CN112063381A

CN112063381A - Mn4+ ion activated perovskite fluoride red light material

Info

Publication number: CN112063381A
Application number: CN202011033878.7A
Authority: CN
Inventors: 周强; 谢晓玲; 普海琦; 施栋鑫; 汪正良
Original assignee: Yunnan Minzu University
Current assignee: Yunnan Minzu University
Priority date: 2020-09-27
Filing date: 2020-09-27
Publication date: 2020-12-11

Abstract

The invention relates to the field of inorganic luminescent materials, and discloses Mn⁴⁺An ion activated perovskite fluoride red light material. Mn of the invention⁴⁺An ion-activated perovskite fluoride red light material, the chemical composition of which is: NaZn_(1‑x)F₃:xMn⁴⁺. x is an active ion Mn⁴⁺Ion relative to Zn²⁺Molar percentage coefficient of ion, 0.0<x is less than or equal to 0.20. The perovskite fluoride of the invention refers to a matrix material NaZnF₃An inorganic compound having a three-dimensional skeleton structure, which is a fluoride and has a perovskite structure. The red light material provided by the invention is characterized in that the material generates strong red light emission under the excitation of 455 nm blue light, the main peak of the emission peak is located at 630 nm, and a strong zero phonon vibration peak exists at 621 nm.

Description

Mn (manganese)4+Ion activated perovskite fluoride red light emitting materials

Technical Field

The invention relates to Mn⁴⁺An ion-activated perovskite fluoride red-light material, in particular to a red-light material with a chemical composition of NaZn_(1-x)F₃:xMn⁴⁺The lattice structure is a three-dimensional skeleton structure with a perovskite structure, and the material can generate red light emission under the excitation of blue light of 420-470 nm, and belongs to the field of inorganic luminescent materials.

Technical Field

Compared with traditional light sources (such as incandescent lamps, halogen lamps, xenon lamps, fluorescent lamps and the like), the phosphor-converted white light emitting diode (pc-WLED) has the greatest characteristics of low energy consumption, strong brightness, high light efficiency, long service life, environmental friendliness and wider application range. Commercialized blue LED chip + yellow phosphor YAG Ce³⁺"white light obtained by combination lacks the red component, color rendering indexR _a) Low color temperature (T _c) The red luminescent material has high content, belongs to a cold light source, has certain irritation to human eyes, and limits the application of the red luminescent material in indoor illumination and other occasions requiring low color temperature and high color rendering index warm white light, so the development of the red luminescent material capable of effectively improving the performance of a white light LED device has important significance.

Perovskite-type compounds are ubiquitous in nature. Compared with the traditional oxide type perovskite, the fluoride type perovskite has the advantages of more stable crystal structure, small refractive index, strong ionicity, wide energy band gap and small electron cloud diffusion effect, can adjust the fluorescence spectrum in the whole visible light range, and has good optical properties. In recent years, rare earth ion-doped perovskite fluorides have been widely studied, but rare earth resources are in short supply, expensive, difficult to separate and purify, unable to meet the requirements of industrial production, and toxic. Manganese is transition metal, has no toxicity, low cost and abundant reserves, and contains multiple valence states, wherein Mn⁴⁺Belongs to a high valence state, and is easy to obtain electrons, exceptd-dIn addition to the transition, ligand ions and Mn are also present⁴⁺The charge transfer transition between the two is easy to be excited in the near ultraviolet region and the visible light region; further, Mn⁴⁺With unfilled 3d³The electron shell layer is easily influenced by a crystal field to enable energy levels to be split, when the electron shell layer is positioned in an octahedral fluoride crystal field, wide excitation peaks and narrow-band emission peaks are shown at 460 nm and 630 nm, the electron shell layer can be well adapted to a white light LED device excited by a blue light chip, and the electron shell layer has a wide application prospect.

Adding Mn⁴⁺Doped into perovskite type fluoride fluorescent powder to improve various performances of white light LEDThe field is widely concerned by the researchers. For this reason, the invention discloses a Mn-containing alloy⁴⁺The red luminescent material which is used as a luminescent center and takes perovskite type fluoride as a substrate and is suitable for a white light LED has the chemical composition of NaZn_(1-x)F₃:xMn⁴⁺. The material is simple in preparation process and good in stability, can be effectively excited by blue light of 460 nm, and is a red light material suitable for a white light LED.

Disclosure of Invention

The invention aims to provide a Mn-based alloy⁴⁺The red luminescent material which takes perovskite fluoride as a matrix and is suitable for the white light LED is used for activating ions.

In order to achieve the above object, the present invention relates to Mn⁴⁺The ion-activated perovskite fluoride red-light material has the chemical composition of NaZn_(1-x)F₃:xMn⁴⁺X is Mn as doped⁴⁺Ion relative to Zn²⁺Coefficient of mole percent of ions, and 0.0< x ≤ 0.20。

The red luminescent material of the invention generates six obvious red light emission peaks under the excitation of 455 nm blue light, and the six obvious red light emission peaks are respectively positioned at 608 nm, 613 nm, 621 nm, 630 nm, 634 nm and 647 nm, wherein the 630 nm is the strongest emission peak, and the 621 nm is a zero phonon vibration peak. The red luminescent material of the invention and Y are mixed₃Al₅O₁₂:Ce³⁺The yellow fluorescent powder and the epoxy resin AB glue are mixed according to a certain proportion and coated on a blue light GaN chip, and the warm white light LED with low color temperature and high color rendering index can be manufactured.

Drawings

FIG. 1 is an XRD diffractogram of a red luminescent material of the present invention;

FIG. 2 shows the excitation spectrum and the emission spectrum of the red light-emitting material of the present invention at room temperature;

FIG. 3 is an electroluminescence spectrum of a red LED manufactured by compounding a red luminescent material and a GaN chip (-460 nm) under a drive current of 20 mA;

FIG. 4 shows a red light emitting material and Y of the present invention₃Al₅O₁₂:Ce³⁺And mixing the yellow fluorescent powder and the epoxy resin AB glue according to a certain proportion, and coating the mixture on a blue light GaN chip to prepare a warm white light LED device, wherein the warm white light LED device has an electroluminescence spectrogram under the conditions of different driving currents (20 milliamperes, 80 milliamperes, 140 milliamperes and 200 milliamperes).

Detailed Description

Embodiment 1:

respectively weighing 0.03 g of epoxy resin A glue, 0.03 g of B glue and Y₃Al₅O₁₂:Ce³⁺Yellow phosphor 0.003 g, NaZn_(1-x)F₃:xMn⁴⁺0.021 g of red fluorescent powder is uniformly mixed in a sample tube of 2.0 ml, coated on a blue light GaN chip prepared in advance, put in an oven at 150 ℃ for drying for 30 minutes, and finally tested under the condition of 20 milliampere current.

FIG. 1 shows the XRD diffraction pattern of the red light material used, and the standard card JCPDS 80-1519 (NaZnF)₃) In contrast, the two were completely identical, and no diffraction peak was observed for any of the hetero phases, indicating that the sample used had a single crystal phase.

FIG. 2 shows the room temperature excitation spectrum (monitoring wavelength of 630 nm) and the emission spectrum (excitation wavelength of 455 nm) of the sample. The sample has strong broadband excitation in an ultraviolet region (320 nm-390 nm) and a blue region (420 nm-480 nm), and has a series of sharp narrow-band emission in a wavelength range of 610-650 nm under the excitation of 455 nm blue light.

Embodiment 2:

respectively weighing 0.03 g of epoxy resin A glue, 0.03 g of B glue and Y₃Al₅O₁₂:Ce³⁺Yellow phosphor 0.003 g, NaZn_(1-x)F₃:xMn⁴⁺0.024 g of red fluorescent powder is evenly mixed in a sample tube of 2.0 ml, coated on a blue light GaN chip prepared in advance, put into a drying oven of 150 ℃ for drying for 30 minutes, and finally tested under the condition of 20 milliampere current.

FIG. 3 is an electroluminescence spectrum of a red LED manufactured by compounding red phosphor powder and a GaN chip (-460 nm) under a drive current of 20 milliamperes. In the figure, the intensity of a blue light excitation band is greatly reduced, and a red light emission peak is obviously enhanced, which indicates that the red light material can effectively absorb blue light.

Embodiment 3:

respectively weighing 0.03 g of epoxy resin A glue, 0.03 g of B glue and Y₃Al₅O₁₂:Ce³⁺Yellow phosphor 0.003 g, NaZn_(1-x)F₃:xMn⁴⁺0.027 g of red phosphor powder is uniformly mixed in a 2.0 ml sample tube, coated on a blue light GaN chip prepared in advance, put into a 150 ℃ oven to be dried for 30 minutes, and finally tested under the condition of 20 milliampere current.

Embodiment 4:

respectively weighing 0.03 g of epoxy resin A glue, 0.03 g of B glue and Y₃Al₅O₁₂:Ce³⁺Yellow phosphor 0.003 g, NaZn_(1-x)F₃:xMn⁴⁺0.027 g of red phosphor powder is uniformly mixed in a 2.0 ml sample tube, coated on a blue light GaN chip prepared in advance, put into a 150 ℃ oven to be dried for 30 minutes, and finally tested under the condition of 80 milliampere current.

Embodiment 5:

respectively weighing 0.03 g of epoxy resin A glue, 0.03 g of B glue and Y₃Al₅O₁₂:Ce³⁺Yellow phosphor 0.003 g, NaZn_(1-x)F₃:xMn⁴⁺0.027 g of red phosphor powder is uniformly mixed in a 2.0 ml sample tube, coated on a blue light GaN chip prepared in advance, put into a 150 ℃ oven to be dried for 30 minutes, and finally tested under the condition of 140 milliampere current.

Embodiment 6:

respectively weighing 0.03 g of epoxy resin A glue, 0.03 g of B glue and Y₃Al₅O₁₂:Ce³⁺Yellow phosphor 0.003 g, NaZn_(1-x)F₃:xMn⁴⁺0.027 g of red phosphor powder is uniformly mixed in a sample tube of 2.0 ml, coated on a blue light GaN chip prepared in advance, put in a drying oven of 150 ℃ for drying for 30 minutes, and finally current of 200 milliamperesThe conditions of (1) were tested.

FIG. 4 is a graph showing the electroluminescence spectra of white LEDs manufactured in examples 3, 4, 5 and 6 at drive currents of 20 mA, 80 mA, 140 mA and 200 mA.

Claims

1. Mn (manganese)⁴⁺An ion-activated perovskite fluoride red light material, the chemical composition of which is: NaZn_(1-x)F₃:xMn⁴⁺. x is Mn as doped⁴⁺Ion relative to Zn²⁺Molar percentage coefficient of ion, 0.0< x ≤ 0.20。

2. Mn according to claim 1⁴⁺The ion-activated perovskite fluoride red-light material is characterized in that the adopted host material NaZnF₃Has a perovskite structure, and Mn⁴⁺Does not change the perovskite configuration of the host material.

3. Mn according to claim 1⁴⁺The ion-activated perovskite fluoride red light material is characterized in that the used excitation light source is blue light with the wavelength of 420-470 nm, and a series of narrow-band red light emission peaks obtained under the irradiation of the blue light are located in the wavelength range of 600-650 nm.

4. A series of narrow-band red emission peaks according to claim 3 characterised in that six distinct red emission peaks are located at 608 nm, 613 nm, 621 nm, 630 nm, 634 nm and 647 nm respectively, with the strongest emission peak at 630 nm and a zero phonon vibration peak at 621 nm.

5. Mn according to claim 1⁴⁺An ion-activated perovskite fluoride red light emitting material, characterized in that said red light emitting material is mixed with Y₃Al₅O₁₂:Ce³⁺The yellow fluorescent powder and the epoxy resin AB glue are mixed according to a certain proportion and coated on a blue light GaN chip to prepare the warm white LED.

6. As claimed in claim 5The warm white LED is characterized by having a lower color temperatureT _c= 3806K) and higher colour rendering index: (b) ((iii)R _a = 87.9）。

7. Mn according to claim 1⁴⁺An ion-activated perovskite fluoride red-emitting material, characterized in that said red light is the CIE coordinates of the emission spectrum of the sample (x = 0.691, y = 0.309) close to the Standard value of red ntsc (national Television Standard committee) (x = 0.67, y = 0.33).