Unlike most electrical conductors, which conduct electricity by electronic motion, the salt
Cu2HgI4 (and the related solid, Ag2HgI4) is a good ionic conductor of electricity at temperatures
a little above room temperature, where it undergoes an order-disorder phase change. The
compound is easily prepared, and its phase change is observable both by increased conductivity
and a color change.
Structure and Phase Change
The low temperature ordered structure of Cu2HgI4 is shown in Figure 9.20C. Although the
overall unit cell is tetragonal, with square bases and rectangular sides, it can be viewed as two
fcc cells of iodide ions, with one cube atop the other. The iodide ions are in the fcc unit cells in
the same positions as the sulfur atoms in ZnS (sphalerite form, check your text!). All of the Cu+
and Hg2+ cations are in tetrahedral holes of the structure that are formed by the iodide ions (there
are two such holes for each iodide), hence three-eighths of these holes will be occupied by the
cations) but with a particular ordering (see Figure 9.20). In this low-temperature phase, the solid
is brick red.
At a temperature of about 67°C, disorder sets in, and the cations are randomly distributed about
all of the tetrahedral holes in the structure. The phase change is accompanied by a color change
to red-brown and a marked increase in electrical conductivity. The color change is due to a small
decrease in the band gap (2.1 to 1.9 eV) with the change in structure. In this high-temperature
phase, the unit cell is a cube, because X-ray diffraction measures the average occupation of the
tetrahedral sites, and the disorder makes it appear that, on average, each tetrahedral site contains
one-forth of a copper ion and one-eighth of a mercury ion.
Conductivity Mechanism
Above the transition temperature, Cu2HgI4 exhibits ionic conductivity (with some electronic
conductivity also). Five-eighths of the tetrahedral holes and all of the octahedral holes formed
by the iodide ions are vacant, and these open sites provide possible pathways for the small
copper cations to move through the crystal, carrying charge. It is easiest for a copper cation to
jump between tetrahedral holes by moving to an octahedral hole and then to the new tetrahedral
hole, rather than jumping directly between tetrahedral holes.