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.


Title: Searching for a route to synthesize in situ epitaxial Pr2Ir2O7 thin films with thermodynamic methods
Abstract In situ growth of pyrochlore iridate thin films has been a long-standing challenge due to the low reactivity of Ir at low temperatures and the vaporization of volatile gas species such as IrO3(g) and IrO2(g) at high temperatures and highPO2. To address this challenge, we combine thermodynamic analysis of the Pr-Ir-O2system with experimental results from the conventional physical vapor deposition (PVD) technique of co-sputtering. Our results indicate that only high growth temperatures yield films with crystallinity sufficient for utilizing and tailoring the desired topological electronic properties and the in situ synthesis of Pr2Ir2O7thin films is fettered by the inability to grow withPO2on the order of 10 Torr at high temperatures, a limitation inherent to the PVD process. Thus, we suggest techniques capable of supplying high partial pressure of key species during deposition, in particular chemical vapor deposition (CVD), as a route to synthesis of Pr2Ir2O7 more » « less
Award ID(s):
1825538 1720415
PAR ID:
10307550
Author(s) / Creator(s):
; ; ; ; ; ;
Publisher / Repository:
Nature Publishing Group
Date Published:
Journal Name:
npj Computational Materials
Volume:
7
Issue:
1
ISSN:
2057-3960
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. The 5drare Earth iridate is an intriguing material with exhibiting exotic electronic and magnetic phases due to spin‐orbit coupled states. Ternary iridium oxidesLn3IrO7contain an unusual Ir5+(5d4) system, which remain a subject of active research. Fabricating epitaxialLn3IrO7films is challenging due to substrate compatibility, but it offers a valuable platform to explore electronic and magnetic behaviors under reduced dimensionality and substrate interactions, revealing novel phenomena based on Ir5+(5d4). In this regard, this demonstrates that Pr3IrO7with its highly anisotropic orthorhombic structure can be epitaxially grown on a cubic (111)‐oriented yttrium‐stabilized ZrO2(YSZ) substrate. Pr3IrO7film exhibits six epitaxial domains, where the (220) and (202) planes aligning epitaxially to YSZ (111) with the threefold symmetry. This diverse domain configuration in Pr3IrO7film leads to unique magnetic properties, exhibiting spin‐glass‐like behavior. Pr3IrO7thin film offers a platform for exploring unconventional magnetic states, and their successful heteroepitaxy on YSZ substrates opens new avenues for discovering novel physical phenomena. 
    more » « less
  2. Glasses prepared by physical vapor deposition (PVD) can have advantageous material properties, such as highly enhanced thermal stability and denser molecular packing, and thin glassy films prepared by PVD are utilized as active layers in organic light emitting diodes (OLEDs). However, the stability and density of PVD glasses with compositions typical of OLED devices are not well studied. Here, we prepared Ir(ppy)3 doped vapor-deposited glasses in three different organic semiconductor hosts; Ir(ppy)3 in a dilute concentration is often used as a light emitter in phosphorescent OLEDs. We studied these glasses during temperature ramping using spectroscopic ellipsometry and found that the Ir(ppy)3 doped PVD glasses have high kinetic stability and high density. Surprisingly, the observed kinetic stability exceeds that of single-component PVD glasses. This work allows further understanding of the material properties influencing OLED performance, thus facilitating the design of durable and stable devices. 
    more » « less
  3. Abstract An improved understanding of catalyst dynamics for the oxygen evolution reaction (OER) in acid is critical for informing the development of highly efficient, stable, and cost‐effective OER catalysts for proton exchange membrane water electrolysis applications. Herein highly tunable, active, and dynamic Ir 5+ materials are studied, Ln3IrO7(Ln = Pr, Nd, Sm, and Eu). Leveraging a combination of in situ and ex situ characterization, as well as an advanced mercury underpotential deposition technique for Ir surface site quantification, the dynamic nature of Ln3IrO7materials throughout electrochemical activation under OER conditions is characterized. The trends are elucidated between intrinsic OER activity, surface Ir site quantity, and metal site dissolution behavior as tuned by the Ln site's atomic number. A critical relationship is uncovered to show that maintenance of excellent OER activity throughout performance testing is correlated with a catalysts’ ability to preserve a high degree of Ir enrichment, where heightened stability of Ir sites interestingly parallels reduced stability of Ln sites throughout testing. It is found that as the Ln site's atomic number is decreased, the materials’ intrinsic OER performance improves, due to an increased thermodynamic driving force for Ln dissolution, which is hypothesized to enable the maintenance of highly active Ir‐based surface motifs. 
    more » « less
  4. Growths of monoclinic (AlxGa1−x)2O3thin films up to 99% Al contents are demonstrated via metalorganic chemical vapor deposition (MOCVD) using trimethylgallium (TMGa) as the Ga precursor. The utilization of TMGa, rather than triethylgallium, enables a significant improvement of the growth rates (>2.5 μm h−1) of β‐(AlxGa1−x)2O3thin films on (010), (100), and (01) β‐Ga2O3substrates. By systematically tuning the precursor molar flow rates, growth of coherently strained phase pure β‐(AlxGa1−x)2O3films is demonstrated by comprehensive material characterizations via high‐resolution X‐ray diffraction (XRD) and atomic‐resolution scanning transmission electron microscopy (STEM) imaging. Monoclinic (AlxGa1−x)2O3films with Al contents up to 99, 29, and 16% are achieved on (100), (010), and (01) β‐Ga2O3substrates, respectively. Beyond 29% of Al incorporation, the (010) (AlxGa1−x)2O3films exhibit β‐ to γ‐phase segregation. β‐(AlxGa1−x)2O3films grown on (01) β‐Ga2O3show local segregation of Al along (100) plane. Record‐high Al incorporations up to 99% in monoclinic (AlxGa1−x)2O3grown on (100) Ga2O3are confirmed from XRD, STEM, electron nanodiffraction, and X‐ray photoelectron spectroscopy measurements. These results indicate great promises of MOCVD development of β‐(AlxGa1−x)2O3films and heterostructures with high Al content and growth rates using TMGa for next‐generation high‐power and high‐frequency electronic devices. 
    more » « less
  5. Abstract We report evidence of a finite density of states at the Fermi level at the surface of epitaxial thin films of the narrow bandgap Mott insulator Sr3Ir2O7(001). The Brillouin zone critical points for Sr3Ir2O7(001) thin films have been determined by a comparison of the band mapping from angle-resolved photoemission spectroscopy and low energy electron diffraction. Angle-resolved x-ray photoemission studies reveal the surface termination of Sr3Ir2O7(001) is Sr–O. The absence of dispersion with photon energy, or changing wave vector along the surface normal, indicates the two-dimensional character of the bands contributing to the density of states close to the Fermi level for Sr3Ir2O7(001) thin films. Thus, the finite density of states at the Fermi level is attributed to surface states or surface resonances. The appearance of a finite density of states at the Fermi level is consistent with the increased conductivity with decreasing film thickness for ultrathin Sr3Ir2O7(001) films. 
    more » « less