WO2020147516A1 - 复相荧光陶瓷及其制备方法 - Google Patents

复相荧光陶瓷及其制备方法 Download PDF

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WO2020147516A1
WO2020147516A1 PCT/CN2019/127262 CN2019127262W WO2020147516A1 WO 2020147516 A1 WO2020147516 A1 WO 2020147516A1 CN 2019127262 W CN2019127262 W CN 2019127262W WO 2020147516 A1 WO2020147516 A1 WO 2020147516A1
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magnesium
fluorescent
spinel
alumina
preparation
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English (en)
French (fr)
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李乾
简帅
王艳刚
李屹
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Shenzhen Appotronics Corp Ltd
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Appotronics Corp Ltd
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Definitions

  • This application relates to the technical field of solid-state lighting, and in particular to a multiphase fluorescent ceramic and a preparation method thereof.
  • laser illumination display technology mainly uses blue laser to excite fluorescent materials to obtain fluorescence in other wavelength bands.
  • the performance requirements of fluorescent materials are also continuously improved.
  • fluorescent materials need to have higher light conversion efficiency, high luminous brightness and higher thermal conductivity to carry higher power density blue Laser etc.
  • Fluorescent materials used in laser lighting display technology can be roughly divided into three categories: One is the fluorescent material formed by encapsulating fluorescent powder through organic polymers such as silicone/organic resin. With the increase of the blue laser power, the heat generated by the phosphor encapsulated by the organic matrix in the light conversion process increases sharply, causing the temperature of the fluorescent material itself to rise sharply, resulting in the aging and yellowing of the organic matrix, resulting in loss of light efficiency, Problems such as reduced life span.
  • the second category is fluorescent glass.
  • the encapsulated phosphor which is mainly an inorganic base glass SiO 2 / group of borosilicate.
  • fluorescent glass Compared with organic resins, fluorescent glass has greatly improved heat resistance, high thermal stability, and low color shift, but its thermal conductivity is not significantly improved compared to organic resins.
  • the third category is fluorescent ceramics. Compared with fluorescent materials encapsulated by organic substrates and inorganic glass substrates, fluorescent ceramics have significant advantages in terms of heat resistance and thermal conductivity.
  • This application protects a multi-phase fluorescent ceramic, which includes an alumina matrix, and fluorescent particles and aluminum-magnesium spinel distributed in the alumina matrix, and the aluminum-magnesium spinel is distributed in all areas. Between the alumina grain boundaries in the alumina matrix.
  • the spinel has a granular and/or columnar structure.
  • the grain size of the granular spinel is 0.2-2um
  • the cross-sectional size of the columnar structure spinel is 0.5- 2um
  • the length is 2-10um.
  • the mass ratio of the aluminum-magnesium spinel in the multiphase fluorescent ceramic is 0.5% to 5%.
  • the fluorescent particles account for 38%-65% of the total mass.
  • the diameter of the fluorescent particles is 2-30 um, and the crystal grain size of the alumina is 1-10 um.
  • the powders of alumina, magnesium-containing compounds, and fluorescent particles are mixed after proportioning, and pressed into a block green;
  • the bulk green body is sintered, and the magnesium-containing compound reacts with alumina to form an aluminum-magnesium spinel, thereby forming an aluminum-magnesium spinel including an alumina matrix, and fluorescent particles and aluminum-magnesium spinel distributed in the alumina matrix Multiphase fluorescent ceramics of stone.
  • the diameter of the magnesium-containing compound and alumina powder is 0.05-0.8um.
  • the magnesium-containing compound is magnesium oxide or magnesium nitrate hexahydrate.
  • an adhesive is also mixed, and before sintering the block blank, a debinding process is performed to decompose and remove the adhesive.
  • cold isostatic pressing is performed on the debinding block blank.
  • the mixed powder is first calcined to decompose the magnesium-containing compound into magnesia, and then the calcined component is ground and sieved to obtain a powder that is pressed into a block green.
  • the fluorescent particles account for 38% to 65% of the total mass of the powder, and the aluminum-magnesium spinel accounts for 0.5% to 5% by mass in the prepared multiphase fluorescent ceramic.
  • the multi-phase fluorescent ceramics provided in the present application and the preparation method thereof are provided by arranging spinel in the multi-phase fluorescent ceramics comprising an alumina matrix and fluorescent particles.
  • the spinel is distributed between the alumina grain boundaries and has a low refractive index.
  • the refractive index of the alumina matrix can scatter the excitation light irradiated into the multiphase fluorescent ceramic, which is beneficial to further improve the luminous efficiency of the multiphase fluorescent ceramic.
  • Figure 1 is a schematic diagram of the birefringence of multiphase fluorescent ceramics
  • FIG. 2 is a top view of the structure of an embodiment of the multiphase fluorescent ceramic of the present application.
  • Figure 3 is a cross-sectional view of the structure of the multiphase fluorescent ceramic shown in Figure 2 along the A-A direction;
  • FIG. 5 is a schematic flow chart of a second embodiment of the method for preparing multiphase fluorescent ceramics according to the present application.
  • FIG. 6 is a schematic flow chart of the third embodiment of the preparation method of the multiphase fluorescent ceramic of the present application.
  • Fig. 7 is a schematic flow chart of a fourth embodiment of the preparation method of multiphase fluorescent ceramics according to the present application.
  • the primary purpose of this application is to provide spinel in a multiphase fluorescent ceramic including an alumina matrix and fluorescent particles.
  • the spinel is distributed between the alumina grain boundaries and its refractive index is lower than that of the alumina matrix.
  • the spinel is used to scatter the excitation light irradiated into the composite fluorescent ceramic, which is beneficial to further improve the luminous efficiency of the composite fluorescent ceramic.
  • FIG. 2 is a top view of the structure of an embodiment of the multi-phase fluorescent ceramic of the present application
  • FIG. 3 is a cross-sectional view of the structure of the multi-phase fluorescent ceramic shown in FIG. 2 along the A-A direction.
  • the multiphase fluorescent ceramic 10 includes an alumina matrix 11, and fluorescent particles 12 and spinels 13 distributed in the alumina matrix 11.
  • the alumina matrix 11 is formed of alumina (Al 2 O 3 ) with fine crystal grains, the alumina crystal grain size may be 1-10 um, and the alumina matrix 11 with compact and fine crystal grains has good light transmittance.
  • the size of the phosphor particles 12 is greater than the size of the alumina crystal grains.
  • the diameter D50 of the phosphor particles 12 is about 2-30um.
  • the larger phosphor particles 12 are evenly distributed in the alumina matrix 11 and are protected by the alumina matrix 11.
  • the crystal grains are continuously surrounded.
  • the phosphor particles 12 can absorb excitation light, for example, can be excited by blue light to emit yellow visible light, and the excited visible light passes through the alumina matrix 11 and exits to the outside of the multiphase fluorescent ceramic 10.
  • the size of the spinel 13 is the smallest, and it may be granular, for example, the size is preferably 0.2-2um, or it may have a columnar structure, for example, the cross-sectional size is preferably 0.5-2um and the length is 2-10um.
  • the mass ratio of the spinel 13 in the multiphase fluorescent ceramic 10 may be 0.5% to 5%.
  • spinel 13 can be produced by the sintering reaction of alumina and magnesium-containing oxides (such as magnesium oxide). Alumina and magnesium-containing oxides are generally added in the form of nanoparticles with a particle size of 0.05-0.8um. Then they form magnesia-aluminum spinel particles with a size of 1 to 5um.
  • magnesium oxide will be solid-dissolved into the crystal lattice of aluminum oxide.
  • the amount of magnesium oxide added (that is, the mass ratio) is generally higher than the solid solution limit of the aluminum oxide crystal lattice, that is, excessive magnesium oxide is added in this application. At the same time, increase the holding time during sintering.
  • alumina and magnesia form a magnesia-aluminum spinel phase, which is distributed in the alumina grain boundary, and the resulting second phase (ie, magnesia-aluminum spinel)
  • the phase can greatly inhibit the growth of alumina crystal grains, so that the size of the alumina crystal grains in the fluorescent ceramic prepared in the present application is small, which is beneficial to the uniform distribution of alumina crystal grains.
  • the spinel 13 with a smaller size is distributed between the alumina grain boundaries in the alumina matrix 11, and its refractive index is lower than that of the alumina matrix 11.
  • the ceramic as the matrix has the first phase, and the encapsulated phosphor has the second phase.
  • the second phase phosphor is evenly distributed in the continuous medium alumina phase. Because the alumina belongs to the trigonal crystal system, there are double Refraction phenomenon, as shown in Figure 1, the excitation light will be scattered in the fluorescent ceramic due to birefringence, and the scattered excitation light in the fluorescent ceramic can then excite more phosphors near it, which shows higher luminous efficiency. Therefore, multiphase fluorescent ceramics are more excellent.
  • the spinel 13 is further introduced.
  • the primary role of the spinel 13 is to act as a scattering particle for the excitation light incident on the inside of the multiphase fluorescent ceramic 10 and the inside of the multiphase fluorescent ceramic 10 excited by the excitation light.
  • the emitted visible light plays a role of scattering, thereby increasing the optical path inside the multiphase fluorescent ceramic 10.
  • the light propagating from the luminous center is not easy to escape laterally through the medium in the multiphase fluorescent ceramic 10, and the light will be limited to one In a relatively small area and repeatedly refracted and scattered between different phase media, more light will eventually escape from the surface of the multiphase fluorescent ceramic 10, thereby enhancing the front light emission effect, which is beneficial to further improve the complex Phase fluorescent ceramic 10 luminous efficiency.
  • this application is equivalent to adding spinel 13 as a scattering phase to the existing multiphase fluorescent ceramics to further improve the luminous efficiency of the multiphase fluorescent ceramics.
  • the spinel 13 is distributed between the alumina grain boundaries in the alumina matrix 11, which can also help to improve the compactness of the composite fluorescent ceramic 10.
  • the spinel 13 as the scattering particles is preferably an aluminum-magnesium spinel, which may be the product of the chemical combination of alumina and a magnesium-containing compound during the sintering process.
  • the magnesia-aluminum spinel has stable properties and uniform distribution. Can play a very good scattering effect.
  • this application also protects a method for preparing the multiphase fluorescent ceramics 10, as shown in FIG. 4, which includes the following steps:
  • S42 Sintering the bulk green body, the magnesium-containing compound reacts with alumina to form an aluminum-magnesium spinel, thereby forming an aluminum-magnesium spinel including an alumina matrix, and fluorescent particles and aluminum-magnesium distributed in the alumina matrix Multiphase fluorescent ceramics of spinel.
  • the preparation methods of this application are different.
  • the proportions of alumina, magnesium-containing compounds and fluorescent particles in the mixture will be different, the pressure required for pressing, and the temperature required for vacuum sintering And time, temperature and time of thermal annealing treatment will also be different.
  • the spinel 13 is an aluminum-magnesium spinel as an example, and the preparation principle and process of the multiphase fluorescent ceramic 10 of the present application will be described in conjunction with the methods shown in FIGS. 5-7.
  • the preparation method of the multiphase fluorescent ceramic 10 includes the following steps:
  • the magnesium-containing compound of this embodiment is magnesium oxide powder.
  • the mixture powder is pressed under a pressure of 80MPa into a block green.
  • the formed block blanks (ie, fluorescent ceramic blanks) are debinding in a muffle furnace to discharge the organic ethanol used as a binder.
  • the debinding process is heat preservation at 500°C for 2 hours and 900°C for 4 hours.
  • the fluorescent ceramic green body After the debinding, the fluorescent ceramic green body is subjected to cooling and static pressure treatment under a pressure of 200 MPa to increase the density of the fluorescent ceramic green body.
  • S56 Sintering the bulk green body, the magnesia reacts with alumina to form an aluminum-magnesium spinel, thereby forming an aluminum-magnesium spinel including an alumina matrix, and fluorescent particles and aluminum-magnesium tips distributed in the alumina matrix Multiphase fluorescent ceramics of spar.
  • the fluorescent ceramic blanks Place the fluorescent ceramic blanks in a vacuum furnace with a vacuum of 10 -3 Pa and sinter at 1700°C for 4 hours. After vacuum sintering, the fluorescent ceramic green body is annealed at 1300°C for 10 hours in an air atmosphere. Then, a composite fluorescent ceramic with a certain thickness and rough surface can be formed.
  • the composite fluorescent ceramic is further thinned, for example, to make the thickness less than 100um, and then polished, and finally a usable composite fluorescent ceramic is obtained.
  • the preparation method of the multiphase fluorescent ceramic 10 includes the following steps:
  • the magnesium-containing compound of this embodiment is magnesium nitrate hexahydrate.
  • High-purity nano-grade alumina powder and magnesium hexahydrate are selected, and the purity of both is preferably above 99%, and the magnesium hexahydrate accounts for 10 wt% of the total mass of the powder.
  • alumina balls are used for ball milling and mixing, and the ball milling time is preferably 24 hours.
  • the mixture powder is pressed under a pressure of 80MPa into a block green.
  • S65 Perform cold isostatic pressing on the block blank after debinding.
  • the formed block ie, fluorescent ceramic green body
  • the debinding process is 500°C for 2 hours and 1000°C for 6 hours.
  • the fluorescent ceramic green body After the debinding, the fluorescent ceramic green body is subjected to cooling and static pressure treatment under a pressure of 200 MPa to increase the density of the fluorescent ceramic green body.
  • the fluorescent ceramic blank Place the fluorescent ceramic blank in a vacuum furnace with a vacuum of 10 -3 Pa and sinter at 1730°C for 4 hours. After vacuum sintering, the fluorescent ceramic green body is annealed at 1350°C for 10 hours in an air atmosphere. Then, a composite fluorescent ceramic with a certain thickness and rough surface can be formed.
  • the composite fluorescent ceramic is further thinned, for example, to make the thickness less than 100um, and then polished, and finally a usable composite fluorescent ceramic is obtained.
  • the preparation method of the multiphase fluorescent ceramic 10 includes the following steps:
  • the magnesium-containing compound of this embodiment is magnesium nitrate hexahydrate.
  • High-purity nano-grade alumina powder and magnesium hexahydrate are selected, and the purity of both is preferably above 99%, and magnesium hexahydrate accounts for 8 wt% of the total mass of the powder.
  • alumina balls are used for ball milling and mixing, and the ball milling time is preferably 24 hours.
  • the sieved powder is calcined in a muffle furnace between 500 and 700° C. for 2 to 5 hours to remove organic components in the powder and decompose the hexamer magnesium nitrate into magnesium oxide. After calcination, the powder is ground and passed through a 200-mesh sieve to obtain a powder with better fluidity, and then the powder is loaded for use.
  • S75 Sintering the bulk green body, the magnesia reacts with alumina to form an aluminum-magnesium spinel, thereby forming an aluminum-magnesium spinel including an alumina matrix, and fluorescent particles and aluminum-magnesium tips distributed in the alumina matrix Multiphase fluorescent ceramics of spar.
  • the graphite mold is placed in an SPS (Spark Plasma Sintering, spark plasma sintering) hot pressing furnace, in a vacuum/argon atmosphere, sintered at 1300°C ⁇ 1600°C for 0.5h ⁇ 4h, and the pressure during sintering is 20 ⁇ 180MPa.
  • SPS Spark Plasma Sintering, spark plasma sintering
  • the fluorescent ceramic green body is annealed at 1300°C for 10 hours in an air atmosphere to form a composite fluorescent ceramic with a certain thickness and rough surface.
  • the composite fluorescent ceramic is further thinned, for example, to make the thickness less than 100um, and then polished to obtain a usable composite fluorescent ceramic.
  • the above-mentioned multiphase fluorescent ceramics 10 can be used as light-emitting elements of various types of display panels, including but not limited to OLED (Organic Light-Emitting Diode, Organic Light-Emitting Diode) display panels, or flexible touch display panels.
  • the display panel can be applied to mobile terminals including but not limited to smart phones, PDAs (Personal Digital Assistants, personal digital assistants or tablet computers), as well as wearable devices worn on limbs or embedded in clothing, jewelry, and accessories .
  • first and second in this application are only used for descriptive purposes, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated.
  • the features defined as “first” and “second” may include at least one of the features either explicitly or implicitly.
  • the meaning of “plurality” is at least two, such as two, three, etc., unless specifically defined otherwise. All the directional indicators (such as up, down, left, right, front, back%) in the embodiments of this application are only used to explain the relative positional relationship between the various components in a specific posture (as shown in the drawings) , Movement, etc., if the specific posture changes, the directional indication will also change accordingly.

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Abstract

一种复相荧光陶瓷及其制备方法，通过在包括氧化铝基体和荧光颗粒的复相荧光陶瓷中设置尖晶石，该尖晶石分布于氧化铝晶界之间，能够对照射入复相荧光陶瓷中的激发光进行散射，从而有利于进一步提高复相荧光陶瓷的发光效率。

Description

复相荧光陶瓷及其制备方法 技术领域
本申请涉及固态照明技术领域，具体涉及一种复相荧光陶瓷及其制备方法。
背景技术
目前，激光照明显示技术主要通过蓝色激光激发荧光材料来获取其他波段的荧光。随着激光照明显示技术的不断发展，对荧光材料的性能要求也不断提高，例如，荧光材料需要有较高的光转换效率、发光亮度高以及较高导热性以承载更高功率密度的蓝色激光等。
用于激光照明显示技术中的荧光材料大致可以分为三类：一类是，通过有机硅胶/有机树脂等有机聚合物对荧光粉进行封装所形成的荧光材料。随着蓝色激光功率的增加，有机基体所封装的荧光粉在进行光转换过程中所产生热量急剧增加，致使荧光材料自身的温度大幅上升，导致有机基体老化泛黄，从而引发光效损失、寿命减少等问题。二类是，荧光玻璃。其主要是将荧光粉封装在SiO 2基/硼硅酸盐基的无机玻璃中。相比较于有机树脂，荧光玻璃在耐热性、高热稳定性、低色偏等性能上有很大改善，但是其在导热性能上较有机树脂并无显著性的提高。三类是，荧光陶瓷。相比较于有机基体和无机玻璃基体封装形成的荧光材料，荧光陶瓷无论是在耐热还是热导率上均有显著的优势。
但是，荧光陶瓷在受到激发时，其发光中心相对较少，导致发光效率较差。对于荧光陶瓷而言，如何进一步提高其发光效率仍是业界孜孜不倦的追求。
发明内容
有于此，本申请有必要提供一种复相荧光陶瓷及其制备方法，以有 利于进一步提高其发光效率。
本申请保护一种复相荧光陶瓷，所述复相荧光陶瓷包括氧化铝基体、以及分布于所述氧化铝基体中的荧光颗粒和铝镁尖晶石，所述铝镁尖晶石分布于所述氧化铝基体中的氧化铝晶界之间。
可选的，所述尖晶石为颗粒状和/或柱状结构，优选颗粒状的所述尖晶石的晶粒尺寸为0.2～2um，柱状结构的所述尖晶石的截面尺寸为0.5～2um、长度为2～10um。
可选的，所述铝镁尖晶石在所述复相荧光陶瓷中的质量占比为0.5％～5％。
可选的，所述荧光颗粒占总体质量的38％～65％。
可选的，所述荧光颗粒的直径为2～30um，所述氧化铝的晶粒尺寸为1～10um。
可选的，将氧化铝、含镁化合物、荧光颗粒的粉体配比后混合，并压制成块体素坯；
将所述块体素坯进行烧结，所述含镁化合物与氧化铝反应形成铝镁尖晶石，从而形成包括氧化铝基体、以及分布于所述氧化铝基体中的荧光颗粒和铝镁尖晶石的复相荧光陶瓷。
可选的，所述含镁化合物和氧化铝粉体的直径为0.05～0.8um。
可选的，所述含镁化合物为氧化镁或六水合硝酸镁。
可选的，在混合粉体时还混合有粘接剂，将所述块体素坯进行烧结之前，先进行排胶工艺，将所述粘接剂分解排除。
可选的，在对排胶后的块体素坯进行烧结之前，将排胶后的块体素坯进行冷等静压处理。
可选的，将混合后的粉体先煅烧，使得含镁化合物分解成氧化镁，然后将煅烧后的成分研磨过筛后得到的粉体压制成块体素坯。
可选的，所述荧光颗粒占粉体总体质量的38％～65％，所述铝镁尖晶石在所制得的复相荧光陶瓷中质量占比为0.5％～5％。
本申请提供的复相荧光陶瓷及其制备方法，通过在包括氧化铝基体和荧光颗粒的复相荧光陶瓷中设置尖晶石，该尖晶石分布于氧化铝晶界 之间且其折射率低于氧化铝基体的折射率，能够对照射入复相荧光陶瓷中的激发光进行散射，从而有利于进一步提高复相荧光陶瓷的发光效率。
附图说明
图1是复相荧光陶瓷的双折射示意图；
图2是本申请的复相荧光陶瓷一实施例的结构俯视图；
图3是图2所示的复相荧光陶瓷沿A-A方向的结构剖视图；
图4是本申请复相荧光陶瓷的制备方法第一实施例的流程示意图；
图5是本申请复相荧光陶瓷的制备方法第二实施例的流程示意图；
图6是本申请复相荧光陶瓷的制备方法第三实施例的流程示意图；
图7是本申请复相荧光陶瓷的制备方法第四实施例的流程示意图。
具体实施方式
本申请的首要目的是：在包括氧化铝基体和荧光颗粒的复相荧光陶瓷中设置尖晶石，该尖晶石分布于氧化铝晶界之间，且其折射率低于氧化铝基体的折射率，通过尖晶石对照射入复相荧光陶瓷中的激发光进行散射，以此有利于进一步提高复相荧光陶瓷的发光效率。
基于上述目的，下面将结合本申请实施例的附图，对本申请实施例中的技术方案进行清楚、完整地描述。可以理解的是，此处描述的具体实施例仅用于解释本申请，而非对本申请的限定。在不冲突的情况下，下述各实施例及其中的技术特征可相互组合。另外还需要说明的是，为了便于描述，所述附图中仅示出了与本申请相关的部分而非全部结构。基于本申请的实施例，本领域普通技术人员在没有作出创造性劳动前提下获得的所有其他实施例，都属于本申请保护的范围。
图2是本申请的复相荧光陶瓷一实施例的结构俯视图，图3是图2所示的复相荧光陶瓷沿A-A方向的结构剖视图。请结合图2和图3所示，所述复相荧光陶瓷10包括氧化铝基体11、以及分布于该氧化铝基体11中的荧光颗粒12和尖晶石13。
氧化铝基体11由晶粒细小的氧化铝(Al 2O 3)形成，氧化铝晶粒大 小可以为1～10um，致密且晶粒细小的氧化铝基体11透光性良好。
荧光粉颗粒12的尺寸大于氧化铝晶粒的尺寸，该荧光粉颗粒12的直径D50约为2～30um，较大的荧光粉颗粒12均匀分布于氧化铝基体11中并被氧化铝基体11的晶粒连续包围。荧光粉颗粒12能够吸收激发光，例如可以受到蓝光的激发而发出黄色的可见光，被激发的可见光穿过氧化铝基体11出射到复相荧光陶瓷10的外面。
尖晶石13的尺寸最小，其可以为颗粒状，例如其尺寸优选为0.2～2um，也可以为柱状结构，例如优选其截面尺寸为0.5～2um、长度为2～10um。所述尖晶石13在复相荧光陶瓷10中的质量占比可以为0.5％～5％。其中，尖晶石13可以通过氧化铝和含镁氧化物(例如氧化镁)烧结反应生成，氧化铝和含镁氧化物一般都以纳米颗粒的形貌加入，颗粒尺寸为0.05～0.8um，烧结之后它们形成1～5um大小的镁铝尖晶石颗粒。在烧结过程中，氧化镁会固溶到氧化铝的晶格中，氧化镁的添加量(即质量占比)一般高于氧化铝晶格的固溶极限，即，本申请添加过量氧化镁，于此同时增加烧结时的保温时间，在此条件下，氧化铝和氧化镁生成镁铝尖晶石相，并分布于氧化铝晶界中，所生成的第二相(即镁铝尖晶石相)可对氧化铝晶粒长大起到极大的抑制作用，故而使得本申请所制备的荧光陶瓷中氧化铝晶粒的尺寸较小，利于氧化铝晶粒分布均匀。
尺寸较小的尖晶石13分布于氧化铝基体11中的氧化铝晶界之间，且其折射率低于所述氧化铝基体11的折射率。
复相荧光陶瓷中，作为基体的陶瓷具有第一相，封装的荧光粉具有第二相，第二相荧光粉均匀分布在连续介质氧化铝相中，由于氧化铝属于三方晶系，其存在双折射现象，如图1所示，激发光在荧光陶瓷中会因双折射而发生散射，荧光陶瓷中被散射的激发光进而可以激发其附近更多的荧光粉，其表现为发光效率更高。因此，复相荧光陶瓷更具优异性。
在本申请中，进一步引入尖晶石13，尖晶石13的首要作用是作为散射粒子，对入射到所述复相荧光陶瓷10内部的激发光、以及复相荧光陶瓷10内部受激发光激发而发出的可见光都起到散射作用，以此增 加复相荧光陶瓷10内部的光程，从发光中心开始传播的光线不易通过复相荧光陶瓷10内的介质横向逃逸，这些光会被限制在一个比较小的区域之内并在不同相介质之间反复折射、散射，最终会有更多的光从复相荧光陶瓷10的表面逃逸而出，以此增强正面出光效果，即有利于进一步提高复相荧光陶瓷10的发光效率。也就是说，本申请相当于在现有的复相荧光陶瓷中添加了尖晶石13做散射相，以进一步提高复相荧光陶瓷的发光效率。
另外，所述尖晶石13分布于氧化铝基体11中的氧化铝晶界之间，还可以有利于提高复相荧光陶瓷10的致密性。
作为散射粒子的尖晶石13优选为铝镁尖晶石，其可以是烧结过程中氧化铝和含镁化合物进行化合作用之后的产物，镁铝尖晶石的性质稳定，分布也很均匀，能够起到很好的散射作用。
为了获得上述复相荧光陶瓷，本申请还保护一种制备复相荧光陶瓷10的方法，如图4所示，包括以下步骤：
S41：将氧化铝、含镁化合物、荧光颗粒的粉体配比后混合，并压制成块体素坯。
S42：将所述块体素坯进行烧结，所述含镁化合物与氧化铝反应形成铝镁尖晶石，从而形成包括氧化铝基体、以及分布于所述氧化铝基体中的荧光颗粒和铝镁尖晶石的复相荧光陶瓷。
对于不同的含镁化合物，本申请的制备方法有所区别，例如，氧化铝、含镁化合物和荧光颗粒在混合物中的占比会有所区别，压制所需的压强、真空烧结所需的温度及时间、热退火处理的温度及时间也会有所区别。下面以尖晶石13为铝镁尖晶石为例，并结合图5～图7所示的方法描述本申请复相荧光陶瓷10的制备原理及过程。
实施例1
请参阅图5，所述复相荧光陶瓷10的制备方法包括如下步骤：
S51：对氧化铝和氧化镁混合物进行第一阶段球磨。
本实施例的含镁化合物为氧化镁粉末。
首先，选取高纯度纳米级别的氧化铝粉末和氧化镁粉末，二者纯度 优选均在99％以上，氧化镁占粉体总质量的2wt％。然后，将二者同少量的无水乙醇一同倒入球磨罐中，其中无水乙醇作为分散剂以有助于氧化铝粉末和氧化镁粉末在球磨的过程中均匀混合。所述第一阶段球磨选用氧化铝球进行球磨混料，且球磨时间优选为24h。
S52：将荧光粉加入经第一阶段球磨的混合物并进行第二阶段球磨。
称取一定量的荧光粉，例如Ce:YAG或Ce:LuAG荧光粉，其占总粉体质量的50％，并添加一定量的PVB(聚乙烯醇缩丁醛)乙醇溶液，其中PVB乙醇溶液作为分散剂。在球磨1h之后，将混合物在70℃下进行真空干燥，然后再随即进行研磨、过筛处理，而后装粉待用。
S53：将经过第二阶段球磨的混合物进行压制以制成块体素坯。
将混合物粉体在80MPa压力下压制成块体素坯。
S54：对所述块体素坯进行排胶工艺，将所述粘接剂分解排除。
S55：将排胶后的块体素坯进行冷等静压处理。
将成型的块体素坯(即荧光陶瓷素坯)在马弗炉中排胶处理，以排出其中作为粘接剂的有机物乙醇，该排胶工艺为500℃保温2h以及900℃保温4h。
在排胶结束之后，将荧光陶瓷素坯在200MPa压力下进行冷却静压处理，以提高荧光陶瓷素坯的致密度。
S56：将所述块体素坯进行烧结，所述氧化镁与氧化铝反应形成铝镁尖晶石，从而形成包括氧化铝基体、以及分布于所述氧化铝基体中的荧光颗粒和铝镁尖晶石的复相荧光陶瓷。
将荧光陶瓷素坯置于真空炉中，真空度为10 -3Pa，1700℃下烧结4h。待真空烧结后，将荧光陶瓷素坯在空气气氛下，1300℃退火处理10h。即可形成一定厚度且表面粗糙的复相荧光陶瓷。
本申请进一步对复相荧光陶瓷进行减薄处理，例如使其厚度为100um以下，再进行抛光处理，最后得到可用的复相荧光陶瓷。
实施例2
请参阅图6，所述复相荧光陶瓷10的制备方法包括如下步骤：
S61：对氧化铝和六合硝酸镁混合物进行第一阶段球磨。
本实施例的含镁化合物为六合硝酸镁。
选取高纯度纳米级别的氧化铝粉末和六合硝酸镁，二者纯度优选均在99％以上，六合硝酸镁占粉体总质量的10wt％。然后，将二者同少量的无水乙醇一同倒入球磨罐中，其中无水乙醇作为分散剂以有助于氧化铝粉末和六合硝酸镁在球磨的过程中均匀混合。所述第一阶段球磨选用氧化铝球进行球磨混料，且球磨时间优选为24h。
S62：将荧光粉加入经第一阶段球磨的混合物并进行第二阶段球磨。
称取一定量的荧光粉，例如Ce:YAG或Ce:LuAG荧光粉，其占总粉体质量的40％，并添加一定量的PVB乙醇溶液，其中PVB乙醇溶液作为分散剂。在球磨0.5h之后，将混合物在70℃下进行真空干燥，然后再随即进行研磨、过筛处理，而后装粉待用。
S63：将经过第二阶段球磨的混合物进行压制以制成块体素坯。
将混合物粉体在80MPa压力下压制成块体素坯。
S64：对所述块体素坯进行排胶工艺，将所述粘接剂分解排除。
S65：将排胶后的块体素坯进行冷等静压处理。
将成型的块体(即荧光陶瓷素坯)在马弗炉中排胶处理，排出其中的有机物乙醇，该排胶工艺为500℃保温2h以及1000℃保温6h。
在排胶结束之后，将荧光陶瓷素坯在200MPa压力下进行冷却静压处理，以提高荧光陶瓷素坯的致密度。
S66：将所述块体素坯进行烧结，所述六合硝酸镁分解成氧化镁，氧化镁与氧化铝反应形成铝镁尖晶石，从而形成包括氧化铝基体、以及分布于所述氧化铝基体中的荧光颗粒和铝镁尖晶石的复相荧光陶瓷。
将荧光陶瓷素坯置于真空炉中，真空度为10 -3Pa，1730℃下烧结4h。待真空烧结后，将荧光陶瓷素坯在空气气氛下，1350℃退火处理10h。即可形成一定厚度且表面粗糙的复相荧光陶瓷。
本申请进一步对复相荧光陶瓷进行减薄处理，例如使其厚度为100um以下，再进行抛光处理，最后得到可用的复相荧光陶瓷。
实施例3
请参阅图7，所述复相荧光陶瓷10的制备方法包括如下步骤：
S71：对氧化铝和六合硝酸镁混合物进行第一阶段球磨。
本实施例的含镁化合物为六合硝酸镁。
选取高纯度纳米级别的氧化铝粉末和六合硝酸镁，二者纯度优选均在99％以上，六合硝酸镁占粉体总质量的8wt％。然后，将二者同少量的无水乙醇一同倒入球磨罐中，其中无水乙醇作为分散剂以有助于氧化铝粉末和六合硝酸镁在球磨的过程中均匀混合。所述第一阶段球磨选用氧化铝球进行球磨混料，且球磨时间优选为24h。
S72：将荧光粉加入经第一阶段球磨的混合物并进行第二阶段球磨。
称取一定量的荧光粉，例如Ce:YAG或Ce:LuAG荧光粉，其占总粉体质量的60％。在球磨0.5h之后，将混合物在70℃下进行真空干燥，然后再随即进行研磨、过筛处理，而后装粉待用。
S73：将经过第二阶段球磨的混合物进行煅烧以将所述六水合硝酸镁分解为氧化镁。
将过筛后的粉体在马弗炉中500～700℃之间进行煅烧2～5h以去除粉体中有机成分，将六合硝酸镁分解成氧化镁。煅烧后将粉体研磨进行过200目筛，得到流动性较好的粉体，而后装粉待用。
S74：将经过煅烧的混合物进行预压处理。
将混合物粉体充填到石墨模具中，在5～20MPa压强下进行预压处理。
S75：将所述块体素坯进行烧结，所述氧化镁与氧化铝反应形成铝镁尖晶石，从而形成包括氧化铝基体、以及分布于所述氧化铝基体中的荧光颗粒和铝镁尖晶石的复相荧光陶瓷。
将石墨模具置于SPS(Spark Plasma Sintering,放电等离子烧结)热压炉中，在真空/氩气气氛中，1300℃～1600℃下保温烧结0.5h～4h，烧结时压力在20～180MPa。待热压烧结后，将荧光陶瓷素坯在空气气氛下，1300℃退火处理10h，即可形成一定厚度且表面粗糙的复相荧光陶瓷。
本申请进一步对复相荧光陶瓷进行减薄处理，例如使其厚度为100um以下，再进行抛光处理，最后得到可用的复相荧光陶瓷。
上述复相荧光陶瓷10可作为各种类型的显示面板的发光件，该显 示面板包括但不限于为OLED(Organic Light-Emitting Diode，有机发光二极管)显示面板、或者柔性触控显示面板。并且，所述显示面板可适用于包括但不限于智能手机、PDA(Personal Digital Assistant，个人数字助理或平板电脑)等移动终端，以及佩戴于肢体或者嵌入于衣物、首饰、配件中的可穿戴设备。
应理解，本申请中的术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括至少一个该特征。“多个”的含义是至少两个，例如两个，三个等，除非另有明确具体的限定。本申请实施例中所有方向性指示(诸如上、下、左、右、前、后……)仅用于解释在某一特定姿态(如附图所示)下各部元件之间的相对位置关系、运动情况等，如果该特定姿态发生改变时，则该方向性指示也相应地随之改变。
再次说明，以上所述仅为本申请的实施例，并非因此限制本申请的专利范围，凡是利用本申请说明书及附图内容所作的等效结构或等效流程变换，例如各实施例之间技术特征的相互结合，或直接或间接运用在其他相关的技术领域，均同理包括在本申请的专利保护范围内。

Claims (12)

  1. 一种复相荧光陶瓷，其特征在于，所述复相荧光陶瓷包括氧化铝基体、以及分布于所述氧化铝基体中的荧光颗粒和尖晶石，所述尖晶石分布于所述氧化铝基体中的氧化铝晶界之间。
  2. 根据权利要求1所述的复相荧光陶瓷，其特征在于，所述尖晶石为颗粒状和/或柱状结构，优选颗粒状的所述尖晶石的晶粒尺寸为0.2～2um，柱状结构的所述尖晶石的截面尺寸为0.5～2um、长度为2～10um。
  3. 根据权利要求1所述的复相荧光陶瓷，其特征在于，所述尖晶石在所述复相荧光陶瓷中的质量占比为0.5％～5％。
  4. 根据权利要求3所述的复相荧光陶瓷，其特征在于，所述荧光颗粒占总体质量的38％～65％。
  5. 根据权利要求3所述的复相荧光陶瓷，其特征在于，所述荧光颗粒的直径为2～30um，所述氧化铝的晶粒尺寸为1～10um。
  6. 一种复相荧光陶瓷的制备方法，其特征在于，所述制备方法包括：
    将氧化铝、含镁化合物、荧光颗粒的粉体配比后混合，并压制成块体素坯；
    将所述块体素坯进行烧结，所述含镁化合物与氧化铝反应形成铝镁尖晶石，从而形成包括氧化铝基体、以及分布于所述氧化铝基体中的荧光颗粒和铝镁尖晶石的复相荧光陶瓷。
  7. 根据权利要求6所述的制备方法，其特征在于，所述含镁化合物和氧化铝粉体的直径为0.05～0.8um。
  8. 根据权利要求6所述的制备方法，其特征在于，所述含镁化合物为氧化镁或六水合硝酸镁。
  9. 根据权利要求6所述的制备方法，其特征在于，在混合粉体时还混合有粘接剂，将所述块体素坯进行烧结之前，先进行排胶工艺，将所述粘接剂分解排除。
  10. 根据权利要求9所述的制备方法，其特征在于，在对排胶后的 块体素坯进行烧结之前，将排胶后的块体素坯进行冷等静压处理。
  11. 根据权利要求6所述的制备方法，其特征在于，将混合后的粉体先煅烧，使得含镁化合物分解成氧化镁，然后将煅烧后的成分研磨过筛后得到的粉体压制成块体素坯。
  12. 根据权利要求6所述的制备方法，其特征在于，所述荧光颗粒占粉体总体质量的38％～65％，所述铝镁尖晶石在所制得的复相荧光陶瓷中质量占比为0.5％～5％。
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