Understanding tapping-mode atomic force microscopy data on the surface of soft block copolymers

In this paper, we focus on better understanding tapping-mode atomic force microscopy (AFM) data of soft block copolymer materials with regard to: (1) phase attribution; (2) the relationship between topography and inside structure; (3) contrast-reversal artifacts; (4) the influence of annealing treatment on topography. The experiments were performed on the surface of poly(styrene–ethylene/butylene–styrene) (SEBS) triblock copolymer acting as a model system. First, by coupling AFM with transmission electron microscopy (TEM) measurements, the phase attribution for AFM images was determined. Secondly, by imaging an atomically flat SEBS surface as well as an AFM tip-scratched SEBS surface, it was confirmed that the contrast in AFM height images of soft block copolymers is not necessarily the result of surface topography but the result of lateral differences in tip-indentation depth between soft and hard microdomains. It was also found that there is an enlarging effect in AFM images on the domain size of block copolymers due to the tip-indention mechanism. Thirdly, based on the tip-indention mechanism, tentative explanations in some detail for the observed AFM artifacts (a reversal in phase image followed by another reversal in height image) as function of imaging parameters were given. Last, it was demonstrated that the commonly used annealing treatments in AFM sample preparation of block copolymers may in some cases lead to a dramatic topography change due to the unexpected order-to-order structure transition.     

电化学法涂层导体CeO_2缓冲层外延生长研究

电化学沉积法制备高温超导YBa2Cu3O7-δ涂层导体缓冲层具有工艺简单、设备要求低、易于连续化批量制备等优点。采用电化学沉积法,在双轴织构的Ni-5at.%W(Ni-5W)金属基带上成功制备出了具有良好c轴取向的CeO2缓冲层薄膜。利用X射线衍射、极图、扫描电子显微镜和原子力显微镜等对上述氧化物薄膜的织构、表面形貌等进行表征。重点研究了薄膜厚度、退火温度、退火时间等工艺对薄膜外延生长及其表面形貌的影响,结果表明:电化学沉积方法制备的CeO2缓冲层具有很好的双轴织构、表面平整、均一,粗糙度低,表现出良好的缓冲层性质。结合金属有机化学溶液超导层的制备技术,本工作展示了一条全化学法制备第二代高温超导带材的技术路线,具有很好的应用前景。     

In situ atomic force microscopy studies of reversible light-induced switching of surface roughness and adhesion in azobenzene-containing PMMA films

Thin films in the range 40-80 nm of a blend of PMMA with an azobenzene derivative have been studied directly during UV and blue light irradiation by atomic force microscopy (AFM), revealing highly reversible changes in the surface roughness and the film adhesion. UV light induces an ≈80% increase in surface roughness, whereas illumination by blue light completely reverses these changes. Based on the observed surface topography and transition kinetics a reversible mass flow mechanisms is suggested, where the polarity changes upon switching trigger a wetting-dewetting transition in a surface segregation layer of the chromophore. Similar AFM measurements of the pull-off force indicate a decrease upon UV and an increase after blue light illumination with a complex kinetic behavior: a rapid initial change, attributed to the change in the cis isomer fraction of the azobenzene derivative, and a more gradual change, indicative of slow structural reorganization.     

A comparative study of surface energy data from atomic force microscopy and from contact angle goniometry

Forces of adhesion have been measured for interactions involving self-assembled monolayers or polymer-film structures that had each been deposited onto a gold-coated glass substrate and a probing, gold-coated cantilever. The data have been fitted into mathematical models that allow the calculation of surface energy by considering the work done for the separation of the identically coated contacting surfaces. These values of surface energy are in close agreement with those from corresponding contact angle determinations, highlighting the potential usefulness of the technique for the study of surfaces at a resolution level approaching 1000 atoms. Comparative studies show that the employment of the atomic force microscopy technique may be preferable for the study of samples that are susceptible to penetration by liquids or for investigations under conditions that exceed the useful limits of conventional probing techniques involving liquids.     

25 nm resolution single molecular fluorescence imaging by scanning near-field optical/atomic force microscopy

High-resolution single molecular near-field fluorescence images were observed by scanning near-field optical/atomic force microscopy (SNOM/AFM). We modified the SNOM/AFM for both high-resolution fluorescence imaging and high-resolution topographic imaging. The imaged fluorophore, Alexa 532, is prepared with a poly-methyl-methacrylate (PMMA) film coating. A fluorescence resolution of 25 nm was obtained with a simultaneous topographic image of a flat surface. A sample prepared with a lower PMMA concentration exhibited a rough surface in the micro area. The results for the flat surface indicated that the fluorescence resolution is worst in the rough surface sample, that the maximum fluorescence intensities for the individual fluorophore are similar, and that the decay rate is faster. Thus, we concluded that the morphological effect is an important factor in fluorescence image resolution and the apparent lifetimes of the fluorescence molecules.     

The liquid-phase adsorption of n-octylamine onto the graphite basal surface studied by tapping-mode atomic force microscopy

Solid-like structures formed on the graphite basal surface following the liquid-phase adsorption of n-octylamine have been studied using tapping-mode atomic force microscopy. Following deposition of a 1 μl droplet and subsequent annealing at 100°C, the amine formed randomly distributed islands categorised into two types based upon the morphology at the vapour interface. Evidence was found for the parallel orientation of the molecular axis at the basal plane, the orientation anticipated from studies of other aliphatic molecules. The results suggest the formation of vertically oriented molecular clusters at the vapour interface. Similarities were found with previous results of the adsorption of n-alkanes at the basal surface, highlighting the importance of n-alkyl chain interactions. Similarities and differences were observed between amine and alkane behaviour at the graphite steps. Annealing at 200°C reduced the island coverage, particularly at steps, and at 300°C no decoration was observed on the surface. The activation energy for surface diffusion and the energy difference between surface and vapour molecules are estimated. Upon deposition of a 5 μl droplet of amine onto graphite, an aggregate morphology decorated terraces and steps. Measurements suggest that the aggregate surface consisted of molecular clusters oriented towards the surface normal.     

Track sensitivity and the surface roughness measurements of CR-39 with atomic force microscope

Atomic Force Microscope (AFM) has been applied to evaluate the surface roughness and the track sensitivity of CR-39 track detector. We experimentally confirmed the inverse correlation between the track sensitivity and the roughness of the detector surface after etching. The surface of CR-39 (CR-39 doped with antioxidant (HARZLAS (TD-1)) and copolymer of CR-39/NIPAAm (TNF-1)) with high sensitivity becomes rough by the etching, while the pure CR-39 (BARYOTRAK) with low sensitivity keeps its original surface clarity even for the long etching.     

Morphology of synthetic DOPA-eumelanin deposited on glass and mica substrates: An atomic force microscopy investigation

Bright field microscopy and atomic force microscopy techniques are used to investigate morphological properties of synthetic eumelanin, obtained by oxidation of l-DOPA solution, deposited on glass and mica substrates. Deposits of eumelanin are characterized by aggregates with different shape and size. On a micrometric scale, filamentous as well as granular structures are present on glass and mica substrates, with a larger density on the former than on the latter. On a nanometric scale, filamentous aggregates, several microns long and about 100 nm wide and high, and granular aggregates, ∼50 nm high and 100 nm wide, are found on both substrates, whereas point-like deposits less than 10 nm high and less than 50 nm wide are found on mica substrate. Dynamic light scattering measurements and atomic force microscopy images support the evidence that eumelanin presents only nanometric point-like aggregates in aqueous solution, whereas such nanoaggregates organize themselves according to granular and filamentous structures when deposition occurs, as a consequence of interactions with the substrate surface.     

Self-assembled structures of alkanethiols on gold-coated cantilever tips and substrates for atomic force microscopy: Molecular organisation and conditions for reproducible deposition

Measurements of surface-liquid interactions (contact-angle goniometry) and tip-surface adhesion forces (atomic force microscopy) combined with infrared spectroscopic studies have been used to investigate surface-preparation and solution-deposition conditions for the reproducible formation of self-assembled molecular structures on gold-coated tips and substrates for atomic force microscopy. Preliminary data show that surface-saturated self-assembled monolayers form reproducibly on prolonged (>20 h) exposure of gold-coated glass substrates to ethanolic solutions of ω-functionalised alkanethiols in the concentration range 80-160 mmol dm⁻³. The data also show that exposure for 16 h to alkanethiol concentrations in the range 160-240 mmol dm⁻³ promote bilayer formation whereas concentrations of 240-320 mmol dm⁻³ result in the deposition of multilayers, the average orientation of which is parallel to that of the first molecular layer; the use of parent 1-undecanethiol solutions at concentrations of 1-80 mmol dm⁻³ results in incomplete monolayer coverage.     

Numerical study of the hydrodynamic drag force in atomic force microscopy measurements undertaken in fluids

When atomic force microscopy (AFM) is employed for in vivo study of immersed biological samples, the fluid medium presents additional complexities, not least of which is the hydrodynamic drag force due to viscous friction of the cantilever with the liquid. This force should be considered when interpreting experimental results and any calculated material properties. In this paper, a numerical model is presented to study the influence of the drag force on experimental data obtained from AFM measurements using computational fluid dynamics (CFD) simulation. The model provides quantification of the drag force in AFM measurements of soft specimens in fluids.The numerical predictions were compared with experimental data obtained using AFM with a V-shaped cantilever fitted with a pyramidal tip. Tip velocities ranging from 1.05 to 105 μm/s were employed in water, polyethylene glycol and glycerol with the platform approaching from a distance of 6000 nm. The model was also compared with an existing analytical model. Good agreement was observed between numerical results, experiments and analytical predictions. Accurate predictions were obtained without the need for extrapolation of experimental data. In addition, the model can be employed over the range of tip geometries and velocities typically utilized in AFM measurements.     

Anomalous scaling in surface roughness evaluation of electrodeposited nanocrystalline Pt thin films

Atomic force microscopy (AFM) is used to measure the surface roughness of crystalline Pt thin films as a function of film thickness and growth rate. Our films were electrodeposited on Au/Cr/glass substrates, under galvanostatic control (constant current density), from a single electrolyte containing Pt⁴⁺ ions. Crystalline structure of the films was confirmed by X-ray diffraction (XRD) technique. The effect of growth rate (deposition current density) and film thickness (deposition time) on the kinetic roughening of the films were studied using AFM and roughness calculation. The data is consistent with a rather complex behaviour known as “anomalous scaling” where both local and large scale roughnesses show power law dependence on the film thickness.     

Atomic force microscopy enabled roughness analysis of nanostructured poly (diaminonaphthalene) doped poly (vinyl alcohol) conducting polymer thin films

The Atomic Force Microscopy (AFM) helps in evaluating parameters like amplitude or height parameters, functional or statistical parameters and spatial parameters which describe the surface topography or the roughness. In this paper, we have evaluated the roughness parameters for the native poly (vinyl alcohol) (PVA), monomer diaminonaphthalene (DAN) doped PVA, and poly (diaminonaphthalene) (PDAN) doped PVA films prepared in different solvents. In addition, distribution of heights, skewness and Kurtosis moments which describe surface asymmetry and flatness properties of a film were also determined. At the same time line profiles, 3D and 2D images of the surface structures at different scanning areas i.e. 5 × 5 μm² and 10 × 10 μm² were also investigated. From the roughness analysis and the surface skewness and coefficient of Kurtosis parameters, it was concluded that for PVA film the surface contains more peaks than valleys and the PDAN doped PVA film has more valleys than peaks. It was also found that the PDAN doped PVA film with acetonitrile solvent was used for substrate in electronics applications because the film gives less fractal morphology. Thus, the AFM analysis with different parameters suggested that the PDAN doped PVA films are smooth at the sub-nanometer scale.     

Interpretation of scanning tunneling microscopy and atomic force microscopy images of 1T-TiS2

The surface of 1T-TiS₂ was examined by scanning tunneling microscopy (STM) and atomic force microscopy (AFM). The STM and AFM images of this compound were interpreted on the basis of the partial electron density ρ(r,E_F) and total electron density ρ(r) of a slab which consists of six (001) 1T-TiS₂ layers. Electronic structure calculations were performed using the ab-initio Hartree–Fock program crystal. It was found that the bright spots in experimental STM images correspond to sulfur atoms at both positive and negative bias voltages. The AFM image showed a periodicity which can be explained by the atomic corrugation at the surface. Structural defects on the surface were also investigated, and their interpretation constitutes experimental proof that only sulfur atoms were detected by scanning probe microscopies.     

In situ observation on Au(1 0 0) surface in molten EMImBF4 by electrochemical atomic force microscopy (EC-AFM)

The Au(1 0 0) surface structure in contact with 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF₄) has been observed using electrochemical atomic force microscopy (EC-AFM) under an electrochemically controlled potential. The AFM images, taken in EMImBF₄ in the potential range from −0.6 to 0.2 V vs. Ag/Ag(I), shows a fourfold symmetry with the distance between protrusions of ≈0.30-0.32 nm. This structure agrees well with the ideal surface structure of Au(1 0 0)-(1 × 1) and it is very similar to that previously obtained in a sulfuric acid aqueous solution.     

DNA adsorption and desorption on mica surface studied by atomic force microscopy

The adsorption of DNA molecules on mica surface and the following desorption of DNA molecules at ethanol-mica interface were studied using atomic force microscopy. By changing DNA concentration, different morphologies on mica surface have been observed. A very uniform and orderly monolayer of DNA molecules was constructed on the mica surface with a DNA concentration of 30 ng/μL. When the samples were immersed into ethanol for about 15 min, various desorption degree of DNA from mica (0-99%) was achieved. It was found that with the increase of DNA concentration, the desorption degree of DNA from the mica at ethanol-mica interface decreased. And when the uniform and orderly DNA monolayers were formed on the mica surface, almost no DNA molecule desorbed from the mica surface in this process. The results indicated that the uniform and orderly DNA monolayer is one of the most stable DNA structures formed on the mica surface. In addition, we have studied the structure change of DNA molecules after desorbed from the mica surface with atomic force microscopy, and found that the desorption might be ascribed to the ethanol-induced DNA condensation.     

Calculation of the optimal imaging parameters for frequency modulation atomic force microscopy

True atomic resolution of conductors and insulators is now routinely obtained in vacuum by frequency modulation atomic force microscopy. So far, the imaging parameters (i.e., eigenfrequency, stiffness and oscillation amplitude of the cantilever, frequency shift) which result in optimal spatial resolution for a given cantilever and sample have been found empirically. Here, we calculate the optimal set of parameters from first principles as a function of the tip–sample system. The result shows that the either the acquisition rate or the signal-to-noise ratio could be increased by up to two orders of magnitude by using stiffer cantilevers and smaller amplitudes than are in use today.     

Observation of multicellular spinning behavior of Proteus mirabilis by atomic force microscopy and multifunctional microscopy

This study aimed to observe the multicellular spinning behavior of Proteus mirabilis by atomic force microscopy (AFM) and multifunctional microscopy in order to understand the mechanism underlying this spinning movement and its biological significance. Multifunctional microscopy with charge-coupled device (CCD) and real-time AFM showed changes in cell structure and shape of P. mirabilis during multicellular spinning movement. Specifically, the morphological characteristics of P. mirabilis, multicellular spinning dynamics, and unique movement were observed. Our findings indicate that the multicellular spinning behavior of P. mirabilis may be used to collect nutrients, perform colonization, and squeeze out competitors. The movement characteristics of P. mirabilis are vital to the organism's biological adaptability to the surrounding environment.     

New control methodology of microcantilevers in atomic force microscopy

We apply an external feedback control technique to vibrating microcantilevers in atomic force microscopy. Here we have no difficulty in getting information on periodic orbits required for application of the external feedback control unlike controlling chaos since stable orbits are used as reference ones. This approach enables us not only to control vibrations of the cantilevers but also to measure the sample surfaces (surface topographies) simultaneously. The efficiency and validity of our approach is demonstrated by numerical simulations and a theoretical analysis with the assistance of numerical computations.     

Observing the effect of water vapor on post-irradiated surface morphology of SiO2 and Si3N4 insulators by atomic force microscopy

In this work, we investigated the effect of water-vapor treatment on the surface morphology of SiO₂ and Si₃N₄ insulators before and after Co⁶⁰ gamma-ray irradiation by using the atomic force microscopy (AFM) operated under non-contact mode. Before irradiation, no apparent surface morphology change was found in SiO₂ samples even they were water vapor treated. However, bright spots were found on post-irradiated water-vapor-treated SiO₂ sample surfaces but not on those without water-vapor treatment. We attributed the bright spots to the negative charge accumulation in the oxide due to charge balancing between hydroxyl (OH⁻) ions adsorbed on SiO₂ surface and electron-hole pairs (ehps) generated during irradiation since they can be annealed out after low temperature annealing process. On the contrary, no bright spots were observed on post-irradiated Si₃N₄ samples with and without water-vapor treatment. This result confirms that Si₃N₄ is a better water-resist passivation layer than SiO₂ layer.     

Deoxyribonucleic acid and chromatin imaging of endometriosis and endometrial carcinoma using atomic force microscopy

Abstract

Introduction: Clinical differential diagnosis of endometrial carcinoma is challenging, as signs and symptoms may vary considerably and there is a lack of reliable diagnostic serum biomarkers.

Aim of the study: The aim of our work was to characterize the deoxyribonucleic acid and chromatin changes in the tissue of patients confirmed to be suffering from endometriosis and endometrial adenocarcinoma and compare it with a healthy control group.

Material and methods: All samples were collected during recommended surgical interventions, and after the DNA isolation, a sonification followed by crosslink of chromatin were done. Consequently, both DNA and chromatin were examined using atomic force microscopy.

Results: A chromatin immunoprecipitation was used for the in vivo observation of conformational chromatin changes. The width of ssDNA showed a significant difference, almost double the control value in the endometrial cancer sample versus control (by 73?±?5% wider, p?<?0.001). In contrast, the height of ssDNA was highest in the frozen pelvis patient sample (by 510?±?12% compared to control, p?<?0.01).

Conclusion: Our results suggest that the horizontal size of single-stranded deoxyribonucleic acid and nucleosomes can help to identify potential patients with endometrial adenocarcinoma, while the height of the same parameter is associated with endometriosis.