arXiv subjects

Karen C. Bustillo

Publications and source records attributed to Karen C. Bustillo.

17 recordsLinked to original sources

arXiv2026

Deterministic patterning and alignment of tellurium quantum wires using nanoscale templates

Tellurium (Te) is an intriguing one-dimensional (1D) semiconductor that has recently attracted considerable interest as a p-type channel material. However, scalable synthesis methods have lacked control over the orientation and patterning of the Te atomic chains, thus limiting its practical use. Guided by theory, we overcome this challenge using nanowire-shaped templates to achieve oriented, single-crystal growth of Te on amorphous substrates. Strong alignment of Te atomic chains is achieved as template widths are reduced to sub-20 nm. This high structural order, confirmed by 4D scanning transmission electron microscopy, enables the observation of pristine quantum transport phenomena for deterministically patterned Te. Field-effect transistors exhibit well-defined conductance plateaus at 77 K due to population of individual 1D subbands. Furthermore, Coulomb blockade emerges at 1.7 K, with the Te channel acting as a gate-tunable quantum dot. This synthesis approach provides a scalable pathway for integration of Te-based quantum materials for future electronic and quantum technologies.

cond-mat.mtrl-sci↗

arXiv2026

Mesoscale Crystallographic Helicity in Confined Tellurium Quantum Wires

Helical order can facilitate symmetry breaking and emergent physical responses in crystalline materials, yet how intrinsic chirality manifests beyond atomic length scales remains poorly understood. Here, the direct observation and quantitative characterization of long-range crystallographic helicity in template-grown tellurium (Te) quantum wires on amorphous substrates are reported. Four-dimensional scanning transmission electron microscopy (4D-STEM) enables quantitative mapping of crystallographic orientation with nanometer-scale spatial resolution. The resulting orientation maps establish continuous mesoscale lattice twisting, providing direct evidence of long-range crystallographic helicity. Correlated orientation and strain mapping reveal pronounced lateral strain heterogeneity, with compressive strain concentrated within the wire interior. Systematic analysis across multiple wires suggests that higher twist rates are generally associated with weaker lateral compressive strain, narrower wires, and better atomic chain - template axis alignment. Complementary first-principles calculations on finite Te nanorods further suggest that twisting is intrinsically accessible in nucleus-scale Te clusters and strain can bias the preferred torsional state. Together, these results support a growth-incorporated, strain-biased picture in which nanoscale confinement and anisotropic strain facilitate torsional relaxation and stabilize mesoscale helicity in Te nanostructures highlighting strain and confinement as potential routes for engineering chiral lattice states in van der Waals nanostructures.

cond-mat.mtrl-sci↗

arXiv2026

Topochemically-engineered coexistence of charge and spin orders in intercalated endotaxial heterostructures

Correlated electron systems that host multiple electronic orders offer routes to multifunctional quantum materials, but strong competition between these orders often prevents their coexistence. Here we show that nanoscale, metastable intercalated heterostructures can stabilize a rare combination of long-range magnetism and a commensurate charge density wave (C-CDW) order in a single material. We synthesize a two-dimensional (2D) metastable crystal, T/H-Fe$_x$TaS2, which comprises an endotaxial polytype heterostructure of 1T-TaS$_2$ and H-TaS$_2$ with Fe intercalated in the van der Waals interfaces. In T/H-Fe$_x$TaS2, Fe intercalants provide localized spins that support ferromagnetism, while 1T layers host a robust commensurate charge density wave (C-CDW) that persists to room temperature. In these intercalated heterostructures, Fe content simultaneously tunes ordering of spin and charge degrees of freedom, positioning topochemically-prepared intercalated endotaxial heterostructures as a route to stabilize and control competing quantum phases in 2D materials.

cond-mat.str-el↗

arXiv2026

Nanocrystal Geometry Governs Phase Transformation Pathways in Palladium Hydride

Pathways and structural dynamics of phase transformations impact performance of materials in energy and information storage technologies. Palladium hydride ($\mathrm{PdH}_x$) nanocrystals are an ideal model system for studying solute-induced phase transformations, where elastic energy from lattice mismatch between $α$-$\mathrm{PdH}_x$ and $β$-$\mathrm{PdH}_x$ phases is often considered a key to determining the transformation pathways. $α/β$-$\mathrm{PdH}_x$ interfacial elastic energy is affected by the confined geometry of a nanocrystal. However, how nanocrystal geometry influences phase transformation pathways is largely unknown. Using in situ liquid phase transmission electron microscopy, we directly visualize hydrogenation in Pd nanocrystals with two geometries -- a nanocube and a hexagonal nanoplate. Both follow similar sequences of an initially curved nucleus, interface flattening, and reverse-stage nucleation; however, their evolving $α/β$-$\mathrm{PdH}_x$ interfaces exhibit geometry-dependent crystallographic alignments. In nanocubes, $\{100\}$-aligned configurations conform to static elastic energy ordering, representing a pathway that maintains a local mechanical equilibrium, whereas nanoplates display both $\{110\}$- and $\{211\}$-aligned interfaces. Theoretical simulations show that geometry determines the accessibility of alternative phase transformation pathways as the system is driven far from equilibrium during hydrogenation. These findings identify geometry as a fundamental parameter for directing phase transformation pathways, offering design principles for accessing atypical configurations and improving properties of intercalation-based devices.

cond-mat.mes-hall↗

arXiv2025

Multi-angle precession electron diffraction (MAPED): a versatile approach to 4D-STEM precession

Precession of a converged beam during acquisition of a 4D-STEM dataset improves strain, orientation, and phase mapping accuracy by averaging over continuous angles of illumination. Precession experiments usually rely on integrated systems, where automatic alignments lead to fast, high-quality results. The dependence of these experiments on specific hardware and software is evident even when switching to non-integrated detectors on a precession tool, as experimental set-up becomes challenging and time-consuming. Here, we introduce multi-angle precession electron diffraction (MAPED): a method to perform electron diffraction by collecting sequential 4D-STEM scans at different incident beam tilts. The multiple diffraction datasets are averaged together post-acquisition, resulting in a single dataset that minimizes the impact of the curvature and orientation of the Ewald sphere relative to the crystal under study. Our results demonstrate that even four additional tilts improved measurement of material properties, namely strain and orientation, as compared to single-tilt 4D-STEM experiments. We show the versatility and flexibility of our MAPED approach with data collected on a number of microscopes with different hardware configurations and a variety of detectors.

physics.ins-det↗

arXiv2025

Neutral but Impactful: Gallium Cluster-Induced Nanopores from Beam-Blanked Gallium Ion Sources

Neutral atoms emitted from liquid metal ion sources are an often-overlooked source of contamination and damage in focused ion beam microscopy. Beyond ions and single atoms, these sources also emit atom clusters. While most studies have investigated charged clusters, here we demonstrate that neutral clusters are also emitted. These neutral clusters bypass the electrostatic beam blanking system, allowing them to impinge on samples even when the ion beam is blanked. We investigate this phenomenon using thin (<20 nm) freestanding membranes of hexagonal boron nitride, silicon, and silicon nitride as targets. Randomly dispersed nanopores that form upon neutral cluster exposure are revealed. The average nanopore diameter is ~2 nm with a narrow size distribution, suggesting that the atom clusters emitted from the source have a preferred size. Various electron microscopy techniques are used to characterize the nanopores, including high-resolution transmission electron microscopy, multislice ptychography, and electron energy-loss spectroscopy. Finally, we show how electron irradiation in the transmission electron microscope can be used to both remove any amorphous material that may clog the pores and to controllably grow the pores to specific sizes. Tunable nanopores such as these are interesting for nanofluidic applications involving size-selective membranes.

cond-mat.mtrl-sci↗

arXiv2025

Local interface effects modulate global charge order and optical properties of 1T-TaS$_2$/1H-WSe$_2$ heterostructures

1T-TaS$_2$ is a layered charge density wave (CDW) crystal exhibiting sharp phase transitions and associated resistance changes. These resistance steps could be exploited for information storage, underscoring the importance of controlling and tuning CDW states. Given the importance of out-of-plane interactions in 1T-TaS$_2$, modulating interlayer interactions by heterostructuring is a promising method for tailoring CDW phase transitions. In this work, we investigate the optical and electronic properties of heterostructures comprising 1T-TaS$_2$ and monolayer 1H-WSe$_2$. By systematically varying the thickness of 1T-TaS$_2$ and its azimuthal alignment with 1H-WSe$_2$, we find that intrinsic moiré strain and interfacial charge transfer introduce CDW disorder in 1T-TaS$_2$ and modify the CDW ordering temperature. Furthermore, our studies reveal that the interlayer alignment impacts the exciton dynamics in 1H-WSe$_2$, indicating that heterostructuring can concurrently tailor the electronic phases in 1T-TaS$_2$ and the optical properties of 1H-WSe$_2$. This work presents a promising approach for engineering optoelectronic behavior of heterostructures that integrate CDW materials and semiconductors.

cond-mat.mtrl-sci↗

arXiv2025

Mapping strain and structural heterogeneities around bubbles in amorphous ionically conductive Bi$_2$O$_3$

While amorphous materials are often approximated to have a statistically homogeneous atomic structure, they frequently exhibit localized structural heterogeneity that challenges simplified models. This study uses 4D scanning transmission electron microscopy to investigate the strain and structural modifications around gas bubbles in amorphous Bi$_2$O$_3$ induced by argon irradiation. We present a method for determining strain fields surrounding bubbles that can be used to measure the internal pressure of the gas. Compressive strain is observed around the cavities, with higher-order crystalline symmetries emerging near the cavity interfaces, suggesting paracrystalline ordering as a result of bubble coarsening. This ordering, along with a compressive strain gradient, indicates that gas bubbles induce significant localized changes in atomic packing. By analyzing strain fields with maximum compressive strains of 3\%, we estimate a lower bound on the internal pressure of the bubbles at 2.5 GPa. These findings provide insight into the complex structural behavior of amorphous materials under stress, particularly in systems with gas inclusions, and offer new methods for probing the local atomic structure in disordered materials. Although considering structural heterogeneity in amorphous systems is non-trivial, these features have crucial impacts on material functionalities, such as mechanical strength, ionic conductivity, and electronic mobility.

cond-mat.mtrl-sci↗

arXiv2024

Operando probing of nanocracking in CuO-derived Cu during CO$_2$ electroreduction

Identifying and controlling active sites in electrocatalysis remains a grand challenge due to restructuring of catalysts in the complex chemical environments during operation. Inactive precatalysts can transform into active catalysts under reaction conditions, such as oxide-derived Cu (OD-Cu) for CO$_2$ electroreduction displaying improved production of multicarbon (C$_{2+}$) chemicals. Revealing the mechanism of active site origin in OD-Cu catalysts requires in situ/operando characterizations of structure, morphology, and valence state evolution with high spatial and temporal resolution. Applying newly developed electrochemical liquid cell transmission electron microscopy combined with X-ray absorption spectroscopy, our multimodal operando techniques unveil the formation pathways of OD-Cu active sites from CuO bicrystal nanowire precatalysts. Rapid reduction of CuO directly to Cu within 60 seconds generates a nanocrack network throughout the nanowire, via formation of "boundary nanocracks" along the twin boundary and "transverse nanocracks" propagating from the surface to the center of the nanowire. The nanocrack network further reconstructs, leading to a highly porous structure rich in Cu nanograins, with a boosted specific surface area and density of active sites for C$_{2+}$ products. These findings suggest a means to optimize active OD-Cu nanostructures through nanocracking by tailoring grain boundaries in CuO precatalysts. More generally, our advanced operando approach opens new opportunities for mechanistic insights to enable improved control of catalyst structure and performance.

cond-mat.mtrl-sci↗

arXiv2024

Tailored topotactic chemistry unlocks heterostructures of magnetic intercalation compounds

The construction of thin film heterostructures has been a widely successful archetype for fabricating materials with emergent physical properties. This strategy is of particular importance for the design of multilayer magnetic architectures in which direct interfacial spin--spin interactions between magnetic phases in dissimilar layers lead to emergent and controllable magnetic behavior. However, crystallographic incommensurability and atomic-scale interfacial disorder can severely limit the types of materials amenable to this strategy, as well as the performance of these systems. Here, we demonstrate a method for synthesizing heterostructures comprising magnetic intercalation compounds of transition metal dichalcogenides (TMDs), through directed topotactic reaction of the TMD with a metal oxide. The mechanism of the intercalation reaction enables thermally initiated intercalation of the TMD from lithographically patterned oxide films, giving access to a new family of multi-component magnetic architectures through the combination of deterministic van der Waals assembly and directed intercalation chemistry.

cond-mat.mtrl-sci↗

arXiv2023

Rotational and Dilational Reconstruction in Transition Metal Dichalcogenide Moiré Bilayers

Lattice reconstruction and corresponding strain accumulation play a key role in defining the electronic structure of two-dimensional moiré superlattices, including those of transition metal dichalcogenides (TMDs). Imaging of TMD moirés has so far provided a qualitative understanding of this relaxation process in terms of interlayer stacking energy, while models of the underlying deformation mechanisms have relied on simulations. Here, we use interferometric four-dimensional scanning transmission electron microscopy to quantitatively map the mechanical deformations through which reconstruction occurs in small-angle twisted bilayer MoS2 and WSe2/MoS2 heterobilayers. We provide direct evidence that local rotations govern relaxation for twisted homobilayers, while local dilations are prominent in heterobilayers possessing a sufficiently large lattice mismatch. Encapsulation of the moiré layers in hBN further localizes and enhances these in-plane reconstruction pathways, suppressing out-of-plane corrugation. We also find that extrinsic uniaxial heterostrain, which introduces a lattice constant difference in twisted homobilayers, leads to accumulation and redistribution of reconstruction strain, demonstrating another route to modify the moiré potential.

cond-mat.mtrl-sci↗

arXiv2023

Design of Electrostatic Aberration Correctors for Scanning Transmission Electron Microscopy

In a scanning transmission electron microscope (STEM), producing a high-resolution image generally requires an electron beam focused to the smallest point possible. However, the magnetic lenses used to focus the beam are unavoidably imperfect, introducing aberrations that limit resolution. Modern STEMs overcome this by using hardware aberration correctors comprised of many multipole lenses, but these devices are complex, expensive, and can be difficult to tune. We demonstrate a design for an electrostatic phase plate that can act as an aberration corrector. The corrector is comprised of annular segments, each of which is an independent two-terminal device that can apply a constant or ramped phase shift to a portion of the electron beam. We show the improvement in image resolution using an electrostatic corrector. Engineering criteria impose that much of the beam within the probe-forming aperture be blocked by support bars, leading to large probe tails for the corrected probe that sample the specimen beyond the central lobe. We also show how this device can be used to create other STEM beam profiles such as vortex beams and beams with a high degree of phase diversity, which improve information transfer in ptychographic reconstructions.

cond-mat.mtrl-sci↗

arXiv2022

Hard ferromagnetism down to the thinnest limit of iron-intercalated tantalum disulfide

Two-dimensional (2D) magnetic crystals hold promise for miniaturized and ultralow power electronic devices that exploit spin manipulation. In these materials, large, controllable magnetocrystalline anisotropy is a prerequisite for the stabilization and manipulation of long-range magnetic order. In known 2D magnetic crystals, relatively weak magnetocrystalline anisotropy results in typically soft ferromagnetism. Here, we demonstrate that ferromagnetic order persists down to the thinnest limit of Fe$_x$TaS$_2$ (Fe-intercalated bilayer 2H-TaS$_2$) with giant coercivities up to 3 tesla. We prepare Fe-intercalated TaS$_2$ by chemical intercalation of van der Waals layered 2H-TaS$_2$ crystals and perform variable-temperature quantum transport, transmission electron microscopy, and confocal Raman spectroscopy measurements to shed new light on the coupled effects of dimensionality, degree of intercalation, and intercalant order/disorder on the hard ferromagnetic behavior of Fe$_x$TaS$_2$. More generally, we show that chemical intercalation gives access to a rich synthetic parameter space for low-dimensional magnets, in which magnetic properties can be tailored by the choice of the host material and intercalant identity/amount, in addition to the manifold distinctive degrees of freedom available in atomically thin, van der Waals crystals.

cond-mat.mtrl-sci↗

arXiv2022

Strong structural and electronic coupling in metavalent PbS moire superlattices

Moire superlattices are twisted bilayer materials, in which the tunable interlayer quantum confinement offers access to new physics and novel device functionalities. Previously, moire superlattices were built exclusively using materials with weak van der Waals interactions and synthesizing moire superlattices with strong interlayer chemical bonding was considered to be impractical. Here using lead sulfide (PbS) as an example, we report a strategy for synthesizing of moire superlattices coupled by strong chemical bonding. We use water-soluble ligands as a removable template to obtain free-standing ultra-thin PbS nanosheets and assemble them into direct-contact bilayers with various twist angles. Atomic-resolution imaging shows the moire periodic structural reconstruction at superlattice interface, due to the strong metavalent coupling. Electron energy loss spectroscopy and theoretical calculations collectively reveal the twist angle26 dependent electronic structure, especially the emergent separation of flat bands at small twist angles. The localized states of flat bands are similar to well-arranged quantum dots, promising an application in devices. This study opens a new door to the exploration of deep energy modulations within moire superlattices alternative to van der Waals twistronics.

cond-mat.mtrl-sci↗

arXiv2021

Strain fields in twisted bilayer graphene

Van der Waals heteroepitaxy allows deterministic control over lattice mismatch or azimuthal orientation between atomic layers to produce long wavelength superlattices. The resulting electronic phases depend critically on the superlattice periodicity as well as localized structural deformations that introduce disorder and strain. Here, we introduce Bragg interferometry, based on four-dimensional scanning transmission electron microscopy, to capture atomic displacement fields in twisted bilayer graphene with twist angles < 2°. Nanoscale spatial fluctuations in twist angle and uniaxial heterostrain are statistically evaluated, revealing the prevalence of short-range disorder in this class of materials. By quantitatively mapping strain tensor fields we uncover two distinct regimes of structural relaxation -- in contrast to previous models depicting a single continuous process -- and we disentangle the electronic contributions of the rotation modes that comprise this relaxation. Further, we find that applied heterostrain accumulates anisotropically in saddle point regions to generate distinctive striped shear strain phases. Our results thus establish the reconstruction mechanics underpinning the twist angle dependent electronic behaviour of twisted bilayer graphene, and provide a new framework for directly visualizing structural relaxation, disorder, and strain in any moiré material.

cond-mat.mes-hall↗

arXiv2020

Temperature Driven Transformation of CsPbBr$_3$ Nanoplatelets into Mosaic Nanotiles in Solution through Self-Assembly

Two-dimensional colloidal halide perovskite nanocrystals are promising materials for light emitting applications. In addition, they can be used as components to create a variety of materials through physical and chemical transformations. Recent studies focused on nanoplatelets that are able to self-assemble and transform on solid substrates. Yet, the mechanism behind the process and the atomic arrangement of their assemblies remain unclear. Here, we present the transformation of self-assembled stacks of CsPbBr$_3$ nanoplatelets in solution, capturing the different stages of the process by keeping the solutions at room temperature and monitoring the nanocrystal morphology over a period of a few months. Using ex-situ transmission electron microscopy and surface analysis, we demonstrate that the transformation mechanism can be understood as oriented attachment, proceeding through the following steps: i) desorption of the ligands from the particles surfaces, causing the merging of nanoplatelet stacks, which first form nanobelts; ii) merging of neighboring nanobelts that form more extended nanoplates; and iii) attachment of nanobelts and nanoplates, which create objects with an atomic structure that resemble a mosaic made of broken nanotiles. We reveal that the starting nanoplatelets merge seamlessly and defect-free on an atomic scale in small and thin nanobelts. However, aged nanobelts and nanoplates, which are mainly stabilized by amine/ammonium ions, link through a bilayer of CsBr. In this case, the atomic columns of neighboring perovskite lattices shift by a half-unit-cell, forming Ruddlesden-Popper planar faults.

physics.app-ph↗

arXiv2018

Lattice nano-ripples revealed in peptide microcrystals by scanning electron nanodiffraction

Changes in lattice structure across sub-regions of protein crystals are challenging to assess when relying on whole crystal measurements. Because of this difficulty, macromolecular structure determination from protein micro and nano crystals requires assumptions of bulk crystallinity and domain block substructure. To evaluate the fidelity of these assumptions in protein nanocrystals we map lattice structure across micron size areas of cryogenically preserved three-dimensional peptide crystals using a nano-focused electron beam. This approach produces diffraction from as few as 1,500 molecules in a crystal, is sensitive to crystal thickness and three-dimensional lattice orientation. Real-space maps reconstructed from unsupervised classification of diffraction patterns across a crystal reveal regions of crystal order/disorder and three-dimensional lattice reorientation on a 20nm scale. The lattice nano-ripples observed in micron-sized macromolecular crystals provide a direct view of their plasticity. Knowledge of these features is a first step to understanding crystalline macromolecular self-assembly and improving the determination of structures from protein nano and microcrystals from single or serial crystal diffraction.

cond-mat.soft↗