Possible reappearance of the charge density wave transition in MxTiSe2 compounds intercalated with 3d metals

Measurements of the electrical resistivity have been performed on MxTiSe2 compounds intercalated with 3d metals (M = Cr, Mn, Fe, Ni) up to x = 0.5. The charge density wave (CDW) transition which is observed in pure TiSe2 below ∼200 K disappears for intercalation x>0.1, while a further increase of the intercalant content (x≥0.25, M = Cr, Mn or Fe) leads to the appearance of pronounced anomalies in the temperature dependences of the resistivity in the same temperature range where the CDW transition takes place in the pure TiSe2 compound. These anomalies in highly intercalated MxTiSe2 are associated with the reappearance of a superstructure formation and associated CDW state. For Mn0.33TiSe2, the structural phase transition was evidenced from both powder neutron diffraction measurements and specific heat data. The observed results are discussed in terms of the degree of deformation of Se-Ti-Se sandwiches, which we believe play a key role in the disappearance and reappearance of the CDW state in MxTiSe2 as a function of increasing M concentration. The change in the electronic structure due to the intercalation seems not to strongly influence the presence of the CDW