Nitrogen oxide green fluorescent material, preparation method and device thereof

Abstract

This invention provides a nitrogen oxide green fluorescent material, its preparation method, and its application. The general chemical formula of the nitrogen oxide green fluorescent material is Ba. 1‑x Eu x LnSiO3N, wherein Ln can be one or more of Sc, Y, La, Gd, or Lu, and Sc is essential, and Sc accounts for >50% (molar ratio) of Ln.

Description

Technical Field

[0001] This invention relates to the field of luminescent material preparation technology, and in particular to a nitrogen oxide green fluorescent material and its preparation method and device. Background Technology

[0002] White light devices, also known as visible light devices, are widely used in lighting, display backlighting, and other industries. White light is a composite light, composed of monochromatic light within the wavelength range of 380–780 nm. The simplest way to achieve white light is by using the so-called three primary colors, namely, white light obtained by combining red, green, and blue light. For currently widely used LED white light devices, as shown in Patent Document 1 (Wang Le, Zheng Zishan, Zhang Hong, Li Yanghui, A high color rendering index, high S / P value white LED and its method of obtaining and application, CN107369742A), it is easy to obtain a high color rendering index white light device by exciting green and red fluorescent materials with a blue light chip. However, to further improve the color rendering index of white light devices, using a violet light chip to excite blue, green, and red fluorescent materials is a more feasible approach, as disclosed in Patent Document 2 (Chen Chao, Yang Xing, Chen Jiachao, Li Yang, A near-ultraviolet / violet light excited single-chip full-spectrum LED and its preparation method, CN110335935B). Therefore, it is particularly important to develop fluorescent materials suitable for violet light excitation.

[0003] Recently, several patent documents have been published regarding green fluorescent materials excited by violet light. For example, patent document 3 (Wang Hao, Zhao Shuai, Guo Yumeng, Dang Yanping, Guo Wenli, Li Shuxin, Wu Bo, Wu Yibo, Shang Yuwei, Yang Dan, A green fluorescent material and its preparation method, CN105694858B) discloses a green fluorescent material and its preparation method. The molecular formula of this fluorescent material is: C 28 H 14 N5O 29 Tb3K2, however, is an organic material and cannot withstand very high temperatures. LED devices can even generate high-temperature environments of up to 200°C during operation, which will cause the aforementioned organic green fluorescent materials to age faster.

[0004] Patent document 4 (Kim Ji-hyun, Kim Yoon-chang, Yoo Yong-chan, Park Do-hyung, Choi Ik-kyu, Kim Min-joo, Heo Kyung-jae, Song Mi-ran, Lee Hyun-deok, Song Jae-hyuk, Kwon Seon-hwa, Song Yu-mi, Seo Jin-hyung, Lee Young-hoon, Kim Ji-hyun, Kim Young-ki, Green Phosphor and Display Device Including the Same, CN101497788A) discloses a green phosphor and a display device including the same, made of chemical formula (Y). 3-x Ce x ) a Al b O cThe green phosphor is represented by x, a, b, and c satisfying the following relationships: 0 < x ≤ 1, 0.5 ≤ a ≤ 3, 3 ≤ b ≤ 9, and 2c = 9a + 3b. A drawback of this phosphor is that its luminescent center is Ce. 3+ Therefore, the emission spectrum has a relatively wide half-width at half-maximum (HWHM), which is suitable for white light illumination, but not for display backlighting, because the fluorescent materials used in display backlighting require a narrow HWHM as much as possible.

[0005] Patent document 5 (Bae Myeong-hoon, Kim Chang-hwan, Yoo Young-cheol, Park Soon-geun, Lee Sang-il, Kim Hyun-kyu, Kim Sung-hoon, Green Phosphor, Green Phosphor Composition and Plasma Display Panel, CN101724399A) discloses a green phosphor with the chemical formula (Lu). 3-x Ce x Al5O 12 The x satisfies the relationship 0 < x < 3. This green fluorescent material is LuAG:Ce, which is widely used in white light illumination. Although LuAG:Ce has high luminous efficiency and stable chemical properties, it has the same problem as patent document 4, namely, the luminescent center of this green phosphor is Ce. 3+ Therefore, its emission spectrum has a wide half-width at half-maximum, which is suitable for white light illumination, but not for display backlighting.

[0006] Patent document 6 (Zhao Li, A green fluorescent powder material containing Ba element nitride oxide and its preparation method, CN101948687A) discloses a green fluorescent material containing Ba nitride oxide, with the general chemical formula (Ba, A). 2- x Si y O z N 2+4y-2z The formula is xEu, where 0 ≤ x < 1.0, 0 < y ≤ 1.0, 1 < z ≤ 2.0, and A is Ca or Sr. The preparation method of this green fluorescent material adopts a two-step approach. The first step synthesizes the precursor A₂SiO₄ for the oxynitride green phosphor, where A is Ca or Sr. This precursor provides a stable crystal structure. The second step involves doping Ba into the matrix structure provided by the precursor. By adjusting the ratio of Si and Ba, the emission wavelength of the green phosphor can be modulated, achieving a peak emission wavelength between 516 and 540 nm. Although the obtained oxynitride green fluorescent material has high luminous brightness, suitable for lighting and use in high color rendering index backlight white LEDs, the synthesis route is cumbersome and costly.

[0007] As an improvement, patent document 7 (Zhao Li, a method for preparing a nitrogen oxide green phosphor material, CN102191045B) discloses a nitrogen oxide green phosphor material with the general chemical formula (Ba, A). 2-x Siy (O, B) z N 2+4y-2z : xEu, where 0≤x<1.0, 0<y≤1.0, 1<z≤2.0, A is Ca or Sr, and B is F or Cl. That is, based on patent document 6, a halogen element is added. The preparation of this oxynitride green fluorescent material also requires a two-step method: first, synthesizing the precursor A₂SiO₄; second, doping elements into the matrix structure provided by the precursor A₂SiO₄, ultimately synthesizing the oxynitride green fluorescent material (Ba, A). 2-x Si y (O, B) z N 2+4y-2z Although the obtained oxynitride green fluorescent material has high luminous brightness, which is satisfactory for lighting and for use in high color rendering index backlight white LEDs, the synthesis route is complicated and the cost is high; moreover, the halogen elements contained in the material will corrode the silver wires and reflectors used in the packaging device, thereby reducing the reliability of the device.

[0008] Similarly, patent document 8 (Gao Shaokang, Li Zhaomei, Hu Xiaolin, Green phosphor for white LED and its preparation method and application, CN102391859A) discloses a green phosphor for white LED and its preparation method and application, the chemical formula of which is Ca6Sr 4-x (Si2O7)3Cl2:xEu 2+ This phosphor is synthesized using CaO, SiO2, CaCl2, and SrCO3 as raw materials, Eu2O3 as an activator, and excess CaCl2 as a flux, via a high-temperature solid-state method under a reducing atmosphere. The phosphor disclosed in this invention can be efficiently excited in the ultraviolet-near-ultraviolet band and exhibits high luminous efficiency, thus it can be used to prepare white LEDs excited by ultraviolet-near-ultraviolet LEDs. Although this phosphor has a low calcination temperature and a simple preparation method, similar to patent document 7, the material disclosed in patent document 8 also contains halogens, which will corrode the silver wires and reflectors used in the encapsulation device, thereby reducing the reliability of the device.

[0009] Patent document 9 (Liu Yongfu, Jiang Jun, Jiang Haochuan, A green phosphor and its preparation method and application, CN105441077A) discloses a green phosphor and its preparation method. The chemical formula of the green phosphor is: (Ba 1-x- y Sr x Eu y )9Lu2Si6O 24Where 0≤x≤0.9999, 0.0001≤y≤0.3, 0.0001≤x+y≤1, and x and y are mole fractions. Although the green phosphor provided by this invention has advantages such as low production cost, simple manufacturing process, and wide excitation wavelength range, as a silicate phosphor, it inherently suffers from low chemical stability and poor thermal quenching characteristics.

[0010] Patent document 10 (Wang Hao, Huang Xiaoyu, Li Kai, Wang Weimin, Fu Zhengyi, A method for preparing a divalent manganese ion-doped MgAlON green phosphor with tunable optical properties, CN108531166A) discloses a method for preparing a divalent manganese ion-doped MgAlON green phosphor with tunable optical properties, the chemical composition of which is Mn z Mg 8-x-3y-z Al 16+x+2y O 32-x N x Where: 0≤x≤3, 0≤y≤2, 0.1≤z≤0.7. Although the emission spectrum of this green fluorescent material has a narrow half-width at half-maximum (WHM), the synthesis of MgAlON requires extremely high temperatures. Furthermore, because the transition element Mn is used as the luminescent center, Mn has poor light absorption, resulting in a low quantum efficiency and a biased absorption of violet light.

[0011] Patent document 11 (Liang Chao, He Jinhua, Fu Yibing, Europium-activated silicate green phosphor and its application in white light-emitting diodes, CN101851508B) discloses a europium-activated silicate green phosphor and its application in white light-emitting diodes, with the chemical formula Ba. (2-x-y-p) Sr x M p Si q O (2+2q) Eu y Wherein, M is at least one of Sc, Y, La, Cr or Er; 0.03 < x ≤ 0.75; 0.001 < y ≤ 0.09; 0.0003 ≤ p ≤ 0.05; 0.75 ≤ q < 1. Similar to patent document 9, as a silicate phosphor, it inherently suffers from low chemical stability and poor thermal quenching characteristics.

[0012] Patent document 12 (Zhao Li, A Green Phosphor Material Containing Al-containing Nitrogen Oxide and Its Preparation Method, CN101948689A) discloses a green phosphor material containing Al-containing nitrogen oxide and its preparation method, which also adopts a two-step synthesis. The first step is to synthesize an Al-containing precursor A2SiO4, where A is one of Ca, Ba, or Sr. The second step is to dope Al into the matrix structure provided by the precursor. By adjusting the ratio of Si and Al, the green phosphor A is modulated. 1-x (Si, Al)y O z N 2 / 3+4 / 3y-2 / 3z The emission wavelength of xEu. Similar to the problems in Patent Documents 6 and 7, although the obtained oxynitride green fluorescent material has high luminous brightness, which is satisfactory for lighting and for use in high color rendering index backlight white LEDs, the synthesis path is complicated and the cost is high.

[0013] Patent document 13 (Huang Lin, Zhang Ge, Wang Jing, A green phosphor and its preparation method and its application in white LED devices, CN108504358A) discloses a green phosphor with the chemical formula: Ca 1-x Sc2O4:xCe 3+ The green phosphor, where 0.001 ≤ x ≤ 0.90, and x is the Ce dopant. 3+ The molar percentage coefficient relative to Ca. Similar to the problems found in Patent Documents 4 and 5, the disadvantage of this phosphor is that the luminescent center of this green phosphor is Ce. 3+ Therefore, the emission spectrum has a relatively wide half-width at half-maximum (HWHM), which is suitable for white light illumination, but not for display backlighting, because the fluorescent materials used in display backlighting require a narrow HWHM as much as possible.

[0014] Patent document 14 (Duan Chengjun, Gu Jingtao, Zhou Weixin, A borate phosphate phosphor emitting green fluorescence and its preparation method and application, CN104449723B) discloses a borate green phosphor with the general chemical formula: (Ln 1-x Tb x )7O6(BO3)(PO4)2, where Ln is a rare earth element, 0.01≤x≤0.1. The green fluorescence emission of this boron phosphate phosphor is entirely due to Tb. 3+ outer electrons 5 D4→ 7 This is due to the F5 magnetic dipole transition. However, although the borophosphate phosphor of this invention has the advantages of simple preparation method and narrow emission spectrum half-maximum width at half maximum, its absorption of violet light is weak, making it difficult to directly apply to white LEDs excited by violet light.

[0015] Patent document 15 (Yang Zhiping, Wang Hailong, Dong Xiuqin, A β-SiAlON:Eu) 2+ The paper CN105295908B discloses a green phosphor with the general chemical formula Eu. a Si b Al c O d N eThe green phosphor is obtained by the following formula: 0 < a ≤ 0.010, 0.4 ≤ b ≤ 0.5, 0.01 ≤ c ≤ 0.02, 0.006 ≤ d ≤ 0.02, 0.47 < e ≤ 0.664. Although the green phosphor obtained by this invention has the advantages of uniform particle size, large average particle size and high luminous intensity, and has broad prospects in the preparation of white LED devices, the synthesis of this phosphor material requires sintering at 1900-2200℃ for 8-12 hours. Such a high synthesis temperature places extremely high demands on the equipment used for sintering phosphors, meaning that the synthesis of this phosphor material is very difficult.

[0016] Patent document 16 (Tao Ying, A core-shell structured aluminate green phosphor and its preparation method, CN102373060B) discloses a core-shell structured aluminate green phosphor and its preparation method. The phosphor comprises a core and a shell. The core is a low-Tb content aluminate green phosphor with a particle size of 3–8 μm, and the shell is an oxide of Ce and Tb, with the composition formula (Ce... x Tb m Ce y Tb n )MgAl 11 O 19 Where 0.6≤x+y≤0.8, 0≤m+n≤0.4, 1≤n:m≤4. Similar to patent document 14, the green fluorescence emission of this aluminate phosphor is entirely due to Tb. 3+ outer electrons 5 D4→ 7 This is due to the F5 magnetic dipole transition. However, although the aluminate phosphor of this invention has the advantages of simple preparation method and narrow emission spectrum half-maximum width at half maximum, its absorption of violet light is weak, making it difficult to directly apply to white LEDs excited by violet light.

[0017] Patent document 17 (Xi Zengwei, Li Yongqiang, Zhang Yanmin, Wang Wubao, Huang Yiqun, Sun Yunfei, A method for manufacturing a borate green phosphor, CN101696356B) discloses a borate green phosphor with the chemical formula (Y). 1-x-y- z Gd x M y Tb z BO3, where X = 0–0.5, y = 0.0–0.05, z = 0.1–1.0, and M is an oxide of Al, Sc, Ce, or La. Similar to Patent Documents 14 and 16, the green fluorescence emission of this borate phosphor is entirely due to Tb. 3+ outer electrons 5 D4→ 7This is due to the F5 magnetic dipole transition. However, although the borate phosphor of this invention has the advantages of simple preparation method and narrow emission spectrum half-maximum width at half maximum, its absorption of violet light is weak, making it difficult to directly apply to white LEDs excited by violet light.

[0018] Patent document 18 (Zhang Jiahua, Xiao Wenge, Zhang Xia, Hao Zhendong, Pan Guohui, A silicate green phosphor and its preparation method, CN104403668B) discloses a silicate green phosphor and its preparation method, wherein the phosphor has the chemical formula Ca. 3-x-y-z Ce x Tb y A z Sc 2-m Mg m Si 3-n Al n O 12 Where A is one or any combination of elements Li, Na, and K; x, y, z, m, and n are mole fractions, with values ​​ranging from 0.005 ≤ x ≤ 0.2, 0.005 ≤ y ≤ 0.5, 0 ≤ z ≤ 0.5, 0 ≤ m ≤ 0.5, and 0 ≤ n ≤ 0.5, respectively. This phosphor is prepared using a high-temperature solid-state method, and its composition is determined by Ce... 3+ and Tb 3+ Co-doping with Ce 3+ 、Tb 3+ Effective energy transfer between them to extend the range of luminescent ions Tb 3+ Within the effective excitation range of the ultraviolet region, Tb was achieved. 3+ The broadening of its excitation spectrum from 250–300 nm to 200–380 nm allows for better matching with UV / UV LED chips. However, Ce... 3+ and Tb 3+ The effective energy transfer efficiency between them is low, therefore, the photoluminescence efficiency of this fluorescent material is low and its practicality is poor.

[0019] In summary, existing literature reveals a severe lack of green fluorescent materials that simultaneously possess a narrow emission spectrum, good chemical stability, high quantum efficiency, and the ability to effectively absorb violet light. Therefore, it is essential to develop a green fluorescent material with a narrow emission spectrum (FWHM), good chemical stability, high quantum efficiency, and the ability to effectively absorb violet light, and to fabricate a device using this material for applications in lighting, display backlighting, and other industries, serving fields such as indoor lighting and high-definition displays. Summary of the Invention

[0020] The primary objective of this invention is to protect a nitrogen oxide green fluorescent material. The general chemical formula of the nitrogen oxide green fluorescent material is: Ba 1-x Eu xLnSiO3N, wherein Ln is one or more of Sc, Y, La, Gd, or Lu, and Sc is essential, with Sc accounting for >50% (molar ratio) of Ln, and 0 < x ≤ 0.2; under violet light excitation, this green fluorescent material can produce an emission wavelength with a main peak range between 505 and 535 nm and a full width at half maximum (FWHM) of the emission spectrum less than or equal to 90 nm. Preferably, in the general chemical formula of the oxynitride green fluorescent material, 0.02 < x ≤ 0.05; the luminescence intensity after aging in a sealed container containing 200°C high-pressure water vapor for 48 hours is not less than 75% of the luminescence intensity at room temperature.

[0021] A second objective of this invention is to provide a method for preparing a green fluorescent material of oxynitrides. The method includes mixing a Ba precursor, an Eu precursor, an Ln precursor, and a Si precursor, and then performing a high-temperature solid-state reaction under a reducing atmosphere to obtain a green fluorescent material of oxynitrides. Specifically, the molar ratio of the Ba precursor, Eu precursor, Ln precursor, and Si precursor is (1-X):X:1:1, and the chemical formula of the obtained material is: Ba 1-x Eu x LnSiO3N, where 0 < x ≤ 0.2.

[0022] This invention also provides a green fluorescent glass and its preparation method. The green fluorescent glass is obtained by mixing the nitrogen oxide green fluorescent material with glass powder and then carrying out a high-temperature solid-state reaction. Specifically, the high-temperature solid-state reaction is carried out in an air atmosphere. The temperature of the high-temperature solid-state reaction is 500-800°C and the time of the high-temperature solid-state reaction is 0.1-1h.

[0023] The present invention also provides a green laser device, the device comprising a violet laser diode and a light-emitting layer, the light-emitting layer comprising the green fluorescent glass.

[0024] The specific plan is as follows:

[0025] A nitrogen oxide green fluorescent material, the general chemical formula of which is:

[0026] Ba 1-x Eu x LnSiO3N

[0027] Wherein, Ln is one or more of Sc, Y, La, Gd, or Lu, and Sc is required, and Sc accounts for more than 50% of the Ln content (molar ratio), and 0 < x ≤ 0.2.

[0028] Preferably, 0.02 < x ≤ 0.05.

[0029] A second objective of this invention is to provide a method for preparing a nitrogen oxide green fluorescent material. The preparation method comprises the following steps:

[0030] Ba precursor, Eu precursor, Ln precursor and Si precursor are mixed and subjected to high-temperature solid-state reaction under a reducing atmosphere to obtain the oxynitride green fluorescent material.

[0031] Preferably, in this step, the molar ratio of Ba, Eu, Ln and Si in the Ba precursor, Eu precursor, Ln precursor and Si precursor is (1-X):X:1:1.

[0032] Preferably, in the above steps, the Ba precursor is selected from one or more of Ba carbonate, Ba oxide, or Ba nitrate; optionally, the Eu precursor is selected from Eu2O3; optionally, the Ln precursor is one or more of Sc2O3, Y2O3, La2O3, Gd2O3, or Lu2O3, wherein Sc2O3 is mandatory; optionally, the Si precursor is SiO2 or Si3N4.

[0033] Preferably, the purity of the Ba precursor, Eu precursor, Ln precursor and Si precursor is not less than 99.5 wt%.

[0034] Preferably, in the above steps, the temperature of the high-temperature solid-phase reaction is between 1500 and 1600°C, and the time of the high-temperature solid-phase reaction under a reducing atmosphere is between 4 and 10 hours.

[0035] This invention also protects a fluorescent glass based on oxynitride green fluorescent material. The manufacturing method is as follows: the oxynitride green fluorescent material is mixed with glass powder and then subjected to a high-temperature solid-state reaction to obtain the oxynitride green fluorescent glass.

[0036] Preferably, the mass ratio of nitrogen oxide green fluorescent material to glass powder is 1:1 to 1:4.

[0037] Preferably, the melting point of the glass powder is 500–800℃.

[0038] Preferably, the temperature for the high-temperature solid-state reaction between the nitrogen oxide green fluorescent material and the glass powder is 500–800°C, and the reaction time is 0.1–1 h.

[0039] This invention also protects a light-emitting device based on a fluorescent glass made of oxynitride green fluorescent material. The light-emitting device includes a violet laser diode and a light-emitting layer, the light-emitting layer comprising the oxynitride green fluorescent glass, and the light-emitting layer emitting green light when excited by the violet laser diode.

[0040] Beneficial effects

[0041] This invention provides a nitrogen oxide green fluorescent material, its preparation method, and its application. The general chemical formula of the nitrogen oxide green fluorescent material is Ba.1-x Eu x LnSiO3N, wherein Ln can be one or more of Sc, Y, La, Gd, or Lu, and Sc is essential, with Sc accounting for >50% (molar ratio) of Ln, and 0 < x ≤ 0.2; under violet light excitation, this green fluorescent material produces an emission wavelength with a main peak range of 505–535 nm and a full width at half maximum (FWHM) of the emission spectrum less than or equal to 90 nm. Compared with existing technologies, the oxynitride green fluorescent material prepared by this invention has a novel chemical composition, a narrower FWHM of the emission spectrum, better chemical stability, high quantum efficiency, and can effectively absorb violet light, thus enabling this luminescent material to be applied in industries such as lighting and display backlights. Attached Figure Description

[0042] Figure 1 The emission spectrum of the luminescent material obtained in Example 6 of this invention;

[0043] Figure 2 The excitation spectrum of the luminescent material obtained in Example 6 of this invention; Detailed Implementation

[0044] The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention.

[0045] To facilitate understanding of the present invention, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of the invention.

[0046] It should be noted that, unless otherwise specified, the embodiments and features described in this application can be combined with each other. The present invention will now be described in detail with reference to the embodiments.

[0047] The general chemical formula of the nitrogen oxide green fluorescent material is as follows:

[0048] Ba 1-x Eu x LnSiO3N

[0049] Ln can be one or more of Sc, Y, La, Gd, or Lu, and Sc is required, and Sc accounts for more than 50% of the Ln content (molar ratio), and 0 < x ≤ 0.2.

[0050] In some embodiments provided by the present invention, x is preferably 0.001, and Ln is preferably Sc; in some embodiments provided by the present invention, x is preferably 0.002, and Ln is preferably Sc; in some embodiments provided by the present invention, x is preferably 0.005, and Ln is preferably Sc; in some embodiments provided by the present invention, x is preferably 0.01, and Ln is preferably Sc; in some embodiments provided by the present invention, x is preferably 0.02, and Ln is preferably Sc; in some embodiments provided by the present invention, x is preferably 0.05, and Ln is preferably Sc; in some embodiments provided by the present invention, x is preferably 0.08, and Ln is preferably Sc; in some embodiments provided by the present invention... In some embodiments, x is preferably 0.1, and Ln is preferably Sc; in some embodiments provided by the present invention, x is preferably 0.15, and Ln is preferably Sc; in some embodiments provided by the present invention, x is preferably 0.2, and Ln is preferably Sc; in some embodiments provided by the present invention, x is preferably 0.05, Ln is preferably Sc and Y, and the molar ratio of Sc to Y is 9:1; in some embodiments provided by the present invention, x is preferably 0.05, Ln is preferably Sc and La, and the molar ratio of Sc to La is 9:1; in some embodiments provided by the present invention, x is preferably 0.05, Ln is preferably Sc and Gd, and the molar ratio of Sc to Gd is 9:1; In some embodiments provided by the invention, x is preferably 0.05, Ln is preferably Sc and Lu, and the molar ratio of Sc to Lu is 9:1; in some embodiments provided by the invention, x is preferably 0.05, Ln is preferably Sc, Y and La, and the molar ratio of Sc to Y and La is 8:1:1; in some embodiments provided by the invention, x is preferably 0.05, Ln is preferably Sc, Y and Gd, and the molar ratio of Sc to Y and Gd is 8:1:1; in some embodiments provided by the invention, x is preferably 0.05, Ln is preferably Sc, Y and Lu, and the molar ratio of Sc to Y and Lu is 8:1:1; in some embodiments provided by the invention, x is preferably 0. 0.05, Ln is preferably Sc, La, and Gd, and the molar ratio of Sc, La, and Gd is 8:1:1; in some embodiments provided by the present invention, x is preferably 0.05, Ln is preferably Sc, La, and Lu, and the molar ratio of Sc, La, and Lu is 8:1:1; in some embodiments provided by the present invention, x is preferably 0.05, Ln is preferably Sc, Y, La, and Gd, and the molar ratio of Sc, Y, La, and Gd is 8:1:1; in some embodiments provided by the present invention, x is preferably 0.05, Ln is preferably Sc, Y, La, and Gd, and the molar ratio of Sc, Y, La, and Gd is 7:1:1:1; in some embodiments provided by the present invention, x is preferably 0.0.05, where Ln is preferably Sc, Y, La, and Lu, and the molar ratio of Sc, Y, La, and Lu is 7:1:1:1; in some embodiments provided by the present invention, x is preferably 0.05, Ln is preferably Sc, La, Gd, and Lu, and the molar ratio of Sc, La, Gd, and Lu is 7:1:1:1; in other embodiments provided by the present invention, x is preferably 0.05, Ln is preferably Sc, Y, La, Gd, and Lu, and the molar ratio of Sc, Y, La, Gd, and Lu is 6:1:1:1:1.

[0051] The specific steps of the method for preparing the nitrogen oxide green fluorescent material are as follows:

[0052] A green fluorescent material of oxynitrides was obtained by mixing Ba precursor, Eu precursor, Ln precursor and Si precursor and carrying out a high-temperature solid-state reaction under a reducing atmosphere.

[0053] In the aforementioned steps, the molar ratio of Ba, Eu, Ln, and Si in the Ba precursor, Eu precursor, Ln precursor, and Si precursor is (1-X):X:1:1, and the chemical formula of the resulting material is: Ba 1-x Eu x LnSiO3N, wherein Ln is one or more of Sc, Y, La, Gd, or Lu, and Sc is required, and Sc accounts for more than 50% of the Ln content (molar ratio), and 0 < x ≤ 0.2.

[0054] In the steps described, the Ba precursor can be any Ba-containing compound well-known in the art, without any special limitations. In this invention, the Ba precursor is preferably selected from one or more of Ba carbonates, Ba oxides, and Ba nitrates, and more preferably from Ba carbonates (i.e., barium carbonate); the Eu precursor is selected from Eu2O3; the Ln precursor is selected from Ln oxides, namely Sc2O3, Y2O3, La2O3, Gd2O3, and Lu2O3; and the Si precursor is SiO2 and Si3N4.

[0055] The purity of the Ba precursor, Eu precursor, Ln precursor and Si precursor is not less than 99.5%. The higher the purity, the fewer impurities in the obtained luminescent material.

[0056] The reducing atmosphere in the above steps can be any dry atmosphere known to those skilled in the art, and there are no special restrictions. In this invention, a nitrogen-hydrogen mixture is preferred.

[0057] In the above steps, the temperature of the high-temperature solid phase is preferably 1500-1600°C, and the atmosphere is a mixture of nitrogen and hydrogen. In some embodiments provided by the present invention, the temperature of the high-temperature solid phase is preferably 1500°C.

[0058] The preferred time for the high-temperature solid phase in the above steps is 4 to 10 hours, more preferably 5 to 8 hours; in some embodiments provided by the present invention, the preferred time for the high-temperature solid phase is 6 hours.

[0059] The high-temperature solid reaction phase is preferably carried out in a high-temperature furnace. After the initial reaction, the furnace is cooled to room temperature to obtain a nitrogen oxide green fluorescent material.

[0060] This invention utilizes a high-temperature solid-state reaction to successfully prepare a green fluorescent material of nitrogen oxides.

[0061] The lighting device made of a nitrogen oxide green fluorescent material comprises at least a violet laser diode and a light-emitting layer. The light-emitting layer is a green fluorescent glass.

[0062] The aforementioned green fluorescent glass uses a chemical formula: Ba 1-x Eu x LnSiO3N (where Ln is one or more of Sc, Y, La, Gd, or Lu, and Sc is essential, and the content of Sc in Ln is >50% (molar ratio), 0 < x ≤ 0.2) is a nitrogen oxide green fluorescent material that is mixed with low melting point glass powder and then subjected to a high-temperature solid-state reaction to finally prepare the material.

[0063] The green fluorescent glass is prepared in an air atmosphere. The temperature of the high-temperature solid-phase reaction is preferably 500-800°C. In some embodiments of the present invention, the temperature of the high-temperature solid-phase reaction is preferably 700°C. The time of the high-temperature solid-phase reaction is preferably 0.1-1 h. In some embodiments of the present invention, the time of the high-temperature solid-phase reaction is preferably 0.5 h, and finally a green fluorescent glass is obtained.

[0064] To further illustrate the present invention, the following describes in detail, with reference to embodiments, a nitrogen oxide green fluorescent material and its preparation method provided by the present invention.

[0065] All reagents used in the following comparative examples and embodiments are commercially available.

[0066] The chemical stability of fluorescent materials was evaluated using a method described in Chinese Patent CN104422676A (Jie Rongjun, Zhou Tianliang, Rapid Aging Equipment, CN104422676A). First, the luminescence intensity of the corresponding fluorescent material at 25°C was recorded and defined as 100 (relative intensity). Then, the samples were aged in a rapid aging equipment at 200°C for 48 hours. After aging, the luminescence intensity of the aged fluorescent material was measured. Generally, if the rapid aging method is used to age the fluorescent material, and the luminescence intensity remains at 75 (relative intensity) after aging at 200°C for 48 hours, the fluorescent material is considered to have good chemical stability.

[0067] In the nitrogen-hydrogen mixed atmosphere used in the following comparative examples and embodiments, the hydrogen volume content was 20%.

[0068] The Ba, Eu, Ln, and Si precursors used in the comparative examples and embodiments are merely illustrative and do not constitute a limitation on the precursor raw materials. The purity of the precursors is not less than 99.5 wt%.

[0069] Comparative Example 1

[0070] The material described in this comparative example, Ba 0.95 Eu 0.05 Si2O2N2, a commercially available product, was used. First, the luminescence intensity of this material at 25℃ was measured and defined as 100 (relative intensity). Then, the material was placed in a rapid aging apparatus and aged at 200℃ for 48 hours. After aging, the luminescence intensity before and after aging was measured, revealing a low luminescence intensity (see Table 1). This indicates that the material corresponding to Comparative Example 1 is not a chemically stable fluorescent material.

[0071] Comparative Example 2

[0072] The material described in this comparative example contains a compound with the chemical formula: Ba 0.95 Eu 0.05 YSiO3N. Using BaCO3, Eu2O3, Y2O3, SiO2, and Si3N4 as raw materials, its composition is as follows: Ba 0.95 Eu 0.05 The raw material was accurately weighed according to the stoichiometric ratio of YSiO3N, and sintered at 1500℃ in a nitrogen-hydrogen mixed atmosphere for 6 hours. After cooling, the product with a nominal chemical composition of Ba was obtained. 0.95 Eu 0.05 YSiO3N material. The emission spectrum of the luminescent material was measured using a fluorescence spectrometer, revealing that the main peak of the emission spectrum is located at 595 nm, and the full width at half maximum (FWHM) of the emission spectrum is 3 nm, clearly corresponding to Eu. 3+ The fd transition indicates that the material obtained in Comparative Example 2 is not a nitrogen oxide green fluorescent material.

[0073] Comparative Example 3

[0074] The material described in this comparative example contains a compound with the chemical formula: Ba 0.95 Eu 0.05 LaSiO3N. Using BaCO3, Eu2O3, La2O3, SiO2, and Si3N4 as raw materials, its composition is as follows: Ba 0.95 Eu 0.05The raw materials for LaSiO3N were accurately weighed according to their stoichiometric ratio, sintered at 1500℃ in a nitrogen-hydrogen mixed atmosphere for 6 hours, and after cooling, the product with a nominal chemical composition of Ba was obtained. 0.95 Eu 0.05 The material is LaSiO3N. The emission spectrum of the luminescent material was measured using a fluorescence spectroscopy instrument. The main peak of the emission spectrum was found to be located at 595 nm, and the full width at half maximum (FWHM) of the emission spectrum was 3 nm, clearly corresponding to Eu. 3+ The fd transition indicates that the material obtained in Comparative Example 3 is not a nitrogen oxide green fluorescent material.

[0075] Comparative Example 4

[0076] The material described in this comparative example contains a compound with the chemical formula: Ba 0.95 Eu 0.05 GdSiO3N. Using BaCO3, Eu2O3, Gd2O3, SiO2, and Si3N4 as raw materials, according to its composition: Ba 0.95 Eu 0.05 The raw materials for GdSiO3N are accurately weighed according to their stoichiometric ratio, sintered at 1500℃ in a nitrogen-hydrogen mixed atmosphere for 6 hours, and after cooling, the product with a nominal chemical composition of Ba is obtained. 0.95 Eu 0.05 The material is GdSiO3N. The emission spectrum of the luminescent material was measured using a fluorescence spectrometer, revealing that the main peak of the emission spectrum is located at 595 nm, and the full width at half maximum (FWHM) of the emission spectrum is 3 nm, clearly corresponding to Eu. 3+ The fd transition indicates that the material obtained in Comparative Example 4 is not a nitrogen oxide green fluorescent material.

[0077] Comparative Example 5

[0078] The material described in this comparative example contains a compound with the chemical formula: Ba 0.95 Eu 0.05 LuSiO3N. Made from BaCO3, Eu2O3, Lu2O3, SiO2, and Si3N4 as raw materials, its composition is as follows: Ba 0.95 Eu 0.05 The raw materials for LuSiO3N were accurately weighed according to their stoichiometric ratio, sintered at 1500℃ in a nitrogen-hydrogen mixed atmosphere for 6 hours, and after cooling, the product with a nominal chemical composition of Ba was obtained. 0.95 Eu 0.05 The material is LuSiO3N. The emission spectrum of the luminescent material was measured using a fluorescence spectroscopy instrument. The main peak of the emission spectrum was found to be located at 595 nm, and the full width at half maximum (FWHM) of the emission spectrum was 3 nm, clearly corresponding to Eu. 3+ The fd transition indicates that the material obtained in Comparative Example 5 is not a nitrogen oxide green fluorescent material.

[0079] Comparative Example 6

[0080] The material described in this comparative example contains a compound with the chemical formula: Ba 0.95 Ce 0.05 ScSiO3N. Using BaCO3, CeO2, Sc2O3, SiO2, and Si3N4 as raw materials, its composition is as follows: Ba 0.95 Ce 0.05 The raw materials were accurately weighed according to the stoichiometric ratio of ScSiO3N, and sintered at 1500℃ in a nitrogen-hydrogen mixed atmosphere for 6 hours. After cooling, the product with a nominal chemical composition of Ba was obtained. 0.95 Ce 0.05 The material ScSiO3N. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer, revealing that its main peak was located at 495 nm, and its full width at half maximum (FWHM) was 121 nm. Although the emission spectrum of the material obtained in Comparative Example 6 contained some green light, it was not a nitrogen oxide green fluorescent material, but rather a cyan-green fluorescent material, and its FWHM was too wide, making it unsuitable for backlighting displays.

[0081] Comparative Example 7

[0082] The material described in this embodiment contains a compound with the chemical formula: Ba 0.999 Eu 0.001 Sc 0.4 Y 0.6 SiO3N. Using BaCO3, Eu2O3, Sc2O3, Y2O3, SiO2, and Si3N4 as raw materials, according to its composition Ba... 0.999 Eu 0.001 Sc 0.4 Y 0.6 The raw materials for SiO3N were accurately weighed according to their stoichiometric ratio, sintered at 1500℃ in a nitrogen-hydrogen mixed atmosphere for 6 hours, and after cooling, the material with a nominal chemical composition of Ba was obtained. 0.999 Eu 0.001 Sc 0.4 Y 0.6SiO3N. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer. The full width at half maximum (FWHM) and the position of the main peak of the emission spectrum are shown in Table 1. Table 1 shows that the material prepared in Comparative Example 7, under 400 nm violet light excitation, has an emission spectrum around 506 nm and a FWHM of approximately 75 nm. Therefore, the material obtained in Comparative Example 7 is a nitrogen oxide green fluorescent material. The luminescence intensity at 25 °C was measured and defined as 100 (relative intensity). The material was then placed in a rapid aging apparatus and aged at 200 °C for 48 h. After aging, the luminescence intensity before and after aging was measured, revealing a low luminescence intensity, as detailed in Table 1. Therefore, the material corresponding to Comparative Example 7 is a green fluorescent material with poor chemical stability.

[0083] Example 1

[0084] The material described in this embodiment contains a compound with the chemical formula: Ba 0.999 En 0.001 ScSiO3N. Using BaCO3, Eu2O3, Sc2O3, SiO2, and Si3N4 as raw materials, according to its composition Ba... 0.999 Eu 0.001 The raw materials for ScSiO3N were accurately weighed according to their stoichiometric ratio, sintered at 1500℃ in a nitrogen-hydrogen mixed atmosphere for 6 hours, and after cooling, the material with a nominal chemical composition of Ba was obtained. 0.999 Eu 0.001 ScSiO3N. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer. The full width at half maximum (FWHM) and the position of the main peak of the emission spectrum are shown in Table 1. Table 1 shows that the material prepared in Example 1, under 400 nm violet light excitation, has an emission spectrum around 507 nm and a FWHM of approximately 77 nm. Therefore, the material obtained in Example 1 is a nitride green fluorescent material. The luminescence intensity at 25°C was measured and defined as 100 (relative intensity). The material was then placed in a rapid aging apparatus and aged at 200°C for 48 hours. The luminescence intensity before and after aging was measured, revealing a high luminescence intensity, as detailed in Table 1. Therefore, the material corresponding to Example 1 is a green fluorescent material with high chemical stability.

[0085] Example 2

[0086] The material described in this embodiment contains a compound with the chemical formula: Ba 0.998 Eu 0.002 ScSiO3N. Using BaCO3, Eu2O3, Sc2O3, SiO2, and Si3N4 as raw materials, according to its composition Ba... 0.998 Eu 0.002The raw materials for ScSiO3N were accurately weighed according to their stoichiometric ratio, sintered at 1500℃ in a nitrogen-hydrogen mixed atmosphere for 6 hours, and after cooling, the material with a nominal chemical composition of Ba was obtained. 0.998 Eu 0.002 ScSiO3N. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer. The full width at half maximum (FWHM) and the position of the main peak of the emission spectrum are shown in Table 1. Table 1 shows that the material prepared in Example 2, under 400 nm violet light excitation, has an emission spectrum around 510 nm and a FWHM of approximately 79 nm. Therefore, the material obtained in Example 2 is a nitride green fluorescent material. The luminescence intensity at 25°C was measured and defined as 100 (relative intensity). The material was then placed in a rapid aging apparatus and aged at 200°C for 48 hours. The luminescence intensity before and after aging was measured, showing a relatively high intensity, as detailed in Table 1. Therefore, the material corresponding to Example 2 is a green fluorescent material with high chemical stability.

[0087] Example 3

[0088] The material described in this embodiment contains a compound with the chemical formula: Ba 0.995 Eu 0.005 ScSiO3N. Using BaCO3, Eu2O3, Sc2O3, SiO2, and Si3N4 as raw materials, according to its composition Ba... 0.995 Eu 0.005 The raw materials for ScSiO3N were accurately weighed according to their stoichiometric ratio, sintered at 1500℃ in a nitrogen-hydrogen mixed atmosphere for 6 hours, and after cooling, the material with a nominal chemical composition of Ba was obtained. 0.995 Eu 0.005 ScSiO3N. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer. The full width at half maximum (FWHM) and the position of the main peak of the emission spectrum are shown in Table 1. Table 1 shows that the material prepared in Example 3, under 400 nm violet light excitation, has an emission spectrum around 515 nm and a FWHM of approximately 81 nm. Therefore, the material obtained in Example 3 is a nitrogen oxide green fluorescent material. The luminescence intensity at 25°C was measured and defined as 100 (relative intensity). The material was then placed in a rapid aging apparatus and aged at 200°C for 48 hours. The luminescence intensity before and after aging was measured, revealing a high luminescence intensity, as detailed in Table 1. Therefore, the material corresponding to Example 3 is a green fluorescent material with high chemical stability.

[0089] Example 4

[0090] The material described in this embodiment contains a compound with the chemical formula: Ba 0.99 Eu 0.01ScSiO3N. Using BaCO3, Eu2O3, Sc2O3, SiO2, and Si3N4 as raw materials, according to its composition Ba... 0.99 Eu 0.01 The raw materials for ScSiO3N were accurately weighed according to their stoichiometric ratio, sintered at 1500℃ in a nitrogen-hydrogen mixed atmosphere for 6 hours, and after cooling, the material with a nominal chemical composition of Ba was obtained. 0.99 Eu 0.01 ScSiO3N. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer. The full width at half maximum (FWHM) and the position of the main peak of the emission spectrum are shown in Table 1. Table 1 shows that the material prepared in Example 4, under 400 nm violet light excitation, has an emission spectrum around 519 nm and a FWHM of approximately 82 nm. Therefore, the material obtained in Example 4 is a nitride green fluorescent material. The luminescence intensity at 25°C was measured and defined as 100 (relative intensity). The material was then placed in a rapid aging apparatus and aged at 200°C for 48 hours. The luminescence intensity before and after aging was measured, revealing a high luminescence intensity, as detailed in Table 1. Therefore, the material corresponding to Example 4 is a green fluorescent material with high chemical stability.

[0091] Example 5

[0092] The material described in this embodiment contains a compound with the chemical formula: Ba 0.98 Eu 0.02 ScSiO3N. Using BaCO3, Eu2O3, Sc2O3, SiO2, and Si3N4 as raw materials, according to its composition Ba... 0.98 Eu 0.02 The raw materials for ScSiO3N were accurately weighed according to their stoichiometric ratio, sintered at 1500℃ in a nitrogen-hydrogen mixed atmosphere for 6 hours, and after cooling, the material with a nominal chemical composition of Ba was obtained. 0.98 Eu 0.02 ScSiO3N. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer. The full width at half maximum (FWHM) and the position of the main peak of the emission spectrum are shown in Table 1. Table 1 shows that the material prepared in Example 5, under 400 nm violet light excitation, has an emission spectrum around 520 nm and a FWHM of approximately 86 nm. Therefore, the material obtained in Example 5 is a nitride green fluorescent material. The luminescence intensity at 25°C was measured and defined as 100 (relative intensity). The material was then placed in a rapid aging apparatus and aged at 200°C for 48 hours. The luminescence intensity before and after aging was measured, revealing a high luminescence intensity, as detailed in Table 1. Therefore, the material corresponding to Example 5 is a green fluorescent material with high chemical stability.

[0093] Example 6

[0094] The material described in this embodiment contains a compound with the chemical formula: Ba 0.95 Eu 0.05 ScSiO3N. Using BaCO3, Eu2O3, Sc2O3, SiO2, and Si3N4 as raw materials, according to its composition Ba... 0.95 Eu 0.05 The raw materials for ScSiO3N were accurately weighed according to their stoichiometric ratio, sintered at 1500℃ in a nitrogen-hydrogen mixed atmosphere for 6 hours, and after cooling, the material with a nominal chemical composition of Ba was obtained. 0.95 Eu 0.05 ScSiO3N. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer. The full width at half maximum (FWHM) and the position of the main peak of the emission spectrum are shown in Table 1. As can be seen from Table 1, the material prepared in Example 6, under 400 nm violet light excitation, has an emission spectrum located near 525 nm (see Table 1). Figure 1 The emission spectrum has a full width at half maximum (FWHM) of approximately 88 nm. Therefore, the material obtained in Example 6 is a nitride green fluorescent material. Measuring the excitation spectrum of this material reveals that it exhibits strong absorption of violet light (see...). Figure 2 The luminescence intensity at 25°C was measured and defined as 100 (relative intensity). The material was then placed in a rapid aging apparatus and aged at 200°C for 48 hours. After aging, the luminescence intensity before and after aging was measured, and it was found that the luminescence intensity was relatively high, as shown in Table 1. It can be seen that the material corresponding to Example 6 is a green fluorescent material with high chemical stability.

[0095] Example 7

[0096] The material described in this embodiment contains a compound with the chemical formula: Ba 0.92 Eu 0.08 ScSiO3N. Using BaCO3, Eu2O3, Sc2O3, SiO2, and Si3N4 as raw materials, according to its composition Ba... 0.92 Eu 0.08 The raw materials for ScSiO3N were accurately weighed according to their stoichiometric ratio, sintered at 1500℃ in a nitrogen-hydrogen mixed atmosphere for 6 hours, and after cooling, the material with a nominal chemical composition of Ba was obtained. 0.92 Eu 0.08ScSiO3N. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer. The full width at half maximum (FWHM) and the position of the main peak of the emission spectrum are shown in Table 1. Table 1 shows that the material prepared in Example 7, under 400 nm violet light excitation, has an emission spectrum around 527 nm and a FWHM of approximately 89 nm. Therefore, the material obtained in Example 7 is a nitride green fluorescent material. The luminescence intensity at 25°C was measured and defined as 100 (relative intensity). The material was then placed in a rapid aging apparatus and aged at 200°C for 48 hours. The luminescence intensity before and after aging was measured, revealing a high luminescence intensity, as detailed in Table 1. Therefore, the material corresponding to Example 7 is a green fluorescent material with high chemical stability.

[0097] Example 8

[0098] The material described in this embodiment contains a compound with the chemical formula: Ba 0.9 Eu 0.1 ScSiO3N. Using BaCO3, Eu2O3, Sc2O3, SiO2, and Si3N4 as raw materials, according to its composition Ba... 0.9 Eu 0.1 The raw materials for ScSiO3N were accurately weighed according to their stoichiometric ratio, sintered at 1500℃ in a nitrogen-hydrogen mixed atmosphere for 6 hours, and after cooling, the material with a nominal chemical composition of Ba was obtained. 0.9 Eu 0.1 ScSiO3N. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer. The full width at half maximum (FWHM) and the position of the main peak of the emission spectrum are shown in Table 1. Table 1 shows that the material prepared in Example 8, under 400 nm violet light excitation, has an emission spectrum around 529 nm and a FWHM of approximately 89 nm. Therefore, the material obtained in Example 8 is a nitride green fluorescent material. The luminescence intensity at 25°C was measured and defined as 100 (relative intensity). The material was then placed in a rapid aging apparatus and aged at 200°C for 48 hours. The luminescence intensity before and after aging was measured, revealing a high luminescence intensity, as detailed in Table 1. Therefore, the material corresponding to Example 8 is a green fluorescent material with high chemical stability.

[0099] Example 9

[0100] The material described in this embodiment contains a compound with the chemical formula: Ba 0.85 Eu 0.15 ScSiO3N. Using BaCO3, Eu2O3, Sc2O3, SiO2, and Si3N4 as raw materials, according to its composition Ba... 0.85 Eu 0.15The raw materials for ScSiO3N were accurately weighed according to their stoichiometric ratio, sintered at 1500℃ in a nitrogen-hydrogen mixed atmosphere for 6 hours, and after cooling, the material with a nominal chemical composition of Ba was obtained. 0.85 Eu 0.15 ScSiO3N. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer. The full width at half maximum (FWHM) and the position of the main peak of the emission spectrum are shown in Table 1. Table 1 shows that the material prepared in Example 9, under 400 nm violet light excitation, has an emission spectrum around 530 nm and a FWHM of approximately 89 nm. Therefore, the material obtained in Example 9 is a nitride green fluorescent material. The luminescence intensity at 25°C was measured and defined as 100 (relative intensity). The material was then placed in a rapid aging apparatus and aged at 200°C for 48 hours. The luminescence intensity before and after aging was measured, revealing a high luminescence intensity, as detailed in Table 1. Therefore, the material corresponding to Example 9 is a green fluorescent material with high chemical stability.

[0101] Example 10

[0102] The material described in this embodiment contains a compound with the chemical formula: Ba 0.8 Eu 0.2 ScSiO3N. Using BaCO3, Eu2O3, Sc2O3, SiO2, and Si3N4 as raw materials, according to its composition Ba... 0.8 Eu 0.2 The raw materials for ScSiO3N were accurately weighed according to their stoichiometric ratio, sintered at 1500℃ in a nitrogen-hydrogen mixed atmosphere for 6 hours, and after cooling, the material with a nominal chemical composition of Ba was obtained. 0.8 Eu 0.2 ScSiO3N. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer. The full width at half maximum (FWHM) and the position of the main peak of the emission spectrum are shown in Table 1. Table 1 shows that the material prepared in Example 10, under 400 nm violet light excitation, has an emission spectrum around 534 nm and a FWHM of approximately 89 nm. Therefore, the material obtained in Example 10 is a nitride green fluorescent material. The luminescence intensity at 25°C was measured and defined as 100 (relative intensity). The material was then placed in a rapid aging apparatus and aged at 200°C for 48 hours. The luminescence intensity before and after aging was measured, revealing a high luminescence intensity, as detailed in Table 10. Therefore, the material corresponding to Example 10 is a green fluorescent material with high chemical stability.

[0103] Example 11

[0104] The material described in this embodiment contains a compound with the chemical formula: Ba 0.95 Eu 0.05 Sc 0.9 Y 0.1SiO3N. Using BaCO3, Eu2O3, Sc2O3, Y2O3, SiO2, and Si3N4 as raw materials, according to its composition Ba... 0.95 Eu 0.05 Sc 0.9 Y 0.1 The raw materials for SiO3N were accurately weighed according to their stoichiometric ratio, sintered at 1500℃ in a nitrogen-hydrogen mixed atmosphere for 6 hours, and after cooling, the material with a nominal chemical composition of Ba was obtained. 0.95 Eu 0.05 Sc 0.9 Y 0.1 SiO3N. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer. The full width at half maximum (FWHM) and the position of the main peak of the emission spectrum are shown in Table 1. Table 1 shows that the material prepared in Example 11, under 400 nm violet light excitation, has an emission spectrum around 526 nm and a FWHM of approximately 88 nm. Therefore, the material obtained in Example 11 is a nitrogen oxide green fluorescent material. The luminescence intensity at 25°C was measured and defined as 100 (relative intensity). The material was then placed in a rapid aging apparatus and aged at 200°C for 48 hours. The luminescence intensity before and after aging was measured, revealing a high luminescence intensity, as detailed in Table 1. Therefore, the material corresponding to Example 11 is a green fluorescent material with high chemical stability.

[0105] Example 12

[0106] The material described in this embodiment contains a compound with the chemical formula: Ba 0.95 Eu 0.05 Sc 0.9 La 0.1 SiO3N. Using BaCO3, Eu2O3, Sc2O3, La2O3, SiO2, and Si3N4 as raw materials, according to its composition Ba... 0.95 Eu 0.05 Sc 0.9 La 0.1 The raw materials for SiO3N were accurately weighed according to their stoichiometric ratio, sintered at 1500℃ in a nitrogen-hydrogen mixed atmosphere for 6 hours, and after cooling, the material with a nominal chemical composition of Ba was obtained. 0.95 Eu 0.05 Sc 0.9 La 0.1SiO3N. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer. The full width at half maximum (FWHM) and the position of the main peak of the emission spectrum are shown in Table 1. Table 1 shows that the material prepared in Example 12, under 400 nm violet light excitation, has an emission spectrum around 527 nm and a FWHM of approximately 87 nm. Therefore, the material obtained in Example 12 is a nitride green fluorescent material. The luminescence intensity at 25°C was measured and defined as 100 (relative intensity). The material was then placed in a rapid aging apparatus and aged at 200°C for 48 hours. The luminescence intensity before and after aging was measured, revealing a high luminescence intensity, as detailed in Table 1. Therefore, the material corresponding to Example 12 is a green fluorescent material with high chemical stability.

[0107] Example 13

[0108] The material described in this embodiment contains a compound with the chemical formula: Ba 0.95 Eu 0.05 Sc 0.9 Gd 0.1 SiO3N. Using BaCO3, Eu2O3, Sc2O3, Gd2O3, SiO2, and Si3N4 as raw materials, according to its composition Ba... 0.95 Eu 0.05 Sc 0.9 Gd 0.1 The raw materials for SiO3N were accurately weighed according to their stoichiometric ratio, sintered at 1500℃ in a nitrogen-hydrogen mixed atmosphere for 6 hours, and after cooling, the material with a nominal chemical composition of Ba was obtained. 0.95 Eu 0.05 Sc 0.9 Gd 0.1 SiO3N. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer. The full width at half maximum (FWHM) and the position of the main peak of the emission spectrum are shown in Table 1. Table 1 shows that the material prepared in Example 13, under 400 nm violet light excitation, has an emission spectrum around 529 nm and a FWHM of approximately 86 nm. Therefore, the material obtained in Example 13 is a nitrogen oxide green fluorescent material. The luminescence intensity at 25°C was measured and defined as 100 (relative intensity). The material was then placed in a rapid aging apparatus and aged at 200°C for 48 hours. The luminescence intensity before and after aging was measured, revealing a high luminescence intensity, as detailed in Table 1. Therefore, the material corresponding to Example 13 is a green fluorescent material with high chemical stability.

[0109] Example 14

[0110] The material described in this embodiment contains a compound with the chemical formula: Ba 0.95 Eu 0.05 Sc 0.9 Lu 0.1SiO3N. Using BaCO3, Eu2O3, Sc2O3, Lu2O3, SiO2, and Si3N4 as raw materials, according to its composition Ba... 0.95 Eu 0.05 Sc 0.9 Lu 0.1 The raw materials for SiO3N were accurately weighed according to their stoichiometric ratio, sintered at 1500℃ in a nitrogen-hydrogen mixed atmosphere for 6 hours, and after cooling, the material with a nominal chemical composition of Ba was obtained. 0.95 Eu 0.05 Sc 0.9 Lu 0.1 SiO3N. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer. The full width at half maximum (FWHM) and the position of the main peak of the emission spectrum are shown in Table 1. Table 1 shows that the material prepared in Example 14, under 400 nm violet light excitation, has an emission spectrum around 522 nm and a FWHM of approximately 85 nm. Therefore, the material obtained in Example 14 is a nitrogen oxide green fluorescent material. The luminescence intensity at 25°C was measured and defined as 100 (relative intensity). The material was then placed in a rapid aging apparatus and aged at 200°C for 48 hours. The luminescence intensity before and after aging was measured, revealing a high luminescence intensity, as detailed in Table 1. Therefore, the material corresponding to Example 14 is a green fluorescent material with high chemical stability.

[0111] Example 15

[0112] The material described in this embodiment contains a compound with the chemical formula: Ba 0.95 Eu 0.05 Sc 0.8 Y 0.1 La 0.1 SiO3N. Using BaCO3, Eu2O3, Sc2O3, Y2O3, La2O3, SiO2, and Si3N4 as raw materials, according to its composition Ba... 0.95 Eu 0.05 Sc 0.8 Y 0.1 La 0.1 The raw materials for SiO3N were accurately weighed according to their stoichiometric ratio, sintered at 1500℃ in a nitrogen-hydrogen mixed atmosphere for 6 hours, and after cooling, the material with a nominal chemical composition of Ba was obtained. 0.95 Eu 0.05 Sc 0.8 Y 0.1 La 0.1SiO3N. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer. The full width at half maximum (FWHM) and the position of the main peak of the emission spectrum are shown in Table 1. Table 1 shows that the material prepared in Example 15, under 400 nm violet light excitation, has an emission spectrum around 530 nm and a FWHM of approximately 85 nm. Therefore, the material obtained in Example 15 is a nitrogen oxide green fluorescent material. The luminescence intensity at 25°C was measured and defined as 100 (relative intensity). The material was then placed in a rapid aging apparatus and aged at 200°C for 48 hours. The luminescence intensity before and after aging was measured, revealing a high luminescence intensity, as detailed in Table 1. Therefore, the material corresponding to Example 15 is a green fluorescent material with high chemical stability.

[0113] Example 16

[0114] The material described in this embodiment contains a compound with the chemical formula: Ba 0.95 Eu 0.05 Sc 0.8 Y 0.1 Gd 0.1 SiO3N. Using BaCO3, Eu2O3, Sc2O3, Y2O3, Gd2O3, SiO2, and Si3N4 as raw materials, according to its composition Ba... 0.95 Eu 0.05 Sc 0.8 Y 0.1 Gd 0.1 The raw materials for SiO3N were accurately weighed according to their stoichiometric ratio, sintered at 1500℃ in a nitrogen-hydrogen mixed atmosphere for 6 hours, and after cooling, the material with a nominal chemical composition of Ba was obtained. 0.95 Eu 0.05 Sc 0.8 Y 0.1 Gd 0.1 SiO3N. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer. The full width at half maximum (FWHM) and the position of the main peak of the emission spectrum are shown in Table 1. Table 1 shows that the material prepared in Example 16, under 400 nm violet light excitation, has an emission spectrum around 533 nm and a FWHM of approximately 86 nm. Therefore, the material obtained in Example 16 is a nitride green fluorescent material. The luminescence intensity at 25°C was measured and defined as 100 (relative intensity). The material was then placed in a rapid aging apparatus and aged at 200°C for 48 hours. The luminescence intensity before and after aging was measured, revealing a high luminescence intensity, as detailed in Table 1. Therefore, the material corresponding to Example 16 is a green fluorescent material with high chemical stability.

[0115] Example 17

[0116] The material described in this embodiment contains a compound with the chemical formula: Ba0.95 Eu 0.05 Sc 0.8 Y 0.1 Lu 0.1 SiO3N. Using BaCO3, Eu2O3, Sc2O3, Y2O3, Lu2O3, SiO2, and Si3N4 as raw materials, according to its composition Ba... 0.95 Eu 0.05 Sc 0.8 Y 0.1 Lu 0.1 The raw materials for SiO3N were accurately weighed according to their stoichiometric ratio, sintered at 1500℃ in a nitrogen-hydrogen mixed atmosphere for 6 hours, and after cooling, the material with a nominal chemical composition of Ba was obtained. 0.95 Eu 0.05 Sc 0.8 Y 0.1 Lu 0.1 SiO3N. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer. The full width at half maximum (FWHM) and the position of the main peak of the emission spectrum are shown in Table 1. Table 1 shows that the material prepared in Example 17, under 400 nm violet light excitation, has an emission spectrum around 529 nm and a FWHM of approximately 82 nm. Therefore, the material obtained in Example 17 is a nitride green fluorescent material. The luminescence intensity at 25°C was measured and defined as 100 (relative intensity). The material was then placed in a rapid aging apparatus and aged at 200°C for 48 hours. The luminescence intensity before and after aging was measured, revealing a high luminescence intensity, as detailed in Table 17. Therefore, the material corresponding to Example 1 is a green fluorescent material with high chemical stability.

[0117] Example 18

[0118] The material described in this embodiment contains a compound with the chemical formula: Ba 0.95 Eu 0.05 Sc 0.8 La 0.1 Gd 0.1 SiO3N. Using BaCO3, Eu2O3, Sc2O3, La2O3, Gd2O3, SiO2, and Si3N4 as raw materials, according to its composition Ba... 0.95 Eu 0.05 Sc 0.8 La 0.1 Gd 0.1 The raw materials for SiO3N were accurately weighed according to their stoichiometric ratio, sintered at 1500℃ in a nitrogen-hydrogen mixed atmosphere for 6 hours, and after cooling, the material with a nominal chemical composition of Ba was obtained. 0.95 Eu 0.05 Sc 0.8 La 0.1 Gd 0.1SiO3N. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer. The full width at half maximum (FWHM) and the position of the main peak of the emission spectrum are shown in Table 1. Table 1 shows that the material prepared in Example 18, under 400 nm violet light excitation, has an emission spectrum around 523 nm and a FWHM of approximately 83 nm. Therefore, the material obtained in Example 18 is a nitrogen oxide green fluorescent material. The luminescence intensity at 25°C was measured and defined as 100 (relative intensity). The material was then placed in a rapid aging apparatus and aged at 200°C for 48 hours. The luminescence intensity before and after aging was measured, revealing a high luminescence intensity, as detailed in Table 1. Therefore, the material corresponding to Example 18 is a green fluorescent material with high chemical stability.

[0119] Example 19

[0120] The material described in this embodiment contains a compound with the chemical formula: Ba 0.95 Eu 0.05 Sc 0.8 La 0.1 Lu 0.1 SiO3N. Using BaCO3, Eu2O3, Sc2O3, La2O3, Lu2O3, SiO2, and Si3N4 as raw materials, according to its composition Ba... 0.95 Eu 0.05 Sc 0.8 La 0.1 Lu 0.1 The raw materials for SiO3N were accurately weighed according to their stoichiometric ratio, sintered at 1500℃ in a nitrogen-hydrogen mixed atmosphere for 6 hours, and after cooling, the material with a nominal chemical composition of Ba was obtained. 0.95 Eu 0.05 Sc 0.8 La 0.1 Lu 0.1 SiO3N. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer. The full width at half maximum (FWHM) and the position of the main peak of the emission spectrum are shown in Table 1. Table 1 shows that the material prepared in Example 19, under 400 nm violet light excitation, has an emission spectrum around 521 nm and a FWHM of approximately 87 nm. Therefore, the material obtained in Example 19 is a nitrogen oxide green fluorescent material. The luminescence intensity at 25°C was measured and defined as 100 (relative intensity). The material was then placed in a rapid aging apparatus and aged at 200°C for 48 hours. The luminescence intensity before and after aging was measured, revealing a high luminescence intensity, as detailed in Table 1. Therefore, the material corresponding to Example 19 is a green fluorescent material with high chemical stability.

[0121] Example 20

[0122] The material described in this embodiment contains a compound with the chemical formula: Ba0.95 Eu 0.05 Sc 0.8 Gd 0.1 Lu 0.1 SiO3N. Using BaCO3, Eu2O3, Sc2O3, Gd2O3, Lu2O3, SiO2, and Si3N4 as raw materials, according to its composition Ba... 0.95 Eu 0.05 Sc 0.8 Gd 0.1 Lu 0.1 The raw materials for SiO3N were accurately weighed according to their stoichiometric ratio, sintered at 1500℃ in a nitrogen-hydrogen mixed atmosphere for 6 hours, and after cooling, the material with a nominal chemical composition of Ba was obtained. 0.95 Eu 0.05 Sc 0.8 Gd 0.1 Lu 0.1 SiO3N. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer. The full width at half maximum (FWHM) and the position of the main peak of the emission spectrum are shown in Table 1. Table 1 shows that the material prepared in Example 20, under 400 nm violet light excitation, has an emission spectrum around 527 nm and a FWHM of approximately 84 nm. Therefore, the material obtained in Example 20 is a nitrogen oxide green fluorescent material. The luminescence intensity at 25°C was measured and defined as 100 (relative intensity). The material was then placed in a rapid aging apparatus and aged at 200°C for 48 hours. The luminescence intensity before and after aging was measured, revealing a high luminescence intensity, as detailed in Table 1. Therefore, the material corresponding to Example 20 is a green fluorescent material with high chemical stability.

[0123] Example 21

[0124] The material described in this embodiment contains a compound with the chemical formula: Ba 0.95 Eu 0.05 Sc 0.7 Y 0.1 La 0.1 Gd 0.1 SiO3N. Using BaCO3, Eu2O3, Sc2O3, Y2O3, La2O3, Gd2O3, SiO2, and Si3N4 as raw materials, according to its composition Ba... 0.95 Eu 0.05 Sc 0.7 Y 0.1 La 0.1 Gd 0.1 The raw materials for SiO3N were accurately weighed according to their stoichiometric ratio, sintered at 1500℃ in a nitrogen-hydrogen mixed atmosphere for 6 hours, and after cooling, the material with a nominal chemical composition of Ba was obtained. 0.95 Eu 0.05 Sc0.7 Y 0.1 La 0.1 Gd 0.1 SiO3N. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer. The full width at half maximum (FWHM) and the position of the main peak of the emission spectrum are shown in Table 1. Table 1 shows that the material prepared in Example 21, under 400 nm violet light excitation, has an emission spectrum around 530 nm and a FWHM of approximately 84 nm. Therefore, the material obtained in Example 21 is a nitrogen oxide green fluorescent material. The luminescence intensity at 25°C was measured and defined as 100 (relative intensity). The material was then placed in a rapid aging apparatus and aged at 200°C for 48 hours. The luminescence intensity before and after aging was measured, revealing a high luminescence intensity, as detailed in Table 1. Therefore, the material corresponding to Example 21 is a green fluorescent material with high chemical stability.

[0125] Example 22

[0126] The material described in this embodiment contains a compound with the chemical formula: Ba 0.95 Eu 0.05 Sc 0.7 Y 0.1 La 0.1 Lu 0.1 SiO3N. Using BaCO3, Eu2O3, Sc2O3, Y2O3, La2O3, Lu2O3, SiO2, and Si3N4 as raw materials, according to its composition Ba... 0.95 Eu 0.05 Sc 0.7 Y 0.1 La 0.1 Lu 0.1 The raw materials for SiO3N were accurately weighed according to their stoichiometric ratio, sintered at 1500℃ in a nitrogen-hydrogen mixed atmosphere for 6 hours, and after cooling, the material with a nominal chemical composition of Ba was obtained. 0.95 Eu 0.05 Sc 0.7 Y 0.1 La 0.1 Lu 0.1SiO3N. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer. The full width at half maximum (FWHM) and the position of the main peak of the emission spectrum are shown in Table 1. Table 1 shows that the material prepared in Example 22, under 400 nm violet light excitation, has an emission spectrum around 524 nm and a FWHM of approximately 86 nm. Therefore, the material obtained in Example 22 is a nitrogen oxide green fluorescent material. The luminescence intensity at 25°C was measured and defined as 100 (relative intensity). The material was then placed in a rapid aging apparatus and aged at 200°C for 48 hours. The luminescence intensity before and after aging was measured, revealing a high luminescence intensity, as detailed in Table 1. Therefore, the material corresponding to Example 22 is a green fluorescent material with high chemical stability.

[0127] Example 23

[0128] The material described in this embodiment contains a compound with the chemical formula: Ba 0.95 Eu 0.05 Sc 0.7 La 0.1 Gd 0.1 Lu 0.1 SiO3N. Using BaCO3, Eu2O3, Sc2O3, La2O3, Gd2O3, Lu2O3, SiO2, and Si3N4 as raw materials, according to its composition Ba... 0.95 Eu 0.0 5Sc 0.7 La 0.1 Gd 0.1 Lu 0.1 The raw materials for SiO3N were accurately weighed according to their stoichiometric ratio, sintered at 1500℃ in a nitrogen-hydrogen mixed atmosphere for 6 hours, and after cooling, the material with a nominal chemical composition of Ba was obtained. 0.95 Eu 0.05 Sc 0.7 La 0.1 Gd 0.1 Lu 0.1 SiO3N. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer. The full width at half maximum (FWHM) and the position of the main peak of the emission spectrum are shown in Table 1. Table 1 shows that the material prepared in Example 23, under 400 nm violet light excitation, has an emission spectrum around 522 nm and a FWHM of approximately 88 nm. Therefore, the material obtained in Example 23 is a nitride green fluorescent material. The luminescence intensity at 25°C was measured and defined as 100 (relative intensity). The material was then placed in a rapid aging apparatus and aged at 200°C for 48 hours. The luminescence intensity before and after aging was measured, revealing a high luminescence intensity, as detailed in Table 1. Therefore, the material corresponding to Example 23 is a green fluorescent material with high chemical stability.

[0129] Example 24

[0130] The material described in this embodiment contains a compound with the chemical formula: Ba 0.95 Eu 0.05 Sc 0.6 Y 0.1 La 0.1 Gd 0.1 Lu 0.1 SiO3N. Using BaCO3, Eu2O3, Sc2O3, Y2O3, La2O3, Gd2O3, Lu2O3, SiO2, and Si3N4 as raw materials, according to its composition Ba... 0.95 Eu 0.05 Sc 0.6 Y 0.1 La 0.1 Gd 0.1 Lu 0.1 The raw materials for SiO3N were accurately weighed according to their stoichiometric ratio, sintered at 1500℃ in a nitrogen-hydrogen mixed atmosphere for 6 hours, and after cooling, the material with a nominal chemical composition of Ba was obtained. 0.95 Eu 0.05 Sc 0.6 Y 0.1 La 0.1 Gd 0.1 Lu 0.1 SiO3N. The emission spectrum of the obtained luminescent material was measured using a fluorescence spectrometer. The full width at half maximum (FWHM) and the position of the main peak of the emission spectrum are shown in Table 1. Table 1 shows that the material prepared in Example 24, under 400 nm violet light excitation, has an emission spectrum around 526 nm and a FWHM of approximately 89 nm. Therefore, the material obtained in Example 24 is a nitride green fluorescent material. The luminescence intensity at 25°C was measured and defined as 100 (relative intensity). The material was then placed in a rapid aging apparatus and aged at 200°C for 48 hours. The luminescence intensity before and after aging was measured, revealing a high luminescence intensity, as detailed in Table 1. Therefore, the material corresponding to Example 24 is a green fluorescent material with high chemical stability.

[0131] Example 25

[0132] The chemical composition of the synthesized product selected in Example 6 is Ba. 0.95 Eu 0.05 ScSiO3N green fluorescent material. The above material is mixed with low-melting-point glass powder at a mass ratio of 1:1. The mixture is placed in a flat-bottomed crucible made of titanium with a bottom diameter of 10 mm and sintered at 700°C for 0.5 h in air. After cooling, a green fluorescent glass is obtained. Encapsulating this green fluorescent glass with a 400 nm violet laser diode yields a green light source.

[0133] Table 1. Emission Spectrum Data of Materials (using 400 nm violet light excitation)

[0134]

[0135]

[0136] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the protection scope of the present invention.

[0137] It should also be noted that the various specific technical features described in the above embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the present invention will not describe the various possible combinations separately.

[0138] Furthermore, various different embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention, they should also be regarded as the content disclosed by the present invention.

Claims

1. A nitrogen oxide green fluorescent material, characterized in that, The general chemical formula of the nitrogen oxide green fluorescent material is: Ba 1-x Eu x LnSiO3N, wherein Ln is one or more of Sc, Y, La, Gd, or Lu, and Sc is essential, and the molar ratio of Sc to Ln is >50%; 0 <x≤0.2。 2. The nitrogen oxide green fluorescent material according to claim 1, characterized in that: In the chemical general formula of the nitrogen oxide green fluorescent material, 0.02 < x ≤ 0.05; optionally, the preparation method of the nitrogen oxide green fluorescent material includes mixing Ba precursor, Eu precursor, Ln precursor and Si precursor, and performing a high-temperature solid-phase reaction under a reducing atmosphere to obtain the nitrogen oxide green fluorescent material. The temperature of the high-temperature solid-phase reaction is 1500 - 1600 °C, and the time of the high-temperature solid-phase reaction is 4 - 10 h.

3. The nitrogen oxide green fluorescent material according to claim 1 or 2, characterized in that: Under ultraviolet light excitation, the main peak range of the emission wavelength generated by the nitrogen oxide green fluorescent material is between 505 - 535 nm, and the full width at half maximum of the emission spectrum is less than or equal to 90 nm; optionally, the luminous intensity of the nitrogen oxide green fluorescent material after aging for 48 h in a sealed container containing high-pressure steam at 200 °C is not less than 75% of the luminous intensity at room temperature.

4. A method for preparing the nitrogen oxide green fluorescent material as described in any one of claims 1-3, characterized in that: Mix Ba precursor, Eu precursor, Ln precursor and Si precursor, and perform a high-temperature solid-phase reaction under a reducing atmosphere to obtain the nitrogen oxide green fluorescent material.

5. The method for preparing the nitrogen oxide green fluorescent material according to claim 4, characterized in that: The molar ratio of Ba, Eu, Ln and Si in Ba precursor, Eu precursor, Ln precursor and Si precursor is (1 - X):X:1:1; the Ba precursor is selected from one or more of Ba carbonate, Ba oxide or Ba nitrate; optionally, the Eu precursor is selected from Eu2O3; optionally, the Ln precursor is one or more of Sc2O3, Y2O3, La2O3, Gd2O3 and Lu2O3, and Sc2O3 is necessary; optionally, the Si precursor is SiO2 and Si3N4; optionally, the purity of Ba precursor, Eu precursor, Ln precursor and Si precursor is not less than 99.5 wt%.

6. The method for preparing the nitrogen oxide green fluorescent material according to claim 4 or 5, characterized in that: The temperature of the high-temperature solid-phase reaction is 1500 - 1600 °C, and the time of the high-temperature solid-phase reaction is 4 - 10 h; Optionally, the reducing atmosphere is ammonia or a nitrogen-hydrogen mixture, and the volume content of hydrogen in the nitrogen-hydrogen mixture is 10 - 25%.

7. A green fluorescent glass containing nitrogen oxides, characterized in that: The nitrogen oxide green fluorescent glass is obtained by performing a high-temperature solid-phase reaction after mixing the nitrogen oxide green fluorescent material described in any one of claims 1 - 3 or the nitrogen oxide green fluorescent material prepared by the preparation method described in any one of claims 4 - 6 with glass powder. The mass ratio of the nitrogen oxide green fluorescent material to the glass powder is 1:1 - 1:4; the melting point of the glass powder is 500 - 800 °C.

8. A method for preparing the oxynitride green fluorescent glass according to claim 7, characterized in that: Mix the nitrogen oxide green fluorescent material described in any one of claims 1 - 3 or the nitrogen oxide green fluorescent material prepared by the preparation method described in any one of claims 4 - 6 with glass powder, and perform a high-temperature solid-phase reaction in an air atmosphere to obtain the nitrogen oxide green fluorescent glass.

9. The method for preparing the oxynitride green fluorescent glass according to claim 8, characterized in that: The temperature of the high-temperature solid-phase reaction is 500 - 800 °C, and the time of the high-temperature solid-phase reaction is 0.1 - 1 h; optionally, the mass ratio of the nitrogen oxide green fluorescent material to the glass powder is 1:1 - 1:4; the melting point of the glass powder is 500 - 800 °C.

10. A laser illumination device, characterized in that: The laser lighting device includes a violet laser diode and a light-emitting layer, wherein the light-emitting layer includes the oxynitride green fluorescent glass of claim 7, or the oxynitride green fluorescent glass prepared by the preparation method of claim 8 or 9.

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