In this work, material-sensitive atomic force microscopy (AFM) techniques were used to analyse the cathodes of lithium–sulfur batteries. A comparison of their nanoscale electrical, electrochemical, and morphological properties was performed with samples prepared by either suspension-spraying or doctor-blade coating with different binders. Morphological studies of the cathodes before and after the electrochemical tests were performed by using AFM and scanning electron microscopy (SEM). The cathodes that contained polyvinylidene fluoride (PVDF) and were prepared by spray-coating exhibited a superior stability of the morphology and the electric network associated with the capacity and cycling stability of these batteries. A reduction of the conductive area determined by conductive AFM was found to correlate to the battery capacity loss for all cathodes. X-ray diffraction (XRD) measurements of Li2S exposed to ambient air showed that insulating Li2S hydrolyses to insulating LiOH. This validates the significance of electrical ex-situ AFM analysis after cycling. Conductive tapping mode AFM indicated the existence of large carbon-coated sulfur particles. Based on the analytical findings, the first results of an optimized cathode showed a much improved discharge capacity of 800 mA·g(sulfur)−1 after 43 cycles.
conductive AFM; high capacity; lithium-sulfur batteries; material-sensitive AFM; sulfur cathode
We present an overview of the bimodal amplitude–frequency-modulation (AM-FM) imaging mode of atomic force microscopy (AFM), whereby the fundamental eigenmode is driven by using the amplitude-modulation technique (AM-AFM) while a higher eigenmode is driven by using either the constant-excitation or the constant-amplitude variant of the frequency-modulation (FM-AFM) technique. We also offer a comparison to the original bimodal AFM method, in which the higher eigenmode is driven with constant frequency and constant excitation amplitude. General as well as particular characteristics of the different driving schemes are highlighted from theoretical and experimental points of view, revealing the advantages and disadvantages of each. This study provides information and guidelines that can be useful in selecting the most appropriate operation mode to characterize different samples in the most efficient and reliable way.
amplitude-modulation; atomic force microscopy; frequency-modulation; phase-locked loop; spectroscopy
Intermodulation atomic force microscopy (ImAFM) is a mode of dynamic atomic force microscopy that probes the nonlinear tip–surface force by measurement of the mixing of multiple modes in a frequency comb. A high-quality factor cantilever resonance and a suitable drive comb will result in tip motion described by a narrow-band frequency comb. We show, by a separation of time scales, that such motion is equivalent to rapid oscillations at the cantilever resonance with a slow amplitude and phase or frequency modulation. With this time-domain perspective, we analyze single oscillation cycles in ImAFM to extract the Fourier components of the tip–surface force that are in-phase with the tip motion (F
I) and quadrature to the motion (F
Q). Traditionally, these force components have been considered as a function of the static-probe height only. Here we show that F
I and F
Q actually depend on both static-probe height and oscillation amplitude. We demonstrate on simulated data how to reconstruct the amplitude dependence of F
I and F
Q from a single ImAFM measurement. Furthermore, we introduce ImAFM approach measurements with which we reconstruct the full amplitude and probe-height dependence of the force components F
I and F
Q, providing deeper insight into the tip–surface interaction. We demonstrate the capabilities of ImAFM approach measurements on a polystyrene polymer surface.
atomic force microscopy; AFM; frequency combs; force spectroscopy; high-quality-factor resonators; intermodulation; multifrequency
atomic force microscopy
Nano-object additives are used in tribological applications as well as in various applications in liquids requiring controlled manipulation and targeting. On the macroscale, nanoparticles in solids and liquids have been shown to reduce friction and wear. On the nanoscale, atomic force microscopy (AFM) studies have been performed in single- and multiple-nanoparticle contact, in dry environments, to characterize friction forces and wear. However, limited studies in submerged liquid environments have been performed and further studies are needed. In this paper, spherical Au nanoparticles were studied for their effect on friction and wear under dry conditions and submerged in water. In single-nanoparticle contact, individual nanoparticles, deposited on silicon, were manipulated with a sharp tip and the friction force was determined. Multiple-nanoparticle contact sliding experiments were performed on nanoparticle-coated silicon with a glass sphere. Wear tests were performed on the nanoscale with AFM as well as on the macroscale by using a ball-on-flat tribometer to relate friction and wear reduction on the nanoscale and macroscale. Results indicate that the addition of Au nanoparticles reduces friction and wear.
AFM; drug delivery; friction; gold nanoparticles; MEMS/NEMS; nanomanipulation
Skin can be damaged by the environment easily. Skin cream is an effective and rapid way to moisten the skin by changing the skin surface properties. Rat skin and pig skin are common animal models for studies and were used as skin samples in this study. The nano- and macroscale friction and durability of damaged skin were measured and compared with those of virgin (intact/undamaged) skin. The effect of skin cream on friction and durability of damaged and virgin skin samples is discussed. The effects of velocity, normal load, relative humidity and number of cycles were studied. The nanoscale studies were performed by using atomic force microscope (AFM), and macroscale studies were performed by using a pin-on-disk (POD) reciprocating tribometer. It was found that damaged skin has different mechanical properties, surface roughness, contact angle, friction and durability compared to that of virgin skin. But similar changes occur after skin cream treatment. Rat and pig skin show similar trends in friction and durability.
atomic force microscopy; damaged skin; pig skin; rat skin; skin cream
Noncontact atomic force microscopy (NC-AFM) is being increasingly used to measure the interaction force between an atomically sharp probe tip and surfaces of interest, as a function of the three spatial dimensions, with picometer and piconewton accuracy. Since the results of such measurements may be affected by piezo nonlinearities, thermal and electronic drift, tip asymmetries, and elastic deformation of the tip apex, these effects need to be considered during image interpretation.
In this paper, we analyze their impact on the acquired data, compare different methods to record atomic-resolution surface force fields, and determine the approaches that suffer the least from the associated artifacts. The related discussion underscores the idea that since force fields recorded by using NC-AFM always reflect the properties of both the sample and the probe tip, efforts to reduce unwanted effects of the tip on recorded data are indispensable for the extraction of detailed information about the atomic-scale properties of the surface.
atomic force microscopy; force spectroscopy; NC-AFM; three-dimensional atomic force microscopy; tip asymmetry; tip elasticity
We introduce drive-amplitude-modulation atomic force microscopy as a dynamic mode with outstanding performance in all environments from vacuum to liquids. As with frequency modulation, the new mode follows a feedback scheme with two nested loops: The first keeps the cantilever oscillation amplitude constant by regulating the driving force, and the second uses the driving force as the feedback variable for topography. Additionally, a phase-locked loop can be used as a parallel feedback allowing separation of the conservative and nonconservative interactions. We describe the basis of this mode and present some examples of its performance in three different environments. Drive-amplutide modulation is a very stable, intuitive and easy to use mode that is free of the feedback instability associated with the noncontact-to-contact transition that occurs in the frequency-modulation mode.
atomic force microscopy; control systems; dissipation; frequency modulation; noncontact
We present the results of atomistic simulations of metallic atomic-force-microscopy tips interacting with ionic substrates, with atomic resolution. Chromium and tungsten tips are used to image the NaCl(001) and MgO(001) surfaces. The interaction of the tips with the surface is simulated by using density-functional-theory calculations employing a mixed Gaussian and plane-wave basis and cluster-tip models. In each case, the apex of the metal cluster interacts more attractively with anions in the surfaces than with cations, over the range of typical imaging distances, which leads to these sites being imaged as raised features (bright) in constant-frequency-shift images. We compare the results of the interaction of a chromium tip with the NaCl surface, with calculations employing exclusively plane-wave basis sets and a fully periodic tip model, and demonstrate that the electronic structure of the tip model employed can have a significant quantitative effect on calculated forces when the tip and surface are clearly separated.
atomic force microscopy; density functional theory; ionic surfaces; metallic asperities; surface interactions
Recently, the compound semiconductor Cu3BiS3 has been demonstrated to have a band gap of ~1.4 eV, well suited for photovoltaic energy harvesting. The preparation of polycrystalline thin films was successfully realized and now the junction formation to the n-type window needs to be developed. We present an investigation of the Cu3BiS3 absorber layer and the junction formation with CdS, ZnS and In2S3 buffer layers. Kelvin probe force microscopy shows the granular structure of the buffer layers with small grains of 20–100 nm, and a considerably smaller work-function distribution for In2S3 compared to that of CdS and ZnS. For In2S3 and CdS buffer layers the KPFM experiments indicate negatively charged Cu3BiS3 grain boundaries resulting from the deposition of the buffer layer. Macroscopic measurements of the surface photovoltage at variable excitation wavelength indicate the influence of defect states below the band gap on charge separation and a surface-defect passivation by the In2S3 buffer layer. Our findings indicate that Cu3BiS3 may become an interesting absorber material for thin-film solar cells; however, for photovoltaic application the band bending at the charge-selective contact has to be increased.
buffer layer; Cu3BiS3; Kelvin probe force microscopy; solar cells
The frequency-resolved viscoelasticity of a hydration layer on a mica surface was studied by pulse-response measurement of a magnetically driven atomic force microscopy cantilever. Resonant ringing of the cantilever due to its 1st and 2nd resonance modes was suppressed by means of the Q-control technique. The Fourier–Laplace transform of the deflection signal of the cantilever gave the frequency-resolved complex compliance of the cantilever–sample system. The significant viscoelasticity spectrum of the hydration layer was successfully derived in a frequency range below 100 kHz by comparison of data obtained at a distance of 300 nm from the substrate with those taken in the proximity of the substrate. A positive value of the real part of the stiffness was determined and is attributed to the reported solidification of the hydration layers.
atomic force microscopy; hydration; pulse-response; quality-factor control; viscoelasticity
Key developments in NC-AFM have generally involved atomically flat crystalline surfaces. However, many surfaces of technological interest are not atomically flat. We discuss the experimental difficulties in obtaining high-resolution images of rough surfaces, with amorphous SiO2 as a specific case. We develop a quasi-1-D minimal model for noncontact atomic force microscopy, based on van der Waals interactions between a spherical tip and the surface, explicitly accounting for the corrugated substrate (modeled as a sinusoid). The model results show an attenuation of the topographic contours by ~30% for tip distances within 5 Å of the surface. Results also indicate a deviation from the Hamaker force law for a sphere interacting with a flat surface.
graphene; model; noncontact atomic force microscopy; SiO2; van der Waals
The adsorption on KBr(001) of a specially designed molecule, consisting of a flat aromatic triphenylene core equipped with six flexible propyl chains ending with polar cyano groups, is investigated by using atomic force microscopy in the noncontact mode (NC-AFM) coupled to Kelvin probe force microscopy (KPFM) in ultrahigh vacuum at room temperature. Two types of monolayers are identified, one in which the molecules lie flat on the surface (MLh) and another in which they stand approximately upright (MLv). The Kelvin voltage on these two structures is negatively shifted relative to that of the clean KBr surface, revealing the presence of surface dipoles with a component pointing along the normal to the surface. These findings are interpreted with the help of numerical simulations. It is shown that the surface–molecule interaction is dominated by the electrostatic interaction of the cyano groups with the K+ ions of the substrate. The molecule is strongly adsorbed in the MLh structure with an adsorption energy of 1.8 eV. In the MLv layer, the molecules form π-stacked rows aligned along the polar directions of the KBr surface. In these rows, the molecules are less strongly bound to the substrate, but the structure is stabilized by the strong intermolecular interaction due to π-stacking.
atomic force microscopy; insulating surfaces; Kelvin force probe microscopy; molecular adsorption
Based on high-resolution noncontact atomic force microscopy (NC-AFM) experiments we reveal a detailed structural model of the polar (111) surface of the insulating ternary metal oxide, MgAl2O4 (spinel). NC-AFM images reveal a 6√3×6√3R30° superstructure on the surface consisting of patches with the original oxygen-terminated MgAl2O4(111) surface interrupted by oxygen-deficient areas. These observations are in accordance with previous theoretical studies, which predict that the polarity of the surface can be compensated by removal of a certain fraction of oxygen atoms. However, instead of isolated O vacancies, it is observed that O is removed in a distinct pattern of line vacancies reflected by the underlying lattice structure. Consequently, by the creation of triangular patches in a 6√3×6√3R30° superstructure, the polar-stabilization requirements are met.
aluminium oxide; metal oxide surfaces; noncontact atomic force microscopy (NC-AFM); polar surfaces; reconstructions; spinel
Noncontact atomic force microscopy provides access to several complementary signals, such as topography, damping, and contact potential. The traditional presentation of such data sets in adjacent figures or in colour-coded pseudo-three-dimensional plots gives only a qualitative impression. We introduce two-dimensional histograms for the representation of multichannel NC-AFM data sets in a quantitative fashion. Presentation and analysis are exemplified for topography and contact-potential data for graphene grown epitaxially on 6H-SiC(0001), as recorded by Kelvin probe force microscopy in ultrahigh vacuum. Sample preparations by thermal decomposition in ultrahigh vacuum and in an argon atmosphere are compared and the respective growth mechanisms discussed.
FM-AFM; graphene; 6H-SiC(0001); KPFM; SPM
The self-assembly properties of a series of functionalized regioregular oligo(3-alkylthiophenes) were investigated by using scanning tunneling microscopy (STM) at the liquid–solid interface under ambient conditions. The characteristics of the 2-D crystals formed on the (0001) plane of highly ordered pyrolitic graphite (HOPG) strongly depend on the length of the π-conjugated oligomer backbone, on the functional groups attached to it, and on the alkyl substitution pattern on the individual thiophene units. Theoretical calculations were performed to analyze the geometry and electronic density of the molecular orbitals as well as to analyze the intermolecular interactions, in order to obtain models of the 2-D molecular ordering on the substrate.
2-D crystals; functionalized oligothiophenes; H-bonding; intermolecular interaction; scanning tunneling microscopy
The role of the cantilever in quantitative Kelvin probe force microscopy (KPFM) is rigorously analyzed. We use the boundary element method to calculate the point spread function of the measuring probe: Tip and cantilever. The calculations show that the cantilever has a very strong effect on the absolute value of the measured contact potential difference even under ultra-high vacuum conditions, and we demonstrate a good agreement between our model and KPFM measurements in ultra-high vacuum of NaCl monolayers grown on Cu(111). The effect of the oscillating cantilever shape on the KPFM resolution and sensitivity has been calculated and found to be relatively small.
boundary elements method; cantilever; convolution; Kelvin probe force microscopy; point spread function