Soft surfaces of nanomaterials enable strong phonon interactions.

Phonons and their interactions with other phonons, electrons or photons drive energy gain, loss and transport in materials. Although the phonon density of states has been measured and calculated in bulk crystalline semiconductors, phonons remain poorly understood in nanomaterials, despite the increasing prevalence of bottom-up fabrication of semiconductors from nanomaterials and the integration of nanometre-sized components into devices. Here we quantify the phononic properties of bottom-up fabricated semiconductors as a function of crystallite size using inelastic neutron scattering measurements and ab initio molecular dynamics simulations. We show that, unlike in microcrystalline semiconductors, the phonon modes of semiconductors with nanocrystalline domains exhibit both reduced symmetry and low energy owing to mechanical softness at the surface of those domains. These properties become important when phonons couple to electrons in semiconductor devices. Although it was initially believed that the coupling between electrons and phonons is suppressed in nanocrystalline materials owing to the scarcity of electronic states and their large energy separation, it has since been shown that the electron-phonon coupling is large and allows high energy-dissipation rates exceeding one electronvolt per picosecond (refs 10-13). Despite detailed investigations into the role of phonons in exciton dynamics, leading to a variety of suggestions as to the origins of these fast transition rates and including attempts to numerically calculate them, fundamental questions surrounding electron-phonon interactions in nanomaterials remain unresolved. By combining the microscopic and thermodynamic theories of phonons and our findings on the phononic properties of nanomaterials, we are able to explain and then experimentally confirm the strong electron-phonon coupling and fast multi-phonon transition rates of charge carriers to trap states. This improved understanding of phonon processes permits the rational selection of nanomaterials, their surface treatments, and the design of devices incorporating them.

Electron Transport through Metal/MoS2 Interfaces: Edge- or Area-Dependent Process?

In ultrathin two-dimensional (2-D) materials, the formation of ohmic contacts with top metallic layers is a challenging task that involves different processes than in bulk-like structures. Besides the Schottky barrier height, the transfer length of electrons between metals and 2-D monolayers is a highly relevant parameter. For MoS2, both short (≤30 nm) and long (≥0.5 µm) values have been reported, corresponding to either an abrupt carrier injection at the contact edge or a more gradual transfer of electrons over a large contact area. Here we use ab initio quantum transport simulations to demonstrate that the presence of an oxide layer between a metallic contact and a MoS2 monolayer, for example, TiO2 in the case of titanium electrodes, favors an area-dependent process with a long transfer length, while a perfectly clean metal-semiconductor interface would lead to an edge process. These findings reconcile several theories that have been postulated about the physics of metal/MoS2 interfaces and provide a framework to design future devices with lower contact resistances.

One-Dimensional Edge Contacts to a Monolayer Semiconductor.

Integration of electrical contacts into van der Waals (vdW) heterostructures is critical for realizing electronic and optoelectronic functionalities. However, to date no scalable methodology for gaining electrical access to buried monolayer two-dimensional (2D) semiconductors exists. Here we report viable edge contact formation to hexagonal boron nitride (hBN) encapsulated monolayer MoS2. By combining reactive ion etching, in situ Ar+ sputtering and annealing, we achieve a relatively low edge contact resistance, high mobility (up to ∼30 cm2 V-1 s-1) and high on-current density (>50 µA/µm at VDS = 3V), comparable to top contacts. Furthermore, the atomically smooth hBN environment also preserves the intrinsic MoS2 channel quality during fabrication, leading to a steep subthreshold swing of 116 mV/dec with a negligible hysteresis. Hence, edge contacts are highly promising for large-scale practical implementation of encapsulated heterostructure devices, especially those involving air sensitive materials, and can be arbitrarily narrow, which opens the door to further shrinkage of 2D device footprint.

Tuning Electron-Phonon Interactions in Nanocrystals through Surface Termination.

We perform ab initio molecular dynamics on experimentally relevant-sized lead sulfide (PbS) nanocrystals (NCs) constructed with thiol or Cl, Br, and I anion surfaces to determine their vibrational and dynamic electronic structure. We show that electron-phonon interactions can explain the large thermal broadening and fast carrier cooling rates experimentally observed in Pb-chalcogenide NCs. Furthermore, our simulations reveal that electron-phonon interactions are suppressed in halide-terminated NCs due to reduction of both the thermal displacement of surface atoms and the spatial overlap of the charge carriers with these large atomic vibrations. This work shows how surface engineering, guided by simulations, can be used to systematically control carrier dynamics.

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.

Length Scale of Diffusive Phonon Transport in Suspended Thin Silicon Nanowires.

Recent experimental advances have revealed that the mean free path (mfp) of phonons contributing significantly to thermal transport in crystalline semiconductors can be several microns long. Almost all of these experiments are based on bulk and thin film materials and use techniques that are not directly applicable to nanowires. By developing a process with which we could fabricate multiple electrically contacted and suspended segments on individual heavily doped smooth Silicon nanowires, we measured phonon transport across varying length scales using a DC self-heating technique. Our measurements show that diffusive thermal transport is still valid across O(100) nm length scales, supporting the diffuse nature of phonon-boundary scattering even on smooth nanowire surfaces. Our work also showcases the self-heating technique as an important alternative to the thermal bridge technique to measure phonon transport across short length scales relevant to mapping the phonon mfp spectrum in nanowires.

Ballistic One-Dimensional InAs Nanowire Cross-Junction Interconnects.

Coherent interconnection of quantum bits remains an ongoing challenge in quantum information technology. Envisioned hardware to achieve this goal is based on semiconductor nanowire (NW) circuits, comprising individual NW devices that are linked through ballistic interconnects. However, maintaining the sensitive ballistic conduction and confinement conditions across NW intersections is a nontrivial problem. Here, we go beyond the characterization of a single NW device and demonstrate ballistic one-dimensional (1D) quantum transport in InAs NW cross-junctions, monolithically integrated on Si. Characteristic 1D conductance plateaus are resolved in field-effect measurements across up to four NW-junctions in series. The 1D ballistic transport and sub-band splitting is preserved for both crossing-directions. We show that the 1D modes of a single injection terminal can be distributed into multiple NW branches. We believe that NW cross-junctions are well-suited as cross-directional communication links for the reliable transfer of quantum information as required for quantum computational systems.

Efficient algorithms for large-scale quantum transport calculations.

Massively parallel algorithms are presented in this paper to reduce the computational burden associated with quantum transport simulations from first-principles. The power of modern hybrid computer architectures is harvested in order to determine the open boundary conditions that connect the simulation domain with its environment and to solve the resulting Schrödinger equation. While the former operation takes the form of an eigenvalue problem that is solved by a contour integration technique on the available central processing units (CPUs), the latter can be cast into a linear system of equations that is simultaneously processed by SplitSolve, a two-step algorithm, on general-purpose graphics processing units (GPUs). A significant decrease of the computational time by up to two orders of magnitude is obtained as compared to standard solution methods.

Minimizing Self-Heating and Heat Dissipation in Ultrascaled Nanowire Transistors.

Through advanced electro-thermal simulations we demonstrate that self-heating effects play a significant role in ultrascaled nanowire field-effect transistors, that some crystal orientations are less favorable than others (⟨111⟩ for n-type applications, ⟨100⟩ for p-type ones), and that Ge might outperform Si at this scale. We further establish a relationship between the dissipated power and the electrical mobility and another one between the current reduction induced by self-heating and the phonon thermal conductivity.

Atomic Scale Plasmonic Switch.

The atom sets an ultimate scaling limit to Moore's law in the electronics industry. While electronics research already explores atomic scales devices, photonics research still deals with devices at the micrometer scale. Here we demonstrate that photonic scaling, similar to electronics, is only limited by the atom. More precisely, we introduce an electrically controlled plasmonic switch operating at the atomic scale. The switch allows for fast and reproducible switching by means of the relocation of an individual or, at most, a few atoms in a plasmonic cavity. Depending on the location of the atom either of two distinct plasmonic cavity resonance states are supported. Experimental results show reversible digital optical switching with an extinction ratio of 9.2 dB and operation at room temperature up to MHz with femtojoule (fJ) power consumption for a single switch operation. This demonstration of an integrated quantum device allowing to control photons at the atomic level opens intriguing perspectives for a fully integrated and highly scalable chip platform, a platform where optics, electronics, and memory may be controlled at the single-atom level.

A generalized Poisson solver for first-principles device simulations.

Electronic structure calculations of atomistic systems based on density functional theory involve solving the Poisson equation. In this paper, we present a plane-wave based algorithm for solving the generalized Poisson equation subject to periodic or homogeneous Neumann conditions on the boundaries of the simulation cell and Dirichlet type conditions imposed at arbitrary subdomains. In this way, source, drain, and gate voltages can be imposed across atomistic models of electronic devices. Dirichlet conditions are enforced as constraints in a variational framework giving rise to a saddle point problem. The resulting system of equations is then solved using a stationary iterative method in which the generalized Poisson operator is preconditioned with the standard Laplace operator. The solver can make use of any sufficiently smooth function modelling the dielectric constant, including density dependent dielectric continuum models. For all the boundary conditions, consistent derivatives are available and molecular dynamics simulations can be performed. The convergence behaviour of the scheme is investigated and its capabilities are demonstrated.

Atomistic simulation of transport phenomena in nanoelectronic devices.

Computational chemistry deals with the first-principles calculation of electronic and crystal structures, phase diagrams, charge distributions, vibrational frequencies, or ion diffusivity in complex molecules and solids. Typically, none of these numerical experiments allows for the calculation of electrical currents under the influence of externally applied voltages. To address this issue, there is an imperative need for an advanced simulation approach capable of treating all kind of transport phenomena (electron, energy, momentum) at a quantum mechanical level. The goal of this tutorial review is to give an overview of the "quantum transport" (QT) research activity, introduce specific techniques such as the Non-equilibrium Green's Function (NEGF) formalism, describe their basic features, and underline their strengths and weaknesses. Three examples from the nanoelectronics field have been selected to illustrate the insight provided by quantum transport simulations. Details are also given about the numerical algorithms to solve the NEGF equations and about strategies to parallelize the workload on supercomputers.

Versatile Nanoscale Three-Terminal Memristive Switch Enabled by Gating.

A three-terminal memristor with an ultrasmall footprint of only 0.07 µm2 and critical dimensions of 70 nm × 10 nm × 6 nm is introduced. The device's feature is the presence of a gate contact, which enables two operation modes: either tuning the set voltage or directly inducing a resistance change. In I-V mode, we demonstrate that by changing the gate voltages between ±1 V one can shift the set voltage by 69%. In pulsing mode, we show that resistance change can be triggered by a gate pulse. Furthermore, we tested the device endurance under a 1 kHz operation. In an experiment with 2.6 million voltage pulses, we found two distinct resistance states. The device response to a pseudorandom bit sequence displays an open eye diagram and a success ratio of 97%. Our results suggest that this device concept is a promising candidate for a variety of applications ranging from Internet-of-Things to neuromorphic computing.

Single neuromorphic memristor closely emulates multiple synaptic mechanisms for energy efficient neural networks.

Biological neural networks do not only include long-term memory and weight multiplication capabilities, as commonly assumed in artificial neural networks, but also more complex functions such as short-term memory, short-term plasticity, and meta-plasticity - all collocated within each synapse. Here, we demonstrate memristive nano-devices based on SrTiO3 that inherently emulate all these synaptic functions. These memristors operate in a non-filamentary, low conductance regime, which enables stable and energy efficient operation. They can act as multi-functional hardware synapses in a class of bio-inspired deep neural networks (DNN) that make use of both long- and short-term synaptic dynamics and are capable of meta-learning or learning-to-learn. The resulting bio-inspired DNN is then trained to play the video game Atari Pong, a complex reinforcement learning task in a dynamic environment. Our analysis shows that the energy consumption of the DNN with multi-functional memristive synapses decreases by about two orders of magnitude as compared to a pure GPU implementation. Based on this finding, we infer that memristive devices with a better emulation of the synaptic functionalities do not only broaden the applicability of neuromorphic computing, but could also improve the performance and energy costs of certain artificial intelligence applications.

Magnetoresistive-coupled transistor using the Weyl semimetal NbP.

Semiconductor transistors operate by modulating the charge carrier concentration of a channel material through an electric field coupled by a capacitor. This mechanism is constrained by the fundamental transport physics and material properties of such devices-attenuation of the electric field, and limited mobility and charge carrier density in semiconductor channels. In this work, we demonstrate a new type of transistor that operates through a different mechanism. The channel material is a Weyl semimetal, NbP, whose resistivity is modulated via a magnetic field generated by an integrated superconductor. Due to the exceptionally large electron mobility of this material, which reaches over 1,000,000 cm2/Vs, and the strong magnetoresistive coupling, the transistor can generate significant transconductance amplification at nanowatt levels of power. This type of device can enable new low-power amplifiers, suitable for qubit readout operation in quantum computers.

Structural Ordering in Ultrasmall Multicomponent Chalcogenides: The Case of Quaternary Cu-Zn-In-Se Nanocrystals.

The compositional tunability of non-isovalent multicomponent chalcogenide thin films and the extent of atomic ordering of their crystal structure is key to the performance of many modern technologies. In contrast, the effects of ordering are rarely studied for quantum-confined materials, such as colloidal nanocrystals. In this paper, the possibilities around composition tunability and atomic ordering are explored in ultrasmall ternary and quaternary quantum dots, taking I-III-VI-group Cu-Zn-In-Se semiconductor as a case study. A quantitative synthesis for 3.3 nm quaternary chalcogenide nanocrystals is developed and shown that cation and cationic vacancy ordering can be achieved in these systems consisting of only 100s of atoms. Combining experiment and theoretical calculations, the relationship between structural ordering and optical properties of the materials are demonstrated. It is found that the arrangement and ordering of cationic sublattice plays an important role in the luminescent efficiency. Specifically, the concentration of Cu-vacancy couples in the nanocrystal correlates with luminescence quantum yield, while structure ordering increases the occurrence of such optically active Cu-vacancy units. On the flip side, the detrimental impact of cationic site disorder in I-III-VI nanocrystals can be mitigated by introducing a cation of intermediate valence, such as Zn (II).

Sub-10 nm carbon nanotube transistor.

Although carbon nanotube (CNT) transistors have been promoted for years as a replacement for silicon technology, there is limited theoretical work and no experimental reports on how nanotubes will perform at sub-10 nm channel lengths. In this manuscript, we demonstrate the first sub-10 nm CNT transistor, which is shown to outperform the best competing silicon devices with more than four times the diameter-normalized current density (2.41 mA/µm) at a low operating voltage of 0.5 V. The nanotube transistor exhibits an impressively small inverse subthreshold slope of 94 mV/decade-nearly half of the value expected from a previous theoretical study. Numerical simulations show the critical role of the metal-CNT contacts in determining the performance of sub-10 nm channel length transistors, signifying the need for more accurate theoretical modeling of transport between the metal and nanotube. The superior low-voltage performance of the sub-10 nm CNT transistor proves the viability of nanotubes for consideration in future aggressively scaled transistor technologies.

An Atomistic Model of Field-Induced Resistive Switching in Valence Change Memory.

In valence change memory (VCM) cells, the conductance of an insulating switching layer is reversibly modulated by creating and redistributing point defects under an external field. Accurately simulating the switching dynamics of these devices can be difficult due to their typically disordered atomic structures and inhomogeneous arrangements of defects. To address this, we introduce an atomistic framework for modeling VCM cells. It combines a stochastic kinetic Monte Carlo approach for atomic rearrangement with a quantum transport scheme, both parametrized at the ab initio level by using inputs from density functional theory. Each of these steps operates directly on the underlying atomic structure. The model thus directly relates the energy landscape and electronic structure of the device to its switching characteristics. We apply this model to simulate field-induced nonvolatile switching between high- and low-resistance states in a TiN/HfO2/Ti/TiN stack and analyze both the kinetics and stochasticity of the conductance transitions. We also resolve the atomic nature of current flow resulting from the valence change mechanism, finding that conductive paths are formed between the undercoordinated Hf atoms neighboring oxygen vacancies. The model developed here can be applied to different material systems to evaluate their resistive switching potential, both for use as conventional memory cells and as neuromorphic computing primitives.

Synthesis and Electronic Structure of Mid-Infrared Absorbing Cu3SbSe4 and CuxSbSe4 Nanocrystals.

Aliovalent I-V-VI semiconductor nanocrystals are promising candidates for thermoelectric and optoelectronic applications. Famatinite Cu3SbSe4 stands out due to its high absorption coefficient and narrow band gap in the mid-infrared spectral range. This paper combines experiment and theory to investigate the synthesis and electronic structure of colloidal CuxSbSe4 nanocrystals. We achieve predictive composition control of size-uniform CuxSbSe4 (x = 1.9-3.4) nanocrystals. Density functional theory (DFT)-parametrized tight-binding simulations on nanocrystals show that the more the Cu-vacancies, the wider the band gap of CuxSbSe4 nanocrystals, a trend which we also confirm experimentally via FTIR spectroscopy. We show that SbCu antisite defects can create mid-gap states, which may give rise to sub-bandgap absorption. This work provides a detailed study of CuxSbSe4 nanocrystals and highlights the potential opportunities as well as challenges for their application in infrared devices.

Disorder-induced bulk photovoltaic effect in a centrosymmetric van der Waals material.

Sunlight is widely seen as one of the most abundant forms of renewable energy, with photovoltaic cells based on pn junctions being the most commonly used platform attempting to harness it. Unlike in conventional photovoltaic cells, the bulk photovoltaic effect (BPVE) allows for the generation of photocurrent and photovoltage in a single material without the need to engineer a pn junction and create a built-in electric field, thus offering a solution that can potentially exceed the Shockley-Queisser efficiency limit. However, it requires a material with no inversion symmetry and is therefore absent in centrosymmetric materials. Here, we demonstrate that breaking the inversion symmetry by structural disorder can induce BPVE in ultrathin PtSe2, a centrosymmetric semiconducting van der Waals material. Homogenous illumination of defective PtSe2 by linearly and circularly polarized light results in a photoresponse termed as linear photogalvanic effect (LPGE) and circular photogalvanic effect (CPGE), which is mostly absent in the pristine crystal. First-principles calculations reveal that LPGE originates from Se vacancies that act as asymmetric scattering centers for the photo-generated electron-hole pairs. Our work emphasizes the importance of defects to induce photovoltaic functionality in centrosymmetric materials and shows how the range of materials suitable for light sensing and energy-harvesting applications can be extended.