Assessing the Effects of Temperature and Oxygen Vacancy on Band Gap Renormalization in LaCrO3-δ: First-Principles and Experimental Corroboration.

Understanding the temperature dependence of functional properties in high-temperature gas sensors is vital for applications in combustion environments. Temperature effect on the electronic structure due to electron-phonon coupling is a key property of interest as this influences other responses of sensors. In this work, we assess the impact of temperature on band gap renormalization of pristine and oxygen-vacant LaCrO3-δ perovskite employing Allen-Heine-Cardona theory with first-principles simulations and corroborate with experimental observation. Antiferromagnetic cubic LaCrO3 shows a direct ground-state band gap of 2.62 eV that is reduced by over 1 eV due to the presence of oxygen vacancies, which can form endothermically. We find excellent agreement in temperature-dependent band gap shift in LaCrO3 between theory and an in-house experiment, proving that the theory can adequately predict renormalization on the band gap in a magnetic system. Band gaps in cubic LaCrO3-δ are found to monotonically narrow by 1.13 eV in pristine and by around 0.62 eV in oxygen-vacant structures as temperature increases from 0 to 1500 K. The predicted band gap variations are rationalized using an analytical model. The experimental zero-temperature band gaps are extracted from the model fits that can provide useful insights on the simulated band gaps.

First-principles exploration of oxygen vacancy impact on electronic and optical properties of ABO3-δ (A = La, Sr; B = Cr, Mn) perovskites.

ABO3-δ perovskites are utilized in many applications including optical gas sensing for energy systems. Understanding the opto-electronic properties allows rational selection of the perovskite-based sensors from a diverse family of ABO3-δ perovskites, associated with the choices of A and B cations and range of oxygen concentrations. Herein, we assess the impact of oxygen vacancies on the electronic structure and optical response of pristine and oxygen-vacant ABO3-δ (A = La, Sr; B = Cr, Mn) perovskites via first-principles calculations. The endothermic formation energy for oxygen vacancies shows that the generation of ABO3-δ defect structures is thermodynamically possible. LaCrO3 and LaMnO3 have direct and indirect ground-state band gaps, respectively, whereas SrCrO3 and SrMnO3 are metallic. In the presence of an oxygen mono-vacancy, however, the band gap decreases in LaCrO3-δ and vanishes in LaMnO3-δ. In contrast to the decrease in the band gaps, the oxygen vacancies in ABO3-δ are found to increase optical absorption in the visible to near-infrared wavelength regime, and thus lower the onset energy of absorption compared with the pristine materials. Our assessments emphasize the role of the oxygen vacancy, or other possible oxygen non-stoichiometry defects, in perovskite oxides with respect to the opto-electronic performance parameters that are of interest for optical gas sensors for energy generation process environments.

Theoretical and experimental study of temperature effect on electronic and optical properties of TiO2: comparing rutile and anatase.

To gain fundamental understanding of the high-temperature optical gas-sensing and light-energy conversion materials, we comparatively investigate the temperature effects on the band gap and optical properties of rutile and anatase TiO2 experimentally and theoretically. Given that the electronic structures of rutile and anatase are fundamentally different, i.e. direct band gap in rutile and indirect gap in anatase, it is not clear whether these materials exhibit different electronic structure renormalizations with temperature. Using ab initio methods, we show that the electron-phonon interaction is the dominant factor for temperature band gap renormalization compared to the thermal expansion. As a result of different contributions from the acoustic and optical phonons, the band gap is found to widen with temperature up to 300 K, and to narrow at higher temperatures. Our calculations suggest that the band gap is narrowed by about 147 meV and 128 meV at 1000 K for rutile and anatase, respectively. Experimentally, for rutile and anatase TiO2 thin films we conducted UV-Vis transmission measurements at different temperatures, and analyzed band gaps from the Tauc plots. For both TiO2 phases, the band gap is found to decrease for temperature above 300 K quantitatively, agreeing with our theoretical results. The temperature effects on the dielectric functions, the refractive index, the extinction coefficient as well as the optical conductivity are also investigated. Rutile and anatase show generally similar optical properties, but differences exist in the long wavelength regime above 600 nm, where we found that the dielectric function of rutile decreases while that of anatase increases with temperature increase.

Anharmonicity Explains Temperature Renormalization Effects of the Band Gap in SrTiO3.

Soft phonon modes in strongly anharmonic crystals are often neglected in calculations of phonon-related properties. Herein, we experimentally measure the temperature effects on the band gap of cubic SrTiO3, and compare with first-principles calculations by accounting for electron-phonon coupling using harmonic and anharmonic phonon modes. The harmonic phonon modes show an increase in the band gap with temperature using either Allen-Heine-Cardona theory or finite-displacement approach, and with semilocal or hybrid exchange-correlation functionals. This finding is in contrast with experimental results that show a decrease in the band gap with temperature. We show that the disagreement can be rectified by using anharmonic phonon modes that modify the contributions not only from the significantly corrected soft modes, but also from the modes that show little correction in frequencies. Our results confirm the importance of soft-phonon modes that are often neglected in the computation of phonon-related properties and particularly in electron-phonon coupling.

Theoretical study of the optical and thermodynamic properties of LaxSr1-xCo1-yFeyO3-δ (x/y = 0.25, 0.5, 0.75) perovskites.

The performance of LaxSr1-xCo1-yFeyO3-δ perovskite systems in applications such as solid oxide fuel cells and catalysis is related to the proportion of substitution atoms. Using a density functional theory method, we investigate the doping effect on the electronic, optical, and thermodynamic properties of LaxSr1-xCo1-yFeyO3-δ (x/y = 0.25, 0.5, 0.75). Our results show that La doping introduces an empty state and pushes the Fermi level upwards. The doping Fe derived states locate away from the Fermi level as compared with Co states. From the results of optical absorption, the peak at 200-300 nm is enhanced and experiences a blue-shift with increasing La concentration. The corresponding peak at 400-700 nm also shows a blue-shift induced by both La and Fe doping, and it could be enhanced by Fe doping while being suppressed by La doping. And the peak above 1500 nm is enhanced by the cooperation of La and Fe doping. From thermodynamic calculations via an Ellingham diagram, it is found that the parent SrCoO3 is the most favorable composition for releasing O2, with both La and Fe doping hampering the reduction reaction. Therefore, the optical and thermodynamic properties of LaxSr1-xCo1-yFeyO3-δ could be adjusted by special doping values.

The influence of oxygen vacancy on the electronic and optical properties of ABO3-δ (A = La, Sr, B = Fe, Co) perovskites.

ABO3-δ (A = La, Sr, B = Fe, Co) perovskites are useful in a wide range of applications, including their recent exploration for application in high-temperature optical oxygen sensing for energy conversion devices such as solid oxide fuel cells. To elucidate the dependence of functional properties and oxygen vacancy formation on defect chemistry and composition, first principles calculations are presented. The obtained results show that oxygen vacancy (VO) formation energies are in the order of LaFeO3 > LaCoO3 > SrFeO3 > SrCoO3. Furthermore, the influence of VO on the electronic and optical properties is investigated for the high temperature stable phases (T = 1100 K). For the LaFeO3 insulator, the VO donated electrons are all localized on the down-spin d3z2-r2 orbitals of the nearest Fe ions. These defect states located in the band gap induce a drop in the energy onset of absorption as pristine bulk → V2+O → V1+O → V0O, and especially, an extra absorption peak appears between 0.5 and 1.5 eV due to V0O and V1+O formation. In the rest of the crystals that expressed a metallic feature, the VO donated electrons partially localize on the down-spin d3z2-r2 orbital and partially delocalize through the lattice, by which the absorption peaks (0.5-2.0 eV for LaCoO3, 0.0-0.5 eV for SrFeO3 and SrCoO3) from the electronic excitation near the Fermi level are enhanced. A high VO concentration of oxygen divacancy in SrFeO3 and SrCoO3 could enhance charge localization on down-spin d3z2-r2 orbitals, resulting in a remarkable increase of optical absorption at 1.5-3.0 eV.

Raman scattering in single-crystal sapphire at elevated temperatures.

Sapphire is a widely used high-temperature material, and this work presents thorough characterization of all the measurable Raman scattering modes in sapphire and their temperature dependencies. Here, Raman scattering in bulk sapphire rods is measured from room temperature to 1081°C and is illustrated as a method of noncontact temperature measurement. A single-line argon ion laser at 488 nm was used to excite the sapphire rods inside a cylindrical furnace. All the anti-Stokes peaks (or lines) were observable through the entire temperature range of interest, while Stokes peaks were observable until they were obscured by background thermal emission. Temperature measurements were found to be most reliable for A1g and Eg modes using the peaks at ±418, ±379, +578, +645, and +750 cm-1 (+ and - are designated for Stokes and anti-Stokes peaks, respectively). The 418 cm-1 peak was found to be the most intense peak. The temperature dependence of peak position, peak width, and peak area of the ±418 and ±379 peaks is presented. For +578, +645, and +750, the temperature dependence of peak position is presented. The peaks' spectral positions provide the most precise temperature information within the experimental temperature range. The resultant temperature calibration curves are given, which indicate that sapphire can be used in high-temperature Raman thermometry with an accuracy of about 1.38°C average standard deviation over the entire >1000°C temperature range.

Electronic Structures, Bonding Configurations, and Band-Gap-Opening Properties of Graphene Binding with Low-Concentration Fluorine.

To better understand the effects of low-level fluorine in graphene-based sensors, first-principles density functional theory (DFT) with van der Waals dispersion interactions has been employed to investigate the structure and impact of fluorine defects on the electrical properties of single-layer graphene films. The results show that both graphite-2 H and graphene have zero band gaps. When fluorine bonds to a carbon atom, the carbon atom is pulled slightly above the graphene plane, creating what is referred to as a CF defect. The lowest-binding energy state is found to correspond to two CF defects on nearest neighbor sites, with one fluorine above the carbon plane and the other below the plane. Overall this has the effect of buckling the graphene. The results further show that the addition of fluorine to graphene leads to the formation of an energy band (BF) near the Fermi level, contributed mainly from the 2p orbitals of fluorine with a small contribution from the p orbitals of the carbon. Among the 11 binding configurations studied, our results show that only in two cases does the BF serve as a conduction band and open a band gap of 0.37 eV and 0.24 eV respectively. The binding energy decreases with decreasing fluorine concentration due to the interaction between neighboring fluorine atoms. The obtained results are useful for sensor development and nanoelectronics.