Abstract
We report the results of a combined experimental and theoretical study on nonstoichiometric thin films grown by reactive magnetron sputtering on -plane sapphire and MgO (100) substrates in an gas mixture using different percentages of . There is a transition from -type to -type behavior in the layers as a function of nitrogen concentration varying from 48 to 52 at. % in CrN films. The compositional change follows a similar trend for all substrates, with a N/Cr ratio increasing from approximately 0.7 to 1.06–1.11 by increasing the percentage of in the gas flow ratio. As a result of the change in stoichiometry, the lattice parameter and the Seebeck coefficient increase together with the increase of N in ; in particular, the Seebeck value coefficient transitions from for to for . Density functional theory calculations show that Cr vacancies can account for the change in the Seebeck coefficient, since they push the Fermi level down in the valence band, whereas N interstitial defects in the form of dumbbells are needed to explain the increasing lattice parameter. Calculations including both types of defects, which have a strong tendency to bind together, reveal a slight increase in the lattice parameter and a simultaneous formation of holes in the valence band. To explain the experimental trends, we argue that both Cr vacancies and dumbbells, possibly in combined configurations, are present in the films. We demonstrate the possibility of controlling the semiconducting behavior of CrN with intrinsic defects from to type, opening possibilities to integrate this compound in energy-harvesting thermoelectric devices.
- Received 16 November 2021
- Revised 10 January 2022
- Accepted 25 February 2022
DOI:https://doi.org/10.1103/PhysRevB.105.104108
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Published by the American Physical Society