Spin and orbital orderings behind multiferroicity in delafossite and related compounds

Coupling between noncollinear magnetic ordering and ferroelectricicty in magnetoelectric multiferroics has been extensively studied in the last decade. Delafossite family compounds with triangular lattice structure provide a great opportunity to study the coupling between spin and electric dipole in multiferroics due to the variety of magnetic phases with different symmetry. This review introduces the magnetic and ferroelectric phase transitions in delafossite ferrites, CuFe(1-x)X(x)O(2) (X = Al, Ga), AgFeO(2) and the related compound α-NaFeO(2). In CuFeO(2), the ferroelectric phase appears under a magnetic field or chemical substitution. The proper screw magnetic ordering with the magnetic point group 21', which has been determined by detailed analysis in neutron diffraction experiments, induces the ferroelectric polarization along the monoclinic b axis in CuFeO2. The cycloidal magnetic orderings are realized in AgFeO(2) and α-NaFeO(2), which are of the point group m1' allowing polarization in the ac plane. The emergence of ferroelectric polarization can be explained by both the extended inverse Dzyaloshinsky-Moriya effect and the d − p hybridization mechanism. These mechanisms are supported by experimental evidence in CuFe(1-x)Ga(x)O2. The polarized neutron diffraction experiment demonstrated one-to-one correspondence between ferroelectric polarization and spin helicity, S(i) × S(j). The incommensurate orbital ordering with 2 Q wave vector, observed by the soft x-ray resonant diffraction experiment, proved that the spin-orbit interaction ties spin and orbital orders to each other, playing a crucial role for the emergence of ferroelectricity in CuFe(1-x)Ga(x)O2.