nanocrystal in an ionic bond forming mode to form a metal ligand which is not easy to fall off, so that the surface defects of the nanocrystal are effectively passivated, and meanwhile, the nanocrystal is endowed with high stability. In addition, the addition of alkali metal ions such as potassium ions reduces the density of organic ligands on the surface of the nanocrystal, thereby greatly improving the electrical transmission performance of the nanocrystal.
Example 2
Example 2 compared with example 1, only step 1 (i.e., preparation of NCs solution) is different, and step 2 (i.e., preparation of light emitting diode) only needs to use NCs solution obtained in corresponding step 1, and the whole process flow sequence, setting of specific parameter conditions and the like in step 2 are the same as those in example 1. The step 1 is as follows:
CsPbBr3preparation of NCs solution: accurately weighing PbBr by electronic balance2(0.250mmol, 0.092g) and tetra-n-octylammonium bromide (0.750mmol, 0.410mg), 5mL of toluene was added as a solvent, and the mixture was stirred on a magnetic stirrer until the starting material was sufficiently dissolved. Respectively preparing Cs with the concentration of 0.1mol/L2CO3With 0.1mol/L concentration of K2CO3Octanoic acid solution of (1). Pipette 300. mu.L of Cs with pipette2CO3Octanoic acid solution of 50. mu. L K2CO3The octanoic acid solution of (a) and 305. mu.L of the octanoic acid solution were thoroughly mixed in a bullet plastic tube. The mixed solution in the bullet plastic tube was quickly dropped into the toluene mixed solution while vigorously stirring at once, and perovskite NCs were formed immediately. After 60 seconds, 1.66mL of a 12mg/mL DDAB toluene solution was added to the vigorously stirred NCs solution, and stirring was stopped after 2 minutes to obtain a crude NCs solution. To the crude solution was added 14mL of ethyl acetate, followed by centrifugation at 13000 r.p.m. for 5 minutes, the centrifuged supernatant was discarded, and the precipitate was redispersed in 2mL of toluene. Subsequently, 4mL of ethyl acetate was added, the mixture was centrifuged at 11000r.p.m for 5 minutes, the supernatant after centrifugation was discarded, and the precipitate was dispersed in 2.4mL of n-hexane. In order to obtain N with uniform particle sizeAnd Cs, carrying out low-speed centrifugation on the NCs solution dispersed in the n-hexane at the rotating speed of 4000 r.p.m., taking out the supernatant by using a syringe after centrifugation, and filtering by using a 0.22 mu m filter to obtain the final usable NCs solution.
Comparative example 2
Comparative example 2 differs from comparative example 1 only in step 1 (i.e., preparation of NCs solution), step 2 (i.e., preparation of light emitting diode) only requires use of NCs solution obtained in corresponding step 1, and the overall process flow sequence, setting of specific parameter conditions, and the like in step 2 are the same as in comparative example 1. The step 1 is as follows:
CsPbBr3preparation of NCs solution: accurately weighing PbBr by electronic balance2(0.250mmol, 0.092g) and tetra-n-octylammonium bromide (0.750mmol, 0.410mg), 5mL of toluene was added as a solvent, and the mixture was stirred on a magnetic stirrer until the starting material was sufficiently dissolved. Preparing Cs with concentration of 0.1mol/L2CO3The octanoic acid solution of (2) was pipetted 300. mu.L of Cs2CO3The octanoic acid solution of (a) and 355. mu.L of the octanoic acid solution were thoroughly mixed in a bullet plastic tube. The mixed solution in the bullet plastic tube was quickly dropped into the toluene mixed solution while vigorously stirring at once, and perovskite NCs were formed immediately. After 60 seconds, 1.66mL of a 12mg/mL DDAB toluene solution was added to the vigorously stirred NCs solution, and stirring was stopped after 2 minutes to obtain a crude NCs solution. To the crude solution was added 14mL of ethyl acetate, followed by centrifugation at 13000 r.p.m. for 5 minutes, the centrifuged supernatant was discarded, and the precipitate was redispersed in 2mL of toluene. Subsequently, 4mL of ethyl acetate was added, the mixture was centrifuged at 11000r.p.m for 5 minutes, the supernatant after centrifugation was discarded, and the precipitate was dispersed in 2.4mL of n-hexane. To obtain NCs having a uniform particle size, NCs solution dispersed in n-hexane was subjected to low-speed centrifugation at 4000 r.p.m., and after centrifugation, the supernatant was taken out by a syringe and filtered with a 0.22 μm filter to obtain NCs solution which was finally usable.
The NCs prepared in example 2 had higher stability and lower defect state density than the NCs prepared in comparative example 2. The PLQY of both solutions was 71% and 92%, respectively.
Example 3
Example 3 compared with example 1, only step 1 (i.e., preparation of NCs solution) is different, and step 3 (i.e., preparation of light emitting diode) only needs to use NCs solution obtained in corresponding step 1, and the whole process flow sequence, setting of specific parameter conditions and the like in step 2 are the same as those in example 1. The step 1 is as follows:
CsPbCl3preparation of NCs solution: accurate weighing of PbCl by electronic balance2(0.250mmol, 0.070g) and tetra-n-octylammonium chloride (0.750mmol, 0.377mg) 5mL of toluene was added as a solvent and placed on a magnetic stirrer and stirred until the starting material was fully dissolved. Respectively preparing Cs with the concentration of 0.1mol/L2CO3With 0.1mol/L concentration of K2CO3Octanoic acid solution of (1). Pipette 300. mu.L of Cs with pipette2CO3Octanoic acid solution of 50. mu. L K2CO3The octanoic acid solution of (a) and 305. mu.L of the octanoic acid solution were thoroughly mixed in a bullet plastic tube. The mixed solution in the bullet plastic tube was quickly dropped into the toluene mixed solution while vigorously stirring at once, and perovskite NCs were formed immediately. After 30s, 1.66mL of a 12mg/mL DDAC toluene solution was added to the vigorously stirred NCs solution, and stirring was stopped after 2 minutes to obtain a crude NCs solution. To the crude solution was added 14mL of ethyl acetate, followed by centrifugation at 13000 r.p.m. for 5 minutes, the centrifuged supernatant was discarded, and the precipitate was redispersed in 2mL of toluene. Subsequently, 4mL of ethyl acetate was added, the mixture was centrifuged at 11000r.p.m for 5 minutes, the supernatant after centrifugation was discarded, and the precipitate was dispersed in 2.4mL of n-octane. To obtain NCs with uniform particle size, NCs solution dispersed in n-octane was subjected to low-speed centrifugation at 4000 r.p.m., after which the supernatant was taken out by a syringe and filtered through a 0.22 μm filter to obtain the finally usable NCs solution.
Comparative example 3
Comparative example 3 differs from comparative example 1 only in step 1 (i.e., preparation of NCs solution), and step 2 (i.e., preparation of light emitting diode) only requires use of NCs solution obtained in corresponding step 1, and the overall process flow sequence, setting of specific parameter conditions, and the like in step 2 are the same as in comparative example 1. The step 1 is as follows:
CsPbCl3preparation of NCs solution: accurate weighing of PbCl by electronic balance2(0.250mmol, 0.070g) and tetra-n-octylammonium chloride (0.750mmol, 0.377mg) 5mL of toluene was added as a solvent and placed on a magnetic stirrer and stirred until the starting material was fully dissolved. Preparing Cs with concentration of 0.1mol/L2CO3The octanoic acid solution of (2) was pipetted 300. mu.L of Cs2CO3The octanoic acid solution of (a) and 355. mu.L of the octanoic acid solution were thoroughly mixed in a bullet plastic tube. The mixed solution in the bullet plastic tube was quickly dropped into the toluene mixed solution while vigorously stirring at once, and perovskite NCs were formed immediately. After 30s, 1.66mL of a 12mg/mL DDAC toluene solution was added to the vigorously stirred NCs solution, and stirring was stopped after 2 minutes to obtain a crude NCs solution. To the crude solution was added 14mL of ethyl acetate, followed by centrifugation at 13000 r.p.m. for 5 minutes, the centrifuged supernatant was discarded, and the precipitate was redispersed in 2mL of toluene. Subsequently, 4mL of ethyl acetate was added, the mixture was centrifuged at 11000r.p.m for 5 minutes, the supernatant after centrifugation was discarded, and the precipitate was dispersed in 2.4mL of n-octane. To obtain NCs with uniform particle size, NCs solution dispersed in n-octane was subjected to low-speed centrifugation at 4000 r.p.m., after which the supernatant was taken out by a syringe and filtered through a 0.22 μm filter to obtain the finally usable NCs solution.
The NCs prepared in example 3 had higher stability and lower defect state density than the NCs prepared in comparative example 3. The PLQY of both solutions was 4% and 10%, respectively.
Example 4
Example 4 compared with example 1, only step 1 (i.e., preparation of NCs solution) is different, and step 2 (i.e., preparation of light emitting diode) only needs to use NCs solution obtained in corresponding step 1, and the whole process flow sequence, setting of specific parameter conditions and the like in step 2 are the same as those in example 1. The step 1 is as follows:
CsPb(Br/Cl)3preparation of NCs solution: accurately weighing PbBr by electronic balance2(0.125mmol，0.046g)、PbCl2(0.125mmol, 0.035g) and IVN-octyl ammonium bromide (0.750mmol, 0.410mg) was added with 5mL of toluene as a solvent and stirred on a magnetic stirrer until the raw material was sufficiently dissolved. Respectively preparing Cs with the concentration of 0.1mol/L2CO3With 0.1mol/L KHCO3Octanoic acid solution of (1). Pipette 300. mu.L of Cs with pipette2CO3Octanoic acid solution, 100. mu.L KHCO3The octanoic acid solution of (a) and 255. mu.L of the octanoic acid solution were thoroughly mixed in a bullet plastic tube. The mixed solution in the bullet plastic tube was quickly dropped into the toluene mixed solution while vigorously stirring at once, and perovskite NCs were formed immediately. After 30s, 1.66mL of a 12mg/mL DDAB toluene solution was added to the vigorously stirred NCs solution, and stirring was stopped after 2 minutes to obtain a crude NCs solution. To the crude solution was added 14mL of ethyl acetate, followed by centrifugation at 13000 r.p.m. for 5 minutes, the centrifuged supernatant was discarded, and the precipitate was redispersed in 2mL of toluene. Subsequently, 4mL of ethyl acetate was added, the mixture was centrifuged at 11000r.p.m for 5 minutes, the supernatant after centrifugation was discarded, and the precipitate was dispersed in 2.4mL of n-hexane. To obtain NCs having a uniform particle size, NCs solution dispersed in n-hexane was subjected to low-speed centrifugation at 4000 r.p.m., and after centrifugation, the supernatant was taken out by a syringe and filtered with a 0.22 μm filter to obtain NCs solution which was finally usable.
Comparative example 4
Comparative example 4 is different from comparative example 1 only in step 1 (i.e., preparation of NCs solution), and step 2 (i.e., preparation of light emitting diode) is only required to use NCs solution obtained in corresponding step 1, and the overall process flow sequence, setting of specific parameter conditions, and the like in step 2 are the same as in comparative example 1. The step 1 is as follows:
CsPb(Br/Cl)3preparation of NCs solution: accurately weighing PbBr by electronic balance2(0.125mmol，0.046g)、PbCl2(0.125mmol, 0.035g) and tetra-n-octylammonium bromide (0.750mmol, 0.410mg), 5mL of toluene was added as a solvent, and the mixture was stirred on a magnetic stirrer until the starting material was sufficiently dissolved. Preparing Cs with concentration of 0.1mol/L2CO3The octanoic acid solution of (2) was pipetted 300. mu.L of Cs2CO3Octanoic acid solution of (2) and (35)5 μ L of caprylic acid solution was mixed well in a bullet plastic tube. The mixed solution in the bullet plastic tube was quickly dropped into the toluene mixed solution while vigorously stirring at once, and perovskite NCs were formed immediately. After 30s, 1.66mL of a 12mg/mL DDAB toluene solution was added to the vigorously stirred NCs solution, and stirring was stopped after 2 minutes to obtain a crude NCs solution. To the crude solution was added 14mL of ethyl acetate, followed by centrifugation at 13000 r.p.m. for 5 minutes, the centrifuged supernatant was discarded, and the precipitate was redispersed in 2mL of toluene. Subsequently, 4mL of ethyl acetate was added, the mixture was centrifuged at 11000r.p.m for 5 minutes, the supernatant after centrifugation was discarded, and the precipitate was dispersed in 2.4mL of n-hexane. To obtain NCs having a uniform particle size, NCs solution dispersed in n-hexane was subjected to low-speed centrifugation at 4000 r.p.m., and after centrifugation, the supernatant was taken out by a syringe and filtered with a 0.22 μm filter to obtain NCs solution which was finally usable.
The NCs prepared in example 4 had higher stability and lower defect state density than the NCs prepared in comparative example 4. The PLQY of both solutions was 12% and 35%, respectively.
Example 5
Example 5 differs from example 1 only in step 1 (i.e., preparation of NCs solution), and step 2 (i.e., preparation of light emitting diode) only requires use of NCs solution obtained in step 1, and the overall process flow sequence, setting of specific parameter conditions, and the like in step 2 are the same as those in example 1. The step 1 is as follows:
CsPb(Br/Cl)3preparation of NCs solution: accurately weighing PbBr by electronic balance2(0.125mmol，0.046g)、PbCl2(0.125mmol, 0.035g) and tetra-n-octylammonium bromide (0.750mmol, 0.410mg), 5mL of toluene was added as a solvent, and the mixture was stirred on a magnetic stirrer until the starting material was sufficiently dissolved. Respectively preparing Cs with the concentration of 0.1mol/L2CO3With 0.1mol/L CH3Octanoic acid solution of COOK. Pipette 300. mu.L of Cs with pipette2CO3Octanoic acid solution (50. mu.L of CH)3COOK octanoic acid solution and 305 mul octanoic acid solution were mixed well in bullet plastic tubes. The bullet head is made of plasticThe mixed solution in the tube was quickly dropped into the toluene mixed solution while vigorously stirring at one time, and blue-light perovskite NCs were immediately formed. After 30s, 1.66mL of a 12mg/mL DDAB toluene solution was added to the vigorously stirred NCs solution, and stirring was stopped after 2 minutes to obtain a crude NCs solution. To the crude solution was added 14mL of ethyl acetate, followed by centrifugation at 13000 r.p.m. for 8 minutes, the centrifuged supernatant was discarded, and the precipitate was redispersed in 2mL of toluene. Subsequently, 4mL of ethyl acetate was added, the mixture was centrifuged at 11000r.p.m for 3 minutes, the supernatant after centrifugation was discarded, and the precipitate was dispersed in 2.4mL of n-hexane. To obtain NCs having a uniform particle size, NCs solution dispersed in n-hexane was subjected to low-speed centrifugation at 4000 r.p.m., and after centrifugation, the supernatant was taken out by a syringe and filtered with a 0.22 μm filter to obtain NCs solution which was finally usable.
Comparative example 5
Comparative example 5 differs from comparative example 1 only in step 1 (i.e., preparation of NCs solution), and step 2 (i.e., preparation of light emitting diode) only requires use of NCs solution obtained in corresponding step 1, and the overall process flow sequence, setting of specific parameter conditions, and the like in step 2 are the same as in comparative example 1. The step 1 is as follows:
CsPb(Br/Cl)3preparation of NCs solution: accurately weighing PbBr by electronic balance2(0.125mmol，0.046g)、PbCl2(0.125mmol, 0.035g) and tetra-n-octylammonium bromide (0.750mmol, 0.410mg), 5mL of toluene was added as a solvent, and the mixture was stirred on a magnetic stirrer until the starting material was sufficiently dissolved. Preparing Cs with concentration of 0.1mol/L2CO3The octanoic acid solution of (2) was pipetted 300. mu.L of Cs2CO3The octanoic acid solution of (a) and 355. mu.L of the octanoic acid solution were thoroughly mixed in a bullet plastic tube. The mixed solution in the bullet plastic tube is quickly dripped into the toluene mixed solution which is vigorously stirred at one time, and blue-light perovskite NCs are formed immediately. After 30s, 1.66mL of a 12mg/mL DDAB toluene solution was added to the vigorously stirred NCs solution, and stirring was stopped after 2 minutes to obtain a crude NCs solution. Adding 14mL of ethyl acetate into the crude liquid, centrifuging for 8 minutes at the rotating speed of 13000 r.p.m., discarding the centrifugation solutionThe precipitate was redispersed in 2mL of toluene. Subsequently, 4mL of ethyl acetate was added, the mixture was centrifuged at 11000r.p.m for 3 minutes, the supernatant after centrifugation was discarded, and the precipitate was dispersed in 2.4mL of n-hexane. To obtain NCs having a uniform particle size, NCs solution dispersed in n-hexane was subjected to low-speed centrifugation at 4000 r.p.m., and after centrifugation, the supernatant was taken out by a syringe and filtered with a 0.22 μm filter to obtain NCs solution which was finally usable.
The NCs prepared in example 5 had higher stability and lower defect state density than the NCs prepared in comparative example 5. The PLQY of both solutions was 12% and 33%, respectively.
Example 6
Example 6 differs from example 1 only in step 1 (i.e., preparation of NCs solution), and step 2 (i.e., preparation of light emitting diode) only requires use of NCs solution obtained in step 1, and the overall process flow sequence, setting of specific parameter conditions, and the like in step 2 are the same as those in example 1. The step 1 is as follows:
CsPb(Br/Cl)3preparation of NCs solution: accurately weighing PbBr by electronic balance2(0.125mmol，0.046g)、PbCl2(0.125mmol, 0.035g) and tetra-n-octylammonium bromide (0.750mmol, 0.410mg), 5mL of toluene was added as a solvent, and the mixture was stirred on a magnetic stirrer until the starting material was sufficiently dissolved. Respectively preparing Cs with the concentration of 0.1mol/L2CO3With 0.1mol/L CH3Octanoic acid solution of COOK. Pipette 300. mu.L of Cs with pipette2CO3Octanoic acid solution (30. mu.L of CH)3COOK octanoic acid solution and 325 μ L octanoic acid solution were mixed well in bullet plastic tubes. The mixed solution in the bullet plastic tube is quickly dripped into the toluene mixed solution which is vigorously stirred at one time, and blue-light perovskite NCs are formed immediately. After 30s, 1.66mL of a 12mg/mL DDAB toluene solution was added to the vigorously stirred NCs solution, and stirring was stopped after 2 minutes to obtain a crude NCs solution. To the crude solution was added 14mL of ethyl acetate, followed by centrifugation at 13000 r.p.m. for 8 minutes, the centrifuged supernatant was discarded, and the precipitate was redispersed in 2mL of toluene. Then continuously adding4mL of ethyl acetate, centrifuging for 3 minutes at a rotation speed of 11000r.p.m, discarding the centrifuged supernatant, and dispersing the precipitate in 2.4mL of n-hexane. To obtain NCs having a uniform particle size, NCs solution dispersed in n-hexane was subjected to low-speed centrifugation at 4000 r.p.m., and after centrifugation, the supernatant was taken out by a syringe and filtered with a 0.22 μm filter to obtain NCs solution which was finally usable.
Comparative example 6
Comparative example 6 differs from comparative example 1 only in step 1 (i.e., preparation of NCs solution), and step 2 (i.e., preparation of light emitting diode) only requires use of NCs solution obtained in corresponding step 1, and the overall process flow sequence, setting of specific parameter conditions, and the like in step 2 are the same as in comparative example 1. The step 1 is as follows:
CsPb(Br/Cl)3preparation of NCs solution: accurately weighing PbBr by electronic balance2(0.125mmol，0.046g)、PbCl2(0.125mmol, 0.035g) and tetra-n-octylammonium bromide (0.750mmol, 0.410mg), 5mL of toluene was added as a solvent, and the mixture was stirred on a magnetic stirrer until the starting material was sufficiently dissolved. Preparing Cs with concentration of 0.1mol/L2CO3The octanoic acid solution of (2) was pipetted 300. mu.L of Cs2CO3The octanoic acid solution of (a) and 355. mu.L of the octanoic acid solution were thoroughly mixed in a bullet plastic tube. The mixed solution in the bullet plastic tube is quickly dripped into the toluene mixed solution which is vigorously stirred at one time, and blue-light perovskite NCs are formed immediately. After 30s, 1.66mL of a 12mg/mL DDAB toluene solution was added to the vigorously stirred NCs solution, and stirring was stopped after 2 minutes to obtain a crude NCs solution. To the crude solution was added 14mL of ethyl acetate, followed by centrifugation at 13000 r.p.m. for 8 minutes, the centrifuged supernatant was discarded, and the precipitate was redispersed in 2mL of toluene. Subsequently, 4mL of ethyl acetate was added, the mixture was centrifuged at 11000r.p.m for 3 minutes, the supernatant after centrifugation was discarded, and the precipitate was dispersed in 2.4mL of n-hexane. To obtain NCs having a uniform particle size, NCs solution dispersed in n-hexane was subjected to low-speed centrifugation at 4000 r.p.m., and after centrifugation, the supernatant was taken out by a syringe and filtered with a 0.22 μm filter to obtain NCs solution which was finally usable.
The NCs prepared in example 6 had higher stability and lower defect state density than the NCs prepared in comparative example 5. The PLQY of both solutions was 12% and 21%, respectively.
The above examples are given by K only+Ion for example, when the alkali metal ion is selected from Na+、K+Other metal ions than K, inorganic salts of origin and salts selected from K+The inorganic salts are the same.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (14)
1. A process for preparing the perovskite nano crystal used to passivate the surface defect by alkali metal ions features that Li is used+、Na+、K+、Rb+One or more of the alkali metal ions are used as alkali metal ions, a ligand solution containing the alkali metal ions is mixed with a ligand solution of a monovalent cation at the A site of the perovskite nanocrystal, and a stirred poor solution of a divalent metal halide taking quaternary ammonium salt as a cosolvent is added within 2s to obtain a mixed solution; after the perovskite is formed, adding a poor solution of an organic ligand into the mixed solution within a certain time to obtain a crude perovskite nanocrystal solution; then, purifying the crude perovskite nanocrystal solution to obtain a perovskite nanocrystal colloidal solution with alkali metal ion passivated surface defects;
wherein the certain time is not more than 60 s;
the halogen element in the divalent metal halide is one or more of F, Cl, Br and I; for the ligand solution containing the alkali metal ions, the alkali metal ions are derived from corresponding alkali metal inorganic salts;
in the ligand solution containing the alkali metal ions and the ligand solution containing the perovskite nanocrystal A-site univalent cations, the ligand solutions are fatty acid solutions and are selected from: one or more of caproic acid, caprylic acid (OTAc), oleic acid;
in the poor solution of the organic ligand, the organic ligand is selected from one or more of didodecyl dimethyl ammonium iodide (DDAB), Didodecyl Dimethyl Ammonium Bromide (DDAB) and Didodecyl Dimethyl Ammonium Chloride (DDAC);
in the poor solution of divalent metal halide and the poor solution of organic ligand, the poor solution is selected from the following group: one or more of trichloromethane, dimethylacetamide, dimethylformamide, N-methylpyrrolidone, dioxane, carbon tetrachloride, toluene, xylene, propionitrile, acetone, ethyl acetate, alcohols and ethers;
the purification treatment specifically comprises the following steps:
(S1) mixing the crude perovskite nanocrystal solution with a first medium solvent, carrying out first centrifugal separation treatment to obtain a precipitate, and then adding a first dispersion liquid into the precipitate to obtain an intermediate solution;
(S2) mixing the intermediate solution obtained in the step (S1) with a second medium solvent, carrying out second centrifugal separation treatment to obtain a precipitate, adding a second dispersion liquid into the precipitate, carrying out third centrifugal separation treatment at a rotating speed of 3000-6000r/min for 3-8min, and collecting the stably dispersed supernatant to obtain the colloidal solution of the alkali metal ion passivated surface defect perovskite nanocrystal.
2. The method according to claim 1, wherein the alkali metal ion is Na+Or K+Wherein, in the step (A),
when the alkali metal ion is Na+When the alkali metal salt is sodium carbonate, sodium bicarbonate, sodium acetate, sodium sulfite, sodium bisulfite, sodium thiosulfate, sodium sulfate, sodium nitrate or sodium nitrite;
when the alkali metal ion is K+When the corresponding alkali metal inorganic salt is potassium carbonate, potassium hydrogencarbonate, potassium acetate, potassium sulfite, potassium hydrogensulfite, thiothiosulfitePotassium sulfate, potassium hydrogen thiosulfate, potassium sulfate, potassium nitrate, or potassium nitrite;
the perovskite nanocrystal A site univalent cation is selected from: cnH2n+1NH3 +、CH5N2 +、Cs+Wherein n is any positive integer; these a-site monovalent cations are derived from the corresponding carbonate;
the divalent metal in the divalent metal halide is selected from Pb2+、Sn2+、Bi2+Or Cu2+。
3. The method according to claim 2, wherein the monovalent cation at the a site of the perovskite nanocrystal is selected from the group consisting of: CH (CH)3NH3 +、C2H5NH3 +、CH5N2 +、Cs+One or more of (a).
4. The method according to claim 2, wherein the monovalent cation at the A site of the perovskite nanocrystal is Cs+The divalent metal in the divalent metal halide is Pb2+。
5. The method according to claim 1, wherein the ligand solution containing the alkali metal ion is prepared by mixing the alkali metal ion and the monovalent cation at the A position in a molar ratio of (0.001-0.5): 1, or a mixture of alkali metal ions and divalent metal ions contained in the divalent metal halide in a molar ratio of (0.001-0.16): 1 in admixture with a ligand solution of said monovalent cation in position a;
the stirring speed is 500-3000r/min for the stirred poor solution of the divalent metal halide taking the quaternary ammonium salt as the dissolution promoter.
6. The method according to claim 5, wherein the ligand solution containing the alkali metal ion is prepared by mixing the alkali metal ion and the monovalent cation at the A position in a molar ratio of (0.001-0.33): 1, or a mixture of alkali metal ions and divalent metal ions contained in the divalent metal halide in a molar ratio of (0.001-0.08): 1 in admixture with a ligand solution of said monovalent cation in position a;
the certain time is 30 s;
the stirring speed of the stirred poor solution of the divalent metal halide taking the quaternary ammonium salt as the dissolution promoter is 1300-1700 r/min.
7. The method according to claim 1, wherein the ligand solution containing the alkali metal ion and the ligand solution containing the monovalent cation at the a site of the perovskite nanocrystal are both octanoic acid (OTAc);
the quaternary ammonium salt is selected from one or more of tetraoctyl ammonium iodide, tetraoctyl ammonium bromide and tetraoctyl ammonium chloride;
the poor solution of the divalent metal halide using the quaternary ammonium salt as the dissolution promoter is the same as the poor solution of the organic ligand in kind.
8. The method according to claim 7, wherein the poor solution of the divalent metal halide and the poor solution of the organic ligand using the quaternary ammonium salt as the solubilizing agent is toluene or chloroform.
9. The method according to claim 1, wherein in the steps (S1) and (S2), the first centrifugal separation process and the second centrifugal separation process are both high-speed centrifugal separation, the rotation speed of the centrifugation is 5000-30000r/min, and the centrifugation time is 3-8 min;
in the step (S2), the rotation speed of the third centrifugal separation treatment is 4000-;
in the steps (S1) and (S2), the first medium solvent and the second medium solvent are both aprotic polar solvents, and each is independently selected from: ethyl acetate, methyl acetate, butanol, acetonitrile, dimethylformamide, acetone or acetonitrile;
in the step (S1), the volume ratio of the first medium solvent to the crude perovskite nanocrystal liquid is (1-5):1 or 1 (1-5);
in the steps (S1) and (S2), the first dispersion and the second dispersion are both aliphatic hydrocarbons selected from one or more of toluene, octane, and hexane;
in the step (S2), the collecting of the stably dispersed supernatant is performed by filtration separation.
10. The method as claimed in claim 9, wherein in the steps (S1) and (S2), the first centrifugal separation treatment and the second centrifugal separation treatment are performed at rotation speeds of 11000-13000r/min and for 5-8 min;
in the step (S1) or the step (S2), both the first medium solvent and the second medium solvent are ethyl acetate or acetonitrile;
in the step (S1), the volume ratio of the first medium solvent to the crude perovskite nanocrystal liquid is 2:1 or 1: 2.
11. Perovskite nanocrystals having surface defects passivated with alkali metal ions obtained by the preparation process according to any one of claims 1 to 10.
12. Use of the alkali metal ion-passivated surface defect perovskite nanocrystal obtained by the preparation method according to any one of claims 1-10 as a light absorbing layer in a solar cell or as a light emitting layer in an electroluminescent device.
13. A solar cell, characterized in that the light absorbing layer material of the solar cell comprises perovskite nanocrystals having surface defects passivated with alkali metal ions obtained by the preparation method according to any one of claims 1 to 10.
14. An electroluminescent device, characterized in that the active layer material of the device comprises perovskite nanocrystals having surface defects passivated with alkali metal ions obtained by the preparation process according to any one of claims 1 to 10.
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