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<p>Bismuth-based glasses have emerged as eco-friendly, lead-free alternatives for advanced optical and shielding applications. In this study, zinc–bismuth borate glasses with the nominal composition (30 − <i>x</i>)Bi<sub>2</sub>O<sub>3</sub>–30B<sub>2</sub>O<sub>3</sub>–40ZnO–<i>x</i>MO (where MO signifies Sm<sub>2</sub>O<sub>3</sub> or CuO, <i>x</i> = 0, 5&#xa0;mol%) were synthesized via the melt-quenching technique. The investigation focused on the quantitative impact of Sm<sub>2</sub>O<sub>3</sub> and CuO doping on the physical, structural and spectroscopic properties of the matrix. The impacts on density, molar volume, structural, mechanical, and photoluminescence properties were extensively investigated. Examination methodologies included X-ray diffraction (XRD), Fourier-transform infrared (FTIR) spectroscopy, and ultrasonic velocity measurements. XRD analysis confirmed the amorphous nature of the synthesized glasses. FTIR spectra indicated an increase in the cross-link density of the Bi<sub>2</sub>O<sub>3</sub>–B<sub>2</sub>O<sub>3</sub>–ZnO network, evidenced by the emergence of [BO<sub>4</sub>] units and an increased presence of [BiO<sub>6</sub>] and [BiO<sub>3</sub>] groups, which collectively enhanced the covalent character of the chemical bonds. Ultrasonic measurements revealed that both longitudinal and shear velocities increased with Sm<sub>2</sub>O<sub>3</sub> doping but decreased with the addition of CuO. This trend is attributed to the enhanced structural connectivity and rigidity induced by Sm<sup>3+</sup> ions. Consequently, mechanical properties (including elastic moduli, microhardness (<i>H</i><sub>u</sub>), Poisson’s ratio, and Debye temperature) showed a significant improvement with Sm<sub>2</sub>O<sub>3</sub> substitution. A direct correlation was observed between microhardness and the softening temperature <i>T</i><sub>s</sub>, the increase in <i>T</i><sub>s</sub> with Sm<sub>2</sub>O<sub>3</sub> and CuO content indicates improved cross-linking and a reduction in non-bridging oxygen (NBO) atoms, aligning with density and FTIR data. Photoluminescence (PL) spectra obtained in the UV–Visible–NIR range exhibited four characteristic emission bands for Sm<sub>2</sub>O<sub>3</sub>-doped glass at 565, 602, 648, and 702&#xa0;nm, corresponding to the <sup>4</sup>G<sub>5/2</sub> to <sup>6</sup>H<sub>5/2, 7/2, 9/2, 11/2</sub> transitions. Additionally, universal emission peaks were observed at 380 and 405&#xa0;nm (Bi<sup>3+</sup> ions), 462&#xa0;nm (band-edge excitation), 469&#xa0;nm (Zn interstitials/vacancies), and 543&#xa0;nm (oxygen vacancy defects). The enhancement in ultrasonic velocities was linked to the structural transition of boron from threefold (BO<sub>3</sub>) to fourfold (BO<sub>4</sub>) coordination, increasing network stiffness. Finally, PL intensity was significantly enhanced by Sm<sup>3+</sup> doping but showed a decrement with Cu<sup>2+</sup> incorporation. The outcomes demonstrate that Sm<sub>2</sub>O<sub>3</sub> doping greatly improves mechanical and optical properties, making these glasses acceptable for photonic purposes.</p>

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Enhancement of structural and photoluminescence characterizations in Sm3+ and Cu2+-doped zinc bismuth borate glasses

  • 期刊论文

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  • 发表日期：

    2026年3月3日

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  • Khaled Hamdy,
  • Ahmed Nabhan,
  • Mohamed Taha,
  • Mohamed I. Shehata,
  • Hoong-Pin Lee,
  • Maher Rashad,
  • Asmaa M. A. Mahmoud

摘要

Bismuth-based glasses have emerged as eco-friendly, lead-free alternatives for advanced optical and shielding applications. In this study, zinc–bismuth borate glasses with the nominal composition (30 − x)Bi2O3–30B2O3–40ZnO–xMO (where MO signifies Sm2O3 or CuO, x = 0, 5 mol%) were synthesized via the melt-quenching technique. The investigation focused on the quantitative impact of Sm2O3 and CuO doping on the physical, structural and spectroscopic properties of the matrix. The impacts on density, molar volume, structural, mechanical, and photoluminescence properties were extensively investigated. Examination methodologies included X-ray diffraction (XRD), Fourier-transform infrared (FTIR) spectroscopy, and ultrasonic velocity measurements. XRD analysis confirmed the amorphous nature of the synthesized glasses. FTIR spectra indicated an increase in the cross-link density of the Bi2O3–B2O3–ZnO network, evidenced by the emergence of [BO4] units and an increased presence of [BiO6] and [BiO3] groups, which collectively enhanced the covalent character of the chemical bonds. Ultrasonic measurements revealed that both longitudinal and shear velocities increased with Sm2O3 doping but decreased with the addition of CuO. This trend is attributed to the enhanced structural connectivity and rigidity induced by Sm3+ ions. Consequently, mechanical properties (including elastic moduli, microhardness (Hu), Poisson’s ratio, and Debye temperature) showed a significant improvement with Sm2O3 substitution. A direct correlation was observed between microhardness and the softening temperature Ts, the increase in Ts with Sm2O3 and CuO content indicates improved cross-linking and a reduction in non-bridging oxygen (NBO) atoms, aligning with density and FTIR data. Photoluminescence (PL) spectra obtained in the UV–Visible–NIR range exhibited four characteristic emission bands for Sm2O3-doped glass at 565, 602, 648, and 702 nm, corresponding to the 4G5/2 to 6H5/2, 7/2, 9/2, 11/2 transitions. Additionally, universal emission peaks were observed at 380 and 405 nm (Bi3+ ions), 462 nm (band-edge excitation), 469 nm (Zn interstitials/vacancies), and 543 nm (oxygen vacancy defects). The enhancement in ultrasonic velocities was linked to the structural transition of boron from threefold (BO3) to fourfold (BO4) coordination, increasing network stiffness. Finally, PL intensity was significantly enhanced by Sm3+ doping but showed a decrement with Cu2+ incorporation. The outcomes demonstrate that Sm2O3 doping greatly improves mechanical and optical properties, making these glasses acceptable for photonic purposes.