CN-118325605-B - Europium-doped sodium-manganese mica red luminescent material and preparation method and application thereof

Abstract

The invention relates to the field of red luminescent materials, and particularly discloses a europium-doped sodium-manganese mica red luminescent material, and a preparation method and application thereof. The chemical general formula of the europium-doped sodium-manganese mica red luminescent material is NaMg a Mn 3‑a AlSi 3 O 10 F 2 :xEu 2+ , x=2mol% -5mol%, and a=2.4-2.8. According to the invention, sodium-manganese mica is used as a luminous matrix, eu 2+ is used as a sensitizer, a part of Mg 2+ in an octahedral position in fluorophlogopite is replaced by Mn 2+ , mn 2+ is used as an activator and appears in the matrix, eu 2+ is doped in the matrix, the red light emission of Mn 2+ is greatly enhanced under the effect of Eu 2+ →Mn 2+ energy transfer, and the interlayer cation K + of the manganese mica is exchanged through Na + to regulate and control the crystal lattice of the mica matrix, so that the europium-doped sodium-manganese mica red luminous material has great application potential in the field of LEDs for plant growth.

Inventors

• SHI SHIKAO
• QI NA

Assignees

• 河北师范大学

Dates

Publication Date

20260505

Application Date

20240416

Claims (10)

1. 1. A europium-doped sodium-manganese mica red luminescent material is characterized in that the chemical general formula is NaMg a Mn 3-a AlSi 3 O 10 F 2 : xEu 2+ ; Wherein x=2mol% -5mol%, a=2.4-2.75, mn 2+ is an activator, and Eu 2+ is a sensitizer.
2. 2. The europium-doped sodium manganese mica red light emitting material according to claim 1, wherein in the chemical formula of the europium-doped sodium manganese mica red light emitting material, x=2.5 to 4mol% and a=2.4 to 2.7.
3. 3. A method for preparing the europium-doped sodium manganese mica red light-emitting material according to claim 1 or 2, which comprises the following steps: And sintering the raw materials of Na 2 SiF 6 、MgO、Al 2 O 3 、SiO 2 、MnCO 3 and Eu 2 O 3 at 1000-1200 ℃ to obtain the europium-doped sodium-manganese mica red luminescent material.
4. 4. The method for preparing the europium-doped sodium-manganese mica red light-emitting material according to claim 3, wherein the molar ratio of Na 2 SiF 6 、MgO、Al 2 O 3 、SiO 2 to MnCO 3 is 0.5 (2.4-2.8): 0.5:2.5 (0.6-0.25).
5. 5. The method for preparing the europium-doped sodium-manganese mica red luminescent material according to claim 3, wherein the sintering adopts a gradient heating mode, and the heating rate is 3-7 ℃ per minute.
6. 6. The method for preparing the europium-doped sodium manganese mica red light-emitting material according to claim 3, wherein the sintering heat preservation time is 4.5-6 hours.
7. 7. A phosphor-converted light emitting diode comprising the europium-doped sodium manganese mica red luminescent material of claim 1 or 2 or a europium-doped sodium manganese mica red luminescent material prepared by the method for preparing the europium-doped sodium manganese mica red luminescent material of any one of claims 3 to 6.
8. 8. A method of making a phosphor converted light emitting diode according to claim 7, comprising the steps of: s1, dispersing the europium-doped sodium-manganese mica red luminescent material in epoxy resin to obtain fluorescent rubber powder; S2, coating the fluorescent glue powder on an ultraviolet chip under the current of 55-65 mA, and drying to obtain the fluorescent powder converted light-emitting diode.
9. 9. The method of claim 8, wherein in step S1, the volume ratio of the europium-doped sodium-manganese mica red luminescent material to the epoxy resin is 1 (0.8-1.2).
10. 10. Use of the phosphor-converted light emitting diode of claim 7 or the phosphor-converted light emitting diode produced by the method for producing a phosphor-converted light emitting diode of claim 8 or 9 in plant cultivation.

Description

Europium-doped sodium-manganese mica red luminescent material and preparation method and application thereof Technical Field The invention relates to the field of red fluorescent materials, in particular to a europium-doped sodium-manganese mica red luminescent material, and a preparation method and application thereof. Background Key parameters of plants during growth are spectral range, illumination time and light intensity. Sunlight can provide energy required by photosynthesis of plants and can also regulate vital activities of the plants (such as seed germination, stem and leaf growth and the like), but the sunlight is not easy to manually control, so that a controllable artificial light source is required to irradiate the plants to better promote the growth of the plants. In the current plant illumination equipment, a Light Emitting Diode (LED) has the advantages of controllable light emitting color, long service life, low radiant heat, environmental friendliness and the like, and becomes a main artificial light source for plant cultivation. Research shows that the photoreceptors of the plants in the red light and far-red light regions are photosensitive pigments, and the photosensitive pigments mainly have two stable existing forms of red light absorption type (P r) and far-red light absorption type (P fr), and have indispensable effects on seed germination, yellowing removal, stem elongation and the like of the plants. The fluorescent material has the characteristic of adjustable luminescence, so that the fluorescent material which can emit light and is matched with the absorption spectrum of the plant photosensitizing pigments P r and P fr is developed, and has important significance for plant illumination. In the transition metal manganese ion doped luminescent material, mn 4+ has a specific 3d 3 electronic structure, mn 2+ has a specific 3d 5 electronic structure, so that the material is very sensitive to the surrounding environment, and manganese ions can be influenced by surrounding ions or a crystal field in a crystal, so that the material shows different luminescence phenomena. Typically Mn 2+ exhibits orange or red emission when in an octahedral coordinated crystal field and green emission when in a tetrahedrally coordinated crystal field. However, limited by the difficulty of selecting matrix materials, relatively few studies have been conducted on Mn 2+, very small doping concentrations (less than 1%), and low luminescence quantum yields. Compared with fluoride fluorescent materials, the oxide fluorescent materials have more stable properties and simpler preparation method. Therefore, it is a key to research to find an oxide luminescent material suitable for activation of Mn 2+ and to increase its luminescence intensity. Mica belongs to one kind of layered silicate, and its laminate is composed of structural units of tetrahedron-octahedron-tetrahedron, similar to sandwich structure, and metal cations such as K +、Na+、Ca2+ or Ba 2+ can be arranged between layers, and the structural units are repeatedly stacked to form mica. The synthetic mica prepared by the high-temperature solid phase method has the characteristics of purity, insulation, strong adhesive force, high transparency, good thermal stability and the like, and the most widely applied synthetic mica is fluorophlogopite (KMg 3AlSi3O10F2). However, there are few reports of mica as a light-emitting substrate. Disclosure of Invention Aiming at the problems of low luminous quantum yield and the like of a red fluorescent material in the prior art, the invention provides a europium-doped sodium-manganese mica red luminescent material, a preparation method and application thereof, wherein the excitation range of the europium-doped sodium-manganese mica red luminescent material is 230-410 nm, the luminous intensity is obviously improved, and when excited by 365nm light, CIE chromaticity coordinates are positioned at (0.721,0.279), so that the europium-doped sodium-manganese mica red luminescent material has huge application potential in the fields of deep red and far red LEDs for plant growth. In order to achieve the above purpose, the present invention provides the following technical solutions. In a first aspect, the invention provides a europium-doped sodium-manganese mica red luminescent material with a chemical formula of NaMg aMn3-aAlSi3O10F2:xEu2+, wherein x=2mol% to 5mol% and a=2.4 to 2.8. Preferably, in the chemical general formula of the europium-doped sodium manganese mica red luminescent material, x=2.5 mol% to 4mol%, and a=2.4 to 2.7. In the chemical general formula of the europium-doped sodium-manganese mica red luminescent material, x is the mole percentage of Eu 2+ to NaMg aMn3-aAlSi3O10F2. Compared with the prior art, the europium-doped sodium-manganese mica red luminescent material provided by the invention has the advantages that a part of Mg 2+ in an octahedral position in fluorophlogopite is replaced by Mn 2+, mn 2+ is