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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. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

The ability to finely tune the properties of magnetic topological insulators (TIs) is crucial for quantum electronics. We studied solid solutions with a general formula GexMn1-xBi2Te4 between two isostructural Z2 TIs, magnetic MnBi2Te4 and nonmagnetic GeBi2Te4 with Z2 invariants of 1;000 and 1;001, respectively. We observed linear x-dependent magnetic properties, composition-independent pairwise exchange interactions, and topological phase transitions (TPTs) between topologically nontrivial phases and the semimetal state. The TPTs are driven purely by the variation of orbital contributions. By tracing the x-dependent Bi 6p contribution to the states near the fundamental gap, the effective spin-orbit coupling variation is extracted. The gapless state observed at x = 0.42 closely resembles a Dirac semimetal above the Néel temperature and shows a magnetic gap below, which is clearly visible in raw photoemission data. The observed behavior demonstrates an ability to precisely control topological and magnetic properties of TIs. Topological insulators with ordered moments of embedded magnetic atoms are viable platforms for quantum electronics, but the practical applications are restricted by the size of their crystals. The authors synthesize a Z2 topological insulator GexMn1-xBi2Te4 in the form of a large crystal with high structural perfection and tunable magnetic and electronic properties. [ABSTRACT FROM AUTHOR]

The strong interaction between graphene and elemental ferromagnetic transition metals results in considerable shifts of the graphene π band away from the Fermi level. At the same time, a weakly-dispersing single-spin conical band feature is found in the proximity of the Fermi level at the K ̄ point in the surface Brillouin zone of epitaxially-aligned graphene/Co(0001). Here, the robustness of this electronic state against twisting angles at the interface is experimentally and theoretically demonstrated by showing the presence of similar band features also in the case of rotated graphene domains on Co(0001). Spin-resolved reciprocal space maps show that the band feature in rotated graphene has similar Fermi velocity and spin polarization as its counterpart in epitaxially-aligned graphene. Density functional theory simulations carried out for the experimentally observed graphene orientations, reproduce the highly spin-polarized conical band feature at the graphene K ̄ point, characterized by a hybrid π -d orbital character. The presence of the conical features in the rotated domains is attributed to the unfolding of the superstructure K ̄ point states exclusively to the K ̄ point of the graphene primitive cell. The similarities found in the electronic character for different graphene orientations are crucial in understanding the magnetic properties of realistic graphene/Co interfaces, facilitating their implementation in spintronics applications. [Display omitted] [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Topological insulators are a promising class of materials for applications in the field of spintronics. New perspectives in this field can arise from interfacing metal-organic molecules with the topological insulator spin-momentum locked surface states, which can be perturbed enhancing or suppressing spintronics-relevant properties such as spin coherence. Here we show results from an angle-resolved photemission spectroscopy (ARPES) and scanning tunnelling microscopy (STM) study of the prototypical cobalt phthalocyanine (CoPc)/Bi2Se3 interface. We demonstrate that that the hybrid interface can act on the topological protection of the surface and bury the Dirac cone below the first quintuple layer. [ABSTRACT FROM AUTHOR]

A metallic system without any further doping was obtained combining, in a bulk film, heterojunctions made by subsequent depositions of C60 and picene layers on Ag(l 11). This is caused by the formed dipole between the two molecules due to the huge difference in electron affinities and the charge transfer from the substrate. The above situation and the expected molecular geometry have also a role when the heterojunction film is doped with potassium. C60 phases diverse from those observed in bulk C60, especially, a metallic state with continuous alkali doping of the LUMO bands was found. This opens the way towards novel bulk molecular heterojunction structures that may create new electronic phases in strongly correlated molecular materials. The present case appears as the only manner known sofar toform a bulk metallic KXC60 system (0 < x < 6) that may evoke the possibility of seeing the awaited dome-shaped region of the doping-temperature phase diagram if the system should show superconductivity. [ABSTRACT FROM AUTHOR]

• Non-periodic Pt vacancy defects are characteristic of graphene/Pt(111) system. • A novel method for synthesis of nano-thin Pt 5 Gd alloy underneath a graphene. • The alloy surface is terminated by Pt atomic layer with "kagome" structure. • Stoichiometric composition of the alloy can be used to control the graphene doping. In the present study we synthesized nano-thin epitaxial Pt x Gd alloys on Pt(111) single crystal surface covered with well-oriented graphene and investigated their electronic and atomic structure at different stages of synthesis. Low-energy electron diffraction, photoelectron spectroscopy and scanning tunneling microscopy data suggest that deposition of Gd on the graphene/Pt(111) system and its further intercalation at 1080 ° C lead to formation of nano-thin Pt 5 Gd alloy covered with a quasi-freestanding graphene. We demonstrate that atomically flat alloy surface is terminated by Pt atomic layer with "kagome" structure. Control of graphene doping through variation of the alloy stoichiometry may open up new opportunities in developing advanced electronics. Owing to a well-known catalytic activity of Pt 5 Gd alloy, our thin-film system is promising for low-cost production of catalysts in the near future. [ABSTRACT FROM AUTHOR]

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 SiO 2 -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.

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 (SiO 2 ) or silicon nitride (Si 3 N 4 ), whereby a few monolayers (MLs) of SiO 2 or Si 3 N 4 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.

Herein the formation of water molecules in the intermediate step of the redox reaction of porphyrins self-metalation on O/Cu(111) is demonstrated. Photoemission measurements show that the temperature on which porphyrins pick-up a substrate metal atom on O/Cu(111) is reduced by about 185±15 K with respect to the pure Cu(111). DFT calculations clearly indicate that the formation of a water molecule is less expensive than the formation of H2 on the O/Cu(111) substrate and, in some cases, it can be also exothermic., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Due to the growing interest in the ferromagnetic properties of Fe-octaethylporphyrins (Fe-OEP) for applications in spintronics, methods to produce stable Fe-porphyrins with no Cl atoms are highly demanded. Here, we demonstrate the formation of Fe-OEP layers on Ag(111) single crystal by the ultra high vacuum in situ metalation of the free-base 2H-2,3,7,8,12,13,17,18-octaethylporphyrin (2H-OEP) molecules. The metalation proceeds exactly as in the case of 2H-5,10,15,20-tetraphenylporphyrin (2H-TPP) on the same substrate. An extensive surface characterization by means of X-ray photoemission spectroscopy, valence band photoemission, and NEXAFS with synchrotron radiation light provides information on molecular conformation and electronic structure in the monolayer and multilayer cases. We demonstrate that the presence of the ethyl groups affects the tilt of the adsorbed molecules, the conformation of the macrocycle, and the polarization screening in multilayers, but has only a minor effect in the metalation process with respect to 2H-TPP.

Metal-dependent conformations: a change in the adaptation of tetraphenylporphyrins (TPPs) on Ag(111) was observed in the presence of a metal ion in the macrocycle. Upon annealing at T>575 K, 2H-TPP molecules increase the overlap of the phenyl π orbitals with the substrate, thus reducing the distance. The presence of Co creates a strong bond between Co dz(2) and the Ag sp states, leaving the porphyrin macrocycle at a larger distance to the surface., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Scratching the surface: Formation of a monolayer of 2H-tetraphenylporphyrins (2H-TPP) on Ag(111), either by sublimation of a multilayer in the range 525-600 K or by annealing (at the same temperature) a monolayer deposited at room temperature, induces a chemical modification of the molecules. Rotation of the phenyl rings into a flat conformation is observed and tentatively explained, by using DFT calculations, as a peculiar reaction due to molecular dehydrogenation., (Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Three distinct wet chemistry recipes were applied to hydrogen-terminated n- and p-Si(100) surfaces in a comparative study of the covalent grafting of two differently substituted 2,2'-bipyridines. The applied reactions require the use of heat, or visible light under a controlled atmosphere, or a suitable potential in an electrochemical cell. In this last case, hydrogen-terminated silicon is the working electrode in a cathodic electrografting (CEG) reaction, in which it is kept under reduction conditions. The resulting Si--C bound hybrids were characterized by a combination of AFM, dynamic contact-angle, and XPS analysis, with the help of theoretical calculations. The three distinct approaches were found to be suitable for obtaining ligand-functionalized Si surfaces. CEG resulted in the most satisfactory anchoring procedure, because of its better correlation between high coverage and preservation of the Si surface from both oxidation and contamination. The corresponding Si-bipyridine hybrid was reacted in a solution of CH3CN containing CuI ions coordinatively bound to the anchored ligands, as evidenced from the XPS binding-energy shift of the N atom donor functions. The reaction gave a 1:2 Cu-bipyridine surface complex, in which two ligands couple to a single CuI ion. The surface complex was characterized by the Cu Auger parameter and Cu/N XPS atomic-ratio values coincident with those for pure, unsupported CuI complex with the same 2,2'-bipyridine. Further support for such a specific metal-ligand interaction at the functionalized Si surface came from the distinct values of Cu2p binding energy and the Cu Auger parameter, which were obtained for the species resulting from CuI ion uptake on hydrogen-terminated Si(100).