Abstract
Europium doped glass-ceramics containing BaF2 nano-crystals have been prepared by using the controlled crystallization of melt-quenched glasses. X-ray diffraction and transmission electron microscopy have confirmed the presence of cubic BaF2 nano-crystalline phase in glass matrix in the ceramized samples. Incorporation of rare earth ions into the formed crystalline phase having low phonon energy of 346 cm−1 has been demonstrated from the emission spectra of Eu3+ ions showing the transitions from upper excitation states 5DJ (J = 1, 2, and 3) to ground states for the glass-ceramics samples. The presence of divalent europium ions in glass and glass-ceramics samples is confirmed from the dominant blue emission corresponding to its 5d-4f transition under an excitation of 300 nm. Increase in the reduction of trivalent europium (Eu3+) ions to divalent (Eu2+) with the extent of ceramization is explained by charge compensation model based on substitution defect mechanisms. Further, the phenomenon of energy transfer from Eu2+ to Eu3+ ion by radiative trap** or re-absorption is evidenced which increases with the degree of ceramization. For the first time, the reduction of Eu3+ to Eu2+ under normal air atmospheric condition has been observed in a BaF2 containing oxyfluoride glass-ceramics system.
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Bae JS, Juong JH, Yi S-S, Park J-C (2003) Improved photoluminescence of pulsed-laser-ablated Y2O3:Eu3+ thin-film phosphors by Gd substitution. Appl Phys Lett 82(21):3629–3631
Wang X-X, Wang J, Shi J-X, Su Q, Gong M-L (2007) Intense red-emitting phosphors for LED solid-state lighting. Mater Res Bull 42(9):1669–1673
Zhao X, Wang X, Chen B, Meng Q, Di W, Ren G, Yang Y (2007) Novel Eu3+-doped red-emitting phosphor Gd2Mo3O9 for white-light-emitting-diodes (WLEDs) applications. J Alloys Compd 433(1–2):352–355
Yang HM, Shi JX, Gong ML (2005) A novel red-emitting phosphor Ca2SnO4:Eu3+. J Solid State Chem 178(3):917–920
Rao RP, Devine DJ (2000) RE-activated lanthanide phosphate phosphors for PDP applications. J Lumin 87–89:1260–1263
Poloman A (1997) Erbium implanted thin film photonic materials. J Appl Phys 82(1):1–39
Oomen EWJL, van Dongen AMA (1989) Europium (III) in oxide glasses: Dependence of the emission spectrum on glass composition. J Non-Crystalline Solids 111(2–3):205–213
Dorenbos P (2003) Energy of the first 4f7–4f65d transition of Eu2+ in inorganic compounds. J Lumin 104(4):239–260
Poort SHM, Reijhoudt HM, van der Kuip HOT, Janssen W, Blasse G (1996) Luminescence of Eu2+ in silicate host lattices with alkaline earth ions in a row. J Alloys Compd 241(1–2):75–81
Kim JS, Jeon PE, Park YH, Choi JC, Park HL (2004) White-light generation through ultraviolet-emitting diode and white-emitting phosphors. Appl Phys Lett 85(17):3696–3698
Chen L-T, Hwang C-S, Chen I-G, Chang S-J (2006) Chromaticity of inhomogeneous broadening effect on CaxSr1-xAl2O4: Eu2+. J Alloy Compd 426(1–2):395–399
Hirata GA, Ramos FE, McKittrick J (2005) Development of luminescent materials with strong UV-blue absorption. Opt Mater 27(7):1301–1304
Gong X, Wu P, Chan W, Chen W (2000) The dependence of conductivity of cellulose, silk and wool on their water content. J Phys Chem Solids 16(1–2):115–121
Bapat VN (1977) Thermoluminescence process in CaSO4:Eu. J Phys C: Solid State Phys 10(16):L465–L467
Qiu J, Kojima K, Miura T, Mitsuyu T, Hirao K (1999) Infrared femtosecond laser pulse induced permanent reduction of Eu3+ to Eu2+ in a fluorozirconate glass. Opt Lett 24(11):786–788
Lian Z, Wang J, Lv YH, Wang SB, Su Q (2007) The reduction of Eu3+ to Eu2+ in air and luminescence properties of Eu2+ activated ZnO–B2O3–P2O5 glasses. J Alloys Compd 430(1–2):257–261
Luo Q, Qiao X, Fan X, Liu S, Yang H, Zhang X (2008) Reduction and luminescence of Europium ions in glass ceramics containing SrF2 nanocrystals. J Non-Crystalline Solids 354(40–41):4691–4694
Luo Q, Fan X, Qiao X, Yang H, Wang M (2009) Eu2+ doped glass-ceramics containing BaF2 nanocrystals as a potential blue phosphor for UV-LED. J Am Ceram Soc 92(4):942–944
Mortier M, Goldner P, Chateau C, Genotelle M (2001) Erbium doped glass-ceramics: concentration effect on crystal structure and energy transfer between active ions. J Alloys Compd 323–324:245–249
Wang Y, Ohwaki J (1993) New transparent vitroceramics codoped with Er3+ and Yb3+ for efficient frequency upconversion. Appl Phys Lett 63(24):3268–3270
Dejneka MJ (1998) Transparent oxyfluoride glass-ceramics. MRS Bull 23:57–62
Dejneka MJ (1998) The luminescence and structure of novel oxyfluoride glass-ceramics. J Non-Cryst Solids 239(1–3):149–155
Honma T, Kusatsugu M, Komatsu T (2009) Synthesis of LaF3 nanocrystals by laser-induced Nd3+ atom heat processing in oxyfluoride glasses. Mater Chem Phys 113(1):124–129
Chen D, Wang Y, Yu Y, Ma E, Bao F, Hu Z, Cheng Y (2006) Influence of Er3+ content on structure and upconversion emission of oxyfluoride glass ceramics containing CaF2 nanocrystals. Mater Chem Phys 95(2–3):264–269
Biswas K, Sontakke AD, Ghosh J, Annapurna K (2010) Enhanced blue emission from transparent oxyfluoride glass-ceramics containing Pr3+:BaF2 nanocrystals. J Am Ceram Soc 93(4):1010–1017
Peng MY, Pei ZW, Hong GY, Su Q (2003) Study on the reduction of Eu3+ → Eu2+ in Sr4Al14O25:Eu prepared in air atmosphere. Chem Phys Lett 371(1–2):1–6
Youngman RE, Sen S (2004) The nature of fluorine in amorphous silica. J Non-Cryst Solids 337(2):182–186
Wang C, Peng M, Jiang N, Jiang X, Zhao C, Qiu J (2007) Tuning the Eu luminecsnence in glass materials synthesized in air by adjusting glass composition. Mater Lett 61(17):3608–3611
Acknowledgement
Authors would like to thank Prof. I. Manna, Director, CGCRI for his kind encouragement and permission to publish this work that was carried out in an In-house project No. OLP-0288. One of us (Mr.A.D.S.) is thankful to the BRNS-DAE for the award of Junior Research Fellowship to him.
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Biswas, K., Sontakke, A.D., Sen, R. et al. Luminescence Properties of Dual Valence Eu Doped Nano-crystalline BaF2 Embedded Glass-ceramics and Observation of Eu2+ → Eu3+ Energy Transfer. J Fluoresc 22, 745–752 (2012). https://doi.org/10.1007/s10895-011-1010-4
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DOI: https://doi.org/10.1007/s10895-011-1010-4