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Integration of molecular switching units into complex electronic circuits is considered to be the next step toward the realization of novel logic and memory devices. This paper reports on an ordered 2D network of neighboring ternary switching units represented by triazatruxene (TAT) molecules organized in a honeycomb lattice on a Ag(111) surface. Using low-temperature scanning tunneling microscopy, the bonding configurations of individual TAT molecules can be controlled, realizing up to 12 distinct states per molecule. The switching between those states shows a strong bias dependence ranging from tens of millivolts to volts. The low-bias switching behavior is explored in active units consisting of two and more interacting TAT molecules that are purposefully defined (programmed) by high-bias switching within the honeycomb lattice. Within such a unit the low-bias switching can be triggered and accessed by single-point measurements on a single TAT molecule, demonstrating up to 9 and 19 distinguishable states in a dyad and a tetrad of coupled molecules, respectively. High experimental control over the desired state, owing to bias-dependent hierarchical switching and pronounced switching directionality, as well as full reversibility, make this system particularly appealing, paving the way to design complex molecule-based memory systems., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

We report on seven new ferrocenyl-( 1 , 3 )- and ferrocenylethynyl-modified N , N ', N ″-triethyltriazatruxenes ( Et TAT s) 4 - 7 as well as the dodecyl counterpart 2 of compound 1 and their use as molecular switching units when deposited on a Ag(111) surface. Such functional units may constitute a new approach to molecule-based high-density information storage and processing. Besides the five compounds 1 - 3 , 6 , and 7 , where the 3-fold rotational symmetry of the triazatruxene (TAT) template is preserved, we also included 2-ethynylferrocenyl-TAT 4 and 2,2'-di(ethynylferrocenyl)-TAT 5 , whose mono- and disubstitution patterns break the 3-fold symmetry of the TAT core. Voltammetric studies indicate that the ferrocenyl residues of compounds 1 - 7 oxidize prior to the oxidation of the TAT core. We have noted strong electrostatic effects on TAT oxidation in the 2,2',2″-triferrocenyl-TAT derivatives 1 and 2 and the 3,3',3″-isomer 3 . The oxidized complexes feature multiple electronic excitations in the near-infrared and the visible spectra, which are assigned to d δ/δ * transitions of the ferrocenium (Fc + ) moieties, as well as TAT → Fc + charge-transfer transitions. The latter are augmented by intervalence charge-transfer contributions Fc → Fc + in mixed-valent states, where only a part of the available ferrocenyl residues is oxidized. Et TAT was previously identified as a directional three-level switching unit when deposited on Ag(111) and constitutes a trinary-digit unit for on-surface information storage. The symmetrically trisubstituted compound 6 retains this property, albeit at somewhat reduced switching rates due to the additional interaction between the ferrocenyl residues and the Ag surface. In particular, the high directionality at low bias and the inversion of the preferred sense of the on-surface rocking motion with either a clockwise or counterclockwise switching sense, depending on the identity of the surface enantiomer, are preserved. Unsymmetrical substitution in mono- and diferrocenylated 4 and 5 alters the underlying ratchet potential in a manner such that a two-state switching between the two degenerate surface conformations of 4 or a pronounced suppression of switching ( 5 ) is observed.

Mesocrystals are a class of nanostructured material, where a multiple-length-scale structure is a prerequisite of many interesting phenomena. Resolving the mesocrystal structure is quite challenging due to their structuration on different length scales. The combination of small- and wide-angle X-ray scattering (SAXS and WAXS) techniques offers the possibility of non-destructively probing mesocrystalline structures simultaneously, over multiple length scales to reveal their microscopic structure. This work describes how high dynamical range of modern detectors sheds light on the weak features of scattering, significantly increasing the information content. The detailed analysis of X-ray diffraction (XRD) from the magnetite mesocrystals with different particle sizes and shapes is described, in tandem with electron microscopy. The revealed features provide valuable input to the models of mesocrystal growth and the choice of structural motif; the impact on magnetic properties is discussed., (© 2022 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Chemically robust single-molecule magnets (SMMs) with sufficiently high blocking temperatures T B are among the key building blocks for the realization of molecular spintronic or quantum computing devices. Such device applications require access to the magnetic system of a SMM molecule by means of electronic transport, which primarily depends on the interaction of magnetic orbitals with the electronic states of the metallic electrodes. Scanning tunneling microscopy in combination with ab initio calculations allows to directly address the unoccupied component of the single-electron molecular orbital that mediates the ferromagnetic exchange coupling between two 4f ions within a lanthanide endohedral dimetallofullerene deposited on a graphene surface. The single-electron metal-metal bond provides a direct access to the molecule's magnetic system in the transport experiments, paving the way for investigation and controlled manipulation of the spin system of individual dimetallofullerene SMMs, essential for molecular spintronics., (© 2021 The Authors. Small published by Wiley-VCH GmbH.)

Single-molecule magnets (SMMs) are among the most promising building blocks for future magnetic data storage or quantum computing applications, owing to magnetic bistability and long magnetic relaxation times. The practical device integration requires realization of 2D surface assemblies of SMMs, where each magnetic unit shows magnetic relaxation being sufficiently slow at application-relevant temperatures. Using X-ray absorption spectroscopy and X-ray magnetic circular dichroism, it is shown that sub-monolayers of Dy 2 @C 80 (CH 2 Ph) dimetallofullerenes prepared on graphene by electrospray deposition exhibit magnetic behavior fully comparable to that of the bulk. Magnetic hysteresis and relaxation time measurements show that the magnetic moment remains stable for 100 s at 17 K, marking the blocking temperature T B(100) , being not only in excellent agreement with that of the bulk sample but also representing by far the highest one detected for a surface-supported single-molecule magnet. The reported findings give a boost to the efforts to stabilize and address the spin degree of freedom in molecular magnets aiming at the realization of SMM-based spintronic units., (© 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

The switching behavior of surface-supported molecular units excited by current, light, or mechanical forces is determined by the shape of the adsorption potential. The ability to tailor the energy landscape in which a molecule resides at a surface gives the possibility of imposing a desired response, which is of paramount importance for the realization of molecular electronic units. Here, by means of scanning tunneling microscopy, a triazatruxene (TAT) molecule on Ag(111) is studied, which shows a switching behavior characterized by transitions of the molecule between three states, and which is attributed to three energetically degenerate bonding configurations. Upon tunneling current injection, the system can be excited and continuously driven, showing a switching directionality close to 100%. Two surface enantiomers of TAT show opposite switching directions pointing at the chirality of the energy landscape of the adsorption potential as a key ingredient for directional switching. Further, it is shown that by tuning the tunneling parameters, the symmetry of the adsorption potential can be controllably adjusted, leading to a suppression of the directionality or an inversion of the switching direction. The findings represent a molecule-surface model system exhibiting unprecedented control of the shape of its adsorption potential., (© 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The modification of graphene band structure, in particular via induced spin-orbit coupling, is currently a great challenge for the scientific community from both a fundamental and applied point of view. Here, we investigate the modification of the electronic structure of graphene (gr) initially adsorbed on Ir(111) via intercalation of one monolayer Pd by means of angle-resolved photoelectron spectroscopy and density functional theory. We reveal that for the gr/Pd/Ir(111) intercalated system, a spin splitting of graphene π states higher than 200 meV is present near the graphene K point. This spin separation arises from the hybridization of the graphene valence band states with spin-polarized quantum well states of a single Pd layer on Ir(111). Our results demonstrate that the proposed approach on the tailoring of the dimensionality of heavy materials interfaced with a graphene layer might lead to a giant spin-orbit splitting of the graphene valence band states.

Single-molecule magnets (SMMs) incorporate key properties that make them promising candidates for the emerging field of spintronics. The challenge to realize ordered SMM arrangements on surfaces and at the same time to preserve the magnetic properties upon interaction with the environment is a crucial point on the way to applications. Here we employ inelastic electron tunneling spectroscopy (IETS) to address the magnetic properties in single Fe 4 complexes that are adsorbed in a highly ordered arrangement on graphene/Ir(111). We are able to substantially reduce the influence of both the tunneling tip and the adsorption environment on the Fe 4 complex during the measurements by using appropriate tunneling parameters in combination with the flat-lying Fe 4 H derivative and a weakly interacting surface. This allows us to perform noninvasive IETS studies on these bulky molecules. From the measurements we identify intermultiplet spin transitions and determine the intramolecular magnetic exchange interaction constant on a large number of molecules. Although a considerable scattering of the exchange constant values is observed, the distribution maximum is located at a value that coincides with that of the bulk. Our findings confirm a retained molecular magnetism of the Fe 4 H complex at the local scale and evaluate the influence of the environment on the magnetic exchange interaction.

EuO is unique, because it belongs to the few solids combining semiconducting properties (E gap = 1.1 eV) with native ferromagnetism. For future applications of EuO, e.g. as spin-filters or for sensors, one has to learn how defined nanostructures can be prepared. Unlike other ceramic oxides, there are no established soft-chemistry routes (e.g. sol-gel) towards EuO nanomaterials e.g. porous materials. This is due to the labile nature of the oxidation state Eu(+ii). We present a particle-based method leading to a EuO aerogel. Instead of making the target material directly, we use nanoparticles of an organic-inorganic hybrid phase (Eu 2 O 3 -benzoate) and assemble those into an aerogel, followed by the transformation into phase-pure EuO. It is shown that organic aldehydes act as capping agents for controlling the morphogenesis of the hybrid particles. Depending on the steric demand of the aldehyde, one obtains plate-like particles or nanorods with increasing aspect ratio. The particles form a gel, when the aspect ratio is increased to >20. After supercritical drying, one receives a nanorod-based aerogel. Treatment of the latter with Eu-vapor leads to reduction of the Eu 2 O 3 domains to EuO while retaining the aerogel structure. Proof of ferromagnetism in the resulting EuO aerogel was delivered by SQUID measurements.

Metal-intercalated graphene on Ir(111) exhibits phonon signatures in inelastic electron tunneling spectroscopy with strengths that depend on the intercalant. Extraordinarily strong graphene phonon signals are observed for Cs intercalation. Li intercalation likewise induces clearly discriminable phonon signatures, albeit less pronounced than observed for Cs. The signal can be finely tuned by the alkali metal coverage and gradually disappears upon increasing the junction conductance from tunneling to contact ranges. In contrast to Cs and Li, for Ni-intercalated graphene the phonon signals stay below the detection limit in all transport ranges. Going beyond the conventional two-terminal approach, transport calculations provide a comprehensive understanding of the subtle interplay between the graphene-electrode coupling and the observation of graphene phonon spectroscopic signatures.

The implementation of graphene in semiconducting technology requires precise knowledge about the graphene-semiconductor interface. In our work the structure and electronic properties of the graphene/n-Ge(110) interface are investigated on the local (nm) and macro (from μm to mm) scales via a combination of different microscopic and spectroscopic surface science techniques accompanied by density functional theory calculations. The electronic structure of freestanding graphene remains almost completely intact in this system, with only a moderate n-doping indicating weak interaction between graphene and the Ge substrate. With regard to the optimisation of graphene growth it is found that the substrate temperature is a crucial factor, which determines the graphene layer alignment on the Ge(110) substrate during its growth from the atomic carbon source. Moreover, our results demonstrate that the preparation route for graphene on the doped semiconducting material (n-Ge) leads to the effective segregation of dopants at the interface between graphene and Ge(110). Furthermore, it is shown that these dopant atoms might form regular structures at the graphene/Ge interface and induce the doping of graphene. Our findings help to understand the interface properties of the graphene-semiconductor interfaces and the effect of dopants on the electronic structure of graphene in such systems.

The electronic properties of graphene can be efficiently altered upon interaction with the underlying substrate resulting in a dramatic change of charge carrier behavior. Here, the evolution of the local electronic properties of epitaxial graphene on a metal upon the controlled formation of multilayers, which are produced by intercalation of atomic carbon in graphene/Ir(111), is investigated. Using scanning tunneling microscopy and Landau-level spectroscopy, it is shown that for a monolayer and bilayers with small-angle rotations, Landau levels are fully suppressed, indicating that the metal-graphene interaction is largely confined to the first graphene layer. Bilayers with large twist angles as well as twisted trilayers demonstrate a sequence of pronounced Landau levels characteristic for a free-standing graphene monolayer pointing toward an effective decoupling of the top layer from the metal substrate. These findings give evidence for the controlled preparation of epitaxial graphene multilayers with a different degree of decoupling, which represent an ideal platform for future electronic and spintronic applications., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

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 (V g ) 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 V g , 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.

Semiconductors with native ferromagnetism barely exist and defined nanostructures are almost unknown. This lack impedes the exploration of a new class of materials characterized by a direct combination of effects on the electronic system caused by quantum confinement effects with magnetism. A good example is EuO for which currently no reliable routes for nanoparticle synthesis can be established. Bottom-up approaches applicable to other oxides fail because of the labile oxidation state +II. Instead of targeting a direct synthesis, the two steps-"structure control" and "chemical transformation"-are separated. The generation of a transitional, hybrid nanophase is followed by its conversion into EuO under full conservation of all morphological features. Hierarchical EuO materials are now accessible in the shape of oriented nanodisks stacked to tubular particles. Magnetically, the coupling of either vortex or onion states has been found. An unexpected temperature dependence is governed by thermally activated transitions between these states., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We demonstrate that electrospray deposition enables the fabrication of highly periodic self-assembled arrays of Fe 4 H single molecule magnets on graphene/Ir(111). The energetic positions of molecular states are probed by means of scanning tunneling spectroscopy, showing pronounced long- and short-ranged spatial modulations, indicating the presence of both locally varying intermolecular as well as adsorption-site dependent molecule-substrate interactions. From the magnetic field dependence of the X-ray magnetic circular dichroism signal, we infer that the magnetic easy axis of each Fe 4 H molecule is oriented perpendicular to the sample surface and that after the deposition the value of the uniaxial anisotropy is identical to the one in bulk. Our findings therefore suggest that the observed interaction of the molecules with their surrounding does not modify the molecular magnetism, resulting in a two-dimensional array of molecular magnets that retain their bulk magnetic properties.

Gaining external control over self-organization is of vital importance for future smart materials. Surfactants are extremely valuable for the synthesis of diverse nanomaterials. Their self-assembly is dictated by microphase separation, the hydrophobic effect, and head-group repulsion. It is desirable to supplement surfactants with an added mode of long-range and directional interaction. Magnetic forces are ideal, as they are not shielded in water. We report on surfactants with heads containing tightly bound transition-metal centers. The magnetic moment of the head was varied systematically while keeping shape and charge constant. Changes in the magnetic moment of the head led to notable differences in surface tension, aggregate size, and contact angle, which could also be altered by an external magnetic field. The most astonishing result was that the use of magnetic surfactants as structure-directing agents enabled the formation of porous solids with 12-fold rotational symmetry., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The complex electronic properties of ZrTe_{5} have recently stimulated in-depth investigations that assigned this material to either a topological insulator or a 3D Dirac semimetal phase. Here we report a comprehensive experimental and theoretical study of both electronic and structural properties of ZrTe_{5}, revealing that the bulk material is a strong topological insulator (STI). By means of angle-resolved photoelectron spectroscopy, we identify at the top of the valence band both a surface and a bulk state. The dispersion of these bands is well captured by ab initio calculations for the STI case, for the specific interlayer distance measured in our x-ray diffraction study. Furthermore, these findings are supported by scanning tunneling spectroscopy revealing the metallic character of the sample surface, thus confirming the strong topological nature of ZrTe_{5}.

We investigate the electronic properties of graphene nanoflakes on Ag(111) and Au(111) surfaces by means of scanning tunneling microscopy and spectroscopy as well as density functional theory calculations. Quasiparticle interference mapping allows for the clear distinction of substrate-derived contributions in scattering and those originating from graphene nanoflakes. Our analysis shows that the parabolic dispersion of Au(111) and Ag(111) surface states remains unchanged with the band minimum shifted to higher energies for the regions of the metal surface covered by graphene, reflecting a rather weak interaction between graphene and the metal surface. The analysis of graphene-related scattering on single nanoflakes yields a linear dispersion relation E(k), with a slight p-doping for graphene/Au(111) and a larger n-doping for graphene/Ag(111). The obtained experimental data (doping level, band dispersions around EF, and Fermi velocity) are very well reproduced within DFT-D2/D3 approaches, which provide a detailed insight into the site-specific interaction between graphene and the underlying substrate.

The origin of the martensitic transition in the magnetic shape memory alloy Ni-Mn-Ga has been widely discussed. While several studies suggest it is electronically driven, the adaptive martensite model reproduced the peculiar nonharmonic lattice modulation. We used femtosecond spectroscopy to probe the temperature and doping dependence of collective modes, and scanning tunneling microscopy revealed the corresponding static modulations. We show that the martensitic phase can be described by a complex charge-density wave tuned by magnetic ordering and strong electron-lattice coupling.

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.

Nanosecond pulsed two-beam laser interference is used to generate two-dimensional temperature patterns on a magnetic thin film sample. We show that the original domain structure of a [Co/Pd] multilayer thin film changes drastically upon exceeding the Curie temperature by thermal demagnetization. At even higher temperatures the multilayer system is irreversibly changed. In this area no out-of-plane magnetization can be found before and after a subsequent ac-demagnetization. These findings are supported by numerical simulations using the Landau-Lifshitz-Bloch formalism which shows the importance of defect sites and anisotropy changes to model the experiments. Thus, a one-dimensional temperature pattern can be transferred into a magnetic stripe pattern. In this way one can produce magnetic nanowire arrays with lateral dimensions of the order of 100 nm. Typical patterned areas are in the range of several square millimeters. Hence, the parallel direct laser interference patterning method of magnetic thin films is an attractive alternative to the conventional serial electron beam writing of magnetic nanostructures.

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.

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.

Realization of graphene moiré superstructures on the surface of 4d and 5d transition metals offers templates with periodically modulated electron density, which is responsible for a number of fascinating effects, including the formation of quantum dots and the site selective adsorption of organic molecules or metal clusters on graphene. Here, applying the combination of scanning probe microscopy/spectroscopy and the density functional theory calculations, we gain a profound insight into the electronic and topographic contributions to the imaging contrast of the epitaxial graphene/Ir(111) system. We show directly that in STM imaging the electronic contribution is prevailing compared to the topographic one. In the force microscopy and spectroscopy experiments we observe a variation of the interaction strength between the tip and high-symmetry places within the graphene moiré supercell, which determine the adsorption sites for molecules or metal clusters on graphene/Ir(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., (© 2012 American Chemical Society)

We use time-resolved Faraday rotation spectroscopy to probe the electron spin dynamics in ZnO and magnetically doped Zn(1-x)Co(x)O sol-gel thin films. In undoped ZnO, we observe an anomalous temperature dependence of the ensemble spin dephasing time T(2), i.e., longer coherence times at higher temperatures, reaching T(2) ∼ 1.2 ns at room temperature. Time-resolved transmission measurements suggest that this effect arises from hole trapping at grain surfaces. Deliberate addition of Co(2+) to ZnO increases the effective electron Landé g factor, providing the first direct determination of the mean-field electron-Co(2+) exchange energy in Zn(1-x)Co(x)O (N(0)α = +0.25 ± 0.02 eV). In Zn(1-x)Co(x)O, T(2) also increases with increasing temperature, allowing spin precession to be observed even at room temperature.

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., (© 2011 IOP Publishing Ltd)

We observe ultraviolet photoluminescence from sputtered ZnO quantum dots which are fabricated with no annealing steps. The nanocrystals are embedded in amorphous SiO2 and exhibit a narrow size distribution of 3.5 ± 0.6 nm. Photoluminescence and transmittance measurements show a shift of ultraviolet emission and absorption of the dots compared to bulk ZnO material. This work paves the way for cheap nanooptical devices in the ultraviolet which are fabricated in a single sputtering run.

The formation of self-assembled monolayers (SAMs) on gold by 2-(5-iodo-2-nitrophenyl) propoxycarbonyl (I-NPPOC)-protected thymidine with an attached mercaptohexyl succinate linker and the kinetics of photochemical release of the I-NPPOC group were monitored using X-ray photoelectron spectroscopy (XPS) and surface plasmon resonance (SPR) detection. In the XPS spectra, the iodine peaks allowed for specific and accurate monitoring of the presence and loss of I-NPPOC groups on the surface. In the SPR experiment, the overall signal change on photoillumination is in accord with a theoretical estimation of the density of I-NPPOC groups in a dense monolayer. The kinetics roughly follow a biexponential time dependence with two very different time constants, corresponding to photochemical quantum yields of 0.22 and 0.0032, respectively.

Zinc oxide (ZnO) nanocrystals (NCs) with high crystalline quality were prepared via radio-frequency magnetron sputtering as a SiO(2)/ZnO/SiO(2) trilayer on Si(100) and Al(2)O(3)(0001) substrates with an intermediate in situ annealing step. Transmission electron microscopy reveals a uniform dispersion of ZnO NCs in the amorphous SiO(2) matrix with typical sizes up to 16 nm with a larger fraction of smaller crystals. The size distribution analysis yields a mean grain size of 5 nm for small particles. Individual ZnO NCs show a well-defined hexagonal close packed wurtzite structure and lattice parameters close to those of bulk ZnO, confirming their high crystalline quality. Mapping of the Zn distribution by means of energy-filtered transmission electron microscopy reveals a strongly non-uniform distribution of Zn within the SiO(2) matrix, corroborating the chemical separation of ZnO NCs from surrounding SiO(2). Optical transmittance measurements confirm the findings of the electron microscopy analysis. The fabrication technique described opens up new possibilities in the preparation of ZnO NCs with high crystalline quality, including growth in monolithic optical cavities without intermediate ex situ fabrication steps.

We report on angle-resolved photoemission studies of the electronic pi states of high-quality epitaxial graphene layers on a Ni(111) surface. In this system the electron binding energy of the pi states shows a strong dependence on the magnetization reversal of the Ni film. The observed extraordinarily large energy shift up to 225 meV of the graphene-derived pi band peak position for opposite magnetization directions is attributed to a manifestation of the Rashba interaction between spin-polarized electrons in the pi band and the large effective electric field at the graphene/Ni interface. Our findings show that an electron spin in the graphene layer can be manipulated in a controlled way and have important implications for graphene-based spintronic devices.

Different approaches to the deposition of Mn(12) single molecule magnets on the Au(111) surface and their characterization by a broad variety of techniques are investigated with respect to their suitability for a profound corroboration of the integrity of the Mn(12) core. In this context, the most recent improvements in the experimental approaches are presented and the latest results on the electronic properties of Mn(12) are linked to each other. The results confirm the high instability of Mn(12) single molecule magnets on surfaces and reveal the need for an amendment of the requirements to define the structural integrity of Mn(12) molecules on surfaces.

A new approach to the deposition of Mn12 single-molecule magnet monolayers on the functionalized Au(111) surface optimized for the investigation by means of scanning tunneling spectroscopy was developed. To demonstrate this method, the new Mn12 complex [Mn12O12(O2CC6H4F)16(EtOH)4].4.4CHCl3 was synthesized and characterized. In MALDI-TOF mass spectra the isotopic distribution of the molecular ion peak of the latter complex was revealed. The complex was grafted to Au(111) surfaces via two different short conducting linker molecules. The Mn12 molecules deposited on the functionalized surface were characterized by means of scanning tunneling microscopy showing homogeneous monolayers of highest quality. Scanning tunneling spectroscopy measurements over a wider energy range compared with previous results could be performed because of the optimized Au(111) surface functionalization. Furthermore, the results substantiate the general suitability of short acidic linker molecules for the preparation of Mn12 monolayers via ligand exchange and represent a crucial step toward addressing the magnetic properties of individual Mn12 single-molecule magnets.

We present a detailed study of the spin-dependent electronic structure of thin epitaxial magnetite films of different crystallographic orientations. Using spin- and angle-resolved photoelectron spectroscopy at room temperature, we determine for epitaxial Fe(3)O(4)(111) films a maximum spin polarization value of -(80 ± 5)% near E(F). The spin-resolved photoelectron spectra for binding energies between 1.5 eV and E(F) show good agreement with the spin-split band structure from density functional theory (DFT) calculations which predict an overall energy gap in the spin-up electron bands in high symmetry directions, thus providing evidence for the half-metallic ferromagnetic state of Fe(3)O(4) in the [111] direction. In the case of the Fe(3)O(4)(100) surface, both the spin-resolved photoelectron spectroscopy experiments and the DFT density of states give evidence for a half-metal to metal transition: the measured spin polarization of about -(55 ± 10)% at E(F) and the theoretical value of -40% are significantly lower than the -100% predicted by local spin density approximation (LSDA) calculations for the bulk magnetite crystal as well as the -(80 ± 5)% obtained for the Fe(3)O(4)(111) films. The experimental findings were corroborated by DFT calculations as due to a surface reconstruction leading to the electronic states in the majority-spin band gap and thus to the reduced spin polarization.