Yellow/Orange-Emitting ABZn2Ga2O7:Bi3+(A = Ca, Sr; B = Ba, Sr) Phosphors: Optical Temperature Sensing and White Light-Emitting Diode Applications,Chemistry of Materials

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Yellow/Orange-Emitting ABZn2Ga2O7:Bi3+(A = Ca, Sr; B = Ba, Sr) Phosphors: Optical Temperature Sensing and White Light-Emitting Diode Applications
Chemistry of Materials ( IF 7.2 ) Pub Date : 2020-03-09 , DOI: 10.1021/acs.chemmater.0c00054
Dongjie Liu _{1,

2} , Xiaohan Yun ₃ , Peipei Dang _{1,

2} , Hongzhou Lian ₁ , Mengmeng Shang ₄ , Guogang Li ₃ , Jun Lin _{1,

5}

Affiliation

Recently, there has been growing interest in developing Bi³⁺-activated luminescence materials for optoelectronic applications. Herein, new yellow/orange-emitting ABZn₂Ga₂O₇:Bi³⁺ (ABZGO, A = Ca, Sr; B = Ba, Sr) phosphors with tunable optical properties are synthesized by an alkaline earth cation substitution. When Sr²⁺ substitutes Ca²⁺ and Ba²⁺, the excitation wavelength has a red shift from 325 to 363 nm, matching well with the n-UV chip based white light-emitting diodes (WLEDs). CaBaZn₂Ga₂O₇:0.01Bi³⁺ (CBZGO:0.01Bi³⁺) exhibits two evident emission peaks at 570 and 393 nm originating from the respective occupation of Ca and Ba sites by Bi³⁺ ions. The optical tuning of the CBZGO:Bi³⁺ phosphor is achieved by changing the Bi³⁺ doping content and excitation wavelength based on the selected site occupation. Differently, both SrBaZn₂Ga₂O₇:0.01Bi³⁺ (SBZGO:0.01Bi³⁺) and Sr₂Zn₂Ga₂O₇:0.01Bi³⁺ (SZGO:0.01Bi³⁺) phosphors exhibit a single broad emission band, peaking at 600 and 577 nm, respectively. Two different Bi³⁺ sites are also verified respectively in SBZGO and SZGO hosts by the Gaussian fitting of the asymmetric PL spectra and lifetime analysis. The different luminescence behaviors of ABZGO:0.01Bi³⁺ phosphors should be ascribed to the synergistic effect of the centroid shift, crystal-field splitting, and Stokes shift. Moreover, the temperature-dependent PL spectra reveal that cation substitutions of Sr²⁺ for Ca²⁺ and Ba²⁺ can efficiently improve the thermal stability of ABZGO:0.01Bi³⁺ phosphors. In view of different thermal responses to various temperatures for two emission peaks of the CBZGO:0.01Bi³⁺ phosphor, an optical thermometer is designed and has a good relative sensitivity (S_r = 1.453% K^–1) at 298 K. Finally, a WLED with CRI = 97.9 and CCT = 3932 K is obtained by combining SZGO:0.01Bi³⁺ and BAM:Eu²⁺ phosphors with a 370 nm n-UV chip, demonstrating that SZGO:0.01Bi³⁺ is an excellent yellow-orange-emitting phosphor for n-UV WLED devices. This work stimulates the exploration of optical tuning by cation substitution to obtain remarkable luminescence materials for optical temperature sensing and WLED applications.

中文翻译：

发出黄色/橙色的ABZn ₂ Ga ₂ O ₇：Bi ³⁺（A = Ca，Sr; B = Ba，Sr）荧光粉：光学温度传感和白光发光二极管应用

近来，对开发用于光电应用的Bi ³⁺活化的发光材料的兴趣日益增长。在此，通过碱土金属阳离子取代合成具有可调的光学性质的新的发黄/橙色的ABZn ₂ Ga ₂ O ₇：Bi ³⁺（ABZGO，A = Ca，Sr； B = Ba，Sr）荧光粉。当Sr ²⁺替代Ca ²⁺和Ba ^2+时，激发波长从325到363 nm发生红移，与基于n-UV芯片的白光发光二极管（WLED）很好地匹配。CaBaZn ₂ Ga ₂ O ₇：0.01Bi ³⁺（CBZGO：0.01Bi ³⁺）在570和393 nm处显示两个明显的发射峰，这是由于Bi ³⁺离子分别占据了Ca和Ba位。CBZGO：Bi ³⁺荧光粉的光学调谐是通过根据选定的位点占用改变Bi ^3+的掺杂含量和激发波长来实现的。不同地，SrBaZn ₂ Ga ₂ O ₇：0.01Bi ³⁺（SBZGO：0.01Bi ³⁺）和Sr ₂ Zn ₂ Ga ₂ O ₇：0.01Bi ³⁺（SZGO：0.01Bi ³⁺）磷光体显示出一个单一的宽发射带，分别在600和577 nm处达到峰值。通过不对称PL谱的高斯拟合和寿命分析，分别在SBZGO和SZGO主机中验证了两个不同的Bi ³⁺位点。ABZGO：0.01Bi ³⁺荧光粉的不同发光行为应归因于质心位移，晶体场分裂和斯托克斯位移的协同效应。此外，温度依赖性PL光谱表明，Sr ²⁺取代Ca ²⁺和Ba ^2+的阳离子可以有效提高ABZGO：0.01Bi ³⁺的热稳定性。荧光粉。考虑到CBZGO：0.01Bi ³⁺荧光粉的两个发射峰对各种温度的不同热响应，设计了一种光学温度计，并在298 K时具有良好的相对灵敏度（S _r = 1.453％K – ¹）。通过将SZGO：0.01Bi ³⁺和BAM：Eu ²⁺荧光粉与370 nm n-UV芯片组合获得CRI = 97.9和CCT = 3932 K的WLED ，表明SZGO：0.01Bi ³⁺是一种优异的黄光-用于n-UV WLED器件的橙色发光磷光体。这项工作刺激了通过阳离子取代的光学调谐的探索，以获得用于光学温度感测和WLED应用的卓越发光材料。

更新日期：2020-04-23

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