Improper ferroics

Figure 6.54 Diagram illustrating several types of order parameters involved in proper and improper ferroics. (After Newnham Cross, 1981.)...

A hexagonal representation of proper and improper primary ferroics as proposed by Newnham Cross (1981) is given in Fig. 6.54. The order parameter for proper ferroics appears on the diagonals of the hexagon, while the sides of the hexagon represent improper ferroics. They indicate the cross-coupled origin of ferroic phenomena. An improper primary ferroic in this classification is distinguished from a true secondary... 

These materials have the ilMnOs R = Sc or small, rare earth cation) stoichiometry,and have been erroneously referred to as hexagonal perovskites. The compounds do not exhibit the perovskite structure. The Mn cations are not octahedrally coordinated, rather the cation is surrounded by five oxide anions in a trigonal prismatic coordination environment. Also the R cations are not 12-coordinate, as would be the case in a perovskite, but are in seven-fold coordination. The materials are multi-ferroic, with anti-ferromagnetic and ferroelectric properties.The nature of the polarity and therefore the ferroelectric behaviour was only recently described. Careful structural studies indicated that although the dipole moments are attributable to the R-O bonds and not the Mn-O bonds, the R-cations are not directly responsible for the ferroelectric behaviour. The noncentrosymmetry is attributable to the tilting of the MnOs polyhedra, which in conjunction with the dipole moments in the R-O bonds results in ferroelectric behaviour. Thus the ferroelectric behaviour in these materials is termed improper " and occurs by a much different mechanism than BaTiOs or even BiFeOs. 

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