Microscopy Mode Research Articles

Physicochemical and biological characteristics of chitosan/κ-carrageenan thin layer-by-layer films for surface modification of nitinol

Thin films based on the natural polysaccharides κ-carrageenan (Carr) and chitosan (Chit) were formed by layer-by-layer deposition technique. Surface topography and mechanical characteristics (Young's modulus, adhesion strength) of the polymer films with different number of layers were determined using various modes of atomic force microscopy (AFM). Polymer films were used to deposit on the surface of nitinol (NiTi) plates. The creation of polysaccharide coatings on nitinol led to a change in surface properties, such as hydrophilicity and root mean square roughness. in vitro cytotoxicity assay for nitinol plates with and without polymer coating by the MG-63 osteoblast-like cell line was conducted and was shown that all the studied samples are not toxic. A decrease in cytotoxicity for samples with a polymer film consisting of 4 layers of chitosan and carrageenan was shown as compared to an uncoated nitinol plates.

Confocal laser scanning microscopy as a real-time quality-assessment tool for industrial graphene synthesis

For the industrial quality control (QC) of the chemical vapor deposition (CVD) graphene, it is essential to develop a method to screen out unsatisfactory graphene films as efficiently as possible. However, previously proposed methods based on Raman spectroscopy or optical imaging after chemical etching are unable to provide non-invasive and fast analysis of large-area graphene films as grown on Cu foil substrates. Here we report that the reflection mode of confocal laser scanning microscopy (CLSM) provides a high-contrast image of graphene on Cu, enabling the real-time evaluation of the coverage and quality of graphene. The reflectance contrast, Rc, was found to be dependent on the incident laser wavelength, of which the maximum was obtained at 405 nm. In addition, Rc decreases with increasing defect density of graphene. The dependence of Rc on the graphene’s quality and laser wavelengths were explained by the tight-binding model calculation based on the Fresnel’s interference formula. Thus, we believe that the reflection mode CLSM would be a very powerful quality-assessment tool for the mass production of CVD graphene films grown on Cu.

Neural network module for tuning an atomic force microscope in the study of photonic crystal films

The article describes the use of neural network algorithms for setting the modes of investigation of photonic crystal films by tapping mode of atomic force microscopy. The photonic crystal thin films and monolayers obtained from colloidal suspensions by methods of sedimentation, centrifugation, vertical deposition, electrophoresis, and Langmuir-Blodgett are studied in this work. Study of films growth kinetics revealed that many factors were critical for reproducible deposition of the structure. To obtain high-quality images of samples, it is very important to get rid of artifacts and correctly configure the scanning parameters. To solve these problems it was proposed to use neural network algorithms. They allow to choose individual settings for each sample. We got acceptable results using a multilayer perceptron with one hidden layer.

Quantitative mapping of high modulus materials at the nanoscale: comparative study between atomic force microscopy and nanoindentation.

Local mechanical properties of submicron features are of particular interest due to their influence on macroscopic material performance and behaviour. This study is focused on local nanomechanical measurements, based on the latest Atomic Force Microscopy (AFM) mode, where the peak force set point is finely controlled at each pixel. After probe calibration, we evaluate the impact of spring constant of two AFM hand-crafted natural full diamond tips with steel cantilevers, used for mapping. Based on the fast capture of the cantilever deflection at each pixel and real time force curve analysis in the elastic region, AFM local measured contact moduli mappings of the silica beads (>50GPa) incorporated in an epoxy resin matrix, are compared with those determined using classical instrumented nanoindentation tests. Our analyses show that with the two AFM probes, without local residual deformation, the high moduli of the silica beads measured with this advanced AFM mode are within the standard deviation of the values determined by classical nanoindentation. LAY DESCRIPTION: The knowledge of material properties at the nanometer scale is a key parameter for well understanding and determining the behavior of material at macroscopic scale. In this paper, we compare two methods (an advanced mode and a classical one) based on the analysis of probes in interaction with the surface of studied material. We focus on a latest developed mode for determining local mechanical properties with a very high spatial resolution. For the advanced mode, we also consider two different hand-crafted probes. Our analyses show that with the high spatial resolution advanced mode, local mechanical properties are well determined. We also highlight the impact of the properties of the used probes for this advanced mode. In a final step, the power of the presented investigation lies in the fact that it does not modify the topography of the surface.

Three-Dimensional (3D) Conductive Network of CNT-Modified Short Jute Fiber-Reinforced Natural Rubber: Hierarchical CNT-Enabled Thermoelectric and Electrically Conductive Composite Interfaces.

Jute fibers (JFs) coated with multiwall carbon nanotubes (MWCNTs) have been introduced in a natural rubber (NR) matrix creating a three-dimensional (3D) electrically conductive percolated network. The JF-CNT endowed electrical conductivity and thermoelectric properties to the final composites. CNT networks fully covered the fiber surfaces as shown by the corresponding scanning electron microscopy (SEM) analysis. NR/JF-CNT composites, at 10, 20 and 30 phr (parts per hundred gram of rubber) have been manufactured using a two-roll mixing process. The highest value of electrical conductivity (σ) was 81 S/m for the 30 phr composite. Thermoelectric measurements revealed slight differences in the Seebeck coefficient (S), while the highest power factor (PF) was 1.80 × 10−2 μW/m K−2 for the 30 phr loading. The micromechanical properties and electrical response of the composite’s conductive interface have been studied in peak force tapping quantitative nanomechanical (PFT QNM) and conductive atomic force microscopy (c-AFM) mode. The JF-CNT create an electrically percolated network at all fiber loadings endowing electrical and thermoelectric properties to the NR matrix, considered thus as promising thermoelectric stretchable materials.

Imaging the Nanophase-separated Structure of Block Copolymer Thin Film by Atomic Force Microscopy in Aqueous Solution

We employed two modes of atomic force microscopy to characterize the nanophase-separated structure of a block copolymer thin film from poly(2-methacryloyloxyethyl phosphorylcholine) and poly(3-(met...

Monolithic quartz platform for cellular contact guidance

Abstract

A study of the electrochemical reactivity of titanium under cathodic polarization by means of combined feedback and redox competition modes of scanning electrochemical microscopy

The effect of cathodic polarization on the electrochemical behavior of the thin titanium dioxide film formed by anodic pretreatment over pure commercial titanium metal for biomaterial application was investigated in situ using scanning electrochemical microscopy (SECM). Quantitative information on the electron transfer rates (keff) at the titanium surface was obtained using the feedback operation of SECM with ferrocene-methanol (FcMeOH) as electrochemical mediator. An increase of keff values with the increase of the negative polarization was detected, a feature that correlates well with the decrease of titanium oxide resistance with increasing cathodic polarization observed using electrochemical impedance spectroscopy (EIS). In addition, SECM operation in the redox competition mode proved that hydrogen was absorbed in the surface oxide film leading to changes in conductivity and electrochemical reactivity.

Chemical and steric effects in simulating noncontact atomic force microscopy images of organic molecules on a Cu (111) substrate

Noncontact mode of atomic force microscopy (nc-AFM) employing a CO-functionalized tip is a very powerful tool for studying molecular structures. However, interpreting nc-AFM images for nonplanar molecules can sometimes be problematic. To illustrate and resolve the nature of such problematic systems, we employ real-space pseudopotentials constructed within density functional theory to simulate nc-AFM images. We focus on several representative nonplanar organic molecules (pentacene, naphthanthrone, olympicene, and 6-phenylhexa-1,3,5-triynybenzene (PHTB)) on a typical substrate: the Cu (111) surface. This substrate results in significant distortions in the molecular geometries of pentacene and naphthanthrone. Including these distortions in simulated nc-AFM imaging notably improves the agreement between the simulated and measured images. In naphthanthrone, the relatively large interaction between the O atom and the Cu substrate offers a straightforward explanation for the absence of the $\mathrm{C}=\mathrm{O}$ bond in the measured image. Nonplanar features such as tilting or twisting are also apparent in olympicene and PHTB. A ``triangular'' bright feature associated with the $\ensuremath{-}\mathrm{C}{\mathrm{H}}_{2}$ group in olympicene appears in simulated and measured nc-AFM images. This feature is directly related to the tilting angle of the molecule with respect to the Cu substrate. The ``defective'' benzene ring feature and the faint ellipsoidal $\mathrm{C}\ensuremath{\equiv}\mathrm{C}$ feature in PHTB can be ascribed to its twisted nature. The ability to simulate such subatomic images in nc-AFM reflects the accuracy and efficiency of calculating quantum forces in real space.

Isotropic three-dimensional imaging with lattice light-sheet difference microscopy

Through the interference of several beams with the same phase at the rear pupil, an optical lattice is generated and used as the excitation light field in lattice light-sheet microscopy (LLSM). Although, LLSM offers fast imaging ability through the dithered mode, it suffers from poor axial resolution. On the other hand, the structured illumination microscopy (SIM) mode in LLSM provides a high but anisotropic spatial resolution at the price of a lower imaging speed. In this Letter, we propose a new, to the best of our knowledge, type of optical lattice by defining the composed beam vectors with different phases. The lattice light-sheet difference microscopy (LLSDM) proposed in this work utilizes the new optical lattice along with the conventional one by simply changing the pattern loaded on the spatial light modulator. Through simulations with parameters obtained from the real acquisition procedures and the microscope properties, we examine the feasibility of LLSDM, and obtain nearly isotropic spatial resolution and great alleviation of the sidelobes. These characteristics enable LLSDM to broaden the accessible imaging content of light-sheet microscopes and further facilitate their applications in life sciences.

Comparative study on the specimen thickness measurement using EELS and CBED methods

Two thickness measurement methods using an electron energy loss spectroscopy (EELS) and 10a convergent beam electron diffraction (CBED) were compared in an Fe-18Mn-0.7C alloy. The thin foil specimen was firstly tilted to satisfy 10a two-beam condition. Low loss spectra of EELS and CBED patterns were acquired in scanning transmission electron microscopy (STEM) and TEM-CBED modes under the two-beam condition. The log-ratio method was used for measuring the thin foil thickness. Kossel-Möllenstedt (K-M) fringe of the mathbf{13}overline{mathbf{1}} diffracted disk of austenite was analyzed to evaluate the thickness. The results prove the good coherency between both methods in the thickness range of 72 ~ 113 nm with a difference of less than 5%.

A MEMS nanoindenter with an integrated AFM cantilever gripper for nanomechanical characterization of compliant materials

This work presents the development of a MEMS nanoindenter that uses exchangeable AFM probes for quasi-static nanomechanical characterization of compliant and ultra-compliant materials. While the electrostatic micro-force transducer of the MEMS nanoindenter provides a maximum indentation depth up to 9.5 µm with a maximum output force of 600 µN, experimental investigations reveal that it can achieve a depth and force resolution better than 4 pm Hz−1/2 and 0.3 nN Hz−1/2, in air for f≥ 1 Hz. A passive AFM probe gripper is integrated into the MEMS nanoindenter, allowing the nanoindenter to utilize various AFM probes as an indenter for material testing. A proof-of-principle experimental setup has been built to investigate the performance of the MEMS nanoindenter prototype. In proof-of-principle experiments, the prototype with a clamped diamond AFM probe successfully identified an atomic step (∼0.31 nm) within a Si < 111 > ultraflat sample using the scanning probe microscopy mode. The nanomechanical measurement capability of the MEMS nanoindenter prototype has been verified by means of measurements of reference polymer samples using a silicon AFM probe and by means of measurements of the elastic properties of a PDMS sample using a spherical diamond-coated AFM probe. Owing to its compact and low-cost but high-resolution capacitive readout system, this MEMS nanoindenter head can be further applied for in-situ quantitative nanomechanical measurements in AFMs and SEMs.

Observation of yttrium oxide segregation in a ZrO2‐SiO2 glass‐ceramic at nanometer dimensions

AbstractDopant segregation at grain boundaries (GBs) in ceramics has been widely reported, while whether similar segregation behavior occurs in glass‐ceramics remains unknown. The distribution of dopant in glass‐ceramics may be totally different due to the existence of glass phase. This study examines the distribution of Y3+ ions in a ZrO2‐SiO2 glass‐ceramic. Two samples were prepared by hot pressing, yttrium oxide‐doped, and undoped 65 mol% ZrO2‐35 mol% SiO2 nanocrystalline glass‐ceramics (NCGCs). The NCGCs had the same microstructure, that is, ZrO2 nanoparticles (NPs) embedded in an amorphous SiO2 matrix. XRD results showed that the undoped NCGC was composed of 20.9 wt% (weight percentage) monoclinic ZrO2 (m‐ZrO2) and 79.1 wt% tetragonal ZrO2 (t‐ZrO2), while the yttrium oxide‐doped NCGC was composed of 9.6 wt% m‐ZrO2 and 90.4 wt% t‐ZrO2. X‐ray energy‐dispersive spectrometry (EDS) results in scanning electron transmission microscopy (STEM) mode demonstrated that Y3+ ions segregated both on the surface of ZrO2 NPs and within the thin intergranular glass film (with a thickness of approximately 7 Å) between ZrO2 NPs in the yttrium oxide‐doped NCGC. Interestingly, no obvious Y signals were detected in the amorphous SiO2 matrix. Density functional theory calculation results showed that Y3+ ions had a strong segregation tendency in the GB area and the segregation of Y3+ ions increased the work of separation of GB layer. These findings provide new understanding of the segregation behavior of dopant in glass‐ceramics, which may offer useful guidance for other researchers to tailor the properties of glass‐ceramics through GB engineering.

Pulsed Force Kelvin Probe Force Microscopy.

Measurement of the contact potential difference (CPD) and work functions of materials are important in analyzing their electronic structures and surface residual charges. Kelvin probe force microscopy (KPFM), an imaging technique of atomic force microscopy, has been widely used for surface potential and work function mapping at the nanoscale. However, the conventional KPFM variants are often limited in their spatial resolution to 30-100 nm under ambient conditions. The continuingly decreasing size and increasing complexity of photoactive materials and semiconductor devices will present future challenges in uncovering their nanometer-scale electrical properties through KPFM. Here, we introduce a KPFM technique based on the pulsed force mode of atomic force microscopy. Our technique, named pulsed force Kelvin Probe Force Microscopy (PF-KPFM), is a single-pass technique that utilizes the intrinsic Fermi level alignment between the AFM tip and the conductive sample without the need for an external oscillating voltage. Induced cantilever oscillations generated by a spontaneous redistribution of electrons between tip and sample are extracted and used to obtain the cantilever oscillation amplitude and to derive the surface potential. The spatial resolution of PF-KPFM is shown to be <10 nm under ambient conditions. The high spatial resolution surface potential mapping enables in situ determination of ohmic and nonohmic contacts between metals and semiconductors, mapping boundaries of ferroelectric domains of BaTiO3, as well as characterization of protein aggregates. High spatial resolution measurements with PF-KPFM will facilitate further studies directed at uncovering electrical properties for emerging photoactive materials, biological samples, and semiconductor devices.

Comparison of fresh and aged lithium iron phosphate cathodes using a tailored electrochemical strain microscopy technique.

Electrochemical strain microscopy (ESM) is a powerful atomic force microscopy (AFM) mode for the investigation of ion dynamics and activities in energy storage materials. Here we compare the changes in commercial LiFePO4 cathodes due to ageing and its influence on the measured ESM signal. Additionally, the ESM signal dynamics are analysed to generate characteristic time constants of the diffusion process, induced by a dc-voltage pulse, which changes the ionic concentration in the material volume under the AFM tip. The ageing of the cathode is found to be governed by a decrease of the electrochemical activity and the loss of available lithium for cycling, which can be stored in the cathode.

Thermal conductivity and diffusivity of triple-cation perovskite halide materials for solar cells

We report on the measurement of thermal conductivity and thermal diffusivity by a modulated thermoreflectance microscopy technique on a mixed-cation perovskite material [Cs0.05(formamidinium0.83methylammonium0.17)0.95Pb(I0.83Br0.17)3] widely applied for solution-processed perovskite solar cells. Such materials are supposed to present improved thermal stability compared to methylammonium-based single cation perovskites. Our measurements are performed on perovskite/TiO2/SnO2:F/SiO2 structures, with perovskite thicknesses ranging between 250 nm and 1000 nm. This configuration is the one of a real solar cell, with the same substrate and intermediate layers as of an operating device. We measured a thermal conductivity kper of 0.26 ± 0.03 W m−1 K−1 and a thermal diffusivity Dper of 3.5 × 10−7 ± 0.5 m2 s−1. The value for thermal conductivity is comparable to the one measured on single cation perovskites, which is generally in the 0.2–0.6 range. The value for thermal diffusivity has not been reported previously.

Coulometric Titration of Active Sites at Mesostructured Cobalt Oxide Spinel by Surface Interrogation Mode of Scanning Electrochemical Microscopy

Cobalt-based transition-metal oxides are promising candidates for the oxygen evolution reaction (OER). However, a complex interplay between the catalyst crystal structures and material morphologies...

Spinodal decomposition of reactively sputtered (V0.64Al0.36)0.49N0.51 thin films

We investigate the decomposition mechanisms of metastable cubic (c-)(V0.64Al0.36)0.49N0.51 thin films, grown by reactive high power pulsed magnetron sputtering, by combination of structural and compositional characterization at the nanometer scale with density functional theory (DFT) calculations. Based on thermodynamic considerations of ∂2∆G/∂x2 < 0, spinodal decomposition is expected for c-V1-xAlxN with x ≥ 0.35. While no indications for spinodal decomposition are observable from laboratory and synchroton diffraction data after annealing in Ar atmosphere at 1300 °C, the formation of wurtzite (w-)AlN is evident after annealing at 900 °C by utilizing high energy synchrotron X-ray diffraction. However, the complementary nature of elemental V and Al maps, obtained by energy dispersive X-ray spectroscopy in scanning transmission electron microscopy mode, imply spinodal decomposition of c-(V0.64Al0.36)0.49N0.51 into V- and Al-rich cubic nitride phases after annealing at 900 °C. These chemical modulations are quantified by atom probe tomography and maximum variations of x in V1-xAlxN are in the range of 0.36 to 0.50. The magnitude of the compositional modulations is enhanced after annealing at 1100 °C as x varies on average between 0.30 and 0.61, while the modulation wavelength remains unchanged at approximately 8 nm. Based on DFT data, the local x variation from 0.30 to 0.61 would cause lattice parameter variations from 4.111 to 4.099 Å. This difference corresponds to a shift of the (200) peak from 44.0 to 44.1°. As the maximum decomposition-induced peak separation magnitude of 0.1° is significantly smaller than the measured full width at half maximum of 0.4°, spinodal decomposition cannot be unravelled by diffraction data. However, consistent with DFT predictions, spinodal decomposition in c-(V0.64Al0.36)0.49N0.51 is revealed by chemical composition characterization at the nanometer scale.

Single-Molecule Manipulation in Zero-Mode Waveguides.

The mechanobiology of receptor-ligand interactions and force-induced enzymatic turnover can be revealed by simultaneous measurements of force response and fluorescence. Investigations at physiologically relevant high labeled substrate concentrations require total internal reflection fluorescence microscopy or zero mode waveguides (ZMWs), which are difficult to combine with atomic force microscopy (AFM). A fully automatized workflow is established to manipulate single molecules inside ZMWs autonomously with noninvasive cantilever tip localization. A protein model system comprising a receptor-ligand pair of streptavidin blocked with a biotin-tagged ligand is introduced. The ligand is pulled out of streptavidin by an AFM cantilever leaving the receptor vacant for reoccupation by freely diffusing fluorescently labeled biotin, which can be detected in single-molecule fluorescence concurrently to study rebinding rates. This work illustrates the potential of the seamless fusion of these two powerful single-molecule techniques.

Screening and characterization of bimetallic Pt–M (M = Y, La, Ce, Pr, Nd, Gd) electrocatalysts for the oxygen reduction reaction

In this study bimetallic platinum–metal (Pt–M; M = Y, La, Ce, Pr, Nd, Gd) electrocatalyst arrays were fabricated through a combinational method using a dispensing system. These Pt-based electrocatalyst arrays were then rapidly screened for their suitability for the oxygen reduction reaction (ORR) by using the tip generation–substrate collection mode of scanning electrochemical microscopy; O2 was generated at the tip and it was reduced at spots of the electrocatalyst on the substrate. Scanning electron microscopy, energy dispersive spectroscopy, and X-ray diffractometry were employed to analyze the surface morphologies, elemental compositions, and crystallinities of the electrocatalysts. Tip/substrate voltammetry, approach curve analysis, and rotating disk electrode analysis were used to examine the kinetics of the potential electrocatalysts for the ORR. Among the prepared electrocatalysts, a spot having the composition Pt7Y3 provided the highest current in 0.01 M H2SO4/0.1 M Na2SO4. The Pt7Y3 electrocatalyst exhibited excellent electrocatalytic activity toward the ORR, with a Tafel slope of 123 mV, a rate constant of 0.023 cm/s, and a transfer coefficient of 0.47. The electron transfer numbers of the binary Pt-based electrocatalysts were all close to 4, indicating that their mechanisms of oxygen reduction followed the four-electron reduction pathway. Furthermore, the percentage of H2O2 produced during the ORR on the Pt7Y3 electrocatalyst was the lowest among these tested systems, with a value of less than 2%.