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

  • Invited Paper: Sol-gel and hybrid materials for optical, photonic and optoelectronic applications
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Abstract

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 °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.

Highlights

  • Glasses showing X-ray response were prepared to dope Sm3+ ions by the sol–gel method.

  • Al2O3–SiO2 glasses were appropriate to dope rare-earth ions exhibiting highly intense photoluminescence, in which the doped-Sm3+ ions were reduced to the Sm2+ by irradiating with X-rays.

  • The reduction of Sm3+ ions proceeded by forming hole centers in oxygen ions bound to Al3+ ions and consequently capturing the emitted electrons in the Sm3+ ions.

  • The reduced Sm2+ ions were easily oxidized to the Sm3+ ions by heating in air

  • The fast redox reaction between Sm3+ and Sm2+ ions would be appropriate for X-ray therapy and sensor applications.

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References

  1. Nogami M, Tomozawa M (1986) ZrO2‐transformation‐toughened glass‐ceramics prepared by the sol‐gel process from metal alkoxides. J Am Ceram Soc 69:99–102. https://doi.org/10.1111/j.1151-2916.1986.tb04709.x

    Article  CAS  Google Scholar 

  2. Nogami M, Nagao R, Wong C, Kasuga T, Hayakawa T (1999) High proton conductivity in porous P2O5−SiO2 glasses. J Phys Chem B 103:9468–9477. https://doi.org/10.1021/jp991277s

    Article  CAS  Google Scholar 

  3. Nogami M, Abe Y, Hirao K, Cho DH (1995) Room temperature persistent spectra hole burning in Sm2+‐doped silicate glasses prepared by the sol‐gel process. Appl Phys Lett 66:2952–2954. https://doi.org/10.1063/1.114240

    Article  Google Scholar 

  4. Nogami M, Enomoto T, Hayakawa T (2002) Enhanced fluorescence of Eu3+ induced by energy transfer from nanosized SnO2 crystals in glass. J Lumin 97:147–152. https://doi.org/10.1016/S0022-2313(02)00217-X

    Article  CAS  Google Scholar 

  5. Hewes RA, Hoffman AV (1971) 4f7-4f7 emission from Eu2+ in the system MF2-AlF3. J Lumin 3:261–280. https://doi.org/10.1016/0022-2313(71)90064-0

    Article  CAS  Google Scholar 

  6. Lubio OJ (1991) Doubly-valent rare-earth ions in halide crystals. J Phys Chem Solids 52:101–174. https://doi.org/10.1016/0022-3697(91)90062-5

    Article  Google Scholar 

  7. Verwey JWM, Dirksen GJ, Blasse G (1992) The luminescence of divalent and trivalent rare earth ions in the crystalline and glass modifications of SrB4O7. J Phys Chem Solids 53:367–375. https://doi.org/10.1016/0022-3697(92)90170-I

    Article  CAS  Google Scholar 

  8. Zhu C, Yang Y, Liang X, Yuan S, Chen G (2007) Composition induced reducing effects on Eu ions in borophosphate glasses. J Am Ceram Soc 90:2984–2986. https://doi.org/10.1111/j.1551-2916.2007.01775.x

    Article  CAS  Google Scholar 

  9. Cao T, Chen G, Lu W, Zhou H, Li J, Zhu Z, You Z, Wang Y, Tu C (2009) Intense red and cyan luminescence in europium doped silicate glasses. J Non Cryst Solids 355:2361–2364. https://doi.org/10.1016/j.jnoncrysol.2009.08.008

    Article  CAS  Google Scholar 

  10. Herrmann A, Fibikar S, Hert D (2009) Time-resolved fluorescence measurements on Eu3+- and Eu2+-doped glasses. J Non Cryst Solids 355:2093–2101. https://doi.org/10.1016/j.jnoncrysol.2009.06.033

    Article  CAS  Google Scholar 

  11. Lin Z, Zeng H, Yang Y, Liang X, Chen G, Sun J (2010) The effect of fluorine anions on the luminescent properties of Eu-doped oxyfluoride and aluminosilicate glasses. J Am Ceram Soc 93:3095–3098. https://doi.org/10.1111/j.1551-2916.2010.04067.x

    Article  CAS  Google Scholar 

  12. Johnston WD, Chelko AJ (1970) Reduction of ions in glass by hydrogen. J Am Ceram Soc 53:295–301. https://doi.org/10.1111/j.1151-2916.1970.tb12111.x

    Article  CAS  Google Scholar 

  13. Smedskjaer MM, Wang J, Yue Y (2011) Tunable photoluminescence induced by thermal reduction in rare earth doped glasses. J Mat Chem 21:6614–6620. https://doi.org/10.1039/C1JM10472A

    Article  CAS  Google Scholar 

  14. Smedskjaer MM, Yue Y, Deubener J, Gunnlaugsson HP, Morup S (2010) Modifying glass surface via internal diffusion. J Non Cryst Solids 356:290–298. https://doi.org/10.1016/j.jnoncrysol.2009.12.004

    Article  CAS  Google Scholar 

  15. Nogami M (2015) Reduction mechanism for Eu ions in Al2O3-containing glasses by heat treatment in H2 gas. J Phys Chem B 119:1778–1784. https://doi.org/10.1021/jp511513n

    Article  CAS  Google Scholar 

  16. Nogami M, Koiwai A, Nonaka T (2016) Control of oxidation state of Eu ions in Na2O–Al2O3–SiO2 glasses. J Am Ceram Soc 99:1248–1254. https://doi.org/10.1111/jace.14111

    Article  CAS  Google Scholar 

  17. Nogami M, Le XH, Vu XQ (2019) Novel silicate glasses in the acceleration of hydrogen diffusion for reducing dopant metal ions. J Non Cryst Solids 503−504:260–267. https://doi.org/10.1016/j.jnoncrysol.2018.10.003

    Article  CAS  Google Scholar 

  18. Nogami M, Abe Y (1994) Sm2+‐doped silicate glasses prepared by a sol‐gel process. Appl Phys Lett 65:1227–1229. https://doi.org/10.1063/1.112078

    Article  CAS  Google Scholar 

  19. Nogami M, Abe Y (1996) Enhanced emission from Eu2+ ions in sol‐gel derived Al2O3–SiO2 glasses. Appl Phys Lett 69:3776–3778. https://doi.org/10.1063/1.116995

    Article  CAS  Google Scholar 

  20. Qiu J, Miura K, Suzuki T, Mitsuyu T, Hirao K (1999) Permanent photoreduction of Sm3+ to Sm2+ inside a sodium aluminoborate glass by an infrared femtosecond pulsed laser. Appl Phys Lett 74:10–12. https://doi.org/10.1063/1.123117

    Article  CAS  Google Scholar 

  21. Qiu J, Nouchi K, Miura K, Mitsuyu T, Hirao K (2000) Room-temperature persistent spectral hole burning of x ray irradiated Sm3+-doped glass. J Phys Condens Matter 12:5061–5067. https://iopscience.iop.org/article/10.1088/0953-8984/12/23/314/pdf

    Article  CAS  Google Scholar 

  22. Fujita K, Yasumoto C, Hirao K (2002) Photochemical reactions of samarium ions in sodium borate glasses irradiated with near-infrared femtosecond laser pulses. J Lumin 98:317–323. https://doi.org/10.1016/S0022-2313(02)00286-7

    Article  CAS  Google Scholar 

  23. Nogami M, Suzuki K (2002) Fast spectral hole burning in Sm2+-Doped Al2O3–SiO2 glasses. Adv Mat 14:923–926. 10.1002/1521-4095(20020618)14:12%3C923::AID-ADMA923%3E3.0.CO;2-D

    Article  CAS  Google Scholar 

  24. Ebendorff-Heidepriem H, Ehrt D (2020) Ultraviolet laser and x-ray induced valence changes and defect formation in europium and terbium doped glasses. Phys Chem Glasses 61:189–201. https://doi.org/10.13036/17533562.61.5.Ebendorff

    Article  Google Scholar 

  25. Okada G, Morrell B, Koughia C, Edgar A, Varoy C, Belev G, Wysokinski T, Chapman D, Kasap S (2011) Spatially resolved measurement of high doses in microbeam radiation therapy using samarium doped fluorophosphate glasses. Appl Phys Lett 99:12110. https://doi.org/10.1063/1.3633102

    Article  CAS  Google Scholar 

  26. Koughia C, Edgar A, Christopher E, Varo R, Okada G, Seggern H, Belev G, Kim CY, Ramaswami J, Sammynaiken R, Kasap S (2011) Samarium-doped fluorochlorozirconate glass–ceramics as red-emitting X-ray phosphors. J Am Ceram Soc 94:543–550. https://doi.org/10.1111/j.1551-2916.2010.04110.x

    Article  CAS  Google Scholar 

  27. Vahedi S, Okada G, Morrell B, Muzar E, Koughia C, Edgar A, Varoy C, George B, Wysokinski T, Chapman D, Kasap S (2012) X-ray induced Sm3+ to Sm2+ conversion in fluorophosphate and fluoroaluminate glasses for the monitoring of high-doses in microbeam radiation therapy. J Appl Phys 112:073108. https://doi.org/10.1063/1.4754564

    Article  CAS  Google Scholar 

  28. Martin V, Okada G, Tonchev D, Belev G, Wysokinski T, Chapman D, Kasap S (2013) Samarium-doped oxyfluoride borophosphate glasses for x-ray dosimetry in Microbeam Radiation Therapy. J Non Cryst Solids 377:137–141. https://doi.org/10.1016/j.jnoncrysol.2012.12.015

    Article  CAS  Google Scholar 

  29. Edgar A, Varoy CR, Koughic C, Okada G, Belev G, Kasap S (2013) High-resolution X-ray imaging with samarium-doped fluoroaluminate and fluorophosphate glass. J Non Cryst Solids 377:124–128. https://doi.org/10.1016/j.jnoncrysol.2012.12.022

    Article  CAS  Google Scholar 

  30. Okada G, Ueda J, Tanabe S, Belev G, Wysokinski T, Chapman D, Tonchev D, Kasap S (2014) Samarium-doped oxyfluoride glass-ceramic as a new fast erasable dosimetric detector material for microbeam radiation cancer therapy applications at the Canadian synchrotron. J Am Ceram Soc 97:2147–2153. https://doi.org/10.1111/jace.12938

    Article  CAS  Google Scholar 

  31. Lian Z, Wang J, Lv Y, Wang S, Su Q (2007) The reduction of Eu3+ to Eu2+ in air and luminescence properties of Eu2+ activated ZnO–B2O3–P2O5 glasses. J Alloy Compd 430:257–261. https://doi.org/10.1016/j.jallcom.2006.05.002

    Article  CAS  Google Scholar 

  32. Kreidl NJ (1983) Inorganic glass-forming systems. In: Uhlmann DR, Kreidl NJ (eds) Glass, science and technology, vol. 1, Academic Press NY, pp 105−299

  33. Nogami M, Vu XQ, Nonaka T, Shimizu T, Ohki S, Deguchi K (2017) Diffusion and reaction of H2 gas for reducing Eu3+ ions in glasses. J Phys Chem Solids 105:54–60. http://www.sciencedirect.com/science/article/pii/S0022369716313142?via%3Dihub

    Article  CAS  Google Scholar 

  34. Risbud S, Kirkpatrick RG, Taglialavore A, Montez B (1987) Solid-state NMR evidence of 4-, 5-, and 6-fold aluminium sites in roller-quenched SiO2−A12O3 glasses. J Am Ceram Soc 70:C10–C12. https://doi.org.ezproxy.ict.nitech.ac.jp/10.1111/j.1151-2916.1987.tb04859.x

    Article  Google Scholar 

  35. Sato RK, McMillan PF, Dennison P, Dupree R (1991) High-resolution 27Al and 29Si MAS NMR investigation of SiO2-Al2O3 glasses. J Phys Chem 95:4483–4489. https://doi.org/10.1021/j100164a057

    Article  CAS  Google Scholar 

  36. Schmucker M, MacKenzie KJD, Schneider H, Meinhold R (1997) NMR studies on rapidly solidified SiO2−A12O3 and SiO2−Al2O3−Na2O-glasses. J Non-Cryst Solids 217:99–105. https://doi.org/10.1016/S0022-3093(97)00127-0

    Article  Google Scholar 

  37. Ho VT, Nogami M, Le XH (2020) Reduction of Sm3+ and Eu3+ ions-co-doped Al2O3–SiO2 glasses and photoluminescence properties. Opt Mat 100:109639. https://doi.org/10.1016/j.optmat.2019.109639

    Article  CAS  Google Scholar 

  38. Capobianco JA, Proulx PP, Bettinelli M, Negrisolo F (1990) Absorption and emission spectroscopy of Eu3+ metaphosphate glasses. Phys Rev B 42:5936–5944. https://doi.org/10.1103/PhysRevB.42.5936

    Article  CAS  Google Scholar 

  39. Friebele EJ, Griscom DL (1979) Radiation effects in glasses. In: Tomozawa M, Doremus RH (eds) Treatise on materials science and technology, vol. 17, Academic Press NY, pp 257-351

  40. Mackey JH, Nahum J (1968) Spectral study of the interconversion of Eu2+ and Eu3+ in silicate glass. Phys Chem Glasses 9:52–63

    CAS  Google Scholar 

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Acknowledgements

Author (MN) is grateful to Drs. S. Ohki, K. Deguchi, and T. Shimizu of National Institute for Material Science for measurement of NMR.

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Authors and Affiliations

  1. Institute of Research and Development, Duy Tan University, 03 Quang Trung, Da Nang, Vietnam

    Masayuki Nogami, Vu xuan Quang, Ho van Tuyen & Le xuan Hung

  2. Nagoya Institute of Technology, Showa, Nagoya, 466-8555, Japan

    Masayuki Nogami

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  1. Masayuki Nogami
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  2. Vu xuan Quang
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Contributions

MN designed the study, collected all the data, and wrote the initial draft. VXQ critically reviewed the manuscript. HVT contributed to data collection of the fluorescence spectra and analyzed them. LXH contributed to data collection of the fluorescence spectra and discussed on data. The first draft of the manuscript was written by NM and all authors read and approved the final manuscript.

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Correspondence to Masayuki Nogami.

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Nogami, M., Quang, V.x., Tuyen, H.v. et al. X-ray responsiveness of sol–gel-derived glasses doped with rare-earth ions. J Sol-Gel Sci Technol 102, 504–512 (2022). https://doi.org/10.1007/s10971-022-05732-0

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