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There has been considerable interest in building switching functions into self-assembled monolayers with switching actuated by external stimuli such as light, electrical current, heat, pressure or chemical changes. In this study, dual switching functionality has been built into azobenzene based molecular monolayers. Switching behaviour has been compared for unsubstituted azobenzene monolayer adsorbates and two other monolayers whose ortho position on the terminal phenyl group is substituted by ethyl and isopropyl chains, respectively. The dual molecular switching functionality with light or protonation actuation is compared. EGaIn contacts to the monolayers have been used to record the J - V curves and characterize the on/off switching. This is complemented with further characterization by transition voltage spectroscopy (TVS), ultraviolet photoelectron spectroscopy (UPS), water contact angle determination, atomic force microscopy (AFM) and theoretical computations. It is concluded that side chains (the ethyl and isopropyl groups) are able to decouple neighbouring azobenzene adsorbates which promotes the photo-efficiency of isomerisation and switching. In addition, acid treatment is also applied to these three molecular layers to try to achieve dual stimuli actuation. The absorption wavelength of the azobenzene moiety red shifts by ∼100 nm for all the three protonated molecules. In the case of the unsubstituted azobenzene, its triggering wavelength is totally reversed once it is protonated. A logic truth table has been constructed for the SAM device, which shows that the simple azobenzene molecular layers exhibit the behaviour of an 'AND' logic gate which uses blue light and acid as two inputs.

Due to its diverse allotropes and intriguing properties, 2D phosphorus, also known as phosphorene, is a material of great interest. Here, the successful growth of flat hexagonal 2D phosphorus on Au(111) is reported. Starting from phosphorus linear chains at low coverage, a porous network and finally an extended 2D flat hexagonal (HexP) layer while increasing phosphorus deposition is formed. Using scanning tunneling microscopy/spectroscopy combined with ab initio calculations, the structure and electronic properties of the as-grown phosphorus structures are followed. The progressive formation of a phosphorus electronic band in the conduction band region is followed. More strikingly, a partial flatband that appears only on the HexP phase characterized by a sharp peak in the electronic spectrum is observed. These bands arise from the hybridization of phosphorus and gold atoms. This novel phosphorus-based structure exhibits remarkable electronic properties due to gold mediated phosphorus-phosphorus electronic coupling. This work paves the way for new interface material developments with attractive electronic properties., (© 2024 The Author(s). Small published by Wiley‐VCH GmbH.)

Phosphorene, a semiconducting two-dimensional material, has recently attracted huge interest due to its potential applications in opto-electronics. The first attempts to synthesize phosphorene were based mainly on mechanical and chemical exfoliations. A few years later, different groups reported the synthesis of phosphorene using the molecular beam epitaxy process, which opened the way for research on physical properties. In this article, we report phosphorus growth on an Au(110) substrate via molecular beam epitaxy. The atomically resolved scanning tunneling microscopy images exhibit a self-assembled phosphorus-dimer structure, which is converted into phosphorus chains when increasing the phosphorus coverage. The chemical composition of the obtained structures is determined via Auger electron and X-ray photoelectron spectroscopies. Density functional theory calculations support the experimental findings.

We synthesized a sublimable molecular spin crossover Fe(II) complex based on the Schiff base tridentate ligand qsal-NEt 2 (5-diethylamino-2-((quinolin-8-ylimino)methyl)phenol). The compound undergoes a transition in temperature with thermally induced excited spin state-trapping (TIESST) for high-temperature sweep rates, which can be suppressed by reducing the sweep rate. The X-ray absorption spectroscopy (XAS) studies on the microcrystalline powder confirm the TIESST effect. The molecules are deposited under ultra-high vacuum on a graphene/SiO 2 substrate as a submonolayer. Investigation of the submonolayer by XAS reveals the molecular integrity and shows a spin crossover for the whole temperature range from 350 to 4 K, with residual HS species at low temperature and no TIESST effect. DFT calculations suggest a distribution of energetically similar adsorption configurations on graphene, i.e. , with smooth crossover behaviour and the absence of TIESST, consistent with very weak intermolecular interactions and the absence of large molecular islands within the submonolayer.

To create complementary metal oxide semiconductor compatible molecular devices, more insights into the electrode property regarding its metal/semiconductor doping level and creating a functional molecular device are required. In this work, we constructed an EGaIn/alkanethiol/Au-Si molecular diode (with a rectification ratio R of 50.70) induced by Schottky barriers within a gold-silicon doped electrode instead of the functional property of molecules. The relationship between the rectification ratio and the number of methylene units in alkanethiol was analyzed, revealing a gradual increase in the ratio from 3.33 for C 6 H 14 S to 50.70 for C 16 H 34 S. The rectification ratio of the junction is well modulated by the temperature due to the change in the Schottky barrier. Such a mechanism is explained by the energy band diagrams of the surface space charge region and a combination of density functional theory and Keldysh-Green formalism calculations.

Intrachain transport in molecular junctions (MJs) longer than 5 nm has been modeled within the theoretical framework of Marcus theory. We show that in oligo(bisthienylbenzene)-based MJs, electronic transport involves polarons, localized on three monomers that are close to 4 nm in length. They hop and tunnel between adjacent localized sites with reorganization energies λ close to 400-600 meV and electronic coupling parameters H ab close to λ/2. As a consequence, the activation energy for intrachain transport, given by the equation Δ G * = (λ/4)(1 - 2 H ab /λ) 2 , is close to zero, and transport along the chain is activationless, in agreement with experimental observation. On the contrary, similar calculations on conjugated oligonaphthalenefluoreneimine wires show that H ab is much less than λ/2 and predict that the activation energies for intrachain hopping between adjacent sites, close to λ/4, are ∼115 meV. This work proposes a new perspective for understanding long-range activationless transport in MJs beyond the tunneling regime.

Monolayer transition metal dichalcogenide VTe 2 exhibits multiple charge density wave (CDW) phases, mainly (4 × 4) and (4 × 1). Here we report facile dynamic and tens-of-nanometer scale switching between these CDW phases with gentle bias pulses in scanning tunneling microscopy. Bias pulses purposely stimulate a reversible random CDW symmetry change between the isotropic (4 × 4) and anisotropic (4 × 1) CDWs, as well as CDW phase slips and rotation. The switching threshold of ∼1.0 V is independent of bias polarity, and the switching rate varies linearly with the tunneling current. Density functional theory calculations indicate that a coherent CDW phase switching incurs an energy barrier of ∼2.0-3.0 eV per (4 × 4) unit cell. While there is a challenge in understanding the observed large-area CDW random fluttering, we provide some possible explanations. The ability to manipulate electronic CDW phases sheds new light on tailoring CDW properties on demand.

Quantum interference (QI) is well recognised as a significant contributing factor to the magnitude of molecular conductance values in both single-molecule and large area junctions. Numerous structure-property relationship studies have shown that para -connected oligo(phenyleneethynylene) (OPE) based molecular wires exemplify the impact of constructive quantum interference (CQI), whilst destructive quantum interference (DQI) effects are responsible for the orders of magnitude lower conductance of analogous meta -contacted OPE derivatives, despite the somewhat shorter effective tunnelling distance. Since molecular conductance is related to the value of the transmission function, evaluated at the electrode Fermi energy, T ( E F ), which in turn is influenced by the presence and relative energy of (anti)resonances, it follows that the relative single-molecule conductance of para - and meta -contacted OPE-type molecules is tuned both by the anchor group and the nature of the electrode materials used in the construction of molecular junctions (gold|molecule|gold vs. gold|molecule|graphene). It is shown here that whilst amine-contacted junctions show little influence of the electrode material on molecular conductance due to the similar electrode-molecule coupling through this anchor group to both types of electrodes, the weaker coupling between thiomethyl and ethynyl anchors and the graphene substrate electrode results in a relative enhancement of the DQI effect. This work highlights an additional parameter space to explore QI effects and establishes a new working model based on the electrode materials and anchor groups in modulating QI effects beyond the chemical structure of the molecular backbone.

We have assembled 4,8,12-tri- n -octyl-4,8,12-triazatrianguleniumtetrafluoroborate (TATA-BF 4 ) on highly oriented pyrolytic graphite (HOPG) and have studied the structure and tunneling properties of this self-assembled monolayer (SAM) using scanning tunneling microscopy (STM) under ambient conditions. We show that the triazatriangulenium cations TATA + form hexagonally packed structures driven by the interaction between the aromatic core and the HOPG lattice, as evidenced by density functional theory (DFT) modeling. According to the DFT results, the three alkyl chains of the platform tend to follow the main crystallographic directions of HOPG, leading to a different STM appearance. The STM contrast of the SAM shows that the monolayer is formed by two types of species, namely, TATA + with BF 4 - counterions on top and without them. The cationic TATA + platform gives rise to a seemingly higher appearance than neutral TATA-BF 4 , in contrast to observations made on metallic substrates. The variation of the STM tunneling parameters does not change the relative difference of contrast, revealing the stability of both species on HOPG. DFT calculations show that TATA-BF 4 on HOPG has sufficient binding energy to resist dissociation into TATA + and BF 4 - , which might occur under the action of the electric field in the tunneling gap during STM scanning., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

It has recently been demonstrated how the nitrogen dopant concentration in graphene can be controlled spatially on the nano-meter scale using a molecular mask. This technique may be used to create ballistic electron optics-like structures of high/low doping regions; for example, to focus electron beams, harnessing the quantum wave nature of the electronic propagation. Here, we employ large-scale Greens function transport calculations based on a tight-binding approach. We first benchmark different tight-binding models of nitrogen in graphene with parameters based on density functional theory (DFT) and the virtual crystal approximation (VCA). Then, we study theoretically how the random distribution within the masked regions and the discreteness of the nitrogen scattering centers impact the transport behavior of sharp n-p and n-n' interfaces formed by different, realistic nitrogen concentrations. We investigate how constrictions for the current can be realized by patterned high/low doping regions with experimentally feasible nitrogen concentrations. The constrictions can guide the electronic current, while the quantized conductance is significantly washed out due to the nitrogen scattering. The implications for device design is that a p-n junction with nitrogen corrugation should still be viable for current focusing. Furthermore, a guiding channel with less nitrogen in the conducting canal preserves more features of quantized conductance and, therefore, its low-noise regime.

Band engineering is employed thoroughly and targets technologically scalable photoanodes for solar water splitting applications. Complex and costly recipes are necessary, often for average performances. Here, we report simple photoanode growth and thermal annealing with effective band engineering results. By comparing Ti-doped hematite photoanodes annealed under nitrogen to photoanodes annealed in air, we found a strongly enhanced photocurrent of more than 200% in the first case. Using electrochemical impedance spectroscopy and synchrotron X-ray spectromicroscopy, we demonstrate that oxidized surface states and increased density of charge carriers are responsible for the enhanced photoelectrochemical (PEC) activity. Surface states are found to be related to the formation of pseudo-brookite clusters by surface Ti segregation. Spectro-ptychography is used for the first time at the Ti L 3 absorption edge to isolate Ti chemical coordination arising from pseudo-brookite cluster contribution. Correlated with electron microscopy investigation and density functional theory calculations, the synchrotron spectromicroscopy data unambiguously prove the origin of enhanced PEC activity of N 2 -annealed Ti-doped hematite nanorods. Finally, we present here a handy and cheap surface engineering method beyond the known oxygen vacancy doping, allowing a net gain in the PEC activity for the hematite-based photoanodes.

Atomically thin bismuth films (2D Bi) are becoming a promising research area due to their unique properties and their wide variety of applications in spintronics, electronic and optoelectronic devices. We report on the structural properties of Bi on Au(110), explored by low-energy electron diffraction (LEED), scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. At a Bi coverage lower than one monolayer (1 ML) various reconstructions are observed, we focus on Bi/Au(110)-c(2 × 2) reconstruction (at 0.5 ML) and Bi/Au(110)-(3 × 3) structure (at 0.66 ML). We propose models for both structures based on STM measurements and further confirm by DFT calculations., (© 2023 IOP Publishing Ltd.)

Lack of reproducibility hampers molecular devices integration into large-scale circuits. Thus, incorporating operando characterization can facilitate the understanding of multiple features producing disparities in different devices. In this work, we report the realization of hybrid molecular graphene field effect transistors (m-GFETs) based on 11-(Ferrocenyl)undecanethiol (FcC 11 SH) micro self-assembled monolayers (μSAMs) and high-quality graphene (Gr) in a back-gated configuration. On the one hand, Gr enables redox electron transfer, avoids molecular degradation and permits operando spectroscopy. On the other hand, molecular electrode decoration shifts the Gr Dirac point (V DP ) to neutrality and generates a photocurrent in the Gr electron conduction regime. Benefitting from this heterogeneous response, the m-GFETs can implement optoelectronic AND/OR logic functions. Our approach represents a step forward in the field of molecular scale electronics with implications in sensing and computing based on sustainable chemicals., (© 2023. The Author(s).)

We show that through the introduction of short dimethylsiloxane chains, it was possible to suppress the crystalline state of CBP in favor of various types of organization, transitioning from a soft crystal to a fluid liquid crystal mesophase, then to a liquid state. Characterized by X-ray scattering, all organizations reveal a similar layered configuration in which layers of edge-on lying CBP cores alternate with siloxane. The difference between all CBP organizations essentially lay on the regularity of the molecular packing that modulates the interactions of neighboring conjugated cores. As a result, the materials show quite different thin film absorption and emission properties, which could be correlated to the features of the chemical architectures and the molecular organizations.

We demonstrate, based on low-temperature scanning tunneling microscopy (STM) and spectroscopy, a pronounced negative differential resistance (NDR) in spin-crossover (SCO) molecular devices, where a Fe II SCO molecule is deposited on surfaces. The STM measurements reveal that the NDR is robust with respect to substrate materials, temperature, and the number of SCO layers. This indicates that the NDR is intrinsically related to the electronic structure of the SCO molecule. Experimental results are supported by density functional theory (DFT) with nonequilibrium Green's function (NEGF) calculations and a generic theoretical model. While the DFT+NEGF calculations reproduce NDR for a special atomically sharp STM tip, the effect is attributed to the energy-dependent tip density of states rather than the molecule itself. We, therefore, propose a Coulomb blockade model involving three molecular orbitals with very different spatial localization as suggested by the molecular electronic structure.

The adsorption of phthalocyanine (H 2 Pc) on the 6H-SiC(0001)-(3 × 3) surface is investigated using X-ray photoelectron spectroscopy (XPS), near edge X-ray absorption fine structure spectroscopy (NEXAFS), and density functional theory (DFT) calculations. Spectral features are tracked from the submonolayer to the multilayer growth regime, observing a significant modification of spectroscopic signals at low coverage with respect to the multilayer films, where molecules are weakly interacting. Molecules stay nearly flat on the surface at the mono and submonolayers. Previously proposed adsorption models, where the molecule binds by two N atoms to corresponding Si adatoms, do not reproduce the experimental spectra at the submonolayer coverage. We find instead that another adsorption model where the molecule replaces the two central H atoms by a Si adatom, effectively forming Si-phthalocyanine (SiPc), is both energetically more stable and yields in combination a better agreement between the experimental and simulated spectra. This suggests that the 6H-SiC(0001)-(3 × 3) surface may be a candidate substrate for the on-surface synthesis of SiPc molecules.

The single-molecular conductance of a redox active viologen molecular bridge between Au|graphene electrodes has been studied in an electrochemical gating configuration in an ionic liquid medium. A clear "off-on-off" conductance switching behaviour has been achieved through gating of the redox state when the electrochemical potential is swept. The Au|viologen|graphene junctions show single-molecule conductance maxima centred close to the equilibrium redox potentials for both reduction steps. The peak conductance of Au|viologen|graphene junctions during the first reduction is significantly higher than that of previously measured Au|viologen|Au junctions. This shows that even though the central viologen moiety is not directly linked to the enclosing electrodes, substituting one gold contact for a graphene one nevertheless has a significant impact on junction conductance values. The experimental data was compared against two theoretical models, namely a phase coherent tunnelling and an incoherent "hopping" model. The former is a simple gating monoelectronic model within density functional theory (DFT) which discloses the charge state evolution of the molecule with electrode potential. The latter model is the collective Kuznetsov Ulstrup model for 2-step sequential charge transport through the redox centre in the adiabatic limit. The comparison of both models to the experimental data is discussed for the first time. This work opens perspectives for graphene-based molecular transistors with more effective gating and fundamental understanding of electrochemical electron transfer at the single molecular level.

This work reports on the electron-induced modification of NaCl thin film grown on Ag(110). We show using low energy electron diffraction that electron beam bombardment leads to desorption and formation of Cl vacancy defects on NaCl surface. The topographic structure of these defects is studied using scanning tunneling microscopy (STM) showing the Cl defects as depressions on the NaCl surface. Most of the observed defects are mono-atomic vacancies and are located on flat NaCl terraces. Auger electron spectroscopy confirms the effect of electron exposure on NaCl thin films showing Cl atoms desorption from the surface. Using density functional theory taken into account the van der Waals dispersion interactions, we confirm the observed experimental STM measurements with STM simulation. Furthermore, comparing the adsorption of defect free NaCl and defective NaCl monolayer on Ag(110) surfaces, we found an increase of the adhesion energy and the charge transfer between the NaCl film and the substrate due to the Cl vacancy. In details, the adhesion energy increases between the NaCl film and the metallic Ag substrate from 30.4 meV Å -2 for the NaCl film without Cl vacancy and from 39.5 meV Å -2 for NaCl film with a single Cl vacancy. The charge transfer from the NaCl film to the Ag substrate is enhanced when the vacancy is created, from 0.63e - to 1.25e - ., (© 2021 IOP Publishing Ltd.)

The use of graphene as a new type of electrode at molecular junctions has led to a renewal of molecular electronics. Indeed, the symmetry breaking induced by the graphene electrode yields different electronic behaviors at the molecular junction and in particular enhanced conductance for longer molecules. In this respect, several studies involving different molecular backbones and anchoring groups have been performed. Here in the same line, we consider oligopthiophene based hybrid gold-graphene junctions and we measure their electrical properties using the STM- I ( s ) method in order to determine their attenuation factor and the effect of specific anchoring groups. The results are supported by density functional theory (DFT) calculations, and exhibit a similar behavior to what is observed at alkane-based junctions.

The emergence of peculiar phenomena in 1D phosphorene chains (P chains) has been proposed in theoretical studies, notably the Stark and Seebeck effects, room temperature magnetism, and topological phase transitions. Attempts so far to fabricate P chains, using the top-down approach starting from a few layers of bulk black phosphorus, have failed to produce reliably precise control of P chains. We show that molecular beam epitaxy gives a controllable bottom-up approach to grow atomically thin, crystalline 1D flat P chains on a Ag(111) substrate. Scanning tunneling microscopy, angle-resolved photoemission spectroscopy, and density functional theory calculations reveal that the armchair-shaped chains are semiconducting with an intrinsic 1.80 ± 0.20 eV band gap. This could make these P chains an ideal material for opto-electronic devices., (© 2021. The Author(s).)

Chemical coupling of functional molecules on top of the so-called platform molecules allows the formation of functional self-assembled monolayers (SAMs). An often-used example of such a platform is triazatriangulenium (TATA), which features an extended aromatic core providing good electronic contact to the underlying metal surface. Here, we present a study of the SAM formation of a TATA platform on Au(111) employing scanning tunneling microscopy (STM) under ambient atmospheric conditions. In solution, the TATA platform is stabilized by BF4 counterions, while after deposition on a gold substrate, the localization of the BF4 counterions remains unknown. We used 1,2,4-trichlorobenzene as a solvent of TATA-BF4 to induce SAM formation on a heated (∼50 °C) Au substrate. We show by STM how to detect and distinguish TATA-BF4 from TATA platforms, which lost their BF4 counterions. Finally, we observe a change of the counterion position on the SAM during the STM scanning, which we explain by an electric-field-induced decrease of the electrostatic interaction in TATA-BF4 on the surface. We applied DFT calculations to reveal the influence of the gold lattice and the electric field of the STM tip on the stability of TATA-BF4 physisorbed on the surface.

The synthesis of blue phosphorene by molecular beam epitaxy (MBE) has recently come under the spotlight due to its potential applications in electronic and optoelectronic devices. However, this synthesis remains a significant challenge. The surface reactivity between the P atoms and the Au atoms should be considered for the P/Au(111) system. In the MBE process, the temperature of the substrate is a key parameter for the growth of blue phosphorene. During the initial growth stage, irregularly shaped Phosphorus clusters grow on top of Au(111) surface at room temperature. When the substrate temperature is increased, these clusters transform into a phosphorene-like structure with a honeycomb lattice. An atom exchange reaction is observed between the P and first layer Au atoms under thermal activation at higher temperature, where the P atoms replace Au atoms to form a blue phosphorene structure within the top Au layer and at the step edges.

The interaction of molecules with surfaces plays a crucial role in the electronic and chemical properties of supported molecules and needs a comprehensive description of interfacial effects. Here, we unveil the effect of the substrate on the electronic configuration of iron porphyrin molecules on Au(111) and graphene, and we provide a physical picture of the molecule-surface interaction. We show that the frontier orbitals derive from different electronic states depending on the substrate. The origin of this difference comes from molecule-substrate orbital selective coupling caused by reduced symmetry and interaction with the substrate. The weak interaction on graphene keeps a ground state configuration close to the gas phase, while the stronger interaction on gold stabilizes another electronic solution. Our findings reveal the origin of the energy redistribution of molecular states for noncovalently bonded molecules on surfaces.

Incorporating functional atomic sites in graphene is essential for realizing advanced two-dimensional materials. Doping graphene with nitrogen offers the opportunity to tune its chemical activity with significant charge redistribution occurring between molecules and substrate. The necessary atomic scale understanding of how this depends on the spatial distribution of dopants, as well as their positions relative to the molecule, can be provided by scanning tunneling microscopy. Here we show that a noncovalently bonded molecule such as CoPc undergoes a variable charge transfer when placed on N-doped graphene; on a nitrogen pair, it undergoes a redox reaction with an integral charge transfer whereas a lower fractional charge transfer occurs over a single nitrogen. Thus, the charge state of molecules can be tuned by suitably tailoring the conformation of dopant atoms.

The single molecule conductance of hybrid platinum/alkanedithiol/graphene junctions has been investigated with a focus on understanding the influence of employing two very different contact types. We call this an "anti-symmetric" configuration, with the two different contacts here being platinum and graphene, which respectively provide very different electronic coupling to the alkanedithiol bridge. The conductance of these junctions is experimentally investigated by using a non-contact scanning tunneling microscopy (STM) based method called the I(s) technique. These experimental determinations are supported by density functional theory (DFT) calculations. These alkanedithiol bridging molecules conduct electric current through the highest occupied molecular orbital (HOMO), and junctions formed with Pt/graphene electrode pairs are slightly more conductive than those formed with Au/graphene electrodes which we previously investigated. This is consistent with the lower work function of gold than that of platinum. The measured conductance decays exponentially with the length of the molecular bridge with a low tunneling decay constant, which has a similar value for Pt/graphene and Au/graphene electrode pairs, respectively. These new results underline the importance of the coupling asymmetry between the two electrodes, more than the type of the metal electrode itself. Importantly, the tunneling decay constant is much lower than that of alkanedithiols with the symmetrical equivalent, i.e. identical metal electrodes. We attribute this difference to the relatively weak van der Waals coupling at the graphene interface and the strong bond dipole at the Pt-S interface, resulting in a decrease in the potential barrier at the interface.

Combining STM measurements on three different substrates (HOPG, MoS 2 , and Au[111]) together with DFT calculations allow for analysis of the origin of the self-assembly of 4-cyano-4'-n-decylbiphenyl (10CB) molecules into kinked row structures using a previously developed phenomenological model. This molecule has an alkyl chain with 10 carbons and a cyanobiphenyl group with a particularly large dipole moment. 10CB represents a toy model that we use here to unravel the relationship between the induced kinked structure, in particular the corresponding chirality expression, and the balanced intermolecular/molecule-substrate interaction. We show that the local ordered structure is driven by the typical alkyl chain/substrate interaction for HOPG and Au[111] and the cyanobiphenyl group/substrate interaction for MoS 2 . The strongest molecule/substrate interactions are observed for MoS 2 and Au[111]. These strong interactions should have led to non-kinked, commensurate adsorbed structures. However, this latter appears impossible due to steric interactions between the neighboring cyanobiphenyl groups that lead to a fan-shape structure of the cyanobiphenyl packing on the three substrates. As a result, the kink-induced chirality is particularly large on MoS 2 and Au[111]. A further breaking of symmetry is observed on Au[111] due to an asymmetry of the facing molecules in the rows induced by similar interactions with the substrate of both the alkyl chain and the cyanobiphenyl group. We calculate that the overall 10CB/Au[111] interaction is of the order of 2 eV per molecule. The close 10CB/MoS 2 interaction, in contrast, is dominated by the cyanobiphenyl group, being particularly large possibly due to dipole-dipole interactions between the cyanobiphenyl groups and the MoS 2 substrate.

We report on Kelvin probe force microscopy (KPFM) and density functional theory (DFT) investigations of charge transfers in vertical heterojunctions between tungsten diselenide (WSe 2 ) layers and graphene on silicon carbide substrates. The experimental data reveal the existence of an interface dipole, which is shown by DFT to originate from the neutralization of the graphene n-doping by an electron transfer towards the transition metal dichalcogenide (TMD) layer. The relative vacuum level shift probed by KPFM between the TMD and the substrate stays constant when passing from monolayer to bilayer graphene, which confirms that the Schottky-Mott model can be rigorously applied to these interfaces by taking into account the charge transfer from the substrate to the TMD. DFT calculations show that the first TMD layer absorbs almost all the excess charges contained in the graphene, and that the second TMD layer shall not play a significant role in the electrostatics of the system. Negatively charged defect at the TMD edges contribute however to the electrostatic landscape probed by KPFM on both TMD layers.

Molecular switches are building blocks of potential interest to store binary information, especially when they can be organized in periodic lattices. Among the variety of possible systems, switches based on hydrogen transfer are of special importance because they allow the switching operation to occur without severe conformational change that may interfere with neighboring molecular units. We have studied the excitation process of hydrogen transfer inside porphyrin molecules assembled on a graphene surface, using a low-temperature scanning tunneling microscope. We show that this hydrogen transfer is induced by an electronic resonant tunneling process through the molecular orbitals. Using nitrogen doping of graphene, we tune the rate of hydrogen transfer by shifting the molecular orbital energies owing to the charge transfer at nitrogen dopant sites in the graphene lattice. The control of the switching process allows the storage of information inside a molecular lattice, which is demonstrated by writing an artificial pattern inside a molecular island.

One of the important issues of molecular spintronics is the control and manipulation of charge transport and, in particular, its spin polarization through single-molecule junctions. Using ab initio calculations, we explore spin-polarized electron transport across single benzene derivatives attached with six different anchoring groups (S, CH 3 S, COOH, CNH 2 NH, NC and NO 2 ) to Ni(1 1 1) electrodes. We find that molecule-electrode coupling, conductance and spin polarization (SP) of electric current can be modified significantly by anchoring groups. In particular, a high spin polarization (SP  >  80%) and a giant magnetoresistance (MR  >  140%) can be achieved for NO 2 terminations and, more interestingly, SP can be further enhanced (up to 90%) by a small voltage. The S and CH 3 S systems, on the contrary, exhibit rather low SP while intermediate values are found for COOH and CNH 2 NH groups. The results are analyzed in detail and explained by orbital symmetry arguments, hybridization and spatial localization of frontier molecular orbitals. We hope that our comparative and systematic studies will provide valuable quantitative information for future experimental measurements on that kind of systems and will be useful for designing high-performance spintronics devices.

Spin-crossover molecules are very appealing for use in multifunctional spintronic devices because of their ability to switch between high-spin and low-spin states with external stimuli such as voltage and light. In actual devices, the molecules are deposited on a substrate, which can modify their properties. However, surprisingly little is known about such molecule-substrate effects. Here we show for the first time, by grazing incidence X-ray diffraction, that an Fe II spin-crossover molecular layer displays a well-defined epitaxial relationship with a metal substrate. Then we show, by both density functional calculations and a mechanoelastic model, that the resulting epitaxial strain and the related internal pressure can induce a partial spin conversion at low temperatures, which has indeed been observed experimentally. Our results emphasize the importance of substrate-induced spin state transitions and raise the possibility of exploiting them.

A combined experimental and theoretical study on molecular junctions with asymmetry in both the electrode type and in the anchoring group type is presented. A scanning tunnelling microscope is used to create the "asymmetric" Au-S-(CH 2 )n-COOH-graphene molecular junctions and determine their conductance. The measurements are combined with electron transport calculations based on density functional theory (DFT) to analyze the electrical conductance and its length attenuation factor from a series of junctions of different molecular length (n). These results show an unexpected trend with a rather high conductance and a smaller attenuation factor for the Au-S-(CH 2 ) n -COOH-graphene configuration compared to the equivalent junction with the "symmetrical" COOH contacting using the HOOC-(CH 2 ) n -COOH series. Owing to the effect of the graphene electrode, the attenuation factor is also smaller than the one obtained for Au/Au electrodes. These results are interpreted through the relative molecule/electrode couplings and molecular level alignments as determined with DFT calculations. In an asymmetric junction, the electrical current flows through the less resistive conductance channel, similarly to what is observed in the macroscopic regime., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Silicon oxide can be formed in a crystalline form, when prepared on a metallic substrate. It is a candidate support catalyst and possibly the ultimately thin version of a dielectric host material for two-dimensional materials and heterostructures. We determine the atomic structure and chemical bonding of the ultimately thin version of the oxide, epitaxially grown on Ru(0001). In particular, we establish the existence of two sublattices defined by metal-oxygen-silicon bridges involving inequivalent substrate sites. We further discover four electronic bands below the Fermi level, at high binding energy, two of them having a linear dispersion at their crossing K point (Dirac cones) and two others forming semiflat bands. While the latter two correspond to hybridized states between the oxide and the metal, the former relate to the topmost silicon-oxygen plane, which is not directly coupled to the substrate. Our analysis is based on high-resolution X-ray photoelectron spectroscopy, angle-resolved photoemission spectroscopy, scanning tunneling microscopy, and density functional theory calculations.

Within the framework of 2D materials, we present four theoretical models of a vertical field-effect transistor (FET) composed of simple alternate graphene and MoS 2 layers. The electronic transport properties at a specific graphene/MoS 2 interface in each configuration are investigated by focusing in particular on the current as a function of the gate voltage. The gate voltage, simulated with a shift of the bands of a specific layer, allows us to tune the current at the interface and the charge transfer between the planes. This analysis of the charge transfer as a function of the gate voltage reveals a strong connection with the transport characteristics as the slope of the current curve. The analysis of physical phenomena at the graphene/MoS 2 interface can further improve the 2D vertical FET performance and contribute to the development of new 2D nanotechnology.

The outstanding properties of porphyrins and the extreme versatility of their synthesis and their functionalisation constitute real assets for the fabrication of opto- and electroactive materials or for biological applications. In the large collection of porphyrinic structures, meso-substituted anthracenylporphyrins are among the less studied. Here, we synthesised the 5,10,15,20-tetra-bromoanthracenylporphyrin (BrTAP) and we investigated its chemical reactivity by post-synthetic modification using Suzuki-Miyaura cross coupling reactions with a series of boronic acids to generate a collection of original tetra-anthracenyl porphyrin based molecules: tetraphenylanthracenylporphyrin (TPAP), tetratolylanthracenylporphyrin (TTAP), tetramethoxyphenylanthracenylporphyrin (TMPAP), tetranaphthylanthracenylporphyrin (TNAP) and tetrapyrenylanthracenylporphyrin (TPyAP). Optical characterisations of these modified porphyrins showed, in most cases, only emission of the porphyrin in the visible region with extinction of the fluorescence of PAHs in the UV or visible region.

A fully metal-free molecular junction (MJ) has been built by using an electrochemically etched carbon fibre STM tip as the top electrode and graphene as the bottom electrode. The corresponding conductance values for 1,n-alkanediamine and 1,n-alkanedithiol (n = 2, 4, 6, 8 and 10) have been measured using the STM-I(s) technique. The tunnelling decay constant of the alkanediamine and alkanedithiol junctions with these carbon contacts is much lower than the corresponding metal contacted junctions of 0.24 and 0.38 per -CH2 unit, but the junction conductance with these carbon contacts is also lower. The carbon fibre tip can be considered a good candidate as an electrode. Compared with a gold tip, the carbon fibre tip leads to correspondingly lower molecular junction conductance.

In this study, we introduce an efficient data sorting algorithm, including filters for noisy signals, conductance mapping for analyzing the most dominant conductance group and sub-population groups. The capacity of our data analysis process has also been corroborated on real experimental data sets of Au-1,6-hexanedithiol-Au and Au-1,8-octanedithiol-Au molecular junctions. The fully automated and unsupervised program requires less than one minute on a standard PC to sort the data and generate histograms. The resulting one-dimensional and two-dimensional log histograms give conductance values in good agreement with previous studies. Our algorithm is a straightforward, fast and user-friendly tool for single molecule charge transport data analysis. We also analyze the data in a form of a conductance map which can offer evidence for diversity in molecular conductance. The code for automatic data analysis is openly available, well-documented and ready to use, thereby offering a useful new tool for single molecule electronics.

A theoretical study of a graphene-like tip used in atomic force microscopy (AFM) is presented. Based on first principles simulations, we proved the low reactivity of this kind of tip, using a MoS 2 monolayer as the testing sample. Our simulations show that the tip-MoS 2 interaction is mediated through weak van der Waals forces. Even on the defective monolayer, the interaction is reduced by one order of magnitude with respect to the values obtained using a highly reactive metallic tip. On the pristine monolayer, the S atoms were imaged for large distances together with the substitutional defects which should be observed as brighter spots in non-contact AFM measurements. This result is in contradiction with previous simulations performed with Cu or Si tips where the metallic defects were imaged for much larger distances than the S atoms. For shorter distances, the Mo sites will be brighter even though a vacancy is formed. On the other hand, the largest conductance value is obtained over the defect formed by two Mo atoms occupying a S divacancy when the half-occupied p y -states of the graphene-like tip find a better coupling with d-orbitals of the highest substitutional atom. Due to the weak interaction, no conductance plateau is formed in any of the sites. A great advantage of this tip lies in the absence of atomic transfer between the tip and the sample leading to a more stable AFM measurement. Finally, and as previously shown, we confirm the atomic resolution in a scanning tunneling microscopy simulation using this graphene-based tip.

Van der Waals heterojunctions composed of graphene and transition metal dichalcogenides have gain much attention because of the possibility to control and tailor band structure, promising applications in two-dimensional optoelectronics and electronics. In this report, we characterized the van der Waals heterojunction MoSe 2 /few-layer graphene with a high-quality interface using cutting-edge surface techniques scaling from atomic to microscopic range. These surface analyses gave us a complete picture of the atomic structure and electronic properties of the heterojunction. In particular, we found two important results: the commensurability between the MoSe 2 and few-layer graphene lattices and a band-gap opening in the few-layer graphene. The band gap is as large as 250 meV, and we ascribed it to an interface charge transfer that results in an electronic depletion in the few-layer graphene. This conclusion is well supported by electron spectroscopy data and density functional theory calculations. The commensurability between the MoSe 2 and graphene lattices as well as the band-gap opening clearly show that the interlayer interaction goes beyond the simple van der Waals interaction. Hence, stacking two-dimensional materials in van der Waals heterojunctions enables us to tailor the atomic and electronic properties of individual layers. It also permits the introduction of a band gap in few-layer graphene by interface charge transfer.

The unique structural and electronic characteristics of graphene make it an attractive contact for fundamental single-molecule electrical studies. With this in mind, we have probed here the electrical conductance of a molecular junction based on α,ω-diaminoalkane chains sandwiched between a gold and a graphene electrode. Using an STM based I(s) method combined with density functional theory-based transport calculations, we demonstrate that the resulting attenuation factor turns out to be much lower when compared to the standard molecular junction between two gold electrodes. This effect is attributed to asymmetric coupling of the molecule through strong chemisorption at the gold electrode and weaker van der Waals contact at graphene. Moreover, this asymmetric coupling induces higher conductance than that in the same hybrid metal-graphene molecular junction using standard thiol anchoring groups.

The ability to trap adatoms with an organic molecule on a surface has been used to obtain a range of molecular functionalities controlled by the choice of the molecular trapping site and local deprotonation. The tetraphenylporphyrin molecule used in this study contains three types of trapping sites: two carbon rings (phenyl and pyrrole) and the center of a macrocycle. Catching a gold adatom on the carbon rings leads to an electronic doping of the molecule, whereas trapping the adatom at the macrocycle center with single deprotonation leads to a molecular rotor and a second deprotonation leads to a molecular jumper. We call "atom trapping chemistry" the control of the structure, electronic, and dynamical properties of a molecule achieved by trapping metallic atoms with a molecule on a surface. In addition to the examples previously described, we show that more complex structures can be envisaged.

Few- and single-layer MoS 2 host substantial densities of defects. They are thought to influence the doping level, the crystal structure, and the binding of electron-hole pairs. We disentangle the concomitant spectroscopic expression of all three effects and identify to what extent they are intrinsic to the material or extrinsic to it, i.e., related to its local environment. We do so by using different sources of MoS 2 -a natural one and one prepared at high pressure and high temperature-and different substrates bringing varying amounts of charged impurities and by separating the contributions of internal strain and doping in Raman spectra. Photoluminescence unveils various optically active excitonic complexes. We discover a defect-bound state having a low binding energy of 20 meV that does not appear sensitive to strain and doping, unlike charged excitons. Conversely, the defect does not significantly dope or strain MoS 2 . Scanning tunneling microscopy and density functional theory simulations point to substitutional atoms, presumably individual nitrogen atoms at the sulfur site. Our work shows the way to a systematic understanding of the effect of external and internal fields on the optical properties of two-dimensional materials.

We present a theoretical study of molecular adsorption on defects on a MoS 2 monolayer. Based on Density Functional Theory, our calculations confirm that small inorganic molecules, such as CO 2 , CO, H 2 O, NO, NO 2 , H 2 and N 2 , remain bonded to the pristine monolayer through weak van der Waals interactions, suggesting that the molecules may easily diffuse over the clean monolayer. On the other hand, the introduction of defects can lead to three different situations, depending on the defect and the molecule considered: physisorption, chemical (strong) bonding to the metallic defects, namely the Mo substitutional atoms on the S vacancies, and dissociation, that can take place spontaneously at 0 K in some specific cases or by the effect of thermal agitation in molecules such as CO 2 or NO 2 on the S vacancy. Our energetic and electronic analyses provide an explanation to such bonding possibilities, showing that in the low interacting situations, the molecules tend to adopt a planar configuration parallel to the monolayer, while a molecular rotation is favored in order to facilitate the bond formation on the reactive sites. Finally, the ab initio based Scanning Tunneling Microscopy (STM) simulations show the fingerprint of each molecule adsorbed on the most reactive site. This work opens the way to the possibility of tuning the catalytic properties of MoS 2 by controlling the creation of specific defects in the MoS 2 monolayer.

Structural defects in the molybdenum disulfide (MoS 2 ) monolayer are widely known for strongly altering its properties. Therefore, a deep understanding of these structural defects and how they affect MoS 2 electronic properties is of fundamental importance. Here, we report on the incorporation of atomic hydrogen in monolayered MoS 2 to tune its structural defects. We demonstrate that the electronic properties of single layer MoS 2 can be tuned from the intrinsic electron (n) to hole (p) doping via controlled exposure to atomic hydrogen at room temperature. Moreover, this hydrogenation process represents a viable technique to completely saturate the sulfur vacancies present in the MoS 2 flakes. The successful incorporation of hydrogen in MoS 2 leads to the modification of the electronic properties as evidenced by high resolution X-ray photoemission spectroscopy and density functional theory calculations. Micro-Raman spectroscopy and angle resolved photoemission spectroscopy measurements show the high quality of the hydrogenated MoS 2 confirming the efficiency of our hydrogenation process. These results demonstrate that the MoS 2 hydrogenation could be a significant and efficient way to achieve tunable doping of transition metal dichalcogenides (TMD) materials with non-TMD elements.

A challenge in molecular spintronics is to control the magnetic coupling between magnetic molecules and magnetic electrodes to build efficient devices. Here we show that the nature of the magnetic ion of anchored metal complexes highly impacts the exchange coupling of the molecules with magnetic substrates. Surface anchoring alters the magnetic anisotropy of the cobalt(II)-containing complex (Co(Pyipa) 2 ), and results in blocking of its magnetization due to the presence of a magnetic hysteresis loop. In contrast, no hysteresis loop is observed in the isostructural nickel(II)-containing complex (Ni(Pyipa) 2 ). Through XMCD experiments and theoretical calculations we find that Co(Pyipa) 2 is strongly ferromagnetically coupled to the surface, while Ni(Pyipa) 2 is either not coupled or weakly antiferromagnetically coupled to the substrate. These results highlight the importance of the synergistic effect that the electronic structure of a metal ion and the organic ligands has on the exchange interaction and anisotropy occurring at the molecule-electrode interface.

We have measured the single-molecule conductance of 1,n-alkanedithiol molecular bridges (n = 4, 6, 8, 10, 12) on a graphene substrate using scanning tunneling microscopy (STM)-formed electrical junctions. The conductance values of this homologous series ranged from 2.3 nS (n = 12) to 53 nS (n = 4), with a decay constant β n of 0.40 per methylene (-CH 2 ) group. This result is explained by a combination of density functional theory (DFT) and Keldysh-Green function calculations. The obtained decay, which is much lower than the one obtained for symmetric gold junctions, is related to the weak coupling at the molecule-graphene interface and the electronic structure of graphene. As a consequence, we show that using graphene nonsymmetric junctions and appropriate anchoring groups may lead to a much-lower decay constant and more-conductive molecular junctions at longer lengths.

Spin cross-over molecules show the unique ability to switch between two spin states when submitted to external stimuli such as temperature, light or voltage. If controlled at the molecular scale, such switches would be of great interest for the development of genuine molecular devices in spintronics, sensing and for nanomechanics. Unfortunately, up to now, little is known on the behaviour of spin cross-over molecules organized in two dimensions and their ability to show cooperative transformation. Here we demonstrate that a combination of scanning tunnelling microscopy measurements and ab initio calculations allows discriminating unambiguously between both states by local vibrational spectroscopy. We also show that a single layer of spin cross-over molecules in contact with a metallic surface displays light-induced collective processes between two ordered mixed spin-state phases with two distinct timescale dynamics. These results open a way to molecular scale control of two-dimensional spin cross-over layers.

Two-dimensional layered MoS2 shows great potential for nanoelectronic and optoelectronic devices due to its high photosensitivity, which is the result of its indirect to direct band gap transition when the bulk dimension is reduced to a single monolayer. Here, we present an exhaustive study of the band alignment and relativistic properties of a van der Waals heterostructure formed between single layers of MoS2 and graphene. A sharp, high-quality MoS2-graphene interface was obtained and characterized by micro-Raman spectroscopy, high-resolution X-ray photoemission spectroscopy (HRXPS), and scanning high-resolution transmission electron microscopy (STEM/HRTEM). Moreover, direct band structure determination of the MoS2/graphene van der Waals heterostructure monolayer was carried out using angle-resolved photoemission spectroscopy (ARPES), shedding light on essential features such as doping, Fermi velocity, hybridization, and band-offset of the low energy electronic dynamics found at the interface. We show that, close to the Fermi level, graphene exhibits a robust, almost perfect, gapless, and n-doped Dirac cone and no significant charge transfer doping is detected from MoS2 to graphene. However, modification of the graphene band structure occurs at rather larger binding energies, as the opening of several miniband-gaps is observed. These miniband-gaps resulting from the overlay of MoS2 and the graphene layer lattice impose a superperiodic potential.

Two-dimensional layered transition metal dichalcogenides (TMDCs) show great potential for optoelectronic devices due to their electronic and optical properties. A metal-semiconductor interface, as epitaxial graphene - molybdenum disulfide (MoS2), is of great interest from the standpoint of fundamental science, as it constitutes an outstanding platform to investigate the interlayer interaction in van der Waals heterostructures. Here, we study large area MoS2-graphene-heterostructures formed by direct transfer of chemical-vapor deposited MoS2 layer onto epitaxial graphene/SiC. We show that via a direct transfer, which minimizes interface contamination, we can obtain high quality and homogeneous van der Waals heterostructures. Angle-resolved photoemission spectroscopy (ARPES) measurements combined with Density Functional Theory (DFT) calculations show that the transition from indirect to direct bandgap in monolayer MoS2 is maintained in these heterostructures due to the weak van der Waals interaction with epitaxial graphene. A downshift of the Raman 2D band of the graphene, an up shift of the A1g peak of MoS2 and a significant photoluminescence quenching are observed for both monolayer and bilayer MoS2 as a result of charge transfer from MoS2 to epitaxial graphene under illumination. Our work provides a possible route to modify the thin film TDMCs photoluminescence properties via substrate engineering for future device design.

Free-base porphyrin molecules offer appealing options to tune the interaction with their environment via the manipulation of their inner hydrogen atoms and molecular conformation. Using scanning tunneling microscopy we show, through a systematic study, that the molecular conformation, electronic gap, wave function, and molecule-substrate interaction are modified by hydrogen switch or removal. Experimental results in combination with ab initio calculations provide an understanding of the underlying physical process.