skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.

Explore Research Products in the PAR
It may take a few hours for recently added research products to appear in PAR search results.


Title: Microkinetic model for reaction and diffusion of titanium interstitial atoms near a TiO 2 (110) surface
Semiconductor surfaces provide efficient pathways for injecting native point defects into the underlying bulk. In the case of interstitial atoms in rutile, the TiO 2 (110) surface exemplifies this behavior, although extended defects in the bulk such as platelets and crystallographic shear planes act as net sources or sinks depending upon specific conditions. The present work constructs a quantitative microkinetic model to describe diffusion and based upon isotopic gas–solid exchange experiments. Key activation barriers for are 0.55 eV for surface injection, 0.50 eV for site-to-site hopping diffusion, and 3.3 eV for dissociation of titanium interstitials from extended defects.  more » « less
Award ID(s):
1709327
PAR ID:
10056769
Author(s) / Creator(s):
;
Date Published:
Journal Name:
Physical Chemistry Chemical Physics
Volume:
20
Issue:
6
ISSN:
1463-9076
Page Range / eLocation ID:
4587 to 4596
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; ; ; (, Journal of Materials Chemistry C)
    The full-Heusler VFe 2 Al has emerged as an important thermoelectric material in its thin film and bulk phases. VFe 2 Al is attractive for use as a thermoelectric materials because of it contains only low-cost, non-toxic and earth abundant elements. While VFe 2 Al has often been described as a semimetal, here we show the electronic and thermal properties of VFe 2 Al can be explained by considering VFe 2 Al as a valence precise semiconductor like many other thermoelectric materials but with a very small band gap ( E g = 0.03 ± 0.01 eV). Using a two-band model for electrical transport and point-defect scattering model for thermal transport we analyze the thermoelectric properties of bulk full-Heusler VFe 2 Al. We demonstrate that a semiconductor transport model can explain the compilation of data from a variety of n and p-type VFe 2 Al compositions assuming a small band-gap between 0.02 eV and 0.04 eV. In this small E g semiconductor understanding, the model suggests that nominally undoped VFe 2 Al samples appear metallic because of intrinsic defects of the order of ∼10 20 defects per cm −3 . We rationalize the observed trends in weighted mobilities ( μ w ) with dopant atoms from a molecular orbital understanding of the electronic structure. We use a phonon-point-defect scattering model to understand the dopant-concentration (and, therefore, the carrier-concentration) dependence of thermal conductivity. The electrical and thermal models developed allow us to predict the zT versus carrier concentration curve for this material, which maps well to reported experimental investigations. 
    more » « less
  2. ; ; ; ; ; ; ; ; (, 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). 
    more » « less
  3. ; (, Applied Physics Letters)
    The surface diffusion kinetics on a Pd77.5Cu6Si16.5 metallic glass is measured using a scratch smoothing method in the range of 107–57 K below the glass transition temperature. Within this temperature range, the surface diffusion coefficients are determined to vary between (8.66 ± 0.80) × 10−19 and (5.90 ± 0.60) × 10−18 m2 s−1. The corresponding activation energy is 0.93 ± 0.18 eV, which is about half the value for bulk diffusion. These measurements also corroborate the correlation between enhanced surface diffusion and liquid fragility in glasses. 
    more » « less
  4. ; ; ; ; (, The Journal of Physical Chemistry C)
    The transformations of complex metal oxides in aqueous settings must be studied to form a chemical understanding of how technologically relevant nanomaterials impact the environment upon disposal. Owing to the inherent heterogeneity and structural complexity of the ternary intercalation material Li(NixMnyCo1-x-y)O2 (NMC), the mechanisms of chemical processes at the solid–water interface are challenging to model. Here, density functional theory (DFT) + solvent ion methodology is used to study the energetics of stepwise release of two surface metals following unique pathways. The study spans different combinations of metal removal and also considers unique patterns of defects formed by modeling the NMC surface in supercells. The approach here also considers the equilibration of the surface with the surroundings between successive metal removals. A key finding is that a second metal removal prefers to proceed at a metal lattice site adjacent to the initial defect, and this is attributed in part to how the resulting slab with two metal vacancies maintains the most antiferromagnetic couplings between the remaining Ni/Mn. 
    more » « less
  5. ; ; ; ; ; ; ; (, Advanced Functional Materials)
    Abstract Engineering a material's work function is of central importance for many technologies and in particular electron emitters used in high‐power vacuum electronics and thermionic energy converters. A low work function surface is typically achieved through unstable surface functional species, especially in high power thermionic electron emitter applications. Discovering and engineering new materials with intrinsic, stable low work functions obtainable without volatile surface species would mark a definitive advancement in the design of electron emitters. This work reports evidence for the existence of a low work function surface on a bulk, monolithic, electrically conductive perovskite oxide: SrVO3. After considering the patch field effect on the heterogeneous emitting surface of the bulk polycrystalline samples, this study suggests the presence of low work function (≈2 eV) emissive grains on SrVO3surface. Emission current densities of 10–100 mA cm–2at ≈1000 °C, comparable to commercial LaB6thermionic cathodes, indicative of an overall effective thermionic work function of 2.3–2.7 eV are obtained. This study demonstrates that perovskites like SrVO3may have intrinsically low work functions comparable to commercialized W‐based dispenser cathodes and suggests that, with further engineering, perovskites may represent a new class of low work function electron emitters. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email