Aitor Mugarza

Electronic and magnetic properties of molecule-metal interfaces: Transition-metal phthalocyanines adsorbed on Ag(100)

We present a systematic investigation of molecule-metal interactions for transition-metal phthalocyanines (TMPc, with TM = Fe, Co, Ni, Cu) adsorbed on Ag(100). Scanning tunneling spectroscopy and density functional theory provide insight into the charge transfer and hybridization mechanisms of TMPc as a function of increasing occupancy of the 3d metal states. We show that all four TMPc receive approximately one electron from the substrate. Charge transfer occurs from the substrate to the molecules, inducing a charge reorganization in FePc and CoPc, while adding one electron to ligand π orbitals in NiPc and CuPc. This has opposite consequences on the molecular magnetic moment: In FePc and CoPc the interaction with the substrate tends to reduce the TM spin, whereas, in NiPc and CuPc, an additional spin is induced on the aromatic Pc ligand, leaving the TM spin unperturbed. In CuPc, the presence of both TM and ligand spins leads to a triplet ground state arising from intramolecular exchange coupling between d and π electrons. In FePc and CoPc the magnetic moment of C and N atoms is antiparallel to that of the TM. The different character and symmetry of the frontier orbitals in the TMPc series leads to varying degrees of hybridization and correlation effects, ranging from the mixed-valence (FePc, CoPc) to the Kondo regime (NiPc, CuPc). Coherent coupling between Kondo and inelastic excitations induces finite-bias Kondo resonances involving vibrational transitions in both NiPc and CuPc and triplet-singlet transitions in CuPc.

Site- and orbital-dependent charge donation and spin manipulation in electron-doped metal phthalocyanines

Chemical doping offers promise as a means of tailoring the electrical characteristics of organic molecular compounds. However, unlike for inorganic semiconductors used in electronics applications, controlling the influence of dopants in molecular complexes is complicated by the presence of multiple doping sites, electron acceptor levels, and intramolecular correlation effects. Here we use scanning tunnelling microscopy to analyse the position of individual Li dopants within Cu- and Ni-phthalocyanine molecules in contact with a metal substrate, and probe the charge transfer process with unprecedented spatial resolution. We show that individual phthalocyanine molecules can host at least three distinct stable doping sites and up to six dopant atoms, and that the ligand and metal orbitals can be selectively charged by modifying the configuration of the Li complexes. Li manipulation reveals that charge transfer is determined solely by dopants embedded in the molecules, whereas the magnitude of the conductance gap is sensitive to the molecule-dopant separation. As a result of the strong spin-charge correlation in confined molecular orbitals, alkali atoms provide an effective way for tuning the molecular spin without resorting to magnetic dopants.

Fieldlike and antidamping spin-orbit torques in as-grown and annealed Ta/CoFeB/MgO layers

We present a comprehensive study of the current-induced spin-orbit torques in perpendicularly magnetized Ta/CoFeB/MgO layers. The samples were annealed in steps up to 300 \ifmmode^\circ\else\textdegree\fi{}C and characterized using x-ray-absorption spectroscopy, transmission electron microscopy, resistivity, and Hall effect measurements. By performing adiabatic harmonic Hall voltage measurements, we show that the transverse (fieldlike) and longitudinal (antidampinglike) spin-orbit torques are composed of constant and magnetization-dependent contributions, both of which vary strongly with annealing. Such variations correlate with changes of the saturation magnetization and magnetic anisotropy and are assigned to chemical and structural modifications of the layers. The relative variation of the constant and anisotropic torque terms as a function of annealing temperature is opposite for the fieldlike and antidamping torques. Measurements of the switching probability using sub-\ensuremath{\mu}s current pulses show that the critical current increases with the magnetic anisotropy of the layers, whereas the switching efficiency, measured as the ratio of magnetic anisotropy energy and pulse energy, decreases. The optimal annealing temperature to achieve maximum magnetic anisotropy, saturation magnetization, and switching efficiency is determined to be between 240 and 270 \ifmmode^\circ\else\textdegree\fi{}C.

Spin tuning of electron-doped metal-phthalocyanine layers

The spin state of organic-based magnets at interfaces is to a great extent determined by the organic environment and the nature of the spin-carrying metal center, which is further subject to modifications by the adsorbate-substrate coupling. Direct chemical doping offers an additional route for tailoring the electronic and magnetic characteristics of molecular magnets. Here we present a systematic investigation of the effects of alkali metal doping on the charge state and crystal field of 3d metal ions in Cu, Ni, Fe, and Mn phthalocyanine (Pc) monolayers adsorbed on Ag. Combined X-ray absorption spectroscopy and ligand field multiplet calculations show that Cu(II), Ni(II), and Fe(II) ions reduce to Cu(I), Ni(I), and Fe(I) upon alkali metal adsorption, whereas Mn maintains its formal oxidation state. The strength of the crystal field at the Ni, Fe, and Mn sites is strongly reduced upon doping. The combined effect of these changes is that the magnetic moment of high- and low-spin ions such as Cu and Ni can be entirely turned off or on, respectively, whereas the magnetic configuration of MnPc can be changed from intermediate (3/2) to high (5/2) spin. In the case of FePc a 10-fold increase of the orbital magnetic moment accompanies charge transfer and a transition to a high-spin state.

Manipulating the Topological Interface by Molecular Adsorbates: Adsorption of Co-Phthalocyanine on Bi2Se3.

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.

Bottom-up synthesis of multifunctional nanoporous graphene

Synthesizing graphene nanopores Nanosize pores in graphene can make its electronic properties more favorable for transistor applications and may also be useful for molecular separations. Moreno et al. used Ullmann coupling to polymerize a dibromo-substituted diphenylbianthracene on a gold surface (see the Perspective by Sinitskii). Cyclodehydrogenation of the resulting polymer produced graphene nanoribbons, and cross-coupling of these structures created a nanoporous graphene sheet with pore sizes of about 1 nanometer. Scanning tunneling spectroscopy revealed an electronic structure in which semiconductor bands with an energy gap of 1 electron volt coexist with localized states created by the pores. Science, this issue p. 199; see also p. 154 Graphene nanoribbons are synthesized on a gold surface and interconnected to create a well-defined pore network. Nanosize pores can turn semimetallic graphene into a semiconductor and, from being impermeable, into the most efficient molecular-sieve membrane. However, scaling the pores down to the nanometer, while fulfilling the tight structural constraints imposed by applications, represents an enormous challenge for present top-down strategies. Here we report a bottom-up method to synthesize nanoporous graphene comprising an ordered array of pores separated by ribbons, which can be tuned down to the 1-nanometer range. The size, density, morphology, and chemical composition of the pores are defined with atomic precision by the design of the molecular precursors. Our electronic characterization further reveals a highly anisotropic electronic structure, where orthogonal one-dimensional electronic bands with an energy gap of ∼1 electron volt coexist with confined pore states, making the nanoporous graphene a highly versatile semiconductor for simultaneous sieving and electrical sensing of molecular species.

Superparamagnetism-induced mesoscopic electron focusing in topological insulators

Recently it has been shown that surface magnetic doping of topological insulators induces backscattering of Dirac states which are usually protected by time-reversal symmetry [Sessi et al., Nat. Commun. 5, 5349 (2014)]. Here we report on quasiparticle interference measurements where, by improved Fermi level tuning, strongly focused interference patterns on surface Mn-doped

Effect of surface reconstruction on the photoemission cross-section of the Au(111) surface state

{\mathrm{Bi}}_{2}{\mathrm{Te}}_{3}

Determination of the photoelectron reference plane in nanostructured surfaces

could be directly observed by means of scanning tunneling microscopy at 4 K. Ab initio and model calculations reveal that their mesoscopic coherence relies on two prerequisites: (i) a hexagonal Fermi surface with large parallel segments (nesting) and (ii) magnetic dopants which couple to a high-spin state. Indeed, x-ray magnetic circular dichroism shows superparamagnetism even at very dilute Mn concentrations. Our findings provide evidence of strongly anisotropic Dirac-fermion-mediated interactions and demonstrate how spin information can be transmitted over long distances, allowing the design of experiments and devices based on coherent quantum effects in topological insulators.

Electronic structure of SixSn(1−x)/Si(111)-(3×3)R30° phases

The photoemission cross-section of the Shockley surface state of Au(111) is studied over a wide range of photon energies both experimentally and theoretically. The measurements are fully understood based on the theoretical analysis within a one-step ab initio theory of photoemission. The constant initial state spectrum is shown to be very sensitive to the structure of the topmost atomic layer. A maximum in the constant initial spectrum at 60 eV is identified as a fingerprint of the Au(111) surface reconstruction.