  MoTe2 is a rare transition-metal ditelluride having two kinds of layered
polytypes, hexagonal structure with trigonal prismatic Mo coordination and
monoclinic structure with octahedral Mo coordination. The monoclinic distortion
in the latter is caused by anisotropic metal-metal bonding. In this work, we
have examined the Nb doping effect on both polytypes of MoTe2 and clarified a
structural phase diagram for Mo1-xNbxTe2 containing four kinds of polytypes. A
rhombohedral polytype crystallizing in polar space group has been newly
identified as a high-temperature metastable phase at slightly Nb-rich
composition. Considering the results of thermoelectric measurements and the
first principles calculations, the Nb ion seemingly acts as a hole dopant in
the rigid band scheme. On the other hand, the significant interlayer
contraction upon the Nb doping, associated with the Te p-p hybridization, is
confirmed especially for the monoclinic phase, which implies a shift of the
p-band energy level. The origin of the metal-metal bonding in the monoclinic
structure is discussed in terms of the d electron counting and the Te p-p
hybridization.
