WO2023123349A1 - Nitrogen oxide green fluorescent material, preparation method, and device - Google Patents

Nitrogen oxide green fluorescent material, preparation method, and device Download PDF

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WO2023123349A1
WO2023123349A1 PCT/CN2021/143664 CN2021143664W WO2023123349A1 WO 2023123349 A1 WO2023123349 A1 WO 2023123349A1 CN 2021143664 W CN2021143664 W CN 2021143664W WO 2023123349 A1 WO2023123349 A1 WO 2023123349A1
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green fluorescent
nitrogen oxide
fluorescent material
oxide green
precursor
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PCT/CN2021/143664
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French (fr)
Chinese (zh)
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周天亮
倪国琴
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苏州君诺新材科技有限公司
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    • C—CHEMISTRY; METALLURGY
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/59—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing silicon

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  • the invention relates to the technical field of luminescent material preparation, in particular to a nitrogen oxide green fluorescent material, a preparation method and a device.
  • White light devices are visible light devices, which are widely used in lighting, display backlight and other industries.
  • White light is composite light, which is composed of monochromatic light in the wavelength range of 380-780nm.
  • the easiest way to achieve white light is to use the so-called three primary colors, that is, to obtain white light by combining red, green and blue light.
  • LED white light devices such as patent document 1 (Wang Le, Zheng Zishan, Zhang Hong, Li Yanghui, a white light LED with high color rendering index and high s/p value and its obtaining method and application, CN107369742A) Given that, it is easy to obtain a white light device with a high color rendering index by exciting the green fluorescent material + red fluorescent material through the blue light chip.
  • 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 the fluorescent material is: C 28 H 14 N 5 O 29 Tb 3 K 2 , but the material It is an organic substance and cannot withstand high temperatures, and LED devices may even generate a high temperature environment of 200°C during operation, which will cause the above-mentioned organic green fluorescent materials to accelerate aging.
  • the disadvantage of the above-mentioned phosphor is that the luminescent center of the green phosphor is Ce 3+ , so the half-maximum width of the emission spectrum is relatively wide, which can be applied to white light lighting, but it is not suitable for display backlight, because the fluorescent light used for display backlight The material requires half-width to be as narrow as possible.
  • Patent Document 5 (Bai Mingxun, Kim Chang-hwan, Liu Yongzhe, Park Chun-geun, Lee Sang-il, Kim Hyun-gyu, Kim Sung-xu, Green phosphor, green phosphor composition and plasma display panel, CN101724399A) discloses a green phosphor , whose chemical formula is (Lu 3-x Cex )Al 5 O 12 , and x satisfies the relationship 0 ⁇ x ⁇ 3.
  • the green fluorescent material is LuAG:Ce widely used in white light illumination.
  • LuAG:Ce has high luminous efficiency and stable chemical properties, its problem is the same as that of patent document 4, that is, the luminescent center of the green phosphor is Ce 3+ , so the half-maximum width of the emission spectrum is wide, and it is suitable for white light. Lighting is OK, but not suitable for application display backlighting.
  • Patent document 6 (Zhao Li, a green fluorescent powder material containing Ba-containing nitrogen oxide and its preparation method, CN101948687A) discloses a green fluorescent material containing Ba-containing nitrogen oxide, whose general chemical formula is (Ba, A) 2-x Si y O z N 2+4y-2z : xEu, where 0 ⁇ x ⁇ 1.0, 0 ⁇ y ⁇ 1.0, 1 ⁇ z ⁇ 2.0, A is Ca or Sr element.
  • the preparation method of the green fluorescent material adopts a two-step method, wherein the first step is to synthesize the precursor A 2 SiO 4 of the nitrogen oxide green fluorescent powder, wherein A is Ca or Sr element, and the precursor provides a stable crystal structure; the second The first step is to dope Ba element in the matrix structure provided by the precursor, and by adjusting the ratio of Si element and Ba element, the emission wavelength of the green phosphor can be modulated so that the peak emission wavelength is between 516-540nm.
  • the obtained oxynitride green fluorescent material has high luminous brightness and is suitable for lighting and backlight white LEDs with high color rendering index, the synthesis path is cumbersome and the cost is high.
  • Patent Document 7 (Zhao Li, a preparation method of nitrogen oxide green phosphor material, CN102191045B) discloses a nitrogen oxide green phosphor material, the general chemical formula of which is (Ba, A ) 2-x Si y (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 element, B is F or Cl element.
  • halogen elements are added, and the preparation of the nitrogen oxide green fluorescent material also requires a two-step method, the first step: the synthesis of the precursor A 2 SiO 4 ; the second step, in the precursor A 2 SiO 4 4 Doping elements into the matrix structure provided, and finally synthesizing the oxynitride green fluorescent material (Ba, A) 2-x Si y (O, B) z N 2+4y-2z :xEu.
  • the obtained oxynitride green fluorescent material has high luminous brightness, it is suitable for lighting and backlight white LED with high color rendering index, but the synthesis path is cumbersome and the cost is high; and the halogen elements contained in the material will corrode the packaging
  • the silver wires and reflective bowls used in the device reduce the reliability of the device.
  • Patent Document 8 (Gao Shaokang, Li Zhaomei, Hu Xiaolin, Green Phosphor Powder for White Light LED and Its Preparation Method and Application, CN102391859A) discloses a green phosphor powder for white light LED and its preparation method and application.
  • the chemical formula of the phosphor powder is Ca 6 Sr 4-x (Si 2 O 7 ) 3 Cl 2 :xEu 2+
  • the phosphor is made of CaO, SiO 2 , CaCl 2 and SrCO 3 as raw materials
  • Eu 2 O 3 as activator with excess CaCl 2 is used as a flux
  • the phosphor powder is synthesized under a reducing atmosphere by a high-temperature solid-state method.
  • the fluorescent powder disclosed by the invention can be efficiently excited in the ultraviolet-near ultraviolet band and has high luminous efficiency, so it can be used to prepare white light LEDs excited by ultraviolet-near ultraviolet LEDs.
  • the calcination temperature of the phosphor powder is low and the preparation method is simple and easy, similar to Patent Document 7, the material disclosed in Patent Document 8 also contains halogen, which will corrode the silver wire and reflective bowl used in the packaging device, thereby reducing the performance of the device. reliability.
  • 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- xy Sr x Eu y ) 9 Lu 2 Si 6 O 24 , wherein, 0 ⁇ x ⁇ 0.9999, 0.0001 ⁇ y ⁇ 0.3, 0.0001 ⁇ x+y ⁇ 1, x and y are mole fractions.
  • the green fluorescent powder provided by the invention has the advantages of low production cost, simple manufacturing process, and wide excitation wavelength range, as a silicate fluorescent powder, it has the disadvantages of low chemical stability and poor thermal quenching characteristics. shortcoming.
  • Patent document 10 (Wang Hao, Huang Xiaoyu, Li Kai, Wang Weimin, Fu Zhengyi, a preparation method of divalent manganese ion-doped MgAlON green phosphor with adjustable optical properties, CN108531166A) discloses a divalent manganese ion-doped MgAlON green phosphor with adjustable optical properties.
  • Manganese ion-doped MgAlON green phosphor preparation method the chemical composition 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.
  • the half-maximum width of the emission spectrum of the green fluorescent material is relatively narrow, the synthesis of MgAlON requires extremely high temperature. At the same time, because the transition element Mn is used as the luminescent center, Mn has poor light absorption, so the quantum efficiency of the material is low. Bias in the absorption of violet light.
  • 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
  • the application in the diode, its chemical formula is Ba (2-xyp) Sr x M p Si q O (2+2q) :Eu y ;
  • M is at least one in 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.
  • silicate phosphor it has the disadvantages of low chemical stability and poor thermal quenching characteristics.
  • Patent document 12 (Zhao Li, a green phosphor material containing Al element nitrogen oxide and its preparation method, CN101948689A) discloses a green phosphor material containing Al element nitrogen oxide and its preparation method, which also adopts two-step synthesis, The first step is to synthesize Al-containing precursor A 2 SiO 4 , where A is one of Ca, Ba or Sr elements; the second step is to dope Al element in the matrix structure provided by the precursor, by adjusting the Si element and The ratio of the Al element modulates the emission wavelength of the green phosphor A 1-x (Si, Al) y O z N 2/3+4/3y-2/3z :xEu. Similar to the problems in Patent Document 6 and Patent Document 7, although the obtained nitrogen oxide green fluorescent material has a high luminance and is suitable for lighting and backlight white LEDs with high color rendering index, the synthesis path is cumbersome and the cost is high. higher.
  • Patent document 13 (Huang Lin, Zhang Ge, Wang Jing, A green phosphor and its preparation method and application in white light LED devices, CN108504358A) discloses a chemical composition formula: Ca 1-x Sc 2 O 4 :xCe 3+ green phosphor, where 0.001 ⁇ x ⁇ 0.90, x is the molar percentage coefficient of doped Ce 3+ relative to Ca.
  • the problem is the same as that of Patent Document 4 and Patent Document 5.
  • the disadvantage of this phosphor is that the luminescent center of the green phosphor is Ce 3+ , so the half-width of the emission spectrum is wide. It can be applied to white light lighting, but the application shows The backlight source is not suitable, because the fluorescent material used for the display backlight source requires the narrower the half-height width, the better.
  • Patent Document 14 (Duan Chengjun, Gu Jingtao, Zhou Weixin, A borophosphate phosphor emitting green fluorescence and its preparation method and application, CN104449723B) discloses a borate green phosphor, the general chemical formula of which is: (Ln 1-x Tb x ) 7 O 6 (BO 3 )(PO 4 ) 2 , where Ln is a rare earth element, 0.01 ⁇ x ⁇ 0.1.
  • Ln is a rare earth element, 0.01 ⁇ x ⁇ 0.1.
  • the emission of green fluorescence of the borophosphate phosphor is entirely due to the 5 D 4 ⁇ 7 F 5 magnetic dipole transition of Tb 3+ outer shell electrons.
  • the borophosphate phosphor powder of the present invention has the advantages of simple preparation method and narrow half-maximum width of the emission spectrum, it has weak absorption of violet light and is difficult to be directly applied to white LEDs excited by violet light.
  • Patent document 15 (Yang Zhiping, Wang Hailong, Dong Xiuqin, a ⁇ -SiAlON:Eu 2+ green phosphor and its preparation method, CN105295908B) discloses a green phosphor with the general chemical formula Eu a Si b Al c O d Ne Powder, where, 0 ⁇ a ⁇ 0.010, 0.4 ⁇ b ⁇ 0.5, 0.01 ⁇ c ⁇ 0.02, 0.006 ⁇ d ⁇ 0.02, 0.47 ⁇ e ⁇ 0.664.
  • the green fluorescent powder obtained by the present invention has the advantages of uniform particles, large average particle size and high luminous intensity, it has broad prospects in the preparation of white light LED devices, but the synthesis of the fluorescent material requires sintering at 1900-2200 ° C for 8-12 hours, Such a high synthesis temperature requires extremely high equipment for sintering phosphor powder, that is, it is very difficult to synthesize the phosphor material.
  • Patent document 16 discloses a core-shell structure aluminate green phosphor and its preparation method, the phosphor includes a core And the outer shell, the particle size of the inner core is low Tb content aluminate green phosphor of 3-8 ⁇ m, the outer shell is the oxide of Ce and Tb, and its composition formula is ( Cex Tb m Ce y Tb n )MgAl 11 O 19 , Among them, 0.6 ⁇ x+y ⁇ 0.8, 0 ⁇ m+n ⁇ 0.4, 1 ⁇ n:m ⁇ 4.
  • the green fluorescence emission of the aluminate phosphor is entirely due to the 5 D 4 ⁇ 7 F 5 magnetic dipole transition of Tb 3+ outer shell electrons.
  • the aluminate phosphor of the present invention has the advantages of simple preparation method and narrow half-maximum width of the emission spectrum, it has weak absorption of violet light and is difficult to be directly applied to white LEDs excited by violet light.
  • 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.
  • the general formula is Ca 3-xyz C x Tb y A z Sc 2-m Mg m Si 3-n Al n O 12 , where A is one of the elements Li, Na, K or any combination thereof; x, y , z, m, and n are mole fractions, and their value ranges are: 0.005 ⁇ x ⁇ 0.2, 0.005 ⁇ y ⁇ 0.5, 0 ⁇ z ⁇ 0.5, 0 ⁇ m ⁇ 0.5, 0 ⁇ n ⁇ 0.5.
  • the phosphor is prepared by a high-temperature solid-phase method. Through the co-doping of Ce 3+ and Tb 3+ , the effective energy transfer between Ce 3+ and Tb 3+ is used to expand the effective emission of Tb 3+ in the ultraviolet region.
  • the excitation range realizes the broadening of the excitation spectrum of Tb 3+ from 250-300nm to 200-380nm, so that it can better match with ultraviolet/violet LED chips.
  • the effective energy transfer efficiency between Ce 3+ and Tb 3+ is low, therefore, the luminous efficiency of the fluorescent material is low and the practicability is poor.
  • the first purpose of the present 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 x LnSiO 3 N, wherein, Ln is one or more of Sc or Y or La or Gd or Lu, and Sc is a necessary , and Sc accounts for more than 50% of the Ln content (molar ratio), 0 ⁇ x ⁇ 0.2; under the excitation of purple light, the green fluorescent material can produce a main peak of emission wavelength ranging from 505 to 535nm, and the half maximum width of the emission spectrum is less than or equal to 90nm.
  • the luminous intensity after aging for 48 hours in a closed container containing high-pressure water vapor at 200°C is no less than 75% of the luminous intensity at room temperature .
  • the second object of the present invention is to provide a preparation method of nitrogen oxide green fluorescent material.
  • the preparation method comprises: mixing Ba precursor, Eu precursor, Ln precursor and Si precursor, and carrying out high-temperature solid-state reaction in reducing atmosphere to obtain a nitrogen oxide green fluorescent material.
  • the molar ratio of Ba precursor, Eu precursor, Ln precursor and Si precursor is (1-X):X:1:1
  • the general chemical formula of the obtained material is: Ba 1-x Eu x LnSiO 3 N, where 0 ⁇ x ⁇ 0.2.
  • the present invention also provides a green fluorescent glass and a preparation method thereof.
  • the green fluorescent glass is obtained by mixing the nitrogen oxide green fluorescent material with glass powder and performing a high-temperature solid-state reaction. Specifically, in an air atmosphere, the High-temperature solid-phase reaction, 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.
  • the present invention also provides a laser green light device, the device includes a violet laser diode and a light emitting layer, and the light emitting layer includes the green fluorescent glass.
  • a kind of nitrogen oxide green fluorescent material is:
  • Ln is one or more of Sc or Y or La or Gd or Lu, and Sc is necessary, and Sc accounts for more than 50% (molar ratio) of Ln content, 0 ⁇ x ⁇ 0.2.
  • the second object of the present invention is to provide a preparation method of nitrogen oxide green fluorescent material.
  • the preparation method is as follows:
  • the Ba precursor, the Eu precursor, the Ln precursor and the Si precursor are mixed, and a high-temperature solid-state reaction is carried out under a reducing atmosphere to obtain the nitrogen oxide green fluorescent material.
  • 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.
  • the Ba precursor is selected from one or more of Ba carbonate, Ba oxide or Ba nitrate; optionally, the Eu precursor is selected from Eu 2 O 3 ;
  • the Ln precursor is one or more of Sc 2 O 3 , Y 2 O 3 , La 2 O 3 , Gd 2 O 3 or Lu 2 O 3 , wherein Sc 2 O 3 is necessary
  • the Si precursors are SiO 2 and Si 3 N 4 .
  • the purity of the Ba precursor, the Eu precursor, the Ln precursor and the Si precursor is not lower than 99.5wt%.
  • the temperature of the high-temperature solid-state reaction is between 1500-1600° C.
  • the time of the high-temperature solid-state reaction is between 4-10 hours under a reducing atmosphere.
  • the invention also protects a kind of fluorescent glass based on nitrogen oxide green fluorescent material.
  • the production method is as follows: mix nitrogen oxide green fluorescent material with glass powder and carry out high-temperature solid-state reaction to obtain nitrogen oxide green fluorescent glass.
  • 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.
  • the temperature for the high-temperature solid-state reaction between the nitrogen oxide green fluorescent material and the glass frit is 500-800°C, and the time for the high-temperature solid-state reaction is 0.1-1 h.
  • the invention also protects a light-emitting device made of fluorescent glass based on nitrogen oxide green fluorescent material.
  • the light-emitting device includes a violet laser diode and a light-emitting layer, the light-emitting layer includes the nitrogen oxide green fluorescent glass, and the light-emitting layer is excited by the violet laser diode to emit green light.
  • the invention provides a nitrogen oxide green fluorescent material and its preparation method and application.
  • the general chemical formula of the nitrogen oxide green fluorescent material is Ba 1-x Eu x LnSiO 3 N, wherein Ln can be Sc or Y or One or more of La or Gd or Lu, and Sc is necessary, and Sc accounts for Ln content>50% (molar ratio), 0 ⁇ x ⁇ 0.2; under the excitation of purple light, the emission wavelength produced by the green fluorescent material
  • the main peak ranges from 505 to 535nm, and the full width at half maximum of the emission spectrum is less than or equal to 90nm.
  • the nitrogen oxide green fluorescent material prepared by the present invention has a brand-new chemical composition, narrow half-maximum width of emission spectrum, good chemical stability, high quantum efficiency and can effectively absorb violet light. Therefore, the luminescent material can be applied to lighting, display backlight and other industries.
  • Fig. 1 is the emission spectrogram of the luminescent material obtained in Example 6 of the present invention.
  • Fig. 2 is the excitation spectrum diagram of the luminescent material obtained in Example 6 of the present invention.
  • the general chemical formula of the nitrogen oxide green fluorescent material is as follows:
  • Ln can be one or more of Sc or Y or La or Gd or Lu, and Sc is necessary, and Sc accounts for more than 50% (molar ratio) of Ln content, 0 ⁇ x ⁇ 0.2.
  • said x is preferably 0.001, and Ln is preferably Sc; in some embodiments provided by the present invention, said x is preferably 0.002, and Ln is preferably Sc; in some provided by the present invention
  • the x is preferably 0.005, and Ln is preferably Sc; in some embodiments provided by the present invention, the x is preferably 0.01, and Ln is preferably Sc; in some embodiments provided by the present invention, the x is preferably 0.02, and Ln is preferably Sc; in some embodiments provided by the invention, said x is preferably 0.05, and Ln is preferably Sc; in some embodiments provided by the invention, said x is preferably 0.08, Ln It is preferably Sc; in some embodiments provided by the present invention, said x is preferably 0.1, and Ln is preferably Sc; in some embodiments provided by the present invention, said x is preferably 0.15, and Ln is preferably Sc; in this invention In some embodiments provided by the invention, the
  • the Ba precursor, the Eu precursor, the Ln precursor and the Si precursor are mixed, and a high-temperature solid-state reaction is carried out under a reducing atmosphere to obtain a nitrogen oxide green fluorescent material.
  • the Ba precursor is a compound containing Ba well known in the art, and there is no special limitation.
  • the Ba precursor is preferably selected from Ba carbonate, Ba oxide and Ba nitric acid.
  • the Eu precursor is selected from Eu 2 O 3
  • the Ln precursor is selected from the oxide of Ln, namely Sc 2 O 3 , Y 2 O 3 , La 2 O 3 , Gd 2 O 3 and Lu 2 O 3
  • the Si precursors are SiO 2 and Si 3 N 4 .
  • the purity of the Ba precursor, Eu precursor, Ln precursor and Si precursor is not lower than 99.5%. The higher the purity, the less impurity in the luminescent material obtained.
  • the reducing atmosphere in the step can be a dry atmosphere well known to those skilled in the art, and there is no special limitation. In the present invention, it is preferably nitrogen-hydrogen mixed gas.
  • the temperature of the high-temperature solid phase in the step 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.
  • the high-temperature solid-phase time in the step is preferably 4-10 hours, more preferably 5-8 hours; in some embodiments provided by the present invention, the high-temperature solid-phase time is preferably 6 hours.
  • the high-temperature solid reaction phase is preferably carried out in a high-temperature furnace. After the reaction is carried out, the furnace is cooled to room temperature to obtain a nitrogen oxide green fluorescent material.
  • the invention adopts high-temperature solid-state reaction to successfully prepare a nitrogen oxide green fluorescent material.
  • the lighting device made of nitrogen oxide green fluorescent material is at least composed of a violet laser diode and a light emitting layer.
  • the luminous layer is a kind of green fluorescent glass.
  • the green fluorescent glass using the general chemical formula: Ba 1-x Eu x LnSiO 3 N (wherein, Ln is one or more of Sc or Y or La or Gd or Lu, and Sc is necessary, and Sc accounts for Ln content>50% (molar ratio), 0 ⁇ x ⁇ 0.2) nitrogen oxide green fluorescent material is mixed with low-melting point glass powder, and then undergoes high-temperature solid-state reaction to be finally prepared.
  • the preparation of the green fluorescent glass is carried out in an air atmosphere, and the temperature of the high-temperature solid-state reaction is preferably 500-800°C.
  • the temperature of the high-temperature solid-state reaction is preferably 700°C °C;
  • the high-temperature solid-phase reaction time is preferably 0.1-1 h, and in some embodiments provided by the present invention, the high-temperature solid-phase reaction time is preferably 0.5 h, and finally a green fluorescent glass is obtained.
  • the chemical stability of fluorescent materials was evaluated with reference to the method given in Chinese patent CN104422676A (Xie Rongjun, Zhou Tianliang, Rapid Aging Equipment, CN104422676A).
  • the volume content of hydrogen is 20%.
  • the Ba precursors, Eu precursors, Ln precursors and Si precursors used in the comparative examples and examples are only examples and do not constitute a limitation on the raw materials of the precursors.
  • the purity of the precursors is not less than 99.5wt%.
  • the material described in this comparative example was obtained from a commercially available product. First measure the luminous intensity of the material at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity lower, see Table 1 for details. It can be seen that the material corresponding to Comparative Example 1 is not a chemically stable fluorescent material.
  • the material described in this comparative example contains the compound chemical formula: Ba 0.95 Eu 0.05 YSiO 3 N.
  • BaCO 3 , Eu 2 O 3 , Y 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, according to the stoichiometric ratio of its composition: Ba 0.95 Eu 0.05 YSiO 3 N, accurately weigh the raw materials at 1500°C , nitrogen and hydrogen in a mixed atmosphere for 6 hours, and after cooling, a material with a nominal chemical composition of Ba 0.95 Eu 0.05 YSiO 3 N can be obtained.
  • the material described in this comparative example contains the compound chemical formula: Ba 0.95 Eu 0.05 LaSiO 3 N. Take BaCO 3 , Eu 2 O 3 , La 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, and accurately weigh the raw materials according to their composition: Ba 0.95 Eu 0.05 LaSiO 3 N stoichiometric ratio, at 1500°C , nitrogen and hydrogen in a mixed atmosphere for 6 hours, and after cooling, a material with a nominal chemical composition of Ba 0.95 Eu 0.05 LaSiO 3 N can be obtained.
  • the material described in this comparative example contains the compound chemical formula: Ba 0.95 Eu 0.05 GdSiO 3 N.
  • BaCO 3 , Eu 2 O 3 , Gd 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, according to the stoichiometric ratio of its composition: Ba 0.95 Eu 0.05 GdSiO 3 N, accurately weigh the raw materials, at 1500°C , nitrogen and hydrogen in a mixed atmosphere for 6 hours, and after cooling, a material with a nominal chemical composition of Ba 0.95 Eu 0.05 GdSiO 3 N can be obtained.
  • the material described in this comparative example contains the compound chemical formula: Ba 0.95 Eu 0.05 LuSiO 3 N.
  • BaCO 3 , Eu 2 O 3 , Lu 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, according to the stoichiometric ratio of its composition: Ba 0.95 Eu 0.05 LuSiO 3 N, accurately weigh the raw materials, at 1500°C , nitrogen and hydrogen in a mixed atmosphere for 6 hours, and after cooling, a material with a nominal chemical composition of Ba 0.95 Eu 0.05 LuSiO 3 N can be obtained.
  • the material described in this comparative example contains the compound chemical formula: Ba 0.95 Ce 0.05 ScSiO 3 N. Taking BaCO 3 , CeO 2 , Sc 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, according to the stoichiometric ratio of its composition: Ba 0.95 Ce 0.05 ScSiO 3 N, accurately weigh the raw materials, at 1500 ° C, nitrogen After sintering in a hydrogen mixed atmosphere for 6 hours and cooling, a material with a nominal chemical composition of Ba 0.95 Ce 0.05 ScSiO 3 N can be obtained.
  • the emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and it was found that the main peak of the emission spectrum was located at 495 nm, and the half-maximum width of the emission spectrum was 121 nm.
  • the emission spectrum of the material obtained in Comparative Example 6 contains certain green light components, it is not a nitrogen oxide green fluorescent material, but a cyan fluorescent material, and the half-maximum width of its emission spectrum is too wide to be suitable for Applied to backlight display.
  • the material described in this embodiment contains compounds with the chemical formula: Ba 0.999 Eu 0.001 Sc 0.4 Y 0.6 SiO 3 N.
  • BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , Y 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, it is accurately weighed according to its stoichiometric ratio of Ba 0.999 Eu 0.001 Sc 0.4 Y 0.6 SiO 3 N
  • the raw materials were taken and sintered at 1500° C. for 6 hours in a mixed atmosphere of nitrogen and hydrogen. After cooling, the nominal chemical composition of the material was Ba 0.999 Eu 0.001 Sc 0.4 Y 0.6 SiO 3 N.
  • the emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Comparative Example 7 is around 506 nm when excited by 400 nm violet light, and the half maximum width of the emission spectrum is about 75 nm. It can be seen that the material obtained in Comparative Example 7 is a nitrogen oxide green fluorescent material.
  • the material described in this embodiment contains compounds with the chemical formula: Ba 0.999 Eu 0.001 ScSiO 3 N. Taking BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, accurately weigh the raw materials according to the stoichiometric ratio of Ba 0.999 Eu 0.001 ScSiO 3 N, Sintering in a mixed atmosphere of nitrogen and hydrogen for 6 hours, after cooling, the nominal chemical composition of the material can be obtained as Ba 0.999 Eu 0.001 ScSiO 3 N.
  • the emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1.
  • the emission spectrum of the material prepared in Example 1 is around 507 nm under the excitation of 400 nm violet light, and the half maximum width of the emission spectrum is about 77 nm.
  • the material obtained in Example 1 is a nitrogen oxide green fluorescent material. Measure the luminous intensity of the measurement at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity is higher than High, see Table 1 for details. It can be seen that the material corresponding to Example 1 is a green fluorescent material with high chemical stability.
  • the material described in this embodiment contains a compound with the chemical formula: Ba 0.998 Eu 0.002 ScSiO 3 N. Take BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, and accurately weigh the raw materials according to their stoichiometric ratio of Ba 0.998 Eu 0.002 ScSiO 3 N. Sintering in a mixed atmosphere of nitrogen and hydrogen for 6 hours, after cooling, the nominal chemical composition of the material can be obtained as Ba 0.998 Eu 0.002 ScSiO 3 N. The emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1.
  • the emission spectrum of the material prepared in Example 2 is around 510 nm when excited by 400 nm violet light, and the half maximum width of the emission spectrum is about 79 nm.
  • the material obtained in Example 2 is a nitrogen oxide green fluorescent material. Measure the luminous intensity of the measurement at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity is higher than High, see Table 1 for details. It can be seen that the material corresponding to Example 2 is a green fluorescent material with high chemical stability.
  • the material described in this embodiment contains a compound with the chemical formula: Ba 0.995 Eu 0.005 ScSiO 3 N.
  • BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, accurately weigh the raw materials according to the stoichiometric ratio of Ba 0.995 Eu 0.005 ScSiO 3 N, Sintering in a mixed atmosphere of nitrogen and hydrogen for 6 hours, after cooling, the nominal chemical composition of the material can be obtained as Ba 0.995 Eu 0.005 ScSiO 3 N.
  • the emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1.
  • the emission spectrum of the material prepared in Example 3 is around 515 nm under the excitation of 400 nm violet light, and the half maximum width of the emission spectrum is about 81 nm.
  • the material obtained in Example 3 is a nitrogen oxide green fluorescent material. Measure the luminous intensity of the measurement at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity is higher than High, see Table 1 for details. It can be seen that the material corresponding to Example 3 is a green fluorescent material with high chemical stability.
  • the material described in this embodiment contains compounds with the chemical formula: Ba 0.99 Eu 0.01 ScSiO 3 N. Take BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, and accurately weigh the raw materials according to their stoichiometric ratio of Ba 0.99 Eu 0.01 ScSiO 3 N. Sintering in a mixed atmosphere of nitrogen and hydrogen for 6 hours, and after cooling, the nominal chemical composition of the material can be obtained as Ba 0.99 Eu 0.01 ScSiO 3 N. The emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1.
  • the emission spectrum of the material prepared in Example 4 is around 519 nm when excited by 400 nm violet light, and the half maximum width of the emission spectrum is about 82 nm.
  • the material obtained in Example 4 is a nitrogen oxide green fluorescent material. Measure the luminous intensity of the measurement at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity is higher than High, see Table 1 for details. It can be seen that the material corresponding to Example 4 is a green fluorescent material with high chemical stability.
  • the material described in this embodiment contains compounds with the chemical formula: Ba 0.98 Eu 0.02 ScSiO 3 N.
  • the emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1.
  • the emission spectrum of the material prepared in Example 5 is around 520 nm under the excitation of 400 nm violet light, and the half maximum width of the emission spectrum is about 86 nm.
  • the material obtained in Example 5 is a nitrogen oxide green fluorescent material. Measure the luminous intensity of the measurement at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity is higher than High, see Table 1 for details. It can be seen that the material corresponding to Example 5 is a green fluorescent material with high chemical stability.
  • the material described in this embodiment contains a compound chemical formula: Ba 0.95 Eu 0.05 ScSiO 3 N.
  • the emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1.
  • the emission spectrum of the material prepared in Example 6 is around 525 nm (see FIG. 1 ) under the excitation of 400 nm violet light, and the half maximum width of the emission spectrum is about 88 nm.
  • the material obtained in Example 6 is a nitrogen oxide green fluorescent material.
  • the excitation spectrum of the material is measured, and it can be seen that the material has a strong absorption of violet light (see Figure 2).
  • Measure the luminous intensity of the measurement at 25°C and define it as 100 (relative intensity) then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity is higher than High, see Table 1 for details.
  • the material corresponding to Example 6 is a green fluorescent material with high chemical stability.
  • the material described in this embodiment contains compounds with the chemical formula: Ba 0.92 Eu 0.08 ScSiO 3 N.
  • the emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1.
  • the emission spectrum of the material prepared in Example 7 is around 527 nm when excited by 400 nm violet light, and the half maximum width of the emission spectrum is about 89 nm.
  • the material obtained in Example 7 is a nitrogen oxide green fluorescent material. Measure the luminous intensity of the measurement at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity is higher than High, see Table 1 for details. It can be seen that the material corresponding to Example 7 is a green fluorescent material with high chemical stability.
  • the material described in this embodiment contains a compound with the chemical formula: Ba 0.9 Eu 0.1 ScSiO 3 N. Take BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, and accurately weigh the raw materials according to their stoichiometric ratio of Ba 0.9 Eu 0.1 ScSiO 3 N. Sintering in a mixed atmosphere of nitrogen and hydrogen for 6 hours, and after cooling, the nominal chemical composition of the material can be obtained as Ba 0.9 Eu 0.1 ScSiO 3 N. The emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1.
  • the emission spectrum of the material prepared in Example 8 is around 529 nm when excited by 400 nm violet light, and the half maximum width of the emission spectrum is about 89 nm.
  • the material obtained in Example 8 is a nitrogen oxide green fluorescent material. Measure the luminous intensity of the measurement at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity is higher than High, see Table 1 for details. It can be seen that the material corresponding to Example 8 is a green fluorescent material with high chemical stability.
  • the material described in this embodiment contains compounds with the chemical formula: Ba 0.85 Eu 0.15 ScSiO 3 N.
  • the emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1.
  • the emission spectrum of the material prepared in Example 9 is around 530 nm when excited by 400 nm violet light, and the half maximum width of the emission spectrum is about 89 nm.
  • the material obtained in Example 9 is a nitrogen oxide green fluorescent material. Measure the luminous intensity of the measurement at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity is higher than High, see Table 1 for details. It can be seen that the material corresponding to Example 9 is a green fluorescent material with high chemical stability.
  • the material described in this embodiment contains compounds with the chemical formula: Ba 0.8 Eu 0.2 ScSiO 3 N. Take BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, and accurately weigh the raw materials according to their stoichiometric ratio of Ba 0.8 Eu 0.2 ScSiO 3 N. Sintering in a mixed atmosphere of nitrogen and hydrogen for 6 hours, after cooling, the nominal chemical composition of the material can be obtained as Ba 0.8 Eu 0.2 ScSiO 3 N. The emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1.
  • the emission spectrum of the material prepared in Example 10 is around 534 nm when excited by 400 nm violet light, and the half maximum width of the emission spectrum is about 89 nm.
  • the material obtained in Example 10 is a nitrogen oxide green fluorescent material. Measure the luminous intensity of the measurement at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity is higher than High, see Table 10 for details. It can be seen that the material corresponding to Example 10 is a green fluorescent material with high chemical stability.
  • the material described in this embodiment contains a compound with the chemical formula: Ba 0.95 Eu 0.05 Sc 0.9 Y 0.1 SiO 3 N.
  • BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , Y 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, it is accurately weighed according to the stoichiometric ratio of Ba 0.95 Eu 0.05 Sc 0.9 Y 0.1 SiO 3 N
  • the raw materials were taken and sintered at 1500° C. for 6 hours in a mixed atmosphere of nitrogen and hydrogen. After cooling, the nominal chemical composition of the material was Ba 0.95 Eu 0.05 Sc 0.9 Y 0.1 SiO 3 N.
  • the emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 11 is around 526 nm when excited by 400 nm violet light, and the full width at half maximum of the emission spectrum is about 88 nm. It can be seen that the material obtained in Example 11 is a nitrogen oxide green fluorescent material.
  • 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 SiO 3 N.
  • BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , La 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, it is accurately weighed according to the stoichiometric ratio of Ba 0.95 Eu 0.05 Sc 0.9 La 0.1 SiO 3 N
  • the raw materials were taken and sintered at 1500° C. for 6 hours in a mixed atmosphere of nitrogen and hydrogen. After cooling, the nominal chemical composition of the material was Ba 0.95 Eu 0.05 Sc 0.9 La 0.1 SiO 3 N.
  • the emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 12 is around 527 nm under the excitation of 400 nm violet light, and the half maximum width of the emission spectrum is about 87 nm. It can be seen that the material obtained in Example 12 is a nitrogen oxide green fluorescent material.
  • the material corresponding to Example 12 is a green fluorescent material with high chemical stability.
  • the material described in this embodiment contains the compound chemical formula: Ba 0.95 Eu 0.05 Sc 0.9 Gd 0.1 SiO 3 N.
  • BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , Gd 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, it is accurately weighed according to its stoichiometric ratio of Ba 0.95 Eu 0.05 Sc 0.9 Gd 0.1 SiO 3 N
  • the raw materials were taken and sintered at 1500° C. for 6 hours in a mixed atmosphere of nitrogen and hydrogen. After cooling, the nominal chemical composition of the material was Ba 0.95 Eu 0.05 Sc 0.9 Gd 0.1 SiO 3 N.
  • the emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 13 is around 529 nm when excited by 400 nm violet light, and the half maximum width of the emission spectrum is about 86 nm. It can be seen that the material obtained in Example 13 is a nitrogen oxide green fluorescent material.
  • the material described in this embodiment contains a compound with the chemical formula: Ba 0.95 Eu 0.05 Sc 0.9 Lu 0.1 SiO 3 N.
  • BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , Lu 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, it is accurately weighed according to its stoichiometric ratio of Ba 0.95 Eu 0.05 Sc 0.9 Lu 0.1 SiO 3 N
  • the raw materials were taken and sintered at 1500° C. for 6 hours in a mixed atmosphere of nitrogen and hydrogen. After cooling, the nominal chemical composition of the material was Ba 0.95 Eu 0.05 Sc 0.9 Lu 0.1 SiO 3 N.
  • the emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 14 is around 522 nm when excited by 400 nm violet light, and the half maximum width of the emission spectrum is about 85 nm. It can be seen that the material obtained in Example 14 is a nitrogen oxide green fluorescent material.
  • Example 14 Measure the luminous intensity of the measurement at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity is higher than High, see Table 1 for details. It can be seen that the material corresponding to Example 14 is a green fluorescent material with high chemical stability.
  • 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 SiO 3 N.
  • BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , Y 2 O 3 , La 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, according to its composition, it is Ba 0.95 Eu 0.05 Sc 0.8 Y 0.1 La 0.1 SiO 3 Stoichiometric ratio of N
  • the raw materials were accurately weighed and sintered at 1500°C for 6 hours in a nitrogen-hydrogen mixed atmosphere. After cooling, the nominal chemical composition of the material was Ba 0.95 Eu 0.05 Sc 0.8 Y 0.1 La 0.1 SiO 3 N.
  • the emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 15 is around 530 nm when excited by 400 nm violet light, and the full width at half maximum of the emission spectrum is about 85 nm. It can be seen that the material obtained in Example 15 is a nitrogen oxide green fluorescent material.
  • Example 15 Measure the luminous intensity of the measurement at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity is higher than High, see Table 1 for details. It can be seen that the material corresponding to Example 15 is a green fluorescent material with high chemical stability.
  • the material described in this embodiment contains the compound chemical formula: Ba 0.95 Eu 0.05 Sc 0.8 Y 0.1 Gd 0.1 SiO 3 N.
  • BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , Y 2 O 3 , Gd 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, according to its composition, it is Ba 0.95 Eu 0.05 Sc 0.8 Y 0.1 Gd 0.1 SiO 3 Stoichiometric ratio of N
  • the raw materials were accurately weighed, sintered at 1500°C for 6 hours in a mixed atmosphere of nitrogen and hydrogen, and after cooling, the nominal chemical composition of the material was Ba 0.95 Eu 0.05 Sc 0.8 Y 0.1 Gd 0.1 SiO 3 N.
  • the emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 16 is around 533 nm under the excitation of 400 nm violet light, and the half maximum width of the emission spectrum is about 86 nm. It can be seen that the material obtained in Example 16 is a nitrogen oxide green fluorescent material.
  • 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 Lu 0.1 SiO 3 N.
  • BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , Y 2 O 3 , Lu 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, according to its composition, it is Ba 0.95 Eu 0.05 Sc 0.8 Y 0.1 Lu 0.1 SiO 3 Stoichiometric ratio of N
  • the raw materials were accurately weighed, sintered at 1500°C for 6 hours in a nitrogen-hydrogen mixed atmosphere, and after cooling, the nominal chemical composition of the material was Ba 0.95 Eu 0.05 Sc 0.8 Y 0.1 Lu 0.1 SiO 3 N.
  • the emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 17 is around 529 nm when excited by 400 nm violet light, and the half maximum width of the emission spectrum is about 82 nm. It can be seen that the material obtained in Example 17 is a nitrogen oxide green fluorescent material.
  • the material corresponding to Example 1 is a green fluorescent material with high chemical stability.
  • 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 SiO 3 N.
  • BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , La 2 O 3 , Gd 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, according to its composition, it is Ba 0.95 Eu 0.05 Sc 0.8 La 0.1 Gd 0.1 SiO 3 Stoichiometric ratio of N
  • the raw materials were accurately weighed, sintered at 1500°C for 6 hours in a mixed atmosphere of nitrogen and hydrogen, and after cooling, the nominal chemical composition of the material was Ba 0.95 Eu 0.05 Sc 0.8 La 0.1 Gd 0.1 SiO 3 N.
  • the emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 18 is around 523 nm under the excitation of 400 nm violet light, and the half maximum width of the emission spectrum is about 83 nm. It can be seen that the material obtained in Example 18 is a nitrogen oxide green fluorescent material.
  • 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 SiO 3 N.
  • BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , La 2 O 3 , Lu 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, according to its composition, it is Ba 0.95 Eu 0.05 Sc 0.8 La 0.1 Lu 0.1 SiO 3 Stoichiometric ratio of N
  • the raw materials were accurately weighed and sintered at 1500°C for 6 hours in a mixed atmosphere of nitrogen and hydrogen. After cooling, the nominal chemical composition of the material was Ba 0.95 Eu 0.05 Sc 0.8 La 0.1 Lu 0.1 SiO 3 N.
  • the emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 19 is around 521 nm under the excitation of 400 nm violet light, and the half maximum width of the emission spectrum is about 87 nm. It can be seen that the material obtained in Example 19 is a nitrogen oxide green fluorescent material.
  • the material described in this embodiment contains a compound with the chemical formula: Ba 0.95 Eu 0.05 Sc 0.8 Gd 0.1 Lu 0.1 SiO 3 N.
  • BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , Gd 2 O 3 , Lu 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, according to its composition, it is Ba 0.95 Eu 0.05 Sc 0.8 Gd 0.1 Lu 0.1 SiO 3 Stoichiometric ratio of N
  • the raw materials were accurately weighed and sintered at 1500°C for 6 hours in a mixed atmosphere of nitrogen and hydrogen. After cooling, the nominal chemical composition of the material was Ba 0.95 Eu 0.05 Sc 0.8 Gd 0.1 Lu 0.1 SiO 3 N.
  • the emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 20 is around 527 nm when excited by 400 nm violet light, and the half-maximum width of the emission spectrum is about 84 nm. It can be seen that the material obtained in Example 20 is a nitrogen oxide green fluorescent material.
  • the material corresponding to Example 20 is a green fluorescent material with high chemical stability.
  • 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 SiO 3 N.
  • BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , Y 2 O 3 , La 2 O 3 , Gd 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, according to its composition, it is Ba 0.95 Eu 0.05 Sc 0.7 Y
  • the stoichiometric ratio of 0.1 La 0.1 Gd 0.1 SiO 3 N Accurately weigh the raw materials, sinter them at 1500°C in a mixed atmosphere of nitrogen and hydrogen for 6 hours, and after cooling, the nominal chemical composition of the material can be obtained as Ba 0.95 Eu 0.05 Sc 0.7 Y 0.1 La 0.1 Gd 0.1 SiO 3 N.
  • the emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 21 is around 530 nm under the excitation of 400 nm violet light, and the half maximum width of the emission spectrum is about 84 nm. It can be seen that the material obtained in Example 21 is a nitrogen oxide green fluorescent material.
  • 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 SiO 3 N.
  • BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , Y 2 O 3 , La 2 O 3 , Lu 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, according to its composition, it is Ba 0.95 Eu 0.05 Sc 0.7 Y
  • the stoichiometric ratio of 0.1 La 0.1 Lu 0.1 SiO 3 N Accurately weigh the raw materials, sinter them at 1500°C in a mixed atmosphere of nitrogen and hydrogen for 6 hours, and after cooling, the nominal chemical composition of the material can be obtained as Ba 0.95 Eu 0.05 Sc 0.7 Y 0.1 La 0.1 Lu 0.1 SiO 3 N.
  • the emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 22 is around 524 nm under the excitation of 400 nm violet light, and the half maximum width of the emission spectrum is about 86 nm. It can be seen that the material obtained in Example 22 is a nitrogen oxide green fluorescent material.
  • the material corresponding to Example 22 is a green fluorescent material with high chemical stability.
  • 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 SiO 3 N.
  • BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , La 2 O 3 , Gd 2 O 3 , Lu 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, according to its composition, it is Ba 0.95 Eu 0.05 Sc 0.7 La
  • the stoichiometric ratio of 0.1 Gd 0.1 Lu 0.1 SiO 3 N Accurately weigh the raw materials, sinter them at 1500°C in a mixed atmosphere of nitrogen and hydrogen for 6 hours, and after cooling, the nominal chemical composition of the material can be obtained as Ba 0.95 Eu 0.05 Sc 0.7 La 0.1 Gd 0.1 Lu 0.1 SiO 3 N.
  • the emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 23 is around 522 nm under the excitation of 400 nm violet light, and the half maximum width of the emission spectrum is about 88 nm. It can be seen that the material obtained in Example 23 is a nitrogen oxide green fluorescent material.
  • 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 SiO 3 N.
  • BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , Y 2 O 3 , La 2 O 3 , Gd 2 O 3 , Lu 2 O 3 , SiO 2 and Si 3 N 4 are used as raw materials, and the composition is Ba 0.95
  • the stoichiometric ratio of Eu 0.05 Sc 0.6 Y 0.1 La 0.1 Gd 0.1 Lu 0.1 SiO 3 N Accurately weigh the raw materials and sinter them at 1500°C for 6 hours in a mixed atmosphere of nitrogen and hydrogen.
  • the nominal chemical composition of the material can be obtained as Ba 0.95 Eu 0.05 Sc 0.6 Y 0.1 La 0.1 Gd 0.1 Lu 0.1 SiO 3 N.
  • the emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 24 is around 526 nm under the excitation of 400 nm violet light, and the half-maximum width of the emission spectrum is about 89 nm. It can be seen that the material obtained in Example 24 is a nitrogen oxide green fluorescent material.
  • the chemical composition synthesized in Example 6 is selected as Ba 0.95 Eu 0.05 ScSiO 3 N green fluorescent material.
  • a green light source can be obtained by packaging the above-mentioned green fluorescent glass with a violet laser diode with an emission wavelength of 400 nm.

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Abstract

The present invention provides a nitrogen oxide green fluorescent material, and a preparation method therefor and an application thereof. The chemical general formula of the nitrogen oxide green fluorescent material is Ba 1-xEu xLnSiO 3N, wherein Ln may be one or more of Sc, Y, La, Gd or Lu, Sc is necessary, Sc accounts for more than 50% (molar ratio) of Ln, and x<x≤0.2; under the excitation of ultraviolet light, a main peak of the emission wavelength generated by the green fluorescent material ranges from 505 nm to 535 nm, and the half-height width of the emission spectrum is less than or equal to 90 nm. Compared with the prior art, the nitrogen oxide green fluorescent material prepared in the present invention has a brand-new chemical composition, is narrow in the half-height width of the emission spectrum, good in chemical stability, high in quantum efficiency and capable of effectively absorbing ultraviolet light, so that the light-emitting material is applied to industries such as illumination and display backlight source industries.

Description

一种氮氧化物绿色荧光材料及制备方法与器件A kind of nitrogen oxide green fluorescent material and its preparation method and device 技术领域technical field
本发明涉发光材料制备技术领域，尤其是涉及一种氮氧化物绿色荧光材料及制备方法与器件。The invention relates to the technical field of luminescent material preparation, in particular to a nitrogen oxide green fluorescent material, a preparation method and a device.
背景技术Background technique
白光器件即可见光器件，广泛应用于照明、显示背光源等行业。而白光是复合光，是由380～780nm波长范围内的单色光构成。最为简便地实现白光的方式便是采用所谓的三原色，即通过红、绿和蓝三色光的复合得到白光。对于目前广泛应用的LED白光器件而言，如专利文件1(王乐，郑紫珊，张宏，李旸晖，一种高显色指数高s/p值白光led及其获得方法和应用，CN107369742A)给出的，很容易通过蓝光芯片激发绿色荧光材料+红色荧光材料获得高显色指数的白光器件。但想进一步提升白光器件的显色指数，采用紫光芯片激发蓝色荧光材料+绿色荧光材料+红色荧光材料是较为可行的方式，如专利文件2(陈朝，杨星，陈佳超，李扬，一种近紫外/紫光激发单芯片全光谱led及其制备方法，CN110335935B)所公开的。因此研发适合紫光激发的荧光材料显得尤为重要。White light devices are visible light devices, which are widely used in lighting, display backlight and other industries. White light is composite light, which is composed of monochromatic light in the wavelength range of 380-780nm. The easiest way to achieve white light is to use the so-called three primary colors, that is, to obtain white light by combining red, green and blue light. For currently widely used LED white light devices, such as patent document 1 (Wang Le, Zheng Zishan, Zhang Hong, Li Yanghui, a white light LED with high color rendering index and high s/p value and its obtaining method and application, CN107369742A) Given that, it is easy to obtain a white light device with a high color rendering index by exciting the green fluorescent material + red fluorescent material through the blue light chip. But to further improve the color rendering index of white light devices, it is more feasible to use purple light chips to excite blue fluorescent materials + green fluorescent materials + red fluorescent materials, such as patent document 2 (Chen Chao, Yang Xing, Chen Jiachao, Li Yang, a A near-ultraviolet/ultraviolet light excitation single-chip full-spectrum LED and a preparation method thereof, disclosed in CN110335935B). Therefore, it is particularly important to develop fluorescent materials suitable for violet excitation.
对于紫光激发的绿色荧光材料，近来公开了一些专利文件，如专利文件3(王浩，赵帅，郭雨萌，党艳萍，郭文莉，李树新，伍波，伍一波，商育伟，杨丹，一种绿色荧光材料及其制备方法，CN105694858B)公开了一种绿色荧光材料及其制备方法，该荧光材料的分子式为：C 28H 14N 5O 29Tb 3K 2，但该材料是有机物，不能承受很高的温度，而LED器件在工作时甚至会产生200℃的高温环境，这会导致上述有机绿色荧光材料加速老化。 For green fluorescent materials excited by purple light, some patent documents have been published recently, such as 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 the fluorescent material is: C 28 H 14 N 5 O 29 Tb 3 K 2 , but the material It is an organic substance and cannot withstand high temperatures, and LED devices may even generate a high temperature environment of 200°C during operation, which will cause the above-mentioned organic green fluorescent materials to accelerate aging.
专利文件4(金志贤，金润昶，刘容赞，朴度炯，崔益圭，金珉周，许京宰，宋美兰，李贤德，宋在爀，权旋和，宋有美，徐真亨，李泳勋，金志炫，金荣基，绿色荧光粉和包括其的显示装置，CN101497788A)公开了一种由化学式(Y 3-xCe x) aAl bO c表示的绿色荧光粉，其中x、a、b和c满足关系：0<x≤1，0.5≤ a≤3，3≤b≤9和2c＝9a+3b。上述荧光粉的缺点在于该绿色荧光粉的发光中心是Ce 3+，因此发射光谱的半高宽较宽，可以应用于白光照明，但应用显示背光源则不合适，因为显示背光源用的荧光材料要求半高宽越窄越好。 Patent Document 4 (Kim Ji-hyun, Kim Yoon-chang, Yoo Yong-chan, Park Do-hyung, Choi Ik-gyu, Kim Min-joo, Heo Kyung-jae, Song Mi-ran, Lee Hyun-duk, Song Jae-hyuk, Kwon Sunhwa, Song Yu-mi, Seo Jin-hyung, Lee Young-hoon, Kim Ji-hyun, Kim Young-ki, green phosphor and others Display device, CN101497788A) discloses a green phosphor represented by the chemical formula (Y 3-x Cex ) a Al b O c , wherein x, a, b and c satisfy the relationship: 0<x≤1, 0.5≤a ≤3, 3≤b≤9 and 2c=9a+3b. The disadvantage of the above-mentioned phosphor is that the luminescent center of the green phosphor is Ce 3+ , so the half-maximum width of the emission spectrum is relatively wide, which can be applied to white light lighting, but it is not suitable for display backlight, because the fluorescent light used for display backlight The material requires half-width to be as narrow as possible.
专利文件5(裵命勋，金昌焕，刘永喆，朴淳根，李相一，金炫圭，金圣勖，绿色荧光粉、绿色荧光粉组合物及等离子体显示面板，CN101724399A)公开了一种绿色荧光粉，其化学式为(Lu 3-xCe x)Al 5O 12，x满足关系0＜x＜3。该绿色荧光材料即广泛应用于白光照明的LuAG:Ce。虽然LuAG:Ce的发光效率高，化学性质稳定，但其存在的问题和专利文件4相同，即该绿色荧光粉的发光中心是Ce 3+，因此发射光谱的半高宽较宽，应用于白光照明可以，但应用显示背光源则不合适。 Patent Document 5 (Bai Mingxun, Kim Chang-hwan, Liu Yongzhe, Park Chun-geun, Lee Sang-il, Kim Hyun-gyu, Kim Sung-xu, Green phosphor, green phosphor composition and plasma display panel, CN101724399A) discloses a green phosphor , whose chemical formula is (Lu 3-x Cex )Al 5 O 12 , and x satisfies the relationship 0<x<3. The green fluorescent material is LuAG:Ce widely used in white light illumination. Although LuAG:Ce has high luminous efficiency and stable chemical properties, its problem is the same as that of patent document 4, that is, the luminescent center of the green phosphor is Ce 3+ , so the half-maximum width of the emission spectrum is wide, and it is suitable for white light. Lighting is OK, but not suitable for application display backlighting.
专利文件6(赵莉，一种含Ba元素氮氧化物绿色荧光粉材料及其制备方法，CN101948687A)公开了一种含Ba的氮氧化物绿色荧光材料，其化学通式为(Ba，A) 2-xSi yO zN 2+4y-2z:xEu，其中0≤x＜1.0，0＜y≤1.0，1＜z≤2.0，A为Ca或Sr元素。该绿色荧光材料的制备方法采取两步法，其中第一步合成氮氧化物绿色荧光粉的前躯体A 2SiO 4，其中A为Ca或Sr元素，该前躯体提供稳定的晶体结构；第二步在前躯体提供的基质结构中掺杂Ba元素，通过调节Si元素和Ba元素的配比，可以调制绿色荧光粉的发光波长，使其发射波长峰值在516～540nm之间。虽然所获得的氮氧化物绿色荧光材料发光亮度较高，满足于照明及用于高显色指数的背光源白光LED，但合成路径繁琐，成本较高。 Patent document 6 (Zhao Li, a green fluorescent powder material containing Ba-containing nitrogen oxide and its preparation method, CN101948687A) discloses a green fluorescent material containing Ba-containing nitrogen oxide, whose general chemical formula is (Ba, A) 2-x Si y O z N 2+4y-2z : xEu, where 0≤x<1.0, 0<y≤1.0, 1<z≤2.0, A is Ca or Sr element. The preparation method of the green fluorescent material adopts a two-step method, wherein the first step is to synthesize the precursor A 2 SiO 4 of the nitrogen oxide green fluorescent powder, wherein A is Ca or Sr element, and the precursor provides a stable crystal structure; the second The first step is to dope Ba element in the matrix structure provided by the precursor, and by adjusting the ratio of Si element and Ba element, the emission wavelength of the green phosphor can be modulated so that the peak emission wavelength is between 516-540nm. Although the obtained oxynitride green fluorescent material has high luminous brightness and is suitable for lighting and backlight white LEDs with high color rendering index, the synthesis path is cumbersome and the cost is high.
作为改进，专利文件7(赵莉，一种氮氧化物绿色荧光粉材料的制备方法，CN102191045B)公开了一种氮氧化物绿色荧光材料，该绿色荧光粉材料的化学通式为(Ba，A) 2-xSi y(O，B) zN 2+4y-2z:xEu，其中0≤x＜1.0，0＜y≤1.0，1＜z≤2.0，A为Ca或Sr元素，B为F或Cl元素。即在专利文件6的基础上添加了卤素元素，制备该氮氧化物绿色荧光材料同样需要采用两步法，第一步：合成前躯体A 2SiO 4；第二步，在前躯体A 2SiO 4提供的基质结构中掺杂元素，最终合成氮氧化物绿色荧光材料(Ba，A) 2-xSi y(O，B) zN 2+4y-2z:xEu。虽然所获得的氮氧化物绿色荧光材料发光亮度较高，满足于照明及用于高显色指数的背光源白光LED，但 合成路径繁琐，成本较高；且材料中含有的卤素元素会腐蚀封装器件中使用的银线及反光碗，从而降低器件的可靠性。 As an improvement, Patent Document 7 (Zhao Li, a preparation method of nitrogen oxide green phosphor material, CN102191045B) discloses a nitrogen oxide green phosphor material, the general chemical formula of which is (Ba, A ) 2-x Si y (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 element, B is F or Cl element. That is, on the basis of patent document 6, halogen elements are added, and the preparation of the nitrogen oxide green fluorescent material also requires a two-step method, the first step: the synthesis of the precursor A 2 SiO 4 ; the second step, in the precursor A 2 SiO 4 4 Doping elements into the matrix structure provided, and finally synthesizing the oxynitride green fluorescent material (Ba, A) 2-x Si y (O, B) z N 2+4y-2z :xEu. Although the obtained oxynitride green fluorescent material has high luminous brightness, it is suitable for lighting and backlight white LED with high color rendering index, but the synthesis path is cumbersome and the cost is high; and the halogen elements contained in the material will corrode the packaging The silver wires and reflective bowls used in the device reduce the reliability of the device.
同样的，专利文件8(高绍康，李兆梅，胡晓琳，白光led用绿色荧光粉及其制备方法和应用，CN102391859A)公开了一种白光LED用绿色荧光粉及其制备方法和应用，该荧光粉的化学式为Ca 6Sr 4-x(Si 2O 7) 3Cl 2:xEu 2+，该荧光粉是以CaO、SiO 2、CaCl 2和SrCO 3为原料，以Eu 2O 3为激活剂，以过量的CaCl 2为助熔剂，采用高温固相法在还原气氛下合成的荧光粉。本发明公开的荧光粉能被紫外－近紫外波段的高效激发，且发光效率高，因此可用于制备由紫外－近紫外LED激发的白光LED。虽然该荧光粉煅烧温度低，制备方法简单易行，但同专利文件7类似，专利文件8中所公开的材料中同样含有卤素，会腐蚀封装器件中使用的银线及反光碗，从而降低器件的可靠性。 Similarly, Patent Document 8 (Gao Shaokang, Li Zhaomei, Hu Xiaolin, Green Phosphor Powder for White Light LED and Its Preparation Method and Application, CN102391859A) discloses a green phosphor powder for white light LED and its preparation method and application. The chemical formula of the phosphor powder is Ca 6 Sr 4-x (Si 2 O 7 ) 3 Cl 2 :xEu 2+ , the phosphor is made of CaO, SiO 2 , CaCl 2 and SrCO 3 as raw materials, Eu 2 O 3 as activator, with excess CaCl 2 is used as a flux, and the phosphor powder is synthesized under a reducing atmosphere by a high-temperature solid-state method. The fluorescent powder disclosed by the invention can be efficiently excited in the ultraviolet-near ultraviolet band and has high luminous efficiency, so it can be used to prepare white light LEDs excited by ultraviolet-near ultraviolet LEDs. Although the calcination temperature of the phosphor powder is low and the preparation method is simple and easy, similar to Patent Document 7, the material disclosed in Patent Document 8 also contains halogen, which will corrode the silver wire and reflective bowl used in the packaging device, thereby reducing the performance of the device. reliability.
专利文件9(刘永福，蒋俊，江浩川，一种绿色荧光粉及其制备方法和应用，CN105441077A)公开了一种绿色荧光粉及其制备方法，该绿色荧光粉的化学式为：(Ba 1-x-ySr xEu y) 9Lu 2Si 6O 24，其中，0≤x≤0.9999，0.0001≤y≤0.3，0.0001≤x+y≤1，x、y为摩尔分数。该发明提供的绿色荧光粉虽然具有生产成本低、制作工艺简单、激发波长范围广等优点，但作为一种硅酸盐荧光粉，本身存在着化学稳定性偏低、热猝灭特性较差的缺点。 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- xy Sr x Eu y ) 9 Lu 2 Si 6 O 24 , wherein, 0≤x≤0.9999, 0.0001≤y≤0.3, 0.0001≤x+y≤1, x and y are mole fractions. Although the green fluorescent powder provided by the invention has the advantages of low production cost, simple manufacturing process, and wide excitation wavelength range, as a silicate fluorescent powder, it has the disadvantages of low chemical stability and poor thermal quenching characteristics. shortcoming.
专利文件10(王皓，黄晓宇，李凯，王为民，傅正义，一种光学性能可调控的二价锰离子掺杂MgAlON绿色荧光粉的制备方法，CN108531166A)公开了一种光学性能可调控的二价锰离子掺杂MgAlON绿色荧光粉的制备方法，化学组成为Mn z:Mg 8-x-3y-zAl 16+x+2yO 32-xN x，其中：0≤x≤3,0≤y≤2,0.1≤z≤0.7。虽然该绿色荧光材料发射光谱的半高宽较窄，但合成MgAlON需要极高的温度，同时由于使用过渡元素Mn作为发光中心，Mn对光的吸收较差，因此该材料的量子效率偏低，对紫光的吸收偏差。 Patent document 10 (Wang Hao, Huang Xiaoyu, Li Kai, Wang Weimin, Fu Zhengyi, a preparation method of divalent manganese ion-doped MgAlON green phosphor with adjustable optical properties, CN108531166A) discloses a divalent manganese ion-doped MgAlON green phosphor with adjustable optical properties. Manganese ion-doped MgAlON green phosphor preparation method, the chemical composition 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 half-maximum width of the emission spectrum of the green fluorescent material is relatively narrow, the synthesis of MgAlON requires extremely high temperature. At the same time, because the transition element Mn is used as the luminescent center, Mn has poor light absorption, so the quantum efficiency of the material is low. Bias in the absorption of violet light.
专利文件11(梁超，何锦华，符义兵，铕激活的硅酸盐绿色荧光粉及其在白光发光二极管中的应用，CN101851508B)公开了一种铕激活的硅酸盐绿色荧光粉及其在白光发光二极管中的应用，其化学式为Ba (2-x-y-p)Sr xM pSi qO (2+2q):Eu y；其中， M为Sc、Y、La、Cr或Er中的至少一种；0.03＜x≤0.75；0.001＜y≤0.09；0.0003≤p≤0.05；0.75≤q＜1。与专利文件9类似，作为一种硅酸盐荧光粉，本身存在着化学稳定性偏低、热猝灭特性较差的缺点。 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 The application in the diode, its chemical formula is Ba (2-xyp) Sr x M p Si q O (2+2q) :Eu y ; Wherein, M is at least one in 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 has the disadvantages of low chemical stability and poor thermal quenching characteristics.
专利文件12(赵莉，一种含Al元素氮氧化物绿色荧光粉材料及其制备方法，CN101948689A)公开了一种含Al元素氮氧化物绿色荧光材料及其制备方法，同样采用两步合成，其中第一步合成含Al元素前躯体A 2SiO 4，其中A为Ca、Ba或Sr元素中的一种；第二步在前躯体提供的基质结构中掺杂Al元素，通过调节Si元素和Al元素的配比，调制绿色荧光粉A 1-x(Si，Al) yO zN 2/3+4/3y-2/3z:xEu的发光波长。和专利文件6和专利文件7存在的问题类似，虽然所获得的氮氧化物绿色荧光材料发光亮度较高，满足于照明及用于高显色指数的背光源白光LED，但合成路径繁琐，成本较高。 Patent document 12 (Zhao Li, a green phosphor material containing Al element nitrogen oxide and its preparation method, CN101948689A) discloses a green phosphor material containing Al element nitrogen oxide and its preparation method, which also adopts two-step synthesis, The first step is to synthesize Al-containing precursor A 2 SiO 4 , where A is one of Ca, Ba or Sr elements; the second step is to dope Al element in the matrix structure provided by the precursor, by adjusting the Si element and The ratio of the Al element modulates the emission wavelength of the green phosphor A 1-x (Si, Al) y O z N 2/3+4/3y-2/3z :xEu. Similar to the problems in Patent Document 6 and Patent Document 7, although the obtained nitrogen oxide green fluorescent material has a high luminance and is suitable for lighting and backlight white LEDs with high color rendering index, the synthesis path is cumbersome and the cost is high. higher.
专利文件13(黄霖，张鸽，王静，一种绿色荧光粉及其制备方法和在白光led器件中的应用，CN108504358A)公开了一种化学组成式为:Ca 1-xSc 2O 4:xCe 3+的绿色荧光粉，其中0.001≤x≤0.90，x为掺杂Ce 3+相对Ca所占的摩尔百分比系数。和专利文件4和专利文件5存在的问题相同，该荧光粉的缺点在于该绿色荧光粉的发光中心是Ce 3+，因此发射光谱的半高宽较宽，应用于白光照明可以，但应用显示背光源则不合适，因为显示背光源用的荧光材料要求半高宽越窄越好。 Patent document 13 (Huang Lin, Zhang Ge, Wang Jing, A green phosphor and its preparation method and application in white light LED devices, CN108504358A) discloses a chemical composition formula: Ca 1-x Sc 2 O 4 :xCe 3+ green phosphor, where 0.001≤x≤0.90, x is the molar percentage coefficient of doped Ce 3+ relative to Ca. The problem is the same as that of Patent Document 4 and Patent Document 5. The disadvantage of this phosphor is that the luminescent center of the green phosphor is Ce 3+ , so the half-width of the emission spectrum is wide. It can be applied to white light lighting, but the application shows The backlight source is not suitable, because the fluorescent material used for the display backlight source requires the narrower the half-height width, the better.
专利文件14(段成军，顾竟涛，周卫新，一种发射绿色荧光的硼磷酸盐荧光粉及其制备方法和应用，CN104449723B)公开了一种硼酸盐绿色荧光粉，该荧光粉的化学通式为：(Ln 1-xTb x) 7O 6(BO 3)(PO 4) 2，式中Ln为稀土元素，0.01≤x≤0.1。该硼磷酸盐荧光粉绿色荧光的发射完全由于Tb 3+外层电子的 5D 4→ 7F 5磁偶极跃迁所致。不过，本发明的硼磷酸盐荧光粉虽然具有制备方法简单、发射光谱半高宽窄的优点，但其对紫光的吸收弱，很难直接应用于紫光激发的白光LED。 Patent Document 14 (Duan Chengjun, Gu Jingtao, Zhou Weixin, A borophosphate phosphor emitting green fluorescence and its preparation method and application, CN104449723B) discloses a borate green phosphor, the general chemical formula of which is: (Ln 1-x Tb x ) 7 O 6 (BO 3 )(PO 4 ) 2 , where Ln is a rare earth element, 0.01≤x≤0.1. The emission of green fluorescence of the borophosphate phosphor is entirely due to the 5 D 4 → 7 F 5 magnetic dipole transition of Tb 3+ outer shell electrons. However, although the borophosphate phosphor powder of the present invention has the advantages of simple preparation method and narrow half-maximum width of the emission spectrum, it has weak absorption of violet light and is difficult to be directly applied to white LEDs excited by violet light.
专利文件15(杨志平，王海龙，董秀芹，一种β-SiAlON:Eu 2+绿色荧光粉及其制备方法，CN105295908B)公开了一种化学通式为Eu aSi bAl cO dN e的绿色荧光粉，式中，0＜a≤0.010，0.4≤b≤0.5，0.01≤c≤0.02，0.006≤d≤0.02，0.47＜e≤0.664。虽然本发明获得的绿色荧光粉具有颗粒均匀、平均粒径大和发光强度 高的优点，在制备白光LED器件上具有广阔的前景，但合成该荧光材料需要在1900～2200℃下烧结8～12h，如此高的合成温度对于烧结荧光粉的设备要求极高，即合成该荧光材料非常困难。 Patent document 15 (Yang Zhiping, Wang Hailong, Dong Xiuqin, a β-SiAlON:Eu 2+ green phosphor and its preparation method, CN105295908B) discloses a green phosphor with the general chemical formula Eu a Si b Al c O d Ne Powder, where, 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 fluorescent powder obtained by the present invention has the advantages of uniform particles, large average particle size and high luminous intensity, it has broad prospects in the preparation of white light LED devices, but the synthesis of the fluorescent material requires sintering at 1900-2200 ° C for 8-12 hours, Such a high synthesis temperature requires extremely high equipment for sintering phosphor powder, that is, it is very difficult to synthesize the phosphor material.
专利文件16(陶颖，一种核壳结构的铝酸盐绿色荧光粉及其制备方法，CN102373060B)公开了一种核壳结构的铝酸盐绿色荧光粉及其制备方法，该荧光粉包括内核和外壳，内核的粒径为3～8μm的低Tb含量铝酸盐绿色荧光粉，外壳为Ce和Tb的氧化物，其组成式为(Ce xTb mCe yTb n)MgAl 11O 19，其中，0.6≤x+y≤0.8，0≤m+n≤0.4，1≤n:m≤4。和专利文件14类似，该铝酸盐荧光粉绿色荧光的发射完全由于Tb 3+外层电子的 5D 4→ 7F 5磁偶极跃迁所致。不过，本发明的铝酸盐荧光粉虽然具有制备方法简单、发射光谱半高宽窄的优点，但其对紫光的吸收弱，很难直接应用于紫光激发的白光LED。 Patent document 16 (Tao Ying, a core-shell structure aluminate green phosphor and its preparation method, CN102373060B) discloses a core-shell structure aluminate green phosphor and its preparation method, the phosphor includes a core And the outer shell, the particle size of the inner core is low Tb content aluminate green phosphor of 3-8 μm, the outer shell is the oxide of Ce and Tb, and its composition formula is ( Cex Tb m Ce y Tb n )MgAl 11 O 19 , Among them, 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 the aluminate phosphor is entirely due to the 5 D 4 → 7 F 5 magnetic dipole transition of Tb 3+ outer shell electrons. However, although the aluminate phosphor of the present invention has the advantages of simple preparation method and narrow half-maximum width of the emission spectrum, it has weak absorption of violet light and is difficult to be directly applied to white LEDs excited by violet light.
专利文件17(席增卫，李永强，张延民，王伍宝，黄毅群，孙云飞，一种硼酸盐绿色荧光粉的制造方法，CN101696356B)公开了一种硼酸盐绿色荧光粉，其化学式为(Y 1-x-y-zGd xM yTb z)BO 3，其中X＝0～0.5，y＝0.0～0.05，z＝0.1～1.0，M是Al、Sc、Ce或La中的氧化物。与专利文件14和专利文件16类似，该硼酸盐荧光粉绿色荧光的发射完全由于Tb 3+外层电子的 5D 4→ 7F 5磁偶极跃迁所致。不过，本发明的硼酸盐荧光粉虽然具有制备方法简单、发射光谱半高宽窄的优点，但其对紫光的吸收弱，很难直接应用于紫光激发的白光LED。 Patent document 17 (Xi Zengwei, Li Yongqiang, Zhang Yanmin, Wang Wubao, Huang Yiqun, Sun Yunfei, a manufacturing method of borate green fluorescent powder, CN101696356B) discloses a kind of borate green fluorescent powder, and its chemical formula is (Y 1- xyz Gd x M y Tb z )BO 3 , wherein X=0-0.5, y=0.0-0.05, z=0.1-1.0, and M is an oxide in Al, Sc, Ce or La. Similar to Patent Document 14 and Patent Document 16, the green fluorescence emission of the borate phosphor is entirely due to the 5 D 4 → 7 F 5 magnetic dipole transition of Tb 3+ outer shell electrons. However, although the borate phosphor of the present invention has the advantages of simple preparation method and narrow half-maximum width of the emission spectrum, its absorption of violet light is weak, so it is difficult to be directly applied to white LEDs excited by violet light.
专利文件18(张家骅，肖文戈，张霞，郝振东，潘国徽，一种硅酸盐绿色荧光粉及其制备方法，CN104403668B)公开了一种硅酸盐绿色荧光粉及其制备方法，荧光粉的学通式为Ca 3-x-y-zCe xTb yA zSc 2-mMg mSi 3-nAl nO 12，其中，A为元素Li、Na、K的一种或其任意组合；x、y、z、m、n为摩尔分数，其取值范围分别为：0.005≤x≤0.2，0.005≤y≤0.5，0≤z≤0.5,0≤m≤0.5,0≤n≤0.5。该荧光粉采用高温固相法制备，其通过Ce 3+和Tb 3+的共掺，利用Ce 3+、Tb 3+之间有效的能量传递来拓展发光离子Tb 3+在紫外光区域的有效激发范围，实现了Tb 3+的激发光谱由250～300nm到200～380nm的展宽，使之能够更好地与紫外/紫光LED芯片 匹配。但Ce 3+和Tb 3+之间有效的能量传递效率较低，因此，该荧光材料的发光效率较低，实用性较差。 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. The general formula is Ca 3-xyz C x Tb y A z Sc 2-m Mg m Si 3-n Al n O 12 , where A is one of the elements Li, Na, K or any combination thereof; x, y , z, m, and n are mole fractions, and their value ranges are: 0.005≤x≤0.2, 0.005≤y≤0.5, 0≤z≤0.5, 0≤m≤0.5, 0≤n≤0.5. The phosphor is prepared by a high-temperature solid-phase method. Through the co-doping of Ce 3+ and Tb 3+ , the effective energy transfer between Ce 3+ and Tb 3+ is used to expand the effective emission of Tb 3+ in the ultraviolet region. The excitation range realizes the broadening of the excitation spectrum of Tb 3+ from 250-300nm to 200-380nm, so that it can better match with ultraviolet/violet LED chips. However, the effective energy transfer efficiency between Ce 3+ and Tb 3+ is low, therefore, the luminous efficiency of the fluorescent material is low and the practicability is poor.
总而言之，从现有的公开文献中可看出，同时满足发射光谱较窄、化学稳定性较好、量子效率高且能有效吸收紫光的绿色荧光材料非常缺乏。因此非常有必要研发一种发射光谱的半高宽较窄、化学稳定性较好、量子效率高且能有效吸收紫光的绿色荧光材料，且用该材料制作出一种的器件，应用于照明、显示背光源等行业，服务于室内照明、高清显示等领域。All in all, it can be seen from the existing public literature that there is a shortage of green fluorescent materials that simultaneously meet the requirements of narrow emission spectrum, good chemical stability, high quantum efficiency and effective absorption of violet light. Therefore, it is very necessary to develop a green fluorescent material with a narrow half-maximum width of the emission spectrum, good chemical stability, high quantum efficiency and effective absorption of violet light, and use this material to make a kind of device, which is applied to lighting, Display backlight and other industries, serving indoor lighting, high-definition display and other fields.
发明内容Contents of the invention
本发明的第一目的是保护一种氮氧化物绿色荧光材料。所述一种氮氧化物绿色荧光材料的化学通式为：Ba 1-xEu xLnSiO 3N，其中，Ln为Sc或Y或La或Gd或Lu中一种或多种，且Sc是必须的，且Sc占Ln含量>50％(摩尔比)，0<x≤0.2；在紫光激发下，该绿色荧光材料可产生发射波长主峰范围介于505～535nm、发射光谱的半高宽小于等于90nm。优选的，所述氮氧化物绿色荧光材料的化学通式中，0.02<x≤0.05；在含有200℃高压水蒸汽的密闭容器内老化48h后的发光强度不低于室温时发光强度的75％。 The first purpose of the present 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 x LnSiO 3 N, wherein, Ln is one or more of Sc or Y or La or Gd or Lu, and Sc is a necessary , and Sc accounts for more than 50% of the Ln content (molar ratio), 0<x≤0.2; under the excitation of purple light, the green fluorescent material can produce a main peak of emission wavelength ranging from 505 to 535nm, and the half maximum width of the emission spectrum is less than or equal to 90nm. Preferably, in the general chemical formula of the nitrogen oxide green fluorescent material, 0.02<x≤0.05; the luminous intensity after aging for 48 hours in a closed container containing high-pressure water vapor at 200°C is no less than 75% of the luminous intensity at room temperature .
本发明的第二目的是提供一种氮氧化物绿色荧光材料的制备方法。所述制备方法包括：将Ba前驱体、Eu前驱体、Ln前驱体和Si前驱体混合，在还原气氛下，进行高温固相反应，得到一种氮氧化物绿色荧光材料。具体的，Ba前驱体、Eu前驱体、Ln前驱体和Si前驱体的摩尔比为(1-X)：X：1：1，所得材料的化学通式为：Ba 1-xEu xLnSiO 3N，其中，0<x≤0.2。 The second object of the present invention is to provide a preparation method of nitrogen oxide green fluorescent material. The preparation method comprises: mixing Ba precursor, Eu precursor, Ln precursor and Si precursor, and carrying out high-temperature solid-state reaction in reducing atmosphere to obtain a nitrogen oxide green fluorescent material. Specifically, the molar ratio of Ba precursor, Eu precursor, Ln precursor and Si precursor is (1-X):X:1:1, and the general chemical formula of the obtained material is: Ba 1-x Eu x LnSiO 3 N, where 0<x≤0.2.
本发明同时提供一种绿色荧光玻璃及其制备方法，所述绿色荧光玻璃是由所述氮氧化物绿色荧光材料与玻璃粉混合后进行高温固相反应得到，具体的，在空气气氛下，进行高温固相反应，所述高温固相反应的温度为500～800℃，高温固相反应的时间为0.1～1h。The present invention also provides a green fluorescent glass and a preparation method thereof. The green fluorescent glass is obtained by mixing the nitrogen oxide green fluorescent material with glass powder and performing a high-temperature solid-state reaction. Specifically, in an air atmosphere, the High-temperature solid-phase reaction, 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.
本发明还提供一种激光绿光器件，所述器件包含了紫光激光二极管及发光层，所述发光层包含所述绿色荧光玻璃。The present invention also provides a laser green light device, the device includes a violet laser diode and a light emitting layer, and the light emitting layer includes the green fluorescent glass.
具体方案如下：The specific plan is as follows:
一种氮氧化物绿色荧光材料，该材料的化学通式为：A kind of nitrogen oxide green fluorescent material, the general chemical formula of this material is:
Ba 1-xEu xLnSiO 3N Ba 1-x Eu x LnSiO 3 N
其中，Ln为Sc或Y或La或Gd或Lu中一种或多种，且Sc是必须的，且Sc占Ln含量>50％(摩尔比)，0<x≤0.2。Wherein, Ln is one or more of Sc or Y or La or Gd or Lu, and Sc is necessary, and Sc accounts for more than 50% (molar ratio) of Ln content, 0<x≤0.2.
优选的，0.02<x≤0.05。Preferably, 0.02<x≤0.05.
本发明的第二目的在于提供一种氮氧化物绿色荧光材料的制备方法。所述制备方法如下步骤：The second object of the present invention is to provide a preparation method of nitrogen oxide green fluorescent material. The preparation method is as follows:
将Ba前驱体、Eu前驱体、Ln前驱体和Si前驱体混合，在还原气氛下，进行高温固相反应，得到所述氮氧化物绿色荧光材料。The Ba precursor, the Eu precursor, the Ln precursor and the Si precursor are mixed, and a high-temperature solid-state reaction is carried out under a reducing atmosphere to obtain the nitrogen oxide green fluorescent material.
优选的，该步骤中，Ba前驱体、Eu前驱体、Ln前驱体和Si前驱体中Ba、Eu、Ln和Si的摩尔比是(1-X)：X：1：1。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.
优选的，上述步骤中，Ba前驱体选自Ba的碳酸盐、Ba的氧化物或Ba的硝酸盐中的一种或多种；任选的，所述Eu前驱体选自Eu 2O 3；任选的，所述Ln前驱体为Sc 2O 3、Y 2O 3、La 2O 3、Gd 2O 3或Lu 2O 3中的一种或多种，其中Sc 2O 3是必须的；任选的，所述Si前驱体为SiO 2和Si 3N 4。 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 Eu 2 O 3 ; Optionally, the Ln precursor is one or more of Sc 2 O 3 , Y 2 O 3 , La 2 O 3 , Gd 2 O 3 or Lu 2 O 3 , wherein Sc 2 O 3 is necessary Optionally, the Si precursors are SiO 2 and Si 3 N 4 .
优选的，Ba前驱体、Eu前驱体、Ln前驱体和Si前驱体的纯度均不低于99.5wt％。Preferably, the purity of the Ba precursor, the Eu precursor, the Ln precursor and the Si precursor is not lower than 99.5wt%.
优选的，上述步骤中，高温固相反应的温度介于1500～1600℃，在还原气氛下，高温固相反应的时间介于4～10h。Preferably, in the above steps, the temperature of the high-temperature solid-state reaction is between 1500-1600° C., and the time of the high-temperature solid-state reaction is between 4-10 hours under a reducing atmosphere.
本发明还保护一种基于氮氧化物绿色荧光材料制作的荧光玻璃。其制作方法如下：将氮氧化物绿色荧光材料与玻璃粉混合后进行高温固相反应，即可得到氮氧化物绿色荧光玻璃。The invention also protects a kind of fluorescent glass based on nitrogen oxide green fluorescent material. The production method is as follows: mix nitrogen oxide green fluorescent material with glass powder and carry out high-temperature solid-state reaction to obtain nitrogen oxide green fluorescent glass.
优选的，氮氧化物绿色荧光材料与玻璃粉的质量比为1：1～1：4。Preferably, the mass ratio of the nitrogen oxide green fluorescent material to the glass powder is 1:1˜1:4.
优选的，玻璃粉的熔点为500～800℃。Preferably, the melting point of the glass powder is 500-800°C.
优选的，氮氧化物绿色荧光材料与玻璃粉进行高温固相反应的温度为 500～800℃，高温固相反应的时间为0.1～1h。Preferably, the temperature for the high-temperature solid-state reaction between the nitrogen oxide green fluorescent material and the glass frit is 500-800°C, and the time for the high-temperature solid-state reaction is 0.1-1 h.
本发明还保护一种基于氮氧化物绿色荧光材料制作荧光玻璃的发光装置。所述发光装置包含紫光激光二极管及发光层，所述发光层包含所述氮氧化物绿色荧光玻璃，所述发光层被所述紫光激光二极管激发而发射绿光。The invention also protects a light-emitting device made of fluorescent glass based on nitrogen oxide green fluorescent material. The light-emitting device includes a violet laser diode and a light-emitting layer, the light-emitting layer includes the nitrogen oxide green fluorescent glass, and the light-emitting layer is excited by the violet laser diode to emit green light.
有益效果Beneficial effect
本发明提供了一种氮氧化物绿色荧光材料及其制备方法及应用，该氮氧化物绿色荧光材料的化学通式为Ba 1-xEu xLnSiO 3N，其中，Ln可以为Sc或Y或La或Gd或Lu中一种或多种，且Sc是必须的，且Sc占Ln含量>50％(摩尔比)，0<x≤0.2；在紫光激发下，该绿色荧光材料产生的发射波长主峰范围介于505～535nm、发射光谱的半高宽小于等于90nm。与现有技术相比，本发明所制备的一种氮氧化物绿色荧光材料具有全新的化学组成，发射光谱的半高宽较窄、化学稳定性较好、量子效率高且能有效吸收紫光，从而使该发光材料应用于应用于照明、显示背光源等行业。 The invention provides a nitrogen oxide green fluorescent material and its preparation method and application. The general chemical formula of the nitrogen oxide green fluorescent material is Ba 1-x Eu x LnSiO 3 N, wherein Ln can be Sc or Y or One or more of La or Gd or Lu, and Sc is necessary, and Sc accounts for Ln content>50% (molar ratio), 0<x≤0.2; under the excitation of purple light, the emission wavelength produced by the green fluorescent material The main peak ranges from 505 to 535nm, and the full width at half maximum of the emission spectrum is less than or equal to 90nm. Compared with the prior art, the nitrogen oxide green fluorescent material prepared by the present invention has a brand-new chemical composition, narrow half-maximum width of emission spectrum, good chemical stability, high quantum efficiency and can effectively absorb violet light. Therefore, the luminescent material can be applied to lighting, display backlight and other industries.
附图说明Description of drawings
图1为本发明实施例6中得到的发光材料的发射光谱图；Fig. 1 is the emission spectrogram of the luminescent material obtained in Example 6 of the present invention;
图2为本发明实施例6中得到的发光材料的激发光谱图；Fig. 2 is the excitation spectrum diagram of the luminescent material obtained in Example 6 of the present invention;
具体实施方式Detailed ways
下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述。The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention.
为便于理解本发明，本发明列举实施例如下。本领域技术人员应该明了，所述实施例仅仅用于帮助理解本发明，不应视为对本发明的具体限制。In order to facilitate understanding of the present invention, the present invention enumerates the following examples. Those skilled in the art should understand that the examples are only used to help understand the present invention, and should not be regarded as specific limitations on the present invention.
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将结合实施例来详细说明本发明。It should be noted that, in the case of no conflict, the embodiments in the present application and the features in the embodiments can be combined with each other. The present invention will be described in detail below in conjunction with examples.
所述一种氮氧化物绿色荧光材料的化学通式如下：The general chemical formula of the nitrogen oxide green fluorescent material is as follows:
Ba 1-xEu xLnSiO 3N Ba 1-x Eu x LnSiO 3 N
其中，Ln可以为Sc或Y或La或Gd或Lu中一种或多种，且Sc是必须的，且Sc占Ln含量>50％(摩尔比)，0<x≤0.2。Wherein, Ln can be one or more of Sc or Y or La or Gd or Lu, and Sc is necessary, and Sc accounts for more than 50% (molar ratio) of Ln content, 0<x≤0.2.
在本发明提供的一些实施例中，所述x优选为0.001，Ln优选为Sc；在本发明提供的一些实施例中，所述x优选为0.002，Ln优选为Sc；在本发明提供的一些实施例中，所述x优选为0.005，Ln优选为Sc；在本发明提供的一些实施例中，所述x优选为0.01，Ln优选为Sc；在本发明提供的一些实施例中，所述x优选为0.02，Ln优选为Sc；在本发明提供的一些实施例中，所述x优选为0.05，Ln优选为Sc；在本发明提供的一些实施例中，所述x优选为0.08，Ln优选为Sc；在本发明提供的一些实施例中，所述x优选为0.1，Ln优选为Sc；在本发明提供的一些实施例中，所述x优选为0.15，Ln优选为Sc；在本发明提供的一些实施例中，所述x优选为0.2，Ln优选为Sc；在本发明提供的一些实施例中，所述x优选为0.05，Ln优选为Sc及Y，且Sc与Y的摩尔比为9：1；在本发明提供的一些实施例中，所述x优选为0.05，Ln优选为Sc及La，且Sc与La的摩尔比为9：1；在本发明提供的一些实施例中，所述x优选为0.05，Ln优选为Sc及Gd，且Sc与Gd的摩尔比为9：1；在本发明提供的一些实施例中，所述x优选为0.05，Ln优选为Sc及Lu，且Sc与Lu的摩尔比为9：1；在本发明提供的一些实施例中，所述x优选为0.05，Ln优选为Sc及Y及La，且Sc与Y与La的摩尔比为8：1：1；在本发明提供的一些实施例中，所述x优选为0.05，Ln优选为Sc及Y及Gd，且Sc与Y与Gd的摩尔比为8：1：1；在本发明提供的一些实施例中，所述x优选为0.05，Ln优选为Sc及Y及Lu，且Sc与Y与Lu的摩尔比为8：1：1；在本发明提供的一些实施例中，所述x优选为0.05，Ln优选为Sc及La及Gd，且Sc及La及Gd的摩尔比为8：1：1；在本发明提供的一些实施例中，所述x优选为0.05，Ln优选为Sc及La及Lu，且Sc及La及Lu的摩尔比为8：1：1；在本发明提供的一些实施例中，所述x优选为0.05，Ln优选为Sc及Gd及Lu，且Sc及Gd及Lu的摩尔比为8：1：1；在本发明提供的一些实施例中，所述x优选为0.05，Ln优选为Sc与Y与La与 Gd，且Sc与Y与La与Gd的摩尔比为7：1：1：1；在本发明提供的一些实施例中，所述x优选为0.05，Ln优选为Sc与Y与La与Lu，且Sc与Y与La与Lu的摩尔比为7：1：1：1；在本发明提供的一些实施例中，所述x优选为0.05，Ln优选为Sc与La与Gd与Lu，且Sc与La与Gd与Lu的摩尔比为7：1：1：1；在本发明提供的另一些实施例中，所述x优选为0.05，Ln优选为Sc与Y与La与Gd与Lu，且Sc与Y与La与Gd与Lu的摩尔比为6：1：1：1：1。In some embodiments provided by the present invention, said x is preferably 0.001, and Ln is preferably Sc; in some embodiments provided by the present invention, said x is preferably 0.002, and Ln is preferably Sc; in some provided by the present invention In an embodiment, the x is preferably 0.005, and Ln is preferably Sc; in some embodiments provided by the present invention, the x is preferably 0.01, and Ln is preferably Sc; in some embodiments provided by the present invention, the x is preferably 0.02, and Ln is preferably Sc; in some embodiments provided by the invention, said x is preferably 0.05, and Ln is preferably Sc; in some embodiments provided by the invention, said x is preferably 0.08, Ln It is preferably Sc; in some embodiments provided by the present invention, said x is preferably 0.1, and Ln is preferably Sc; in some embodiments provided by the present invention, said x is preferably 0.15, and Ln is preferably Sc; in this invention In some embodiments provided by the invention, the x is preferably 0.2, Ln is preferably Sc; in some embodiments provided by the invention, the x is preferably 0.05, Ln is preferably Sc and Y, and the molar ratio of Sc and Y The ratio is 9:1; in some embodiments provided by the present invention, the 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 Among them, the 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 present invention, the x is preferably 0.05, and Ln is preferably Sc and Lu, and the molar ratio of Sc to Lu is 9:1; in some embodiments provided by the present invention, the x is preferably 0.05, Ln is preferably Sc, Y and La, and the molar ratio of Sc to Y to La is 8:1:1; in some embodiments provided by the present invention, the x is preferably 0.05, Ln is preferably Sc, Y and Gd, and the molar ratio of Sc to Y to Gd is 8:1:1; in this In some embodiments provided by the invention, the x is preferably 0.05, Ln is preferably Sc, Y and Lu, and the molar ratio of Sc to Y to Lu is 8:1:1; in some embodiments provided by the invention, The x is preferably 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, the x is preferably 0.05, Ln It 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, the x is preferably 0.05, and Ln is preferably Sc, Gd and Lu, And the molar ratio of Sc, Gd and Lu is 8:1:1; in some embodiments provided by the present invention, the x is preferably 0.05, Ln is preferably Sc and Y and La and Gd, and Sc and Y and La The molar ratio with Gd is 7:1:1:1; in some embodiments provided by the present invention, the x is preferably 0.05, Ln is preferably Sc and Y and La and Lu, and Sc and Y and La and Lu The molar ratio is 7:1:1:1; in some embodiments provided by the present invention, the x is preferably 0.05, Ln is preferably Sc and La and Gd and Lu, and the moles of Sc and La and Gd and Lu The ratio is 7:1:1:1; in other embodiments provided by the present invention, the x is preferably 0.05, Ln is preferably Sc and Y and La and Gd and Lu, and Sc and Y and La and Gd and The molar ratio of Lu is 6:1:1:1:1.
所述一种氮氧化物绿色荧光材料制备方法的具体步骤如下：The specific steps of the preparation method of the nitrogen oxide green fluorescent material are as follows:
将Ba前驱体、Eu前驱体、Ln前驱体和Si前驱体混合，在还原气氛下，进行高温固相反应，得到一种氮氧化物绿色荧光材料。The Ba precursor, the Eu precursor, the Ln precursor and the Si precursor are mixed, and a high-temperature solid-state reaction is carried out under a reducing atmosphere to obtain a nitrogen oxide green fluorescent material.
所述步骤中，Ba前驱体、Eu前驱体、Ln前驱体和Si前驱体中Ba、Eu、Ln和Si的摩尔比(1-X)：X：1：1，所得材料的化学通式为：Ba 1-xEu xLnSiO 3N，其中，Ln为Sc或Y或La或Gd或Lu中一种或多种，且Sc是必须的，且Sc占Ln含量>50％(摩尔比)，0<x≤0.2。 In the step, the molar ratio of Ba, Eu, Ln and Si in the Ba precursor, Eu precursor, Ln precursor and Si precursor (1-X): X: 1: 1, the general chemical formula of the obtained material is : Ba 1-x Eu x LnSiO 3 N, wherein, Ln is one or more of Sc or Y or La or Gd or Lu, and Sc is necessary, and Sc accounts for Ln content>50% (molar ratio), 0<x≤0.2.
所述步骤中，Ba前驱体为本领域熟知的包含Ba的化合物即可，并无特殊的限制，本发明中优选为Ba前驱体选自Ba的碳酸盐、Ba的氧化物和Ba的硝酸盐中的一种或多种，更优选为Ba的碳酸盐(即碳酸钡)；Eu前驱体选自Eu 2O 3；所述Ln前驱体选自Ln的氧化物，即Sc 2O 3、Y 2O 3、La 2O 3、Gd 2O 3和Lu 2O 3；所述Si前驱体为SiO 2和Si 3N 4。 In the step, the Ba precursor is a compound containing Ba well known in the art, and there is no special limitation. In the present invention, the Ba precursor is preferably selected from Ba carbonate, Ba oxide and Ba nitric acid. One or more salts, more preferably Ba carbonate (ie barium carbonate); the Eu precursor is selected from Eu 2 O 3 ; the Ln precursor is selected from the oxide of Ln, namely Sc 2 O 3 , Y 2 O 3 , La 2 O 3 , Gd 2 O 3 and Lu 2 O 3 ; the Si precursors are SiO 2 and Si 3 N 4 .
所述Ba前驱体、Eu前驱体、Ln前驱体和Si前驱体的纯度均不低于99.5％，纯度越高，得到的发光材料的杂质越少。The purity of the Ba precursor, Eu precursor, Ln precursor and Si precursor is not lower than 99.5%. The higher the purity, the less impurity in the luminescent material obtained.
所述步骤中还原气氛为本领域技术人员熟知的干燥气氛即可，并无特殊的限制，本发明中优选为氮气氢气混合气。The reducing atmosphere in the step can be a dry atmosphere well known to those skilled in the art, and there is no special limitation. In the present invention, it is preferably nitrogen-hydrogen mixed gas.
所述步骤中高温固相的温度优选为1500～1600℃，气氛为氮气氢气混合气，在本发明提供的一些实施例中，所述高温固相的温度优选为1500℃。The temperature of the high-temperature solid phase in the step 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.
所述步骤中高温固相的时间优选为4～10h，更优选为5～8h；在本发明提供的一些实施例中，所述高温固相的时间优选为6h。The high-temperature solid-phase time in the step is preferably 4-10 hours, more preferably 5-8 hours; in some embodiments provided by the present invention, the high-temperature solid-phase time is preferably 6 hours.
所述高温固反应相优选在高温炉内进行。实施反应后，随炉冷却至室温，即可得到一种氮氧化物绿色荧光材料。The high-temperature solid reaction phase is preferably carried out in a high-temperature furnace. After the reaction is carried out, the furnace is cooled to room temperature to obtain a nitrogen oxide green fluorescent material.
本发明采用高温固相反应，成功制备一种氮氧化物绿色荧光材料。The invention adopts high-temperature solid-state reaction to successfully prepare a nitrogen oxide green fluorescent material.
所述的一种氮氧化物绿色荧光材料制作的照明器件，至少由紫光激光二极管及发光层组成。所述发光层为一种绿色荧光玻璃。The lighting device made of nitrogen oxide green fluorescent material is at least composed of a violet laser diode and a light emitting layer. The luminous layer is a kind of green fluorescent glass.
所述一种绿色荧光玻璃，使用所述的一种化学通式为：Ba 1-xEu xLnSiO 3N(其中，Ln为Sc或Y或La或Gd或Lu中一种或多种，且Sc是必须的，且Sc占Ln含量>50％(摩尔比)，0<x≤0.2)的氮氧化物绿色荧光材料与低熔点玻璃粉混合后，进行高温固相反应，最终制备而成。 The green fluorescent glass, using the general chemical formula: Ba 1-x Eu x LnSiO 3 N (wherein, Ln is one or more of Sc or Y or La or Gd or Lu, and Sc is necessary, and Sc accounts for Ln content>50% (molar ratio), 0<x≤0.2) nitrogen oxide green fluorescent material is mixed with low-melting point glass powder, and then undergoes high-temperature solid-state reaction to be finally prepared.
所述的绿色荧光玻璃制备，在空气气氛下进行，所述高温固相反应的温度优选为500～800℃，在本发明提供的一些实施例中，所述高温固相反应的温度优选为700℃；高温固相反应的时间优选为0.1～1h，在本发明提供的一些实施例中，所述高温固相的时间优选为0.5h，最终得到一种绿色荧光玻璃。The preparation of the green fluorescent glass is carried out in an air atmosphere, and the temperature of the high-temperature solid-state reaction is preferably 500-800°C. In some embodiments provided by the present invention, the temperature of the high-temperature solid-state reaction is preferably 700°C °C; the high-temperature solid-phase reaction time is preferably 0.1-1 h, and in some embodiments provided by the present invention, the high-temperature solid-phase reaction time is preferably 0.5 h, and finally a green fluorescent glass is obtained.
为了进一步说明本发明，以下结合实施例对本发明提供的一种氮氧化物绿色荧光材料及其制备方法进行详细描述。In order to further illustrate the present invention, a nitrogen oxide green fluorescent material provided by the present invention and its preparation method are described in detail below in conjunction with the examples.
以下对比例和实施例中所用的试剂均为市售。The reagents used in the following comparative examples and examples are all commercially available.
参考中国专利CN104422676A给出的方法(解荣军，周天亮，快速老化设备，CN104422676A)评价荧光材料的化学稳定性。先记录对应荧光材料在25℃下的发光强度并定义为100(相对强度)，然后将样品在快速老化设备中于温度200℃下老化48h。老化结束后，测量老化后荧光材料的发光强度。一般认为，如果采用快速老化的方法对荧光材料的进行老化，200℃下老化48h后荧光材料的发光强度能保持在75(相对强度)，即可认为荧光材料具有较好的化学稳定性。The chemical stability of fluorescent materials was evaluated with reference to the method given in Chinese patent CN104422676A (Xie Rongjun, Zhou Tianliang, Rapid Aging Equipment, CN104422676A). First record the luminous intensity of the corresponding fluorescent material at 25°C and define it as 100 (relative intensity), and then age the sample at a temperature of 200°C for 48h in a rapid aging device. After aging, measure the luminous intensity of the aged fluorescent material. It is generally believed that if the fluorescent material is aged by a rapid aging method, and the luminous intensity of the fluorescent material can be maintained at 75 (relative intensity) after aging at 200°C for 48 hours, it can be considered that the fluorescent material has good chemical stability.
下述对比例和实施例中采用的氮气氢气混合气氛中，氢气体积含量为20％。In the mixed atmosphere of nitrogen and hydrogen adopted in the following comparative examples and examples, the volume content of hydrogen is 20%.
对比例和实施例中采用的Ba前驱体、Eu前驱体、Ln前驱体和Si前驱体仅为示例，并不构成对前驱体原料的限制，前驱体的纯度均不低于99.5wt％。The Ba precursors, Eu precursors, Ln precursors and Si precursors used in the comparative examples and examples are only examples and do not constitute a limitation on the raw materials of the precursors. The purity of the precursors is not less than 99.5wt%.
对比例1Comparative example 1
本对比例所述的材料，Ba 0.95Eu 0.05Si 2O 2N 2，来自市售商业产品。先测量该材料在25℃下的发光强度并定义为100(相对强度)，然后将该材料放入快速老化设备，在200℃下老化48h后取出，测量老化前后的发光强度，发现其发光强度较低，具体见表1。可见对比例1对应的材料不是化学稳定性的荧光材料。 The material described in this comparative example, Ba 0.95 Eu 0.05 Si 2 O 2 N 2 , was obtained from a commercially available product. First measure the luminous intensity of the material at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity lower, see Table 1 for details. It can be seen that the material corresponding to Comparative Example 1 is not a chemically stable fluorescent material.
对比例2Comparative example 2
本对比例所述的材料，其包含的化合物化学式为：Ba 0.95Eu 0.05YSiO 3N。以BaCO 3、Eu 2O 3、Y 2O 3、SiO 2和Si 3N 4为原料，按照其成分为：Ba 0.95Eu 0.05YSiO 3N的化学计量比准确称取所述原料，在1500℃、氮气氢气混合气氛中烧结6h，待冷却后，即可获得名义化学组成为Ba 0.95Eu 0.05YSiO 3N的材料。使用荧光光谱仪测量所得发光材料的发射光谱，发现其发射光谱的主峰位于595nm处，发射光谱的半高宽为3nm，显然对应Eu 3+的f-d跃迁，即对比例2所获得的材料不是一种氮氧化物绿色荧光材料。 The material described in this comparative example contains the compound chemical formula: Ba 0.95 Eu 0.05 YSiO 3 N. Taking BaCO 3 , Eu 2 O 3 , Y 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, according to the stoichiometric ratio of its composition: Ba 0.95 Eu 0.05 YSiO 3 N, accurately weigh the raw materials at 1500°C , nitrogen and hydrogen in a mixed atmosphere for 6 hours, and after cooling, a material with a nominal chemical composition of Ba 0.95 Eu 0.05 YSiO 3 N can be obtained. Use a fluorescence spectrometer to measure the emission spectrum of the obtained luminescent material, and find that the main peak of the emission spectrum is located at 595nm, and the half-maximum width of the emission spectrum is 3nm, which obviously corresponds to the fd transition of Eu 3+ , that is, the material obtained in Comparative Example 2 is not a Nitride green fluorescent material.
对比例3Comparative example 3
本对比例所述的材料，其包含的化合物化学式为：Ba 0.95Eu 0.05LaSiO 3N。以BaCO 3、Eu 2O 3、La 2O 3、SiO 2和Si 3N 4为原料，按照其成分为：Ba 0.95Eu 0.05LaSiO 3N的化学计量比准确称取所述原料，在1500℃、氮气氢气混合气氛中烧结6h，待冷却后，即可获得名义化学组成为Ba 0.95Eu 0.05LaSiO 3N的材料。使用荧光光谱仪测量所得发光材料的发射光谱，发现其发射光谱的主峰位于595nm处，发射光谱的半高宽为3nm，显然对应Eu 3+的f-d跃迁，即对比例3所获得的材料不是一种氮氧化物绿色荧光材料。 The material described in this comparative example contains the compound chemical formula: Ba 0.95 Eu 0.05 LaSiO 3 N. Take BaCO 3 , Eu 2 O 3 , La 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, and accurately weigh the raw materials according to their composition: Ba 0.95 Eu 0.05 LaSiO 3 N stoichiometric ratio, at 1500°C , nitrogen and hydrogen in a mixed atmosphere for 6 hours, and after cooling, a material with a nominal chemical composition of Ba 0.95 Eu 0.05 LaSiO 3 N can be obtained. Use a fluorescence spectrometer to measure the emission spectrum of the obtained luminescent material, and find that the main peak of the emission spectrum is located at 595nm, and the half-maximum width of the emission spectrum is 3nm, which obviously corresponds to the fd transition of Eu 3+ , that is, the material obtained in Comparative Example 3 is not a Nitride green fluorescent material.
对比例4Comparative example 4
本对比例所述的材料，其包含的化合物化学式为：Ba 0.95Eu 0.05GdSiO 3N。以BaCO 3、Eu 2O 3、Gd 2O 3、SiO 2和Si 3N 4为原料，按照其成分为：Ba 0.95Eu 0.05GdSiO 3N的化学计量比准确称取所述原料，在1500℃、氮气氢气混合气氛中烧结6h，待冷却后，即可获得名义化学组成为Ba 0.95Eu 0.05GdSiO 3N的材料。使用荧光光谱仪测量所得发光材料的发射光谱，发现其发射光谱的主峰位于595nm处，发射光 谱的半高宽为3nm，显然对应Eu 3+的f-d跃迁，即对比例4所获得的材料不是一种氮氧化物绿色荧光材料。 The material described in this comparative example contains the compound chemical formula: Ba 0.95 Eu 0.05 GdSiO 3 N. Taking BaCO 3 , Eu 2 O 3 , Gd 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, according to the stoichiometric ratio of its composition: Ba 0.95 Eu 0.05 GdSiO 3 N, accurately weigh the raw materials, at 1500°C , nitrogen and hydrogen in a mixed atmosphere for 6 hours, and after cooling, a material with a nominal chemical composition of Ba 0.95 Eu 0.05 GdSiO 3 N can be obtained. Use a fluorescence spectrometer to measure the emission spectrum of the obtained luminescent material, and find that the main peak of the emission spectrum is located at 595nm, and the half-maximum width of the emission spectrum is 3nm, which obviously corresponds to the fd transition of Eu 3+ , that is, the material obtained in Comparative Example 4 is not a Nitride green fluorescent material.
对比例5Comparative example 5
本对比例所述的材料，其包含的化合物化学式为：Ba 0.95Eu 0.05LuSiO 3N。以BaCO 3、Eu 2O 3、Lu 2O 3、SiO 2和Si 3N 4为原料，按照其成分为：Ba 0.95Eu 0.05LuSiO 3N的化学计量比准确称取所述原料，在1500℃、氮气氢气混合气氛中烧结6h，待冷却后，即可获得名义化学组成为Ba 0.95Eu 0.05LuSiO 3N的材料。使用荧光光谱仪测量所得发光材料的发射光谱，发现其发射光谱的主峰位于595nm处，发射光谱的半高宽为3nm，显然对应Eu 3+的f-d跃迁，即对比例5所获得的材料不是一种氮氧化物绿色荧光材料。 The material described in this comparative example contains the compound chemical formula: Ba 0.95 Eu 0.05 LuSiO 3 N. Taking BaCO 3 , Eu 2 O 3 , Lu 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, according to the stoichiometric ratio of its composition: Ba 0.95 Eu 0.05 LuSiO 3 N, accurately weigh the raw materials, at 1500°C , nitrogen and hydrogen in a mixed atmosphere for 6 hours, and after cooling, a material with a nominal chemical composition of Ba 0.95 Eu 0.05 LuSiO 3 N can be obtained. Use a fluorescence spectrometer to measure the emission spectrum of the obtained luminescent material, and find that the main peak of the emission spectrum is located at 595nm, and the half-maximum width of the emission spectrum is 3nm, which obviously corresponds to the fd transition of Eu 3+ , that is, the material obtained in Comparative Example 5 is not a Nitride green fluorescent material.
对比例6Comparative example 6
本对比例所述的材料，其包含的化合物化学式为：Ba 0.95Ce 0.05ScSiO 3N。以BaCO 3、CeO 2、Sc 2O 3、SiO 2和Si 3N 4为原料，按照其成分为：Ba 0.95Ce 0.05ScSiO 3N的化学计量比准确称取所述原料，在1500℃、氮气氢气混合气氛中烧结6h，待冷却后，即可获得名义化学组成为Ba 0.95Ce 0.05ScSiO 3N的材料。使用荧光光谱仪测量所得发光材料的发射光谱，发现其发射光谱的主峰位于495nm处，发射光谱的半高宽为121nm。虽然对比例6所获得材料的发射光谱中包含一定的绿光成分，但其不是一种氮氧化物绿色荧光材料，而是青绿色荧光材料，且其发射光谱的半高宽太宽，不适合应用于背光显示。 The material described in this comparative example contains the compound chemical formula: Ba 0.95 Ce 0.05 ScSiO 3 N. Taking BaCO 3 , CeO 2 , Sc 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, according to the stoichiometric ratio of its composition: Ba 0.95 Ce 0.05 ScSiO 3 N, accurately weigh the raw materials, at 1500 ° C, nitrogen After sintering in a hydrogen mixed atmosphere for 6 hours and cooling, a material with a nominal chemical composition of Ba 0.95 Ce 0.05 ScSiO 3 N can be obtained. The emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and it was found that the main peak of the emission spectrum was located at 495 nm, and the half-maximum width of the emission spectrum was 121 nm. Although the emission spectrum of the material obtained in Comparative Example 6 contains certain green light components, it is not a nitrogen oxide green fluorescent material, but a cyan fluorescent material, and the half-maximum width of its emission spectrum is too wide to be suitable for Applied to backlight display.
对比例7Comparative example 7
本实施例所述的材料，其包含的化合物化学式为：Ba 0.999Eu 0.001Sc 0.4Y 0.6SiO 3N。以BaCO 3、Eu 2O 3、Sc 2O 3、Y 2O 3、SiO 2和Si 3N 4为原料，按照其成分为Ba 0.999Eu 0.001Sc 0.4Y 0.6SiO 3N的化学计量比准确称取所述原料，在1500℃、氮气氢气混合气氛中烧结6h，待冷却后，即可获得材料名义化学组成为Ba 0.999Eu 0.001Sc 0.4Y 0.6SiO 3N。使用荧光光谱仪测量所得发光材料的发射光谱，发射光谱的半高宽、发射光谱的主峰位置见表1。从表1可以看出，对比例7制得材料在400nm紫光激发下，发射光谱位于506nm附近，发射光谱的半高宽有 75nm左右。可见对比例7获得材料是一种氮氧化物绿色荧光材料。测量该测量在25℃下的发光强度并定义为100(相对强度)，然后将该材料放入快速老化设备，在200℃下老化48h后取出，测量老化前后的发光强度，发现其发光强度较低，具体见表1。可见对比例7对应的材料是化学稳定性较差的绿色荧光材料。 The material described in this embodiment contains compounds with the chemical formula: Ba 0.999 Eu 0.001 Sc 0.4 Y 0.6 SiO 3 N. Using BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , Y 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, it is accurately weighed according to its stoichiometric ratio of Ba 0.999 Eu 0.001 Sc 0.4 Y 0.6 SiO 3 N The raw materials were taken and sintered at 1500° C. for 6 hours in a mixed atmosphere of nitrogen and hydrogen. After cooling, the nominal chemical composition of the material was Ba 0.999 Eu 0.001 Sc 0.4 Y 0.6 SiO 3 N. The emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Comparative Example 7 is around 506 nm when excited by 400 nm violet light, and the half maximum width of the emission spectrum is about 75 nm. It can be seen that the material obtained in Comparative Example 7 is a nitrogen oxide green fluorescent material. Measure the luminous intensity of the measurement at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity is higher than low, see Table 1 for details. It can be seen that the material corresponding to Comparative Example 7 is a green fluorescent material with poor chemical stability.
实施例1Example 1
本实施例所述的材料，其包含的化合物化学式为：Ba 0.999Eu 0.001ScSiO 3N。以BaCO 3、Eu 2O 3、Sc 2O 3、SiO 2和Si 3N 4为原料，按照其成分为Ba 0.999Eu 0.001ScSiO 3N的化学计量比准确称取所述原料，在1500℃、氮气氢气混合气氛中烧结6h，待冷却后，即可获得材料名义化学组成为Ba 0.999Eu 0.001ScSiO 3N。使用荧光光谱仪测量所得发光材料的发射光谱，发射光谱的半高宽、发射光谱的主峰位置见表1。从表1可以看出，实施例1制得材料在400nm紫光激发下，发射光谱位于507nm附近，发射光谱的半高宽有77nm左右。可见实施例1获得材料是一种氮氧化物绿色荧光材料。测量该测量在25℃下的发光强度并定义为100(相对强度)，然后将该材料放入快速老化设备，在200℃下老化48h后取出，测量老化前后的发光强度，发现其发光强度较高，具体见表1。可见实施例1对应的材料是化学稳定性高的绿色荧光材料。 The material described in this embodiment contains compounds with the chemical formula: Ba 0.999 Eu 0.001 ScSiO 3 N. Taking BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, accurately weigh the raw materials according to the stoichiometric ratio of Ba 0.999 Eu 0.001 ScSiO 3 N, Sintering in a mixed atmosphere of nitrogen and hydrogen for 6 hours, after cooling, the nominal chemical composition of the material can be obtained as Ba 0.999 Eu 0.001 ScSiO 3 N. The emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 1 is around 507 nm under the excitation of 400 nm violet light, and the half maximum width of the emission spectrum is about 77 nm. It can be seen that the material obtained in Example 1 is a nitrogen oxide green fluorescent material. Measure the luminous intensity of the measurement at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity is higher than High, see Table 1 for details. It can be seen that the material corresponding to Example 1 is a green fluorescent material with high chemical stability.
实施例2Example 2
本实施例所述的材料，其包含的化合物化学式为：Ba 0.998Eu 0.002ScSiO 3N。以BaCO 3、Eu 2O 3、Sc 2O 3、SiO 2和Si 3N 4为原料，按照其成分为Ba 0.998Eu 0.002ScSiO 3N的化学计量比准确称取所述原料，在1500℃、氮气氢气混合气氛中烧结6h，待冷却后，即可获得材料名义化学组成为Ba 0.998Eu 0.002ScSiO 3N。使用荧光光谱仪测量所得发光材料的发射光谱，发射光谱的半高宽、发射光谱的主峰位置见表1。从表1可以看出，实施例2制得材料在400nm紫光激发下，发射光谱位于510nm附近，发射光谱的半高宽有79nm左右。可见实施例2获得材料是一种氮氧化物绿色荧光材料。测量该测量在25℃下的发光强度并定义为100(相对强度)，然后将该材料放入快速老化设备，在200℃下老化48h后取出，测量老化前后的 发光强度，发现其发光强度较高，具体见表1。可见实施例2对应的材料是化学稳定性高的绿色荧光材料。 The material described in this embodiment contains a compound with the chemical formula: Ba 0.998 Eu 0.002 ScSiO 3 N. Take BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, and accurately weigh the raw materials according to their stoichiometric ratio of Ba 0.998 Eu 0.002 ScSiO 3 N. Sintering in a mixed atmosphere of nitrogen and hydrogen for 6 hours, after cooling, the nominal chemical composition of the material can be obtained as Ba 0.998 Eu 0.002 ScSiO 3 N. The emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 2 is around 510 nm when excited by 400 nm violet light, and the half maximum width of the emission spectrum is about 79 nm. It can be seen that the material obtained in Example 2 is a nitrogen oxide green fluorescent material. Measure the luminous intensity of the measurement at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity is higher than High, see Table 1 for details. It can be seen that the material corresponding to Example 2 is a green fluorescent material with high chemical stability.
实施例3Example 3
本实施例所述的材料，其包含的化合物化学式为：Ba 0.995Eu 0.005ScSiO 3N。以BaCO 3、Eu 2O 3、Sc 2O 3、SiO 2和Si 3N 4为原料，按照其成分为Ba 0.995Eu 0.005ScSiO 3N的化学计量比准确称取所述原料，在1500℃、氮气氢气混合气氛中烧结6h，待冷却后，即可获得材料名义化学组成为Ba 0.995Eu 0.005ScSiO 3N。使用荧光光谱仪测量所得发光材料的发射光谱，发射光谱的半高宽、发射光谱的主峰位置见表1。从表1可以看出，实施例3制得材料在400nm紫光激发下，发射光谱位于515nm附近，发射光谱的半高宽有81nm左右。可见实施例3获得材料是一种氮氧化物绿色荧光材料。测量该测量在25℃下的发光强度并定义为100(相对强度)，然后将该材料放入快速老化设备，在200℃下老化48h后取出，测量老化前后的发光强度，发现其发光强度较高，具体见表1。可见实施例3对应的材料是化学稳定性高的绿色荧光材料。 The material described in this embodiment contains a compound with the chemical formula: Ba 0.995 Eu 0.005 ScSiO 3 N. Using BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, accurately weigh the raw materials according to the stoichiometric ratio of Ba 0.995 Eu 0.005 ScSiO 3 N, Sintering in a mixed atmosphere of nitrogen and hydrogen for 6 hours, after cooling, the nominal chemical composition of the material can be obtained as Ba 0.995 Eu 0.005 ScSiO 3 N. The emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 3 is around 515 nm under the excitation of 400 nm violet light, and the half maximum width of the emission spectrum is about 81 nm. It can be seen that the material obtained in Example 3 is a nitrogen oxide green fluorescent material. Measure the luminous intensity of the measurement at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity is higher than High, see Table 1 for details. It can be seen that the material corresponding to Example 3 is a green fluorescent material with high chemical stability.
实施例4Example 4
本实施例所述的材料，其包含的化合物化学式为：Ba 0.99Eu 0.01ScSiO 3N。以BaCO 3、Eu 2O 3、Sc 2O 3、SiO 2和Si 3N 4为原料，按照其成分为Ba 0.99Eu 0.01ScSiO 3N的化学计量比准确称取所述原料，在1500℃、氮气氢气混合气氛中烧结6h，待冷却后，即可获得材料名义化学组成为Ba 0.99Eu 0.01ScSiO 3N。使用荧光光谱仪测量所得发光材料的发射光谱，发射光谱的半高宽、发射光谱的主峰位置见表1。从表1可以看出，实施例4制得材料在400nm紫光激发下，发射光谱位于519nm附近，发射光谱的半高宽有82nm左右。可见实施例4获得材料是一种氮氧化物绿色荧光材料。测量该测量在25℃下的发光强度并定义为100(相对强度)，然后将该材料放入快速老化设备，在200℃下老化48h后取出，测量老化前后的发光强度，发现其发光强度较高，具体见表1。可见实施例4对应的材料是化学稳定性高的绿色荧光材料。 The material described in this embodiment contains compounds with the chemical formula: Ba 0.99 Eu 0.01 ScSiO 3 N. Take BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, and accurately weigh the raw materials according to their stoichiometric ratio of Ba 0.99 Eu 0.01 ScSiO 3 N. Sintering in a mixed atmosphere of nitrogen and hydrogen for 6 hours, and after cooling, the nominal chemical composition of the material can be obtained as Ba 0.99 Eu 0.01 ScSiO 3 N. The emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 4 is around 519 nm when excited by 400 nm violet light, and the half maximum width of the emission spectrum is about 82 nm. It can be seen that the material obtained in Example 4 is a nitrogen oxide green fluorescent material. Measure the luminous intensity of the measurement at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity is higher than High, see Table 1 for details. It can be seen that the material corresponding to Example 4 is a green fluorescent material with high chemical stability.
实施例5Example 5
本实施例所述的材料，其包含的化合物化学式为：Ba 0.98Eu 0.02ScSiO 3N。以BaCO 3、Eu 2O 3、Sc 2O 3、SiO 2和Si 3N 4为原料，按照其成分为Ba 0.98Eu 0.02ScSiO 3N的化学计量比准确称取所述原料，在1500℃、氮气氢气混合气氛中烧结6h，待冷却后，即可获得材料名义化学组成为Ba 0.98Eu 0.02ScSiO 3N。使用荧光光谱仪测量所得发光材料的发射光谱，发射光谱的半高宽、发射光谱的主峰位置见表1。从表1可以看出，实施例5制得材料在400nm紫光激发下，发射光谱位于520nm附近，发射光谱的半高宽有86nm左右。可见实施例5获得材料是一种氮氧化物绿色荧光材料。测量该测量在25℃下的发光强度并定义为100(相对强度)，然后将该材料放入快速老化设备，在200℃下老化48h后取出，测量老化前后的发光强度，发现其发光强度较高，具体见表1。可见实施例5对应的材料是化学稳定性高的绿色荧光材料。 The material described in this embodiment contains compounds with the chemical formula: Ba 0.98 Eu 0.02 ScSiO 3 N. Take BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, and accurately weigh the raw materials according to their stoichiometric ratio of Ba 0.98 Eu 0.02 ScSiO 3 N, at 1500°C, Sintering in a mixed atmosphere of nitrogen and hydrogen for 6 hours, after cooling, the nominal chemical composition of the material can be obtained as Ba 0.98 Eu 0.02 ScSiO 3 N. The emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 5 is around 520 nm under the excitation of 400 nm violet light, and the half maximum width of the emission spectrum is about 86 nm. It can be seen that the material obtained in Example 5 is a nitrogen oxide green fluorescent material. Measure the luminous intensity of the measurement at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity is higher than High, see Table 1 for details. It can be seen that the material corresponding to Example 5 is a green fluorescent material with high chemical stability.
实施例6Example 6
本实施例所述的材料，其包含的化合物化学式为：Ba 0.95Eu 0.05ScSiO 3N。以BaCO 3、Eu 2O 3、Sc 2O 3、SiO 2和Si 3N 4为原料，按照其成分为Ba 0.95Eu 0.05ScSiO 3N的化学计量比准确称取所述原料，在1500℃、氮气氢气混合气氛中烧结6h，待冷却后，即可获得材料名义化学组成为Ba 0.95Eu 0.05ScSiO 3N。使用荧光光谱仪测量所得发光材料的发射光谱，发射光谱的半高宽、发射光谱的主峰位置见表1。从表1可以看出，实施例6制得材料在400nm紫光激发下，发射光谱位于525nm附近(见图1)，发射光谱的半高宽有88nm左右。可见实施例6获得材料是一种氮氧化物绿色荧光材料。测量该材料的激发光谱，可见该材料对紫光有较强的吸收(见图2)。测量该测量在25℃下的发光强度并定义为100(相对强度)，然后将该材料放入快速老化设备，在200℃下老化48h后取出，测量老化前后的发光强度，发现其发光强度较高，具体见表1。可见实施例6对应的材料是化学稳定性高的绿色荧光材料。 The material described in this embodiment contains a compound chemical formula: Ba 0.95 Eu 0.05 ScSiO 3 N. Take BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, and accurately weigh the raw materials according to their stoichiometric ratio of Ba 0.95 Eu 0.05 ScSiO 3 N. Sintering in a mixed atmosphere of nitrogen and hydrogen for 6 hours, after cooling, the nominal chemical composition of the material can be obtained as Ba 0.95 Eu 0.05 ScSiO 3 N. The emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 6 is around 525 nm (see FIG. 1 ) under the excitation of 400 nm violet light, and the half maximum width of the emission spectrum is about 88 nm. It can be seen that the material obtained in Example 6 is a nitrogen oxide green fluorescent material. The excitation spectrum of the material is measured, and it can be seen that the material has a strong absorption of violet light (see Figure 2). Measure the luminous intensity of the measurement at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity is higher than High, see Table 1 for details. It can be seen that the material corresponding to Example 6 is a green fluorescent material with high chemical stability.
实施例7Example 7
本实施例所述的材料，其包含的化合物化学式为：Ba 0.92Eu 0.08ScSiO 3N。以BaCO 3、Eu 2O 3、Sc 2O 3、SiO 2和Si 3N 4为原料，按照其成分为Ba 0.92Eu 0.08ScSiO 3N 的化学计量比准确称取所述原料，在1500℃、氮气氢气混合气氛中烧结6h，待冷却后，即可获得材料名义化学组成为Ba 0.92Eu 0.08ScSiO 3N。使用荧光光谱仪测量所得发光材料的发射光谱，发射光谱的半高宽、发射光谱的主峰位置见表1。从表1可以看出，实施例7制得材料在400nm紫光激发下，发射光谱位于527nm附近，发射光谱的半高宽有89nm左右。可见实施例7获得材料是一种氮氧化物绿色荧光材料。测量该测量在25℃下的发光强度并定义为100(相对强度)，然后将该材料放入快速老化设备，在200℃下老化48h后取出，测量老化前后的发光强度，发现其发光强度较高，具体见表1。可见实施例7对应的材料是化学稳定性高的绿色荧光材料。 The material described in this embodiment contains compounds with the chemical formula: Ba 0.92 Eu 0.08 ScSiO 3 N. Take BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, and accurately weigh the raw materials according to their stoichiometric ratio of Ba 0.92 Eu 0.08 ScSiO 3 N , at 1500°C, Sintering in a mixed atmosphere of nitrogen and hydrogen for 6 hours, after cooling, the nominal chemical composition of the material can be obtained as Ba 0.92 Eu 0.08 ScSiO 3 N. The emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 7 is around 527 nm when excited by 400 nm violet light, and the half maximum width of the emission spectrum is about 89 nm. It can be seen that the material obtained in Example 7 is a nitrogen oxide green fluorescent material. Measure the luminous intensity of the measurement at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity is higher than High, see Table 1 for details. It can be seen that the material corresponding to Example 7 is a green fluorescent material with high chemical stability.
实施例8Example 8
本实施例所述的材料，其包含的化合物化学式为：Ba 0.9Eu 0.1ScSiO 3N。以BaCO 3、Eu 2O 3、Sc 2O 3、SiO 2和Si 3N 4为原料，按照其成分为Ba 0.9Eu 0.1ScSiO 3N的化学计量比准确称取所述原料，在1500℃、氮气氢气混合气氛中烧结6h，待冷却后，即可获得材料名义化学组成为Ba 0.9Eu 0.1ScSiO 3N。使用荧光光谱仪测量所得发光材料的发射光谱，发射光谱的半高宽、发射光谱的主峰位置见表1。从表1可以看出，实施例8制得材料在400nm紫光激发下，发射光谱位于529nm附近，发射光谱的半高宽有89nm左右。可见实施例8获得材料是一种氮氧化物绿色荧光材料。测量该测量在25℃下的发光强度并定义为100(相对强度)，然后将该材料放入快速老化设备，在200℃下老化48h后取出，测量老化前后的发光强度，发现其发光强度较高，具体见表1。可见实施例8对应的材料是化学稳定性高的绿色荧光材料。 The material described in this embodiment contains a compound with the chemical formula: Ba 0.9 Eu 0.1 ScSiO 3 N. Take BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, and accurately weigh the raw materials according to their stoichiometric ratio of Ba 0.9 Eu 0.1 ScSiO 3 N. Sintering in a mixed atmosphere of nitrogen and hydrogen for 6 hours, and after cooling, the nominal chemical composition of the material can be obtained as Ba 0.9 Eu 0.1 ScSiO 3 N. The emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 8 is around 529 nm when excited by 400 nm violet light, and the half maximum width of the emission spectrum is about 89 nm. It can be seen that the material obtained in Example 8 is a nitrogen oxide green fluorescent material. Measure the luminous intensity of the measurement at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity is higher than High, see Table 1 for details. It can be seen that the material corresponding to Example 8 is a green fluorescent material with high chemical stability.
实施例9Example 9
本实施例所述的材料，其包含的化合物化学式为：Ba 0.85Eu 0.15ScSiO 3N。以BaCO 3、Eu 2O 3、Sc 2O 3、SiO 2和Si 3N 4为原料，按照其成分为Ba 0.85Eu 0.15ScSiO 3N的化学计量比准确称取所述原料，在1500℃、氮气氢气混合气氛中烧结6h，待冷却后，即可获得材料名义化学组成为Ba 0.85Eu 0.15ScSiO 3N。使用荧光光谱仪测量所得发光材料的发射光谱，发射光谱的半高宽、发射光谱的主峰位置见表1。 从表1可以看出，实施例9制得材料在400nm紫光激发下，发射光谱位于530nm附近，发射光谱的半高宽有89nm左右。可见实施例9获得材料是一种氮氧化物绿色荧光材料。测量该测量在25℃下的发光强度并定义为100(相对强度)，然后将该材料放入快速老化设备，在200℃下老化48h后取出，测量老化前后的发光强度，发现其发光强度较高，具体见表1。可见实施例9对应的材料是化学稳定性高的绿色荧光材料。 The material described in this embodiment contains compounds with the chemical formula: Ba 0.85 Eu 0.15 ScSiO 3 N. Take BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, and accurately weigh the raw materials according to their stoichiometric ratio of Ba 0.85 Eu 0.15 ScSiO 3 N, at 1500°C, Sintering in a mixed atmosphere of nitrogen and hydrogen for 6 hours, after cooling, the nominal chemical composition of the material can be obtained as Ba 0.85 Eu 0.15 ScSiO 3 N. The emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 9 is around 530 nm when excited by 400 nm violet light, and the half maximum width of the emission spectrum is about 89 nm. It can be seen that the material obtained in Example 9 is a nitrogen oxide green fluorescent material. Measure the luminous intensity of the measurement at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity is higher than High, see Table 1 for details. It can be seen that the material corresponding to Example 9 is a green fluorescent material with high chemical stability.
实施例10Example 10
本实施例所述的材料，其包含的化合物化学式为：Ba 0.8Eu 0.2ScSiO 3N。以BaCO 3、Eu 2O 3、Sc 2O 3、SiO 2和Si 3N 4为原料，按照其成分为Ba 0.8Eu 0.2ScSiO 3N的化学计量比准确称取所述原料，在1500℃、氮气氢气混合气氛中烧结6h，待冷却后，即可获得材料名义化学组成为Ba 0.8Eu 0.2ScSiO 3N。使用荧光光谱仪测量所得发光材料的发射光谱，发射光谱的半高宽、发射光谱的主峰位置见表1。从表1可以看出，实施例10制得材料在400nm紫光激发下，发射光谱位于534nm附近，发射光谱的半高宽有89nm左右。可见实施例10获得材料是一种氮氧化物绿色荧光材料。测量该测量在25℃下的发光强度并定义为100(相对强度)，然后将该材料放入快速老化设备，在200℃下老化48h后取出，测量老化前后的发光强度，发现其发光强度较高，具体见表10。可见实施例10对应的材料是化学稳定性高的绿色荧光材料。 The material described in this embodiment contains compounds with the chemical formula: Ba 0.8 Eu 0.2 ScSiO 3 N. Take BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, and accurately weigh the raw materials according to their stoichiometric ratio of Ba 0.8 Eu 0.2 ScSiO 3 N. Sintering in a mixed atmosphere of nitrogen and hydrogen for 6 hours, after cooling, the nominal chemical composition of the material can be obtained as Ba 0.8 Eu 0.2 ScSiO 3 N. The emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 10 is around 534 nm when excited by 400 nm violet light, and the half maximum width of the emission spectrum is about 89 nm. It can be seen that the material obtained in Example 10 is a nitrogen oxide green fluorescent material. Measure the luminous intensity of the measurement at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity is higher than High, see Table 10 for details. It can be seen that the material corresponding to Example 10 is a green fluorescent material with high chemical stability.
实施例11Example 11
本实施例所述的材料，其包含的化合物化学式为：Ba 0.95Eu 0.05Sc 0.9Y 0.1SiO 3N。以BaCO 3、Eu 2O 3、Sc 2O 3、Y 2O 3、SiO 2和Si 3N 4为原料，按照其成分为Ba 0.95Eu 0.05Sc 0.9Y 0.1SiO 3N的化学计量比准确称取所述原料，在1500℃、氮气氢气混合气氛中烧结6h，待冷却后，即可获得材料名义化学组成为Ba 0.95Eu 0.05Sc 0.9Y 0.1SiO 3N。使用荧光光谱仪测量所得发光材料的发射光谱，发射光谱的半高宽、发射光谱的主峰位置见表1。从表1可以看出，实施例11制得材料在400nm紫光激发下，发射光谱位于526nm附近，发射光谱的半高宽有88nm左右。可见实施例11获得材料是一种氮氧化物绿色荧光材料。测量该测 量在25℃下的发光强度并定义为100(相对强度)，然后将该材料放入快速老化设备，在200℃下老化48h后取出，测量老化前后的发光强度，发现其发光强度较高，具体见表1。可见实施例11对应的材料是化学稳定性高的绿色荧光材料。 The material described in this embodiment contains a compound with the chemical formula: Ba 0.95 Eu 0.05 Sc 0.9 Y 0.1 SiO 3 N. Using BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , Y 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, it is accurately weighed according to the stoichiometric ratio of Ba 0.95 Eu 0.05 Sc 0.9 Y 0.1 SiO 3 N The raw materials were taken and sintered at 1500° C. for 6 hours in a mixed atmosphere of nitrogen and hydrogen. After cooling, the nominal chemical composition of the material was Ba 0.95 Eu 0.05 Sc 0.9 Y 0.1 SiO 3 N. The emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 11 is around 526 nm when excited by 400 nm violet light, and the full width at half maximum of the emission spectrum is about 88 nm. It can be seen that the material obtained in Example 11 is a nitrogen oxide green fluorescent material. Measure the luminous intensity of the measurement at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity is higher than High, see Table 1 for details. It can be seen that the material corresponding to Example 11 is a green fluorescent material with high chemical stability.
实施例12Example 12
本实施例所述的材料，其包含的化合物化学式为：Ba 0.95Eu 0.05Sc 0.9La 0.1SiO 3N。以BaCO 3、Eu 2O 3、Sc 2O 3、La 2O 3、SiO 2和Si 3N 4为原料，按照其成分为Ba 0.95Eu 0.05Sc 0.9La 0.1SiO 3N的化学计量比准确称取所述原料，在1500℃、氮气氢气混合气氛中烧结6h，待冷却后，即可获得材料名义化学组成为Ba 0.95Eu 0.05Sc 0.9La 0.1SiO 3N。使用荧光光谱仪测量所得发光材料的发射光谱，发射光谱的半高宽、发射光谱的主峰位置见表1。从表1可以看出，实施例12制得材料在400nm紫光激发下，发射光谱位于527nm附近，发射光谱的半高宽有87nm左右。可见实施例12获得材料是一种氮氧化物绿色荧光材料。测量该测量在25℃下的发光强度并定义为100(相对强度)，然后将该材料放入快速老化设备，在200℃下老化48h后取出，测量老化前后的发光强度，发现其发光强度较高，具体见表1。可见实施例12对应的材料是化学稳定性高的绿色荧光材料。 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 SiO 3 N. Using BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , La 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, it is accurately weighed according to the stoichiometric ratio of Ba 0.95 Eu 0.05 Sc 0.9 La 0.1 SiO 3 N The raw materials were taken and sintered at 1500° C. for 6 hours in a mixed atmosphere of nitrogen and hydrogen. After cooling, the nominal chemical composition of the material was Ba 0.95 Eu 0.05 Sc 0.9 La 0.1 SiO 3 N. The emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 12 is around 527 nm under the excitation of 400 nm violet light, and the half maximum width of the emission spectrum is about 87 nm. It can be seen that the material obtained in Example 12 is a nitrogen oxide green fluorescent material. Measure the luminous intensity of the measurement at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity is higher than High, see Table 1 for details. It can be seen that the material corresponding to Example 12 is a green fluorescent material with high chemical stability.
实施例13Example 13
本实施例所述的材料，其包含的化合物化学式为：Ba 0.95Eu 0.05Sc 0.9Gd 0.1SiO 3N。以BaCO 3、Eu 2O 3、Sc 2O 3、Gd 2O 3、SiO 2和Si 3N 4为原料，按照其成分为Ba 0.95Eu 0.05Sc 0.9Gd 0.1SiO 3N的化学计量比准确称取所述原料，在1500℃、氮气氢气混合气氛中烧结6h，待冷却后，即可获得材料名义化学组成为Ba 0.95Eu 0.05Sc 0.9Gd 0.1SiO 3N。使用荧光光谱仪测量所得发光材料的发射光谱，发射光谱的半高宽、发射光谱的主峰位置见表1。从表1可以看出，实施例13制得材料在400nm紫光激发下，发射光谱位于529nm附近，发射光谱的半高宽有86nm左右。可见实施例13获得材料是一种氮氧化物绿色荧光材料。测量该测量在25℃下的发光强度并定义为100(相对强度)，然后将该材料放入快速老化设备，在200℃下老化48h后取出，测量老化前后的发光强度，发现其发光强度较高，具体见表1。可见实施例13对应的材料是化学稳定性高的绿色荧光材料。 The material described in this embodiment contains the compound chemical formula: Ba 0.95 Eu 0.05 Sc 0.9 Gd 0.1 SiO 3 N. Using BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , Gd 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, it is accurately weighed according to its stoichiometric ratio of Ba 0.95 Eu 0.05 Sc 0.9 Gd 0.1 SiO 3 N The raw materials were taken and sintered at 1500° C. for 6 hours in a mixed atmosphere of nitrogen and hydrogen. After cooling, the nominal chemical composition of the material was Ba 0.95 Eu 0.05 Sc 0.9 Gd 0.1 SiO 3 N. The emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 13 is around 529 nm when excited by 400 nm violet light, and the half maximum width of the emission spectrum is about 86 nm. It can be seen that the material obtained in Example 13 is a nitrogen oxide green fluorescent material. Measure the luminous intensity of the measurement at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity is higher than High, see Table 1 for details. It can be seen that the material corresponding to Example 13 is a green fluorescent material with high chemical stability.
实施例14Example 14
本实施例所述的材料，其包含的化合物化学式为：Ba 0.95Eu 0.05Sc 0.9Lu 0.1SiO 3N。以BaCO 3、Eu 2O 3、Sc 2O 3、Lu 2O 3、SiO 2和Si 3N 4为原料，按照其成分为Ba 0.95Eu 0.05Sc 0.9Lu 0.1SiO 3N的化学计量比准确称取所述原料，在1500℃、氮气氢气混合气氛中烧结6h，待冷却后，即可获得材料名义化学组成为Ba 0.95Eu 0.05Sc 0.9Lu 0.1SiO 3N。使用荧光光谱仪测量所得发光材料的发射光谱，发射光谱的半高宽、发射光谱的主峰位置见表1。从表1可以看出，实施例14制得材料在400nm紫光激发下，发射光谱位于522nm附近，发射光谱的半高宽有85nm左右。可见实施例14获得材料是一种氮氧化物绿色荧光材料。测量该测量在25℃下的发光强度并定义为100(相对强度)，然后将该材料放入快速老化设备，在200℃下老化48h后取出，测量老化前后的发光强度，发现其发光强度较高，具体见表1。可见实施例14对应的材料是化学稳定性高的绿色荧光材料。 The material described in this embodiment contains a compound with the chemical formula: Ba 0.95 Eu 0.05 Sc 0.9 Lu 0.1 SiO 3 N. Using BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , Lu 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, it is accurately weighed according to its stoichiometric ratio of Ba 0.95 Eu 0.05 Sc 0.9 Lu 0.1 SiO 3 N The raw materials were taken and sintered at 1500° C. for 6 hours in a mixed atmosphere of nitrogen and hydrogen. After cooling, the nominal chemical composition of the material was Ba 0.95 Eu 0.05 Sc 0.9 Lu 0.1 SiO 3 N. The emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 14 is around 522 nm when excited by 400 nm violet light, and the half maximum width of the emission spectrum is about 85 nm. It can be seen that the material obtained in Example 14 is a nitrogen oxide green fluorescent material. Measure the luminous intensity of the measurement at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity is higher than High, see Table 1 for details. It can be seen that the material corresponding to Example 14 is a green fluorescent material with high chemical stability.
实施例15Example 15
本实施例所述的材料，其包含的化合物化学式为：Ba 0.95Eu 0.05Sc 0.8Y 0.1La 0.1SiO 3N。以BaCO 3、Eu 2O 3、Sc 2O 3、Y 2O 3、La 2O 3、SiO 2和Si 3N 4为原料，按照其成分为Ba 0.95Eu 0.05Sc 0.8Y 0.1La 0.1SiO 3N的化学计量比准确称取所述原料，在1500℃、氮气氢气混合气氛中烧结6h，待冷却后，即可获得材料名义化学组成为Ba 0.95Eu 0.05Sc 0.8Y 0.1La 0.1SiO 3N。使用荧光光谱仪测量所得发光材料的发射光谱，发射光谱的半高宽、发射光谱的主峰位置见表1。从表1可以看出，实施例15制得材料在400nm紫光激发下，发射光谱位于530nm附近，发射光谱的半高宽有85nm左右。可见实施例15获得材料是一种氮氧化物绿色荧光材料。测量该测量在25℃下的发光强度并定义为100(相对强度)，然后将该材料放入快速老化设备，在200℃下老化48h后取出，测量老化前后的发光强度，发现其发光强度较高，具体见表1。可见实施例15对应的材料是化学稳定性高的绿色荧光材料。 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 SiO 3 N. Using BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , Y 2 O 3 , La 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, according to its composition, it is Ba 0.95 Eu 0.05 Sc 0.8 Y 0.1 La 0.1 SiO 3 Stoichiometric ratio of N The raw materials were accurately weighed and sintered at 1500°C for 6 hours in a nitrogen-hydrogen mixed atmosphere. After cooling, the nominal chemical composition of the material was Ba 0.95 Eu 0.05 Sc 0.8 Y 0.1 La 0.1 SiO 3 N. The emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 15 is around 530 nm when excited by 400 nm violet light, and the full width at half maximum of the emission spectrum is about 85 nm. It can be seen that the material obtained in Example 15 is a nitrogen oxide green fluorescent material. Measure the luminous intensity of the measurement at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity is higher than High, see Table 1 for details. It can be seen that the material corresponding to Example 15 is a green fluorescent material with high chemical stability.
实施例16Example 16
本实施例所述的材料，其包含的化合物化学式为：Ba 0.95Eu 0.05Sc 0.8Y 0.1Gd 0.1SiO 3N。以BaCO 3、Eu 2O 3、Sc 2O 3、Y 2O 3、Gd 2O 3、SiO 2和Si 3N 4为原料，按照其成分为Ba 0.95Eu 0.05Sc 0.8Y 0.1Gd 0.1SiO 3N的化学计量比准确称取所述原料，在1500℃、氮气氢气混合气氛中烧结6h，待冷却后，即可获得材料名义化学组成为Ba 0.95Eu 0.05Sc 0.8Y 0.1Gd 0.1SiO 3N。使用荧光光谱仪测量所得发光材料的发射光谱，发射光谱的半高宽、发射光谱的主峰位置见表1。从表1可以看出，实施例16制得材料在400nm紫光激发下，发射光谱位于533nm附近，发射光谱的半高宽有86nm左右。可见实施例16获得材料是一种氮氧化物绿色荧光材料。测量该测量在25℃下的发光强度并定义为100(相对强度)，然后将该材料放入快速老化设备，在200℃下老化48h后取出，测量老化前后的发光强度，发现其发光强度较高，具体见表1。可见实施例16对应的材料是化学稳定性高的绿色荧光材料。 The material described in this embodiment contains the compound chemical formula: Ba 0.95 Eu 0.05 Sc 0.8 Y 0.1 Gd 0.1 SiO 3 N. Using BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , Y 2 O 3 , Gd 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, according to its composition, it is Ba 0.95 Eu 0.05 Sc 0.8 Y 0.1 Gd 0.1 SiO 3 Stoichiometric ratio of N The raw materials were accurately weighed, sintered at 1500°C for 6 hours in a mixed atmosphere of nitrogen and hydrogen, and after cooling, the nominal chemical composition of the material was Ba 0.95 Eu 0.05 Sc 0.8 Y 0.1 Gd 0.1 SiO 3 N. The emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 16 is around 533 nm under the excitation of 400 nm violet light, and the half maximum width of the emission spectrum is about 86 nm. It can be seen that the material obtained in Example 16 is a nitrogen oxide green fluorescent material. Measure the luminous intensity of the measurement at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity is higher than High, see Table 1 for details. It can be seen that the material corresponding to Example 16 is a green fluorescent material with high chemical stability.
实施例17Example 17
本实施例所述的材料，其包含的化合物化学式为：Ba 0.95Eu 0.05Sc 0.8Y 0.1Lu 0.1SiO 3N。以BaCO 3、Eu 2O 3、Sc 2O 3、Y 2O 3、Lu 2O 3、SiO 2和Si 3N 4为原料，按照其成分为Ba 0.95Eu 0.05Sc 0.8Y 0.1Lu 0.1SiO 3N的化学计量比准确称取所述原料，在1500℃、氮气氢气混合气氛中烧结6h，待冷却后，即可获得材料名义化学组成为Ba 0.95Eu 0.05Sc 0.8Y 0.1Lu 0.1SiO 3N。使用荧光光谱仪测量所得发光材料的发射光谱，发射光谱的半高宽、发射光谱的主峰位置见表1。从表1可以看出，实施例17制得材料在400nm紫光激发下，发射光谱位于529nm附近，发射光谱的半高宽有82nm左右。可见实施例17获得材料是一种氮氧化物绿色荧光材料。测量该测量在25℃下的发光强度并定义为100(相对强度)，然后将该材料放入快速老化设备，在200℃下老化48h后取出，测量老化前后的发光强度，发现其发光强度较高，具体见表17。可见实施例1对应的材料是化学稳定性高的绿色荧光材料。 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 Lu 0.1 SiO 3 N. Using BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , Y 2 O 3 , Lu 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, according to its composition, it is Ba 0.95 Eu 0.05 Sc 0.8 Y 0.1 Lu 0.1 SiO 3 Stoichiometric ratio of N The raw materials were accurately weighed, sintered at 1500°C for 6 hours in a nitrogen-hydrogen mixed atmosphere, and after cooling, the nominal chemical composition of the material was Ba 0.95 Eu 0.05 Sc 0.8 Y 0.1 Lu 0.1 SiO 3 N. The emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 17 is around 529 nm when excited by 400 nm violet light, and the half maximum width of the emission spectrum is about 82 nm. It can be seen that the material obtained in Example 17 is a nitrogen oxide green fluorescent material. Measure the luminous intensity of the measurement at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity is higher than High, see Table 17 for details. It can be seen that the material corresponding to Example 1 is a green fluorescent material with high chemical stability.
实施例18Example 18
本实施例所述的材料，其包含的化合物化学式为：Ba 0.95Eu 0.05Sc 0.8La 0.1Gd 0.1SiO 3N。以BaCO 3、Eu 2O 3、Sc 2O 3、La 2O 3、Gd 2O 3、SiO 2和Si 3N 4为原料，按照其成分为Ba 0.95Eu 0.05Sc 0.8La 0.1Gd 0.1SiO 3N的化学计量比准确称取所述原料，在1500℃、氮气氢气混合气氛中烧结6h，待冷却后，即可获得材料名义化学组成为Ba 0.95Eu 0.05Sc 0.8La 0.1Gd 0.1SiO 3N。使用荧光光谱仪测量所得发光材料的发射光谱，发射光谱的半高宽、发射光谱的主峰位置见表1。从表1可以看出，实施例18制得材料在400nm紫光激发下，发射光谱位于523nm附近，发射光谱的半高宽有83nm左右。可见实施例18获得材料是一种氮氧化物绿色荧光材料。测量该测量在25℃下的发光强度并定义为100(相对强度)，然后将该材料放入快速老化设备，在200℃下老化48h后取出，测量老化前后的发光强度，发现其发光强度较高，具体见表1。可见实施例18对应的材料是化学稳定性高的绿色荧光材料。 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 SiO 3 N. Using BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , La 2 O 3 , Gd 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, according to its composition, it is Ba 0.95 Eu 0.05 Sc 0.8 La 0.1 Gd 0.1 SiO 3 Stoichiometric ratio of N The raw materials were accurately weighed, sintered at 1500°C for 6 hours in a mixed atmosphere of nitrogen and hydrogen, and after cooling, the nominal chemical composition of the material was Ba 0.95 Eu 0.05 Sc 0.8 La 0.1 Gd 0.1 SiO 3 N. The emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 18 is around 523 nm under the excitation of 400 nm violet light, and the half maximum width of the emission spectrum is about 83 nm. It can be seen that the material obtained in Example 18 is a nitrogen oxide green fluorescent material. Measure the luminous intensity of the measurement at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity is higher than High, see Table 1 for details. It can be seen that the material corresponding to Example 18 is a green fluorescent material with high chemical stability.
实施例19Example 19
本实施例所述的材料，其包含的化合物化学式为：Ba 0.95Eu 0.05Sc 0.8La 0.1Lu 0.1SiO 3N。以BaCO 3、Eu 2O 3、Sc 2O 3、La 2O 3、Lu 2O 3、SiO 2和Si 3N 4为原料，按照其成分为Ba 0.95Eu 0.05Sc 0.8La 0.1Lu 0.1SiO 3N的化学计量比准确称取所述原料，在1500℃、氮气氢气混合气氛中烧结6h，待冷却后，即可获得材料名义化学组成为Ba 0.95Eu 0.05Sc 0.8La 0.1Lu 0.1SiO 3N。使用荧光光谱仪测量所得发光材料的发射光谱，发射光谱的半高宽、发射光谱的主峰位置见表1。从表1可以看出，实施例19制得材料在400nm紫光激发下，发射光谱位于521nm附近，发射光谱的半高宽有87nm左右。可见实施例19获得材料是一种氮氧化物绿色荧光材料。测量该测量在25℃下的发光强度并定义为100(相对强度)，然后将该材料放入快速老化设备，在200℃下老化48h后取出，测量老化前后的发光强度，发现其发光强度较高，具体见表1。可见实施例19对应的材料是化学稳定性高的绿色荧光材料。 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 SiO 3 N. Using BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , La 2 O 3 , Lu 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, according to its composition, it is Ba 0.95 Eu 0.05 Sc 0.8 La 0.1 Lu 0.1 SiO 3 Stoichiometric ratio of N The raw materials were accurately weighed and sintered at 1500°C for 6 hours in a mixed atmosphere of nitrogen and hydrogen. After cooling, the nominal chemical composition of the material was Ba 0.95 Eu 0.05 Sc 0.8 La 0.1 Lu 0.1 SiO 3 N. The emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 19 is around 521 nm under the excitation of 400 nm violet light, and the half maximum width of the emission spectrum is about 87 nm. It can be seen that the material obtained in Example 19 is a nitrogen oxide green fluorescent material. Measure the luminous intensity of the measurement at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity is higher than High, see Table 1 for details. It can be seen that the material corresponding to Example 19 is a green fluorescent material with high chemical stability.
实施例20Example 20
本实施例所述的材料，其包含的化合物化学式为：Ba 0.95Eu 0.05Sc 0.8Gd 0.1Lu 0.1SiO 3N。以BaCO 3、Eu 2O 3、Sc 2O 3、Gd 2O 3、Lu 2O 3、SiO 2和Si 3N 4为原料，按照其成分为Ba 0.95Eu 0.05Sc 0.8Gd 0.1Lu 0.1SiO 3N的化学计量比准确称取所述原料，在1500℃、氮气氢气混合气氛中烧结6h，待冷却后，即可获得材料名义化学组成为Ba 0.95Eu 0.05Sc 0.8Gd 0.1Lu 0.1SiO 3N。使用荧光光谱仪测量所得发光材料的发射光谱，发射光谱的半高宽、发射光谱的主峰位置见表1。从表1可以看出，实施例20制得材料在400nm紫光激发下，发射光谱位于527nm附近，发射光谱的半高宽有84nm左右。可见实施例20获得材料是一种氮氧化物绿色荧光材料。测量该测量在25℃下的发光强度并定义为100(相对强度)，然后将该材料放入快速老化设备，在200℃下老化48h后取出，测量老化前后的发光强度，发现其发光强度较高，具体见表1。可见实施例20对应的材料是化学稳定性高的绿色荧光材料。 The material described in this embodiment contains a compound with the chemical formula: Ba 0.95 Eu 0.05 Sc 0.8 Gd 0.1 Lu 0.1 SiO 3 N. Using BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , Gd 2 O 3 , Lu 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, according to its composition, it is Ba 0.95 Eu 0.05 Sc 0.8 Gd 0.1 Lu 0.1 SiO 3 Stoichiometric ratio of N The raw materials were accurately weighed and sintered at 1500°C for 6 hours in a mixed atmosphere of nitrogen and hydrogen. After cooling, the nominal chemical composition of the material was Ba 0.95 Eu 0.05 Sc 0.8 Gd 0.1 Lu 0.1 SiO 3 N. The emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 20 is around 527 nm when excited by 400 nm violet light, and the half-maximum width of the emission spectrum is about 84 nm. It can be seen that the material obtained in Example 20 is a nitrogen oxide green fluorescent material. Measure the luminous intensity of the measurement at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity is higher than High, see Table 1 for details. It can be seen that the material corresponding to Example 20 is a green fluorescent material with high chemical stability.
实施例21Example 21
本实施例所述的材料，其包含的化合物化学式为：Ba 0.95Eu 0.05Sc 0.7Y 0.1La 0.1Gd 0.1SiO 3N。以BaCO 3、Eu 2O 3、Sc 2O 3、Y 2O 3、La 2O 3、Gd 2O 3、SiO 2和Si 3N 4为原料，按照其成分为Ba 0.95Eu 0.05Sc 0.7Y 0.1La 0.1Gd 0.1SiO 3N的化学计量比准确称取所述原料，在1500℃、氮气氢气混合气氛中烧结6h，待冷却后，即可获得材料名义化学组成为Ba 0.95Eu 0.05Sc 0.7Y 0.1La 0.1Gd 0.1SiO 3N。使用荧光光谱仪测量所得发光材料的发射光谱，发射光谱的半高宽、发射光谱的主峰位置见表1。从表1可以看出，实施例21制得材料在400nm紫光激发下，发射光谱位于530nm附近，发射光谱的半高宽有84nm左右。可见实施例21获得材料是一种氮氧化物绿色荧光材料。测量该测量在25℃下的发光强度并定义为100(相对强度)，然后将该材料放入快速老化设备，在200℃下老化48h后取出，测量老化前后的发光强度，发现其发光强度较高，具体见表1。可见实施例21对应的材料是化学稳定性高的绿色荧光材料。 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 SiO 3 N. Using BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , Y 2 O 3 , La 2 O 3 , Gd 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, according to its composition, it is Ba 0.95 Eu 0.05 Sc 0.7 Y The stoichiometric ratio of 0.1 La 0.1 Gd 0.1 SiO 3 N Accurately weigh the raw materials, sinter them at 1500°C in a mixed atmosphere of nitrogen and hydrogen for 6 hours, and after cooling, the nominal chemical composition of the material can be obtained as Ba 0.95 Eu 0.05 Sc 0.7 Y 0.1 La 0.1 Gd 0.1 SiO 3 N. The emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 21 is around 530 nm under the excitation of 400 nm violet light, and the half maximum width of the emission spectrum is about 84 nm. It can be seen that the material obtained in Example 21 is a nitrogen oxide green fluorescent material. Measure the luminous intensity of the measurement at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity is higher than High, see Table 1 for details. It can be seen that the material corresponding to Example 21 is a green fluorescent material with high chemical stability.
实施例22Example 22
本实施例所述的材料，其包含的化合物化学式为：Ba 0.95Eu 0.05Sc 0.7Y 0.1La 0.1Lu 0.1SiO 3N。以BaCO 3、Eu 2O 3、Sc 2O 3、Y 2O 3、La 2O 3、Lu 2O 3、SiO 2和Si 3N 4为原料，按照其成分为Ba 0.95Eu 0.05Sc 0.7Y 0.1La 0.1Lu 0.1SiO 3N的化学计量比准确称取所述原料，在1500℃、氮气氢气混合气氛中烧结6h，待冷却后，即可获得材料名义化学组成为Ba 0.95Eu 0.05Sc 0.7Y 0.1La 0.1Lu 0.1SiO 3N。使用荧光光谱仪测量所得发光材料的发射光谱，发射光谱的半高宽、发射光谱的主峰位置见表1。从表1可以看出，实施例22制得材料在400nm紫光激发下，发射光谱位于524nm附近，发射光谱的半高宽有86nm左右。可见实施例22获得材料是一种氮氧化物绿色荧光材料。测量该测量在25℃下的发光强度并定义为100(相对强度)，然后将该材料放入快速老化设备，在200℃下老化48h后取出，测量老化前后的发光强度，发现其发光强度较高，具体见表1。可见实施例22对应的材料是化学稳定性高的绿色荧光材料。 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 SiO 3 N. Using BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , Y 2 O 3 , La 2 O 3 , Lu 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, according to its composition, it is Ba 0.95 Eu 0.05 Sc 0.7 Y The stoichiometric ratio of 0.1 La 0.1 Lu 0.1 SiO 3 N Accurately weigh the raw materials, sinter them at 1500°C in a mixed atmosphere of nitrogen and hydrogen for 6 hours, and after cooling, the nominal chemical composition of the material can be obtained as Ba 0.95 Eu 0.05 Sc 0.7 Y 0.1 La 0.1 Lu 0.1 SiO 3 N. The emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 22 is around 524 nm under the excitation of 400 nm violet light, and the half maximum width of the emission spectrum is about 86 nm. It can be seen that the material obtained in Example 22 is a nitrogen oxide green fluorescent material. Measure the luminous intensity of the measurement at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity is higher than High, see Table 1 for details. It can be seen that the material corresponding to Example 22 is a green fluorescent material with high chemical stability.
实施例23Example 23
本实施例所述的材料，其包含的化合物化学式为：Ba 0.95Eu 0.05Sc 0.7La 0.1Gd 0.1Lu 0.1SiO 3N。以BaCO 3、Eu 2O 3、Sc 2O 3、La 2O 3、Gd 2O 3、Lu 2O 3、SiO 2和Si 3N 4为原料，按照其成分为Ba 0.95Eu 0.05Sc 0.7La 0.1Gd 0.1Lu 0.1SiO 3N的化学计量比准确称取所述原料，在1500℃、氮气氢气混合气氛中烧结6h，待冷却后，即可获得材料名义化学组成为Ba 0.95Eu 0.05Sc 0.7La 0.1Gd 0.1Lu 0.1SiO 3N。使用荧光光谱仪测量所得发光材料的发射光谱，发射光谱的半高宽、发射光谱的主峰位置见表1。从表1可以看出，实施例23制得材料在400nm紫光激发下，发射光谱位于522nm附近，发射光谱的半高宽有88nm左右。可见实施例23获得材料是一种氮氧化物绿色荧光材料。测量该测量在25℃下的发光强度并定义为100(相对强度)，然后将该材料放入快速老化设备，在200℃下老化48h后取出，测量老化前后的发光强度，发现其发光强度较高，具体见表1。可见实施例23对应的材料是化学稳定性高的绿色荧光材料。 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 SiO 3 N. Using BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , La 2 O 3 , Gd 2 O 3 , Lu 2 O 3 , SiO 2 and Si 3 N 4 as raw materials, according to its composition, it is Ba 0.95 Eu 0.05 Sc 0.7 La The stoichiometric ratio of 0.1 Gd 0.1 Lu 0.1 SiO 3 N Accurately weigh the raw materials, sinter them at 1500°C in a mixed atmosphere of nitrogen and hydrogen for 6 hours, and after cooling, the nominal chemical composition of the material can be obtained as Ba 0.95 Eu 0.05 Sc 0.7 La 0.1 Gd 0.1 Lu 0.1 SiO 3 N. The emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 23 is around 522 nm under the excitation of 400 nm violet light, and the half maximum width of the emission spectrum is about 88 nm. It can be seen that the material obtained in Example 23 is a nitrogen oxide green fluorescent material. Measure the luminous intensity of the measurement at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity is higher than High, see Table 1 for details. It can be seen that the material corresponding to Example 23 is a green fluorescent material with high chemical stability.
实施例24Example 24
本实施例所述的材料，其包含的化合物化学式为：Ba 0.95Eu 0.05Sc 0.6Y 0.1La 0.1Gd 0.1Lu 0.1SiO 3N。以BaCO 3、Eu 2O 3、Sc 2O 3、Y 2O 3、La 2O 3、Gd 2O 3、Lu 2O 3、SiO 2和Si 3N 4为原料，按照其成分为Ba 0.95Eu 0.05Sc 0.6Y 0.1La 0.1Gd 0.1Lu 0.1SiO 3N的化学计量比准确称取所述原料，在1500℃、氮气氢气混合气氛中烧结6h，待冷却后，即可获得材料名义化学组成为Ba 0.95Eu 0.05Sc 0.6Y 0.1La 0.1Gd 0.1Lu 0.1SiO 3N。使用荧光光谱仪测量所得发光材料的发射光谱，发射光谱的半高宽、发射光谱的主峰位置见表1。从表1可以看出，实施例24制得材料在400nm紫光激发下，发射光谱位于526nm附近，发射光谱的半高宽有89nm左右。可见实施例24获得材料是一种氮氧化物绿色荧光材料。测量该测量在25℃下的发光强度并定义为100(相对强度)，然后将该材料放入快速老化设备，在200℃下老化48h后取出，测量老化前后的发光强度，发现其发光强度较高，具体见表1。可见实施例24对应的材料是化学稳定性高的绿色荧光材料。 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 SiO 3 N. BaCO 3 , Eu 2 O 3 , Sc 2 O 3 , Y 2 O 3 , La 2 O 3 , Gd 2 O 3 , Lu 2 O 3 , SiO 2 and Si 3 N 4 are used as raw materials, and the composition is Ba 0.95 The stoichiometric ratio of Eu 0.05 Sc 0.6 Y 0.1 La 0.1 Gd 0.1 Lu 0.1 SiO 3 N Accurately weigh the raw materials and sinter them at 1500°C for 6 hours in a mixed atmosphere of nitrogen and hydrogen. After cooling, the nominal chemical composition of the material can be obtained as Ba 0.95 Eu 0.05 Sc 0.6 Y 0.1 La 0.1 Gd 0.1 Lu 0.1 SiO 3 N. The emission spectrum of the obtained luminescent material was measured by a fluorescence spectrometer, and the full width at half maximum of the emission spectrum and the position of the main peak of the emission spectrum are shown in Table 1. It can be seen from Table 1 that the emission spectrum of the material prepared in Example 24 is around 526 nm under the excitation of 400 nm violet light, and the half-maximum width of the emission spectrum is about 89 nm. It can be seen that the material obtained in Example 24 is a nitrogen oxide green fluorescent material. Measure the luminous intensity of the measurement at 25°C and define it as 100 (relative intensity), then put the material into the rapid aging equipment, take it out after aging for 48 hours at 200°C, measure the luminous intensity before and after aging, and find that its luminous intensity is higher than High, see Table 1 for details. It can be seen that the material corresponding to Example 24 is a green fluorescent material with high chemical stability.
实施例25Example 25
选择实施例6所合成的化学组成为Ba 0.95Eu 0.05ScSiO 3N绿色荧光材料。将上述材料与低熔点玻璃粉按照质量比1：1相混合，将上述混合物置于金属钛制作的底部直径为10mm的平底坩埚中，在空气气氛下，700℃烧结0.5h后，待样品冷却，即可获得一种绿色荧光玻璃。将上述绿色荧光玻璃与发射波长为400nm的紫光激光二极管进行封装，即可获得一种绿色光源。 The chemical composition synthesized in Example 6 is selected as Ba 0.95 Eu 0.05 ScSiO 3 N green fluorescent material. Mix the above-mentioned materials with low-melting-point glass powder according to the mass ratio of 1:1, put the above-mentioned mixture in a flat-bottomed crucible made of metal titanium with a bottom diameter of 10mm, and sinter at 700°C for 0.5h in an air atmosphere, and then wait for the sample to cool , a green fluorescent glass can be obtained. A green light source can be obtained by packaging the above-mentioned green fluorescent glass with a violet laser diode with an emission wavelength of 400 nm.
表1材料发射光谱数据表(使用400nm的紫光激发)Table 1 Material emission spectrum data table (using 400nm purple light excitation)
Figure PCTCN2021143664-appb-000001
Figure PCTCN2021143664-appb-000001
Figure PCTCN2021143664-appb-000002
Figure PCTCN2021143664-appb-000002
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节，在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，这些简单变型均属于本发明的保护范围。The preferred embodiments of the present invention have been described in detail above, but 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 solutions of the present invention. These simple modifications All belong to the protection scope of the present invention.
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合。为了避免不必要的重复，本发明对各种可能的组合方式不再另行说明。In addition, it should be noted that the various specific technical features described in the above specific implementation manners may be combined in any suitable manner if there is no contradiction. In order to avoid unnecessary repetition, various possible combinations are not further described in the present invention.
此外，本发明的各种不同的实施方式之间也可以进行任意组合，只要其不违背本发明的思想，其同样应当视为本发明所公开的内容。In addition, various combinations of different embodiments of the present invention can also be combined arbitrarily, as long as they do not violate the idea of the present invention, they should also be regarded as the disclosed content of the present invention.

Claims (10)

  1. 一种氮氧化物绿色荧光材料，其特征在于，所述氮氧化物绿色荧光材料的化学通式为：Ba 1-xEu xLnSiO 3N，其中，Ln为Sc或Y或La或Gd或Lu中一种或多种，且Sc是必须的，且Sc占Ln含量>50％(摩尔比)；0<x≤0.2。 A kind of nitrogen oxide green fluorescent material is characterized in that, the general chemical formula of described nitrogen oxide green fluorescent material is: Ba 1-x Eu x LnSiO 3 N, wherein, Ln is Sc or Y or La or Gd or Lu One or more of them, and Sc is necessary, and Sc accounts for more than 50% of the Ln content (molar ratio); 0<x≤0.2.
  2. 根据权利要求1所述氮氧化物绿色荧光材料，其特征在于：所述氮氧化物绿色荧光材料的化学通式中，0.02<x≤0.05；任选的，所述氮氧化物绿色荧光材料的制备方法包括，将Ba前驱体、Eu前驱体、Ln前驱体和Si前驱体混合，在还原气氛下，进行高温固相反应，得到所述氮氧化物绿色荧光材料，优选的，高温固相反应的温度为1500～1600℃，高温固相反应的时间为4～10h。According to the nitrogen oxide green fluorescent material according to claim 1, it is characterized in that: in the chemical general formula of the nitrogen oxide green fluorescent material, 0.02<x≤0.05; optionally, the nitrogen oxide green fluorescent material The preparation method includes mixing Ba precursors, Eu precursors, Ln precursors and Si precursors, and performing a high-temperature solid-state reaction in a reducing atmosphere to obtain the nitrogen oxide green fluorescent material, preferably, a high-temperature solid-state reaction The temperature is 1500-1600°C, and the high-temperature solid-state reaction time is 4-10 hours.
  3. 根据权利要求1或2所述氮氧化物绿色荧光材料，其特征在于：在紫光激发下，所述氮氧化物绿色荧光材料产生的发射波长主峰范围介于505～535nm、发射光谱的半高宽小于等于90nm；任选的，所述氮氧化物绿色荧光材料在含有200℃高压水蒸汽的密闭容器内老化48h后的发光强度不低于室温时发光强度的75％。According to the nitrogen oxide green fluorescent material according to claim 1 or 2, it is characterized in that: under the excitation of purple light, the emission wavelength main peak range of the nitrogen oxide green fluorescent material is between 505-535nm, and the full width at half maximum of the emission spectrum less than or equal to 90nm; optionally, the luminous intensity of the nitrogen oxide green fluorescent material after aging for 48 hours in a closed container containing high-pressure water vapor at 200°C is no less than 75% of the luminous intensity at room temperature.
  4. 一种如权利要求1-3任一项所述氮氧化物绿色荧光材料的制备方法，其特征在于：将Ba前驱体、Eu前驱体、Ln前驱体和Si前驱体混合，在还原气氛下，进行高温固相反应，得到所述氮氧化物绿色荧光材料。A preparation method for nitrogen oxide green fluorescent material as claimed in any one of claims 1-3, characterized in that: Ba precursor, Eu precursor, Ln precursor and Si precursor are mixed, under reducing atmosphere, A high-temperature solid-state reaction is carried out to obtain the nitrogen oxide green fluorescent material.
  5. 根据权利要求4所述氮氧化物绿色荧光材料的制备方法，其特征在于：Ba前驱体、Eu前驱体、Ln前驱体和Si前驱体中Ba、Eu、Ln和Si的摩尔比(1-X)：X：1：1；所述Ba前驱体选自Ba的碳酸盐、Ba的氧化物或Ba的硝酸盐中的一种或多种；任选的，所述Eu前驱体选自Eu 2O 3；任选的，所述Ln前驱体为Sc 2O 3、Y 2O 3、La 2O 3、Gd 2O 3和Lu 2O 3中的一种或多种，其中Sc 2O 3是必须的；任选的，所述Si前驱体为SiO 2和Si 3N 4；任选的，所述Ba前驱体、Eu前驱体、Ln前驱体和Si前驱体的纯度均不低于99.5wt％。 According to the preparation method of the described nitrogen oxide green fluorescent material of claim 4, it is characterized in that: the mol ratio of Ba, Eu, Ln and Si in Ba precursor, Eu precursor, Ln precursor and Si precursor (1-× ): 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 Eu 2 O 3 ; Optionally, the Ln precursor is one or more of Sc 2 O 3 , Y 2 O 3 , La 2 O 3 , Gd 2 O 3 and Lu 2 O 3 , wherein Sc 2 O 3 is necessary; optionally, the Si precursors are SiO 2 and Si 3 N 4 ; optionally, the purity of the Ba precursor, Eu precursor, Ln precursor and Si precursor is not less than 99.5 wt%.
  6. 根据权利要求4或5所述氮氧化物绿色荧光材料的制备方法，其特征在于：所述高温固相反应的温度为1500～1600℃，高温固相反应的时间为4～10h；According to the preparation method of nitrogen oxide green fluorescent material according to claim 4 or 5, it is characterized in that: the temperature of the high-temperature solid-state reaction is 1500-1600°C, and the time of the high-temperature solid-state reaction is 4-10 hours;
    任选的，所述还原气氛为氨气或氮气氢气混合气，优选的，氮气氢气混合气中氢气的体积含量为10～25％。Optionally, the reducing atmosphere is ammonia or nitrogen-hydrogen mixed gas, preferably, the volume content of hydrogen in the nitrogen-hydrogen mixed gas is 10-25%.
  7. 一种氮氧化物绿色荧光玻璃，其特征在于：所述氮氧化物绿色荧光玻璃是由权利要求1-3任一项所述氮氧化物绿色荧光材料，或者是由权利要求4-6任一项所述制备方法制备得到的氮氧化物绿色荧光材料，与玻璃粉混合后进行高温固相反应得到，优选的，所述氮氧化物绿色荧光材料与所述玻璃粉的质量比为1：1～1：4；所述玻璃粉的熔点为500～800℃。A kind of nitrogen oxide green fluorescent glass, characterized in that: the nitrogen oxide green fluorescent glass is made of the nitrogen oxide green fluorescent material according to any one of claims 1-3, or is made of any one of claims 4-6 The nitrogen oxide green fluorescent material prepared by the preparation method described in the item is obtained by mixing with glass powder and performing a high-temperature solid-state reaction. Preferably, 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. 一种权利要求7所述氮氧化物绿色荧光玻璃的制备方法，其特征在于：将权利要求1-3任一项所述的一种氮氧化物绿色荧光材料，或者是由权利要求4-6任一项所述制备方法制备得到的氮氧化物绿色荧光材料，与玻璃粉混合，在空气气氛下，进行高温固相反应，得到所述氮氧化物绿色荧光玻璃。A preparation method of nitrogen oxide green fluorescent glass according to claim 7, characterized in that: a kind of nitrogen oxide green fluorescent material according to any one of claims 1-3, or by claim 4-6 The nitrogen oxide green fluorescent material prepared by any one of the preparation methods is mixed with glass powder, and subjected to a high-temperature solid-state reaction in an air atmosphere to obtain the nitrogen oxide green fluorescent glass.
  9. 根据权利要求8所述氮氧化物绿色荧光玻璃的制备方法，其特征在于：所述高温固相反应的温度为500～800℃，高温固相反应的时间为0.1～1h；任选的，所述氮氧化物绿色荧光材料与所述玻璃粉的质量比为1：1～1：4；所述玻璃粉的熔点为500～800℃。According to the preparation method of nitrogen oxide green fluorescent glass according to claim 8, it is 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 0.1-1h; optionally, the 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. 一种激光照明器件，其特征在于：所述激光照明器件包含紫光激光二极管及发光层，所述发光层包含权利要求7所述氮氧化物绿色荧光玻璃，或者包含权利要求8或9所述制备方法制备得到的氮氧化物绿色荧光玻璃。A laser lighting device, characterized in that: the laser lighting device includes a violet laser diode and a light-emitting layer, and the light-emitting layer includes the nitrogen oxide green fluorescent glass described in claim 7, or includes the prepared glass according to claim 8 or 9. Methods The nitrogen oxide green fluorescent glass was prepared.
PCT/CN2021/143664 2021-12-31 2021-12-31 Nitrogen oxide green fluorescent material, preparation method, and device WO2023123349A1 (en)

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