Green luminescent material and preparation method thereof

Abstract

The invention provides a green luminescent material, the chemical composition expression of which is Ba < 1-x > Zn < 1-y > Al < 10 > O < 17 >: xEu < 2 + >, yMn < 2 + >, wherein x is not less than 0.01 and not more than 0.15; 0.05 < = y < = 0.65. The preparation method has the characteristics of simplicity in preparation, low cost, high safety and suitability for large-scale production. The green luminescent material can be excited by near ultraviolet, has the strongest emission peak at the wavelength of 510-540 nm, and is narrow in emission spectrum full width at half maximum, high in luminescent intensity and excellent in thermal stability. The green luminescent material meets the application requirements of preparation of a photoluminescent device on the performance of the luminescent material.

Description

Technical Field

[0001] The present invention belongs to the technical field of luminescent materials, and in particular relates to a green luminescent material and a preparation method thereof. Background Art

[0002] With the rapid development of the high-definition video industry, people have put forward higher requirements for liquid crystal display technology, one of the important indicators is color gamut, coverage and color coordinate triangle area. The LED backlight used for LCD usually uses a combination of blue LED and one or two luminescent materials. Therefore, the luminescent material plays an important role in improving the color gamut coverage. In order to promote the development of display technology, luminescent materials with high brightness, narrow half-peak width and high stability are urgently needed.

[0003] For luminescent materials, the peak position and half-width (FWHM) are key factors affecting the color gamut, color purity and luminous efficiency of display devices. In order to improve the color and display effect of the display, it is of great significance to develop a luminescent material with narrow emission half-width and high luminous intensity. Usually, LED backlight sources are based on InGaN blue light emitting chips, narrow-band green light emitting β-SiAlON:Eu 2+ And commercial red light powder K2SiF6:Mn 4+ (KSF). The human eye is more sensitive to green light, and narrow-band green luminescent materials are of great significance for improving the color gamut of display devices. Among the current mainstream green luminescent materials for LED backlight display, β-SiAlON:Eu 2+ It has excellent luminous efficiency and stability, but it has the problem of relatively wide half-peak width of emission spectrum and large particle size. 2+ Doped green luminescent materials have attracted the attention of many researchers due to their good performance, but due to the 2+ middle 3 The spin-forbidden transition of d5 electrons has low absorption efficiency, resulting in low external quantum efficiency. In recent years, with the development of semiconductor technology, the efficiency of near-ultraviolet LED chips has gradually improved. The solution of combining near-ultraviolet LED chips with red, green and blue luminescent materials has shown more and more potential. Therefore, it is very important to develop corresponding efficient, stable and easy-to-prepare narrow-band green luminescent materials. Summary of the invention

[0004] In view of the problems of the prior art, the present invention provides a green luminescent material and a preparation method thereof, which has the characteristics of simple preparation, low cost, high safety and suitability for large-scale production. The obtained green luminescent material can be efficiently excited by near-ultraviolet light, has a wide half-width of the emission spectrum, high luminescence intensity and excellent thermal stability.

[0005] To achieve the above object, the first aspect of the present invention provides a narrow-band green luminescent material, the chemical composition of which is expressed as: Ba1-x Zn 1-y Al 10 O 17 :xEu 2+ ,yMn 2+ ; Wherein 0.01≤x≤0.15; 0.05≤y≤0.65; the green luminescent material can be excited by near-ultraviolet light and has the strongest emission peak at a wavelength of 510nm-540nm.

[0006] A second aspect of the present invention provides a method for preparing a green luminescent material, characterized by comprising the following steps:

[0007] According to the chemical formula and stoichiometric ratio, raw materials containing Ba, Zn, Al, Eu and Mn elements are weighed into a grinding container, ground manually or by ball milling, placed in a reaction container, and sintered in a reducing atmosphere at a sintering temperature of 1350°C to 1550°C for 3h to 10h. After cooling to room temperature, the product is ground to obtain the green luminescent material.

[0008] Preferably, the raw material containing Ba element is at least one of BaCO3, Ba(HCO3)2, Ba(OH)2, and Ba(CH3COO)2;

[0009] Preferably, the raw material containing Zn element is at least one of ZnO, ZnCO3, and Zn(CH3COO)2;

[0010] Preferably, the raw material containing Al element is at least one of Al2O3 and Al(OH)3;

[0011] Preferably, the raw material containing Eu element is Eu2O3;

[0012] Preferably, the raw material containing the Mn element is at least one of MnCO3, MnO, and Mn(CH3COO)2;

[0013] A third aspect of the present invention provides an application of a green luminescent material, wherein the green luminescent material is used for preparing a photoluminescent device.

[0014] Compared with the prior art, the present invention has the following advantages:

[0015] 1. The green luminescent material described in the present invention can be excited by 250-400nm near-ultraviolet light, and the emission spectrum covers the range of 500-550nm, with a narrow half-peak width, high luminescent intensity and excellent thermal stability.

[0016] 2. The particle size distribution of the green luminescent material described in the present invention is uniform.

[0017] 3. The color gamut of the LED device obtained by the green phosphor prepared by the method of the present invention can reach 115% of the NTSC standard (National Television Committee standard of the United States), which can meet the application requirements of optoelectronic devices for the light color performance of luminescent materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 The XRD diffraction pattern of the product obtained in Example 1 and the standard data card comparison chart;

[0019] Figure 2 is the excitation spectrum and emission spectrum of the product obtained in Example 5;

[0020] Figure 3 is a SEM image of the product obtained in Example 5;

[0021] Figure 4 It is a data diagram of the performance (color coordinate diagram, emission spectrum) of the color conversion LED device packaged with the product obtained in Example 7. DETAILED DESCRIPTION

[0022] The technical solution of the present invention is further described below by specific implementation methods. The embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0023] Example 1

[0024] A method for preparing green luminescent material

[0025] Weigh 0.1184 g of barium carbonate (BaCO3), 0.2968 g of aluminum hydroxide (Al(OH)3), 0.0566 g of zinc carbonate (ZnCO3), 0.0013 g of europium oxide (Eu2O3), and 0.0024 g of manganese acetate (Mn(CH3COO)2) respectively, add anhydrous ethanol to the above raw materials in an agate mortar and grind them manually. After grinding evenly, put them into a corundum crucible and sinter them in a reducing gas atmosphere at a sintering temperature of 1350°C and a sintering time of 6 hours. Then cool to room temperature and grind the product to obtain the green luminescent material.

[0026] Example 2

[0027] A method for preparing green luminescent material

[0028] Weigh 0.1172 g of barium carbonate (BaCO3), 0.3068 g of aluminum oxide (Al2O3), 0.0517 g of zinc carbonate (ZnCO3), 0.0021 g of europium oxide (Eu2O3), and 0.0084 g of manganese acetate (Mn(CH3COO)2) respectively, grind the above raw materials manually in an agate mortar, put them into a corundum crucible after grinding evenly, and sinter them in a reducing gas atmosphere at a sintering temperature of 1400°C and a sintering time of 6 hours. Then cool them to room temperature and grind the products to obtain the green luminescent material.

[0029] Example 3

[0030] A method for preparing green luminescent material

[0031] Weigh 0.1159 g of barium carbonate (BaCO3), 0.3068 g of aluminum oxide (Al2O3), 0.0568 g of zinc carbonate (ZnCO3), 0.0063 g of europium oxide (Eu2O3), and 0.0152 g of manganese acetate (Mn(CH3COO)2) respectively, add anhydrous ethanol to the above raw materials in an agate mortar and grind them manually. After grinding evenly, put them into a corundum crucible and sinter them in a reducing gas atmosphere at a sintering temperature of 1450°C and a sintering time of 6 hours. Then cool to room temperature and grind the product to obtain the green luminescent material.

[0032] Example 4

[0033] A method for preparing green luminescent material

[0034] Weigh 0.1148 g of barium carbonate (BaCO3), 0.3068 g of aluminum oxide (Al2O3), 0.0319 g of zinc oxide (ZnO), 0.0084 g of europium oxide (Eu2O3), and 0.0242 g of manganese carbonate (MnCO3) respectively, add anhydrous ethanol to the above raw materials in an agate mortar and grind them manually. After grinding evenly, put them into a corundum crucible and sinter them in a reducing gas atmosphere at a sintering temperature of 1550°C and a sintering time of 6 hours. Then cool to room temperature and grind the product to obtain the green luminescent material.

[0035] Example 5

[0036] A method for preparing green luminescent material

[0037] Weigh 0.1172 g of barium carbonate (BaCO3), 0.2968 g of aluminum hydroxide (Al(OH)3), 0.0270 g of zinc oxide (ZnO), 0.0021 g of europium oxide (Eu2O3), and 0.0310 g of manganese carbonate (MnCO3) respectively, add anhydrous ethanol to the above raw materials in an agate mortar and grind them manually. After grinding evenly, put them into a corundum crucible and sinter them in a reducing gas atmosphere at a sintering temperature of 1550°C and a sintering time of 4 hours. Then cool to room temperature and grind the product to obtain the green luminescent material.

[0038] Example 6

[0039] A method for preparing green luminescent material

[0040] Weigh 0.1172 g of barium carbonate (BaCO3), 0.2968 g of aluminum hydroxide (Al(OH)3), 0.0221 g of zinc oxide (ZnO), 0.0021 g of europium oxide (Eu2O3), and 0.0379 g of manganese carbonate (MnCO3) respectively, add anhydrous ethanol to the above raw materials in an agate mortar and grind them manually. After grinding evenly, put them into a corundum crucible and sinter them in a reducing gas atmosphere at a sintering temperature of 1550°C and a sintering time of 4 hours. Then cool them to room temperature and grind the products to obtain the green luminescent material.

[0041] Example 7

[0042] A method for preparing green luminescent material

[0043] Weigh 0.1172 g of barium carbonate (BaCO3), 0.2968 g of aluminum hydroxide (Al(OH)3), 0.0172 g of zinc oxide (ZnO), 0.0021 g of europium oxide (Eu2O3), and 0.0448 g of manganese carbonate (MnCO3) respectively, add anhydrous ethanol to the above raw materials in an agate mortar and grind them manually. After grinding evenly, put them into a corundum crucible and sinter them in a reducing gas atmosphere at a sintering temperature of 1550°C and a sintering time of 6 hours. Then cool to room temperature and grind the product to obtain the green luminescent material.

[0044] The above embodiments are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with the technology to understand the content of the present invention and implement it accordingly, and they cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.

Claims

1. A green luminescent material, characterized in that: Its chemical composition expression is: Ba 1-x Zn 1-y Al 10 O 17 :xEu 2+ ,yMn 2 + ; Wherein 0.01≤x≤0.15; 0.05≤y≤0.65; the green luminescent material can be excited by near-ultraviolet light and has the strongest emission peak at a wavelength of 510nm-540nm.

2. The green luminescent material according to claim 1, characterized in that: The emission spectrum half-width of the green luminescent material ranges from 25 to 40 nm.

3. A method for preparing a green luminescent material, characterized in that: The method comprises the following steps: According to the chemical formula and stoichiometric ratio, raw materials containing Ba, Zn, Al, Eu and Mn elements are weighed into a grinding container, ground manually or by ball milling, placed in a reaction container, and sintered in a reducing atmosphere at a sintering temperature of 1350°C to 1550°C for 3h to 10h. After cooling to room temperature, the product is ground to obtain the green luminescent material.

4. The preparation method according to claim 4, characterized in that: The raw material containing Ba element in the step is at least one of BaCO3, Ba(HCO3)2, Ba(OH)2, and Ba(CH3COO)2; the raw material containing Zn element is at least one of ZnO, ZnCO3, and Zn(CH3COO)2; the raw material containing Al element is at least one of Al2O3 and Al(OH)3; the raw material containing Eu element is Eu2O3; the raw material containing Mn element is at least one of MnCO3, MnO, and Mn(CH3COO)2.

5. The green luminescent material according to claim 1 is used in a photoluminescent device.

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