Temperature- and size-dependent photoluminescence in colloidal CdTe and CdxZn1-xTe quantum dots

Semiconductor colloidal quantum dots (QDs) of CdTe and alloyed CdxZn1-xTe QDs with N-acetyl-L-cysteine capping ligands are synthesized by a reflux method in aqueous solution. Alloying provides a new degree of freedom to tune the optical and electronic properties of the nanocrystals. The photoluminescence (PL) of CdxZn1-xTe QDs is sharper and displays a highly enhanced quantum yield (QY) of 65% relative to the 16% of CdTe QDs. The fluorescence of CdxZn1-xTe QDs is observed to be highly stable for over 12 months without degradation, while that of CdTe QDs begins to mildly flocculate around 8 months of storage. To characterise the material structure and composition, UV-Vis absorption spectroscopy, x-ray powder diffraction, transmission electron microscopy, and inductively coupled plasma mass spectrometry measurements are carried out. To understand the fundamental processes that play in the luminescence behaviour, temperature- and size-dependent PL spectra are investigated in the range 80-300 K. The Varshni and O'Donnell equations fit well on the PL peak emission energies and the Huang-Rhys parameter indicates the strengthening of exciton-phonon coupling in the nanocrystals upon alloying and with decreasing nanocrystal sizes. PL linewidth analysis reveals that the inhomogeneous broadening is considerably reduced in CdxZn1-xTe QDs relative to CdTe. Moreover, the quantum confinement effect of the nanocrystals leads to an increase in exciton-acoustic phonon interactions with the coefficients ranging between 26.9 and 95.6 mu eV K-1 compared to the bulk CdTe value of 0.72 mu eV K-1. Exciton-longitudinal optical phonon interactions are made stronger by the ZnTe alloying with the coefficients lying in the range between 24.8 and 41.7 meV and also with the effect of increasing crystal size. An Arrhenius plot of PL integrated area is used to calculate the thermal activation energy value E-a of the non-radiative recombination channel, which is 132 meV for CdTe QDs and a higher value of 185 meV for CdxZn1-xTe QDs. This is consistent with the observed QY enhancement in CdxZn1-xTe QDs as a higher E-a value indicates reduced generation of non-radiative recombination centres and a decrease in defect densities upon alloying. CdxZn1-xTe QDs with enhanced fluorescence properties serve both as a medium for studying fundamental effects of alloying and its properties, and for practical applications such as biomedical labelling and optoelectronics.