WO2020052256A1 - 一种多孔荧光陶瓷及其制备方法、发光装置和投影装置 - Google Patents

一种多孔荧光陶瓷及其制备方法、发光装置和投影装置 Download PDF

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WO2020052256A1
WO2020052256A1 PCT/CN2019/086931 CN2019086931W WO2020052256A1 WO 2020052256 A1 WO2020052256 A1 WO 2020052256A1 CN 2019086931 W CN2019086931 W CN 2019086931W WO 2020052256 A1 WO2020052256 A1 WO 2020052256A1
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fluorescent ceramic
ceramic
light
phase
porous
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French (fr)
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周萌
段银祥
张世忠
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Shenzhen Appotronics Corp Ltd
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Appotronics Corp Ltd
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Definitions

  • the invention relates to the technical field of fluorescent ceramics, in particular to a porous fluorescent ceramic and a preparation method thereof, a light emitting device and a projection device.
  • Semiconductor LED (Light Emitting Diode, light emitting diode) or LD (laser Diode, laser diode) lamps have the advantages of energy saving, environmental protection, long life, small size, light weight, sturdy structure, and low operating voltage.
  • mainstream semiconductor lighting devices use blue LEDs or LDs to excite yellow wavelength conversion materials to emit yellow light, and partially unabsorbed blue and yellow light are mixed to achieve white light emission.
  • the main problem with this solution is the uniformity of the emitted white light.
  • the color of the emitted light depends on the ratio of the amount of unabsorbed blue light and converted yellow light.
  • the concentration of the activator in the wavelength conversion material is the same, compared to the blue light perpendicular to the direction of the incident optical axis, the blue light traveling far from the vertical angle has a longer optical path, and the blue light at this angle will be more strongly absorbed and converted into Yellow light, which results in the formation of a so-called "yellow ring" when viewed at a greater angle, which means that the light is not uniform.
  • the main purpose of the present invention is to provide a porous fluorescent ceramic, which aims to solve the technical problems of poor mechanical properties and low light efficiency of the existing porous fluorescent ceramics.
  • the present invention provides a porous fluorescent ceramic.
  • a porous fluorescent ceramic includes a fluorescent ceramic phase and a pore phase dispersed in the fluorescent ceramic phase, and is characterized in that at least a part of the pore phase is located in crystal grains of the fluorescent ceramic phase.
  • the crystal size of the fluorescent ceramic phase is 10-20um.
  • the size of the pore phase is 0.5-1.5um.
  • the porosity of the porous fluorescent ceramic is 1% to 10%. More preferably, the porosity of the porous fluorescent ceramic is 3 to 5%.
  • the fluorescent ceramic phase is a garnet system. More preferably, the fluorescent ceramic phase is Y 3 Al 5 O 12 : Ce or Lu 3 Al 5 O 12 : Ce.
  • the pore phase is at least one of a spherical hole, an oval hole, or an elongated hole.
  • the present invention also provides a light source device, including an excitation light source and any of the porous fluorescent ceramics described above, wherein the excitation light source is capable of emitting excitation light for exciting the porous fluorescent ceramic to emit light. Excited by light.
  • the present invention further provides a projection device, which is characterized in that it includes:
  • a light modulation device that modulates light from the light source device according to image information to form image light
  • a projection optical system that projects the image light.
  • the present invention also provides a method for preparing a fluorescent ceramic, which is characterized by including the following steps:
  • the oxide raw material is weighed according to the stoichiometric ratio of the fluorescent ceramic, and the particle size of the oxide raw material is 1 to 1000 nm, and then an adhesive, a sintering aid and a solvent are added, and the raw material powder is obtained by ball milling for 8 to 24 hours;
  • the raw material powder obtained in S1 is sieved, pre-pressed, and then cold isostatically compacted at 100 to 300 MPa to obtain a ceramic green body;
  • the ceramic green body obtained by S3 is sintered in an inert atmosphere to obtain a fluorescent ceramic.
  • the sintering time is 6 to 10 hours, the sintering temperature is 1550 to 1800 ° C, and the heating rate is 10 to 20 ° C / min.
  • the oxide raw material includes yttrium oxide, cerium oxide, and alumina;
  • the particle diameter of the yttrium oxide and cerium oxide is 20-50 nm;
  • the particle diameter of the alumina is 100-300 nm.
  • the porous fluorescent ceramic of the present invention introduces a pore phase into the ceramic grains, and when the pore phase is located in the crystal grains, it is beneficial to the improvement of the mechanical properties and light efficiency of the ceramic itself.
  • the pore phase inside the ceramic grains will not restrict the growth of ceramic grains.
  • the ceramic grains in the ceramic can grow larger, which is conducive to the improvement of its light efficiency.
  • the phase is introduced into the crystal grain, which avoids the introduction of defects when the pore phase is located at the grain boundary of the ceramic grain, can prevent the ceramic from breaking along the grain boundary, and improves the mechanical properties of the fluorescent ceramic.
  • the fluorescent ceramic of the present invention when applied to a light source device, the light conversion efficiency and mechanical properties of the fluorescent ceramic can also be improved when the pore phase inside the crystal grains can improve light uniformity.
  • FIG. 1 is a schematic structural diagram of an embodiment of the present invention
  • FIG. 2 is a schematic structural diagram of another embodiment of the present invention.
  • FIG. 3 is a schematic structural diagram of a light emitting device according to the present invention.
  • FIG. 4 is an electron micrograph of Embodiment 1 of the present invention.
  • FIG. 5 is another electron microscope image of Embodiment 1 of the present invention.
  • a porous fluorescent ceramic 1 provided by the present invention includes a fluorescent ceramic phase 11 and a pore phase 12 dispersed in the fluorescent ceramic phase 11. At least part of the pore phase 12 is located in the fluorescent ceramic phase. 11 in the grain.
  • the porous fluorescent ceramic 1 is a polycrystalline ceramic
  • the pore phase 12 dispersed in the fluorescent ceramic phase 11 specifically includes a pore phase 121 and a part of the crystalline phase 111 inside the fluorescent ceramic grain 111
  • the pore phase 122 is located at the grain boundary 112 of the fluorescent ceramic.
  • the state of the pore phase in the ceramic can be achieved by controlling the particle diameter of the raw material and the temperature rising program.
  • the pore phases 12 may all be located inside the crystal grains of the fluorescent ceramic.
  • the porous fluorescent ceramic in the above embodiment introduces the pore phase into the ceramic grains, and when the pore phase is located in the crystal grains, it is beneficial to the mechanical performance and light efficiency of the ceramic itself.
  • the pore phase inside the ceramic grains will not restrict the growth of ceramic grains.
  • the ceramic grains in the ceramic can grow larger, which is conducive to the improvement of its light efficiency.
  • the phase is introduced into the crystal grain, which avoids the introduction of defects when the pore phase is located at the grain boundary of the ceramic grain, can prevent the ceramic from breaking along the grain boundary, and improves the mechanical properties of the fluorescent ceramic.
  • the light efficiency referred to here refers to the conversion efficiency of the excited light emitted by the excitation light to excite the fluorescent ceramics; generally speaking, shorter wavelength light is used as the excitation light, such as ultraviolet light, blue light, etc., and the wavelength of the excited light is generally longer than Excitation light, such as green light, yellow light, red light, etc.
  • the grain size of the fluorescent ceramic phase is 10-20um.
  • the grain size range of the fluorescent ceramic in the present invention is obtained through experimental optimization.
  • the grain size particle diameter
  • the grain size is too small, which is not conducive to controlling the pore phase inside the grain.
  • the pore phase will concentrate more on the grain boundary.
  • the particle size is greater than 20um, the mechanical strength of the ceramic will decrease due to the excessive grain size.
  • the mechanical There is a negative correlation between strength and grain size.
  • the grain size of the fluorescent ceramics allows the fluorescent ceramics to obtain higher light conversion efficiency, due to the consideration of the mechanical strength of the ceramics, the grain size should not be larger than 20um.
  • the size of the pore phase is 0.5-1.5um. It can be understood that if the size of the pore phase is too small, that is, less than 0.5 um, it is difficult to maintain stability during the preparation of the fluorescent ceramic, and it will diffuse and collect into a larger pore phase during sintering at high temperature. However, if the pore phase is too large, that is, greater than 1.5um, on the one hand, it is difficult to realize due to the limitation of the preparation process and raw materials, and on the other hand, the light emitted by the excitation light source will be backscattered in the fluorescent ceramic, resulting in available light. Reduce, reduce the light conversion efficiency of the entire fluorescent ceramic or light source device.
  • the porosity of the porous fluorescent ceramic is 1% to 10%. More preferably, the porosity of the porous fluorescent ceramic is 3 to 5%.
  • the "porosity" is defined as a unitless number and represents the proportion of the total volume occupied by the pore phase volume of the article. Specifically, in this embodiment, the ratio of the volume of the pore phase to the volume of the fluorescent ceramic is referred to.
  • the porosity is too small, the transparency of the fluorescent ceramic is too large, the scattering effect on the excitation light is reduced, and the uniform light effect cannot be achieved. When the porosity is too large, the backscatter of the fluorescent ceramic increases, which reduces the light conversion efficiency of the entire fluorescent ceramic or the light source device.
  • backscattering means that the excitation light incident on the fluorescent ceramic is directly scattered out of the fluorescent ceramic from the incident direction (that is, the incident surface) without conversion. Since this part of the backscattered excitation light does not participate in the excitation of the fluorescent ceramic, Therefore, the increase in backscattering reduces the light conversion efficiency of the fluorescent ceramic or the light source device.
  • the key point in the above embodiment is to determine the parameter range of the number of pore phases (that is, porosity) and the size (the size of the pore phases) in the fluorescent ceramics, so that the fluorescent ceramics have uniformity in color and A balance is achieved between scattered and reduced light efficiency, ensuring the overall performance of the fluorescent ceramic.
  • the above porosity range and / or the target average pore phase size range solves this problem and is optimal for scattering.
  • the relevant pore phase can be obtained and maintained during the manufacturing process through appropriate process control.
  • the fluorescent ceramic phase 11 is a garnet system. More preferably, the fluorescent ceramic phase 11 is Y 3 Al 5 O 12 : Ce or Lu 3 Al 5 O 12 : Ce. Y 3 Al 5 O 12 : Ce is also based on cerium-activated yttrium aluminum garnet (Y 3 Al 5 O 12 ), also known as YAG: Ce; of course, erbium can also be doped into the YAG structure to slightly change the emitted light (Gd-YAG: Ce). Cerium ions partially absorb blue light (wavelength of about 420-490 nm) emitted by the excitation light source and re-emit yellow light with a broad spectrum of about 570 nm.
  • the combination of the blue light not involved in the excitation and the yellow light emitted after the excitation provides the required white light.
  • Lu 3 Al 5 O 12 Ce, which is also based on cerium-activated hafnium aluminum garnet (Lu 3 Al 5 O 12 ), is also called LuAG: Ce, which has similar characteristics to YAG: Ce. More details.
  • the pore phase 12 is at least one of a spherical hole, an oval hole, or an elongated hole.
  • shape of the pore phase 12 is generally spherical, which is related to the sintering temperature and time during the preparation process.
  • the actual experimental results show that the pore phases located inside the ceramic grains are more likely to form spherical or oval holes; while the pore phases located at the grain boundaries are more likely to have elongated holes.
  • the invention introduces the pore phase into the inside of the crystal grains of the fluorescent ceramic, and when the pore phase is located in the crystal grains, it is beneficial to the improvement of the mechanical properties and the light efficiency of the ceramic itself. Its light efficiency is improved; on the other hand, the introduction of the pore phase into the grains avoids the introduction of defects when the pore phase is located at the grain boundaries of the ceramic grains, which can prevent the ceramics from breaking along the grain boundaries, and improves the mechanical properties of the fluorescent ceramics.
  • the fluorescent ceramic of the present invention when applied to a light source device, the light conversion efficiency and mechanical properties of the fluorescent ceramic can also be improved when the pore phase inside the crystal grains can improve light uniformity.
  • the second aspect of the present invention also provides a light source device.
  • the light source device includes an excitation light source 2 and any of the porous fluorescent ceramics 1 described above.
  • the excitation light source 2 can emit excitation light for exciting the porous structure.
  • the fluorescent ceramic 1 emits excited light.
  • the excitation light source emits light with a shorter wavelength, such as ultraviolet light, blue light, and the like.
  • the type of the excitation light source may be at least one of an LED (Light Emitting Diode, light emitting diode) or an LD laser diode (Laser diode, laser diode).
  • LED Light Emitting Diode, light emitting diode
  • LD laser diode Laser diode, laser diode
  • other types of existing light sources can also be used as the excitation light source.
  • the setting manner of the light source device may be slightly different.
  • the porous fluorescent ceramic 1 is directly attached to the blue LED light emitting chip, and the porous fluorescent ceramic is selected from YAG: Ce.
  • the light source device is a white light LED light source. The blue light emitted by the blue LED light emitting chip excites the porous fluorescent ceramic on the one hand to obtain a broad spectrum of yellow light, and on the other hand, the unexcited blue light and yellow light are mixed to obtain white light. .
  • the porous fluorescent ceramic 1 can be excited by a blue light LD (laser diode). Since the laser diode has a very high brightness, the light source device receiving the laser light with high brightness is excited by the blue light laser diode. Therefore, the above-mentioned light source device can be applied to the field of projection display.
  • a blue light LD laser diode
  • a third aspect of the present invention also provides a projection device including: the light source device described above; a light modulation device that modulates light from the light source device according to image information to form image light; and projection optics System, the projection optical system projects the image light.
  • the fourth aspect of the present invention also provides a method for preparing a porous fluorescent ceramic.
  • the porous fluorescent ceramics are prepared by wet mixing, tablet molding and atmosphere sintering.
  • the specific preparation process is as follows:
  • the oxide raw material is weighed according to the stoichiometric ratio of the fluorescent ceramic, and the particle size of the oxide raw material is 1 to 1000 nm, and then an adhesive, a sintering aid and a solvent are added, and the raw material powder is obtained by ball milling for 8 to 24 hours;
  • the raw material powder obtained in S1 is sieved, pre-pressed, and then cold isostatically compacted at 100 to 300 MPa to obtain a ceramic green body;
  • the ceramic green body obtained by S3 is sintered in an inert atmosphere to obtain a fluorescent ceramic.
  • the sintering time is 6 to 10 hours, the sintering temperature is 1550 to 1800 ° C, and the heating rate is 10 to 20 ° C / min.
  • the porous fluorescent ceramics are prepared by wet mixing, tabletting and atmosphere sintering.
  • the specific preparation process is as follows:
  • the oxide raw materials are accurately weighed according to the stoichiometric ratio.
  • yttrium oxide (Y 2 O 3 ), aluminum oxide (Al 2 O 3 ), and cerium oxide (CeO 2 ) are specifically mentioned.
  • Ce 3+ in the luminescent ceramics The ion concentration is 0.1 to 0.5%, preferably 0.2 to 0.4%.
  • the cerium oxide (CeO 2 ) raw material is weighed according to a 0.3% metering ratio. It should be noted that the raw materials are yttrium oxide, cerium oxide, and alumina.
  • the particle diameters of the particles are all in the nanometer range of 1 to 1000 nm.
  • the particle diameters of yttrium oxide and cerium oxide are preferably 20 to 50 nm, and the particle diameters of alumina are preferably 100 to 300 nm.
  • the selection of the particle size of the raw materials is very important for controlling the distribution of the pore phase in the fluorescent ceramic phase, and directly affects the size of the pore phase and the proportion of the proportion inside the crystal grains.
  • the adhesive is PVB, the content of which is 2 to 5%; the sintering aid is TEOS, whose content is 0.2 to 0.5%; the solvent is anhydrous ethanol, and the amount is preferably to completely disperse the above raw materials. It is not specifically limited here.
  • dispersants such as PEG, CTAB, and SDS can be optionally added.
  • the ball milling time is 8 to 24 hours, preferably 14 to 18 hours. After mixing, the slurry is poured out into a drying box for drying.
  • the ceramic green body obtained by S3 is sintered in a temperature range of 600 to 1000 ° C. for 4 to 10 hours to remove organic substances such as adhesives and dispersants in the green body.
  • the specific temperature is 1000 ° C.
  • the sintering time is 4 hours.
  • a lower temperature can be used for a longer time, such as a temperature of 600 degrees Celsius, and the sintering time is 10 hours.
  • the ceramic green body obtained by S3 is sintered in an inert atmosphere to obtain a fluorescent ceramic.
  • sintering is performed in a nitrogen atmosphere.
  • the sintering time is 6 to 10 hours
  • the sintering temperature is 1550 to 1800 ° C
  • the heating rate is 10 ⁇ 20 °C / min
  • the size and porosity of pores can be controlled by controlling the sintering time and sintering temperature.
  • the inert atmosphere may also include Ar and the like.
  • the state of the stomata phase in the ceramic can be achieved, and the state of the stomata phase in the ceramic grains can be achieved, which affects the mechanical properties of the ceramic (ceramics are more likely to fracture along the grain boundary ) Important factor.
  • the microstructure of the porous fluorescent ceramic (sample # 1) prepared by using this embodiment is shown in FIGS. 4 and 5.
  • the ceramic grain size of sample No. 1 is about 10-20um
  • the pore phase is closed pores
  • the size of the pore phase is 0.5-1.5um
  • the porosity is 3-5%.
  • the number of the pore phases 121 in the crystal grains 111 of the fluorescent ceramic phase is much larger than that of the pore phases 122 in the grain boundaries 121, and the pore phases 121 in the crystal grains 111 of the fluorescent ceramic phase are circular or oval.
  • yttrium oxide (Y 2 O 3 ), alumina (Al 2 O 3 ), and cerium oxide (CeO 2 ) according to the stoichiometric ratio.
  • the particle size of cerium oxide (CeO 2 ) is 20-50 nm, and yttrium oxide
  • the particle size of the aluminum oxide is 200 to 300 nm, and the particle size of the aluminum oxide is 1 to 2 um. Then add an adhesive, a sintering aid, and a certain amount of a solvent, the amount of which is the same as that of the first embodiment;
  • the ceramic green body obtained by S3 is sintered in a temperature range of 600 to 1000 ° C. for 4 to 10 hours to remove organic substances such as adhesives and dispersants in the green body.
  • the specific temperature of this comparative example is 1000 ° C, and the sintering time is 4 hours.
  • the ceramic green body obtained by S3 is sintered in a temperature range of 600 to 1000 ° C. for 4 to 10 hours to remove organic substances such as adhesives and dispersants in the green body.
  • the specific temperature of this comparative example is 1000 ° C, and the sintering time is 4 hours.
  • the ceramic green body obtained from S3 is sintered in an inert atmosphere to obtain a fluorescent ceramic.
  • sintering is performed in a nitrogen atmosphere.
  • the sintering time is 4-6 hours, the sintering temperature is 1550-1800 ° C, and the heating rate is 5 ⁇ 8 ° C / min.
  • the ceramic grain size of the 2 # sample is 2-10um.
  • the pore phase exists completely between the grain boundaries.
  • the pore phase has a size of 0.2 to 2 um, and the porosity is 3 to 5%.
  • the sample No. 1 # has a higher luminous flux, that is, the porous fluorescent ceramic prepared by the present invention has a higher luminous efficiency.

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Abstract

一种多孔荧光陶瓷及其制备方法、发光装置和投影装置，其中，多孔荧光陶瓷包括荧光陶瓷相以及分散在荧光陶瓷相中的孔相，至少部分孔相位于荧光陶瓷相的晶粒内。位于晶粒内部的孔相能够提高出光均匀性，并能够提高荧光陶瓷的光转换效率和机械性能。

Description

一种多孔荧光陶瓷及其制备方法、发光装置和投影装置 技术领域
本发明涉及荧光陶瓷技术领域，尤其涉及一种多孔荧光陶瓷及其制备方法、发光装置和投影装置。
背景技术
半导体LED(Light Emitting Diode，发光二极管)或者LD(laser Diode，激光二极管)灯具有节能环保、使用寿命长、体积小、重量轻、结构坚固、工作电压低等优点，被誉为是继白炽灯、荧光灯、高强度气体灯之后的第四代照明灯具。目前主流的半导体照明器件是采用蓝光LED或者LD激发黄色波长转换材料发出黄光，部分未吸收的蓝光和黄光混合实现白光出射，该方案存在的主要问题在于出射的白光的均匀性，光源最终出射的光的颜色取决于未吸收的蓝光和转换的黄光的量的比例。在波长转换材料中激活剂浓度相同时，与垂直入射光轴方向的蓝光相比，远离垂直角度的传播的蓝光具有更长的光程，该角度上的蓝光将更强烈地被吸收并转换成黄光，这导致在更大角度处观看时形成所谓的“黄色环”，也即出光不均匀。
为解决形成黄色环的问题，从而获得均匀的白光，在现有的技术中公开了在荧光陶瓷转换材料中引入第二相作为散射中心。但是，荧光陶瓷转换材料中第二相的引入会降低波长转换装置的机械性能或者光效。
上述内容仅用于辅助理解本发明的技术方案，并不代表承认上述内容是现有技术。
发明内容
本发明的主要目的在于提供一种多孔荧光陶瓷，旨在解决现有多孔荧光陶瓷机械性能差和光效低的技术问题。
为实现上述目的，本发明提供一种多孔荧光陶瓷。
一种多孔荧光陶瓷，包括荧光陶瓷相以及分散在所述荧光陶瓷相中的孔相，其特征在于，至少部分所述孔相位于所述荧光陶瓷相的晶粒内。优选地，所述荧光陶瓷相的晶粒大小为10～20um。
优选地，所述孔相的尺寸为0.5～1.5um。
优选地，所述多孔荧光陶瓷的气孔率为1％～10％。更为优选地，所述多孔荧光陶瓷的气孔率为3～5％。
优选地，所述荧光陶瓷相为石榴石体系。更为优选地，所述荧光陶瓷相为Y 3Al 5O 12:Ce或Lu 3Al 5O 12:Ce。
优选地，所述孔相为球形孔、卵圆形孔或长形孔中的至少一种。
此外，第二方面，本发明还提供一种光源装置，其特征在于，包括激发光源和上述任一所述的多孔荧光陶瓷，所述激发光源能够发出激发光用于激发所述多孔荧光陶瓷发出受激发光。
第三方面，本发明还提供一种投影装置，其特征在于，包括：
上述的光源装置，
光调制装置，该光调制装置根据图像信息对来自所述光源装置的光进行调制，从而形成图像光，以及
投影光学系统，该投影光学系统对所述图像光进行投影。
第四方面，本发明还提供一种荧光陶瓷的制备方法，其特征在于，包括如下步骤：
S1：原料混合，
根据荧光陶瓷的化学计量比称取氧化物原料，所述氧化物原料的粒径为1～1000nm，再加入粘接剂、烧结助剂以及溶剂，球磨8～24h，干燥获得原料粉体；
S2：压片成型，
将S1得到的原料粉体过筛，预压成型，然后100～300Mpa冷等静压压实得到陶瓷生坯；
S3：预烧结排除有机物，
将S3得到的陶瓷生坯在600～1000℃的温度范围内预烧结4～10h排除有机物；
S4：陶瓷烧结，
将S3得到的陶瓷坯体置于惰性气氛中进行烧结得到荧光陶瓷，烧结时间为6～10h，烧结温度为1550～1800℃，升温速率为10～20℃/min。
优选地，所述氧化物原料包括氧化钇、氧化铈和氧化铝；
优选地，所述氧化钇、氧化铈的粒径为20～50nm；
优选地，所述氧化铝的粒径为100～300nm。
本发明的一种多孔荧光陶，将孔相引入到陶瓷晶粒内，当孔相位于晶粒内时，对陶瓷本身的机械性能提升和光效提升都是有益的。一方面，位于陶瓷晶粒内部的孔相不会限制陶瓷晶粒的生长，在烧结制备过程中陶瓷中的陶瓷晶粒可以生长更大，有利于其光效的提升；另一方面，将孔相引入晶粒内，避免了孔相位于陶瓷晶粒的晶界时引入缺陷，能够避免陶瓷沿晶界断裂，提高了荧光陶瓷的机械性能。
因此，当本发明的荧光陶瓷应用于光源装置中时，位于晶粒内部的孔相能够提高出光均匀性的情况下，还能够提高荧光陶瓷的光转换效率和机械性能。
附图说明
图1是本发明实施方式的结构示意图；
图2为本发明另一实施方式结构示意图；
图3为本发明的发光装置的结构示意图；
图4为本发明实施例一的一个电镜图；
图5为本发明实施例一的另一个电镜图；
本发明目的的实现、功能特点及优点将结合实施例，参照附图做进一步说明。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，均属于本发明保护的范围。 应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
请参见附图1和附图2，本发明提供的一种多孔荧光陶瓷1，包括荧光陶瓷相11以及分散在所述荧光陶瓷相11中的孔相12，至少部分孔相12位于荧光陶瓷相11的晶粒内。
在一些实施方式中，参见附图2所示，多孔荧光陶瓷1为多晶陶瓷，分散于荧光陶瓷相11中的孔相12具体包括了部分位于荧光陶瓷晶粒111内的孔相121和部分位于荧光陶瓷晶界112的孔相122。
需要说明的是，本发明可以通过控制原料的粒径和升温程序可以实现孔相处于陶瓷内的状态。
优选地，在其他一些实施方式中，孔相12可以全部位于荧光陶瓷的晶粒内部。
需要说明的是，以上实施方式中的多孔荧光陶瓷，将孔相引入到陶瓷晶粒内，当孔相位于晶粒内时，对陶瓷本身的机械性能提升和光效提升都是有益的。一方面，位于陶瓷晶粒内部的孔相不会限制陶瓷晶粒的生长，在烧结制备过程中陶瓷中的陶瓷晶粒可以生长更大，有利于其光效的提升；另一方面，将孔相引入晶粒内，避免了孔相位于陶瓷晶粒的晶界时引入缺陷，能够避免陶瓷沿晶界断裂，提高了荧光陶瓷的机械性能。这里所指的光效是指激发光激发荧光陶瓷所发出的受激发光的转换效率；一般而言，用较短波长的光作为激发光，如紫外光、蓝光等，受激发光波长一般长于激发光，如绿光、黄光、红光等。
在一些具体的实施方式中，荧光陶瓷相的晶粒大小为10～20um。本发明中的荧光陶瓷的晶粒大小范围经过试验优化得到，其中，当晶粒大小(粒径)小于10um时，晶粒尺寸太小，不利于将孔相控制在晶粒内部，当晶粒小于10um时，孔相将更多的集中于晶界；当粒径大于20um时，由于晶粒尺寸过大，陶瓷机械强度将降低；一般而言，在致密的多晶陶瓷中，陶瓷的机械强度与晶粒大小呈负相关。可以理解，虽然荧光陶瓷中晶粒更大的粒径能让荧光陶瓷获得更高的光转换效率，但出于陶瓷机械强度的考虑，晶粒粒径不宜大于20um。通过陶瓷晶粒粒径的控制一方面可以控制孔相位于荧光陶瓷相中 的具体位置，即位于荧光陶瓷晶粒内的孔相的比例，另一方面也可以控制陶瓷的光转换效率及机械性能。
优选地，孔相的尺寸为0.5～1.5um。可以理解如果孔相的尺寸太小，即小于0.5um，其在荧光陶瓷制备过程中难以保持稳定，在高温下烧结过程中将会扩散汇集为较大尺寸的孔相。然而，如果孔相太大，即大于1.5um，一方面由于制备工艺和原料的限制，实现难度较大，另一方面由于激发光源发射的光在荧光陶瓷中会存在后向散射，导致可利用的光减少，降低整个荧光陶瓷或光源装置的光转换效率。
优选地，多孔荧光陶瓷的气孔率为1％～10％。更为优选地，多孔荧光陶瓷的气孔率为3～5％。需要说明的是，此处“气孔率”定义为无单位的数，代表物品的被孔相体积占据的总体积的比例。具体地，本实施例中是指孔相体积与荧光陶瓷体积的比例。同样，气孔率太小，荧光陶瓷的透明度过大，对激发光的散射作用降低，无法实现匀光的作用。气孔率过大，荧光陶瓷的后向散射增大，降低整个荧光陶瓷或光源装置的光转换效率。这里的后向散射是指入射于荧光陶瓷的激发光未经转换被直接从入射方向(也即入射面)散射出荧光陶瓷，由于这部分被后向散射的激发光并没有参与荧光陶瓷激发，因此后向散射增大会降低荧光陶瓷或光源装置的光转换效率。
可以理解，以上实施方式中的关键点是确定荧光陶瓷中的孔相的数目(也即气孔率)和尺寸(孔相的尺寸)的参数范围，以使得荧光陶瓷在颜色均匀性与由于后向散射而减小的光效率之间获得平衡，确保荧光陶瓷的整体性能。并且，上述的气孔率范围和/或的目标平均孔相的尺寸大小范围解决了这个问题且对于散射是最优的，同时也能通过适当的工艺控制在制造过程中获得并保持相关孔相。
在一些具体的实施方式中，荧光陶瓷相11为石榴石体系。更为优选地，荧光陶瓷相11为Y 3Al 5O 12:Ce或Lu 3Al 5O 12:Ce。Y 3Al 5O 12:Ce也即基于铈活化的钇铝石榴石(Y 3Al 5O 12)，也被称为YAG:Ce；当然也可将钆掺杂入YAG结构以轻微改变发射光(Gd-YAG:Ce)的颜色。铈离子部分地吸收由激发光光源发射的蓝光(波长约420-490nm)且重新发射具有570nm左右宽光谱的黄光。一些实施方式中，上述未参与激发的蓝光和受激发后发出的黄光的混合提供了所需的白光。同理，Lu 3Al 5O 12:Ce也即基于铈活化的镥铝石榴石(Lu 3Al 5O 12)，也 被称为LuAG:Ce，其具有与YAG:Ce类似的特性，这里不再赘述。
优选地，孔相12为球形孔、卵圆形孔或长形孔中的至少一种。需要说明的是，孔相12的形状一般而言以球形为主，这与其制备过程中的烧结温度、时间等有关系。事实上，实际的实验结果表明，位于陶瓷晶粒内部的孔相更倾向于形成球形孔或卵圆形孔；而位于晶界的孔相出现长形孔的概率更高。
本发明通过将孔相引入到荧光陶瓷的晶粒内部，孔相位于晶粒内时，对陶瓷本身的机械性能提升和光效提升都是有益的，一方面陶瓷晶粒可以生长更大，有利于其光效的提升；另一方面，将孔相引入晶粒内，避免了孔相位于陶瓷晶粒的晶界时引入缺陷，能够避免陶瓷沿晶界断裂，提高了荧光陶瓷的机械性能。
因此，当本发明的荧光陶瓷应用于光源装置中时，位于晶粒内部的孔相能够提高出光均匀性的情况下，还能够提高荧光陶瓷的光转换效率和机械性能。
本发明第二方面还提供一种光源装置，如附图3所示，光源装置包括激发光源2和上述任一所述的多孔荧光陶瓷1，激发光源2能够发出激发光用于激发所述多孔荧光陶瓷1发出受激发光。
可以理解，一般而言激发光源发出波长较短的光，如紫外光、蓝光等。激发光源的类型可以为LED(LightEmittingDiode，发光二极管)或LD激光二极管(Laser diode，激光二极管)中的至少一种。当然，现有的其他种类的光源也可以作为激发光源。
需要说明的是，在不同的应用场景中，光源装置的设置方式可以略有差异。在一个具体的实施方式中，将多孔荧光陶瓷1直接贴合于蓝光LED发光芯片上，并且多孔荧光陶瓷选用YAG:Ce。该实施方式中，光源装置为一发白光的LED光源，其中，蓝光LED发光芯片所发出的蓝光一方面激发多孔荧光陶瓷获得宽谱黄光，另一方面未激发的蓝光与黄光混合得到白光。
在另一些实施方式中，多孔荧光陶瓷1可以被蓝光LD(激光二极管)激发，由于激光二极管具有很高的亮度，因此采用蓝光激光二极管激发获得受激光的光源装置的亮度高。因此，上述光源装置可以应用于投影显示领域。
本发明第三方面还提供一种投影装置，包括：上述的光源装置；光调制 装置，该光调制装置根据图像信息对来自所述光源装置的光进行调制，从而形成图像光；以及，投影光学系统，该投影光学系统对所述图像光进行投影。
本发明第四方面还提供一种多孔荧光陶瓷的制备方法。
在一些实施方式中采用湿法混料、压片成型及气氛烧结的方式制备多孔荧光陶瓷，具体制备流程如下：
S1：原料混合，
根据荧光陶瓷的化学计量比称取氧化物原料，所述氧化物原料的粒径为1～1000nm，再加入粘接剂、烧结助剂以及溶剂，球磨8～24h，干燥获得原料粉体；
S2：压片成型，
将S1得到的原料粉体过筛，预压成型，然后100～300Mpa冷等静压压实得到陶瓷生坯；
S3：预烧结排除有机物，
将S3得到的陶瓷生坯在600～1000℃的温度范围内预烧结4～10h排除有机物；
S4：陶瓷烧结，
将S3得到的陶瓷坯体置于惰性气氛中进行烧结得到荧光陶瓷，烧结时间为6～10h，烧结温度为1550～1800℃，升温速率为10～20℃/min。
实施例一
本实施例采用湿法混料、压片成型及气氛烧结的方式制备多孔荧光陶瓷，具体制备流程如下：
S1：原料混合
根据化学计量比准确称量氧化物原料，本实施例中具体为氧化钇(Y 2O 3)、氧化铝(Al 2O 3)、氧化铈(CeO 2)；其中，发光陶瓷中Ce 3+离子的浓度为0.1～0.5％，优选0.2～0.4％，本实施例具体为按照0.3％的计量比称取氧化铈(CeO 2)原料；需要说明的是，原料氧化钇、氧化铈、氧化铝的粒径均为纳米级1～1000nm，其中氧化钇、氧化铈的粒径优选为20～50nm，氧化铝的粒径优选100～300nm。原料粒径的选择对于控制孔相在荧光陶瓷相中的分布至关重要，直接影响孔 相的大小和位于晶粒内部的比例大小。
氧化物原料称取后再加入粘接剂、烧结助剂及一定量的溶剂；
本实施例具体地，粘接剂为PVB，其含量为2～5％；烧结助剂为TEOS，其含量为0.2～0.5％；溶剂为无水乙醇，其量以能完全分散上述原料为宜，这里并不具体限定。
此外，可选择性加入分散剂，如PEG、CTAB、SDS等。
球磨时间为8～24h，优选14～18h，待混合均匀后将浆料倒出置于干燥箱进行干燥。
S2：压片成型
将S1得到的混合均匀的干燥的粉体进行过筛以减少物理团聚，称取一定量的粉体进行压片处理；本实施例具体地，先采用10～30MPa单轴向压片成型，后进行100～300Mpa冷等静压压实得到陶瓷生坯。
S3：预烧结排除有机物
将S3得到的陶瓷生坯在600～1000℃的温度范围内烧结4～10h以除去生坯中粘接剂、分散剂等有机物。本实施例具体温度为1000℃，烧结时间为4小时。其他实施例中也可以采用较低的温度配合更长的时间，如温度600摄氏度，烧结时间为10小时。
S4：陶瓷烧结
将S3得到的陶瓷坯体置于惰性气氛中进行烧结得到荧光陶瓷；本实施例具体地，在氮气氛围中进行烧结，烧结时间为6～10h，烧结温度为1550～1800℃，升温速率为10～20℃/min，通过控制烧结时间及烧结温度可以控制气孔的大小及气孔率。可以理解，惰性气氛还可以包括Ar等。
需要说明的是，通过控制原料的粒径和升温程序可以实现气孔相处于陶瓷内的状态，也可以实现气孔相处于陶瓷晶粒内的状态，是影响陶瓷的机械性能(陶瓷更易沿晶界断裂)的重要因素。
采用本实施例制备得到的多孔荧光陶瓷(1#号样品)显微结构如图4和图5所示。
如图4和图5所示，其中1#号样品的陶瓷晶粒大小约为10～20um，孔相为闭气孔，孔相的大小为0.5～1.5um，气孔率为3～5％。其中，位于荧光陶瓷相的晶粒111内的孔相121的数量远大于位于晶界121的孔相122，并且位于 荧光陶瓷相的晶粒111内的孔相121为圆形或卵形。
对比例一
在实施例一的基础上，通过改变部分原料及相关参数的由此制备得到对比例一的2#样品。具体制备流程如下：
S1：原料混合
根据化学计量比准确称量氧化钇(Y 2O 3)、氧化铝(Al 2O 3)、氧化铈(CeO 2)，其中氧化铈(CeO 2)的粒径大小为20～50nm，氧化钇的粒径大小为200～300nm，氧化铝的粒径大小为1～2um。再加入粘接剂、烧结助剂及一定量的溶剂，其添加量与实施例一相同；
S2：压片成型
将S1得到的混合均匀的干燥的粉体进行过筛以减少物理团聚，称取一定量的粉体进行压片处理；本实施例具体地，先采用10～30MPa单轴向压片成型，后进行100～300Mpa冷等静压压实得到陶瓷生坯。
S3：预烧结排除有机物
将S3得到的陶瓷生坯在600～1000℃的温度范围内烧结4～10h以除去生坯中粘接剂、分散剂等有机物。本对比例的具体温度为1000℃，烧结时间为4小时。
S3：预烧结排除有机物
将S3得到的陶瓷生坯在600～1000℃的温度范围内烧结4～10h以除去生坯中粘接剂、分散剂等有机物。本对比例的具体温度为1000℃，烧结时间为4小时。
S4：陶瓷烧结
将S3得到的陶瓷坯体置于惰性气氛中进行烧结得到荧光陶瓷；本实施例具体地，在氮气氛围中进行烧结，烧结时间为4～6h，烧结温度为1550～1800℃，升温速率为5～8℃/min。
2#样品的陶瓷晶粒大小为2～10um。孔相完全存在于晶界间，孔相大小为0.2～2um，气孔率为3～5％。
对1#号样品和2#样品进行对比测试。1#号样品的机械性能强于2#样品；并且，采用蓝光激光器在2.4W的功率下照射样品，并获得其发光的光通量。
具体如表1所示：
表1
样品编号 蓝光功率(w) 流明(lm) CIE_x CIE_y
1# 2.4 508 0.3984 0.5201
2# 2.4 476 0.3957 0.5162
如表1所示，在相同的激发功率情况下，1#号样品具有更高的光通量，也即本发明所制备的多孔荧光陶瓷具备更高光效。
需要说明的是，在本文中，术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含，从而使得包括一系列要素的过程、方法、物品或者系统不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种过程、方法、物品或者系统所固有的要素。在没有更多限制的情况下，由语句“包括一个……”限定的要素，并不排除在包括该要素的过程、方法、物品或者系统中还存在另外的相同要素。
上述本发明实施例序号仅仅为了描述，不代表实施例的优劣。
以上仅为本发明的优选实施例，并非因此限制本发明的专利范围，凡是利用本发明说明书及附图内容所作的等效结构或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围内。

Claims (9)

  1. 一种多孔荧光陶瓷，包括荧光陶瓷相以及分散在所述荧光陶瓷相中的孔相，其特征在于，至少部分所述孔相位于所述荧光陶瓷相的晶粒内。2、如权利要求1所述的多孔荧光陶瓷，其特征在于，所述荧光陶瓷相的晶粒大小为10～20um。
  2. 如权利要求1所述的多孔荧光陶瓷，其特征在于，所述孔相的尺寸为0.5～1.5um。
  3. 如权利要求1所述的多孔荧光陶瓷，其特征在于，所述多孔荧光陶瓷的气孔率为1％～10％。
  4. 如权利要求1所述的多孔荧光陶瓷，其特征在于，所述荧光陶瓷相为石榴石体系。
  5. 如权利要求1所述的多孔荧光陶瓷，其特征在于，所述孔相为球形孔、卵圆形孔或长形孔中的至少一种。
  6. 一种光源装置，其特征在于，包括激发光源和权利要求1～7任一所述的多孔荧光陶瓷，所述激发光源能够发出激发光用于激发所述多孔荧光陶瓷发出受激发光。
  7. 一种投影装置，其特征在于，包括：
    权利要求7所述的光源装置；
    光调制装置，该光调制装置根据图像信息对来自所述光源装置的光进行调制，从而形成图像光；以及
    投影光学系统，该投影光学系统对所述图像光进行投影。
  8. 一种多孔荧光陶瓷的制备方法，其特征在于，包括如下步骤：
    S1：原料混合，
    根据荧光陶瓷的化学计量比称取氧化物原料，所述氧化物原料的粒径为1～1000nm，再加入粘接剂、烧结助剂以及溶剂，球磨8～24h，干燥获得原料粉体；
    S2：压片成型，
    将S1得到的原料粉体过筛，预压成型，然后100～300Mpa冷等静压压实得到陶瓷生坯；
    S3：预烧结排除有机物，
    将S3得到的陶瓷生坯在600～1000℃的温度范围内预烧结4～10h排除有机物；
    S4：陶瓷烧结，
    将S3得到的陶瓷坯体置于惰性气氛中进行烧结得到荧光陶瓷，烧结时间为6～10h，烧结温度为1550～1800℃，升温速率为10～20℃/min。
  9. 如权利要求9所述的制备方法，其特征在于，所述氧化物原料包括氧化钇、氧化铈和氧化铝；
    所述氧化钇、氧化铈的粒径为20～50nm；
    所述氧化铝的粒径为100～300nm。
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20230213172A1 (en) * 2020-06-08 2023-07-06 Ngk Spark Plug Co., Ltd. Fluorescent plate, wavelength conversion member, and light source device
US20240027883A1 (en) * 2022-07-22 2024-01-25 Seiko Epson Corporation Wavelength conversion device, light source device, and projector
US20240158694A1 (en) * 2019-04-11 2024-05-16 Nichia Corporation Method for producing rare earth aluminate sintered body

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021243522A1 (zh) * 2020-06-01 2021-12-09 苏州君诺新材科技有限公司 含气孔的荧光陶瓷的制造方法
CN114455976B (zh) * 2021-12-28 2022-09-09 广州光联电子科技有限公司 荧光玻璃-陶瓷复合材料的制备方法及复合材料
CN117185832A (zh) * 2022-06-01 2023-12-08 深圳市绎立锐光科技开发有限公司 复相荧光陶瓷、复相荧光陶瓷的制备方法以及发光装置

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101851096A (zh) * 2009-04-03 2010-10-06 中国科学院上海硅酸盐研究所 高掺杂Yb,Er:YAG透明陶瓷及其制备方法
EP2397453A1 (en) * 2010-06-18 2011-12-21 Ceské Vysoké Ucení Technické V Praze Method for preparation of synthetic garnets based in luag or yag
CN107474839A (zh) * 2016-06-07 2017-12-15 深圳市光峰光电技术有限公司 一种发光陶瓷

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103913935B (zh) * 2013-01-09 2016-05-25 台达电子工业股份有限公司 用于立体投影装置的光源系统
DE102015102842A1 (de) * 2015-02-27 2016-09-01 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Leuchtstoffkompositkeramik sowie Verfahren zu deren Herstellung

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101851096A (zh) * 2009-04-03 2010-10-06 中国科学院上海硅酸盐研究所 高掺杂Yb,Er:YAG透明陶瓷及其制备方法
EP2397453A1 (en) * 2010-06-18 2011-12-21 Ceské Vysoké Ucení Technické V Praze Method for preparation of synthetic garnets based in luag or yag
CN107474839A (zh) * 2016-06-07 2017-12-15 深圳市光峰光电技术有限公司 一种发光陶瓷

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LI, MING: "Low Temperature Synthesis of YAG Powder and Rapid Fabrication of Transparent YAG Ceramic", CHINA MASTER'S THESES FULL-TEXT DATABASE, ENGINEERING TECHNOLOGY I, no. 3, 15 March 2017 (2017-03-15), pages 7, 8, 18 - 31-38, ISSN: 1674-0246 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20240158694A1 (en) * 2019-04-11 2024-05-16 Nichia Corporation Method for producing rare earth aluminate sintered body
US20230213172A1 (en) * 2020-06-08 2023-07-06 Ngk Spark Plug Co., Ltd. Fluorescent plate, wavelength conversion member, and light source device
US11796156B2 (en) * 2020-06-08 2023-10-24 Niterra Co., Ltd. Fluorescent plate, wavelength conversion member, and light source device
US20240027883A1 (en) * 2022-07-22 2024-01-25 Seiko Epson Corporation Wavelength conversion device, light source device, and projector

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