Temperature dependent optical properties of PbS nanocrystals

Abstract

A comprehensive study of the optical properties of PbS nanocrystals (NCs) is reported that includes the temperature dependent absorption, photoluminescence (PL) and PL lifetime in the range of 3–300 K. The absorption and PL are found to display different temperature dependent behaviour though both redshift as temperature is reduced. This results in a temperature dependent Stokes shift which increases from ∼75 meV at 300 K with reducing temperature until saturating at ∼130 meV below ∼150 K prior to a small reduction to 125 meV upon cooling from 25 to 3 K. The PL lifetime is found to be single exponential at 3 K with a lifetime of τ1 = 6.5 μs. Above 3 K biexponential behaviour is observed with the lifetime for each process displaying a different temperature dependence. The Stokes shift is modelled using a three-level rate equation model incorporating temperature dependent parameter values obtained via fitting phenomenological relationships to the observed absorption and PL behaviour. This results in a predicted energy difference between the two emitting states of ∼6 meV which is close to the excitonic exchange energy splitting predicted theoretically for these systems.