Partitioning of a heterotelechelic polystyrene to separate interfaces of thin films

Heterotelechelic deuteropolystyrenes have been synthesised with a tertiary amine functionality at one end and a fluorocarbon group at the other end of the polymer chain. A layer of this polymer, circa 120 ? thick, has been attached to the surface of a silicon substrate and subsequently covered with a much thicker layer of hydrogenous polystyrene. The combination has then been annealed at 413 K under vacuum for defined times and the subsequent distribution of the deutero heterotelechelic polymer determined using nuclear reaction analysis and neutron reflectometry. The influences of annealing time, molecular weight and thickness of the hydrogenous polymer have been examined. Nuclear reaction analysis showed that an excess of the heterotelechelic polymer formed at both interfaces with a larger excess remaining at the substrate-polymer interface. When the molecular weight of the hydrogenous polymer is lower than that of the deuteropolymer, the deutero layer is initially swollen by the hydrogenous polymer but the thickness then decreases as deutero polymer becomes detached from the silicon substrate and an additional excess layer is eventually formed at the vacuum-polymer surface. When the molecular weight of the hydrogenous polymer is higher, there is an initial shrinkage of the deuteropolymer layer, but the original thickness (∼ radius of gyration of the deuteropolymer) is regained on prolonged annealing. There is no evidence for bridging between the two interfaces by the heterotelechelic polymer. After five days annealing the volume fraction distribution of the deuteropolymer at the silicon substrate was well described by a self-consistent field model where the only adjustable parameter was the sticking energy of the tertiary amine group to the silicon substrate for which a value of 8k _B T was obtained. Comparison of the dependence of the equilibrium layer thickness of the deuteropolymer on the equilibrium grafting density at the silicon surface with the predictions of scaling theory for brush-like polymer layers suggested that the grafted molecules were in the ideal, unperturbed brush region. Received 12 October 2000 and Received in final form 27 March 2001     

Atomic structure of Bi-dimer row selectively adsorbed on Si(5 5 12)-2 × 1 surface

In order to understand the atomic structure of nanostructures self-assembled on the template with one-dimensional symmetry, Bi/Si(5 5 12) system has been chosen and Bi-adsorption steps have been studied by STM. With Bi adsorption, the clean Si(5 5 12) is transformed to (3 3 7) terraces with disordered boundary due to mismatched periodicities between (3 3 7) and (5 5 12), and Bi-dimer rows are formed inside the (3 3 7) unit as follows: Initially, when Bi atoms are deposited at the adsorption temperature of about 450 °C, they selectively replace Si-dimers and Si-adatoms and form adsorbed Bi-dimers and Bi-adatoms, respectively. If additional Bi is supplied, the Bi-dimers adsorb on the Bi-dimers and Bi-adatoms in the first layer. These adsorbed dimers in the second layer are facing each other to form a Bi-dimer pair with relatively stable p³bonding. Finally, a single Bi-dimer adsorbs above the Bi-dimer pair in the second layer, at which point the Bi layer thickness saturates. It has been concluded that the Bi-dimer pair with stable p³ bonding is the composing element in the second layer and such site-selective adsorption is possible due to the substrate-strain relaxation through inserting Bi-buffer layer limited to specific sites of the substrate.     

Rheological aging and rejuvenation in solid friction contacts

We study the low-velocity (0.1-100 μm s^-1) frictional properties of interfaces between a rough glassy polymer and smooth silanized glass, a configuration which gives direct access to the rheology of the adhesive joints in which shear localizes. We show that these joints exhibit the full phenomenology expected for confined quasi-2D soft glasses: they strengthen logarithmically when aging at rest, and weaken (rejuvenate) when sliding. Rejuvenation is found to saturate at large velocities. Moreover, aging at rest is shown to be strongly accelerated when waiting under finite stress below the static threshold. Received 20 February 2002 and Received in final form 16 May 2002     

Atomic scale friction between clean graphite surfaces

We investigate atomic scale friction between clean graphite surfaces by using molecular dynamics. The simulation reproduces atomic scale stick-slip motion and a low frictional coefficient, both of which are observed in experiments using frictional force microscope. It is made clear that the microscopic origin of low frictional coefficients of graphite lies on the honeycomb structure of each layer, not only on the weak interlayer interaction as believed so far.     

Fabrication of a Mono-Domain Alignment Ferroelectric Liquid Crystal Device Using a Polar Self-Assembled Monolayer

A mono-domain ferroelectric liquid crystal device (FLCD) is fabricated using a novel method. The cell used in this method is an asymmetric cell, typically the combination of a polar self-assembled monolayer (SAM) for one substrate and a rubbed polyimide for the other substrate. A defect-free alignment of ferroelectric liquid crystal is fabricated without applying a dc voltage to remove degeneracy in the layer structure. The contact angles of self-assembled monolayer and PI-2942 are measured and the polarity of SAM is higher than the PI alignment. It is found that the polarity of self-assembled monolayer is a key factor in the formation of mono-domain alignment of FLC.     

Dewetting of thin polymer films

We study the dewetting of thin polymer films deposited on slippery substrate. Recent experiments on these systems have revealed many unexpected features. We develop here a model that takes into account the rheological properties of polymer melts, focussing on two dewetting geometries (the receding of a straight edge, and the opening of a hole). We show that the friction law associated with the slippage between the film and the substrate has a direct influence on the dewetting dynamic. In addition, we demonstrate that residual stresses, which can be stored in the films due to their viscoelasticity, are a source of destabilization for polymer films, and accelerate the dewetting process.     

The influence of hard-baking temperature applied for SU8 sensor layer on the sensitivity of capacitive chemical sensor

SU8, the near-UV photosensitive epoxy-based polymer was used as a sensor layer in the capacitive chemical sensor, ready for integration with a generic double-metal CMOS technology. It was observed that the response of the sensor slowly increases with the temperature applied in hard-baking process as long as it remains below 300°C. At this temperature the response of the sensor abruptly increases and becomes almost threefold. It was shown that fully crosslinked structure of the sensor layer becomes opened and disordered when the sensor is hard-baked at temperatures between 300°C and 320°C, that is, still well below the degradation temperature of the polymer. These changes in chemical structure were analyzed by Fourier-transform infrared spectroscopy. The temperature-dependent changes of the sensor layer structure enable one to prepare a combination of capacitive chemical sensors with good discrimination between some volatile organic compounds.     

Systematic study of the effect of disorder on nanotribology of self-assembled monolayers

The adhesion and friction between pairs of ordered and disordered self-assembled monolayers on SiO2 are studied using molecular dynamics. The disorder is introduced by randomly removing chains from a well ordered crystalline substrate and by attaching chains to an amorphous substrate. The adhesion force between monolayers at a given separation increases monotonically with chain length at full coverage and with coverage for fixed chain length. Friction simulations are performed at shear velocities between 0.02-2 m/s at constant applied pressures between 200 and 600 MPa. Stick-slip motion is observed at full coverage but disappears with disorder. With random defects, the friction becomes insensitive to chain length, defect density, and substrate.     

Polyelectrolyte multilayer formation: Electrostatics and short-range interactions

We investigate the phenomenon of multilayer formation via layer-by-layer deposition of alternating charged polyelectrolytes. Using mean-field theory, we find that a strong short-range attraction between the two types of polymer chains is essential for the formation of multilayers. For strong enough short-range attraction, the adsorbed amount per layer increases (after an initial decrease), and finally it stabilizes in the form of a polyelectrolyte multilayer that can be repeated hundreds of times. For weak short-range attraction between any two adjacent layers, the adsorbed amount (per added layer) decays as the distance from the surface increases, until the chains stop adsorbing altogether. The dependence of the threshold value of the short-range attraction as function of the polymer charge fraction and salt concentration is calculated.     

Patterning of polypyrrole using a fluoropolymer as an adsorption-protecting molecule

Patterning of the conducting polymer polypyrrole (PPy) was achieved using perfluoropolyether (PFPE) as a mask material. The fluoropolymer PFPE has both hydrophobic and oleophobic properties that allowed the generation of passivated patterns against PPy deposition. We exploited these properties to achieve the selective micropattern deposition of PPy, by simple chemical oxidation in an aqueous solution. Using a microcontact printing method, circle patterns with exposed carboxyl groups were prepared, while other region was protected by PFPE. Chemical oxidation of PPy on the patterned substrate resulted in selective deposition of PPy onto only the carboxylate-terminated regions, with little deposition on the PFPE layer. Cross-sectional analysis of the pattern revealed that the PFPE layer would form a hole-like structure around the carboxylate-terminated surfaces, with PPy deposition only in the holes. The PFPE layer had little influence on surface smoothness, compared to other self-assembled monolayers. These results suggest that PFPE can be used as a protective material for the surface modification and patterning of various materials.     

Localized grafting through chemical lift-off

In this work we present two techniques that provide localized functionalization of the surface of materials. Both lead to localized grafted thin organic films (10-200 nm). The localization is brought by a chemical lift-off process, which relies on patterned weakly bonded films as sacrificial layers, combined with electrochemical (SEEP) or chemical (GraftFast©) processes which provides the final robust pattern on the surface. Both grafting processes, which were recently described, take advantage of the redox activation of diazonium salts associated with vinylic monomers in aqueous solution, and lead to similar grafted polymer films. Thanks to the high difference in adhesion between the grafted polymer and the patterned sacrificial layer (either an ink or weakly bound self-assembled monolayers), the latter may be easily removed, which unveils uncovered areas of the substrate.     

Spin injection in an organic device with a spin polarized self-assembled monolayer

We propose to achieve spin injection in an organic device by a spin polarized self-assembled monolayer (SPSAM), which is used to tune the spin-dependent coupling between electrode and organic polymer. The results show that spin injection can be realized by both the spin selection and spin manipulation effects of the SPSAM. Interestingly, we found spin polarized wave-packet as a consequence of the spin injection, which is a mix of a normal spin polaron and a spinless bipolaron.     

Scaling properties of the growing monolayer on the disordered substrate

We present results of theoretical and numerical studies the pattern formation processes in adsorptive system with the disordered substrate, representing high-entropy alloy. The lateral diffusivity of adatoms on the substrate is represented as a quenched spatial disorder. By taking into account a transference of adsorbate between first two layers we construct the reaction-diffusion model, describing evolution of adsorbate concentration on the disordered substrate. It will be shown, that at elevated values of the pressure inside a chamber the quenched spatial disorder will induce pattern formation in the system. We will show that the strength of the spatial disorder can control dynamics of nanostructured film growth, type of surface structures and scaling properties of the growing layer. This study provides an insight into details of self-organization of adatoms on the high-entropy alloys in adsorptive systems.     

Local friction at a sliding interface between an elastomer and a rigid spherical probe

This paper reports on spatially resolved measurements of the shear stress distribution at a frictional interface between a flat rubber substrate and a glass lens. Silicone rubber specimens marked close to their surface by a colored pattern have been prepared in order to measure the surface displacement field induced by the steady-state friction of the spherical probe. The deconvolution of this displacement field then provides the actual shear stress distribution at the contact interface. When a smooth glass lens is used, a nearly constant shear stress is achieved within the contact. On the other hand, a bell-shaped shear stress distribution is obtained with rough lenses. These first results suggest that simple notions of real contact area and constant interface shear stress cannot account for the observed changes in local friction when roughness is varied.     

Self-assembled monolayers of decanethiol on Au(111)/mica

We report here a preparation for thin gold films on mica substrates. We have investigated the influence of the substrate temperature and the evaporation rate on the morphology of the films. After careful outgasing of the substrate, 100 nm of Au is evaporated onto the mica surface maintained at high temperature. After slow cooling, ex situ characterizations are performed using AFM and STM. For our purposes, the best compromise between roughness and grain size is found to occur for an evaporation rate of 2 ?s^-1 onto a mica substrate maintained at 460 C. We have used these substrates for STM and AFM study of decanethiol self-assembled monolayers (SAMs). We present results for gold samples immersed for a few seconds in decanethiol solutions, revealing an incomplete organization of the films. The organization process is discussed through comparison between AFM and STM data recorded on the SAMs. Then we present molecular resolution STM pictures of ordered SAMs for longer immersion times. Received 25 May 1999     

Stranski–Krastanow growth of multilayer In(Ga)As/GaAs QDs on Germanium substrate

We have described Stranski–Krastanow growth of multilayer In(Ga)As/GaAs QDs on Ge substrate by MBE. The growth technique includes deposition of a thin germanium buffer layer followed by migration-enhanced epitaxy (MEE) grown GaAs layer at 350°C. The MEE layer was overgrown by a thin low-temperature (475°C) grown GaAs layer with a subsequent deposition of a thick GaAs layer grown at 590°C. The sample was characterized by AFM, cross-sectional TEM and temperature-dependent PL measurements. The AFM shows dense formation of QDs with no undulation in the wetting layer. The XTEM image confirms that the sample is free from structural defects. The 8 K PL emission exhibits a 1051 nm peak, which is similar to the control sample consisting of In(Ga)As/GaAs QDs grown on GaAs substrate, but the observed emission intensity is lower. The similar slopes of Arrhenius plot of the integrated PL intensity for the as-grown QD sample grown on Ge substrate as well as for a reference QD sample grown on GaAs substrate are found to be identical, indicating a similar carrier emission process for both the samples. This in turn indicates coherent formation of QDs on Ge substrate. We presume due to the accumulated strain associated with the self-assembled growth of nanostructures on Ge that nonradiative recombination centers are introduced in the GaAs barrier in between the QD layers, which in turn degrades the overall optical quality of the sample.     

摩擦导致的聚合物表层微观结构改变

应用大规模分子动力学方法, 模拟了锥形探头在非晶态聚合物薄膜表面的滑动摩擦过程, 研究了摩擦导致的聚合物薄膜表层微观结构改变, 以及探头与基体间黏着作用、滑动速度和分子链长度对基体表层微观结构改变的影响. 当探头与基体之间为黏着作用时, 摩擦导致基体表面滑痕区域的键取向沿滑动方向重新取向, 导致表层分子链回转半径沿滑动方向伸长, 并且这些表层微观结构的改变程度随滑动速度的减小而增大. 在摩擦导致结构改变的过程中, 链端单体和链中单体的贡献作用不同, 形成了不同的分子链拉伸变形机制. 当样本缠结度较大或探头滑动速度较小时, 相比于链中单体, 探头对链端单体的拖曳作用使更多分子链发生拉伸变形. 研究还发现, 在探头与聚合物薄膜系统中, 使薄膜表层微观结构发生改变是摩擦能量耗散的重要途径.     

Two-dimensional micelle formation of polystyrene-poly(vinylpyridine) diblock copolymers on mice surfaces

We have used atomic force microscopy to study the adsorption of PolyStyrene-Poly(VinylPyridine) (PS-PVP) block copolymers from a selective solvent onto atomically smooth mica surfaces. At certain copolymer concentrations, we observe a highly regular array of spherical surface micelles covering macroscopic areas of the substrate surface. Evidence is given for a thin homogeneous layer underneath the micelles which is probably due to adsorption of free copolymer chains and brush formation prior to the formation of the micellar structures. We discuss the quality of the self-assembled structures regarding different types of defects and try to identify means for improving the long range periodicity of the structures.