High-efficiency narrow-band green nitride fluorescent material, preparation method and application thereof

Abstract

The application discloses a high-efficiency narrow-band green nitride fluorescent material and a preparation method and application thereof, and relates to the field of fluorescent materials. 3‑x Eu x Al4Si3N 10 , wherein 0 The crystal structure of the fluorescent material corresponds to a base matrix and belongs to an orthorhombic system, and a space group is Immm. Under excitation of 405 nm violet light, the main peak of an emission spectrum of the fluorescent material is located at 515-545 nm, a half-height width of the emission spectrum is 60-80 nm, and a quantum efficiency is greater than 80%, so that the fluorescent material can be applied to a white light LED device.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of fluorescent materials, and in particular to a high-efficiency narrow-band green nitride fluorescent material and a preparation method and application thereof. BACKGROUND

[0002] White LED light source is the most widely used lighting device today, and its principle of realizing white light output is to use LED to excite fluorescent material, and the light emitted by the fluorescent material under the excitation of the LED is mixed with the light emitted by the LED which is not absorbed by the fluorescent material to obtain white light, as disclosed in patent document 1 (Song Kai-xin, Jiang Jun, Li Wei, Qin Hui-bin, A kind of white light led fluorescent powder and its preparation method, CN102295927A). Obviously, the fluorescent material plays a key role in the white LED light source, and to some extent determines the light color and electrical quality of the white LED light source.

[0003] Because the fluorescent material has the advantages of structural diversity, high luminous efficiency, good thermal stability and chemical stability, etc., as disclosed in non-patent document 1 (Zhou Tian-liang, Jie Rong-jun, Research progress of nitride (oxide) fluorescent powder, Functional Materials, 2014, 17, 17001-17011 / 6), the nitride (oxide) fluorescent material occupies an important position in the white LED fluorescent material. Non-patent document 2 (Yang Zhi-gang, Synthesis and luminescent properties of rare earth doped M-Si-Al-O-N materials, Doctoral thesis of Lanzhou University, 2013) believes that in the nitride (oxide) and nitride oxide matrix material, the nitrogen element has relatively small electronegativity and large electron cloud expansion effect, which can effectively promote the splitting of rare earth ion Sd energy level in the crystal field, reduce the energy level difference between 5d-4f, and cause red shift of excitation and emission wavelength. Therefore, in general, the pure nitrogen-containing nitride fluorescent material mostly emits long-wavelength light (such as red light, or deep red light), and the nitride oxide fluorescent material containing both oxygen and nitrogen mostly emits short-wavelength light (such as green light, cyan light).

[0004] For example, for nitride oxide, patent document 2 (Yang Zhi-ping, Dong Xiu-qin, Liu Shao-peng, Zhao Jin-xin, A kind of nitride oxide blue fluorescent powder and its preparation method and application, CN106479498A) discloses a blue nitride oxide fluorescent material, whose chemical formula is Ba 1-x-y-z-m A1 x A2 y A3 zSi2O2N2:mEu, A1 is at least one of Sr, Ca, Mg, Mn, Zn or Cu, A2 is at least one of Li, Na or K, A3 is at least one of Y, Sc, La, Ga, Gd or Lu; in the formula, 0≤x≤0.1, 0≤y≤0.1, 0≤z≤0.1, 0

[0005] As for nitride oxides, patent document 3 (Zhang Liangliang, He Shuai, Zhang Jiahua, Zhang Xia, Hao Zhendong, Pan Guohui, Wu Huajun, Fluorescent-enhanced silicon-based nitride oxide cyan fluorescent powder and preparation method thereof, CN107722982A) discloses a cyan nitride oxide fluorescent material, whose chemical general formula is (Ba 1-x-y-z-m M x R y A z )O·0.5SiO2·0.5Si3N4:mEu, wherein 0.01≤m≤0.05, 0≤x≤0.2, 0.005≤y≤0.2, 0.5≤y / z≤1, 0

[0006] As for nitride oxides, patent document 4 (You Weixiong, Xiao Zongliang, Ye Xinyu, A nitride oxide green fluorescent powder and a preparation method thereof, CN104774615A) discloses a green nitride oxide fluorescent material, whose chemical general formula is (M 1-x Eu x )3Al 2-y Si y O 6-y N y , wherein M=one or more of Ca, Sr and Ba, 0

[0007] As for nitride oxides, patent document 5 (Jiao Huan, Wang Xiaoming, Zheng Hongwei, Yang Suya, Song Jianing, A wide-spectrum yellow-green-emitting nitride oxide fluorescent powder and a preparation method thereof, CN114540015A) discloses a yellow-green nitride oxide fluorescent material, whose chemical general formula is Ba 1-2x Si6N 8-y O y :xCe 3+ / xA +wherein A represents one of Li, Na, K, Rb, Cs; 0.005≤x≤0.1; 0

[0008] As for nitride, patent document 8 (Setsu Xiaojun, Kishima Naoren, Fluorescent material and method for manufacturing the same, composition containing the fluorescent material, light emitting device, illuminating device, image display device, and nitrogen-containing compound, CN101663372B) discloses an orange nitride fluorescent material, whose chemical general formula is R 1-x Ca(BO2N)2:xEu 2+ wherein x is 0.001-0.10. The excitation band of this fluorescent material covers the ultraviolet and blue light region, and the emission spectrum is in the yellow light region.

[0009] Obviously, in general, the nitride fluorescent material containing both oxygen and nitrogen mostly emits short-wavelength light (such as green light, cyan light).

[0010] As for nitride, patent document 8 (Setsu Xiaojun, Kishima Naoren, Fluorescent material and method for manufacturing the same, composition containing the fluorescent material, light emitting device, illuminating device, image display device, and nitrogen-containing compound, CN101663372B) discloses an orange nitride fluorescent material, whose chemical general formula is R 1-x-y-z M x L y Ce z )Al 1-y+z Si 4+y-z N7, wherein M is Ca or Ba, L is Li, Na or K, Ce is trivalent cerium ion, x, y, z are element mole fractions, 0.01≤x≤0.1, 0.01≤z≤0.1, 0.1≤y / z≤0.99. This fluorescent material can be excited by 250-350 nm ultraviolet light and 420-460 nm blue light, and the emission spectrum is in the 550-565 nm yellow light region.

[0011] As for nitride, patent document 8 (Setsu Xiaojun, Kishima Naoren, Fluorescent material and method for manufacturing the same, composition containing the fluorescent material, light emitting device, illuminating device, image display device, and nitrogen-containing compound, CN101663372B) discloses an orange nitride fluorescent material, whose chemical general formula is R 3-x-y-z+w2 M z A 1.5x+y-w2 Si 6-w1-w2 Al w1+w2 O y+w1 N 11-y-w1wherein R represents La, Gd, Lu, Y and / or Sc, M represents Ce, Eu, Mn, Yb, Pr and / or Tb, A represents Ba, Sr, Ca, Mg and / or Zn, 1 / 7≤(3-x-y-z+w2) / 6<1 / 2, 0<(1.5x+y-w2) / 6<9 / 2, 0<x<3, 0≤y<2, 0<z<1, 0≤w1≤5, 0≤w2≤5, 0≤w1+w2≤5. A representative chemical formula thereof is La 2.15 Ce 0.10 Ca 1.23 Si6N 11 The fluorescent material can be excited by blue light and emits light spectrum near 590 nm, which is in the orange light region.

[0012] As for nitride, patent document 9 (Teng Xiaoming, He Jinhua, Liang Chao, Fu Yibing, Liu Kai, A kind of nitride red fluorescent powder and its preparation method, CN102899038A) discloses a red nitride fluorescent material, whose chemical general formula is L 2-x-y-z M5N8:Eu x / R y / R ′ z wherein L is at least one of Ca, Sr or Ba; M is at least one of Si or Ge, wherein Si is necessary; R is at least one of Na or K; R ′ is at least one of La, Sm or Sc; 0.001≤x≤0.5, 0.0001≤y≤0.01, 0.0001≤z≤0.01, and y=z. A representative chemical formula thereof is Ca 1.988 Si5N8: Eu 0.01 / Na 0.001 / La 0.001 The fluorescent material can be excited by blue light and emits light spectrum near 620 nm, which is in the positive red light region.

[0013] As for nitride, patent document 10 (He Jinhua, Teng Xiaoming, Liang Chao, Fu Yibing, An aluminum nitride fluorescent material, preparation method, application and light emitting device, CN102766455A) discloses a red nitride fluorescent material, whose chemical general formula is L x SiAlN3:R y Eu 1-x-y wherein 0.8≤x≤0.95, 0.01≤y≤0.18, L is selected from one or any combination of two of Ca and Sr, and R is selected from one or any combination of two of Cu and Mn. A representative chemical formula thereof is Ca 0.92 SiAlN3:Cu 0.04 Eu 0.06The fluorescent material can be excited by blue light, and the emission spectrum is located near 645 nm, which is in the red light region.

[0014] As for nitride, patent document 11 (Chaokefu, Hu Dahai, Saqier, Ma Yizhi, Li Xiang, A kind of nitride fluorescent powder and its preparation method, CN112126426A) discloses a deep red nitride fluorescent material, which has a general chemical formula (representative) of M3Al3N5: Ce, wherein M = one or any combination of two of Ca, Ba, Sr and Mg. The fluorescent material can be excited by light with a wavelength range of 320-450 nm, and the emission spectrum is located near 670 nm, which is in the deep red light region.

[0015] Obviously, in general, most of the pure nitrogen-containing nitride fluorescent materials emit long-wavelength light (such as red light, or deep red light).

[0016] In addition, as for the synthesis method of nitride fluorescent material, non-patent document 3 (Liu Wenquan, Shi Ruixin, Duan Ruxia, Huerji, Wu Wenjie, Chaokefu, Baofuquan, Li Qi, Xin Yi, Tegus, Ca x Preparation of Ca 1-x AlSiN3:xEu red fluorescent powder and luminescent performance research, Journal of Luminescence, 2017, 38, 10:1295) believes that when using alloy raw materials, nitride fluorescent materials can be prepared under more relatively mild conditions.

[0017] In summary, there is still a lack of nitride fluorescent materials that can emit green light under violet light excitation, with narrow band and high quantum efficiency. As for the violet excitation of Ba 3-x Eu x Al4Si3N 10 The high-efficiency, narrow-band and green-emitting behavior of (0 < x ≤ 0.1, the crystal structure of the fluorescent material corresponding to the substrate belongs to the orthorhombic system, and the space group is Immm) is disclosed for the first time. SUMMARY

[0018] The purpose of the present application is to solve the above-mentioned problems in the prior art, and to provide a high-efficiency narrow-band green nitride fluorescent material and a preparation method thereof. Under the excitation of 405 nm violet light, the main peak of the emission spectrum of the high-efficiency narrow-band green nitride fluorescent material is located in the range of 515-545 nm, the full width at half maximum of the emission spectrum is in the range of 60-80 nm, and the quantum efficiency is > 80%.

[0019] Therefore, the first purpose of the present application is to provide a high-efficiency narrow-band green nitride fluorescent material.

[0020] A high-efficiency narrow-band green nitride fluorescent material, which can be represented by the chemical formula:

[0021] Ba 3-x Eu x Al4Si3N 10

[0022] wherein 0 < x ≤ 0.1.

[0023] Preferably, the x can be 0.05.

[0024] A second object of the present application is to provide a preparation method of the high-efficiency narrow-band green nitride fluorescent material. The preparation method comprises the following steps: mixing Ba precursor, Eu precursor and Al precursor, and performing high-temperature solid-phase reaction under the atmosphere of ammonia gas with the pressure of 10-20 MPa to obtain the high-efficiency narrow-band green nitride fluorescent material.

[0025] Preferably, the Ba precursor is selected from BaSi alloy; the Eu precursor is selected from EuSi alloy; and the Al precursor is selected from AlN.

[0026] Preferably, the molar ratio of Ba to Si in the Ba precursor is 1:1; and the molar ratio of Eu to Si in the Eu precursor is 1:1.

[0027] Preferably, the molar ratio of Ba, Eu and Al in the Ba precursor, the Eu precursor and the Al precursor is (3-x):x:4, wherein 0 < x ≤ 0.1.

[0028] Preferably, the purity of the Ba precursor, the Eu precursor and the Al precursor is not less than 99.5%.

[0029] Preferably, the temperature of the high-temperature solid-phase reaction is 1000-1400℃, the atmosphere is ammonia gas, the pressure of the ammonia gas is 10-20 MPa, and the time of the high-temperature solid-phase reaction is 4-10 h.

[0030] A further object of the present application is to provide a white light LED device. The white light LED device comprises a high-efficiency narrow-band green nitride fluorescent material (corresponding to the chemical formula of Ba 3-x Eu x Al4Si3N 10 wherein 0 < x ≤ 0.1) and a purple light LED chip capable of generating 380-425 nm.

[0031] Compared with the prior art, the technical scheme of the present application has the following beneficial effects:

[0032] The present application provides a high-efficiency narrow-band green nitride fluorescent material with a brand-new crystal structure, and the chemical formula of the fluorescent material is: Ba 3-x Eu x Al4Si3N 10wherein 0 < x ≤ 0.1. The crystal structure of the fluorescent material corresponding to the substrate belongs to the orthorhombic system, and the space group is Immm. The fluorescent material takes Eu 2+ as the activator, and under the excitation of 405 nm violet light, the main peak of the emission spectrum is located between 515 nm and 545 nm, the half-width of the emission spectrum is in the range of 60 nm to 80 nm, and the quantum efficiency is greater than 80%, so that the fluorescent material can be applied to a white light LED device. BRIEF DESCRIPTION OF DRAWINGS

[0033] Figure 1 is the emission spectrum of the material obtained in Comparative Example 1 under the excitation of 405 nm.

[0034] Figure 2 is the emission spectrum of the material obtained in Comparative Example 3 under the excitation of 405 nm.

[0035] Figure 3 is the emission spectrum of the material obtained in Comparative Example 5 under the excitation of 405 nm.

[0036] Figure 4 is the X-ray diffraction pattern of the material obtained in Example 1.

[0037] Figure 5 is the crystal structure diagram of the material obtained in Example 1.

[0038] Figure 6 is the excitation and emission spectrum diagram of the material obtained in Example 1.

[0039] Figure 7 is the emission spectrum of the material obtained in Example 6 under the excitation of 405 nm.

[0040] Figure 8 is the spectrum diagram of the full-spectrum LED device obtained in Example 12. DETAILED DESCRIPTION

[0041] The technical solutions in the embodiments of the present application will be described clearly and completely below in combination with the embodiments of the present application.

[0042] In order to facilitate the understanding of the present application, the present application lists the following embodiments. It should be understood by those skilled in the art that the embodiments are only used to help understand the present application, and should not be regarded as specific limitations of the present application. It should be noted that the embodiments in the present application and the features in the embodiments can be combined with each other without conflict. The present application will be described in detail below in combination with the embodiments.

[0043] The present application proposes a high-efficiency narrow-band green nitride fluorescent material, which has the chemical formula:

[0044] Ba 3-x Eu xAl4Si3N 10

[0045] wherein 0 < x ≤ 0.1.

[0046] In an embodiment of the present application, the x is preferably 0.005; in an embodiment of the present application, the x is preferably 0.01; in an embodiment of the present application, the x is preferably 0.02; in an embodiment of the present application, the x is preferably 0.03; in an embodiment of the present application, the x is preferably 0.04; in an embodiment of the present application, the x is preferably 0.05; in an embodiment of the present application, the x is preferably 0.06; in an embodiment of the present application, the x is preferably 0.07; in an embodiment of the present application, the x is preferably 0.08; in an embodiment of the present application, the x is preferably 0.09; in another embodiment of the present application, the x is preferably 0.1.

[0047] The present application also provides a preparation method of the high-efficiency narrow-band green nitride fluorescent material, which comprises the following steps: mixing Ba precursor, Eu precursor and Al precursor, and performing high-temperature solid-phase reaction under the atmosphere of ammonia gas with a pressure of 10-20 MPa to obtain the high-efficiency narrow-band green nitride fluorescent material.

[0048] In the above step, the molar ratio of Ba to Si in the Ba precursor is 1:1; the molar ratio of Eu to Si in the Eu precursor is 1:1; and the molar ratio of Ba, Eu and Al in the Ba precursor, the Eu precursor and the Al precursor is (3-x):x:4, wherein 0 < x ≤ 0.1.

[0049] In the above step, the Ba precursor is selected from BaSi alloy; the Eu precursor is selected from EuSi alloy; and the Al precursor is selected from AlN.

[0050] The purity of the Ba precursor, the Eu precursor and the Al precursor is not less than 99.5%, and the higher the purity, the less the impurities of the obtained fluorescent powder.

[0051] In the above step, the temperature of the high-temperature solid phase is preferably 1000-1400℃, and the atmosphere is ammonia gas atmosphere; in some embodiments provided by the present application, the temperature of the high-temperature solid phase is preferably 1200℃; the gas pressure of the ammonia gas atmosphere is 10-20 MPa, and the gas pressure of the ammonia gas atmosphere is preferably 15 MPa in the present application.

[0052] In the above step, the time of the high-temperature solid phase is preferably 4-10h, and more preferably 5-8h; in some embodiments provided by the present application, the time of the high-temperature solid phase is preferably 6h.

[0053] The high-temperature solid-phase reaction is preferably performed in a high-temperature furnace; after the reaction is performed, the furnace is cooled to room temperature, and a high-efficiency narrow-band green nitride fluorescent material is obtained.

[0054] The high-temperature solid-phase reaction is preferably performed in a high-temperature furnace; after the reaction is performed, the furnace is cooled to room temperature, and a high-efficiency narrow-band green nitride fluorescent material is obtained.

[0055] The application also provides a white light LED device. The white light LED device comprises at least a high-efficiency narrow-band green nitride fluorescent material represented by Ba 3- x Eu x Al4Si3N 10 (wherein, 0

[0056] The specific manufacturing steps comprise: mixing a high-efficiency narrow-band green nitride fluorescent material with cyan fluorescent powder, yellow fluorescent powder, red fluorescent powder and epoxy resin, coating the mixture on the surface of a purple light LED chip capable of emitting light of 380-425 nm, and then curing at 150°C for 2h, to obtain a white light LED device.

[0057] In order to further illustrate the application, the high-efficiency narrow-band green nitride fluorescent material and the preparation method thereof provided by the application are described in detail below in combination with examples. The reagents used in the following comparative examples and examples are commercially available.

[0058] Comparative Example 1

[0059] The raw materials are BaSi and AlN, and the molar ratio of Ba and Al in BaSi and AlN is 3:4. After the raw materials are ground and mixed uniformly, they are loaded into a crucible, and then sintered at 1200°C for 6h in a high-temperature furnace under an ammonia atmosphere of 15MPa, and then cooled to room temperature in the furnace, to obtain a material with a theoretical chemical composition of Ba 10 .

[0060] The luminescent performance of the material corresponding to Comparative Example 1 is analyzed by a fluorescence spectrometer, and the results are shown in Table 1. Figure 1 Since no possible luminescent center is doped in the comparative example, Comparative Example 1 does not emit light.

[0061] Comparative Example 2

[0062] The raw materials are BaSi, EuSi and AlN, and the molar ratio of Ba, Eu and Al in BaSi, EuSi and AlN is 2.85:0.15:4. After the raw materials are ground and mixed uniformly, they are loaded into a crucible, and then sintered at 1200°C for 6h in a high-temperature furnace under an ammonia atmosphere of 15MPa, and then cooled to room temperature in the furnace, to obtain a material with a theoretical chemical composition of Ba 2.85 Eu0.15 Al4Si3N 10 The material has a theoretical chemical composition of Ba

[0063] The luminescent performance of the material corresponding to Comparative Example 2 was analyzed by using a fluorescence spectrometer. The results showed that the main peak of the emission spectrum of the material obtained in Comparative Example 2 was located at 562 nm, and the half-height width of the emission spectrum was 91 nm. The quantum efficiency of the material corresponding to Comparative Example 2 was tested by using a quantum efficiency tester. The results showed that the quantum efficiency of the material obtained in Comparative Example 2 was 20.4%, which was relatively low. The specific data are shown in Table 1. Although the material obtained in Comparative Example 2 was a green luminescent material, the concentration of Eu was too high, resulting in concentration quenching effect of the material obtained in Comparative Example 2, and the luminescent intensity and the quantum efficiency were both low.

[0064] That is, Comparative Example 2 did not have the possibility of being applied to a white light LED device (package).

[0065] Comparative Example 3

[0066] The raw materials were BaSi, SrSi, EuSi and AlN, and the molar ratio of Ba, Sr, Eu and Al in BaSi, SrSi, EuSi and AlN was 1.95:1:0.05:4. After the above raw materials were ground and uniformly mixed, they were loaded into a crucible, and then sintered at 1200°C for 6h in a high-temperature furnace under the atmosphere of 15 MPa of ammonia gas, and then cooled to room temperature in the furnace to obtain a material with a theoretical chemical composition of Ba 1.95 SrEu 0.05 Al4Si3N 10 The material has a theoretical chemical composition of Ba

[0067] The luminescent performance of the material corresponding to Comparative Example 3 was analyzed by using a fluorescence spectrometer, and the results are shown in Table 1. Figure 2 Due to the substitution of part of Ba with Sr, the main peak of the emission spectrum of the material obtained in Comparative Example 3 was located at 593 nm, which was orange light, rather than green light. The half-height width of the emission spectrum was 102 nm, and the half-height width of the emission spectrum was relatively wide. The quantum efficiency of the material corresponding to Comparative Example 3 was tested by using a quantum efficiency tester. The results showed that the quantum efficiency of the material obtained in Comparative Example 3 was 10.7%, which was relatively low. The specific data are shown in Table 1. It can be seen that after the substitution of Ba with Sr, the luminescent intensity and the quantum efficiency of the obtained luminescent material were too low to have commercial application value.

[0068] That is, Comparative Example 3 was an orange luminescent material, rather than a high-efficiency narrow-band green luminescent material, and the luminescent intensity was too low to have the possibility of being applied to a white light LED device (package).

[0069] Comparative Example 4

[0070] The raw materials are Ba3N2, Eu3N2, AlN and Si3N4, the molar ratio of Ba, Eu, Al and Si in Ba3N2, Eu3N2, AlN and Si3N4 is 2.95:0.05:4:3, the above raw materials are ground and mixed uniformly, then loaded into a crucible, sintered at 1200°C for 6h in a high-temperature furnace under the atmosphere of 15MPa ammonia, and cooled to room temperature in the furnace to obtain a material with a theoretical chemical composition of Ba 2.95 Eu 0.05 Al4Si3N 10 .

[0071] The luminescent performance of the material corresponding to Comparative Example 4 is analyzed by a fluorescence spectrometer. The results show that the main peak of the emission spectrum of the material obtained in Comparative Example 4 is located at 532 nm, and the half-height width of the emission spectrum is 70 nm. The quantum efficiency of the material corresponding to Comparative Example 4 is tested by a quantum efficiency tester. The results show that the quantum efficiency of the material obtained in Comparative Example 4 is 11.9%, which is relatively low. The specific data are shown in Table 1. The material obtained in Comparative Example 4 is analyzed by an X-ray diffractometer. The results show that there is a part of BaSiN2 impurity phase in the obtained material. That is, although the most stable all-nitride raw materials are used to synthesize nitride fluorescent materials, the target pure phase cannot be obtained due to the existence of side reactions. Although the material obtained in Comparative Example 4 is a green luminescent material, its luminescent intensity and quantum efficiency are low due to the existence of impurity phase.

[0072] That is, Comparative Example 4 does not have the possibility of being applied to white light LED devices (packaging).

[0073] Comparative Example 5

[0074] The raw materials are BaSi, EuSi and AlN, the molar ratio of Ba, Eu and Al in BaSi, EuSi and AlN is 2.95:0.05:4, the above raw materials are ground and mixed uniformly, then loaded into a crucible, sintered at 1200°C for 6h in a high-temperature furnace under the atmosphere of 15MPa nitrogen, and cooled to room temperature in the furnace to obtain a material with a theoretical chemical composition of Ba 2.95 Eu 0.05 Al4Si3N 10 .

[0075] The luminescent performance of the material corresponding to Comparative Example 5 is analyzed by a fluorescence spectrometer, and the results are as follows Figure 3The results show that the main peak of the emission spectrum of the material obtained in Comparative Example 5 is located at 531 nm, and the half-height width of the emission spectrum is 68 nm. The quantum efficiency of the material corresponding to Comparative Example 5 is tested by using a quantum efficiency tester. Since the atmosphere is a nitrogen atmosphere, the reducing capacity is poorer than that of ammonia, and the results show that the quantum efficiency of the material obtained in Comparative Example 5 is 16.6%, which is relatively low. The specific data are shown in Table 1. Although the material obtained in Comparative Example 5 is a green light-emitting material, the luminescence intensity and quantum efficiency thereof are low due to the fact that a suitable reaction atmosphere is not selected.

[0076] That is, Comparative Example 5 does not have the possibility of being applied to a white light LED device (package).

[0077] Example 1

[0078] The raw materials are BaSi, EuSi and AlN, and the molar ratio of Ba, Eu and Al in BaSi, EuSi and AlN is 2.995:0.005:4. After the above raw materials are ground and uniformly mixed, they are loaded into a crucible, and then sintered at 1200°C for 6h in a high-temperature furnace under an ammonia atmosphere of 15 MPa, and then cooled to room temperature in the furnace to obtain a material with a theoretical chemical composition of Ba 2.995 Eu 0.005 Al4Si3N 10 .

[0079] The structure of the material obtained in Example 1 is analyzed by X-ray diffraction, and the diffraction spectrum is shown in Figure 4 . By comparison through powder structure database retrieval, the diffraction data are completely different from the diffraction spectrum of the known nitride fluorescent material, which indicates that the material obtained in Example 1 is a nitride fluorescent material with a completely new structure. Since an alloy is selected as the raw material instead of a full nitride powder, the obtained material does not contain obvious impurity phases. Through single crystal diffraction analysis combined with powder structure refinement data, it is shown that the crystal structure of the material (matrix) belongs to an orthorhombic system, and the space group is Immm, Figure 5 . The crystal structure diagram of the material (matrix) is given. The fluorescent powder corresponding to Example 1 is analyzed by using a fluorescence spectrometer, and the excitation and emission spectrum diagrams thereof are shown in Figure 6 . The material can absorb ultraviolet-blue light, and under 405 nm violet light excitation, the main peak of the emission spectrum is located at 515 nm, and the half-height width of the emission spectrum is 60 nm. The quantum efficiency of the material is tested by using a quantum efficiency tester, and the value is 82.3%, which is shown in Table 1. The quantum efficiency value is extremely high, which indicates that the material has extremely high packaging practical value.

[0080] It can be seen that the embodiment 1 is a high-efficiency narrow-band green nitride fluorescent material, under the excitation of 405 nm violet light, the main peak of the emission spectrum of the high-efficiency narrow-band green nitride fluorescent material is located at 515-545 nm, the half-height width of the emission spectrum is in the range of 60-80 nm, the quantum efficiency is >80%, and the high-efficiency narrow-band green nitride fluorescent material can be used for white light LED device packaging.

[0081] Embodiment 2

[0082] The raw materials are BaSi, EuSi and AlN, the molar ratio of Ba, Eu and Al in the BaSi, EuSi and AlN is 2.99:0.01:4, the above raw materials are ground and uniformly mixed, then are loaded into a crucible, and are sintered at 1200 DEG C for 6h in a high-temperature furnace under the atmosphere of 15 MPa ammonia, and are cooled to room temperature with the furnace, to obtain a material with a theoretical chemical composition of Ba 2.99 Eu 0.01 Al4Si3N 10 .

[0083] The structure of the material obtained in the embodiment 2 is analyzed by X-ray diffraction. The results show that the crystal structure of the obtained material is the same as that of the embodiment 1. The corresponding fluorescent powder in the embodiment 2 is analyzed by a fluorescence spectrometer. The results show that the obtained material can absorb ultraviolet-blue light, under the excitation of 405 nm violet light, the main peak of the emission spectrum is located at 518 nm, and the half-height width of the emission spectrum is 62 nm. The quantum efficiency of the material is tested by a quantum efficiency tester, and the value is 83.6%, as shown in Table 1. The quantum efficiency value of the fluorescent material is extremely high, which indicates that the material has extremely high packaging practical value.

[0084] It can be seen that the embodiment 2 is a high-efficiency narrow-band green nitride fluorescent material, under the excitation of 405 nm violet light, the main peak of the emission spectrum of the high-efficiency narrow-band green nitride fluorescent material is located at 515-545 nm, the half-height width of the emission spectrum is in the range of 60-80 nm, the quantum efficiency is >80%, and the high-efficiency narrow-band green nitride fluorescent material can be used for white light LED device packaging.

[0085] Embodiment 3

[0086] The raw materials are BaSi, EuSi and AlN, the molar ratio of Ba, Eu and Al in the BaSi, EuSi and AlN is 2.98:0.02:4, the above raw materials are ground and uniformly mixed, then are loaded into a crucible, and are sintered at 1200 DEG C for 6h in a high-temperature furnace under the atmosphere of 15 MPa ammonia, and are cooled to room temperature with the furnace, to obtain a material with a theoretical chemical composition of Ba 2.98 Eu 0.02 Al4Si3N 10 .

[0087] The structure of the material obtained in Example 3 was analyzed by X-ray diffraction. The results show that the crystal structure of the obtained material is the same as that of Example 1. The corresponding phosphor in Example 3 was analyzed by a fluorescence spectrometer. The results show that the material obtained in Example 3 can absorb ultraviolet-blue light, and under 405 nm violet light excitation, the main peak of the emission spectrum is located at 522 nm, and the half-height width of the emission spectrum is 65 nm. The quantum efficiency of the material was tested by a quantum efficiency tester, and the value was 88.5%, as shown in Table 1. The quantum efficiency value of the fluorescent material is extremely high, indicating that the material has extremely high packaging practical value.

[0088] It can be seen that Example 3 is a high-efficiency narrow-band green nitride fluorescent material. Under 405 nm violet light excitation, the main peak of the emission spectrum of the high-efficiency narrow-band green nitride fluorescent material is located at 515-545 nm, the half-height width of the emission spectrum is in the range of 60-80 nm, and the quantum efficiency is >80%, which can be used for white light LED device packaging.

[0089] Example 4

[0090] The raw materials are BaSi, EuSi and AlN, and the molar ratio of Ba, Eu and Al in BaSi, EuSi and AlN is 2.97:0.03:4. After the above raw materials are ground and uniformly mixed, they are loaded into a crucible, and then sintered at 1200°C for 6h in a high-temperature furnace under an ammonia atmosphere of 15 MPa, and then cooled to room temperature in the furnace to obtain a material with a theoretical chemical composition of Ba 2.97 Eu 0.03 Al4Si3N 10 .

[0091] The structure of the material obtained in Example 4 was analyzed by X-ray diffraction. The results show that the crystal structure of the obtained material is the same as that of Example 1. The corresponding phosphor in Example 4 was analyzed by a fluorescence spectrometer. The results show that the material obtained in Example 4 can absorb ultraviolet-blue light, and under 405 nm violet light excitation, the main peak of the emission spectrum is located at 525 nm, and the half-height width of the emission spectrum is 66 nm. The quantum efficiency of the material was tested by a quantum efficiency tester, and the value was 87.1%, as shown in Table 1. The quantum efficiency value of the fluorescent material is extremely high, indicating that the material has extremely high packaging practical value.

[0092] It can be seen that Example 4 is a high-efficiency narrow-band green nitride fluorescent material. Under 405 nm violet light excitation, the main peak of the emission spectrum of the high-efficiency narrow-band green nitride fluorescent material is located at 515-545 nm, the half-height width of the emission spectrum is in the range of 60-80 nm, and the quantum efficiency is >80%, which can be used for white light LED device packaging.

[0093] Example 5

[0094] The raw materials are BaSi, EuSi and AlN, the molar ratio of Ba, Eu and Al in BaSi, EuSi and AlN is 2.96:0.04:4, the above raw materials are ground and mixed uniformly, then are loaded into a crucible, sintered at 1200°C for 6h in a high-temperature furnace under the atmosphere of 15MPa ammonia, and cooled to room temperature with the furnace, to obtain a material with the theoretical chemical composition of Ba 2.96 Eu 0.04 Al4Si3N 10 .

[0095] The structure of the material obtained in Example 5 is analyzed by X-ray diffraction. The results show that the crystal structure of the obtained material is the same as that of Example 1. The corresponding phosphor in Example 5 is analyzed by a fluorescence spectrometer. The results show that the material obtained in Example 5 can absorb ultraviolet-blue light, and under the excitation of 405nm violet light, the main peak of the emission spectrum is located at 527nm, and the half-height width of the emission spectrum is 68nm. The quantum efficiency of the material is tested by a quantum efficiency tester, and the value is 88.2%, as shown in Table 1. The quantum efficiency value of the phosphor is extremely high, indicating that the material has extremely high packaging practical value.

[0096] It can be seen that Example 5 is a high-efficiency narrow-band green nitride phosphor. Under the excitation of 405nm violet light, the main peak of the emission spectrum of the high-efficiency narrow-band green nitride phosphor is located at 515-545nm, the half-height width of the emission spectrum is in the range of 60-80nm, and the quantum efficiency is >80%, which can be used for white light LED device packaging.

[0097] Example 6

[0098] The raw materials are BaSi, EuSi and AlN, the molar ratio of Ba, Eu and Al in BaSi, EuSi and AlN is 2.95:0.05:4, the above raw materials are ground and mixed uniformly, then are loaded into a crucible, sintered at 1200°C for 6h in a high-temperature furnace under the atmosphere of 15MPa ammonia, and cooled to room temperature with the furnace, to obtain a material with the theoretical chemical composition of Ba 2.95 Eu 0.05 Al4Si3N 10 .

[0099] The structure of the material obtained in Example 6 is analyzed by X-ray diffraction. The results show that the crystal structure of the obtained material is the same as that of Example 1. The corresponding phosphor in Example 6 is analyzed by a fluorescence spectrometer. The results are as follows: Figure 7The results show that the material obtained in Example 6 can absorb ultraviolet-blue light, and under 405 nm violet light excitation, the main peak of the emission spectrum is located at 530 nm, and the half-height width of the emission spectrum is 69 nm. The quantum efficiency of the material is tested by using a quantum efficiency tester, and the value is 93.9%, as shown in Table 1. The quantum efficiency value of the fluorescent material is extremely high, indicating that the material has extremely high packaging practical value.

[0100] It can be seen that Example 6 is a high-efficiency narrow-band green nitride fluorescent material, and under 405 nm violet light excitation, the main peak of the emission spectrum of the high-efficiency narrow-band green nitride fluorescent material is located at 515-545 nm, the half-height width of the emission spectrum is in the range of 60-80 nm, and the quantum efficiency is > 80%, which can be used for white light LED device packaging.

[0101] Example 7

[0102] The raw materials are BaSi, EuSi and AlN, and the molar ratio of Ba, Eu and Al in BaSi, EuSi and AlN is 2.94:0.06:4. After the above raw materials are ground and uniformly mixed, they are loaded into a crucible, and then sintered at 1200°C for 6h in a high-temperature furnace under the atmosphere of 15 MPa ammonia gas, and then cooled to room temperature in the furnace to obtain a material with a theoretical chemical composition of Ba 2.94 Eu 0.06 Al4Si3N 10 .

[0103] The structure of the material obtained in Example 7 is analyzed by X-ray diffraction. The results show that the crystal structure of the obtained material is the same as that of Example 1. The corresponding fluorescent powder in Example 7 is analyzed by using a fluorescence spectrometer. The results show that the material obtained in Example 7 can absorb ultraviolet-blue light, and under 405 nm violet light excitation, the main peak of the emission spectrum is located at 535 nm, and the half-height width of the emission spectrum is 72 nm. The quantum efficiency of the material is tested by using a quantum efficiency tester, and the value is 90.7%, as shown in Table 1. The quantum efficiency value of the fluorescent material is extremely high, indicating that the material has extremely high packaging practical value.

[0104] It can be seen that Example 7 is a high-efficiency narrow-band green nitride fluorescent material, and under 405 nm violet light excitation, the main peak of the emission spectrum of the high-efficiency narrow-band green nitride fluorescent material is located at 515-545 nm, the half-height width of the emission spectrum is in the range of 60-80 nm, and the quantum efficiency is > 80%, which can be used for white light LED device packaging.

[0105] Example 8

[0106] The raw materials are BaSi, EuSi and AlN, the molar ratio of Ba, Eu and Al in BaSi, EuSi and AlN is 2.93:0.07:4, the above raw materials are ground and mixed uniformly, then are loaded into a crucible, sintered at 1200°C for 6h in a high-temperature furnace under the atmosphere of 15MPa ammonia, and cooled to room temperature in the furnace to obtain a material with the theoretical chemical composition of Ba 2.93 Eu 0.07 Al4Si3N 10 .

[0107] The structure of the material obtained in Example 8 is analyzed by X-ray diffraction. The results show that the crystal structure of the obtained material is the same as that of Example 1. The corresponding fluorescent powder in Example 8 is analyzed by a fluorescence spectrometer. The results show that the material obtained in Example 8 can absorb ultraviolet-blue light, and under the excitation of 405nm violet light, the main peak of the emission spectrum is located at 537nm, and the half-height width of the emission spectrum is 75nm. The quantum efficiency of the material is tested by a quantum efficiency tester, and the value is 83.4%, as shown in Table 1. The quantum efficiency value of the fluorescent material is extremely high, indicating that the material has extremely high packaging practical value.

[0108] It can be seen that Example 8 is a high-efficiency narrow-band green nitride fluorescent material. Under the excitation of 405nm violet light, the main peak of the emission spectrum of the high-efficiency narrow-band green nitride fluorescent material is located at 515-545nm, the half-height width of the emission spectrum is in the range of 60-80nm, and the quantum efficiency is >80%, which can be used for white light LED device packaging.

[0109] Example 9

[0110] The raw materials are BaSi, EuSi and AlN, the molar ratio of Ba, Eu and Al in BaSi, EuSi and AlN is 2.93:0.07:4, the above raw materials are ground and mixed uniformly, then are loaded into a crucible, sintered at 1200°C for 6h in a high-temperature furnace under the atmosphere of 15MPa ammonia, and cooled to room temperature in the furnace to obtain a material with the theoretical chemical composition of Ba 2.92 Eu 0.08 Al4Si3N 10 .

[0111] The structure of the material obtained in Example 9 was analyzed by X-ray diffraction. The results show that the crystal structure of the obtained material is the same as that of Example 1. The corresponding phosphor in Example 9 was analyzed by a fluorescence spectrometer. The results show that the material obtained in Example 9 can absorb ultraviolet-blue light, and under 405 nm violet light excitation, the main peak of the emission spectrum is located at 539 nm, and the half-height width of the emission spectrum is 77 nm. The quantum efficiency of the material was tested by a quantum efficiency tester, and the value was 86.9%, as shown in Table 1. The quantum efficiency value of the phosphor material is extremely high, indicating that the material has extremely high packaging practical value.

[0112] It can be seen that Example 9 is a high-efficiency narrow-band green nitride phosphor material. Under 405 nm violet light excitation, the main peak of the emission spectrum of the high-efficiency narrow-band green nitride phosphor material is located at 515-545 nm, the half-height width of the emission spectrum is in the range of 60-80 nm, and the quantum efficiency is >80%, which can be used for white light LED device packaging.

[0113] Example 10

[0114] The raw materials are BaSi, EuSi and AlN, and the molar ratio of Ba, Eu and Al in BaSi, EuSi and AlN is 2.91:0.09:4. After the above raw materials are ground and uniformly mixed, they are loaded into a crucible, sintered at 1200°C for 6h in a high-temperature furnace under an ammonia atmosphere of 15 MPa, and cooled to room temperature in the furnace to obtain a material with a theoretical chemical composition of Ba 2.91 Eu 0.09 Al4Si3N 10 .

[0115] The structure of the material obtained in Example 10 was analyzed by X-ray diffraction. The results show that the crystal structure of the obtained material is the same as that of Example 1. The corresponding phosphor in Example 10 was analyzed by a fluorescence spectrometer. The results show that the material obtained in Example 10 can absorb ultraviolet-blue light, and under 405 nm violet light excitation, the main peak of the emission spectrum is located at 540 nm, and the half-height width of the emission spectrum is 79 nm. The quantum efficiency of the material was tested by a quantum efficiency tester, and the value was 88.1%, as shown in Table 1. The quantum efficiency value of the phosphor material is extremely high, indicating that the material has extremely high packaging practical value.

[0116] It can be seen that Example 10 is a high-efficiency narrow-band green nitride phosphor material. Under 405 nm violet light excitation, the main peak of the emission spectrum of the high-efficiency narrow-band green nitride phosphor material is located at 515-545 nm, the half-height width of the emission spectrum is in the range of 60-80 nm, and the quantum efficiency is >80%, which can be used for white light LED device packaging.

[0117] Example 11

[0118] The raw materials are BaSi, EuSi and AlN, the molar ratio of Ba, Eu and Al in BaSi, EuSi and AlN is 2.9:0.1:4, the above raw materials are ground and mixed uniformly, then are loaded into a crucible, sintered at 1200℃ for 6h in a high temperature furnace under 15MPa ammonia atmosphere, and cooled to room temperature in the furnace, to obtain a material with theoretical chemical composition of Ba 2.9 Eu 0.1 Al4Si3N 10 .

[0119] The structure of the material obtained in Example 11 is analyzed by X-ray diffraction. The results show that the crystal structure of the obtained material is the same as that of Example 1. The corresponding phosphor in Example 11 is analyzed by a fluorescence spectrometer. The results show that the material obtained in Example 11 can absorb ultraviolet-blue light, and under 405nm violet light excitation, the emission spectrum main peak is located at 545nm, and the half-height width of the emission spectrum is 80nm. The quantum efficiency of the material is tested by a quantum efficiency tester, and the value is 80.2%, as shown in Table 1. The quantum efficiency value of the phosphor is extremely high, indicating that the material has extremely high packaging practical value.

[0120] It can be seen that Example 11 is a high-efficiency narrow-band green nitride phosphor. Under 405nm violet light excitation, the main peak of the emission spectrum of the high-efficiency narrow-band green nitride phosphor is located at 515-545nm, the half-height width of the emission spectrum is in the range of 60-80nm, and the quantum efficiency is >80%, which can be used for white light LED device packaging.

[0121] Table 1 Luminescent properties of the materials corresponding to the examples and comparative examples

[0122]

[0123] Example 12

[0124] The BaSi2O2N2:Eu cyan phosphor, the Ba 2.95 Eu 0.05 Al4Si3N 10 green phosphor synthesized in Example 6, Y3Al5O 12 :Ce yellow phosphor and CaAlSiN3:Eu red phosphor are mixed uniformly with epoxy resin according to a mass ratio of 1:2.55:0.52:0.36:12, the above mixture is coated on a violet LED with emission spectrum main peak at 410nm for packaging, and then cured at 150℃ for 2h, to obtain a white light LED device with color rendering index of 93.9. The spectrum of the device is shown in Figure 8 .

[0125] The above examples are only used to illustrate the embodiments of the present application and explain the technical features of the present application, and are not used to limit the protection scope of the present application. Any changes or equivalent arrangements that can be easily completed by those skilled in the art shall fall within the scope of the present application, and the protection scope of the present application shall be subject to the claims.

Claims

1. A highly efficient narrow-band green nitride phosphor, characterized by: The high-efficiency narrow-band green nitride fluorescent material has a chemical formula of Ba 3-x Eu x Al4Si3N 10 , wherein 0 < x ≤ 0.1; under excitation of 405 nm violet light, a main peak of an emission spectrum of the high-efficiency narrow-band green nitride fluorescent material is located at 515-545 nm, a half-height width of the emission spectrum is 60-80 nm, and a quantum efficiency is > 80%.

2. The high-efficiency narrow-band green nitride fluorescent material according to claim 1, characterized in that: The x is 0.

05.

3. The method for preparing a high-efficiency narrow-band green nitride fluorescent material according to any one of claims 1-2, characterized in that: The Ba precursor, the Eu precursor and the Al precursor are mixed, and high-temperature solid-phase reaction is carried out under the atmosphere with ammonia pressure of 10-20 MPa, so as to obtain the high-efficiency narrow-band green nitride fluorescent material; wherein the Ba precursor is selected from BaSi alloy, the Eu precursor is selected from EuSi alloy, and the Al precursor is selected from AlN.

4. The method for preparing a high-efficiency narrow-band green nitride fluorescent material according to claim 3, wherein: In the Ba precursor, the molar ratio of Ba and Si is 1:

1.

5. The method for preparing a high-efficiency narrow-band green nitride fluorescent material according to claim 3, wherein: In the Eu precursor, the molar ratio of Eu and Si is 1:

1.

6. The method for preparing a high-efficiency narrow-band green nitride fluorescent material according to claim 3, wherein: In the Ba precursor, the Eu precursor and the Al precursor, the molar ratio of Ba, Eu and Al is (3-x):x:4, wherein 0 7. The method for preparing a high-efficiency narrow-band green nitride fluorescent material according to claim 3, wherein: The temperature of the high-temperature solid-phase reaction is 1000-1400 DEG C, and the time of the high-temperature solid-phase reaction is 4-10 h.

8. The use of a high-efficiency narrow-band green nitride fluorescent material according to any one of claims 1 to 2 or a high-efficiency narrow-band green nitride fluorescent material obtained by the production method according to any one of claims 3 to 7, characterized in that: A white light LED device is prepared.

9. A white LED device, characterized by: The high-efficiency narrow-band green nitride fluorescent material of any one of claims 1-2 or the high-efficiency narrow-band green nitride fluorescent material prepared by the method of any one of claims 3-7.

10. A white LED device as defined in claim 9, wherein: A violet light LED chip with peak wavelength of 380-425 nm is further included.

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