Chalcogenides such as GeTe, PbTe, Sb2Te3, and Bi2Se3 are characterized by an unconventional combination of properties enabling a plethora of applications ranging from thermo‐electrics to phase change materials, topological insulators, and photonic switches. Chalcogenides possess pronounced optical absorption, relatively low effective masses, reasonably high electron mobilities, soft bonds, large bond polarizabilities, and low thermal conductivities. These remarkable characteristics are linked to an unconventional bonding mechanism characterized by a competition between electron delocalization and electron localization. Confinement, that is, the reduction of the sample dimension as realized in thin films should alter this competition and modify chemical bonds and the resulting properties. Here, pronounced changes of optical and vibrational properties are demonstrated for crystalline films of GeTe, while amorphous films of GeTe show no similar thickness dependence. For crystalline films, this thickness dependence persists up to remarkably large thicknesses above 15 nm. X‐ray diffraction and accompanying simulations employing density functional theory relate these changes to thickness dependent structural (Peierls) distortions, due to an increased electron localization between adjacent atoms upon reducing the film thickness. A thickness dependence and hence potential to modify film properties for all chalcogenide films with a similar bonding mechanism is expected.

MoTe 2 has a stable hexagonal semiconducting phase (2H) as well as two semimetallic phases with monoclinic (1T′) and orthorhombic (T d ) structures. A structural change can thus be accompanied by a significant change in electronic transport properties. The two semimetallic phases are connected by a temperature driven transition and could exhibit topological properties. Here we make extensive Raman measurements as a function of layer thickness, temperature, and electrostatic doping on few layer 2H-MoTe 2 and also on 1T′-MoTe 2 and T d -WTe 2 . Recent work in MoTe 2 has raised the possibility of a 2H-1T′ transition through technology compatible pathways. It has been claimed that such a transition, of promise for device applications, is activated by electrostatic gating. We investigate this claim and find that few-layer tellurides are characterized by high mobility of Te ions, even in ambient conditions and especially through the variation of external parameters like electric field or temperature. These can generate Te clusters, vacancies at crystalline sites, and facilitate structural transitions. We however find that the purported 2H-1T′ transition in MoTe 2 cannot be obtained by a pure electrostatic field.