Terahertz-slicing - an all-optical synchronization for 4th generation light sources.

A conceptually new approach to synchronizing accelerator-based light sources and external laser systems is presented. The concept is based on utilizing a sufficiently intense accelerator-based single-cycle terahertz pulse to slice a thereby intrinsically synchronized femtosecond-level part of a longer picosecond laser pulse in an electro-optic crystal. A precise synchronization of the order of 10 fs is demonstrated, allowing for real-time lock-in amplifier signal demodulation. We demonstrate successful operation of the concept with three benchmark experiments using a 4th generation accelerator-based terahertz light source, i.e. (i) far-field terahertz time-domain spectroscopy, (ii) terahertz high harmonic generation spectroscopy, and (iii) terahertz scattering-type scanning near-field optical microscopy.

Multidomain Skyrmion Lattice State in Cu2OSeO3.

Magnetic skyrmions in chiral magnets are nanoscale, topologically protected magnetization swirls that are promising candidates for spintronics memory carriers. Therefore, observing and manipulating the skyrmion state on the surface level of the materials are of great importance for future applications. Here, we report a controlled way of creating a multidomain skyrmion state near the surface of a Cu2OSeO3 single crystal, observed by soft resonant elastic X-ray scattering. This technique is an ideal tool to probe the magnetic order at the L3 edge of 3d metal compounds giving an average depth sensitivity of ∼50 nm. The single-domain 6-fold-symmetric skyrmion lattice can be broken up into domains, overcoming the propagation directions imposed by the cubic anisotropy by applying the magnetic field in directions deviating from the major cubic axes. Our findings open the door to a new way to manipulate and engineer the skyrmion state locally on the surface or on the level of individual skyrmions, which will enable applications in the future.

Néel-type skyrmion lattice with confined orientation in the polar magnetic semiconductor GaV4S8.

Following the early prediction of the skyrmion lattice (SkL)--a periodic array of spin vortices--it has been observed recently in various magnetic crystals mostly with chiral structure. Although non-chiral but polar crystals with Cnv symmetry were identified as ideal SkL hosts in pioneering theoretical studies, this archetype of SkL has remained experimentally unexplored. Here, we report the discovery of a SkL in the polar magnetic semiconductor GaV4S8 with rhombohedral (C3v) symmetry and easy axis anisotropy. The SkL exists over an unusually broad temperature range compared with other bulk crystals and the orientation of the vortices is not controlled by the external magnetic field, but instead confined to the magnetic easy axis. Supporting theory attributes these unique features to a new Néel-type of SkL describable as a superposition of spin cycloids in contrast to the Bloch-type SkL in chiral magnets described in terms of spin helices.

In situ self-assembled organic interface layers for the controlled growth of oligothiophene thin films on ferroelectric Pb(Zr(0.2)Ti(0.8))O3.

We introduce an in situ vacuum procedure for the optimal preparation and analysis of self-assembled monolayers (SAMs) as used in organic molecular electronics on ferroelectric lead zirconate titanate (PZT) substrates. Excellent ordering of oligothiophene semiconductor layers is heavily promoted through the presence of an interfacial bi-functional SAM layer that binds to both the oxidic PZT surface and the organic semiconductor molecules. The described method can be extended to other material combinations, featuring a variety of substrate materials and molecular functionalities.

Optically controlled interparticle distance tuning and welding of single gold nanoparticle pairs by photochemical metal deposition.

We report on the in-situ controlled tuning of the particle gap in single pairs of gold nanodisks by photochemical metal deposition. The optically induced growth of nanodisk dimers fabricated by electron beam lithography leads to a decrease of the interparticle gap width down to 0 nm. Due to the increasing particle size and stronger plasmonic coupling, a smooth redshift of the localized surface plasmon (LSP) resonances is observed in such particle pairs during the growth process. The interparticle gap width, and hence the LSP resonance, can be tuned to any desired spectral position. The experimental results we obtain with this nanoscale fabrication technique are well described by the so-called plasmon ruler equation. Consequently, both the changes in particle diameter as well as in gap width can be characterized in-situ via far-field read-out of the optical properties of the dimers.

Near-field coupling of a single fluorescent molecule and a spherical gold nanoparticle.

Near-field coupling of a single gold nanoparticle (GNP) to a single fluorescent molecule is investigated here for varying separation d between the two. While the emission quantum efficiency of the coupled system generally decreases for d!0, a pronounced near-field enhancement is observed under certain conditions, partly outweighing the efficiency loss at small distances. We report on optimizing these conditions by varying the excitation field direction and the three-dimensional relative configuration between the GNP and the fluorophore. Furthermore, we examine how the sphere diameter, the surrounding medium, as well as the absorption and emission wavelengths of the molecular dipole influence the fluorescence yield. Our results are of high practical relevance for all GNP-mediated application fields such as fluorescence microscopy, scattering near-field optical microscopy, bioanalytics, and medical applications.

Polarization driven conductance variations at charged ferroelectric domain walls.

Conducting domain walls (CDWs) in ferroelectric materials are promising candidates for applications in a manifold of nanoscale, optoelectronic devices. Characterization of their microscopic properties, however, remains challenging due to their small dimension and highly insulating environment. Here, we inspect individual CDWs in single-crystalline LiNbO3 by the combination of photoemission electron microscopy (PEEM) and second harmonic generation (SHG) microscopy. While SHG unveils the overall domain wall inclination angle α, PEEM is sensitive to local conductance variations, both at and away from the domain wall. Thus, the two imaging techniques deliver complementary information over a large field of view. In agreement with earlier theoretical predictions we find that the local conductance is dictated by α and reveal a quantitative connection between them. Our results help to elucidate the electronic structure of CDWs and underline the value of PEEM as a non-contact characterization tool for mapping local conductance variations in highly resistive environments.

Dielectric polarization and refractive indices of ultrathin barium titanate films on strontium titanate single crystals.

The electrical and optical properties of ultrathin films of tetragonal barium titanate (BaTiO(3)) on strontium titanate (SrTiO(3)) single-crystal substrates are theoretically investigated using a microscopic quantum mechanical model based on the orbital approximation in correlation with the dipole-dipole interaction. First-, second-, and third-order electronic polarizabilities had to be considered in this calculation in order to obtain accurate results for both the dielectric spontaneous polarization and the refractive indices of the BaTiO(3) overlayer. The spontaneous polarization is drastically reduced in the film as its thickness decreases. However, an electronic polarization appears within the SrTiO(3) substrate in the neighbourhood of the interface. This polarization, which vanishes far away from the interface into the SrTiO(3) bulk, is induced by the polarization of the BaTiO(3) film. Furthermore, we find the refractive index for both the BaTiO(3) film and the SrTiO(3) substrate to be deeply reduced for light polarized perpendicular to the surface.

Optical nanoscopy of transient states in condensed matter.

Recently, the fundamental and nanoscale understanding of complex phenomena in materials research and the life sciences, witnessed considerable progress. However, elucidating the underlying mechanisms, governed by entangled degrees of freedom such as lattice, spin, orbit, and charge for solids or conformation, electric potentials, and ligands for proteins, has remained challenging. Techniques that allow for distinguishing between different contributions to these processes are hence urgently required. In this paper we demonstrate the application of scattering-type scanning near-field optical microscopy (s-SNOM) as a novel type of nano-probe for tracking transient states of matter. We introduce a sideband-demodulation technique that allows for probing exclusively the stimuli-induced change of near-field optical properties. We exemplify this development by inspecting the decay of an electron-hole plasma generated in SiGe thin films through near-infrared laser pulses. Our approach can universally be applied to optically track ultrafast/-slow processes over the whole spectral range from UV to THz frequencies.

Conductivity and magnetoresistance of La0.7Ce0.3MnO(3-δ) thin films under photoexcitation.

La0.7Ce0.3MnO3 thin films of different thicknesses, degrees of CeO2-phase segregation and oxygen deficiency, grown on SrTiO3 single crystal substrates, were comparatively investigated with respect to both their spectral and temperature-dependent photoconductivity (PC) and their magnetoresistance (MR) behaviour under photoexcitation. While as-grown films were insensitive to optical excitation, oxygen reduction appeared to be an effective way to decrease the film resistance, but the film thickness was found to play a minor role. However, from the evaluation of the spectral behaviour of the PC and the comparison of the MR of the LCeMO/substrate-samples with a bare substrate under illumination we find that the photoconductivity data reflects not only contributions from (i) photogenerated charge carriers in the film and (ii) carriers injected from the photoconductive substrate (as concluded from earlier works), but also (iii) a decisive parallel photoconduction in the SrTiO3 substrate. Furthermore--also by analyzing the MR characteristics--the unexpected occurence of a strong electroresistive effect in the sample with the highest degree of CeO2 segregation and oxygen deficiency could be attributed to the electroresistance of the SrTiO3 substrate as well. The results suggest a critical reconsideration and possibly a reinterpretation of several previous photoconductivity and electroresistance investigations of manganite thin films on SrTiO3.

The Mn(2+)/Mn(3+) state of La0.7Ce0.3MnO3 by oxygen reduction and photodoping.

Films of cerium-doped LaMnO3, which has been intensively discussed as an electron-doped counterpart to hole-doped mixed-valence lanthanum manganites during the past decade, were analyzed by x-ray photoemission spectroscopy with respect to their manganese valence under photoexcitation. The comparative analysis of the Mn 3s exchange splitting of La0.7Ce0.3MnO3 (LCeMO) films in the dark and under illumination clearly shows that both oxygen reduction and illumination are able to decrease the Mn valence towards a mixed 2+/3+ state, independently of the film thickness and the degree of CeO2 segregation. Charge-injection from the photoconductive SrTiO3 substrate into the Mn eg band with carrier lifetimes in the range of tens of seconds and intrinsic generation of electron-hole pairs within the films are discussed as two possible sources of the Mn valence shift and the subsequent electron doping.

Unwinding of a skyrmion lattice by magnetic monopoles.

Skyrmion crystals are regular arrangements of magnetic whirls that exist in a wide range of chiral magnets. Because of their topology, they cannot be created or destroyed by smooth rearrangements of the direction of the local magnetization. Using magnetic force microscopy, we tracked the destruction of the skyrmion lattice on the surface of a bulk crystal of Fe(1-x)Co(x)Si (x = 0.5). Our study revealed that skyrmions vanish by a coalescence, forming elongated structures. Numerical simulations showed that changes of topology are controlled by singular magnetic point defects. They can be viewed as quantized magnetic monopoles and antimonopoles, which provide sources and sinks of one flux quantum of emergent magnetic flux, respectively.

Near-field examination of perovskite-based superlenses and superlens-enhanced probe-object coupling.

A planar slab of negative-index material works as a superlens with sub-diffraction-limited resolution, as propagating waves are focused and, moreover, evanescent waves are reconstructed in the image plane. Here we demonstrate a superlens for electric evanescent fields with low losses using perovskites in the mid-infrared regime. The combination of near-field microscopy with a tunable free-electron laser allows us to address precisely the polariton modes, which are critical for super-resolution imaging. We spectrally study the lateral and vertical distributions of evanescent waves around the image plane of such a lens, and achieve imaging resolution of λ/14 at the superlensing wavelength. Interestingly, at certain distances between the probe and sample surface, we observe a maximum of these evanescent fields. Comparisons with numerical simulations indicate that this maximum originates from an enhanced coupling between probe and object, which might be applicable for multifunctional circuits, infrared spectroscopy and thermal sensors.

Large photoconductivity of oxygen-deficient La(0.7)Ca(0.3)MnO(3)/SrTiO(3) heterostructures.

The electrical resistance of stoichiometric and oxygen-deficient epitaxial 10 nm thick La(0.7)Ca(0.3)MnO(3) thin films on SrTiO(3) under photoexcitation covering the visible to the ultraviolet range has been investigated systematically as a function of illumination intensity, wavelength and temperature. In contrast to as-prepared films, the oxygen-deficient samples exhibit large photoconductivity of several orders of magnitude at low temperatures. By our detailed comparative analysis of the electrical conductivity of the film/substrate heterostructure and the bare substrate we are able to elucidate contributions of both carrier generation in the film and carrier injection from the substrate to the observed effect.

Interface dipole formation of different ZnPcCl(8) phases on Ag(111) observed by Kelvin probe force microscopy.

Recently, we investigated the adsorption of octachloro zinc phthalocyanine (ZnPcCl(8)) on Ag(111) by scanning tunneling microscopy. Compared to the standard phthalocyanine, halogenated phthalocyanine molecules show a much more complex binding behavior, which results in the formation of three different structural phases. These phases follow from the ordering process with the formation of 8, 4 and 0 intermolecular hydrogen-halogen bonds (Abel et al 2006 ChemPhysChem 7 82). In the present work we investigate these phases by Kelvin probe force microscopy in order to quantitatively deduce the electric interface barrier of the first monolayer. Our measurements reveal that the binding behavior does not only affect the structural ordering but also the interface dipole formation, which leads to different work functions. The fact that we observe interface barriers of opposite signs between ordered and disordered molecular layers underlines the importance of exactly knowing the molecular arrangement at the interface when assembling organic molecule devices.

Anisotropy contrast in phonon-enhanced apertureless near-field microscopy using a free-electron laser.

We demonstrate the imaging of ferroelectric domains in BaTiO3, using an infrared-emitting free-electron laser as a tunable optical source for scattering scanning near-field optical microscopy and spectroscopy. When the laser is tuned into the spectral vicinity of a phonon resonance, ferroelectric domains can be resolved due to the anisotropy of the dielectric properties of the material. Slight detuning of the wavelength gives rise to a contrast reversal clearly evidencing the resonant character of the excitation. The near-field domain contrast shows that the orientation of the dielectric tensor with respect to the sample surface has a clear influence on the near-field signal.

Photolabile carboxylic acid protected terpolymers for surface patterning. Part 2: Photocleavage and film patterning.

The surface properties of films made of p-methoxyphenacyl derivative terpolymers, associated with photocleavage by UV irradiation, and their optical patterning are investigated. The deprotection reaction has been monitored by UV and FTIR spectroscopy, contact angle measurements, and X-ray photoelectron spectroscopy, revealing the photoremoval of the protecting p-methoxyphenacyl group in high yields under mild conditions. Parallel and serial patterning of the films has been performed by selective irradiation through optical masks and by laser irradiation via fiber tips of a scanning near-field optical microscope, respectively. By irradiation of photolabile protected functional groups, free carboxylic groups become exposed to the surface with which fluorescent dyes and proteins can be associated specifically.

Adsorption of PTCDA on a partially KBr covered Ag(111) substrate.

Ordered growth of 3,4,9,10-perylene-tetracarboxylic-dianhydride (PTCDA) on Ag(111) partially covered by one or two monolayers of KBr was investigated by non-contact AFM with molecular resolution. Different adsorption patterns are found on the pure substrate, the one covered by a single monolayer, and the one covered by two monolayers KBr. Simulations with an extended Ising-type model reproduce these experimental patterns very well. The adsorbate-adsorbate and the adsorbate-substrate interaction parameters obtained from the simulation are discussed with respect to the interactions at the Ag(111)|KBr interface. As a result, alkali halide covered metals can be used for tuning the interactions and designing adsorption systems, which opens up new possibilities in the control of self-assembled nanostructures.