Composition and size-dependent extinction coefficient of colloidal PbSe quantum dots

Abstract

Inductively coupled plasma mass spectrometry (ICP-MS) was combined with UV-vis-NIR spectrophotometry and transmission electron microscopy to determine the nanocrystal composition and molar extinction coefficient e of colloidal PbSe quantum dot (Q-PbSe) suspensions. The ICP-MS results show a nonstoichiometric Pb/Se ratio, with a systematic excess of lead for all samples studied. The observed ratio is consistent with a faceted spherical Q-PbSe model, composed of a quasi stoichiometric Q-PbSe core terminated by a Pb surface shell. At high photon energies, we find that e scales with the nanocrystal volume, irrespective of the Q-PbSe size. From ε, we calculated a size-independent absorption coefficient. Its value is in good agreement with the theoretical value for bulk PbSe. At the band gap, ε is sizedependent. The resulting absorption coefficient increases quadratically with decreasing Q-PbSe size. Calculations of the oscillator strength of the first optical transition are in good agreement with theoretical tight binding calculations, showing that the oscillator strength increases linearly with Q-PbSe size. © 2007 American Chemical Society.