Jiménez José A, Hedge Vinod, Viswanath C S Dwaraka, Amesimenu Richard
Center for Advanced Materials Science, Department of Biochemistry, Chemistry & Physics, Georgia Southern University, Statesboro, Georgia 30460, United States.
Department of Physics, Manipal Institute of Technology Bengaluru, Manipal Academy of Higher Education, Manipal, Karnataka 576104, India.
ACS Phys Chem Au. 2024 Oct 21;4(6):720-735. doi: 10.1021/acsphyschemau.4c00066. eCollection 2024 Nov 27.
Dysprosium-doped glasses are of interest for applications in light-emitting devices, yet the full range of effects of Dy ions on glass properties is not fully understood. In this work, phosphate glasses with 50PO-(50 - )BaO-DyO (0 ≤ ≤ 4.0 mol %) nominal compositions were prepared by melting and the impact of Dy ions on glass physical, structural, thermo-mechanical, and optical properties was evaluated. Following refractive index, density, and X-ray diffraction characterizations, the glasses were studied comprehensively through Raman spectroscopy, X-ray photoelectron spectroscopy, dilatometry, optical absorption, and photoluminescence (PL) spectroscopy. The thorough investigation and data analyses shed light on the Dy-driven structural and thermal properties reported here for the first time. The thermal expansion behavior was put in context with the reported data for other lanthanides and analyzed in the framework of the high ionic field strengths, leading to tighter glass networks. Further, a detailed analysis of the absorption, PL, and emission decay curves was carried out, providing insights into the origin of the optical behavior. Supported is the hypothesis that the cross-relaxation channels between Dy ions taking place at low concentrations are responsible for the decrease in the decay times while the PL attractive for lighting applications still improves. Conversely, high Dy concentrations facilitate the emission quenching proceeding via an electric dipole-dipole interaction likely incorporating the resonant excitation migration pathway for Dy-Dy mean distances shorter than ∼15 Å.
掺镝玻璃在发光器件应用中备受关注，然而镝离子对玻璃性能的全面影响尚未完全明晰。在本研究中，通过熔融法制备了标称组成为50PO-(50 - )BaO-DyO（0 ≤ ≤ 4.0 mol%）的磷酸盐玻璃，并评估了镝离子对玻璃物理、结构、热机械和光学性能的影响。在进行折射率、密度和X射线衍射表征之后，通过拉曼光谱、X射线光电子能谱、热膨胀法、光吸收和光致发光（PL）光谱对玻璃进行了全面研究。此次深入的研究和数据分析首次揭示了镝离子驱动的结构和热性能。将热膨胀行为与其他镧系元素的报道数据相结合，并在高离子场强的框架内进行分析，结果表明会形成更紧密的玻璃网络。此外，还对吸收、PL和发射衰减曲线进行了详细分析，从而深入了解光学行为的起源。支持这样一种假设：低浓度下镝离子之间的交叉弛豫通道是导致衰减时间缩短的原因，而对于照明应用具有吸引力的PL仍会得到改善。相反，高浓度的镝会促进通过电偶极 - 偶极相互作用发生的发射猝灭，这种相互作用可能包含了镝 - 镝平均距离小于约15 Å时的共振激发迁移途径。
