The C1s core levels of polycyclic aromatic hydrocarbons and styrenic polymers: A first-principles study.

Understanding core level shifts in aromatic compounds is crucial for the correct interpretation of x-ray photoelectron spectroscopy (XPS) of polycyclic aromatic hydrocarbons (PAHs), including acenes, as well as of styrenic polymers, which are increasingly relevant for the microelectronic industry, among other applications. The effect of delocalization through π aromatic systems on the stabilization of valence molecular orbitals has been widely investigated in the past. However, little has been reported on the impact on the deeper C1s core energy levels. In this work, we use first-principles calculations at the level of many body perturbation theory to compute the C1s binding energies of several aromatic systems. We report a C1s red shift in PAHs and acenes of increasing size, both in the gas phase and in the molecular crystal. C1s red shifts are also calculated for stacked benzene and naphthalene pairs at decreasing intermolecular distances. A C1s red shift is in addition found between oligomers of poly(p-hydroxystyrene) and polystyrene of increasing length, which we attribute to ring-ring interactions between the side-chains. The predicted shifts are larger than common instrumental errors and could, therefore, be detected in XPS experiments.

Peak Broadening in Photoelectron Spectroscopy of Amorphous Polymers: The Leading Role of the Electrostatic Landscape.

The broadening in photoelectron spectra of polymers can be attributed to several factors, such as light source spread, spectrometer resolution, the finite lifetime of the hole state, and solid-state effects. Here, for the first time, we set up a computational protocol to assess the peak broadening induced for both core and valence levels by solid-state effects in four amorphous polymers by using a combination of density functional theory, many-body perturbation theory, and classical polarizable embedding. We show that intrinsic local inhomogeneities in the electrostatic environment induce a Gaussian broadening of 0.2-0.7 eV in the binding energies of both core and semivalence electrons, corresponding to a full width at half-maximum (FWHM) of 0.5-1.7 eV for the investigated systems. The induced broadening is larger in acrylate-based than in styrene-based polymers, revealing the crucial role of polar groups in controlling the roughness of the electrostatic landscape in the solid matrix.

Chalcogenide Ovonic Threshold Switching Selector.

Today's explosion of data urgently requires memory technologies capable of storing large volumes of data in shorter time frames, a feat unattainable with Flash or DRAM. Intel Optane, commonly referred to as three-dimensional phase change memory, stands out as one of the most promising candidates. The Optane with cross-point architecture is constructed through layering a storage element and a selector known as the ovonic threshold switch (OTS). The OTS device, which employs chalcogenide film, has thereby gathered increased attention in recent years. In this paper, we begin by providing a brief introduction to the discovery process of the OTS phenomenon. Subsequently, we summarize the key electrical parameters of OTS devices and delve into recent explorations of OTS materials, which are categorized as Se-based, Te-based, and S-based material systems. Furthermore, we discuss various models for the OTS switching mechanism, including field-induced nucleation model, as well as several carrier injection models. Additionally, we review the progress and innovations in OTS mechanism research. Finally, we highlight the successful application of OTS devices in three-dimensional high-density memory and offer insights into their promising performance and extensive prospects in emerging applications, such as self-selecting memory and neuromorphic computing.

Dilute Rhenium Doping and its Impact on Defects in MoS2.

Substitutionally doped 2D transition metal dichalcogenides are primed for next-generation device applications such as field effect transistors (FET), sensors, and optoelectronic circuits. In this work, we demonstrate substitutional rhenium (Re) doping of MoS2 monolayers with controllable concentrations down to 500 ppm by metal-organic chemical vapor deposition (MOCVD). Surprisingly, we discover that even trace amounts of Re lead to a reduction in sulfur site defect density by 5-10×. Ab initio models indicate the origin of the reduction is an increase in the free-energy of sulfur-vacancy formation at the MoS2 growth-front when Re is introduced. Defect photoluminescence (PL) commonly seen in undoped MOCVD MoS2 is suppressed by 6× at 0.05 atomic percent (at. %) Re and completely quenched with 1 at. % Re. Furthermore, we find that Re-MoS2 transistors exhibit a 2× increase in drain current and carrier mobility compared to undoped MoS2, indicating that sulfur vacancy reduction improves carrier transport in the Re-MoS2. This work provides important insights on how dopants affect 2D semiconductor growth dynamics, which can lead to improved crystal quality and device performance.

Benchmarking First-Principles Reaction Equilibrium Composition Prediction.

The availability of thermochemical properties allows for the prediction of the equilibrium compositions of chemical reactions. The accurate prediction of these can be crucial for the design of new chemical synthesis routes. However, for new processes, these data are generally not completely available. A solution is the use of thermochemistry calculated from first-principles methods such as Density Functional Theory (DFT). Before this can be used reliably, it needs to be systematically benchmarked. Although various studies have examined the accuracy of DFT from an energetic point of view, few studies have considered its accuracy in predicting the temperature-dependent equilibrium composition. In this work, we collected 117 molecules for which experimental thermochemical data were available. From these, we constructed 2648 reactions. These experimentally constructed reactions were then benchmarked against DFT for 6 exchange-correlation functionals and 3 quality of basis sets. We show that, in reactions that do not show temperature dependence in the equilibrium composition below 1000 K, over 90% are predicted correctly. Temperature-dependent equilibrium compositions typically demonstrate correct qualitative behavior. Lastly, we show that the errors are equally caused by errors in the vibrational spectrum and the DFT electronic ground state energy.

Improving Accuracy and Transferability of Machine Learning Chemical Activation Energies by Adding Electronic Structure Information.

Predicting chemical activation energies is one of the longstanding and important challenges in computational chemistry. Recent advances have shown that machine learning can be used to create tools to predict them. Such tools can significantly decrease the computational cost for these predictions compared to traditional methods, which require an optimal path search along a high-dimensional potential energy surface. To enable this new route, we need both large and accurate datasets and a compact yet complete description of the reactions. Although data for chemical reactions is becoming increasingly available, the key step of encoding the reaction as an efficient descriptor remains a big challenge. In this paper, we demonstrate that including electronic energy levels in the description of the reaction significantly improves the prediction accuracy and transferability. Feature importance analysis further demonstrates that electronic energy levels have a higher importance than some structural information and typically require less space in the reaction encoding vector. In general, we observe that the results of the feature importance analysis relate well to the domain knowledge of fundamental chemical principles. This work can help to build better chemical reaction encodings for machine learning and thus improve the predictions of machine learning models for reaction activation energies. These models could ultimately be used to recognize reaction limiting steps in large reaction systems, allowing to account for bottlenecks at the design stage.

Graphene and Beyond: Recent Advances in Two-Dimensional Materials Synthesis, Properties, and Devices.

Since the isolation of graphene in 2004, two-dimensional (2D) materials research has rapidly evolved into an entire subdiscipline in the physical sciences with a wide range of emergent applications. The unique 2D structure offers an open canvas to tailor and functionalize 2D materials through layer number, defects, morphology, moiré pattern, strain, and other control knobs. Through this review, we aim to highlight the most recent discoveries in the following topics: theory-guided synthesis for enhanced control of 2D morphologies, quality, yield, as well as insights toward novel 2D materials; defect engineering to control and understand the role of various defects, including in situ and ex situ methods; and properties and applications that are related to moiré engineering, strain engineering, and artificial intelligence. Finally, we also provide our perspective on the challenges and opportunities in this fascinating field.

Modeling X-ray Photoelectron Spectroscopy of Macromolecules Using GW.

We propose a simple additive approach to simulate X-ray photoelectron spectra (XPS) of macromolecules based on the GW method. Single-shot GW (G0W0) is a promising technique to compute accurate core-electron binding energies (BEs). However, its application to large molecules is still unfeasible. To circumvent the computational cost of G0W0, we break the macromolecule into tractable building blocks, such as isolated monomers, and sum up the theoretical spectra of each component, weighted by their molar ratio. In this work, we provide a first proof of concept by applying the method to four test polymers and one copolymer and show that it leads to an excellent agreement with experiments. The method could be used to retrieve the composition of unknown materials and study chemical reactions, by comparing the simulated spectra with experimental ones.

Microcanonical RT-TDDFT simulations of realistically extended devices.

In this paper, real-time time-dependent density functional theory (RT-TDDFT) calculations of realistically sized nanodevices are presented. These microcanonical simulations rely on a closed boundary approach based on recent advances in the software package CP2K. The obtained results are compared to those derived from the open-boundary Non-equilibrium Green's Function (NEGF) formalism. A good agreement between the "current vs. voltage" characteristics produced by both methods is demonstrated for three representative device structures, a carbon nanotube field-effect transistor, a GeSe selector for crossbar arrays, and a conductive bridging random-access memory cell. Different approaches to extract the electrostatic contribution from the RT-TDDFT Hamiltonian and to incorporate the result into the NEGF calculations are presented.

Layer-controlled epitaxy of 2D semiconductors: bridging nanoscale phenomena to wafer-scale uniformity.

The rapid cadence of MOSFET scaling is stimulating the development of new technologies and accelerating the introduction of new semiconducting materials as silicon alternative. In this context, 2D materials with a unique layered structure have attracted tremendous interest in recent years, mainly motivated by their ultra-thin body nature and unique optoelectronic and mechanical properties. The development of scalable synthesis techniques is obviously a fundamental step towards the development of a manufacturable technology. Metal-organic chemical vapor deposition has recently been used for the synthesis of large area TMDs, however, an important milestone still needs to be achieved: the ability to precisely control the number of layers and surface uniformity at the nano-to micro-length scale to obtain an atomically flat, self-passivated surface. In this work, we explore various fundamental aspects involved in the chemical vapor deposition process and we provide important insights on the layer-dependence of epitaxial MoS2 film's structural properties. Based on these observations, we propose an original method to achieve a layer-controlled epitaxy of wafer-scale TMDs.

Toward an Understanding of the Electric Field-Induced Electrostatic Doping in van der Waals Heterostructures: A First-Principles Study.

Since the discovery of graphene, a broad range of two-dimensional (2D) materials has captured the attention of the scientific communities. Materials, such as hexagonal boron nitride (hBN) and the transition metal dichalcogenides (TMDs) family, have shown promising semiconducting and insulating properties that are very appealing for the semiconductor industry. Recently, the possibility of taking advantage of the properties of 2D-based heterostructures has been investigated for low-power nanoelectronic applications. In this work, we aim at evaluating the relation between the nature of the materials used in such heterostructures and the amplitude of the layer-to-layer charge transfer induced by an external electric field, as is typically present in nanoelectronic gated devices. A broad range of combinations of TMDs, graphene, and hBN has been investigated using density functional theory. Our results show that the electric field induced charge transfer strongly depends on the nature of the 2D materials used in the van der Waals heterostructures and to a lesser extent on the relative orientation of the materials in the structure. Our findings contribute to the building of the fundamental understanding required to engineer electrostatically the doping of 2D materials and to establish the factors that drive the charge transfer mechanisms in electron tunneling-based devices. These are key ingredients for the development of 2D-based nanoelectronic devices.

Mechanical and Electronic Properties of Thin-Film Transistors on Plastic, and Their Integration in Flexible Electronic Applications.

The increasing interest in flexible electronics and flexible displays raises questions regarding the inherent mechanical properties of the electronic materials used. Here, the mechanical behavior of thin-film transistors used in active-matrix displays is considered. The change of electrical performance of thin-film semiconductor materials under mechanical stress is studied, including amorphous oxide semiconductors. This study comprises an experimental part, in which transistor structures are characterized under different mechanical loads, as well as a theoretical part, in which the changes in energy band structures in the presence of stress and strain are investigated. The performance of amorphous oxide semiconductors are compared to reported results on organic semiconductors and covalent semiconductors, i.e., amorphous silicon and polysilicon. In order to compare the semiconductor materials, it is required to include the influence of the other transistor layers on the strain profile. The bending limits are investigated, and shown to be due to failures in the gate dielectric and/or the contacts. Design rules are proposed to minimize strain in transistor stacks and in transistor arrays. Finally, an overview of the present and future applications of flexible thin-film transistors is given, and the suitability of the different material classes for those applications is assessed.

First-principles material modeling of solid-state electrolytes with the spinel structure.

Ionic diffusion through the novel (AlxMg1-2xLix)Al2O4 spinel electrolyte is investigated using first-principles calculations, combined with the Kinetic Monte Carlo algorithm. We observe that the ionic diffusion increases with the lithium content x. Furthermore, the structural parameters, formation enthalpies and electronic structures of (AlxMg1-2xLix)Al2O4 are calculated for various stoichiometries. The overall results indicate the (AlxMg1-2xLix)Al2O4 stoichiometries x = 0.2…0.3 as most promising. The (AlxMg1-2xLix)Al2O4 electrolyte is a potential candidate for the all-spinel solid-state battery stack, with the material epitaxially grown between well-known spinel electrodes, such as LiyMn2O4 and Li4+3yTi5O12 (y = 0…1). Due to their identical crystal structure, a good electrolyte-electrode interface is expected.

Capturing wetting states in nanopatterned silicon.

Spectacular progress in developing advanced Si circuits with reduced size, along the track of Moore's law, has been relying on necessary developments in wet cleaning of nanopatterned Si wafers to provide contaminant free surfaces. The most efficient cleaning is achieved when complete wetting can be realized. In this work, ordered arrays of silicon nanopillars on a hitherto unexplored small scale have been used to study the wetting behavior on nanomodulated surfaces in a substantial range of surface treatments and geometrical parameters. With the use of optical reflectance measurements, the nanoscale water imbibition depths have been measured and the transition to the superhydrophobic Cassie-Baxter state has been accurately determined. For pillars of high aspect ratio (about 15), the transition occurs even when the surface is grafted with a hydrophilic functional group. We have found a striking consistent deviation between the contact angle measurements and the straightforward application of the classical wetting models. Molecular dynamics simulations show that these deviations can be attributed to the long overlooked atomic-scale surface perturbations that are introduced during the nanofabrication process. When the transition condition is approached, transient states of partial imbibition that characterize intermediate states between the Wenzel and Cassie-Baxter states are revealed in our experiments.

Stability of Si epoxide defects in Si nanowires: a mixed reactive force field/DFT study.

Modeling the oxidation process of silicon nanowires through reactive force field based molecular dynamics simulations suggests that the formation of Si epoxide defects occurs both at the Si/SiOx interface and at the nanowire surface, whereas for flat surfaces, this defect is experimentally observed to occur only at the interface as a result of stress. In this paper, we argue that the increasing curvature stabilizes the defect at the nanowire surface, as suggested by our density functional theory calculations. The latter can have important consequences for the opto-electronic properties of thin silicon nanowires, since the epoxide induces an electronic state within the band gap. Removing the epoxide defect by hydrogenation is expected to be possible but becomes increasingly difficult with a reduction of the diameter of the nanowires.

Work-function modification of Au and Ag surfaces upon deposition of self-assembled monolayers: influence of the choice of the theoretical approach and the thiol decomposition scheme.

We have characterized theoretically the work-function modifications of the (111) surfaces of gold and silver upon deposition of self-assembled monolayers based on methanethiol and trifluoromethanethiol. A comparative analysis is made between the experimental results and those obtained from two widely used approaches based on density functional theory. The contributions to the total work-function modifications are estimated on the basis of two decomposition schemes of the thiol molecules that have been proposed in the literature. The contributions are found to differ significantly between the two approaches, as do the corresponding adsorption energies.

Reactive molecular dynamics simulations on SiO2-coated ultra-small Si-nanowires.

The application of core-shell Si-SiO(2) nanowires as nanoelectronic devices strongly depends on their structure, which is difficult to tune precisely. In this work, we investigate the formation of the core-shell nanowires at the atomic scale, by reactive molecular dynamics simulations. The occurrence of two temperature-dependent oxidation mechanisms of ultra-small diameter Si-NWs is demonstrated. We found that control over the Si-core radius and the SiO(x) (x≤ 2) oxide shell is possible by tuning the growth temperature and the initial Si-NW diameter. Two different structures were obtained, i.e., ultrathin SiO(2) silica nanowires at high temperature and Si core|ultrathin SiO(2) silica nanowires at low temperature. The transition temperature is found to linearly decrease with the nanowire curvature. Finally, the interfacial stress is found to be responsible for self-limiting oxidation, depending on both the initial Si-NW radius and the oxide growth temperature. These novel insights allow us to gain control over the exact morphology and structure of the wires, as is needed for their application in nanoelectronics.

Atomic imaging of nucleation of trimethylaluminum on clean and H2O functionalized Ge(100) surfaces.

The direct reaction of trimethylaluminum (TMA) on a Ge(100) surface and the effects of monolayer H(2)O pre-dosing were investigated using ultrahigh vacuum techniques, such as scanning tunneling microscopy (STM), scanning tunneling spectroscopy (STS), and x-ray photoelectron spectroscopy (XPS), and density functional theory (DFT). At room temperature (RT), a saturation TMA dose produced 0.8 monolayers (ML) of semi-ordered species on a Ge(100) surface due to the dissociative chemisorption of TMA. STS confirmed the chemisorption of TMA passivated the bandgap states due to dangling bonds. By annealing the TMA-dosed Ge surface, the STM observed coverage of TMA sites decreased to 0.4 ML at 250 °C, and to 0.15 ML at 450 °C. XPS analysis showed that only carbon content was reduced during annealing, while the Al coverage was maintained at 0.15 ML, consistent with the desorption of methyl (-CH(3)) groups from the TMA adsorbates. Conversely, saturation TMA dosing at RT on the monolayer H(2)O pre-dosed Ge(100) surface followed by annealing at 200 °C formed a layer of Ge-O-Al bonds with an Al coverage a factor of two greater than the TMA only dosed Ge(100), consistent with Ge-OH activation of TMA chemisorption and Ge-H blocking of CH(3) chemisorption. The DFT shows that the reaction of TMA has lower activation energy and is more exothermic on Ge-OH than Ge-H sites. It is proposed that the H(2)O pre-dosing enhances the concentration of adsorbed Al and forms thermally stable Ge-O-Al bonds along the Ge dimer row which could serve as a nearly ideal atomic layer deposition nucleation layer on Ge(100) surface.

Bandgap opening in oxygen plasma-treated graphene.

We report a change in the semimetallic nature of single-layer graphene after exposure to oxygen plasma. The resulting transition from semimetallic to semiconducting behavior appears to depend on the duration of the exposure to the plasma treatment. The observation is confirmed by electrical, photoluminescence and Raman spectroscopy measurements. We explain the opening of a bandgap in graphene in terms of functionalization of its pristine lattice with oxygen atoms. Ab initio calculations show more details about the interaction between carbon and oxygen atoms and the consequences on the optoelectronic properties, that is, on the extent of the bandgap opening upon increased functionalisation density.

Exciton migration in rigid-rod conjugated polymers: an improved Förster model.

The dynamics of interchain and intrachain excitation energy transfer taking place in a polyindenofluorene endcapped with perylene derivatives is explored by means of ultrafast spectroscopy combined with correlated quantum-chemical calculations. The experimental data indicate faster exciton migration in films with respect to solution as a result of the emergence of efficient channels involving hopping between chains in close contact. These findings are supported by theoretical simulations based on an improved Forster model. Within this model, the rates are expressed according to the Fermi golden rule on the basis of (i) electronic couplings that take account of the detailed shape of the excited-state wave functions (through the use of a multicentric monopole expansion) and (ii) spectral overlap factors computed from the simulated acceptor absorption and donor emission spectra with explicit coupling to vibrations (considered within a displaced harmonic oscillator model); inhomogeneity is taken into account by assuming a distribution of chromophores with different conjugation lengths. The calculations predict faster intermolecular energy transfer as a result of larger electronic matrix elements and suggest a two-step mechanism for intrachain energy transfer with exciton hopping along the polymer backbone as the limiting step. Injecting the calculated hopping rates into a set of master equations allows the modeling of the dynamics of exciton transport along the polyindenofluorene chains and yields ensemble-averaged energy-transfer rates in good agreement with experiment.