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Incorporation of elastomers into bioelectronics that reduces the mechanical mismatch between electronics and biological systems could potentially improve the long-term electronics-tissue interface. However, the chronic stability of elastomers in physiological conditions has not been systematically studied. Here, using electrochemical impedance spectrum we find that the electrochemical impedance of dielectric elastomers degrades over time in physiological environments. Both experimental and computational results reveal that this phenomenon is due to the diffusion of ions from the physiological solution into elastomers over time. Their conductivity increases by 6 orders of magnitude up to 10

Understanding the electrical and thermal transport properties of materials is critical to the design of electronics, sensors, and energy conversion devices. Computational modeling can accurately predict material properties but, in order to be reliable, requires accurate descriptions of electron and phonon states and their interactions. While first-principles methods are capable of describing the energy spectrum of each carrier, using them to compute transport properties is still a formidable task, both computationally demanding and memory intensive, requiring integration of fine microscopic scattering details for estimation of macroscopic transport properties. To address this challenge, we present Phoebe—a newly developed software package that includes the effects of electron–phonon, phonon–phonon, boundary, and isotope scattering in computations of electrical and thermal transport properties of materials with a variety of available methods and approximations. This open source C++ code combines MPI-OpenMP hybrid parallelization with GPU acceleration and distributed memory structures to manage computational cost, allowing Phoebe to effectively take advantage of contemporary computing infrastructures. We demonstrate that Phoebe accurately and efficiently predicts a wide range of transport properties, opening avenues for accelerated computational analysis of complex crystals.

Electronic transport in narrow gap semiconductors is characterized by spontaneous vertical transitions between carriers in the valence and conduction bands, a phenomenon also known as Zener tunneling. However, this effect is not captured by existing models based on the Boltzmann transport equation. In this work, we propose a new fully first principles model for electronic transport using the Wigner distribution function and implement it to solve the equations of motion for electrons. The formalism generalizes the Boltzmann equation to materials with strong interband coupling and include transport contributions from off-diagonal components of the charge current operator. We illustrate the method with a study of Bi2Se3, showing that interband tunneling dominates the electron transport dynamics at experimentally relevant small doping concentrations, a behavior that is likely shared with other semiconductors, including topological insulators. Surprisingly, Zener tunneling occurs also between band subvalleys separated by energy much larger than the band gap.

We present a combined treatment of the non-equilibrium dynamics and transport of electrons and phonons by carrying out \textit{ab initio} calculations of the fully coupled electron and phonon Boltzmann transport equations. We find that the presence of mutual drag between the two carriers causes the thermopower to be enhanced and dominated by the transport of phonons, rather than electrons as in the traditional semiconductor picture. Drag also strongly boosts the intrinsic electron mobility, thermal conductivity and the Lorenz number. Impurity scattering is seen to suppress the drag-enhancement of the thermal and electrical conductivities, while having weak effects on the enhancement of the Lorenz number and thermopower. We demonstrate these effects in \textit{n}-doped 3C-SiC at room temperature, and explain their origins. This work establishes the roles of microscopic scattering mechanisms in the emergence of strong drag effects in the transport of the interacting electron-phonon gas.

We present a first-principles study of the temperature- and density-dependent intrinsic electrical resistivity of graphene. We use density-functional theory and density-functional perturbation theory together with very accurate Wannier interpolations to compute all electronic and vibrational properties and electron-phonon coupling matrix elements; the phonon-limited resistivity is then calculated within a Boltzmann-transport approach. An effective tight-binding model, validated against first-principles results, is also used to study the role of electron-electron interactions at the level of many-body perturbation theory. The results found are in excellent agreement with recent experimental data on graphene samples at high carrier densities and elucidate the role of the different phonon modes in limiting electron mobility. Moreover, we find that the resistivity arising from scattering with transverse acoustic phonons is 2.5 times higher than that from longitudinal acoustic phonons. Last, high-energy, optical, and zone-boundary phonons contribute as much as acoustic phonons to the intrinsic electrical resistivity even at room temperature and become dominant at higher temperatures., 7 pages 5 figures

Structural properties of Li 7 − x La 3 Ta x Zr 2 − x O 12 garnets with x = 0–2 were clarified by means of Rietveld analysis using results of X-ray diffraction and neutron diffraction at room temperature and at low temperature. In this work the controversy between Awaka [1] and Murugan [2] concerning the crystal structure of Li 7 La 3 Zr 2 O 12 was solved. It was shown that the tetragonally derived garnet structure of space group I 4 1 / acd described by Awaka [1] is the thermodynamically stable structure for Li 7 La 3 Zr 2 O 12 . In the three-dimensional sub-network of this structure, lithium is ordered and occupies all octahedral sites as well as one third of the tetrahedral sites. Li 7 − x La 3 Ta x Zr 2 − x O 12 garnets with x = 0.125–2 crystallize in the garnet structure, space group Ia 3 ¯ d . As the tantalum content increases, the lattice parameter at room temperature decreases from a = 12.9833(1) A for Li 6.875 La 3 Ta 0.125 Zr 1.875 O 12 down to a = 12.81224(7) A for Li 5 La 3 Ta 2 O 12 . In Li 6.5 La 3 Ta 0.5 Zr 1.5 O 12 garnet, lithium atoms are statistically partitioned among octahedral sites (occ.: 0.80(2)) and tetrahedral sites (occ.: 0.56(4)). In the cases of ordered Li 7 La 3 Zr 2 O 12 tetragonally derived garnet and statistically disordered Li 6.5 La 3 Ta 0.5 Zr 1.5 O 12 garnet, lithium partitioning remains unchanged as temperature decreases.

We report an ab initio study of vibrational and thermodynamic properties of TiNiSn, a half-Heusler alloy that has been investigated in the context of thermoelectrics, based on density functional theory and density functional perturbation theory. The quasiharmonic approximation, where the Helmholtz free energy obtained from phonons of multiple strained structures is fitted to a model equation of state, is employed to estimate thermodynamic properties. Good quantitative correspondence is achieved between experimental observations and our theoretical calculation for various thermodynamic quantities: lattice parameter, thermal expansion coefficient, and heat capacity. Estimates of lattice thermal conductivity are also provided by using a semianalytic model previously proposed in the literature. Though this yields good qualitative agreement, a more accurate ab initio approach that explicitly includes anharmonic interactions between atoms should be employed for quantitative predictions of thermal conductivity.

Lithium/air batteries, based on their high theoretical specific energy, are an extremely attractive technology for electrical energy storage that could make long-range electric vehicles widely affordable. However, the impact of this technology has so far fallen short of its potential due to several daunting challenges. In nonaqueous Li/air cells, reversible chemistry with a high current efficiency over several cycles has not yet been established, and the deposition of an electrically resistive discharge product appears to limit the capacity. Aqueous cells require water-stable lithium-protection membranes that tend to be thick, heavy, and highly resistive. Both types of cell suffer from poor oxygen redox kinetics at the positive electrode and deleterious volume and morphology changes at the negative electrode. Closed Li/air systems that include oxygen storage are much larger and heavier than open systems, but so far oxygen- and OH − -selective membranes are not effective in preventing contamination of cells. In this review we discuss the most critical challenges to developing robust, high-energy Li/air batteries and suggest future research directions to understand and overcome these challenges. We predict that Li/air batteries will primarily remain a research topic for the next several years. However, if the fundamental challenges can be met, the Li/air battery has the potential to significantly surpass the energy storage capability of today’s Li-ion batteries.

We use rigorous group-theoretic techniques and molecular dynamics to investigate the connection between structural symmetry and ionic conductivity in the garnet family of solid Li-ion electrolytes. We identify new ordered phases and order-disorder phase transitions that are relevant for conductivity optimization. Ionic transport in this materials family is controlled by the frustration of the Li sublattice caused by incommensurability with the host structure at non-integer Li concentrations, while ordered phases explain regions of sharply lower conductivity. Disorder is therefore predicted to be optimal for ionic transport in this and other conductor families with strong Li interaction., Comment: 6 pages, 4 figures, and supplementary information

We screen a large chemical space of perovskite alloys for systems with optimal properties to accommodate a morphotropic phase boundary (MPB) in their composition-temperature phase diagram, a crucial feature for high piezoelectric performance. We start from alloy end points previously identified in a high-throughput computational search. An interpolation scheme is used to estimate the relative energies between different perovskite distortions for alloy compositions with a minimum of computational effort. Suggested alloys are further screened for thermodynamic stability. The screening identifies alloy systems already known to host an MPB and suggests a few others that may be promising candidates for future experiments. Our method of investigation may be extended to other perovskite systems, e.g., (oxy-)nitrides, and provides a useful methodology for any application of high-throughput screening of isovalent alloy systems.

The ab initio $GW$ method is considered as the most accurate approach for calculating the band gaps of semiconductors and insulators. Yet its application to transition metal oxides (TMOs) has been hindered by the failure of traditional approximations developed for conventional semiconductors. In this work, we examine the effects of these approximations on the values of band gaps for ZnO, Cu$_2$O, and TiO$_2$. In particular, we explore the origin of the differences between the two widely used plasmon-pole models. Based on the comparison of our results with the experimental data and previously published calculations, we discuss which approximations are suitable for TMOs and why., Comment: This is an author-created, un-copyedited version of an article published in Journal of Physics: Condensed Matter. IOP Publishing Ltd is not responsible for any errors or omissions in this version of the manuscript or any version derived from it. The Version of Record is available online at doi:10.1088/0953-8984/26/47/475501

The materials class of skutterudites is one of the promising thermoelectric materials due to its decent electronic properties and cage-like structural feature that can be filled with guest atoms. First principles calculations have been performed in order to investigate electronic band structures and related transport properties of pnictogen-substitued skutterudites filled with alkaline-earth elements (MxCo4A6Te6 where M=Ca, Sr, or Ba, A=Ge or Sn, and x=0.5 or 1). The Seebeck coefficient and the power factor, which are electronic transport properties related to thermoelectricity, are computed by using the Boltzmann transport formalism within the constant-relaxation-time-approximation. The results are compared against the corresponding properties of the unfilled pnictogen-substitued ternary skutterudites (CoA1.5Te1.5) to identify the effects of filling, based on which the potential of filled pnictogen-substituted skutterudites for thermoelectric applications is evaluated. The possible changes in the ionic character of the interatomic bonding, which was suspected to be an important scattering source, are probed by analyzing the projected density of states.

First-principles calculations have been performed to investigate electronic band structures, vibrational characters, and related transport properties of pnictogen-substituted skutterudites filled with alkaline-earth elements ( MxCo4A6B6, where M = Ca, Sr, or Ba, A = Ge or Sn, B = Se or Te, and x = 0.5 or 1). Electronic transport properties related to thermoelectricity, including the Seebeck coefficient and the electrical conductivity, are computed by using the Boltzmann transport formalism within the constant-relaxation-time approximation. The results are compared against the corresponding properties of the unfilled pnictogen-substituted ternary skutterudites ( CoA1.5B1.5) to identify the effects of filling to estimate the potential for thermoelectric applications. The changes in the ionic character of the interatomic bonding between the Group 14 (A) and Group 16 (B) elements, which was suspected to be a major scattering source in unfilled pnictogen-substituted ternary skutterudites, are probed by analyzi...

First principles calculations are used to investigate electronic band structure and vibrational spectra of pnictogen substituted ternary skutterudites. We compare the results with the prototypical binary composition CoSb$_3$ to identify the effects of substitutions on the Sb site, and evaluate the potential of ternary skutterudites for thermoelectric applications. Electronic transport coefficients are computed within the Boltzmann transport formalism assuming a constant relaxation time, using a new methodology based on maximally localized Wannier function interpolation. Our results point to a large sensitivity of the electronic transport coefficients to carrier concentration and to scattering mechanisms associated with the enhanced polarity. The ionic character of the bonds is used to explain the detrimental effect on the thermoelectric properties.

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The thermal conductivity of disordered silicon-germanium alloys is computed from density-functional perturbation theory and with relaxation times that include both harmonic and anharmonic scattering terms. We show that this approach yields an excellent agreement at all compositions with experimental results and provides clear design rules for the engineering of nanostructured thermoelectrics. For Si(x)Ge(1-x), more than 50% of the heat is carried at room temperature by phonons of mean free path greater than 1 mu m, and an addition of as little as 12% Ge is sufficient to reduce the thermal conductivity to the minimum value achievable through alloying. Intriguingly, mass disorder is found to increase the anharmonic scattering of phonons through a modification of their vibration eigenmodes, resulting in an increase of 15% in thermal resistivity.

We use ab initio computations to investigate the effect of filler ions on the properties of CoSb3 skutterudites. We analyze global and local structural effects of filling, using the Ba-filled system as an example. We show that the deformation of Sb network induced by the filler affects primarily nearest neighboring Sb sites around the filler site as the soft Sb rings accommodate the distortion. Rearrangement of Sb atoms affects the electronic band structure and we clarify the effect of this local strain on the band gap. We compute the phonon dispersions and identify the filler-dominated modes from the lowest-frequency optical modes at Gamma. Their weak dispersion across the Brillouin zone indicates that they are localized and a force-constant analysis shows that the filler vibration is strongly coupled with nearby Sb atoms.

We perform ab-initio computations to investigate the family of CoSb3 skutterudites in an attempt to develop deeper understanding of the effect of fillers. Primary focus is on Ba-filled CoSb3 systems, while Ca and Sr-filled systems are also compared for checking consistency. We analyze both global and local structural effects of filling. We show the specific deformation of Sb network introduced by the filler. Such a deformation is localized around the filler site since soft Sb rings accommodate the distortion. Rearrangement of Sb atoms affects the band structures, and we perform additional analysis to clarify the effect of volume on the band gap. Phonon dispersions are briefly discussed, and filler-dominated vibrations are identified. These modes form the first optical modes at Γ. They manifest themselves in phonon dispersion curves as flat lines, showing that they are localized, while filler vibration is strongly coupled with nearby Sb atoms.

We characterize the response of isolated single- (SWNT) and multi-wall (MWNT) carbon nanotubes and bundles to static electric fields using first-principles calculations and density-functional theory. The longitudinal polarizability of SWNTs scales as the inverse square of the band gap, while in MWNTs and bundles it is given by the sum of the polarizabilities of the constituent tubes. The transverse polarizability of SWNTs is insensitive to band gaps and chiralities and is proportional to the square of the effective radius; in MWNTs the outer layers dominate the response. The transverse response is intermediate between metallic and insulating, and a simple electrostatic model based on a scale-invariance relation captures accurately the first-principles results. Dielectric response of non-chiral SWNTs in both directions remains linear up to very high values of applied field., Submitted to Phys. Rev. Lett. on 09/28/2005

We study correlated electron states in frustrated geometry of a triangular lattice. The interplay of long range interactions and finite residual entropy of a classical system gives rise to unusual effects in equilibrium ordering as well as in transport. A novel correlated fluid phase is identified in a wide range of densities and temperatures above freezing into commensurate solid phases. The charge dynamics in the correlated phase is described in terms of a height field, its fluctuations, and topological defects. We demonstrate that the height field fluctuations give rise to a ``free'' charge flow and finite dc conductivity. We show that freezing into the solid phase, controlled by the long range interactions, manifests itself in singularities of transport properties., 19 pages, 10 figures

A mechanical interpretation of the frequency trend observed in Ca-, Sr-, and Ba-filled CoSb3 skutterudites is presented. Relevant vibrational frequencies computed at the zone center are presented for fully filled, half-filled, and unfilled systems. The frequency of the filler vibrations increases as the mass of the filler atom increases, which is a counterintuitive trend that is difficult to explain within the classical “rattler” concept. As an alternative theory, we propose the interpretation of the filler vibrations as modified Sb ring vibrations instead. The energetically degenerate Sb ring vibrations in unfilled CoSb3 split into two separate groups of vibrations through the mechanical interaction introduced by fillers, and one of the group forms the filler vibrations. A one-dimensional mass-spring model is also presented for illustrative purposes. The frequency trend of the ab initio phonons at the zone center is reproduced by the model, substantiating our interpretation. The result suggests that engi...

Experimental thermal conductivity of bulk materials are often modeled using Debye approximation together with functional forms of relaxation time with fitting parameters. While such models can fit the temperature dependence of thermal conductivity of bulk materials, the Debye approximation leads to large error in the actual phonon mean free path, and consequently, the predictions of the thermal conductivity of the nanostructured materials using the same relaxation time are not correct even after considering additional size effect on the mean free path. We investigate phonon mean free path distribution inside fully unfilled (Co4Sb12) and fully filled (LaFe4Sb12) bulk skutterudites by fitting their thermal conductivity to analytical models which employ different phonon dispersions. We show that theoretical thermal conductivity predictions of the nanostructured samples are in agreement with the experimental data obtained for samples of different grain sizes only when the full phonon dispersion is considered.

The Li/oxygen battery may achieve a high practical specific energy as its theoretical specific energy is 11,400 Wh/kg Li assuming Li 2 O 2 is the product. To help understand the physics of the Li/oxygen battery we present the first physics-based model that incorporates the major thermodynamic, transport, and kinetic processes. We obtain a good match between porous-electrode experiments and simulations by using an empirical fit to the resistance of the discharge products (which include carbonates and oxides when using carbonate solvents) as a function of thickness that is obtained from flat-electrode experiments. The experiments and model indicate that the discharge products are electronically resistive, limiting their thickness to tens of nanometers and their volume fraction in one of our discharged porous electrodes to a few percent. Flat-electrode experiments, where pore clogging is impossible, show passivation similar to porous-electrode experiments and allow us to conclude that electrical passivation is the dominant capacity-limiting mechanism in our cells. Although in carbonate solvents Li 2 O 2 is not the dominant discharge product, we argue that the implications of this model, (i.e., electrical passivation by the discharge products limits the capacity) also apply if Li 2 O 2 is the discharge product, as it is an intrinsic electronic insulator.

Electronic properties of ternary skutterudites AX3/2Y3/2 (A=Co, X=Ge, Sn and Y=S, Te) are investigated using first principles calculations to clarify recent experimental results. Band derivatives are computed accurately within an approach based on Maximally Localized Wannier Functions (MLWFs). Band structures exhibit larger effective masses compared to parental binary CoSb3. Our results also indicate a more parabolic dispersion near the top of the valence band and a multivalley character in both conduction and valence band. Despite the improved thermopower these skutterudites has relatively low power factor due to increased resistivity. The fundamental cause of such large resistivity seems to be associated with the ionicity of the bonding.

The near-exponential expansion in computing resources over the last few decades has enabled a rapid increase in the capabilities of computational science, including applications to materials research. In order to harness the available resources and accelerate the field of materials design, it is critically important to develop robust and reusable automation software for preparing and performing multistep computational workflows, starting with crystal structures and ending with material properties. In the domain of first-principles calculations of crystalline materials, we highlight emerging tools for automated symmetry analysis of the atomic and electronic structure. With automation capabilities in hand, the ever-increasing amount of data also becomes a serious bottleneck in terms of organization, analysis, and reproducibility. We describe some of the progress and strategic challenges in the development of a general infrastructure for coupling computational automation with data management, emphasizing data reproducibility and provenance capture.