  The nonstoichiometric NaxCoO2 system exhibits extraordinary physical
properties that correlate with temperature and Na concentration in its layered
lattice without evident long-range structure modification when conventional
crystallographic techniques are applied. For instance, Na0.7CoO2, a
thermodynamically stable phase, shows large thermoelectric power;
water-intercalated Na0.33CoO2.1.3H2O is a newly discovered superconductor with
Tc ~ 4K, and Na0.5CoO2 exhibits an unexpected charge ordering transition at
around Tco ~ 55 K. Recent studies suggest that the transport and magnetic
properties in the NaxCoO2 system strongly depend on the charge carrier density
and local structural properties. Here we report a combined variable temperature
transmission electron microscopy and Raman scattering investigation on
structural transformations in Na0.5CoO2 single crystals. A series of structural
phase transitions in the temperature range from 80 K to 1000 K are directly
identified and the observed superstructures and modulated phases can be
interpreted by Na-ordering. The Raman scattering measurements reveal phase
separation and a systematic evolution of active modes along with phase
transitions. Our work demonstrates that the high mobility and ordering of
sodium cations among the CoO2 layers are a key factor for the presence of
complex structural properties in NaxCoO2 materials, and also demonstrate that
the combination of electron diffraction and Raman spectroscopy measurements is
an efficient way for studying the cation ordering and phase transitions in
related systems.
