Materials science: The ultrasmoothness of diamond-like carbon surfaces

The ultrasmoothness of diamond-like carbon coatings is explained by an atomistic/continuum multiscale model. At the atomic scale, carbon ion impacts induce downhill currents in the top layer of a growing film. At the continuum scale, these currents cause a rapid smoothing of initially rough substrates by erosion of hills into neighboring hollows. The predicted surface evolution is in excellent agreement with atomic force microscopy measurements. This mechanism is general, as shown by similar simulations for amorphous silicon. It explains the recently reported smoothing of multilayers and amorphous transition metal oxide films and underlines the general importance of impact-induced downhill currents for ion deposition, polishing, and nanopattering.

90° domain dynamics and relaxation in thin ferroelectric/ferroelastic films

We investigated the dynamics and relaxation of 90° domains in 60-nm-thick lead-zirconium titanate (PbZr0.3 T0.7 O3) films, with enhanced piezoresponse force microscopy. We show that under opposite electric fie ld, ferroelectric domains are reversibly switched while ferroelastic domains reorganize in a nonreversible way. Moreover, we show that the relaxation-time constant of 90° domains is two orders of magnitude shorter than for the previously reported 180° domains relaxation. Furthermore, we demonstrate the influence of geometry and scale on the relaxation process. Finally, we propose a relaxation mechanism for ferroelastic-ferroelectric systems, with implications for devices based on these materials. © 2010 The American Physical Society.

A single-rate context-dependent learning process underlies rapid adaptation to familiar object dynamics.

Motor learning has been extensively studied using dynamic (force-field) perturbations. These induce movement errors that result in adaptive changes to the motor commands. Several state-space models have been developed to explain how trial-by-trial errors drive the progressive adaptation observed in such studies. These models have been applied to adaptation involving novel dynamics, which typically occurs over tens to hundreds of trials, and which appears to be mediated by a dual-rate adaptation process. In contrast, when manipulating objects with familiar dynamics, subjects adapt rapidly within a few trials. Here, we apply state-space models to familiar dynamics, asking whether adaptation is mediated by a single-rate or dual-rate process. Previously, we reported a task in which subjects rotate an object with known dynamics. By presenting the object at different visual orientations, adaptation was shown to be context-specific, with limited generalization to novel orientations. Here we show that a multiple-context state-space model, with a generalization function tuned to visual object orientation, can reproduce the time-course of adaptation and de-adaptation as well as the observed context-dependent behavior. In contrast to the dual-rate process associated with novel dynamics, we show that a single-rate process mediates adaptation to familiar object dynamics. The model predicts that during exposure to the object across multiple orientations, there will be a degree of independence for adaptation and de-adaptation within each context, and that the states associated with all contexts will slowly de-adapt during exposure in one particular context. We confirm these predictions in two new experiments. Results of the current study thus highlight similarities and differences in the processes engaged during exposure to novel versus familiar dynamics. In both cases, adaptation is mediated by multiple context-specific representations. In the case of familiar object dynamics, however, the representations can be engaged based on visual context, and are updated by a single-rate process.

Increasing the design strength of glass – fractography and stress testing

Brittleness is the unintended, but inevitable consequence of producing a transparent ceramic for architectural applications such as the soda-lime glass. Its tensile strength is particularly sensitive to surface imperfections, such as that from natural weathering and malicious damage. Although a significant amount of testing of new glass has been carried out, there has been surprisingly little testing on weathered glass. Due to the variable nature of the causes of surface damage, the lack of data on weathered glass leads to a considerable degree of uncertainty in the long-term strength of exposed glass. This paper presents the results of recent tests on weathered annealed glass which has been exposed to natural weathering for more than 20 years. The tests include experimental investigations using the co-axial ring setup as well as optical and atomic force microscopy of the glass surfaces. The experimental data from these tests is subsequently used to extend existing fracture mechanics-based models to predict the strength of weathered glass. It is shown that using an automated approach based directly on finite element analysis results can give an increase in effective design strength in the order of 70 to 100% when compared to maximum stress methods. It is also shown that by combining microscopy and strength test results, it is possible to quantitatively characterise the damage on glass surfaces.

Optical trapping of carbon nanotubes and graphene

We study optical trapping of nanotubes and graphene. We extract the distribution of both centre-of-mass and angular fuctuations from three-dimensional tracking of these optically trapped carbon nanostructures. The optical force and torque constants are measured from auto and cross-correlation of the tracking signals. We demonstrate that nanotubes enable nanometer spatial, and femto-Newton force resolution in photonic force microscopy by accurately measuring the radiation pressure in a double frequency optical tweezers. Finally, we integrate optical trapping with Raman and photoluminescence spectroscopy demonstrating the use of a Raman and photoluminescence tweezers by investigating the spectroscopy of nanotubes and graphene fakes in solution. Experimental results are compared with calculations based on electromagnetic scattering theory. © 2011 by the Author(s); licensee Accademia Peloritana dei Pericolanti, Messina, Italy.

Ferroelectric-carbon nanotube memory devices

One-dimensional ferroelectric nanostructures, carbon nanotubes (CNT) and CNTinorganic oxides have recently been studied due to their potential applications for microelectronics. Here, we report coating of a registered array of aligned multi-wall carbon nanotubes (MWCNT) grown on silicon substrates by functional ferroelectric Pb(Zr,Ti)O 3 (PZT) which produces structures suitable for commercial prototype memories. Microstructural analysis reveals the crystalline nature of PZT with small nanocrystals aligned in different directions. First-order Raman modes of MWCNT and PZT/MWCNT/n-Si show the high structural quality of CNT before and after PZT deposition at elevated temperature. PZT exists mostly in the monoclinic Cc/Cm phase, which is the origin of the high piezoelectric response in the system. Lowloss square piezoelectric hysteresis obtained for the 3D bottom-up structure confirms the switchability of the device. Currentvoltage mapping of the device by conducting atomic force microscopy (c-AFM) indicates very low transient current. Fabrication and functional properties of these hybrid ferroelectriccarbon nanotubes is the first step towards miniaturization for future nanotechnology sensors, actuators, transducers and memory devices. © 2012 IOP Publishing Ltd.

Controllable chemical vapor deposition of large area uniform nanocrystalline graphene directly on silicon dioxide

Metal-catalyst-free chemical vapor deposition (CVD) of large area uniform nanocrystalline graphene on oxidized silicon substrates is demonstrated. The material grows slowly, allowing for thickness control down to monolayer graphene. The as-grown thin films are continuous with no observable pinholes, and are smooth and uniform across whole wafers, as inspected by optical-, scanning electron-, and atomic force microscopy. The sp 2 hybridized carbon structure is confirmed by Raman spectroscopy. Room temperature electrical measurements show ohmic behavior (sheet resistance similar to exfoliated graphene) and up to 13 of electric-field effect. The Hall mobility is ∼40 cm 2/Vs, which is an order of magnitude higher than previously reported values for nanocrystalline graphene. Transmission electron microscopy, Raman spectroscopy, and transport measurements indicate a graphene crystalline domain size ∼10 nm. The absence of transfer to another substrate allows avoidance of wrinkles, holes, and etching residues which are usually detrimental to device performance. This work provides a broader perspective of graphene CVD and shows a viable route toward applications involving transparent electrodes. © 2012 American Institute of Physics.

Optical trapping of nanotubes with cylindrical vector beams

We use laser beams with radial and azimuthal polarization to optically trap carbon nanotubes. We measure force constants and trap parameters as a function of power showing improved axial trapping efficiency with respect to linearly polarized beams. The analysis of the thermal fluctuations highlights a significant change in the optical trapping potential when using cylindrical vector beams. This enables the use of polarization states to shape optical traps according to the particle geometry, as well as paving the way to nanoprobe-based photonic force microscopy with increased performance compared to a standard linearly polarized configuration. © 2012 Optical Society of America.

Performing quantitative MFM measurements on soft magnetic nanostructures.

We have extended our previous work (Rawlings et al 2010 Phys. Rev. B 82 085404) on simulating magnetic force microscopy (MFM) images for magnetically soft samples to include an accurate representation of coated MFM tips. We used an array of square 500 nm nanomagnets to evaluate our improved MFM model. A quantitative comparison between model and experiment was performed for lift heights ranging from 20 to 100 nm. No fitting parameters were used in our comparison. For all lift heights the qualitative agreement between model and experiment was significantly improved. At low lift heights, where the magnetic signal was strong, the difference between theory and experiment was less than 30%.

Nucleation, growth, and control of ferroelectric-ferroelastic domains in thin polycrystalline films

The unique response of ferroic materials to external excitations facilitates them for diverse technologies, such as nonvolatile memory devices. The primary driving force behind this response is encoded in domain switching. In bulk ferroics, domains switch in a two-step process: nucleation and growth. For ferroelectrics, this can be explained by the Kolmogorov-Avrami-Ishibashi (KAI) model. Nevertheless, it is unclear whether domains remain correlated in finite geometries, as required by the KAI model. Moreover, although ferroelastic domains exist in many ferroelectrics, experimental limitations have hindered the study of their switching mechanisms. This uncertainty limits our understanding of domain switching and controllability, preventing thin-film and polycrystalline ferroelectrics from reaching their full technological potential. Here we used piezoresponse force microscopy to study the switching mechanisms of ferroelectric-ferroelastic domains in thin polycrystalline Pb 0.7Zr0.3TiO3 films at the nanometer scale. We have found that switched biferroic domains can nucleate at multiple sites with a coherence length that may span several grains, and that nucleators merge to form mesoscale domains, in a manner consistent with that expected from the KAI model. © 2012 American Physical Society.

Properties of trench defects in InGaN/GaN quantum well structures

The structural and optical properties of trench defects, which are poorly understood yet commonly occurring defects observed on the surfaces of InGaN multiple quantum wells (MQW), are reported. These defects comprise near-circular trenches which enclose areas of MQW which give rise to a red shift in peak photoluminescence emission and a change in cathodoluminescence intensity with respect to the surrounding material. Atomic force microscopy shows that the height of trench-enclosed areas differs from that of the surrounding quantum well structure, and that trenches are unrelated to the commonly observed V-defects in InGaN films, despite being occasionally intersected by them. Cross-sectional electron microscopy analysis of trenches with raised centres suggests that the red shift in the observed cathodoluminescence peak emission may be due to the quantum wells being thicker in the trench-enclosed regions than in the surrounding quantum well area. The mechanism of trench formation and its implication for the control of the emission properties of light-emitting diodes is discussed. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Correlations between the morphology and emission properties of trench defects in InGaN/GaN quantum wells

Atomic force microscopy (AFM) and scanning electron microscopy (SEM) with cathodoluminescence (CL) were performed on exactly the same defects in a blue-emitting InGaN/GaN multiple quantum well (QW) sample enabling the direct correlation of the morphology of an individual defect with its emission properties. The defects in question are observed in AFM and SEM as a trench partially or fully enclosing a region of the QW having altered emission properties. Their sub-surface structure has previously been shown to consist of a basal plane stacking fault (BSF) in the plane of the QW stack, and a stacking mismatch boundary (SMB) which opens up into a trench at the sample surface. In CL, the material enclosed by the trench may emit more or less intensely than the surrounding material, but always exhibits a redshift relative to the surrounding material. A strong correlation exists between the width of the trench and both the redshift and the intensity ratio, with the widest trenches surrounding regions which exhibit the brightest and most redshifted emission. Based on studies of the evolution of the trench width with the number of QWs from four additional MQW samples, we conclude that in order for a trench defect to emit intense, strongly redshifted light, the BSF must be formed in the early stages of the growth of the QW stack. The data suggest that the SMB may act as a non-radiative recombination center. © 2013 American Institute of Physics.

Self-assembled multilayer graphene oxide membrane and carbon nanotubes synthesized using a rare form of natural graphite

The fabrication of flexible multilayer graphene oxide (GO) membrane and carbon nanotubes (CNTs) using a rare form of high-purity natural graphite, vein graphite, is reported for the first time. Graphite oxide is synthesized using vein graphite following Hummer's method. By facilitating functionalized graphene sheets in graphite oxide to self-assemble, a multilayer GO membrane is fabricated. Electric arc discharge is used to synthesis CNTs from vein graphite. Both multilayer GO membrane and CNTs are investigated using microscopy and spectroscopy experiments, i.e., scanning electron microscopy (SEM), atomic force microscopy (AFM), high-resolution transmission electron microscopy (HRTEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), core level photoelectron spectroscopy, and C K-edge X-ray absorption spectroscopy (NEXAFS), to characterize their structural and topographical properties. Characterization of vein graphite using different techniques reveals that it has a large number of crystallites, hence the large number of graphene sheets per crystallite, preferentially oriented along the (002) plane. NEXAFS and core level spectra confirm that vein graphite is highly crystalline and pure. Fourier transform infrared (FT-IR) and C 1s core level spectra show that oxygen functionalities (-C-OH, -CO,-C-O-C-) are introduced into the basal plane of graphite following chemical oxidation. Carbon nanotubes are produced from vein graphite through arc discharge without the use of any catalyst. HRTEM confirm that multiwalled carbon nanotube (MWNTs) are produced with the presence of some structure in the central pipe. A small percentage of single-walled nanotubes (SWNTs) are also produced simultaneously with MWNTs. Spectroscopic and microscopic data are further discussed here with a view to using vein graphite as the source material for the synthesis of carbon nanomaterials. © 2013 American Chemical Society.

Between scylla and charybdis: Hydrophobic graphene-guided water diffusion on hydrophilic substrates

The structure of water confined in nanometer-sized cavities is important because, at this scale, a large fraction of hydrogen bonds can be perturbed by interaction with the confining walls. Unusual fluidity properties can thus be expected in the narrow pores, leading to new phenomena like the enhanced fluidity reported in carbon nanotubes. Crystalline mica and amorphous silicon dioxide are hydrophilic substrates that strongly adsorb water. Graphene, on the other hand, interacts weakly with water. This presents the question as to what determines the structure and diffusivity of water when intercalated between hydrophilic substrates and hydrophobic graphene. Using atomic force microscopy, we have found that while the hydrophilic substrates determine the structure of water near its surface, graphene guides its diffusion, favouring growth of intercalated water domains along the C-C bond zigzag direction. Molecular dynamics and density functional calculations are provided to help understand the highly anisotropic water stripe patterns observed.

Reversible nanoscale switching of polytwin orientation in a ferroelectric thin film induced by a local electric field

The response to a local, tip-induced electric field of ferroelastic domains in thin polycrystalline lead zirconate titanate films with predominantly (110) orientation has been studied using Enhanced Piezoresponse Force Microscopy. Two types of reversible polytwin switching between well-defined orientations have been observed. When a-c domains are switched to other forms of a-c domains, the ferroelastic domain walls rotate in-plane by 109.5°, and when a-c domains are switched to c-c domains (or vice-versa), the walls rotate by 54.75°. © 2013 AIP Publishing LLC.