Metal halide perovskites have shown great performance for various applications, including solar cells, light emitting diodes, and radiation detectors, but they still suffer from the toxicity of lead and instability. Here we report the use of lanthanide series as trivalent metals to obtain low toxicity and highly stable double perovskites (Cs2NaLnCl6, Ln=Tb or Eu) with high scintillation light yield. The crystals exhibit typical f-f transitions of lanthanide cations, while Cs2NaTbCl6 exhibits strong green photoluminescence, and Cs2NaEuCl6 exhibits red photoluminescence. Under X-ray radiations, the light yield of Cs2NaTbCl6 reaches 46600 photons MeV?1, much higher than that of the commercially used (Lu,Y)2SiO5:Ce3+ crystals (LYSO, 28500 photons MeV?1), and previously reported lead-based perovskites (14000 photons MeV?1). As a new member of lead-free perovskites, lanthanide-based double perovskites open up a new route toward radiation detections and potential medical imaging.
the Major State Basic Research Development Program of China(2016YFB0700702)
the National Natural Science Foundation of China(5171101030,51602114)
the HUST Key Innovation Team for Interdisciplinary Promotion(2016JCTD111)
the Open Fund of State Key Laboratory of Luminescence and Applications(SKLA-2016-08)
This work was supported by the Major State Basic Research Development Program of China (2016YFB0700702), the National Natural Science Foundation of China (5171101030, 51602114), the HUST Key Innovation Team for Interdisciplinary Promotion (2016JCTD111) and the Open Fund of State Key Laboratory of Luminescence and Applications (SKLA-2016-08). The authors thank the Analytical and Testing Center of HUST and the facility support of the Center for Nanoscale Characterization and Devices, WNLO.
The authors declare that they have no conflict of interest.
The supporting information is available online at
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Figure 1
XRD patterns of Cs2NaTbCl6 (a) and Cs2NaEuCl6 (b) crystals, and the related Rietveld refinement results. Crosses represent the measured results, red lines are refinement results, blue lines are the difference profile between measured and refinement results, black vertical lines represent the standard diffractions. (c) Crystal structure of Cs2NaLnCl6, while Ln represents trivalent rare earth ions. (d) The images of as-prepared Cs2NaTbCl6 (up) and under ultraviolet light radiations (down). (e) The images of as-prepared Cs2NaEuCl6 (up) and under ultraviolet light radiations (down) (color online).
Figure 2
The excitation and emission spectra (a), color-coded contour maps of wavelength dependent emission spectra (b), and decay curve and fluorescence lifetimes (c) of Cs2NaTbCl6. The excitation and emission spectra (d), color-coded contour maps of wavelength dependent emission spectra (e), and decay curve and fluorescence lifetimes (f) of Cs2NaEuCl6 (color online).
Figure 3
The temperature dependent PL spectra of Cs2NaTbCl6 for 5D4→7F6 transitions (a) and 5D4→7F5 transitions (c), and the plots of integrated PL intensity vs. temperature (b and d). The sample was irradiated under
Figure 4
The generated voltage of multiplier tubes by scintillation light of Cs2NaTbCl6 (red line), Cs2NaEuCl6 (blue line), and (Lu,Y)2SiO5:Ce3+ (LYSO, black line), respectively (color online).
Material | Average voltage response (mV) | Standard deviation of voltage response (mV) | Light yield (photons MeV?1) |
LYSO | 2.234 | 0.016 | 28500 |
Cs2NaTbCl6 | 3.652 | 0.018 | 46600 |
Cs2NaEuCl6 | 0.098 | 0.014 | 1250 |
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