André Beyer

Controlled doping of phthalocyanine layers by cosublimation with acceptor molecules: A systematic Seebeck and conductivity study

We investigate the doping of vanadyl–phthalocyanine by a fluorinated form of tetracyano-quinodimethane as an example of controlled doping of thin organic dye films by cosublimation of matrix and dopant. The electrical parameters of the films derived from conductivity and Seebeck measurements show that the results largely follow standard models used to describe the doping of crystalline semiconductors; e.g., a smooth shift of the Fermi level towards the valence states with increasing doping is observed. Other effects, like the superlinear increase of conductivity with the molar doping ratio, need the inclusion of additional effects like percolation.

One Nanometer Thin Carbon Nanosheets with Tunable Conductivity and Stiffness

Atomically thin (similar to 1 nm) carbon films and membranes whose electrical behavior can be tuned from insulating to conducting are fabricated by a novel route. These films present arbitrary size and shape based on molecular self-assembly, electron irradiation, and pyrolysis, and their technical applicability is demonstrated by their incorporation into a microscopic pressure sensor.

Controlled p-doping of pigment layers by cosublimation: Basic mechanisms and implications for their use in organic photovoltaic cells

Abstract We present a systematic study on doping of vanadyl- and zinc-pathalocyanine by a fully fluorinated form of tetracyano-quinodimethane as an example of controlled doping of thin organic films by cosublimation of matrix and dopant. The films are characterized in situ by temperature dependent Seebeck and conductivity measurements. We observe a drastic increase of conductivity and a corresponding shift of the Fermi level towards the valence states with increasing dopant concentration. We thus conclude that doping has the potential of both reducing the series resistance and increasing the photovoltage of organic solar cells. As a first step to exploit this potential, we present two different ways of preparing diodes with rectification ratios in excess of 10 4 using doped phthalocyanines. By adding an undoped interlayer between the contact and the doped layer, we have produced diodes which work already in the strict absence of oxygen and are stable in air. To increase the efficiency of charge carrier generation in photovoltaic cells, we need to use photoactive donor–acceptor-heterojunctions. We present here first examples of pn- and pin-type heterojunctions combining p-doped and nominally undoped layers.

A new technique for fabricating three-dimensional micro- and nanostructures of various shapes

In this paper we show that complex three-dimensional micro- and nanostructure shells can be formed by directional rolling up of thin strained Si/SiGe heterostructures. By lifting strain-designed Si/SiGe films using a sacrificial layer from the substrate and by a proper patterning prior to the etching almost arbitrary-shaped three-dimensional structures can be fabricated. A technique for controlling the shape and location of the structures is proposed and realized. In addition we show that it is possible to obtain cylindrical objects with the axes perpendicular to the substrate surface, and the objects themselves can be located at prescribed places on the substrate.

Toward Plasmonics with Nanometer Precision: Nonlinear Optics of Helium-Ion Milled Gold Nanoantennas

Plasmonic nanoantennas are versatile tools for coherently controlling and directing light on the nanoscale. For these antennas, current fabrication techniques such as electron beam lithography (EBL) or focused ion beam (FIB) milling with Ga(+)-ions routinely achieve feature sizes in the 10 nm range. However, they suffer increasingly from inherent limitations when a precision of single nanometers down to atomic length scales is required, where exciting quantum mechanical effects are expected to affect the nanoantenna optics. Here, we demonstrate that a combined approach of Ga(+)-FIB and milling-based He(+)-ion lithography (HIL) for the fabrication of nanoantennas offers to readily overcome some of these limitations. Gold bowtie antennas with 6 nm gap size were fabricated with single-nanometer accuracy and high reproducibility. Using third harmonic (TH) spectroscopy, we find a substantial enhancement of the nonlinear emission intensity of single HIL-antennas compared to those produced by state-of-the-art gallium-based milling. Moreover, HIL-antennas show a vastly improved polarization contrast. This superior nonlinear performance of HIL-derived plasmonic structures is an excellent testimonial to the application of He(+)-ion beam milling for ultrahigh precision nanofabrication, which in turn can be viewed as a stepping stone to mastering quantum optical investigations in the near-field.

Novel carbon nanosheets as support for ultrahigh-resolution structural analysis of nanoparticles

The resolution in transmission electron microscopy (TEM) has reached values as low as 0.08 nm. However, these values are not accessible for very small objects in the size range of a few nanometers or lower, as they have to be placed on some support, which contributes to the overall electron-scattering signal, thereby blurring the contrast. Here, we report on the use of nanosheets made from cross-linked aromatic self-assembled monolayers as TEM sample supports. When transferred onto a copper grid, a single 1.6-nm-thick nanosheet can cover the grid and is free standing within the micron-sized openings. Despite its thinness, the sheet is stable under the impact of the electron beam. Micrographs taken from nanoclusters onto these nanosheets show highly increased contrast in comparison to the images taken from amorphous carbon supports. In scanning transmission electron microscopy with nanosheet support, a size analysis of sub-nanometer Au clusters was performed and single Au atoms were resolved.

Nanocrystalline-to-amorphous transition in nanolaminates grown by low temperature atomic layer deposition and related mechanical properties

We report on a comprehensive structural and nanoindentation study of nanolaminates of Al2O3 and ZnO synthesized by atomic layer deposition (ALD). By reducing the bilayer thickness from 50 nm to below 1 nm, the nanocrystal size could be controlled in the nanolaminate structure. The softer and more compliant response of the multilayers as compared to the single layers of Al2O3 and ZnO is attributed to the structural change from nanocrystalline to amorphous at smaller bilayer thicknesses. It is also shown that ALD is a unique technique for studying the inverse Hall-Petch softening mechanism (E. Voce and D. Tabor, J. Inst. Metals 79(12), 465 (1951)) related to grain size effects in nanomaterials.

Mechanically Stacked 1‐nm‐Thick Carbon Nanosheets: Ultrathin Layered Materials with Tunable Optical, Chemical, and Electrical Properties

Carbon nanosheets are mechanically stable, free-standing two-dimensional materials with a thickness of ≈1 nm and well defined physical and chemical properties. They are made by radiation-induced cross-linking of aromatic self-assembled monolayers. Herein, a route is presented to the scalable fabrication of multilayer nanosheets with tunable electrical, optical, and chemical properties on insulating substrates. Stacks of up to five nanosheets with sizes of ≈1 cm(2) on oxidized silicon are studied. Their optical characteristics are investigated by visual inspection, optical microscopy, UV-vis reflection spectroscopy, and model calculations. Their chemical composition is studied by X-ray photoelectron spectroscopy. The multilayer samples are then annealed in an ultrahigh vacuum at various temperatures up to 1100 K. A subsequent investigation by Raman, X-ray photoelectron, and UV-vis reflection spectroscopy, as well as by electrical four-point probe measurements, demonstrates that the layered nanosheets transform into nanocrystalline graphene. This structural and chemical transformation is accompanied by changes in the optical properties and electrical conductivity and opens up a new path for the fabrication of ultrathin functional conductive coatings.

Imaging nanocarbon materials: soot particles in flames are not structurally homogeneous.

For the first time, nascent soot particles are probed by using helium-ion microscopy (HIM). HIM is a technique that is similar to scanning electron microscopy (SEM) but it can achieve higher contrast and improved surface sensitivity, especially for carbonaceous materials. The HIM microscope yields images with a high contrast, which allows for the unambiguous recognition of smaller nascent soot particles than those observed in previous transmission electron microscopy studies. The results indicate that HIM is ideal for rapid and reliable probing of the morphology of nascent soot, with surface details visible down to approximately 5 nm, and particles as small as 2 nm are detectable. The results also show that nascent soot is structurally and chemically inhomogeneous, and even the smallest particles can have shapes that deviate from a perfect sphere.

Structure–activity relation of spinel-type Co–Fe oxides for low-temperature CO oxidation

A series of cobalt ferrite thin films was prepared via pulsed spray evaporation chemical vapour deposition (PSE-CVD). The samples were comprehensively characterised in terms of structure, surface, morphology, and optical and redox properties. Both X-ray diffraction (XRD) and Raman analysis show that all samples exhibited an inverse spinel structure. X-ray photoelectron spectroscopy (XPS) results indicate that the films were mainly composed of Co, Fe and O species, and an increase in the Co : Fe ratio with Fe substitution by Co was observed. Helium ion microscopy (HIM) images show the film morphology to be dependent on the Co : Fe ratio. The investigation of the optical property using ultraviolet-visible spectroscopy reveals that the increase in the Co content results in an increase in the band gap energy. In situ emission FTIR spectroscopy was used to evaluate the redox properties of the samples, and a shift of the redox temperature to higher values was observed upon increase in the Co content. The effect of Fe substitution by Co in the mixed oxide systems on their catalytic performance for CO oxidation was investigated. Co–Fe oxides exhibit substantially better catalytic performance than the single α-Fe2O3. The catalytic performance of the Co–Fe oxides towards CO oxidation was discussed with respect to the participation of surface and lattice oxygen in the oxidation process. According to XPS and temperature-programmed reduction/oxidation (TPR/TPO) results, a suprafacial mechanism where CO molecules react with surface-adsorbed oxygen functions to form CO2 was proposed as the dominant mechanism.