Efficient three-photon luminescence (3PL) from a scintillating silicate glass co-doped with Gd³⁺ and Tb³⁺ was generated by using a focused femtosecond laser beam at 800 nm. Four emission bands centered at 496, 541, 583, and 620 nm were identified as the electronic transitions between the energy levels of Tb³⁺ followed by three-photon absorption (3PA) in Gd³⁺ and Tb³⁺ and the resonant energy transfer from Gd³⁺ to Tb³⁺. More interestingly, a strong polarization dependence of the 3PL was observed and it is ascribed to the polarization dependent 3PA in Gd³⁺ and Tb³⁺ and/or the angular distribution of photogenerated electrons in the glass.

© 2013 OSA

1. G. Zanella, R. Zannoni, R. Dall’Igna, B. Locardi, P. Polato, M. Bettinelli, and A. Marigo, “A new cerium scintillating glass for X-ray detection,” Nucl. Instr. Meth. A345(1), 198–201 (1994). [CrossRef]
2. D. F. Anderson, “Properties of the high-density scintillator cerium fluoride,” EEE Trans. Nucl. Sci.36(1), 137–140 (1989). [CrossRef]
3. G. Zanella and R. Zannoni, “The detective quantum efficiency of an imaging detector,” Nucl. Instr. Meth. A359(3), 474–477 (1995). [CrossRef]
4. C. Pedrini, B. Moine, J. C. Gacon, and B. Jacquier, “One- and two-photon spectroscopy of Ce3+ ions in LaF3-CeF3 mixed crystals,” J. Phys. Condens. Matter4(24), 5461–5470 (1992). [CrossRef]
5. M. Nikl and C. Pedrini, “Photoluminescence of heavily doped CeF3:Cd2+ single crystals,” Solid State Commun.90(3), 155–159 (1994). [CrossRef]
6. M. Nikl, “Scintillation detectors for X-rays,” Meas. Sci. Technol.17(4), R37–R54 (2006). [CrossRef]
7. M. C. Aznar, C. E. Andersen, L. Bøtter-Jensen, S. Å. J. Bäck, S. Mattsson, F. Kjaer-Kristoffersen, and J. Medin, “Real-time optical-fibre luminescence dosimetry for radiotherapy: physical characteristics and applications in photon beams,” Phys. Med. Biol.49(9), 1655–1669 (2004). [CrossRef] [PubMed]
8. W. P. Siegmund, P. Nass, J. P. Fabre, W. Flegel, V. Zacek, G. Martellotti, and G. Wilquet, “Glasses as active and passive components for scintillating fiber detectors,” SPIE1737, 2–13 (1993). [CrossRef]
9. J. A. Mares, M. Nikl, K. Nitsch, N. Solovieva, A. Krasnikov, and S. Zazubovich, “A role of Gd3+ in scintillating process in Tb-doped Na-Gd phosphate glasses,” J. Lumin.94–95, 321–324 (2001). [CrossRef]
10. D. He, C. Yu, J. Cheng, S. Li, and L. Hu, “Energy transfer between Gd3+ and Tb3+ in phosphate glass,” J. Rare Earths29(1), 48–51 (2011). [CrossRef]
11. G. H. Dicke, Spectra and Energy Levels of Rare-Earth Ions (Wiley, 1968).
12. S. Zhang, B. Zhu, S. Zhou, S. Xu, and J. Qiu, “Multi-photon absorption upconversion luminescence of a Tb3+-doped glass excited by an infrared femtosecond laser,” Opt. Express15(11), 6883–6888 (2007). [CrossRef] [PubMed]
13. A.-H. Li, Z. R. Zheng, Q. Lü, L. Sun, W.-Z. Wu, W.-L. Liu, Y.-Q. Yang, and T.-Q. Lü, “Two-photon-excited luminescence in a Tb3+ -doped lithium niobate crystal pumped by a near-infrared femtosecond laser,” Opt. Lett.33(9), 1014–1016 (2008). [CrossRef] [PubMed]
14. K. Hanaoka, K. Kikuchi, S. Kobayashi, and T. Nagano, “Time-Resolved long-lived luminescence imaging method employing luminescent lanthanide probes with a new microscopy system,” J. Am. Chem. Soc.129(44), 13502–13509 (2007). [CrossRef] [PubMed]
15. K. L. Wong, W. M. Kwok, W. T. Wong, D. L. Phillips, and K. W. Cheah, “Green and red three-photon upconversion from polymeric lanthanide(III) complexes,” Angew. Chem. Int. Ed. Engl.43(35), 4659–4662 (2004). [CrossRef] [PubMed]
16. H. C. Aspinall, “Chiral lanthanide complexes: coordination chemistry and applications,” Chem. Rev.102(6), 1807–1850 (2002). [CrossRef] [PubMed]
17. S. Wang, Q. Qian, Q. Y. Zhang, Z. M. Yang, and Z. H. Jiang, “Gd3+-sensitized Tb3+-doped scintillating silicate glasses,” J. Inor. Materi.24(4), 773–777 (2009). [CrossRef]
18. J. Fu, M. Kobayashi, and J. M. Parker, “Terbium-activated heavy scintillating glasses,” J. Lumin.128(1), 99–104 (2008). [CrossRef]
19. M. C. Downer and A. Bivas, “Third- and fourth-order analysis of the intensities and polarization dependence of two-photon absorption lines of Gd3+ in LaF3 and aqueous solution,” Phys. Rev. B28(7), 3677–3696 (1983). [CrossRef]
20. R. Francini, U. M. Grassano, S. Boiko, G. G. Tarasov, and A. Scacco, “Anisotropy of two-photon excited f-f transitions of Eu2+ in KMgF3,” J. Chem. Phys.110(1), 457–464 (1999). [CrossRef]
21. M. C. Downer, C. D. Cordero-Montalvo, and H. Crosswhite, “Study of new 4f7 levels of Eu2+ in GaF2 and SrF2 using two-photon absorption spectroscopy,” Phys. Rev. B28(9), 4931–4943 (1983). [CrossRef]
22. H. J. Seo, B. K. Moon, and T. Tsuboi, “Two-photon excitation spectroscopy of 4f7-4f7 transitions of Eu2+ ions doped in a KMgF3 crystal,” Phys. Rev. B62(19), 12688–12695 (2000). [CrossRef]
23. P. G. Kazansky, H. Inouye, T. Mitsuyu, K. Miura, J. Qiu, K. Hirao, and F. Starrost, “Anomalous anisotropic light scattering in Ge-doped silica glass,” Phys. Rev. Lett.82(10), 2199–2202 (1999). [CrossRef]

Angew. Chem. Int. Ed. Engl.

• K. L. Wong, W. M. Kwok, W. T. Wong, D. L. Phillips, and K. W. Cheah, “Green and red three-photon upconversion from polymeric lanthanide(III) complexes,” Angew. Chem. Int. Ed. Engl.43(35), 4659–4662 (2004). [CrossRef] [PubMed]

Chem. Rev.

• H. C. Aspinall, “Chiral lanthanide complexes: coordination chemistry and applications,” Chem. Rev.102(6), 1807–1850 (2002). [CrossRef] [PubMed]

EEE Trans. Nucl. Sci.

• D. F. Anderson, “Properties of the high-density scintillator cerium fluoride,” EEE Trans. Nucl. Sci.36(1), 137–140 (1989). [CrossRef]

J. Am. Chem. Soc.

• K. Hanaoka, K. Kikuchi, S. Kobayashi, and T. Nagano, “Time-Resolved long-lived luminescence imaging method employing luminescent lanthanide probes with a new microscopy system,” J. Am. Chem. Soc.129(44), 13502–13509 (2007). [CrossRef] [PubMed]

J. Chem. Phys.

• R. Francini, U. M. Grassano, S. Boiko, G. G. Tarasov, and A. Scacco, “Anisotropy of two-photon excited f-f transitions of Eu2+ in KMgF3,” J. Chem. Phys.110(1), 457–464 (1999). [CrossRef]

J. Inor. Materi.

• S. Wang, Q. Qian, Q. Y. Zhang, Z. M. Yang, and Z. H. Jiang, “Gd3+-sensitized Tb3+-doped scintillating silicate glasses,” J. Inor. Materi.24(4), 773–777 (2009). [CrossRef]

J. Lumin.

• J. Fu, M. Kobayashi, and J. M. Parker, “Terbium-activated heavy scintillating glasses,” J. Lumin.128(1), 99–104 (2008). [CrossRef]
• J. A. Mares, M. Nikl, K. Nitsch, N. Solovieva, A. Krasnikov, and S. Zazubovich, “A role of Gd3+ in scintillating process in Tb-doped Na-Gd phosphate glasses,” J. Lumin.94–95, 321–324 (2001). [CrossRef]

J. Phys. Condens. Matter

• C. Pedrini, B. Moine, J. C. Gacon, and B. Jacquier, “One- and two-photon spectroscopy of Ce3+ ions in LaF3-CeF3 mixed crystals,” J. Phys. Condens. Matter4(24), 5461–5470 (1992). [CrossRef]

J. Rare Earths

• D. He, C. Yu, J. Cheng, S. Li, and L. Hu, “Energy transfer between Gd3+ and Tb3+ in phosphate glass,” J. Rare Earths29(1), 48–51 (2011). [CrossRef]

Meas. Sci. Technol.

• M. Nikl, “Scintillation detectors for X-rays,” Meas. Sci. Technol.17(4), R37–R54 (2006). [CrossRef]

Nucl. Instr. Meth. A

• G. Zanella and R. Zannoni, “The detective quantum efficiency of an imaging detector,” Nucl. Instr. Meth. A359(3), 474–477 (1995). [CrossRef]
• G. Zanella, R. Zannoni, R. Dall’Igna, B. Locardi, P. Polato, M. Bettinelli, and A. Marigo, “A new cerium scintillating glass for X-ray detection,” Nucl. Instr. Meth. A345(1), 198–201 (1994). [CrossRef]

Opt. Express

• S. Zhang, B. Zhu, S. Zhou, S. Xu, and J. Qiu, “Multi-photon absorption upconversion luminescence of a Tb3+-doped glass excited by an infrared femtosecond laser,” Opt. Express15(11), 6883–6888 (2007). [CrossRef] [PubMed]

Opt. Lett.

• A.-H. Li, Z. R. Zheng, Q. Lü, L. Sun, W.-Z. Wu, W.-L. Liu, Y.-Q. Yang, and T.-Q. Lü, “Two-photon-excited luminescence in a Tb3+ -doped lithium niobate crystal pumped by a near-infrared femtosecond laser,” Opt. Lett.33(9), 1014–1016 (2008). [CrossRef] [PubMed]

Phys. Med. Biol.

• M. C. Aznar, C. E. Andersen, L. Bøtter-Jensen, S. Å. J. Bäck, S. Mattsson, F. Kjaer-Kristoffersen, and J. Medin, “Real-time optical-fibre luminescence dosimetry for radiotherapy: physical characteristics and applications in photon beams,” Phys. Med. Biol.49(9), 1655–1669 (2004). [CrossRef] [PubMed]

Phys. Rev. B

• M. C. Downer and A. Bivas, “Third- and fourth-order analysis of the intensities and polarization dependence of two-photon absorption lines of Gd3+ in LaF3 and aqueous solution,” Phys. Rev. B28(7), 3677–3696 (1983). [CrossRef]
• M. C. Downer, C. D. Cordero-Montalvo, and H. Crosswhite, “Study of new 4f7 levels of Eu2+ in GaF2 and SrF2 using two-photon absorption spectroscopy,” Phys. Rev. B28(9), 4931–4943 (1983). [CrossRef]
• H. J. Seo, B. K. Moon, and T. Tsuboi, “Two-photon excitation spectroscopy of 4f7-4f7 transitions of Eu2+ ions doped in a KMgF3 crystal,” Phys. Rev. B62(19), 12688–12695 (2000). [CrossRef]

Phys. Rev. Lett.

• P. G. Kazansky, H. Inouye, T. Mitsuyu, K. Miura, J. Qiu, K. Hirao, and F. Starrost, “Anomalous anisotropic light scattering in Ge-doped silica glass,” Phys. Rev. Lett.82(10), 2199–2202 (1999). [CrossRef]

Solid State Commun.

• M. Nikl and C. Pedrini, “Photoluminescence of heavily doped CeF3:Cd2+ single crystals,” Solid State Commun.90(3), 155–159 (1994). [CrossRef]

SPIE

• W. P. Siegmund, P. Nass, J. P. Fabre, W. Flegel, V. Zacek, G. Martellotti, and G. Wilquet, “Glasses as active and passive components for scintillating fiber detectors,” SPIE1737, 2–13 (1993). [CrossRef]

Other

• G. H. Dicke, Spectra and Energy Levels of Rare-Earth Ions (Wiley, 1968).

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