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Rocksalt structure nitrides emerge as a promising class of semiconductors for high-temperature thermoelectric and plasmonic applications. Controlling the bandgap and strain is essential for the development of a wide variety of electronic devices. Here we use (Ti 0.5 Mg 0.5 ) 1−x Al x N as a model system to explore and demonstrate the tunability of both the bandgap and the strain state in rocksalt structure nitrides, employing a combined experimental and computational approach. (Ti 0.5 Mg 0.5 ) 1−x Al x N layers with x ≤ 0.44 deposited on MgO(001) substrates by reactive co-sputtering at 700 °C are epitaxial single crystals with a solid-solution B1 rocksalt structure. The lattice mismatch with the substrate decreases with increasing x , leading to a transition in the strain-state from partially relaxed (74% and 38% for x = 0 and 0.09) to fully strained for x ≥ 0.22. First-principles calculations employing 64-atom Special Quasirandom Structures (SQS) indicate that the lattice constant decreases linearly with x according to a = (4.308 − 0.234 x ) Å for 0 ≤ x ≤ 1. In contrast, the measured relaxed lattice parameter a o = (4.269 − 0.131 x ) Å is linear only for x ≤ 0.33, its composition dependence is less pronounced, and x > 0.44 leads to the nucleation of secondary phases. The fundamental (indirect) bandgap predicted using the same SQS supercells and the HSE06 functional increases from 1.0 to 2.6 eV for x = 0–0.75. In contrast, the onset of the measured optical absorption due to interband transitions increases only from 2.3 to 2.6 eV for x = 0–0.44, suggesting that the addition of Al in the solid solution relaxes the electron momentum conservation and causes a shift from direct to indirect gap transitions. The resistivity increases from 9.0 to 708 μΩ m at 77 K and from 6.8 to 89 μΩ m at 295 K with increasing x = 0–0.44, indicating an increasing carrier localization associated with a randomization of cation site occupation and the increasing bandgap which also causes a 33% reduction in the optical carrier concentration. The overall results demonstrate bandgap and strain engineering in rocksalt nitride semiconductors and show that, in contrast to conventional covalent semiconductors, the random cation site occupation strongly affects optical transitions. 

Ti0.5Mg0.5N has recently been predicted to be a semiconductor with a 1.3 eV band gap and promising properties for thermoelectric and plasmonic devices. As a first step towards experimental validation, epitaxial Ti0.5Mg0.5N(001) layers are deposited on MgO(001) by reactive magnetron co-sputtering from titanium and magnesium targets at 600 °C in pure N2 atmospheres. X-ray diffraction ω-2θ scans, ω-rocking curves, φ-scans, and high resolution reciprocal space maps show that Ti0.5Mg0.5N alloys form a pseudobinary rocksalt structure and are single crystals with a cube-on-cube epitaxial relationship with the substrate: (001)TiMgN║(001)MgO and [100]TiMgN║[100]MgO. A 275-nm-thick Ti0.5Mg0.5N layer is fully relaxed and exhibits a 002 ω-rocking curve width ω = 0.73°, while a 36-nm-thick layer is fully strained and has a ω = 0.49°. These results indicate a thickness-dependent strain state which suggests a critical thickness for misfit dislocation nucleation and glide which is between 36 and 275 nm. A measured negative temperature coefficient of resistivity in combination with a low optical absorption coefficient of 0.25 × 105 cm 1 for λ = 740 nm, and a vanishing density of states at the Fermi level measured by x-ray photoelectron spectroscopy support the prediction that Ti0.5Mg0.5N is a semiconductor.