Issue 48, 2021

Structural insights on Li+ doped P[6 with combining macron] crystals of upconverting NaYF4:Yb3+/M3+ (M3+ = Er3+ or Tm3+) through extensive synchrotron radiation-based X-ray probing

Abstract

Explaining the intensification of upconversion luminescence (UCL) from a single phase NIR-upconverting (UC) crystal due to non-lanthanide dopant insertion appears challenging in the absence of proper mechanistic investigation. In this paper, through extensive synchrotron based X-ray probing, we made an attempt to understand the variations in the structural attributes of UC crystals generated through non-lanthanide ion doping. The structures of the NaYF4/Yb3+/M3+ (M3+ = Er3+/Tm3+) UC crystals doped with different Li+ concentrations were primarily investigated using Rietveld refinement analysis from synchrotron X-ray diffraction (SXRD) and supported with absorption data (XAFS), where necessary. The structural investigation was also supported by TEM, HRTEM, XANES, FT-IR and Raman spectroscopy. Rietveld analysis revealed that all the generated Li+ doped NaYF4 crystals belong to the P[6 with combining macron] space group. Most of the Li+ ions were found to be localized in octahedral voids and lattice positions, simultaneously, in the P[6 with combining macron] crystal structures. The overall study showed that the change in the UCL intensity behavior with Li+ incorporation could not be predicted from the lattice parameters, morphology or the particle size variation. A detailed XAFS study rather suggested the possible existence of local lattice disorder, which was found to be reflected in terms of lattice strain obtained from Williamson–Hall analysis, irrespective of the activator ions. The remarkable coherence between the variation trends of UCL intensity and lattice strain indicated that the perturbation of the local symmetry field is in some way connected with the local disorder that may not always manifest through average structural attributes like lattice parameters.

Graphical abstract: Structural insights on Li+ doped P [[6 with combining macron]]  crystals of upconverting NaYF4:Yb3+/M3+ (M3+ = Er3+ or Tm3+) through extensive synchrotron radiation-based X-ray probing

Supplementary files

Article information

Article type
Paper
Submitted
17 ሴፕቴ 2021
Accepted
30 ኦክቶ 2021
First published
01 ኖቬም 2021

CrystEngComm, 2021,23, 8631-8640

Structural insights on Li+ doped P[6 with combining macron] crystals of upconverting NaYF4:Yb3+/M3+ (M3+ = Er3+ or Tm3+) through extensive synchrotron radiation-based X-ray probing

P. Verma, D. Sarkar, P. Rajput, M. N. Singh, R. Sharma and S. Giri, CrystEngComm, 2021, 23, 8631 DOI: 10.1039/D1CE01253C

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