Metal‐Supported Aluminosilicate Ultrathin Films as a Versatile Tool for Studying the Surface Chemistry of Zeolites

The application of a variety of “surface‐science” techniques to elucidate surface structures and mechanisms of chemical reactions at zeolite surfaces has long been considered as almost impossible because of the poor electrical and thermal conductivity of those materials. Here, we show that the growth of a thin aluminosilicate film on a metal single crystal under controlled conditions results in adequate and well‐defined model systems for zeolite surfaces. In principle, silicate films that contain metals other than Al (e.g. Ti, Fe, etc) may be prepared in a similar way. We believe that this approach opens up a new playground for experimental and theoretical modeling of zeolites, aimed at a fundamental understanding of structure–reactivity relationships in such materials.     

Polydiacetylene nanowires in ultrathin films

In this paper the results of studies carried out on thin films of new poly[bis(carbazol-9-ylmethyl)diacetylene]s (PCDAs) are reported. The preparation of the films has required clever synthesis to make processable the conjugated polymers without degrading their optoelectronic properties. To this end, the parent poly(diacetylene), (polyDCHD), has been modified by introducing long alkyl or acyl chains in the 3 and 6 positions of the carbazole rings. Electronic absorption spectra and linear and nonlinear optical characterization of three types of PCDAs are reported and compared.     

Structural relaxation of stacked ultrathin polystyrene films

The T_g depression and kinetic behavior of stacked polystyrene ultrathin films is investigated by differential scanning calorimetry (DSC) and compared with the behavior of bulk polystyrene. The fictive temperature (T_f) was measured as a function of cooling rate and as a function of aging time for aging temperatures below the nominal glass transition temperature (T_g). The stacked ultrathin films show enthalpy overshoots in DSC heating scans which are reduced in height but occur over a broader temperature range relative to the bulk response for a given change in fictive temperature. The cooling rate dependence of the limiting fictive temperature, T_f′, is also found to be higher for the stacked ultrathin film samples; the result is that the magnitude of the T_g depression between the ultrathin film sample and the bulk is inversely related to the cooling rate. We also find that the rate of physical aging of the stacked ultrathin films is comparable with the bulk when aging is performed at the same distance from T_g; however, when conducted at the same aging temperature, the ultrathin film samples show accelerated physical aging, that is, a shorter time is required to reach equilibrium for the thin films due to their depressed T_g values. The smaller distance from T_g also results in a reduced logarithmic aging rate for the thin films compared with the bulk, although this is not indicative of longer relaxation times. The DSC heating curves obtained as a function of cooling rate and aging history are modeled using the Tool-Narayanaswamy-Moynihan model of structural recovery; the stacked ultrathin film samples show lower β values than the bulk, consistent with a broader distribution of relaxation times. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2741–2753, 2008     

A novel method for determining the melting behavior of ultrathin films

Experiments were performed on ultrathin (ca. 35 nm thick) Langmuir-Blodgett films of a double-bond-containing material (vinyl tetracosanoate). The melting/flow point of this deposited material, before and afterin situ polymerization by means of electron beams, was determined by using a Mettler FP5/52 hot stage in conjunction with a polarizing microscope. The melting/flow point observed in the deposited films was found to be higher than the bulk melting point as determined by the capillary method or differential scanning calorimetry. This apparent violation of the principle that a given substance's melting point becomes lower as the sample becomes thinner is explained in terms of the fact that the thin-film process observed is really a combination of two processes, initial melting and subsequent de-wetting, whereas the bulk process involves melting alone.     

Viscoelastic properties of ultrathin polycarbonate films by liquid dewetting

A liquid dewetting method for the determination of the viscoelastic properties of ultrathin polymer films has been extended to study thickness effects on the properties of ultrathin polycarbonate (PC) films. PC films with film thicknesses ranging from 4 to 299 nm were placed on glycerol at temperatures from below the macroscopic glass transition temperature (T_g) to above it with the dewetting responses being monitored. It is found that the isothermal creep results for films of the same thickness, but dewetted at different temperatures can be superposed into one master curve, which is consistent with the fact of PC being a thermorheologically simple material. Furthermore, the results show that the T_g of PC thin films is thickness dependent, but the dependence is weaker than the results for freely standing films and similar to literature data for PC films supported on rigid substrates. It was also found that the rubbery plateau region for the PC films stiffens dramatically, but still less than what has been observed for freely standing polycarbonate films. The rubbery stiffening is discussed in terms of a recently reported model that relates macroscopic segmental dynamics with the stiffening. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1559–1566     

Differential AC-chip calorimeter for glass transition measurements in ultrathin films

A differential AC-chip calorimeter capable of measuring the step in heat capacity at the glass transition in nanometer-thin films is described. Because of the differential setup, pJ/K sensitivity is achieved. Heat capacity can be measured for sample masses below 1 ng in broad temperature range as needed for the study of the glass transition in nanometer-thin polymeric films. Relative accuracy is sufficient to investigate the changes in heat capacity as the step at the glass transition of polystyrene. The step is about 25% of the total heat capacity of polystyrene. The calorimeter allows for the frequency dependent measurement of complex heat capacity in the frequency range from 1 Hz to 1 kHz. The glass transition in thin polystyrene films (50–4 nm) was determined at well-defined experimental time scales. No thickness dependency of the glass transition temperature was observed within the error limits (±3 K)—neither at constant frequency (40 Hz) nor for the trace in the activation diagram (1 Hz–1 kHz). © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2996–3005, 2006     

Wrapping and inclusion of organic molecules with ultrathin,amorphous metal oxide films

In this review, we overview metal oxide nanostructures in which organic molecules play important roles as templates, as structural units, and, in some cases, as hosts. Their structural precision and diversity are discussed from the viewpoint of the topology of a metal-oxygen network. Supramolecular capsules of metal oxides are prepared by the self-assembly of polyoxometalates. Zeolites and mesoporous materials are synthesized by using organic molecules with their assemblies acting as templates. The topological networking of silsesquioxanes makes it possible to produce novel nanocomposites and microporous materials. In the final section, we demonstrate our recent studies into molecular imprinting, the encapsulation of a fluorescent dye, and the wrapping of individual polymer chains. Ultrathin, amorphous metal oxide films can retain the shape of organic molecules and can be used to create molecular composites by precisely wrapping individual molecules. These films are also effective in insulating molecular functions from external environments. The advantages of amorphous metal oxides are discussed in relation to the properties of the corresponding crystalline metal oxides and their potential prospects in nanotechnology.     

Fabrication of ultrathin films with large third-order nonlinear optical properties.

An ultrathin composite film containing anionic Ag-His complexes (His: L-Histidine) and oppositely charged BH-PPV was fabricated by means of the electrostatic layer-by-layer self-assembly technique. UV/Vis spectra showed a continuous deposition process of Ag-His complexes and BH-PPV. The film structure was characterized by using small-angle X-ray diffraction, AFM, and SEM. The nonlinear optical properties of the ultrathin film were studied by using the Z-scan technique with a laser duration of 8 ns at a wavelength of 532 nm. The film sample exhibited a strong nonlinear saturated absorption, with an alpha2 value of -3.9 x 10(-5) mW(-1) and a self-defocusing effect with an n2 value of -4.78 x 10 (-12) m2W(-1).     

Calorimetric glass transition temperature and absolute heat capacity of polystyrene ultrathin films

The absolute heat capacity and glass transition temperature (T_g) of unsupported ultrathin films were measured with differential scanning calorimetry with the step-scan method in an effort to further examine the thermodynamic behavior of glass-forming materials on the nanoscale. Films were stacked in layers with multiple preparation methods. The absolute heat capacity in both the glass and liquid states decreased with decreasing film thickness, and T_g also decreased with decreasing film thickness. The magnitude of the T_g depression was closer to that observed for films supported on rigid substrates than that observed for freely standing films. The stacked thin films regained bulk behavior after the application of pressure at a high temperature. The effects of various preparation methods were examined, including the use of polyisobutylene as an interleaving layer between the polystyrene films. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3518–3527, 2006     

Sensing the glass transition in thin and ultrathin polymer films via fluorescence probes and labels

Fluorescence was used to characterize the glass transition in thin and ultrathin supported polymer films with common chromophores. The temperature dependence of the fluorescence intensity exhibits a transition or break upon cooling from the rubbery state to the glassy state, and this is identified as the glass transition. A variety of chromophores are investigated including pyrene, anthracene, and phenanthrene either as dopants, covalently attached to the polymer as a label, or both. The particular choice of the chromophore as well as the nature of the attachment, in the case of labels, have significant impact on the success of this method. Problematic cases include those in which the excited‐state chromophore undergoes significant photochemistry in addition to fluorescence or those in which the particular attachment of the chromophore as a label may allow for conformational interactions that affect the fluorescence quantum yield in a nontrivial way. Polymers that have an intrinsic fluorescence unit, for example, polystyrene, may allow for the fluorescence sensing of the glass transition without added dopants or labels. Finally, it is demonstrated that this technique holds promise for the study of the glass transition in polymer blends and within specific locations in multilayer films. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2745–2758, 2002     

Crystal growth rate in ultrathin films of poly(ethylene oxide)

Many dynamical properties of polymers, including segmental relaxation and chain diffusion, exhibit anomalies in thin‐film samples. We extend the studies of thin‐film dynamics to the case of semicrystalline polymers and present a study of the crystal growth rate for thin films of poly(ethylene oxide). We used optical microscopy and quartz crystal microbalance techniques to characterize the kinetics of crystallization for films with thicknesses from 40 to 1000 nm for a range of temperatures near the melting point. A remarkable slowing down of the crystal growth is observed at all temperatures studied for films with a thickness of less than ～100 nm. The results can be used to suggest reductions of the mobility of chains at the crystal/amorphous interface. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2615–2621, 2001     

Reflection–absorption infrared spectroscopy investigation of the crystallization kinetics of poly(ethylene terephthalate) ultrathin films

Reflection–absorption infrared spectroscopy was used to study the crystallization behavior of poly(ethylene terephthalate) (PET) ultrathin films. The crystallinity of ultrathin films was estimated by the fraction of trans conformers of PET. The isothermal and nonisothermal crystallization kinetics of ultrathin films with different thicknesses were investigated. The thinner PET film showed slower kinetics during isothermal crystallization than the thicker film. Moreover, the final crystallinity of films with various thicknesses were reduced with decreasing thickness. An Avrami equation was used to fit the acquired results. The Avrami exponents decreased with the film thickness. As for the nonisothermal crystallization, the cold‐crystallization starting temperature shifted to a lower temperature as the film thickness increased. The influence of the substrate on the crystallization kinetics of the films was also studied. The half‐crystallization times and final crystallinities of ultrathin films adsorbed onto a self‐assembled‐monolayer‐treated surface and an untreated substrate were clearly different, although their thickness dependence was similar. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4440–4447, 2004     

Synthesis and properties of highly thermally stable ultrathin films of fluorine-containing hyperbranched polybenzoxazoles

In this paper, we aimed to develop ultrathin films of hyperbranched polybenzoxazole with a thickness in the range between 1 and 100 nm. They are expected to have great potential for various applications as functional materials due to their high thermal stability, good chemical resistance and mechanical strength. The synthesis of various hyperbranched poly(o-hydroxyamide)s as precursors of polybenzoxazole was examined by the polycondensation of 2,2-bis(3-amino-4-hydroxyphenyl)propane (AHP) and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (AHFP) with 1,3,5-benzenetricarbonyl trichloride (BCC), yielding the corresponding hyperbranched poly(o-hydroxyamide), poly(AHFP_m-co-AHP_n-co-BCC_2.0), with M_n in the range between 12,870 and 22,210 in satisfactory yields. Poly(AHFP_3.0-co-BCC_2.0), poly(AHFP_2.25-co-AHP_0.75-co-BCC_2.0), and poly(AHFP_1.50-co-AHP_1.50-co-BCC_2.0) showed good solubility and film-forming ability, and ultrathin films 8.9–88.6 nm thick were prepared on silicon wafers. Heating of the ultrathin films of poly(AHFP_m-co-AHP_n-co-BCC_2.0) on a hot plate at 350 °C for 1 h afforded the corresponding ultrathin films of hyperbranched polybenzoxazole, poly(AHFP_m-cyclo-AHP_n-cyclo-BCC_2.0), with a thickness of 5.3–82.4 nm. Double-layer thin films consisting of resist materials on top of hyperbranched polybenzoxazole were also prepared.     

Nanomechanical properties in ultrathin polymer films: Measurement on rectangular versus circular bubbles

Prior studies of inflation of circular membranes of ultrathin polystyrene (PS) films have evidenced a reduced glass transition temperature (T_g) and rubbery stiffening, whose origins remain unclear. Here, we describe results from inflation of rectangular, ultrathin films of the same PS material. The bubble shapes obtained from the experiment are consistent with finite element (FE) simulations. The accuracy of three approximate solutions for modulus obtained from the inflation of the thin, rectangular films was evaluated by comparison with FE analysis. The best among the three solutions was used to determine the creep compliance and rubbery stiffness of the thin films. It is found that the reduction of T_g and the rubbery stiffening for rectangular bubbles are consistent with results obtained using circular bubbles, although there is some indication that the rectangular bubbles give somewhat greater rubbery stiffening. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012