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We fabricated a heterojunction structure composed of n-CdS and p-C10H10N2 films. The CdS film was prepared using the CBD method, while the C10H10N2 film was prepared using the spin coating method. Later, we performed the current-voltage (I-V) measurement of this PN diode which we made using Keithley 2400 sourcemeter. As can be seen from the logI-V diagram, this heterojunction structure exhibits rectifying properties. Using traditional methods, an ideality factor (n) of 1.93 and a barrier height value (Φb) of 0.79 eV were determined. An ideality factor of more than one indicates non-ideal I-V behavior in the CdS/C10H10N2 heterojunction diode formed. The interface layer, interface states and series resistance are some of the causes of this deviation. Moreover, Cheung's functions and a modified Norde function were used to determine the diode parameters, such as ideality factor, barrier height, and series resistance. With the Cheung method, n=4.33, series resistance (RS)=168.65 kΩ and Φb=0.62 eV were found. Additionally, RS=686.08 kΩ and Φb=0.78 eV were found by the Norde method. Consistent barrier height values were found in all methods through comparison, suggesting compatibility. However, it was discovered that the series resistance values yielded by the Norde function exceeded those obtained by the Cheung functions. [ABSTRACT FROM AUTHOR]

The weak interface interaction and solid-solid phase transition have long been a conundrum for 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX)-based polymer-bonded explosives (PBX). A two-step strategy that involves the pretreatment of HMX to endow eOH groups on the surface via polyalcohol bonding agent modification and in situ coating with nitrate ester-containing polymer, was proposed to address the problem. Two types of energetic polyetherdglycidyl azide polymer (GAP) and nitrate modified GAP (GNP) were grafted onto HMX crystal based on isocyanate addition reaction bridged through neutral polymeric bonding agent (NPBA) layer. The morphology and structure of the HMX-based composites were characterized in detail and the core-shell structure was validated. The grafted polymers obviously enhanced the adhesion force between HMX crystals and fluoropolymer (F2314) binder. Due to the interfacial reinforcement among the components, the two HMX-based composites exhibited a remarkable increment of phase transition peak temperature by 10.2ºC and 19.6ºC with no more than 1.5% shell content, respectively. Furthermore, the impact and friction sensitivity of the composites decreased significantly as a result of the barrier produced by the grafted polymers. These findings will enhance the future prospects for the interface design of energetic composites aiming to solve the weak interface and safety concerns. [ABSTRACT FROM AUTHOR]

The electronic structure of ultrathin Cs/Bi2Se3 interfaces has been studied by photo electron spectroscopy using synchrotron radiation. The experiments were carried out in situ in ultrahigh vacuum with submonolayer Cs coverages on Bi2Se3 samples. It was found that the adsorption of Cs causes changes in the core level spectra of Bi 4f, Bi 5d, Se 3d. It has been established that Cs atoms are adsorbed predominantly on Bi atoms in the upper surface layer. The states of the valence band were studied for a clean Bi2Se3 surface and for the Cs/Bi2Se3 interface. Near the Fermi level, 2D topological states have been found. Two induced surface states appear in the region of the valence band upon adsorption of Cs. [ABSTRACT FROM AUTHOR]

Extractive text summarization selects asmall subset of sentences from a document, which gives good "coverage" of a document. When given a set of term weights indicating the importance of the terms, the concept of coverage may be formalized into a combinatorial optimization problem known as the budgeted maximum coverage problem. Extractive methods in this class are known to beamong the best of classic extractive summarization systems. This paper gives a synopsis of thesoftware package occams, which is a multilingual extractive single and multi-document summarization package based on an algorithm giving an optimal approximation to the budgeted maximum coverage problem. The occams package is written in Python and provides an easy-to-use modular interface, allowing it to work in conjunction with popular Python NLP packages, such as nltk, stanza or spacy. [ABSTRACT FROM AUTHOR]

The article focuses on the American Vacuum Society (AVS), an interdisciplinary professional society founded in 1953 with 4000 members worldwide, facilitating networking among professionals in various fields related to materials, interfaces, and processing. Topics include AVS's organizational structure, its international collaborations and affiliations with societies like JVSS and TFS, and its flagship event, the Annual International Symposium and Exhibition.

We design a one-dimensional locally resonant phononic crystal (LRPC) comprised of a substrate beam periodically attached with twin resonators. By alternating the position of the resonators, the bandgap forming mechanisms of the LRPC, namely, the band folding-induced bandgaps (BFBGs) and the locally resonant bandgap (LRBG), are analyzed. A broadband "pseudo-bandgap" formed by the LRBG and BFBG can be achieved. The topological properties of the LRPC are then studied, and it is found that the topological interface states can occur only in the BFBGs but not in the LRBG. By constructing a finite LRPC formed by two PCs with distinct topological properties connecting with each other, we numerically and experimentally demonstrate the existence of multiple topological interface states in the BFBGs. The interface state within the subwavelength regime can be achieved with strong energy localization and is little affected by material damping, while for the interface state at high frequencies, it is shown that damping could considerably weaken the energy localization. This work provides guidelines for the design of low-frequency elastic topological systems. [ABSTRACT FROM AUTHOR]

The interface of Pt/TiO2 plays an essential role in device engineering and chemical reactions. Here, we report the electrostatic potential distribution of a Pt/TiO2 interface by electron holography. The decrease in the electrostatic potential exists at TiO2 in the vicinity of the interface, indicating the presence of negative charge due to electron transfer from TiO2 and Pt. The decrease in the electrostatic potential can be understood in the difference in work functions between Pt and TiO2. This study reveals the interplay between Pt and TiO2 and the usefulness of electron holography for probing the potential in nanoscale interfaces. [ABSTRACT FROM AUTHOR]

We grow AlN/4H-SiC and AlN/6H-SiC heterostructures by physical vapor deposition and characterize the heterointerface with micro-scale resolution. We investigate the spatial stress and strain distribution in these heterostructures using confocal Raman spectroscopy. We measure the spectral shifts of various vibrational Raman modes across the heterointerface and along the entire depth of the 4H- and 6H-SiC layers. Using the earlier experimental prediction for the phonon-deformation potential constants, we determine the stress tensor components in SiC as a function of the distance from the AlN/SiC heterointerface. Despite the fact that the lattice parameter of SiC is smaller than that of AlN, the SiC layers are compressively strained at the heterointerface. This counterintuitive behavior is explained by different coefficients of thermal expansion of SiC and AlN when the heterostructures are cooled from growth to room temperature. The compressive stress values are maximum at the heterointerface, approaching 1 GPa, and relax to the equilibrium value on the scale of several tens of micrometers from the heterointerface. [ABSTRACT FROM AUTHOR]

An in-depth understanding of the electrode–electrolyte interaction and electrochemical reactions at the electrode–solution interfaces in rechargeable batteries is essential to develop novel electrolytes and electrode materials with high performance. In this perspective, we highlight the advantages of the interface-specific sum-frequency generation (SFG) spectroscopy on the studies of the electrode–solution interface for the Li-ion and Li—O2 batteries. The SFG studies in probing solvent adsorption structures and solid-electrolyte interphase formation for the Li-ion battery are briefly reviewed. Recent progress on the SFG study of the oxygen reaction mechanisms and stability of the electrolyte in the Li—O2 battery is also discussed. Finally, we present the current perspective and future directions in the SFG studies on the electrode–electrolyte interfaces toward providing deeper insight into the mechanisms of discharging/charging and parasitic reactions in novel rechargeable battery systems. [ABSTRACT FROM AUTHOR]

Methylammonium lead iodide (CH3NH3PbI3) is one of the most attractive materials for optoelectronic applications, and it is the most typical absorber in perovskite solar cells, which are unprecedentedly successful devices in terms of power conversion efficiency. In this work, the conductivity and capacitance spectra of symmetrically contacted Au/CH3NH3PbI3/Au thick pellets are measured via impedance spectroscopy at different temperatures in dark equilibrium. The experimental conductivity spectra are parameterized and showed to follow the formalism of hopping DC conductivity in the CH3NH3PbI3 bulk. The presence of several regimes for the general Jonscher's "universal" conductivity-frequency response is highlighted and associated with the ionic-electronic overlapping conductivities. For the capacitance spectra, the general features of electrode polarization capacitance at the CH3NH3PbI3/Au interfaces are identified but yet are found to be in disagreement with some trends of classical ionic conductivity models, unable to separate different contributions. Accordingly, an analytical model is proposed accounting for hopping processes where the low frequency activation energy is split into ionic and electronic components. Our parameterizations and analytical model discern between the bulk/interface and ionic/electronic phenomena and estimate the multiple activation energies in this hybrid halide perovskite. [ABSTRACT FROM AUTHOR]

Methylammonium lead iodide (CH3NH3PbI3) is one of the most attractive materials for optoelectronic applications, and it is the most typical absorber in perovskite solar cells, which are unprecedentedly successful devices in terms of power conversion efficiency. In this work, the conductivity and capacitance spectra of symmetrically contacted Au/CH3NH3PbI3/Au thick pellets are measured via impedance spectroscopy at different temperatures in dark equilibrium. The experimental conductivity spectra are parameterized and showed to follow the formalism of hopping DC conductivity in the CH3NH3PbI3 bulk. The presence of several regimes for the general Jonscher's "universal" conductivity-frequency response is highlighted and associated with the ionic-electronic overlapping conductivities. For the capacitance spectra, the general features of electrode polarization capacitance at the CH3NH3PbI3/Au interfaces are identified but yet are found to be in disagreement with some trends of classical ionic conductivity models, unable to separate different contributions. Accordingly, an analytical model is proposed accounting for hopping processes where the low frequency activation energy is split into ionic and electronic components. Our parameterizations and analytical model discern between the bulk/interface and ionic/electronic phenomena and estimate the multiple activation energies in this hybrid halide perovskite. [ABSTRACT FROM AUTHOR]

Finding an optimal match between two different crystal structures underpins many important materials science problems, including describing solid-solid phase transitions and developing models for interface and grain boundary structures. In this work, we formulate the matching of crystals as an optimization problem where the goal is to find the alignment and the atom-to-atom map that minimize a given cost function such as the Euclidean distance between the atoms. We construct an algorithm that directly solves this problem for large finite portions of the crystals and retrieves the periodicity of the match subsequently. We demonstrate its capacity to describe transformation pathways between known polymorphs and to reproduce experimentally realized structures of semi-coherent interfaces. Additionally, from our findings, we define a rigorous metric for measuring distances between crystal structures that can be used to properly quantify their geometric (Euclidean) closeness. [ABSTRACT FROM AUTHOR]

The effect of interfacial fluorination on the structure, electronic properties, and performance of the HfO2/Al2O3 interface in charge-trapping memory (CTM) devices is investigated using the first-principles calculation. The impact of the interface states on the characteristics of traps in the HfO2 trapping layer at the HfO2/Al2O3 interface is studied first, and the results indicate that the interfacial states lead to performance degradation with respect to both reliability and the memory window of CTM devices during program/erase cycles. In the study of F passivation, F substitutions (FO) and F interstitials (Fi) tend to improve the thermal stability of the interface for higher interfacial F contents. Further, the FO-passivated interface is energetically more stable than the Fi-passivated interface. In addition, the FO-passivated interface can reduce the interface states that are partially (or completely) caused by breaking covalent interfacial bonds. Furthermore, a substantially improved HfO2/Al2O3 interface, with effective interfacial passivation in CTM devices, is obtained. Therefore, this study helps explain the intrinsic principle of interface passivation and opens new ways for performance improvement of the HfO2/Al2O3 interface in CTM devices. [ABSTRACT FROM AUTHOR]

The effects of interfacial In0.53Ga0.47As layers on Al2O3/GaAs0.51Sb0.49 metal-oxide-semiconductor (MOS) structures on InP substrates have systematically been studied. It is found that the interfacial InGaAs layers can reduce Dit values of the Al2O3/GaAsSb MOS interfaces down to 3–4 × 1011 cm−2 eV−1, which is almost one order of the magnitude lower than in the MOS interfaces without any InGaAs interfacial layers. It is also found that the InGaAs thickness of 1.0–1.5 nm is sufficient to reduce Dit to this low value. In order to obtain these results, the influence of an additional parasitic conductance and capacitance related to the GaAsSb/InP heterointerface needs to be considered, because the C-V characteristics of Al2O3/GaAs0.51Sb0.49/InP MOS capacitors in the accumulation region exhibit strong frequency dispersion, regardless of the InGaAs interfacial layer. We present through simulation of the C-V characteristics using a 2-dimensional device simulator that the correction of this series resistance and capacitance by using an equivalent circuit model can effectively eliminate the influence of the potential barrier at the GaAsSb/InP heterointerface from the experimental C-V ones, allowing us to employ the conventional conductance method for extracting interface trap density (Dit). [ABSTRACT FROM AUTHOR]

Graphite flake (GF)/Cu composites have received much attention as a promising thermal management material. This work provides a homogenization method to examine the effect of interfacial characteristics on the thermal conductivity of GFs/Cu composite. The finite element homogenization method is used to establish models of representative volume elements of material microstructure and interfacial layers, respectively, considering the distribution morphology and thermophysical properties of interface compositions. The interfacial layers are considered equivalent heat conduction materials, including interface compositions, pores, and Kapitza thermal resistances between compositions. The results of the thermal conductivity obtained by the approach were compared with the experimental results in the literature, and it shows good agreement. The results have indicated that the thermal conductivity of GFs/Cu composites is strongly affected by graphite sizes, graphite volume contents, interface contents, pore shapes, the relative density of interfacial layers, and whether the interface component is continuous has a significant influence. [ABSTRACT FROM AUTHOR]

An interface crack in 1D piezoelectric quasicrystalline space is considered. Both conducting and mixed conducting-permeable electric conditions at the crack faces are studied. The matrix–vector representations of the phonon, phason and electric quantities via the sectional-holomorphic function are derived. Two types of electrical conditions at the crack faces are considered – conducting case and mixed conducting-permeable case. A Riemann problem of linear relationship and a combined Dirichlet–Riemann boundary value problem are derived. Exact analytical solutions of the mentioned problems are presented and the simple analytical formulas for all required values are given and numerically illustrated. [ABSTRACT FROM AUTHOR]

The high theoretical specific energy of lithium/sulfur (Li/S) cells (2600 Wh/kg) has positioned the Li/S cell as one of the most promising candidates for the beyond lithium‐ion cell. Despite the evident advantages, there are remaining problems mainly associated with the unique solution‐based reaction chemistry involving lithium polysulfide (Li‐PS) that hinder the commercialization of the Li/S cells. Incorporating solid‐state electrolytes (SSEs) can avoid the Li‐PS shuttle problem while preserving the benefits of Li/S cells, but it introduces other challenges related to the electrode/electrolyte solid interfaces. This topical review summarizes the current status of solid‐state Li/S cells and their major challenges and discusses the recent efforts to improve cell performance and durability. Various solid‐state electrolytes, including oxides, sulfides, and solid polymer electrolytes, are briefly reviewed. In particular, we focus on the recent progress to improve the interfacial properties by two major approaches, morphological and chemical modifications of the electrode/electrolyte interfaces. The design strategy and implementation to overcome the prominent issues associated with sulfur electrodes are critically discussed. Also, several electrochemical and physicochemical characterization methods to examine the electron/ion transport at the interface are outlined. Given the superior theoretical physicochemical properties of the Li/S cells, we emphasize that the inappropriate interfacial design of the solid‐state Li/S cells is the major challenge to bring solid‐state Li/S cells to a commercially attractive level. [ABSTRACT FROM AUTHOR]

We analyse features of the patterns formed from a simple model for a martensitic phase transition that fragments the unit square into rectangles. This is a fragmentation model that can be encoded by a general branching random walk. An important quantity is the distribution of the lengths of the interfaces in the pattern, and we establish limit theorems for some of the asymptotics of the interface profile. In particular, we are able to use a general branching process to show almost sure power law decay of the number of interfaces of at least a certain size and a general branching random walk to examine the numbers of rectangles of a certain aspect ratio. In doing so we extend a theorem on the growth of the general branching random walk as well as developing results on the tail behaviour of the limiting random variable in our general branching process. [ABSTRACT FROM AUTHOR]

In this study, we used molecular dynamics (MD) simulations to investigate the atomic ordering in the liquid aluminum (Al) adjacent to the amorphous substrate with smooth and rough surfaces. This study revealed that the liquid exhibited layering within about 5 atomic layers but no visible in-plane atomic ordering at the interface with the smooth amorphous surface, and neither layering nor in-plane atomic ordering with the rough surface of the amorphous substrate. However, the smooth amorphous surface induced some local ordered structure in the liquid at the interface by a structural templating mechanism, which promoted heterogeneous nucleation by creating a 2-dimensional (2D) nucleus in the third layer. The amorphous substrate with a rough surface had no effect on the nucleation in the liquid, leading to the occurrence of homogeneous nucleation with an undercooling 100 K larger than that of heterogeneous nucleation on the smooth amorphous substrate. This study confirmed that structural templating is a general mechanism for heterogeneous nucleation. [ABSTRACT FROM AUTHOR]

We theoretically study the valley aspect of lateral tunneling transport in valleytronic materials, using AB-stacked (Bernal-stacked) bilayer graphene as a material example. A lateral structure with multiple well/barrier interfaces is considered. A full-zone tight-binding method is employed, allowing for the study of intervalley mixing in electron states. We study the degree of tunneling current valley contrast under the condition of a source-drain bias or barrier asymmetry. For a single-barrier structure, it is found that the intervalley mixing is negligible, and the contrast is positively correlated with the barrier width and height. For a double-barrier structure, the effect of resonant tunneling is investigated. The intervalley mixing is shown to be significantly enhanced at resonant tunneling. In addition, the resonant levels are found valley split, and a proposal is given which exploits the splitting for the generation of a sizable tunneling current valley polarization. Based on a simple model using momentum-shifted thermal distribution for obliquely incident electrons, the temperature dependence of tunneling current valley polarization is also examined. An interesting crossover from the valley-orbit interaction-dominant polarization to the warping-dominant polarization is found to occur as the temperature is increased. [ABSTRACT FROM AUTHOR]

We propose a novel heterostructure system consisting of compounds with chemical formula A 2 Mo 3 O 8 (A, B: Zn, Mg, Cd) that can host a two-dimensional electron/hole gas (2DEG/2DHG). The formation of a 2DEG/2DHG in these heterostructures, which have a low interfacial strain, is driven by a polarization discontinuity at the interface. The sheet carrier densities and charge localization in these heterostructures are comparable to other well-known heterostructures that host 2DEG opening up the possibility of a wide variety of applications. [ABSTRACT FROM AUTHOR]

The influence of growth rate and substrate temperature on the two-dimensional electron gas (2DEG) of LaVO 3 / SrTiO 3 interfaces has been investigated. It is found that both growth rate and substrate temperature can modulate the structural and electrical properties of the LaVO 3 / SrTiO 3 interfaces through oxygen substrate-to-film transfer. When the LaVO 3 thin films are deposited at a low substrate temperature and a high growth rate, the LaVO 3 / SrTiO 3 interfaces exhibit weak oxygen substrate-to-film transfer and resultant low density of oxygen vacancies in the SrTiO 3 substrate. As a result, the intrinsic effect (polar discontinuity and/or dielectric screening) dominates the interfacial conduction, while the oxygen vacancies play a minor role. In contrast, the oxygen substrate-to-film transfer (oxygen vacancies in the SrTiO 3 substrate) can be enhanced (increased) by depositing the LaVO 3 thin films at lower growth rates and/or higher substrate temperatures. In this case, the contribution of oxygen vacancies to the interfacial conduction would prevail over the intrinsic effect. Our results elucidate the origins of 2DEG in the LaVO 3 / SrTiO 3 interfaces and may also be important for other SrTiO 3 -based heterointerfaces. [ABSTRACT FROM AUTHOR]

The introduction of a two-dimensional oxide layer at the interface between an organic semiconductor and a ferromagnetic metal (spinterface) can help in tailoring the formation of spin-polarized hybridized interface states. Here, we consider the case of a Cr 4 O 5 monolayer at the C 60 / Fe (001) interface, which is already known to feature the occurrence of spin-polarized states in the fullerene molecules. In this work, we employ scanning tunneling microscopy/spectroscopy and photoemission spectroscopy to show that the C 60 / Cr 4 O 5 / Fe (001) spinterface is characterized by the formation of a well-ordered fullerene monolayer and of strongly hybridized interface states. These experimental results are discussed in terms of state-of-the-art ab initio calculations of the structural, electronic, and magnetic properties at the interface. [ABSTRACT FROM AUTHOR]

Magnetic properties arising at interfaces of perovskite oxides such as La0.7Sr0.3CoO3 (LSCO) and La0.7Sr0.3MnO3 (LSMO) depend sensitively on the fine details of their structural properties. In this work, we use high-resolution transmission electron microscopy and spectroscopy to examine the structural and electronic phenomena at the interfaces in two LSCO/LSMO bilayers with reversed growth order. Two different strain mechanisms are at work in these films: compressive or tensile epitaxial strain, and distortion of the octahedral tilt pattern to maintain a network of corner-sharing octahedra. While the epitaxial strain is constant regardless of the growth order, the modification of the octahedral tilt pattern depends on whether the film is grown directly on the substrate or as the second sublayer. As a consequence, exchange spring behavior is observed only when the LSCO sublayer is grown first. The different mechanisms of strain accommodation within the oxygen octahedra network in each material proved to be of critical importance in determining the interfacial structure and thus magnetic and electronic properties of the bilayers. [ABSTRACT FROM AUTHOR]

Strain engineering is the art of inducing controlled lattice distortions in a material to modify specific physicochemical properties. Strain engineering is applied not only for basic fundamental studies of physics and chemistry of solids but also for device fabrication through the development of materials with new functionalities. Thin films are one of the most important tools for strain engineering. Thin films can in fact develop large strain due to the crystalline constraints at the interface with the substrate and/or as a result of specific morphological features that can be selected by an appropriate tuning of the deposition parameters. Within this context, the in situ measurement of the substrate curvature is a powerful diagnostic tool allowing real time monitoring of the stress state of the growing film. This paper reviews a few recent applications of this technique and presents new measurements that point out the great potentials of the substrate curvature measurement in strain engineering. Our study also shows how, due to the high sensitivity of the technique, the correct interpretation of the results can be in certain cases not trivial and require complementary characterizations and an accurate knowledge of the physicochemical properties of the materials under investigation. [ABSTRACT FROM AUTHOR]

While current descriptions of thermal transport exist for well-ordered solids, i.e., crystal lattices, new methods are needed to describe thermal transport in systems with lack of symmetry such as structurally/compositionally disordered solids and interfaces. In this tutorial, we discuss the formalism, implementation, and application of two recently developed methods, Green-Kubo modal analysis and interface conductance modal analysis, to predict the thermal conductivity and thermal interface conductance, respectively. Specifically, these methods enable the prediction of phonon contributions to transport in crystalline materials with any level of defects, up through fully amorphous solids, dilute to fully random alloys, molecules, nanostructures, and across interfaces involving any of these material classes—all within a single and unified perspective. This tutorial article not only describes the methods, but also provides example codes that can be used for their direct implementation. The design and functionality of the codes is also discussed in order to reduce the barrier to more extensive utilization of these approaches by others. [ABSTRACT FROM AUTHOR]

First-principles molecular dynamics simulations of the stability of the NaCl-type (B1) SiC and SiN interfaces in TiX/one multilayer SiY (X,Y=C,N) heterostructures were carried out as functions of temperature. It was previously shown that the SiX interfaces in the heterostructures based on transition metal compounds could be dynamically unstable owing to the elongated interfacial Si-X bonds compared to the Si-X bonds in the B1-SiX phases in equilibrium. However, this criterion is not satisfied for some SiX(111) interfaces. The aim of this work is to study the temperature-induced changes in the structure of the heterostructures under consideration and to clarify a possible origin of instability of the interfaces in them. It is shown that, at finite temperatures, the interfacial layer in the TiN(001)/SiC heterostructure transforms into the zinc blende-type (B3) SiC-like layer, whereas the interfaces in other (001) heterostructures transform into amorphous-like interfacial layers. The TiC(111)/SiC and TiN(111)/SiN heterostructures are stable up to 1400 K. The TiN(111)/B3-like SiC and TiC(111)/B3-like SiN systems form during static relaxation of the initial heterostructures. The phase transformations of the interfaces are explained in terms of dynamical and elastic stability criteria. In contrast to the (111) interfacial layers, all the B1-(001) interfaces are found to be dynamically unstable. The formation of the B3-(111) interfaces occurs due to the elastic instability of the corresponding B1-(111) interface. [ABSTRACT FROM AUTHOR]

Competing fracture in the transfer of thin films from a relatively rigid host substrate to a flexible polymer substrate is studied using finite element simulations with cohesive zone models. Cohesive zone models for delamination based on traction-separation relations with a maximum stress criterion for damage initiation and mode-independent fracture energy for complete separation are explored to identify important parameters that affect transfer printing. Successful transfer of a thin film to a relatively compliant polymer substrate from a stiffer substrate depends on relative crack lengths, interface strengths, and fracture energies. Interface selection occurs where the mode-mix at the crack tip is predominantly due to normal stresses, despite the interface toughness being mode-independent. The observations and the fracture maps developed here predict the interface selection directly with material properties of the interfaces, substrates, and films. [ABSTRACT FROM AUTHOR]

While the electrostatic potential and the counterion distribution produced by interfaces with idealized geometries can be well-described by analytical models, the same does not hold true for the interaction between surfaces with different and arbitrary geometries. Besides, the geometry of a charged interface may also affect the counterion adsorption, potentially modulating the electrostatic potential and the solvent organization close to the interfaces, demanding molecular details to be taken into account. The complex electrostatics of a sodium dodecyl sulfate micelle in the presence of monolayers of the same surfactant at the water-vapor interface was assessed by a set of molecular dynamics simulations. The electrostatic potential was evaluated numerically, and its total magnitude was decomposed into contributions arising from each species comprising the system. The counterion adsorption was stronger at the flat interfaces due to the more favorable formation of sodium bridges, where the same counterion is bounded to two or more anionic heads, while water reorientation was more pronounced near the micelle. These opposing effects counteracted each other so that the overall electrostatic potential changes were similar for both interfaces. The increase in the counterion concentration between the micelle and the interface originates a double layer mediated repulsion amounting to a free energy barrier of at least 14 kJ/mol, preventing the micelle to get closer to the monolayers. It is noteworthy that the hydrophobic regions had electrostatic potential contributions as large as those arising from the hydrophilic regions, mostly due to the orderly orientation of the terminal methyl groups. [ABSTRACT FROM AUTHOR]

Widely employed Near-Edge X-Ray Absorption Fine Structure (NEXAFS) spectroscopy probes a system by excitation of core electrons to unoccupied states. A variety of different methodologies are available to simulate corresponding spectra from first-principles. Core-level occupation constraints within ground-state Density-Functional Theory represent a numerically most efficient means to this end that provides access to large systems, examples being surface adsorption, proteins, polymers, liquids, and buried, condensed phase interfaces (e.g., solid-liquid and solid-solid). Here, we systematically investigate the performance of different realizations of this approximate approach through the simulation of K-edge NEXAFS-spectra of a set of carbon and nitrogen-containing organic molecules. Variational collapse to the ground state and oscillatory convergence are the major complications of these approximate computational protocols. We present a modified version of the maximum-overlap method to achieve a self-consistent inclusion of electrons in virtual states for systems where convergence is hampered due to degeneracies. Our results demonstrate that reliable spectra allowing for a semi-quantitative analysis of experimental data are already obtained at the semi-local level of density functionals and with standard numeric atomic orbital basis sets. [ABSTRACT FROM AUTHOR]

Ultrafast hydrogen-bond fluctuation dynamics of water at charged monolayer interfaces were studied by the use of steady-state and 2D heterodyne-detected vibrational sum frequency generation (HD-VSFG) spectroscopy. Specifically, the effect of hydrogen-bond ability of the interface on the dynamics was investigated by comparing two monolayer interfaces that provide different hydrogen bond abilities: hydrogen bonding octadecylammonium (ODA) monolayer (pH = 2) and non-hydrogen bonding 1,2-dipalmitoyl-3-trimethyl-ammonium propane (DPTAP) monolayer. The steady-state HD-VSFG spectra and their ionic strength dependence revealed that water molecules at both of ODA and DPTAP interfaces are H-down oriented, pointing their H away from the interface, and that the contributions of the electrical double layer in the interfacial spectra of these interfaces are comparable to each other. However, 2D HD-VSFG data clearly indicated that the ultrafast hydrogen-bond fluctuation of water at the ODA interface is significantly suppressed, compared to that at the DPTAP interfaces. The obtained results suggest that the hydrogen-bond fluctuation of the topmost interfacial water at a positively charged interface is significantly affected by the hydrogen-bonding ability of the interface even in the case that the interfacial water molecules act as a hydrogen-bond acceptor to the head group of the monolayer. [ABSTRACT FROM AUTHOR]

The assembling of metal phthalocyanines on the rippled moiré superlattice of graphene/Ir(111) intercalated with one Co layer is driven by the site-dependent polarization field induced by the incommensurate graphene-Co interface. We have performed an X-ray absorption and photoemission study to unveil the role of the metallic centers and of the organic ligands in the molecule-Co interaction process mediated by graphene. Notably, we consider different electronic molecular orbitals, i.e. phthalocyanines with Cu and Mn metallic ions. The spectroscopic response suggests almost unaltered CuPc molecular states upon adsorption, and the rippled graphene carpet decouples completely the electronic interaction between the molecules and the Co layer, while a slight hybridization is present for MnPcs. MnPc molecules, trapped in the valleys of the moiré graphene superlattice, slightly intermix, through the orbitals protruding out of the molecular plane, with the underlying Co, while the organic ligands are almost unaltered. Graphene acts as an interlayer and mediates the interaction between metal phthalocyanines and the metallic substrate, preventing a strong chemical intermixing and enabling the assembly of almost unaltered molecules, preserving their electronic/magnetic state. [ABSTRACT FROM AUTHOR]

Phoretic particles self-propel using self-generated physico-chemical gradients at their surface. Within a suspension, they interact hydrodynamically by setting the fluid around them into motion and chemically by modifying the chemical background seen by their neighbours. While most phoretic systems evolve in confined environments due to buoyancy effects, most models focus on their interactions in unbounded flows. Here, we propose a first model for the interaction of phoretic particles in Hele-Shaw confinement and show that in this limit, hydrodynamic and phoretic interactions share not only the same scaling but also the same form, albeit in opposite directions. In essence, we show that phoretic interactions effectively reverse the sign of the interactions that would be obtained for swimmers interacting purely hydrodynamically. Yet, hydrodynamic interactions cannot be neglected as they significantly impact the magnitude of the interactions. This model is then used to analyse the behavior of a suspension. The suspension exhibits swirling and clustering collective modes dictated by the orientational interactions between particles, similar to hydrodynamic swimmers, but here governed by the surface properties of the phoretic particle; the reversal in the sign of the interaction tends to slow down the swimming motion of the particles. [ABSTRACT FROM AUTHOR]

Classical molecular dynamics simulations at the interfaces of two (meth)acrylate polymers, poly(2-methoxyethylacrylate) (PMEA) and poly(methyl methacrylate) (PMMA), upon contact with water are performed to elucidate interfacial molecular structures from the interface-specific nonlinear spectroscopic point of view. PMEA has methoxy oxygen in the side chain, while PMMA does not have it, and its impacts on the interfacial structure are particularly focused on. The force fields of PMEA and PMMA used in the classical simulation are modeled so as to reproduce the radial distribution functions and the vibrational density of states calculated by ab initio molecular dynamics simulations, where a stronger hydrogen-bonding interaction between water and methoxy oxygen of PMEA than the conventional molecular modeling predicts is found. The imaginary part of the second order nonlinear susceptibility is theoretically calculated for these two interfaces, showing a definite difference between them. The origin of the spectral difference is discussed on the basis of the decomposition analysis of the spectra and the interfacial molecular structures. [ABSTRACT FROM AUTHOR]

We formulate a new theory for how caging constraints in glass-forming liquids at a surface or interface are modified and then spatially transferred, in a layer-by-layer bootstrapped manner, into the film interior in the context of the dynamic free energy concept of the Nonlinear Langevin Equation (NLE) theory approach. The dynamic free energy at any mean location (cage center) involves contributions from two adjacent layers where confining forces are not the same. At the most fundamental level of the theory, the caging component of the dynamic free energy varies essentially exponentially with distance from the interface, saturating deep enough into the film with a correlation length of modest size and weak sensitivity to the thermodynamic state. This imparts a roughly exponential spatial variation of all the key features of the dynamic free energy required to compute gradients of dynamical quantities including the localization length, jump distance, cage barrier, collective elastic barrier, and alpha relaxation time. The spatial gradients are entirely of dynamical, not structural or thermodynamic, origin. The theory is implemented for the hard sphere fluid and diverse interfaces which can be a vapor, a rough pinned particle solid, a vibrating (softened) pinned particle solid, or a smooth hard wall. Their basic description at the level of the spatially heterogeneous dynamic free energy is identical, with the crucial difference arising from the first layer where dynamical constraints can be weakened, softened, or hardly changed depending on the specific interface. Numerical calculations establish the spatial dependence and fluid volume fraction sensitivity of the key dynamical property gradients for five different model interfaces. A comparison of the theoretical predictions for the dynamic localization length and glassy modulus with simulations and experiments for systems with a vapor interface reveals good agreement. The present advance sets the stage for using the Elastically Collective NLE theory to make quantitative predictions for the alpha relaxation time gradient, decoupling phenomena, Tg gradient, and many film-averaged properties of both model and experimental (colloids, molecules, and polymers) systems with diverse interfaces and chemical makeup. [ABSTRACT FROM AUTHOR]

Markov state models (MSMs) are quantitative models of protein dynamics that are useful for uncovering the structural fluctuations that proteins undergo, as well as the mechanisms of these conformational changes. Given the enormity of conformational space, there has been ongoing interest in identifying a small number of states that capture the essential features of a protein. Generally, this is achieved by making assumptions about the properties of relevant features—for example, that the most important features are those that change slowly. An alternative strategy is to keep as many degrees of freedom as possible and subsequently learn from the model which of the features are most important. In these larger models, however, traditional approaches quickly become computationally intractable. In this paper, we present enspara, a library for working with MSMs that provides several novel algorithms and specialized data structures that dramatically improve the scalability of traditional MSM methods. This includes ragged arrays for minimizing memory requirements, message passing interface-parallelized implementations of compute-intensive operations, and a flexible framework for model construction and analysis. [ABSTRACT FROM AUTHOR]

We discuss grand canonical simulations based on density-functional theory to study the thermodynamic properties of electrochemical interfaces of metallic electrodes in aqueous environments. Water is represented using implicit solvation, here via the self-consistent continuum solvation (SCCS) model, providing a charge-density dependent dielectric boundary. The electrochemical double layer is accounted for in terms of a phenomenological continuum description. It is shown that the experimental potentials of zero charge and interfacial capacitances can be reproduced for an optimized SCCS parameter set [ρmin = 0.0013, ρmax = 0.010 25]. By performing a detailed derivation and analysis of the interface energetics for selected electrochemical systems, we are able to relate the widely used approach of the computational hydrogen electrode (CHE) to a general grand canonical description of electrified interfaces. In particular, charge-neutral CHE results are shown to be an upper-boundary estimate for the grand canonical interfacial free energies. In order to demonstrate the differences between the CHE and full grand canonical calculations, we study the pristine (100), (110), and (111) surfaces for Pt, Au, Cu, and Ag, and H or Cl electrosorbed on Pt. The calculations support the known surface reconstructions in the aqueous solution for Pt and Au. Furthermore, the predicted potential-pH dependence of proton coverage, surface charge, and interfacial pseudocapacitance for Pt is found to be in close agreement with experimental or other theoretical data as well as the predicted equilibrium shapes for Pt nanoparticles. Finally, Cl is found to interact more strongly than H with the interfacial fields, leading to significantly altered interface energetics and structure upon explicit application of an electrode potential. This work underscores the strengths and eventual limits of the CHE approach and might guide further understanding of the thermodynamics of electrified interfaces. [ABSTRACT FROM AUTHOR]

We present a local free-energy functional-based generic continuum model for material interfaces with a specific emphasis on electrified solid/liquid interfaces. The model enables a description of multicomponent phases at interfaces and includes the effects of specific non-electrostatic interactions (specific adsorption), ion size disparity, and the explicit presence of neutral species. In addition to the optimization of electrostatic, non-electrostatic, and steric forces, the model can be easily modified to explore the effects of other channels for equilibration, including local chemical transformations driven by equilibrium constants and electrochemical reactions driven by the electrode potential. In this way, we show that, upon accounting for these effects, local speciation in the vicinity of the interface can be drastically different from what is expected from restricted models and minor species (from the bulk perspective) may become dominant due to the effects of local pH. We evaluate the ionic contribution to the surface tension at the interface and show how this could impact the structure of air/liquid interfaces. On the same footing, an attempt to describe electrochemical metal dissolution is made. The model allows estimates of the mutual population of newly produced ions depending on their charge and size and could be useful for interpretation of electrochemical and spectroscopic measurements if the dissolution involves different metal ions (species). With these advances, the proposed model may be used as an ingredient within a hybrid ab initio-continuum methodology to model biased interfaces. [ABSTRACT FROM AUTHOR]

Temperature dependent kinetics for back-electron transfer (BET) from electrons in TiO2 or SnO2/TiO2 core/shell nanoparticles to oxidized donor-bridge-acceptor (D-B-A) sensitizers is reported over a 110° range. Two D-B-A sensitizers (CF3-p and CF3-x) were utilized that differed only by the nature of the bridging ligand: a xylyl spacer that largely insulated the two redox active centers and a phenyl bridge that promoted strong electronic coupling and an adiabatic electron transfer mechanism. An Arrhenius analysis revealed that the activation energies were significantly larger for the core/shell oxides, Ea = 32 ± 4 kJ/mol, compared to TiO2 alone, Ea = 22 ± 6 kJ/mol. The barriers for BET on sensitized TiO2 were within the same range as previous literature reports, while this study represents the first quantification for SnO2/TiO2 core/shell materials. Two different models were proposed to rationalize the larger barrier for the core/shell materials: (1) a band edge offset model and (2) a low energy trap state model with recombination from the TiO2 rutile polymorph shell. The latter model was preferred and is in better agreement with the experimental data. The kinetic analysis also afforded the forward and reverse rate constants for the intramolecular equilibrium. In accordance with theoretical predictions and previous research, the absolute value of the free energy change was smaller for the adiabatic equilibrium provided by the phenyl bridge, i.e., | ΔGoad | < | ΔGo |. [ABSTRACT FROM AUTHOR]

Continuum electrolyte models represent a practical tool to account for the presence of the diffuse layer at electrochemical interfaces. However, despite the increasing popularity of these in the field of materials science, it remains unclear which features are necessary in order to accurately describe interface-related observables such as the differential capacitance (DC) of metal electrode surfaces. We present here a critical comparison of continuum diffuse-layer models that can be coupled to an atomistic first-principles description of the charged metal surface in order to account for the electrolyte screening at electrified interfaces. By comparing computed DC values for the prototypical Ag(100) surface in an aqueous solution to experimental data, we validate the accuracy of the models considered. Results suggest that a size-modified Poisson-Boltzmann description of the electrolyte solution is sufficient to qualitatively reproduce the main experimental trends. Our findings also highlight the large effect that the dielectric cavity parameterization has on the computed DC values. [ABSTRACT FROM AUTHOR]

Infrared spectroscopy is a widely employed analytical tool in (electrochemical) surface science as the spectra contain a wealth of information about the interaction of interfacial adsorbates with their environment. Separating and quantifying individual contributions, for example, of co-adsorbates, the substrate or electric field effects, on the overall spectral response, however, is often non-trivial as the various interactions manifest themselves in similar spectral behavior. Here, we present an experimental approach to differentiate between and quantify potential-induced coverage dependence and field-related Stark effects observed in a sulfate band shift of 93.5 ± 1.5 cm−1/V in electrochemical infrared spectra of the showcase sulfate/Au(111) interface. In combination with a simple linear model equation used to describe the potential-induced peak shift of the sulfate stretch vibration, we determine the coverage dependence contribution to be 15.6 ± 1.2 cm−1/θSO and the Stark effect to amount to 75.6 ± 2.7 cm−1/V. Our work provides a novel route to gain fundamental insight into interfacial adsorbate interactions in electrochemical surface science. [ABSTRACT FROM AUTHOR]

Tasker type III polar terminations of ionic crystals carry a net surface charge as well as a dipole moment and are fundamentally unstable. In contact with electrolytes, such polar surfaces can be stabilized by adsorption of counterions from the solution to form electric double layers. In a previous work [T. Sayer et al., J. Chem. Phys 147, 104702 (2017)], we reported on a classical force field based molecular dynamics study of a prototype model system, namely, a NaCl(111) slab interfaced with an aqueous NaCl solution on both sides. A serious hurdle in the simulation is that the finite width of the slab admits an electric field in the solid perturbing the theoretical charge balance at the interface of semi-infinite systems [half the surface charge density for NaCl(111)]. It was demonstrated that the application of a finite macroscopic field E canceling the internal electric field can recover the correct charge compensation at the interface. In the present work, we expand this method by applying a conjugate electric displacement field D. The benefits of using D instead of E as the control variable are two fold: it does not only speed up the convergence of the polarization in the simulation but also leads to a succinct expression for the biasing displacement field involving only structural parameters which are known in advance. This makes it feasible to study the charge compensating phenomenon of this prototype system with density functional theory based molecular dynamics, as shown in this work. [ABSTRACT FROM AUTHOR]

The lifetime, coupling, and localization dynamics of electronic states in molecular films near metal electrodes fundamentally determine their propensity to act as precursors or reactants in chemical reactions, crucial for a detailed understanding of charge transport and degradation mechanisms in batteries. In the current study, we investigate the formation dynamics of small polarons and their role as intermediate electronic states in thin films of dimethyl sulfoxide (DMSO) on Cu(111) using time- and angle-resolved two-photon photoemission spectroscopy. Upon photoexcitation, a delocalized DMSO electronic state is initially populated two monolayers from the Cu surface, becoming a small polaron on a 200 fs time scale, consistent with localization due to vibrational dynamics of the DMSO film. The small polaron is a precursor state for an extremely long-lived and weakly coupled multilayer electronic state, with a lifetime of several seconds, thirteen orders of magnitude longer than the small polaron. Although the small polaron in DMSO has a lifetime of 140 fs, its role as a precursor state for long-lived electronic states could make it an important intermediate in multistep battery reactivity. [ABSTRACT FROM AUTHOR]

High Resolution Transmission Electron Microscopy (HR TEM) is used to identify the size, shape, and interface structure of platinum nanoparticles and carbon support of a fuel cell catalyst. Using these insights, models accessible to quantum chemical methods are designed in order to rationalize the observed features. Thus, basal plane and prism face models of the carbon black material are considered, interacting with Pt clusters of sizes up to 1 nm. Particular attention is paid to the electronic structure of the carbon support, namely, the radical character of graphene zig-zag edges. The results show that a stronger interaction is found when the nanoparticle is at the zig-zag edge of a basal plane due to the combination of dispersion interaction with the support structure and covalent interaction with carbon atoms at the edge. In this case, a distortion of both the Pt nanoparticle and the carbon support is observed, which corresponds to the observations from the HR TEM investigation. Furthermore, the analysis of the charge transfer upon interaction and the influence of the potential on the charge states and structure is carried out on our model systems. In all cases, a clear charge transfer is observed from the carbon support to the Pt nanoparticle. Finally, we show that changing the potential not only can change the charge state of the system but can also affect the nature of the interaction between Pt nanoparticles and carbon supports. [ABSTRACT FROM AUTHOR]

Using first principles molecular dynamics simulations, we probe the electrochemical double layer formed at the interface between the hematite surface and water. We consider two terminations of the (001) surface, viz., the fully hydroxylated (OH) and the stoichiometric (FeO3Fe) termination. We explicitly incorporate the counterions (Na+ and F−) in the solution, and model both specific and nonspecific adsorption of F− ions. We find that F− ions prefer to bind directly to the Fe ions (specific adsorption), with a substantial energy gain (0.75 eV/ion). We investigate the effect of the interface and the counterions on the dipole of individual water molecules. We find significant deviations of +0.2/−0.15 D for dipoles of the first solvation shell water molecules of F−/Na+ ions, respectively. Additionally, the hydration layers at the interface show an enhancement in the dipole moment resulting from stronger hydrogen bonding interactions between the water molecules and surface charged species. Furthermore, we analyze the electrostatic potential profile at the solid/liquid interface as a function of the kind of counterion present in the double layer and compute the capacitance of the compact (Helmholtz) layer. We find that our results (40.3 ± 3.5 μF/cm2 for the OH termination and 51 ± 5 μF/cm2 for the FeO3Fe termination) compare favorably with values reported by potentiometric titration based experimental studies (10–100 μF/cm2). [ABSTRACT FROM AUTHOR]

Interfacial electrochemistry and photo(electro)catalysis are key processes that convert the energy of photons or electrons to chemical bonds in many energy conversion and storage technologies. Achieving a molecular level understanding of the fundamental interfacial structure, energetics, dynamics, and reaction mechanisms that govern these processes represents a broad frontier for chemical physics and physical chemistry. This Special Topic contains a collection of articles that range from the development of new experimental and computational techniques to the novel application of those techniques for mechanistic studies, as the principal investigators seek a fundamental molecular understanding of both electrode/electrolyte interfaces and the relevant electrocatalytic, photocatalytic, and photoelectrochemical reactions taking place thereabout. Altogether, this collection of articles captures the current state of this very active, frontier research field and highlights the current and remaining key scientific challenges and opportunities. [ABSTRACT FROM AUTHOR]