Structures and spectroscopic characteristics of barium-sulfur-telluro-borate glasses: Role of Sm3+ and Dy3+ Co-activation
Introduction
Due to the sharp and non-ambiguous spectral features, the rare-earth (RE) ions became the fundamental sources of the optimized technological materials particularly in the fields of optics, solar concentrators, and radiation dosimetry [1,2]. The technological advancement drives the need of developing novel and strategic optical materials with an optimized performance aimed at meeting the ensuing needs. In this regard, the selection of the suitable host matrix for the RE doping to match a specific requirement remains challenging [2,3]. The crystals and glasses are found to be the excellent gain materials (for example laser and amplifiers) with minimal scattering loss and thereby emerged as the dominant host for RE ions [4]. While crystal hosts are characterized by narrow bandwidth due to the settlement of the active RE ions in only specific site of the crystal lattice, the glasses due to their random atomic arrangements offer the advantage of having the broader absorption and emission bandwidths [4] thanks to the occupation of many divergent sites by the RE ions. Among the various types of glass hosts, oxide system demonstrates striking spectroscopic features due to the high quantum efficiency and good RE ions solubility [5,6]. In the context of the reported uniform and unique spectroscopic attributes, the telluro-borate oxide glasses, in particular, are the outstanding hosts for the RE ions intake for both mono and co-doped systems [7,8].
The co-doping of the glass hosts with two non-identical RE ions has become a favorable way to minimize the luminescence quenching effect, thereby increasing the luminescence efficiency [9]. To illustrate this, Peng et al. (2019) reported the enhancement in the luminescence efficiency of Eu3+ activated oxyfluoride glass host by co-doping with Yb3+ ions [10]. However, the low radiative lifetime was recorded. Similarly, the up-conversion luminescence enhancement of the Ho3+/Yb3+ co-doped tellurite glass in the visible region was demonstrated by Li et al. (2019) [11]. The NIR and visible region emission enhancement by co-doping niobium germanate glass with Er3+/Yb3+ ions was shown by Marcondes et al. [12]. In addition, Afef (2017) et al. successfully achieved an enhanced stimulated emission cross-section in the phosphate-based glass matrix with Nd3+/Yb3+ co-doping. However, the branching ratio and radiative lifetimes were low [13].
Among all the fifteen RE ions, the Sm3+ demonstrates strong fluorescence in the wavelength range of 450–750 nm (visible region), substantial emission cross-section, small non-radiative decay associated with the high energy gap and enhanced quantum efficiency [14,15]. The fluorescence of Sm3+ is due the electric dipole electronic transitions 4G5/2 to 6Hi/2 levels (i = 5, 7, 9 and 11 respectively), where the strength of the transition is a function of the Sm3+ concentration [16]. The Sm3+ has a wide range of applications for example in the color display, high-density optical storage and undersea communication devices [17]. Additionally, the Dy3+ displays strong fluorescence in the wavelength range of 470–500 nm and 570–750 nm [18]. The luminescence of Dy3+ is due to the 4F9/2 to 6H11/2, 6H13/2 (yellow) and 6H15/2 (blue) transitions [18]. The suitability of the Dy3+ doped telluro-borate glass as a white light generator was reported by Uma and Marimuthu [19]. The high symmetry of Dy3+ in the multi-component telluro-borate glass can promote the luminescence, thus making it suitable for the white light generation at 378 nm excitation [20]. The low level of di-electric loss (at high frequencies) of the Dy3+ doped telluro-borate glass suggests its suitability for the application in the photonic devices [21].
Our earlier report [22] disclosed the striking spectroscopic features of the newly developed samarium doped barium sulfur telluro-borate glass matrix. In this work, the impact of dysprosium co-doping on the structural and spectroscopic traits of the synthesized glass matrix was extensively investigated via systematic analyses. The Dy3+↔Dy3+, Dy3+↔Sm3+, and Sm3+↔Sm3+ energy transfer mechanisms were analyzed and the transfer channels were proposed. In addition, the evaluated absorption, emission and radiative properties in the present study were compared with the earlier state of the art reports. To the best of our knowledge, for the first time, the influence of Sm3+ and Dy3+co-doping on the proposed glass host is explored.
Section snippets
Materials and methods
A series of Sm3+/Dy3+ co-activated barium sulfur telluroborate glasses with the composition of (69-x)B2O3–15BaSO4–15TeO2-1Sm2O3-xDy2O3 (0.5 ≤ x ≤ 2.5 mol%) was prepared using the standard melt quenching technique. The Sigma Aldrich's supplied good purity (≥99.5%) powdered chemicals (Sm2O3, Dy2O3, B2O3, BaSO4, and TeO2) were used as initial reagents to prepare the samples. Proper weighing of the chemicals was conducted via the Mettler Toledo digital scale at a resolution of ±0.001 g. All the
XRD analysis
The XRD pattern of the as-synthesized BSTSmDy1.0 glass is displayed in Fig. 2. The pattern is completely devoid of sharp Bragg peaks but marked by ample tiny bumps in the region of 20° to 50°. All the remaining samples exhibited the same pattern. The absence of any sharp intensity peak thus confirmed the glassy nature of the as-quenched samples [23].
FTIR analysis
The FTIR spectral analysis was used to scrutinize the changes in the vibrational modes of the various functional groups in the synthesized glasses.
Conclusions
The barium-sulfur-telluro-borate glasses activated with Dy3+ and Sm3+ were synthesized using the melt quenching method and systematically characterized to explore the possibility of getting the visible laser and white light-emitting diodes. The XRD patterns of the as-quenched samples confirmed their glassy states. The FTIR and de-convoluted Raman spectra revealed the presence of BO4, BO3, TeO4, and TeO3 functional groups inside the glasses. The room temperature UV-VIS-NIR spectra of the samples
CRediT authorship contribution statement
I. Abdullahi: Conceptualization, Investigation, Formal analysis, Writing - original draft. S. Hashim: Supervision, Funding acquisition, Writing - review & editing, Resources. S.K. Ghoshal: Writing - review & editing, Supervision, Project administration, Visualization, Validation. A.U. Ahmad: Data curation, Visualization.
Declaration of competing interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgements
This work was supported by the Ministry of Education Malaysia and Universiti Teknologi Malaysia through UTMSHINE Signature Grants (No. 07G82 and 07G90).
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