四方AgGd（WO_4）_2：Eu~（3+）红色荧光粉的制备
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摘要
白光LED拥有发光效率高、节能、无热辐射、无污染等众多优点,被视为“绿色照明光源”的明日之星,是固体照明的重要光源,应用前景广泛。要实现白光发射的主要途径之一是利用稀土发光材料的荧光体转换技术,将LED芯片发射的蓝光／紫外光转换成白光。但目前所开发的白光LED用红色荧光粉的发光效率较低,不能满足要求,因此需要我们寻找新型高效的白光LED用红色荧光粉。本文利用高温固相反应法制备了AgGd(WO4)2:Eu3+红色荧光材料,讨论了温度对其物相及发光性能的影响,并通过向基质中掺杂Mo6+以及敏化剂Tb3+的能量传递来改进其发光性能。
采用高温固相法在750～1100℃制备了AgGd(WO4)2:Eu3+,物相分析表明AgGd(WO4)2存在单斜和四方两种结构,其中四方相尚未有文献报道；光谱分析表明AgGd(WO4)2:Eu3+可在以近紫外和蓝光作为激发源的LED芯片中用作红色荧光粉；AgGd(WO4)2:Eu3+的发光强度与Eu3+掺杂量和烧结温度有一定的关系,并且四方AgGd(WO4)2:Eu3+的发光强度高于单斜AgGd(WO4)2:Eu3+的发光强度。
为改进AgGd(WO4)2:Eu3+发光性能,向AgGd(WO4)2:Eu3+中掺杂了与W6+同一副族的Mo6+,物相分析表明Mo6+的掺杂并未改变AgGd(WO4)2的结构,但当Mo6+掺杂量逐渐增加时,AgGd(W1-yMoyO4)2晶胞体积逐渐减小；Mo6+的掺杂有助于提高AgGd(WO4)2:Eu3+的发光强度,Mo6+、Eu3+的掺杂量决定了AgGd(W1-yMoyO4)2的发光强度。
通过掺入敏化剂Tb3+,可以进一步提高AgGd(WO4)2:Eu3+和AgGd(W0.7Mo0.3O4)2:Eu3+的发光强度。光谱分析表明,AgGd(WO4)2:Tb3+以及AgGd(W0.7Mo0.3O4)2:Tb3+的发射光谱为Tb3+的特征发射光谱,AgGd(WO4)2:Tb3+和AgGd(W0.7Mo0.3O4)2:Tb3+的发光强度与Tb3+掺杂量有一定的关系。在AgGd(WO4)2:Eu3+, Tb3+和AgGd(W0.7Mo0.3O4)2:Eu3+, Tb3+体系中,Eu3+和Tb3+的特征发射峰同时存在,Tb3+的发射强度由于Eu3+的加入而减弱,而Eu3+的发射强度由于Tb3+的加入而增强,存在由Tb3+向Eu3+的能量传递,此观点得到了光谱研究和荧光寿命测试结果的支持,并且在AgGd(W0.7Mo0.3O4)2:Eu3+, Tb3+体系中的能量传递效率大于在AgGd(WO4)2:Eu3+, Tb3+体系中的能量传递效率。
White Light-emitting diode (WLED) as the one of hopeful green illumination light source has extensively applied in solid-state lighting, due to its lots of advantages, such as high efficacy, energy saving, and envirnment-friendly. The mainstream scheme to abtain WLED is phosphor conversion. However, the current red phosphors used for WLED displays a rather low efficient emission under near-UV light excitation. So prepare red phosphors with highly-efficientunder excitation of near-UV light is the biggest problem for WLED. In this work, a new red phosphor AgGd(WO4)2:Eu3+ was prepared by solid-state reaction. The influence of temperature on the luminescent properties and structure was discussed. Two method, codoping Mo6+ in matrix and energy transfer between sensitizer Tb3+ and Eu3+, were adoped to improve the luminescent properties of AgGd(WO4)2:Eu3+.
AgGd(WO4)2:Eu3+ was synthesized by solid-state reaction in the temperature range of 750～1100℃. AgGd(WO4)2 has two homogenous structures, monocline phase and tetragonal phase. Whereas, the tetragonal phase AgGd(WO4)2 was not reported in literatures. The PL results showed that AgGd(WO4)2:Eu3+ was a red phosphor, which could be used in near-UV and blue light LED. The emission intensity of AgGd(WO4)2:Eu3+ was affected by annealing temperature. Additionally, the emission intensity of the tetragonal phase was higher than the monocline phase AgGd(WO4)2:Eu3+.
In order to improve the luminescent properties of AgGd(WO4)2:Eu3+, Mo6+ ions was doped in AgGd(WO4)2:Eu3+. The results indicated that the structure of AgGd(WO4)2 was not changed, while the lattice volume of which was decreased and the emission intensity was enhanced with the increase of Mo6+.
The second method was taked to improve the AgGd(WO4)2:Eu3+. The sensitizer Tb3+ was co-doped to enhance the PL intensity of AgGd(WO4)2:Eu3+. Characteristic emission of Tb3+ can be detected in AgGd(WO4)2:Tb3+ and AgGd(W0.7Mo0.3O4)2:Tb3+. For the AgGd(WO4)2:Eu3+,Tb3+ and AgGd(W0.7Mo0.3O4)2:Eu3+,Tb3+, the energy transfer from Tb3+to Eu3+can be measured. However, the energy transfer efficiency of AgGd(W0.7Mo0.3O4)2:Eu3+, Tb3+ was higher than that of AgGd(WO4)2:Eu3+,Tb3+.
采用高温固相法在750～1100℃制备了AgGd(WO4)2:Eu3+,物相分析表明AgGd(WO4)2存在单斜和四方两种结构,其中四方相尚未有文献报道；光谱分析表明AgGd(WO4)2:Eu3+可在以近紫外和蓝光作为激发源的LED芯片中用作红色荧光粉；AgGd(WO4)2:Eu3+的发光强度与Eu3+掺杂量和烧结温度有一定的关系,并且四方AgGd(WO4)2:Eu3+的发光强度高于单斜AgGd(WO4)2:Eu3+的发光强度。
为改进AgGd(WO4)2:Eu3+发光性能,向AgGd(WO4)2:Eu3+中掺杂了与W6+同一副族的Mo6+,物相分析表明Mo6+的掺杂并未改变AgGd(WO4)2的结构,但当Mo6+掺杂量逐渐增加时,AgGd(W1-yMoyO4)2晶胞体积逐渐减小；Mo6+的掺杂有助于提高AgGd(WO4)2:Eu3+的发光强度,Mo6+、Eu3+的掺杂量决定了AgGd(W1-yMoyO4)2的发光强度。
通过掺入敏化剂Tb3+,可以进一步提高AgGd(WO4)2:Eu3+和AgGd(W0.7Mo0.3O4)2:Eu3+的发光强度。光谱分析表明,AgGd(WO4)2:Tb3+以及AgGd(W0.7Mo0.3O4)2:Tb3+的发射光谱为Tb3+的特征发射光谱,AgGd(WO4)2:Tb3+和AgGd(W0.7Mo0.3O4)2:Tb3+的发光强度与Tb3+掺杂量有一定的关系。在AgGd(WO4)2:Eu3+, Tb3+和AgGd(W0.7Mo0.3O4)2:Eu3+, Tb3+体系中,Eu3+和Tb3+的特征发射峰同时存在,Tb3+的发射强度由于Eu3+的加入而减弱,而Eu3+的发射强度由于Tb3+的加入而增强,存在由Tb3+向Eu3+的能量传递,此观点得到了光谱研究和荧光寿命测试结果的支持,并且在AgGd(W0.7Mo0.3O4)2:Eu3+, Tb3+体系中的能量传递效率大于在AgGd(WO4)2:Eu3+, Tb3+体系中的能量传递效率。
White Light-emitting diode (WLED) as the one of hopeful green illumination light source has extensively applied in solid-state lighting, due to its lots of advantages, such as high efficacy, energy saving, and envirnment-friendly. The mainstream scheme to abtain WLED is phosphor conversion. However, the current red phosphors used for WLED displays a rather low efficient emission under near-UV light excitation. So prepare red phosphors with highly-efficientunder excitation of near-UV light is the biggest problem for WLED. In this work, a new red phosphor AgGd(WO4)2:Eu3+ was prepared by solid-state reaction. The influence of temperature on the luminescent properties and structure was discussed. Two method, codoping Mo6+ in matrix and energy transfer between sensitizer Tb3+ and Eu3+, were adoped to improve the luminescent properties of AgGd(WO4)2:Eu3+.
AgGd(WO4)2:Eu3+ was synthesized by solid-state reaction in the temperature range of 750～1100℃. AgGd(WO4)2 has two homogenous structures, monocline phase and tetragonal phase. Whereas, the tetragonal phase AgGd(WO4)2 was not reported in literatures. The PL results showed that AgGd(WO4)2:Eu3+ was a red phosphor, which could be used in near-UV and blue light LED. The emission intensity of AgGd(WO4)2:Eu3+ was affected by annealing temperature. Additionally, the emission intensity of the tetragonal phase was higher than the monocline phase AgGd(WO4)2:Eu3+.
In order to improve the luminescent properties of AgGd(WO4)2:Eu3+, Mo6+ ions was doped in AgGd(WO4)2:Eu3+. The results indicated that the structure of AgGd(WO4)2 was not changed, while the lattice volume of which was decreased and the emission intensity was enhanced with the increase of Mo6+.
The second method was taked to improve the AgGd(WO4)2:Eu3+. The sensitizer Tb3+ was co-doped to enhance the PL intensity of AgGd(WO4)2:Eu3+. Characteristic emission of Tb3+ can be detected in AgGd(WO4)2:Tb3+ and AgGd(W0.7Mo0.3O4)2:Tb3+. For the AgGd(WO4)2:Eu3+,Tb3+ and AgGd(W0.7Mo0.3O4)2:Eu3+,Tb3+, the energy transfer from Tb3+to Eu3+can be measured. However, the energy transfer efficiency of AgGd(W0.7Mo0.3O4)2:Eu3+, Tb3+ was higher than that of AgGd(WO4)2:Eu3+,Tb3+.
引文
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