Abstract Materials that blend physical properties that are usually mutually exclusive could facilitate devices with novel functionalities. For example, the doped perovskite alkaline earth stannates BaSnO 3 and SrSnO 3 show the intriguing combination of high light transparency and high electrical conductivity. Understanding such emergent physics requires deep insight into the materials’ electronic structures. Moreover, the band structure at the surfaces of those materials can deviate significantly from their bulk counterparts, thereby unlocking novel physical phenomena. Employing angle-resolved photoemission spectroscopy and ab initio calculations, we reveal the existence of a 2-dimensional metallic state at the SnO 2 -terminated surface of 1% La-doped BaSnO 3 thin films. The observed surface state is characterized by a distinct carrier density and a lower effective mass compared to the bulk conduction band, of about 0.12 m e . These particular surface state properties place BaSnO 3 among the materials suitable for engineering highly conductive transition metal oxide heterostructures.
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Metallic line defect in wide-bandgap transparent perovskite BaSnO 3
A line defect with metallic characteristics has been found in optically transparent BaSnO 3 perovskite thin films. The distinct atomic structure of the defect core, composed of Sn and O atoms, was visualized by atomic-resolution scanning transmission electron microscopy (STEM). When doped with La, dopants that replace Ba atoms preferentially segregate to specific crystallographic sites adjacent to the line defect. The electronic structure of the line defect probed in STEM with electron energy-loss spectroscopy was supported by ab initio theory, which indicates the presence of Fermi level–crossing electronic bands that originate from defect core atoms. These metallic line defects also act as electron sinks attracting additional negative charges in these wide-bandgap BaSnO 3 films.
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- NSF-PAR ID:
- 10217871
- Date Published:
- Journal Name:
- Science Advances
- Volume:
- 7
- Issue:
- 3
- ISSN:
- 2375-2548
- Page Range / eLocation ID:
- eabd4449
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Detailed microstructure analysis of epitaxial thin films is a vital step towards understanding essential structure-property relationships. Here, a combination of transmission electron microscopy (TEM) techniques is utilized to determine in detail the microstructure of epitaxial La-doped BaSnO3films grown on two different perovskite substrates: LaAlO3and PrScO3. These BaSnO3films are of high current interest due to outstanding electron mobility at ambient. The rotational disorder of low-angle grain boundaries, namely the in-plane twist and out-of-plane tilt, is visualized by conventional TEM under a two-beam condition, and the degree of twists in grains of such films is quantified by selected-area electron diffraction. The investigation of the atomic arrangement near the film-substrate interfaces, using high-resolution annular dark-field scanning TEM imaging, reveals that edge dislocations with a Burgers vector along [001] result in the out-of-plane tilt. It is shown that such TEM-based analyses provide detailed information about the microstructure of the films, which, when combined with complimentary high-resolution X-ray diffraction, yields a complete structural characterization of the films. In particular, stark differences in out-of-plane tilt on the two substrates are shown to result from differences in misfit dislocation densities at the interface, explaining a puzzling observation from X-ray diffraction.
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Abstract Perovskite oxides are ABO3‐type compounds with a crystal structure capable of accommodating a large number of elements at A‐ and B‐sites. Owing to their flexible structure and complex chemistry, they exhibit a wide range of functionalities as well as novel ground states at the interface. However, in comparison with conventional semiconductors such as silicon, they possess orders of magnitude lower room‐temperature electron mobilities limiting their room‐temperature electronic applications. For example, in a prototypical doped SrTiO3, the room‐temperature electron mobility remains below 10 cm2V−1s−1regardless of the defect minimization. Discovery of high room‐temperature mobility in alkaline‐earth stannates such as BaSnO3and SrSnO3constitutes a significant advancement toward all‐perovskite electronic and spintronic devices. Alkaline‐earth stannates also possess wide‐to‐ultra wide bandgaps that make them potentially suitable candidate for transparent conductors, power electronic devices, and high electron mobility transistors. This article provides an overview of the recent progress made to these materials' electrical properties with particular emphasis on the advancements in the molecular beam epitaxy approaches for their synthesis, and defect control.
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The molecule-based ferrimagnetic semiconductor vanadium tetracyanoethylene (V[TCNE] x , x [Formula: see text] 2) has garnered interest from the quantum information community due to its excellent coherent magnonic properties and ease of on-chip integration. Despite these attractive properties, a detailed understanding of the electronic structure and mechanism for long-range magnetic ordering have remained elusive due to a lack of detailed atomic and electronic structural information. Previous studies via x-ray absorption near edge spectroscopy and the extended x-ray absorption fine structure have led to various proposed structures, and in general, V[TCNE] x is believed to be a three-dimensional network of octahedrally coordinated V 2+ , each bonded to six TCNE molecules. Here, we elucidate the electronic structure, structural ordering, and degradation pathways of V[TCNE] x films by correlating calculations of density functional theory (DFT) with scanning transmission electron microscopy and electron energy-loss spectroscopy (EELS) of V[TCNE] x films. Low-loss EELS measurements reveal a bandgap and an excited state structure that agree quantitatively with DFT modeling, including an energy splitting between apical and equatorial TCNE ligands within the structure, providing experimental results directly backed by theoretical descriptions of the electronic structure driving the robust magnetic ordering in these films. Core-loss EELS confirms the presence of octahedrally coordinated V +2 atoms. Upon oxidation, changes in the C1s- π* peak indicate that C=C of TCNE is preferentially attacked. Furthermore, we identify a relaxation of the structural ordering as the films age. These results lay the foundation for a more comprehensive and fundamental understanding of magnetic ordering and dynamics in these classes of metal–ligand compounds.more » « less
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MXenes, a new class of 2D transition metal carbides and carbonitrides, show great promise in supercapacitors, Li‐ion batteries, fuel cells, and sensor applications. A unique combination of their metallic conductivity, hydrophilic surface, and excellent mechanical properties renders them attractive for transparent conductive electrode application. Here, a simple, scalable method is proposed to fabricate transparent conductive thin films using delaminated Ti3C2MXene flakes by spray coating. Homogenous films, 5–70 nm thick, are produced at ambient conditions over a large area as shown by scanning electron microscopy and atomic force microscopy. The sheet resistances (
Rs ) range from 0.5 to 8 kΩ sq−1at 40% to 90% transmittance, respectively, which corresponds to figures of merit (the ratio of electronic to optical conductivities,σ DC/σ opt) around 0.5–0.7. Flexible, transparent, and conductive films are also produced and exhibit stableRs values at up to 5 mm bend radii. Furthermore, the films' optoelectronic properties are tuned by chemical or electrochemical intercalation of cations. The films show reversible changes of transmittance in the UV–visible region during electrochemical intercalation/deintercalation of tetramethylammonium hydroxide. This work shows the potential of MXenes to be used as transparent conductors in electronic, electrochromic, and sensor applications.
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1126/sciadv.abd4449
