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1. Synthesis of anthradithiophene containing conjugated polymers via a cross-coupling strategy

   https://doi.org/10.1039/d0ra09195b  

   Hussain, Waseem A.; Plunkett, Kyle N. (January 2021, RSC Advances)

   New conjugated polymers that incorporate dihexylanthradithiophene (DHADT) in the main chain were prepared by Stille, Sonogashira, and Yamamoto cross-coupling polymerization reactions. The polymerization chemistry is enabled by a soluble 5,11-dibromodihexylanthradithiophene monomer that is capable of cross-coupling reactions. Five readily soluble DHADT containing polymers were prepared and characterized experimentally and computationally. These polymers possess HOMO energies of −5.18 eV to −5.43 eV and LUMO energies of −3.0 eV to −2.82 eV. The notable optical features include broad absorption and band gaps ranging from 1.62 eV to 2.15 eV. Polymers were tested in organic field effect transistors and were found to operate in the p-type regime. 

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2. Al Composition Dependence of Band Offsets for SiO ₂ on α-(Al _x Ga _1−x ) ₂ O ₃

   https://doi.org/10.1149/2162-8777/ac39a8  

   Xia, Xinyi; Fares, Chaker; Ren, Fan; Hassa, Anna; von Wenckstern, Holger; Grundmann, Marius; Pearton, S. J. (November 2021, ECS Journal of Solid State Science and Technology)

   Valence band offsets for SiO 2 deposited by Atomic Layer Deposition on α -(Al x Ga 1-x ) 2 O 3 alloys with x = 0.26–0.74 were measured by X-ray Photoelectron Spectroscopy. The samples were grown with a continuous composition spread to enable investigations of the band alignment as a function of the alloy composition. From measurement of the core levels in the alloys, the bandgaps were determined to range from 5.8 eV (x = 0.26) to 7 eV (x = 0.74). These are consistent with previous measurements by transmission spectroscopy. The valence band offsets of SiO 2 with these alloys of different composition were, respectively, were −1.2 eV for x = 0.26, −0.2 eV for x = 0.42, 0.2 eV for x = 0.58 and 0.4 eV for x = 0.74. All of these band offsets are too low for most device applications. Given the bandgap of the SiO 2 was 8.7 eV, this led to conduction band offsets of 4.1 eV (x = 0.26) to 1.3 eV (x = 0.74). The band alignments were of the desired nested configuration for x > 0.5, but at lower Al contents the conduction band offsets were negative, with a staggered band alignment. This shows the challenge of finding appropriate dielectrics for this ultra-wide bandgap semiconductor system. 

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3. Mechanism for Long Photocurrent Time Constants in α-Ga ₂ O ₃ UV Photodetectors

   https://doi.org/10.1149/2162-8777/acc900  

   Polyakov, A. Y.; Almaev, A. V.; Nikolaev, V. I.; Pechnikov, A. I.; Shchemerov, V. I.; Vasilev, A. A.; Yakimov, E. B.; Kochkova, A. I.; Kopyev, V. V.; Kushnarev, B. O; et al (April 2023, ECS Journal of Solid State Science and Technology)

   Deep centers and their influence on photocurrent spectra and transients were studied for interdigitated photoresistors on α -Ga 2 O 3 undoped semi-insulating films grown by Halide Vapor Phase Epitaxy (HVPE) on sapphire. Characterization involving current-voltage measurements in the dark and with monochromatic illumination with photons with energies from 1.35 eV to 4.9 eV, Thermally Stimulated Current (TSC), Photoinduced Current Transients Spectroscopy (PICTS) showed the Fermi level in the dark was pinned at E c −0.8 eV, with other prominent centers being deep acceptors with optical thresholds near 2.3 eV and 4.9 eV and deep traps with levels at E c −0.5 eV, E c −0.6 eV. Measurements of photocurrent transients produced by illumination with photon energies 2.3 eV and 4.9 eV and Electron Beam Induced Current (EBIC) imaging point to the high sensitivity and external quantum efficiency values being due to hole trapping enhancing the lifetime of electrons and inherently linked with the long photocurrent transients. The photocurrent transients are stretched exponents, indicating the strong contribution of the presence of centers with barriers for electron capture and/or of potential fluctuations. 

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4. Ionization energies and cationic bond dissociation energies of RuB, RhB, OsB, IrB, and PtB

   https://doi.org/10.1063/5.0107086  

   Merriles, Dakota M.; Morse, Michael D. (August 2022, The Journal of Chemical Physics)

   Two-photon ionization thresholds of RuB, RhB, OsB, IrB, and PtB have been measured using resonant two-photon ionization spectroscopy in a jet-cooled molecular beam and have been used to derive the adiabatic ionization energies of these molecules. From the measured two-photon ionization thresholds, IE(RuB) = 7.879(9) eV, IE(RhB) = 8.234(10) eV, IE(OsB) = 7.955(9) eV, IE(IrB) = 8.301(15) eV, and IE(PtB) = 8.524(10) eV have been assigned. By employing a thermochemical cycle, cationic bond dissociation energies of these molecules have also been derived, giving D0(Ru+–B) = 4.297(9) eV, D0(Rh+–B) = 4.477(10) eV, D0(Os–B+) = 4.721(9) eV, D0(Ir–B+) = 4.925(18) eV, and D0(Pt–B+) = 5.009(10) eV. The electronic structures of the resulting cationic transition metal monoborides (MB+) have been elucidated using quantum chemical calculations. Periodic trends of the MB+ molecules and comparisons to their neutral counterparts are discussed. The possibility of quadruple chemical bonds in all of these cationic transition metal monoborides is also discussed. 

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5. Integrating density functional theory with machine learning for enhanced band gap prediction in metal oxides

   https://doi.org/10.1039/D4CP03397C  

   Ezeakunne, Chidozie; Lamichhane, Bipin; Kattel, Shyam (March 2025, Physical Chemistry Chemical Physics)

   In this study, we used a combination of density functional theory with Hubbard U correction (DFT+U) and machine learning (ML) to accurately predict the band gaps and lattice parameters of metal oxides: TiO2 (rutile and anatase), cubic ZnO, cubic ZnO2, cubic CeO2, and cubic ZrO2. Our results show that including Up values for oxygen 2p orbitals alongside Ud/f for metal 3d or 4f orbitals significantly enhances the accuracy of these predictions. Through extensive DFT+U calculations, we identify optimal (Up, Ud/f) integer pairs that closely reproduce experimentally measured band gaps and lattice parameters for each oxide: (8 eV, 8 eV) for rutile TiO2; (3 eV, 6 eV) for anatase TiO2; (6 eV, 12 eV) for c-ZnO; (10 eV, 10 eV) for c-ZnO2; (9 eV, 5 eV) for c-ZrO2; and (7 eV, 12 eV) for c-CeO2. Our ML analysis showed that simple supervised ML models can closely reproduce these DFT+U results at a fraction of the computational cost and generalize well to related polymorphs. Our approach builds on existing high-throughput DFT+U frameworks by providing fast pre-DFT estimates of structural properties and band gaps. Since this work does not aim to improve the underlying DFT+U method, the ML model shares its limitations. We also note that the reported values of Up strongly depend on the choice of correlated orbitals, and caution is recommended with a different choice of correlated orbitals. 

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