Volume and surface effects on two-photonic and three-photonic processes in dry co-doped upconversion nanocrystals

Despite considerable advances in synthesizing high-quality core/shell upconversion(UC)nanocrystals(NC;UCNC)and UCNC photophysics,the application of near-infrared(NIR)-excitable lanthanide-doped UCNC in the life and material sciences is still hampered by the relatively low upconversion luminescence(UCL)of UCNC of small size or thin protecting shell.To obtain deeper insights into energy transfer and surface quenching processes involving Yb^(3+) and Er^(3+) ions,we examined energy loss processes in differently sized solid core NaYF_(4) nanocrystals doped with either Yb^(3+)(YbNC;20%Yb^(3+))or Er^(3+)(ErNC;2%Er^(3+))and co-doped with Yb^(3+) and Er^(3+)(YbErNC;20%Yb^(3+) and 2%Er^(3+))without a surface protection shell and coated with a thin and a thick NaYF_(4) shell in comparison to single and co-doped bulk materials.Luminescence studies at 375 nm excitation demonstrate back-energy transfer(BET)from the ^(4)G_(11/2) state of Er^(3+) to the ^(2)F_(5/2) state of Yb^(3+),through which the red Er^(3+) ^(4)F_(9/2) state is efficiently populated.Excitation power density(P)-dependent steady state and time-resolved photoluminescence measurements at different excitation and emission wavelengths enable to separate surface-related and volume-related effects for two-photonic and three-photonic processes involved in UCL and indicate a different influence of surface passivation on the green and red Er3+emission.The intensity and lifetime of the latter respond particularly to an increase in volume of the active UCNC core.We provide a three-dimensional random walk model to describe these effects that can be used in the future to predict the UCL behavior of UCNC.