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CN-122012096-A - Rare earth ion doped sodium yttrium fluoride nano-material and preparation method and application thereof

CN122012096ACN 122012096 ACN122012096 ACN 122012096ACN-122012096-A

Abstract

The invention relates to the technical field of nano luminescent materials, in particular to a rare earth ion doped sodium yttrium fluoride nano material, a preparation method and application thereof. The doping amount of ytterbium can influence the intensity of red light emitted by the nano material under the excitation of 1208 nm near infrared light, the doping amount of thulium can influence the intensity of green light emitted by the nano material under the excitation of 1208 nm near infrared light, the doping amount of holmium can influence the intensity of blue light emitted by the nano material under the excitation of 1208 nm near infrared light, and the chromaticity diagram (CIE) coordinate position of the nano material is 0.3012,0.3158 by adjusting the doping amounts of ytterbium, thulium and holmium, so that the fluorescent light LED device belongs to a white light range and can be used for a white light LED device. In addition, the molar ratio of the yttrium source, the ytterbium source, the thulium source and the holmium source influences the luminescence color of the nanomaterial under the excitation of 980 nm and 1208 nm near infrared light, and can be used for optical anti-counterfeiting.

Inventors

  • LIU GUOFENG
  • HUANG BINGQI
  • Li fengze
  • ZHANG WENCHANG
  • ZHANG ZHANCHANG
  • LI YUEYANG
  • LI XIAOLIN
  • XU SHICAI
  • ZHANG JUNYE
  • LI BINGWEN
  • WANG RUI
  • LI ZHEN
  • LIN XIAOHUI
  • LI CHONGHUI

Assignees

  • 德州学院

Dates

Publication Date
20260512
Application Date
20260205

Claims (10)

  1. 1. A rare earth ion doped sodium yttrium fluoride nano-material is characterized by comprising a chemical composition of NaYF 4 :Yb 3+ /Tm 3+ /Ho 3+ , wherein the molar ratio of Y 3+ to Yb 3+ 、Tm 3+ 、Ho 3+ is (12-88.9), 5-60, 1-10 and 0.1-15.
  2. 2. The rare earth ion doped sodium yttrium fluoride nanomaterial of claim 1, wherein the molar ratio of Y 3+ to Yb 3+ 、Tm 3+ 、Ho 3+ is 38:50:7:5; Or the molar ratio of Y 3+ to Yb 3+ 、Tm 3+ 、Ho 3+ is (12 to 88.9): (5 to 60): (1 to 10): (0.1 to 15), in particular ：（86.7~86.9）：10：3：（0.1~0.3）、（84~86）：10：3：（1~3）、（80~82）：10：3：（5~7）、（72~78）：10：3：（9~15）、（86.3~86.7）：10：3：（0.3~0.7）.
  3. 3. The method for preparing the rare earth ion doped sodium yttrium fluoride nanomaterial of claim 1 or 2, characterized by comprising the following steps: adding a sodium source into an ethylenediamine tetraacetic acid (EDTA) water solution, then adding an yttrium source, an ytterbium source, a thulium source, a holmium source and a fluorine source, and performing heat treatment in an acidic environment to obtain the rare earth ion doped sodium yttrium fluoride nano-material.
  4. 4. The method of claim 3, wherein the sodium source is sodium hydroxide; Or, the yttrium source is yttrium acetate; Or, the ytterbium source is ytterbium acetate; or, the thulium source is thulium acetate; Or, the holmium source is holmium acetate; Or, the fluorine source is ammonium fluoride; or the molar ratio of the sodium source to the ethylenediamine tetraacetic acid is (1.9-2.3) (0.4-0.7); Or the concentration of the ethylenediamine tetraacetic acid aqueous solution is 0.08-0.014 mol/L; or the molar ratio of the sodium source to the fluorine source is (1.9-2.3) (6-7); Or, the molar ratio of the yttrium source to the ytterbium source to the thulium source to the holmium source is (12-88.9): (5-60): (1-10): (0.1-15); Or the temperature of the heat treatment is 180-250 ℃, preferably 200 ℃, and the time of the heat treatment is 19-23 h, preferably 20h.
  5. 5. The application of the rare earth ion doped sodium yttrium fluoride nano-material prepared by the preparation method of claim 1 or 2 or the rare earth ion doped sodium yttrium fluoride nano-material prepared by the preparation method of claim 3 or 4 in optical anti-counterfeiting and white light LED devices.
  6. 6. The application of claim 5, wherein the rare earth ion doped sodium yttrium fluoride nano-material is used in optical anti-counterfeiting application ：（86.7~86.9）：10：3：（0.1~0.3）、（84~86）：10：3：（1~3）、（80~82）：10：3：（5~7）、（72~78）：10：3：（9~15）、（86.3~86.7）：10：3：（0.3~0.7）; Or when the rare earth ion doped sodium yttrium fluoride nano-material white light LED device is applied, the molar ratio of Y 3+ to Yb 3+ 、Tm 3+ 、Ho 3+ is 38:50:7:5.
  7. 7. An anti-counterfeiting ink is characterized by comprising the rare earth ion doped sodium yttrium fluoride nano-material prepared by the preparation method of claim 1 or 2 or the rare earth ion doped sodium yttrium fluoride nano-material prepared by the preparation method of claim 3 or 4.
  8. 8. The anti-counterfeit ink according to claim 7, wherein the molar ratio of Y 3+ to Yb 3+ 、Tm 3+ 、Ho 3+ is (12-88.9): (5-60): (1-10): (0.1-15), in particular ：（86.7~86.9）：10：3：（0.1~0.3）、（84~86）：10：3：（1~3）、（80~82）：10：3：（5~7）、（72~78）：10：3：（9~15）、（86.3~86.7）：10：3：（0.3~0.7）.
  9. 9. A white LED device comprising the rare earth ion doped yttrium sodium fluoride nanomaterial of claim 1 or 2 or the rare earth ion doped yttrium sodium fluoride nanomaterial prepared by the preparation method of claim 3 or 4.
  10. 10. The white LED device of claim 9, wherein the molar ratio of Y 3+ to Yb 3+ 、Tm 3+ 、Ho 3+ is 38:50:7:5.

Description

Rare earth ion doped sodium yttrium fluoride nano-material and preparation method and application thereof Technical Field The invention relates to the technical field of nano luminescent materials, in particular to a rare earth ion doped sodium yttrium fluoride nano material, a preparation method and application thereof. Background The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art. White light LEDs are receiving wide attention due to their high efficiency, long life, energy conservation, environmental protection, and the like. The most widely used and mature white light LED technology In the market is a fluorescent powder conversion type, one of the white light LED technology is formed by organically combining a blue light LED and a yellow fluorescent powder which can be effectively excited by blue light, the white light LED commonly used at present is realized by combining Y 3Al5O12:Ce3+ yellow fluorescent powder with a Ga (In) N blue wafer, but the white light LED has the problem of red light missing In light emission, further the color temperature is higher, the color rendering index is poor, and the light emitting efficiency is low. In addition, in recent years, various anti-counterfeiting means are endangered by consumers and merchants in order to avoid disturbing the market by counterfeiting and inferior products. The existing anti-counterfeiting means mainly comprise an ink printing anti-counterfeiting technology, a two-dimensional code anti-counterfeiting technology and a holographic anti-counterfeiting technology. The two-dimensional code anti-counterfeiting technology and means have the advantages and the characteristics, the two-dimensional code anti-counterfeiting is convenient for consumers to inquire and verify, but is relatively easy to copy, and the anti-counterfeiting effect is limited. Holographic anti-counterfeiting is a physical anti-counterfeiting method, and has the advantages of playing the role of appearance decoration and meeting the requirement of difficulty in copying by representing three-dimensional, dynamic or color changes through refraction, reflection, diffraction and the like of light, and has the defect of higher requirements on the material and flatness of the outer surface of a pasted object. The anti-counterfeiting strength of the anti-counterfeiting ink is higher than that of the two-dimensional code, but the cost is also higher. The rare earth luminescent nano material has the characteristics of narrow emission band, long fluorescence lifetime, low toxicity, large Stokes displacement, adjustable luminescent color, no light bleaching and flickering and the like, and has wide application prospect in the fields of biomedicine, anti-counterfeiting marks, illumination display and the like due to the excellent luminescent properties. Disclosure of Invention In order to overcome the problems, the invention provides a rare earth ion doped sodium yttrium fluoride nano-material, and a preparation method and application thereof. In order to achieve the technical purpose, the invention adopts the following technical scheme: In a first aspect of the invention, a rare earth ion doped sodium yttrium fluoride nano-material is provided, and the chemical composition of the nano-material is NaYF 4:Yb3+/Tm3+/Ho3+, wherein the molar ratio of Y 3+ to Yb 3+、Tm3+、Ho3+ is (12-88.9): (5-60): (1-10): (0.1-15). In one or more embodiments, the molar ratio of Y 3+ to Yb 3+、Tm3+、Ho3+ is 38:50:7:5. The chromaticity diagram (CIE) coordinate position of the rare earth ion doped sodium yttrium fluoride nano-material under 1208 nm near infrared light excitation in the molar ratio is 0.3012,0.3158, and belongs to the white light range. In one or more embodiments, the molar ratio of Y 3+ to Yb 3+、Tm3+、Ho3+ is (12 to 88.9): 5 to 60): 1 to 10): 0.1 to 15, specifically ：（86.7~86.9）：10：3：（0.1~0.3）、（84~86）：10：3：（1~3）、（80~82）：10：3：（5~7）、（72~78）：10：3：（9~15）、（86.3~86.7）：10：3：（0.3~0.7）; Specifically, when the molar ratio of Y 3+ to Yb 3+、Tm3+、Ho3+ is (86.7-86.9) 10:3 (0.1-0.3), the rare earth ion doped sodium yttrium fluoride nano-material emits purple light under the excitation of 980 nm near infrared light; the molar ratio of Y 3+ to Yb 3+、Tm3+、Ho3+ is (84-86) 10:3 (1-3), and the rare earth ion doped sodium yttrium fluoride nano-material emits blue light under the excitation of 980 nm near infrared light; the molar ratio of Y 3+ to Yb 3+、Tm3+、Ho3+ is (80-82) 10:3 (5-7), and the rare earth ion doped sodium yttrium fluoride nano-material emits green light under the excitation of 980 nm near infrared light; When the molar ratio of Y 3+ to Yb 3+、Tm3+、Ho3+ is (72-78) 10:3 (9-15), the rare earth ion doped sodium yttrium fluoride nano-material emits yellow orange lig