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1. Bandgap and strain engineering in epitaxial rocksalt structure (Ti _0.5 Mg _0.5 ) _1−x Al _x N(001) semiconductors

   https://doi.org/10.1039/d0tc03598j  

   Wang, Baiwei; Zhang, Minghua; Adhikari, Vijaya; Fang, Peijiao; Khare, Sanjay V.; Gall, Daniel (September 2020, Journal of Materials Chemistry C)

   null (Ed.)

   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. 

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2. Strengthened relaxor behavior in (1− x )Pb(Fe _0.5 Nb _0.5 )O ₃ – x BiFeO ₃

   https://doi.org/10.1039/C9TC05883D  

   Prah, Uroš; Dragomir, Mirela; Rojac, Tadej; Benčan, Andreja; Broughton, Rachel; Chung, Ching-Chang; Jones, Jacob L.; Sherbondy, Rachel; Brennecka, Geoff; Uršič, Hana (March 2020, Journal of Materials Chemistry C)

   null (Ed.)

   A systematic study of (1− x )Pb(Fe 0.5 Nb 0.5 )O 3 – x BiFeO 3 ( x = 0–0.5) was performed by combining dielectric and electromechanical measurements with structural and microstructural characterization in order to investigate the strengthening of the relaxor properties when adding BiFeO 3 into Pb(Fe 0.5 Nb 0.5 )O 3 and forming a solid solution. Pb(Fe 0.5 Nb 0.5 )O 3 crystalizes in monoclinic symmetry exhibiting ferroelectric-like polarization versus electric field ( P–E ) hysteresis loop and sub-micron-sized ferroelectric domains. Adding BiFeO 3 to Pb(Fe 0.5 Nb 0.5 )O 3 favors a pseudocubic phase and a gradual strengthening of the relaxor behavior of the prepared ceramics. This is indicated by a broadening of the peak in temperature-dependent permittivity, narrowing of P–E hysteresis loops and decreasing size of ferroelectric domains resulting in polar nanodomains for x = 0.20 composition. The relaxor behavior was additionally confirmed by Vogel–Fulcher analysis. For the x ≥ 0.30 compositions, broad high-temperature anomalies are observed in dielectric permittivity versus temperature measurements in addition to the frequency-dispersive peak located close to room temperature. These samples also exhibit pinched P–E hysteresis loops. The observed pinching is most probably related to the reorganization of polar nanoregions under the electric field as shown by synchrotron X-ray diffraction measurements as well as by piezo-response force microscopy analysis, while in part affected by the presence of charged point defects and anti-ferroelectric order, as indicated from rapid cooling experiments and high-resolution transmission electron microscopy, respectively. 

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3. Correlation between oxygen evolution reaction activity and surface compositional evolution in epitaxial La _0.5 Sr _0.5 Ni _1-x Fe _x O _3-δ thin films

   https://doi.org/10.1039/D2NR05373J  

   Adiga, Prajwal; Wang, Le; Wong, Cindy; Matthews, Bethany E; Bowden, Mark E; Spurgeon, Steven Richard; Sterbinsky, George E.; Blum, Monika; Choi, Min-Ju; Tao, Jinhui; et al (January 2023, Nanoscale)

   Water electrolysis can use renewable electricity to produce green hydrogen, a portable fuel and sustainable chemical precursor. Improving electrolyzer efficiency hinges on the activity of the oxygen evolution reaction (OER) catalyst. Earth-abundant, ABO3-type perovskite oxides offer great compositional, structural, and electronic tunability, with previous studies showing compositional substitution can increase the OER activity drastically. However, the relationship between the tailored bulk composition and that of the surface, where OER occurs, remains unclear. Here, we study the effects of electrochemical cycling on the OER activity of La 0.5 Sr 0.5 Ni 1-x Fe x O 3-δ (x = 0-0.5) epitaxial films grown by oxide molecular beam epitaxy as a model Sr-containing perovskite oxide. Electrochemical testing and surface-sensitive spectroscopic analyses show Ni segregation, which is affected by electrochemical history, along with surface amorphization, coupled with changes in OER activity. Our findings highlight the importance of surface composition and electrochemical cycling conditions in understanding OER performance on mixed metal oxide catalysts, suggesting common motifs of the active surface with high surface area systems. 

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4. The Magnetism of Nonstoichiometric Sr ₂ Cr _1+x Re _1–x O ₆ (0 < x < 0.5) Double Perovskites

   https://doi.org/10.1021/acs.inorgchem.3c03435  

   da_Cruz_Pinha_Barbosa, Victor; Das, Shreya; Saha-Dasgupta, Tanusri; Woodward, Patrick M (December 2023, Inorganic Chemistry)
5. A new semiconductor: Ti0.5Mg0.5N(001)

   https://doi.org/10.1109/NANOTECH.2018.8653564  

   Wang, Baiwei; Gall, Daniel (November 2018, 2018 IEEE Nanotechnology Symposium (ANTS), Albany, NY, 2018)

   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. 

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