Traditionally, the formation of off-stoichiometric compounds is believed to be the growth effect rather than the intrinsic tendency of the system. However, here, using the example of La 3 Te 4 , we demonstrate that in n-type gapped metals having a large internal gap between principal band edges and the Fermi level inside of the principal conduction band, Fermi-level instability can develop, resulting in a decrease in the formation energy for acceptor defects. Specifically, La vacancies in La 3 Te 4 form spontaneously to produce the acceptor states and remove a fraction of free carriers from the principal conduction band via electron−hole recombination. Such a unique self-doping mechanism allows stabilization of a range of off-stoichiometric La 3−x Te 4 compounds, which have different electronic properties. Moreover, we thus show how controlling synthesis conditions can be used as a knob to reach the target functionality, including the controllable metal-to-insulator transition.

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Using the first-principles calculations and La3Te4 as an example of an n-type gapped metal, we demonstrate that gapped metals can develop spontaneous defect formation resulting in off-stoichiometric compounds. Importantly, these...