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CN-119193147-B - Rare earth doped ABF3Perovskite type nano luminescent material, preparation method and application thereof

CN119193147BCN 119193147 BCN119193147 BCN 119193147BCN-119193147-B

Abstract

The invention discloses a rare earth doped ABF 3 perovskite type nano luminescent material and a preparation method and application thereof, wherein the general formula of the luminescent material is ABF 3 :x mol％Ln n+ , wherein A is at least one of alkali metal Li, na, K, rb, cs, B is at least one of alkaline earth metal or transition metal Mg, ca, sr, ba, mn, zn, cd, co, ni, cu, F represents fluorine element, ln represents lanthanide rare earth element, x mol% represents the percentage of lanthanide rare earth ion in the total number of moles of alkaline earth metal or transition metal and lanthanide rare earth element, x is more than 0 and less than or equal to 80, and n is 2 or 3. The hydroxyl defects in the nano luminescent material are effectively inhibited, rare earth ions are doped in the nano luminescent material in a different valence mode, cross relaxation among the rare earth ions can be promoted, and high-order nonlinear photon avalanche up-conversion of the nano luminescent material at room temperature is realized.

Inventors

  • ZHENG WEI
  • ZHANG MEIRAN
  • CHEN XUEYUAN
  • HUANG PING

Assignees

  • 闽都创新实验室
  • 中国科学院福建物质结构研究所

Dates

Publication Date
20260512
Application Date
20230626

Claims (13)

  1. 1. A rare earth doped ABF 3 perovskite type nano luminescent material is characterized in that the general formula of the luminescent material is ABF 3 : x mol%Ln n+ , wherein A is one of alkali metals Li, na, K, rb, cs, B is one of alkaline earth metals or transition metals Mg, ca, sr, ba, mn, zn, cd, co, ni, cu, F represents fluorine element, ln represents lanthanide rare earth element, x mol% represents the percentage of lanthanide rare earth ions in the total number of moles of alkaline earth metals or transition metals and lanthanide rare earth elements, x is more than or equal to 1 and less than or equal to 80, and n is 2 or 3; the luminescent material is of a core-shell-like structure, wherein the central area is made of rare earth elements, and the peripheral areas are A, B and fluorine elements; the luminescent material can realize high-order nonlinear photon avalanche up-conversion at room temperature; Dissolving B salt, ln salt and fluorohydrogenation A in an organic solvent, and heating for reaction to obtain the rare earth doped ABF 3 perovskite type nano luminescent material; The B salt is selected from Mg (CH 3 COO) 2 、Ca(CH 3 COO) 2 、Sr(CH 3 COO) 2 or Ba(CH 3 COO) 2 、Mn(CH 3 COO) 2 、Zn(CH 3 COO) 2 、Cd(CH 3 COO) 2 、Co(CH 3 COO) 2 、Cu(CH 3 COO) 2 or Ni (one of CH 3 COO) 2 ; The Ln salt is selected from one or more of La(CH 3 COO) 3 、Ce(CH 3 COO) 3 、Pr(CH 3 COO) 3 、Nd(CH 3 COO) 3 、Sm(CH 3 COO) 3 、Eu(CH 3 COO) 3 、Gd(CH 3 COO) 3 、Tb(CH 3 COO) 3 、Dy(CH 3 COO) 3 、Ho(CH 3 COO) 3 、Er(CH 3 COO) 3 、Tm(CH 3 COO) 3 、Yb(CH 3 COO) 3 、Lu(CH 3 COO) 3 、Y(CH 3 COO) 3 、Sc(CH 3 COO) 3 .
  2. 2. The material of claim 1, wherein A is K or Na and B is Mg or Zn.
  3. 3. The material of claim 1, wherein Ln n+ is selected from at least one of Ho 3+ 、Er 3+ 、Tm 3+ 、Tb 3+ 、Eu 3+ 、Ce 3 + 、Sm 3+ 、Dy 3+ 、Nd 3+ 、Pr 3+ 、Gd 3+ 、Sc 3+ 、Lu 3+ 、Yb 3+ 、Y 3+ 、La 3+ .
  4. 4. The material according to claim 1, characterized in that the luminescent material is KMgF 3 : 20 mol%Yb 3+ , 2 mol%Er 3+ 、KMgF 3 : 20 mol%Yb 3+ , 1 mol%Ho 3+ 、KMgF 3 : 1mol%Yb 3+ 、KMgF 3 : 5mol%Yb 3+ 、KMgF 3 : 10mol%Yb 3+ 、KMgF 3 : 20mol%Yb 3+ 、KMgF 3 : 30mol%Yb 3+ 、 or KMgF 3 : 1mol%Tm 3+ 、KMgF 3 : 3mol%Tm 3 + 、KMgF 3 : 5mol%Tm 3+ or NaMgF 3 : 5mol%Yb 3+ or KZnF 3 : 2mol%Yb 3+ .
  5. 5. The material of claim 1, wherein the luminescent material has a particle size of 5-200 nm.
  6. 6. The material of claim 1, wherein the luminescent material is in a cubic phase or an orthogonal phase.
  7. 7. The material of claim 1, wherein the heating reaction is for a period of time ranging from 1 to 240 min and wherein the heating reaction is at a temperature ranging from 100 to 400: 400 oC.
  8. 8. The material of claim 1, wherein the organic solvent is selected from at least one of oleic acid, oleylamine, trioctylamine, and octadecene.
  9. 9. The material of claim 1, wherein the molar ratio of B salt to Ln salt is (1-y): y.
  10. 10. The material according to claim 1, wherein the amount of fluorohydrogenation a is 1 to 5 times the sum of the moles of B salt and Ln salt.
  11. 11. The material of claim 1, wherein the method further comprises dispersing the rare earth doped ABF 3 perovskite-type nano luminescent material in a nonpolar organic solvent to obtain a rare earth doped ABF 3 perovskite-type nano luminescent material solution.
  12. 12. The material of claim 11, wherein the non-polar organic solvent is selected from at least one of n-hexane, cyclohexane, chloroform, methylene chloride, or toluene.
  13. 13. Use of a material according to any one of claims 1-12 in the fields of super-resolution imaging, single molecule tracking, optical security and coding.

Description

Rare earth doped ABF 3 perovskite type nano luminescent material and preparation method and application thereof Technical Field The invention belongs to the technical field of nano luminescent materials, and particularly relates to a rare earth doped ABF 3 perovskite type nano luminescent material, a preparation method and application thereof. Background The perovskite structure has the general formula of ABF 3 (wherein A is alkali metal ion and B is divalent metal cation), and is an ideal rare earth doped matrix material because of the advantages of high optical transparency, low phonon energy, good thermal stability, anisotropy, wide band gap and the like. At present, the method for preparing the rare earth doped ABF 3 perovskite type nanocrystalline mainly comprises the methods of water/solvothermal and high-temperature coprecipitation and the like. Wherein, the water/solvent thermal method has long reaction time, and the prepared nanocrystalline is easy to agglomerate and has uncontrollable grain diameter. In addition, when the method is used for preparing the nanocrystalline, hydroxyl groups in a reaction system easily replace fluorine ions to enter the nanocrystalline to form hydroxyl defects, so that the luminescence of the nanocrystalline is seriously quenched. The high-temperature coprecipitation method for preparing the nano crystal has mild reaction and easily controlled reaction conditions, and the monodisperse rare earth doped nano crystal can be obtained by adopting the method. However, the previous researchers used this method to prepare ABF 3 perovskite nanocrystals mainly used NH 4 F and AOH as fluorine and a sources. The use of AOH increases the hydroxyl content in the system, and a large number of hydroxyl groups participate in the nucleation and growth processes of the nanocrystalline, so that a large number of hydroxyl defects are generated on the surface and inside of the nanocrystalline, and the luminous efficiency of the nanocrystalline is affected. In addition, the nano-crystal prepared by taking NH 4 F as a fluorine source has smaller particle size, and the regulation and control of the particle size of the nano-crystal are difficult to realize. Limited by the type of reaction precursor and the preparation method, the preparation of the rare earth doped ABF 3 perovskite type nanocrystalline with high-efficiency luminescence is still a great difficulty at present. The rare earth doped photon avalanche up-conversion nanocrystalline has wide application prospect in the technical fields of super-resolution biological imaging, micro laser, single molecule tracing, quantum optics and the like. However, the realization of high-order nonlinear photon avalanche up-conversion of rare earth nanocrystals at normal temperature is still a significant challenge in the field of rare earth luminescence due to fluorescence quenching effects such as hydroxyl defects on the surface and in the interior of the nanocrystals. Because the rare earth ions are doped in the ABF 3 in a different valence way, rare earth ion clusters are easy to form, the cross relaxation process between the rare earth ions can be promoted, and the photon avalanche up-conversion process can be realized. Therefore, a new synthesis technology is developed to realize the controlled synthesis of the high-efficiency rare earth doped ABF 3 perovskite type nano luminescent material, and the method has important significance for realizing the high-order nonlinear photon avalanche up-conversion of rare earth ions and the application of the high-order nonlinear photon avalanche up-conversion in the fields of super-resolution imaging and the like. Disclosure of Invention In order to overcome the defects of the prior art, the invention provides a rare earth doped ABF 3 perovskite type nano luminescent material, which has a general formula of ABF 3:x mol％Lnn+, wherein A is at least one selected from alkali metals Li, na, K, rb, cs, B is at least one selected from alkaline earth metals or transition metals Mg, ca, sr, ba, mn, zn, cd, co, ni, cu, F represents fluorine element, ln represents lanthanide rare earth element, x mol% represents the percentage of lanthanide rare earth ions in the total number of moles of alkaline earth metals or transition metals and lanthanide rare earth elements, x is 0< x is less than or equal to 80, and n is 2 or 3. According to an embodiment of the invention, a is K and/or Na. According to an embodiment of the invention, B is Mg and/or Zn. According to an embodiment of the present invention, the Ln n+ is selected from at least one of Ho3+、Er3+、Tm3+、Tb3+、Eu3+、Eu2+、Ce3+、Sm3+、Sm2+、Dy3+、Nd3+、Pr3+、Gd3+、Sc3+、Lu3+、Yb3+、Yb2+、Y3+、La3+, preferably at least one of Yb 3+、Er3+、Ho3+、Tm3+. According to an embodiment of the invention, 0.0001% x 80, preferably 0.01 x 40, preferably 1 x 40, and more preferably 1 x 30. Illustratively, x is 0.01, 1, 2, 3, 5, 10, 15, 20, 25, 30, 35, 40. According to an embodiment of the invention, t