Inorganic host matrices provide a tunable luminescence
environment
for lanthanide ions, allowing for the modulation of upconversion luminescence
(UCL) properties. AREF
4
(A = alkali metal, RE = rare earth)
have a low phonon energy and a high optical damage threshold, making
them widely used as the host matrix for UCL materials. However, the
impact mechanism of alkali metal ions and lanthanide lattice ions
on transient UCL dynamics in AREF
4
remains unclear. This
study utilized a high-power nanosecond-pulsed laser at 976 nm to excite
Yb–Er codoped NaLnF
4
and LiLnF
4
(Ln:
Y, Lu, and Gd) microcrystals (MCs). All samples exhibit multiband
emission, and the transient UC dynamics are discussed in detail. Compared
with LiLnF
4
, NaLnF
4
has higher UC efficiency
and red to green (R/G) ratio. Lanthanide ions (Y, Lu, and Gd) affect
the energy transfer (ET) distance in Yb–Er codoped systems,
thereby altering UC efficiency and the R/G ratio. The energy level
coupling between Gd
3+
and Er
3+
prolongs the
duration of the UC emission. Specifically, the red emission lifetime
of NaGdF
4
is five times longer than that of NaYF
4
. Our research contributes to exploring excellent alternative host
matrices for NaYF
4
in the fields of rapid-response optoelectronic
devices, micro–nano lasers, and stimulated emission depletion
(STED) microscopy.