4.6 Article

X-ray responsiveness of sol-gel-derived glasses doped with rare-earth ions

Journal

JOURNAL OF SOL-GEL SCIENCE AND TECHNOLOGY
Volume 102, Issue 3, Pages 504-512

Publisher

SPRINGER
DOI: 10.1007/s10971-022-05732-0

Keywords

Rare-earth; Photoluminescence; Sol-gel; Glass; X-rays; Redox reaction

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Rare-earth doped glasses have shown potential applications in light-emitting devices. However, developing silicate glasses with excellent photoluminescence performance remains difficult. In this study, we investigated the reduction of rare-earth ions in doped glasses through heating in a hydrogen gas atmosphere or X-ray irradiation. We successfully synthesized Al2O3-SiO2 glasses doped with Sm3+ and Eu3+ ions, which exhibited strong photoluminescence. The Sm3+ and Eu3+ ions were reduced to their divalent states when heated in hydrogen gas, while only Sm3+ ions were reduced to Sm2+ ions when irradiated with X-rays. It was also found that the reduced Sm2+ ions in the glass could easily be oxidized to Sm3+ ions by heating in air. The fast redox reaction between Sm3+ and Sm2+ ions makes the Sm3+-doped Al2O3-SiO2 glasses suitable for X-ray therapy and sensor applications.
Rare-earth doped glasses have garnered interest due to their potential applications in light-emitting devices. Although the sol-gel technique is useful in preparing them at moderately low temperatures, developing silicate glasses with excellent photoluminescence performance remains a formidable challenge due to their low solubility in the glass matrix and the difficulty in controlling valence states of rare-earth ions (RE). Here, we investigated whether these RE ions are reduced by heating in a hydrogen gas atmosphere or by irradiating with X-rays. We have succeeded in synthesizing Sm3+ and Eu3+ ion-doped Al2O3-SiO2 glasses with exceptionally strong photoluminescence. When heated in hydrogen gas, the Sm3+ and Eu3+ ions were reduced to their divalent states. However, when irradiated with X-rays, only Sm3+ ions were reduced to Sm2+; no reduction occurred in the Eu3+ ions. This was because when irradiated with X-rays, the hole centers become trapped in the oxygen ions bound to the Al3+ ions, and the electrons released from the oxygen ions are consequently captured by the nearest Sm3+ ions, resulting in the formation of Sm2+. In contrast, such a reduction does not occur in the Eu3+-doped glasses. It was further found that the reduced Sm2+ ions are easily oxidized to Sm3+ ions by heating at 250 degrees C in air. Thus, the Sm3+-doped Al2O3-SiO2 glasses could be used for X-ray therapy and sensor applications due to their fast redox reactions. The Sm3+ ions doped in Al2O3-SiO2 glasses are reduced by irradiating X-ray and the reduced Sm2+ ions are easily oxidized by heating in air. The fast redox reaction between Sm3+ and Sm2+ ions would be appropriate for X-ray therapy and sensor applications. [GRAPHICS]

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