Strong Electron-Vibration Signals in Weakly Coupled Molecular Junctions: Activation of Spin-Crossover.

Manipulating individual molecular spin states with electronic current has the potential to revolutionize quantum information devices. However, it is still unclear how a current can cause a spin transition in single-molecule devices. Here, we propose a spin-crossover (SCO) mechanism induced by electron-phonon coupling in an iron(II) phthalocyanine molecule situated on a graphene-decoupled Ir(111) substrate. We performed simulations of both elastic and inelastic electron tunneling spectroscopy (IETS), which reveal current-induced Fe-N vibrations and an underestimation of established electron-vibration signals. Going beyond standard perturbation theory, we examined molecules in various charge and spin states using the Franck-Condon framework. The increased probability of spin switching suggests that notable IETS signals indicate SCO triggered by the inelastic vibrational excitation associated with Fe-N stretching.

Molecular Bridge Engineering for Tuning Quantum Electronic Transport and Anisotropy in Nanoporous Graphene.

Recent advances on surface-assisted synthesis have demonstrated that arrays of nanometer wide graphene nanoribbons can be laterally coupled with atomic precision to give rise to a highly anisotropic nanoporous graphene structure. Electronically, this graphene nanoarchitecture can be conceived as a set of weakly coupled semiconducting 1D nanochannels with electron propagation characterized by substantial interchannel quantum interferences. Here, we report the synthesis of a new nanoporous graphene structure where the interribbon electronic coupling can be controlled by the different degrees of freedom provided by phenylene bridges that couple the conducting channels. This versatility arises from the multiplicity of phenylene cross-coupling configurations, which provides a robust chemical knob, and from the interphenyl twist angle that acts as a fine-tunable knob. The twist angle is significantly altered by the interaction with the substrate, as confirmed by a combined bond-resolved scanning tunneling microscopy (STM) and ab initio analysis, and should accordingly be addressable by other external stimuli. Electron propagation simulations demonstrate the capability of either switching on/off or modulating the interribbon coupling by the corresponding use of the chemical or the conformational knob. Molecular bridges therefore emerge as efficient tools to engineer quantum transport and anisotropy in carbon-based 2D nanoarchitectures.

Enhancement of Graphene Phonon Excitation by a Chemically Engineered Molecular Resonance.

The abstraction of pyrrolic hydrogen from a single phthalocyanine on graphene turns the molecule into a sensitive probe for graphene phonons. The inelastic electron transport measured with a scanning tunneling microscope across the molecular adsorbate and graphene becomes strongly enhanced for a graphene out-of-plane acoustic phonon mode. Supporting density functional and transport calculations elucidate the underlying physical mechanism. A molecular orbital resonance close to the Fermi energy controls the inelastic current while specific phonon modes of graphene are magnified due to their coupling to symmetry-equivalent vibrational quanta of the molecule.

Unveiling the Multiradical Character of the Biphenylene Network and Its Anisotropic Charge Transport.

Recent progress in the on-surface synthesis and characterization of nanomaterials is facilitating the realization of new carbon allotropes, such as nanoporous graphenes, graphynes, and 2D π-conjugated polymers. One of the latest examples is the biphenylene network (BPN), which was recently fabricated on gold and characterized with atomic precision. This gapless 2D organic material presents uncommon metallic conduction, which could help develop innovative carbon-based electronics. Here, using first principles calculations and quantum transport simulations, we provide new insights into some fundamental properties of BPN, which are key for its further technological exploitation. We predict that BPN hosts an unprecedented spin-polarized multiradical ground state, which has important implications for the chemical reactivity of the 2D material under practical use conditions. The associated electronic band gap is highly sensitive to perturbations, as seen in finite temperature (300 K) molecular dynamics simulations, but the multiradical character remains stable. Furthermore, BPN is found to host in-plane anisotropic (spin-polarized) electrical transport, rooted in its intrinsic structural features, which suggests potential device functionality of interest for both nanoelectronics and spintronics.

Proposal for All-Electrical Spin Manipulation and Detection for a Single Molecule on Boron-Substituted Graphene.

All-electrical writing and reading of spin states attract considerable attention for their promising applications in energy-efficient spintronics devices. Here we show, based on rigorous first-principles calculations, that the spin properties can be manipulated and detected in molecular spinterfaces, where an iron tetraphenyl porphyrin (FeTPP) molecule is deposited on boron-substituted graphene (BG). Notably, a reversible spin switching between the S=1 and S=3/2 states is achieved by a gate electrode. We can trace the origin to a strong hybridization between the Fe-d_{z^{2}} and B-p_{z} orbitals. Combining density functional theory with nonequilibrium Green's function formalism, we propose an experimentally feasible three-terminal setup to probe the spin state. Furthermore, we show how the in-plane quantum transport for the BG, which is non-spin polarized, can be modified by FeTPP, yielding a significant transport spin polarization near the Fermi energy (>10% for typical coverage). Our work paves the way to realize all-electrical spintronics devices using molecular spinterfaces.

Characterization and Manipulation of Intervalley Scattering Induced by an Individual Monovacancy in Graphene.

Intervalley scattering involves microscopic processes that electrons are scattered by atomic-scale defects on the nanoscale. Although central to our understanding of electronic properties of materials, direct characterization and manipulation of range and strength of the intervalley scattering induced by an individual atomic defect have so far been elusive. Using scanning tunneling microscope, we visualize and control intervalley scattering from an individual monovacancy in graphene. By directly imaging the affected range of monovacancy-induced intervalley scattering, we demonstrate that it is inversely proportional to the energy; i.e., it is proportional to the wavelength of massless Dirac fermions. A giant electron-hole asymmetry of the intervalley scattering is observed because the monovacancy is charged. By further charging the monovacancy, the bended electronic potential around the monovacancy softens the scattering potential, which, consequently, suppresses the intervalley scattering of the monovacancy.

Spin-Polarizing Electron Beam Splitter from Crossed Graphene Nanoribbons.

Junctions composed of two crossed graphene nanoribbons (GNRs) have been theoretically proposed as electron beam splitters where incoming electron waves in one GNR can be split coherently into propagating waves in two outgoing terminals with nearly equal amplitude and zero back-scattering. Here we scrutinize this effect for devices composed of narrow zigzag GNRs taking explicitly into account the role of Coulomb repulsion that leads to spin-polarized edge states within mean-field theory. We show that the beam-splitting effect survives the opening of the well-known correlation gap and, more strikingly, that a spin-dependent scattering potential emerges which spin polarizes the transmitted electrons in the two outputs. By studying different ribbons and intersection angles we provide evidence that this is a general feature with edge-polarized nanoribbons. A near-perfect polarization can be achieved by joining several junctions in series. Our findings suggest that GNRs are interesting building blocks in spintronics and quantum technologies with applications for interferometry and entanglement.

Siesta: Recent developments and applications.

A review of the present status, recent enhancements, and applicability of the Siesta program is presented. Since its debut in the mid-1990s, Siesta's flexibility, efficiency, and free distribution have given advanced materials simulation capabilities to many groups worldwide. The core methodological scheme of Siesta combines finite-support pseudo-atomic orbitals as basis sets, norm-conserving pseudopotentials, and a real-space grid for the representation of charge density and potentials and the computation of their associated matrix elements. Here, we describe the more recent implementations on top of that core scheme, which include full spin-orbit interaction, non-repeated and multiple-contact ballistic electron transport, density functional theory (DFT)+U and hybrid functionals, time-dependent DFT, novel reduced-scaling solvers, density-functional perturbation theory, efficient van der Waals non-local density functionals, and enhanced molecular-dynamics options. In addition, a substantial effort has been made in enhancing interoperability and interfacing with other codes and utilities, such as wannier90 and the second-principles modeling it can be used for, an AiiDA plugin for workflow automatization, interface to Lua for steering Siesta runs, and various post-processing utilities. Siesta has also been engaged in the Electronic Structure Library effort from its inception, which has allowed the sharing of various low-level libraries, as well as data standards and support for them, particularly the PSeudopotential Markup Language definition and library for transferable pseudopotentials, and the interface to the ELectronic Structure Infrastructure library of solvers. Code sharing is made easier by the new open-source licensing model of the program. This review also presents examples of application of the capabilities of the code, as well as a view of on-going and future developments.

Nonequilibrium Bond Forces in Single-Molecule Junctions.

Passing a current across two touching C60 molecules imposes a nonequilibrium population of bonding and antibonding molecular orbitals, which changes the equilibrium bond character and strength. A current-induced bond force therefore contributes to the total force at chemical-bond distances. The combination of first-principles calculations with scanning probe experiments exploring currents and forces in a wide C60-C60 distance range consistently evidences the presence of current-induced attraction that occurs when the two molecules are on the verge of forming a chemical bond. The unique opportunity to arrange matter at the atomic scale with the atomic force and scanning tunneling microscope tip has enabled closely matching molecular junctions in theory and experiment. The findings consequently represent the first report of current-induced bond forces at the single-molecule level and further elucidate the intimate relation between charge transport and force. The results are relevant to molecular electronics and chemical reactions in the presence of a current.

Electron Transport in Nanoporous Graphene: Probing the Talbot Effect.

Electrons in graphene can show diffraction and interference phenomena fully analogous to light thanks to their Dirac-like energy dispersion. However, it is not clear how this optical analogy persists in nanostructured graphene, for example, with pores. Nanoporous graphene (NPG) consisting of linked graphene nanoribbons has recently been fabricated using molecular precursors and bottom-up assembly (Moreno et al. Science 2018, 360, 199). We predict that electrons propagating in NPG exhibit the interference Talbot effect, analogous to photons in coupled waveguides. Our results are obtained by parameter-free atomistic calculations of real-sized NPG samples based on seamlessly integrated density functional theory and tight-binding regions. We link the origins of this interference phenomenon to the band structure of the NPG. Most importantly, we demonstrate how the Talbot effect may be detected experimentally using dual-probe scanning tunneling microscopy. Talbot interference of electron waves in NPG or other related materials may open up new opportunities for future quantum electronics, computing, or sensing.

Quantum Interference Engineering of Nanoporous Graphene for Carbon Nanocircuitry.

Bottom-up prepared carbon nanostructures appear as promising platforms for future carbon-based nanoelectronics due to their atomically precise and versatile structure. An important breakthrough is the recent preparation of nanoporous graphene (NPG) as an ordered covalent array of graphene nanoribbons (GNRs). Within NPG, the GNRs may be thought of as 1D electronic nanochannels through which electrons preferentially move, highlighting NPG's potential for carbon nanocircuitry. However, the π-conjugated bonds bridging the GNRs give rise to electronic crosstalk between the individual 1D channels, leading to spatially dispersing electronic currents. Here, we propose a chemical design of the bridges resulting in destructive quantum interference, which blocks the crosstalk between GNRs in NPG, electronically isolating them. Our multiscale calculations reveal that injected currents can remain confined within a single, 0.7 nm wide, GNR channel for distances as long as 100 nm. The concepts developed in this work thus provide an important ingredient for the quantum design of future carbon nanocircuitry.

Understanding and Engineering Phonon-Mediated Tunneling into Graphene on Metal Surfaces.

Metal-intercalated graphene on Ir(111) exhibits phonon signatures in inelastic electron tunneling spectroscopy with strengths that depend on the intercalant. Extraordinarily strong graphene phonon signals are observed for Cs intercalation. Li intercalation likewise induces clearly discriminable phonon signatures, albeit less pronounced than observed for Cs. The signal can be finely tuned by the alkali metal coverage and gradually disappears upon increasing the junction conductance from tunneling to contact ranges. In contrast to Cs and Li, for Ni-intercalated graphene the phonon signals stay below the detection limit in all transport ranges. Going beyond the conventional two-terminal approach, transport calculations provide a comprehensive understanding of the subtle interplay between the graphene-electrode coupling and the observation of graphene phonon spectroscopic signatures.

Stacked Janus Device Concepts: Abrupt pn-Junctions and Cross-Plane Channels.

Janus transition metal dichalcogenides with a built-in structural cross-plane (cp) asymmetry have recently emerged as a new class of two-dimensional materials with a large cp dipole. Using first-principles calculations, and a tailored transport method, we demonstrate that stacking graphene and MoSSe Janus structures result in record high homogeneous doping of graphene and abrupt, atomically thin, cross-plane pn-junctions. We show how graphene in contrast to metals can act as electrodes to Janus stacks without screening the cp dipole and predict a large photocurrent response dominated by a cp transport channel in a few-layer stacked device. The photocurrent is above that of a corresponding thin-film silicon device illustrating the great potential of Janus stacks, for example, in photovoltaic devices.

A Graphene-Edge Ferroelectric Molecular Switch.

We show that polar molecules (water, ammonia, and nitrogen dioxide) adsorbed solely at the exposed edges of an encapsulated graphene sheet exhibit ferroelectricity, collectively orienting and switching reproducibly between two available states in response to an external electric field. This ferroelectric molecular switching introduces drastic modifications to the graphene bulk conductivity and produces a large and ambipolar charge bistability in micrometer-size graphene devices. This system comprises an experimental realization of envisioned memory capacitive ("memcapacitive") devices whose capacitance is a function of their charging history, here conceived via confined and correlated polar molecules at the one-dimensional edge of a two-dimensional crystal.

Field Effect in Graphene-Based van der Waals Heterostructures: Stacking Sequence Matters.

Stacked van der Waals (vdW) heterostructures where semiconducting two-dimensional (2D) materials are contacted by overlaid graphene electrodes enable atomically thin, flexible electronics. We use first-principles quantum transport simulations of graphene-contacted MoS2 devices to show how the transistor effect critically depends on the stacking configuration relative to the gate electrode. We can trace this behavior to the stacking-dependent response of the contact region to the capacitive electric field induced by the gate. The contact resistance is a central parameter and our observation establishes an important design rule for ultrathin devices based on 2D atomic crystals.

Flexural-Phonon Scattering Induced by Electrostatic Gating in Graphene.

Graphene has an extremely high carrier mobility partly due to its planar mirror symmetry inhibiting scattering by the highly occupied acoustic flexural phonons. Electrostatic gating of a graphene device can break the planar mirror symmetry, yielding a coupling mechanism to the flexural phonons. We examine the effect of the gate-induced one-phonon scattering on the mobility for several gate geometries and dielectric environments using first-principles calculations based on density functional theory and the Boltzmann equation. We demonstrate that this scattering mechanism can be a mobility-limiting factor, and show how the carrier density and temperature scaling of the mobility depends on the electrostatic environment. Our findings may explain the high deformation potential for in-plane acoustic phonons extracted from experiments and, furthermore, suggest a direct relation between device symmetry and resulting mobility.

Mechanochemistry Induced Using Force Exerted by a Functionalized Microscope Tip.

Atomic-scale mechanochemistry is realized from force exerted by a C60 -functionalized scanning tunneling microscope tip. Two conformers of tin phthalocyanine can be prepared on coinage-metal surfaces. A transition between these conformers is induced on Cu(111) and Ag(100). Density-functional calculations reveal details of this reaction. Because of the large energy barrier of the reaction and the strong interaction of SnPc with Cu(111), the process cannot be achieved by electrical means.

Graphene Nanobubbles as Valley Filters and Beam Splitters.

The energy band structure of graphene has two inequivalent valleys at the K and K^{'} points of the Brillouin zone. The possibility to manipulate this valley degree of freedom defines the field of valleytronics, the valley analogue of spintronics. A key requirement for valleytronic devices is the ability to break the valley degeneracy by filtering and spatially splitting valleys to generate valley polarized currents. Here, we suggest a way to obtain valley polarization using strain-induced inhomogeneous pseudomagnetic fields (PMFs) that act oppositely on the two valleys. Notably, the suggested method does not involve external magnetic fields, or magnetic materials, unlike previous proposals. In our proposal the strain is due to experimentally feasible nanobubbles, whose associated PMFs lead to different real space trajectories for K and K^{'} electrons, thus allowing the two valleys to be addressed individually. In this way, graphene nanobubbles can be exploited in both valley filtering and valley splitting devices, and our simulations reveal that a number of different functionalities are possible depending on the deformation field.

Manipulating the voltage drop in graphene nanojunctions using a gate potential.

Graphene is an attractive electrode material to contact nanostructures down to the molecular scale since it can be gated electrostatically. Gating can be used to control the doping and the energy level alignment in the nanojunction, thereby influencing its conductance. Here we investigate the impact of electrostatic gating in nanojunctions between graphene electrodes operating at finite bias. Using quantum transport simulations based on density functional theory, we show that the voltage drop across symmetric junctions changes dramatically and controllably in gated systems compared to non-gated junctions. In particular, for p-type(n-type) carriers the voltage drop is located close to the electrode with positive(negative) polarity, the potential of the junction is pinned to the negative(positive) electrode. We trace this behaviour back to the vanishing density of states of graphene in the proximity of the Dirac point. Due to the electrostatic gating, each electrode exposes different density of states in the bias window between the two different electrode Fermi energies, thereby leading to a non-symmetry in the voltage drop across the device. This selective pinning is found to be independent of device length when carriers are induced either by the gate or dopant atoms, indicating a general effect for electronic circuitry based on graphene electrodes. We envision this could be used to control the spatial distribution of Joule heating in graphene nanostructures, and possibly the chemical reaction rate around high potential gradients.

Tunneling spectra of graphene on copper unraveled.

Scanning tunneling spectroscopy is often employed to study two-dimensional (2D) materials on conductive growth substrates, in order to gain information on the electronic structures of the 2D material-substrate systems, which can lead to insight into 2D material-substrate interactions, growth mechanisms, etc. The interpretation of the spectra can be complicated, however. Specifically for graphene grown on copper, there have been conflicting reports of tunneling spectra. A clear understanding of the mechanisms behind the variability is desired. In this work, we have revealed that the root cause of the variability in tunneling spectra is the variation in graphene-substrate coupling under various experimental conditions, providing a salutary perspective on the important role of 2D material-substrate interactions. The conclusions are drawn from measured data and theoretical calculations for monolayer, AB-stacked bilayer, and twisted bilayer graphene coexisting on the same substrates in areas with and without intercalated oxygen, demonstrating a high degree of consistency. The Van Hove singularities of the twisted graphene unambiguously indicate the Dirac energy between them, lending strong evidence to our assignment of the spectral features. In addition, we have discovered an O-Cu superstructure that has never been observed before.