Structures and spectroscopic characteristics of barium-sulfur-telluro-borate glasses: Role of Sm3+ and Dy3+ Co-activation

https://doi.org/10.1016/j.matchemphys.2020.122862Get rights and content

Highlights

  • Sm3+/Dy3+ co-activated barium-sulfo-telluro-borate glasses were prepared.

  • Sm3+/Dy3+ co-doping influences the spectroscopic traits of the glasses.

  • Advanced radiative properties of glasses were obtained.

  • Proposed glasses were shown to be suitable for lasing and white light application.

Abstract

This paper reports the preparation of some samarium ions (Sm3+) and dysprosium ions (Dy3+) co-doped barium-sulfur-telluro-borate glasses using the standard melt quenching. The influence of the co-doping on the structures and spectroscopic traits of these glasses was analyzed to determine the feasibility of achieving an intense lasing and white light-emitting action. The XRD pattern of the as-quenched samples confirmed their glassy nature. The FTIR and Raman spectra showed the existence of BO4, BO3, TeO4, and TeO3 functional groups. The EDX spectra and elemental maps confirmed the presence of right elements and their homogeneous distribution in the glass network. The absorption spectra revealed the characteristics peaks of the Dy3+ and Sm3+. The intense absorption transitions from 6H15/2 to 6P7/2, 4I15/2, 6Fk/2 and 6Hj/2 levels were matched to the Dy3+ and the weak transitions from the 6H5/2 to 6F5/2, 6F3/2, 6H15/2 and 6F1/2 levels were due to the Sm3+. The Judd-Ofelt intensity and radiative parameters were calculated to complement the experimental optical results. The luminescence spectra of the glasses revealed the characteristic emission bands of the co-activated ions which were ascribed to the energy transfer mechanisms from the Dy3+ to Sm3+. Raman and decay curve analyses revealed the low phonon energy (680 cm−1) and a decreasing trend in the lifetimes of the excited states, respectively. The achieved high value of the branching ratio of 85.8% for the 4F9/2 → 6H13/2 transition in BSTSmDy1.5 sample indicated its lasing potency. The CIE plot of the glasses exhibited their prospect for the white light generation.

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).

References (58)

  • M. Shoaib et al.

    Physical and luminescence properties of samarium doped oxide and oxyfluoride phosphate glasses

    Mater. Chem. Phys.

    (2019)
  • Y.A. Tanko et al.

    Prominent spectral features of Sm3+ ion in disordered zinc tellurite glass

    Res. Phys.

    (2016)
  • P.P. Pawar et al.

    Physical, thermal, structural and optical properties of Dy3+ doped lithium alumino-borate glasses for bright W-LED

    J. Lumin.

    (2017)
  • B.C. Jamalaiah et al.

    White light generation in Dy2O3 -doped NBSAZB glasses

    Opt. Mater. (Amst).

    (2017)
  • A.B.F.A. Mohammed et al.

    Structural, thermal, optical and dielectric studies of Dy3+: B2O3-ZnO-PbO-Na2O-CaO glasses for white LEDs application

    Opt. Mater. (Amst).

    (2017)
  • I. Abdullahi et al.

    Waveguide laser potency of samarium doped BaSO4-TeO2-B2O3 glasses : evaluation of structural and optical qualities

    J. Lumin.

    (2019)
  • N. Deopa et al.

    Spectral studies of Eu3+ doped lithium lead alumino borate glasses for visible photonic applications

    Optic Laser. Technol.

    (2018)
  • K. Maheshvaran et al.

    Composition dependent structural and optical properties of Sm3+ doped boro-tellurite glasses

    J. Lumin.

    (2011)
  • K. Annapoorani et al.

    Structural and spectroscopic behavior of Er3+ : Yb3+ co-doped lithium telluroborate glasses

    Phys. B Phys. Condens. Matter

    (2015)
  • K. Annapoorani et al.

    Spectroscopic properties of Eu3+ ions doped Barium telluroborate glasses for red laser applications

    J. Non-Cryst. Solids

    (2017)
  • V.P. Tuyen et al.

    Dy3+ ions as optical probes for studying structure of boro-tellurite glasses

    J. Lumin.

    (2016)
  • S. Zulfiqar Ali Ahamed et al.

    Spectroscopic and laser properties of Sm3+ ions doped lithium fluoroborate glasses for efficient visible lasers

    Spectrochim. Acta Part A Mol. Biomol. Spectrosc.

    (2013)
  • P.P. Pawar et al.

    Physical and optical properties of Dy3+/Pr3+ Co-doped lithium borate glasses for W-LED

    J. Alloys Compd.

    (2016)
  • V.H. Rao et al.

    Luminescence properties of Sm3+ ions doped heavy metal oxide tellurite-tungstate-antimonate glasses

    Ceram. Int.

    (2017)
  • V. Uma et al.

    Effect of ZnO on the spectroscopic properties of Dy3+ doped zinc telluroborate glasses for white light generation

    J. Non-Cryst. Solids

    (2018)
  • C.K. Jayasankar et al.

    Spectroscopic investigations of Dy3+ ions in borosulphate glasses

    Phys. B.

    (1997)
  • K. Mariselvam et al.

    Concentration-dependence and luminescence studies of erbium doped barium lithium fluoroborate glasses

    Optic Laser. Technol.

    (2019)
  • N. Deopa et al.

    Spectroscopic investigations on Dy3+ ions doped zinc lead alumino borate glasses for photonic device applications

    J. Rare Earths

    (2019)
  • H.K. Obayes et al.

    Structural and optical properties of strontium/copper co-doped lithium borate glass system

    Phys. B Condens. Matter

    (2016)
  • Cited by (40)

    View all citing articles on Scopus
    View full text