Size Effects in ZnO: The Cluster to Quantum Dot Transition

The use of tetraalkylammonium hydroxides to prepare ZnO colloids with diameters ranging from 1 to 6 nm is described. The position of the first excitonic transition has been measured by UV-vis spectrometry and correlated with the particle size, which has been measured using high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), and ultracentrifugation (UC). The exciton transition is first visible at 265–270 nm corresponding to particle diameters around 1 nm; the exciton absorption band then becomes sharper and narrower, while the band red-shifts only slowly. Based on the sizing data from HRTEM, XRD, and UC, it is concluded that the quantum size effect at sizes less than the Bohr radius is significantly less than predicted from the Kayanuma equation. Based on the blue-shift in the trap emission as a function of nanocrystal size, the effective masses of the electron and hole (me, mh) remain constant in particles down to 1 nm in diameter, with a relative value given by me/(me+mh)=0.55 ± 0.04.

EXCITONIC PHOTOLUMINESCENCE IN PENTACENE SINGLE CRYSTAL

Photoluminescence of pentacene single crystals is studied in the temperature range of 7 K to 200 K under excitation with He-Ne laser light. Photoluminescence spectra consist of four broad bands, L1 to L4. The highest energy band, L1, located close to the lowest exciton absorption band mainly appears for //b-polarization. The intensity of the second one, L2, with Stokes-shift of about 1500 cm -1, decreases as temperature rises above 30 K and disappears at 100 K. The bands, L3 and L4, which are located at lower energy, are observed at higher temperatures up to 200 K. Based on their energy positions, the band L2 is assigned to a shallow self-trapped exciton luminescence band, and the bands L3 and L4 to deep self-trapped exciton luminescence bands. By comparing this result with reported result on tetracene crystals, self-trapped excitons are considered to be more stable in pentacene.