Structural evolution of perfluoro-pentacene films on Ag(111): transition from 2D to 3D growth

The structural evolution and thermal stability of perfluoro-pentacene (PF-PEN) thin films on Ag(111) have been studied by means of low-temperature scanning tunnelling microscopy (STM), low-energy electron diffraction (LEED), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and thermal desorption spectroscopy (TDS). Well-defined monolayer films can be prepared by utilizing the different adsorption energy of mono- and multilayer films and selectively desorbing multilayers upon careful heating at 380 K, whereas at temperatures above 400 K, a dissociation occurs. In the first monolayer, the molecules adopt a planar adsorption geometry and form a well-ordered commensurate (6 × 3) superstructure where molecules are uniformly oriented with their long axis along the <110> azimuth. This molecular orientation is also maintained in the second layer, where molecules exhibit a staggered packing motif, whereas further deposition leads to the formation of isolated, tall islands. Moreover, on smooth silver surfaces with extended terraces, growth of PF-PEN onto beforehand prepared long-range ordered monolayer films at elevated temperature leads to needle-like islands that are uniformly aligned at substrate steps along <110> azimuth directions.     

Hydration of hydrophilic thiolate monolayers visualized by atomic force microscopy

Monolayers of mercaptoundecanol and mercaptoundecanoic acid were prepared on Au(111) films, immersed in aqueous solutions, and probed by frequency-modulation atomic force microscopy. The pN-order tip-surface force was observed over the monolayers as a function of vertical and lateral coordinates, together with the topography of the monolayers. The observed force distribution was modulated between adjacent OH endgroups in the mercaptoundecanol monolayer, as opposed to on top of COOH and COO(-) endgroups in the mercaptoundecanoic acid monolayer. Models of the interfacial hydrogen bond between water and the endgroups were proposed. The force distribution was insensitive to the electrolyte composition. There was no qualitative sign of tip-induced confinement of water.     

Self-assembled silane monolayers: fabrication with nanoscale uniformity

Illustrating direct connections between surface chemical events and mechanical and topological characteristics of self-assembled monolayers derived from octadecyltrichlorosilane (OTS) adsorption on Si(100), layers prepared in the presence and absence of moisture have been characterized. Uniform and robust self-assembled monolayers are demonstrated provided the Si(100) surface is fully hydroxylated by treatment in piranha solution and the dried surface is exposed to OTS under strict anhydrous conditions. With nanoscale resolution, the uniform mechanical properties are confirmed by interfacial force microscopy while the uniform topological properties are evident in atomic force microscopy images. The monolayer character of the OTS coverage is confirmed by X-ray photoelectron spectroscopy, ellipsometry, and patterning experiments. Analogous surfaces, prepared in the presence of moisture, exhibit nonuniform topological and mechanical properties.     

Nanoparticle assembly at fluid interfaces: structure and dynamics

The self-assembly of nanoparticles at fluid interfaces, driven by the reduction in interfacial energy, was investigated. With spherical, tri-n-octyl-phosphine-oxide covered cadmium selenide (CdSe) nanoparticles (1-8 nm), thermal fluctuations compete with the interfacial segregation giving rise to a size-dependent self-assembly of the particles. The structure of the nanoparticle assembly was studied using electron microscopy, atomic force microscopy, and X-ray scattering in situ, which indicate that the particles form a densely packed monolayer. The energetics of the adsorption of nanoparticles onto the interface was revealed by time-dependent fluorescence studies on a mixture of two different sized nanoparticles at the interface. The dynamics of the nanoparticles at the fluid interface, probed using fluorescence photobleaching methods, suggests a liquid-like behavior. The results have implications in the design of hierarchical self-assemblies of nanoparticles for the one-step fabrication of devices on multiple length scales.     

Adsorption of phenylphosphonic acid on GaAs (100) surfaces

The adsorption of phenylphosphonic acid (PPA) on GaAs (100) surfaces from solutions in acetonitrile/water mixtures was studied using Fourier transform infrared spectroscopy in attenuated total reflection in multiple internal reflections (ATR/MIR), X-ray photoelectron spectroscopy (XPS), high-resolution electron energy loss spectroscopy (HREELS), and atomic force microscopy (AFM). ATR/MIR in situ showed that the accumulation of PPA molecules near the GaAs surface increased with the water concentration in the solution. For water contents lower than 4%, ATR/MIR and XPS results are consistent with the formation of a low-density monolayer. A mechanism is proposed for H2O percentages lower than 4% involving the creation of interfacial bonds through a Br?nsted acid-base reaction, which involves the surface hydroxyl groups most probably bound to Ga. It was found that the morphology of the final layer depended strongly on the water concentration in the adsorbing solution. For water concentrations equal to or higher than 5%, the amount of adsorbed molecules drastically increased and was accompanied by modifications in the infrared spectral region corresponding to P-O and P=O. This sudden change indicates a deprotonation of the acid. XPS studies revealed the presence of extra oxygen atoms as well as gallium species in the layer, leading to the conclusion that phosphonate and hydrogenophosphonate ions are present in the PPA layer intercalated with H3O+ and Ga3+ ions. This mechanism enables the formation of layers approximately 10 times thicker than those obtained with lower H2O percentages. HREELS indicated that the surface is composed of regions covered by PPA layers and uncovered regions, but the uncovered regions disappeared for water contents equal to or higher than 5%. XPS results are interpreted using a model consisting of a monolayer partially covering the surface and a thick layer. This model is consistent with AFM images revealing roughness on the order of 7 nm for the thick layer and 0.2-0.5 nm for the thin layer. Sonication proves to be an effective method for reducing layer thickness.     

Ge(001) as a template for long-range assembly of π-stacked coronene rows

The adsorption of coronene molecules (C(24)H(12)) on the Ge(001) surface has been studied by means of scanning tunnelling microscopy (STM). Upon room temperature deposition, the coronene molecules adsorb in an upright geometry forming compact layers patterned in rows for coverages of one monolayer and less, being the only example investigated so far in which a pure aromatic hydrocarbon forms a well-ordered monolayer on a non-passivated semiconductor surface. At half monolayer, the molecular rows consist of long chains of π-stacked molecules and the distance between molecular planes is 8 ?. This configuration is maintained upon cooling the system below the transition temperature of Ge(001) (~220 K), but the molecular layer experiences also a transition from rows perpendicular to rows parallel to the Ge dimer rows. We interpret our observations in terms of a weak bonging between molecules and substrate, which facilitates the formation of large ordered domains of molecules, revealing Ge(001) as an ideal template for the growth of this and other aromatic hydrocarbons.     

Adsorption and Bioactivity of Protein A on Silicon Surfaces Studied by AFM and XPS

The adsorption of protein A on silicon surfaces was studied by atomic force microscopy (AFM) and X-ray photoelectron spectroscopy. The deposition was made statically from various concentrations of protein A in water solution. The biological activity was checked by the immobilization of rabbit immunoglobulin G. The protein adsorption occurs in least two different phases and leads to a multilayer film. The first monolayer of proteins is rapidly adsorbed on the surface. The adsorption of the second layer of proteins occurs much more slowly (a thousand times slower) and also involves the third monolayer. The protein A of the first monolayer is denaturated and biologically inactive. On the contrary, the proteins of the second monolayer keep their natural diameter and remain biologically active. AFM artifacts such as the convolution with small objects and the resulting estimation of the coverage ratio are discussed. Copyright 2001 Academic Press.     

Nanostructured collagen layers obtained by adsorption and drying

The supramolecular organization of collagen adsorbed from a 7 microg/ml solution on polystyrene was investigated as a function of the adsorption duration (from 1 min to 24 h) and of the drying conditions (fast drying under a nitrogen flow, slow drying in a water-saturated atmosphere). The morphology of the created surfaces was examined by atomic force microscopy (AFM), while complementary information regarding the adsorbed amount and the organization of the adsorbed layers was obtained using radioassays, X-ray photoelectron spectroscopy (XPS), and wetting measurements. The collagen adsorbed amount increased up to an adsorption duration of 5 h and then leveled off at a value of 0.9 microg/cm2. For samples obtained by fast drying, modeling of the N/C ratios obtained by XPS in terms of thickness and surface coverage, in combination with the adsorbed amount, water contact angle measurements and AFM images, indicated that the adsorbed layer formed a felt starting from 30 min of adsorption, the density and/or the thickness of which increased with the adsorption time. Upon slow drying, the collagen layers formed after adsorption times up to about 2 h underwent a strong reorganization. The obtained nanopatterns were attributed to dewetting, the liquid film being ruptured and adsorbed collagen being displaced by the water meniscus. At higher adsorption times, the organization of the collagen layer was similar to that obtained after fast drying, because the onset of dewetting and/or collagen displacement were prevented by the high density of the collagen felt.     

Effect of water sorption on the dielectric behavior of calcium chondroitin-4-sulfate

The dielectric properties of calcium chondroitin-4-sulfate were studied as a function of frequency, temperature, and water content. The dielectric constant changes very little with water content below “monolayer” coverage, and after that the dielectric constant follows the shape of the adsorption isotherm. The dielectric behavior is discussed as affected by interfacial polarization and by the increase in the rotational freedom of the polymer side chains.     

Development of a constant surface pressure penetration langmuir balance based on axisymmetric drop shape analysis

A new constant pressure pendant-drop penetration surface balance has been developed combining a pendant-drop surface balance, a rapid-subphase-exchange technique, and a fuzzy logic control algorithm. Beside the determination of insoluble monolayer compression-expansion isotherms, it allows performance of noninvasive kinetic studies of the adsorption of surfactants added to the new subphase onto the free surface and of the adsorption/penetration/reaction of the former onto/into/with surface layers, respectively. The interfacial pressure pi is a fundamental parameter in these studies: by working at constant pi one controls the height of the energy barrier to adsorption/penetration and can select different regimes and steps of the adsorption/penetration process. In our device a solution drop is formed at the tip of a coaxial double capillary, connected to a double microinjector. Drop profiles are extracted from digital drop micrographs and fitted to the equation of capillarity, yielding pi, the drop volume V, and the interfacial area A. pi is varied changing V (and hence A) with the microinjector. Control is based on a case-adaptable modulated fuzzy-logic PID algorithm able to maintain constant pi (or A) under a wide range of experimental conditions. The drop subphase liquid can be exchanged quantitatively by the coaxial capillaries. The adsorption/penetration/reaction kinetics at constant pi are then studied monitoring A(t), i.e., determining the relative area change necessary at each instant to compensate the pressure variation due to the interaction of the surfactant in the subsurface with the surface layer. A fully Windows-integrated program manages the whole setup. Examples of experimental protein adsorption and monolayer penetration kinetics are presented.     

Influence of dielectric barrier plasma treatment of ZnMgAl alloy-coated steel on the adsorption of organophosphonic acid monolayers

The adsorption of octadecyl phosphonic acid (ODPA) on oxide-covered surfaces of ZnMgAl alloy coatings is described as a function of a dielectric barrier discharge (DBD) pretreatment step. The ODPA monolayer formation enables the investigation of the influence of the DBD treatment on the resulting interfacial bond formation and surface coverage. Surface characterisation by means of surface spectroscopy (PM-IRRAS, XPS) and surface electrochemistry (cyclic voltammetry) showed that the DBD pretreatment with Ar, Ar/O₂ and Ar/H₂O gas mixtures leads to improved barrier properties of the adsorbed ODPA monolayer. Moreover, during ODPA monolayer formation from ethanolic solution, a partial etching of the surface oxide layer occurs.     

Auto-organized nano-structure of collagen on Gemini surfactant monolayer

Two kinds of Gemini surfactant monolayer, which showed different hydrophobic property, were selected as adsorption substrates for collagen. The topographic images of collagen were investigated by using an atomic force microscopy (AFM). Their auto-organized nano-structures were influenced by the property of substrate and the process of sample preparation, such as concentration of collagen solution, adsorption time and drying condition. Network-like structures formed on the both Gemini monolayers. With increasing concentration of collagen solution and adsorption time, the density of the network-like structure increased and their strands became wider and the mesh sizes decreased apparently. Contrary to the reference, the network-like structures of collagen also formed on the less hydrophobic Gemini surfactant monolayer even after very short adsorption time, which was considered to result from the more hydrophobic patch on it.     

Adsorption and Exchange Dynamics in Aging Hydroxyethylcellulose Layers on Silica

The adsorption kinetics of hydroxyethylcellulose (HEC) on silica and relaxations in adsorbed HEC layers were probed using total internal reflectance fluorescence and near-Brewster reflectivity. Like many random-coil polymers, HEC was found to adsorb at the transport-limited rate. Relaxations occurred at nearly constant interfacial mass when HEC layers were exposed to aqueous solvent, causing the subsequent exchange of chains between the layer and the free solution to become increasingly hindered. Eventually, on the time scale of a day, layers became immobilized and unable to accommodate chains from free solution. A continued fluorescence decay, beyond time scales that could be probed with self exchange, suggested further relaxations of the adsorbed HEC. The polydisperse HEC system (with an average molecular weight near 450,000) behaved qualitatively similar to molecular weight standard polyethylene oxide (PEO) layers on silica. For instance, relaxations in PEO layers occurred on a time scale of 10-20 h, like the HEC layers. Young layers of the latter, however, exhibited self-exchange kinetics that were an order of magnitude slower than PEO layers of similar age. This difference in adsorbed layer dynamics was attributed to HEC's stiffer backbone, compared with flexible PEO. Copyright 2000 Academic Press.     

Acetonitrile as Adsorbate or Solvent to Probe the Crystal Face Specificity of Metal–Water Interaction at Silver Electrode/Solution Interfaces

The crystal face specificity of metal–water interaction at Ag electrode/solution interfaces is investigated by using acetonitrile (ACN) as a probe molecule of the water interfacial structure or as a solvent in which water is a solute. Capacitance and voltammetric curves suggest that ACN is weakly adsorbed from aqueous solution on Ag in the order (111) > (100) > (110). Apparent inconsistencies of adsorption parameters are explained by the occurrence of two ACN adsorption modes: (i) directly on the metal surface and (ii) on the water layer adsorbed on the metal surface. Ag surface oxidation in ACN in the presence of variable amounts of water suggests that water has an inhibiting effect on Ag oxidation, the diminution of the water content in ACN leading to free anodic dissolution of the metal surface.     

Solvent-controlled organization of self-assembled polymeric monolayers on gold: an easy approach for the construction of protein resistant surfaces

Protein resistant surfaces based on poly(ethylene glycol) (PEG) coatings are extensively applied in the fields of biosensors, tissue engineering, fundamental cell-surface interaction research, and drug delivery systems. The structural organization of the PEG film on the surface has a significant effect on the performance of the film to resist protein adsorption. In this paper, we report an approach using solvent to control the organization of the polymeric monolayer on gold. A water soluble copolymer with grafted PEG side chains and alkyl disulfide side chains was synthesized. A polymeric monolayer was fabricated on a gold surface from different solutions (water- and toluene-based) of the copolymer. The organization of the polymeric monolayers was characterized by means of ellipsometry, cyclic voltammetry, contact angle, X-ray photoelectron spectroscopy, and atomic force microscopy. It was proven that the structural organization of the polymeric monolayer on a gold surface could be controlled by the solvent. A polymeric monolayer with PEG enriched at the outer level is obtained when water is used as the solvent. Various types of proteins, including fibrinogen, albumin, and normal human serum, were used to test the protein resistance of the gold surfaces modified by the polymeric monolayers. The polymeric monolayer formed from a water solution of the copolymer showed excellent protein resistance. In addition, by using water as the solvent, patterning of the polymeric monolayer could easily be achieved through a combination of lift-off and self-assembly. We believe that the approach reported here provides an easy, fast, and efficient way to fabricate a robust protein resistant surface.     

Effect of organic solvents on J aggregation of pseudoisocyanine dye at mica/water interfaces: morphological transition from three-dimension to two-dimension

Morphological and spectroscopic properties of pseudoisocyanine (PIC) J aggregates produced at mica/solution interfaces have been characterized by absorption/fluorescence spectroscopy, fluorescence microscopy, and atomic force microscopy. Addition of organic solvents (1-propanol (PrOH) or 1,4-dioxane (Dox)) into aqueous solutions of the PIC dye induced a transition of the morphology of the interfacial J aggregates. The characteristic feature of this transition is the thickness (or height) change of the aggregate domain layers from three-dimensions to two-dimensions: The domain area of the J aggregates was dependent on the amount of the organic cosolvent, while the domain thickness was dependent on the type of the cosolvent. In pure aqueous solution, the J aggregates at the mica/water interface had a three-dimensional structure with the height of approximately 3 nm (multilayer structure). In mixed solvents of PrOH/water or Dox/water (5 or 10 vol%), the interfacial aggregates became a bilayer or monolayer structure, respectively, assuming that PIC molecules are adsorbed on their molecular plane perpendicular to the mica surface. Meanwhile, optical properties (band width and peak position) of the J band were invariant upon addition of the organic cosolvents, suggesting that molecular packing in the J aggregates is essentially unchanged. These results revealed that spectroscopic properties of the interfacial PIC J aggregates were determined only by the lateral (two-dimensional) interaction within the adsorbed monolayer of PIC molecules on mica, and interlayer interaction in the multilayered J aggregate was consequently small.     

On the Behavior of Nonionic Surfactants at the N-Heptane/Silica Gel Interface: Influence of the Presence of Interfacial Water Inferred from Adsorption Isotherms and Calorimetric Data

The behavior of two polydisperse nonionic surfactants, poly (oxyethylene) glycol alkylphenyl ether TX-35 and TX-100, at the prewetted silica gel/n-heptane and dried silica gel/n-heptane interfaces has been compared by the determination of the average adsorption isotherms of the polydisperse surfactants and of displacement enthalpies. From HPLC experiments, we could also separately quantify the adsorption of each ethyleneoxide (EO) fractions for silica gel from the polydisperse surfactant solution. The adsorption isotherms clearly indicate an incomplete preferential adsorption of the large (EO) chains over the small ones, as well on dried silica gel as on a prehydrated sample. This preferential adsorption and its driving force follow the solubility rules of the poly(oxyethylene) glycol alkylphenyl ether in an apolar solvent and support the idea of a solubility-limited adsorption: solubility in organic solvents of the smaller (EO) chains is much more significant than that of the longer ones and hence prevents adsorption of the smaller species. Consequently, it is observed that the presence of interfacial water decreases the affinity of TX-35 molecules for the hydrophilic silica surface due to the hydration of (EO) chains. In contrast, for TX-100 adsorption after the prewetting treatment the clearest trend is a drastic increase of the adsorption ascribed to the additional solubilization (and micellization) of the TX-100 molecules in the interfacial aqueous phase. The differential molar enthalpies of displacement show a change in the adsorption mechanism, depending on the presence of molecular water on the surface. In the initial part of the adsorption isotherm, a prevailing exothermic process is obtained with prehydrated silica and suggests that hydration of the polar heads of TX-35 and the solubilization of the TX-35 in interfacial water are occurring. For higher equilibrium concentrations, the enthalpies of displacement observed with the prehydrated adsorbent become slightly lower than those obtained with dry silica gel. It may be that this difference is due to the micellization phenomenon of the surfactant species with longer EO chains in interfacial water. These features emphasize the influence of interfacial water on the adsorption of EO fractions from organic solvent. Copyright 2000 Academic Press.     

Spectroscopic analysis of the tribological behavior of a model boundary layer lubricant

Highly ordered alkanethiol self-assembled monolayers (SAMs) on gold substrates are suitable models of boundary layer lubricants and may be used in actual nanoscale device applications. Here, such monolayers were studied by spectroscopic methods as a function of tribological wear (rubbing) using a pin-on-disk microtribometer. The coefficient of friction (COF) (ratio of the frictional force to the load) was measured with the tribometer, and reflectance infrared spectra and X-ray photoelectron spectra were obtained as the monolayer film failed and the COF changed. The results show that it is possible to correlate disorder in the monolayer film with tribological failure of the film, and that continued rubbing produces a chemical change in the monolayer film. Disorder in the monolayer is distinct from the influence of wear in the underlying gold substrate. Aged SAMs, having sulfonate rather than thiol headgroups and initially less well ordered, behave differently to the well-ordered freshly prepared SAMs. Interestingly, they show a lower COF over many more cycles of exposure to the rubbing pin. The impact of the mechanism of film failure in boundary layer lubrication is discussed.     

Crust effect on multiscale pattern formations in drying micelle solution drops on solid substrates

Spherical micelles of a polystyrene-b-poly(dimethylsiloxane) (PS-b-PDMS) diblock copolymer with the number-average molecular weight of 193 000 g/mol for PS and 39 000 g/mol for PDMS were obtained by using n-dodecane or n-octane as the selective solvent for the PDMS block. The drying process of micelle solution drops with relatively high polymer concentration on solid substrates and the resultant drying patterns were studied using optical microscopy and atomic force microscopy. The drying drops exhibited an inner solution "cap" connecting with an outer gelled "foot" through a transition zone. A crust was first formed on the surface of the transition zone and remained on the top of the foot region. An inhomogeneous stress perpendicular to the radial direction within the crust, which was due to the solvent evaporation accompanied by the receding of the solution cap, induced regular 45 degrees -tilted stripes (pleats) in the transition zone and main radial cracks in the foot region. The stripes and cracks have periods of a few and tens of microns, respectively. Concave micelle "bricks" were also observed between cracks. In addition to micelle close packing, these patterns demonstrate that drying micelle solution drops may provide a potential means to manipulate fine and multiscale structures for technological applications.     

PS纳米球在羧甲基化壳聚糖自组装膜表面静电吸附行为研究

用AFM研究了PS纳米球在自组装有羧甲基化壳聚糖(CM-CHI)单层膜的云母基底上的吸附行为及CM-CHI自组装膜形貌对PS纳米球吸附行为的影响.重点考察了盐浓度,吸附时间和温度对PS自组装动力学的影响.在CM-CHI自组装膜制备条件一定的情况下,20℃时PS最大覆盖率对应的盐浓度为0.5mol/L,平衡吸附时间为20min,对应的覆盖率约为48.0%.CM-CHI自组装膜形貌对覆盖率的影响主要表现为PS纳米球在由不同方法制备的CM-CHI自组装膜上的覆盖率在最宜吸附盐浓度,平衡吸附时间内随吸附温度的升高而显著增大,当PS吸附温度为60℃时甚至有部分覆盖率达65.0%.此外,还讨论了有关CM-CHI自组装膜是否干燥及PS自组装循环中冲洗用水盐浓度对PS纳米球覆盖率的影响.