Phonon Transport in GaAs and InAs Twinning Superlattices.

Crystal phase engineering gives access to new types of periodic nanostructures, such as the so-called twinning superlattices, where the motif of the superlattice is determined by a periodic rotation of the crystal. Here, by means of atomistic nonequilibrium molecular dynamics calculations, we study to what extent these periodic systems can be used to alter phonon transport in a controlled way, similar to what has been predicted and observed in conventional superlattices based on heterointerfaces. We focus on twinning superlattices in GaAs and InAs and highlight the existence of two different transport regimes: in one, each interface behaves like an independent scatterer; in the other, a segment with a sufficiently large number of closely spaced interfaces is seen by propagating phonons as a metamaterial with its own thermal properties. In this second scenario, we distinguish the case where the phonon mean free path is smaller or larger than the superlattice segment, pointing out a different dependence of the thermal resistance with the number of interfaces.

Atomistic Insights on the Full Operation Cycle of a HfO2-Based Resistive Random Access Memory Cell from Molecular Dynamics.

We characterize the atomic processes that underlie forming, reset, and set in HfO2-based resistive random access memory (RRAM) cells through molecular dynamics (MD) simulations, using an extended charge equilibration method to describe external electric fields. By tracking the migration of oxygen ions and the change in coordination of Hf atoms in the dielectric, we characterize the formation and dissolution of conductive filaments (CFs) during the operation of the device with atomic detail. Simulations of the forming process show that the CFs form through an oxygen exchange mechanism, induced by a cascade of oxygen displacements from the oxide to the active electrode, as opposed to aggregation of pre-existing oxygen vacancies. However, the filament breakup is dominated by lateral, rather than vertical (along the filament), motion of vacancies. In addition, depending on the temperature of the system, the reset can be achieved through a redox effect (bipolar switch), where oxygen diffusion is governed by the applied bias, or by a thermochemical process (unipolar switch), where the diffusion is driven by temperature. Unlike forming and similar to reset, the set process involves lateral oxygen atoms as well. This is driven by field localization associated with conductive paths.

Scattering in Terms of Bohmian Conditional Wave Functions for Scenarios with Non-Commuting Energy and Momentum Operators.

Without access to the full quantum state, modeling quantum transport in mesoscopic systems requires dealing with a limited number of degrees of freedom. In this work, we analyze the possibility of modeling the perturbation induced by non-simulated degrees of freedom on the simulated ones as a transition between single-particle pure states. First, we show that Bohmian conditional wave functions (BCWFs) allow for a rigorous discussion of the dynamics of electrons inside open quantum systems in terms of single-particle time-dependent pure states, either under Markovian or non-Markovian conditions. Second, we discuss the practical application of the method for modeling light-matter interaction phenomena in a resonant tunneling device, where a single photon interacts with a single electron. Third, we emphasize the importance of interpreting such a scattering mechanism as a transition between initial and final single-particle BCWF with well-defined central energies (rather than with well-defined central momenta).

3D Bi2Te3 Interconnected Nanowire Networks to Increase Thermoelectric Efficiency.

3D interconnected nanowire scaffoldings are shown to increase the thermoelectric efficiency in comparison to similar diameter 1D nanowires and films grown under similar electrodeposition conditions. Bi2Te3 3D nanonetworks offer a reduction in thermal conductivity (κT) while preserving the high electrical conductivity of the films. The reduction in κT is modeled using the hydrodynamic heat transport equation, and it can be understood as a heat viscosity effect due to the 3D nanostructuration. In addition, the Seebeck coefficient is twice that of nanowires and films, and up to 50% higher than in a single crystal. This increase is interpreted as a nonequilibrium effect that the geometry of the structure induces on the distribution function of the phonons, producing an enhanced phonon drag. These thermoelectric metamaterials have higher performance and are fabricated with large areas by a cost-effective method, which makes them suitable for up-scale production.

Revisiting the Role of Irradiance in the Determination of Sunscreens' Sun Protection Factor.

The efficacy of a sunscreen tends to be associated with its sun protection factor (SPF) value, a figure determined in a test that relies on the independence of the SPF value to both UV radiation dose and irradiance. We probe these assumptions when photoinduced product degradation is present, and we estimate that the theoretical limit for their validity is when the sunfilter active molecule relaxation time is faster than ∼10 ns. While such threshold relaxation time should be compatible with the expected ultrafast relaxation mechanisms of sunfilter molecules (picoseconds), recent research on sunfilter photodynamics has identified the existence of much longer-lived molecular states. Such long lifetimes could compromise sunscreen performance and make the SPF value very different in natural sun irradiance conditions than in the solar simulated conditions typically used in SPF determination tests.

Phonon transport across crystal-phase interfaces and twin boundaries in semiconducting nanowires.

We combine state-of-the-art Green's-function methods and nonequilibrium molecular dynamics calculations to study phonon transport across the unconventional interfaces that make up crystal-phase and twinning superlattices in nanowires. We focus on two of their most paradigmatic building blocks: cubic (diamond/zinc blende) and hexagonal (lonsdaleite/wurtzite) polytypes of the same group-IV or III-V material. Specifically, we consider InP, GaP and Si, and both the twin boundaries between rotated cubic segments and the crystal-phase boundaries between different phases. We reveal the atomic-scale mechanisms that give rise to phonon scattering in these interfaces, quantify their thermal boundary resistance and illustrate the failure of common phenomenological models in predicting those features. In particular, we show that twin boundaries have a small but finite interface thermal resistance that can only be understood in terms of a fully atomistic picture.

Phonon Engineering in Twinning Superlattice Nanowires.

One of the current challenges in nanoscience is tailoring the phononic properties of a material. This has long been a rather elusive task because several phonons have wavelengths in the nanometer range. Thus, high quality nanostructuring at that length-scale, unavailable until recently, is necessary for engineering the phonon spectrum. Here we report on the continuous tuning of the phononic properties of a twinning superlattice GaP nanowire by controlling its periodicity. Our experimental results, based on Raman spectroscopy and rationalized by means of ab initio theoretical calculations, give insight into the relation between local crystal structure, overall lattice symmetry, and vibrational properties, demonstrating how material engineering at the nanoscale can be successfully employed in the rational design of the phonon spectrum of a material.

The thermal boundary resistance at semiconductor interfaces: a critical appraisal of the Onsager vs. Kapitza formalisms.

We critically readdress the definition of thermal boundary resistance at an interface between two semiconductors. By means of atomistic simulations we provide evidence that the widely used Kapitza formalism predicts thermal boundary resistance values in good agreement with the more rigorous Onsager non-equilibrium thermodynamics picture. The latter is, however, better suited to provide physical insight on interface thermal rectification phenomena. We identify the factors that determine the temperature profile across the interface and the source of interface thermal rectification. To this end we perform non-equilibrium molecular dynamics computational experiments on a Si-Ge system with a graded compositional interface of varying thickness, considering thermal bias of different sign.

Electrical contact resistance in graphite-graphene contacts from ab initio methods.

We study the ballistic transmission and the contact resistance (R c) of a graphite-graphene contact in a top contact geometry from first principles. We find that the calculated R c's depend on the amount of graphene-graphite overlap, but quickly saturate for transfer lengths of the order of a few tens of Å. For contacts overlapping more than this transfer length, the R c can be lower than the 100 [Formula: see text] mark. On the other hand, edge graphite-graphene contacts are expected to have very low contact resistance.

Collective thermal transport in pure and alloy semiconductors.

Conventional models for predicting thermal conductivity of alloys usually assume a pure kinetic regime as alloy scattering dominates normal processes. However, some discrepancies between these models and experiments at very small alloy concentrations have been reported. In this work, we use the full first principles kinetic collective model (KCM) to calculate the thermal conductivity of Si1-xGex and InxGa1-xAs alloys. The calculated thermal conductivities match well with the experimental data for all alloy concentrations. The model shows that the collective contribution must be taken into account at very low impurity concentrations. For higher concentrations, the collective contribution is suppressed, but normal collisions have the effect of significantly reducing the kinetic contribution. The study thus shows the importance of the proper inclusion of normal processes even for alloys for accurate modeling of thermal transport. Furthermore, the phonon spectral distribution of the thermal conductivity is studied in the framework of KCM, providing insights to interpret the superdiffusive regime introduced in the truncated Lévy flight framework.

Full-field thermal imaging of quasiballistic crosstalk reduction in nanoscale devices.

Understanding nanoscale thermal transport is of substantial importance for designing contemporary semiconductor technologies. Heat removal from small sources is well established to be severely impeded compared to diffusive predictions due to the ballistic nature of the dominant heat carriers. Experimental observations are commonly interpreted through a reduction of effective thermal conductivity, even though most measurements only probe a single aggregate thermal metric. Here, we employ thermoreflectance thermal imaging to directly visualise the 2D temperature field produced by localised heat sources on InGaAs with characteristic widths down to 100 nm. Besides displaying effective thermal performance reductions up to 50% at the active junctions in agreement with prior studies, our steady-state thermal images reveal that, remarkably, 1-3 µm adjacent to submicron devices the crosstalk is actually reduced by up to fourfold. Submicrosecond transient imaging additionally shows responses to be faster than conventionally predicted. A possible explanation based on hydrodynamic heat transport, and some open questions, are discussed.

Optical Emission in Hexagonal SiGe Nanowires.

Recent advances in the synthetic growth of nanowires have given access to crystal phases that in bulk are only observed under extreme pressure conditions. Here, we use first-principles methods based on density functional theory and many-body perturbation theory to show that a suitable mixing of hexagonal Si and hexagonal Ge yields a direct bandgap with an optically permitted transition. Comparison of the calculated radiative lifetimes with typical values of nonradiative recombination mechanisms indicates that optical emission will be the dominant recombination mechanism. These findings pave the way to the development of silicon-based optoelectronic devices, thus far hindered by the poor light emission efficiency of cubic Si.

Heat transport through a solid-solid junction: the interface as an autonomous thermodynamic system.

We perform computational experiments using nonequilibrium molecular dynamics simulations, showing that the interface between two solid materials can be described as an autonomous thermodynamic system. We verify the local equilibrium and give support to the Gibbs description of the interface also away from the global equilibrium. In doing so, we reconcile the common formulation of the thermal boundary resistance as the ratio between the temperature discontinuity at the interface and the heat flux with a more rigorous derivation from nonequilibrium thermodynamics. We also show that thermal boundary resistance of a junction between two pure solid materials can be regarded as an interface property, depending solely on the interface temperature, as implicitly assumed in some widely used continuum models, such as the acoustic mismatch model. Thermal rectification can be understood on the basis of different interface temperatures for the two flow directions.

Thermal Rectification by Design in Telescopic Si Nanowires.

We show that thermal rectification by design is possible by joining/growing Si nanowires (SiNWs) with sections of appropriately selected diameters (i.e., telescopic nanowires). This is done, first, by showing that the heat equation can be applied at the nanoscale (NW diameters down to 5 nm). We (a) obtain thermal conductivity versus temperature, κ(T), curves from molecular dynamics (MD) simulations for SiNWs of three different diameters, then (b) we conduct MD simulations of a telescopic NW built as the junction of two segments with different diameters, and afterward (c) we verify that the MD results for thermal rectification in telescopic NWs are very well reproduced by the heat equation with κ(T) of the segments from MD. Second, we apply the heat equation to predict the amount of thermal rectification in a variety of telescopic SiNWs with segments made from SiNWs where κ(T) has been experimentally measured, obtaining r values up to 50%. This methodology can be applied to predict the thermal rectification of arbitrary heterojunctions as long as the κ(T) data of the constituents are available.

Room temperature observation of quantum confinement in single InAs nanowires.

Quantized conductance in nanowires can be observed at low temperature in transport measurements; however, the observation of sub-bands at room temperature is challenging due to temperature broadening. So far, conduction band splitting at room temperature has not been observed in III-V nanowires mainly due to the small energetic separations between the sub-bands. We report on the measurement of conduction sub-bands at room temperature, in single InAs nanowires, using Kelvin probe force microscopy. This method does not rely on charge transport but rather on measurement of the nanowire Fermi level position as carriers are injected into a single nanowire transistor. As there is no charge transport, electron scattering is no longer an issue, allowing the observation of the sub-bands at room temperature. We measure the energy of the sub-bands in nanowires with two different diameters, and obtain excellent agreement with theoretical calculations based on an empirical tight-binding model.

Engineering of the chemical reactivity of the Ti/HfO2 interface for RRAM: experiment and theory.

The Ti/HfO2 interface plays a major role for resistance switching performances. However, clear interface engineering strategies to achieve reliable and reproducible switching have been poorly investigated. For this purpose, we present a comprehensive study of the Ti/HfO2 interface by a combined experimental-theoretical approach. Based on the use of oxygen-isotope marked Hf*O2, the oxygen scavenging capability of the Ti layer is clearly proven. More importantly, in line with ab initio theory, the combined HAXPES-Tof-SIMS study of the thin films deposited by MBE clearly establishes a strong impact of the HfO2 thin film morphology on the Ti/HfO2 interface reactivity. Low-temperature deposition is thus seen as a RRAM processing compatible way to establish the critical amount of oxygen vacancies to achieve reproducible and reliable resistance switching performances.

Correlation-mediated processes for electron-induced switching between Néel states of Fe antiferromagnetic chains.

The controlled switching between two quasistable Néel states in adsorbed antiferromagnetic Fe chains has recently been achieved by Loth et al. [Science 335, 196 (2012)] using tunneling electrons from an STM tip. In order to rationalize their data, we evaluate the rate of tunneling electron-induced switching between the Néel states. Good agreement is found with the experiment, permitting us to identify three switching mechanisms: (i) low STM voltage direct electron-induced transitions, (ii) intermediate STM voltage switching via spin-wave-like excitation, and (iii) high STM voltage transitions mediated by domain-wall formation. Spin correlations in the antiferromagnetic chains are the switching driving force, leading to a marked chain-size dependence.

NH3 molecular doping of silicon nanowires grown along the [112], [110], [001], and [111] orientations.

: The possibility that an adsorbed molecule could provide shallow electronic states that could be thermally excited has received less attention than substitutional impurities and could potentially have a high impact in the doping of silicon nanowires (SiNWs). We show that molecular-based ex-situ doping, where NH3 is adsorbed at the sidewall of the SiNW, can be an alternative path to n-type doping. By means of first-principle electronic structure calculations, we show that NH3 is a shallow donor regardless of the growth orientation of the SiNWs. Also, we discuss quantum confinement and its relation with the depth of the NH3 doping state, showing that the widening of the bandgap makes the molecular donor level deeper, thus more difficult to activate.

Molecular doping and subsurface dopant reactivation in si nanowires.

Impurity doping in semiconductor nanowires, while increasingly well understood, is not yet controllable at a satisfactory degree. The large surface-to-volume area of these systems, however, suggests that adsorption of the appropriate molecular complexes on the wire sidewalls could be a viable alternative to conventional impurity doping. We perform first-principles electronic structure calculations to assess the possibility of n- and p-type doping of Si nanowires by exposure to NH(3) and NO(2). Besides providing a full rationalization of the experimental results recently obtained in mesoporous Si, our calculations show that while NH(3) is a shallow donor, NO(2) yields p-doping only when passive surface segregated B atoms are present.

Microscopic dielectric response functions in semiconductor quantum dots.

We calculate and model the microscopic dielectric response function for quantum dots using first principle methods. We find that the response is bulklike inside the quantum dots, and the reduction of the macroscopic dielectric constants is a surface effect. We present a model for the microscopic dielectric function which reproduces well the directly calculated results and can be used to solve the Poisson equation in a nanosystem.