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Journal of the Optical Society of America B

Journal of the Optical Society of America B


  • Editor: Henry van Driel
  • Vol. 29, Iss. 8 — Aug. 1, 2012
  • pp: 1854–1862

Pr3+ cluster management in CaF2 by codoping with Lu3+ or Yb3+ for visible lasers and quantum down-converters

D. Serrano, A. Braud, J. L. Doualan, P. Camy, and R. Moncorgé  »View Author Affiliations

JOSA B, Vol. 29, Issue 8, pp. 1854-1862 (2012)

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The codoping of CaF2:Pr3+ with Yb3+ or Lu3+ ions is shown to avoid the clustering of Pr3+ ions, which otherwise prevent Pr3+ doped CaF2 to be used for various photonic applications. The breaking of Pr3+ clusters by Lu3+ ions paves the way towards the development of a Pr3+ doped CaF2 visible laser. On the other hand, the formation of Pr3+-Yb3+ clusters in place of Pr3+ clusters leads to extremely efficient energy transfers between Pr3+ and Yb3+ which could be used for quantum cutting applications. Two types of clusters are observed for both types of codopings. Pr3+ to Yb3+ energy transfer analysis shows that for one of the clusters an ultrafast energy transfer takes place with a rate of 5×107s1, which is likely due to exchange interaction.

© 2012 Optical Society of America

OCIS Codes
(160.2540) Materials : Fluorescent and luminescent materials
(160.5690) Materials : Rare-earth-doped materials
(260.2160) Physical optics : Energy transfer
(260.3800) Physical optics : Luminescence

ToC Category:
Physical Optics

Original Manuscript: April 25, 2012
Revised Manuscript: May 23, 2012
Manuscript Accepted: May 25, 2012
Published: July 3, 2012

D. Serrano, A. Braud, J. L. Doualan, P. Camy, and R. Moncorgé, "Pr3+ cluster management in CaF2 by codoping with Lu3+ or Yb3+ for visible lasers and quantum down-converters," J. Opt. Soc. Am. B 29, 1854-1862 (2012)

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  1. T. Gün, P. Metz, and G. Huber, “Power scaling of laser diode pumped Pr3+:LiYF4 CW lasers: efficient laser operation at 522.6 nm; 545.9 nm; 607.2 nm and 639.5 nm,” Opt. Lett. 36, 1002–1004 (2011). [CrossRef]
  2. B. Xu, P. Camy, J. L. Doualan, Z. Cai, and R. Moncorgé, “Visible laser operation of Pr3+-doped fluoride crystals pumped by a 469 nm blue laser,” Opt. Express 19, 1191–1197 (2011). [CrossRef]
  3. P. Camy, J. L. Doualan, R. Moncorgé, J. Bengoechea, and U. Weichmann, “Diode-pumped Pr3+:KY3F10 red laser,” Opt. Lett. 32, 1462–1464 (2007). [CrossRef]
  4. T. Trupke and M. A. Green, “Improving solar cell efficiencies by down-conversion of high-energy photons,” J. Appl. Phys. 92, 1668–1674 (2002). [CrossRef]
  5. B. M. van der Ende, L. Aarts, and A. Meijerink, “Near-infrared quantum cutting for photovoltaics,” Adv. Mater. 21, 3073–3077(2009). [CrossRef]
  6. D. Serrano, A. Braud, J.-L. Doualan, P. Camy, A. Benayad, V. Ménard, and R. Moncorgé, “Ytterbium sensitization in KY3F10:Pr3+, Yb3+ for silicon solar cells efficiency enhancement,” Opt. Mater. 33, 1028–1031 (2011). [CrossRef]
  7. L. Aarts, B. van der Ende, M. F. Reid, and A. Meijerink, “Downconversion for solar cells in YF3:Pr3+, Yb3+,” Spectrosc.Lett. 43, 373–381 (2010). [CrossRef]
  8. J. T. van Wijngaarden, S. Scheidelaar, T. J. H. Vlugt, M. F. Reid, and A. Meijerink, “Energy transfer mechanism for downconversion in the (Pr3+, Yb3+) couple,” Phys. Rev. B 81, 155112 (2010). [CrossRef]
  9. D. Serrano, A. Braud, J.-L. Doualan, P. Camy, and R. Moncorgé, “Highly efficient energy transfer in Pr3+, Yb3+ codoped CaF2 for luminescent solar converters,” J. Opt. Soc. Am. B 28, 1760–1765 (2011). [CrossRef]
  10. B. Bleaney, P. M. Llewellyn, and D. A. Jones, “Paramagnetic resonance of uranium ions,” Proc. Phys. Soc. London B 69, 858–860 (1956). [CrossRef]
  11. J. L. Merz and P. S. Pershan, “Charge conversion of irradiated rare-earth ions in calcium fluoride. I,” Phys. Rev. 162, 217–235 (1967). [CrossRef]
  12. C. Andeen, J. Fontanella, M. C. Wintersgill, P. J. Welcher, R. J. Kimble, and G. E. Matthews, “Clusters in rare-erath-doped alkaline earth fluorides,” J. Phys. C 14, 3557–3574 (1981). [CrossRef]
  13. P. J. Bendall, C. R. A. Catlow, J. Corish, and P. W. M. Jacobs, “Defect aggregation in anion-excess fluorites II. Clusters containing more than two impurity atoms,” J. Solid State Chem. 51, 159–169 (1984). [CrossRef]
  14. S. A. Payne, J. A. Caird, L. L. Chase, L. K. Smith, N. D. Nielsen, and W. F. Krupke, “Spectroscopy and gain measurements of Nd3+ in SrF2 and other fluorite-structure hosts,” J. Opt. Soc. Am. B 8, 726–740 (1991). [CrossRef]
  15. E. Friedman and W. Low, “Effect of thermal treatment of paramagnetic resonance spectra of rare earth impurities in calcium fluoride,” J. Chem. Phys. 33, 1275–1276 (1960). [CrossRef]
  16. J. Corish, C. R. A. Catlow, P. W. M. Jacobs, and S. H. Ong, “Deffect aggregation in anion-excess fluorites. Dopant monomers and dimers,” Phys. Rev. B 25, 6425–6438 (1982). [CrossRef]
  17. J. Sierro, “ESR detection of the hydrolysis of solid CaF2,” J. Chem. Phys. 34, 2183–2184 (1961). [CrossRef]
  18. D. R. Tallant, D. S. Moore, and J. C. Wright, “Defect equilibria in fluorite structure crystals,” J. Chem. Phys. 67, 2897–2907 (1977). [CrossRef]
  19. M. B. Seelbinder and J. C. Wright, “Identification of higher order clusters in charge compensated materials using three-body energy transfer,” J. Chem. Phys. 75, 5070–5079 (1981). [CrossRef]
  20. S. A. Kazanskii, A. I. Ryskin, A. E. Nikiforov, A. Y. Zakharov, M. Y. Ougrumov, and G. S. Shakurov, “EPR spectra and crystal field of hexamer rare-earth clusters in fluorites,” Phys. Rev. B 72, 014127 (2005). [CrossRef]
  21. V. Petit, P. Camy, J. L. Doualan, X. Portier, and R. Moncorgé, “Spectroscopy of Yb3+:CaF2: From isolated centers to clusters,” Phys. Rev. B 78085131 (2008). [CrossRef]
  22. V. A. Chernyshev, A. E. Nikiforov, V. P. Volodin, and G. S. Slepukhin, “Electronic structure of Yb3+ impurity centers in fluorites,” Phys. Solid State 52, 1874–1879 (2010). [CrossRef]
  23. M. Siebold, S. Bock, U. Schramm, B. Xu, J. L. Doualan, P. Camy, and R. Moncorgé, “Yb:CaF2-a new old laser crystal,” Appl. Phys. B 97, 327–338 (2009). [CrossRef]
  24. S. Ricaud, F. Druon, D. N. Papadopoulos, A. Pellegrina, F. Balembois, P. Georges, A. Courjaud, P. Camy, J. L. Doualan, and R. Moncorgé, “High-power diode-pumped cryogenically cooled Yb:CaF2 laser with extremely low quantum defect,” Opt. Lett. 36, 1602–1604 (2011). [CrossRef]
  25. P. Camy, J. L. Doualan, S. Renard, A. Braud, V. Ménard, and R. Moncorgé, “Tm3+:CaF2 for 1.9 μm laser operation,” Opt. Commun. 236, 395–402 (2004). [CrossRef]
  26. C. Labbé, J. L. Doualan, P. Camy, R. Moncorgé, and M. Thuau, “The 2.8 μm laser properties of Er3+ doped CaF2 crystals,” Opt. Comm. 209, 193–199 (2002). [CrossRef]
  27. J. Kliava, P. Evesque, and J. Duran, “Laser selective excitation and energy transfer in a multisite system: CaF2:Pr3+,” J. Phys. C: Solid State Phys. 11, 3357–3368 (1978). [CrossRef]
  28. K. H. Petit, P. Evesque, and J. Duran, “Dimers and clusters in CaF2:Pr3+. Laser selective excitation and time-resolved spectroscopy,” J. Phys. C: Solid State Phys. 14, 5081–5090 (1981). [CrossRef]
  29. L. van Pieterson, R. P. A. Dullens, P. S. Peijzel, and A. Meijerink, “Site-selective laser spectroscopy of 4fn−4fn−15d transitions in CaF2:Pr3+ with F−, D−, H−, Li+, or Na+ charge compensation,” J. Chem. Phys. 115, 9393–9400 (2001). [CrossRef]
  30. J. Chrysochoos, P. W. M. Jacobs, and M. J. Stillman, “Laser induced emission spectra of Pr3+ in CaF2 at low temperatures,” J. Lum. 28, 177–190 (1983). [CrossRef]
  31. T. Boonyarith, J. P. D. Martin, B. Luo, and N. B. Manson, “Zeeman measurements of Pr3+ centres in CaO and CaF2,” J. Lumin. 51, 149–156 (1992). [CrossRef]
  32. W. A. Hargreaves, “Energy levels of tetragonally sited Pr3+ ions in calcium fluoride crystals,” Phys. Rev. B 6, 3417–3422 (1972). [CrossRef]
  33. B. M. Tissue and J. C. Wright, “Site-selective laser spectroscopy of CaF2:Pr3+,R3+ (R3+=Y3+, Gd3+, Nd3+),” Phys. Rev. B 36, 9781–9789 (1987). [CrossRef]
  34. D. W. Pack, W. J. Manthey, and D. S. McClure, “Ce+:Na+ pairs in CaF2 and SrF2. Absorption and laser-excitation spectroscopy, and the observation of hole burning,” Phys. Rev. B 40, 9930–9944 (1989). [CrossRef]
  35. G. D. Jones and R. J. Reeves, “Na+, Li+ and cubic centres in rare-earth-doped CaF2 and SrF2,” J. Lum. 87–89, 1108–1111 (2000). [CrossRef]
  36. J. P. Laval, A. Mikou, and B. Frit, “Short-range order in heavily doped CaF2:Ln3+ fluorites a powder neutron diffraction study,” Solid State Ionics 28–30, 1300–1304 (1988). [CrossRef]
  37. T. Balaji, G. Lifante, E. Daran, R. Legros, and G. Lacoste, “Growth by molecular beam epitaxy and characterization of CaF2:Pr3+ planar waveguides,” Thin Solid Films 339, 187–193 (1999). [CrossRef]
  38. R. B. Barthem, R. Buisson, and J. C. Vial, “Coexistence of two excitation transfer mechanisms in LiYF4:Pr,” J. Lum. 38, 190–192 (1987). [CrossRef]
  39. J. Hormadaly and R. Reisfeld, “Intensity parameters and laser analysis of Pr3+ and Dy3+ in oxide glasses,” J. Non-Cryst. Solids 30, 337–348 (1979). [CrossRef]
  40. M. Eyal, E. Greenberg, R. Reisfeld, and N. Spector, “Spectroscopy of praseodymium (III) in zirconium fluoride glass,” Chem. Phys. Lett. 117, 108–114 (1985). [CrossRef]
  41. A. I. Burshtein, “The influence of the migration mechanism of approaching particles on the energy transfer between them,” J. Lum. 21, 317–321 (1980). [CrossRef]
  42. D. L. Dexter, “A theory of sensitized luminescence in solids,” J. Chem. Phys. 21, 836–850 (1953). [CrossRef]
  43. M. Inokuti and F. Hirayama, “Influence of energy transfer by the exchange mechanism on donor luminescence,” J. Chem. Phys. 43, 1978–1989 (1965). [CrossRef]
  44. V. S. Mironov, “Superexchange mechanism of energy transfer between neighboring lanthanide ions in dielectric crystals,” Opt. Spectrosc. 88, 372–376 (2000). [CrossRef]
  45. L. A. Diaz-Torres, O. Barbosa-Garcia, C. W. Struck, and R. A. McFarlane, “Analysis of experimental Nd3+ emission transients with fast sub-microsecond decay component and a subsequent non-exponential long-term decay with Monte-Carlo simulations,” J. Lum. 78, 69–86 (1998). [CrossRef]
  46. V. Lupei and A. Lupei, “Emission dynamics of the F43/2 level of Nd3+ in YAG at low pump intensities,” Phys. Rev. B 61, 8087–8098 (2000). [CrossRef]
  47. W. B. Smith and R. C. Powell, “Energy transfer in CaWO4:Sm3+,” J. Chem. Phys. 76, 854–859 (1982). [CrossRef]
  48. P. W. Anderson, “New approach to the theory of superexchange interactions,” Phys. Rev. 115, 2–13 (1959). [CrossRef]

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