Free-standing smectic films at high temperature

Optical reflectivity studies on free-standing liquid crystal films above the bulk smectic temperature range have revealed different melting phenomena. Our measurements are performed on tilted smectic phases (smectic C*, smectic C) using optical microscopy in polarized light in order to visualize the changes of the film structure. We observe the formation of twodimensional defect structures from string-like lines in very thick (about 1000 layers) as well as in thin (about 20 layers) films. In thick films these structures nucleate around the temperature of the bulk smectic-cholesteric phase transition, while in thin films the formation of the defects occurs well above this temperature and just before the thinning transitions. In thick and intermediate thickness films, cholesteric or nematic droplets and a ‘quasi-smectic’ structure are observed. The films exhibiting the ‘quasi-smectic’ structure definitely exist at higher temperatures than the smectic films with the same thickness.     

The structure and crystallization of thin water films on Pt(111)

When water is adsorbed on Pt(111) above 135 K several different ice structures crystallize, depending on the thickness of the ice layer. At low coverage water forms extended islands of ice with a (square root(37) x square root(37))R25(o) unit cell, which compresses as the monolayer saturates to form a (square root(39) x square root(39))R16(o) structure. The square root(39) low-energy electron diffraction (LEED) pattern becomes more intense as the second layer grows, remaining bright for films up of 10-15 layers and then fading and disappearing for films more than ca. 40 layers thick. The ice multilayer consists of an ordered square root(39) wetting layer, on which ice grows as a crystalline film which progressively loses its registry to the wetting layer. Ice films more than ca. 50 layers thick develop a hexagonal LEED pattern, the entire film and wetting layer reorienting to form an incommensurate bulk ice. These changes are reflected in the vibrational spectra which show changes in line shape and intensity associated with the different ice structures. Thin amorphous solid water films crystallize to form the same phases observed during growth, implying that these structures are thermodynamically stable and not kinetic phases formed during growth. The change from a square root(39) registry to incommensurate bulk ice at ca. 50 layers is associated with a change in crystallization kinetics from nucleation at the Pt(111) interface in thin films to nucleation of incommensurate bulk ice in amorphous solid water films more than 50 layers thick.     

Interface induced crystal structures of dioctyl-terthiophene thin films

Temperature dependent structural and morphological investigations on semiconducting dioctyl-terthiophene (DOTT) thin films prepared on silica surfaces reveals the coexistence of surface induce order and distinct crystalline/liquid crystalline bulk polymorphs. X-ray diffraction and scanning force microscopy measurements indicate that at room temperature two polymorphs are present: the surface induced phase grows directly on the silica interface and the bulk phase on top. At elevated temperatures the long-range order gradually decreases, and the crystal G (340 K), smectic F (348 K), and smectic C (360 K) phases are observed. Indexation of diffraction peaks reveals that an up-right standing conformation of DOTT molecules is present within all phases. A temperature stable interfacial layer close to the silica-DOTT interface acts as template for the formation of the different phases. Rapid cooling of the DOTT sample from the smectic C phase to room temperature results in freezing into a metastable crystalline state with an intermediated unit cell between the room temperature crystalline phase and the smectic C phase. The understanding of such interfacial induced phases in thin semiconducting liquid crystal films allows tuning of crystallographic and therefore physical properties within organic thin films.     

Investigation of the helix unwinding process in thick freely suspended smectic films

Optical and electro-optical measurements have been performed on free-standing chiral smectic films sufficiently thick (10 000 layers) to preserve the natural smectic helix. The Goldstone mode appears at about 200Hz, showing that these films are a much better approximation of the 'ideal' smectic bulk state than a thick planar sample between glass plates (where the Goldstone mode is found at about 3 kHz). In these films the unwinding of the helix is studied, as a function of applied electric field, by monitoring Bragg reflections and their Fourier components. When the helix deforms, a reflection appears which at first sight might be taken for a subharmonic, but must be interpreted as the main 'full pitch mode' reflection relative to the 'half pitch' reflection from the undeformed helix. Our measurements further confirm that in anticlinic materials no helix unwinding takes place prior to the antiferroelectric-ferroelectric transition.     

Bulk optical properties in binary mixtures of antiferroelectric liquid crystal compounds showing V-shaped switching

In order to clarify the origin of the V-shaped switching observed in thin cells ofantiferroelectric/ ferrielectric liquid crystals, bulk properties have been studied by means of helical pitch and conoscope measurements using thick free-standing films of binary mixtures with various mixing ratios. In the temperature range showing V-shaped switching in thin cells, helical structure clearly exists, indicating the existence of ordered phases. Some indistinct phase changes with temperature, coexistence of phases and quasi-continuous phase changes with an applied electric field were observed, suggesting a system with weak inter-layer correlation. By comparing the phase diagrams made using thin homogeneous cells and thick free-standing films, it was found that V-shaped switching occurs in the region where various subphases exist in the bulk. The appearance of many indistinct phases is consistent with the weak interlayer correlation. In this way, it was concluded that the V-shaped switching occurs in tilted smectic layers, in which the tilt direction is weakly correlated along the layer normal.     

Layer-thinning transitions in free-standing smectic A films

In the present paper a discrete mean-field model for thin smectic A liquid crystal films with two boundary surfaces is offered. The model accounts for the recently observed phenomenon of layer-thinning transitions in free-standing smectic A films upon heating. In particular, the model predicts the observed multiple layer jumps, as well as, for films thinner than 13 layers, the observed power law dependence of the layer-thinning transition temperatures on film thickness.     

2D Zeolite Coatings: Langmuir–Schaefer Deposition of 3 nm Thick MFI Zeolite Nanosheets

Stable suspensions of zeolite nanosheets (3 nm thick MFI layers) were prepared in ethanol following acid treatment, which partially removed the associated organic structure‐directing agent. Nanosheets from these suspensions could then be dispersed at the air–water interface and transferred to silicon wafers using Langmuir–Schaefer deposition. Using layer‐by‐layer deposition, control on coating thickness was demonstrated. In‐plane X‐ray diffraction (XRD) revealed that the deposited nanosheets contract upon calcination similar to bulk MFI crystals. Different methods for secondary growth resulted in preferentially oriented thin films of MFI, which had sub‐12‐nm thickness in certain cases. Upon calcination, there was no contraction detectable by in‐plane XRD, indicating well‐intergrown MFI films that are strongly attached to the substrate.     

Planar and non-planar solidification of optically organised smectic films

This letter describes an original freezing process that yields homogeneous solid films at ambient temperature with preservation of the layered structure of the chiral smectic phase. One of the most remarkable features of the process is its ability to provide complexly bent films with arbitrary three-dimensional shapes. Their optical homogeneity is observed in the planar as well as in the bent films. The method is very simple. After forming the films by spreading the liquid crystal above a hole in a glass slice placed over a hot stage, the film is heated from below. The hot film is exposed to ambient temperature. Then, a solid object at room temperature with a specifically adapted shape is immersed in the liquid film. The mechanical constraints imposed by the object curves the film and stabilises various solid two- and three-dimensional structures. Their homogeneous optical properties are due to long-range organisation of the molecular orientation (tilt), which combines with a complex helical arrangement of the frozen smectic layers.     

Poly(L-lysine) containing azobenzene units in the side chains: influence of the degree of substitution on liquid crystalline structure and thermotropic behaviour

The structure of poly(L-lysine)s containing between 20% and 100% of azobenzene units in the side chains has been studied by X-ray diffraction, between room temperature and 250 C. Except for samples having very low contents of azobenzene, the polymers are found to exhibit mesomorphic structures of the smectic A1 type deriving from the beta -structure of polypeptides. For polymers in which all lysine residues were substituted, the polypeptide main chains are arranged in layers corresponding to the sheets of a polypeptide 'antiparallel' beta -structure, and the side chains are perpendicular to the smectic layers. For polymers containing both substituted and free lysine side chains, each smectic layer results from the superposition of two layers: one layer contains the free lysine side chains; the other contains the azobenzenemodified lysine side chains and the polypeptide main chains that are arranged in 'antiparallel' beta -structures. All polymers exhibit only one smectic A mesophase as a function of temperature. The thickness of the smectic layers increases with increasing temperature until a thickness is reached that corresponds to the maximum interaction between the azobenzene mesogens in their trans -configuration.     

Thin film order of symmetric diblock copolymers

The ordering in thin films of symmetric diblock copolymers of polystyrene and poly(methyl methacrylate) has been investigated by neutron reflectivity as a function of film thickness and temperature. The order-disorder transition in the thin films was found to lose its first order character in that the transition occurs in a continuous manner without the correlation length becoming infinite. In addition, a transition from a partially to fully ordered state was observed which was fully reversible. This transition depended in a power law manner on the film thickness and extrapolates to the bulk order-disorder transition temperature for thick films.     

Conductivity of novel,thin-film,heterogeneous polymer electolyte systems

Over the last few years polymer electrolytes have generated much interest as potential components in devices such as batteries and smart windows. Some new systems synthesised recently have been proved to be excellent candidates for the preparation of thin films, especially Langmuir-Blodgett (LB) films. This technique enables the production of single- or multi-molecular layers of precisely known thickness. The work in this paper concentrates on the investigation of a bilayer structure composed of two different types of polyether-alkyl polymer electrolyte utilising the alternate-layer LB technique. We have demonstrated the viability of producing bilayer structures 19 molecular layers (approximately 450 Å) thick. In addition, samples prepared by using ions in the subphase exhibit higher conductivities than those without added ions, demonstrating that ion uptake from the subphase is taking place. Also, conductivity normal to the layer planes was extremely low in contrast to the higher values obtained on bulk samples. This demonstrates that ions are unable to cross the alkyl layers in the highly ordered LB system.     

The use of small-angle electron scattering to compare the structure of craze found in thin films with that found in bulk materials

Small-angle electron scattering (SAES) has been used to examine the structure of crazes in polystyrene. It has been shown theoretically that the analysis of SAES is similar to the equivalent x-ray patterns (SAXS) except perhaps for the higher-angle scattering. A direct comparison of the SAES patterns from crazes in films of ca. 400 nm thickness with SAXS patterns from crazes in films of ca. 1 mm thickness has shown that the craze structures are similar in form for the thin and thick films but the fibrils are about three times larger in the thin films.     

STRATIFICATION IN EMULSION FILMS

Formation of films possessing a layered or stratified structure has been observed with foam films from liquid crystals, from concentrated surfactant solutions and in liquid layers on the surface of water. The stratifying films have a structure similar to that of the smectic phase which soaps are known to form in the bulk solution at high concentrations. The repeating units of which such films are built are the so-called black films: each unit consists of two surfactant layers interleaved by a thin aqueous core. In the study presented here we have observed that stratification can also take place in emulsion films from concentrated aqueous surfactant solutions. We have compared these results with those obtained for foam films using the same surfactant, i.e. sodium dodecylsulfate.     

Smectic order induced at homeotropically aligned nematic surfaces: a neutron reflection study

Neutron reflection was used to measure the buildup of layers at a solid surface as the smectic phase is approached from higher temperatures in a nematic liquid crystal. The liquid crystal was 4-octyl-4'-cyanobiphenyl (8CB), and the solid was silicon with one of five different surface treatments that induce homeotropic alignment: (i) silicon oxide; (ii) a cetyltrimethylammonium bromide coating; (iii) an octadecyltrichlorosilane monolayer; (iv) an n-n-dimethyl-n-octadecyl-3- aminopropyltrimethyloxysilyl chloride monolayer; and (v) a lecithin coating. The development of surface smectic layers in the nematic phase of 8CB was followed by measuring specular reflectivity and monitoring the pseudo-Bragg peak from the layers. The scattering data were processed to remove the scattering from short-ranged smecticlike fluctuations in the bulk nematic phase from the specular reflection. The pseudo-Bragg peak at scattering vector Q approximately 0.2 A(-1) therefore corresponded to the formation of long-range smectic layers at the surface. The amplitude of the smectic density wave decayed with increasing distance from the surface, and the characteristic thickness of this smectic region diverged as the transition temperature was approached. It was found that the characteristic thickness for some of the surface treatments was greater than the correlation length in the bulk nematic. The different surfaces gave different values of the smectic order parameter at the surface. This suggests that the interaction with the surface is significantly different from a "hard wall" which would give the same values of the smectic order parameter and penetration depths similar to the bulk correlation length. Comparison of the different surfaces also suggested that the strength and range of the surface smectic ordering may be varied independently.     

Vanadium oxides on aluminum oxide supports. 1. Surface termination and reducibility of vanadia films on alpha-Al2O3(0001)

Using density functional theory and statistical thermodynamics, we obtained the phase diagram of thin VnOm films of varying thickness (approximately 2-6 A, 1-6 vanadium layers) supported on alpha-Al2O3(0001). Depending on the temperature, oxygen pressure, and vanadium concentration, films with different thickness and termination may form. In ultrahigh vacuum (UHV), at room temperature and for low vanadium concentrations, an ultrathin (1 x 1) O=V-terminated film is most stable. As more vanadium is supplied, the thickest possible films form. Their structures and terminations correspond to previous findings for the (0001) surface of bulk V2O3 [Kresse et al., Surf. Sci. 2004, 555, 118]. The presence of surface vanadyl (O=V) groups is a prevalent feature. They are stable up to at least 800 K in UHV. Vanadyl oxygen atoms induce a V(2p) core-level shift of about 2 eV on the surface V atoms. The reducibility of the supported films is characterized by the energy of oxygen defect formation. For the stable structures, the results vary between 4.11 and 3.59 eV per 1/2O2. In contrast, oxygen removal from the V2O5(001) surface is much easier (1.93 eV). This provides a possible explanation for the lower catalytic activity of vanadium oxides supported on alumina compared to that of crystalline vanadia particles.     

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.     

Dual capacitor technique for measurement of through‐plane modulus of thin polymer films

Polymer thin films are widely used as coatings and interlevel dielectrics in microelectronic applications. In thin‐film structures, stresses are generated due to interaction with adjacent layers and film shrinkage due to solvent evaporation or curing. This causes polymer chain orientation resulting in anisotropic (direction dependent) film properties. The dual capacitor technique has been developed to measure in situ, the through‐plane (z) stress‐strain behavior of thin polymer films. A parallel plate capacitor device and an interdigitated electrode structure were used as sensors to detect changes in dielectric permittivity and thickness of thin polymer films under compression. The analytical and finite element models used to interpret the capacitance measurements have been presented. The Clausius–Mossotti equation was used to determine the volume change in the film from the permittivity measurements. Results have been reported for 10–14 μm thick, Cyclotene 4026‐46 benzocyclobutene films and 10–12 μm thick films of polyimide PI‐2611. The Cyclotene 4026‐46 films were found to be mechanically isotropic, whereas the PI‐2611 films were highly anisotropic. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1634–1644, 2000     

Theory of nematic–smectic phase separation in thin twisted liquid crystal cells

Recently it has been shown experimentally by the authors that a highly twisted thin nematic cell at low temperatures can separate into a smectic A region in the middle of the cell surrounded by twisted nematic layers at the boundaries. In this case the twist is expelled into the nematic layers and the nematic–smectic A transition temperature is strongly depressed. We present a thermodynamic theory of such a phase transition in a twisted nematic cell, taking into account that the smectic A slab inside the nematic cell can be stable only if the decrease of free energy in the smectic region overcomes the increase in distortion energy of the twist deformation in the nematic layers plus the energy of the nematic–smectic A interface. In such a system the equilibrium thickness of the smectic A slab corresponds to the minimum of the total free energy of the whole cell, which includes all the bulk and surface contributions. Existing experimental data are at least qualitatively explained by the results of the present theory. This opens a unique possibility to study the properties of the nematic–smectic interface which is perpendicular to the smectic layers.     

IN SITU OBSERVATION OF MELTING AND CRYSTALLIZATION BEHAVIORS OF POLY(ε-CAPROLACTONE) ULTRA-THIN FILMS BY AFM TECHNIQUE

The melting and crystallization behaviors of poly(ε-caprolactone) (PCL) ultra-thin films with thickness from 15 nm to 8 nm were studied by AFM technique equipped with a hot-stage in real-time. It was found that melting can erase the spherulitic structure for polymer film with high thickness. However, annealing above the melting point can not completely erase the tree-like structure for the thinner polymer film. Generally, the structure formation of thin polymer films of PCL is controlled not only by melting and crystallization but also by dewetting during thermal annealing procedures, and dewetting predominates in the structure formation of ultra-thin films. However, the presence of tree-like morphology at 75 °C may be due to the strong interaction between PCL and mica surface, which may stick the PCL chains onto the mica surface during thermal annealing process. Moreover, the growth of the dendrites was investigated and it was found that crystallization is followed from a dewetted sample, and the branches did not grow with the stems. The crystallization of polymer in the ultra-thin films is a diffusion-controlled process. Both melting and crystallization behaviors of PCL in thin films are influenced by film thickness.     

Effect of alignment layer on V-shaped switching in a chiral smectic liquid crystal

The influence of the alignment layer on V-shaped switching in thin homogeneous cells of a chiral smectic liquid crystal were studied by means of electro-optic and switching current measurements.Severalpolyimides withdifferent chemicalstructures wereusedas thealignment layer in thin homogeneous cells; V-shaped switching was observed with some of them and W-shaped switching with others. It was also shown that the switching current constantly flows during the V-shaped transmittance change. In order to clarify this effect of the alignment layer on V-shaped switching, polyimide films with various polarity and thickness were examined. It is concluded that thick alignment layers assist liquid crystal materials in realizing V-shaped switching, even if the materials are not ideal for this process.