Tapping Mode Atomic Force Microscopy Research Articles

Synthesis of a Rod-rod Diblock Copolymer, Poly(3-hexylthiophene)-block-poly(furfuryl isocyanate), through the Anionic Polymerization with an Oxyanionic Macroinitiator

A rod-rod diblock copolymer (diBCP), poly(3-hexylthiophene)-block-poly(furfuryl isocyanate) (P3HT-b-PFIC), was synthesized through the anionic polymerization with an oxyanionic macroinitiator of P3HT. The properties of the diBCP (molecular weight, dispersity, composition, thermal stability, UV-visible absorption, and thin film morphology) were determined by various analytical methods. P3HT-b-PFIC was blended with C60 in a toluene solution to prepare a thin film of binary electron donor/acceptor system. Such blending enabled partial conjugation of the two components by the Diels-Alder reaction between furan and C60 at 60 °C for 3 h; the mixture was then spin-cast as a thin film, and annealed at 250 °C for 24 h. Tapping-mode atomic force microscopy (AFM) revealed that P3HT and C60 domains had nanoscale interfaces without a large phase segregation. This result indicated that the microphase separation of C60-functionalized P3HT-b-PFIC preserved even at high temperature provided free C60 molecules with channels to diffuse on the sides of P3HT domain, thus preventing the macroscopic crystallization of free C60 through the interfacial stabilization.

Nickel Nanofilms Electrolessly Deposited on Organosilane Nanorings and Characterized by Contact Mode AFM Combined with Magnetic Sample Modulation

Surface structures of magnetic nanorings were made using electroless deposition of Ni onto patterned templates of an amine-functionalized organosilane. Samples were prepared by chemical approaches based on colloidal lithography employing a surface mask of size-sorted, monodisperse silica spheres. Surface changes were evaluated after key points of the reactions using imaging modes of atomic force microscopy (AFM). Nanopatterns of 3-aminopropyltriethoxysilane (APTES) were prepared on Si(111) by applying a heated vapor to a surface mask of silica spheres. After rinsing, the particle mask was removed to reveal ring-shaped nanopatterns presenting amine groups at the interface. Organosilane nanopatterns were then immersed in a solution of Pd catalyst followed by treatment in a Ni plating bath. Changes in surface morphology after each reaction step were characterized ex situ using tapping-mode AFM to follow the time course of nanofabrication. Images of the Ni nanorings acquired with AFM were compared with SEM micrographs to further elucidate the morphology of the metal coatings. The magnetic character of the nanostructures was investigated with magnetic sample modulation (MSM-AFM), which is a hybrid of contact mode AFM combined with magnetic actuation of samples. Surface maps of the vibration of diamagnetic Pd and magnetic Ni nanorings were obtained with MSM-AFM, providing insight on processes of electroless plating. Fine details of the surface corrugation and grain structure of the Ni coated areas of the sample detected with SEM were sensitively resolved with MSM-AFM that were not apparent in AFM topography frames. Chemistry-based steps with electroless deposition (ELD) of metal and colloidal lithography provide a practical route for reproducible nanofabrication of highly regular geometries with high-throughput.

Preferential Face-on and Edge-on Orientation of Thiophene Oligomers by Rational Molecular Design.

Precise control over the supramolecular organization of organic semiconducting materials guiding to exclusive face-on or edge-on orientation is a challenging task. In the present work, we study the preferential packing of thiophene oligomers induced through rational molecular designing and self-assembly. The acceptor-donor-acceptor-type oligomers having 2-(1,1-dicyano-methylene)rhodanine as acceptor (OT1) favored a face-on packing, whereas that of functionalized with N-octyl rhodanine (OT2) preferred an edge-on packing as evident from 2D-grazing incidence angle X-ray diffraction, tapping-mode atomic force microscopy (AFM) and Raman spectroscopy analyses. The oligomers exhibited anisotropic conductivity in the self-assembled state as an outcome of the preferred orientation, revealed by the conducting AFM experiment.

2018 IEEE Transactions on Control Systems Technology Outstanding Paper Award

The following paper was selected for the <italic xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2018 IEEE Transactions on Control Systems Technology Outstanding Paper Award</i> from papers that appeared in 2016–2017: “Multimode Q Control in Tapping-Mode AFM: Enabling Imaging on Higher Flexural Eigenmodes” by Michael G. Ruppert and S. O. Reza Moheimani Vol. 24, No. 4, pp. 1149–1159, July 2016.

Experimental Setup for Dynamic Analysis of Micro- and Nano-Mechanical Systems in Vacuum, Gas, and Liquid.

An experimental setup to perform dynamic analysis of a micro- and nano-mechanical system in vacuum, gas, and liquid is presented. The setup mainly consists of a piezoelectric excitation part and the chamber that can be either evacuated for vacuum, or filled with gas or water. The design of the piezoelectric actuator was based on a Langevin transducer. The chamber is made out of materials that can sustain: vacuum, variety of gases and different types of liquids (mild acids, alkalies, common alcohols and oils). All the experiments were performed on commercial cantilevers used for contact and tapping mode Atomic Force Microscopy (AFM) with stiffness 0.2 N/m and 48 N/m, respectively, in vacuum, air and water. The performance of the setup was evaluated by comparing the measured actuator response to a finite element model. The frequency responses of the two AFM cantilevers measured were compared to analytical equations. A vacuum level of 0.6 mbar was obtained. The setup has a bandwidth of 10–550 kHz in vacuum and air, and a bandwidth of 50–550 kHz in liquid. The dynamic responses of the cantilevers show good agreement with theory in all media.

Atomic force microscopy analysis of the effect of plasma treatment on gas permeable contact lens surface topography.

Using atomic force microscopy (AFM) to investigate anterior surface topography (AST) in worn and unworn, plasma surface-treated (PST) and untreated (UT) gas permeable (GP) lenses, and influence of surface topography on in vivo comfort. GP lens AST evaluated with AFM in tapping mode, using an uncoated, 40 nm symmetric tip (sampling frequency: 300 kHz), at five randomised locations, over a 100μm2 area, to produce mean average roughness (Ra) and root mean square (RMS) values for each sample. Four unworn lenses (two PST, two UT) were examined (Quasar/Boston EO material). Twenty worn lenses (ten PST, ten UT) of same design and material as unworn lenses collected after 3 months lens wear. General wearing comfort reported by visual analogue scale (VAS) at 3 months visit. For sample preparation, two worn UT GP lenses were divided into four segments; each segment underwent a different lens rinse and drying method. Unworn: UT lenses had significantly higher mean RMS and Ra values compared to PST (Mann-Whitney, p < 0.05). Worn: UT Median RMS values were significantly higher than PST (Mann-Whitney, p < 0.05). Comfort: no correlation found between general comfort and RMS or Ra scores. Sample preparation: Method 4 (purified, distilled water rinse/nitrogen gas dry) produced optimum median RMS and Ra values. Unworn PST GP lenses had lower Ra and RMS values compared with unworn UT GP lenses. After 3 months wear, PST lenses had smoother surface topographies than UT lenses. No relationship was found between surface topography and lens wear comfort. Sample preparation protocol directly impacts AFM results.

AFM-Based Force Spectroscopy Guided by Recognition Imaging: A New Mode for Mapping and Studying Interaction Sites at Low Lateral Density.

Ligand binding to receptors is one of the most important regulatory elements in biology as it is the initiating step in signaling pathways and cascades. Thus, precisely localizing binding sites and measuring interaction forces between cognate receptor–ligand pairs leads to new insights into the molecular recognition involved in these processes. Here we present a detailed protocol about applying a technique, which combines atomic force microscopy (AFM)-based recognition imaging and force spectroscopy for studying the interaction between (membrane) receptors and ligands on the single molecule level. This method allows for the selection of a single receptor molecule reconstituted into a supported lipid membrane at low density, with the subsequent quantification of the receptor–ligand unbinding force. Based on AFM tapping mode, a cantilever tip carrying a ligand molecule is oscillated across a membrane. Topography and recognition images of reconstituted receptors are recorded simultaneously by analyzing the downward and upward parts of the oscillation, respectively. Functional receptor molecules are selected from the recognition image with nanometer resolution before the AFM is switched to the force spectroscopy mode, using positional feedback control. The combined mode allows for dynamic force probing on different pre-selected molecules. This strategy results in higher throughput when compared with force mapping. Applied to two different receptor–ligand pairs, we validated the presented new mode.

Development and Preliminary Evaluation of a System to Rapidly Measure Coefficient of Friction on Soft Contact Lenses

This study was undertaken to 1. develop an apparatus to rapidly measure coefficient of friction (COF) on soft contact lenses; 2. determine if COFs measured on two daily-disposable lens models before and after wear are consistent with changes in lens surface morphology observed in parallel atomic force microscopy (AFM) images. Methods: A stress rheometer was adapted to measure COF on a soft contact lens by custom fabrication of a rapid-mount sample stage for increased throughput. Five subjects were randomly assigned to wear daily disposable nesofilcon A and delefilcon A contact lenses bilaterally for 4 hours, after which time lenses were removed. Static and kinetic COFs of lenses worn on left eyes was measured, while lenses worn on right eyes were imaged in parallel by AFM in tapping mode. Root mean square (RMS) surface roughness was calculated for all lenses to determine the effect of wear on surface topography. Results: Both static and kinetic COFs measured on unworn delefilcon A silicone hydrogel lenses were greater than on nesofilcon A traditional hydrogel lenses. Static COF on nesofilcon A increased significantly after wear, while kinetic COF trended higher but did not change significantly. Similarly, static COF on delefilcon A also increased significantly after wear, and kinetic COF trended higher but did not change significantly, both remaining greater than on worn nesofilcon A. Parallel AFM analysis demonstrated that nesofilcon A lenses are smoother than are delefilcon A out of the package. Both lenses attracted deposits during wear, but the nesofilcon A surface was less altered by on-eye wear than was the delefilcon A surface. Conclusion: A system to rapidly measure static and kinetic COFs was successfully developed. Static and kinetic COFs measured on delefilcon A were greater than on nesofilcon A lenses. More deposits and greater surface roughness were observed after wear on delefilcon A relative to nesofilcon A. Parallel AFM images of worn and unworn lenses were not predictive of measured COFs, but increased roughness visible by AFM was consistent with observed increases in COF, although not all increases were statistically significant.

Wavelet analysis of higher harmonics in tapping mode atomic force microscopy

Higher harmonics have been widely used to characterize nanomechanical properties of the sample surface in tapping mode atomic force microscopy. They are usually analyzed by the Fourier transform method which provides time-averaged amplitude and phase information. In this paper, we apply the analytic wavelet transform to analyze higher harmonics. The intuitive descriptions of higher harmonics are obtained by the time-frequency analysis of the tip motion signal. The temporal evolutions of the higher harmonics are analyzed. The higher harmonics extracted by the analytic wavelet transform are closely related to the wavelet parameters. Different time and frequency features of higher harmonics can be analyzed through adjusting the wavelet parameters. Moreover, the root-mean-square amplitude and the peak amplitude obtained by the analytic wavelet transform can provide better characterization of sample properties than the amplitude obtained by the Fourier transform method.

Production of cyclo-hafnium metal–organic thin film using a specific method

Cyclo-hafnium metal–organic thin film was successfully synthesized and deposited on amorphous glass using a specific method, where amorphous substrate was used for synthesis and coating. Then, the film was annealed at 300 °C in an oven (ambient conditions). Optical and structural properties of the films were also investigated within the study. The structure of the film was analyzed using the mid-infrared spectrum. Optical properties were investigated via the UV–Vis spectroscopic technique. Film thickness was measured with AFM (tapping mode). Surface properties and elemental ratio of the films were examined and measured with SEM and EDX analysis. The highest transmittance and lowest reflectance values within the visible range were identified. The characteristic triethanolamine and hafnium-oxide peaks were observed in the infrared spectrum. FIR spectra of the films were found to be in accordance with the literature. SEM images of the films revealed that the surface of the films is fragile. EDX analysis of hafnium, organic parts of the compound and some minerals of amorphous glass were shown.

Nanostructures of functionalized zinc phthalocyanines prepared with colloidal lithography: Evaluation of surface orientation and dimensions using scanning probe microscopy

Patterned arrays of nanoholes and nanorings were prepared using colloidal lithography combined with steps of solution immersion and vapor deposition of organosilanes. Samples prepared with colloidal lithography exhibit millions of reproducible test structures with a periodic arrangement throughout areas of the surface according to the dimensions and spacing of the particle mask. Views of the size and morphology of nanopatterns obtained with atomic force microscopy (AFM) can provide information of progressive steps of chemical reactions as nanostructures are grown within spatially confined areas surrounded by a resist film. A surface mask of colloidal latex or silica spheres was used to protect discrete areas of a Si(111) substrate from the deposition of organosilanes. When the mask was removed, the uncovered areas of the surface revealed regularly-shaped, small sites of uncovered substrate available for further reaction steps to build hierarchical surface structures. Nanostructures of zinc phthalocyanines (ZnPcs) were constructed using amine-terminated nanopatterns as sites for binding. Spatial selectivity was achieved for directing the attachment of ZnPcs to the surface using resist films of 2-methoxy(polyethyleneoxy)propyl]trichlorosilane (PEO-silane) and also with octadecyltrimethoxysilane (OTMS). The molecule chosen as a linker was (3-aminopropyl)triethoxysilane (APTES) which presents an amine group at the interface. In general, phthalocyanine molecules tend to bind in a coplanar orientation by physisorption to the surface and can stack together through pi-pi interactions between adjacent macrocycles. However, the nature of the substituents will also influence whether the molecules assemble on surfaces in a side-on orientation or with the macrocycle oriented in a coplanar arrangement. Hydroxyl and isothiocyanate pendant groups were attached to the macrocycles of ZnPcs chosen for this study, to investigate conformational differences when attached to APTES nanopatterns. The size and morphology of nanostructures was visualized and sensitively measured with tapping-mode AFM. The elastic response of samples patterned with ZnPc was mapped with force modulation AFM. Changes in the height of nanostructures indicate whether the macrocycles are oriented upright or parallel to the surface plane, or if multilayers were formed.

Development of superhydrophobic coatings on AISI 304 austenitic stainless steel with different surface pretreatments

In the context of increasing industrial importance of superhydrophobic surfaces, three different pretreatments on an austenitic stainless steel surface have been tested to be coated with a silane-based solution containing SiO2 nanoparticles, in order to obtain superhydrophobic surfaces. The pretreatments are (i) an acetone degreaser, (ii) this one followed by a hot air treatment and acid pickling, and (iii) the previous one followed by an alkaline etching. Pretreated surfaces have been characterized by X-ray photoelectron spectroscopy, tapping-mode atomic force microscopy and contact angle measurements. After the three pretreatments, a solution of methyltrimethoxysilane and tetraethoxysilane in white spirit solvent and 1% of SiO2 (% by wt.) has been used to prepare a superhydrophobic coating on them. The hydrophobicity of the developed coatings has been studied using water contact angle measurements (static angles and advancing and receding angles). Besides, scanning electron microscope has been used to study the coatings. The results show that different tailored surfaces can be obtained in stainless steels using these pretreatments, obtaining surfaces that exhibit different physicochemical characteristics that may condition the formation of superhydrophobic coatings on them.

Atomic Force Microscopy Local Oxidation of GeO Thin Films

Metastable germanium monoxide (GeO) thin-insulating films have been investigated as a new promising material for atomic force microscope (AFM) oxidation lithography. The kinetics of GeO layer oxidation performed in the tapping mode of AFM was found to have a logarithmic relationship to oxide height versus pulse duration. Effect of humidity on oxidation of germanium monoxide thin films was studied at relative humidity 40, 60, 80%. When local anodic oxidation of GeO layer was carried out by AFM operating in the contact mode in high voltage (≥9 V) regime and at high relative humidity (RH = 80%), the size and shape of fabricated oxide was changed drastically.

Tapping Mode AFM Imaging in Liquids with blueDrive Photothermal Excitation

Abstract

Fundamental frequencies of a torsional cantilever nano beam for dynamic atomic force microscopy (dAFM) in tapping mode

The aim of this investigation is to study the motion of an elastically restrained beam used in tapping mode atomic force microscopy (TM-AFM), which is to be utilized in manufacturing at nano-scale. TM-AFM uses high frequency oscillations to remove material or shape nano structures. Euler–Bernoulli theory and Eringen’s theory of non-local continuum are used to model the nano machining structure composed of a nanobeam and a single degree of freedom, spring-mass system. The system is modelled as a beam with a torsional spring boundary condition that is rigidly restrained in the transverse direction at one end; and at the free end is a transverse linear spring attached to the tip. The other end of the spring is attached to a mass, resulting in a single degree of freedom spring-mass system. When the linear spring constant is infinite, the free end behaves as a beam with a concentrated tip mass. When the mass is infinite, the boundary condition is that of a linear spring. When the tip mass is zero, the configuration is that of a torsionally restrained-free beam. The motion of the tip of the beam and tip mass can be investigated to observe the tip frequency response, displacement and force. The tip displacement frequency contains information about the maximum displacement amplitude and therefore the sample penetration depth.

Recent development of PeakForce Tapping mode atomic force microscopy and its applications on nanoscience

Abstract Nanoscience is a booming field incorporating some of the most fundamental questions concerning structure, function, and applications. The cutting-edge research in nanoscience requires access to advanced techniques and instrumentation capable of approaching these unanswered questions. Over the past few decades, atomic force microscopy (AFM) has been developed as a powerful platform, which enables in situ characterization of topological structures, local physical properties, and even manipulating samples at nanometer scale. Currently, an imaging mode called PeakForce Tapping (PFT) has attracted more and more attention due to its advantages of nondestructive characterization, high-resolution imaging, and concurrent quantitative property mapping. In this review, the origin, principle, and advantages of PFT on nanoscience are introduced in detail. Three typical applications of this technique, including high-resolution imaging of soft samples in liquid environment, quantitative nanomechanical property mapping, and electrical/electrochemical property measurement will be reviewed comprehensively. The future trends of PFT technique development will be discussed as well.

Direct Measurement of Photoinduced Force for Nanoscale Infrared Spectroscopy and Chemical-Sensitive Imaging

Measurement of photoinduced mechanical responses by atomic force microscopy (AFM) because of sample infrared resonances enables chemical-sensitive microscopy with spatial resolution orders of magnitude better than the optical diffraction limit. However, the origin of noncontact photoinduced force between the AFM tip and the samples of infrared resonances is still under debate. To investigate its origin, we implemented synchronized infrared pulse excitation and mechanical detection with a stationary cantilever of AFM in the peak force tapping mode. An attractive photoinduced force at nanonewton level between the AFM tip and the sample is observed. A spectral profile of the force corresponds to the infrared absorption of the sample. To interpret these findings, we modified the expected intermolecular force profile by adding the photothermal expansion as a contributing factor. The direct measurement of photoinduced force enables a new analytical method of nanoscale infrared spectroscopy and imaging with 10 n...

Energy Dissipated in Tapping Mode Atomic Force Microscopes due to Humidity

Phase imaging is an important imaging model of atomic force microscopes (AFMs). It provides many sample properties that the height image does not. The phase information reflects the energy dissipation of the probe and sample interactions. Therefore, the energy dissipation between the tip and sample in the tapping mode is of great significance for understanding the mechanism of phase imaging experimentally and theoretically. In this paper, we propose a new method for measuring energy dissipation in tapping mode AFMs. The formation and rupture processes of liquid bridges are studied by this method. Finally, the experimental results are compared with the theoretical model. The comparison shows that the method of experimental measurement and the formation mechanism of liquid bridges in the tapping mode are reliable.

Structure-Function Correlative Microscopy of Peritubular and Intertubular Dentine.

Peritubular dentine (PTD) and intertubular dentine (ITD) were investigated by 3D correlative Focused Ion Beam (FIB)-Scanning Electron Microscopy (SEM)-Energy Dispersive Spectroscopy (EDS) tomography, tapping mode Atomic Force Microscopy (AFM) and scattering-type Scanning Near-Field Optical Microscopy (s-SNOM) mapping. The brighter appearance of PTD in 3D SEM-Backscattered-Electron (BSE) imaging mode and the corresponding higher grey value indicate a greater mineral concentration in PTD (~160) compared to ITD (~152). However, the 3D FIB-SEM-EDS reconstruction and high resolution, quantitative 2D map of the Ca/P ratio (~1.8) fail to distinguish between PTD and ITD. This has been further confirmed using nanoscale 2D AFM map, which clearly visualised biopolymers and hydroxyapatite (HAp) crystallites with larger mean crystallite size in ITD (32 ± 8 nm) than that in PTD (22 ± 3 nm). Correlative microscopy reveals that the principal difference between PTD and ITD arises primarily from the nanoscale packing density of the crystallites bonded together by thin biopolymer, with moderate contribution from the chemical composition difference. The structural difference results in the mechanical properties variation that is described by the parabolic stiffness-volume fraction correlation function introduced here. The obtained results benefit a microstructure-based mechano-chemical model to simulate the chemical etching process that can occur in human dental caries and some of its treatments.

Morphological studies of polyurethane based pressure sensitive adhesives by tapping mode atomic force microscopy

The polyurethane pressure sensitive adhesive (PUPSA) films have been prepared on polypropylene sheets with coating bars. The topographical information of the dried films is investigated using phase images by using Atomic Force Microscope (AFM) in tapping mode. The film develops a segmental architecture by using different compositions. Various samples of PUPSA comprising of polypropylene glycol PPG (Mn = 425, 1000, 2000 and 2700 g-mol−1) and hydroxyl terminated polybutadiene HTPB (Mn = 1984 and 2912 g-mol−1) along with three different isocyanates: 1,6 hexane diisocyanate (HDI), isophorone diisocyanate (IPDI) and hexamethylene diisocyanate (H12MDI) have been used for capturing the images through AFM. The samples contained 40 wt.% of solid content containing different nature of macrodiols and diisocyanate. Due to varying composition, dispersion in domain area along with different contour and dimension has been observed in the images. Apparently, there seems no correlation of spherulites and lamellae in different domains. However, the properties imparted by high molecular weight HTPB resulted in non-adhesive stiff material.