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.

Charge Transfer and Orbital Reconstruction at an Organic-Oxide Interface.

The two-dimensional electron system (2DES) located at the surface of strontium titanate (STO) and at several other STO-based interfaces has been an established platform for the study of novel physical phenomena since its discovery. Here we report how the interfacing of STO and tetracyanoquinodimethane (TCNQ) results in a charge transfer that depletes the number of free carriers at the STO surface, with a strong impact on its electronic structure. Our study paves the way for efficient tuning of the electronic properties, which promises novel applications in the framework of oxide/organic-based electronics.

Sublattice Ferrimagnetism in Quasifreestanding Graphene.

We show that graphene can be magnetized by coupling to a ferromagnetic Co film through a Au monolayer. The presence of dislocation loops under graphene leads to a ferrimagnetic ordering of moments in the two C sublattices. It is shown that the band gap of ∼80 meV in the K[over ¯] point has a magnetic nature and exists for ferrimagnetic ordering. Interplay between Rashba and exchange couplings is evidenced by spin splitting asymmetry in spin-ARPES measurements and fully supported by DFT calculation of a (9×9) unit cell. Owing to sign-opposite Berry curvatures for K[over ¯] and K[over ¯]^{'} valleys, the synthesized system is promising for the realization of a circular dichroism Hall effect.

Anomalies at the Dirac Point in Graphene and Its Hole-Doped Compositions.

We study the properties of the Dirac states in SiC-graphene and its hole-doped compositions employing angle-resolved photoemission spectroscopy and density functional theory. The symmetry-selective measurements for the Dirac bands reveal their linearly dispersive behavior across the Dirac point which was termed as the anomalous region in earlier studies. No gap is observed even after boron substitution that reduced the carrier concentration significantly from 3.7×10^{13} cm^{-2} in SiC-graphene to 0.8×10^{13} cm^{-2} (5% doping). The anomalies at the Dirac point are attributed to the spectral width arising from the lifetime and momentum broadening in the experiments. The substitution of boron at the graphitic sites leads to a band renormalization and a shift of the Dirac point towards the Fermi level. The internal symmetries appear to be preserved in SiC-graphene even after significant boron substitutions. These results suggest that SiC-graphene is a good platform to realize exotic science as well as advanced technology where the carrier properties like concentration, mobility, etc., can be tuned keeping the Dirac fermionic properties protected.

Orbital Mapping of Semiconducting Perylenes on Cu(111).

Semiconducting O-doped polycyclic aromatic hydrocarbons constitute a class of molecules whose optoelectronic properties can be tailored by acting on the π-extension of the carbon-based frameworks and on the oxygen linkages. Although much is known about their photophysical and electrochemical properties in solution, their self-assembly interfacial behavior on solid substrates has remained unexplored so far. In this paper, we have focused our attention on the on-surface self-assembly of O-doped bi-perylene derivatives. Their ability to assemble in ordered networks on Cu(111) single-crystalline surfaces allowed a combination of structural, morphological, and spectroscopic studies. In particular, the exploitation of the orbital mapping methodology based on angle-resolved photoemission spectroscopy, with the support of scanning tunneling microscopy and low-energy electron diffraction, allowed the identification of both the electronic structure of the adsorbates and their geometric arrangement. Our multi-technique experimental investigation includes the structure determination from powder X-ray diffraction data for a specific compound and demonstrates that the electronic structure of such large molecular self-assembled networks can be studied using the reconstruction methods of molecular orbitals from photoemission data even in the presence of segregated chiral domains.

Turning Low-Nanoscale Intrinsic Silicon Highly Electron-Conductive by SiO2 Coating.

Impurity doping in silicon (Si) ultra-large-scale integration is one of the key challenges which prevent further device miniaturization. Using ultraviolet photoelectron spectroscopy and X-ray absorption spectroscopy in the total fluorescence yield mode, we show that the lowest unoccupied and highest occupied electronic states of ≤3 nm thick SiO2-coated Si nanowells shift by up to 0.2 eV below the conduction band and ca. 0.7 eV below the valence band edge of bulk silicon, respectively. This nanoscale electronic structure shift induced by anions at surfaces (NESSIAS) provides the means for low-nanoscale intrinsic Si (i-Si) to be flooded by electrons from an external (bigger, metallic) reservoir, thereby getting highly electron- (n-) conductive. While our findings deviate from the behavior commonly believed to govern the properties of silicon nanowells, they are further confirmed by the fundamental energy gap as per nanowell thickness when compared against published experimental data. Supporting our findings further with hybrid density functional theory calculations, we show that other group IV semiconductors (diamond, Ge) do respond to the NESSIAS effect in accord with Si. We predict adequate nanowire cross-sections (X-sections) from experimental nanowell data with a recently established crystallographic analysis, paving the way to undoped ultrasmall silicon electronic devices with significantly reduced gate lengths, using complementary metal-oxide-semiconductor-compatible materials.

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.

Interface Chemistry of Graphene/Cu Grafted By 3,4,5-Tri-Methoxyphenyl.

Chemical reaction with diazonium molecules has revealed to be a powerful method for the surface chemical modification of graphite, carbon nanotubes and recently also of graphene. Graphene electronic structure modification using diazonium molecules is strongly influenced by graphene growth and by the supporting materials. Here, carrying on a detailed study of core levels and valence band photoemission measurements, we are able to reconstruct the interface chemistry of trimethoxybenzenediazonium-based molecules electrochemically grafted on graphene on copper. The band energy alignment at the molecule-graphene interface has been traced revealing the energy position of the HOMO band with respect to the Fermi level.

Origin of the Flat Band in Heavily Cs-Doped Graphene.

A flat energy dispersion of electrons at the Fermi level of a material leads to instabilities in the electronic system and can drive phase transitions. Here we show that the flat band in graphene can be achieved by sandwiching a graphene monolayer by two cesium (Cs) layers. We investigate the flat band by a combination of angle-resolved photoemission spectroscopy experiment and the calculations. Our work highlights that charge transfer, zone folding of graphene bands, and the covalent bonding between C and Cs atoms are the origin of the flat energy band formation. Analysis of the Stoner criterion for the flat band suggests the presence of a ferromagnetic instability. The presented approach is an alternative route for obtaining flat band materials to twisting bilayer graphene which yields thermodynamically stable flat band materials in large areas.

Electronic structure of MAPbI3 and MAPbCl3: importance of band alignment.

Since their first appearance, organic-inorganic perovskite absorbers have been capturing the attention of the scientific community. While high efficiency devices highlight the importance of band level alignment, very little is known on the origin of the strong n-doping character observed in the perovskite. Here, by means of a highly accurate photoemission study, we shed light on the energy alignment in perovskite-based devices. Our results suggest that the interaction with the substrate may be the driver for the observed doping in the perovskite samples.

Iron Phthalocyanine and Ferromagnetic Thin Films: Magnetic Behavior of Single and Double Interfaces.

Metal-phthalocyanines are quasi-planar heterocyclic macrocycle molecules with a highly conjugated structure. They can be engineered at the molecular scale (central atom, ligand) to tailor new properties for organic spintronics devices. In this study, we evaluated the magnetic behavior of FePc in a ∼1 nm molecular film sandwiched between two ferromagnetic films: cobalt (bottom) and nickel (top). In the single interface, FePc in contact with a Co film is magnetically coupled with the inorganic film magnetization, though the relatively small Fe(Pc) X-ray magnetic circular dichroism (XMCD) signal in remanence, with respect to that observed in applied field of 6 T, suggests that a fraction of molecules in the organometallic film have their magnetic moment not aligned or antiparallel with respect to Co. When in contact with two interfaces, Fe(Pc) XMCD doubles, indicating that part of the Fe(Pc) are now aligned with the Ni topmost layer, saturated at 1 T. We discussed the relevance of the finding in terms of understanding and developing hybrid organic/inorganic spin devices.

Intrinsic ultrasmall nanoscale silicon turns n-/p-type with SiO2/Si3N4-coating.

Impurity doping of ultrasmall nanoscale (usn) silicon (Si) currently used in ultralarge scale integration (ULSI) faces serious miniaturization challenges below the 14 nm technology node such as dopant out-diffusion and inactivation by clustering in Si-based field-effect transistors (FETs). Moreover, self-purification and massively increased ionization energy cause doping to fail for Si nano-crystals (NCs) showing quantum confinement. To introduce electron- (n-) or hole- (p-) type conductivity, usn-Si may not require doping, but an energy shift of electronic states with respect to the vacuum energy between different regions of usn-Si. We show in theory and experiment that usn-Si can experience a considerable energy offset of electronic states by embedding it in silicon dioxide (SiO2) or silicon nitride (Si3N4), whereby a few monolayers (MLs) of SiO2 or Si3N4 are enough to achieve these offsets. Our findings present an alternative to conventional impurity doping for ULSI, provide new opportunities for ultralow power electronics and open a whole new vista on the introduction of p- and n-type conductivity into usn-Si.

Resonance Raman Spectrum of Doped Epitaxial Graphene at the Lifshitz Transition.

We employ ultra-high vacuum (UHV) Raman spectroscopy in tandem with angle-resolved photoemission (ARPES) to investigate the doping-dependent Raman spectrum of epitaxial graphene on Ir(111). The evolution of Raman spectra from pristine to heavily Cs doped graphene up to a carrier concentration of 4.4 × 1014 cm-2 is investigated. At this doping, graphene is at the onset of the Lifshitz transition and renormalization effects reduce the electronic bandwidth. The optical transition at the saddle point in the Brillouin zone then becomes experimentally accessible by ultraviolet (UV) light excitation, which achieves resonance Raman conditions in close vicinity to the van Hove singularity in the joint density of states. The position of the Raman G band of fully doped graphene/Ir(111) shifts down by ∼60 cm-1. The G band asymmetry of Cs doped epitaxial graphene assumes an unusual strong Fano asymmetry opposite to that of the G band of doped graphene on insulators. Our calculations can fully explain these observations by substrate dependent quantum interference effects in the scattering pathways for vibrational and electronic Raman scattering.

Synthesis and spectroscopic characterization of alkali-metal intercalated ZrSe2.

We report on the synthesis and spectroscopic characterization of alkali metal intercalated ZrSe2 single crystals. ZrSe2 is produced by chemical vapour transport and then Li is intercalated. Intercalation is performed from the liquid phase (via butyllithium) and from the vapour phase. Raman spectroscopy of intercalated ZrSe2 reveals phonon energy shifts of the Raman active A1g and Eg phonon modes, the disappearance of two-phonon modes and new low wavenumber Raman modes. Angle-resolved photoemission spectroscopy is used to perform a mapping of the Fermi surface revealing an electron concentration of 4.7 × 1014 cm-2. We also perform vapour phase intercalation of K and Cs into ZrSe2 and observe similar changes in the Raman modes as for the Li case.

Publisher Correction: Multi-orbital charge transfer at highly oriented organic/metal interfaces.

The original version of this Article contained an error in the spelling of the author Claus Michael Schneider, which was incorrectly given as Claus Michael Schneidery. This has now been corrected in both the PDF and HTML versions of the Article.

Multi-orbital charge transfer at highly oriented organic/metal interfaces.

The molecule-substrate interaction plays a key role in charge injection organic-based devices. Charge transfer at molecule-metal interfaces strongly affects the overall physical and magnetic properties of the system, and ultimately the device performance. Here, we report theoretical and experimental evidence of a pronounced charge transfer involving nickel tetraphenyl porphyrin molecules adsorbed on Cu(100). The exceptional charge transfer leads to filling of the higher unoccupied orbitals up to LUMO+3. As a consequence of this strong interaction with the substrate, the porphyrin's macrocycle sits very close to the surface, forcing the phenyl ligands to bend upwards. Due to this adsorption configuration, scanning tunneling microscopy cannot reliably probe the states related to the macrocycle. We demonstrate that photoemission tomography can instead access the Ni-TPP macrocycle electronic states and determine the reordering and filling of the LUMOs upon adsorption, thereby confirming the remarkable charge transfer predicted by density functional theory calculations.Charge transfer at molecule-metal interfaces affects the overall physical and magnetic properties of organic-based devices, and ultimately their performance. Here, the authors report evidence of a pronounced charge transfer involving nickel tetraphenyl porphyrin molecules adsorbed on copper.

Spectroscopic observation of oxygen dissociation on nitrogen-doped graphene.

Carbon nanomaterials' reactivity towards oxygen is very poor, limiting their potential applications. However, nitrogen doping is an established way to introduce active sites that facilitate interaction with gases. This boosts the materials' reactivity for bio-/gas sensing and enhances their catalytic performance for the oxygen reduction reaction. Despite this interest, the role of differently bonded nitrogen dopants in the interaction with oxygen is obscured by experimental challenges and has so far resisted clear conclusions. We study the interaction of molecular oxygen with graphene doped via nitrogen plasma by in situ high-resolution synchrotron techniques, supported by density functional theory core level simulations. The interaction leads to oxygen dissociation and the formation of carbon-oxygen single bonds on graphene, along with a band gap opening and a rounding of the Dirac cone. The change of the N 1 s core level signal indicates that graphitic nitrogen is involved in the observed mechanism: the adsorbed oxygen molecule is dissociated and the two O atoms chemisorb with epoxy bonds to the nearest carbon neighbours of the graphitic nitrogen. Our findings help resolve existing controversies and offer compelling new evidence of the ORR pathway.

Spin-Orbit Coupling Induced Gap in Graphene on Pt(111) with Intercalated Pb Monolayer.

Graphene is one of the most promising materials for nanoelectronics owing to its unique Dirac cone-like dispersion of the electronic state and high mobility of the charge carriers. However, to facilitate the implementation of the graphene-based devices, an essential change of its electronic structure, a creation of the band gap should controllably be done. Brought about by two fundamentally different mechanisms, a sublattice symmetry breaking or an induced strong spin-orbit interaction, the band gap appearance can drive graphene into a narrow-gap semiconductor or a 2D topological insulator phase, respectively, with both cases being technologically relevant. The later case, characterized by a spin-orbit gap between the valence and conduction bands, can give rise to the spin-polarized topologically protected edge states. Here, we study the effect of the spin-orbit interaction enhancement in graphene placed in contact with a lead monolayer. By means of angle-resolved photoemission spectroscopy, we show that intercalation of the Pb interlayer between the graphene sheet and the Pt(111) surface leads to formation of a gap of ∼200 meV at the Dirac point of graphene. Spin-resolved measurements confirm the splitting to be of a spin-orbit nature, and the measured near-gap spin structure resembles that of the quantum spin Hall state in graphene, proposed by Kane and Mele [ Phys. Rev. Lett. 2005 , 95 , 226801 ]. With a bandstructure tuned in this way, graphene acquires a functionality going beyond its intrinsic properties and becomes more attractive for possible spintronic applications.