Enhanced Blue Emission from Transparent Oxyfluoride Glass–Ceramics Containing Pr3+:BaF2 Nanocrystals

Transparent glass–ceramics containing Pr3+:BaF2 nanocrystals in the chemical composition of SiO2–BaF2–K2CO3–La2O3–Sb2O3 oxyfluoride glass systems have been prepared from melt quenching and with a subsequent heat-treatment method. The luminescence and structural properties of these materials have been evaluated and the results are reported. Rietveld analysis of X-ray diffraction patterns and investigation of transmission electron microscopy confirmed the presence of BaF2 nanocrystals dispersed in the heat-treated glass matrices. Measured UV-Vis-NIR absorption spectra exhibited nine bands of the transitions 3H4→3P2, (1I6, 3P1), 3P0, 1D2, 1G4, 3F3, 3F2, 3H6, and 3H5 from all the samples with nondegenerated 1I6 and 3P1 levels in the glass–ceramics. The photoluminescence spectra show an enhancement in the intensities upon ceramization, indicating the incorporation of Pr3+ ions into BaF2 nanocrystals that possess a low phonon energy (346 cm−1). This has further been corroborated from the observation of a significant threefold increase in the relative intensity ratio of blue (3P0→3H4) to red (1D2→3H4, 3P0→3H6) emissions from glass–ceramics compared with the glass. This is due to a significant decrease of multiphonon nonradiative relaxation from the 3P0 to the 1D2 level of Pr3+ in glass–ceramics. Time-resolved spectra exhibit 3P0-level decays faster than the 1D2 level.

[1]  W. White,et al.  The structure of alkaline earth aluminosilicate glasses as determined by vibrational spectroscopy , 1991 .

[2]  C. Rüssel,et al.  Self-organized nano-crystallisation of BaF2 from Na2O/K2O/BaF2/Al2O3/SiO2 glasses , 2009 .

[3]  Anthony J. Kenyon,et al.  Recent developments in rare-earth doped materials for optoelectronics , 2002 .

[4]  En Ma,et al.  A new transparent oxyfluoride glass ceramic with improved luminescence , 2007 .

[5]  Christiane Görller-Walrand,et al.  On the color of the trivalent lanthanide ions , 1995 .

[6]  B. Judd,et al.  OPTICAL ABSORPTION INTENSITIES OF RARE-EARTH IONS , 1962 .

[7]  G. S. Ofelt Intensities of Crystal Spectra of Rare‐Earth Ions , 1962 .

[8]  A. K. Tyagi,et al.  Synthesis and characterization of M1−xNdxF2+x (M = Sr2+, Ca2+; 0.00 ≤ x ≤ 1.00) , 2003 .

[9]  S. Pelli,et al.  Tm3+-activated transparent oxy-fluoride glass–ceramics: structural and spectroscopic properties , 2004 .

[10]  Xiaojun Wang,et al.  The dependence of persistent phosphorescence on annealing temperatures in CaTiO3:Pr3+ nanoparticles prepared by a coprecipitation technique , 2008 .

[11]  R. Jagannathan,et al.  Absorption and Emission Spectral Properties of Pr3+, Nd3+, and Eu3+ Ions in Heavy-Metal Oxide Glasses , 2004 .

[12]  I. Ardelean,et al.  Structural study of the Fe2O3-B2O3-BaO glass system by FTIR spectroscopy , 2003 .

[13]  S. Fujihara,et al.  Sol–Gel Synthesis of Silica‐Based Oxyfluoride Glass‐Ceramic Thin Films: Incorporation of Eu3+ Activators into Crystallites , 2001 .

[14]  R. Jagannathan,et al.  Judd‐Ofelt Parameters, Hypersensitivity, and Emission Characteristics of Ln3+ (Nd3+, Ho3+, and Er3+) Ions Doped in PbO‐PbF2 Glasses , 2004 .

[15]  K. Annapurna,et al.  Absorption and emission spectral analysis of Pr3+: tellurite glasses , 2007 .

[16]  B. Jacquier,et al.  Upconversion mechanisms of a praseodymium-doped fluoride fibre amplifier , 1996 .

[17]  G. Jose,et al.  Application of a modified Judd–Ofelt theory to Pr3+ doped phosphate glasses and the evaluation of radiative properties , 2003 .

[18]  A. Gualtieri,et al.  The Quantitative Determination of the Crystalline and the Amorphous Content by the Rietveld Method: Application to Glass Ceramics with Different Absorption Coefficients , 2004 .

[19]  Matthew John Dejneka,et al.  Transparent Oxyfluoride Glass Ceramics , 1998 .

[20]  H. Rietveld A profile refinement method for nuclear and magnetic structures , 1969 .

[21]  W. A. Sibley,et al.  Optical transitions of Er 3 + ions in fluorozirconate glass , 1983 .

[22]  Soga,et al.  Compositional dependence of Judd-Ofelt parameters of Er3+ ions in alkali-metal borate glasses. , 1992, Physical review. B, Condensed matter.

[23]  D. Ehrt,et al.  Dehydration of phosphate glasses , 1993 .

[24]  S. Tanabe,et al.  Improved Fluorescence from Tm‐Ho‐ and Tm‐Ho‐Eu‐Codoped Transparent PbF2 Glass‐Ceramics for S+‐Band Amplifiers , 2004 .

[25]  P. Rodnyi,et al.  Variation of 5d -level position and emission properties of BaF2:Pr crystals , 2005 .

[26]  C. Pantano,et al.  Structural characterization of CaO-B2O3-Al2O3-SiO2 xerogels and glasses , 1992 .

[27]  M. Mortier,et al.  Erbium doped glass–ceramics: concentration effect on crystal structure and energy transfer between active ions , 2001 .

[28]  Junichi Ohwaki,et al.  New transparent vitroceramics codoped with Er3+ and Yb3+ for efficient frequency upconversion , 1993 .

[29]  Matthew John Dejneka,et al.  The luminescence and structure of novel transparent oxyfluoride glass-ceramics , 1998 .