CN110204324A - 一种绿色荧光透明陶瓷的制备方法和应用 - Google Patents

一种绿色荧光透明陶瓷的制备方法和应用 Download PDF

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CN110204324A
CN110204324A CN201910400899.9A CN201910400899A CN110204324A CN 110204324 A CN110204324 A CN 110204324A CN 201910400899 A CN201910400899 A CN 201910400899A CN 110204324 A CN110204324 A CN 110204324A
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green fluorescence
preparation
crystalline ceramics
ceramics
chemical formula
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CN110204324B (zh
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肖文戈
邱建荣
刘小峰
谭德志
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Zhejiang University ZJU
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Zhejiang University ZJU
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Priority to PCT/CN2019/089463 priority patent/WO2020228066A1/zh
Priority to US17/421,007 priority patent/US12006263B2/en
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Abstract

本发明公开了一种绿色荧光透明陶瓷的制备方法和应用。按化学式Ca3‑x‑yCexAySc2‑zBzSi3‑ mCmO12中元素化学计量比，各个元素称取以氧化物、碳酸盐或者硝酸盐为原料，原料混合经退火后高温熔化，冷却后低温退火；将玻璃放入高温炉中保温和升温处理，析晶与致密化烧结，最后切割、还原、表面抛光处理；A为Lu、Y、Gd、La和Na中的至少一种；B为Zr、Hf和Mg中的至少一种；C为Al和P中的至少一种；x、y、z、m取值范围分别为：0.001≤x≤0.06，0≤y≤0.06，0≤z≤0.06,0≤m≤0.3。本发明通过玻璃晶化和致密化烧结相结合的方法，工艺简单、成本低，获得致密度高、透过率可调、量子效率高的荧光透明陶瓷。

Description

一种绿色荧光透明陶瓷的制备方法和应用
技术领域
本发明属于发光材料技术领域，具体涉及一种绿色荧光透明陶瓷的制备方法和应用。
背景技术
白光LED由于具有节能环保、寿命长、体积小、全固态等优点，而被认为是有望取代传统照明的第四代照明光源。随着白光LED的不断发展和成熟，以及人们对高品质照明的需求，半导体固态照明光源朝着高稳定性、高光学品质和高激发密度的方向发展。基于大功率蓝光LED芯片和蓝色激光二极管(LD)的大功率固态光源对所使用的荧光转换材料在物理化学稳定性、荧光温度特性等方面提出了更高要求。具有物理化学稳定性优异、热导率高、可见光透过率可调的荧光转换块体材料，如荧光透明陶瓷(US20090105065和US20080138919)、荧光玻璃陶瓷(CN103964691B和CN103395997B)，有望取代传统的“荧光粉+有机材料”，并由于其具备荧光转换和封装的双重功能而更好地应用于高功率照明和显示领域。
荧光透明陶瓷不仅具备优异的机械和力学性能，更具有良好的导热性，这不但有利于热量的扩散，还能提高器件的稳定性。人们可以通过控制制备工艺来精确调节荧光透明陶瓷对可见光的散射程度，优化荧光转换体对光的散射、透过和吸收，从而获得高质量的白光LED或者全转换单色光LED。此外，荧光透明陶瓷比“荧光粉+有机材料”对光的散射低很多，所需激活剂掺杂浓度可以低一个数量级，内量子效率和荧光温度特性更好。目前，能够应用于半导体固态照明的荧光透明陶瓷主要是具有石榴石结构的稀土铝酸盐(Re3Al3O12)。它们的合成条件均为高压、高温(＞1650℃)、高真空，工艺复杂、价格高昂。
硅酸盐石榴石绿色荧光粉Ca3Sc2Si3O12:Ce3+(Journal of The ElectrochemicalSociety,2007,154(1):J35-J38.)的内量子效率高且热稳定性优异。中国专利201610957170.8公开了一种通过常规的高压、高温、高真空烧结法制备的基于Ca3Sc2Si3O12的全光谱荧光陶瓷转换体，但是其烧结工艺复杂，且致密度低(≤98％)，对光的散射严重，限制了其在大功率照明与显示领域的应用。
发明内容
本发明的目的是针对现有技术中的不足，提供一种绿色荧光透明陶瓷的制备方法。该方法无需高压、高真空就可以制备出致密度高、透过率可调的绿色荧光透明陶瓷。
本发明所述的绿色荧光透明陶瓷的制备方法，其特征在于：
一、一种绿色荧光透明陶瓷：
按化学式Ca3-x-yCexAySc2-zBzSi3-mCmO12中各元素的化学计量比配制制备而成，A为Lu、Y、Gd、La和Na中的至少一种，可以是两种及以上的混合；B为Zr、Hf和Mg中的至少一种；C为Al和P中的至少一种；x、y、z、m取值范围分别为：0.001≤x≤0.06，0≤y≤0.06，0≤z≤0.06,0≤m≤0.3。
二、一种绿色荧光透明陶瓷的制备方法，方法包括以下步骤：
(1)按化学式Ca3-x-yCexAySc2-zBzSi3-mCmO12中各元素的化学计量比，各个元素称取以氧化物、碳酸盐或者硝酸盐为起始原料，将上述原料混合均匀，经退火后，在高温(大于1600摄氏度)下充分熔化，快速冷却后得到透明的玻璃，并在700～950℃低温下退火1～10h去除玻璃的内部应力；
(2)将步骤(1)所得到的玻璃放入高温炉中，在1000～1200℃保温0～10h，随后将温度升高至1400～1500℃，并在空气或者真空中进行析晶与致密化烧结，保温时间为5～80h，获得具有一定直线透过率的荧光透明陶瓷；
(3)将步骤(2)所得的荧光透明陶瓷依次进行切割、还原、表面抛光的处理，得到量子效率高、透过率可调的荧光透明陶瓷。
本发明方法将玻璃成分经处理制备得到陶瓷材料，并且实现了量子效率高和透过率可调，能制备基于大功率蓝光LED或者LD的发光器件。
所述的化学式Ca3-x-yCexAySc2-zBzSi3-mCmO12中，A为Lu、Y、Gd、La和Na中的至少一种，可以是两种及以上的混合；B为Zr、Hf和Mg中的至少一种；C为Al和P中的至少一种；x、y、z、m取值范围分别为：0.001≤x≤0.06，0≤y≤0.06，0≤z≤0.06,0≤m≤0.3。
所述化学式中的元素的原料除了P以外优选均采用氧化物和碳酸盐。
所述化学式中的P元素的原料采用磷酸氢二铵或磷酸二氢铵。
本发明所述的绿色荧光透明陶瓷在基于大功率蓝光LED或LD的固态照明与显示领域的应用。
本发明制备得到的绿色荧光透明陶瓷能与半导体固态光源封装获得大功率绿光或者白光器件及其在照明与显示领域中的应用。
所述半导体固态光源为发射波长为420～480nm的LED或者LD。本发明的有益效果：
本发明涉及的绿色荧光透明陶瓷的制备方法，不需要长时间球磨、冷等静压、高真空以及热压烧结等特殊实验条件，合成简单、成本低。此外，本发明所获得的绿色荧光透明陶瓷致密度高、透过率可调而且荧光量子效率高，可以结合大功率蓝光LED或蓝光LD封装出大功率固态发光器件。
附图说明
图1为本发明实施例2中荧光透明陶瓷的XRD谱图；
图2为本发明实施例2中荧光透明陶瓷的激发和发射光谱图；
图3为本发明实施例2和实施例3中荧光透明陶瓷的透过率谱图；
图4为本发明实施例2中荧光透明陶瓷与450nm蓝光LED封装的LED器件的电致发光光谱及参数图；
图5为本发明实施例2中荧光透明陶瓷与450nm蓝光LD封装的大功率发光器件的光谱及参数图；
图6为本发明实施例2中荧光透明陶瓷与450nm蓝光LD封装的大功率发光器件的光通量随激发光功率的变化曲线图；
图7为本发明实施例2中荧光透明陶瓷的扫描电子显微图。
具体实施方式
下面结合附图和具体实施例对本发明作进一步说明。
本发明的实施例如下：
实施例中采用市购的高纯CaCO3，Na2CO3，SiO2，ZrO2，HfO2，Al2O3，NH4H2PO4，CeO2，Sc2O3，Tb4O7(5N)，Gd2O3(5N)，La2O3，Y2O3，Lu2O3，制备本发明各实施例。
实施例1
Ca2.999Ce0.001Sc2Si3O12的制备
按化学计量比称取CaCO3：3.0016克，Sc2O3：1.3791克，SiO2：1.8025克，CeO2：0.0017克，放入玛瑙研钵中，加入5ml酒精，研磨30min后，使用手动压片机将混合粉体压制成薄片，并放入高温箱式炉中，在1100℃保温6h，待自然冷却后，截取该薄片的二十分之一，放入配备有双光束二氧化碳激光器的气悬浮炉中，使用高纯氧气作为载气，对样品进行悬浮熔炼，使样品保持熔融状态约30s，通过切断激光使熔体快速冷却，获得具有相应组分的玻璃球。将所获得的玻璃球放入高温箱式炉中，以2℃/min的速度升至900℃，保温3h去除玻璃内部应力，再以3℃/min的速度升至1050℃，保温2h，最后，以4℃/min的速度升至1450℃，常压(0.1Mpa)下进行致密化烧结，时间为20h，自然冷却后，得到致密化的球形荧光透明陶瓷。将球形荧光透明陶瓷切割成片状，放入管式炉中，通入5％H2/95％N2，在1350℃下保温4h，进一步提高荧光量子效率。最后，对荧光透明陶瓷片进行表面抛光处理，即获得化学式为Ca2.999Ce0.001Sc2Si3O12的荧光透明陶瓷。本实施例样品的激发和发射光谱与实施例2相似，内量子效率为94％，厚度为0.5mm时600nm处的直线透过率为3％。
实施例2
Ca2.994Ce0.006Sc2Si3O12的制备
除了将致密化烧结时间的设置为40h外，其他制备步骤和工艺条件与实施例1相同。本实施例样品的内量子效率为93％。
附图1是本实施例制备的样品的XRD图谱。从附图1可知，该荧光透明陶瓷除了属于石榴石结构的立方晶相外，无任何杂相。
附图2是本实施例制备的样品的激发和发射光谱。从附图2可知，该荧光陶瓷在420～480nm的蓝光激发下，发射出峰值为505nm的宽带绿光。
从附图3的直线透过率谱可知，本实施例制备的样品，厚度为0.5mm时600nm处的直线透过率为7％，且对450nm附近的蓝光有很强的吸收。
附图4是使用0.3mm厚度的本实施例样品结合450nm蓝光LED封装的LED器件的光谱及参数图。该器件在20mA下的流明效率为84lm/W，其光谱覆盖蓝光到绿光区域，可以应用于基于LED的照明与显示领域。
附图5是使用0.7mm厚度的本实施例样品结合450nm蓝光LD封装的大功率发光器件的光谱及参数图。在6.4W的激发光功率下，激光光斑半径仅为0.3mm的区域内，能够获得高达837lm的光通量。从该器件的光通量随激发光功率的变化曲线图(附图6)可知，光通量在高达28W/mm2的激发光功率密度也不饱和，最大光通量为1410lm，最大光光转换效率为178lm/W。因而可以应用于基于大功率LED或者LD的照明与显示领域。
附图7是本实施例制备的样品在表面抛光后经1350℃热腐蚀2h后的扫描电子显微图。由该图可知，气孔极少，致密度高达99.5％。
实施例3
Ca2.98Ce0.01Gd0.01Sc2Si3O12的制备
除了使用高温真空炉进行烧结，并将真空度设置0.1Pa外，其他制备步骤和工艺条件与实施例2相同。本实施例样品的激发和发射光谱与实施例2相似，内量子效率为91％，厚度为0.5mm时600nm处的直线透过率为56％(附图3)。
实施例4至实施例23：按表1中各实施例化学式组成及其化学计量比称取相应原料，致密化温度为1450℃，其保温时间和真空度见表1，其他步骤与上述实施例皆相同。表1中所述透过率值均为0.5mm厚的样品在波长为600nm处的直线透过率。
表1实施例1-23
实施例 化学式 致密化时间 真空度 透过率
1 Ca<sub>2.999</sub>Ce<sub>0.001</sub>Sc<sub>2</sub>Si<sub>3</sub>O<sub>12</sub> 20h 0.1Mpa 3％
2 Ca<sub>2.994</sub>Ce<sub>0.006</sub>Sc<sub>2</sub>Si<sub>3</sub>O<sub>12</sub> 40h 0.1Mpa 7％
3 Ca<sub>2.98</sub>Ce<sub>0.01</sub>Gd<sub>0.01</sub>Sc<sub>2</sub>Si<sub>3</sub>O<sub>12</sub> 40h 0.1Pa 56％
4 Ca<sub>2.98</sub>Ce<sub>0.01</sub>La<sub>0.01</sub>Sc<sub>2</sub>Si<sub>3</sub>O<sub>12</sub> 40h 0.1Mpa 26％
5 Ca<sub>2.98</sub>Ce<sub>0.01</sub>Tb<sub>0.01</sub>Sc<sub>2</sub>Si<sub>3</sub>O<sub>12</sub> 40h 0.1Mpa 23％
6 Ca<sub>2.98</sub>Ce<sub>0.01</sub>Y<sub>0.01</sub>Sc<sub>2</sub>Si<sub>3</sub>O<sub>12</sub> 40h 0.1Mpa 15％
7 Ca<sub>2.98</sub>Ce<sub>0.01</sub>Lu<sub>0.01</sub>Sc<sub>2</sub>Si<sub>3</sub>O<sub>12</sub> 40h 0.1Mpa 5％
8 Ca<sub>2.98</sub>Ce<sub>0.01</sub>Na<sub>0.01</sub>Sc<sub>2</sub>Si<sub>3</sub>O<sub>12</sub> 40h 0.1Mpa 23％
9 Ca<sub>2.994</sub>Ce<sub>0.006</sub>Sc<sub>1.98</sub>Zr<sub>0.02</sub>Si<sub>3</sub>O<sub>12</sub> 40h 0.1Mpa 30％
10 Ca<sub>2.994</sub>Ce<sub>0.006</sub>Sc<sub>1.98</sub>Hf<sub>0.02</sub>Si<sub>3</sub>O<sub>12</sub> 40h 0.1Mpa 26％
11 Ca<sub>2.994</sub>Ce<sub>0.006</sub>Sc<sub>1.98</sub>Mg<sub>0.02</sub>Si<sub>3</sub>O<sub>12</sub> 40h 0.1Mpa 20％
12 Ca<sub>2.994</sub>Ce<sub>0.006</sub>Sc<sub>2</sub>Si<sub>2.97</sub>Al<sub>0.03</sub>O<sub>12</sub> 40h 0.1Mpa 15％
13 Ca<sub>2.994</sub>Ce<sub>0.006</sub>Sc<sub>2</sub>Si<sub>2.97</sub>P<sub>0.03</sub>O<sub>12</sub> 40h 0.1Mpa 30％
14 Ca<sub>2.994</sub>Ce<sub>0.006</sub>Sc<sub>1.99</sub>Hf<sub>0.01</sub>Si<sub>2.99</sub>P<sub>0.01</sub>O<sub>12</sub> 40h 0.1Mpa 20％
15 Ca<sub>2.994</sub>Ce<sub>0.006</sub>Sc<sub>1.99</sub>Zr<sub>0.01</sub>Si<sub>2.99</sub>P<sub>0.01</sub>O<sub>12</sub> 40h 0.1Mpa 22％
16 Ca<sub>2.994</sub>Ce<sub>0.006</sub>Sc<sub>1.99</sub>Zr<sub>0.01</sub>Si<sub>2.99</sub>Al<sub>0.01</sub>O<sub>12</sub> 40h 0.1Mpa 18％
17 Ca<sub>2.984</sub>Ce<sub>0.006</sub>Gd<sub>0.01</sub>Sc<sub>1.99</sub>Zr<sub>0.01</sub>Si<sub>2.99</sub>Al<sub>0.01</sub>O<sub>12</sub> 40h 0.1Mpa 21％
18 Ca<sub>2.988</sub>Ce<sub>0.006</sub>Na<sub>0.006</sub>Sc<sub>1.99</sub>Zr<sub>0.01</sub>Si<sub>3</sub>O<sub>12</sub> 40h 0.1Mpa 28％
19 Ca<sub>2.984</sub>Ce<sub>0.006</sub>Gd<sub>0.01</sub>Sc<sub>1.99</sub>Zr<sub>0.01</sub>Si<sub>2.99</sub>Al<sub>0.01</sub>O<sub>12</sub> 40h 0.1Mpa 20％
20 Ca<sub>2.984</sub>Ce<sub>0.006</sub>Na<sub>0.01</sub>Sc<sub>1.99</sub>Zr<sub>0.01</sub>Si<sub>2.99</sub>Al<sub>0.01</sub>O<sub>12</sub> 40h 0.1Mpa 16％
21 Ca<sub>2.98</sub>Ce<sub>0.01</sub>Gd<sub>0.01</sub>Sc<sub>2</sub>Si<sub>3</sub>O<sub>12</sub> 5h 0.1Mpa 1％
22 Ca<sub>2.98</sub>Ce<sub>0.01</sub>Gd<sub>0.01</sub>Sc<sub>2</sub>Si<sub>3</sub>O<sub>12</sub> 80h 0.1Mpa 42％
23 Ca<sub>2.98</sub>Ce<sub>0.01</sub>Gd<sub>0.01</sub>Sc<sub>2</sub>Si<sub>3</sub>O<sub>12</sub> 40h 0.1Mpa 30％
由此可见，本发明通过不同的元素配比、保温条件、烧结条件等等工艺条件能调节光透过率，适当延长烧结保温时间能实现更高的透过率。本发明的光透过率最高可达到56％，实现了极高的致密性。
显然，上述实施例仅仅是为了清楚的说明所作的举例，在上述说明的基础上还可以做出其他形式的变动或变化，由此所引申出的显而易见的变化或变动仍属于本发明的保护范围之内。本发明实施例中玻璃的制备采用了气悬浮炉法，然而，其制备方法并不局限于此，其他能够将原料充分熔化且快速冷却的方法均可以获得本发明所述的玻璃。本发明实施例中所采用的原料也可以使用含有相应元素但不引入外来杂质的其他化合物。

Claims (7)

1.一种绿色荧光透明陶瓷，其特征在于：按化学式Ca3-x-yCexAySc2-zBzSi3-mCmO12中各元素的化学计量比配制制备而成，A为Lu、Y、Gd、La和Na中的至少一种；B为Zr、Hf和Mg中的至少一种；C为Al和P中的至少一种；x、y、z、m取值范围分别为：0.001≤x≤0.06，0≤y≤0.06，0≤z≤0.06,0≤m≤0.3。
2.一种绿色荧光透明陶瓷的制备方法，其特征在于：方法包括以下步骤：
(1)按化学式Ca3-x-yCexAySc2-zBzSi3-mCmO12中各元素的化学计量比，各个元素称取以氧化物、碳酸盐或者硝酸盐为起始原料，将上述原料混合均匀，经退火后，在高温下充分熔化，冷却后得到透明的玻璃，并在700～950℃低温下退火1～10h去除玻璃的内部应力；
(2)将步骤(1)所得到的玻璃放入高温炉中，在1000～1200℃保温0～10h，随后将温度升高至1400～1500℃，并在空气或者真空中进行析晶与致密化烧结，保温时间为5～80h，获得荧光透明陶瓷；
(3)将步骤(2)所得的荧光透明陶瓷依次进行切割、还原、表面抛光的处理，得到量子效率高、透过率可调的荧光透明陶瓷。
3.根据权利要求1所述的一种绿色荧光透明陶瓷的制备方法，其特征在于，
所述的化学式Ca3-x-yCexAySc2-zBzSi3-mCmO12中，A为Lu、Y、Gd、La和Na中的至少一种；B为Zr、Hf和Mg中的至少一种；C为Al和P中的至少一种；x、y、z、m取值范围分别为：0.001≤x≤0.06，0≤y≤0.06，0≤z≤0.06,0≤m≤0.3。
4.根据权利要求3所述的一种绿色荧光透明陶瓷的制备方法，其特征在于，所述化学式中的元素的原料除了P以外均采用氧化物和碳酸盐。
5.根据权利要求3所述的一种绿色荧光透明陶瓷的制备方法，其特征在于，所述化学式中的P元素的原料采用磷酸氢二铵或磷酸二氢铵。
6.一种绿色荧光透明陶瓷，其特征在于，权利要求2-5任一所述制备方法制成的绿色荧光透明陶瓷。
7.一种权利要求6所述的绿色荧光透明陶瓷在基于大功率蓝光LED或LD的固态照明与显示领域的应用。
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