Obtaining
highly efficient photoluminescence with Mn4+-activated
phosphors, which have been extensively studied in diverse
lighting devices, requires the precise control of the manganese valence
states. However, this control is difficult to achieve because manganese
ions can have various valence states ranging from divalent to heptavalent.
Additionally, the concentrations of Mn ions in each valence state,
especially the effective Mn4+ concentration, have never
been quantitatively determined in a phosphor crystal lattice. The
relationship between the effective Mn4+ concentration and
the luminescence properties of Mn4+-activated phosphors
is of current interest for improving the phosphor properties. In the
present study, the effective Mn4+ concentration in Li2TiO3:Mn4+ (LTO:Mn) phosphors prepared
by the sol–gel method with heating at various temperatures
was quantitatively analyzed by X-ray absorption near-edge spectroscopy.
Moreover, the effect of the existence of Mn2+, Mn3+, and Mn4+ ions on the photoluminescence efficiency was
investigated. The effective Mn4+ concentration was found
to be over 60% in all phosphor samples. The quantum efficiencies (QEs)
of all LTO:Mn phosphors strongly depend on the effective Mn4+ concentration. In particular, the LTO:Mn phosphor prepared by heating
at 800 °C (LTO:Mn@800) contained the highest effective Mn4+ concentration of 98.1% and exhibited the highest internal
QE of 31.6%. The results of this work provide new and important insights
for the development of Mn4+-activated phosphors with high
efficiency.
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