Ab Initio Electronic, Magnetic, and Optical Properties of Fe Phthalocyanine on Cr2O3(0001).

The organic molecules adsorbed on antiferromagnetic surfaces can produce interesting interface states, characterized by charge transfer mechanisms, hybridization of molecular-substrate orbitals, as well as magnetic couplings. Here, we apply an ab initio approach to study the adsorption of Fe phthalocyanine on stoichiometric Cr2O3(0001). The molecule binds via a bidentate configuration forming bonds between two opposite imide N atoms and two protruding Cr ones, making this preferred over the various possible adsorption structures. In addition to the local modifications at these sites, the electronic structure of the molecule is weakly influenced. The magnetic structure of the surface Cr atoms shows a moderate influence of molecule adsorption, not limited to the atoms in the close proximity of the molecule. Upon optical excitation at the onset, electron density moves toward the molecule, enhancing the ground state charge transfer. We investigate this movement of charge as a mechanism at the base of light-induced modifications of the magnetic structure at the interface.

Achieving High Substitutional Incorporation in Mn-Doped Graphene.

Despite its broad potential applications, substitution of carbon by transition metal atoms in graphene has so far been explored only to a limited extent. We report the realization of substitutional Mn doping of graphene to a record high atomic concentration of 0.5%, which was achieved using ultralow-energy ion implantation. By correlating the experimental data with the results of ab initio Born-Oppenheimer molecular dynamics calculations, we infer that direct substitution is the dominant mechanism of impurity incorporation. Thermal annealing in ultrahigh vacuum provides efficient removal of surface contaminants and additional implantation-induced disorder, resulting in Mn-doped graphene that, aside from the substitutional Mn impurities, is essentially as clean and defect-free as the as-grown layer. We further show that the Dirac character of graphene is preserved upon substitutional Mn doping, even in this high concentration regime, making this system ideal for studying the interaction between Dirac conduction electrons and localized magnetic moments. More generally, these results show that ultralow energy ion implantation can be used for controlled functionalization of graphene with substitutional transition-metal atoms, of relevance for a wide range of applications, from magnetism and spintronics to single-atom catalysis.

Enhancement of Magnetic Stability in Antiferromagnetic CoO Films by Adsorption of Organic Molecules.

Antiferromagnets are a class of magnetic materials of great interest in spintronic devices because of their stability and ultrafast dynamics. When interfaced with an organic molecular layer, antiferromagnetic (AF) films are expected to form a spinterface that can allow fine control of specific AF properties. In this paper, we investigate spinterface effects on CoO, an AF oxide. To access the magnetic state of the antiferromagnet, we couple it to a ferromagnetic Co film via an exchange bias (EB) effect. In this way, the formation of a spinterface is detected through changes induced on the CoO/Co EB system. We demonstrate that C60 and Gaq3 adsorption on CoO shifts its blocking temperature; in turn, an increase in both the EB fields and the coercivities is observed on the EB-coupled Co layer. Ab initio calculations for the CoO/C60 interface indicate that the molecular adsorption is responsible for a charge redistribution on the CoO layer that alters the occupation of the d orbitals of Co atoms and, to a smaller extent, the p orbitals of oxygen. As a result, the AF coupling between Co atoms in the CoO is enhanced. Considering the granular nature of CoO, a larger AF stability upon molecular adsorption is then associated with a larger number of AF grains that are stable upon reversal of the Co layer.

Crystal phase engineering of silicene by Sn-modified Ag(111).

The synthesis of silicene by direct growth on silver is characterized by the formation of multiple phases and domains, posing severe constraints on the spatial charge conduction towards a technological transfer of silicene to electronic transport devices. Here we engineer the silicene/silver interface by two schemes, namely, either through decoration by Sn atoms, forming an Ag2Sn surface alloy, or by buffering the interface with a stanene layer. Whereas in both cases Raman spectra confirm the typical features as expected from silicene, by electron diffraction we observe that a very well-ordered single-phase 4 × 4 monolayer silicene is stabilized by the decorated surface, while the buffered interface exhibits a sharp phase at all silicon coverages. Both interfaces also stabilize the ordered growth of a phase in the multilayer range, featuring a single rotational domain. Theoretical ab initio models are used to investigate low-buckled silicene phases (4 × 4 and a competing one) and various structures, supporting the experimental findings. This study provides new and promising technology routes to manipulate the silicene structure by controlled phase selection and single-crystal silicene growth on a wafer-scale.

Ordered assembly of non-planar vanadyl-tetraphenylporphyrins on ultra-thin iron oxide.

Stabilizing ordered assemblies of molecules represents the first step towards the construction of molecular devices featuring hybrid (organic-inorganic) interfaces where molecules can be easily functionalized in view of specific applications. Molecular layers of planar metal-tetraphenylporphyrins (MTPP) grown on an ultrathin iron oxide [namely Fe(001)-p(1 × 1)O] show indeed a high degree of structural order. The generality of such a picture is tested by exploiting non-planar porphyrins, such as vanadyl-TPP (VOTPP). These molecules feature a VO2+ ion in their center, with the O atom protruding out of the plane of the porphyrin ring. In this work, by employing diffraction, photoemission and X-ray absorption, we prove that non-planar VOTPP can nevertheless form a square and ordered superstructure, where porphyrin molecules lie flat with respect to the underlying substrate. Ab initio density functional theory simulations are used to elucidate the VO bond orientation with respect to the iron substrate.

Steric hindrance in the on-surface synthesis of diethynyl-linked anthracene polymers.

Hybrid sp-sp2 structures can be efficiently obtained on metal substrates via on-surface synthesis. The choice of both the precursor and the substrate impacts on the effectiveness of the process and the stability of the formed structures. Here we demonstrate that using anthracene-based precursor molecules on Au(111) the formation of polymers hosting sp carbon chains is affected by the steric hindrance between aromatic groups. In particular, by scanning tunneling microscopy experiments and density functional theory simulations we show that the de-metalation of organometallic structures induces a lateral separation of adjacent polymers that prevents the formation of ordered domains. This study contributes to the understanding of the mechanisms driving the on-surface synthesis processes, a fundamental step toward the realization of novel carbon-based nanostructures with perspective applications in nanocatalysis, photoconversion, and nano-electronics.

Magnetic properties of coordination clusters with {Mn4} and {Co4} antiferromagnetic cores.

We present a joint experimental and theoretical characterization of the magnetic properties of coordination clusters with an antiferromagnetic core of four magnetic ions. Two different compounds are analyzed, with Co and Mn ions in the core. While both molecules are antiferromagnetic, they display different sensitivities to external magnetic field, according to the different atomic magnetic moments and strength of the intra-molecular magnetic couplings. In particular, the dependence of the magnetization versus field of the two molecules switches with temperature: at low temperature the magnetization is smaller in {Mn4} than in Co4, while the opposite happens at high temperature. Through a detailed analysis of the electronic and magnetic properties of the two compounds we identify a stronger magnetic interaction between the magnetic ions in {Mn4} with respect to {Co4}. Moreover {Co4} displays not negligible spin-orbit related effects that could affect the spin lifetime in future antiferromagnetic spintronic applications. We highlight the necessity to account for these spin-orbit effects together with electronic correlation effects for a reliable description of these compounds.

Doping Graphene with Substitutional Mn.

We report the incorporation of substitutional Mn atoms in high-quality, epitaxial graphene on Cu(111), using ultralow-energy ion implantation. We characterize in detail the atomic structure of substitutional Mn in a single carbon vacancy and quantify its concentration. In particular, we are able to determine the position of substitutional Mn atoms with respect to the Moiré superstructure (i.e., local graphene-Cu stacking symmetry) and to the carbon sublattice; in the out-of-plane direction, substitutional Mn atoms are found to be slightly displaced toward the Cu surface, that is, effectively underneath the graphene layer. Regarding electronic properties, we show that graphene doped with substitutional Mn to a concentration of the order of 0.04%, with negligible structural disorder (other than the Mn substitution), retains the Dirac-like band structure of pristine graphene on Cu(111), making it an ideal system in which to study the interplay between local magnetic moments and Dirac electrons. Our work also establishes that ultralow-energy ion implantation is suited for substitutional magnetic doping of graphene. Given the flexibility, reproducibility, and scalability inherent to ion implantation, our work creates numerous opportunities for research on magnetic functionalization of graphene and other two-dimensional materials.

Tailoring the magnetic ordering of the Cr4O5/Fe(001) surface via a controlled adsorption of C60 organic molecules.

We analyse the spinterface formed by a C60 molecular layer on a Fe(001) surface covered by a two-dimensional Cr4O5 layer. We consider different geometries, by combining the high symmetry adsorption sites of the surface with three possible orientations of the molecules in a fully relaxed Density Functional Theory calculation. We show that the local hybridization between the electronic states of the Cr4O5 layer and those of the organic molecules is able to modify the magnetic coupling of the Cr atoms. Both the intra-layer and the inter-layer magnetic interaction is indeed driven by O atoms of the two-dimensional oxide. We demonstrate that the C60 adsorption on the energetically most stable site turns the ferromagnetic intra-layer coupling into an antiferromagnetic one, and that antiferromagnetic to ferromagnetic switching and spin patterning of the substrate could be possible by adsorption on other sites.

Keto-enol tautomerization drives the self-assembly of leucoquinizarin on Au(111).

The self-assembly of leucoquinizarin molecules on Au(111) surfaces is shown to be characterized by the molecules mostly being in their keto-enolic tautomeric form, with evidence of their temporary switching to other tautomeric forms. This reveals a metastable chemistry of the assembled molecules, to be considered for their possible employment in the formation of more complex hetero-organic interfaces.

Dramatic efficiency boost of single-walled carbon nanotube-silicon hybrid solar cells through exposure to ppm nitrogen dioxide in air: An ab-initio assessment of the measured device performances.

We observed a 73% enhancement of the power conversion efficiency (PCE) of a photovoltaic cell based on a single wall carbon nanotube/Si hybrid junction after exposing the device to a limited amount (10 ppm) of NO2 diluted in dry air. On the basis of a computational modeling of the junction, this enhancement is discussed in terms of both carbon nanotube (CNT) p-doping, induced by the interaction with the oxidizing molecules, and work function changes across the junction. Unlike studies so far reported, where the PCE enhancement was correlated only qualitatively to CNT doping, our study (i) provides a novel and reversible path to tune and considerably enhance the cell efficiency by a few ppm gas exposure, and (ii) shows computational results that quantitatively relate the observed effects to the electrostatics of the cell through a systematic calculation of the work function. These effects have been cross-checked by exposing the cell to reducing molecules (i.e·NH3) that resulted to be detrimental to the cell efficiency, consistently with the theoretical ab-initio calculations.

Structural, Electronic, and Vibrational Properties of a Two-Dimensional Graphdiyne-like Carbon Nanonetwork Synthesized on Au(111): Implications for the Engineering of sp-sp2 Carbon Nanostructures.

Graphdiyne, atomically thin two-dimensional (2D) carbon nanostructure based on sp-sp2 hybridization is an appealing system potentially showing outstanding mechanical and optoelectronic properties. Surface-catalyzed coupling of halogenated sp-carbon-based molecular precursors represents a promising bottom-up strategy to fabricate extended 2D carbon systems with engineered structure on metallic substrates. Here, we investigate the atomic-scale structure and electronic and vibrational properties of an extended graphdiyne-like sp-sp2 carbon nanonetwork grown on Au(111) by means of the on-surface synthesis. The formation of such a 2D nanonetwork at its different stages as a function of the annealing temperature after the deposition is monitored by scanning tunneling microscopy (STM), Raman spectroscopy, and combined with density functional theory (DFT) calculations. High-resolution STM imaging and the high sensitivity of Raman spectroscopy to the bond nature provide a unique strategy to unravel the atomic-scale properties of sp-sp2 carbon nanostructures. We show that hybridization between the 2D carbon nanonetwork and the underlying substrate states strongly affects its electronic and vibrational properties, modifying substantially the density of states and the Raman spectrum compared to the free standing system. This opens the way to the modulation of the electronic properties with significant prospects in future applications as active nanomaterials for catalysis, photoconversion, and carbon-based nanoelectronics.

Scanning tunneling microscopy and Raman spectroscopy of polymeric sp-sp2 carbon atomic wires synthesized on the Au(111) surface.

Long linear carbon nanostructures based on sp-hybridization can be synthesized by exploiting on-surface synthesis of halogenated precursors evaporated on Au(111), thus opening a way to investigations by surface-science techniques. By means of an experimental approach combining scanning tunneling microscopy and spectroscopy (STM and STS) with ex situ Raman spectroscopy we investigate the structural, electronic and vibrational properties of polymeric sp-sp2 carbon atomic wires composed by sp-carbon chains connected through phenyl groups. Density-functional-theory (DFT) calculations of the structure and the electronic density of states allow us to simulate STM images and to compute Raman spectra. The comparison of experimental data with DFT simulations unveil the properties and the formation stages as a function of the annealing temperature. Atomic-scale structural information from STM complement the Raman sensitivity to the single molecular bond to open the way to detailed understanding of these novel carbon nanostructures.

Fingerprints of sp¹ Hybridized C in the Near-Edge X-ray Absorption Spectra of Surface-Grown Materials.

Carbon structures comprising sp 1 chains (e.g., polyynes or cumulenes) can be synthesized by exploiting on-surface chemistry and molecular self-assembly of organic precursors, opening to the use of the full experimental and theoretical surface-science toolbox for their characterization. In particular, polarized near-edge X-ray absorption fine structure (NEXAFS) can be used to determine molecular adsorption angles and is here also suggested as a probe to discriminate sp 1 /sp 2 character in the structures. We present an ab initio study of the polarized NEXAFS spectrum of model and real sp 1 /sp 2 materials. Calculations are performed within density functional theory with plane waves and pseudopotentials, and spectra are computed by core-excited C potentials. We evaluate the dichroism in the spectrum for ideal carbynes and highlight the main differences relative to typical sp 2 systems. We then consider a mixed polymer alternating sp 1 C 4 units with sp 2 biphenyl groups, recently synthesized on Au(111), as well as other linear structures and two-dimensional networks, pointing out a spectral line shape specifically due to the the presence of linear C chains. Our study suggests that the measurements of polarized NEXAFS spectra could be used to distinctly fingerprint the presence of sp 1 hybridization in surface-grown C structures.

GeVn complexes for silicon-based room-temperature single-atom nanoelectronics.

We propose germanium-vacancy complexes (GeVn) as a viable ingredient to exploit single-atom quantum effects in silicon devices at room temperature. Our predictions, motivated by the high controllability of the location of the defect via accurate single-atom implantation techniques, are based on ab-initio Density Functional Theory calculations within a parameterfree screened-dependent hybrid functional scheme, suitable to provide reliable bandstructure energies and defect-state wavefunctions. The resulting defect-related excited states, at variance with those arising from conventional dopants such as phosphorous, turn out to be deep enough to ensure device operation up to room temperature and exhibit a far more localized wavefunction.

Magnetic Moments and Electron Transport through Chromium-Based Antiferromagnetic Nanojunctions.

We report the electronic, magnetic and transport properties of a prototypical antiferromagnetic (AFM) spintronic device. We chose Cr as the active layer because it is the only room-temperature AFM elemental metal. We sandwiched Cr between two non-magnetic metals (Pt or Au) with large spin-orbit coupling. We also inserted a buffer layer of insulating MgO to mimic the structure and finite resistivity of a real device. We found that, while spin-orbit has a negligible effect on the current flowing through the device, the MgO layer plays a crucial role. Its effect is to decouple the Cr magnetic moment from Pt (or Au) and to develop an overall spin magnetization. We have also calculated the spin-polarized ballistic conductance of the device within the Büttiker⁻Landauer framework, and we have found that for small applied bias our Pt/Cr/MgO/Pt device presents a spin polarization of the current amounting to ≃25%.

Growth and electronic structure of 2D hexagonal nanosheets on a corrugated rectangular substrate.

Graphene and h-BN are grown by chemical vapor deposition in ultra high vacuum conditions on the Pt(110) surface. Scanning tunneling microscopy measurements and low-energy electron diffraction data indicate that graphene forms a variety of differently oriented incommensurate domains although with a strong preference to align its [Formula: see text] direction with the [Formula: see text] direction of Pt. Meanwhile, h-BN exhibits a c(8 × 10) commensurate superstructure, which presents a high level of defectivity that implies local variation of the periodicity (i.e. mixed c(8 × 10) and c(8 × 12) patches) and the introduction of local defects. The combination of advanced photoemission spectroscopy data (angle-resolved photoemission spectroscopy from the valence band) and ab initio calculations indicates that both 2D materials interact weakly with the substrate: graphene exhibits neutral doping and is morphologically flat, even if it nucleates on the relatively highly corrugated rectangular (110) surface. In the case of h-BN, the interaction is slightly stronger and is characterized by a small electron transfer from surface Pt atoms to nitrogen atoms. The (110) termination of Pt is therefore a quite interesting surface for the growth of 2D materials because given its low symmetry, it may favor the growth of selectively oriented domains but does not affect their pristine electronic properties.

Sticking of atomic hydrogen on graphene.

Recent years have witnessed an ever growing interest in the interactions between hydrogen atoms and a graphene sheet. Largely motivated by the possibility of modulating the electric, optical and magnetic properties of graphene, a huge number of studies have appeared recently that added to and enlarged earlier investigations on graphite and other carbon materials. In this review we give a glimpse of the many facets of this adsorption process, as they emerged from these studies. The focus is on those issues that have been addressed in detail, under carefully controlled conditions, with an emphasis on the interplay between the adatom structures, their formation dynamics and the electric, magnetic and chemical properties of the carbon sheet.