Arc-discharge synthesized multiwalled carbon nanotubes (AD-MWNT), or related MWNTs, exhibit a good quality compared to the more common type of MWNT synthesized by catalytic chemical vapor deposition methods. Yet experimental measurements on these are rather few and typically have not correlated data from different measurement techniques. Here, the authors report Raman spectroscopy, scanning probe microscopy, conductivity measurements, and force microscopy on single AD-MWNTs. The results demonstrate the high quality of AD-MWNTs and are compatible with the view of them as the best approximation of MWNTs as an assembly of defect-free concentric individual single-walled carbon nanotubes. The authors also demonstrate conductance measurements over a step on the surface of an AD-MWNT, which is due to an abruptly broken outer layer(s), whereby the interlayer resistance is measured.
Electron induced dissociation of physisorbed H2, HD, and D2 proceeds, as we observe in electron energy-loss measurements of the resulting atomic species, with a high quantum efficiency via the 2Σg+ core excited electron scattering resonances. We find that the predominant decay of the temporary H2- state to the neutral excited 3Σu+ parent state, which is intramolecularly antibonding, provides a sufficiently long-lived channel for dissociation to occur with high probability, even in the proximity of a metal surface.
We show by electron energy-loss measurements that desorption of physisorbed H2 and D2 induced by low-energy electrons takes place with large cross sections, predominantly via resonance excitation of the molecule-surface vibrational mode. The observed H2, D2 cross-section ratio supports a picture where rotation-translation conversion of the resonance excited j=0→2 rotational transition contributes to the desorption of H2, while this channel is energetically closed for D2
Our high-resolution electron energy-loss measurements concern physisorbed H2 and comprise dif- ferential cross sections for the excitation of the internal H2 modes and the H2-surface bonding mode and their combinations and extend over the electron impact energy range of the classical low-energy H2 2Σu resonance. Comparison with corresponding data for the excitation of the internal modes of gas phase H2 reveals that strong elastic electron reflectivity from the Cu(100) substrate profoundly distorts the inelastic scattering pattern for physisorbed H2. We find that this influence can be corrected for and that the resulting peak cross sections agree with the H2 gas phase data, in accordance with theoretical predictions for the excitation of the internal H2 vibration. We have used corrected cross sections for the rotational mode spectra of physisorbed H2, HD, and D2 in a model concerning elec- tron induced desorption via rotation-translation energy conversion. These spectra include transitions from the ground state as well as excited levels of the physisorption potential well. H2 and HD can desorb from all levels while D2, for energetic reason, can only desorb from the excited levels. This model gives a satisfactory account of the observed desorption cross sections and predicts character- istic velocity distributions of the desorbing molecules. The cross section data for H2 and HD reveals that direct bound-free transitions also contribute to the electron induced desorption.
Morphological control and characterization of blend films is key in the development of viable polymer solar cells. Spontaneous formation of vertical compositional gradients during solution processing has been shown for polyfluorene:PCBM blends and rationalized with thermodynamic and kinetic models of nucleation and spinodal decomposition.[1, 2] The extent of vertical stratification is affected by polymer side-chain modification aimed at controlling polymer:fullerene miscibility.[3] Here we present high-resolution film morphology results for several polymer:fullerene systems as obtained from near-edge X-ray fine structure spectroscopy (NEXAFS) in partial and in total electron yield modes. Blend films were found to be polymer- enriched at the surface. Dynamic secondary ion mass spectrometry (dSIMS) and NEXAFS give compositional information at different depths, resulting in a more complete picture of the film morphology.
The surface composition in spin-coated films of polyfluorene:fullerene blends was determined quantitatively by near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. By comparing partial and total electron yield spectra, we found vertical compositional differences in the surface region. Furthermore, the orientation of the polymer chains was investigated by variable-angle NEXAFS. Blend films of poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole] with [6,6]-phenyl-C61-butyric acid methyl ester in two different blend ratios were studied. Results showed polymer enrichment of the surfaces for films with a polymer:fullerene weight ratio of 20:80 and of 50:50, spin-coated from both chlorobenzene and chloroform solutions. The angular dependence of the NEXAFS spectra of the pure polymer films showed a preferential plane-on orientation, which was slightly stronger in the subsurface region than at the surface. In blend films, this orientational preference was less pronounced and the difference between surface and subsurface vanished
Fullerenes are common electron acceptors in organic solar cells. Here the photostability in air of the electronic structures of spin-coated PCBM ([6,6]-phenyl-C61-butyric acid methyl ester) and evaporated C60 films are studied using ultraviolet photoelectron spectroscopy (UPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. After exposing these materials in air to simulated sunlight, the filled and empty molecular orbitals are strongly altered, indicating that the conjugated π-system of the C60-cage has degraded. Even a few minutes in normal lab light induces changes. These results stress the importance of protecting fullerene-based films from light and air during processing, operation, and storage.
Achieving control over the nanomorphology of blend films of the fullerene derivative [6,6]-phenyl C61-butyric acid methyl ester, PCBM, with light-absorbing conjugated polymers is an important challenge in the development of efficient solution-processed photovoltaics. Here, three new polyfluorene copolymers are presented, tailored for enhanced miscibility with the fullerene through the introduction of polymer segments with modified side chains, which enhance the polymer’s polar character. The composition of the spincoated polymer:PCBM films is analyzed with dynamic secondary ion mass spectrometry (dSIMS). The dSIMS depth profiles demonstrate compositional variations perpendicular to the surface plane, as a result of vertical phase separation, directed by the substrate. These variations propagate to a higher degree through the film for the polymers with a larger fraction of modified side chains. The surface composition of the films is studied by Near-edge X-ray absorption fine structure spectroscopy (NEXAFS). Quantitative analysis of the NEXAFS spectra through a linear combination fit with the spectra of the pure components yields the surface composition. The resulting blend ratios reveal polymer-enrichment of the film surface for all three blends, which also becomes stronger as the polar character of the polymer increases. Comparison of the NEXAFS spectra collected with two different sampling depths shows that the vertical composition gradient builds up already in the first nanometers underneath the surface of the films. The results obtained with this new series of polymers shed light on the onset of formation of lamellar structures in thin polymer:PCBM films prepared from highly volatile solvents
The fullerene derivative [6,6]-phenyl-C61-butyric acid methyl ester plays a key role for electron transport in polymer solar cells. We have studied the unoccupied molecular orbitals of PCBM by near edge X-ray absorption fine structure spectroscopy and were able to assign the main resonances to molecular moieties by comparison with calculated sum spectra of individual carbons. We analyzed specifically the origin of the high-energy shoulder to the first π∗-resonance and identified contributions from the lowest-energy transition of a specific carbon in the phenyl and from transitions to higher unoccupied orbitals of the unmodified carbons in the C60-cage.
A method for in-situ measurements of electrical properties of thin film heterostructures using TEM and SEM has been developed. This method allows measurements of the conductance in a thin film heterostructure in a direction along the film planes in thin TEM foils. The advantage is that the properties can be directly correlated to the local atomic structure. The specimens are cross section TEM samples prepared with standard grinding, polishing and ion beam milling techniques
We describe a new type of scanning electron microscope which works by directly imaging the electron field-emission sites on a nanotip. Electrons are extracted from the nanotip through a nanoscale aperture, accelerated in a high electric field and focussed to a spot using a microscale einzel lens. If the whole microscope (accelerating section and lens) and the focal length are both restricted in size to below 10 microns, then computer simulations show that the effects of aberration are extremely small and it is possible to have a system with approximately unit magnification, at electron energies as low as 300 eV. Thus a typical emission site of 1 nm diameter will produce an image of the same size and an atomic emission site with give a resolution of 0.1-0.2 nm (1-2 Å), and because the beam is not allowed to expand beyond 100nm in diameter the depth of field is large and the contribution to the beam spot size from chromatic aberrations is less than 0.02 nm (0.2 Å) for 500 eV electrons. Since it is now entirely possible to make stable atomic sized emitters (nanopyramids) it is expected that this instrument will have atomic resolution. Furthermore the brightness of the beam is determined only by the field-emission and can be up to a million times larger than in a typical (high-energy) electron microscope. The construction of this microscope, based on using a nanotip electron source which is mounted on a nanopositioner so that it can be positioned at the correct point adjacent to the microscope, entrance aperture, is described. In this geometry the scanning is achieved by moving the sample using piezos. Two methods for the construction of the microscope column are reviewed and the results of preliminary tests are described. The advantages of this low energy, bright-beam, electron microscope with atomic resolution are described. It can be used in either scanning mode or diffraction mode. The major advantage over existing microscopes is that because it works at very low energies the elastic backscattering is sensitive to the atomic species and so these can be identified directly without any energy discrimination on the detector. Furthermore it is also possible to use the microscope to do low energy electron diffraction which, because the scattering cross-section is large, can be carried out on single molecules. If these are biological samples such as DNA, proteins and viruses then the low energy means that the radiation damage is minimised. Some possibilities for mounting these samples, which can reduce radiation damage, are discussed. Finally we show a system for producing holograms of single protein molecules
Electrons backscattered from a scanning tunnelling microscope operating in the field emission mode have been collected to produce images of a rough Si(111) surface. We have obtained a spatial resolution of about 40 nm in such images. Comparison between backscattered electron images and topographic images reveals that edge enhancement and shadowing are important contrast mechanisms.
Electrical characterization of nanostructures, such as nanotubes and wires, is a demanding task that is vital for future applications of nanomaterials. The nanostructures should ideally be analyzed in a free-standing state and also allow for other material characterizations to be made of the same individual nanostructures. Several methods have been used for electrical characterizations of carbon nanotubes in the past. The results are widely spread, both between different characterizations methods and within the same materials. This raises questions regarding the reliability of different methods and their accuracy, and there is a need for a measurement standard and classification scheme for carbon nanotube materials. Here we examine a two-probe method performed inside a transmission electron microscope in detail, addressing specifically the accuracy by which the electrical conductivity of individual carbon nanotubes can be determined. We show that two-probe methods can be very reliable using a suitable thermal cleaning method of the contact points. The linear resistance of the outermost nanotube wall can thus be accurately determined even for the highest crystallinity materials, where the linear resistance is only a few kΩ/µm. The method can thereby by used as a valuable tool for future classification schemes of various nanotube material classes.
The material properties of graphene and carbon nanotubes are highly sensitive to defects. Future exploitation of these materials will thereby rely on both a detailed understanding and classification schemes for material quality. Here we have used electron diffraction to measure the mean effective crystallite size of individual multiwalled carbon nanotubes, while also probing their electrical resistance. At room temperature we find a drastic shift in linear resistance of two orders of magnitude at a critical grain size of about 11 nm, which we interpret as an effect from quantum confinement and edge effects in the individual crystallites. For the regions above and below the critical grain size value we suggest a scaling model for the electrical conductivity within a single layer of a multiwalled carbon nanotube which connects its electrical conductivity with the effective crystallite size and tube diameter.
The different fabrication methods that have been developed for making carbon nanotubes will provide materials with different levels of crystallinity. As crystallinity is qualitatively known to have a profound influence on material properties, this raises the need for standardised quantitative analysis. Here we show how transmission electron microscopy can be used to provide quantitative information about effective crystallite sizes in individual nanotubes which we link to the mechanical behaviour of the tubes. The method relies on a thorough analysis of diffraction patterns and a careful extraction of instrumental and sample contributions to the peak shapes. We find that arc-discharge grown tubes have crystallite sizes that are comparable to the circumference of the outer tube walls, while commercial catalytically grown tubes have much smaller crystallites implying that each cylindrical nanotube wall can be thought of as a patchwork of small graphene-like grains. The clear differences in crystallite sizes are then compared to known differences in mechanical behaviour, such as a substantial disparity in stiffness and significantly different behaviours under bending stress.
We have measured the bending stiffness of as-grown vertically aligned carbon nanofibers using atomic force microscopy inside a scanning electron microscope. We show that the assumption of a uniform internal structure is inadequate in describing nanofibers mechanical properties and that a dual phase model is needed. We present a model in which different Young’s moduli are assigned to the inner graphitic core and the outer amorphous carbon shell and show that it provides a better fit to the measurements. We obtain values of 11±8 GPa and 63±14 GPa for the Young’s modulus of the inner core and the outer shell, respectively.
Vertically aligned carbon nanofibers (VACNFs) are synthesized in a plasma-enhanced chemical vapor deposition process (PECVD) in which the position, diameter, length, and alignment of individual nanofibers can be controlled accurately. This has provided an unprecedented opportunity to realize a new bottom-up-engineered material with excellent mechanical and electrical properties which could exploit the third dimension at a reasonable cost. VACNFs have been already employed in a number of applications including electron emitters, gene delivery arrays, and nanoelectromechanical systems. However, no direct measurement of the Young’s modulus of VACNFs has been reported yet. Qi et al. have used nanoindentation method to measure the collective response of a forest of VACNFs with a distribution in length and diameter of the constituent nanofibers. Kaul et al., have reported in situ uniaxial compression tests on individual VACNFs but they have not provided enough information to evaluate the accuracy of their measurements. Indirect estimation of the VACNFs Young’s modulus has also been reported by Eriksson et al. from measurements of the resonance frequency of a nanofiber deposited on top of an excitation electrode. Here, we report on direct measurements of VACNFs Young’s modulus using a piezoresistive atomic force microscope (AFM) cantilever implemented inside a scanning electron microscope (SEM). The VACNFs were grown from Ni catalyst seeds, patterned using electron-beam lithography on top of a stoichiometric TiN underlayer. The VACNFs were grown in a commercially available PECVD chamber (AIXTRON BlackMagic™). The nanofibers were approached from the side and pushed at the tip (resembling a cantilever beam) and force-deflection curves were obtained. By calibrating the AFM sensor the bending stiffness of the nanofiber could be determined. The Young’s modulus was then estimated by taking the nanofibers dimensions into account. The sub-nano Newton force precision provided by the AFM force-sensor together with the fact the individual VACNFs could be observed in the SEM simultaneously during the measurements, has enabled us to measure the nanofibers Young’s modulus with a high precision. Preliminary measurements indicate that VACNFs posses a Young’s modulus between 40 to 100 GPa which is comparable to CVD grown carbon nanotubes of similar diameter
We explore the growth of vertically aligned carbon nanofibers by plasma enhanced chemical vapor deposition, using lithographically defined Ni catalyst seeds on TiN. TiN is selected for being an electrically conducting diffusion barrier suitable for the realization of electronic devices. We show that the rate of Ni diffusion correlates to both the level of oxygen content in the TiN film and to the film resistivity. The synthesis of the nanofibers was characterized using electron microscopy with an emphasis on three growth parameters: substrate temperature, plasma power, and chamber pressure. We propose that a catalyst surface free from carbon deposits throughout the process will induce diffusion-limited growth. The growth will shift towards a supply-limited process when the balance between acetylene, as the effective carbon bearing gas, and atomic hydrogen, as the main etching agent, is skewed in favor of acetylene. This determines whether the dominating growth mode will be vertically aligned tip-type or disordered base-type, by affecting the competition between the formation of the first graphitic sheets on the catalyst surface and at the catalyst-substrate interface
Thermal treatment of carbon nanotubes (CNTs) can significantly improve their mechanical, electrical and thermal properties due to reduced defects and increased crystallinity. In this work we investigate the effect of annealing at 3000 degrees C of vertically aligned CNT arrays synthesized by chemical vapor deposition (CVD) on graphite. Raman measurements show a drastically reduced amount of defects and, together with transmission electron microscope (TEM) diffraction measurements, an increased average crystallite size of around 50%, which corresponds to a 124% increase in Young's modulus. We also find a tendency for CNTs to bond to each other with van der Waals (vdW) forces, which causes individual CNTs to closely align with each other. This bonding causes a densification effect on the entire CNT array, which appears at temperatures >1000 degrees C. The densification onset temperature corresponds to the thermal decomposition of oxygen containing functional groups, which otherwise prevents close enough contact for vdW bonding. Finally, the remaining CVD catalyst on the bottom of the CNT array is evaporated during annealing, enabling direct anchoring of the CNTs to the underlying graphite substrate.
Adsorption of atomic hydrogen has a remarkable influence on the structure and morphology of the Cu(100) surface. We have examined two specific situations; the well-known reconstructed p(2 × 2)-H surface and a one-dimensional (6 × 1)-H surface resembling the stripe reconstruction observed in an electrochemical environment. High resolution electron energy loss spectroscopy and density functional calculations show that the H atoms occupy only surface sites and that H bonding in induced 3-fold Cu surface hollow sites is a structural key element. The calculations support a transient scenario in which H absorption in subsurface sites is a critical intermediate step in the reconstruction of the Cu surface. We find clear evidence in terms of characteristic properties, like the H–Cu bond lengths and the dipole excited vibrational mode spectra, that these structures consist of two-dimensional and one-dimensional structures of surface hydride.
Characterizing physical properties of individual nanotubes is crucial for their implementation in nano electromechanical systems (NEMS). This requires measurements on suspended or free-standing structures together with accurate determination of the nanotubes dimensions. In situ methods are often used where physical measurements are performed inside electron microscopes [1-3]. Transmission electron microscopy (TEM) has the advantage of high resolution, providing accurate determination of both dimensions and the internal structure. The space inside a TEM is however rather restricted, leaving limited room for additional probes [4]. Scanning electron microscopy (SEM) on the other hand, has a large specimen chamber which facilitates the addition of probes, but the image resolution is lower, making the evaluation of material properties less accurate or even impossible for very thin nanotubes [1]. One way to solve this is to first measure the physical properties inside an SEM, and then determine the diameter using a TEM afterwards [1]. This approach requires transfer of the nanotube from the SEM to a suitable TEM sample holder, and analysis of the same sample-location in both instruments. It would thereby be advantageous to obtain accurate structural information directly inside the SEM [2]. We have studied the mechanisms involved in SEM image formation of small multiwalled nanotubes, 2-5 nm in diameter. The electron-probe shape in an SEM broadens the sample details, and the image can be seen as a convolution of the secondary electron yield at each sample position and the probe shape. By comparing SEM and TEM images, we found that the probe intensity profile was best described by a linear combination of Gaussian and Lorentzian distributions. Using the obtained probe shape, the SEM images could then be deconvoluted to reveal more details, including the inner diameter in some cases. We also show how the outer diameter can be obtained by differentiating image profiles, a method that does not require any detailed knowledge regarding the probe shape and is reliable down to dimensions comparable to the electron-probe size. This significantly improves the capabilities of in-situ SEM experiments by enabling accurate characterizations of nanofibres inside SEM instruments, without the need for subsequent TEM imaging
We present a detailed analysis of the image formation mechanisms that are involved in the imaging of carbon nanotubes with scanning electron microscopy (SEM). We show how SEM images can be modelled by accounting for surface enhancement effects together with the absorption coefficient for secondary electrons, and the electron-probe shape. Images can then be deconvoluted, enabling retrieval of the intrinsic nanotube dimensions. Accurate estimates of their dimensions can thereby be obtained even for structures that are comparable to the electron-probe size (on the order of 2 nm). We also present a simple and robust model for obtaining the outer diameter of nanotubes without any detailed knowledge about the electron-probe shape.
We present a detailed experimental study of the onset of rippling in highly crystalline carbon nanotubes. Modeling has shown that there should be a material constant, called the critical length, describing the dependence of the critical strain on the nanotube outer radius. Surprisingly, we have found very large variations, by a factor of three, in the critical length. We attribute this to a supporting effect from the inner walls in multiwalled concentric nanotubes. We provide an analytical expression for the maximum deflection prior to rippling, which is an important design consideration in nanoelectromechanical systems utilizing nanotubes.
We report measurements of the bending stiffness in free standing carbon nanotubes, using atomic force microscopy inside a scanning electron microscope. Two regimes with different bending stiffness were observed, indicative of a rippling deformation at high curvatures. The observed critical strains for rippling were in the order of a few percent and comparable to previous modeling predictions. We have also found indications that the presence of defects can give a higher critical strain value and a concomitant reduction in Youngs modulus.
We have studied the mechanical behavior of multi-walled carbon nanotubes for bending strains beyond the onset for rippling and buckling. We found a characteristic drop in the bending stiffness at the rippling and buckling onset and the relative retained stiffness was dependent on the nanotube dimensions and crystallinity. Thin tubes are more prone to buckle, where some lose all of their bending stiffness, while thicker tubes are more prone to ripple and on average retain about 20\% of their bending stiffness. In defect rich tubes the bending stiffness is very low prior to rippling but these tubes retain up to 70\% of their initial bending stiffness.
We present a measurement system that combines an environmental scanning electron microscope (ESEM) and an atomic force microscope (AFM). This combination enables studies of static and dynamic mechanical properties of hydrated specimens, such as individual living cells. The integrated AFM sensor provides direct and continuous force measurement based on piezoresistive force transduction, allowing the recording of events in the millisecond range. The in situ ESEM-AFM setup was used to study Pichia pastoris wild-type yeast cells. For the first time, a quantified measure of the osmotic response of an individual yeast cell inside an ESEM is presented. With this technique, cell size changes due to humidity variations can be monitored with nanometre accuracy. In addition, mechanical properties were extracted from load–displacement curves. A Young's modulus of 13–15 MPa was obtained for the P. pastoris yeast cells. The developed method is highly interesting as a complementary tool for the screening of drugs directed towards cellular water transport activity and provides new possibilities of studying mechanosensitive regulation of aquaporins.
Environmental scanning electron microscopy has been extensively used for studying the wetting properties of different materials. For some types of investigation, however, the traditional ways of conducting in situ dynamic wetting experiments do not offer sufficient control over the wetting process. Here, we present a novel method for controlled wetting of materials in the environmental scanning electron microscope (ESEM). It offers improved control of the point of interaction between the water and the specimen and renders it more accessible for imaging. It also enables the study of water transport through a material by direct imaging. The method is based on the use of a piezo-driven nanomanipulator to bring a specimen in contact with a water reservoir in the ESEM chamber. The water reservoir is established by local condensation on a Peltier-cooled surface. A fixture was designed to make the experimental setup compatible with the standard Peltier cooling stage of the microscope. The developed technique was successfully applied to individual cellulose fibers, and the absorption and transport of water by individual cellulose fibers were imaged.
This article overviews the scientific results of the microstructural features observed in 316 L stainless steel manufactured by the laser powder bed fusion (LPBF) method obtained by the authors, and discusses the results with respect to the recently published literature. Microscopic features of the LPBF microstructure, i.e., epitaxial nucleation, cellular structure, microsegregation, porosity, competitive colony growth, and solidification texture, were experimentally studied by scanning and transmission electron microscopy, diffraction methods, and atom probe tomography. The influence of laser power and laser scanning speed on the microstructure was discussed in the perspective of governing the microstructure by controlling the process parameters. It was shown that the three-dimensional (3D) zig-zag solidification texture observed in the LPBF 316 L was related to the laser scanning strategy. The thermal stability of the microstructure was investigated under isothermal annealing conditions. It was shown that the cells formed at solidification started to disappear at about 800 °C, and that this process leads to a substantial decrease in hardness. Colony boundaries, nevertheless, were quite stable, and no significant grain growth was observed after heat treatment at 1050 °C. The observed experimental results are discussed with respect to the fundamental knowledge of the solidification processes, and compared with the existing literature data.
Today many applications require new effective approaches in energy delivery on demand. Supercapacitors are viewed as essential energy storage devices that can continuously provide quick energy. The performance of supercapacitors is mostly determined by electrode materials that can store energy via electrostatic charge accumulation. This study presents new sustainable cellulose-derived composite electrodes which consist of carbon nanofibrous (CNF) mats covered with vapor-grown carbon nanotubes (CNTs). The CNF/CNT electrodes have high electrical conductivity and surface area: two most important features that are responsible for good electrochemical performance of supercapacitor electrodes. The results show that the composite electrodes have fairly high values of specific capacitance, energy and power density and can retain excellent performance over at least 2 000 cycles. All of that makes us think that sustainable cellulose-derived composites can be extensively used in future as supercapacitor electrodes.