Amplitude Modulation Atomic Force Microscopy Research Articles

Thickness measurement of thin films using atomic force microscopy based scratching

Thin-film thickness measurements using atomic force microscopy (AFM) comprise two steps: 1. AFM scratching in order to produce an exposed film edge, and 2. subsequent AFM measurement of the corresponding step height across the exposed edge. Although the technique is known, many open questions have limited its wider applications. In order to clarify the open questions, here we first demonstrate how to determine the normal force applied during the scratching in contact mode needed to completely remove films from substrates. In order to determine film thickness from processed AFM images, we discuss two procedures based on the histogram method and polynomial step-function fitting. Mechanisms of the scratching process are elucidated by the analysis of lateral forces and their enhancement during the film peeling. Phase maps of scratched domains recorded in amplitude modulation AFM (tapping) mode display a clear contrast compared to pristine films. Therefore, we suggest their utilization as simple indicators of spatial domains with completely removed films. As an example, here the measurements were done on polymer films fabricated by layer-by-layer deposition of oppositely charged polyelectrolytes composed of poly(allylamine hydrochloride) and poly(sodium 4-styrenesulfonate), while the applicability of the presented method on other materials is discussed in detail.

Tailored Microcantilever Optimization for Multifrequency Force Microscopy.

Microcantilevers are at the heart of atomic force microscopy (AFM) and play a significant role in AFM-based techniques. Recent advancements in multifrequency AFM require the simultaneous excitation and detection of multiple eigenfrequencies of microcantilevers to assess more data channels to quantify the material properties. However, to achieve higher spatiotemporal resolution there is a need to optimize the structure of microcantilevers. In this study, the architecture of the cantilever with gold nanoparticles using a dip-coating method is modified, aiming to tune the higher eigenmodes of the microcantilever as integer multiples of its fundamental frequency. Through the theoretical methodology and simulative model, that integer harmonics improve the coupling in multifrequency AFM measurements is demonstrated, leading to enhanced image quality and resolution. Furthermore, via the combined theoretical-experimental approach, the interplay between induced mass and stiffness change of the modified cantilever depending on the attached particle location, size, mass, and geometry is found. To validate the results of this predictive model, tapping-mode AFM is utilized and bimodal Amplitude Modulation AFM techniques to examine and quantify the impact of tuning higher-order eigenmodes on the imaging quality of a polystyrene-polymethylmethacrylate (PS-PMMA) block co-polymer assembly deposited on a glass slide and Highly Ordered Pyrolytic Graphite (HOPG).

Visualization of Electrolyte Reaction Field Near the Negative Electrode of a Lead Acid Battery by Means of Amplitude/Frequency Modulation Atomic Force Microscopy

The precise observation of a solid-liquid interface by means of frequency modulation atomic force microscopy (FM-AFM) was performed, demonstrating its applicability to a study on lead acid batteries using an electrochemical test cell for in-liquid FM-AFM embedded with a specialized cantilever holder. The consistency and reproducibility of each surface profile observed via amplitude modulation AFM and FM-AFM were verified properly in a strong acidic electrolyte. In terms of FM-AFM, the ability to observe remarkable changes in the force mapping is the most beneficial, especially near the negative electrode surface. The localization of lignosulfonate (LS) added into the electrolyte as an expander could be visualized since this characteristic force mapping was captured when LS was added to electrolyte.

Long-Range Electrification of an Air/Electrolyte Interface and Probing Potential of Zero Charge by Conductive Amplitude-Modulated Atomic Force Microscopy.

The structure of an electrical double layer (EDL) at the interface of electrode/electrolyte or air/electrode/electrolyte is a fundamental aspect, however not fully understood. The potential of zero charge (PZC) is one of the clues to dictate the EDL, where the excess charge on the electrode surface is zero. Here, a nanoscale configuration of immersion method was proposed by integrating an electrochemical system into conductive atomic force spectroscopy under the amplitude modulation (AM) mode and agarose gel as the solid-liquid electrolyte. The PZC of boron-doped diamond was determined to be at 0.2 V (vs Ag/AgCl). By AM spectroscopy, the capacitive force shows remote electrification without direct electrode/electrolyte contact, which is dependent on the population of ions at the air/electrolyte interface. The surface potential by alignment of water is also evaluated. Prospectively, our study could benefit applications such as PZC measurement and non-electrode electrochemical processes at the air/electrolyte interface.

Insights and guidelines to interpret forces and deformations at the nanoscale by using a tapping mode AFM simulator: dForce 2.0.

Amplitude modulation (tapping mode) AFM is the most versatile AFM mode for imaging surfaces at the nanoscale in air and liquid environments. However, it remains challenging to estimate the forces and deformations exerted by the tip. We introduce a new simulator environment to predict the values of the observables in tapping mode AFM experiments. The relevant feature of dForce 2.0 is the incorporation of contact mechanics models aimed to describe the properties of ultrathin samples. These models were essential to determine the forces applied on samples such as proteins, self-assembled monolayers, lipid bilayers, and few-layered materials. The simulator incorporates two types of long-range magnetic forces. The simulator is written in an open-source code (Python) and it can be run from a personal computer.

Stability and contrast in bimodal amplitude modulation atomic force microscopy for different mode combinations in ambient air

Bimodal amplitude modulation atomic force microscopy (AM-AFM) is widely used in nanoscale topography and mechanical property imaging for a variety of materials. In this paper, the stability of the amplitude/phase spectroscopy curves and the imaging contrast in bimodal AM-AFM for different mode combinations are investigated computationally in ambient air. The results show that with the second mode amplitude used for topography feedback on a stiff material, the amplitude/phase spectroscopy would probably undergo volatile fluctuation, leading to unstable imaging. With the third mode amplitude set for topography imaging, it would be difficult for the feedback to maintain the prescribed amplitude since a large cantilever position variation is required for different sample moduli. With the first mode amplitude set for topography feedback, the amplitude and the phase of the second mode vary monotonically with sample modulus or viscosity in comparison with the third or the fourth mode, which is suitable for compositional contrast imaging. These results would provide useful guidelines for optimum imaging in bimodal AFM measurements.

Topographical changes in high-protein, milk powders as a function of moisture sorption using amplitude-modulation atomic force microscopy

This study aimed to examine how microscopic morphological developments, such as lactose crystallisation, swelling of particles and changes in surface roughness, occur as a function of moisture sorption in skimmed-milk (SMP), milk protein concentrate (MPC) and whey protein isolate (WPI) powders. Atomic force microscopy (AFM) has the potential to identify high-resolution, microstructural changes in high-protein, milk powder particles. A sample preparation technique was developed, which allowed a single-layer of uniformly distributed powder particles to be applied to a mica surface for subsequent AFM analysis. An amplitude modulation (AM)-AFM technique was used, and analysis showed that equilibration of powders under conditions of increasing relative humidity (RH) causes changes in topography and increased surface roughness. In SMP, significant surface changes were observed due to the development of lactose crystallisation and eventual stacking of crystal layers with increased moisture sorption. MPC, however, showed characteristic ‘dimples and folds', which may have been due to shrinkage and compaction of surfaces. With higher moisture content, the number of surface-folds and height-ranges increased, with MPC powders, held at 85% RH appearing highly jagged. The surfaces of WPI powders were smooth but were characterised by the presence of broken powder fragments. Such fragments were absent in SMP and MPC powders, suggesting that WPI powders were the most friable. WPI powders appeared not to change as a function of moisture sorption. AM-AFM was used to provide high-resolution, three-dimensional images of HPMP particles at nano- and micrometre length scales.

A fast first-principles approach to model atomic force microscopy on soft, adhesive, and viscoelastic surfaces

Quantitative atomic force microscopy (AFM) on soft polymers remains challenging due to the lack of easy-to-use computational models that accurately capture the physics of the interaction between the tip and sticky, viscoelastic samples. In this work, we enhance Attard’s continuum mechanics-based model, arguably the most rigorous contact model for adhesive viscoelastic samples, via three key enabling strategies. First, the original model’s formalism is rearranged to enable a fast and explicit solution of the model’s ordinary differential equations (ODEs). Second, the deformed surface is reconstructed using a complete set of optimized orthogonal basis functions as opposed to Attard’s original, computationally expensive radial discretization. Third, the model’s governing ODEs are solved using a multi-step numerical method to further stabilize the solution when using for soft and sticky samples. Implementing these enhancements, enhanced Attard’s model (EAM) is more stable, 3+ orders of magnitude faster, and equally accurate when compared to the original model. These facilitate EAM’s inclusion into simulations of various AFM operating modes. We demonstrate EAM based simulations of quasi-static force spectroscopy and amplitude modulation AFM approach curves on soft sticky polymer surfaces. On a typical desktop computer, simulation of an amplitude modulation approach curve with EAM takes less than a minute as compared to ≈15 h by the original Attard’s model. We expect EAM to be of interest to the AFM community because it facilitates the inclusion of rigorous models of tip-sample contact in simulations on polymer samples. EAM is available as part of the VEDA set of simulation tools deployed on nanoHUB.org cyber-infrastructure.

Effect of Eigenmode Frequency on Loss Tangent Atomic Force Microscopy Measurements

Atomic Force Microscopy (AFM) is no longer used as a nanotechnology tool responsible for topography imaging. However, it is widely used in different fields to measure various types of material properties, such as mechanical, electrical, magnetic, or chemical properties. One of the recently developed characterization techniques is known as loss tangent. In loss tangent AFM, the AFM cantilever is excited, similar to amplitude modulation AFM (also known as tapping mode); however, the observable aspects are used to extract dissipative and conservative energies per cycle of oscillation. The ratio of dissipation to stored energy is defined as tanδ. This value can provide useful information about the sample under study, such as how viscoelastic or elastic the material is. One of the main advantages of the technique is the fact that it can be carried out by any AFM equipped with basic dynamic AFM characterization. However, this technique lacks some important experimental guidelines. Although there have been many studies in the past years on the effect of oscillation amplitude, tip radius, or environmental factors during the loss tangent measurements, there is still a need to investigate the effect of excitation frequency during measurements. In this paper, we studied four different sets of samples, performing loss tangent measurements with both first and second eigenmode frequencies. It is found that performing these measurements with higher eigenmode is advantageous, minimizing the tip penetration through the surface and therefore minimizing the error in loss tangent measurements due to humidity or artificial dissipations that are not dependent on the actual sample surface.

Effect of molecular weight and architecture on nanoscale viscoelastic heterogeneity at the surface of polymer films

Dissipated energy mapping in amplitude-modulation atomic force microscopy was employed to characterize the nanoscale heterogeneous behavior of the viscoelastic response at the surface of polystyrene (PS) films of different molecular weight and architecture. By using an ultra-sharp probe with tip radius of ~1 nm, we were able to visualize the viscoelastic heterogeneities at the free surface of all PS samples. While the length scale of these heterogeneities at the surface of linear PS films was measured to be ~2.2 nm nearly independent of the molecular weight, it was significantly increased to ~3.1 nm at the surface of four-arm star-shaped PS films. We also demonstrated that similar nanoscale heterogeneous features were not observed when using a common probe with tip radius of ~10 nm, thereby confirming the intrinsic nature of the observed viscoelastic heterogeneities with sizes on the order of a few nanometers at the surface of PS films. This result provides important insights into the fundamental role of the molecular architecture in controlling the heterogeneous dynamics and many associated physical properties of amorphous polymer surfaces.

Effect of tip radius on the nanoscale viscoelastic measurement of polymers using loss tangent method in amplitude modulation AFM

We study the influence of tip radius on the viscoelastic characterization of polymers using a recently developed loss tangent (tan δ) method operated in amplitude modulation atomic force microscopy (AM-AFM) mode. By decreasing the tip radius, we found that AM-AFM tan δ of a homogeneous polystyrene film decreased close to the bulk limit value, which can be ascribed to a reduced effect of the probe/sample adhesive interaction for a smaller tip. Decreasing the tip radius also shifted the tan δ values of nanostructured blocks in a poly(styrene-b-isoprene-b-styrene) triblock copolymer film to their bulk limits, but in different trends for glassy styrene and rubbery isoprene blocks. Besides minimizing the effect of the adhesive interaction, we demonstrate that reducing the tip radius being smaller than the characteristic size of nanostructured domains is critical to obtain their true tan δ image.

Nanomechanical properties of potato flakes using atomic force microscopy

Characterizing the nanomechanical properties of plants at the sub-cellular level is important in understanding the dynamic processes underpinning both potato plant growth and downstream effects of industrial food processing. Here, we measured nanomechanical properties and mapped the elastic properties of two types of industrial potato flakes that provide both optimal and sub-optimal results during food manufacturing by employing both amplitude-modulation and force-modulation atomic force microscopy (AFM) in air. The amplitude-modulation AFM revealed that sub-optimal potato flakes were more compliant when compared to the optimal samples. Furthermore, the elastic modulus maps demonstrated optimal potato samples to be significantly stiffer than the sub-optimal samples. Therefore, our results provide evidence that probing the elastic properties of potato flakes can be a first step in providing food industries with a quantitative differential assessment between optimal and sub-optimal samples.

Sub-10nm spatial resolution for electrical properties measurements using bimodal excitation in electric force microscopy.

We demonstrate that under ambient and humidity-controlled conditions, operation of bimodal excitation single-scan electric force microscopy with no electrical feedback loop increases the spatial resolution of surface electrical property measurements down to the 5nm limit. This technical improvement is featured on epitaxial graphene layers on SiC, which is used as a model sample. The experimental conditions developed to achieve such resolution are discussed and linked to the stable imaging achieved using the proposed method. The application of the herein reported method is achieved without the need to apply DC bias voltages, which benefits specimens that are highly sensitive to polarization. Besides, it allows the simultaneous parallel acquisition of surface electrical properties (such as contact potential difference) at the same scanning rate as in amplitude modulation atomic force microscopy (AFM) topography measurements. This makes it attractive for applications in high scanning speed AFM experiments in various fields for material screening and metrology of semiconductor systems.

Nanostructure of a deep eutectic solvent at solid interfaces

HypothesisDeep eutectic solvents (DESs) are an attractive class of tunable solvents. However, their uptake for relevant applications has been limited due to a lack of detailed information on their structure-property relationships, both in the bulk and at interfaces. The lateral nanostructure of the DES-solid interfaces is likely to be more complex than previously reported and requires detailed, high-resolution investigation. ExperimentsWe employ a combination of high-resolution amplitude-modulated atomic force microscopy and molecular dynamics simulations to elucidate the lateral nanostructure of a DES at the solid-liquid interface. Specifically, the lateral and near-surface nanostructure of the DES choline chloride:glycerol is probed at the mica and highly-ordered pyrolytic graphite interfaces. FindingsThe lateral nanostructure of the DES-solid interface is heterogeneous and well-ordered in both systems. At the mica interface, the DES is strongly ordered via polar interactions. The adsorbed layer has a distinct rhomboidal symmetry with a repeat spacing of ~0.9 nm comprising all DES species. At the highly ordered pyrolytic graphite interface, the adsorbed layer appears distinctly different, forming an apolor-driven row-like structure with a repeat spacing of ~0.6 nm, which largely excludes the chloride ion. The interfacial nanostructure results from a delicate balance of substrate templating, liquid-liquid interactions, species surface affinity, and packing constraints of cations, anions, and molecular components within the DES. For both systems, distinct near-surface nanostructural layering is observed, which becomes more pronounced close to the substrate. The surface nanostructures elucidated here significantly expand our understanding of DES interfacial behavior and will enhance the optimization of DES systems for surface-based applications.

Enhanced strain rate sensitivity in thermal-cycling-rejuvenated metallic glasses

Strain rate sensitivity (SRS) is an effective parameter to demonstrate the deformation mechanism of metallic materials. However, despite extensive research, the meanings of the SRS of metallic glasses (MGs) were still vague and controversial results largely remained. In the present study, with altering the microstructural features of the magnetron sputtering CuZr MG before and after thermal cycling treatment, the effects of size of both positive and negative flow units on SRS were evaluated by amplitude-modulation atomic force microscopy (AM-AFM) and nanoindentation testing. Positive SRS index m was derived in the CuZr MG, and m increased from 0.014 to 0.040 after thermal cycling. The mechanism of the enhanced SRS and underlying microstructural evolution were explored and proposed. It shows the competition between time scales of atom rearrangement within flow units and applied loading strain rate causes the change of SRS, and both the size of positive and negative flow units play crucial roles in determining the magnitude of SRS.

Visualization of molecular binding sites at the nanoscale in the lift-up mode by amplitude-modulation atomic force microscopy.

We report a new approach to visualize the local distribution of molecular recognition sites with nanoscale resolution by amplitude-modulation atomic force microscopy. By integrating chemical modification of probes, photothermal excitation to drive a cantilever, and lift-up scanning over surface topography, we successfully visualized binding sites provided by streptavidin on a solid surface for biotin attached on an AFM probe. The optimization of measurement conditions was discussed in detail, and the application of the technique was verified with a different ligand-receptor system.

Comparison of Different Excitation Schemes in Bimodal Atomic Force Microscopy in Air and Liquid Environments

Bimodal amplitude modulation atomic force microscopy (AM-AFM) is widely used in nanoscale topography and compositional contrast imaging for various materials. In this work, we use computational simulation to compare the dynamic behaviors of AFM cantilevers in three commonly used excitation schemes in bimodal AM-AFM, i.e., the cantilever base excitation, the cantilever end excitation, and the uniform excitation along the length of the cantilever, in both air and liquid environments. The amplitude and phase spectroscopy curves and the frequency responses acquired from the three excitation schemes are compared and discussed. The results would be useful in guiding the selection of excitation methods and the optimization of imaging conditions.

Highly sensitive AFM using self-excited weakly coupled cantilevers

In this article, we propose a method, using weakly coupled cantilevers, to enhance the sensitivity of atomic force microscopy (AFM) by several orders of magnitudes. There are two major dynamics AFM methods, i.e., amplitude modulation AFM and frequency modulation AFM (FM-AFM). In FM-AFM, which is based on the eigenfrequency shift of a single cantilever, the enhancement in sensitivity is restricted because of the limitations of miniaturization in the manufacturing process. By contrast, we used coupled cantilevers based on the eigenmode shift, which corresponds to the amplitude ratio between the cantilevers. This enabled us to increase the sensitivity by reducing the coupling stiffness between cantilevers without relying on further miniaturization. In addition, to detect the eigenmode shift, even in high-viscosity environments, we produced self-excitation in the weakly coupled cantilevers by feedback control. Using this prototype system of coupled macroscale cantilevers subjected to the magnetic force, which simulates the atomic force, we confirmed the high sensitivity of the proposed method.

Power transfer in bimodal amplitude modulation atomic force microscopy in liquids: A numerical investigation

Bimodal amplitude modulation atomic force microscopy (AM-AFM) is an emerging technique for compositional imaging in liquids. In this work, we investigate the power transfer in bimodal AM-AFM in liquids by a numerical analysis. Power items are calculated by direct numerical integral and the corresponding amplitude and phase response is presented. Results show power balance is satisfied for each mode. The power transfer in each mode is significantly small compared to the external input power and most of the power is dissipated into the surrounding medium, especially for a large setpoint or cantilever-sample separation. The power transfer among different modes is complex and strongly depends on the cantilever and imaging parameters. Power transfer between different modes goes up with increasing free amplitude of the second mode. In addition, a stiffer sample will produce a more complex force spectra, which perturbs the cantilever oscillation more heavily compared to a compliant sample. Besides, the non-driven higher mode of a softer cantilever is more likely to be momentarily excited. The power items and cantilever response during imaging are also provided, revealing the phases in bimodal AFM in liquids may not be utilized to characterize the sample elasticity due to the non-monotonic trends. Instead, the amplitude of the second mode could be used to characterize the elasticity of the sample with moderate to high moduli.

Combined Experimental and Simulation Study of Amplitude Modulation Atomic Force Microscopy Measurements of Self-Assembled Monolayers in Water.

Atomic force microscopy (AFM) can be used to measure surface properties at the nanoscale. However, interpretation of measurements from amplitude modulation AFM (AM-AFM) in liquid is not straightforward due to the interactions between the AFM tip, the surface being imaged, and the water. In this work, amplitude-distance measurements and molecular dynamics simulations of AM-AFM were employed to study the effect of surface chemistry on the amplitude of tip oscillation in water. The sample surfaces consisted of self-assembled monolayers where the hydrophilicity or hydrophobicity was determined by the terminal group of the alkanethiols. Analysis showed that surface chemical composition influences the hydration structure near the interface which affects the forces experienced by the tip and in turn changes the amplitude profile. This observation could aid our understanding of AM-AFM measurements of interfacial phenomena on various surfaces in water.