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
atomic force microscopy
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
The combination of electrodeposition and polymeric templates created by heavy-ion irradiation followed by chemical track etching provides a large variety of poly- and single-crystalline nanowires of controlled size, geometry, composition, and surface morphology. Recent results obtained by our group on the fabrication, characterization and size-dependent properties of nanowires synthesized by this technique are reviewed, including investigations on electrical resistivity, surface plasmon resonances, and thermal instability.
electrodeposition; etched ion-track membrane; finite-size effects; heavy ion irradiation; nanowire; radiation-induced nanostructures
Single- and multilayer graphene and highly ordered pyrolytic graphite (HOPG) were exposed to a pure hydrogen low-temperature plasma (LTP). Characterizations include various experimental techniques such as photoelectron spectroscopy, Raman spectroscopy and scanning probe microscopy. Our photoemission measurement shows that hydrogen LTP exposed HOPG has a diamond-like valence-band structure, which suggests double-sided hydrogenation. With the scanning tunneling microscopy technique, various atomic-scale charge-density patterns were observed, which may be associated with different C–H conformers. Hydrogen-LTP-exposed graphene on SiO2 has a Raman spectrum in which the D peak to G peak ratio is over 4, associated with hydrogenation on both sides. A very low defect density was observed in the scanning probe microscopy measurements, which enables a reverse transformation to graphene. Hydrogen-LTP-exposed HOPG possesses a high thermal stability, and therefore, this transformation requires annealing at over 1000 °C.
graphane; HOPG; hydrogenation; plasma
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
We recently introduced a method that allows the controlled deposition of nanoscale metallic patterns at defined locations using the tip of an atomic force microscope (AFM) as a “mechano-electrochemical pen”, locally activating a passivated substrate surface for site-selective electrochemical deposition. Here, we demonstrate the reversibility of this process and study the long-term stability of the resulting metallic structures. The remarkable stability for more than 1.5 years under ambient air without any observable changes can be attributed to self-passivation. After AFM-activated electrochemical deposition of copper nanostructures on a polycrystalline gold film and subsequent AFM imaging, the copper nanostructures could be dissolved by reversing the electrochemical potential. Subsequent AFM-tip-activated deposition of different copper nanostructures at the same location where the previous structures were deleted, shows that there is no observable memory effect, i.e., no effect of the previous writing process on the subsequent writing process. Thus, the four processes required for reversible information storage, “write”, “read”, “delete” and “re-write”, were successfully demonstrated on the nanometer scale.
atomic force microscopy; electrochemical deposition; electrochemistry; nanoelectronics; nanofabrication; nanolithography; nanotechnology; MEMS and NEMS; reversible processes; scanning probe microscopy and lithography
A double-lateral-gate p-type junctionless transistor is fabricated on a low-doped (1015) silicon-on-insulator wafer by a lithography technique based on scanning probe microscopy and two steps of wet chemical etching. The experimental transfer characteristics are obtained and compared with the numerical characteristics of the device. The simulation results are used to investigate the pinch-off mechanism, from the flat band to the off state. The study is based on the variation of the carrier density and the electric-field components. The device is a pinch-off transistor, which is normally in the on state and is driven into the off state by the application of a positive gate voltage. We demonstrate that the depletion starts from the bottom corner of the channel facing the gates and expands toward the center and top of the channel. Redistribution of the carriers due to the electric field emanating from the gates creates an electric field perpendicular to the current, toward the bottom of the channel, which provides the electrostatic squeezing of the current.
AFM nanolithography; junctionless transistors; pinch-off; scanning probe microscope; simulation
We present an overview of experimental and numerical methods to determine the spring constant of a quartz tuning fork in qPlus configuration. The simple calculation for a rectangular cantilever is compared to the values obtained by the analysis of the thermal excitation and by the direct mechanical measurement of the force versus displacement. To elucidate the difference, numerical simulations were performed taking account of the real geometry including the glue that is used to mount the tuning fork.
atomic force microscopy; finite element method; spring constant; thermal fluctuation; tuning fork
We report on an experimental analysis of the charge transport through sulfur-free photochromic molecular junctions. The conductance of individual molecules contacted with gold electrodes and the current–voltage characteristics of these junctions are measured in a mechanically controlled break-junction system at room temperature and in liquid environment. We compare the transport properties of a series of molecules, labeled TSC, MN, and 4Py, with the same switching core but varying side-arms and end-groups designed for providing the mechanical and electrical contact to the gold electrodes. We perform a detailed analysis of the transport properties of TSC in its open and closed states. We find rather broad distributions of conductance values in both states. The analysis, based on the assumption that the current is carried by a single dominating molecular orbital, reveals distinct differences between both states. We discuss the appearance of diode-like behavior for the particular species 4Py that features end-groups, which preferentially couple to the metal electrode by physisorption. We show that the energetic position of the molecular orbital varies as a function of the transmission. Finally, we show for the species MN that the use of two cyano end-groups on each side considerably enhances the coupling strength compared to the typical behavior of a single cyano group.
diarylethene; mechanically controllable break-junction; molecular electronics; photoswitching; single-molecule junctions
Recent advances in near-edge X-ray-absorption fine-structure spectroscopy coupled with transmission X-ray microscopy (NEXAFS–TXM) allow large-area mapping investigations of individual nano-objects with spectral resolution up to E/ΔE = 104 and spatial resolution approaching 10 nm. While the state-of-the-art spatial resolution of X-ray microscopy is limited by nanostructuring process constrains of the objective zone plate, we show here that it is possible to overcome this through close coupling with high-level theoretical modelling. Taking the example of isolated bundles of hydrothermally prepared sodium titanate nanotubes ((Na,H)TiNTs) we are able to unravel the complex nanoscale structure from the NEXAFS–TXM data using multichannel multiple-scattering calculations, to the extent of being able to associate specific spectral features in the O K-edge and Ti L-edge with oxygen atoms in distinct sites within the lattice. These can even be distinguished from the contribution of different hydroxyl groups to the electronic structure of the (Na,H)TiNTs.
multichannel multiple scattering; nanotubes; NEXAFS; sodium titanates
Scanning- and colloidal-probe atomic force microscopy were used to study the mechanical properties of poly(L-lysine)/hyaluronan (PLL/HA)n films as a function of indentation velocity and the number of polymer deposition steps n. The film thickness was determined by two independent AFM-based methods: scratch-and-scan and newly developed full-indentation. The advantages and disadvantages of both methods are highlighted, and error minimization techniques in elasticity measurements are addressed. It was found that the film thickness increases linearly with the bilayer number n, ranging between 400 and 7500 nm for n = 12 and 96, respectively. The apparent Young’s modulus E ranges between 15 and 40 kPa and does not depend on the indenter size or the film bilayer number n. Stress relaxation measurements show that PLL/HA films have a viscoelastic behaviour, regardless of their thickness. If indentation is performed several times at the same lateral position on the film, a viscous/plastic deformation takes place.
atomic force microscopy; polyelectrolyte multilayers; stress relaxation; viscoelasticity; Young’s modulus
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
Nano-object additives are used in tribological applications as well as in various applications in liquids requiring controlled manipulation and targeting. On the macroscale, nanoparticles in solids and liquids have been shown to reduce friction and wear. On the nanoscale, atomic force microscopy (AFM) studies have been performed in single- and multiple-nanoparticle contact, in dry environments, to characterize friction forces and wear. However, limited studies in submerged liquid environments have been performed and further studies are needed. In this paper, spherical Au nanoparticles were studied for their effect on friction and wear under dry conditions and submerged in water. In single-nanoparticle contact, individual nanoparticles, deposited on silicon, were manipulated with a sharp tip and the friction force was determined. Multiple-nanoparticle contact sliding experiments were performed on nanoparticle-coated silicon with a glass sphere. Wear tests were performed on the nanoscale with AFM as well as on the macroscale by using a ball-on-flat tribometer to relate friction and wear reduction on the nanoscale and macroscale. Results indicate that the addition of Au nanoparticles reduces friction and wear.
AFM; drug delivery; friction; gold nanoparticles; MEMS/NEMS; nanomanipulation
Modern high-speed atomic force microscopes generate significant quantities of data in a short amount of time. Each image in the sequence has to be processed quickly and accurately in order to obtain a true representation of the sample and its changes over time. This paper presents an automated, adaptive algorithm for the required processing of AFM images. The algorithm adaptively corrects for both common one-dimensional distortions as well as the most common two-dimensional distortions. This method uses an iterative thresholded processing algorithm for rapid and accurate separation of background and surface topography. This separation prevents artificial bias from topographic features and ensures the best possible coherence between the different images in a sequence. This method is equally applicable to all channels of AFM data, and can process images in seconds.
adaptive algorithm; artifact correction; atomic force microscopy; high-speed atomic force microscope; image processing
Skin can be damaged by the environment easily. Skin cream is an effective and rapid way to moisten the skin by changing the skin surface properties. Rat skin and pig skin are common animal models for studies and were used as skin samples in this study. The nano- and macroscale friction and durability of damaged skin were measured and compared with those of virgin (intact/undamaged) skin. The effect of skin cream on friction and durability of damaged and virgin skin samples is discussed. The effects of velocity, normal load, relative humidity and number of cycles were studied. The nanoscale studies were performed by using atomic force microscope (AFM), and macroscale studies were performed by using a pin-on-disk (POD) reciprocating tribometer. It was found that damaged skin has different mechanical properties, surface roughness, contact angle, friction and durability compared to that of virgin skin. But similar changes occur after skin cream treatment. Rat and pig skin show similar trends in friction and durability.
atomic force microscopy; damaged skin; pig skin; rat skin; skin cream
We report on the use of scanning force microscopy as a versatile tool for the electrical characterization of nanoscale memristors fabricated on ultrathin La0.7Sr0.3MnO3 (LSMO) films. Combining conventional conductive imaging and nanoscale lithography, reversible switching between low-resistive (ON) and high-resistive (OFF) states was locally achieved by applying voltages within the range of a few volts. Retention times of several months were tested for both ON and OFF states. Spectroscopy modes were used to investigate the I–V characteristics of the different resistive states. This permitted the correlation of device rectification (reset) with the voltage employed to induce each particular state. Analytical simulations by using a nonlinear dopant drift within a memristor device explain the experimental I–V bipolar cycles.
conductive scanning probe micoscopy; memristor; 3-D modes; resistive switching; scanning probe microscopy
Monitoring emissions in high-temperature-combustion applications is very important for regulating the discharge of gases such as NO2 and CO as well as unburnt fuel into the environment. This work reports the detection of H2 and CO gases by employing a metal–metal oxide nanocomposite (gold–yttria stabilized zirconia (Au–YSZ)) film fabricated through layer-by-layer physical vapor deposition (PVD). The change in the peak position of the localized surface plasmon resonance (LSPR) was monitored as a function of time and gas concentration. The responses of the films were preferential towards H2, as observed from the results of exposing the films to the gases at temperatures of 500 °C in a background of dry air. Characterization of the samples by XRD and SEM enabled the correlation of material properties with the differences in the CO- and H2-induced LSPR peak shifts, including the relative desensitization towards NO2. Sensing characteristics of films with varying support thicknesses and metal-particle diameters have been studied, and the results are presented. A comparison has been made to films fabricated through co-sputtered PVD, and the calibration curves of the sensing response show a preferential response towards H2. The distinction between H2 and CO responses is also seen through the use of principal-component analysis (PCA). Such material arrangements, which can be tuned for their selectivity by changing certain parameters such as particle size, support thickness, etc., have direct applications within optical chemical sensors for turbine engines, solid-oxide fuel cells, and other high-temperature applications.
hydrogen detection; nanocomposites gold nanoparticles; optical sensor; plasmonics; physical vapor deposition; surface plasmon resonance
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
The optoelectronic performance of thin films of single-walled carbon nanotubes (SWCNTs) was studied with respect to the properties of both individual nanotubes and their bundles. The SWCNTs were synthesized in a hot wire generator aerosol reactor, collected by gas filtration and dry-transferred onto various substrates. By thus completely avoiding liquid dispersion steps, we were able to avoid any artifacts from residual surfactants or sonication. We found that bundle lengths determined the thin-film performance, as would be expected for highly resistive bundle–bundle junctions. However, we found no evidence that contact resistances were affected by the bundle diameters, although they did play a secondary role by simply affecting the absorption. The individual SWCNT diameters and their graphitization level as gauged by the Raman D band intensity did not show any clear correlation with the overall performance.
bundle diameter; sheet resistance; SWCNT; thin film; transmittance
Paper with antimicrobial properties was developed through in situ growth of ZnO nanorods. The targeted application for this type of paper is in health centers as wallpaper, writing paper, facemasks, tissue paper, etc. The paper was tested on three model microbes, Gram-positive bacteria Staphylococcus aureus, Gram-negative bacteria Escherichia coli and common airborne fungus Aspergillus niger. No viable bacterial colonies or fungal spores could be detected in the areas surrounding test samples of the antimicrobial paper. Gram-negative bacteria Escherichia coli were found to be inhibited in an area that is 239% and 163% the area of the paper sample under different room lighting conditions, i.e., halogen and fluorescent lamp illumination, respectively. For Gram-positive bacteria Staphylococcus aureus the zones of inhibition surrounding the paper samples are 102% and 70%, and for Aspergillus niger, 224% and 183% of the sample area, under similar lighting conditions.
antimicrobial; nanorod; paper; photocatalysis; zinc oxide
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