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1. Electrical properties of α-Ga ₂ O ₃ films grown by halide vapor phase epitaxy on sapphire with α-Cr ₂ O ₃ buffers

   https://doi.org/10.1063/5.0090832  

   Polyakov, Alexander; Nikolaev, Vladimir; Stepanov, Sergey; Almaev, Alexei; Pechnikov, Alexei; Yakimov, Eugene; Kushnarev, Bogdan O.; Shchemerov, Ivan; Scheglov, Mikhail; Chernykh, Alexey; et al (June 2022, Journal of Applied Physics)

   We report on growth and electrical properties of α-Ga 2 O 3 films prepared by halide vapor phase epitaxy (HVPE) at 500 °C on α-Cr 2 O 3 buffers predeposited on sapphire by magnetron sputtering. The α-Cr 2 O 3 buffers showed a wide microcathodoluminescence (MCL) peak near 350 nm corresponding to the α-Cr 2 O 3 bandgap and a sharp MCL line near 700 nm due to the Cr + intracenter transition. Ohmic contacts to Cr 2 O 3 were made with both Ti/Au or Ni, producing linear current–voltage ( I– V) characteristics over a wide temperature range with an activation energy of conductivity of ∼75 meV. The sign of thermoelectric power indicated p-type conductivity of the buffers. Sn-doped, 2- μm-thick α-Ga 2 O 3 films prepared on this buffer by HVPE showed donor ionization energies of 0.2–0.25 eV, while undoped films were resistive with the Fermi level pinned at E C of 0.3 eV. The I– V and capacitance–voltage ( C– V) characteristics of Ni Schottky diodes on Sn-doped samples using a Cr 2 O 3 buffer indicated the presence of two face-to-face junctions, one between n-Ga 2 O 3 and p-Cr 2 O 3 , the other due to the Ni Schottky diode with n-Ga 2 O 3 . The spectral dependence of the photocurrent measured on the structure showed the presence of three major deep traps with optical ionization thresholds near 1.3, 2, and 2.8 eV. Photoinduced current transient spectroscopy spectra of the structures were dominated by deep traps with an ionization energy of 0.95 eV. These experiments suggest another pathway to obtain p–n heterojunctions in the α-Ga 2 O 3 system. 

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2. Metallic vs. semiconducting properties of quasi-one-dimensional tantalum selenide van der Waals nanoribbons

   https://doi.org/10.1039/d1nr07772d  

   Kargar, Fariborz; Krayev, Andrey; Wurch, Michelle; Ghafouri, Yassamin; Debnath, Topojit; Wickramaratne, Darshana; Salguero, Tina T.; Lake, Roger K.; Bartels, Ludwig; Balandin, Alexander A. (April 2022, Nanoscale)

   We conducted a tip-enhanced Raman scattering spectroscopy (TERS) and photoluminescence (PL) study of quasi-1D TaSe 3− δ nanoribbons exfoliated onto gold substrates. At a selenium deficiency of δ ∼ 0.25 (Se/Ta = 2.75), the nanoribbons exhibit a strong, broad PL peak centered around ∼920 nm (1.35 eV), suggesting their semiconducting behavior. Such nanoribbons revealed a strong TERS response under 785 nm (1.58 eV) laser excitation, allowing for their nanoscale spectroscopic imaging. Nanoribbons with a smaller selenium deficiency (Se/Ta = 2.85, δ ∼ 0.15) did not show any PL or TERS response. The confocal Raman spectra of these samples agree with the previously-reported spectra of metallic TaSe 3 . The differences in the optical response of the nanoribbons examined in this study suggest that even small variations in Se content can induce changes in electronic band structure, causing samples to exhibit either metallic or semiconducting character. The temperature-dependent electrical measurements of devices fabricated with both types of materials corroborate these observations. The density-functional-theory calculations revealed that substitution of an oxygen atom in a Se vacancy can result in band gap opening and thus enable the transition from a metal to a semiconductor. However, the predicted band gap is substantially smaller than that derived from the PL data. These results indicate that the properties of van der Waals materials can vary significantly depending on stoichiometry, defect types and concentration, and possibly environmental and substrate effects. In view of this finding, local probing of nanoribbon properties with TERS becomes essential to understanding such low-dimensional systems. 

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3. Examining the electron transport in chalcogenide perovskite BaZrS ₃

   https://doi.org/10.1039/d1tc00374g  

   Osei-Agyemang, Eric; Koratkar, Nikhil; Balasubramanian, Ganesh (March 2021, Journal of Materials Chemistry C)

   null (Ed.)

   Orthorhombic BaZrS 3 is a potential optoelectronic material with prospective applications in photovoltaic and thermoelectric devices. While efforts exist on understanding the effects of elemental substitution and material stability, fundamental knowledge on the electronic transport properties are sparse. We employ first principles calculations to examine the electronic band structure and optical band gap and interrogate the effect of electron transport on electrical and thermal conductivities, and Seebeck coefficient, as a function of temperature and chemical potential. Our results reveal that BaZrS 3 has a band gap of 1.79 eV in proximity of the optimal 1.35 eV recommended for single junction photovoltaics. An absorption coefficient of 3 × 10 5 cm −1 at photon energies of 3 eV is coupled with an early onset to optical absorption at 0.5 eV, significantly below the optical band gap. The carrier effective mass being lower for electrons than holes, we find the Seebeck coefficient to be higher for holes than electrons. A notable (≈1.0 at 300 K) upper limit to the thermoelectric figure of merit, obtained due to high Seebeck coefficient (3000 μV K −1 ) and ultra-low electron thermal conductivity, builds promise for BaZrS 3 as a thermoelectric. 

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4. Surface and dynamical properties of GeI ₂

   https://doi.org/10.1088/2053-1583/ac4715  

   Dhingra, Archit; Lipatov, Alexey; Lu, Haidong; Chagoya, Katerina; Dalton, Joseph; Gruverman, Alexei; Sinitskii, Alexander; Blair, Richard G; Dowben, Peter A (January 2022, 2D Materials)

   Abstract GeI 2 is an interesting two-dimensional wide-band gap semiconductor because of diminished edge scattering due to an absence of dangling bonds. Angle-resolved x-ray photoemission spectroscopy indicates a germanium rich surface, and a surface to bulk core-level shift of 1.8 eV in binding energy, between the surface and bulk components of the Ge 2p 3/2 core-level, making clear that the surface is different from the bulk. Temperature dependent studies indicate an effective Debye temperature ( θ D ) of 186 ± 18 K for the germanium x-ray photoemission spectroscopy feature associated with the surface. These measurements also suggest an unusually high effective Debye temperature for iodine (587 ± 31 K), implying that iodine is present in the bulk of the material, and not the surface. From optical absorbance, GeI 2 is seen to have an indirect (direct) optical band gap of 2.60 (2.8) ± 0.02 (0.1) eV, consistent with the expectations. Temperature dependent magnetometry indicates that GeI 2 is moment paramagnetic at low temperatures (close to 4 K) and shows a diminishing saturation moment at high temperatures (close to 300 K and above). 

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5. Absorption spectra of benzoic acid in water at different pH and in the presence of salts: insights from the integration of experimental data and theoretical cluster models

   https://doi.org/10.1039/C9CP06728K  

   Karimova, Natalia V.; Luo, Man; Grassian, Vicki H.; Gerber, R. Benny (March 2020, Physical Chemistry Chemical Physics)

   The absorption spectra of molecular organic chromophores in aqueous media are of considerable importance in environmental chemistry. In this work, the UV-vis spectra of benzoic acid (BA), the simplest aromatic carboxylic acid, in aqueous solutions at varying pH and in the presence of salts are measured experimentally. The solutions of different pH provide insights into the contributions from both the non-dissociated acid molecule and the deprotonated anionic species. The microscopic interpretation of these spectra is then provided by quantum chemical calculations for small cluster models of benzoic species (benzoic acid and benzoate anion) with water molecules. Calculations of the UV-vis absorbance spectra are then carried out for different clusters such as C 6 H 5 COOH·(H 2 O) n and C 6 H 5 COO − ·(H 2 O) n , where n = 0–8. The following main conclusions from these calculations and the comparison to experimental results can be made: (i) the small water cluster yields good quantitative agreement with observed solution experiments; (ii) the main peak position is found to be very similar at different levels of theory and is in excellent agreement with the experimental value, however, a weaker feature about 1 eV to lower energy (red shift) of the main peak is correctly reproduced only by using high level of theory, such as Algebraic Diagrammatic Construction (ADC); (iii) dissociation of the BA into ions is found to occur with a minimum of water molecules of n = 8; (iv) the deprotonation of BA has an influence on the computed spectrum and the energetics of the lowest energy electronic transitions; (v) the effect of the water on the spectra is much larger for the deprotonated species than for the non-dissociated acid. It was found that to reproduce experimental spectrum at pH 8.0, additional continuum representation for the extended solvent environment must be included in combination with explicit solvent molecules ( n ≥ 3); (vi) salts (NaCl and CaCl 2 ) have minimal effect on the absorption spectrum and; (vii) experimental results showed that B-band of neutral BA is not sensitive to the solvent effects whereas the effect of the water on the C-band is significant. The water effects blue-shift this band up to ∼0.2 eV. Overall, the results demonstrate the ability to further our understanding of the microscopic interpretation of the electronic structure and absorption spectra of BA in aqueous media through calculations restricted to small cluster models. 

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