Three-dimensional Atomic Force Microscopy Research Articles

Light-induced enhancement of quantum dot photovoltaic devices with nitrogen doped titanium oxide capping layers

For the first time it is reported that nitrogen-doped titanium oxide with light annealing can improve the device performance by 300% when acting as an interfacial layer between CdSe quantum dot/poly-3-hexylthiophene and the cathode in the photovoltaic devices. Substitutional N doping with a concentration of 1.2at.% was found by X-ray photoelectron spectroscopy which was responsible for 0.1eV band gap reduction of TiOx. Photoluminescence and the external quantum efficiency spectrum confirmed the enhanced charge collection and association rate after light annealing. Three-dimensional atomic force microscopy results agreed with the series resistance measurements, confirming that a good contact was achieved. The topography study also indicated that the active layer morphology changed upon light annealing. Improved stability and longer lifetime were also found with TiOxNy capped devices, which were optimized with light annealing. TiOx capped devices were also evaluated for comparison in this study.

Three-Dimensional Atomic Force Microscopy: Interaction Force Vector by Direct Observation of Tip Trajectory

The prospect of a robust three-dimensional atomic force microscope (AFM) holds significant promise in nanoscience. Yet, in conventional AFM, the tip-sample interaction force vector is not directly accessible. We scatter a focused laser directly off an AFM tip apex to rapidly and precisely measure the tapping tip trajectory in three-dimensional space. This data also yields three-dimensional cantilever spring constants, effective masses, and hence, the tip-sample interaction force components via Newton's second law. Significant lateral forces representing 49 and 13% of the normal force (Fz = 152 ± 17 pN) were observed in common tapping mode conditions as a silicon tip intermittently contacted a glass substrate in aqueous solution; as a consequence, the direction of the force vector tilted considerably more than expected. When addressing the surface of a lipid bilayer, the behavior of the force components differed significantly from that observed on glass. This is attributed to the lateral mobility of the lipid membrane coupled with its elastic properties. Direct access to interaction components Fx, Fy, and Fz provides a more complete view of tip dynamics that underlie force microscope operation and can form the foundation of a three-dimensional AFM in a plurality of conditions.

Amino Acid Precursors from a Simulated Lower Atmosphere of Titan: Experiments of Cosmic Ray Energy Source with 13C- and 18O-Stable Isotope Probing Mass Spectrometry

The organic haze of aerosols that shrouds the Saturnian moon Titan has previously been studied by both observations and laboratory simulation experiments. Here we report the abiotic formation of amino acid precursors in complex organic molecules during experimental simulation of the environment near Titan's surface with proton irradiation. Pyrolysis of the organic molecules formed in the simulated Titan atmosphere by proton irradiation at 600°C yielded compounds that contained HCN and NH₃ (m/z = 27 and 17). These experimental results are consistent with the molecular information obtained by pyrolysis gas chromatography/mass spectrometry (pyrolysis GC/MS) of samples collected by the Huygens probe to Titan. Scanning electron microscopy (SEM) and three-dimensional atomic force microscopy (AFM) images of the irradiation products reveal nanometer-scale filaments and globules in complex amorphous structures (approximately 1000 Da). Isotope probing experiments by matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS) show that oxygen atoms were incorporated into the racemic amino acids by hydrolysis of ¹⁸O-labeled water. We suggest that the amino acid precursors possibly formed after water hydrolysis, as suggested in a previous observational study (C. A. Griffith, T. Owen, T. R. Geballe, J. Rayner, and P. Rannou, Science, 2003, 300, 628). We propose that cosmic rays are a significant and effective energy source for producing complex organics and amino acid precursors in Titan's atmospheric haze.

THE INFLUENCE OF OXYGEN-CONTAINING FUNCTIONAL GROUPS ON THE SURFACE BEHAVIOR AND ROUGHNESS CHARACTERISTICS OF GRAPHENE OXIDE

The effects of oxygen-containing functional groups on the surface roughness of graphene oxide are thoroughly studied using three-dimensional atomic force microscopy images, ball-and-stick model and wire-frame view results. Moreover, X-ray diffraction method and Fourier transform infrared spectroscopy are employed for characterizing the structural and chemical behavior of graphene oxide, respectively. Graphene oxide sheets show a clear concavity on one side when the aggregation of functional groups increased on the other side. This behavior could be the main reason for the surface fluctuation of graphene oxide sheets that is observed in microscopic images. In addition, the individual graphene oxide sheet presents greater values of mean roughness compared to multilayered sheets.

Statistical analysis on morphology development of some semialicyclic polyimides using atomic force microscopy

The morphological features and surface texture parameters of some polyimide films prepared from a flexible and alicyclic dianhydride, in combination with five aromatic diamines, were evaluated by atomic force microscopy (AFM) in order to determine their applicability in electronics. By means of the surface roughness, shape of the surface height distribution, and angular and radial texture, a precise description of the actual surface topographies at the interface with other materials was made. The polyimide structures led to the development of different surface morphologies (from granular to porous and from bumpy to spiky). The relief diversity was described by the entropy of morphology, which had a similar trend with the root mean square roughness, which presents low values, i.e. 0.5-1.8 nm. Three-dimensional AFM images and the corresponding angular spectra, together with texture aspect ratio and texture direction index (close to 1), indicate that no predominant orientation exists on the investigated surfaces. The redundancy in the morphology was associated with the concept of fractals, the maximum redundancy being achieved for the polyimide with the most complex polymer chain conformation. These results provide useful insights in selecting the polyimide structure, which has the optimal morphology, roughness, orientation, bearing properties, or self-similarity for microelectronic applications such as: substrate for display backplanes, planar technology, microelectronic packaging, etc.

Fabrication and morphological characterizations of immobilized silver-loaded titanium dioxide nanoparticles/polyvinyl alcohol nanocomposites

This study is concerned to the immobilization of silver-loaded titanium dioxide (AT) nanoparticles (NPs) into or onto polyvinyl alcohol (PVA) as matrix. The nanocomposites films were fabricated via solution casting method. The optical properties and morphology of the NPs and nanocomposites were characterized by dynamic light scattering, transmission electron microscopy, fourier transform infrared spectroscopy, ultraviolet–visible spectroscopy, contact angle measurements, field emission scanning electron microscopy (FE-SEM), and atomic force microscopy (AFM). The obtained results of FE-SEM analysis for nanocomposites indicate that the 40–80 nm AT NPs are homogenously distributed in PVA matrix. The unsymmetrical parts of peaks and valleys for nanocomposites in three-dimensional AFM images were related to the residual of AT NPs in outsides, although in the majority of locations it showed similar patterns of peaks and valleys. The studies of nanocomposites by using UV revealed that existence of the AT NPs were increased the shield properties against UV light. Reinforcement of PVA with AT nanomaterials enhances the properties of the prepared films and develops their applications in different industrial fields such as packaging.

Surface morphological and compositional changes of GaN films induced by swift heavy-ion irradiations

Wurtzite GaN films irradiated at room temperature with 308 MeV Xe-129(35+) or 230 MeV Pb-208(27+) ions have been studied by atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The three-dimensional AFM images showed that swellings of the GaN films were caused by the ion irradiations at very low fluences. In comparison with the Xe ions, the Pb ions led to a much more pronounced swelling. The XPS results indicated that after the Xe and Pb irradiations, the contents of Ga and N dangling bonds in the GaN increased, and the contents of Ga-O and N-O bonds in the surface layer also increased. In the case of the Pb irradiation, a peak associated with the defect of interstitial N was detected in the N 1s core-level spectrum, implying the formation of N-2 bubbles close to the GaN surface. However, no homonuclear Ga-Ga bond was found according to the related Ga 3d spectrum. The dramatic experimental results are discussed and the distinct difference of irradiation damages in GaN induced individually by the Xe and Pb ions is analyzed.

Percolation effect in copper- and nickel-doped Bi2Te3 crystals

The (0001) surface morphology of Bi2Te3〈M〉 (M = Cu, Ni) layered crystals has been studied using atomic force microscopy (AFM) and scanning electron microscopy. Two- and three-dimensional AFM images reveal charge transport paths through inhomogeneities created by nanostructured elements (5–20 nm) in the Te(1)-Te(1) interlayer spaces. The nanoparticle distribution in the (0001) plane is similar to the arrangement of model two-dimensional percolation clusters on a square lattice. The carrier mobility in Bi2Te3〈0.5 wt % Ni〉 crystals varies anomalously between 80 and 120 K.

New developments at Physikalisch Technische Bundesanstalt in three-dimensional atomic force microscopy with tapping and torsion atomic force microscopy mode and vector approach probing strategy

A new three-dimensional atomic force microscopy (3D-AFM) for true 3D measurements of nanostructures has been developed at Physikalisch Technische Bundesanstalt (PTB), the national metrology institute of Germany. In its configuration, two piezo actuators are applied to drive the AFM cantilever near its vertical and torsional resonant frequencies. In such a way, the AFM tip can probe the surface with a vertical and/or a lateral oscillation, offering high 3D probing sensitivity. For enhancing measurement flexibility as well as reducing tip wear, a vector approach probing (VAP) method is applied. The sample is measured point by point using this method. At each probing point, the tip is approached toward the surface in its normal direction until the desired tip-sample interaction is detected and is then immediately withdrawn from the surface. Preliminary experimental results show promising performance of the PTB system. The measurement of an IVPS 100 sample using a flared AFM tip showed a repeatability of its 3D profiles better than 1 nm (p-v). A single crystal critical dimension reference material having features with almost vertical sidewalls was also measured using a flared AFM tip. These results show that the feature has average left and right sidewall angles of 89.5 and 89.4, respectively. However, the nonuniformity of the feature width within the measurement window of 1 μm may be up to 10 nm. The standard deviation of the average middle CD values from 10 repeated measurements is 0.1 nm. In addition, an investigation of long-term measurement stability was performed on a PTB photomask. The results changed at a rate of about 0.00033 nm per line, which confirms the high measurement stability and the very low tip wear of the system.

Karyotype Analysis of Buckwheat Using Atomic Force Microscopy

Karyotype analysis and classification of buckwheat chromosomes were performed without chemical banding or staining using atomic force microscopy (AFM). Fagopyrum esculentum (common buckwheat) and Fagopyrum tartaricum (Tartarian buckwheat) chromosomes were isolated from root tissues using an enzymatic maceration technique and spread over a glass substrate. Air-dried chromosomes had a surface with ridges, and the height of common and tartary buckwheat were approximately 350 and 150 nm. Volumes of metaphase sets of buckwheat chromosomes were calculated using three-dimensional AFM measurements. Chromosomes were morphologically characterized by the size, volume, arm lengths, and ratios. The calculated volumes of the F. esculentum and F. tartaricum chromosomes were in the ranges of 1.08-2.09 μm3 and 0.49-0.78 μm3, respectively. The parameters such as the relative arm length, centromere position, and the chromosome volumes measured using AFM provide accurate karyomorphological classification by avoiding the subjective inconsistencies in banding patterns of conventional methods. The karyotype evolutionary trend indicates that F. esculentum is an ancient species compared to F. tartaricum. This is the first report of a cytological karyotype of buckwheat using AFM.

Three-dimensional imaging of undercut and sidewall structures by atomic force microscopy

Sidewall surface roughness is an important parameter in electronic device manufacture. At present, no high resolution technique exists to quantitatively characterize this property for undercut structures created by semiconductor processing techniques. We developed a three-dimensional atomic force microscope (3D-AFM) to measure the surface roughness of undercut sidewalls with nanometer precision. Decoupled from the positional scanner, the 3D-AFM probe had a variable tilt up to 40° off the normal. Nonorthogonal scans resolved the sidewall surface roughness, base width, and acute critical angle for undercut structures, including a metal overhang and the transmission line of a photonic device. Compatible with standard cantilevers, the 3D-AFM demonstrates great potential for characterizing the sidewalls of soft materials such as photoresist.

Detailed three-dimensional size and shape characterisation of UHMWPE wear debris

Atomic force microscopy (AFM) is used to characterise UHMWPE wear debris from a knee prosthesis actuated under constant load. The size and shape of debris particles is quantified in all three spatial dimensions. Artificially limiting the analysis to the two-dimensional projections of the particles onto the substrate plane, it has been found that equivalent shape ratio (ESR) plotted as a function of equivalent circle diameter (ECD) follows a trend observed before. Inclusion of the third, vertical spatial dimension of particle height shows that such two-dimensional analysis, as it is often based on SEM images, can greatly misrepresent the actual particle shape. The three-dimensional AFM information indicates that for the prosthesis and the conditions studied here debris particles tend to be deformed independent of their volumetric size. Fractionation of debris particles according to size was achieved with a new filtration protocol. It is demonstrated that with this protocol debris particles settle uniformly across the filter and that particle abundance as function of size can thus reliable be established.

Effects of sodium hypochlorite and ethylenediaminetetraacetic acid on rotary nickel-titanium instruments evaluated using atomic force microscopy

To use atomic force microscopy (AFM) to evaluate the effects of sodium hypochlorite (NaOCl) and ethylenediaminetetraacetic acid (EDTA) on the surface characteristics of ProTaper rotary nickel-titanium instruments. A total of twenty ProTaper (Dentsply Maillefer, Ballaigues, Switzerland) instruments (S1, S2, F1, F2) were divided into five groups: no immersion, immersion in 5.25% NaOCl for 5 or 10min and immersion in 17% EDTA for 5 or 10min. Twenty surface areas along 3-mm sections at the tip of the files (perfect squares of 1x1μm) were analysed by AFM operating in contact mode under ambient conditions. Three-dimensional images (400x400 lines) were processed using Gwyddion software, and the roughness average (Ra) and the root mean square value (RMS) of the scanned surface profiles were recorded. Data were analysed by means of anova and paired samples t-test. Three-dimensional AFM images of the surface of ProTaper instruments, including new and those immersed in NaOCl and EDTA solutions, revealed topographic irregularities at the nanometric scale. RMS and Ra values of instruments treated with NaOCl and EDTA solutions were statistically higher than that of the new ones (P<0.05). Atomic force microscopy three-dimensional images and roughness values indicated that short-term contact between NaOCl and EDTA endodontic irrigants and ProTaper instruments caused alterations in the surface of instruments.

Three‐Dimensional Atomic Force Microscopy – Taking Surface Imaging to the Next Level

Materials properties are ultimately determined by the nature of the interactions between the atoms that form the material. On surfaces, the site-specific spatial distribution of force and energy fields governs the phenomena encountered. This article reviews recent progress in the development of a measurement mode called three-dimensional atomic force microscopy (3D-AFM) that allows the dense, three-dimensional mapping of these surface fields with atomic resolution. Based on noncontact atomic force microscopy, 3D-AFM is able to provide more detailed information on surface properties than ever before, thanks to the simultaneous multi-channel acquisition of complementary spatial data such as local energy dissipation and tunneling currents. By illustrating the results of experiments performed on graphite and pentacene, we explain how 3D-AFM data acquisition works, what challenges have to be addressed in its realization, and what type of data can be extracted from the experiments. Finally, a multitude of potential applications are discussed, with special emphasis on chemical imaging, heterogeneous catalysis, and nanotribology.

Accelerated molecular dynamics simulation of low-velocity frictional sliding

Accelerated molecular dynamics (MD) simulations are implemented to model the sliding process of atomic force microscope (AFM) experiments and to lower the sliding speeds below those in a conventional MD simulation. In this study the hyperdynamics method, originally devised to extend MD time scales for non-driven systems, is applied to the frictional sliding system. This technique is combined with a parallel algorithm that simultaneously simulates the system over a range of slider positions so that the overall acceleration rate is approximately the number of processors multiplied by the boost factor from the hyperdynamics method. The new methodologies are tested using two-dimensional and three-dimensional Lennard-Jones AFM models. Direct comparison with the results from conventional MD shows close agreement validating the methods. The acceleration rate achieved in this study is four orders of magnitude in 2D and three orders of magnitude in 3D.

Atomic-scale simulations on the sliding of incommensurate surfaces: The breakdown of superlubricity

Molecular dynamics simulations of frictional sliding in an atomic force microscope (AFM) show a clear dependence of superlubricity between incommensurate surfaces on tip compliance and applied normal force. While the kinetic friction vanishes for rigid tips and low normal force, superlubric behavior breaks down for softer tips and high normal force. The simulations provide evidence that the Frenkel-Kontorova-Tomlinson (FKT) scaling applies equally to a more realistic three-dimensional (3D) incommensurate AFM model except in the limit of very low stiffness and high normal load. Unlike the FKT model in which the breakdown of superlubricity coincides with the emergence of the metastable states, in the 3D model some metastable states appear to reduce frictional force leading to nonmonotonic dependence of force on normal load and tip compliance. Metastable states vary with the slider positions and the relative stabilities of these metastable states result in varying transition mechanisms depending on sliding velocity.

Atomic force microscopy study of the surface morphology of a TlGaSe2 crystal

The surface morphology of a TlGaSe2 single crystal has been studied by atomic force microscopy (AFM). Using an appropriate imaging mode, we obtained three-dimensional AFM images of the crystal surface, its Fourier spectrum, and height distribution. The crystal is shown to be rather uniform in surface profile, with a local surface height within 25 nm in a 5 × 5 µm area.

Observation of the ultrastructure of anterior cruciate ligament graft by atomic force microscopy

This study presented the fibril ultrastructure of retrieved grafts from the reconstruction of anterior cruciate ligament (ACL) using atomic force microscopy (AFM). The tapping mode images of the AFM were taken from different areas of the longitudinally cut grafts. Regular arrangement of collagen fibrils was found in certain areas of the graft. In many areas, however, the fibrils were not well arranged in a single direction, with some smaller fibrils oriented vertically to larger parallel fibrils. The crossing and tangling of fibrils in ACL grafts was well represented in the three-dimensional AFM image. This abnormality of graft ultrastructure might indicate the possible alteration of the mechanical environment after ACL reconstruction. This study demonstrated the suitability and importance of ultrastructure observation of ACL grafts by AFM.

Estimation of Three-Dimensional Atomic Force Microscope Tip Shape from Atomic Force Microscope Image for Accurate Measurement

We studied methods of estimating three-dimensional (3-D) tip structure using impulse response technique. We have proposed a 3-D tip estimation method using an infinite small diameter standard column as the impulse response technique. The standard column has been made by image processing of a finite-small-diameter-column standard sample by a software elimination technique. We demonstrated how to obtain the 3-D atomic force microscope (AFM) pyramidal tip shape using a commercial pyramidal tip and a 665-nm-diameter-column sample. The estimated tip radii are 10–15 nm in various profiles of the top. The results indicate that the method is effective to estimate a 3-D AFM tip structure in order to obtain an accurate AFM image.

Exocytosis of a Single Bovine Adrenal Chromaffin Cell: The Electrical and Morphological Studies

Exocytosis of a single bovine adrenal chromaffin cell, triggered by histamine stimulation, was investigated via the electric responses detected with single-walled carbon-nanotube field-effect transistors (SWCNT-FET) and the morphological changes acquired by atomic force microscopy (AFM). Secretion of chromogranin A (CgA), stored in the vesicles of a single chromaffin cell, can be monitored in situ by the antibody against CgA (CgA-antibody) functionalized on the SWCNT-FET devices. The SWCNT-FET can further discriminate the amount of released CgA with different levels of histamine stimulations. The AFM morphological studies on a chromaffin cell indicate that the depression structures on the cell surface, caused by the histamine-evoked exocytotic fusion pores, appeared much more frequently than those without histamine stimulation or with the pretreatment of mepyramine before histamine stimulation. The vesicle diameters are about 50 nm calculated from the obtained three-dimensional AFM images. In comparison, the fusion pores of chromaffin cells stimulated by high-K (+) buffer solution were also investigated to have a wider-ranging distribution of vesicle diameters of 60-260 nm. This work demonstrates that the combination of novel techniques, SWCNT-FET and AFM, can provide further insights into the fundamental properties of exocytosis in neuroendocrine cells.