Rohan Mishra

p-type doping of MoS2 thin films using Nb

We report on the first demonstration of p-type doping in large area few-layer films of (0001)-oriented chemical vapor deposited MoS2. Niobium was found to act as an efficient acceptor up to relatively high density in MoS2 films. For a hole density of 3.1 × 1020 cm−3, Hall mobility of 8.5 cm2 V−1 s−1 was determined, which matches well with the theoretically expected values. X-ray diffraction scans and Raman characterization indicated that the film had good out-of-plane crystalline quality. Absorption measurements showed that the doped sample had similar characteristics to high-quality undoped samples, with a clear absorption edge at 1.8 eV. Scanning transmission electron microscope imaging showed ordered crystalline nature of the Nb-doped MoS2 layers stacked in the [0001] direction. This demonstration of substitutional p-doping in large area epitaxial MoS2 could help in realizing a wide variety of electrical and opto-electronic devices based on layered metal dichalcogenides.

Direct observation of ferroelectric field effect and vacancy-controlled screening at the BiFeO3/LaxSr1−xMnO3 interface

The development of interface-based magnetoelectric devices necessitates an understanding of polarization-mediated electronic phenomena and atomistic polarization screening mechanisms. In this work, the LSMO/BFO interface is studied on a single unit-cell level through a combination of direct order parameter mapping by scanning transmission electron microscopy and electron energy-loss spectroscopy. We demonstrate an unexpected ~5% lattice expansion for regions with negative polarization charge, with a concurrent anomalous decrease of the Mn valence and change in oxygen K-edge intensity. We interpret this behaviour as direct evidence for screening by oxygen vacancies. The vacancies are predominantly accumulated at the second atomic layer of BFO, reflecting the difference of ionic conductivity between the components. This vacancy exclusion from the interface leads to the formation of a tail-to-tail domain wall. At the same time, purely electronic screening is realized for positive polarization charge, with insignificant changes in lattice and electronic properties. These results underline the non-trivial role of electrochemical phenomena in determining the functional properties of oxide interfaces. Furthermore, these behaviours suggest that vacancy dynamics and exclusion play major roles in determining interface functionality in oxide multilayers, providing clear implications for novel functionalities in potential electronic devices.

Independent Ordering of Two Interpenetrating Magnetic Sublattices in the Double Perovskite Sr2CoOsO6

The insulating, fully ordered, double perovskite Sr2CoOsO6 undergoes two magnetic phase transitions. The Os(VI) ions order antiferromagnetically with a propagation vector k = (1/2, 1/2, 0) below TN1 = 108 K, while the high-spin Co(II) ions order antiferromagnetically with a propagation vector k = (1/2, 0, 1/2) below TN2 = 70 K. Ordering of the Os(VI) spins is accompanied by a structural distortion from tetragonal I4/m symmetry to monoclinic I2/m symmetry, which reduces the frustration of the face centered cubic lattice of Os(VI) ions. Density functional theory calculations show that the long-range Os-O-Co-O-Os and Co-O-Os-O-Co superexchange interactions are considerably stronger than the shorter Os-O-Co interactions. The poor energetic overlap between the 3d orbitals of Co and the 5d orbitals of Os appears to be responsible for this unusual inversion in the strength of short and long-range superexchange interactions.

Oxygen-Vacancy-Induced Polar Behavior in (LaFeO3)2/(SrFeO3) Superlattices

Complex oxides displaying ferroelectric and/or multiferroic behavior are of high fundamental and applied interest. In this work, we show that it is possible to achieve polar order in a superlattice made up of two nonpolar oxides by means of oxygen vacancy ordering. Using scanning transmission electron microscopy imaging, we show the polar displacement of magnetic Fe ions in a superlattice of (LaFeO3)2/(SrFeO3) grown on a SrTiO3 substrate. Using density functional theory calculations, we systematically study the effect of epitaxial strain, octahedral rotations, and surface terminations in the superlattice and find them to have a negligible effect on the antipolar displacements of the Fe ions lying in between SrO and LaO layers of the superlattice (i.e., within La0.5Sr0.5FeO3 unit cells). The introduction of oxygen vacancies, on the other hand, triggers a polar displacement of the Fe ions. We confirm this important result using electron energy loss spectroscopy, which shows partial oxygen vacancy ordering in the region where polar displacements are observed and an absence of vacancy ordering outside of that area.

In Situ Observation of Oxygen Vacancy Dynamics and Ordering in the Epitaxial LaCoO3 System

Vacancy dynamics and ordering underpin the electrochemical functionality of complex oxides and strongly couple to their physical properties. In the field of the epitaxial thin films, where connection between chemistry and film properties can be most clearly revealed, the effects related to oxygen vacancies are attracting increasing attention. In this article, we report a direct, real-time, atomic level observation of the formation of oxygen vacancies in the epitaxial LaCoO3 thin films and heterostructures under the influence of the electron beam utilizing scanning transmission electron microscopy (STEM). In the case of LaCoO3/SrTiO3 superlattice, the formation of the oxygen vacancies is shown to produce quantifiable changes in the interatomic distances, as well as qualitative changes in the symmetry of the Co sites manifested as off-center displacements. The onset of these changes was observed in both the [100]pc and [110]pc orientations in real time. Additionally, annular bright field images directly show the formation of oxygen vacancy channels along [110]pc direction. In the case of 15 u.c. LaCoO3 thin film, we observe the sequence of events during beam-induced formation of oxygen vacancy ordered phases and find them consistent with similar processes in the bulk. Moreover, we record the dynamics of the nucleation, growth, and defect interaction at the atomic scale as these transformations happen. These results demonstrate that we can track dynamic oxygen vacancy behavior with STEM, generating atomic-level quantitative information on phase transformation and oxygen diffusion.

Emerging Diluted Ferromagnetism in High‐Tc Superconductors Driven by Point Defect Clusters

Defects in ceramic materials are generally seen as detrimental to their functionality and applicability. Yet, in some complex oxides, defects present an opportunity to enhance some of their properties or even lead to the discovery of exciting physics, particularly in the presence of strong correlations. A paradigmatic case is the high‐temperature superconductor YBa2Cu3O7‐δ (Y123), in which nanoscale defects play an important role as they can immobilize quantized magnetic flux vortices. Here previously unforeseen point defects buried in Y123 thin films that lead to the formation of ferromagnetic clusters embedded within the superconductor are unveiled. Aberration‐corrected scanning transmission microscopy has been used for exploring, on a single unit‐cell level, the structure and chemistry resulting from these complex point defects, along with density functional theory calculations, for providing new insights about their nature including an unexpected defect‐driven ferromagnetism, and X‐ray magnetic circular dichroism for bearing evidence of Cu magnetic moments that align ferromagnetically even below the superconducting critical temperature to form a dilute system of magnetic clusters associated with the point defects.

Atomic-scale engineering of the electrostatic landscape of semiconductor surfaces.

A low-temperature scanning tunneling microscope was used in conjunction with density functional theory calculations to determine the binding sites and charge states of adsorbed Ga and Mn atoms on GaAs(110). To quantify the adatom charge states (both +1e), the Coulomb interaction with an individual Mn acceptor is measured via tunneling spectroscopy and compared with theoretical predictions. Several methods for positioning these charged adatoms are demonstrated, allowing us to engineer the electrostatic landscape of the surface with atomic precision.

Defect states and disorder in charge transport in semiconductor nanowires

We present a comprehensive investigation into disorder-mediated charge transport in InP nanowires in the statistical doping regime. At zero gate voltage, transport is well described by the space charge limited current model and hopping transport, but positive gate voltage (electron accumulation) reveals a previously unexplored regime of nanowire charge transport that is not well described by existing theory. The ability to continuously tune between these regimes provides guidance for the extension of existing models and directly informs the design of next-generation nanoscale electronic devices.

First principles calculation of polarization induced interfacial charges in GaN/AlN heterostructures

We propose a method to calculate polarization induced interfacial charges in semiconductor heterostructures using classical electrostatics applied to real-space band diagrams from first principles calculations and apply it to GaN/AlN heterostructures with ultrathin AlN layers (4–6 monolayers). We show that the calculated electric fields and interfacial charges are independent of the exchange-correlation functionals used (local density approximation and hybrid). We also find the calculated interfacial charge of (6.8±0.4)×1013 cm−2 to be in excellent agreement with experiments and the value of 6.58×1013 cm−2 calculated from bulk polarization constants, validating the use of bulk constants even for very thin films.

Atmospheric pressure chemical vapor deposition of methylammonium bismuth iodide thin films

We demonstrate the atmospheric pressure chemical vapor deposition of methyl ammonium bismuth iodide ((CH3NH3)3Bi2I9 or MA3Bi2I9) films. MA3Bi2I9 possesses an indirect optical bandgap of 1.80 eV and a room temperature excitonic peak at 511 nm. In contrast to recent reports, the films are n-type semiconductors with a room temperature carrier concentration of 3.36 × 1018 cm−3 and a Hall mobility of 18 cm2 V−1 s−1, which are superior to those of solution-processed, undoped films. The precursors used for the deposition are methylammonium iodide and bismuth iodide which are co-sublimated at 199 °C and 230 °C, respectively, in an Ar flow inside a tube furnace with a variable temperature profile. The substrate temperature is set at 160 °C, and dense polycrystalline films (∼775 nm thick) are deposited. Extensive characterization combined with first-principles density functional theory calculations unravels the synthesis–structure–property relationship in these films. The degradation of properties under ambient conditions results from film oxidation with a characteristic bi-exponential decay in resistivity, signifying a fast surface oxidation followed by a slower oxidation of the bulk.