WO2018170974A1 - 一种高功率半导体光源激发用玻璃陶瓷及其制备方法和应用 - Google Patents

一种高功率半导体光源激发用玻璃陶瓷及其制备方法和应用 Download PDF

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WO2018170974A1
WO2018170974A1 PCT/CN2017/080641 CN2017080641W WO2018170974A1 WO 2018170974 A1 WO2018170974 A1 WO 2018170974A1 CN 2017080641 W CN2017080641 W CN 2017080641W WO 2018170974 A1 WO2018170974 A1 WO 2018170974A1
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light source
semiconductor light
glass ceramic
glass
power semiconductor
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French (fr)
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王静
余金波
张学杰
司帅晨
梁琼云
陈瑜
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Sun Yat Sen University
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Sun Yat Sen University
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
    • C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B25/00—Annealing glass products
    • C03B25/02—Annealing glass products in a discontinuous way
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0054—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing PbO, SnO2, B2O3
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
    • C03C14/006—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of microcrystallites, e.g. of optically or electrically active material
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/122—Silica-free oxide glass compositions containing oxides of As, Sb, Bi, Mo, W, V, Te as glass formers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21K—NON-ELECTRIC LIGHT SOURCES USING LUMINESCENCE; LIGHT SOURCES USING ELECTROCHEMILUMINESCENCE; LIGHT SOURCES USING CHARGES OF COMBUSTIBLE MATERIAL; LIGHT SOURCES USING SEMICONDUCTOR DEVICES AS LIGHT-GENERATING ELEMENTS; LIGHT SOURCES NOT OTHERWISE PROVIDED FOR
    • F21K9/00—Light sources using semiconductor devices as light-generating elements, e.g. using light-emitting diodes [LED] or lasers
    • F21K9/20—Light sources comprising attachment means
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
    • F21V9/00—Elements for modifying spectral properties, polarisation or intensity of the light emitted, e.g. filters
    • F21V9/30—Elements containing photoluminescent material distinct from or spaced from the light source
    • F21V9/32—Elements containing photoluminescent material distinct from or spaced from the light source characterised by the arrangement of the photoluminescent material
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2204/00—Glasses, glazes or enamels with special properties
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2214/00—Nature of the non-vitreous component
    • C03C2214/16—Microcrystallites, e.g. of optically or electrically active material

Definitions

  • the invention belongs to the technical field of high-power white light laser illumination and display, and more particularly to a glass ceramic for exciting high-power semiconductor light source and a preparation method and application thereof.
  • High-power white light semiconductor light sources are cutting-edge technologies for special lighting and display. Since the high-power semiconductor light source can generate a large amount of heat in a short time, the irradiated material reaches a high temperature higher than 200 ° C, which makes it impossible to package a semiconductor white light source packaged with a conventional semiconductor light source and an organic material such as silica gel. Withstanding such high temperatures, it is impossible to achieve greater lumens and brightness by using high-power semiconductor excitation light excitation, and it is unable to meet the urgent need for special light sources. In order to overcome this practical problem, the use of glass ceramics with both luminescent and encapsulating functions to prepare white light semiconductor light sources has become a new choice.
  • glass has the advantages of high thermal conductivity, adjustable refractive index, and good heat aging resistance. If a glass with an adjustable refractive index, a high transmittance in the visible light region, and a low remelting temperature can be found, it can be better after the composite YAG:Ce 3+ phosphor is made into a YAG:Ce 3+ -PiG composite. holding YAG: Ce 3+ phosphor emitting performance is not affected, the YAG: Ce 3+ -PiG composite material having both fluorescent conversion function, but also with the capsulation function, can actually be applied to a high-power white light source Light conversion encapsulation material.
  • the high-power white light semiconductor light source prepared by using the glass ceramic has a more promising application in the special illumination and display field than the conventional low-power white light semiconductor light source.
  • the invention also provides a method for preparing the above-mentioned high-power semiconductor light source excitation glass ceramic.
  • the invention also provides the application of the above-mentioned high-power semiconductor light source excitation glass ceramic in preparing high-power white light illumination and display light source.
  • the invention provides a glass ceramic for excitation of a high-power semiconductor light source, wherein the composition expression of the glass ceramic is (1-x)A:xB, wherein x is a weight percentage of B, and x ranges from 1 to 30%;
  • a: b: c: d (40 to 60): (15 to 20): (5 to 20): (15 to 20).
  • a:b:c:d (50 to 60): (17.5 to 20): (5 to 10): (17.5 to 20).
  • M is Ca, Ba or Sr.
  • the invention also provides a preparation method of the high-power semiconductor light source excitation glass ceramic, which comprises the following steps:
  • the parent glass powder in S1 and the YAG:Ce 3+ phosphor are mixed according to the weight percentage, and the reaction is melted, and the glass ceramic for exciting the high-power semiconductor light source is obtained by heat preservation, annealing and polishing.
  • the high temperature melting temperature in the step S1 is 900 to 1100 ° C, and the high temperature melting time is 5 min to 60 min.
  • the time of grinding in step S1 is 6 to 24 hours.
  • the temperature of the melting reaction in step S2 is 600 ° C to 750 ° C, the holding time is 10 to 50 min; the annealing temperature is 200 ° C to 400 ° C, and the annealing time is 3 h to 5 h.
  • the invention simultaneously protects the application of the high-power semiconductor light source excitation glass ceramic in preparing high-power white light illumination and display light source.
  • the high power semiconductor light source excitation glass ceramic is combined with a blue semiconductor light source to prepare a high power white light illumination and display light source.
  • the present invention has the following advantages and benefits:
  • the mother glass has a low sintering temperature and a refractive index of 1.81 to 1.88; the mother glass has no crystallization during the preparation of the final product and the mother glass itself does not absorb blue light.
  • the glass ceramic provided by the invention has a laser quantum efficiency of 70-80%, and the light-efficiency of the white light semiconductor light source is 300-400 lm/W in combination with a high-power blue semiconductor light source.
  • the utility model has the advantages of high light conversion efficiency and excellent luminescence performance
  • the preparation method provided by the invention has the advantages of low cost, excellent performance, green pollution-free, and is suitable for large-scale industrial production, and can be applied to an illumination source and a display light source, such as a car headlight.
  • searchlights, projectors, laser cinemas and other fields has great application prospects in the field of high-power white light illumination and display.
  • Figure 1 is the XRD of the precursor glass prepared in Example 1 and the YAG:Ce 3+ -PiG sample.
  • Example 2 is an SEM image of a YAG:Ce 3+ -PiG sample prepared in Example 2.
  • Figure 3 is the excitation and emission spectra of YAG:Ce 3+ -PiG prepared in Example 4 (excitation and emission spectra of YAG:Ce 3+ phosphors, excitation and emission of YAG:Ce 3+ -PiG glass ceramics, respectively) Spectra, where the excitation wavelength is 450 nm and the emission wavelength is 550 nm)
  • Example 4 is an electro-spectral spectrum of a white light laser source prepared by combining YAG:Ce 3+ -PiG prepared in Example 5 with a high-power blue semiconductor light source.
  • FIG. 5 is a graph showing the current versus the current of the laser driving current of the white light laser source prepared by combining YAG:Ce 3+ -PiG prepared in Example 5 with a high power blue semiconductor light source.
  • the pure antimony trioxide (Sb 2 O 3 ), boric acid (H 3 BO 3 ), zinc oxide (ZnO), and potassium carbonate (K 2 CO 3 ) were accurately weighed according to Table 1.
  • the accurately weighed raw materials are ground in an agate mortar for 1 to 2 hours, transferred to a crucible, and then melted in a furnace at 900 ° C for 30 min.
  • the molten glass liquid is poured into a graphite mold and quenched, and the broken glass is taken out, and the broken glass is taken. Grinding was carried out for 6 hours and ground into A powder for use.
  • the XRD curve of YAG:Ce 3+ phosphor is seen in Glassfrit, and the standard card PDF#33-0040 is seen in JPDSS (33-0040). It can be seen that there is no new crystal formation during the synthesis of the glass matrix, and the crystal diffraction peaks in the YAG:Ce 3+ -PiG glass ceramics correspond one-to-one with the diffraction peaks of the standard cards of YAG:Ce 3+ phosphors and YAG. It is indicated that the synthesized YAG:Ce 3+ -PiG glass ceramic (high-power semiconductor light source excitation glass ceramic) contains YAG:Ce 3+ phosphor.
  • the pure antimony trioxide (Sb 2 O 3 ), boric acid (H 3 BO 3 ), zinc oxide (ZnO), and potassium carbonate (K 2 CO 3 ) were accurately weighed according to Table 2.
  • the accurately weighed raw materials are ground in an agate mortar for 1 to 2 hours, transferred to a crucible, and then melted in a furnace at 950 ° C for 15 min.
  • the molten glass is poured into a graphite mold and quenched to remove the broken glass and the broken glass. Grinding was carried out for 6 hours and ground into A powder for use.
  • the dark granular part of the figure is YAG:Ce 3+ phosphor, the light part is glass material;
  • Figure 2b is Figure 2b
  • the EDS spectrum data corresponding to Area1 and Area2, the elements of Area 1 are Y, Al, O, Ce, etc.
  • the elements are Y 3 Al 5 O 12 :Ce 3+ , which does not contain glass components, and the composition of Area 2
  • the elements such as Sb, K, Zn, and O are constituent elements of glass, and do not contain Y 3 Al 5 O 12 :Ce 3+ . It can be seen that the YAG:Ce 3+ phosphor is well present in the glass without corrosion and damage.
  • Pure bismuth trioxide (Sb 2 O 3 ), boric acid (H 3 BO 3 ), zinc oxide (ZnO), sodium carbonate (Na 2 CO 3 ) were accurately weighed according to Table 3.
  • the accurately weighed raw materials are ground in an agate mortar for 1 to 2 hours, transferred to a crucible, and then melted in a furnace at 920 ° C for 30 min.
  • the molten glass liquid is poured into a graphite mold and quenched, and the broken glass is taken out, and the broken glass is taken. Grinding was carried out for 6 hours and ground into A powder for use.
  • Pure bismuth trioxide (Sb 2 O 3 ), boric acid (H 3 BO 3 ), zinc oxide (ZnO), and potassium carbonate (K 2 CO 3 ) were accurately weighed according to Table 4.
  • the accurately weighed raw materials are ground in an agate mortar for 1 to 2 hours, transferred to a crucible, and then melted in a furnace at 950 ° C for 15 min.
  • the molten glass is poured into a graphite mold and quenched to remove the broken glass and the broken glass. Grinding was carried out for 6 hours and ground into A powder for use.
  • Figure 3 is the YAG: Ce 3+ -PiG excitation emission spectra of glass ceramic, an emission spectrum and YAG: Ce 3+ phosphor emission spectra are consistent, the excitation spectrum and YAG: Ce 3+ phosphor excitation spectrum of slight The difference is due to the glass matrix's absorption of light before 400 nm.
  • Pure bismuth trioxide (Sb 2 O 3 ), boric acid (H 3 BO 3 ), zinc oxide (ZnO), and potassium carbonate (K 2 CO 3 ) were accurately weighed according to Table 5.
  • the accurately weighed raw materials are ground in an agate mortar for 1 to 2 hours, transferred to a crucible, and then melted in a furnace at 930 ° C for 20 min.
  • the molten glass liquid is poured into a graphite mold and quenched, and the broken glass is taken out, and the broken glass is taken. Grinding was carried out for 6 hours and ground into A powder for use.
  • FIG. 5 are test data of the sample on the laser semiconductor light source, wherein the spectrum of FIG. 4 is an electroluminescence spectrum diagram under different driving currents, and FIG. 5 is a lumen variation curve corresponding to different driving currents of FIG. 4. The specific data is shown in Table 6:
  • Pure bismuth trioxide (Sb 2 O 3 ), boric acid (H 3 BO 3 ), zinc oxide (ZnO), and lithium carbonate (Li 2 CO 3 ) were accurately weighed according to Table 7.
  • the accurately weighed raw materials are ground in an agate mortar for 1 to 2 hours, transferred to a crucible, and then melted in a furnace at 930 ° C for 20 min.
  • the molten glass liquid is poured into a graphite mold and quenched, and the broken glass is taken out, and the broken glass is taken. Grinding was carried out for 6 hours and ground into A powder for use.

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Abstract

本发明公开了一种高功率半导体光源激发用玻璃陶瓷，所述玻璃陶瓷的组成表达式为(1-x)A:xB，其中，x为B的重量百分比，x的取值范围为1～30％；A为母体玻璃，组成为：aSb2O3-bB2O3-cZnO-dM2O，a、b、c、d均为摩尔百分比，a+b+c+d＝100％，M2O中M代表碱金属，M2O为碱金属氧化物或碱金属碳酸盐；B为YAG:Ce3+荧光粉。本发明提供的母体玻璃具有较低的重熔温度，母体玻璃在制备最终产物过程中无析晶且母体玻璃本身对蓝光没有吸收。产物玻璃陶瓷与高功率蓝光半导体光源结合制备出白光半导体光源的光效为300～400lm/W。本发明提供的制备方法成本低廉、性能优异、绿色无污染、适宜于大规模工业化生产等优点，能够应用在照明光源和显示光源，如汽车大灯、探照灯、投影仪、激光电影院等领域。

Description

一种高功率半导体光源激发用玻璃陶瓷及其制备方法和应用 技术领域
本发明属于高功率白光激光照明与显示技术领域，更具体地，涉及一种高功率半导体光源激发用玻璃陶瓷及其制备方法和应用。
背景技术
高功率白光半导体光源是特殊照明与显示的前沿技术。由于高功率的半导体光源能够短时间内产生大量的热，使得被照射的材料达到高于200℃的高温，这使得采用传统的半导体光源与硅胶等有机材料封装的半导体白光光源的封装材料因无法承受如此高的温度，而无法通过使用高功率的半导体激发光激发而实现更大的流明和亮度，亦无法满足人们对特殊光源的迫切需求。为克服这一实用化难题，采用兼具发光与封装功能的玻璃陶瓷制备白光半导体光源成为新的选择。众所周知，玻璃具有热导率较高，折射率可调，耐热老化性能好等优势。若能找到一种折射率可调、可见光区的透过率高、重熔温度低的玻璃，在复合YAG:Ce3+荧光粉制成YAG:Ce3+-PiG复合材料后，能够较好的保持YAG:Ce3+荧光粉的发光性能不受影响，则该YAG:Ce3+-PiG复合材料既具有荧光转换功能，又具有封装功能，是一种可以实际应用于高功率白光光源的光转换封装材料。用该玻璃陶瓷制备出的高功率白光半导体光源相较于传统的低功率白光半导体光源，其在特殊照明与显示领域的应用更具前景。
发明内容
本发明的目的在于根据现有技术中的不足，提供了一种高功率半导体光源激发用玻璃陶瓷。
本发明同时提供上述高功率半导体光源激发用玻璃陶瓷的制备方法。
本发明还提供上述高功率半导体光源激发用玻璃陶瓷在制备高功率白光照明与显示光源中的应用。
本发明的目的通过以下技术方案实现：
本发明提供了一种高功率半导体光源激发用玻璃陶瓷，所述玻璃陶瓷的组成表达式为(1-x)A:xB，其中，x为B的重量百分比，x的取值范围为1～30％；A为母体玻璃，组成为：aSb2O3-bB2O3-cZnO-dM2O，a、b、c、d均为摩尔百分比， a+b+c+d＝100％，M2O中M代表碱金属，M2O为碱金属氧化物或碱金属碳酸盐；B为YAG:Ce3+荧光粉。
优选地，a:b:c:d＝(40～60):(15～20):(5～20):(15～20)。
优选地，a:b:c:d＝(50～60):(17.5～20):(5～10):(17.5～20)。
优选地，M为Ca、Ba或Sr。
本发明同时提供所述的高功率半导体光源激发用玻璃陶瓷的制备方法，包括如下步骤：
S1.按照摩尔百分比将母体玻璃的各组成原料混合，高温熔融后，冷却，研磨后得到母体玻璃粉末；
S2.将S1中母体玻璃粉末与YAG:Ce3+荧光粉按照重量百分比混合，熔融反应，经过保温，退火，抛光得到所述高功率半导体光源激发用玻璃陶瓷。
优选地，步骤S1中所述的高温熔融的温度为900～1100℃，高温熔融的时间为5min～60min。
优选地，步骤S1中研磨的时间6～24h。
优选地，步骤S2中熔融反应的温度为600℃～750℃，保温时间为10～50min；退火温度为200℃～400℃，退火时间为3h～5h。
本发明同时保护所述的高功率半导体光源激发用玻璃陶瓷在制备高功率白光照明与显示光源中的应用。
进一步地，所述高功率半导体光源激发用玻璃陶瓷与蓝光半导体光源结合制备高功率白光照明与显示光源。
与现有技术相比，本发明具有如下优点和有益效果：
本发明提供的高功率半导体光源激发用玻璃陶瓷中，母体玻璃熔结温度较低，折射率为1.81～1.88；母体玻璃在制备最终产物过程中无析晶且母体玻璃本身对蓝光没有吸收。本发明提供的玻璃陶瓷的激光量子效率为70～80％，与高功率蓝光半导体光源结合制备出白光半导体光源的光效为300～400lm/W。具有光转换效率高、发光性能优异等特性，本发明提供的制备方法成本低廉、性能优异、绿色无污染、适宜于大规模工业化生产等优点，能够应用在照明光源和显示光源，如汽车大灯、探照灯、投影仪、激光电影院等领域，在高功率白光照明与显示领域有很大的应用前景。
附图说明
图1为实施例1所制备的母体玻璃与YAG:Ce3+-PiG样品的XRD。
图2为实施例2所制备的YAG:Ce3+-PiG样品SEM图。
图3为实施例4所制备的YAG:Ce3+-PiG的激发与发射光谱(分别为YAG：Ce3+荧光粉的激发与发射光谱、YAG:Ce3+-PiG玻璃陶瓷的激发与发射光谱，其中激发波长为450nm，监测发射波长为550nm)
图4为实施例5所制备出的YAG:Ce3+-PiG与高功率蓝光半导体光源结合制备白光激光光源的电致光谱图。
图5为实施例5所制备出的YAG:Ce3+-PiG与高功率蓝光半导体光源结合制备白光激光光源的流明随激光驱动电流的电流变化曲线。
具体实施方式
以下结合具体实施例和附图来进一步说明本发明，但实施例并不对本发明做任何形式的限定。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
除非特别说明，本发明所用试剂和材料均为市购。
实施例1：
B:A＝23:77玻璃陶瓷的合成工艺
表1实施例1母体玻璃的原料组成及合成工艺
原料 Sb2O3 H3BO3 ZnO K2CO3
质量(g) 17.4911 2.1642 0.4070 2.4186
A的组成为a:b:c:d＝60:17.5:5:17.5,如表1所示对应质量。按照表1精确称量分析纯的三氧化二锑(Sb2O3)、硼酸(H3BO3)、氧化锌(ZnO)、碳酸钾(K2CO3)。将精确称量的原料在玛瑙研钵中研磨1～2h后，转移至坩埚中，而后在900℃炉中熔融30min，将熔融玻璃液倒入石墨模具中骤冷，取出碎玻璃，对碎玻璃进行6h研磨，磨成A粉末备用。按照B和A粉末质量分数为23:77进行称量，在玛瑙研钵中充分研磨0.5h，然后倒入坩埚中，并放入700℃炉中熔融30min，再将熔融玻璃液倒入预热的石墨模具中成型，最后再放入350℃炉中退火4h，即可得到样品。再用金刚石线性切割机切制适当的厚度后，抛光至双面达到镜面，即可用得到符合要求的封装用YAG:Ce3+-PiG玻璃陶瓷。其中图1即为所合成 YAG:Ce3+-PiG玻璃陶瓷的XRD图，其中，YAG：Ce3+荧光粉的XRD曲线见Glassfrit，标准卡片PDF#33-0040见JPCDS(33-0040)，可见玻璃基质在合成过程中并未有新的晶体生成，且YAG:Ce3+-PiG玻璃陶瓷中的晶体衍射峰与YAG:Ce3+荧光粉及YAG的标准卡片的衍射峰一一对应，说明合成的YAG:Ce3+-PiG玻璃陶瓷(高功率半导体光源激发用玻璃陶瓷)中含有YAG:Ce3+荧光粉。
实施例2：B:A＝5:95玻璃陶瓷的合成工艺
表2实施例2母体玻璃的原料组成及合成工艺
原料 Sb2O3 H3BO3 ZnO K2CO3
质量(g) 16.0335 2.4733 0.4070 2.7641
A的组成为a:b:c:d＝55:20:5:20,如表2所示对应质量。按照表2精确称量分析纯的三氧化二锑(Sb2O3)、硼酸(H3BO3)、氧化锌(ZnO)、碳酸钾(K2CO3)。将精确称量的原料在玛瑙研钵中研磨1～2h后，转移至坩埚中，而后在950℃炉中熔融15min，将熔融玻璃液倒入石墨模具中骤冷，取出碎玻璃，对碎玻璃进行6h研磨，磨成A粉末备用。按照B和A粉末质量分数为5:95进行称量，在玛瑙研钵中充分研磨0.5h，然后倒入坩埚中，并放入650℃炉中熔融30min，再将熔融玻璃液倒入预热的石墨模具中成型，最后再放入350℃中退火3h，即可得到样品。再用金刚石线性切割机切制适当的厚度后，抛光至双面达到镜面，即可用得到符合要求的封装用YAG:Ce3+-PiG玻璃陶瓷。图2即为该样品的SEM图，图2a为SEM图，图中的深色的颗粒状的部分即为YAG:Ce3+荧光粉，浅色的部分为玻璃原料；图2b为图2a中Area1和Area2对应的EDS能谱数据，Area 1部分的组成元素为Y、Al、O、Ce等元素为Y3Al5O12:Ce3+，不含有玻璃组分，而Area 2部分的组成元素为Sb、K、Zn、O等元素为玻璃的组成元素，不含有Y3Al5O12:Ce3+。可见YAG:Ce3+荧光粉很好的存在于玻璃中，未出现侵蚀和破坏等情况。
实施例3：B:A＝5:95玻璃陶瓷的合成工艺
表3实施例2母体玻璃的原料组成及合成工艺
原料 Sb2O3 H3BO3 ZnO Na2CO3
质量(g) 13.1183 2.1642 1.6282 1.8548
A的组成为a:b:c:d＝60:17.5:5:17.5,如表3所示对应质量。按照表3精确称量分析纯的三氧化二锑(Sb2O3)、硼酸(H3BO3)、氧化锌(ZnO)、碳酸钠(Na2CO3)。将精确称量的原料在玛瑙研钵中研磨1～2h后，转移至坩埚中，而后在920℃炉中熔融30min，将熔融玻璃液倒入石墨模具中骤冷，取出碎玻璃，对碎玻璃进行6h研磨，磨成A粉末备用。按照B和A粉末质量分数为5:95进行称量，在玛瑙研钵中充分研磨0.5h，然后倒入坩埚中，并放入700℃炉中熔融30min，再将熔融玻璃液倒入预热的石墨模具中成型，最后再放入350℃炉中退火4h，即可得到样品。再用金刚石线性切割机切制适当的厚度后，抛光至双面达到镜面，即可用得到符合要求的封装用YAG:Ce3+-PiG玻璃陶瓷。
实施例4：B:A＝5:95玻璃陶瓷的合成工艺
表4实施例4母体玻璃的原料组成及合成工艺
原料 Sb2O3 H3BO3 ZnO K2CO3
质量(g) 11.6607 2.4733 1.6282 2.7641
A的组成为a:b:c:d＝55:20:5:20,如表4所示对应质量。按照表4精确称量分析纯的三氧化二锑(Sb2O3)、硼酸(H3BO3)、氧化锌(ZnO)、碳酸钾(K2CO3)。将精确称量的原料在玛瑙研钵中研磨1～2h后，转移至坩埚中，而后在950℃炉中熔融15min，将熔融玻璃液倒入石墨模具中骤冷，取出碎玻璃，对碎玻璃进行6h研磨，磨成A粉末备用。按照B和A粉末质量分数为5:95进行称量，在玛瑙研钵中充分研磨0.5h，然后倒入氧化铝坩埚中，并放入700℃炉中熔融30min，再将熔融玻璃液倒入预热的石墨模具中成型，最后再放入350℃炉中退火4h，即可得到样品。再用金刚石线性切割机切制适当的厚度后，抛光至双面达到镜面，即可用得到符合要求的封装用YAG:Ce3+-PiG玻璃陶瓷。图3即为YAG:Ce3+-PiG玻璃陶瓷的激发发射光谱，其发射光谱与YAG:Ce3+荧光粉的发射光谱基本吻合，激发光谱与YAG:Ce3+荧光粉的激发光谱略有差异，这是由于玻璃基质对400nm之前的光有吸收。
实施例5：B:A＝23:77玻璃陶瓷的合成工艺
表5实施例5母体玻璃的原料组成及合成工艺
原料 Sb2O3 H3BO3 ZnO K2CO3
质量(g) 14.5759 2.4733 0.8141 2.7641
A的组成为a:b:c:d＝50:20:10:20,如表5所示对应质量。按照表5精确称量分析纯的三氧化二锑(Sb2O3)、硼酸(H3BO3)、氧化锌(ZnO)、碳酸钾(K2CO3)。将精确称量的原料在玛瑙研钵中研磨1～2h后，转移至坩埚中，而后在930℃炉中熔融20min，将熔融玻璃液倒入石墨模具中骤冷，取出碎玻璃，对碎玻璃进行6h研磨，磨成A粉末备用。按照B和A粉末质量分数为23:77进行称量，在玛瑙研钵中充分研磨0.5h，然后倒入氧化铝坩埚中，并放入690℃炉中熔融30min，再将熔融玻璃液倒入预热的石墨模具中成型，最后再放入350℃炉中退火4h，即可得到样品。再用金刚石线性切割机切制适当的厚度后,抛光至双面达到镜面，即可用得到符合要求的封装用YAG:Ce3+-PiG玻璃陶瓷。图4、图5为样品在激光半导体光源上的测试数据，其中图4的光谱图为不同驱动电流下的电致光谱图，图5为图4不同驱动电流对应的流明变化曲线。具体数据见表6所示：
表6样品蓝光半导体光源激发下的效率测试
样品 实施例5
激光内效率 80.1％
流明效率lm/W 366.93
蓝光吸收率 93.6％
实施例6：B:A＝23:77玻璃陶瓷的合成工艺
表7实施例6母体玻璃的原料组成及合成工艺
原料 Sb2O3 H3BO3 ZnO Li2CO3
质量(g) 14.5759 2.4733 0.8141 1.4778
A的组成为a:b:c:d＝50:20:10:20,如表7所示对应质量。按照表7精确称量分析纯的三氧化二锑(Sb2O3)、硼酸(H3BO3)、氧化锌(ZnO)、碳酸锂(Li2CO3)。将精确称量的原料在玛瑙研钵中研磨1～2h后，转移至坩埚中，而后在930℃炉中熔融20min，将熔融玻璃液倒入石墨模具中骤冷，取出碎玻璃，对碎玻璃进行6h研磨，磨成A粉末备用。按照B和A粉末质量分数为23:77进行称量，在玛瑙研钵中充分研磨0.5h，然后倒入氧化铝坩埚中，并放入690℃炉中熔融30min，再将熔融玻璃液倒入预热的石墨模具中成型，最后再放入350℃炉中退火4h，即可得到样品。再用金刚石线性切割机切制适当的厚度后,抛光至双面达到镜面，即可用得到符合要求的封装用YAG:Ce3+-PiG玻璃陶瓷。

Claims (10)

  1. 一种高功率半导体光源激发用玻璃陶瓷，其特征在于，所述玻璃陶瓷的组成表达式为(1-x)A:xB，其中，x为B的重量百分比，x的取值范围为1～30％；A为母体玻璃，组成为：aSb2O3-bB2O3-cZnO-dM2O，a、b、c、d均为摩尔百分比，a+b+c+d＝100％，M2O中M代表碱金属，M2O为碱金属氧化物或碱金属碳酸盐；B为YAG:Ce3+荧光粉。
  2. 根据权利要求1所述的高功率半导体光源激发用玻璃陶瓷，其特征在于，a:b:c:d＝(40～60):(15～20):(5～20):(15～20)。
  3. 根据权利要求2所述的高功率半导体光源激发用玻璃陶瓷，其特征在于，a:b:c:d＝(50～60):(17.5～20):(5～10):(17.5～20)。
  4. 根据权利要求1所述的高功率半导体光源激发用玻璃陶瓷，其特征在于，M为Li、Na或K。
  5. 一种权利要求1所述的高功率半导体光源激发用玻璃陶瓷的制备方法，其特征在于，包括如下步骤：
    S1.按照摩尔百分比将母体玻璃的各组成原料混合，高温熔融后，冷却，研磨后得到母体玻璃粉末；
    S2.将S1中母体玻璃粉末与YAG:Ce3+荧光粉按照重量百分比混合，熔融反应，经过保温，退火，抛光得到所述高功率半导体光源激发用玻璃陶瓷。
  6. 根据权利要求5所述的制备方法，其特征在于，步骤S1中所述的高温熔融的温度为900～1100℃，高温熔融的时间为5min～60min。
  7. 根据权利要求5所述的制备方法，其特征在于，步骤S1中研磨的时间6～24h。
  8. 根据权利要求5所述的制备方法，其特征在于，步骤S2中熔融反应的温度为600℃～750℃，保温时间为10～50min；退火温度为200℃～400℃，退火时间为3h～5h；
  9. 权利要求1至4任一所述的高功率半导体光源激发用玻璃陶瓷在制备高功率白光照明与显示光源中的应用。
  10. 根据权利要求9所述的应用，其特征在于，所述高功率半导体光源激发用玻璃陶瓷与蓝光半导体光源结合制备高功率白光照明与显示光源。
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