WO2022134040A1 - 一种eu2+离子掺杂钇铝石榴石结构荧光粉的制备方法 - Google Patents

一种eu2+离子掺杂钇铝石榴石结构荧光粉的制备方法 Download PDF

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WO2022134040A1
WO2022134040A1 PCT/CN2020/139543 CN2020139543W WO2022134040A1 WO 2022134040 A1 WO2022134040 A1 WO 2022134040A1 CN 2020139543 W CN2020139543 W CN 2020139543W WO 2022134040 A1 WO2022134040 A1 WO 2022134040A1
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aluminum garnet
yttrium aluminum
powder
garnet structure
preparation
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French (fr)
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邾强强
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苏州君诺新材科技有限公司
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals

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  • the invention relates to the technical field of fluorescent powder, and more particularly, to a preparation method of a fluorescent powder with a yttrium aluminum garnet structure.
  • White LEDs occupy a dominant position in today's lighting and display markets because of their high efficiency, environmental protection, and long life.
  • fluorescent materials play a decisive role in the luminous performance of the final device.
  • the yttrium aluminum garnet structure material has good mechanical properties, high thermal stability and chemical stability. By doping the yttrium aluminum garnet structure with different rare earth ions, luminescent materials that meet applications in different fields can be obtained.
  • Eu ions As one of the most commonly used doped rare earth ions in fluorescent materials, Eu ions have shown good application effects in the fields of lighting and display. When doped into a fluorescent host material, Eu ions with different valence states have different luminescence properties, among which Eu 3+ ions exhibit a linear luminescence spectrum, while Eu 2+ ions exhibit broad spectrum luminescence. For Eu ion-doped yttrium aluminum garnet structure fluorescent materials, since Eu ions replace the lattice site of Y 3+ ions, in order to maintain the valence balance, Eu ions tend to enter the yttrium aluminum garnet in the form of Eu 3+ in the structure.
  • Eu 3+ -containing oxide Eu 2 O 3 is usually used as the synthesis raw material, which leads to the final obtained phosphor even under the synthesis condition of reducing atmosphere.
  • the luminescence of Eu 2+ ions is also extremely weak, which can only be expressed as the linear luminescence spectrum of Eu 3+ . Therefore, the Eu ion-doped yttrium-aluminum-garnet-structured fluorescent materials generally cannot meet the application requirements of high-color rendering white light LED devices for broad-spectrum fluorescent materials.
  • the inventors have found that Eu 2+ ions are also stably present in some silicon oxynitrides in addition to their halides and sulfides. Therefore, in the process of synthesizing Eu ion-doped yttrium aluminum garnet phosphors, silicon oxynitride containing Eu 2+ can be synthesized first, and then the silicon oxynitride can be used as an Eu source to realize the doping of Eu 2+ ions miscellaneous.
  • the invention provides a preparation method of Eu 2+ ion doped yttrium aluminum garnet structure phosphor, comprising the following steps:
  • step c) the mixed raw materials are calcined at high temperature under a reducing atmosphere to obtain Eu 2+ ion-doped yttrium aluminum garnet structure phosphors.
  • the EuSi 2 O 2 N 2 powder is prepared according to the following method:
  • EuSi 2 O 2 N 2 According to the chemical formula EuSi 2 O 2 N 2 , appropriate amounts of Eu 2 O 3 , Si 3 N 4 and SiO 2 powder raw materials were respectively weighed, and the powder raw materials were mixed uniformly and then calcined at high temperature by solid-phase reaction method under reducing atmosphere to obtain EuSi 2 O 2 N 2 powder.
  • the reduction atmosphere for the synthesis and reduction of EuSi 2 O 2 N 2 powder is an ammonia gas atmosphere.
  • the calcination temperature of the solid-phase reaction method for synthesizing EuSi 2 O 2 N 2 powder is 1300-1500°C, the heating rate is 4°C/min-10°C/min, and the holding time is 3-6h.
  • the co-solvent in the step b) is BaF 2 , H 3 BO 3 or other kinds of co-solvents as required.
  • the mixing method in the step b) is manual mixing using an agate mortar or mixing through a ball milling process.
  • the step c) is specifically:
  • Step c1) placing the mixed raw materials in an alumina or boron nitride crucible;
  • Step c2) The mixed raw materials are calcined at high temperature under a reducing atmosphere at 1400-1600°C.
  • the reducing atmosphere in step c2) is nitrogen atmosphere
  • the heating rate is 4°C/min ⁇ 10°C/min
  • the holding time is 3-5h.
  • the invention provides a preparation method of Eu 2+ ion-doped yttrium aluminum garnet structure fluorescent powder, which can be simply and quickly realized in the yttrium aluminum garnet structure by a two-step solid-phase reaction method under the condition of using common and easy-to-obtain raw materials Eu 2+ ion doping.
  • the method has the advantages of simple process, low cost, easy industrialized continuous production, and broad industrial application prospect.
  • Example 2 is the excitation and emission spectra of phosphors prepared in Example 1 and Comparative Example of the present invention
  • Fig. 4 is the excitation and emission spectra of phosphor powder prepared in Example 2 of the present invention
  • Fig. 5 is the XRD pattern of phosphor powder prepared in Example 3 of the present invention.
  • FIG. 6 is the excitation and emission spectra of the phosphor powder prepared in Example 3 of the present invention.
  • the invention provides a preparation method of Eu 2+ ion doped yttrium aluminum garnet structure phosphor, comprising the following steps: step a) synthesizing EuSi 2 O 2 N 2 powder; step b) mixing the obtained EuSi 2 O 2 N 2 powder with other oxide raw materials and co-solvents; step c) calcining the mixed raw materials at high temperature under reducing conditions to obtain Eu 2 + Ion-doped yttrium aluminum garnet structure phosphor.
  • the preparation method of the EuSi 2 O 2 N 2 powder there is no particular limitation on the preparation method of the EuSi 2 O 2 N 2 powder, and methods well known to those skilled in the art can be used, preferably the following method is used: Weigh an appropriate amount of EuSi 2 O 2 N 2 according to the chemical formula EuSi 2 O 2 N 2 . 2 O 3 , Si 3 N 4 and SiO 2 powder raw materials, mix each powder raw material uniformly in an agate mortar, and then put the mixed raw materials into boron nitride or silicon nitride crucible by solid-phase reaction method
  • the EuSi 2 O 2 N 2 powder is obtained by calcining at high temperature under the condition of ammonia gas atmosphere.
  • the calcination temperature of the solid-phase reaction method is preferably 1300-1500°C, the heating rate is preferably 4°C/min ⁇ 10°C/min, and the holding time is preferably 3-6h.
  • step b) of the present invention there is no particular limitation on the co-solvent, preferably BaF 2 or H 3 BO 3 ; there is no particular limitation on other raw materials for synthesizing yttrium aluminum garnet structure phosphors, preferably the oxidation of corresponding elements Material powder raw materials; the mixing method of raw materials is manual mixing using an agate mortar or mixing through a ball milling process.
  • the co-solvent preferably BaF 2 or H 3 BO 3
  • other raw materials for synthesizing yttrium aluminum garnet structure phosphors preferably the oxidation of corresponding elements
  • Material powder raw materials the mixing method of raw materials is manual mixing using an agate mortar or mixing through a ball milling process.
  • the mixed raw materials are calcined at high temperature
  • the used crucible is preferably an alumina or boron nitride crucible
  • the used atmosphere can be a reducing atmosphere such as a nitrogen atmosphere, a nitrogen-hydrogen mixed atmosphere, and a carbon atmosphere.
  • the high temperature calcination temperature is preferably 1400-1600°C
  • the heating rate is preferably 4°C/min-10°C/min
  • the holding time is preferably 3-5h.
  • the present invention has no particular limitation on the furnace used for high temperature calcination, and a device well known to those skilled in the art can be used, preferably an atmosphere furnace of metal resistance heating type, graphite resistance heating type or silicon molybdenum rod resistance heating type.
  • the present invention provides a preparation method of Eu 2+ ion-doped yttrium aluminum garnet structure phosphor, which is simple and rapid in the yttrium aluminum garnet structure using a two-step solid-phase reaction method under the condition of using common and easily obtained raw materials.
  • Eu 2+ ion doping is realized in the garnet structure.
  • the present invention does not need to use expensive and poor stability compounds such as Eu 2+ halides and sulfides as synthetic raw materials, and does not require the use of Eu 2+ ions.
  • the Eu 2 O 3 raw material needs to be first subjected to a reduction treatment by means of a strong reducing acid.
  • the method of the invention has the advantages of simple process, low cost, easy industrialized continuous production and broad industrial application prospect.
  • the obtained powder was taken out and put into an agate mortar and ground into powder to obtain EuSi 2 O 2 N 2 powder.
  • the chemical formula Y 2.9 Eu 0.1 Al 5 O 12 weigh 0.1g EuSi 2 O 2 N 2 , 1.2210g Y 2 O 3 , and 0.9508g Al 2 O 3 starting powder, add 0.1g BaF 2 as a co-solvent, and put them together.
  • the atmosphere furnace is evacuated, and then the reducing gas nitrogen is introduced, and the temperature rises to 1000 °C at a heating rate of 5 °C/min, and then 4 °C.
  • the heating rate of °C/min was raised to 1500 °C, and the temperature was kept for 4 hours.
  • the temperature was lowered to 600 °C at a cooling rate of 4 °C/min, and then cooled to room temperature naturally.
  • the obtained powder was taken out and put into an agate mortar and ground into powder.
  • Comparative Example 1 Direct use of Eu 2 O 3 powder as Eu source
  • the heating rate of °C/min was raised to 1500 °C, and the temperature was kept for 4 hours. Then, the temperature was lowered to 600 °C at a cooling rate of 4 °C/min, and then cooled to room temperature naturally. The obtained powder was taken out and put into an agate mortar and ground into powder.
  • the obtained powder was taken out and put into an agate mortar and ground into powder to obtain EuSi 2 O 2 N 2 powder.
  • the chemical formula Y 2.9 Eu 0.1 Al 4 GaO 12 weigh 0.1 g EuSi 2 O 2 N 2 , 1.2210 g Y 2 O 3 , 0.7606 g Al 2 O 3 , 0.3496 g Ga 2 O 3 starting powder, and add 0.1 g BaF 2 As a co-solvent, they were put into a ball mill together and milled in a planetary ball mill for 12 hours. After taking out the slurry, it was dried in a drying oven for 10 hours to obtain the final mixed powder raw material. Transfer the mixed raw material powder into an alumina crucible and put it into a tubular atmosphere.
  • the atmosphere furnace is evacuated, and then the reducing gas nitrogen is introduced, and the temperature rises to 1000 °C at a heating rate of 5 °C/min, and then 4 °C.
  • the heating rate of °C/min was increased to 1450 °C, and the temperature was kept for 4 hours.
  • the temperature was lowered to 600 °C at a cooling rate of 4 °C/min, and then cooled to room temperature naturally.
  • the obtained powder was taken out and put into an agate mortar and ground into powder to obtain Eu ion-doped yttrium aluminum garnet structure phosphor.
  • the obtained powder was taken out and put into an agate mortar and ground into powder to obtain EuSi 2 O 2 N 2 powder.
  • the chemical formula GdY 1.9 Eu 0.1 Al 4 GaO 12 weigh 0.1 g EuSi 2 O 2 N 2 , 0.8002 g Y 2 O 3 , 0.6761 g Gd 2 O 3 , 0.9508 g Al 2 O 3 starting powder, and add 0.1 g BaF 2 As a co-solvent, they were put into a ball mill together and milled in a planetary ball mill for 12 hours. After taking out the slurry, it was dried in a drying oven for 10 hours to obtain the final mixed powder raw material.
  • the atmosphere furnace is evacuated, and then the reducing gas nitrogen is introduced, and the temperature rises to 1000 °C at a heating rate of 5 °C/min, and then 4 °C.
  • the heating rate of °C/min was increased to 1450 °C, and the temperature was kept for 4 hours.
  • the temperature was lowered to 600 °C at a cooling rate of 4 °C/min, and then cooled to room temperature naturally.
  • the obtained powder was taken out and put into an agate mortar and ground into powder to obtain Eu ion-doped yttrium aluminum garnet structure phosphor.

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Abstract

一种Eu2+离子掺杂钇铝石榴石结构荧光粉的制备方法，首先将原料Eu2O3、Si3N4和SiO2混合均匀，在还原气氛条件下高温煅烧合成含Eu2+的硅氧氮化物EuSi2O2N2；然后使用EuSi2O2N2作为Eu源，和其他各元素氧化物类原料进行混料在还原气氛条件下加热至1400-1600℃得到Eu2+离子掺杂钇铝石榴石结构荧光粉。所述制备方法可以在使用常用易获取原料的条件下，利用两步固相反应法简单快速的在钇铝石榴石结构中实现Eu2+离子掺杂；该方法工艺简单，成本低廉，易于工业化连续生产，具有广阔的工业应用前景。

Description

一种Eu2+离子掺杂钇铝石榴石结构荧光粉的制备方法 技术领域
本发明涉及荧光粉技术领域，更具体地说，涉及一种钇铝石榴石结构荧光粉的制备方法。
背景技术
白光LED以其高效、环保、长寿命等优点，在当今照明及显示市场占据了主导地位，而荧光材料作为白光LED器件中的关键材料之一，对最终器件的发光性能起到了决定性的作用。钇铝石榴石结构材料具有良好的机械性能、高的热稳定性及化学稳定性，通过在钇铝石榴石结构中掺杂不同稀土离子，可以获得满足不同领域应用的发光材料。
Eu离子作为荧光材料最为常用的掺杂稀土离子之一，在照明及显示领域都表现出了良好的应用效果。在掺杂到荧光基质材料中，不同价态的Eu离子具有不同的发光特性，其中Eu 3+离子表现为线状发光光谱，而Eu 2+离子则为宽光谱发光。针对Eu离子掺杂钇铝石榴石结构荧光材料，由于Eu离子取代的是Y 3+离子的格位，因此为了保持价态平衡，Eu离子更倾向于以Eu 3+的形式进入钇铝石榴石结构中。而在Eu离子掺杂钇铝石榴石结构荧光材料的合成过程中，通常采用含Eu 3+的氧化物Eu 2O 3作为合成原料，这导致即使在还原气氛合成条件下，最终获得的荧光粉中Eu 2+离子的发光也极其微弱，只能表现为Eu 3+的线状发光光谱。因此通常Eu离子掺杂钇铝石榴石结构荧光材料无法满足高显色白光LED器件对宽光谱荧光材料的应用需求。
目前，为了在钇铝石榴石结构实现Eu 2+离子的掺杂，通常是在合成过程中使用含Eu 2+的卤化物(EuF 2、EuCl 2)、硫化物(EuS)作为合成原料(参见非专利文献1)，或者使用强还原性酸首先对Eu 2O 3原料进行还原处理(参见非专利文献2)。由于含Eu 2+的卤化物、硫化物通常价格昂贵且稳定性差，而使用强还原性酸对Eu 2O 3原料进行还原处理需要借助液相法来进行荧光粉的合成，这使得目前Eu 2+离子掺杂钇铝石榴石结构荧光粉还无法进行工业化连续生产，只能在实验 室条件下进行少量合成。
现有技术文献：
Havlak,Lubomir,et al."J.Phys.Chem.C"2016,120,21751-21761；
Zhu,Qiang Qiang,et al."J.Am.Ceram.Soc."2013,96(3),701-703.
发明内容
为解决上述问题，本发明提供一种Eu 2+离子掺杂钇铝石榴石结构荧光粉的制备方法，在使用常用易获取原料的条件下，利用两步固相反应法简单快速的在钇铝石榴石结构中实现Eu 2+离子掺杂。该方法工艺简单，成本低廉，易于工业化连续生产，具有广阔的工业应用前景。
发明人发现Eu 2+离子除了存在于其卤化物和硫化物中，也可以稳定存在于在一些硅氧氮化物中。因此，在合成Eu离子掺杂钇铝石榴石荧光粉的过程中，可以先合成含Eu 2+的硅氧氮化物，再以该硅氧氮化物作为Eu源，以实现Eu 2+离子的掺杂。同时，含Eu 2+硅氧氮化物原料中微量的Si，N元素也可以进入钇铝石榴石结构中，用于解决Eu 2+离子取代Y 3+离子所产生的电荷不平衡问题，进一步保证Eu 2+离子在钇铝石榴石结构中的稳定存在。
具体的，针对化学式为Y 3-x-y-zEu xLu yGd zAl 5-aGa aO 12(0<x≤0.3，0≤y<3，0≤z<3，0≤a<5，x+y+z≤3)的Eu离子掺杂钇铝石榴石荧光粉，本发明提供了一种Eu 2+离子掺杂钇铝石榴石结构荧光粉的制备方法，包括以下步骤：
步骤a)合成EuSi 2O 2N 2粉体；
步骤b)将获得的EuSi 2O 2N 2粉体和其他氧化物类原料及助溶剂进行混合；
步骤c)将混合原料在还原气氛条件下进行高温煅烧，得到Eu 2+离子掺杂钇铝石榴石结构荧光粉。
优选的，所述EuSi 2O 2N 2粉体按照如下方法制备：
根据化学式EuSi 2O 2N 2分别称取适量Eu 2O 3、Si 3N 4和SiO 2粉体原料，将各粉体原料混合均匀后通过固相反应法在还原气氛条件下进行高温煅烧获得EuSi 2O 2N 2粉体。
优选的，混合原料置于氮化硼或氮化硅坩埚中进行高温固相反应。
优选的，EuSi 2O 2N 2粉体合成还原气氛条件为氨气气氛。
优选的，EuSi 2O 2N 2粉体合成固相反应法的煅烧温度为1300-1500℃，升温速率为4℃/min～10℃/min，保温时间为3-6h。
优选的，所述步骤b)中助溶剂为BaF 2、H 3BO 3或根据需要选择其他种类的助溶剂。
优选的，所述步骤b)中混料方法为使用玛瑙研钵手动混料或者通过球磨工艺进行混料。
优选的，所述步骤c)具体为：
步骤c1)将所述混合原料置于氧化铝或氮化硼坩埚中；
步骤c2)将所述混合原料在1400-1600℃还原气氛条件下进行高温煅烧。
优选的，步骤c2)的还原气氛为氮气气氛，升温速率为4℃/min～10℃/min，保温时间为3-5h。
本发明的技术效果：
本发明提供一种Eu 2+离子掺杂钇铝石榴石结构荧光粉的制备方法，在使用常用易获取原料的条件下，利用两步固相反应法简单快速的在钇铝石榴石结构中实现Eu 2+离子掺杂。该方法工艺简单，成本低廉，易于工业化连续生产，具有广阔的工业应用前景。
附图说明
图1为本发明实施例1和对比例制备荧光粉的XRD图；
图2为本发明实施例1和对比例制备荧光粉的激发和发射光谱；
图3为本发明实施例2制备荧光粉的XRD图；
图4为本发明实施例2制备荧光粉的激发和发射光谱
图5为本发明实施例3制备荧光粉的XRD图；
图6为本发明实施例3制备荧光粉的激发和发射光谱。
具体实施方式
下面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，都属于本发明保护的范围。
针对化学式为Y 3-x-y-zEu xLu yGd zAl 5-aGa aO 12(0<x≤0.3，0≤y<3，0≤z<3，0≤a<5，x+y+z≤3)的Eu离子掺杂钇铝石榴石结构荧光粉，本发明提供了一种Eu 2+离子掺杂钇铝石榴石结构荧光粉的制备方法，包括以下步骤：步骤a)合成EuSi 2O 2N 2粉体；步骤b)将获得的EuSi 2O 2N 2粉体和其他氧化物类原料及助溶剂进行混合；步骤c)将混合原料在还原条件下进行高温煅烧，得到Eu 2+离子掺杂钇铝石榴石结构荧光粉。
本发明对于所述EuSi 2O 2N 2粉体的制备方法并无特别限制，可以采用本领域技术人员熟知的方法，优选按照如下方法制备：根据化学式EuSi 2O 2N 2分别称取适量Eu 2O 3、Si 3N 4和SiO 2粉体原料，将各粉体原料在玛瑙研钵中混合均匀，然后将混合后的原料放入氮化硼或氮化硅坩埚中通过固相反应法在氨气气氛条件下进行高温煅烧获得EuSi 2O 2N 2粉体，固相反应法的煅烧温度优选为1300-1500℃，升温速率优选为4℃/min～10℃/min，保温时间优选为3-6h。
本发明步骤b)中对于所述助溶剂并无特别限制，优选为BaF 2或H 3BO 3；对合成钇铝石榴石结构荧光粉的其他原料也无特殊限制，优选为相对应元素的氧化物类粉体原料；原料的混料方法为使用玛瑙研钵手动混料或者通过球磨工艺进行混料。
在步骤c)中，本发明对所述混合原料进行高温煅烧，所使用的坩埚优选为氧化铝或氮化硼坩埚；所使用气氛可以为氮气气氛、氮氢混合气氛、碳气氛等还原性气氛，优选在氮气气氛中进行；高温煅烧温度优选为1400-1600℃，升温速率优选为4℃/min～10℃/min，保温时间优选为3-5h。
本发明对于用于高温煅烧的炉子并无特别限制，可以采用本领域技术人员熟知的装置，优选为金属电阻加热型、石墨电阻加热型或硅钼棒电阻加热型的气氛炉。
综上所述，本发明提供一种Eu 2+离子掺杂钇铝石榴石结构荧光粉 的制备方法，在使用常用易获取原料的条件下，利用两步固相反应法简单快速的在钇铝石榴石结构中实现Eu 2+离子掺杂。相比于已报道Eu 2+离子掺杂钇铝石榴石结构荧光粉的合成方法，本发明不需要使用Eu 2+的卤化物、硫化物等价格昂贵且稳定性差的化合物作为合成原料，也不需要借助强还原性酸来首先对Eu 2O 3原料进行还原处理。本发明方法工艺简单，成本低廉，易于工业化连续生产，具有广阔的工业应用前景。
为了进一步说明本发明的技术方案，下面结合实施例对本发明优选实施方案进行描述，但是应当理解，这些描述只是为进一步说明本发明的特征和优点，而不是对本发明权利要求的限制。
下述实施例中所使用的实验方法如无特殊说明，均为常规方法，所使用的材料、试剂、还原性气体，如无特殊说明，均可从商业途径得到。
实施例1：本专利提供的方法，使用EuSi 2O 2N 2粉体作为Eu源
据化学式EuSi 2O 2N 2，称取1g Eu 2O 3、0.3986g Si 3N 4、0.1704g SiO 2起始粉料放入玛瑙研钵中进行手动混料，待原料混合均匀后转移到氮化硼坩埚中放入管式气氛中，首先对气氛炉进行抽真空操作，然后通入还原性气体氨气，以5℃/min升温速度升到1000℃，然后以4℃/min的升温速度升到1400℃，保温5h，然后以4℃/min的降温速度降温至600℃后自然冷却至室温，将得到的粉体取出后放入玛瑙研钵中研碎成粉末得到EuSi 2O 2N 2粉体。据化学式Y 2.9Eu 0.1Al 5O 12，称取0.1g EuSi 2O 2N 2、1.2210g Y 2O 3、0.9508gAl 2O 3起始粉料，加入0.1g BaF 2作为助溶剂，共同放入球磨罐中于行星球磨机中球磨12h，取出浆料后在干燥箱中干燥10h，得到最终的混合粉体原料。将混合原料粉体转移到氧化铝坩埚中放入管式气氛中，首先对气氛炉进行抽真空操作，然后通入还原性气体氮气，以5℃/min升温速度升到1000℃，然后以4℃/min的升温速度升到1500℃，保温4h，然后以4℃/min的降温速度降温至600℃后自然冷却至室温，将得到的粉体取出后放入玛瑙研钵中研碎成粉末得到Eu离子掺杂钇铝石榴石结构荧光粉。
对比例1：直接使用Eu 2O 3粉体作为Eu源
据化学式Y 2.9Eu 0.1Al 5O 12，称取0.0656g Eu 2O 3、1.2210g Y 2O 3、0.9508gAl 2O 3起始粉料，加入0.1g BaF 2作为助溶剂，共同放入球磨罐中于行星球磨机中球磨12h，取出浆料后在干燥箱中干燥10h，得到最终的混合粉体原料。将混合原料粉体转移到氧化铝坩埚中放入管式气氛中，首先对气氛炉进行抽真空操作，然后通入还原性气体氮气，以5℃/min升温速度升到1000℃，然后以4℃/min的升温速度升到1500℃，保温4h，然后以4℃/min的降温速度降温至600℃后自然冷却至室温，将得到的粉体取出后放入玛瑙研钵中研碎成粉末得到Eu离子掺杂钇铝石榴石结构荧光粉。
利用XRD(X射线衍射仪)对得到的荧光粉的相纯度进行测试分析，结果如图1所示；利用荧光光谱仪对得到荧光粉的发光性能进行测试，结果如图2所示。通过实施例1和对比例测试结果可以看出，使用EuSi 2O 2N 2粉体作为Eu源，不会影响荧光粉的物相，得到的荧光粉为Eu 2+离子的宽光谱发光，而使用Eu 2O 3作为原料合成的荧光粉为Eu 3+的线光谱发光。
实施例2
据化学式EuSi 2O 2N 2，称取1g Eu 2O 3、0.3986g Si 3N 4、0.1704g SiO 2起始粉料放入玛瑙研钵中进行手动混料，待原料混合均匀后转移到氮化硼坩埚中放入管式气氛中，首先对气氛炉进行抽真空操作，然后通入还原性气体氨气，以5℃/min升温速度升到1000℃，然后以4℃/min的升温速度升到1400℃，保温5h，然后以4℃/min的降温速度降温至600℃后自然冷却至室温，将得到的粉体取出后放入玛瑙研钵中研碎成粉末得到EuSi 2O 2N 2粉体。据化学式Y 2.9Eu 0.1Al 4GaO 12，称取0.1g EuSi 2O 2N 2、1.2210gY 2O 3、0.7606gAl 2O 3、0.3496g Ga 2O 3起始粉料，加入0.1g BaF 2作为助溶剂，共同放入球磨罐中于行星球磨机中球磨12h，取出浆料后在干燥箱中干燥10h，得到最终的混合粉体原料。将混合原料粉体转移到氧化铝坩埚中放入管式气氛中，首先对气氛炉进行抽真空操作，然后通入还原性气体氮气，以5℃/min升温速度升 到1000℃，然后以4℃/min的升温速度升到1450℃，保温4h，然后以4℃/min的降温速度降温至600℃后自然冷却至室温，将得到的粉体取出后放入玛瑙研钵中研碎成粉末得到Eu离子掺杂钇铝石榴石结构荧光粉。
实施例3
据化学式EuSi 2O 2N 2，称取1g Eu 2O 3、0.3986g Si 3N 4、0.1704g SiO 2起始粉料放入玛瑙研钵中进行手动混料，待原料混合均匀后转移到氮化硼坩埚中放入管式气氛中，首先对气氛炉进行抽真空操作，然后通入还原性气体氨气，以5℃/min升温速度升到1000℃，然后以4℃/min的升温速度升到1400℃，保温5h，然后以4℃/min的降温速度降温至600℃后自然冷却至室温，将得到的粉体取出后放入玛瑙研钵中研碎成粉末得到EuSi 2O 2N 2粉体。据化学式GdY 1.9Eu 0.1Al 4GaO 12，称取0.1g EuSi 2O 2N 2、0.8002gY 2O 3、0.6761g Gd 2O 3、0.9508gAl 2O 3起始粉料，加入0.1g BaF 2作为助溶剂，共同放入球磨罐中于行星球磨机中球磨12h，取出浆料后在干燥箱中干燥10h，得到最终的混合粉体原料。将混合原料粉体转移到氧化铝坩埚中放入管式气氛中，首先对气氛炉进行抽真空操作，然后通入还原性气体氮气，以5℃/min升温速度升到1000℃，然后以4℃/min的升温速度升到1450℃，保温4h，然后以4℃/min的降温速度降温至600℃后自然冷却至室温，将得到的粉体取出后放入玛瑙研钵中研碎成粉末得到Eu离子掺杂钇铝石榴石结构荧光粉。

Claims (6)

  1. 一种Eu 2+离子掺杂钇铝石榴石结构荧光粉的制备方法，包括以下步骤：
    步骤a)合成EuSi 2O 2N 2粉体；
    步骤b)将获得的EuSi 2O 2N 2粉体和其他氧化物类原料及助溶剂进行混合；
    步骤c)将混合原料在还原气氛条件下进行高温煅烧，得到Eu 2+离子掺杂钇铝石榴石结构荧光粉。
  2. 根据权利要求1所述的制备方法，其特征在于，所述步骤a)中EuSi 2O 2N 2粉体采用原料Eu 2O 3、Si 3N 4和SiO 2通过高温固相反应法在还原气氛条件下合成。
  3. 根据权利要求1所述的制备方法，其特征在于，所述助溶剂为BaF 2、H 3BO 3或根据需要选择其他种类的助溶剂。
  4. 根据权利要求1所述的制备方法，其特征在于，所述步骤b)中混料方法为使用玛瑙研钵手动混料或者通过球磨工艺进行混料。
  5. 根据权利要求1所述的制备方法，其特征在于，所述步骤c)具体为：
    步骤c1)将所述混合原料置于氧化铝或氮化硼坩埚中；
    步骤c2)将所述混合原料在1400-1600℃还原气氛条件下进行高温煅烧。
  6. 权利要求1～5任意一项所述方法制备的Eu 2+离子掺杂钇铝石榴石结构荧光粉，其化学式为Y 3-x-y-zEu xLu yGd zAl 5-aGa aO 12，其中0<x<0.3，0≤y<3，0≤z<3，0≤a<5，x+y+z≤3。
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US5140449A (en) * 1991-05-31 1992-08-18 Hughes Aircraft Company Liquid crystal light valve in combination with a cathode ray tube containing a far-red emitting double-activated yttrium aluminum garnet phosphor
CN1844305A (zh) * 2006-04-14 2006-10-11 厦门大学 钇铝石榴石制备方法
CN101602944A (zh) * 2009-07-09 2009-12-16 宁波大学 一种稀土离子掺杂的钇铝石榴石纳米荧光粉体的生产方法
CN103160280A (zh) * 2011-12-08 2013-06-19 陈引幹 钇铝石榴石荧光材料其制法及包含其的发光二极管装置
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US5140449A (en) * 1991-05-31 1992-08-18 Hughes Aircraft Company Liquid crystal light valve in combination with a cathode ray tube containing a far-red emitting double-activated yttrium aluminum garnet phosphor
CN1844305A (zh) * 2006-04-14 2006-10-11 厦门大学 钇铝石榴石制备方法
CN101602944A (zh) * 2009-07-09 2009-12-16 宁波大学 一种稀土离子掺杂的钇铝石榴石纳米荧光粉体的生产方法
CN103347981A (zh) * 2010-09-27 2013-10-09 三星电子株式会社 荧光物质及其制备方法
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