Xin Shuangyu, Gao Miao, Ma Jialing, Dai Heng, Zhu Ge
Key Laboratory of New Energy and Rare Earth Resource Utilization of State Ethnic Affairs Commission, College of Physics and Materials Engineering, Dalian Minzu University, 18 Liaohe West Road, Dalian, 116600, P. R. China.
College of New Energy, Bohai University, Jinzhou, 121000, P. R. China.
Dalton Trans. 2020 Nov 17;49(44):15800-15809. doi: 10.1039/d0dt02899a.
The development of novel white-light-emission phosphors is of great importance for applications in lighting and display fields. Trivalent Dy3+ is widely used as a potential luminescence center for white-light emission. However, Dy3+-doped phosphors often suffer a poor yellow to blue ratio due to the deficiency of its 4F9/2 → 6H15/2 transition, low luminescence efficiency, and unsatisfactory thermal stability. The importance of the present research work is that we have achieved a tunable white light in a single phased stannate phosphor Sr3Al10SnO20:Dy3+ with robust thermal stability. The crystal structure, phase purity, and chemical composition were investigated via X-ray diffraction Rietveld structure refinement, scanning electron microscopy, and energy dispersive spectrometry. The luminescence spectra indicated that Sr3Al10SnO20:Dy3+ not only exhibited characteristic 4F9/2 → 6HJ/2 (J=11, 13, and 15) inherent transition emissions of Dy3+, but also showed an abnormal blue band emission, which was identified through X-ray photoelectric spectroscopy as the T1 → S0 transitions of Sn2+, resulting from the valence variation of Sn4+. The efficient energy transfer from Sn2+ to Dy3+ was also confirmed and the transfer efficiency was calculated. Owing to the valence-variation-induced emission of Sn2+, a tunable white light could be realized from a cool to warm white light region, with Commission Internationale de l'Eclairage coordinates and a correlative color temperature varying from (0.277, 0.333) and 8634 K to (0.353, 0.404) and 4913 K, respectively. The luminescent and defects formation mechanism as well as the luminescence kinetics were further investigated. Moreover, Sr3Al10SnO20:Dy3+ had a high quantum efficiency (∼34.6%) and a super-stable thermal stability behavior (82.5% at 240 °C of the initial integral emission intensity at 30 °C) with a large activation energy (ΔE ∼ 0.1654 eV). Finally, a charge-compensation test was performed to further verify the effect of defects on the luminescence property and the related mechanism was discussed. The current work provides a novel method to achieve tunable white-light emission in Dy3+ single-doped phosphors and the related mechanism is effectual for other rare earths for potential applications in lighting and display fields.
新型白光发射荧光粉的开发对于照明和显示领域的应用具有重要意义。三价Dy3+被广泛用作白光发射的潜在发光中心。然而,由于Dy3+的4F9/2→6H15/2跃迁不足、发光效率低以及热稳定性不理想,Dy3+掺杂的荧光粉往往具有较差的黄蓝比。本研究工作的重要性在于,我们在具有强大热稳定性的单相锡酸盐荧光粉Sr3Al10SnO20:Dy3+中实现了可调谐白光。通过X射线衍射Rietveld结构精修、扫描电子显微镜和能量色散光谱对晶体结构、相纯度和化学成分进行了研究。发光光谱表明,Sr3Al10SnO20:Dy3+不仅表现出Dy3+固有的4F9/2→6HJ/2(J = 11、13和15)特征跃迁发射,还表现出异常的蓝带发射,通过X射线光电子能谱确定为Sn2+的T1→S0跃迁,这是由Sn4+的价态变化引起的。还证实了从Sn2+到Dy3+的有效能量转移并计算了转移效率。由于Sn2+的价态变化诱导发射,从冷白光到暖白光区域可以实现可调谐白光,国际照明委员会坐标和相关色温分别从(0.277, 0.333)和8634 K变化到(0.353, 0.404)和4913 K。进一步研究了发光和缺陷形成机制以及发光动力学。此外,SrAl10SnO20:Dy3+具有高量子效率(约34.6%)和超稳定的热稳定性行为(在240°C时为30°C时初始积分发射强度的82.5%),具有较大的活化能(ΔE约0.1654 eV)。最后,进行了电荷补偿测试以进一步验证缺陷对发光性能的影响并讨论了相关机制。目前的工作提供了一种在Dy3+单掺杂荧光粉中实现可调谐白光发射的新方法,并且相关机制对其他稀土在照明和显示领域的潜在应用是有效的。