Finite-size effects on band structure of CdS nanocrystallites studied by positron annihilation

Quantum confinement effects in nanocrystalline CdS were studied using positrons as spectroscopic probes to explore the defect characteristics. The lifetime of positrons annihilating at the vacancy clusters on nanocrystalline grain surfaces increased remarkably consequent to the onset of such finite-size effects. The Doppler broadened line shape was also found to reflect rather sensitively such distinct changes in the electron momentum redistribution scanned by the positrons, owing to the widening of the band gap. The nanocrystalline sizes of the samples used were confirmed from x-ray diffraction and high resolution transmission electron microscopy and the optical absorption results supported the quantum size effects. Positron annihilation results indicated distinct qualitative changes between CdS nanorods and the bulk sample, notwithstanding the identical x-ray diffraction pattern and close resemblance of the optical absorption spectra. The results are promising in the event of positron annihilation being proved to be a very successful tool for the study of such finite-size effects in semiconductor nanoparticles.