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: Carrier localization in perovskite nickelates from oxygen vacancies
Point defects, such as oxygen vacancies, control the physical properties of complex oxides, relevant in active areas of research from superconductivity to resistive memory to catalysis. In most oxide semiconductors, electrons that are associated with oxygen vacancies occupy the conduction band, leading to an increase in the electrical conductivity. Here we demonstrate, in contrast, that in the correlated-electron perovskite rare-earth nickelates, R NiO 3 ( R is a rare-earth element such as Sm or Nd), electrons associated with oxygen vacancies strongly localize, leading to a dramatic decrease in the electrical conductivity by several orders of magnitude. This unusual behavior is found to stem from the combination of crystal field splitting and filling-controlled Mott–Hubbard electron–electron correlations in the Ni 3 d orbitals. Furthermore, we show the distribution of oxygen vacancies in NdNiO 3 can be controlled via an electric field, leading to analog resistance switching behavior. This study demonstrates the potential of nickelates as testbeds to better understand emergent physics in oxide heterostructures as well as candidate systems in the emerging fields of artificial intelligence.  more » « less
Award ID(s):
1751739
PAR ID:
10149049
Author(s) / Creator(s):
; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ;
Date Published:
Journal Name:
Proceedings of the National Academy of Sciences
Volume:
116
Issue:
44
ISSN:
0027-8424
Page Range / eLocation ID:
21992 to 21997
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; (, Applied Physics Letters)
    Phase pure PbZr 0.52 Ti 0.48 O 3 (PZT) films with up to 13 mol. % Nb were prepared on Pt-coated Si substrates using chemical solution deposition; charge compensation for Nb was accomplished by reducing the concentration of lead in the film. For high Nb doping levels, (1) superoxidation of the PZT film surface makes the PZT/Pt interface more p-type and, hence reduces electron injection over the Schottky barrier, (2) the bulk charge transport mechanism changes from electron trapping by Ti 4+ to hole migration between lead vacancies, and (3) the ionic conductivity due to migration of oxygen vacancies decreases. For [Formula: see text] Nb, electrical degradation was controlled via field-induced accumulation of oxygen vacancies near the cathode, which, in turn, leads to Schottky barrier lowering and electron trapping by Ti 4+ . In phase pure 13 mol. % Nb doped PZT films, on the other hand, the increase in the leakage current during electrical degradation was dominated by hole migration between lead vacancies ([Formula: see text]. A much lower lifetime and drastic increase in the leakage current upon electrical degradation was observed in mixed phase PNZT films, which was attributed to (1) a more electrically conductive pyrochlore phase and (2) a high concentration of lead vacancies. 
    more » « less
  2. ; ; ; ; (, AIP Advances)
    We report our studies of the thickness dependence of electrical resistivity and lattice constants in strained epitaxial thin films of calcium manganese oxide. Our results indicate the potential of bi-axial lattice mismatch strain as a handle for modulating electrical resistivity. We observe thickness dependence of lattice constants consistent with what is expected for strain relaxation for films thicker than 400 Å. At lower thickness values, anomalies are observed suggestive of reduced oxygen stoichiometry. We observe a remarkable decrease in electrical resistivity with decreasing film thickness. The resistivity of our thinnest films (5–7 nm) is about three orders of magnitude lower than the resistivity of bulk CaMnO3. Resistivity increases as the film thickness increases, along with the progression of strain relaxation. It is noteworthy that the thickness dependence of resistivity we observe in CMO thin films is the opposite of what has been reported for their hole-doped rare earth manganite counterpart La0.67Ca0.33MnO3 (LCMO), where tensile lattice mismatch strain suppresses metallicity, leading to the increase in resistivity with film thickness. We believe that the enhanced conductivity in our thinnest films is related to the possible oxygen deficiency promoted by tensile strain. Recent x-ray absorption measurements have revealed reduced oxygen content and associated changes in Mn valence states in tensile-strained CMO thin films, as also predicted by density functional theory calculations. This report is the first observation of electrical transport behavior possibly indicative of strain–oxygen stoichiometry coupling. 
    more » « less
  3. ; ; ; ; ; ; ; ; ; (, Physical Chemistry Chemical Physics)
    In this paper, ordered TiO 2 nanotubes were grown on a Ti substrate via electrochemical anodization and subsequently annealed at 450 °C for 4 h under various atmospheres to create different point defects. Oxygen-deficient environments such as Ar and N 2 were used to develop oxygen vacancies, while a water vapor (WV) atmosphere was used to generate titanium vacancies. Computational models by density functional theory predicted that the presence of oxygen vacancies would cause electronic conductivity to increase, while the presence of Ti vacancies could lead to decreased conductivity. The predictions were confirmed by two-point electrical conductivity measurements and Mott–Schottky analysis. Raman spectroscopy was also conducted to confirm the presence of defects. The annealed samples were then evaluated as anodes in lithium-ion batteries. The oxygen-deficient samples had an improvement in capacity by 10% and 25% for Ar- and N 2 -treated samples, respectively, while the WV-treated sample displayed a capacity increase of 24% compared to the stoichiometric control sample (annealed in O 2 ). Electrochemical impedance spectroscopy studies revealed that the WV-treated sample's increased capacity was a consequence of its higher Li diffusivity. The results suggest that balanced electrical and ionic conductivity in nanostructured metal oxide anodes can be tuned through defect generation using heat treatments in various atmospheres for improved electrochemical properties. 
    more » « less
  4. ; (, ChemCatChem)
    Abstract Multifunctional materials that are capable of facilitating multiple electrocatalytic processes are highly desirable. This work reports the observation of bifunctional electrocatalytic properties for water‐splitting in layered oxides, featuring 2‐dimensional layers of octahedrally coordinated transition metals separated by alkaline‐earth or rare‐earth metals. Remarkably, these materials are able to catalyze both half‐reactions of water‐splitting,i. e., oxygen‐evolution reaction (OER) and hydrogen‐evolution reaction (HER). Electrical charge‐transport studies of SrLaFe1‐xCoxO4‐δin a wide range of temperatures, 25 to 800 °C, indicate semiconducting behavior for all three compounds, where there is a systematic increase in electrical conductivity as a function of temperature. The end member of the series, SrLaCoO4‐δ, exhibits the highest electrical charge transport and best electrocatalytic activity toward both OER and HER. This catalyst also features the highest degree of polyhedral distortion as well as the presence of oxygen‐vacancies. In addition, the transition metals in this material have a favorable electronic configuration for enhanced electrocatalytic activity. 
    more » « less
  5. ; ; ; ; ; ; ; ; ; (, Nature Communications)
    Abstract Oxide heterostructures exhibit a vast variety of unique physical properties. Examples are unconventional superconductivity in layered nickelates and topological polar order in (PbTiO3)n/(SrTiO3)nsuperlattices. Although it is clear that variations in oxygen content are crucial for the electronic correlation phenomena in oxides, it remains a major challenge to quantify their impact. Here, we measure the chemical composition in multiferroic (LuFeO3)9/(LuFe2O4)1superlattices, mapping correlations between the distribution of oxygen vacancies and the electric and magnetic properties. Using atom probe tomography, we observe oxygen vacancies arranging in a layered three-dimensional structure with a local density on the order of 1014 cm−2, congruent with the formula-unit-thick ferrimagnetic LuFe2O4layers. The vacancy order is promoted by the locally reduced formation energy and plays a key role in stabilizing the ferroelectric domains and ferrimagnetism in the LuFeO3and LuFe2O4layers, respectively. The results demonstrate pronounced interactions between oxygen vacancies and the multiferroic order in this system and establish an approach for quantifying the oxygen defects with atomic-scale precision in 3D, giving new opportunities for deterministic defect-enabled property control in oxide heterostructures. 
    more » « less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email