Potassium doping of vertically aligned multi-walled carbon nanotubes.

Alkali metal doping of multi-walled carbon nanotubes is of great interest, both fundamentally to explore the effect of dopants on quasi-one-dimensional electrical systems and for energy applications such as alkali metal storage. We present an investigation with complementary photoemission and Raman spectroscopies, fully carried out in an ultra-high vacuum, to unveil the electronic and vibrational response of a forest of highly aligned multi-walled carbon nanotubes by in situ potassium doping. The charge donation by the alkali adatoms induces a plasmon mode, and the density of states undergoes an energy shift consistent with electron donation and band filling of the multi-walled carbon nanotube band structure. The π-states in the valence band and the Raman peaks unveil an evolution that can be ascribed to charge donation and partially to a tensile strain exerted by the K adatoms on the carbon lattice. All these effects are thermally reversible, fostering these materials as a potential system for electronic charge harvesting.

Tuning the Electronic Response of Metallic Graphene by Potassium Doping.

Electron doping of graphene has been extensively studied on graphene-supported surfaces, where the metallicity is influenced by the substrate. Herewith we propose potassium adsorption on free-standing nanoporous graphene, thus eluding any effect due to the substrate. We monitor the electron migration in the π* downward-shifted conduction band. In this rigid band shift, we correlate the spectral density of the π* state in the upper Dirac cone with the associated plasmon, blue-shifted with increasing K dose, as deduced by electron energy loss spectroscopy. These results are confirmed by the Dirac plasmon activated by the C 1s emitted electrons, thanks to spatially resolved photoemission. This crosscheck constitutes a reference on the correlation between the electronic π* states in the conduction band and the Dirac plasmon evolution upon in situ electron doping of fully free-standing graphene.

Room-temperature synthesis of 2D-Ti3C2Tx nano-sheets by organic base treatment.

The growing demand for improved electrochemical performance in energy storage systems has stimulated research into advanced two-dimensional (2D) materials for electrodes. In this work, we obtain a layered MXene compound by exfoliating a titanium aluminum carbide precursor using tetramethylammonium hydroxide (TMAOH) ions in a full room temperature process followed by manual shaking. The hexagonal crystal structure and composition of the layered materials are characterized using different techniques. X-Ray diffraction shows the formation of 2D nano-sheets before and after the TMAOH treatment via its characteristic (002) diffraction peak, bringing to light an increase in the interlayer spacing after treatment. Scanning electron microscopy images confirm the layered morphology, whose composition is determined by energy dispersive x-ray analysis for the bulk material and by x-ray photoelectron spectroscopy for the surface of the obtained compounds. This study demonstrates a promising route to enhance delamination of this MXene 2D material in a low-cost room-temperature approach.

Gap Opening in Double-Sided Highly Hydrogenated Free-Standing Graphene.

Conversion of free-standing graphene into pure graphane─where each C atom is sp3 bound to a hydrogen atom─has not been achieved so far, in spite of numerous experimental attempts. Here, we obtain an unprecedented level of hydrogenation (≈90% of sp3 bonds) by exposing fully free-standing nanoporous samples─constituted by a single to a few veils of smoothly rippled graphene─to atomic hydrogen in ultrahigh vacuum. Such a controlled hydrogenation of high-quality and high-specific-area samples converts the original conductive graphene into a wide gap semiconductor, with the valence band maximum (VBM) ∼ 3.5 eV below the Fermi level, as monitored by photoemission spectromicroscopy and confirmed by theoretical predictions. In fact, the calculated band structure unequivocally identifies the achievement of a stable, double-sided fully hydrogenated configuration, with gap opening and no trace of π states, in excellent agreement with the experimental results.

Tuning the Magnetic Coupling of a Molecular Spin Interface via Electron Doping.

Mastering the magnetic response of molecular spin interfaces by tuning the occupancy of the molecular orbitals, which carry the spin magnetic moment, can be accomplished by electron doping. We propose a viable route to control the magnetization direction and magnitude of a molecular spin network, in a graphene-mediated architecture, achieved via alkali doping of manganese phthalocyanine (MnPc) molecules assembled on cobalt intercalated under a graphene membrane. The antiparallel magnetic alignment of the MnPc molecules with the underlying Co layer can be switched to a ferromagnetic state by electron doping. Multiplet calculations unveil an enhanced magnetic state of the Mn centers with a 3/2 to 5/2 spin transition induced by alkali doping, as confirmed by the steepening of the hysteresis loops, with higher saturation magnetization values. This new molecular spin configuration can be aligned by an external field, almost independently from the hard-magnet substrate effectively behaving as a free magnetic layer.

Towards free-standing graphane: atomic hydrogen and deuterium bonding to nano-porous graphene.

Graphane is formed by bonding hydrogen (and deuterium) atoms to carbon atoms in the graphene mesh, with modification from the pure planar sp2 bonding towards an sp3 configuration. Atomic hydrogen (H) and deuterium (D) bonding with C atoms in fully free-standing nano porous graphene (NPG) is achieved, by exploiting low-energy proton (or deuteron) non-destructive irradiation, with unprecedented minimal introduction of defects, as determined by Raman spectroscopy and by the C 1s core level lineshape analysis. Evidence of the H- (or D-) NPG bond formation is obtained by bringing to light the emergence of a H- (or D-) related sp3-distorted component in the C 1s core level, clear fingerprint of H-C (or D-C) covalent bonding. The H (or D) bonding with the C atoms of free-standing graphene reaches more than 1/4 (or 1/3) at% coverage. This non-destructive H-NPG (or D-NPG) chemisorption is very stable at high temperatures up to about 800 K, as monitored by Raman and x-ray photoelectron spectroscopy, with complete healing and restoring of clean graphene above 920 K. The excellent chemical and temperature stability of H- (and D-) NPG opens the way not only towards the formation of semiconducting graphane on large-scale samples, but also to stable graphene functionalisation enabling futuristic applications in advanced detectors for the ß-spectrum analysis.

Empty electron states in cobalt-intercalated graphene.

The dispersion of the electronic states of epitaxial graphene (Gr) depends significantly on the strength of the bonding with the underlying substrate. We report on empty electron states in cobalt-intercalated Gr grown on Ir(111), studied by angle-resolved inverse photoemission spectroscopy and x-ray absorption spectroscopy, complemented with density functional theory calculations. The weakly bonded Gr on Ir preserves the peculiar spectroscopic features of the Gr band structure, and the empty spectral densities are almost unperturbed. Upon intercalation of a Co layer, the electronic response of the interface changes, with an intermixing of the Gr π* bands and Co d states, which breaks the symmetry of π/σ states, and a downshift of the upper part of the Gr Dirac cone. Similarly, the image potential of Ir(111) is unaltered by the Gr layer, while a downward shift is induced upon Co intercalation, as unveiled by the image state energy dispersion mapped in a large region of the surface Brillouin zone.

Metal phthalocyanines interaction with Co mediated by a moiré graphene superlattice.

The assembling of metal phthalocyanines on the rippled moiré superlattice of graphene/Ir(111) intercalated with one Co layer is driven by the site-dependent polarization field induced by the incommensurate graphene-Co interface. We have performed an X-ray absorption and photoemission study to unveil the role of the metallic centers and of the organic ligands in the molecule-Co interaction process mediated by graphene. Notably, we consider different electronic molecular orbitals, i.e. phthalocyanines with Cu and Mn metallic ions. The spectroscopic response suggests almost unaltered CuPc molecular states upon adsorption, and the rippled graphene carpet decouples completely the electronic interaction between the molecules and the Co layer, while a slight hybridization is present for MnPcs. MnPc molecules, trapped in the valleys of the moiré graphene superlattice, slightly intermix, through the orbitals protruding out of the molecular plane, with the underlying Co, while the organic ligands are almost unaltered. Graphene acts as an interlayer and mediates the interaction between metal phthalocyanines and the metallic substrate, preventing a strong chemical intermixing and enabling the assembly of almost unaltered molecules, preserving their electronic/magnetic state.

Ferromagnetic and Antiferromagnetic Coupling of Spin Molecular Interfaces with High Thermal Stability.

We report an advanced organic spin-interface architecture with magnetic remanence at room temperature, constituted by metal phthalocyanine molecules magnetically coupled with Co layer(s), mediated by graphene. Fe- and Cu-phthalocyanines assembled on graphene/Co have identical structural configurations, but FePc couples antiferromagnetically with Co up to room temperature, while CuPc couples ferromagnetically with weaker coupling and thermal stability, as deduced by element-selective X-ray magnetic circular dichroic signals. The robust antiferromagnetic coupling is stabilized by a superexchange interaction, driven by the out-of-plane molecular orbitals responsible of the magnetic ground state and electronically decoupled from the underlying metal via the graphene layer, as confirmed by ab initio theoretical predictions. These archetypal spin interfaces can be prototypes to demonstrate how antiferromagnetic and/or ferromagnetic coupling can be optimized by selecting the molecular orbital symmetry.

Three-dimensional microporous graphene decorated with lithium.

Three-dimensional (3D) graphene-based architectures can combine the two-dimensional properties of graphene with the high surface-to-volume ratio required for a large variety of technological applications. We present a spectro-microscopy study of stable microporous 3D few-layer graphene structures with a very low density of defects/edges and of unsaturated bonds, as deduced by Raman and core level photoemission spectroscopy. These qualities make these interconnected graphene networks ideal candidates to accommodate lithium adatoms, with a high density of Li per unit volume and a Li uptake per C atom higher than the value observed for graphite, as confirmed by core level photoemission spectroscopy.

Chemical vapor deposition growth of boron-carbon-nitrogen layers from methylamine borane thermolysis products.

This work investigates the growth of B-C-N layers by chemical vapor deposition using methylamine borane (MeAB) as the single-source precursor. MeAB has been synthesized and characterized, paying particular attention to the analysis of its thermolysis products, which are the gaseous precursors for B-C-N growth. Samples have been grown on Cu foils and transferred onto different substrates for their morphological, structural, chemical, electronic and optical characterizations. The results of these characterizations indicate a segregation of h-BN and graphene-like (Gr) domains. However, there is an important presence of B and N interactions with C at the Gr borders, and of C interacting at the h-BN-edges, respectively, in the obtained nano-layers. In particular, there is a significant presence of C-N bonds, at Gr/h-BN borders and in the form of N doping of Gr domains. The overall B:C:N contents in the layers is close to 1:3:1.5. A careful analysis of the optical bandgap determination of the obtained B-C-N layers is presented, discussed and compared with previous seminal works with samples of similar composition.

High quality epitaxial graphene by hydrogen-etching of 3C-SiC(111) thin-film on Si(111).

Etching with atomic hydrogen, as a preparation step before the high-temperature growth process of graphene onto a thin 3C-SiC film grown on Si(111), greatly improves the structural quality of topmost graphene layers. Pit formation and island coalescence, which are typical of graphene growth by SiC graphitization, are quenched and accompanied by widening of the graphene domain sizes to hundreds of nanometers, and by a significant reduction in surface roughness down to a single substrate bilayer. The surface reconstructions expected for graphene and the underlying layer are shown with atomic resolution by scanning tunnelling microscopy. Spectroscopic features typical of graphene are measured by core-level photoemission and Raman spectroscopy.

Mixing of MnPc electronic states at the MnPc/Au(110) interface.

Manganese-phthalocyanines form assembled chains with a variety of ordered super-structures, flat lying along the Au(110) reconstructed channels. The chains first give rise to a ×5 symmetry reconstruction, while further deposition of MnPc leads to a ×7 periodicity at the completion of the first single layer. A net polarization with the formation of an interface dipole is mainly due to the molecular π-states located on the macrocycles pyrrole rings, while the central metal ion induces a reduction in the polarization, whose amount is related to the Mn-Au interaction. The adsorption-induced interface polarization is compared to other 3d-metal phthalocyanines, to unravel the role of the central metal atom configuration in the interaction process of the d-states. The MnPc adsorption on Au(110) induces the re-hybridization of the electronic states localized on the central metal atom, promoting a charge redistribution of the molecular orbitals of the MnPc molecules. The molecule-substrate interaction is controlled by a symmetry-determined mixing between the electronic states, involving also the molecular empty orbitals with d character hybridized with the nitrogen atoms of the pyrrole ring, as deduced by photoemission and X-ray absorption spectroscopy exploiting light polarization. The symmetry-determined mixing between the electronic states of the Mn metal center and of the Au substrate induces a density of states close to the Fermi level for the ×5 phase.

A long-range ordered array of copper tetrameric units embedded in an on-surface metal organic framework.

We report on the assembly of a highly ordered array of copper tetrameric clusters, coordinated into a metal-organic network. The ordered cluster array has been achieved by the deposition of tetrahydroxyquinone molecules on the Cu(111) surface at room temperature, and subsequent thermally activated dehydrogenation with the formation of tetraoxyquinone tetra-anions with a 4 × 4 periodicity. The supramolecular organic network acts as a spacer for the highly ordered two-dimensional network of copper tetramers at the very surface.

In-vacuum thermolysis of ethane 1,2-diamineborane for the synthesis of ternary borocarbonitrides.

High-temperature (1000 °C) thermolytic decomposition of ethane 1,2-diamineborane (BH3NH2CH2CH2NH2BH3) deposited onto a Cu foil has been performed in an ultra-high-vacuum environment. A combined thermolytic, structural (x-ray diffraction), microscopic (scanning electron microscopy) and spectroscopic (Raman, x-ray photoemission spectroscopy) analysis, has identified a ternary borocarbonitride (BCN) compound as a result of the process. The obtained BCN compound is nanocrystalline, surrounded by crystallites of ammonium hydroxide borate hydrate. The ternary compound presents a 0.2:0.6:0.2 B:C:N composition in the bulk and 0.11:0.76:0.13 stoichiometry at the very surface, richer in C-C networks with respect to the bulk. Furthermore, the resulting BCN compound does not show oxidation at the surface due to the in-vacuum thermolysis of the single precursor.

An advanced lithium-ion battery based on a graphene anode and a lithium iron phosphate cathode.

We report an advanced lithium-ion battery based on a graphene ink anode and a lithium iron phosphate cathode. By carefully balancing the cell composition and suppressing the initial irreversible capacity of the anode in the round of few cycles, we demonstrate an optimal battery performance in terms of specific capacity, that is, 165 mAhg(-1), of an estimated energy density of about 190 Wh kg(-1) and a stable operation for over 80 charge-discharge cycles. The components of the battery are low cost and potentially scalable. To the best of our knowledge, complete, graphene-based, lithium ion batteries having performances comparable with those offered by the present technology are rarely reported; hence, we believe that the results disclosed in this work may open up new opportunities for exploiting graphene in the lithium-ion battery science and development.

Metal-phthalocyanine ordered layers on Au(110): metal-dependent adsorption energy.

Iron-phthalocyanine and cobalt-phthalocyanine chains, assembled along the Au(110)-(1×2) reconstructed channels, present a strong interaction with the Au metallic states, via the central metal ion. X-ray photoemission spectroscopy from the metal-2p core-levels and valence band high-resolution ultraviolet photoelectron spectroscopy bring to light signatures of the interaction of the metal-phthalocyanine single-layer with gold. The charge transfer from Au to the molecule causes the emerging of a metal-2p core level component at lower binding energy with respect to that measured in the molecular thin films, while the core-levels associated to the organic macrocycle (C and N 1s) are less influenced by the adsorption, and the macrocycles stabilize the interaction, inducing a strong interface dipole. Temperature Programmed Desorption experiments and photoemission as a function of temperature allow to estimate the adsorption energy for the thin-films, mainly due to the molecule-molecule van der Waals interaction, while the FePc and CoPc single-layers remain adsorbed on the Au surface up to at least 820 K.

Intermixing of Unoccupied States of Metal Phthalocyanine Chains Assembled on Au(110).

A detailed inverse photoemission study unveils the unoccupied electronic structure induced by the adsorption of CuPc and CoPc phthalocyanines on Au(110) reconstructed channels. The different behavior in the two systems is related to the different intermixing of orbitals with the underlying gold states. Broadening of the density of states at the Fermi level is detected after CoPc adsorption, absent in the case CuPc. A detailed comparison with the element-selective X-ray absorption spectroscopy enlightens and complements the IPES results and confirms a surface-driven intermixing of the CoPc orbitals involved in the interaction, with the out-of-plane Co 3dz2 orbital strongly hybridized with the gold electronic states. Moreover, the contribution of the 3d empty states to the IPES data is reported for FePc, CoPc, and CuPc thin films.

Protecting TiS3 Photoanodes for Water Splitting in Alkaline Media by TiO2 Coatings.

Titanium trisulfide (TiS3) nanoribbons, when coated with titanium dioxide (TiO2), can be used for water splitting in the KOH electrolyte. TiO2 shells can be prepared through thermal annealing to regulate the response of TiS3/TiO2 heterostructures by controlling the oxidation time and growth atmosphere. The thickness and structure of the TiO2 layers significantly influence the photoelectrocatalytic properties of the TiS3/TiO2 photoanodes, with amorphous layers showing better performance than crystalline ones. The oxide layers should be thin enough to transfer photogenerated charge through the electrode-electrolyte interface while protecting TiS3 from KOH corrosion. Finally, the performance of TiS3/TiO2 heterostructures has been improved by coating them with various electrocatalysts, NiSx being the most effective. This research presents new opportunities to create efficient semiconductor heterostructures to be used as photoanodes in corrosive alkaline aqueous solutions.

Energetics and hierarchical interactions of metal-phthalocyanines adsorbed on graphene/Ir(111).

The adsorption of metal-phthalocyanine (MPc) layers (M = Fe, Co, Cu) assembled on graphene/Ir(111) is studied by means of temperature-programmed X-ray photoemission spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS). The balance between interaction forces among the organometallic molecules and the underlying graphene gives rise to flat-lying molecular layers, weakly interacting with the underlying graphene. Further MPc layers pile up face-on onto the first layer, up to a few nanometers thickness, as deduced by NEXAFS. The FePc, CoPc, and CuPc multilayers present comparable desorption temperatures, compatible with molecule-molecule interactions dominated by van der Waals forces between the π-conjugated macrocycles. The MPc single layers desorb from graphene/Ir at higher temperatures. The CuPc single layer desorbs at lower temperature than the FePc and CoPc single layers, suggesting a higher adsorption energy of the FePc and CoPc single layers on graphene/Ir with respect to CuPc, with increasing molecule-substrate interaction in the order E(CuPc) < E(FePc) ~ E(CoPc).