WO2013044490A1 - 一种氮化合物发光材料及其制法以及由其制成的照明光源 - Google Patents

一种氮化合物发光材料及其制法以及由其制成的照明光源 Download PDF

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WO2013044490A1
WO2013044490A1 PCT/CN2011/080391 CN2011080391W WO2013044490A1 WO 2013044490 A1 WO2013044490 A1 WO 2013044490A1 CN 2011080391 W CN2011080391 W CN 2011080391W WO 2013044490 A1 WO2013044490 A1 WO 2013044490A1
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light
luminescent material
nitrogen compound
emitting material
nitrogen
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PCT/CN2011/080391
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English (en)
French (fr)
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王海嵩
鲍鹏
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北京宇极科技发展有限公司
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Priority to JP2013535258A priority Critical patent/JP5752257B2/ja
Priority to US13/882,475 priority patent/US8796722B2/en
Priority to PCT/CN2011/080391 priority patent/WO2013044490A1/zh
Priority to KR1020137011101A priority patent/KR101484428B1/ko
Priority to DE112011103246.3T priority patent/DE112011103246B4/de
Publication of WO2013044490A1 publication Critical patent/WO2013044490A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/7729—Chalcogenides
    • C09K11/7731—Chalcogenides with alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/0883—Arsenides; Nitrides; Phosphides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/77348—Silicon Aluminium Nitrides or Silicon Aluminium Oxynitrides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/26—Materials of the light emitting region
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

Definitions

  • the present invention relates to the field of semiconductors, and more particularly to a nitrogen compound luminescent material, a method of preparing the same, and an illumination source made therefrom.
  • GaN-based LED Light-Emitting Diode
  • Solid-state lighting in the 21st century. It has the advantages of small size, low power consumption, long life, mercury-free environment, high efficiency, low maintenance and so on. It can be widely used in various lighting facilities, including indoor lighting, traffic signals/indicators, car taillights/headlights, outdoor large screens, displays and advertising screens, etc., which replace the various bulbs currently used and The trend of fluorescent lights.
  • This new type of green light source will surely become a new generation of lighting system, which has broad and far-reaching significance for energy conservation, environmental protection and improving people's quality of life.
  • White LED manufacturing technology mainly includes: (1) a combination of three monochromatic LEDs (blue, green, red); (2) blue LED + yellow phosphor; (3) ultraviolet LED + red, green and blue phosphor.
  • blue LEDs blue LED + yellow phosphor
  • ultraviolet LED + red, green and blue phosphor there are few phosphors that can be effectively excited by blue LEDs.
  • white light is obtained by using the yttrium aluminum garnet YAG: Ce fluorescent material in combination with the blue LED through the complementary color principle.
  • YAG yttrium aluminum garnet YAG: Ce fluorescent material in combination with the blue LED through the complementary color principle.
  • the color of the light emitted by YAG is yellowish green, only a cool white color with a higher color temperature can be obtained, and the color rendering index needs to be further improved.
  • red phosphors that can be excited by blue light are mainly dominated by sulfides doped with divalent europium.
  • sulfides doped with divalent europium.
  • divalent europium such as (Ca, Sr, Ba)S: Eu 2+ .
  • the sulphide phosphor has poor chemical and thermal stability, easily reacts with moisture in the air, is easily decomposed by heat, and has exhaust gas in the production process, polluting the environment.
  • nitrides composed of SiN4 basic units have attracted extensive attention as substrates for phosphors.
  • the present invention is directed to the defects in the above-mentioned fields, and provides a nitrogen compound red luminescent material which is chemically stable and excellent in luminescent properties, and can be excited by an ultraviolet LED or a blue LED to use a nitrogen compound red luminescent material for a white LED; the excitation wavelength is 200- Between 500nm, the emission wavelength is between 500-800 nm, the luminescence intensity is high, and the temperature characteristics are good.
  • Another object of the present invention is to provide a method of manufacturing the luminescent material, which is simple and easy to handle. Easy to mass produce, non-polluting, and low cost.
  • This manufacturing method can prepare a fine phosphor having high luminous intensity, uniform particles, and a particle diameter of 15 ⁇ m or less.
  • a nitrogen compound luminescent material having a chemical formula of: Wherein M is an alkaline earth metal, 0 ⁇ x ⁇ 0.2; 0 ⁇ y ⁇ 0.5; C is a carbon element.
  • the alkaline earth metal is one or more of Li, Mg, Ca, Sr, Ba.
  • the M must contain a Ca element.
  • the M is a combination of Ca, Sr or Ca, Li.
  • the method for preparing the above nitrogen compound luminescent material comprises the following steps:
  • a metal element containing a M an oxide, a nitride, a nitrate, a carbonate or a halide, a nitride containing a Eu, a nitrate, an oxide or a halide, a nitride containing an A1, an oxide, a nitrate, a carbonate or a halide, a metal element, a nitride, an oxide or a nitrate containing Si, and a simple substance or a compound containing a C element, which are uniformly mixed by grinding to obtain a mixture;
  • the calcined product is further subjected to pulverization, impurity removal, drying, and classification to obtain a nitrogen compound luminescent material.
  • the inert gas in the gas pressure sintering method is nitrogen gas, and the nitrogen pressure is 1-200 atmospheres.
  • the inert gas in the solid phase reaction method is atmospheric nitrogen gas, and the flow rate is 0.1 - 3 liter / minute.
  • the high temperature calcination temperature is 1200 to 1900 ° C
  • the calcination time is 0.5 to 30 hours
  • the calcination may be carried out a plurality of times.
  • the step (1) further comprises a reactive flux, the flux being one or more of a halide containing M or A1 or boric acid.
  • reaction flux is added in an amount of 0.01-10% by weight based on the total weight of the raw materials.
  • the impurity removal comprises pickling or water washing.
  • a white LED illumination source characterized by: comprising a blue LED, a green luminescent material and the above-mentioned red luminescent material.
  • the luminescent material of the present invention can emit red light having a spectrum in the range of 500-800 nm and a maximum emission wavelength of 600-700 nm when excited by an excitation source such as ultraviolet, near-ultraviolet or blue light such as an LED.
  • an excitation source such as ultraviolet, near-ultraviolet or blue light such as an LED.
  • the nitrogen compound phosphor capable of emitting red light under the excitation of ultraviolet-blue light provided by the present invention improves the temperature characteristics and the luminescence intensity of the luminescent material by doping carbon.
  • the invention adopts a simple element of carbon as a reaction raw material, as long as the purpose is to pass the surface with other raw materials.
  • the oxide (MO z ) reacts at a high temperature to reduce the oxygen content of the final nitride product and improve the luminescence property; the reaction formula is: 2MO z + 2zC + mN2 ⁇ 2MN m + 2zCO; (2) the carbon element enters the matrix nitrogen
  • the crystal lattice of the material increases the degree of crystal field splitting, improves the luminescence performance, and improves the luminescence intensity.
  • the compound of the present invention increases the luminescence intensity by reducing the oxygen content of the final product and increasing the phase purity. Since the bonding chemical bond between the C element and the doped Eu element is also mainly a covalent bond (similar to the chemical bond between the N element and the Eu element), the temperature characteristics of the luminescent material are favored.
  • the invention introduces an inert protective gas during the high-temperature roasting process, and the purpose of introducing the shielding gas is to (1) protect certain nitride raw materials and reaction products from decomposition at high temperatures and (2) function as a reducing atmosphere.
  • the inert gas is usually N 2 or a mixture of N 2 and H 2 , and a high pressure or a normal pressure can be used.
  • the raw material Before the high-temperature calcination, the raw material may be mixed with solvent ethanol or n-hexidine to make the raw material mixture more uniform.
  • the flux M or A1 halide or boric acid may be added before calcination. Excessive reaction impurities need to be removed during the post-treatment of the reaction.
  • the impurities are generally oxides containing M or/and A1 or/and Si elements, which can be removed by pickling or water washing, and the remaining impurities. Then it turns into a gas volatilization.
  • the luminescent material synthesized by the invention When the luminescent material synthesized by the invention is excited by an excitation source such as ultraviolet, near ultraviolet or blue light, such as an LED, it can emit red light having a spectrum in the range of 500-800 nm and a maximum emission wavelength of 600-700 nm, and thus can be illuminated with other luminescent materials such as green.
  • the material is coated on the blue LED chip to prepare a novel white LED; and other luminescent materials such as blue and green luminescent materials can be coated on the ultraviolet or near-ultraviolet LED chip to prepare a novel white LED, and the energy conversion is high;
  • Color LEDs can be prepared by matching with blue LEDs, UV LEDs or near-ultraviolet LEDs, or by mixing other luminescent materials.
  • the preparation method of the invention has the advantages of simple process and easy mass production; and the wavelength is adjustable and the luminous intensity is improved by partially replacing the element.
  • the luminescent material synthesis method provided by the invention has the advantages of simple method, easy operation, easy mass production, no pollution, low cost and the like.
  • the luminescent material of the present invention is a nitrogen compound, which has very stable properties and good temperature characteristics.
  • the luminescent material of the present invention has a very wide excitation spectrum (200-500 nm), and the excitation effect is particularly good.
  • the preparation method of the luminescent material provided by the invention is simple and practical, non-polluting, easy to mass-produce, and easy to operate.
  • the white light LED prepared by the invention has high color rendering index, high luminous efficiency and wide color temperature range.
  • Example 1 is an emission spectrum and an excitation spectrum of Example 1. In the figure, the ordinate indicates the luminescence intensity, and the abscissa indicates the luminescence wavelength.
  • 2 is an X-ray diffraction spectrum of Example 1.
  • Figure 3 is a scanning electron micrograph of Example 1.
  • Fig. 4 is an emission spectrum and an excitation spectrum of Example 7; in the figure, the ordinate indicates the luminescence intensity, and the abscissa indicates the luminescence wavelength.
  • Figure 5 is a scanning electron micrograph of Example 7.
  • Fig. 6 is an emission spectrum and an excitation spectrum of Example 11; in the figure, the ordinate indicates the luminescence intensity, and the abscissa indicates the luminescence wavelength.
  • Fig. 7 is a scanning electron micrograph of Example 11.
  • Figure 8 is a graph showing the luminescence spectrum of the white LED illumination source prepared in Example 11. detailed description
  • Example 1 Ca. . 99 AlSiC. 2 N 2 . 9733 : Eu 0 . 01
  • the materials used in the synthesis of Example 1 were Ca 3 N 2 , Si 3 N 4 , A1N, EuN, and high-purity carbon powder. 100 g of the raw materials shown below were weighed and mixed, and 0.5 wt% of CaF 2 was added as a flux.
  • the powder was placed in a mortar and mixed in a glove box (oxygen content ⁇ ?111, moisture content ⁇ lppm).
  • the mortar is made of agate. Loosely mix the powder into the bowl and remove it from the glove box.
  • the tantalum material is molybdenum.
  • the tube furnace was heated after being evacuated and filled with nitrogen, and the heating rate was 10 ° C / min, and the nitrogen pressure was 1 atm. After heating to 1600 ° C, the temperature is kept for 6 hours. After the heat is kept, the power is turned off and the furnace is cooled. The fired sample was taken out, and the fluorescence spectrum and the photograph of the particle morphology were measured after pulverization, grinding, and pickling.
  • Figure 1 shows the luminescence spectrum of Example 1.
  • the excitation spectrum (EX) clearly shows that the material can be excited by blue light as well as ultraviolet light.
  • the emission spectrum (EM) is a broad spectrum with a coverage of 550-800 nm, a full width at half maximum (FWHM) of approximately 90 nm, and an emission peak at 652 nm. Broad spectrum emission spectra indicate 5d to 4f from Eu 2+ The electronic transition, not the electronic transition from Eu 3+ 4f to 4f. Since the raw material uses trivalent Eu (EuN), we believe that Eu 3+ in the raw material is reduced to Eu 2+ under a carbon atmosphere.
  • EuN trivalent Eu
  • Example 1 It can be seen from the luminescence spectrum of the material of Example 1 that the material emits red light and is capable of absorbing blue or ultraviolet light, and is a red phosphor which can be applied to white LEDs.
  • 2 is an X-ray diffraction spectrum of Example 1. It can be judged from the map that the material of Example 1 conforms to JCPDS card No. 39-0747 and has a crystal structure similar to that of CaAlSiN 3 .
  • Figure 3 is a scanning electron micrograph of the material of Example 1.
  • the crystal particles have better crystallinity, the surface of the particles is smooth, the size is relatively uniform, and the average particle size is about 12 ⁇ , which has a slight agglomeration.
  • Example 7 Cao.i9Sro.8AlSiCo.oiN 2 .9867: Euo.oi
  • the materials used in the synthesis of Example 7 were Ca 3 N 2 , Si 3 N 4 , A1N, EuN, and SiC. 100 g of the raw material shown below was weighed and mixed with 0.2 wt% of SrF 2 as a flux.
  • the powder was placed in a mortar and mixed in a glove box (oxygen content ⁇ 2111, moisture content ⁇ lppm) in an agate mortar.
  • the mixed powder was loosely placed in a crucible, and then taken out from the glove box and placed in a high temperature graphite furnace.
  • the tantalum material is boron nitride.
  • the graphite furnace was evacuated (10 - 3 torr). The temperature was raised after charging with nitrogen, the heating rate was 10 ° C / min, and the nitrogen pressure was 10 atm. After heating to 1800 ° C, keep warm for 6 hours. After the heat is over, turn off the power and cool with the furnace.
  • FIG. 4 shows the luminescence spectrum of Example 7.
  • the excitation spectrum (EX) of Example ⁇ was also relatively broad, indicating that the luminescent material could be excited by blue light and ultraviolet light.
  • the emission spectrum (EM) is a broad spectrum with a coverage of 550-850 nm, a full width at half maximum (FWHM) of approximately 88 nm, and an emission peak at 624 nm. Broad spectrum emission spectra indicate 5d to 4f from Eu 2+ The electronic transition, not the electronic transition from Eu 3+ 4f to 4f.
  • Example 7 Compared with Example 1, the emission spectrum of Example 7 produces a blue shift, that is, the emission spectrum shifts to a short wavelength, which is mainly caused by the fact that the lattice volume is increased and the degree of crystal field splitting is decreased, thereby causing Eu.
  • the 5d electron orbital energy of 2+ rises and the emission wavelength becomes shorter.
  • Example 7 had an X-ray diffraction pattern similar to that of Example 1, and it was also confirmed that the material of Example 7 had a crystal structure similar to CaAlSiN 3 . It can be seen from the luminescence spectrum of the material of the embodiment that the material emits red light and is capable of absorbing blue light or ultraviolet light, and is a red phosphor which can be applied to a white light LED.
  • FIG. 5 is a scanning electron micrograph of the material of Example 7.
  • the crystal particles have better crystallinity, the surface of the particles is smooth, the size is relatively uniform, and the average particle size is about 16 ⁇ , which has a slight agglomeration.
  • Example 11 Cao.84Lio.iSro.iAlSiCo.o2N 2 .9733: Euo.oi
  • the materials used in the synthesis of Example 11 were Ca 3 N 2 , Si 3 N 4 , A1N, EuN, Li 3 N and high purity carbon. powder. 100 g of the raw materials shown below were weighed and mixed, and 0.5 wt% of NH 4 F was added as a flux.
  • the powder was placed in a mortar and mixed in a glove box (oxygen content ⁇ 2111, moisture content ⁇ lppm) in an agate mortar.
  • the mixed powder was loosely placed in a crucible, and then taken out from the glove box and placed in a high temperature graphite furnace.
  • the tantalum material is boron nitride.
  • the graphite furnace was heated under a vacuum (10 - 3 torr) and charged with nitrogen, and the heating rate was 10 ° C / min, and the nitrogen pressure was 1 atm. After heating to 1600 ° C, the temperature is kept for 8 hours. After the heat is kept, the power is turned off and the furnace is cooled. The fired sample was taken out, and the fluorescence spectrum and the photograph of the particle morphology were measured after pulverization, grinding, and pickling.
  • FIG. 6 shows the luminescence spectrum of Example 11.
  • the excitation spectrum (EX) of Example 11 was also relatively broad, indicating that the luminescent material could be excited by blue light and ultraviolet light.
  • the absorption of blue light in Example 11 was enhanced.
  • the emission spectrum (EM) is a broad spectrum with a coverage of 550-850 nm, a full width at half maximum (FWHM) of approximately 92 nm, and an emission peak at 642 nm. Broad spectrum emission spectra indicate 5d to 4f from Eu 2+ The electronic transition, not the electronic transition from Eu 3+ 4f to 4f.
  • Example 11 Compared to Example 1, the emission spectrum of Example 11 produced a blue shift, i.e., the emission spectrum shifted toward a short wavelength.
  • Example 7 had an X-ray diffraction pattern similar to that of Example 1, and it was also confirmed that the material of Example 11 had a crystal structure similar to that of CaAlSiN 3 . It can be seen from the luminescence spectrum of the material of the example , that the material emits red light and can absorb blue light or ultraviolet light, and is a red phosphor which can be applied to a white light LED.
  • Figure 7 is a scanning electron micrograph of the material of Example 11.
  • the crystallinity of the crystal particles is relatively good, the surface of the particles is smooth, the size is relatively uniform, the average particle size is about 6 ⁇ , and the dispersibility is relatively high.
  • Example 13 Production of High Color Rendering White LED Electric Light Source A certain amount of the red phosphor (Ca0.84Li0.1Sr0.1AlSiC0.02N2.9733:Eu0.01) of the inventive example 11 was weighed, and the silicate (Sr, Ba) 2Si ⁇ 4: Eu2+ green phosphor and Ethylene Garnet YAG:Ce3+ yellow phosphor, uniformly dispersed in epoxy resin, and the mixture obtained by mixing defoaming treatment is coated on a commercially available blue LED (light emission wavelength) On a chip of 453 nm), after 15 CTC and 0.5 hour drying, the package is completed.
  • the red phosphor Ca0.84Li0.1Sr0.1AlSiC0.02N2.9733:Eu0.01
  • the silicate (Sr, Ba) 2Si ⁇ 4: Eu2+ green phosphor and Ethylene Garnet YAG:Ce3+ yellow phosphor uniformly dispersed in epoxy resin, and the mixture obtained by mixing
  • Fig. 8 shows an illuminating spectrum of a white LED manufactured by using the red phosphor of Example 13. Its optical parameters are shown in Table 2.
  • the red phosphor and other green phosphors described in the present invention are utilized.
  • Al 5 0 12 : Ce 3+ , not limited to the listed phosphors) and yellow phosphors (eg YAG: Ce 3+ , a-sialon: Eu 2+ , La 3 Si 6 N u : Ce 3+ , (Sr, Ba)Si 2 0 2 N 2 :Eu 2+ , not limited to the listed phosphors) are combined in different ratios, and a white LED light source is prepared in combination with a blue LED chip.

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Abstract

一种氮化合物发光材料及其制法以及由其制成的照明光源，属于LED无机发光材料领域。氮化合物发光材料，其化学式为：M1-yEuyAlSiCxN3-4/3x其中，M为Li，Mg，Ca，Sr，Ba中的一种或几种；0<x≤0.2；0<y<0.5；C为碳元素。其制备方法包括将前体混合物在惰性气氛保护下采用气压烧结法或固相反应法进行高温焙烧，产物经粉碎、除杂、烘干、分级得到发光材料。该发光材料被紫外、近紫外或蓝光等激发光源如LED激发时，能发射波谱在500-800nm范围且最大发射波长位于600-700nm的红色光，具有激发波长范围宽、高效、稳定的特点，制备方法简单、易于批量生产、无污染。用上述发光材料配合紫外、近紫外或蓝光LED以及其它发光材料如绿色荧光粉可制得新型白光LED光源。

Description

说明书
一种氮化合物发光材料及其制法以及由其制成的照明光源 技术领域
本发明涉及半导体领域， 特别是涉及一种氮化合物发光材料及其制备方法以及由其制 成的照明光源。
背景技术
GaN基发光二极管 LED (Light-Emitting Diode)是一种被誉为 21世纪固态照明的新型发 光器件， 具有体积小、 省电、 寿命长、 不含污染环境的汞、 高效率、 低维修等优点， 可广 泛用于各种照明设施上， 包括室内照明、 交通信号 /指示灯、 汽车尾灯 /前照灯、 户外用超 大型屏幕、 显示屏和广告屏等， 有取代目前使用的各式灯泡和荧光灯的趋势。 这种新型的 绿色光源必将成为新一代照明***， 对节能、 环保、 提高人们的生活质量等方面具有广泛 而深远的意义。 白光 LED的制造技术主要包括： （1)三种单色 LED (蓝、 绿、 红)的组合； (2) 蓝光 LED +黄色荧光粉； （3) 紫外 LED + 红绿蓝三色荧光粉。 但是， 可被蓝光 LED 有效激发的无机发光材料很少。 目前， 主要以钇铝石榴石 YAG: Ce荧光材料与蓝光 LED 结合通过补色原理得到白光。 但是， 由于 YAG发出的光色偏黄绿， 只能得到色温较高的 冷色调白光， 而且其显色指数有待于进一步提高。为了获得不同色温的白光 (从冷色调到暖 色调)以及更高的显色指数， 需要添加红色荧光粉。
目前，能被蓝光 (420-480nm)激发的红色荧光粉主要以掺杂两价铕的硫化物为主。如 (Ca, Sr, Ba)S: Eu2+。 但是， 硫化物荧光粉的化学性和热稳定性很差， 易与空气中的水份发生 反应， 受热易分解， 而且在生产过程中有废气排出， 污染环境。 最近， 由 SiN4基本单元 构成的氮化物作为荧光粉的基材受到了广泛的关注。 由于较强的共价键性和较大的晶体场 ***， 该类化合物在稀土元素如二价铕的掺杂下能在较长的波长发光， 如发红色光的 M2Si5N8:Eu2+ (M = Sr, Ca, Ba)。 该氮化物红色荧光粉虽然具有很高的量子效率， 但是其 光衰比较严重， 限制了其广泛的使用。 发明内容
本发明针对上述领域的缺陷， 提供一种氮化合物红色发光材料， 其化学性质稳定、 发 光性能优异， 能被紫外 LED或蓝光 LED激发的白光 LED用氮化合物红色发光材料；其激 发波长在 200-500nm之间， 发光波长在 500-800 nm之间， 发光强度高， 温度特性好。
本发明的另一目的是提供一种制造该发光材料的方法， 该制造方法简单、 易于操作、 易于量产、 无污染、 成本低。 该制造方法可以制备高发光强度、 颗粒均匀、 粒径在 15μηι 以下的微细荧光粉。
本发明的再一目的是提供一种由该发光材料所制成的白光 LED照明光源， 其显色指数 高， 发光效率高， 色温范围宽。
一种氮化合物发光材料， 其化学式为：
Figure imgf000003_0001
其中， M为碱土金属， 0<x<0.2; 0<y<0.5; C为碳元素。
所述碱土金属为 Li, Mg, Ca, Sr, Ba中的一种或几种。
所述 M必须含有 Ca元素。
所述 M为 Ca, Sr组合或 Ca, Li组合。
所述 0·01≤χ≤0·1 ; 0≤y≤0.1。
上述氮化合物发光材料的制备方法， 包括如下步骤：
(1)用含 M的金属单质、 氧化物、 氮化物、 硝酸盐、 碳酸盐或者卤化物， 含 Eu的氮化物、 硝酸盐、 氧化物或者卤化物， 含 A1 的氮化物、 氧化物、 硝酸盐、 碳酸盐或者卤化物， 含 Si的金属单质、氮化物、 氧化物或者硝酸盐， 以及含 C元素的单质或者化合物为原料， 研 磨混合均匀， 得到混合物；
(2)将混合物在惰性气体保护下用气压烧结法或固相反应法进行高温焙烧，得到焙烧产物；
(3)将焙烧产物再经粉碎、 除杂、 烘干、 分级， 即制得氮化合物发光材料。
可选地， 所述气压烧结法中惰性气体为氮气， 氮气压力为 1-200个大气压。
可选地， 所述固相反应法中的惰性气体为常压氮气， 流量为 0.1 - 3 升 /分钟。
可选地， 所述高温焙烧的温度为 1200-1900°C， 焙烧时间为 0.5-30小时， 焙烧可以多 次进行。
可选地， 所述步骤（1 ) 中还添加有反应助熔剂， 所述助熔剂为含 M或者 A1的卤化物 或硼酸中的一种或几种。
可选地， 所述反应助熔剂的添加量为原料总重量的 0.01-10%。
可选地， 所述除杂包括酸洗或水洗。
一种白光 LED照明光源， 其特征在于： 含有蓝光 LED、绿色发光材料和上述的红色发 光材料。
本发明的发光材料， 在被紫外、 近紫外或蓝光等激发光源如 LED激发时， 能发射波谱 在 500-800nm范围且最大发射波长位于 600-700nm的红色光。 本发明提供的能够在紫外- 蓝光的激发下发射红色光的氮化合物荧光粉， 通过掺杂碳元素改善了该发光材料的温度特 性和发光强度。 本发明采用碳元素单质为反应原料， 其只要目的是通过与其它原料表面的 氧化物 （MOz)在高温下反应， 减少最终氮化物产物的氧含量， 提高发光性能； 该反应式 为： 2MOz + 2zC + mN2→2MNm + 2zCO; (2)使碳元素进入基质氮化物材料的晶格， 增加 晶体场***程度， 改善发光性能， 提高发光强度。 本发明的化合物由于减少了最终产物的 氧含量， 提高相纯度， 从而提高发光强度。 由于 C元素与掺杂 Eu元素之间的结合化学键 也是以共价键为主（与 N元素和 Eu元素之间的化学键性相似）， 因此有利于发光材料的温 度特性。
本发明在高温焙烧的过程中通入惰性保护气体， 通入保护气的目的是 (1)保护某些氮化 物原料以及反应产物在高温下发生分解和 (2)起到还原气氛的作用。 惰性气体常采用 N2， 或是采用 N2与 H2的混合气体， 可采用高压， 也可采用常压。 在高温焙烧前， 原料研磨混 合时可加入溶剂乙醇或正己垸使原料混合更均匀， 焙烧前可加入助熔剂 M或者 A1的卤化 物或是硼酸。 反应的后处理过程中需将多余的反应杂质除去， 上述原料经过高温焙烧后， 杂质一般为含 M或 /和 A1或 /和 Si元素的氧化物， 可采用酸洗或水洗除去， 其余的杂质则 化为气体挥发了。
本发明合成的发光材料被紫外、近紫外或蓝光等激发光源如 LED激发时， 能发射波谱 在 500-800nm范围且最大发射波长位于 600-700nm的红色光， 因此可以和其它发光材料 如绿色发光材料涂敷在蓝光 LED芯片上制备出新型的白光 LED; 也可以和其它发光材料 如蓝色、 绿色发光材料涂敷在紫外或近紫外 LED芯片上制备出新型的白光 LED, 能量转 换高； 还可以和蓝光 LED、 紫外 LED或近紫外 LED相匹配， 或混合其他发光材料， 制 备彩色 LED。
本发明制备方法工艺简单， 易于实现量产的目的； 通过部分置换元素的方法实现波长 可调和发光强度的改善。 本发明所提供的发光材料合成方法具有方法简单、 易于操作、 易实现量产、 无污染、 成本低等优点。
本发明的特点是：
(1)本发明的发光材料是氮化合物， 性能非常稳定， 温度特性好。
(2)本发明的发光材料的激发光谱范围非常宽 （200-500nm)， 激发效果都特别好。
(3)本发明所提供的发光材料的制备方法简单实用、 无污染、 易量产、 易操作。
(4)本发明所制备的白光 LED显色指数高， 发光效率高， 色温范围宽。
附图说明
图 1 为实施例 1的发射光谱和激发光谱；图中纵坐标表示发光强度，横坐标表示发光波长。 图 2 为实施例 1的 X-射线衍射图谱。 图 3 为实施例 1的扫描电镜照片。
图 4为实施例 7的发射光谱和激发光谱；图中纵坐标表示发光强度，横坐标表示发光波长。 图 5 为实施例 7的扫描电镜照片。
图 6为实施例 11的发射光谱和激发光谱；图中纵坐标表示发光强度，横坐标表示发光波长。 图 7为实施例 11的扫描电镜照片。
图 8为采用实施例 11所制备的白光 LED照明光源的发光光谱。 具体实施方式
下面结合实施例对本发明进一步的详细说明。
Figure imgf000005_0001
实施例 1 Ca。.99AlSiC。 2N2.9733:Eu0.01 合成实施例 1材料所采用的原料为 Ca3N2, Si3N4, A1N, EuN,和高纯碳粉。称取如下所示 的 100克原料进行混料， 添加 0.5wt% CaF2为助熔剂。
Ca3N2 35.3246 克
Si3N4 33.7048 克
A1N 29.59898克
EuN 1.1984 克
C 0.1733 克
称取上述原料后将粉料置于研钵中在手套箱 （氧含量< ?111，水分含量< lppm) 混合 均匀。 研钵是玛瑙材质。 将混合完毕的粉料松松地分别装入坩埚中， 然后从手套箱取出放 置于高温管式炉中。 坩埚材料是钼材质。 管式炉经抽真空、 充入氮气后开始升温， 升温速 率为 10°C/min， 氮气压力为 1个大气压。 升温至 1600°C后保温 6小时， 保温结束后关闭 电源， 随炉冷却。 取出烧成的样品， 经粉碎、 研磨、 酸洗后测荧光光谱和拍摄颗粒形貌照 片。
图 1给出了实施例 1的发光光谱。 激发光谱 （EX)很清楚地表明， 该材料能够被蓝光 以及紫外光激发。发射光谱（EM)是一个宽谱，覆盖范围为 550-800 nm,其半高宽（FWHM) 大约是 90nm, 发射峰位于 652 nm. 宽谱发射光谱表明是来自于 Eu2+的 5d到 4f的电子跃 迁， 而不是来自 Eu3+的 4f到 4f的电子跃迁。 由于原料采用三价的 Eu (EuN)， 我们认为在 碳气氛条件下原料中的 Eu3+被还原成 Eu2+。 从实施例 1材料的发光光谱可以看出， 该材料 发射红光， 且能够吸收蓝光或者紫外光， 是一种能够应用于白光 LED的红色荧光粉。 图 2 是实施例 1的 X-射线衍射图谱。从图谱可以判定，实施例 1材料符合 JCPDS卡片第 39-0747 号， 具有和 CaAlSiN3—致的晶体结构。
图 3是实施例 1材料的扫描电镜照片。 晶体颗粒的结晶度比较好， 颗粒表面光滑， 大 小比较均一， 平均粒径大约在 12μηι左右， 有轻微的团聚现象。 实施例 7 Cao.i9Sro.8AlSiCo.oiN2.9867:Euo.oi 合成实施例 7材料所采用的原料为 Ca3N2， Si3N4, A1N, EuN，和 SiC。称取如下所示的 100 克原料进行混料， 添加 0.2wt% SrF2为助熔剂。
Ca3N2 5.1761 克
Sr3N2 42.9300克
Si3N4 25.7337 克
A1N 22.5989克
EuN 0.9150 克
SiC 2.6464克
称取上述原料后将粉料置于研钵中在手套箱 （氧含量< 2111，水分含量< lppm)在玛 瑙研钵中混合均匀。 将混合完毕的粉料松松地分别装入坩埚中， 然后从手套箱取出放置于 高温石墨炉中。 坩埚材料是氮化硼材质。 石墨炉经抽真空 （10— 3 torr). 充入氮气后开始升 温， 升温速率为 10°C/min, 氮气压力为 10个大气压。 升温至 1800°C后保温 6小时， 保温 结束后关闭电源， 随炉冷却。 取出烧成的样品， 经粉碎、 研磨、 酸洗后测试荧光光谱和拍 摄颗粒形貌照片。 图 4出了实施例 7发光光谱。 和实施例 1一样， 实施例 Ί的激发光谱 （EX)也比较 宽， 说明该发光材料能够被蓝光以及紫外光激发。 发射光谱 （EM) 是一个宽谱， 覆盖范 围为 550-850 nm， 其半高宽（FWHM)大约是 88nm， 发射峰位于 624 nm. 宽谱发射光谱 表明是来自于 Eu2+的 5d到 4f的电子跃迁， 而不是来自 Eu3+的 4f到 4f的电子跃迁。 相比 较于实施例 1， 实施例 7的发射光谱产生蓝移， 即发射光谱向短波长移动， 这主要是以 Sr 部分取代 Ca以后， 晶格体积增大导致晶体场***程度下降， 从而导致 Eu2+的 5d电子轨道 能量上升， 发射波长变短。 实施例 7具有和实施例 1相似的 X射线衍射图谱， 也证实实施 例 7材料具有和 CaAlSiN3—样的晶体结构。从实施例 Ί材料的发光光谱可以看出，该材料 发射红光， 且能够吸收蓝光或者紫外光， 是一种能够应用于白光 LED的红色荧光粉。 图 5是实施例 7材料的扫描电镜照片。 晶体颗粒的结晶度比较好， 颗粒表面光滑， 大小比 较均一， 平均粒径大约在 16μηι左右， 有轻微的团聚现象。 实施例 11 Cao.84Lio.iSro.iAlSiCo.o2N2.9733:Euo.oi 合成实施例 11材料所采用的原料为 Ca3N2, Si3N4, A1N， EuN, Li3N和高纯碳粉。称取如下所 示的 100克原料进行混料， 添加 0.5wt% NH4F为助熔剂。
Ca3N2 29.2360 克
Sr3N2 6.8558克
Li3N 0.8218克
Si3N4 32.8767 克
A1N 28.8717克
EuN 1.1690 克
C 0.1690 克
称取上述原料后将粉料置于研钵中在手套箱 （氧含量< 2111，水分含量< lppm)在玛 瑙研钵中混合均匀。 将混合完毕的粉料松松地分别装入坩埚中， 然后从手套箱取出放置于 高温石墨炉中。 坩埚材料是氮化硼材质。 石墨炉经抽真空 （10- 3 torr)、 充入氮气后开始升 温， 升温速率为 10°C/min， 氮气压力为 1个大气压。 升温至 1600°C后保温 8小时， 保温 结束后关闭电源， 随炉冷却。 取出烧成的样品， 经粉碎、 研磨、 酸洗后测试荧光光谱和拍 摄颗粒形貌照片。
图 6出了实施例 11发光光谱。和实施例 1一样，实施例 11的激发光谱 （EX)也比较 宽， 说明该发光材料能够被蓝光以及紫外光激发。另外，相比较实施例 1和 7的激发光谱， 实施例 11对蓝光的吸收得到加强。发射光谱（EM)是一个宽谱， 覆盖范围为 550-850 nm， 其半高宽（FWHM)大约是 92nm， 发射峰位于 642 nm. 宽谱发射光谱表明是来自于 Eu2+ 的 5d到 4f的电子跃迁， 而不是来自 Eu3+的 4f到 4f的电子跃迁。相比较于实施例 1， 实施 例 11的发射光谱产生蓝移， 即发射光谱向短波长移动。 实施例 7具有和实施例 1相似的 X 射线衍射图谱， 也证实实施例 11材料具有和 CaAlSiN3—样的晶体结构。 从实施例 Ί材料 的发光光谱可以看出， 该材料发射红光， 且能够吸收蓝光或者紫外光， 是一种能够应用于 白光 LED的红色荧光粉。
图 7是实施例 11材料的扫描电镜照片。 晶体颗粒的结晶度比较好， 颗粒表面光滑， 大小比较均一， 平均粒径大约在 6μηι左右， 分散性比较高。
其它实施例材料的合成采用了实施例 1、 7、 11里描述的方法，但也不限于上述方法。 实施例 13 高显色白光 LED电光源的制造 称 取 一 定 量 的 本 发 明 实 施 例 11 的 红 色 荧 光 粉 (Ca0.84Li0.1Sr0.1AlSiC0.02N2.9733:Eu0.01) , 硅酸盐 (Sr，Ba)2Si〇4: Eu2+绿色荧光粉以及乙 铝石榴石 YAG:Ce3+黄色荧光粉， 均匀分散在环氧树脂中， 经混合脱泡处理后得到的混合 物涂敷在市售的蓝光 LED (发光波长为 453 nm)的芯片上，在经 15CTC和 0.5小时的烘干后， 即完成封装. 蓝光 LED发射的蓝光和荧光粉发射的红光、 黄光和绿光混合后，产生色坐标 为 x = 0.4192， y = 0.4036， 显色指数为 Ra = 94, 对应于色温 T = 3300K的暖白光。 图 8给 出了采用实施例 13红色荧光粉所制造的白光 LED的发光光谱图。 其光学参数如表 2。
表 2 白光 LED实施例的光学参数
Figure imgf000008_0001
根据实施例 13所述的方法和制备白光 LED的常识， 利用本发明所描述的红色荧光 粉和其他绿色荧光粉 （如 SrSi202N2 : Eu2+、 -sialon : Eu2\ Lu3Al5012 : Ce3+, 不限于所列荧光 粉） 以及黄色荧光粉 （如 YAG:Ce3+、 a-sialon:Eu2+、 La3Si6Nu:Ce3+、 （Sr,Ba)Si202N2:Eu2+， 不限于所列荧光粉）进行不同比例的组合， 并结合蓝光 LED芯片制备白光 LED光源。

Claims

权利要求书
1、 一种氮化合物发光材料， 其化学式为： M yEuyAlSiCxN3— 4/3x， 其中， M 为碱土金 属， 0<x≤0.2; 0<y<0.5; C为碳元素。
2、 根据权利要求 1所述的氮化合物发光材料， 所述碱土金属为 Li，Mg, Ca, Sr, Ba中 的一种或几种。
3、 根据权利要求 2所述的氮化合物发光材料， 所述 M为 Ca与其它元素的组合。
4、 根据权利要求 3所述的氮化合物发光材料， 所述 M为 Ca，Sr组合或 Ca，Li组合。
5、 根据权利要求 1-4任一所述的氮化合物发光材料， 其中 0.01≤x≤0.1 ; 0.01≤y≤0.1。
6、 权利要求 1-5任一氮合化物发光材料的制备方法， 包括如下步骤：
(1)用含 M的金属单质、 氧化物、 氮化物、 硝酸盐、 碳酸盐或者卤化物， 含 Eu的氮化物、 硝酸盐、 氧化物或者卤化物， 含 A1 的氮化物、 氧化物、 硝酸盐、 碳酸盐或者卤化物， 含 Si的金属单质、氮化物、 氧化物或者硝酸盐， 以及含 C元素的单质或者化合物为原料， 研 磨混合均勾， 得到混合物；
(2)将混合物在惰性气体保护下用气压烧结法或固相反应法进行高温焙烧，得到焙烧产物；
(3)将焙烧产物再经粉碎、 除杂、 烘干、 分级， 即制得氮化合物发光材料。
7、权利要求 6所述的制备方法，所述气压烧结法中惰性气体为氮气，氮气压力为 1-200 个大气压， 所述固相反应法中的惰性气体为常压氮气， 流量为 0.1 - 3 升 /分钟。
8、 权利要求 6所述的制备方法， 所述高温焙烧的温度为 1200-1900°C， 焙烧时间为 0.5-30小时， 焙烧可以多次进行。
9、 权利要求 6所述的制备方法， 所述步骤 （1 ) 中还添加有反应助熔剂， 所述助熔剂 为含 M或者 A1的卤化物或硼酸中的一种或几种。
10、权利要求 9所述的制备方法，所述反应助熔剂的添加量为原料总重量的 0.01-10%。
11、 权利要求 6所述的制备方法， 所述除杂包括酸洗或水洗。
12、 一种白光 LED照明光源， 其特征在于： 含有蓝光 LED、 绿色发光材料和权利要求 1-5任一所述的红色发光材料。
PCT/CN2011/080391 2011-09-29 2011-09-29 一种氮化合物发光材料及其制法以及由其制成的照明光源 WO2013044490A1 (zh)

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