Monatomic (Fe, Co) and bimetallic (FePt and CoPt) nanoparticles were prepared by exploiting the self-organization of precursor loaded reverse micelles. Achievements and limitations of the preparation approach are critically discussed. We show that self-assembled metallic nanoparticles can be prepared with diameters d = 2–12 nm and interparticle distances D = 20–140 nm on various substrates. Structural, electronic and magnetic properties of the particle arrays were characterized by several techniques to give a comprehensive view of the high quality of the method. For Co nanoparticles, it is demonstrated that magnetostatic interactions can be neglected for distances which are at least 6 times larger than the particle diameter. Focus is placed on FePt alloy nanoparticles which show a huge magnetic anisotropy in the L10 phase, however, this is still less by a factor of 3–4 when compared to the anisotropy of the bulk counterpart. A similar observation was also found for CoPt nanoparticles (NPs). These results are related to imperfect crystal structures as revealed by HRTEM as well as to compositional distributions of the prepared particles. Interestingly, the results demonstrate that the averaged effective magnetic anisotropy of FePt nanoparticles does not strongly depend on size. Consequently, magnetization stability should scale linearly with the volume of the NPs and give rise to a critical value for stability at ambient temperature. Indeed, for diameters above 6 nm such stability is observed for the current FePt and CoPt NPs. Finally, the long-term conservation of nanoparticles by Au photoseeding is presented.
Co; CoPt; core–shell particles; FePt; magnetic anisotropy; magnetic particles; plasma etching; reverse micelles; self-assembly
This review focuses and summarizes recent studies on the functionalization of carbon nanotubes oriented perpendicularly to their substrate, so-called vertically aligned carbon nanotubes (VA-CNTs). The intrinsic properties of individual nanotubes make the VA-CNTs ideal candidates for integration in a wide range of devices, and many potential applications have been envisaged. These applications can benefit from the unidirectional alignment of the nanotubes, the large surface area, the high carbon purity, the outstanding electrical conductivity, and the uniformly long length. However, practical uses of VA-CNTs are limited by their surface characteristics, which must be often modified in order to meet the specificity of each particular application. The proposed approaches are based on the chemical modifications of the surface by functionalization (grafting of functional chemical groups, decoration with metal particles or wrapping of polymers) to bring new properties or to improve the interactions between the VA-CNTs and their environment while maintaining the alignment of CNTs.
aligned; carbon nanotubes; fluorination; functionalization; graphene; nitration; oxidation
The catalytic properties of nanostructured Au and their physical origin were investigated by using the low-temperature CO oxidation as a test reaction. In order to distinguish between structural effects (structure–activity correlations) and bimetallic/bifunctional effects, unsupported nanoporous gold (NPG) samples prepared from different Au alloys (AuAg, AuCu) by selective leaching of a less noble metal (Ag, Cu) were employed, whose structure (surface area, ligament size) as well as their residual amount of the second metal were systematically varied by applying different potentials for dealloying. The structural and chemical properties before and after 1000 min reaction were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The catalytic behavior was evaluated by kinetic measurements in a conventional microreactor and by dynamic measurements in a temporal analysis of products (TAP) reactor. The data reveal a clear influence of the surface contents of residual Ag and Cu species on both O2 activation and catalytic activity, while correlations between activity and structural parameters such as surface area or ligament/crystallite size are less evident. Consequences for the mechanistic understanding and the role of the nanostructure in these NPG catalysts are discussed.
AuAg alloy; AuCu alloy; CO oxidation; dynamic studies; kinetics; nanoporous Au (NPG) catalyst; oxygen storage capacity (OSC); temporal analysis of products (TAP)
We have developed a new procedure for efficient combing of DNA on a silicon substrate, which allows reproducible deposition and alignment of DNA molecules across lithographically defined patterns. The technique involves surface modification of Si/SiO2 substrates with a hydrophobic silane by using gas-phase deposition. Thereafter, DNA molecules are aligned by dragging the droplet on the hydrophobic substrate with a pipette tip. Using this procedure, DNA molecules were stretched to an average value of 122% of their contour length. Furthermore, we demonstrated combing of ca. 900 nm long stretches of genomic DNA across nanofabricated electrodes, which was not possible by using other available combing methods. Similar results were also obtained for DNA–peptide conjugates. We suggest this method as a simple yet reliable technique for depositing and aligning DNA and DNA derivatives across nanofabricated patterns.
AFM; DNA molecular combing; DNA–peptide complexes; molecular electronics; surface modification
The influence of applied normal load and roughness on the tribological behavior between the indenter and sample surface during nanoindentation-based scratching has been experimentally investigated by using different surfaces (fused silica and diamond-like carbon) featuring various degrees of roughness. At a sufficiently low applied normal load, wherein the contact is elastic, the friction coefficient is constant. However, at increased normal loads the contact involves plastic deformation and the friction coefficient increases with increasing normal load. The critical load range for a transition from predominantly elastic to plastic contact, between the indenter and sample surface, increases with increasing size of indenter and decreases with roughness. Distinct differences between the present experimental results and the existing theoretical models/predictions are discussed.
nanoindentation; nanotribology; scratch testing; surface roughness
We investigate the excitation as well as propagation of magnetic modes in plasmonic nanostructures. Such structures are particularly suited for excitation with cylindrical vector beams. We study magneto-inductive coupling between adjacent nanostructures. We utilize high-resolution lithographic techniques for the preparation of complex nanostructures consisting of gold as well as aluminium. These structures are subsequently characterized by linear optical spectroscopy. The well characterized and designed structures are afterwards studied in depth by exciting them with radial and azimuthally polarized light and simultaneously measuring their plasmonic near-field behavior. Additionally, we attempt to model and simulate our results, a project which has, to the best of our knowledge, not been attempted so far.
near-field microscopy; oligomers; plasmons; radial and azimuthal polarization
The electronic and structural properties of oligo- and polythiophenes that can be used as building blocks for molecular electronic devices have been studied by using periodic density functional theory calculations. We have in particular focused on the effect of substituents on the electronic structure of thiophenes. Whereas singly bonded substituents, such as methyl, amino or nitro groups, change the electronic properties of thiophene monomers and dimers, they hardly influence the band gap of polythiophene. In contrast, phenyl-substituted polythiophenes as well as vinyl-bridged polythiophene derivatives exhibit drastically modified band gaps. These effects cannot be explained by simple electron removal or addition, as calculations for charged polythiophenes demonstrate.
band gaps; conducting polymers; density functional theory calculations; molecular electronics; oligothiophenes
We demonstrate the coupling of single color centers in diamond to plasmonic and dielectric photonic structures to realize novel nanophotonic devices. Nanometer spatial control in the creation of single color centers in diamond is achieved by implantation of nitrogen atoms through high-aspect-ratio channels in a mica mask. Enhanced broadband single-photon emission is demonstrated by coupling nitrogen–vacancy centers to plasmonic resonators, such as metallic nanoantennas. Improved photon-collection efficiency and directed emission is demonstrated by solid immersion lenses and micropillar cavities. Thereafter, the coupling of diamond nanocrystals to the guided modes of micropillar resonators is discussed along with experimental results. Finally, we present a gas-phase-doping approach to incorporate color centers based on nickel and tungsten, in situ into diamond using microwave-plasma-enhanced chemical vapor deposition. The fabrication of silicon–vacancy centers in nanodiamonds by microwave-plasma-enhanced chemical vapor deposition is discussed in addition.
CVD diamond doping; diamond; nanophotonics; NV center; plasmonic resonator; solid immersion lens
Patterning of materials at sub-10 nm dimensions is at the forefront of nanotechnology and employs techniques of various complexity, efficiency, areal scale, and cost. Colloid-based patterning is known to be capable of producing individual sub-10 nm objects. However, ordered, large-area nano-arrays, fully integrated into photonic or electronic devices have remained a challenging task. In this work, we extend the practice of colloidal lithography to producing large-area sub-10 nm point-contact arrays and demonstrate their circuit integration into spin-photo-electronic devices. The reported nanofabrication method should have broad application areas in nanotechnology as it allows ballistic-injection devices, even for metallic materials with relatively short characteristic relaxation lengths.
magnetic point contact arrays; spin laser; sub-10 nm colloidal lithography
We report on the synthesis and magnetic characterization of ultralong (1 cm) arrays of highly ordered coaxial nanowires with nickel cores and graphene stacking shells (also known as metal-filled carbon nanotubes). Carbon-containing nickel nanowires are first grown on a nanograted surface by magnetron sputtering. Then, a post-annealing treatment favors the metal-catalyzed crystallization of carbon into stacked graphene layers rolled around the nickel cores. The observed uniaxial magnetic anisotropy field oriented along the nanowire axis is an indication that the shape anisotropy dominates the dipolar coupling between the wires. We further show that the thermal treatment induces a decrease in the coercivity of the nanowire arrays. This reflects an enhancement of the quality of the nickel nanowires after annealing attributed to a decrease of the roughness of the nickel surface and to a reduction of the defect density. This new type of graphene–ferromagnetic-metal nanowire appears to be an interesting building block for spintronic applications.
carbon; ferromagnetic; graphene; nanofabrication; nanowires; nickel; phase separation
The most important limitation for a significant increase of the areal storage density in magnetic recording is the superparamagnetic effect. Below a critical grain size of the used CoCrPt exchange-decoupled granular films the information cannot be stored for a reasonable time (typically ten years) due to thermal fluctuations arbitrary flipping of the magnetization direction. An alternative approach that may provide higher storage densities is the use of so-called percolated media, in which defect structures are imprinted in an exchange-coupled magnetic film. Such percolated magnetic films are investigated in the present work. We employ preparation routes that are based on (i) self-assembly of Au nanoparticles and (ii) homogeneous size-reduction of self-assembled polystyrene particles. On such non-close-packed nanostructures thin Fe films or Co/Pt multilayers are grown with in-plane and out-of-plane easy axis of magnetization. The impact of the particles on the magnetic switching behavior is measured by both integral magnetometry and magnetic microscopy techniques. We observe enhanced coercive fields while the switching field distribution is broadened compared to thin-film reference samples. It appears possible to tailor the magnetic domain sizes down to the width of an unperturbed domain wall in a continuous film, and moreover, we observe pinning and nucleation at or close to the imprinted defect structures.
colloidal lithography; magnetic data storage; magnetic nanostructures; percolated films
For many applications it is desirable to have nanoparticles positioned on top of a given substrate well separated from each other and arranged in arrays of a certain geometry. For this purpose, a method is introduced combining the bottom-up self-organization of precursor-loaded micelles providing Au nanoparticles (NPs), with top-down electron-beam lithography. As an example, 13 nm Au NPs are arranged in a square array with interparticle distances >1 µm on top of Si substrates. By using these NPs as masks for a subsequent reactive ion etching, the square pattern is transferred into Si as a corresponding array of nanopillars.
electron beam lithography; nanoparticles; positioning; self-assembling; unconventional lithography
We report on the electronic transport through nanoscopic metallic contacts under the influence of external light fields. Various processes can be of relevance here, whose underlying mechanisms can be studied by comparing different kinds of atomic contacts. For this purpose two kinds of contacts, which were established by electrochemical deposition, forming a gate-controlled quantum switch (GCQS), have been studied. We demonstrate that in these kinds of contacts thermal effects resulting from local heating due to the incident light, namely thermovoltage and the temperature dependences of the electrical resistivity and the electrochemical (Helmholtz) double layer are the most prominent effects.
atom transistor; atomic contacts; cyclic voltammogram; electrochemically closed break junction; electronic transport; (Helmholtz) double layer; light-induced signals; temperature-induced changes; thermovoltage
Regular arrays of metallic nano-triangles – so called Fischer patterns – are fabricated by nano-sphere lithography. We studied such gold nano-triangle arrays on silicon or glass substrates. A series of different samples was investigated with a parabolic mirror based confocal microscope where the sample is scanned through the laser focus. By employing higher order laser modes (azimuthally and radially polarised laser beams), we can excite the Fischer patterns using either a pure in-plane (x,y) electric field or a strongly z-directional (optical axis of the optical microscope) electric field. We collected and evaluated the emitted luminescence and thereby investigated the respectively excited plasmonic modes. These varied considerably: firstly with the light polarisation in the focus, secondly with the aspect ratio of the triangles and thirdly with the employed substrate. Moreover, we obtained strongly enhanced Raman spectra of an adenine (sub-)monolayer on gold Fischer patterns on glass. We thus showed that gold Fischer patterns are promising surface-enhanced Raman scattering (SERS) substrates.
Fischer pattern; higher order laser modes; localised surface plasmons; near field; surface-enhanced Raman scattering
A combination of a “top-down” approach (substrate-conformal imprint lithography) and two “bottom-up” approaches (dewetting and dealloying) enables fabrication of perfectly ordered 2-dimensional arrays of nanoporous gold nanoparticles. The dewetting of Au/Ag bilayers on the periodically prepatterned substrates leads to the interdiffusion of Au and Ag and the formation of an array of Au–Ag alloy nanoparticles. The array of alloy nanoparticles is transformed into an array of nanoporous gold nanoparticles by a following dealloying step. Large areas of this new type of material arrangement can be realized with this technique. In addition, this technique allows for the control of particle size, particle spacing, and ligament size (or pore size) by varying the period of the structure, total metal layer thickness, and the thickness ratio of the as-deposited bilayers.
dealloying; dewetting; nanoimprint lithography; nanoparticles; nanoporous gold; ordered arrays
ZnO nanowires are normally exposed to an oxygen atmosphere to achieve high performance in UV photodetection. In this work we present results on a UV photodetector fabricated using a flexible ZnO nanowire sheet embedded in polydimethylsiloxane (PDMS), a gas-permeable polymer, showing reproducible UV photoresponse and enhanced photoconduction. PDMS coating results in a reduced response speed compared to that of a ZnO nanowire film in air. The rising speed is slightly reduced, while the decay time is prolonged by about a factor of four. We conclude that oxygen molecules diffusing in PDMS are responsible for the UV photoresponse.
permeable polymer; photoresponse; polydimethylsiloxane; UV photodetection; ZnO nanowires
Surface coating with an organic self-assembled monolayer (SAM) can enhance surface reactions or the absorption of specific gases and hence improve the response of a metal oxide (MOx) sensor toward particular target gases in the environment. In this study the effect of an adsorbed organic layer on the dynamic response of zinc oxide nanowire gas sensors was investigated. The effect of ZnO surface functionalisation by two different organic molecules, tris(hydroxymethyl)aminomethane (THMA) and dodecanethiol (DT), was studied. The response towards ammonia, nitrous oxide and nitrogen dioxide was investigated for three sensor configurations, namely pure ZnO nanowires, organic-coated ZnO nanowires and ZnO nanowires covered with a sparse layer of organic-coated ZnO nanoparticles. Exposure of the nanowire sensors to the oxidising gas NO2 produced a significant and reproducible response. ZnO and THMA-coated ZnO nanowire sensors both readily detected NO2 down to a concentration in the very low ppm range. Notably, the THMA-coated nanowires consistently displayed a small, enhanced response to NO2 compared to uncoated ZnO nanowire sensors. At the lower concentration levels tested, ZnO nanowire sensors that were coated with THMA-capped ZnO nanoparticles were found to exhibit the greatest enhanced response. ΔR/R was two times greater than that for the as-prepared ZnO nanowire sensors. It is proposed that the ΔR/R enhancement in this case originates from the changes induced in the depletion-layer width of the ZnO nanoparticles that bridge ZnO nanowires resulting from THMA ligand binding to the surface of the particle coating. The heightened response and selectivity to the NO2 target are positive results arising from the coating of these ZnO nanowire sensors with organic-SAM-functionalised ZnO nanoparticles.
gas sensor; nanowire; tris(hydroxymethyl)aminomethane; self-assembled monolayer; zinc oxide
The effect of depositing FeO nanoparticles with a diameter of 10 nm onto the surface of MgB2 thin films on the critical current density was studied in comparison with the case of uncoated MgB2 thin films. We calculated the superconducting critical current densities (J
c) from the magnetization hysteresis (M–H) curves for both sets of samples and found that the J
c value of FeO-coated films is higher at all fields and temperatures than the J
c value for uncoated films, and that it decreases to ~105 A/cm2 at B = 1 T and T = 20 K and remains approximately constant at higher fields up to 7 T.
critical current; magnesium diboride; nanoparticles; pinning; superconductivity
The self-assembly properties of a series of functionalized regioregular oligo(3-alkylthiophenes) were investigated by using scanning tunneling microscopy (STM) at the liquid–solid interface under ambient conditions. The characteristics of the 2-D crystals formed on the (0001) plane of highly ordered pyrolitic graphite (HOPG) strongly depend on the length of the π-conjugated oligomer backbone, on the functional groups attached to it, and on the alkyl substitution pattern on the individual thiophene units. Theoretical calculations were performed to analyze the geometry and electronic density of the molecular orbitals as well as to analyze the intermolecular interactions, in order to obtain models of the 2-D molecular ordering on the substrate.
2-D crystals; functionalized oligothiophenes; H-bonding; intermolecular interaction; scanning tunneling microscopy
Optical properties of two series of fully conjugated cyclo[n]thiophenes were analyzed experimentally and theoretically. The absorption spectra reveal a shift to higher wavelengths with increasing size of the cycles, which can be successfully described by an excitonic approach based on a Frenkel exciton Hamiltonian. Furthermore, intriguing new bands in the absorption and fluorescence spectra of the smaller macrocycles disclose the dominance of their ring strain.
conjugated macrocycles; Frenkel exciton model; oligothiophene; photophysical properties
The photodissociation of small organic molecules, namely methyl iodide, methyl bromide, and methyl chloride, adsorbed on a metal surface was investigated in real time by means of femtosecond-laser pump–probe mass spectrometry. A weakly interacting gold surface was employed as substrate because the intact adsorption of the methyl halide molecules was desired prior to photoexcitation. The gold surface was prepared as an ultrathin film on Mo(100). The molecular adsorption behavior was characterized by coverage dependent temperature programmed desorption spectroscopy. Submonolayer preparations were irradiated with UV light of 266 nm wavelength and the subsequently emerging methyl fragments were probed by photoionization and mass spectrometric detection. A strong dependence of the excitation mechanism and the light-induced dynamics on the type of molecule was observed. Possible photoexcitation mechanisms included direct photoexcitation to the dissociative A-band of the methyl halide molecules as well as the attachment of surface-emitted electrons with transient negative ion formation and subsequent molecular fragmentation. Both reaction pathways were energetically possible in the case of methyl iodide, yet, no methyl fragments were observed. As a likely explanation, the rapid quenching of the excited states prior to fragmentation is proposed. This quenching mechanism could be prevented by modification of the gold surface through pre-adsorption of iodine atoms. In contrast, the A-band of methyl bromide was not energetically directly accessible through 266 nm excitation. Nevertheless, the one-photon-induced dissociation was observed in the case of methyl bromide. This was interpreted as being due to a considerable energetic down-shift of the electronic A-band states of methyl bromide by about 1.5 eV through interaction with the gold substrate. Finally, for methyl chloride no photofragmentation could be detected at all.
femtosecond laser spectroscopy; gold; methyl halide photodissociation; surface chemistry; time-of-flight mass spectrometry
We introduce a scheme to obtain the deconvolved density of states (DOS) of the tip and sample, from scanning tunneling spectra determined in the constant-current mode (z–V spectroscopy). The scheme is based on the validity of the Wentzel–Kramers–Brillouin (WKB) approximation and the trapezoidal approximation of the electron potential within the tunneling barrier. In a numerical treatment of z–V spectroscopy, we first analyze how the position and amplitude of characteristic DOS features change depending on parameters such as the energy position, width, barrier height, and the tip–sample separation. Then it is shown that the deconvolution scheme is capable of recovering the original DOS of tip and sample with an accuracy of better than 97% within the one-dimensional WKB approximation. Application of the deconvolution scheme to experimental data obtained on Nb(110) reveals a convergent behavior, providing separately the DOS of both sample and tip. In detail, however, there are systematic quantitative deviations between the DOS results based on z–V data and those based on I–V data. This points to an inconsistency between the assumed and the actual transmission probability function. Indeed, the experimentally determined differential barrier height still clearly deviates from that derived from the deconvolved DOS. Thus, the present progress in developing a reliable deconvolution scheme shifts the focus towards how to access the actual transmission probability function.
deconvolution; Nb DOS; STM; STS
Aiming at model systems with close-to-realistic transport properties, we have prepared and studied planar Au/TiO2 thin-film model catalysts consisting of a thin mesoporous TiO2 film of 200–400 nm thickness with Au nanoparticles, with a mean particle size of ~2 nm diameter, homogeneously distributed therein. The systems were prepared by spin-coating of a mesoporous TiO2 film from solutions of ethanolic titanium tetraisopropoxide and Pluronic P123 on planar Si(100) substrates, calcination at 350 °C and subsequent Au loading by a deposition–precipitation procedure, followed by a final calcination step for catalyst activation. The structural and chemical properties of these model systems were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), N2 adsorption, inductively coupled plasma ionization spectroscopy (ICP–OES) and X-ray photoelectron spectroscopy (XPS). The catalytic properties were evaluated through the oxidation of CO as a test reaction, and reactivities were measured directly above the film with a scanning mass spectrometer. We can demonstrate that the thin-film model catalysts closely resemble dispersed Au/TiO2 supported catalysts in their characteristic structural and catalytic properties, and hence can be considered as suitable for catalytic model studies. The linear increase of the catalytic activity with film thickness indicates that transport limitations inside the Au/TiO2 film catalyst are negligible, i.e., below the detection limit.
Au catalysis; Au/TiO2; CO oxidation; gold nanoparticles; model catalysts; thin-film catalyst