Thermally boosted upconversion and downshifting luminescence in Sc2(MoO4)3:Yb/Er with two-dimensional negative thermal expansion.Rare earth (RE3+)-doped phosphors generally suffer from thermal quenching, in which their photoluminescence (PL) intensities decrease at high temperatures.  Herein, we report a class of unique two-dimensional negative-thermal-expansion phosphor of Sc2(MoO4)3:Yb/Er.  By virtue of the reduced distances between sensitizers and emitters as well as confined energy migration with increasing the temperature, a 45-fold enhancement of green upconversion (UC) luminescence and a 450-fold enhancement of near-infrared downshifting (DS) luminescence of Er3+ are achieved upon raising the temperature from 298 to 773 K. The thermally boosted UC and DS luminescence mechanism is systematically investigated through in situ temperature-dependent Raman spectroscopy, synchrotron X-ray diffraction and PL dynamics.  Moreover, the luminescence lifetime of 4I13/2 of Er3+ in Sc2(MoO4)3:Yb/Er displays a strong temperature dependence, enabling luminescence thermometry with the highest relative sensitivity of 12.3%/K at 298 K and low temperature uncertainty of 0.11 K at 623 K. These findings may gain a vital insight into the design of negative-thermal-expansion RE3+-doped phosphors for versatile applications.
THERM