For their incorporation in molecular spintronic devices, it is mandatory to understand how the properties of spin-crossover molecules are modified when they are in direct contact with metallic substrates and how the growth of molecular films is governed by the substrate. In this context, we investigate in detail the structure of [FeII(HB(3,5-(CH3)2Pz)3)2] (Pz = pyrazolyl) ultrathin films adsorbed on Cu(110) using grazing incidence X-ray diffraction measurements, along with their spin-crossover properties measured by X-ray absorption spectroscopy. For submonolayer coverage, the molecules self-assemble into two equivalent domains that are in a perfect epitaxial relationship with the Cu(110) substrate at room temperature. In parallel, the molecules are fully locked in a high spin (HS) state at low temperature. Density functional theory calculations show that there is a complex interplay between the epitaxial strain effect and the binding to the substrate that governs the orientation growth and the spin-crossover properties of the molecular films. For thicker thicknesses, a layer-by-layer growth of the (100) planes of the molecular bulk crystal with the release of the epitaxial constraint is observed, while the spin-crossover properties of the films are partially recovered with the opening of a hysteresis. The results obtained are very different from those observed on thin films adsorbed on Cu(111), indicating that not only the nature of the substrate but also its symmetry influences the spin-crossover properties of molecules.

Au(111) with its famous surface reconstruction has led to many studies, but its subsurface structure has never been determined. Here, we study the Au(677) surface which is a vicinal of Au(111) with steps and surface reconstruction, showing an array of surface dislocations. By using surface x-ray diffraction and atomistic simulations, we are able to quantitatively determine the complete structure and the strain fields associated with the surface reconstruction described in terms of surface dislocations, especially a stair-rod dislocation lying parallel to the surface step. The stair-rod dislocation strain field adds up to the one due to the step dipole, explaining the extraordinary regularity of the step array. We can also give new insights on the strain field associated with the Au(111) surface discommensuration lines (22×sqrt[3] reconstruction) and find that it penetrates deeply into the bulk, in contrast with commonly used surface reconstruction models.

Monolayer transition metal dichalcogenide VTe2 exhibits multiple charge density wave (CDW) phases, mainly (4 x 4) and (4 x 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 x 4) and anisotropic (4 x 1) CDWs, as well as CDW phase slips and rotation. The switching threshold of similar to 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 similar to 2.0-3.0 eV per (4 x 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.

We synthesized a sublimable molecular spin crossover Fe(II) complex based on the Schiff base tridentate ligand qsal-NEt2 (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/SiO2 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.

We investigate the combination of nitrogen doping and vacancies in highly ordered pyrolytic graphite (HOPG), to engineer defect sites with adjustable electronic properties. We combine scanning tunneling microscopy and spectroscopy and density functional theory calculations to reveal the synergistic effects of nitrogen and vacancies in HOPG. Our findings reveal a remarkable shift of the vacancy-induced resonance peak from an unoccupied state in pristine HOPG to an occupied state in nitrogen-doped HOPG. This shift directly correlates with the shift of the charge neutrality point resulting from the n-doping induced by substitutional nitrogen. These results open new avenues for defect engineering in graphite or graphene and achieving novel functionalities for chemical activity or electronic properties.

Alkali atom doping is an efficient way to induce charge transfer and Fermi level tuning in layered materials through intercalation. However, there is a general lack of microscopic understanding of the effect of doping inhomogeneity in geometric and electronic aspects. Here, we report surface doping of a bulk VSe2 crystal by sodium. Na atoms form intercalated subsurface islands that modify the electronic phase of the top layer of VSe2. In addition to n-doping, the charge density wave of the intercalated VSe2 surface layer changes from the (4 x 4) bulk phase to the (3x7$\sqrt 3 {\bm{ \times }}\sqrt 7 $) known in monolayer phase of VSe2. Surprisingly, an electronic state at the edges of Na-intercalated area shift anomalously upward in energy as detected by scanning tunneling spectroscopy. This is explained by a local gating effect resulting from local dipoles at the edges. The study illustrates a clear example of intercalation effect that should be general in alkali-intercalated bulk layered materials.

The coupling of graphene with a ferromagnetic material opens opportunities for technological innovations in spintronics. To obtain this coupling it is necessary to control the elaboration of interfaces at the atomic scale. Here, we present results on cobalt intercalation between graphene and a buffer layer supported on a SiC(0001) substrate. As a result, we obtain cobalt islands covered by graphene whose local electronic properties are measured by scanning tunneling microscopy and spectroscopy. These islands reveal two very distinct shapes and properties. Small-islands with atomic height and very narrow size distribution and, more interestingly, flat cobalt nanodots lower than one nanometer high, that are encapsulated by graphene. Compared to a graphene monolayer on SiC, those nanodots exhibit very different spectroscopic signatures. Using dI/dV local differential conductance spectra together with an analysis of image potential surface states measured thanks to dz/dV spectra, we show that graphene on the nanodots is neutrally charged. Moreover, its 4.65 eV work function is surprisingly larger than the predicted value of 3.8 eV for graphene on Co. First principle calculations show that those Co nanodots can be seen as cobalt bilayer sandwiched between two carbon planes.

Spin-crossover molecules present the unique property of having two spin states that can be controlled by light excitation at low temperature. Here, we report on the photoexcitation of [FeII((3, 5-(CH3)2Pz)3BH)2] (Pz = pyrazolyl) ultrathin films, with thicknesses ranging from 0.9 to 5.3 monolayers, adsorbed on Cu(111) substrate. Using X-ray absorption spectroscopy measurements, we confirm the anomalous light-induced spin-state switching observed for sub-monolayer coverage and demonstrate that it is confined to the first molecular layer in contact with the metallic substrate. For higher coverages, the well-known light-induced excited spin-state trapping effect is recovered. Combining continuous light excitation with thermal cycling, we demonstrate that at low temperature light-induced thermal hysteresis is measured for the thicker films, while for sub-monolayer coverage, the light enables extension of the thermal conversion over a large temperature range. Mechanoelastic simulations underline that, due to the intermolecular interactions, opposite behaviors are observed in the different layers composing the films.

In this paper, we discuss in the framework of a mechanoelastic model the electronic and mechanical behavior of a single layer of spin crossover molecules self-organized on a substrate. We consider the molecules situated in a face-centered-cubic structure interacting in between and with sites in the substrate by the way of connecting springs with given elastic constants. The main experimental results are reproduced, i.e., typical thermal tran-sitions with their incompleteness of the hysteresis loop, residual fractions after low-temperature relaxations, cooperativity, or kinetic features. However, we prove that the simple model, implying fixed neighbors on the substrate for every spin crossover molecule, leads in some cases to unphysical situations, corresponding to unexpected large curvatures of the spin crossover layer. Therefore, to go further, we allow every spin crossover molecule to change its adsorption site on the substrate at every moment, by connecting to the closest molecules on the substrate. This approach, corroborated with the use of different densities of the sites on the substrate, allows us to simulate further experimental observations, such as the appearance of cracks inside the layer or periodic arrangements of apparent heights of spin crossover molecules on the layer leading to moire patterns, for which experimental data are also provided.

We identify and manipulate commonly occurring defects in black phosphorus, combining scanning tunneling microscopy experiments with density functional theory calculations. A ubiquitous defect, imaged at negative bias as a bright dumbbell extending over several nanometers, is shown to arise from a substitutional Sn impurity in the second sublayer. Another frequently observed defect type is identified as arising from an interstitial Sn atom; this defect can be switched to a more stable configuration consisting of a Sn substitutional defect + P adatom, by application of an electrical pulse via the STM tip. DFT calculations show that this pulse-induced structural transition switches the system from a non-magnetic configuration to a magnetic one. We introduce States Projected Onto Individual Layers (SPOIL) quantities which provide information about atom-wise and orbital-wise contributions to bias-dependent features observed in STM images.

Controlling the spatial distribution of dopants in graphene is the gateway to the realization of graphene‐based electronic components. Here, it is shown that a submonolayer of self‐assembled physisorbed molecules can be used as a resist during a post‐synthesis nitrogen doping process to realize a nanopatterning of nitrogen dopants in graphene. The resulting formation of domains with different nitrogen concentrations allows obtaining n–n’ and p–n junctions in graphene. A scanning tunneling microscopy is used to measure the electronic properties of the junctions at the atomic scale and reveal their intrinsic width that is found to be ≈7 nm corresponding to a sharp junction regime.

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 FeII 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.

WO3 nanostructures have been synthesized on Au(111) through the solution-processing method. Three types of structures have been obtained: reticulated polymeric structures, two dimensional WO3 (111), and three-dimensional islands. Their electronic properties have been probed by scanning tunneling spectroscopy. The reticulated structure has a featureless spectrum. WO3 (111) shows n-type semiconducting properties with resonances corresponding to surface states arising from W 5d states. These oxide nanostructures efficiently decouple the electronic states of molecular adsorbates from the metal substrate.

Bistable spin-crossover molecules are particularly interesting to the development of innovative electronic and spintronic devices as they present two spin states that can be controlled by external stimuli. In this purpose, being able to switch at will the spin state of a single molecule in a dense molecular array is a key milestone. However, the elastic interactions between the molecules favour more cooperative behaviour where patches of neighbouring molecules switches simultaneously. We demonstrate here that the interaction of iron II spin-crossover molecules with a metallic substrate can strongly reduce their cooperative behaviour until addressing independently single molecular spin state. Mechanoelastic model is able to reproduce well such findings.

Spin-crossover molecules are very attractive compounds to realize multifunctional spintronic devices. Understanding their properties when deposited on metals is therefore crucial for their future rational implementation as ultrathin films in such devices. Using X-ray absorption spectroscopy, we study the thermal transition of the spin-crossover compound FeII((3,5-(CH3)2Pz)3BH)2 from submonolayer to multilayers on a Cu(111) substrate. We determine how the residual fraction of high spin molecules at low temperature, as well as the bistability range and the temperature of switching, depends on the layer thickness. The most spectacular effect is the clear opening of a 35 ± 9 K thermal hysteresis loop for a 3.0 ± 0.7 monolayers thick film. To better understand the role played by the substrate and the dimensionality on the thermal bistability, we have performed Monte Carlo Arrhenius simulations in the framework of a mechanoelastic model that include a molecule-substrate interaction. This model reproduces well the main features observed experimentally and can predict how the spin-crossover transition is modified by the thickness and the substrate interaction.

The tris pyrazolyl borate ligand imposes a rigid scaffold around Fe(ii) ensuring a robust magnetic anisotropy when the molecules assembled as monolayers suffer from the dissymmetric environment of the substrate/vacuum interface.

Bistable spin-crossover molecules are particularly interesting for the development of innovative electronic and spintronic devices as they present two spin states that can be controlled by external stimuli. In this paper, we report the voltage-induced switching of the high spin/low spin electronic states of spin-crossover molecules self-assembled in dense 2D networks on Au(111) and Cu(111) by scanning tunneling microscopy at low temperature. On Au(111), voltage pulses lead to the nonlocal switching of the molecules from any─high or low─spin state to the other followed by a spontaneous relaxation toward their initial state within minutes. On the other hand, on Cu(111), single molecules can be addressed at will. They retain their new electronic configuration after a voltage pulse. The memory effect demonstrated on Cu(111) is due to an interplay between long-range intermolecular interaction and molecule/substrate coupling as confirmed by mechanoelastic simulations.

Creating topological defects in graphene can induce unexpected electronic properties. We present scanning tunneling microscopy studies of defect formation catalyzed by gold on few-layer graphene on SiC(000-1) [1]. A very high density of quasi-one dimensional defects is obtained thanks to a two-steps process. Those defects, the so called flower defects [2], are promoted by gold atoms thanks to a drastic decrease of their formation energy, as evidenced by first-principles calculations. Scanning tunneling spectroscopy studies exhibit localized electronic states at high energy which depends on the twisted angle between the two upper graphene surface layers, very similar to electronic states observed on extended grain boundary loops [3]. Interestingly, we observe low energy states near the Fermi level which are localized asymmetrically on the defect, breaking their apparent 6-fold symmetry. Those unknown in-(pseudo)-gap states could deserve future experiments and theoretical developments [4].