Greg Stone

Dislocation motion and grain boundary migration in two-dimensional tungsten disulphide

Dislocations have a significant effect on mechanical, electronic, magnetic and optical properties of crystals. For a dislocation to migrate in bulk crystals, collective and simultaneous movement of several atoms is needed. In two-dimensional crystals, in contrast, dislocations occur on the surface and can exhibit unique migration dynamics. Dislocation migration has recently been studied in graphene, but no studies have been reported on dislocation dynamics for two-dimensional transition metal dichalcogenides with unique metal-ligand bonding and a three-atom thickness. This study presents dislocation motion, glide and climb, leading to grain boundary migration in a tungsten disulphide monolayer. Direct atomic-scale imaging coupled with atomistic simulations reveals a strikingly low-energy barrier for glide, leading to significant grain boundary reconstruction in tungsten disulphide. The observed dynamics are unique and different from those reported for graphene. Through strain field mapping, we also demonstrate how dislocations introduce considerable strain along the grain boundaries and at the dislocation cores.

Directionally controlled 3D ferroelectric single crystal growth in LaBGeO5 glass by femtosecond laser irradiation

Laser-fabrication of complex, highly oriented three-dimensional ferroelectric single crystal architecture with straight lines and bends is demonstrated in lanthanum borogermanate model glass using a high repetition rate femtosecond laser. Scanning micro-Raman microscopy shows that the c-axis of the ferroelectric crystal is aligned with the writing direction even after bending. A gradual rather than an abrupt transition is observed for the changing lattice orientation through bends up to approximately 14 degrees. Thus the single crystal character of the line is preserved along the bend through lattice straining rather than formation of a grain boundary.

Nanoscale structural evolution of electrically driven insulator to metal transition in vanadium dioxide

The structural evolution of tensile strained vanadium dioxide thin films was examined across the electrically driven insulator-to-metal transition by nanoscale hard X-ray diffraction. A metallic filament with rutile (R) structure was found to be the dominant conduction pathway for an electrically driven transition, while the majority of the channel area remained in the monoclinic M1 phase. The filament dimensions were estimated using simultaneous electrical probing and nanoscale X-ray diffraction. Analysis revealed that the width of the conducting channel can be tuned externally using resistive loads in series, enabling the M1/R phase ratio in the phase coexistence regime to be tuned.

Local probing of the interaction between intrinsic defects and ferroelectric domain walls in lithium niobate

We demonstrate the capability of confocal Raman spectroscopy to characterize nanoscale interactions of defects with ferroelectric domain walls by identifying defect-related frequency shifts in congruent lithium niobate. These shifts resemble those observed for an external field applied anti-parallel to the ferroelectric axis, suggesting a small reduction of the electric polarization. Density functional theory calculations suggest that this reduction results from a change in the intrinsic defect cluster structure and polarization at the domain wall.

Polar Oxides without Inversion Symmetry through Vacancy and Chemical Order

One synthetic modality for materials discovery proceeds by forming mixtures of two or more compounds. In transition metal oxides (TMOs), chemical substitution often obeys Vegards principle, and the resulting structure and properties of the derived phase follow from its components. A change in the assembly of the components into a digital nanostructure, however, can stabilize new polymorphs and properties not observed in the constituents. Here we formulate and demonstrate a crystal-chemistry design approach for realizing digital TMOs without inversion symmetry by combining two centrosymmetric compounds, utilizing periodic anion-vacancy order to generate multiple polyhedra that together with cation order produce a polar structure. We next apply this strategy to two brownmillerite-structured TMOs known to display centrosymmetric crystal structures in their bulk, Ca2Fe2O5 and Sr2Fe2O5. We then realize epitaxial (SrFeO2.5)1/(CaFeO2.5)1 thin film superlattices possessing both anion-vacancy order and Sr and Ca chemical order at the subnanometer scale, confirmed through synchrotron-based diffraction and aberration corrected electron microscopy. Through a detailed symmetry analysis and density functional theory calculations, we show that A-site cation ordering lifts inversion symmetry in the superlattice and produces a polar compound. Our results demonstrate how control of anion and cation order at the nanoscale can be utilized to produce acentric structures markedly different than their constituents and open a path toward novel structure-based property design.

Influence of ferroelectric domain walls on the Raman scattering process in lithium tantalate and niobate

We report changes in the Raman spectra at ferroelectric domain walls in near-stoichiometric LiNbO3 and stoichiometric LiTaO3. We find a decrease of intensity for the regular bulk Raman peaks along with increases of intensity in spectral regions that correspond to phonons, which propagate at an angle with respect to the incident light. In the backscattering geometry, such modes are not supported in the bulk crystal due to momentum conservation. We confirm that these changes are due to the domain wall itself and are independent of intrinsic defects or charging effects.

Atomic scale imaging of competing polar states in a Ruddlesden–Popper layered oxide

Layered complex oxides offer an unusually rich materials platform for emergent phenomena through many built-in design knobs such as varied topologies, chemical ordering schemes and geometric tuning of the structure. A multitude of polar phases are predicted to compete in Ruddlesden–Popper (RP), An+1BnO3n+1, thin films by tuning layer dimension (n) and strain; however, direct atomic-scale evidence for such competing states is currently absent. Using aberration-corrected scanning transmission electron microscopy with sub-Ångstrom resolution in Srn+1TinO3n+1 thin films, we demonstrate the coexistence of antiferroelectric, ferroelectric and new ordered and low-symmetry phases. We also directly image the atomic rumpling of the rock salt layer, a critical feature in RP structures that is responsible for the competing phases; exceptional quantitative agreement between electron microscopy and density functional theory is demonstrated. The study shows that layered topologies can enable multifunctionality through highly competitive phases exhibiting diverse phenomena in a single structure.

Creating Ruddlesden-Popper phases by hybrid molecular beam epitaxy

The synthesis of a 50 unit cell thick n = 4 Srn+1TinO3n+1 (Sr5Ti4O13) Ruddlesden-Popper (RP) phase film is demonstrated by sequentially depositing SrO and TiO2 layers in an alternating fashion using hybrid molecular beam epitaxy (MBE), where Ti was supplied using titanium tetraisopropoxide (TTIP). A detailed calibration procedure is outlined for determining the shuttering times to deposit SrO and TiO2 layers with precise monolayer doses using in-situ reflection high energy electron diffraction (RHEED) as feedback. Using optimized Sr and TTIP shuttering times, a fully automated growth of the n = 4 RP phase was carried out over a period of >4.5 h. Very stable RHEED intensity oscillations were observed over the entire growth period. The structural characterization by X-ray diffraction and high resolution transmission electron microscopy revealed that a constant periodicity of four SrTiO3 perovskite unit cell blocks separating the double SrO rocksalt layer was maintained throughout the entire film thickness w...

Observation of Quasi-Two-Dimensional Polar Domains and Ferroelastic Switching in a Metal, Ca3Ru2O7

Polar domains arise in insulating ferroelectrics when free carriers are unable to fully screen surface-bound charges. Recently discovered binary and ternary polar metals exhibit broken inversion symmetry coexisting with free electrons that might be expected to suppress the electrostatic driving force for domain formation. Contrary to this expectation, we report the first direct observation of polar domains in single crystals of the polar metal Ca3Ru2O7. By a combination of mesoscale optical second-harmonic imaging and atomic-resolution scanning transmission electron microscopy, the polar domains are found to possess a quasi-two-dimensional slab geometry with a lateral size of ∼100 μm and thickness of ∼10 nm. Electronic structure calculations show that the coexistence of electronic and parity-lifting orders arise from anharmonic lattice interactions, which support 90° and 180° polar domains in a metal. Using in situ transmission electron microscopy, we also demonstrate a strain-tuning route to achieve ferroelastic switching of polar metal domains.

Aberration Corrected STEM Imaging of Domain Walls in Congruent LiNbO 3

LiNbO3 is a ferroelectric crystal at room temperature belonging to the R3c space group, and has a Curie temperature of 1140C [1]. The spontaneous electrical polarization of LiNbO3 is 71 μC/cm [2] while it’s piezoelectric modulus, the d33 value, is 31.5pm/V [3]. The combination of high Curie temperature, electrical polarization and d33 has led to applications as diverse as pyroelectric sensors, ferroelectric memory, quasi-phase matched second harmonic generators, optical switching etc. A multitude of these applications depend on the precise manipulation and control of domain walls in LiNbO3. The exact structure of the domain wall is however a subject of ongoing controversy on whether it is a pure Ising wall, or has a mixed Ising-Neel-Bloch nature [4]. In this work, for the first time we image domain walls with atomic resolution to measure displacements across them.