Mukherjee Sumanta, Pathak Nimai, Ali Kawsar, Das Debarati, Dutta Dhanadeep
Fuel Chemistry Division, Bhabha Atomic Research Centre, Mumbai, 400085, India.
Radiochemistry Division, Bhabha Atomic Research Centre, Mumbai, 400085, India.
Phys Chem Chem Phys. 2022 May 11;24(18):10915-10927. doi: 10.1039/d2cp01031c.
A novel approach to generate a wide range of color characteristics such as near white, yellow, orange and red in MgF, by proper tailoring of the defect structure and varying the composition of Eu and Tb dopant ions have been presented here. It has been observed from positron annihilation lifetime spectroscopy (PALS) study that various defect centers such as mono vacancies and their cluster forms exist in the system, whose amount varies upon varying the dopant ion's composition. The experimentally observed positron lifetime values of the defect centers also matched well with the theoretically calculated lifetime values using the MIKA-DOPPLER package. It has been found that a few vacancies or defect centers act as color centers, while the cluster vacancies change the local symmetry of the rare earth ion by inducing more distortion surrounding them thereby resulting in different emission characteristics in the photoluminescence (PL) study. The defect-related host emission in combination with the green and red emission from Tb and Eu ions generated near-white-light in some of the compounds, while other compounds showed a variety of other color characteristics due to the Tb → Euenergy transfer dynamics. The various defect-related emissions, the role of the defect-related trap state in the decay kinetics and the energy-transfer dynamics were also understood by analyzing the electronic structure using HSE06 hybrid functional calculation.
本文提出了一种新方法,通过适当调整缺陷结构并改变Eu和Tb掺杂离子的组成,在MgF中产生一系列广泛的颜色特性,如近白色、黄色、橙色和红色。通过正电子湮没寿命谱(PALS)研究观察到,系统中存在各种缺陷中心,如单空位及其簇状形式,其数量随掺杂离子组成的变化而变化。实验观察到的缺陷中心的正电子寿命值也与使用MIKA-DOPPLER软件包理论计算的寿命值非常匹配。已经发现,一些空位或缺陷中心充当色心,而簇状空位通过在其周围引起更多畸变来改变稀土离子的局部对称性,从而在光致发光(PL)研究中产生不同的发射特性。在一些化合物中,与缺陷相关的基质发射与Tb和Eu离子产生的绿色和红色发射相结合,产生了近白光,而其他化合物由于Tb→Eu能量转移动力学而表现出各种其他颜色特性。通过使用HSE06杂化泛函计算分析电子结构,还了解了各种与缺陷相关的发射、缺陷相关陷阱态在衰减动力学中的作用以及能量转移动力学。