Abstract
CaF2:Ln3+ (Ln = Ce, Tb, Eu) phosphors with highly uniform shapes have been successfully synthesized by a simple hydrothermal method directly. The as-prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence (PL) and lifetime. The results indicated that the pH values, organic additive and reaction time have a significant effect on the morphology and dimensions of CaF2 microcrystals and the possible formation mechanism was also proposed. Furthermore, the energy transfer from Ce3+ to Tb3+ and from Tb3+ to Eu3+ and from Ce3+ to Tb3+ to Eu3+ was observed and the corresponding mechanisms were discussed in detail. The CaF2:Ln3+ phosphors may have potential optical applications in near-UV and violet LEDs.
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Quan ZW, Xu HW, Wang CY, Wen XD, Wang YX, Zhu JL, Li RP, Sheehan CJ, Wang ZW, Smilgies DM, Luo ZP, Fang JY (2014) Solvent-mediated self-assembly of nanocube superlattices. J Am Chem Soc 136:1352–1359
Dong H, Li XJ, Peng Q, Wang X, Chen JP, Li YD (2005) Monodisperse magnetic single-crystal ferrite microspheres. Angew Chem Int Ed 44:2782–2785
Li G, Hou Z, Peng C, Wang W, Cheng Z, Li C, Lian H, Lin J (2010) Electrospinning derived one-dimensional LaOCl: Ln3+ (Ln = Eu/Sm, Tb, Tm) nanofibers, nanotubes and microbelts with multicolor-tunable emission. Adv Funct Mater 20:3446–3456
Huang CH, Chan TS, Liu WR, Wang D, Chiu YC, Ye H, Yeh YT, Chen TM (2012) Crystal structure of blue–white–yellow color-tunable Ca4Si2O7F2:Eu2+, Mn2+ phosphor and investigation of color tunability through energy transfer for single-phase white-light near-ultraviolet LEDs. J Mater Chem 22:20210–20216
Zhang Y, Geng DL, Kang XJ, Shang MM, Wu Y, Li XJ, Lian HZ, Cheng ZY, Lin J (2013) Rapid, large-scale, morphology-controllable synthesis of YOF:Ln3+(Ln = Tb, Eu, Tm, Dy, Ho, Sm) nano-/microstructures with multicolor tunable emission properties. Inorg Chem 52:12986–12994
Wang LS, Zhou YH, Quan ZW, Lin J (2005) Formation mechanisms and morphology dependent luminescence properties of Y2O3:Eu phosphors prepared by spray pyrolysis process. Mater Lett 59:1130–1133
Li JG, Li X, Sun X, Ishigaki TJ (2008) Monodispersed colloidal spheres for uniform Y2O3:Eu3+ red-phosphor particles and greatly enhanced luminescence by simultaneous Gd3+ doping. Phys Chem C 112:11707–11716
Wang H, Lin CK, Liu XM, Lin J (2005) Monodisperse spherical core-shell-structured phosphors obtained by functionalization of silica spheres with Y2O3:Eu3+ layers for field emission displays. Appl Phys Lett 87:181907
Song KC, Kang Y (2000) Preparation of high surface area tin oxide powders by a homogeneous precipitation method. Mater Lett 42:283–289
Feng W, Sun LD, Zhang YW, Yan CH (2010) Synthesis and assembly of rare earth nanostructures directed by the principle of coordination chemistry in solution-based process. Coord Chem Rev 254:1038–1053
Zhou L, Hu SS, Zhou XJ, Tang JF, Yang J (2016) One-step surfactant-free synthesis of Eu3+ activated NaTb(MoO4)2 microcrystals with controllable shape and their multicolor luminous properties. CrystEngComm 8:7590–7600
Mao YB, Zhang F, Wong SS (2006) Ambient template-directed synthesis of single-crystalline alkaline-earth metal fluoride nanowires. Adv Mater 18:1895–1899
Wang WS, Zhen L, Xu CY, Chen JZ, Shao WZ (2009) Aqueous solution synthesis of CaF2 hollow microspheres via the Ostwald ripening process at room temperature. ACS Appl Mater Interfac 1:780–788
Feldmann C, Roming M, Trampert K (2006) Polyol-mediated synthesis of nanoscale CaF2 and CaF2:Ce, Tb. Small 2:1248–1250
Liu YS, Tu DT, Zhu HM, Ma E, Chen XY (2013) Lanthanide-doped luminescent nano-bioprobes: from fundamentals to biodetection. Nanoscale 5:1369–1384
Gao P, Xie Y, Li Z (2006) Controlling the size of BaF2 nanocubes from 1000 to 10 nm. Eur J Inorg Chem 2006:3261–3265
Quan ZW, Yang PP, Li CX, Yang J, Yang DM, Jin Y, Lian HZ, Li HY, Lin J (2009) Shape and phase-controlled synthesis of KMgF3 colloidal nanocrystals via microwave irradiation. J Phys Chem C 113:4018–4025
Sokolov NS, Suturin SM (2000) MBE-growth peculiarities of fluoride (CdF2–CaF2) thin film structures. Thin Solid Films 367:112–119
Pilvi T, Arstila K, Leskel M, Ritala M (2007) Novel ALD process for depositing CaF2 thin films. Chem Mater 19:3387–3392
Sun XM, Li YD (2003) Size-controllable luminescent single crystal CaF2 nanocubes. Chem Commun 17:1768–1769
Quan ZW, Yang DM, Yang PP, Zhang XM, Lian HZ, Liu XM, Lin J (2008) Uniform colloidal alkaline earth metal fluoride nanocrystals: nonhydrolytic synthesis and luminescence properties. Inorg Chem 47:9509–9517
Blednov AV, Gorbenko OY, Samoilenkov SV, Amelichev VA, Lebedev VA, Napolskii KS, Kaul AR (2010) Epitaxial calcium and strontium fluoride films on highly mismatched oxide and metal substrates by MOCVD: texture and morphology. Chem Mater 22:175–185
Zhang XM, Quan ZW, Yang J, Yang PP, Lian HZ, Lin J (2008) Solvothermal synthesis of well-dispersed MF2 (M = Ca, Sr, Ba) nanocrystals and their optical properties. Nanotechnology 19:075603
Pandurangappa C, Lakshminarasappa BN, Nagabhushana BM (2010) Synthesis and characterization of CaF2 nanocrystals. J Alloys Compd 489:592–595
Cao CY, Qin WP, Zhang JS, Wang Y, Wang GF, Wei GD, Zhu PF, Wang LL, Jin LZ (2008) Up-conversion white light of Tm3+/Er3+/Yb3+ tri-doped CaF2 phosphors. Opt Commun 281:1716–1719
Setlur AA, Heward WJ, Gao Y, Srivastava AM (2006) Crystal chemistry and luminescence of Ce3+-doped Lu2CaMg2(Si, Ge)3O12 and its use in LED based lighting. Chem Mater 18:3314–3322
Ye S, Xiao F, Pan Y, Ma Y, Zhang Q (2010) Phosphors in phosphorconverted white light-emitting diodes: recent advances in materials, techniques and properties. Mater Sci Eng R 71:1–34
Xia ZG, Liu RS (2012) Tunable blue–green color emission and energy transfer of Ca2Al3O6F:Ce3+, Tb3+ phosphors for near-UV white LEDs. J Phys Chem C 116:15604–15609
Blasse G (1991) Optical electron transfer between metal ions and its consequences. Struct Bonding 76:153–187
Setlur AA (2012) Sensitizing Eu3+ with Ce3+ and Tb3+ to make narrow-line red phosphors for light emitting diodes. Electrochem Solid State Lett 15:J25–J27
Zhang CM, Li CX, Peng C, Chai RT, Huang SS, Yang DM, Cheng ZY, Lin J (2010) Facile and controllable synthesis of monodisperse CaF2 and CaF2:Ce3+/Tb3+ hollow spheres as efficient luminescent materials and smart drug carriers. Chem Eur J 16:5672–5680
Zheng W, Zhou SY, Chen Z, Hu P, Liu YS, Tu DT, Zhu HM, Li RF, Huang MD, Chen XY (2013) Sub-10 nm lanthanide-doped CaF2 nanoprobes for time-resolved luminescent biodetection. Angew Chem 125:6803–6808
Ritter BJ, Thoralf KK, Rurackand EK (2014) Nanoscale CaF2 doped with Eu3+ and Tb3+ through fluorolytic sol–gel-synthesis. J Mater Chem C 2:8607
Chen LM, Hong ZR, Li G, Yang Y (2009) Recent progress in polymer solar cells: manipulation of polymer: fullerene morphology and the formation of efficient inverted polymer solar cells. Adv Mater 21:1434–1449
Zhang XG, Zhou LY, Pang Q, Shi JX, Gong MG (2014) Tunable luminescence and Ce3+ → Tb3+ → Eu3+ energy transfer of broadband-excited and narrow line red emitting Y2SiO5:Ce3+, Tb3+, Eu3+ Phosphor. J Phys Chem C 118:7591–7598
Li CX, Quan ZW, Yang PP, Huang SS, Lian HZ, Lin J (2008) Shape-controllable synthesis and upconversion properties of lutetium fluoride (doped with Yb3+/Er3+) microcrystals by hydrothermal process. J Phys Chem C 112:13395–13404
Xu L, Yang XY, Zhai Z, Chao X, Zhang ZH, Hou WH (2011) EDTA-mediated hydrothermal synthesis of NaEu(MoO4)2 microrugbies with tunable size and enhanced luminescence properties. CrystEngComm 13:4921–4929
Luo Y, Yang RH, Zhang XL, Hu B, Hu SS, Zhou L, Yang J (2015) Shape-controllable hydrothermal synthesis of NaTbF4:Eu3+ microcrystals with energy transfer from Tb to Eu and multicolor luminescence properties. CrystEngComm 17:7762–7771
Zhao B, Yuan L, Hu SS, Zhang XM, Zhou XJ, Tang JF, Yang J (2016) One-step hydrothermal synthesis of Sc2Mo3O12:Ln3+ (Ln = Eu, Tb, Dy, Tb/Eu, Dy/Eu) nanosheets and their multicolor tunable luminescence. New J Chem 40:9211–9222
Zhang XG, Gong ML (2015) Photoluminescence and energy transfer of Ce3+, Tb3+, and Eu3+ doped KBaY(BO3)2 as near ultraviolet-excited color-tunable phosphors. Ind Eng Chem Res 54:7632–7639
Wen DW, Shi JX (2013) A novel narrow-line red emitting Na2Y2B2O7:Ce33+, Tb3+, Eu3+ phosphor with high efficiency activated by terbium chain for near-UV white LEDs. Dalton Trans 42:16621–16629
Zhou J, Xia Z (2015) Luminescence color tuning of Ce3+, Tb3+ and Eu3+ codoped and tri-doped BaY2Si3O10 phosphors via energy transfer. J Phys Chem C 3:7552–7560
Acknowledgements
This project is financially supported by the National Natural Science Foundation of China (51302229 and 51302228), the Fundamental Research Funds for the Central Universities (XDJK2016C147 and XDJK2015B019) and the Scientific Research Foundation for Returned Scholars, Ministry of Education of China (46th).
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Zhao, B., Shen, D., Tan, Q. et al. Morphology-controllable synthesis, energy transfer and luminescence properties of Ce3+/Tb3+/Eu3+-doped CaF2 microcrystals. J Mater Sci 52, 5857–5870 (2017). https://doi.org/10.1007/s10853-017-0822-2
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DOI: https://doi.org/10.1007/s10853-017-0822-2