A novel “water-in-oil” type reverse microemulsion assisted synthesis detail on the formation of mixed cubic and hexagonal (α + β) phase NaYF4:Yb,Er nanoparticles and their upconversion emission properties are presented. The effect of surfactants, fluorine precursors on the crystallographic phase fraction, crystallite size of NaYF4:Yb,Er nanoparticles on red upconversion emission is discussed. The NaYF4:Yb,Er nanoparticles synthesized with CTAB, and oleic acid surfactants give larger crystallite size and moderate hexagonal/cubic phase fraction. It has resulted very intense upconversion red emission. The oleic-acid-free preparation of NaYF4:Yb,Er nanoparticles resulted highly-agglomerated nanoparticles and low crystallite size, which gives less-intense upconversion emission. The cubic and hexagonal phase fractions of NaYF4:Yb,Er depends on surfactants, microemulsion, molar concentrations of precursors, and post-calcination. All these factors influence the mondispersibility and upconversion red emission properties. The 980 nm laser pump power dependent upconversion emission studies have confirmed the typical two-photon behavior in α + β phase NaYF4:Yb,Er nanoparticles. Their decay life was also measured to correlate the upconversion red emission intensity. The effect of mixed α + β phase NaYF4:Yb,Er nanoparticles on the 1530 nm NIR emission is also presented.
Mixed phase NaYF4:Yb,Er nanoparticles were prepared by reverse microemulsion.
The hexagonal/cubic phase fraction is changed by varying surfactants/precursors.
Visible upconversion and NIR emissions are observed under 980 nm excitation.
CTAB-OA assisted synthesis yielded uniform nanospheres and strong upconversion.
OA free preparation resulted in agglomerated particles affects the upconversion.
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Zhou B, Shi B, Jin D, Liu X (2015) Controlling upconversion nanocrystals for emerging applications. Nat Nanotechnol 10:924
L.F.J.a.H.J (1971) Guggenheim, infrared‐pumped visible laser. Appl Phys Lett 19:44–47
Jiangli W, Xueqiu Y, Shuohui C, Jianming L, Jihuai W, Zhong C (2018) Enhancement of the photovoltaic properties of dye-sensitized solar cells using Y0.80Yb0.18Er0.02OF nanorods. Energy Technol 6:744–751
Park BJ, Hong AR, Park S, Kyung K-U, Lee K, Seong Jang H (2017) Flexible transparent displays based on core/shell upconversion nanophosphor-incorporated polymer waveguides. Sci Rep. 7:45659
Kostyuk GEL, Vorotnov AB, Sencha AD, Peskova LM, Sokolova NN, Liang EA, Vodeneev L, Balalaeva VA, Zvyagin IV (2018) Real-time tracking of Yb3+, Tm3+ doped NaYF4 nanoparticles in living cancer cells. Sovremennye Tehnologii v Med 10:57–63
Renero-Lecuna C, Martín-Rodríguez R, Valiente R, González J, Rodríguez F, Krämer KW, Güdel HU (2011) Origin of the high upconversion green luminescence efficiency in β-NaYF4:2%Er3+,20%Yb3+. Chem Mater 23:3442–3448
Méndez-Ramos J, Yanes AC, Santana-Alonso A, del-Castillo J (2013) Highly efficient up-conversion and bright white light in RE co-doped KYF4 nanocrystals in sol-gel silica matrix. Chem Phys Lett 555:196–201
Grzyb T, Balabhadra S, Przybylska D, Węcławiak M (2015) Upconversion luminescence in BaYF5, BaGdF5 and BaLuF5 nanocrystals doped with Yb3+/Ho3+, Yb3+/Er3+ or Yb3+/Tm3+ ions. J Alloy Compd 649:606–616
Gunaseelan M, Yamini S, Kumar GA, Santhosh C, Senthilselvan J (2018) Photon upconversion characteristics of intense green emitting BaYF5:Yb3+,Er3+ nanoclusters prepared by reverse microemulsion. Mater Res Bull 107:366–378
Yamini S, Sakthi Priya P, Gunaseelan M, Senthilselvan J (2017) Structural phase transformations in KYF4:Er3+ nanoparticles synthesized by hydrothermal method for upconversion applications. AIP Conf Proc 1832:030021
Murali G, Mishra RK, Lee JM, Chae YC, Kim J, Suh YD, Lim D-k, Lee SH (2017) Aspect-ratio controlled synthesis and tunable luminescence of YF3:Yb3+/Er3+ upconversion nanocrystals. Cryst Growth Des 17:3055–3061
Krämer KW, Biner D, Frei G, Güdel HU, Hehlen MP, Lüthi SR (2004) Hexagonal sodium yttrium fluoride based green and blue emitting upconversion phosphors. Chem Mater 16:1244–1251
Kumar A, Tiwari SP, Joaquim CGEdS, Kumar K (2018) Security writing application of thermal decomposition assisted NaYF4:Er3+/Yb3+ upconversion phosphor. Laser Phys Lett 15:075901
Xie S, Tong C, Tan H, Li N, Gong L, Xu J, Xu L, Zhang C (2018) Hydrothermal synthesis and inkjet printing of hexagonal-phase NaYF4: Ln3+ upconversion hollow microtubes for smart anti-counterfeiting encryption. Mater Chem Front 2:1997–2005
Wang M, Zhu Y, Mao C (2015) Synthesis of NIR-Responsive NaYF4:Yb,Er upconversion fluorescent nanoparticles using an optimized solvothermal method and their applications in enhanced development of latent fingerprints on various smooth substrates. Langmuir 31:7084–7090
Gao X, Li T, He J, Ye K, Song X, Wang N, Su J, Hui C, Zhang X (2017) Synthesis of Yb3+, Ho3+ and Tm3+ co-doped β-NaYF4 nanoparticles by sol-gel method and the multi-color upconversion luminescence properties. J Mater Sci: Mater Electron 28:11644–11653
Yang D, Chen D, He H, Pan Q, Xiao Q, Qiu J, Dong G (2016) Controllable phase transformation and mid-infrared emission from Er3+-Doped Hexagonal-/Cubic-NaYF4 nanocrystals. Sci Rep. 6:29871
Shan J, Ju Y (2007) Controlled synthesis of lanthanide-doped NaYF4 upconversion nanocrystals via ligand induced crystal phase transition and silica coating. Appl Phys Lett 91:123103
Zeng Q, Xue B, Zhang Y, Wang D, Liu X, Tu L, Zhao H, Kong X, Zhang H (2013) Facile synthesis of NaYF4:Yb, Ln/NaYF4:Yb core/shell upconversion nanoparticles via successive ion layer adsorption and one-pot reaction technique. CrystEngComm 15:4765–4772
Gunaseelan M, Yamini S, Kumar GA, Senthilselvan J (2018) Highly efficient upconversion luminescence in hexagonal NaYF4:Yb3+, Er3+ nanocrystals synthesized by a novel reverse microemulsion method. Optical Mater 75:174–186
Li C, Yang J, Quan Z, Yang P, Kong D, Lin J (2007) Different microstructures of β-NaYF4 fabricated by hydrothermal process: effects of pH values and fluoride sources. Chem Mater 19:4933–4942
Yajuan S, Yue C, Lijin T, Yi Y, Xianggui K, Junwei Z, Hong Z (2007) Controlled synthesis and morphology dependent upconversion luminescence of NaYF4:Yb, Er nanocrystals. Nanotechnology 18:275609
He L, Zou X, He X, Lei F, Jiang N, Zheng Q, Xu C, Liu Y, Lin D (2018) Reducing grain size and enhancing luminescence of NaYF4:Yb3+, Er3+ upconversion materials. Cryst Growth Des 18:808–817
Jiang T, Qin W, Zhou J (2016) Hydrothermal synthesis and aspect ratio dependent upconversion luminescence of NaYF4:Yb3+, Er3+ microcrystals. J Nanosci Nanotechnol 16:3806–3810
Gunaseelan M, Senthilselvan J (2016) Synthesis and characterization of α-NaYF4: Yb, Er nanoparticles by reverse microemulsion method. AIP Conf Proc 1728:020574
Patterson AL (1939) The scherrer formula for X-ray particle size determination. Phys Rev 56:978–982
Lee JS, De Angelis RJ (1996) X-ray diffraction patterns from nanocrystalline binary alloys. Nanostruct Mater 7:805–812
Biju V, Sugathan N, Vrinda V, Salini SL (2008) Estimation of lattice strain in nanocrystalline silver from X-ray diffraction line broadening. J Mater Sci 43:1175–1179
Williamson GK, Hall WH (1953) X-ray line broadening from filed aluminium and wolfram. Acta Metall 1:22–31
Ghosh P, Patra A (2008) Influence of crystal phase and excitation wavelength on luminescence properties of Eu3+-Doped sodium yttrium fluoride nanocrystals. J Phys Chem C 112:19283–19292
Ostwald W (1897) Studien über die Bildung und Umwandlung fester Körper. Zeitschrift für Physikalische Chemie 22(1):289–330
Pal M, García Serrano J, Santiago P, Pal U (2007) Size-controlled synthesis of spherical TiO2 nanoparticles: morphology, crystallization, and phase transition. J Phys Chem C 111:96–102
Wang F, Liu X (2009) Recent advances in the chemistry of lanthanide-doped upconversion nanocrystals. Chem Soc Rev 38:976–989
Digonnet M (Ed) (2001) Rare-earth-doped fiber lasers and amplifiers, revised and expanded. Boca Raton: CRC Press, https://doi.org/10.1201/9780203904657
Becker PC (1999) Erbium-doped fiber amplifiers: fundamentals and technology, In: NA Olsson, JR Simpson (eds), Academic Press, San Diego
Vetrone F, Boyer J-C, Capobianco JA (2004) Significance of Yb3+ concentration on the upconversion mechanisms in codoped Y2O3:Er3+, Yb3+ nanocrystals. J Appl Phys 96:661–667
Li Y, Hong G, Zhang Y, Yu Y (2008) Red and green upconversion luminescence of Gd2O3:Er3+, Yb3+ nanoparticles. J Alloy Compd 456:247–250
Feng W, Juan W, Xiaogang L (2010) Direct evidence of a surface quenching effect on size-dependent luminescence of upconversion nanoparticles. Angew Chem Int Ed 49:7456–7460
Liu G (2015) Advances in the theoretical understanding of photon upconversion in rare-earth activated nanophosphors. Chem Soc Rev 44:1635–1652
Pedraza FJ, Rightsell C, Kumar GA, Giuliani J, Monton C, Sardar DK (2017) Emission enhancement through Nd3+-Yb3+ energy transfer in multifunctional NaGdF4 nanocrystals. Appl Phys Lett 110:223107
Qin H, Wu D, Sathian J, Xie X, Ryan M, Xie F (2018) Tuning the upconversion photoluminescence lifetimes of NaYF4:Yb3+, Er3+ through lanthanide Gd3+ doping. Sci Rep 8:12683
The author MG extends his sincere gratitude for the award of research fellowship and JS is grateful to UGC-UPE Phase II program. Authors are grateful to Professor C. Santhosh, Head of the Department of atomic and molecular spectroscopy, Manipal Academy of Higher Education, India for UV-Vis-NIR absorption characterization. GAK and DKS acknowledge the (NSF-PREM) grant NO-DMR-0934218.
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Gunaseelan, M., Yamini, S., Kumar, G.A. et al. Reverse microemulsion synthesis of mixed α and β phase NaYF4:Yb,Er nanoparticles: calcination induced phase formation, morphology, and upconversion emission. J Sol-Gel Sci Technol (2020). https://doi.org/10.1007/s10971-020-05340-w
- Mixed phase
- Oleic acid