The effects of the addition of fibres of bacterial cellulose (FBC) to commercial starch of Mater-Bi® have been investigated. FBC produced by cultivating Acetobacter xylinum for 21 days in glucose-based medium were purified by sodium hydroxide 2.5 wt % and sodium hypochlorite 2.5 wt % overnight, consecutively. To obtain water-free BC nanofibres, the pellicles were freeze dried at a pressure of 130 mbar at a cooling rate of 10 °C min−1. Both Mater-Bi and FBC were blended by using a mini twin-screw extruder at 160 °C for 10 min at a rotor speed of 50 rpm. Tensile tests were performed according to ASTM D638 to measure the Young’s modulus, tensile strength and elongation at break. A field emission scanning electron microscope was used to observe the morphology at an accelerating voltage of 10 kV. The crystallinity (T
c) and melting temperature (T
m) were measured by DSC. Results showed a significant improvement in mechanical and thermal properties in accordance with the addition of FBC into Mater-Bi. FBC is easily incorporated in Mater-Bi matrix and produces homogeneous Mater-Bi/FBC composite. The crystallinity of the Mater-Bi/FBC composites decrease in relation to the increase in the volume fraction of FBC.
bacterial cellulose; bio-nanocomposites; Mater-Bi; mechanical; thermal
The magnetic and electronic properties of single-molecule magnets are studied by X-ray absorption spectroscopy and X-ray magnetic circular dichroism. We study the magnetic coupling of ultrathin Co and Ni films that are epitaxially grown onto a Cu(100) substrate, to an in situ deposited submonolayer of TbPc2 molecules. Because of the element specificity of the X-ray absorption spectroscopy we are able to individually determine the field dependence of the magnetization of the Tb ions and the Ni or Co film. On both substrates the TbPc2 molecules couple antiferromagnetically to the ferromagnetic films, which is possibly due to a superexchange interaction via the phthalocyanine ligand that contacts the magnetic surface.
magnetic anisotropy; magnetic coupling; single molecule magnets; X-ray absorption spectroscopy
One of the big challenges of the 21st century is the utilization of nanotechnology for energy technology. Nanoscale structures may provide novel functionality, which has been demonstrated most convincingly by successful applications such as dye-sensitized solar cells introduced by M. Grätzel. Applications in energy technology are based on the transfer and conversion of energy. Following the example of photosynthesis, this requires a combination of light harvesting, transfer of energy to a reaction center, and conversion to other forms of energy by charge separation and transfer. This may be achieved by utilizing hybrid nanostructures, which combine metallic and nonmetallic components. Metallic nanostructures can interact strongly with light. Plasmonic excitations of such structures can cause local enhancement of the electrical field, which has been utilized in spectroscopy for many years. On the other hand, the excited states in metallic structures decay over very short lifetimes. Longer lifetimes of excited states occur in nonmetallic nanostructures, which makes them attractive for further energy transfer before recombination or relaxation sets in. Therefore, the combination of metallic nanostructures with nonmetallic materials is of great interest. We report investigations of hybrid nanostructured model systems that consist of a combination of metallic nanoantennas (fabricated by nanosphere lithography, NSL) and oxide nanoparticles. The oxide particles were doped with rare-earth (RE) ions, which show a large shift between absorption and emission wavelengths, allowing us to investigate the energy-transfer processes in detail. The main focus is on TiO2 nanoparticles doped with Eu3+, since the material is interesting for applications such as the generation of hydrogen by photocatalytic splitting of water molecules. We use high-resolution techniques such as confocal fluorescence microscopy for the investigation of energy-transfer processes. The experiments are supported by simulations of the electromagnetic field enhancement in the vicinity of well-defined nanoantennas. The results show that the presence of the nanoparticle layer can modify the field enhancement significantly. In addition, we find that the fluorescent intensities observed in the experiments are affected by agglomeration of the nanoparticles. In order to further elucidate the possible influence of agglomeration and quenching effects in the vicinity of the nanoantennas, we have used a commercial organic pigment containing Eu, which exhibits an extremely narrow particle size distribution and no significant agglomeration. We demonstrate that quenching of the Eu fluorescence can be suppressed by covering the nanoantennas with a 10 nm thick SiOx layer.
confocal microscopy; energy transfer; field enhancement; light harvesting; luminescence; nano-antennas; nanosphere lithography; nanostructures; plasmonics; simulation; TiO2 nanoparticles
Synthetic diamond films can be prepared on a waferscale by using chemical vapour deposition (CVD) on suitable substrates such as silicon or silicon dioxide. While such films find a wealth of applications in thermal management, in X-ray and terahertz window design, and in gyrotron tubes and microwave transmission lines, their use for nanoscale optical components remains largely unexplored. Here we demonstrate that CVD diamond provides a high-quality template for realizing nanophotonic integrated optical circuits. Using efficient grating coupling devices prepared from partially etched diamond thin films, we investigate millimetre-sized optical circuits and achieve single-mode waveguiding at telecoms wavelengths. Our results pave the way towards broadband optical applications for sensing in harsh environments and visible photonic devices.
diamond devices; integrated optics; nanophotonics; waveguiding circuits
In this study the highly ordered corneal nanonipple structure observed on the Mourning Cloak butterfly (Nymphalis antiopa) is analyzed with a particular emphasis on the high-angle grain-boundary-like defects that are observed between individual nanonipple crystals. It is shown that these grain boundaries are generated by rows of topological coordination defects, which create very specific misorientations between adjacent crystals. These specific orientations form coincidence site lattices, which (i) have unit cells larger than the unit cell in each individual crystal and (ii) extend from one crystal to the next, effectively creating order over areas larger than the individual crystals. A comparison to similar coincidence site lattices in engineering materials is made and the importance of such arrangements in terms of nipple packing density, corneal lens curvature and potential optical properties is discussed.
butterfly-eye structure; coordination defects; sigma grain boundaries
Herein, we present an approach for the rapid, straightforward and economical preparation of a tailored reactor device using three-dimensional (3D) printing, which can be directly linked to a high-resolution electrospray ionisation mass spectrometer (ESI-MS) for real-time, in-line observations. To highlight the potential of the setup, supramolecular coordination chemistry was carried out in the device, with the product of the reactions being recorded continuously and in parallel by ESI-MS. Utilising in-house-programmed computer control, the reactant flow rates and order were carefully controlled and varied, with the changes in the pump inlets being mirrored by the recorded ESI-MS spectra.
continuous parallel analysis; ESI-MS; 3D printing; reactionware; supramolecular chemistry
The mycobacterial porin MspA is one of the most stable channel proteins known to date. MspA forms vesicles at low concentrations in aqueous buffers. Evidence from dynamic light scattering, transmission electron microscopy and zeta-potential measurements by electrophoretic light scattering indicate that MspA behaves like a nanoscale surfactant. The extreme thermostability of MspA allows these investigations to be carried out at temperatures as high as 343 K, at which most other proteins would quickly denature. The principles of vesicle formation of MspA as a function of temperature and the underlying thermodynamic factors are discussed here. The results obtained provide crucial evidence in support of the hypothesis that, during vesicle formation, nanoscopic surfactant molecules, such as MspA, deviate from the principles underlined in classical surface chemistry.
charge-interaction; hydrophobic interaction; liposome-type cluster; protein cluster; supramolecular; temperature influence; zeta potential
The effect of solvation on the adsorption of organic molecules on graphite at room temperature has been addressed with force-field molecular dynamics simulations. As a model system, the solvation of a bis(terpyridine) isomer in water and 1,2,4-trichlorobenzene was studied with an explicit solvation model. The inclusion of solvation has a noticeable effect on adsorption energies. Although the results of the various considered force fields differ quite significantly, they all agree that the adsorption of BTP from the TCB solvent is almost thermoneutral. The substrate simply acts as a template to allow a planar arrangement of the network, which is stabilized by the intermolecular interaction. Using an atomic thermodynamics approach, the order of the stability of various network structures as a function of the chemical potential is derived yielding a sequence in agreement with the experiment.
computer simulations; energy related; force-field calculations; nanomaterials; solvation
Infrared spectra of hydrogenated diamond nanocrystals of one nanometer length are calculated by ab initio methods. Positions of atoms are optimized via density functional theory at the level of the generalized gradient approximation of Perdew, Burke and Ernzerhof (PBE) using 3-21G basis states. The frequencies in the vibrational spectrum are analyzed against reduced masses, force constants and intensities of vibration. The spectrum can be divided into two regions depending on the properties of the vibrations or the gap separating them. In the first region, results show good matching to several experimentally obtained lines. The 500 cm−1 broad-peak acoustical branch region is characterized by pure C–C vibrations. The optical branch is centered at 1185 cm−1. Calculations show that several C–C vibrations are mixed with some C–H vibrations in the first region. In the second region the matching also extends to C–H vibration frequencies that include different modes such as symmetric, asymmetric, wagging, scissor, rocking and twisting modes. In order to complete the picture of the size dependence of the vibrational spectra, we analyzed the spectra of ethane and adamantane. The present analysis shows that acoustical and optical branches in diamond nanocrystals approach each other and collapse at 963 cm−1 in ethane. Variation of the highest reduced-mass-mode C–C vibrations from 1332 cm−1 of bulk diamond to 963 cm−1 for ethane (red shift) is shown. The analysis also shows the variation of the radial breathing mode from 0 cm−1 of bulk diamond to 963 cm−1 for ethane (blue shift). These variations compare well with experiment. Experimentally, the above-mentioned modes appear shifted from their exact positions due to overlap with neighboring modes.
ab initio; diamond; infrared spectroscopy; nanocrystals; vibration
The method of successive ion layer adsorption and reaction was applied for the deposition of CdS nanoparticles onto a mesoporous In2O3 substrate. The filling of the nanopores in In2O3 films with CdS particles mainly occurs during the first 30 cycles of the SILAR deposition. The surface modification of In2O3 with CdS nanoparticles leads to the spectral sensitization of photoelectrochemical processes that manifests itself in a red shift of the long-wavelength edge in the photocurrent spectrum by 100–150 nm. Quantum-confinement effects lead to an increase of the bandgap from 2.49 to 2.68 eV when decreasing the number of SILAR cycles from 30 to 10. The spectral shift and the widening of the Raman line belonging to CdS evidences the lattice stress on the CdS/In2O3 interfaces and confirms the formation of a close contact between the nanoparticles.
cadmium sulfide (CdS); indium oxide (In2O3); nanoparticles; successive ionic layer adsorption and reaction (SILAR)
The electrical compensation effect of the nitrogen incorporation at the SiO2/4H-SiC (p-type) interface after thermal treatments in ambient N2O is investigated employing both scanning spreading resistance microscopy (SSRM) and scanning capacitance microscopy (SCM). SSRM measurements on p-type 4H-SiC areas selectively exposed to N2O at 1150 °C showed an increased resistance compared to the unexposed ones; this indicates the incorporation of electrically active nitrogen-related donors, which compensate the p-type doping in the SiC surface region. Cross-sectional SCM measurements on SiO2/4H-SiC metal/oxide/semiconductor (MOS) devices highlighted different active carrier concentration profiles in the first 10 nm underneath the insulator–substrate interface depending on the SiO2/4H-SiC roughness.
The electrically active incorporated nitrogen produces both a compensation of the acceptors in the substrate and a reduction of the interface state density (D
it). This result can be correlated with the 4H-SiC surface configuration. In particular, lower D
it values were obtained for a SiO2/SiC interface on faceted SiC than on planar SiC. These effects were explained in terms of the different surface configuration in faceted SiC that enables the simultaneous exposition at the interface of atomic planes with different orientations.
4H-SiC; metal/oxide/semiconductor; nitrogen incorporation
Atomic force microscopes have become indispensable tools for mechanical characterization of nanoscale and submicron structures. However, materials with complex geometries, such as electrospun fiber networks used for tissue scaffolds, still pose challenges due to the influence of tension and bending modulus on the response of the suspended structures. Here we report mechanical measurements on electrospun silk fibers with various treatments that allow discriminating among the different mechanisms that determine the mechanical behavior of these complex structures. In particular we were able to identify the role of tension and boundary conditions (pinned versus clamped) in determining the mechanical response of electrospun silk fibers. Our findings show that high-resolution mechanical imaging with torsional harmonic atomic force microscopy provides a reliable method to investigate the mechanics of materials with complex geometries.
atomic force microscopy; nanomechanical characterization; silk fibers; tissue scaffolds; torsional harmonic cantilevers
Chemical vapour deposition (CVD) on catalytic metals is one of main approaches for high-quality graphene growth over large areas. However, a subsequent transfer step to an insulating substrate is required in order to use the graphene for electronic applications. This step can severely affect both the structural integrity and the electronic properties of the graphene membrane. In this paper, we investigated the morphological and electrical properties of CVD graphene transferred onto SiO2 and on a polymeric substrate (poly(ethylene-2,6-naphthalene dicarboxylate), briefly PEN), suitable for microelectronics and flexible electronics applications, respectively. The electrical properties (sheet resistance, mobility, carrier density) of the transferred graphene as well as the specific contact resistance of metal contacts onto graphene were investigated by using properly designed test patterns. While a sheet resistance R
sh ≈ 1.7 kΩ/sq and a specific contact resistance ρc ≈ 15 kΩ·μm have been measured for graphene transferred onto SiO2, about 2.3× higher R
sh and about 8× higher ρc values were obtained for graphene on PEN. High-resolution current mapping by torsion resonant conductive atomic force microscopy (TRCAFM) provided an insight into the nanoscale mechanisms responsible for the very high ρc in the case of graphene on PEN, showing a ca. 10× smaller “effective” area for current injection than in the case of graphene on SiO2.
conductive AFM; contact resistance; graphene; mobility; PEN; sheet resistance; SiO2
We critically discuss the extraction of intrinsic cantilever properties, namely eigenfrequency f
n, quality factor Q
n and specifically the stiffness k
n of the nth cantilever oscillation mode from thermal noise by an analysis of the power spectral density of displacement fluctuations of the cantilever in contact with a thermal bath. The practical applicability of this approach is demonstrated for several cantilevers with eigenfrequencies ranging from 50 kHz to 2 MHz. As such an analysis requires a sophisticated spectral analysis, we introduce a new method to determine k
n from a spectral analysis of the demodulated oscillation signal of the excited cantilever that can be performed in the frequency range of 10 Hz to 1 kHz regardless of the eigenfrequency of the cantilever. We demonstrate that the latter method is in particular useful for noncontact atomic force microscopy (NC-AFM) where the required simple instrumentation for spectral analysis is available in most experimental systems.
AFM; cantilever; noncontact atomic force microscopy (NC-AFM); Q-factor; thermal excitation; resonance; spectral analysis; stiffness
This study investigates the controlled chemical functionalization of silicon oxide nanostructures prepared by AFM-anodization lithography of alkyl-terminated silicon. Different conditions for the growth of covalently bound mono-, multi- or submonolayers of distinctively functional silane molecules on nanostructures have been identified by AFM-height investigations. Routes for the preparation of methyl- or amino-terminated structures or silicon surfaces are presented and discussed. The formation of silane monolayers on nanoscopic silicon oxide nanostructures was found to be much more sensitive towards ambient humidity than, e.g., the silanization of larger OH-terminated silica surfaces. Amino-functionalized nanostructures have been successfully modified by the covalent binding of functional fluorescein dye molecules. Upon excitation, the dye-functionalized structures show only weak fluorescence, which may be an indication of a relatively low surface coverage of the dye molecules on length scale that is not accessible by standard AFM measurements.
AFM lithography; amino-functionalization; local anodic oxidation; octadecyl-trichlorosilane; silicon oxide nanostructures
Background: ZnO nanostructures are promising candidates for the development of novel electronic devices due to their unique electrical and optical properties. Here, photoconductive atomic force microscopy (PC-AFM) has been applied to investigate transient photoconductivity and photocurrent spectra of upright-standing ZnO nanorods (NRs). With a view to evaluate the electronic properties of the NRs and to get information on recombination kinetics, we have also performed time-resolved photoluminescence measurements macroscopically.
Results: Persistent photoconductivity from single ZnO NRs was observed for about 1800 s and was studied with the help of photocurrent spectroscopy, which was recorded locally. The photocurrent spectra recorded from single ZnO NRs revealed that the minimum photon energy sufficient for photocurrent excitation is 3.1 eV. This value is at least 100 meV lower than the band-gap energy determined from the photoluminescence experiments.
Conclusion: The obtained results suggest that the photoresponse in ZnO NRs under ambient conditions originates preferentially from photoexcitation of charge carriers localized at defect states and dominates over the oxygen photodesorption mechanism. Our findings are in agreement with previous theoretical predictions based on density functional theory calculations as well as with earlier experiments carried out at variable oxygen pressure.
AFM; nanorods; photoconductive AFM; photoconductivity; ZnO
We present an overview of the bimodal amplitude–frequency-modulation (AM-FM) imaging mode of atomic force microscopy (AFM), whereby the fundamental eigenmode is driven by using the amplitude-modulation technique (AM-AFM) while a higher eigenmode is driven by using either the constant-excitation or the constant-amplitude variant of the frequency-modulation (FM-AFM) technique. We also offer a comparison to the original bimodal AFM method, in which the higher eigenmode is driven with constant frequency and constant excitation amplitude. General as well as particular characteristics of the different driving schemes are highlighted from theoretical and experimental points of view, revealing the advantages and disadvantages of each. This study provides information and guidelines that can be useful in selecting the most appropriate operation mode to characterize different samples in the most efficient and reliable way.
amplitude-modulation; atomic force microscopy; frequency-modulation; phase-locked loop; spectroscopy
Nanofibers containing ferrocene (Fc) have been prepared for the first time by electrospinning. In this paper, Fc was dispersed uniformly throughout the poly(vinypyrrolidone) (PVP) matrix for the purpose of combining the properties of PVP and Fc. The effects of solvents and Fc concentration on the morphologies and diameters of nanofibers were investigated. In the DMF/ethanol solvent, the morphologies of the obtained nanofibers significantly changed with the increase of Fc concentration. The results demonstrated that the morphologies of the nanofibers could be controlled through adjusting solvents and Fc concentration. Scanning electron microscopy (SEM) showed that the diameters of the obtained composite fibers were about 30–200 nm at different Fc concentrations. Thermogravimetric analysis (TGA) results confirmed the presence of ferrocene within the PVP nanofibers. X-ray diffraction (XRD) results showed that the crystalline structure of Fc in the fibers was amorphous after the electrospinning process. A biological evaluation of the antimicrobial activity of Fc/PVP nanofibers was carried out by using Gram-negative Escherichia coli (E. coli) as model organisms. The nanofibers fabricated by this method showed obvious antibacterial activity. Electrochemical properties were characterized based on cyclic voltammetry measurements. The CV results showed redox peaks corresponding to the Fc+/Fc couple, which suggested that Fc molecules encapsulated inside PVP nanofibers retian their electrochemical activity. The properties and facile preparation method make the Fc/PVP nanofibers promising for antibacterial and sensing applications.
composites; electrochemistry; electrospinning; membranes; porous materials
Numerical simulations of current–voltage curves in electron-only devices are used to discuss the influence of charged defects on the information derived from fitting space-charge-limited current models to the data. Charged, acceptor-like defects lead to barriers impeding the flow of electrons in electron-only devices and therefore lead to a reduced current that is similar to the situation where the device has a built-in voltage. This reduced current will lead to an underestimation of the mobilities and an overestimation of characteristic tail slopes if analytical equations are used to analyze the data. Correcting for the barrier created by the charged defects can, however, be a successful way to still be able to obtain reasonably accurate mobility values.
current–voltage curves; electron-only device; drift–diffusion; mobility; simulation; traps
The plastic behaviour of individual Cu crystallites under nanoextrusion is studied by molecular dynamics simulations. Single-crystal Cu fcc nanoparticles are embedded in a spherical force field mimicking the effect of a contracting carbon shell, inducing pressure on the system in the range of gigapascals. The material is extruded from a hole of 1.1–1.6 nm radius under athermal conditions. Simultaneous nucleation of partial dislocations at the extrusion orifice leads to the formation of dislocation dendrites in the particle causing strain hardening and high flow stress of the material. As the extrusion orifice radius is reduced below 1.3 Å we observe a transition from displacive plasticity to solid-state amorphisation.
dislocation interactions; mechanical properties; molecular dynamics; nanoparticle; simulation
Self-assembled two-dimensional arrays of either 14 nm hcp-Co or 6 nm ε-Co particle components were treated by hydrogen plasma for various exposure times. A change of hysteretic sample behavior depending on the treatment duration is reported, which can be divided in two time scales: oxygen reduction increases the particle magnetization during the first 20 min, which is followed by an alteration of the magnetic response shape. The latter depends on the respective particle species. Based on the Landau–Lifshitz equations for a discrete set of magnetic moments, we propose a model that relates the change of the hysteresis loops to a dipole-driven ordering of the magnetocrystalline easy axes within the particle plane due to the high spatial aspect ratio of the system.
dipolar particle coupling; magnetic nanoparticles; magnetocrystalline anisotropy; monolayers
The recent achievement of atomic resolution with dynamic atomic force microscopy (dAFM) [Fukuma et al., Appl. Phys. Lett.
2005, 87, 034101], where quality factors of the oscillating probe are inherently low, challenges some accepted beliefs concerning sensitivity and resolution in dAFM imaging modes. Through analysis and experiment we study the performance metrics for high-resolution imaging with dAFM in liquid media with amplitude modulation (AM), frequency modulation (FM) and drive-amplitude modulation (DAM) imaging modes. We find that while the quality factors of dAFM probes may deviate by several orders of magnitude between vacuum and liquid media, their sensitivity to tip–sample forces can be remarkable similar. Furthermore, the reduction in noncontact forces and quality factors in liquids diminishes the role of feedback control in achieving high-resolution images. The theoretical findings are supported by atomic-resolution images of mica in water acquired with AM, FM and DAM under similar operating conditions.
atomic force microscopy; dAFM; high-resolution; liquids
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)