Photoluminescence of a freely suspended monolayer of quantum dots encapsulated into layer-by-layer films

A single monolayer of CdSe/ZnS quantum dots (QDs) has been encapsulated into a 60 nm free-suspended layer-by-layer (LbL) film. The QD monolayer showed a low light-emission within this film in contact with supporting solid substrates, but the manifold increase of photoluminescencence intensity was observed when the film was lifted and freely suspended over the microfabricated cylindrical cavities. This phenomenon was discussed in relationship with the effect of the elimination of the surface quenching enhanced by optical reflection from highly reflective silicon cavities. We suggest that a significant increase of the photoluminescence intensity of QD monolayers suspended over the microfabricated array can be interesting for future diagnostic and sensing applications.     

Free surface-induced bilayer smectic A phase in polar liquid crystals

Here the influence of the free surface on both a thick (semi-infinite) layer and a thin freely suspended film of a polar liquid crystal is investigated. It is shown that within the temperature range of the monolayer smectic A phase (S_A1) the interaction between polar molecules and the free surface of the liquid crystal gives rise to a bilayer smectic A, a structure with long range antiferroelectric order (S_A2) in the surface region of the semi-infinite layer. The dependence of the bilayer smectic order parameter on the strength of the interaction between the constituent molecules and the free surface as well as temperature and the distance to the free surface are determined. Sufficiently far from the S_A1-S_A2 transition the latter dependence has an exponential character and the depth of the S_A2 phase penetration into bulk liquid crystal is equal to the longitudinal correlation length for the bilayer smectic A structure fluctuations in the S_A1 phase. However, near the S_A1-S_A2 transition the bilayer smectic order parameter decays non-exponentially and more rapidly with increasing distance to the free surface. In addition, it is found that the bilayer S_A2 phase can form several smectic layers at the free surface of a semi-infinite polar liquid crystal layer with the S_A1 phase. Finally, it is shown that in a freely suspended film the free surface-induced S_A2 phase can completely occupy the volume of the sample. Hence in a freely suspended polar liquid crystal film the S_A1-S_A2 transition occurs with decreasing film thickness.     

Perforated, freely suspended layer-by-layer nanoscale membranes

Ultrathin, perforated, and freely suspended membranes with uniform nanopores in the range of tens of nanometers have been fabricated using a fast, simple method of spin-assisted layer-by-layer assembly on hydrophobic substrates. Membranes with thicknesses down to 20 nm were robust enough to be released from the sacrificial substrates, transferred onto various surfaces, and suspended over microscopic openings. The nanopore size can be controlled by tuning the number of polyelectrolyte bilayers, spinning speed, and a proper selection of hydrophobic substrates. We demonstrate that the formation of nanopores is caused by the partial dewetting of polyelectrolyte layers in the course of their deposition on the underlying hydrophobic surfaces. The nanoscale thickness of perforated membranes with relatively uniform size and a high concentration of nanopores provides perspectives for higher rates of transport through freely suspended LbL membranes. The highly perforated LbL membranes introduced here can serve as a novel platform for ultrafine separation considering an intriguing combination of nanopores, nanoscale membrane thickness, and easy functionalization.     

Vibrational properties of the compressed and the relaxed 1,4,5,8-naphthalene-tetracarboxylic dianhydride monolayer on Ag(111)

Layers of 1,4,5,8-naphthalene-tetracarboxylic dianhydride (NTCDA) grown on Ag(111) at about 80 K have been investigated using Fourier transform infrared spectroscopy, spot profile analysis low-energy electron diffraction, and temperature programmed desorption. Specifically, the compressed and the relaxed monolayer, as well as the transformation between the two ordered phases have been analyzed in detail. It is found that the two monolayer phases display distinctly different vibrational spectra and can thus be discriminated with high accuracy and sensitivity. For the NTCDA/Ag(111) monolayer strong in-plane vibrational modes point at a marked dynamic charge transfer between molecule and metal substrate and provide clear evidence for an efficient electronic coupling to the Ag(111) surface in conjunction with a partially filled electronic level at the Fermi energy. The bilayer, on the other hand, is largely electronically decoupled from the substrate and, according to the vanishing infrared-active in-plane vibrational modes, is oriented parallel to the surface. On the basis of spectroscopic data the metastable nature of the bilayer phase is identified as such, leading to an improved understanding of processes encountered in the course of layer preparation and resolving inconsistencies reported in the literature.     

Generating suspended single-walled carbon nanotubes across a large surface area via patterning self-assembled catalyst-containing block copolymer thin films

Using self-assembled block copolymers as templates, catalytically active nanostructures with controlled size and space have been produced. A self-assembled polystyrene-b-polyferrocenylsilane thin film and monolayer of surface micelles of cobalt-complexed polystyrene-b-poly(2-vinylpyridine) are fully compatible with novolac-based conventional photoresists. Combining bottom-up self-assembly of catalyst-containing block copolymers with top-down microfabrication processing, plateaus covered with arrays of catalytically active nanostructures have been generated. Spatially selective growth of suspended single-walled carbon nanotubes over a large surface area has been achieved. Greatly enhanced Raman signals have been detected from the suspended tubes. This facile method of creating highly ordered catalyst nanostructures on top of posts enables the rational synthesis of suspended carbon nanotubes, thus facilitating the study of CNT properties by optical methods and enabling the fabrication of devices based on suspended CNTs.     

Atomic Force Microscopy of freely suspended liquid crystal films transferred to octadecyltriethoxysilane self-assembled monolayers

Thin freely suspended films of 4-(2-methylbutyl)phenyl 4'-octylbiphenyl-4-carboxylate (8SI) in the smectic C phase were transferred to self-assembled monolayer coated glass and imaged by atomic force microscopy. Upon rapid cooling to room temperature, the smectic C quenches into a lamellar phase, exhibiting islands and single smectic layer steps. The surface of such films can be imaged with molecular resolution, revealing a partially disordered lattice of fixed molecular positions. Over a period of several days these films undergo a transition to a crystal phase having a different film morphology.     

Atomic Force Microscopy of freely suspended liquid crystal films transferred to octadecyltriethoxysilane self-assembled monolayers

Thin freely suspended films of 4-(2-methylbutyl)phenyl 4'-octylbiphenyl-4-carboxylate (8SI) in the smectic C phase were transferred to self-assembled monolayer coated glass and imaged by atomic force microscopy. Upon rapid cooling to room temperature, the smectic C quenches into a lamellar phase, exhibiting islands and single smectic layer steps. The surface of such films can be imaged with molecular resolution, revealing a partially disordered lattice of fixed molecular positions. Over a period of several days these films undergo a transition to a crystal phase having a different film morphology.     

Oscillations in thin nematic layers

In the present paper a thin nematic liquid crystal layer between two identical boundary surfaces (solid walls or free surfaces in the case of a freely suspended film) is considered. In a mean field approximation it is shown that the interference between the boundary surface-induced smectic density waves results in oscillations of the free energy of the nematic layer and disjoining pressure acting on the boundary surfaces. Theoretical dependence of disjoining pressure on the nematic layer thickness is in qualitative agreement with experiment. Also we have considered a thin film of polar nematic in which in addition to an ordinary monolayer smectic A phase (S_A1) with the layer thickness d equal to the molecular length l the partial bilayer smectic A phase (S_Ad) occurs. It is shown that the variation of the distance between the boundary surfaces can result in the oscillatory S_A1-A_Ad phase transitions in this nematic film     

Thermodynamic and real-space structural evidence of a 2D critical point in phospholipid monolayers

The two-dimensional phase diagram of phospholipid monolayers at air-water interfaces has been constructed from Langmuir compression isotherms. The coexistence region between the solid and fluid phases of the monolayer ends at the critical temperature of the transition. The small-scale lateral structure of the monolayers has been imaged by atomic force microscopy in the nm to microm range at distinct points in the phase diagram. The lateral structure is immobilized by transferring the monolayer from an air-water interface to a solid mica support using Langmuir-Blodgett techniques. A transfer protocol that ensures preservation of the structure during the transfer has been established. The lateral structure reflecting the density fluctuations has been visualized and quantitatively characterized as the monolayer passes through a series of first-order phase transitions and ultimately approaches a critical point. The critical behavior inferred from the thermodynamic as well as the structural data is found to be consistent with the 2D Ising universality class. Additional results are presented demonstrating the presence of striped phases and coexisting domains in binary mixtures.     

Gold nanoparticle self-assembly in two-component lipid Langmuir monolayers

Self-assembly processes are considered to be fundamental factors in supramolecular chemistry. Langmuir monolayers of surfactants or lipids have been shown to constitute effective 2D "templates" for self-assembled nanoparticles and colloids. Here we show that alkyl-coated gold nanoparticles (Au NPs) adopt distinct configurations when incorporated within Langmuir monolayers comprising two lipid components at different mole ratios. Thermodynamic and microscopy analyses reveal that the organization of the Au NP aggregates is governed by both lipid components. In particular, we show that the configurations of the NP assemblies were significantly affected by the extent of molecular interactions between the two lipid components within the monolayer and the monolayer phases formed by each individual lipid. This study demonstrates that multicomponent Langmuir monolayers significantly modulate the self-assembly properties of embedded Au NPs and that parameters such as the monolayer composition, surface pressure, and temperature significantly affect the 2D nanoparticle organization.     

Liquid-crystal phase diagrams of binary mixtures of hard spherocylinders

We have built the liquid crystal phase diagram of several binary mixtures of freely rotating hard spherocylinders employing a second-order virial density functional theory with Parsons scaling, suitably generalized to deal with mixtures and smectic phases. The components have the same diameter and aspect ratio of moderate value, typical of many mesogens. Attention has been paid to smectic-smectic demixing and the types of arrangement that rods can adopt in layered phases. Results are shown to depend on the aspect ratio of the individual components and on the ratio of their lengths. Smectic phases are seen not to easily mix together at sufficiently high pressures. Layered phases where the longer rods are the majority component have a smectic-A structure. In the opposite case, a smectic-A(2) phase is obtained where the shorter particles populate the layers and the longer ones prefer to stay parallel to the latter in the interlayer region.     

Progress in characterization of Langmuir monolayers by consideration of compressibility

Over decades, information about the rheological properties of the condensed monolayer phases has been obtained by introduction of a two-dimensional compressibility which is defined on the basis of the surface pressure-molecular area (Pi-A) features of the monolayer. Since the last decade, fundamental progress was attained in the experimental determination of the main characteristics of Langmuir monolayers in microscopic and molecular scale. Already smallest changes in the molecular structure of the amphiphile can result in changes in the molecular arrangement in the monolayer and thus, in changes of the main characteristics of the monolayer such as, the surface pressure-area per molecule (Pi-A) isotherms, the shape and texture of the condensed phase domains and the two-dimensional lattice structure. As the classical equations of state allowed only characterisation of the fluid (gaseous, liquid-expanded) state, thermodynamically based equations of state, which consider also the aggregation of the monolayer material to the condensed phase, have been developed. The present review focuses particularly to amphiphilic monolayers, the Pi-A isotherms of which indicate the existence of two condensed phases. For this case, the experimental results of the differences in the structure features and phase properties are discussed. The generalisation of the equation of state for Langmuir monolayers developed for the case that one, two or more phase transitions in the monolayer take place, is in agreement with the experimental results that the two-dimensional compressibility of the condensed phases undergoes a jump at the phase transition, whereas the compressibility is proportional to the surface pressure within one of the condensed phases. An example is presented which explains the procedure of the theoretical analysis of Pi-A isotherms indicating the existence of two condensed phases. An element of the procedure is the application of the general principle that the behaviour of any thermodynamic system is determined by the stability condition. An interesting anisotropy of the compressibility is revealed by GIXD studies of the S-phase of octadecanol monolayers. However, similar studies performed close to the LS-S-phase transition would result in a thermodynamically impossible negative compressibility. Close to this phase transition, the compressibility cannot be determined from the positions of the maxima because the monolayer is in a disordered state attributed to elastic distortions by fluctuations with the structure of the new phase in the surrounding matrix without destroying the quasi-long-range positional order.     

Structure of CO2 adsorbed on the KCl(100) surface

The structure and dynamics of the adsorbate CO(2)/KCl(100) from a diluted phase to a saturated monolayer have been investigated with He atom scattering (HAS), low-energy electron diffraction (LEED), and polarization dependent infrared spectroscopy (PIRS). Two adsorbate phases with different CO(2) coverage have been found. The low-coverage phase is disordered at temperatures near 80 K and becomes at least partially ordered at lower temperatures, characterized by a (2√2×√2)R45° diffraction pattern. The saturated 2D phase has a high long-range order and exhibits (6√2×√2)R45° symmetry. Its isosteric heat of adsorption is 26 ± 4 kJ mol(-1). According to PIRS, the molecules are oriented nearly parallel to the surface, the average tilt angle in the saturated monolayer phase is 10° with respect to the surface plane. For both phases, structure models are proposed by means of potential calculations. For the saturated monolayer phase, a striped herringbone structure with 12 inequivalent molecules is deduced. The simulation of infrared spectra based on the proposed structures and the vibrational exciton approach gives reasonable agreement between experimental and simulated infrared spectra.     

Phase behavior of mixed submonolayer films of krypton and xenon on graphite

Using the results of extensive Monte Carlo simulations in the canonical and grand canonical ensembles, we discuss the phase behavior of mixed submonolayer films of krypton and xenon adsorbed on the graphite basal plane. The calculations have been performed using two- and three-dimensional models of the systems studied. It has been demonstrated that out-of-plane motion does not affect the properties of the films as long as the total density is well below the monolayer completion and at moderate temperatures. For the total densities close to the monolayer completion, the promotion of particles to the second layer considerably affects the film properties. Our results are in a reasonable agreement with the available experimental data. The melting point of submonolayer films has been shown to exhibit non-monotonous changes with the film composition, and reaches minimum for the xenon concentration of about 50%. At the temperatures below the melting point, the structure of solid phases depends upon the film composition and the temperature; one can also distinguish commensurate and incommensurate phases. Two-dimensional calculations have demonstrated that for the xenon concentration between about 15% and 65% the adsorbed film exhibits the formation of a superstructure, in which each Xe atom is surrounded by six Kr atoms. This superstructure is stable only at very low temperatures and transforms into the mixed commensurate (√3×√3)R30° phase upon the increase of temperature. Such a superstructure does not appear when a three-dimensional model is used. Grand canonical ensemble calculations allowed us to show that for the xenon concentration of about 3% the phase diagram topology of monolayer films changes from the krypton-like (with incipient triple point) to the xenon-like (with ordinary triple point).     

Free surface-induced bilayer smectic A phase in polar liquid crystals

Abstract

Here the influence of the free surface on both a thick (semi-infinite) layer and a thin freely suspended film of a polar liquid crystal is investigated. It is shown that within the temperature range of the monolayer smectic A phase (S_A1 ) the interaction between polar molecules and the free surface of the liquid crystal gives rise to a bilayer smectic A, a structure with long range antiferroelectric order (S_A2 ) in the surface region of the semi-infinite layer. The dependence of the bilayer smectic order parameter on the strength of the interaction between the constituent molecules and the free surface as well as temperature and the distance to the free surface are determined. Sufficiently far from the S_A1 -S_A2 transition the latter dependence has an exponential character and the depth of the S_A2 phase penetration into bulk liquid crystal is equal to the longitudinal correlation length for the bilayer smectic A structure fluctuations in the S_A1 phase. However, near the S_A1 -S_A2 transition the bilayer smectic order parameter decays non-exponentially and more rapidly with increasing distance to the free surface. In addition, it is found that the bilayer S_A2 phase can form several smectic layers at the free surface of a semi-infinite polar liquid crystal layer with the S_A1 phase. Finally, it is shown that in a freely suspended film the free surface-induced S_A2 phase can completely occupy the volume of the sample. Hence in a freely suspended polar liquid crystal film the S_A1 -S_A2 transition occurs with decreasing film thickness.     

Thermodynamics of the liquid states of Langmuir monolayers

The liquid states and the liquid-liquid equilibrium of surfactant molecules forming an interphase between air and water have been considered using Monte Carlo computer simulations. Specifically, the expanded and compressed liquid phases observed for surfactant molecules were characterized as a function of pressure and temperature. Simple modified beadlike potentials were implemented in order to describe the interparticle forces between the hydrophobic and hydrophilic portions of surfactant molecules at the air/water interface. A simulation box was defined such that the monolayer was exposed to an externally applied lateral pressure in a modified isothermal-isobaric ensemble, whereas the water bath was modeled in a canonical ensemble. The simulation resembles the experimental setup used to measure lateral pressure (Pi) versus area isotherms obtained with Langmuir troughs. The applied lateral pressure-surface area phase diagram clearly showed the coexistence of the expanded and compressed liquid phases within certain temperature and pressure ranges. Distribution functions of distances and enthalpies for the monolayer were computed to clearly identify each liquid phase and the coexistence region.     

Fatty-acid monolayers at the nematic/water interface: phases and liquid-crystal alignment

The two-dimensional (2D) phases of fatty-acid monolayers (hexadecanoic, octadecanoic, eicosanoic, and docosanoic acids) have been studied at the interface of a nematic liquid crystal (LC) and water. When observed between crossed polarizers, the LC responds to monolayer structure owing to mesoscopic alignment of the LC by the adsorbed molecules. Similar to Langmuir monolayers at the air/water interface, the adsorbed monolayer at the nematic/water interface displays distinct thermodynamic phases. Observed are a 2D gas, isotropic liquid, and two condensed mesophases, each with a characteristic anchoring of the LC zenithal tilt and azimuth. By varying the monolayer temperature and surface concentration we observe reversible first-order phase transitions from vapor to liquid and from liquid to condensed. A temperature-dependent transition between two condensed phases appears to be a reversible swiveling transition in the tilt azimuth of the monolayer. Similar to monolayers at the air/water interface, the temperature of the gas/liquid/condensed triple-point temperature increased by about 10 degrees C for a two methylene group increase in chain length. However, the absolute value of the triple-point temperatures are depressed by about 40 degrees C compared to those of analogous monolayers at the air/water interface. We also observe a direct influence by the LC layer on the mesoscopic and macroscopic structure of the monolayer by analyzing the shapes and internal textures of gas domains in coexistence with a 2D liquid. An effective anisotropic line tension arises from elastic forces owing to deformation of the nematic director across phase boundaries. This results in the deformation of the domain from circular to elongated, with a distinct singularity. The LC elastic energy also gives rise to transition zones displaying mesoscopic realignment of the director tilt or azimuth between adjacent regions with a sudden change in anchoring.     

Optical measurements of an acylated azacrown at the air-water interface

In this study, a cyclame derivative bearing four aliphatic chain substituents shows, like many amphiphiles, solid-condensed as well as liquid-expanded phases. In contrast to the classical amphiphiles, the onset of its phase transition is characterized by a bump-like shape whose amplitude is a function of the compression speed. Ellipsometry which is very sensitive to the monolayer physical state changes, and fluorescence microscopy which has contributed significantly to the understanding of the phenomena occurring in the phase transition region have been used to investigate the monolayer behavior of this compound. This study shows that in the liquid-expanded state, the film is homogeneous and remains as such until either the maximum amplitude of the bump is reached or the beginning of the plateau sets in. Thereafter, heterogeneity with formation of diamond-like domains appears with domain sizes varying with compression speed. The formation of the domains coincides with a change in the ellipsometric zone differences. From this ellipsometric behavior, a change in the distribution of the orientation of the molecules is suggested to take place at the onset of the phase transition.     

Bindungsverhältnisse in den kristallinen Phasen von Caesiumhydroxid und -deuterohydroxid,CsOH und CsOD

Bonding Conditions in Crystalline Phases of CsOH and CsOD The crystalline phases of CsOH and CsOD have been investigated between 23 K and the melting point by x-ray and neutron diffraction experiments as well as by calorimetric, IR, and Ramanspectroscopic measurements. For crystal data see ?Inhaltsübersicht”?. In the modification stable at low temperatures which resembles a TlI-type like structure the charge-asymmetric hydroxide ions are onedimensional hydrogen bonded. Certain forms of movements of the anions occur by warming up. In the high temperature NnC1-type structure the anions rotate quasi freely. The results of the various methods of investigation of the alkali metal hydroxides in the solid state are discussed with respect to the chemical bonding in these compounds.     

Quantised charging of monolayer-protected nanoparticles

Metal nanoparticles coated with an organic monolayer, so-called monolayer protected clusters (MPCs), can show quantised charging at room temperature due to their sub-attofarad capacitance arising from the core size and the nature of the protecting monolayer. In this tutorial review, we examine the factors affecting the energetics of MPC charging. In the first section, the underlying physics of quantised charging is outlined and we give an overview of the various methods that can be used to measure single electron transfer to nanoparticles. In the subsequent sections, we discuss how electrochemical measurements can be used to give information on the quantised charging of freely diffusing and films of immobilised MPCs. The predictions of models used to determine MPC capacitance are compared with experimental data from the literature.