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Viscoelastic characterization of materials at the micro- and nanoscales is commonly performed with the aid of force-distance relationships acquired using atomic force microscopy (AFM). The general strategy for existing methods is to fit the observed material behavior to specific viscoelastic models, such as generalized viscoelastic models or power-law rheology models, among others. Here we propose a new method to invert and obtain the viscoelastic properties of a material through the use of the Z-transform, without using a model. We present the rheological viscoelastic relations in their classical derivation and their Z-domain correspondence. We illustrate the proposed technique on a model experiment involving a traditional ramp-shaped force-distance AFM curve, demonstrating good agreement between the viscoelastic characteristics extracted from the simulated experiment and the theoretical expectations. We also provide a path for calculating standard viscoelastic responses from the extracted material characteristics. The new technique based on the Z-transform is complementary to previous model-based viscoelastic analyses and can be advantageous with respect to Fourier techniques due to its generality. Additionally, it can handle the unbounded inputs traditionally used to acquire force-distance relationships in AFM, such as “ramp” functions, in which the cantilever position is displaced linearly with time for a finite period of time.

Atomic force microscopy (AFM) techniques have provided and continue to provide increasingly important insights into surface morphology, mechanics, and other critical material characteristics at the nanoscale. One attractive implementation involves extracting meaningful material properties, which demands physically accurate models specifically designed for AFM experimentation and simulation. The AFM community has pursued the precise quantification and extraction of rate-dependent material properties, in particular, for a significant period of time, attempting to describe the standard viscoelastic response of materials. AFM static force spectroscopy (SFS) is one approach commonly used in pursuit of this goal. It is capable of acquiring rich temporal insight into the behavior of a sample. During AFM-SFS experiments the cantilever base approaches samples with a nearly constant velocity, which is manipulated to investigate different timescales of the mechanical response. This manuscript seeks to build upon our previous work and presents an approach to extracting useful linear viscoelastic information from AFM-SFS experiments. In addition, the basis for selecting and restricting the model parameters for fitting is discussed from the perspective of applying this technique on a practical level. This work begins with a guided discussion that develops a fit function from fundamental laws, continues with conditioning a raw SFS experimental dataset, and concludes with the fit and prediction of viscoelastic response parameters such as storage modulus, loss modulus, loss angle, and compliance. These steps constitute a complete guide to leveraging AFM-SFS data to estimate key material parameters, with a series of detailed insights into both the methodology and supporting analytical choices.

Atomic force microscopy (AFM) is an important tool for measuring a variety of nanoscale surface properties, such as topography, viscoelasticity, electrical potential and conductivity. Some of these properties are measured using contact methods (static contact or intermittent contact), while others are measured using noncontact methods. Some properties can be measured using different approaches. Conductivity, in particular, is mapped using the contact-mode method. However, this modality can be destructive to delicate samples, since it involves continuously dragging the cantilever tip on the surface during the raster scan, while a constant tip–sample force is applied. In this paper we discuss a possible approach to develop an intermittent-contact conductive AFM mode based on Fourier analysis, whereby the measured current response consists of higher harmonics of the cantilever oscillation frequency. Such an approach may enable the characterization of soft samples with less damage than contact-mode imaging. To explore its feasibility, we derive the analytical form of the tip–sample current that would be obtained for attractive (noncontact) and repulsive (intermittent-contact) dynamic AFM characterization, and compare it with results obtained from numerical simulations. Although significant instrumentation challenges are anticipated, the modelling results are promising and suggest that Fourier-based higher-harmonics current measurement may enable the development of a reliable intermittent-contact conductive AFM method.

Environmental control on graphene is becoming increasingly necessary to study fundamental processes and to achieve graphene-based technological developments. Here, we designed dynamic actuation on split graphene fluid-environments by supporting graphene sheets on mesoporous thin films (air up - nanopore-confined fluid down). This approach allows transporting species and performing nanochemistry at specific sites under the graphene membrane. We also show distinctive behavior affecting graphene permeability linked to the driving force of the involved water-nanopore interplay processes. This novel precise control of graphene environment offers possibilities for further graphene-based technological developments, such as sensor and actuator tools highly required in lab-on-a-chip devices, as well as to perform fundamental yet elusive studies on water interactions in integrated nanomaterials. Fil: Gimenez, Rocio Aldana. Comisión Nacional de Energía Atómica; Argentina Fil: Barrionuevo, Santiago. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina Fil: Berli, Claudio Luis Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto de Desarrollo Tecnológico para la Industria Química. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnológico para la Industria Química; Argentina Fil: Ibañez, Francisco Javier. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina Fil: Bellino, Martin Gonzalo. Comisión Nacional de Energía Atómica; Argentina

Atomic force microscopy (AFM) is a widely use technique to acquire topographical, mechanical, or electromagnetic properties of surfaces, as well as to induce surface modifications at the micrometer and nanometer scale. Viscoelastic materials, examples of which include many polymers and biological materials, are an important class of systems, the mechanical response of which depends on the rate of application of the stresses imparted by the AFM tip. The mechanical response of these materials thus depends strongly on the frequency at which the characterization is performed, so much so that important aspects of behavior may be missed if one chooses an arbitrary characterization frequency regardless of the materials properties. In this paper we present a linear viscoelastic analysis of intermittent-contact, nearly resonant dynamic AFM characterization of such materials, considering the possibility of multiple characteristic times. We describe some of the intricacies observed in their mechanical response and alert the reader about situations where mischaracterization may occur as a result of probing the material at frequency ranges or with probes that preclude observation of its viscoelastic behavior. While we do not offer a solution to the formidable problem of inverting the frequency-dependent viscoelastic behavior of a material from dynamic AFM observables, we suggest that a partial solution is offered by recently developed quasi-static force–distance characterization techniques, which incorporate viscoelastic models with multiple characteristic times and can help inform dynamic AFM characterization.

In this short paper we explore the use of higher eigenmodes in single-eigenmode amplitude-modulation atomic force microscopy (AFM) for the small-indentation imaging of soft viscoelastic materials. In viscoelastic materials, whose response depends on the deformation rate, the tip–sample forces generated as a result of sample deformation increase as the tip velocity increases. Since the eigenfrequencies in a cantilever increase with eigenmode order, and since higher oscillation frequencies lead to higher tip velocities for a given amplitude (in viscoelastic materials), the sample indentation can in some cases be reduced by using higher eigenmodes of the cantilever. This effect competes with the lower sensitivity of higher eigenmodes, due to their larger force constant, which for elastic materials leads to greater indentation for similar amplitudes, compared with lower eigenmodes. We offer a short theoretical discussion of the key underlying concepts, along with numerical simulations and experiments to illustrate a simple recipe for imaging soft viscoelastic matter with reduced indentation.

Kelvin probe force microscopy (KPFM) has been used for the characterization of metals, insulators, and semiconducting materials on the nanometer scale. Especially in semiconductors, the charge dynamics are of high interest. Recently, several techniques for time-resolved measurements with time resolution down to picoseconds have been developed, many times using a modulated excitation signal, e.g., light modulation or bias modulation that induces changes in the charge carrier distribution. For fast modulation frequencies, the KPFM controller measures an average surface potential, which contains information about the involved charge carrier dynamics. Here, we show that such measurements are prone to artifacts due to frequency mixing, by performing numerical dynamics simulations of the cantilever oscillation in KPFM subjected to a bias-modulated signal. For square bias pulses, the resulting time-dependent electrostatic forces are very complex and result in intricate mixing of frequencies that may, in some cases, have a component at the detection frequency, leading to falsified KPFM measurements. Additionally, we performed fast Fourier transform (FFT) analyses that match the results of the numerical dynamics simulations. Small differences are observed that can be attributed to transients and higher-order Fourier components, as a consequence of the intricate nature of the cantilever driving forces. These results are corroborated by experimental measurements on a model system. In the experimental case, additional artifacts are observed due to constructive or destructive interference of the bias modulation with the cantilever oscillation. Also, in the case of light modulation, we demonstrate artifacts due to unwanted illumination of the photodetector of the beam deflection detection system. Finally, guidelines for avoiding such artifacts are given.

We explore the contact problem of a flat-end indenter penetrating intermittently a generalized viscoelastic surface, containing multiple characteristic times. This problem is especially relevant for nanoprobing of viscoelastic surfaces with the highly popular tapping-mode AFM imaging technique. By focusing on the material perspective and employing a rigorous rheological approach, we deliver analytical closed-form solutions that provide physical insight into the viscoelastic sources of repulsive forces, tip–sample dissipation and virial of the interaction. We also offer a systematic comparison to the well-established standard harmonic excitation, which is the case relevant for dynamic mechanical analysis (DMA) and for AFM techniques where tip–sample sinusoidal interaction is permanent. This comparison highlights the substantial complexity added by the intermittent-contact nature of the interaction, which precludes the derivation of straightforward equations as is the case for the well-known harmonic excitations. The derivations offered have been thoroughly validated through numerical simulations. Despite the complexities inherent to the intermittent-contact nature of the technique, the analytical findings highlight the potential feasibility of extracting meaningful viscoelastic properties with this imaging method.

Bioinspired design has been central in the development of hierarchical nanocomposites. Particularly, the nacre-mimetic brick-and-mortar structure has shown excellent mechanical properties, as well as gas-barrier properties and optical transparency. Along with these intrinsic properties, the layered structure has also been utilized in sensing devices. Here we extend the multifunctionality of nacre-mimetics by designing an optically transparent and electron conductive coating based on PEDOT:PSS and nanoclays Laponite RD and Cloisite Na+. We carry out extensive characterization of the nanocomposite using transmittance spectra (transparency), conductive atomic force microscopy (conductivity), contact-resonance force microscopy (mechanical properties), and SEM combined with a variety of stress-strain AFM experiments and AFM numerical simulations (internal structure). We further study the nanoclay’s response to the application of pressure with multifrequency AFM and conductive AFM, whereby increases and decreases in conductivity can occur for the Laponite RD composites. We offer a possible mechanism to explain the changes in conductivity by modeling the coating as a 1-dimensional multibarrier potential for electron transport, and show that conductivity can change when the separation between the barriers changes under the application of pressure, and that the direction of the change depends on the energy of the electrons. We did not observe changes in conductivity under the application of pressure with AFM for the Cloisite Na+ nanocomposite, which has a large platelet size compared with the AFM probe diameter. No pressure-induced changes in conductivity were observed in the clay-free polymer either.

Organic photovoltaic systems comprising donor polymers and acceptor fullerene derivatives are attractive for inexpensive energy harvesting. Extensive research on polymer solar cells has provided insight into the factors governing device-level efficiency and stability. However, the detailed investigation of nanoscale structures is still challenging. Here we demonstrate the analysis and modification of unidentified surface aggregates. The aggregates are characterized electrically by Kelvin probe force microscopy and conductive atomic force microscopy (C-AFM), whereby the correlation between local electrical potential and current confirms a defective charge transport. Bimodal AFM modification confirms that the aggregates exist on top of the solar cell structure, and is used to remove them and to reveal the underlying active layer. The systematic analysis of the surface aggregates suggests that the structure consists of PCBM molecules.

Significant progress has been accomplished in the development of experimental contact-mode and dynamic-mode atomic force microscopy (AFM) methods designed to measure surface material properties. However, current methods are based on one-dimensional (1D) descriptions of the tip–sample interaction forces, thus neglecting the intricacies involved in the material behavior of complex samples (such as soft viscoelastic materials) as well as the differences in material response between the surface and the bulk. In order to begin to address this gap, a computational study is presented where the sample is simulated using an enhanced version of a recently introduced model that treats the surface as a collection of standard-linear-solid viscoelastic elements. The enhanced model introduces in-plane surface elastic forces that can be approximately related to a two-dimensional (2D) Young’s modulus. Relevant cases are discussed for single- and multifrequency intermittent-contact AFM imaging, with focus on the calculated surface indentation profiles and tip–sample interaction force curves, as well as their implications with regards to experimental interpretation. A variety of phenomena are examined in detail, which highlight the need for further development of more physically accurate sample models that are specifically designed for AFM simulation. A multifrequency AFM simulation tool based on the above sample model is provided as supporting information.

This paper introduces a quasi-3-dimensional (Q3D) viscoelastic model and software tool for use in atomic force microscopy (AFM) simulations. The model is based on a 2-dimensional array of standard linear solid (SLS) model elements. The well-known 1-dimensional SLS model is a textbook example in viscoelastic theory but is relatively new in AFM simulation. It is the simplest model that offers a qualitatively correct description of the most fundamental viscoelastic behaviors, namely stress relaxation and creep. However, this simple model does not reflect the correct curvature in the repulsive portion of the force curve, so its application in the quantitative interpretation of AFM experiments is relatively limited. In the proposed Q3D model the use of an array of SLS elements leads to force curves that have the typical upward curvature in the repulsive region, while still offering a very low computational cost. Furthermore, the use of a multidimensional model allows for the study of AFM tips having non-ideal geometries, which can be extremely useful in practice. Examples of typical force curves are provided for single- and multifrequency tapping-mode imaging, for both of which the force curves exhibit the expected features. Finally, a software tool to simulate amplitude and phase spectroscopy curves is provided, which can be easily modified to implement other controls schemes in order to aid in the interpretation of AFM experiments.

We examine different approaches to model viscoelasticity within atomic force microscopy (AFM) simulation. Our study ranges from very simple linear spring–dashpot models to more sophisticated nonlinear systems that are able to reproduce fundamental properties of viscoelastic surfaces, including creep, stress relaxation and the presence of multiple relaxation times. Some of the models examined have been previously used in AFM simulation, but their applicability to different situations has not yet been examined in detail. The behavior of each model is analyzed here in terms of force–distance curves, dissipated energy and any inherent unphysical artifacts. We focus in this paper on single-eigenmode tip–sample impacts, but the models and results can also be useful in the context of multifrequency AFM, in which the tip trajectories are very complex and there is a wider range of sample deformation frequencies (descriptions of tip–sample model behaviors in the context of multifrequency AFM require detailed studies and are beyond the scope of this work).

We present an exploratory study of multimodal tapping-mode atomic force microscopy driving more than three cantilever eigenmodes. We present tetramodal (4-eigenmode) imaging experiments conducted on a thin polytetrafluoroethylene (PTFE) film and computational simulations of pentamodal (5-eigenmode) cantilever dynamics and spectroscopy, focusing on the case of large amplitude ratios between the fundamental eigenmode and the higher eigenmodes. We discuss the dynamic complexities of the tip response in time and frequency space, as well as the average amplitude and phase response. We also illustrate typical images and spectroscopy curves and provide a very brief description of the observed contrast. Overall, our findings are promising in that they help to open the door to increasing sophistication and greater versatility in multi-frequency AFM through the incorporation of a larger number of driven eigenmodes, and in highlighting specific future research opportunities.

This paper presents computational simulations of single-mode and bimodal atomic force microscopy (AFM) with particular focus on the viscoelastic interactions occurring during tip–sample impact. The surface is modeled by using a standard linear solid model, which is the simplest system that can reproduce creep compliance and stress relaxation, which are fundamental behaviors exhibited by viscoelastic surfaces. The relaxation of the surface in combination with the complexities of bimodal tip–sample impacts gives rise to unique dynamic behaviors that have important consequences with regards to the acquisition of quantitative relationships between the sample properties and the AFM observables. The physics of the tip–sample interactions and its effect on the observables are illustrated and discussed, and a brief research outlook on viscoelasticity measurement with intermittent-contact AFM is provided.

This paper presents experiments on Nafion® proton exchange membranes and numerical simulations illustrating the trade-offs between the optimization of compositional contrast and the modulation of tip indentation depth in bimodal atomic force microscopy (AFM). We focus on the original bimodal AFM method, which uses amplitude modulation to acquire the topography through the first cantilever eigenmode, and drives a higher eigenmode in open-loop to perform compositional mapping. This method is attractive due to its relative simplicity, robustness and commercial availability. We show that this technique offers the capability to modulate tip indentation depth, in addition to providing sample topography and material property contrast, although there are important competing effects between the optimization of sensitivity and the control of indentation depth, both of which strongly influence the contrast quality. Furthermore, we demonstrate that the two eigenmodes can be highly coupled in practice, especially when highly repulsive imaging conditions are used. Finally, we also offer a comparison with a previously reported trimodal AFM method, where the above competing effects are minimized.

This paper illustrates through numerical simulation the complexities encountered in high-damping AFM imaging, as in liquid enviroments, within the specific context of multifrequency atomic force microscopy (AFM). The focus is primarily on (i) the amplitude and phase relaxation of driven higher eigenmodes between successive tip–sample impacts, (ii) the momentary excitation of non-driven higher eigenmodes and (iii) base excitation artifacts. The results and discussion are mostly applicable to the cases where higher eigenmodes are driven in open loop and frequency modulation within bimodal schemes, but some concepts are also applicable to other types of multifrequency operations and to single-eigenmode amplitude and frequency modulation methods.

The resonance frequency, amplitude, and phase response of the first two eigenmodes of two contact-resonance atomic force microscopy (CR-AFM) configurations, which differ in the method used to excite the system (cantilever base vs sample excitation), are analyzed in this work. Similarities and differences in the observables of the cantilever dynamics, as well as the different effect of the tip–sample contact properties on those observables in each configuration are discussed. Finally, the expected accuracy of CR-AFM using phase-locked loop detection is investigated and quantification of the typical errors incurred during measurements is provided.

In this work we report the stimulation of astrocytic calcium signalling using an organic cell sensing and stimulating transistor (O-CST). We demonstrate that astroglial cells can adhere and proliferate on these devices giving us the possibility to stimulate bioelectrical activity in this type of cells. By the use of a microfluorimetric calcium imaging approach we show that our device is able to evoke an increase in intracellular calcium levels. This research opens a new path in the study of glial cells and their bioelectrical activity.

Characterization of subsurface morphology and mechanical properties with nanoscale resolution and depth control is of significant interest in soft matter fields like biology, polymer science, and even in future applications like nanomanufacturing, where buried structural and compositional features are important to the functionality of the system. However, controllably "feeling" the subsurface is a challenging task for which the available imaging tools are relatively limited. In this paper, we propose a trimodal atomic force microscopy (AFM) imaging scheme, whereby three eigenmodes of the microcantilever probe are used as separate control "knobs" to simultaneously measure the topography, modulate sample indentation by the tip during tip-sample impact, and map compositional contrast, respectively. We illustrate this multifrequency imaging approach through computational simulation and experiments conducted on ultrathin polymer films with embedded glass nanoparticles in ambient air. By actively increasing the tip-sample indentation using a higher eigenmode of the cantilever, we are able to gradually and controllably reveal glass nanoparticles which are buried tens of nanometers deep under the surface, while still being able to refocus on the surface.

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.

We demonstrate a simple and robust procedure for the fabrication of rhodamine-doped nanoporous poly(methyl methacrylate) (PMMA) films, whose optical properties, such as anti-reflection, fluorescence and absorption can be tailored to specific applications. By exploiting phase separation of a binary polymer blend (PMMA and polystyrene), we fabricated foam-like nanoporous films that could be easily and cost-effectively integrated into the fabrication process of optical components. We link film morphology, studied by multifrequency atomic force microscopy (AFM), to the effective refractive index of the films for use as anti-reflection coatings. The film's morphology leads to superior broadband anti-reflection performance compared with homogeneous films. For applications involving optical filters and spectral conversion layers (e.g., for photovoltaic applications), we doped the films with the fluorescent molecule rhodamine, whereby simple variations in the fabrication process enabled us to prepare rhodamine-doped nanoporous PMMA with tunable fluorescence and absorption, without losing the anti-reflective properties. The above combination of optical properties makes the films attractive for a wide range of applications.

The aim of this work is to develop an equivalent circuit model for the metal-organic semiconductor-electrolyte structures that are typically used as transducers in biosensor devices. In particular, a perylene derivative material is implemented in the active layer of a gold-semiconductor-electrolyte stack. Our approach is extending the standard range of the bias voltages applied for devices that operate in water. This particular characterisation protocol allows to distinguish and investigate the different mechanisms that occur at the different layers and interfaces: adsorption of ions in the semiconductor; accumulation and charge exchange of carriers at the semiconductor/electrolyte interface; percolation of the ionic species through the organic semiconductor; ion diffusion across the electrolyte; ion adsorption and charge exchange at the platinum interface. We highlight the presence of ion percolation through the organic semiconductor layer, which is described in the equivalent circuit model by means of a de Levie impedance. The presence of percolation has been demonstrated by environmental scanning electron microscopy and profilometry analysis. Although percolation is much more evident at high negative bias values, it is still present even at low bias conditions. The very good agreement between the model and the experimental data makes the model a valid tool for studying the transducing mechanisms between organic films and the physiological environment.

Using atomic force microscopy (AFM), supported by semicontinuum numerical simulations, we determine the effect of tip-subsurface van der Waals interactions on nanoscale friction and adhesion for suspended and silicon dioxide supported graphene of varying thickness. While pull-off force measurements reveal no layer number dependence for supported graphene, suspended graphene exhibits an increase in pull-off force with thickness. Further, at low applied loads, friction increases with increasing number of layers for suspended graphene, in contrast to reported trends for supported graphene. We attribute these results to a competition between local forces that determine the deformation of the surface layer, the profile of the membrane as a whole, and van der Waals forces between the AFM tip and subsurface layers. We find that friction on supported monolayer graphene can be fit using generalized continuum mechanics models, from which we extract the work of adhesion and interfacial shear strength. In addition, we show that tip-sample adhesive forces depend on interactions with subsurface material and increase in the presence of a supporting substrate or additional graphene layers.

The cantilever dynamics in single-frequency scanning probe microscopy (SPM) are undefined due to having only two output variables, which leads to poorly understood image contrast. To address this shortcoming, generalized phase imaging scanning probe microscopy (GP-SPM), based on broad band detection and multi-eigenmode operation, is developed and demonstrated on diamond nanoparticles with different functionalization layers. It is shown that rich information on tip-surface interactions can be acquired by separating the response amplitude, instant resonance frequency, and quality factor. The obtained data allow high-resolution imaging even in the ambient environment. By tuning the strength of tip-surface interaction, different surface functionalizations can be discerned.

Since the 1980s, atomic force microscopy (AFM) has rapidly developed into a versatile, high-resolution characterization technique, available in a variety of imaging modes. Within intermittent-contact tapping-mode, imaging bistability and sample mechanical damage continue to be two of the most important challenges faced daily by AFM users. Recently, a new double-control-loop tapping-mode imaging algorithm (frequency and amplitude modulation AFM, FAM-AFM) was proposed and evaluated within numerical simulations, demonstrating a reduction in the repulsive tip–sample forces and the absence of bistability. This article presents a much simpler algorithm, frequency and force modulation AFM (FFM-AFM), which requires only a single control loop and offers the same benefits as FAM-AFM. The concept is applied to calculate the cross-sectional scan of a carbon nanotube sample resting on a silicon surface, which is then compared to a previously reported image obtained in conventional amplitude-modulation tapping-mode, shown to be in agreement with the experimental result.

A new intermittent-contact atomic force microscopy (AFM) mode (frequency and force modulation AFM, FFM-AFM) has been recently proposed to characterize soft samples. This method uses excitation force frequency and amplitude modulation to eliminate bistability and reduce the tip-sample forces. This letter describes theoretical modeling of FFM-AFM applied to a single bacteriorhodopsin molecule on a substrate, showing that its cross section can be measured without damage, in contrast to conventional tapping-mode AFM. Speculations are made regarding nonideal conditions and the ability of FFM-AFM to perform quantitative nanoelasticity measurements.

This project focused on the development of single-pass multifrequency atomic force microscopy methods for the rapid multi-function nanoscale characterization of energy-relevant materials.

Recent experiments reveal that a scanning tunneling microscopy (STM) probe tip can generate a highly localized strain field in a graphene drumhead, which in turn leads to pseudomagnetic fields in the graphene that can spatially confine graphene charge carriers in a way similar to a lithographically defined quantum dot (QD). While these experimental findings are intriguing, their further implementation in nanoelectronic devices hinges upon the knowledge of key underpinning parameters, which still remain elusive. In this paper, we first summarize the experimental measurements of the deformation of graphene membranes due to interactions with the STM probe tip and a back gate electrode. We then carry out systematic coarse grained, (CG), simulations to offer a mechanistic interpretation of STM tip-induced straining of the graphene drumhead. Our findings reveal the effect of (i) the position of the STM probe tip relative to the graphene drumhead center, (ii) the sizes of both the STM probe tip and graphene drumhead, as well as (iii) the applied back-gate voltage, on the induced strain field and corresponding pseudomagnetic field. These results can offer quantitative guidance for future design and implementation of reversible and on-demand formation of graphene QDs in nanoelectronics., Comment: 21 pages, 9 figures

Process engineering design relies on a host of mechanical devices that enable transport phenomena to take place under controlled conditions. These devices include pipes, valves, pumps, chemical reactors, heat exchangers, packed columns, etc. Mass, energy, and momentum transfer will also be essential phenomena in nanoprocess engineering, particularly at the interface between micro- and nanodevices. Control valves are one of the most fundamental components. In this paper we explore the design of a silicon cantilever valve for fluid transport control at the molecular level (34.5–70 nm in length). We utilize design elements that can be synthesized with existing or emerging chemical and solid state fabrication methods. Thus, the valve is constructed with functionalized silicon surfaces, single-wall carbon nanotubes, and organic monolayers. While molecular mechanics design limitations were overcome with help from classical engineering approximations, nonlinear effects, such as nanotube crimping (for an in-line valve design), are accounted for through full-physics atomistic simulations. Optimal design geometries and operating deflection ranges have been estimated for a device containing over 75 000 atoms.

Applications of microbubbles (MBs) in diagnostic and therapeutic interventions critically depend on their stability and scattering properties. The shell chemistry of MBs defines these properties. We investigated the effects of shell chemistry on the size, abundance, acoustic response, and mechanical properties of MBs by varying the poly(ethylene glycol) (PEG) molar ratio (0 to 100%) in a two-lipid (DPPC and DPPE-PEG2000) component shell formulation. Increasing PEG concentration from 0% to 10% resulted in an increase in the number of MBs by at least 10-fold, with adverse effects upon further increases. Microbubbles made with 5–10% PEG generated the strongest fundamental as well as nonlinear (subharmonic and second harmonic) components at the excitation frequency of 2.25 MHz. We used interfacial rheological models to determine the mechanical properties of MB shells as functions of PEG concentration using experimentally measured attenuation values. We also employed atomic force microscopy (AFM) to perform th...

Addition of a strong base to Nafion® proton exchange membranes is a common practice in industry to increase their overall performance in fuel cells. Here, we investigate the evolution of the nano-rheological properties of Nafion thin films as a function of the casting pH, via characterization with static and dynamic, contact and intermittent-contact atomic force microscopy (AFM) techniques. The addition of KOH causes non-monotonic changes in the viscoelastic properties of the films, which behave as highly dissipative, softer materials near neutral pH values, and as harder, more elastic materials at extreme pH values. We quantify this behavior through calculation of the temporal evolution of the compliance and the glassy compliance under static AFM measurements. We complement these observations with dynamic AFM metrics, including dissipated power and virial (for intermittent-contact-mode measurements), and contact resonance frequency and quality factor (for dynamic contact-mode measurements). We explain th...

We introduce a novel and potentially powerful, yet relatively simple extension of the spectral inversion method, which offers the possibility of carrying out 4-dimensional (4D) atomic force spectroscopy. With the extended spectral inversion method it is theoretically possible to measure the tip–sample forces as a function of the three Cartesian coordinates in the scanning volume (x, y and z) and the vertical velocity of the tip, through a single 2-dimensional (2D) surface scan. Although signal-to-noise ratio limitations can currently prevent the accurate experimental implementation of the 4D method, and the extraction of rate-dependent material properties from the force maps is a formidable challenge, the spectral inversion method is a promising approach due to its dynamic nature, robustness, relative simplicity and previous successes.

Multi-frequency atomic force microscopy (AFM), in which the microcantilever is driven at more than one frequency, has emerged as a promising technique for simultaneous topographical imaging and material property mapping. While enabling significant advantages over traditional tapping-mode AFM, the greater dynamic complexity of multi-frequency AFM also requires deeper understanding on the part of the user in order to properly interpret the results obtained. This paper illustrates this challenge by exploring a few key dynamic non-idealities, which if neglected could lead to errors of interpretation. These non-ideal phenomena offer a unique opportunity for mechanical engineers to make significant contributions to nanoscale science by providing an increased understanding of the imaging process dynamics and by developing mitigation strategies for dynamics-related artifacts.Copyright © 2012 by ASME

We have recently reported on experimental observations of silk-elastin-like protein polymers (SELPs) that self-assembled into 1-dimensional nanofibers on mica surfaces upon application of a mechanical stimulus with atomic force microscopy (AFM) in water. SELPs are genetically engineered block co-polymers made of silk-like blocks (Gly-Ala-Gly-Ala-Gly-Ser) from Bombyx mori (silkworm) and elastin-like blocks (Gly-Val-Gly-Val-Pro) from mammalian elastin. The experiment consisted of adsorbing the protein polymer onto a freshly cleaved mica surface, followed by AFM characterization under different sets of imaging parameters, each of which led to different nanofiber coverage rates. In order to gain further understanding of the factors governing the self-assembly process, we utilized multimodal AFM simulation to formulate and guide the implementation of a suitable force modulation strategy, which allowed us to observe trends of the surface coverage rate as a function of the applied peak forces. The simulations suggest that a nearly linear control of the peak tapping forces can be achieved by following simple scaling laws based on the harmonic oscillator model.

Topographical imaging with atomic force microscopy (AFM) has become an established method since its invention in 1986. However, there exist a variety of imaging artifacts that can distort the acquired images, especially when using sharp probes such as carbon nanotubes or nanowires. This paper briefly discusses common imaging artifacts occurring at sharp step edges and explores theoretically their mitigation with spectral and multi-frequency methods that can perform simultaneous topographical imaging and force spectroscopy. The work focuses on the spectral inversion method, which has been experimentally validated by others [Stark et al., Proc. Natl. Acad. Sci. USA 99, 8473–8478 (2002); Sahin et al., Nature Nanotech. 2, 507–514 (2007)], and on a recently proposed dual-frequency-modulation method, which has been demonstrated within computational simulations and is under experimental implementation in our laboratory [Solares & Chawla, Meas. Sci. & Technol. 19, No. 055502; Chawla & Solares, Meas. Sci. & Technol. 20, No. 015501].

The ability of atomic force microscopy (AFM) to acquire tip-sample interaction force curves has allowed researchers to understand the mechanical behavior of numerous materials at the nanoscale. However, AFM force spectroscopy with the most commonly used techniques can be a slow process for non-uniform samples, as it often requires the measurement to be performed at one fixed surface point at a time. In this paper we present two dynamic AFM based spectroscopy methods, one requiring operation in single-frequency-modulation mode and another using dual-frequency-modulation, which could allow a more rapid acquisition of topography and tip-sample interaction force curves. Numerical simulation results are provided along with discussions on the benefits and limitations of both.

This report was generated as part of a Student Temporary Employment Program Internship from July 2006 through June 2007. The report presents basic didactic concepts and reviews recent progress in the scientific literature on atomic force microscopy (AFM). A new AFM technique is studied. The novel AFM approach is based on force and frequency modulation (FFM-AFM) that enables nondestructive AFM measurements of soft samples such as biological materials in solution. The vibrational properties of the AFM cantilever probe are examined to determine extermal conditions that the sample is likely to experience.

When using single-walled carbon nanotube (SWNT) probes to create AFM images of SWNT samples in tapping mode, elastic deformations of the probe and sample result in a decrease in the apparent width of the sample. Here we show that there are two major mechanisms for this effect, smooth gliding and snapping, and compare their dynamics to the case when a conventional silicon tip is used to image a bare silicon surface. Using atomistic and continuum simulations, we analyze in detail the shape of the tip−sample interaction potential for three model cases and show that in the absence of adhesion and friction forces, more than two discrete, physically meaningful solutions of the oscillation amplitude are possible when snapping occurs (in contrast to the existence of one attractive and one repulsive solution for conventional silicon AFM tips). We present experimental results indicating that a continuum of amplitude solutions is possible when using SWNT tips and explain this phenomenon with dynamic simulations that explicitly include tip−sample adhesion and friction forces. We also provide simulation results of SWNT tips imaging Si(111)−CH_3 surface step edges and Au nanocrystals, which indicate that SWNT probe multistability may be a general phenomenon, not limited to SWNT samples.

We have previously reported that 4−6 nm diameter single-wall carbon nanotube (SWNT) probes used for tapping-mode atomic force microscopy (AFM) can exhibit lateral resolution that is significantly better than the probe diameter when prone nanotubes are imaged on a flat SiO_2 surface. To further investigate this phenomenon, accurate models for use in atomistic molecular dynamics simulations were constructed on the basis of transmission electron microscopy (TEM) and AFM data. Probe−sample interaction potentials were generated by utilization of force fields derived from ab initio quantum mechanics calculations and material bulk and surface properties, and the resulting force curves were integrated numerically with the AFM cantilever equation of motion. The simulations demonstrate that, under the AFM imaging conditions employed, elastic deformations of both the probe and sample nanotubes result in a decrease of the apparent width of the sample. This behavior provides an explanation for the unexpected resolution improvement and illustrates some of the subtleties involved when imaging is performed with SWNT probes in place of conventional silicon probes. However, the generality of this phenomenon for other AFM imaging applications employing SWNT probes remains to be explored.

Adsorption, chemisorption, and reconstruction at the surfaces of ferroelectric materials can all contribute toward the pinning of ferroelectric polarization, which is called the electrical imprint effect. Here, we show that the opposite is also true: freshly cleaved, atomically flat surfaces of (001) oriented BaTiO3 exhibit a persistent change in surface chemistry that is driven by ferroelectric polarization. This surface modification is explored using lateral force microscopy (LFM), while the ferroelectric polarization is probed using piezoresponse force microscopy. We find that immediately after cleaving BaTiO3, LFM reveals friction contrast between ferroelectric domains. We also find that this surface modification remains after the ferroelectric domain distribution is modified, resulting in an imprint of the original ferroelectric domain distribution on the sample surface. This friction imprint effect has implications for surface patterning as well as ferroelectric device operation and failure.

We investigate the effects of the frequency and density of a nanomechanical stimulus on nucleation and growth of silk-elastin-like protein polymer (SELP) nanofibers. Repetitive tappings are crucial to create nucleation areas and a potential molecular level mechanism was proposed. Using this technique mechanically guided nanofiber patterns were successfully created.

One common application of atomic force microscopy (AFM) is the acquisition of tip–sample interaction force curves. However, this can be a slow process when the user is interested in studying non-uniform samples, because existing contact- and dynamic-mode methods require that the measurement be performed at one fixed surface point at a time. This paper proposes an AFM method based on dual frequency modulation using two cantilevers in series, which could be used to measure the tip–sample interaction force curves and topography of the entire sample with a single surface scan, in a time that is comparable to the time needed to collect a topographic image with current AFM imaging modes. Numerical simulation results are provided along with recommended parameters to characterize tip–sample interactions resembling those of conventional silicon tips and carbon nanotube tips tapping on silicon surfaces.

The characterization of deep surface trenches with atomic force microscopy (AFM) presents significant challenges due to the sharp step edges that disturb the instrument and prevent it from faithfully reproducing the sample topography. Previous authors have developed AFM methodologies to successfully characterize semiconductor surface trenches with dimensions on the order of tens of nanometers. However, the study of imaging fidelity for features with dimensions smaller than 10 nm has not yet received sufficient attention. Such a study is necessary because small features in some cases lead to apparently high-quality images that are distorted due to tip and sample mechanical deformation. This paper presents multi-scale simulations, illustrating common artifacts affecting images of nanoscale trenches taken with fine carbon nanotube probes within amplitude-modulation and frequency-force-modulation AFM (AM-AFM and FFM-AFM, respectively). It also describes a methodology combining FFM-AFM with a step-in/step-out algorithm analogous to that developed by other groups for larger trenches, which can eliminate the observed artifacts. Finally, an overview of the AFM simulation methods is provided. These methods, based on atomistic and continuum simulation, have been previously used to study a variety of samples including silicon surfaces, carbon nanotubes and biomolecules.