Charge transport in a single molecule transistor probed by scanning tunneling microscopy.

We report on the scanning tunneling microscopy/spectroscopy (STM/STS) study of cobalt phthalocyanine (CoPc) molecules deposited onto a back-gated graphene device. We observe a clear gate voltage (Vg) dependence of the energy position of the features originating from the molecular states. Based on the analysis of the energy shifts of the molecular features upon tuning Vg, we are able to determine the nature of the electronic states that lead to a gapped differential conductance. Our measurements show that capacitive couplings of comparable strengths exist between the CoPc molecule and the STM tip as well as between CoPc and graphene, thus facilitating electronic transport involving only unoccupied molecular states for both tunneling bias polarities. These findings provide novel information on the interaction between graphene and organic molecules and are of importance for further studies, which envisage the realization of single molecule transistors with non-metallic electrodes.

Highly Ordered Surface Self-Assembly of Fe4 Single Molecule Magnets.

Single molecule magnets (SMMs) have attracted considerable attention due to low-temperature magnetic hysteresis and fascinating quantum effects. The investigation of these properties requires the possibility to deposit well-defined monolayers or spatially isolated molecules within a well-controlled adsorption geometry. Here we present a successful fabrication of self-organized arrays of Fe4 SMMs on hexagonal boron nitride (h-BN) on Rh(111) as template. Using a rational design of the ligand shell optimized for surface assembly and electrospray as a gentle deposition method, we demonstrate how to obtain ordered arrays of molecules forming perfect hexagonal superlattices of tunable size, from small islands to an almost perfect monolayer. High-resolution low temperature scanning tunneling microscopy (STM) reveals that the Fe4 molecule adsorbs on the substrate in a flat geometry, meaning that its magnetic easy axis is perpendicular to the surface. By scanning tunneling spectroscopy (STS) and density functional theory (DFT) calculations, we infer that the majority- and minority-spin components of the spin-split lowest unoccupied molecular orbital (LUMO) can be addressed separately on a submolecular level.

In situ fabrication of quasi-free-standing epitaxial graphene nanoflakes on gold.

Addressing the multitude of electronic phenomena theoretically predicted for confined graphene structures requires appropriate in situ fabrication procedures yielding graphene nanoflakes (GNFs) with well-defined geometries and accessible electronic properties. Here, we present a simple strategy to fabricate quasi-free-standing GNFs of variable sizes, performing temperature programmed growth of graphene flakes on the Ir(111) surface and subsequent intercalation of gold. Using scanning tunneling microscopy (STM), we show that epitaxial GNFs on a perfectly ordered Au(111) surface are formed while maintaining an unreconstructed, singly hydrogen-terminated edge structure, as confirmed by the accompanying density functional theory (DFT) calculations. Using tip-induced lateral displacement of GNFs, we demonstrate that GNFs on Au(111) are to a large extent decoupled from the Au(111) substrate. The direct accessibility of the electronic states of a single GNF is demonstrated upon analysis of the quasiparticle interference patterns obtained by low-temperature STM. These findings open up an interesting playground for diverse investigations of graphene nanostructures with possible implications for device fabrication.

Fundamental quantum noise mapping with tunnelling microscopes tested at surface structures of subatomic lateral size.

We present a measurement scheme that enables quantitative detection of the shot noise in a scanning tunnelling microscope while scanning the sample. As test objects we study defect structures produced on an iridium single crystal at low temperatures. The defect structures appear in the constant current images as protrusions with curvature radii well below the atomic diameter. The measured power spectral density of the noise is very near to the quantum limit with Fano factor F = 1. While the constant current images show detailed structures expected for tunnelling involving d-atomic orbitals of Ir, we find the current noise to be without pronounced spatial variation as expected for shot noise arising from statistically independent events.

Size-selected epitaxial nanoislands underneath graphene moiré on Rh(111).

We use in situ scanning tunneling microscopy (STM) to investigate intercalation of the ferromagnetic 3d metals Ni and Fe underneath a graphene monolayer on Rh(111). Upon thermal annealing of graphene/Rh(111) with the deposited metal on top, we observe the formation of epitaxial monatomic nanoislands grown pseudomorphically on Rh(111) and covered by graphene. The size and shape of intercalated nanoislands is strongly influenced by the local spatial variation of the graphene-Rh bonding strength. In particular, the side length of the intercalated nanoislands shows maxima around discrete values imposed by the periodicity of the graphene moiré. Intercalation can be performed efficiently and without any visible damage of the graphene overlayer in the studied temperature range between 670 and 870 K. We identify the main intercalation path to be via diffusion through pre-existing lattice defects in graphene, accompanied by the second mechanism which is based on the material diffusion via metal-generated defects followed by the defect healing of the graphene lattice. We deem these graphene-capped and sharply confined ferromagnetic nanoislands interesting in the fields of spintronics and nanomagnetism.

Spin resolved photoelectron spectroscopy of [Mn6(III)Cr(III)]3+ single-molecule magnets and of manganese compounds as reference layers.

Properties of the manganese-based single-molecule magnet [Mn(6)(III)Cr(III)](3+) are studied. It contains six Mn(III) ions arranged in two bowl-shaped trinuclear triplesalen building blocks linked by a hexacyanochromate and exhibits a large spin ground state of S(t) = 21/2. The dominant structures in the electron emission spectra of [Mn(6)(III)Cr(III)](3+) resonantly excited at the L(3)-edge are the L(3)M(2, 3)M(2, 3), L(3)M(2, 3)V and L(3)VV Auger emission groups following the decay of the primary p(3/2) core hole state. Significant differences of the Auger spectra from intact and degraded [Mn(6)(III)Cr(III)](3+) show up. First measurements of the electron spin polarization in the L(3)M(2, 3)V and L(3)VV Auger emission peaks from the manganese constituents in [Mn(6)(III)Cr(III)](3+) resonantly excited at the L(3)-edge near 640 eV by circularly polarized synchrotron radiation are reported. In addition spin resolved Auger electron spectra of the reference substances MnO, Mn(2)O(3) and Mn(II)(acetate)(2)·4H(2)O are given. The applicability of spin resolved electron spectroscopy for characterizing magnetic states of constituent atoms compared to magnetic circular dichroism (MCD) is verified: the spin polarization obtained from Mn(II)(acetate)(2)·4H(2)O at room temperature in the paramagnetic state compares to the MCD asymmetry revealed for a star-shaped molecule with a Mn(4)(II)O(6) core at 5 K in an external magnetic field of 5 T.