Wende Xiao

Tunability of Supramolecular Kagome Lattices of Magnetic Phthalocyanines Using Graphene-Based Moire Patterns as Templates

Self-assembly of various phthalocyanine (Pc) molecules and a derivative on an epitaxial graphene monolayer (MG) has been investigated by means of in situ ultrahigh vacuum scanning tunneling microscopy. The formation of regular Kagome lattices that duplicate the lattice of the moire pattern of MG was observed, demonstrating that MG can act as a wonderful template for the fabrication of unique nanoarchitectures with remarkable properties. Varying the central metal ion of the Pc molecule affords Kagome lattices with tunable molecular spins, providing ideal two-dimensional model systems for studying frustration physics.

C60/corannulene on Cu(110): a surface-supported bistable buckybowl-buckyball host-guest system.

Corannulene (COR) buckybowls were proposed as near ideal hosts for fullerene C60, but direct complexation of C60 and COR has remained a challenge in supramolecular chemistry. We report the formation of surface-supported COR-C60 host-guest complexes by deposition of C60 onto a COR lattice on Cu(110). Variable-temperature scanning tunneling microscopy studies reveal two distinctly different states of C60 on the COR host lattice, with different binding energies and bowl-ball separations. The transition from a weakly bound precursor state to a strongly bound host-guest complex is found to be thermally activated. Simple model calculations show that this bistability originates from a subtle interplay between homo- and heteromolecular interactions.

Reversible Single Spin Control of Individual Magnetic Molecule by Hydrogen Atom Adsorption

The reversible control of a single spin of an atom or a molecule is of great interest in Kondo physics and a potential application in spin based electronics. Here we demonstrate that the Kondo resonance of manganese phthalocyanine molecules on a Au(111) substrate have been reversibly switched off and on via a robust route through attachment and detachment of single hydrogen atom to the magnetic core of the molecule. As further revealed by density functional theory calculations, even though the total number of electrons of the Mn ion remains almost the same in the process, gaining one single hydrogen atom leads to redistribution of charges within 3d orbitals with a reduction of the molecular spin state from S = 3/2 to S = 1 that directly contributes to the Kondo resonance disappearance. This process is reversed by a local voltage pulse or thermal annealing to desorb the hydrogen atom.

Reversible achiral-to-chiral switching of single Mn--phthalocyanine molecules by thermal hydrogenation and inelastic electron tunneling dehydrogenation.

Induction of chirality in planar adsorbates by hydrogenation of phthalocyanine molecules on a gold surface is demonstrated. This process merely lowers the molecular symmetry from 4- to 2-fold, but also breaks the mirror symmetry of the entire adsorbate complex (molecule and surface), thus rendering it chiral without any realignment at the surface. Repositioning of single molecules by manipulation with the scanning tunneling microscope (STM) causes interconversion of enantiomers. Dehydrogenation of the adsorbate by means of inelastic electron tunneling restores the mirror symmetry of the adsorbate complex. STM as well as density functional theory (DFT) calculations show that chirality is actually imprinted into the electronic molecular system by the surface, i.e., the lowest unoccupied orbital is devoid of mirror symmetry.

Epitaxial growth of large-area bilayer graphene on Ru(0001)

Large-area bilayer graphene (BG) is grown epitaxially on Ru(0001) surface and characterized by low temperature scanning tunneling microscopy. The lattice of the bottom layer of BG is stretched by 1.2%, while strain is absent from the top layer. The lattice mismatch between the two layers leads to the formation of a moire pattern with a periodicity of ∼21.5 nm and a mixture of AA- and AB-stacking. The √3 × √3 superstructure around atomic defects is attributed to the inter-valley scattering of the delocalized π-electrons, demonstrating that the as-grown BG behaves like intrinsic free-standing graphene.

Room-Temperature, Low-Barrier Boron Doping of Graphene.

Doping graphene with boron has been difficult because of high reaction barriers. Here, we describe a low-energy reaction route derived from first-principles calculations and validated by experiments. We find that a boron atom on graphene on a ruthenium(0001) substrate can replace a carbon by pushing it through, with substrate attraction helping to reduce the barrier to only 0.1 eV, implying that the doping can take place at room temperature. High-quality graphene is grown on a Ru(0001) surface and exposed to B2H6. Scanning tunneling microscopy/spectroscopy and X-ray photoelectron spectroscopy confirmed that boron is indeed incorporated substitutionally without disturbing the graphene lattice.

Stacking-dependent electronic property of trilayer graphene epitaxially grown on Ru(0001)

The growth, atomic structure, and electronic property of trilayer graphene (TLG) on Ru(0001) were studied by low temperature scanning tunneling microscopy and spectroscopy in combined with tight-binding approximation (TBA) calculations. TLG on Ru(0001) shows a flat surface with a hexagonal lattice due to the screening effect of the bottom two layers and the AB-stacking in the top two layers. The coexistence of AA- and AB-stacking in the bottom two layers leads to three different stacking orders of TLG, namely, ABA-, ABC-, and ABB-stacking. STS measurements combined with TBA calculations reveal that the density of states of TLG with ABC- and ABB-stacking is characterized by one and two sharp peaks near to the Fermi level, respectively, in contrast to the V-shaped feature of TLG with ABA-stacking. Our work demonstrates that TLG on Ru(0001) might be an ideal platform for exploring stacking-dependent electronic properties of graphene.

Revealing the Atomic Site-Dependent g Factor within a Single Magnetic Molecule via the Extended Kondo Effect

The site-dependent g factor of a single magnetic molecule, with intramolecular resolution, is demonstrated for the first time by low-temperature, high-magnetic-field scanning tunneling microscopy of dehydrogenated Mn-phthalocyanine molecules on Au(111). This is achieved by exploring the magnetic-field dependence of the extended Kondo effect at different atomic sites of the molecule. Importantly, an inhomogeneous distribution of the g factor inside a single molecule is revealed. Our results open up a new route to access local spin properties within a single molecule.

Selective adsorption of metal-phthalocyanine on Au(111) surface with hydrogen atoms

Metal phthalocyanine (MPc, M = Mn, Fe) molecules grown on reconstructed Au(111) with and without hydrogen atoms at submonolayer coverage are investigated by low temperature scanning tunneling microscopy. It is found out that the attachment of H atoms to the central metal of the MnPc molecules leads to the change of the molecules’ selective adsorption from fcc to hcp regions at low coverage. The two configurations of MnPc molecules on Au(111) are replaced by only one configuration of H-MnPc/Au(111). FePc molecules adsorb on fcc regions of Au(111) with two configurations, which are similar to that of MnPc. However, unlike H-MnPc, H-FePc molecules have two configurations on Au(111). Density function theory calculations show that the different configuration change by attachment of H atoms for MnPc and FePc molecules is due to the electronic structure change at the central metal atoms of the molecules.

Construction of two-dimensional hydrogen clusters on Au(111) directed by phthalocyanine molecules

Low-dimensional H2 aggregates have been successfully fabricated on Au(111) surfaces and investigated by means of low temperature scanning tunneling microscopy. We use manganese phthalocyanine (MnPc) molecules anchored on the Au(111) surface to efficiently collect and pin hydrogen molecules. A two-dimensional (2D) molecular hydrogen cluster is formed around the MnPc. The hydrogen cluster exhibits bias-dependent topography and spatial-dependent conductance spectra, which are rationalized by the exponentially decreasing threshold energy with distance from the central MnPc to activate the motion of the H2 molecules. This exponential drop reveals an interfacial phase behavior in the 2D cluster.