Interpreting the conductive atomic force microscopy measured inhomogeneous nanoscale surface electrical properties of Al‐doped ZnO films

In this work, conductive atomic force microscopy is used to study the inhomogeneous surface electrical conductivity of Al‐doped ZnO thin films at a nanoscale dimension. To this end, Al‐doped ZnO films were deposited onto the soda lime glass substrates at substrate temperature (T_s) varying from 303 to 673 K in radio frequency magnetron sputtering. The obtained local surface electrical conductivity values are found to be influenced by their bulk electrical resistivity, surface topography and tip geometry. Further, the average (local) surface conductivity from the film surface is found to increase with increasing T_s from 303 to 623 K, beyond which they decrease until 673 K. Copyright © 2016 John Wiley & Sons, Ltd.     

Comparative characterisation by atomic force microscopy and ellipsometry of soft and solid thin films

Ellipsometry and atomic force microscopy (AFM) were used to study the film thickness and the surface roughness of both ‘soft’ and solid thin films. ‘Soft’ polymer thin films of polystyrene and poly(styrene–ethylene/butylene–styrene) block copolymer were prepared by spin‐coating onto planar silicon wafers. Ellipsometric parameters were fitted by the Cauchy approach using a two‐layer model with planar boundaries between the layers. The smooth surfaces of the prepared polymer films were confirmed by AFM. There is good agreement between AFM and ellipsometry in the 80–130 nm thickness range. Semiconductor surfaces (Si) obtained by anisotropic chemical etching were investigated as an example of a randomly rough surface. To define roughness parameters by ellipsometry, the top rough layers were treated as thin films according to the Bruggeman effective medium approximation (BEMA). Surface roughness values measured by AFM and ellipsometry show the same tendency of increasing roughness with increased etching time, although AFM results depend on the used window size. The combined use of both methods appears to offer the most comprehensive route to quantitative surface roughness characterisation of solid films. Copyright © 2007 John Wiley & Sons, Ltd.     

Synthesis and property of helical poly(phenylacetylene)s bearing chiral ruthenium complexes and real space imaging of meso- and nanoscopic structures by atomic force microscopy

Novel sets of helical poly(phenylacetylene)s bearing a chiral ruthenium (Ru) complex with opposite chirality (Δ and Λ forms) as a bulky pendant (poly- 1 and poly- 2 ) were synthesized through the polymerization of the corresponding optically pure phenylacetylenes with a rhodium catalyst, and their structures in solution and morphology on solid substrates were investigated with NMR, ultraviolet–visible, and circular dichroism (CD) spectroscopies and with atomic force microscopy (AFM), respectively. The obtained cis–transoidal polymers (poly- 1 and poly- 2 ) showed characteristic Cotton effects in the region of metal-to-ligand charge transfer of the chiral Ru pendants. Poly- 1 and poly- 2 were thought to have a predominantly one-handed helical conformation induced by the chiral pendants. However, the apparent Cotton effects derived from the helically twisted π-conjugated polymer backbone could not be observed, probably because of the strong chiral chromophoric pendants. However, in the AFM images, the helical polymers adsorbed on mica could be easily discerned as isolated strands, and the visualization and discrimination of the right- and left-handed helical structures of the chiral polymers were achieved by high-resolution AFM imaging. On the basis of the AFM observations together with the CD measurements and computational calculation results, possible structures of poly- 1 and poly- 2 were examined. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4621–4640, 2004     

Application of colloid probe atomic force microscopy to the adhesion of thin films of viscous and viscoelastic silicone fluids

The adhesive characteristics of thin films (0.2-2 μm) of linear poly(dimethylsiloxane) (PDMS) liquids with a wide range of molecular weights have been measured using an atomic force microscope with a colloid probe (diameters 5 and 12 μm) for different separation velocities. The data were consistent with a residual film in the contact region having a thickness of ～6 nm following an extended dwell time before separation of the probe. It was possible to estimate the maximum adhesive force as a function of the capillary number, Ca, by applying existing theoretical models based on capillary interactions and viscous flow except at large values of Ca in the case of viscoelastic fluids, for which it was necessary to develop a nonlinear viscoelastic model. The compliance of the atomic force microscope colloid beam was an important factor in governing the retraction velocity of the probe and therefore the value of the adhesive force, but the inertia of the beam and viscoelastic stress overshoot effects were not significant in the range of separation velocities investigated.     

Surface structure of thin asymmetric PS-b-PMMA diblock copolymers investigated by atomic force microscopy

Asymmetric poly(styrene-b-methyl methacrylate) (PS-b-PMMA) diblock copolymers of molecular weight M_n = 29,700 g mol⁻¹ (M_PS = 9300 g mol⁻¹M_PMMA = 20,100 g mol⁻¹, PD = 1.15, χ_PS = 0.323, χ_PMMA = 0.677) and M_n = 63,900 g mol⁻¹ (M_PS = 50,500 g mol⁻¹, M_PMMA = 13,400 g mol⁻¹, PD = 1.18, χ_PS = 0.790, χ_PMMA = 0.210) were prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization. Atomic force microscopy (AFM) was used to investigate the surface structure of thin films, prepared by spin-coating the diblock copolymers on a silicon substrate. We show that the nanostructure of the diblock copolymer depends on the molecular weight and volume fraction of the diblock copolymers. We observed a perpendicular lamellar structure for the high molar mass sample and a hexagonal-packed cylindrical patterning for the lower molar mass one. Small-angle X-ray scattering investigation of these samples without annealing did not reveal any ordered structure. Annealing of PS-b-PMMA samples at 160 °C for 24 h led to a change in surface structure.     

Quantitative study of filled rubber microstructure by optical and atomic force microscopy

A comprehensive approach is proposed for studying the microstructure of filled rubbers by optical and atomic force microscopy (AFM). The optical results are found to be dependent on the illumination angle. Algorithms based on the mathematical morphology are developed for the processing of optical images (removing scratches, identifying agglomerates). AFM-images are treated by a segmentation method which separates a continuous surface into segments that match filler. Parameters of secondary filler structures and the size of an area of homogeneous filler dispersion are obtained from the analysis of the segmented images. Seven carbon black filled rubbers with different mixing times are investigated. The combination of AFM with optical imaging techniques makes it possible to perform a quantitative structural analysis at scales from tens of nanometers to tens of microns, and to establish the relationship between the mixing time and the filler microstructure over the whole range of filler peculiarities.     

An atomic force microscope (AFM) and tapping mode AFM study of the solvent-induced crystallization of polycarbonate thin films

Thin films of bisphenol-A polycarbonate (PC) were progressively crystallized in a controllable manner under the action of an appropriate plasticizing agent. No conducting layer was applied to the polymer surface, so that imaging with the atomic force microscope (AFM) left the sample exposed for additional plasticizer treatment. The PC sample was observed many times throughout the crystallization process using the AFM in both the contact and tapping modes. Data regarding the growth process for spherulites in addition to high-resolution morphology studies were achieved. © 1996 John Wiley & Sons, Inc.     

Quantitative determination of surface energy using atomic force microscopy: the case of hydrophobic/hydrophobic contact and hydrophilic/hydrophilic contact

Atomic force microscopy (AFM) has been used to determine the surface energy of chemically modified surfaces at a local scale. In order to achieve this aim, it was necessary to graft both the AFM tip and the substrate with the same chemical functional groups. Two different organothiols terminated either by hydrophilic or hydrophobic chemical functionalities were used. Grafting process classically reported shows that after UV/ozone treatment for 30 min, the tip is coated by thermal deposition with 4‐5‐nm‐thick titanium layer followed by a 30‐nm‐thick gold layer. Finally, the tip is grafted by organothiols. The thickness of the layer deposited on the tip is of the same order of magnitude as the tip radius. To avoid the use of Ti and to decrease the thickness of the gold layer, we have developed a new way of grafting by using organic molecules like (3‐mercaptopropyl)triethoxysilane (MPS) as a linkage agent. Then this way of grafting was checked. Finally, AFM force‐distance curves, between grafted tips and chemically modified surface, were carried out in contact mode. Calibration of the various parts of the apparatus and especially of the cantilever (spring constant and tip radius) is of major importance to reach quantitative data. Finally, by applying a suitable theory of contact, we were able to determine the surface energy of our system. Copyright © 2005 John Wiley & Sons, Ltd.     

Quantitative analysis of protein adsorption via atomic force microscopy and surface plasmon resonance

Surface properties have a significant influence on the performance of biomedical devices. The influence of surface chemistry on the amount and distribution of adsorbed proteins has been evaluated by a combination of atomic force microscopy (AFM) and surface plasmon resonance (SPR). Adsorption of albumin, fibrinogen, and fibronectin was analyzed under static and dynamic conditions, employing self-assembled monolayers (SAMs) as model surfaces. AFM was performed in tapping mode with antibody-modified tips. Phase-contrast images showed protein distribution on SAMs and phase-shift entity provided information on protein conformation. SPR analysis revealed substrate-specific dynamics in each system investigated. When multi-protein solutions and diluted human plasma interacted with SAMs, SPR data suggested that surface chemistry governs the equilibrium composition of the protein layer.     

Observation of adhesive force and energy of adsorbents on rubber substrates by atomic force microscopy

We observed the surface morphology and adhesive interaction of adsorbents on rubber substrates by atomic force microscopy (AFM). The detachment of adsorbents from rubber substrates is an important issue for various machines like home appliances and laundry machine. Since a clean surface of the functioning parts is required, a frequent cleaning process must be developed. In particular, dust and lint have a tendency to bind to the rubber surface of a laundry machine. Several practical methods have been attempted to remove these particles from the surface. Pure water, detergent, sodium hypochlorite (65 °C), and cold water (18 °C) are treated onto artificial dust and lint mixtures on rubber with water fluid by rapid rpm. The dust‐and‐lint adsorbents are investigated by AFM after the treatment, and topographic images and force–distance (F–D) curves were generated for the samples. The roughness, measured as the root mean square, is a key factor to judge the cleaning quality. From the F–D curves, we are able to obtain adhesive energy in addition to adhesive force which will yield qualitative measures of the interactions between the remaining adsorbents and the rubber surface. Considering the values that were measured, hot water with water fluid by rapid rpm offers the best performance when cleaning the surface. The chemical like sodium hypochlorite is good for thinning the materials, but it solidifies them, which is eventually detrimental to proper functioning. Copyright © 2014 John Wiley & Sons, Ltd.     

Behavior of thin films of poly(oxyethylene)-poly(oxybutylene) copolymers studied by brewster angle microscopy and atomic force microscopy

Surface films of two copolymers of ethylene oxide (E) and butylene oxide (B), namely E23B8 and E87B18, have been examined by Brewster angle microscopy (BAM) and atomic force microscopy (AFM). Isotherms taken on unsupported films of these copolymers at the air-water interface showed a clear gas to liquid phase transition for E57B18 and a barely discernible phase transition for E23B8. The BAM studies showed a gradual brightening of the films as the surface pressure was increased, which was associated with a film thickening and/or a film densification. Several bright spots were also observed within the films, with the number of spots increasing gradually as the film surface pressure was increased. AFM studies of these films did not show any localized ordering, which fits in with the results from our previous X-ray study of these copolymers [Hodges, C. S.; Neville, F.; Konovalov, O.; Gidalevitz, D.; Hamley, I. W.; Langmuir 2006, 22 (21), 8821-8825], where no long-range ordering was observed. AFM imaging showed two sizes of particulates that were irregularly spaced across the film. The larger particulates were associated with silica contaminants from the copolymer synthesis, whereas the smaller particulates were assumed to be aggregated copolymer. An analysis of the semidilute region of the isotherm showed that while both copolymers had intermixed ethylene oxide and butylene oxide units, the lower molecular weight E23B8 copolymer manifested significantly more intermixing than E87B18.     

Probing the in-plane composition of thin polymer films with grazing-incidence small-angle neutron scattering and atomic force microscopy

The surface morphologies of confined, dewetted polymer films were investigated with atomic force microscopy (AFM) and grazing-incidence small-angle neutron scattering (GISANS). On examining homopolymer films of deuterated polystyrene (dPS) both techniques reveal the resulting droplet structure which is described by one most prominent in-plane length. Due to the contrast resulting from deuteration in the case of polymer blend films of dPS and poly(p-methyl styrene) GISANS is able to probe the in-plane composition of the dewetting structure. An additional phase separation process at different length scales gives rise to a sub- and superstructure which is not detectable by AFM. In addition, the influence of the wavelength used in the GISANS experiments on the structures observed is discussed. Received: 13 April 1999 Accepted in revised form: 29 June 1999     

Single polymer molecules adsorbed to mica and the oppositely charged polymer/surfactant complexes formed at the air–water interface visualized by atomic force microscopy

In the present study, the structure and morphology of single sodium poly(styrenesulfonate) (PSS) molecules adsorbed to mica surface from the natural aqueous solution is investigated using atomic force microscopy technique. Results show that single PSS molecules are observed which show a morphology of wormlike coils. Meanwhile, single sodium poly(styrenesulfonate) (PSS)/Hexadecyltrimethylammonium bromide (CTAB) complexes deposited on mica from the air–water interface are also observed. However, the PSS/CTA⁺ complexes show different conformations by appearing in the morphology of circular patches. Experimental data are in fair agreement with the theoretical analysis.     

Real-time enzymatic degradation study of poly[(R)-3-hydroxybutyric acid] copolymer thin film by atomic force microscopy in buffer solution

In situ observation of lamellar crystals during the enzymatic degradation by poly(hydroxybutyrate) (PHB) depolymerase is carried out on the thin films of poly[((R)-3-hydroxybutyric acid)-co-(16 mol-%-(R)-3-hydroxypentanoic acid)] using atomic force microscopy in buffer solution. Erosion of lamellar crystals and formation of splintered morphology along the crystal growth direction are directly observed during the course of the enzymatic degradation process. The changes in lamellar morphologies caused by enzymatic degradation are discussed in terms of lamellar crystal growth process.

AFM images of a P[(R)-3HB-co-(R)-3HV] thin film before and during enzymatic degradation.     

Nanoscale structural and electronic properties of ultrathin blends of two polyaromatic molecules: a Kelvin probe force microscopy investigation.

We describe a Kelvin Probe Force Microscopy (KPFM) study on the morphological and electronic properties of complex mono and bi-molecular ultrathin films self-assembled on mica. These architectures are made up from an electron-donor (D), a synthetic all-benzenoid polycyclic aromatic hydrocarbon, and an electron-acceptor (A), perylene-bis-dicarboximide. The former molecule self-assembles into fibers in single component films, while the latter molecule forms discontinuous layers. Taking advantage of the different solubility and self-organizing properties of the A and D molecules, multicomponent ultrathin films characterized by nanoscale phase segregated fibers of D embedded in a discontinuous layer of A are formed. The direct estimation of the surface potential, and consequently the local workfunction from KPFM images allow a comparison of the local electronic properties of the blend with those of the monocomponent films. A change in the average workfunction values of the A and D nanostructures in the blend occurs which is primarily caused by the intimate contact between the two components and the molecular order within the nanostructure self-assembled at the surface. Additional roles can be ascribed to the molecular packing density, to the presence of defects in the film, to the different conformation of the aliphatic peripheral chains that might cover the conjugated core and to the long-range nature of the electrostatic interactions employed to map the surface by KPFM limiting the spatial and potential resolution. The local workfunction studies of heterojunctions can be of help to tune the electronic properties of active multicomponent films, which is crucial for the fabrication of efficient organic electronic devices as solar cells.     

Imaging surfaces of nano‐scale roughness by atomic force microscopy with carbon nanotubes as tips: a comparative study

Accurate knowledge of the nanoroughness of surfaces is crucial for many applications related to optics, electronics or tribology. Although atomic force microscopy (AFM) can image surfaces with a nanometre spatial resolution, the finite size of standard tips means that pores, pits or grooves with dimensions similar to or smaller than the tip apex will not be accurately imaged. Furthermore, standard tips are made of silicon or silicon nitride and are prone to wear. Mitigation may arise from the availability of AFM tips with a carbon nanotube (CNT) at their foremost end. This study compares the imaging performance of ultrasharp Si tips, CNT AFM tips prepared by a Langmuir‐Blodgett (LB) technique, and of CNT AFM tips prepared by a chemical vapour deposition (CVD) technique. The free length of the CNT AFM tips is in the range 80–200 and 600–750 nm, respectively. A polycrystalline niobium film surface is imaged that shows nanoroughness. The measurements demonstrate that CNT AFM tips allow excellent imaging if the scan parameters are adjusted very carefully. Nevertheless, in some cases distortions are found. The measured average grain diameter is 19.9 ± 3.6 nm in the case of a CNT AFM tip made by the LB technique, and 18.0 ± 3.3 nm in the case of a CNT AFM tip made by CVD. In addition to cross‐sections of topography images, also the power spectral density (PSD) is analyzed. An empirical approach for the readout of the characteristic length is suggested that involves the first derivative of the decadic logarithm of the PSD. Copyright © 2011 John Wiley & Sons, Ltd.     

Details of surface features in aromatic polyamide reverse osmosis membranes characterized by scanning electron and atomic force microscopy

In the present article, some new events on the surface morphology of the aromatic polyamide thin‐film‐composite (TFC) membranes were demonstrated in conjunction with their inherent chemical nature. In addition, the detailed, quantitative understanding of the microscopic surface features was shown to be essential in controlling the water permeability and eventually developing the high performance membranes. The surface roughness and the surface area were mainly affected by the existence or nonexistence of the crosslinking and/or the free amide groups not pertinent to the formation of the hydrogen bonding, which in turn contributed to the water permeability. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1429–1440, 1999     

Mechanism of solid|liquid interfacial reactions. The reactive dissolution of p-chloranil in aqueous solution as studied by the channel flow cell with electrochemical detection and atomic force microscopy

A quantitative study of the hydrolytic dissolution of solid p-chloranil at alkaline pH using a combination of the channel flow cell and in situ atomic force microscopy measurements shows that the dissolution is driven by reaction of the substrate with hydroxide ions at, or very close to, the dissolving surface. The dissolution rate equation, deduced from the channel flow cell for single crystals of p-chloranil, is rate/mol cm⁻² s⁻¹ = 3.8 × 10⁻⁷ [OH⁻]₀ where [OH⁻]₀/M is the hydroxide ion concentration adjacent to the solid surface. An analogous rate law is derived for pressed pellet substrates. The novel application of the atomic force microscope to make absolute measurements of surface averaged dissolution rates is described. Comparison with the independent channel flow cell data reveals good mechanistic agreement and consistency of rate constants provided it is recognised that a thick stagnant diffusion layer can be present under the usual conditions employed for AFM.     

Morphology of poly(ε‐caprolactone)‐b‐poly(ethylene glycol)‐b‐poly(ε‐caprolactone) assemblies in diluted aqueous solution and gel studied by atomic force microscopy

Morphologies of poly(ε‐caprolactone)‐b‐poly(ethylene glycol)‐b‐poly(ε‐caprolactone) (PCL‐PEG‐PCL) triblock copolymer self‐assemblies in the diluted solution and in gel were studied by atomic force microscopy (AFM). The copolymer self‐assembled into wormlike aggregates, of uniform diameter, in water. The wormlike aggregates arranged in order to form separate clusters in the diluted copolymer solution; at a higher copolymer concentration, the clusters became bigger and bigger, and packed together to form gel. Copyright © 2008 John Wiley & Sons, Ltd.