Force Curve Measurements with the AFM: Application to the In Situ Determination of Grafted Silicon-Wafer Surface Energies

The atomic force microscope (AFM) can be used to perform surface force measurements in the quasi-static mode (cantilever is not oscillating) to investigate nanoscale surface properties. Nevertheless, there is still a lack of literature proposing a complete systematic and rigorous experimental procedure that enables one to obtain reproducible and significant quantitative data. This article focuses on the fundamental experimental difficulties arising when making force curve measurements with the AFM in air. On the basis of this AFM calibration procedure, quantitative assessment values were used to determine, in situ, SAM (or Self Assembled Monolayer)-tip thermodynamic work of adhesion at a local scale, which have been found to be in good agreement with quoted values. Finally, determination of surface energies of functionalised silicon wafers (as received, CH₃, OH functionalised silicon wafers) with the AFM (at a local scale) is also proposed and compared with the values obtained by wettability (at a macroscopic scale). In particular, the effect of the capillary forces is discussed.     

Atomic Force Microscope Techniques for Adhesion Measurements

The Atomic Force Microscope (AFM) has become a powerful apparatus for performing real-time, quantitative force measurements between materials. Recently the AFM has been used to measure adhesive interactions between probes placed on the AFM cantilever and sample surfaces. This article reviews progress in this area of adhesion measurement, and describes a new technique (Jump Mode) for obtaining adhesion maps of surfaces. Jump mode has the advantage of producing fast, quantitative adhesion maps with minimal memory usage.     

Atomic Force Microscope Techniques for Adhesion Measurements

The Atomic Force Microscope (AFM) has become a powerful apparatus for performing real-time, quantitative force measurements between materials. Recently the AFM has been used to measure adhesive interactions between probes placed on the AFM cantilever and sample surfaces. This article reviews progress in this area of adhesion measurement, and describes a new technique (Jump Mode) for obtaining adhesion maps of surfaces. Jump mode has the advantage of producing fast, quantitative adhesion maps with minimal memory usage.     

Single-Molecule AFM Study of Polystyrene Grafted at Gold Surfaces

Single-molecule studies under poor solvent conditions show that atomic force microscopy (AFM) measurements of contour lengths of polystyrene 12K and 17K relate well to gel permeation chromatography (GPC) data when grafting concentrations are low (not greater than 0.7 mM). Contact angles and ellipsometry have been used to characterize the surfaces and indicate low grafting densities at this grafting concentration. Persistence lengths (p) of different length polystyrene chains, when fitted to a WLC (worm-like chain) model, show values of p = 0.23 nm±0.10 nm and p = 0.25 nm±0.13 nm, for 12 K and 17 K polystyrene, respectively, when the persistence lengths are fitted to log-normal distributions. These values are close to the expected theoretical value of 0.23 nm and further confirm that mostly single molecules were studied on these polystyrene surfaces. Higher grafting concentrations (≥1 mM) resulted in pulling multiple molecules.     

Measuring the Surface and Bulk Modulus of Polished Polymers with AFM and Nanoindentation

Abstract

A new method to determine the elastic modulus of a material using the atomic force microscope (AFM) was proposed by Tang et al. [Nanotechnology 19, 495713 (2008)] and is used in this study. This method models the cantilever and the sample as two springs in a series. The properties of both the spring and cantilever are determined on two reference samples with known mechanical properties and these properties are then used to find the elastic modulus of an unknown sample. The indentation depth achieved with AFM is in the nanometer range (30–130 nm in this study); and hence when this technique is performed on polymers, whose surface structure is different from their bulk structure, AFM gives a measure of the surface elastic modulus. In the present study, after employing AFM to measure the surface modulus of five polymers, traditional depth-sensing nanoindentation, with penetration depths of about 1 μm, was used to determine the elastic modulus in the bulk. The mean values for elastic modulus from the AFM were within 5–50% of the nanoindentation results, suggesting the existence of a surface modulus for polished polymers.     

Maximum Force Technique for the Measurement of the Surface Tension of a Small Droplet by AFM

An atomic force microscope (AFM) is used to measure the meniscus force on a vertical quartz rod as the rod is pulled through an air/liquid interface. A fluid bridge forms between the liquid and the base of the rod as the rod is withdrawn from the liquid. The force reaches a maximum as the bridge necks down and finally detaches from the rod. The maximum force on the rod is independent of the material of the rod and can be used to calculate the surface tension of the liquid. Alternately, if the surface tension of the liquid is known, the maximum force of the meniscus can be used to calibrate the spring constant of the AFM cantilever. The contact angle of the liquid on the rod was calculated as the rod was inserted into the liquid droplet. Contact angle hysteresis was observed. Results are presented of the measurement of the meniscus force of water, 10^?3 M cetyl trimethyl ammonium bromide (CTAB) and tetradecane as the rod is withdrawn from the liquid.     

Maximum Force Technique for the Measurement of the Surface Tension of a Small Droplet by AFM

An atomic force microscope (AFM) is used to measure the meniscus force on a vertical quartz rod as the rod is pulled through an air/liquid interface. A fluid bridge forms between the liquid and the base of the rod as the rod is withdrawn from the liquid. The force reaches a maximum as the bridge necks down and finally detaches from the rod. The maximum force on the rod is independent of the material of the rod and can be used to calculate the surface tension of the liquid. Alternately, if the surface tension of the liquid is known, the maximum force of the meniscus can be used to calibrate the spring constant of the AFM cantilever. The contact angle of the liquid on the rod was calculated as the rod was inserted into the liquid droplet. Contact angle hysteresis was observed. Results are presented of the measurement of the meniscus force of water, 10^-3 M cetyl trimethyl ammonium bromide (CTAB) and tetradecane as the rod is withdrawn from the liquid.     

Surface crystallization of poly(ethylene terephtalate) studied by atomic force microscopy

Poly(ethylene terephtalate) (PET) crystallization was shown by atomic force microscopy (AFM) to occur at 85 °C in the first few nanometers near the polymer-air interface. The surface was fully transformed into spherulites after 30 min, while no signs of bulk crystallization were observed by FTIR. All the observed spherulites presented a nucleation centre, indicating that the crystallization process started at the surface of the film. Tapping mode AFM confirmed that the spherulites were not covered by an amorphous layer. The most probable explanation is a decrease of T_g near the surface. Due to the poor crystallization conditions, the constitutive units of the spherulites were small crystalline blocks. By changing the annealing time, it was possible to produce PET surfaces with different surface fractions consisting of semi-crystalline material (spherulites) and amorphous matrix. This provided a controlled surface heterogeneity on the submicrometer scale, with a contrast in terms of stiffness, roughness and swelling by organic solvents.     

Force spectrum of a few chains grafted on an AFM tip: Comparison of the experiment to a self-consistent mean field theory simulation

A simulation model based on self-consistent mean field theory (SCMFT) has been developed to inspect the approaching process of the polymer chain grafted AFM tip to a substrate. The effects of various controlling parameters, such as grafting position, chain number, chain length, as well as solvent- and substrate-chain interactions, on the force curve were investigated. Real force spectroscopy of AFM tips modified by poly(ethylene glycol) (PEG) chains interacting with the fresh mica has been recorded, and several typical types of the force curves that correspond to the different states of the grafting chain were assorted. The simulations fit the experimental results well, providing a strong support to the model.     

Fabrication of nanochannels with ladder nanostructure at the bottom using AFM nanoscratching method

This letter presents a novel atomic force microscopy (AFM)-based nanomanufacturing method combining the tip scanning with the high-precision stage movement to fabricate nanochannels with ladder nanostructure at the bottom by continuous scanning with a fixed scan size. Different structures can be obtained according to the matching relation of the tip feeding velocity and the precision stage moving velocity. This relationship was first studied in detail to achieve nanochannels with different ladder nanostructures at the bottom. Machining experiments were then performed to fabricate nanochannels on an aluminum alloy surface to demonstrate the capability of this AFM-based fabrication method presented in this study. Results show that the feed value and the tip orientation in the removing action play important roles in this method which has a significant effect on the machined surfaces. Finally, the capacity of this method to fabricate a large-scale nanochannel was also demonstrated. This method has the potential to advance the existing AFM tip-based nanomanufacturing technique of the formation these complex structures by increasing the removal speed, simplifying the processing procedure and achieving the large-scale nanofabrication.     

Tracking the hydrophobicity recovery of PDMS compounds using the adhesive force determined by AFM force distance measurements

Polydimethylsiloxane (PDMS) materials show the unique phenomenon that when exposed to electrical discharge, such as corona discharge, their hydrophobic surface becomes hydrophilic. However, after a certain relaxation time they gradually regain their hydrophobicity. In this study the adhesive force obtained by AFM force distance measurements using a hydrophilic Si₃N₄ probe is used to track the recovery of the hydrophobicity. The time constant of the recovery can be determined by measuring the adhesive force as a function of the recovery time after corona exposure. It is shown how these time constants can be used to monitor the recovery rate as a function of corona treatment time for both filled and unfilled PDMS compounds.     

Atmospheric plasma modification of polyimide sheet for joining to titanium with high temperature adhesive

This investigation highlights the rationale of adhesive bonding of atmospheric pressure plasma treated high temperature resistant polymeric sheet such as polyimide sheet (Meldin 7001), with titanium sheets. The surface of polyimide (PI) sheet was treated with atmospheric pressure plasma for different exposure times. The surface energy was found to increase with increase in exposure time. However, longer exposure time of plasma, results in deterioration of the surface layer of PI resulting in degradation and embrittlement.Contact angle measurements with sessile drop technique were carried out for estimation of surface energy. SEM (EDS) and AFM analyses of treated and untreated specimens were carried out to examine the surface characteristics and understanding morphological changes following surface treatment. Untreated samples and atmospheric pressure plasma treated samples of polyimide Meldin 7001 sheet were bonded together as well as with titanium substrates to form overlap joints. Single lap shear tensile testing of these adhesively bonded joints was performed to measure bond strength and to investigate the effect of surface treatment on adhesive bond strength. An optimized plasma treatment time results in maximum adhesive bond strength and consequently, this technology is highly acceptable for aviation and space applications.     

The interactions of amphiphilic latexes with surfaces: the effect of surface modifications and ionic strength

The effect of surface modifications brought about by a polymeric stabilizer on the interactions between polymer colloid particles and various substrates in aqueous media are directly measured using atomic force microscopy. The interactions of polystyrene particles with grafted hydrophilic ‘hairs’ of hydroxypropyl cellulose (denoted HPC/PS), of molecular weight ∼10⁵, with mica, silica and graphite substrates are measured. HPC/PS is found to be compatibilized so that it will interact with both hydrophobic and hydrophilic substrates. The observed jump-to contact between HPC/PS and silica is characteristic of polymer solutions and is the result of the grafted hairy layer. Further direct evidence of HPC-substrate interaction is seen in a secondary adhesion with mica. The adhesion of the particles was found to follow the order silica>graphite>mica. The magnitudes of these interactions are rationalized in terms of the interactions of each of the substrate, core polymer and surface modification. It is concluded that the combined effects of surface roughness and hairy layer collapse due to compression give rise to the observed trend.     

Direct measurement of electrostatic fields using single Teflon nanoparticle attached to AFM tip

Abstract

A single 210-nm Teflon nanoparticle (sTNP) was attached to the vertex of a silicon nitride (Si₃N₄) atomic force microscope tip and charged via contact electrification. The charged sTNP can then be considered a point charge and used to measure the electrostatic field adjacent to a parallel plate condenser using 30-nm gold/20-nm titanium as electrodes. This technique can provide a measurement resolution of 250/100 nm along the X- and Z-axes, and the minimum electrostatic force can be measured within 50 pN.

PACS

07.79.Lh, 81.16.-c, 84.37. + q     

Behaviors of time-dependent and time-independent adhesion forces revealed using an AFM under different humidities and measuremental protocols

Adhesion forces between a tipless cantilever and a silicon wafer were measured on an atomic force microscope (AFM) at two relative humidities (RH). Experimental results show that the behaviors of the adhesion force are largely influenced by the RH and measurement protocols. The capillary contribution to the measured adhesion force is time-dependent at low RH (31±1%) and time-independent at high RH (52±1%) due to different equilibrium times of water bridges. The time-dependent adhesion force increases logarithmically with contact time until saturation is reached. The effects of loading force, approach velocity, retraction velocity and measurement number on the adhesion force can be explained by the logarithmic contact time dependence of the adhesion force. However, the time-independent adhesion force decreases with dwell time, and increases with retraction velocity. No dependence of the adhesion force on loading force and approach velocity is found. The adhesion force by consecutively measurements on the same location shows fluctuations, and the trend is unpredictable.     

Plastic deformation of spherulitic semi-crystalline polymers: An in situ AFM study of polybutene under tensile drawing

The plastic deformation of semi-crystalline polybutene (PB) has been studied at the micrometric and nanometric scales by Atomic Force Microscopy (AFM). Owing to a movable tensile drawing stage, capturing images from the same locus of the sample allowed for quasi in situ observations of the plastic processes. In the case of PB films having an average spherulite diameter of about 20 μm, the macroscopic deformation was homogeneous over the whole gauge length of the sample, up to rupture. In parallel, the local deformation at the scale of the spherulites was very close to homogeneous and obeyed an affine deformation law over the whole strain range: the shape of the deformed spherulites was kept roughly elliptical up to rupture without clues of fibrillar transformation. The inter-spherulitic boundaries displayed very high cohesion. Fragmentation of the crystalline lamellae proved to be a predominant process, while crystal slip could not be detected at the scale of the AFM resolution, i.e. a few nanometers. Wide-angle and small-angle X-ray scattering yet revealed the occurrence of crystal plastic shear. Similar observations have been made in the case of PB films having an average spherulite diameter of about 5 μm. In the conclusion, a comparison is made with a previous study regarding the deformation mechanisms of a PB sample having 200 μm wide spherulites which displayed brittle behavior.     

A Study on Hydrophobic Surface Coatings with Abrasion Resistance Property

The aim of this study is to synthesize a hydrophobic surface coating with abrasion-resistant inorganic-organic hybrid materials. First, the copolymer of poly (MMA-co-MPTS)-colloid silica was synthesized by using the free radical polymerization of the methyl methacrylate (MMA) with γ-methacrylate propyltriethoxysilane (γ-MPTS). Next, the copolymer was hydrolyzed with tetraethoxylsilane (TEOS), fluoroalkylsilane (FAS), and colloid silica in the weak acid condition by a sol-gel process to obtain the surface coatings of hybrid material of poly (MMA-co-MPTS)-colloid silica. Finally, the effects of the colloid silica content on the optical properties, abrasion resistance, and morphology of the hybrid surface coatings were discussed in this study.     

Preparation and Investigation of Novel PVA/Silica Nanocomposites with Potential Application in NLO

This research describes the synthesis of organomodfied sillica nanoparticles (NP)s /polyvinyl alcohol (PVA) nanocomposites (NC)s through consecutive three-steps. In the first step the surface modifier, namely 1-(benzo[d]thiazol-2-yl)-3-(3-(triethoxysilyl)propyl)urea, was prepared from the reaction of benzo[d]thiazol-2-amine and 3-isocyanatopropyl triethoxysilane. With success in the first step, the surface modifications of silica NPs were achieved by sol-gel procedure and at the final step, the preparation of PVA/silica NCs were targeted. The optical properties and morphology of the NPs and NCs were characterized. This investigation clearly showed that the new coupling agent could effectively prevent the agreggation of NPs.     

The influence of aminophylline on the nanostructure and nanomechanics of T lymphocytes: an AFM study

Although much progress has been made in the illustration of the mechanism of aminophylline (AM) treating asthma, there is no data about its effect on the nanostructure and nanomechanics of T lymphocytes. Here, we presented atomic force spectroscopy (AFM)-based investigations at the nanoscale level to address the above fundamental biophysical questions. As increasing AM treatment time, T lymphocytes'' volume nearly double increased and then decreased. The changes of nanostructural features of the cell membrane, i.e., mean height of particles, root-mean-square roughness (Rq), crack and fragment appearance, increased with AM treatment time. T lymphocytes were completely destroyed with 96-h treatment, and they existed in the form of small fragments. Analysis of force-distance curves showed that the adhesion force of cell surface decreased significantly with the increase of AM treatment time, while the cell stiffness increased firstly and then decreased. These changes were closely correlated to the characteristics and process of cell oncosis. In total, these quantitative and qualitative changes of T lymphocytes'' structure and nanomechanical properties suggested that AM could induce T lymphocyte oncosis to exert anti-inflammatory effects for treating asthma. These findings provide new insights into the T lymphocyte oncosis and the anti-inflammatory mechanism and immune regulation actions of AM.