arXiv subjects

Sokrates T. Pantelides

Publications and source records attributed to Sokrates T. Pantelides.

At least 37 records · Page 2Linked to original sources

arXiv2021

Unique features of polarization in ferroelectric ionic conductors

Ferroelectrics that are also ionic conductors offer possibilities for novel applications with high tunability, especially if the same atomic species causes both phenomena. In particular, at temperatures just below the Curie temperature, polarized states may be sustainable as the mobile species is driven in a controlled way over the energy barrier that governs ionic conduction, resulting in unique control of the polarization. This possibility was recently demonstrated in CuInP2S6, a layered ferroelectric ionic conductor in which Cu ions cause both ferroelectricity and ionic conduction. Here, we show that the commonly used approach to calculate the polarization of evolving atomic configurations in ferroelectrics using the modern theory of polarization, namely concerted (synchronous) migration of the displacing ions, is not well suited to describe the polarization evolution as the Cu ions cross the van der Waals gaps. We introduce an asynchronous Cu-migration scheme, which reflects the physical process by which Cu ions migrate, resolves the difficulties, and describes the polarization evolution both for normal ferroelectric switching and for transitions across the van der Waals gaps, providing a single framework to discuss ferroelectric ionic conductors.

cond-mat.mtrl-sci↗

arXiv2021

Intrinsically Honeycomb-patterned Hydrogenated Graphene with Spin Polarized Edge-states

Since the advent of graphene ushered the era of two-dimensional materials, many forms of hydrogenated graphene have been reported, exhibiting diverse properties ranging from a tunable band gap to ferromagnetic ordering. Patterned hydrogenated graphene with micron-scale patterns has been fabricated by lithographic means. Here we report successful millimeter-scale synthesis of an intrinsically honeycomb patterned form of hydrogenated graphene on Ru(0001) by epitaxial growth followed by hydrogenation. Combining scanning tunneling microscopy observations with density-functional-theory (DFT) calculations, we reveal that an atomic-hydrogen layer intercalates between graphene and Ru(0001). The result is a hydrogen honeycomb structure that serves as a template for the final hydrogenation, which converts the graphene into graphane only over the template, yielding honeycomb-patterned hydrogenated graphene (HPHG). In effect, HPHG is a form of patterned graphane. DFT calculations find that the unhydrogenated graphene regions embedded in the patterned graphane exhibit spin-polarized edge states. This type of growth mechanism provides new pathways for the fabrication of intrinsically patterned graphene-based materials.

cond-mat.mtrl-sci↗

arXiv2021

Synthesis and properties of free-standing monolayer amorphous carbon

Bulk amorphous materials have been studied extensively and are widely used, yet their atomic arrangement remains an open issue. Although they are generally believed to be Zachariasen continuous random networks, recent experimental evidence favours the competing crystallite model in the case of amorphous silicon. In two-dimensional materials, however, the corresponding questions remain unanswered. Here we report the synthesis, by laser-assisted chemical vapour deposition, of centimetre-scale, free-standing, continuous and stable monolayer amorphous carbon, topologically distinct from disordered graphene. Unlike in bulk materials, the structure of monolayer amorphous carbon can be determined by atomic-resolution imaging. Extensive characterization by Raman and X-ray spectroscopy and transmission electron microscopy reveals the complete absence of long-range periodicity and a threefold-coordinated structure with a wide distribution of bond lengths, bond angles, and five-, six-, seven- and eight-member rings. The ring distribution is not a Zachariasen continuous random network, but resembles the competing (nano)crystallite model. We construct a corresponding model that enables density-functional-theory calculations of the properties of monolayer amorphous carbon, in accordance with observations. Direct measurements confirm that it is insulating, with resistivity values similar to those of boron nitride grown by chemical vapour deposition. Free-standing monolayer amorphous carbon is surprisingly stable and deforms to a high breaking strength, without crack propagation from the point of fracture. The excellent physical properties of this stable, free-standing monolayer amorphous carbon could prove useful for permeation and diffusion barriers in applications such as magnetic recording devices and flexible electronics.

cond-mat.mtrl-sci↗

arXiv2021

Atomically sharp interface enabled ultrahigh-speed, nonvolatile memory devices

Development of memory devices with ultimate performance has played a key role in innovation of modern electronics. As a mainstream technology nonvolatile memory devices have manifested high capacity and mechanical reliability, however current major bottlenecks include low extinction ratio and slow operational speed. Although substantial effort has been employed to improve their performance, a typical hundreds of micro- or even milli- second write time remains a few orders of magnitude longer than their volatile counterparts. We have demonstrated nonvolatile, floating-gate memory devices based on van der Waals heterostructures with atomically sharp interfaces between different functional elements, and achieved ultrahigh-speed programming/erasing operations verging on an ultimate theoretical limit of nanoseconds with extinction ratio up to 10^10. This extraordinary performance has allowed new device capabilities such as multi-bit storage, thus opening up unforeseen applications in the realm of modern nanoelectronics and offering future fabrication guidelines for device scale-up.

physics.app-ph↗

arXiv2020

Quantum Prediction of Ultra-Low Thermal Conductivity in Lithium Intercalation Materials

Lithium-intercalated layered transition-metal oxides, LixTMO2, brought about a paradigm change in rechargeable batteries in recent decades and show promise for use in memristors, a type of device for future neural computing and on-chip storage. Thermal transport properties, although being a crucial element in limiting the charging/discharging rate, package density, energy efficiency, and safety of batteries as well as the controllability and energy consumption of memristors, are poorly managed or even understood yet. Here, for the first time, we employ quantum calculations including high-order lattice anharmonicity and find that the thermal conductivity k of LixTMO2 materials is significantly lower than hitherto believed. More specifically, the theoretical upper limit of k of LiCoO2 is 6 W/m-K, 2-6 times lower than the prior theoretical predictions. Delithiation further reduces k by 40-70% for LiCoO2 and LiNbO2. Grain boundaries, strains, and porosity are yet additional causes of thermal-conductivity reduction, while Li-ion diffusion and electrical transport are found to have only a minor effect on phonon thermal transport. The results elucidate several long-standing issues regarding the thermal transport in lithium-intercalated materials and provide guidance toward designing high-energy-density batteries and controllable memristors.

cond-mat.mtrl-sci↗

arXiv2020

Atomically-Precise, Custom-Design Origami Graphene Nanostructures

The construction of atomically-precise carbon nanostructures holds promise for developing novel materials for scientific study and nanotechnology applications. Here we show that graphene origami is an efficient way to convert graphene into atomically-precise, complex, and novel nanostructures. By scanning-tunneling-microscope manipulation at low temperature, we repeatedly fold and unfold graphene nanoislands (GNIs) along arbitrarily chosen direction. A bilayer graphene stack featuring a tunable twist angle and a tubular edge connection between the layers are formed. Folding single-crystal GNIs creates tubular edges with specified chirality and one-dimensional electronic features similar to those of carbon nanotubes, while folding bi-crystal GNIs creates well-defined intramolecular junctions. Both origami structural models and electronic band structures were computed to complement analysis of the experimental results. The present atomically-precise graphene origami provides a platform for constructing novel carbon nanostructures with engineered quantum properties and ultimately quantum machines.

cond-mat.mtrl-sci↗

arXiv2019

Formation energies of charged defects in two-dimensional materials -- resolution of long-standing difficulties

Formation energies of charged point defects in semiconductors are calculated using periodic supercells, which entail a divergence arising from long-range Coulombic interactions. The divergence is typically removed by the so-called jellium approach. Recently, Wu, Zhang and Pantelides [WZP, Phys. Rev. Lett. 119, 105501 (2017)] traced the origin of the divergence to the assumption that charged defects are formed by physically removing electrons from or adding electrons to the crystal, violating charge neutrality, a key principle of statistical mechanics that determines the Fermi level. An alternative theory was constructed by recognizing that "charged" defects form by trading carriers with the energy bands, whereby supercells are always charge-neutral so that no divergence is present and no ad-hoc procedures need to be adopted for calculations. Here we give a more detailed exposition of the foundations of both methods and show that the jellium approach can be derived from the statistical-mechanics-backed WZP definition by steps whose validity cannot be assessed a priori. In particular, the divergence appears when the charge density of band carriers is dropped, leaving a supercharged crystal. In the case of charged defects in two-dimensional (2D) materials, unphysical fields appear in vacuum regions. None of these pathological features are present in the reformulated theory. Finally, we report new calculations in both bulk and 2D materials. The WZP approach yields formation energies that differ from jellium values by up to ~1 eV. By analyzing the spatial distribution of wave functions and defect potentials, we provide insights into the inner workings of both methods and demonstrate that the failure of the jellium approach to include the neutralizing electron density of band carriers, as is the case in the physical system, is responsible for the numerical differences between the two methods.

cond-mat.mtrl-sci↗

arXiv2019

Atomic-Resolution Visualization and Doping Effects of Complex Structures in Intercalated Bilayer Graphene

Molecules intercalating two-dimensional (2D) materials form complex structures that have been mostly characterized by spatially averaged techniques. Here we use aberration-corrected scanning transmission electron microscopy and density-functional-theory (DFT) calculations to study the atomic structure of bilayer graphene (BLG) and few-layer graphene (FLG) intercalated with FeCl$_3$. In BLG we discover two distinct intercalated structures that we identify as monolayer-FeCl$_3$ and monolayer-FeCl$_2$. The two structures are separated by atomically sharp boundaries and induce large but different free-carrier densities in the graphene layers, $7.1\times10^{13}$ cm$^{-2}$ and $7.1\times10^{13}$ cm$^{-2}$ respectively. In FLG, we observe multiple FeCl$_3$ layers stacked in a variety of possible configurations with respect to one another. Finally, we find that the microscope's electron beam can convert the FeCl$_3$ monolayer into FeOCl monolayers in a rectangular lattice. These results reveal the need for a combination of atomically-resolved microscopy, spectroscopy, and DFT calculations to identify intercalated structures and study their properties.

cond-mat.mtrl-sci↗

arXiv2019

Giant negative electrostriction and dielectric tunability in a van der Waals layered ferroelectric

The interest in ferroelectric van der Waals crystals arises from the potential to realize ultrathin ferroic systems owing to the reduced surface energy of these materials and the layered structure that allows for exfoliation. Here, we quantitatively unravel giant negative electrostriction of van der Waals layered copper indium thiophosphate (CIPS), which exhibits an electrostrictive coefficient Q33 as high as -3.2 m4/C2 and a resulting bulk piezoelectric coefficient d33 up to -85 pm/V. As a result, the electromechanical response of CIPS is comparable in magnitude to established perovskite ferroelectrics despite possessing a much smaller spontaneous polarization of only a few uC/cm2. In the paraelectric state, readily accessible owing to low transition temperatures, CIPS exhibits large dielectric tunability, similar to widely-used barium strontium titanate, and as a result both giant and continuously tunable electromechanical response. The persistence of electrostrictive and tunable responses in the paraelectric state indicates that even few layer films or nanoparticles will sustain significant electromechanical functionality, offsetting the inevitable suppression of ferroelectric properties in the nanoscale limit. These findings can likely be extended to other ferroelectric transition metal thiophosphates and (quasi-) two-dimensional materials and might facilitate the quest towards novel ultrathin functional devices incorporating electromechanical response.

cond-mat.mtrl-sci↗

arXiv2019

Tunable Thermal Energy Transport across Diamond Membranes and Diamond-Si Interfaces by Nanoscale Graphoepitaxy

The development of electronic devices, especially those that involve heterogeneous integration of materials, has led to increased challenges in addressing their thermal operational-temperature demands. The heat flow in these systems is significantly influenced or even dominated by thermal boundary resistance at interface between dissimilar materials. However, controlling and tuning heat transport across an interface and in the adjacent materials has so far drawn limited attention. In this work, we grow chemical-vapor-deposited (CVD) diamond on silicon substrates by graphoepitaxy and experimentally demonstrate tunable thermal transport across diamond membranes and diamond-silicon interfaces. We observed the highest diamond-silicon thermal boundary conductance (TBC) measured to date and increased diamond thermal conductivity due to strong grain texturing in the diamond near the interface. Additionally, non-equilibrium molecular-dynamics (NEMD) simulations and a Landauer approach are used to understand the diamond-silicon TBC. These findings pave the way for tuning or increasing thermal conductance in heterogeneously integrated electronics that involve polycrystalline materials and will impact applications including electronics thermal management and diamond growth.

cond-mat.mes-hall↗

arXiv2018

Diffuson-driven Ultralow Thermal Conductivity in Amorphous Nb2O5 Thin Films

Niobium pentoxide (Nb2O5) has been extensively reported for applications of electrochemical energy storage, memristors, solar cells, light emitting diodes (LEDs), and electrochromic devices. The thermal properties of Nb2O5 play a critical role in device performance of these applications. However, very few studies on the thermal properties of Nb2O5 have been reported and a fundamental understanding of heat transport in Nb2O5 is still lacking. The present work closes this gap and provides the first study of thermal conductivity of amorphous Nb2O5 thin films. Ultralow thermal conductivity is observed without any size effect in films as thin as 48 nm, which indicates that propagons contribute negligibly to the thermal conductivity and that the thermal transport is dominated by diffusons. Density-function-theory (DFT) simulations combined with a diffuson-mediated minimum-thermal-conductivity model confirms this finding. Additionally, the measured thermal conductivity is lower than the amorphous limit (Cahill model), which proves that the diffuson model works better than the Cahill model to describe the thermal conduction mechanism in the amorphous Nb2O5 thin films. Additionally, the thermal conductivity does not change significantly with oxygen vacancy concentration. This stable and low thermal conductivity facilitates excellent performance for applications such as memristors.

cond-mat.mes-hall↗

arXiv2018

Intrinsic interfacial van der Waals monolayers and their effect on the high-temperature superconductor FeSe/SrTiO$_3$

The sensitive dependence of monolayer materials on their environment often gives rise to unexpected properties. It was recently demonstrated that monolayer FeSe on a SrTiO$_3$ substrate exhibits a much higher superconducting critical temperature T$_C$ than the bulk material. Here, we examine the interfacial structure of FeSe / SrTiO$_3$ and the effect of an interfacial Ti$_{1+x}$O$_2$ layer on the increased T$_C$ using a combination of scanning transmission electron microscopy and density functional theory. We find Ti$_{1+x}$O$_2$ forms its own quasi-two-dimensional layer, bonding to both the substrate and the FeSe film by van der Waals interactions. The excess Ti in this layer electron-dopes the FeSe monolayer in agreement with experimental observations. Moreover, the interfacial layer introduces symmetry-breaking distortions in the FeSe film that favor a T$_C$ increase. These results suggest that this common substrate may be functionalized to modify the electronic structure of a variety of thin films and monolayers.

cond-mat.mtrl-sci↗

arXiv2018

Mechanisms of pyroelectricity in three- and two-dimensional materials

Pyroelectricity is a very promising phenomenon in three- and two-dimensional (2D) materials, but first-principles calculations have not so far been used to elucidate the underlying mechanisms. Here we report density-functional theory (DFT) calculations based on the Born-Szigeti theory of pyroelectricity, by combining fundamental thermodynamics and the modern theory of polarization. We find satisfactory agreement with experimental data in the case of bulk benchmark materials, showing that the so-called electron-phonon renormalization, whose contribution has been viewed as negligible, is important. We predict out-of-plane pyroelectricity in the recently synthesized Janus MoSSe monolayer and in-plane pyroelectricity in the group-IV monochalcogenide GeS monolayer. It is notable that the so-called secondary pyroelectricity is found to be dominant in GeS monolayer. The present work opens a theoretical route to study the pyroelectric effect using DFT and provides a valuable tool in the search for new candidates for pyroelectric applications.

cond-mat.mtrl-sci↗

arXiv2017

Spatially and spectrally resolved orbital angular momentum interactions in plasmonic vortex generators

Understanding the near-field electromagnetic interactions that produce optical orbital angular momentum (OAM) is central to the integration of twisted light into nanotechnology. Here, we examine the cathodoluminescence (CL) of plasmonic vortices carrying OAM generated in spiral nanostructures through scanning transmission electron microscopy (STEM). The nanospiral geometry defines the photonic local density of states (LDOS) sampled by STEM-CL, which provides access to the phase and amplitude of the plasmonic vortex with nanometer spatial and meV spectral resolution. We map the full spectral dispersion of the plasmonic vortex in the spiral structure and examine the effects of increasing topological charge on the plasmon phase and amplitude in the detected CL signal. The vortex is mapped in CL over a broad spectral range, and deviations between the predicted and detected positions of near-field optical signatures of as much as 5 per cent are observed. Finally, enhanced luminescence is observed from concentric spirals of like handedness compared to that from concentric spirals of opposite handedness, indicating the potential to couple plasmonic vortices to chiral nanostructures for sensitive detection and manipulation of optical OAM.

physics.optics↗

arXiv2016

Large-area and high-quality 2D transition metal telluride

Atomically thin transitional metal ditellurides like WTe2 and MoTe2 have triggered tremendous research interests because of their intrinsic nontrivial band structure. They are also predicted to be 2D topological insulators and type-II Weyl semimetals. However, most of the studies on ditelluride atomic layers so far rely on the low-yield and time-consuming mechanical exfoliation method. Direct synthesis of large-scale monolayer ditellurides has not yet been achieved. Here, using the chemical vapor deposition (CVD) method, we demonstrate controlled synthesis of high-quality and atom-thin tellurides with lateral size over 300 μm. We found that the as-grown WTe2 maintains two different stacking sequences in the bilayer, where the atomic structure of the stacking boundary is revealed by scanning transmission electron microscope (STEM). The low-temperature transport measurements revealed a novel semimetal-to-insulator transition in WTe2 layers and an enhanced superconductivity in few-layer MoTe2. This work paves the way to the synthesis of atom-thin tellurides and also quantum spin Hall devices.

cond-mat.mtrl-sci↗

arXiv2016

Unified Band Theoretic Description of Electronic and Magnetic Properties of Vanadium Dioxide Phases

The debate about whether the insulating phases of vanadium dioxide (VO2) can be described by band theory or must be described by a theory of strong electron correlations remains unresolved even after decades of research. Energy-band calculations using hybrid exchange functionals or including self-energy corrections account for the insulating or metallic nature of different phases, but have not yet successfully accounted for the observed magnetic orderings. Strongly-correlated theories have had limited quantitative success. Here we report that, by using hard pseudopotentials and an optimized hybrid exchange functional, the energy gaps and magnetic orderings of both monoclinic VO2 phases and the metallic nature of the high-temperature rutile phase are consistent with available experimental data, obviating an explicit role for strong correlations. We also report a potential candidate for the newly-found metallic monoclinic phase and present a detailed magnetic structure of the M2 monoclinic phase.

cond-mat.mtrl-sci↗

arXiv2015

The Effect of Intrinsic Crumpling on the Mechanics of Free-Standing Graphene

Free-standing graphene is inherently crumpled in the out-of-plane direction due to dynamic flexural phonons and static wrinkling. We explore the consequences of this crumpling on the effective mechanical constants of graphene. We develop a sensitive experimental approach to probe stretching of graphene membranes under low applied stress at cryogenic to room temperatures. We find that the in-plane stiffness of graphene is between 20 and 100 N/m at room temperature, much smaller than 340 N/m (the value expected for flat graphene). Moreover, while the in-plane stiffness only increases moderately when the devices are cooled down to 10 K, it approaches 300 N/m when the aspect ratio of graphene membranes is increased. These results indicate that softening of graphene at temperatures less than 400 K is caused by static wrinkling, with only a small contribution due to flexural phonons. Together, these results explain the large variation in reported mechanical constants of graphene devices and paves the way towards controlling their mechanical properties.

cond-mat.mes-hall↗

arXiv2015

Theory of inelastic multiphonon scattering and carrier capture by defects in semiconductors. Application to capture cross sections

Inelastic scattering and carrier capture by defects in semiconductors are the primary causes of hot-electron-mediated degradation of power devices, which holds up their commercial development. At the same time, carrier capture is a major issue in the performance of solar cells and light-emitting diodes. A theory of nonradiative inelastic scattering by defects, however, is non-existent, while the the- ory for carrier capture by defects has had a long and arduous history. Here we report the construction of a comprehensive theory of inelastic scattering by defects, with carrier capture being a special case. We distinguish between capture under thermal equilibrium conditions and capture under non-equilibrium conditions, e.g., in the presence of electrical current or hot carriers where carriers undergo scattering by defects and are described by a mean free path. In the thermal-equilibrium case, capture is mediated by a non-adiabatic perturbation Hamiltonian, originally identified by Huang and Rhys and by Kubo, which is equal to linear electron-phonon coupling to first order. In the non-equilibrium case, we demonstrate that the primary capture mechanism is within the Born-Oppenheimer approximation, with coupling to the defect potential inducing Franck-Condon electronic transitions, followed by multiphonon dissipation of the transition energy, while the non-adiabatic terms are of secondary importance. We report density-functional-theory calculations of the capture cross section for a prototype defect using the Projector-Augmented-Wave which allows us to employ all-electron wavefunctions. We adopt a Monte Carlo scheme to sample multiphonon configurations and obtain converged results. The theory and the results represent a foundation upon which to build engineering-level models for hot-electron degradation of power devices and the performance of solar cells and light-emitting diodes.

cond-mat.mtrl-sci↗