Current Optics and Photonics

Optical Society of Korea (한국광학회)
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Precipitation of Eu3+ - Yb3+ Codoped ZnAl2O4 Nanocrystals on Glass Surface by CO2 Laser Irradiation

  • Bae, Chang-hyuck (Department of Physics, Chungbuk National University) ;
  • Lim, Ki-Soo (Department of Physics, Chungbuk National University) ;
  • Babu, P. (Department of Physics, Govt. Degree College)
  • Received : 2018.01.11
  • Accepted : 2018.01.30
  • Published : 2018.02.25
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Abstract

We present a novel and simple method to enable spatially selective $ZnAl_2O_4$ nanocrystal formation on the surface of $B_2O_3$-$Al_2O_3$-ZnO-CaO-$K_2O$ glass by employing localized laser heating. Optimized precipitation of glass-ceramics containing nanocrystals doped with $Eu^{3+}$ and $Yb^{3+}$ ions was performed by controlling $CO_2$ laser power and scan speed. Micro-x-ray diffraction and transmission electron microscopy revealed the mean size and morphology of nanocrystals, and energy dispersive x-ray spectroscopy showed the lateral distribution of elements in the imaged area. Laser power and scan speed controled annealing temperature for crystalization in the range of 1.4-1.8 W and 0.01-0.3 mm/s, and changed the size of nanocrystals and distribution of dopant ions. We also report more than 20 times enhanced downshift visible emission under ultraviolet excitation, and 3 times increased upconversion emission from $Eu^{3+}$ ions assisted by efficient sensitizer $Yb^{3+}$ ions in nanocrystals under 980 nm excitation. The confocal microscope revealed the depth profile of $Eu^{3+}$ ions by showing their emission intensity variation.

Keywords

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FIG. 1. XRD patterns of glass-ceramics containing ZnAl2O4 nanocrystals precipitated by CO2 laser irradiation with 1.8 W and 0.1 mm/s and 0.01 mm/s scan speeds. The lowest scan corresponds to glass.

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FIG. 2. TEM images of ZnAl2O4 nanocrystals precipitated by CO2 laser irradiation with 1.8 W and 0.1 mm/s scan speed: (a) TEM image showing the lattice constant 0.145 nm for the (440) plane, (b) TEM image of ZnAl2O4 nanocrystals, (c) Distribution of Zn ions.

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FIG. 3. TEM and EDS images of nanocrystals precipitated by CO2 laser irradiation with 1.8 W and 0.01 mm/s scan speed: (a) TEM image, and (b-f) EDS images of Zn, Al, O, Eu, and Yb ions.

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FIG. 4. Downshift emission spectra under 365 nm excitation from Eu3+ and Yb3+ co-doped glass-ceramics treated by (a) various CO2 laser powers and (b) scan speeds.

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FIG. 5. Upconversion emission spectra under 980 nm excitation from Eu3+ and Yb3+ co-doped glass-ceramics treated by (a) various CO2 laser powers and (b) scan speeds.

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FIG. 6. Fluorescence images from Eu3+ and Yb3+ co-doped glass-ceramics obtained with 1.8 W and 0.01 mm/s scan speeds: (a) surface emission profile (100 μm × 800 μm), (b) fluorescence images from 0, 10, 20, 30, 40, 50, 70, 80, 90, 100 μm below the surface.

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