CN111454719A - double perovskite fluoride red luminescent material for white light LED - Google Patents

double perovskite fluoride red luminescent material for white light LED Download PDF

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Publication number
CN111454719A
CN111454719A CN202010465479.1A CN202010465479A CN111454719A CN 111454719 A CN111454719 A CN 111454719A CN 202010465479 A CN202010465479 A CN 202010465479A CN 111454719 A CN111454719 A CN 111454719A
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white light
luminescent material
double perovskite
red
red luminescent
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周强
施栋鑫
汪正良
普海琦
谢晓玲
叶艳青
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Yunnan Minzu University
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Yunnan Minzu University
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    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/62Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing gallium, indium or thallium
    • C09K11/626Halogenides
    • C09K11/628Halogenides with alkali or alkaline earth metals
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00Semiconductor 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
    • H01L33/48Semiconductor 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 characterised by the semiconductor body packages
    • H01L33/50Wavelength conversion elements
    • H01L33/501Wavelength conversion elements characterised by the materials, e.g. binder
    • H01L33/502Wavelength conversion materials
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02BCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

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Abstract

The invention relates to the field of inorganic luminescent materials, and discloses a fluoride Rb prepared from double perovskite 2KGaF6the chemical composition of the double perovskite fluoride red luminescent material is Rb 2KGa1‑xF6:xMn4+X is Mn as doped 4+Ion-opposed Ga 3+Molar percentage coefficient of ion, 0.0 <the red luminescent material is characterized in that the material generates red light emission mainly with the emission wavelength of 628 nm under blue light of 420-470 nm, and has a strong zero phonon vibration peak at the position of 620 nm.

Description

double perovskite fluoride red luminescent material for white light LED
Technical Field
the invention relates to a double perovskite fluoride red luminescent material for white light L ED, in particular to a double perovskite fluoride red luminescent material with a chemical composition of Rb 2KGa1-xF6:xMn4+a fluoride red luminescent material which generates a series of narrow-band red light emission peaks (610-650 nm) under the excitation of blue light (420-470 nm) and is suitable for white light L ED, Belongs to the field of inorganic luminescent material preparation.
Background
compared with other lighting sources (incandescent lamps, halogen tungsten lamps, fluorescent lamps, HID lamps and the like), the white light L ED has the advantages of low use voltage, low energy consumption, strong applicability, high stability, no pollution to the environment and the like, is an energy-saving and environment-friendly green light source, and is the primary choice for developing environment-friendly light sources nowadays with increasing attention paid to environmental protection problems.
Blue light chip composite Y 3Al5O12:Ce3+the white light L ED prepared by the method has high luminous efficiency and good thermal stability, but has the problems of irritation to human eyes, low comfort level and the like, and the inherent expression of high color temperature (A) T c >6000K) And a low color rendering index of ( R a <80). In order to solve the problem, a certain proportion of red fluorescent powder is added into the device to form a 'blue-yellow-red' three-color system to realize warm white light emission, and the aims of reducing color temperature and improving color rendering index can be achieved. Therefore, the development of red light emitting materials that can be excited by blue light is a current research focus.
Mn4+The outermost electron configuration of the ion is 3d 3Energy level splitting can occur in a strong octahedral crystal field environment to generate Mn 4+Of ions d-dTransition, and exhibits broad absorption bands in the ultraviolet and blue regions of the excitation spectrum, respectively, which are respectively assigned to Mn 4+Of ions 4A2g4T1gAnd 4A2g4T2gA spin-allowed transition; at the same time, an emission spectrum is generated 2Eg→4A2gthe characteristic is just suitable for white light LED excited by a blue light chip, and if the characteristic can be suitable for the blue light chip, the quality of the white light can be effectively improved 4+There are often differences in luminescence properties among different matrix systems. At present, Mn is suitable 4+Doped radicals Materials are mainly classified into two major classes, oxides and fluorides. When Mn is present 4+In an oxide matrix, the absorption is generally at 300 nm, the emission is generally in the long-wave region after 700 nm, some emission spectra are even outside the human eye sensitivity range, and the color purity of red light is not high Chem. Mater.,2015, 27, 2938.](ii) a In contrast, Mn 4+When in a fluoride matrix, the strongest absorption is generally at 460 nm and the emission is in the range of 600 to 650 nm ACS Appl. Mater. Interfaces, 2017,9, 8805.]therefore, the performance improvement of the white light LED by the red luminescent material taking fluoride as the matrix can be obviously improved.
for this reason, the invention discloses a white LED containing Mn 4+The red luminescent material which is a luminescent center and takes double perovskite fluoride as a matrix has the chemical composition of Rb 2KGa1-xF6:xMn4+the material has excellent light emitting characteristics of wide blue light excitation band and narrow red light emitting peak, and is a red light emitting material suitable for white light L ED.
Disclosure of Invention
the invention aims to provide a white LED light source which is suitable for white LED and uses Mn 4+The red luminescent material takes ions as active centers and double perovskite fluoride as a matrix.
in order to achieve the purpose, the invention relates to a double perovskite fluoride red luminescent material for white light L ED, which has the chemical composition of Rb 2KGa1-xF6:xMn4+X is Mn as doped 4+Ion-opposed Ga 3+Molar percentage coefficient of ion, 0.0 <x ≤ 0.20。
The red luminescent material has strong red light emission under the excitation of blue light with the wavelength of 420-470 nm, and the red light emission is formed by Mn 4+The ion phonon vibration band and the zero phonon vibration peak, wherein the main emission peak is positioned at 628 nm, and the zero phonon vibration peak is positioned at 620 nm. The red luminescent material of the invention and Y are mixed 3Al5O12:Ce3+Yellow fluorescent powder and epoxy resin AB adhesive the white L ED is mixed according to a certain proportion and coated on a blue light GaN chip to prepare warm white L ED with low color temperature and high color rendering index.
Drawings
FIG. 1 is an XRD diffraction pattern of a red luminescent material according to the present invention;
FIG. 2 is an EDS spectrum of the red luminescent material according to the present invention;
FIG. 3 shows the excitation and emission spectra of the red phosphor of the present invention at room temperature;
FIG. 4 shows a red phosphor and Y according to the present invention 3Al5O12:Ce3+mixing yellow fluorescent powder and epoxy resin AB glue according to a certain proportion, and coating the mixture on a blue light GaN chip to prepare a white light L ED device, wherein the white light L ED device has an electroluminescence spectrogram under the working condition of 20 mA;
FIG. 5 is a graph of the electroluminescence spectra of a white light L ED at different currents (20 mA, 60mA, 100mA, 140 mA).
Detailed Description
Example 1:
Respectively weighing 0.03 g of epoxy resin A glue, 0.03 g of epoxy resin B glue and 0.03 g of epoxy resin Y 3Al5O12:Ce3+Yellow phosphor 0.003 g, Rb 2KGa1- xF6:xMn4+0.012 g of red luminescent material was mixed and stirred in a 2.0 ml sample tube to homogenize the mixture. Then, the mixture was coated on a blue GaN chip prepared in advance, and then dried in an oven at 120 ℃ for 2 hours, and finally tested under a current of 20 mA.
Wherein Rb used 2KGa1-xF6:xMn4+The XRD powder diffraction pattern of the red luminescent material is shown in figure 1, and the diffraction peak of the sample and the matrix material Rb 2KGaF6The standard card diffraction peaks of (A) are completely consistent, indicating that the sample has a single crystalline phase.
Rb2KGa1-xF6:xMn4+The EDS energy spectrum of the red luminescent material is shown in figure 2, a sample contains six elements of Rb, K, Ga, Mn, F and Au, wherein Au is caused by gold spraying during sample test, and the rest five elements and Rb 2KGa1-xF6:xMn4+The element types contained in (1) are completely consistent.
Shown in FIG. 3 as Rb 2KGa1-xF6:xMn4+Excitation and emission spectra at room temperature. The strongest absorption peaks of the excitation spectrum are respectively positioned at 358 nm and 462 nm; the emission spectrum consists of several narrow emission peaks of 610-650 nm, where the strongest emission of the phonon vibration band is located at 628 nm and the zero phonon vibration peak is located at 620 nm.
Example 2:
Respectively weighing 0.03 g of epoxy resin A glue, 0.03 g of epoxy resin B glue and 0.03 g of epoxy resin Y 3Al5O12:Ce3+Yellow phosphor 0.003 g, Rb 2KGa1- xF6:xMn4+0.018 g of red luminescent material was mixed and stirred in a 2.0 ml sample tube to homogenize the mixture. Then, the mixture was coated on a blue GaN chip prepared in advance, and then dried in an oven at 120 ℃ for 2 hours, and finally tested under a current of 20 mA.
FIG. 4 is an electroluminescence spectrum of L ED white light LED produced in this embodiment, Rb 2KGa1-xF6:xMn4+the red luminescent material is added into a white L ED luminescent system to ensure the color temperature of white light T c Reduced to 3824K and color rendering index R a the white light L ED is increased to 90.2, and various performance indexes of the white light L ED are optimized.
Example 3:
Respectively weighing 0.03 g of epoxy resin A glue, 0.03 g of epoxy resin B glue and 0.03 g of epoxy resin Y 3Al5O12:Ce3+Yellow phosphor 0.003 g, Rb 2KGa1- xF6:xMn4+0.024 g of red luminescent material was mixed and stirred in a 2.0 ml sample tube to homogenize. Then, the mixture was coated on a blue GaN chip prepared in advance, and then dried in an oven at 120 ℃ for 2 hours, and finally tested under a current of 20 mA.
Example 4:
Respectively weighing 0.03 g of epoxy resin A glue, 0.03 g of epoxy resin B glue and 0.03 g of epoxy resin Y 3Al5O12:Ce3+Yellow phosphor 0.003 g, Rb 2KGa1- xF6:xMn4+0.018 g of red luminescent material was mixed and stirred in a 2.0 ml sample tube to homogenize the mixture. Then, the mixture was coated on a blue GaN chip prepared in advance, and then dried in an oven at 120 ℃ for 2 hours, and finally tested under a current of 60 mA.
Example 5:
Respectively weighing 0.03 g of epoxy resin A glue, 0.03 g of epoxy resin B glue and 0.03 g of epoxy resin Y 3Al5O12:Ce3+Yellow phosphor 0.003 g, Rb 2KGa1- xF6:xMn4+0.018 g of red luminescent material was mixed and stirred in a 2.0 ml sample tube to homogenize the mixture. Then, the mixture was coated on a blue GaN chip prepared in advance, and then dried in an oven at 120 ℃ for 2 hours, and finally tested under a current of 100 mA.
Example 6:
Respectively weighing 0.03 g of epoxy resin A glue, 0.03 g of epoxy resin B glue and 0.03 g of epoxy resin Y 3Al5O12:Ce3+Yellow phosphor 0.003 g, Rb 2KGa1- xF6:xMn4+0.018 g of red luminescent material was mixed and stirred in a 2.0 ml sample tube to homogenize the mixture. Then, the mixture was coated on a blue GaN chip prepared in advance, and then dried in an oven at 120 ℃ for 2 hours, and finally tested under a current of 140 mA.
FIG. 5 is a graph showing electroluminescence spectra of white light L ED prepared in practical examples 2, 4, 5 and 6 at drive currents of 20mA, 60 mA, 100 mA and 140 mA.

Claims (6)

1. A double perovskite fluoride red luminescent material for white light L ED has the chemical composition of Rb 2KGa1-xF6:xMn4+. x is Mn as doped 4+Ion-opposed Ga 3+Molar percentage coefficient of ion, 0.0 <x ≤ 0.20。
2. The method of claim 1 the double perovskite fluoride red luminescent material for white light L ED is characterized in that the adopted host material Rb is 2KGaF6Has a double perovskite structure, and Mn 4+Does not change the double perovskite configuration of the host material.
3. the double perovskite fluoride red luminescent material for the white light L ED as claimed in claim 1, which is characterized in that under the excitation of blue light, a series of narrow-band red light emission peaks with the wavelength of 610-650 nm can be generated.
4. The narrow-band red emission according to claim 3 wherein the four sharp red emission peaks are located at 612nm, 620 nm, 628 nm and 645 nm, respectively, wherein 628 nm is the strongest emission peak and each emission peak has a half-peak width of less than 5 nm.
5. the double perovskite fluoride red phosphor for a white light LED as claimed in claim 1, wherein the red phosphor is mixed with Y 3Al5O12: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 warm white light L ED.
6. the warm white L ED of claim 5, characterized by a lower color temperature(s) ((s)) T c <4000 K) And a higher color rendering index: ( R a >90)。
CN202010465479.1A 2020-05-28 2020-05-28 double perovskite fluoride red luminescent material for white light LED Pending CN111454719A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113201329A (en) * 2021-04-27 2021-08-03 云南民族大学 Perovskite type fluoride luminescent material and preparation method thereof

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113201329A (en) * 2021-04-27 2021-08-03 云南民族大学 Perovskite type fluoride luminescent material and preparation method thereof
CN113201329B (en) * 2021-04-27 2022-07-12 云南民族大学 Perovskite type fluoride luminescent material and preparation method thereof

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