Experimental studies of successive structural
phase transitions of KNiCl3 and related crystals (KNiCl3-family
crystals) RbMnBr3, TlFeCl3, TlCoCl3, RbFeBr3, RbCoBr3 and
RbVBr3 with dielectric and diffraction methods were summarized.
Their
prototype structure is the CsNiCl3-type structure, which
is known to contain NiCl3 linear-chain substructure. Some
phases
of GroupsI(KNiCl3, RbMnBr3, TlFeCl3 and TlCoCl3) , II(RbFeBr3)
and III(RbCoBr3 and RbVBr3) crystals were shown to be ferroelectric
with spontaneous polarization parallel to the chain (c-axis).
Transition points and space group symmetries of each phase
were listed. It was discussed that those structural phase
transitions can be attributed to competition between the
distortion of
NiCl6 octahedra which are directly connected to the spontaneous
polarization and that of KCl12 polyhedra which might be closely
related to the softening of vibrational K4-mode. The reasons
why some crystals with the CsNiCl3-type structure (such as
RbNiBr3) does not undergo such structural phase transitions
and why the spontaneous polarization of Group I KNiCl3-family
crystals disappears in phase V remain unsolved. |