Atomic Force Microscopy Phase Contrast Research Articles

Insight into the photoluminescence and morphological characteristics of transition metals (TM = Mn, Ni, Co, Cu)-doped ZnO semiconductor: a comparative study

In this work, undoped and transition metal (TM = Mn, Ni, Co, Cu)-doped ZnO thin films were grown on Si substrate using the ultrasonic spray pyrolysis technique, adhering to the same deposition conditions to compare their morphological and photoluminescent characteristics. X-ray Photoelectron Spectroscopy (XPS), Atomic Force Microscopy (AFM), and Photoluminescence (PL) spectroscopy were used to investigate the chemical composition, morphology, and luminescence properties, respectively. XPS results indicate that Mn and Ni ions have bivalent and trivalent electronic states coexisting in the ZnO lattice, Cu ions have both monovalent and bivalent states, and Co ions have only bivalent states. Besides, there is a considerable increase in the level of oxygen vacancies observed upon TM doping. The topographic and phase-contrast AFM images, supported by their associated statistical parameters and mean height distribution histograms, reveal that TM doping increases the tendency for crystalline grains to coalesce in 3D, resulting in a more roughened surface, larger grains with prominent boundaries, increased porosity, and an inhomogeneous height distribution. PL spectra of TM-ZnO show a broadening of the ZnO band gap accompanied by different luminescence behavior compared to pure ZnO regarding both UV and visible emissions. CuZnO is characterized by a green luminescence, CoZnO and MnZnO by a red luminescence, and ZnO and NiZnO by a broad visible luminescence. The possible mechanism for defect luminescence in each TM-ZnO sample was systematically investigated. The chromaticity color coordinates of the PL emissions show that the films provide different color regions well distributed on the CIE chromaticity diagram. The findings regarding the coexistence of two valence states of TM doping, the level of oxygen vacancies, the grain coalescence process, and the luminescence characteristics are carefully correlated and discussed herein.

Long-term stability and tree-ring oxidation of WSe2 using phase-contrast AFM.

In this work, we use atomic force microscopy (AFM) to investigate the long-term evolution of oxidative defects of tungsten diselenide (WSe2) in ambient conditions over a period of 75 months, which is the longest such study performed on any layered material. In particular, we find that phase-imaging AFM of mechanically exfoliated WSe2 crystals provides convenient, direct identification of exposed and covered step-edges, and together with topographic thickness measurements allows complete determination of the layer arrangement in a multilayer flake. Step-edges with low or no phase-contrast consistently exhibit long-term stability in ambient conditions, indicating that they are covered and effectively protected by above-lying WSe2 layers. On the contrary, step-edges with initial high phase-contrast are clearly degraded after medium- to long-term exposure to ambient conditions (up to six months), indicating that these are not covered by other layers. Similar behaviour was observed for MoTe2 and MoS2. The correlation between phase-contrast and step order was confirmed by cross-sectional transmission electron microscopy. By comparing the phase-contrast line-traces in different locations and at different times, we find that long-term storage in ambient conditions led to evolution of a distinct ring-like pattern resembling the tree-lines arising from seasonal changes. Indeed the phase-contrast showed correlation with the average amount of sun-hours registered at the storage location. Storage in darkness slowed down the evolution of the tree-ring lines, in accordance with this explanation. Our work provides a unique dataset on long-term degradation of one of the most stable transition metal dichalcogenides, as well as insights into the conditions causing acceleration or inhibition of the degradation process.

Optical anisotropy of interface-bound exciton emission in a-plane ZnO/Zn1-xMgxO MQWs with Zn1-yMgyO buffer layer

The anisotropic exciton emission in a-plane nonpolar ZnO/ZnMgO MQWs offers opportunity for anisotropic photonic devices. By introducing Zn1-yMgyO buffer layer between r-plane sapphire substrate and MQWs, we investigated the structural and optical properties of ten-period a-plane ZnO/Zn1−xMgxO (ZnO/ZnMgO) multiple quantum wells (MQWs) with different widths of Zn1−xMgxO barrier layers grown by pulsed-laser deposition on Zn1-yMgyO buffered r-plane sapphire. Polarization-dependent photoluminescence spectra reveal that two additional linear polarizations of interface-bound exciton emission with E⊥c orienting at ~± 50° with respect to the regular a-plane MQWs are attributed to the generation of (0 0 0 2)-oriented nano-domains (NDs). As evidenced by XRD and TEM, we found four sets of (0 0 0 2)-oriented MQWs NDs are embedded in regular a-plane ZnO/ZnMgO MQWs with 90° in-plane rotation from one another which are inclined by 27.6° towards the [1 1 2¯ 0]-direction of the ZnO/ZnMgO MQWs. The existence of (0 0 0 2)-oriented NDs is further confirmed by the phase-contrast atomic force microscopy that modulates the optical anisotropy of interface-bound exciton emission in a-plane nonpolar ZnO/ZnMgO MQWs.

Atomic Force Microscopy Study of Cross-Sections of Perovskite Layers

Improvement of methods for imaging of the volume structure of photoactive layers is one of the important directions towards development of highly efficient solar cells. In particular, volume structure of photoactive layer has critical influence on perovskite solar cell performance and life time. In this study, a perovskite photoactive layer cross-section was prepared by using Focused Ion Beam (FIB) and imaged by Atomic Force Microscopy (AFM) methods. The proposed approach allows using advances of AFM for imaging structure of perovskites in volume. Two different types of perovskite layers was investigated: FAPbBr3 and MAPbBr3. The heterogeneous structure inside film, which consist of large crystals penetrating the film as well as small particles with sizes of several tens nanometers, is typical for FAPbBr3. The ordered nanocrystalline structure with nanocrystals oriented at 45 degree to film surface is observed in MAPbBr3. An optimized sample preparation route, which includes FIB surface polishing by low energy Ga ions at the angles around 10 degree to surface plane, is described and optimal parameters of surface treatment are discussed. Use of AFM phase contrast method provides high contrast imaging of perovskite structure due to strong dependence of phase shift of oscillating probe on materials properties. The described method of imaging can be used for controllable tuning of perovskite structure by changes of the sample preparation routes.

Three-Dimensional Microphase Separation and Synergistic Permeability in Stacked Lipid-Polymer Hybrid Membranes.

We present new structures of soft-material thin films that augment the functionality of substrate-mediated delivery systems. A hybrid material composed of phospholipids and block copolymers adopts a multilayered membrane structure supported on a solid surface. The hybrid films comprise intentional intramembrane heterogeneities that register across multilayers. These stacked domains convey unprecedented enhancement and control of permeability of solutes across micrometer-thick films. Using grazing incidence X-ray scattering, phase contrast atomic force microscopy, and confocal microscopy, we observed that in each lamella, lipid and polymers partition unevenly within the membrane plane segregating into lipid- or polymer-rich domains. Interestingly, we found evidence that like-domains align in registry across multilayers, thereby making phase separation three-dimensional. Phase boundaries exist over extended length scales to compensate the height mismatch between lipid and polymer molecules. We show that microphase separation in hybrid films can be exploited to augment the capability of drug-eluting substrates. Lipid-polymer hybrid films loaded with paclitaxel show synergistic permeability of drug compared to single-component counterparts. We present a thorough structural study of stacked lipid-polymer hybrid membranes and propose that the presence of registered domains and domain boundaries impart enhanced drug release functionality. This work offers new perspectives in designing thin films for controlled delivery applications.

Direct Observation of Asphaltene Nanoparticles on Model Mineral Substrates.

The propensity for adherence to solid surfaces of asphaltenes, a complex solubility class of heteropolycyclic aromatic compounds from the heavy fraction of crude oil, has long been the root cause of scale deposition and remains an intractable problem in the petroleum industry. Although the adhesion is essential to understanding the process of asphaltene deposition, the relationship between the conformation of asphaltene molecules on mineral substrates and its impact on adhesion and mechanical properties of the deposits is not completely understood. To rationalize the primary processes in the process of organic scale deposition, here we use atomic force microscopy (AFM) to visualize the morphology of petroleum asphaltenes deposited on model mineral substrates. High imaging contrast was achieved by the differential adhesion of the tip between asphaltenes and the mineral substrate. While asphaltenes form smooth continuous films on all substrates at higher concentrations, they deposit as individual nanoparticles at lower concentrations. The size, shape, and spatial distribution of the nanoaggregates are strongly affected by the nature of the substrate; while uniformly distributed spherical particles are formed on highly polar and hydrophilic substrates (mica), irregular islands and thicker patches are observed with substrates of lower polarity (silica and calcite). Asphaltene nanoparticles flatten when adsorbed on highly oriented pyrolytic graphite due to π-π interactions with the polycyclic core. Force-distance profiles provide direct evidence of the conformational changes of asphaltene molecules on hydrophilic/hydrophobic substrates that result in dramatic changes in adhesion and mechanical properties of asphaltene deposits. Such an understanding of the nature of adhesion and mechanical properties tuned by surface properties, on the level of asphaltene nanoaggregates, would contribute to the design of efficient asphaltene inhibitors for preventing asphaltene fouling on targeted surfaces. Unlike flat surfaces, the AFM phase contrast images of defected calcite surfaces show that asphaltenes form continuous deposits to fill the recesses, and this process could trigger the onset for asphaltene deposition.

Visualization of steps and surface reconstructions in Helium Ion Microscopy with atomic precision

Helium Ion Microscopy is known for its surface sensitivity and high lateral resolution. Here, we present results of a Helium Ion Microscopy based investigation of a surface confined alloy of Ag on Pt(111). Based on a change of the work function of 25meV across the atomically flat terraces we can distinguish Pt rich from Pt poor areas and visualize the single atomic layer high steps between the terraces. Furthermore, dechanneling contrast has been utilized to measure the periodicity of the hcp/fcc pattern formed in the 2–3 layers thick Ag/Pt alloy film. A periodicity of 6.65nm along the 〈11¯2〉 surface direction has been measured. In terms of crystallography a hcp domain is obtained through a lateral displacement of a part of the outermost layer by 1/3 of a nearest neighbor spacing along 〈11¯2〉. This periodicity is measured with atomic precision: coincidence between the Ag and the Pt lattices is observed for 23 Ag atoms on 24 Pt atoms. The findings are perfectly in line with results obtained with Low Energy Electron Microscopy and Phase Contrast Atomic Force Microscopy.

Surface Charge and Carbon Contamination on an Electron-Beam-Irradiated Hydroxyapatite Thin Film Investigated by Photoluminescence and Phase Imaging in Atomic Force Microscopy

The surface properties of hydroxyapatite, including electric charge, can influence the biological response, tissue compatibility, and adhesion of biological cells and biomolecules. Results reported here help in understanding this influence by creating charged domains on hydroxyapatite thin films deposited on silicon using electron beam irradiation and investigating their shape, properties, and carbon contamination for different doses of incident injected charge by two methods. Photoluminescence laser scanning microscopy was used to image electrostatic charge trapped at pre-existing and irradiation-induced defects within these domains, while phase imaging in atomic force microscopy was used to image the carbon contamination. Scanning Auger electron spectroscopy and Kelvin probe force microscopy were used as a reference for the atomic force microscopy phase contrast and photoluminescence laser scanning microscopy measurements. Our experiment shows that by combining the two imaging techniques the effects of trapped charge and carbon contamination can be separated. Such separation yields new possibilities for advancing the current understanding of how surface charge influences mediation of cellular and protein interactions in biomaterials.

Atomic force microscopy reveals two phases in single stranded DNA self-assembled monolayers

We have investigated the structure of single-stranded (ss) DNA self-assembled monolayers (SAMs) on gold by combining peak force tapping, Kelvin probe and phase contrast atomic force microscopy (AFM) techniques. The adhesion, surface potential and phase shift signals show heterogeneities in the DNA film structure at two levels: microscale and nanoscale; which cannot be clearly discerned in the topography. Firstly, there is multilayer aggregation covering less than 5% of the surface. The DNA multilayers seem to be ordered phases and their existence suggests that DNA end-to-end interaction can play a role in the self-assembly process. Secondly, we find the formation of two phases in the DNA monolayer, which differ both in surface energy and surface potential. We relate the two domains to differences in the packing density and in the ssDNA conformation. The discovered heterogeneities in ssDNA SAMs provide a new scenario in our vision of these relevant films that have direct consequences on their biological, chemical and physical properties.

Polymer structure and morphology of low density polyethylene filled with silica nanoparticles

AbstractThe effect of silica nanoparticles on structure and morphology of low density polyethylene (LDPE) was investigated. To prepare the nanocomposites, SiO2 nanoparticles were dispersed in a LDPE with cryogenic high‐energy ball milling (HEBM). Films of these nanocomposites with different loads (0%, 1.8%, 2.3%, 3.3%, 7.9%, 16.5% wt/wt) were obtained by hot pressing. Differential scanning calorimetry (DSC) was used to study the nonisothermal melting and crystallization of the films. The morphological characterization was done by atomic force microscopy (AFM). To determine the most representative periodical spacing associated to the LDPE crystallites, a new approach based on the first moment of the frequency distribution obtained from the fast Fourier transform of the AFM phase contrast images was used. Ultracryomicrotomed surfaces of the nanocomposites revealed an efficient dispersion of the nanoparticles throughout the polymer bulk. Although HEBM promotes the formation of the metastable monoclinic phase in the LDPE, nanocomposites in the form of films did not show important differences in their thermal and morphological characteristics, suggesting that there are not high interactions between the polar nanoparticles and the nonpolar polymer and that thermal treatment is enough to eliminate the specific microstructure induced by HEBM. POLYM. COMPOS., 33:2009–2021, 2012. © 2012 Society of Plastics Engineers

Size dependent mechanical properties of electrospun polymer fibers from a composite structure

The elastic modulus of individual electrospun polyvinyl-alcohol (PVA) fibers was measured using atomic force microscopy (AFM) based bending tests. Results indicated an increase in the elastic modulus as the fiber diameter decreased. Consideration of electrospun fibers as a composite structure consisting of a shell region of aligned polymer chains surrounding a bulk-like isotropic core was analytically modeled and showed good agreement with the experimental data. Phase contrast AFM imaging of focused ion beam (FIB) prepared PVA fiber cross-sections provided a method of observing the shell–core structure directly and supported the model proposed. These findings indicate the potential for considerable polymer chain alignment for the production of high performance fibers using electrospinning methods.

Atomic force microscopy applied to the quantification of nano-precipitates in thermo-mechanically treated microalloyed steels

Abstract Quantification of nanometer-size precipitates in microalloyed steels has been traditionally performed using transmission electron microscopy (TEM), in spite of its complicated sample preparation procedures, prone to preparation errors and sample perturbation. In contrast to TEM procedures, atomic force microscopy (AFM) is performed on the as-prepared specimen, with sample preparation requirements similar to those for optical microscopy (OM), rendering three-dimensional representations of the sample surface with vertical resolution of a fraction of a nanometer. In AFM, contrast mechanisms are directly related to surface properties such as topography, adhesion, and stiffness, among others. Chemical etching was performed using 0.5% nital, at time intervals between 4 and 20 s, in 4 s steps, until reaching the desired surface finish. For the present application, an average surface-roughness peak-height below 200 nm was sought. Quantification results of nanometric precipitates were obtained from the statistical analysis of AFM images of the microstructure developed by microalloyed Nb and V–Mo steels. Topography and phase contrast AFM images were used for quantification. The results obtained using AFM are consistent with similar TEM reports.

Extending AFM Phase Image of Nanocomposite Structures to 3D using FIB

ABSTRACTThe mechanical behavior of nanocomposites is critically dependent on their structural composition. In this paper we use Focused Ion Beam (FIB) microscopy to prepare surfaces from a layered polymer nanocomposite for investigation using phase contrast atomic force microscopy (AFM). Phase contrast AFM provides mechanical information on the surface examined and, by combining with the sequential cross-sectioning of FIB, can extend the phase contract AFM into three dimensions.

Surface nanostructure of Hevea brasiliensis natural rubber latex particles

Natural rubber (NR) from the Hevea brasiliensis tree is the main commercial feedstock for rubber and latex dipping industries. NR latex particles in a matured commercial latex concentrate are stabilized by charged groups derived from proteins, long-chain fatty acid soaps and polypeptides adsorbed on the particle surface. The colloidal stability of the latex is extremely sensitive to pH as well as to the ionic environment of the dispersing medium. Previous work on particle microelectrophoresis has shown that the charge on the particle surface is derived mainly from carboxylic groups of long chain fatty acids ( ca. 86%). Freshly collected field latex from the tree, on the other hand, is believed to be stabilized by proteins and phospholipids before hydrolysis sets in upon leaving the tree. The exact arrangement of the adsorbed proteins and phospholipids and the thickness of this adsorbed layer have yet to be successfully determined. The present study has been focused on unraveling the arrangement of these proteins and phospholipids on the particle surface of a freshly tapped NR latex. In order to visualize these molecules, they were imaged using phase contrast atomic force microscopy (AFM). Moreover, the molecules in the particle were labeled with fluorescent Rhodamine B (RB) and uncharged fluorescein-5(6)-isothiocyanate (FITC), and monitored by confocal laser scanning microscopy (CLSM) thereby permitting an in situ observation of their locations on and inside the particles. The selective labeling of the proteins and phospholipids with RB and FITC in protein-free as well as in protein-and-lipid-free latex particles permitted an unequivocal determination of their presence both on the surface and in the interior of the particles. An indentation study of the surface layer of the original untreated NR particle was also carried out to confirm the hypothesis of a core–shell structure with a mixed layer of proteins and phospholipids surrounding the hydrophobic core of polyisoprene particles. According to the obtained results, the surface of the particles in freshly tapped latex is distinctly different from that of a matured latex concentrate.

PHYSICAL PROPERTIES OF CONTACT LENSES CHARACTERIZED BY SCANNING PROBE MICROSCOPY AND OPTOMAGNETIC FINGERPRINT

In this paper we present applied physics research results of gas-permeable contact lenses (CL) that are manufactured from fluorosilicone acrylate based material (Boston™ type). During contact lenses production the conformation states of polymers belonging to near surface layers of CL surface are changed. Since CL quality crucially depends on surface roughness and optical properties, the properties of surface molecules conformation state and their orientation come into perspective as important factors acting on the molecular level. Therefore, we investigated CL surface by phase contrast atomic force microscopy (PC-AFM), magnetic force microscopy (MFM), and optomagnetic fingerprint (OMF) technique and found out that surface quality and magnetic properties of contact lenses have influence on physical properties of light transmission and that these changes can be detected on the nanolevel of magnetism, as well as optomagnetism. These results carry important biophysically based implications for CL industry, biomedical application industry and applied optical science.

10.1007/s11447-008-2003-2

The mechanism of the formation of phase contrast in atomic force microscopy (AFM) is studied for various conditions of an oscillating tip interacting with the surface. A phase shift is detected in oscillations of the resonating AFM tip during its interaction with the substrate surface when the AFM tip moves over the surface. We substantiate kinetic mechanism of the formation of phase contrast in AFM, which is initiated when the velocity of the AFM tip moving over the substrate surface increases as a result of increasing friction force. A dependence of the kinetic contrast in AFM on the effective roughness of the surface is discovered. Images of the distribution of copper impurity over the silicon surface under atmospheric conditions are obtained using the method of kinetic phase contrast in AFM.

Effect of latex on surface structure and wetting of pigment coatings

The amount and type of latex binder has a significant effect on both the structure and chemical properties of pigment coatings, which affects critical surface properties, e.g., gloss, ink setting rate via liquid absorption, and spreading properties. Increased knowledge is required for improved optimization in practical applications of pigment coating layers. To this end, the effect of binder amount for two different styrene–butadiene latices in kaolin pigment coatings on a base paper was studied, by measuring the surface topography, surface chemistry, and liquid absorption of these coatings. The topography was thoroughly analyzed from nanometer to millimeter length scales by atomic force microscopy (AFM), confocal optical microscopy (COM), and X-ray tomography. The area fractions of latex and pigments on the surface of the coating were determined from AFM phase contrast images, and the contact angles for pure latex and kaolin fractions were determined by using the Cassie equation. An explicit value for the effective surface area of the coatings was determined from the topographic data, which was used for determining the Wenzel correction for the contact angles. Work of adhesion and surface energy components were determined for the samples using three different methods (Owens–Wendt, Wu, vOCG). The latex was found to be evenly distributed over the surfaces, based on AFM phase imaging and ToF–SIMS mapping. The latex binder amount significantly affected the wetting behavior and interfacial properties of the coating layer. The results of this fundamental study can be used for optimization of functional properties of pigment coating systems by regulation of the amount and properties of their latex binder.

Fracture toughness evaluation of precursor-derived Si–C–N ceramics using the crack opening displacement approach

Difficulties in the fabrication of representative test specimens and in the application of suitable test procedures e.g., in the measurement of the test parameters viz., load, crack length etc., have so far limited the intrinsic fracture mechanical characterization of the precursor-derived ceramics (PDC). The present work reports the evaluation of the crack tip toughness ( K I 0) of Si–C–N ceramics, using the novel crack opening displacement (COD) approach. The fully dense PDC test specimens synthesized from a poly(ureamethylvinyl)silazane precursor covered material structures ranging from partly organic amorphous to inorganic nano-crystalline states. Critically loaded cracks were achieved using either a special loading fixture or with Vickers indentation. Crack tip CODs were measured with the atomic force microscopy (AFM). Fractography of the fracture surfaces were performed using topographic, frictional and phase contrast AFM. The measured K I 0 values ranged from 0.6 to 1.2 MPa m 1/2. The net change in crack resistance was affected by the stripping of OFC-hydrogen atoms in the amorphous materials and by the segregated turbostratic graphite phase in the phase-separated materials. Nano-scale crack deflection observed even in the amorphous materials indicated the presence of structural and compositional inhomogeneities within the amorphous network.

Kinetic contrast in atomic force microscopy

The mechanism of the formation of phase contrast in atomic force microscopy (AFM) is studied for various conditions of an oscillating tip interacting with the surface. A phase shift is detected in oscillations of the resonating AFM tip during its interaction with the substrate surface when the AFM tip moves over the surface. We substantiate kinetic mechanism of the formation of phase contrast in AFM, which is initiated when the velocity of the AFM tip moving over the substrate surface increases as a result of increasing friction force. A dependence of the kinetic contrast in AFM on the effective roughness of the surface is discovered. Images of the distribution of copper impurity over the silicon surface under atmospheric conditions are obtained using the method of kinetic phase contrast in AFM.

Ultrastructural appearance of embedded and polished wood cell walls as revealed by Atomic Force Microscopy

Atomic Force Microscopy (AFM) was used to investigate the ultrastructural appearance of transverse wood cell wall surfaces in embedded and polished Norway spruce wood blocks. The prepared surfaces showed only little height differences, suitable for high resolution AFM phase contrast imaging. Our results revealed randomly arranged wood cell wall components in the thick secondary 2 (S2) layers of the tracheid cell walls. It is concluded that the observed distribution pattern of the cellulose fibril/matrix structure is close to the original cell wall structure. In this context, the plasticity of wood cell wall components to re-arrange and adjust to different conditions resulting in diverse structural pattern is discussed.