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CN-122012092-A - Cation-substituted enhanced double perovskite near-infrared luminescent material, and preparation method and application thereof

CN122012092ACN 122012092 ACN122012092 ACN 122012092ACN-122012092-A

Abstract

The invention discloses a cation substitution enhanced double perovskite near infrared luminescent material, a preparation method and application thereof, and belongs to the technical field of luminescent materials. The chemical composition general formula of the material is Ba 2‑x/y M x/y Sc 0.98 SbO 6 :0.02Fe 3+ , wherein x is more than or equal to 0 and less than or equal to 2 when M=Mg 2+ , and y is more than or equal to 0 and less than or equal to 2 when M=Zn 2+ . The material takes Fe 3+ as an activating ion, can generate broadband near infrared emission of 700-1100 nm under the excitation of 340-365 nm ultraviolet light, and has a main peak at about 840-nm. By introducing a cationic substitution strategy of partially substituting Ba 2+ with Zn 2+ or Mg 2+ , the local lattice environment of Fe 3+ can be regulated and controlled, so that the near infrared luminous intensity of the material is improved by up to 5 times. The near infrared luminescent material provided by the invention has the advantages of simple preparation process, single phase, high synthesis efficiency, and excellent luminous intensity and thermal stability. The near infrared LED device constructed based on the material and the commercial ultraviolet LED chip has higher light efficiency and potential application value in the fields of night vision illumination, infrared sensing, optical communication and the like.

Inventors

  • ZHANG DAN
  • CUI JIAJUN
  • WANG PENG
  • MA CHONGGENG

Assignees

  • 重庆邮电大学

Dates

Publication Date
20260512
Application Date
20260113

Claims (10)

  1. 1. A cation-substituted enhanced double perovskite near-infrared luminescent material, a preparation method and application thereof are characterized in that the chemical composition general formula is Ba 2-x/y M x/y Sc 0.98 SbO 6 : 0.02Fe 3+ , wherein x is more than or equal to 0 and less than or equal to 2 when M=Mg 2+ , and y is more than or equal to 0 and less than or equal to 2 when M=Zn 2+ .
  2. 2. The luminescent material according to claim 1, wherein 0≤x≤1, 0≤y≤1.
  3. 3. The luminescent material according to claim 2, wherein x=0.8 and y=0.5.
  4. 4. The near infrared light emitting material of claim 1, wherein the chemical formula is ：Ba 2 Sc 0.98 Fe 0.02 SbO 6 、Ba 1.7 Mg 0.3 Sc 0.98 Fe 0.02 SbO 6 、Ba 1.5 Mg 0.5 Sc 0.98 Fe 0.02 SbO 6 、Ba 1.2 Mg 0.8 Sc 0.98 Fe 0.02 SbO 6 、Ba 1.0 Mg 1.0 Sc 0.98 Fe 0.02 SbO 6 、Ba 1.7 Zn 0.3 Sc 0.98 Fe 0.02 SbO 6 、Ba 1.5 Zn 0.5 Sc 0.98 Fe 0.02 SbO 6 、Ba 1.2 Zn 0.8 Sc 0.98 Fe 0.02 SbO 6 、Ba 1.0 Zn 1.0 Sc 0.98 Fe 0.02 SbO 6 .
  5. 5. A method for preparing a near infrared luminescent material according to any one of claims 1-4, comprising the steps of: (1) Accurately weighing raw materials according to the stoichiometric ratio of the general formula Ba 2-x/y M x/y Sc 0.98 SbO 6 : 0.02Fe 3+ , wherein x is more than or equal to 0 and less than or equal to 2 when M=Mg 2+ , and y is more than or equal to 0 and less than or equal to 2 when M=Zn 2+ ; (2) Adding ethanol into the raw materials in the step (1), grinding and uniformly mixing to obtain a raw material mixture; (3) Calcining the raw material mixture in the step (2) at high temperature in an air atmosphere or an argon atmosphere, and grinding to obtain the double perovskite-based near infrared luminescent material.
  6. 6. The method for producing a double perovskite-based near infrared light emitting material as claimed in claim 5, wherein the raw material of step (1) is as follows, The barium source is one or more of barium oxide, barium carbonate or barium nitrate; the zinc source is one or more of zinc oxide, zinc carbonate or zinc nitrate; the magnesium source is one or more of magnesium oxide, magnesium carbonate or magnesium nitrate; the antimony source is one or more of antimony oxide and antimony chloride; The iron source is one or more of ferric oxide and ferric chloride.
  7. 7. The preparation method of claim 5, wherein the raw materials in the step (2) are uniformly mixed by grinding for 20-55 minutes, and 10-20 ml ethanol is required to be added in the grinding process.
  8. 8. The method according to claim 5, wherein the calcination in the step (3) is carried out by placing the raw material mixture in an alumina crucible, using a tube furnace or a box furnace, the calcination temperature is 1300-1500 ℃, the temperature rising speed is 1-10 ℃ per minute, the holding time is 5-10 hours, and the atmosphere is an air atmosphere or a nitrogen atmosphere.
  9. 9. The method according to claim 5, wherein the step (3) is carried out by grinding the sintered body in a mortar for 5 to 25 minutes to obtain the double perovskite-based near infrared light emitting material.
  10. 10. A near-infrared LED light-emitting device is characterized by comprising an ultraviolet chip and a near-infrared light-emitting material for LED encapsulation, wherein the near-infrared light-emitting material is the broadband near-infrared light-emitting material according to any one of claims 1-4.

Description

Cation-substituted enhanced double perovskite near-infrared luminescent material, and preparation method and application thereof Technical Field The invention belongs to the technical field of inorganic luminescent materials, and particularly relates to a cation-substituted enhanced double perovskite near infrared luminescent material, and a preparation method and application thereof. Background The near infrared light source has the unique advantages of strong penetrability, small damage to biological tissues, difficult interference by ambient light and the like, and has wide application prospects in the fields of night vision illumination, infrared sensing, optical communication, biomedical imaging, food detection and the like. With the rapid development of the above fields, the demand for high-performance near infrared luminescent materials is urgent, especially near infrared luminescent materials which are matched with commercial ultraviolet/blue light LED chips, have high luminous intensity, excellent thermal stability and simple preparation process, and become one of the research hot spots in the current luminescent material field. At present, reported near infrared luminescent materials mainly comprise rare earth ion/transition metal ion activated near infrared luminescent materials, quantum dot-based near infrared luminescent materials and the like. The near infrared luminescent material activated by rare earth ions (such as Nd 3+、Er3+、Yb3+ and the like) has the defects of rare earth element resources, high price, narrow emission spectrum bandwidth and the like, and is difficult to meet certain application scenes (such as infrared sensing, optical communication and the like) requiring broadband near infrared light. The quantum dot-based near infrared luminescent material has the problems of poor chemical stability, higher toxicity, large-scale preparation difficulty and the like, and limits the popularization and application of the quantum dot-based near infrared luminescent material in actual devices. The near infrared luminescent material activated by transition metal ions (such as Fe 3+、Cr3+、Ni2+ and the like) gradually becomes an ideal choice for replacing rare earth-based near infrared luminescent materials by virtue of the advantages of rich resources, low cost, capability of realizing broadband near infrared emission and the like. Wherein, the 3d 5 electron configuration of Fe 3+ ions can generate 4T1g(4G)→6A1g(6 S) transition in a crystal field, can realize broadband near infrared emission in the range of 700-1100 nm, and is highly matched with application requirements in the fields of night vision illumination, infrared sensing and the like. Therefore, the development of the Fe 3+ activated near infrared luminescent material has important practical value. The choice of matrix material is critical to the luminescent properties of the Fe 3+ activated near infrared luminescent material. The double perovskite structure material is widely used as a matrix of a luminescent material because of high structural rigidity, strong crystal structure adjustability, good chemical stability and the like. However, the existing Fe 3+ activated near-infrared luminescent material based on the double perovskite matrix generally has the problem of low luminous intensity, and the requirements of actual devices on light efficiency are difficult to meet. This is mainly because the local lattice environment of Fe 3+ ions in the matrix is not ideal, resulting in a lower probability of luminescence transition. In addition, part of the materials have the defects of complex preparation process, impure phase, poor thermal stability and the like, and further limit the industrialized application of the materials. In order to improve the luminescence property of the Fe 3+ activated double perovskite-based near infrared luminescent material, researchers try various modification strategies such as doping ion regulation and control, preparation process optimization and the like, but the effect is not ideal. Among them, cationic substitution as an effective means of adjusting lattice environment has been demonstrated to significantly affect the luminescence properties of activated ions. However, at present, research on partially replacing the a-site Ba 2+ ion in the double perovskite matrix with a divalent ion such as Mg 2+、Zn2+ and improving the near infrared luminous intensity by controlling the local lattice environment of the Fe 3+ ion has yet to be further studied. Therefore, aiming at the technical defects of low luminous intensity, complex preparation process and the like of the existing Fe 3+ activated near infrared luminous material, the double perovskite-based near infrared luminous material which is high in luminous intensity, excellent in thermal stability and simple in preparation process and has great significance for promoting the development of near infrared LED devices and expanding the application of the near