Optical grating recording in highly organized thin films of Disperse Red 1

Optical grating recording with submicrometer spatial resolution, which can handle grey-level patterns, has been investigated in photochromic material made of Disperse Red 1 (DR1) molecules vacuum-deposited on a glass substrate. Holographic gratings of periods Λ within the range of 0.6 μm - 12 μm were recorded by 514.5 nm light from cw Ar⁺ laser using a degenerate two-wave mixing technique. Despite the very small DR1 layer thickness (∼ 0.1 μm), the diffraction efficiency measured in a Raman-Nath scattering regime reached 2 %. The obtained amplitude gratings were analysed with an optical microscope and Fourier transforms. Grating profiles were analysed in relation to exposure conditions and in correlation with molecular organisation. Polarising microscopy studies revealed the presence of light-induced optical anisotropy. Following that, we have checked the possibility of polarisation-sensitive recording in this medium.     

Freezing of polymer thin films and surfaces: The small molecular weight puzzle

Experimental observations (ellipsometry, scanning force microscopy, and nuclear magnetic recsonance (NMR)) of the freezing behavior of thin supported films as well as the free surface of atactic polystyrene are reported, taken at a particularly small molecular weight of 2 kg/mol. Remarkably, we find the same effect of reduction of the glass transition temperature, T_g, as observed earlier with much longer molecules. Furthermore, surface melting is observed by NMR, with the molten layer thickness similar to what has been observed with larger molecular weight. We conclude that molecular geometry effects cannot account for these observations, and that a consistent explanation must be presentable in a continuum picture. On the basis of the capillary mode spectrum of the free surface and of the supported films, we present such a model and find that it accounts very consistently with all observations made so far, at least with polystyrene. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2968–2979, 2006     

Holographic grating relaxation studies of probe diffusion in amorphous polymers

Probe diffusion of camphorquinone, thymoquinone, and diacetyl in polymers was studied by the laser-induced holographic grating relaxation (HGR) technique in polymers. The effects of changing the probe size and various parameters of the polymer, such as the molecular weight, chain conformation, and the glass transition temperature, on the probe diffusion coefficient have been investigated. Furthermore, effects of cross-linking and plasticizing the chains of the polymer host on the probe diffusion coefficient were also studied. Temperature-dependent studies show that except for the very low molecular weight poly(methyl methacrylate), all probe diffusion coefficient data above the glass transition temperature fit well to the WLF equation. ©1995 John Wiley & Sons, Inc.     

Bismuth titanate thin films prepared by wet-chemical techniques: effect of sol ageing time

In this work, layered perovskite bismuth titanate (Bi₄Ti₃O₁₂) thin films were fabricated on α-alumina substrates by spin coating process. Precursor sol was prepared by sol–gel process from bismuth nitrate and titanium butoxide in concentrated acetic acid, with diethylamine as a stabilizer. Processes occurring in the precursor sol were followed in the ageing period of 20 days. Thin films prepared from the as-synthesized and aged sols are crack-free, with the thickness of ~1 μm, uniform surface texture and rounded grains having grain size in nanometer range. Sintering of thin films was performed at various temperatures, and sintered thin films exhibited dense structure, fully crystallized with typical Aurivillius phase and without any preferred orientation and impurity phase. The influence of ageing of the precursor sol on the microstructure of obtained thin films was also investigated. Direct relation between hydrodynamic diameter of precursor particles and the morphology and the grain size of the obtained films was observed.     

Anomalous roughness evolution of rubrene thin films observed in real time during growth

We study the growth and structure of thin films of the organic semiconductor rubrene during organic molecular beam deposition (OMBD) on silicon oxide in situ and in real time using X-ray scattering. Using in situ grazing incidence diffraction (GID) we find a small degree of local order but an otherwise largely disordered structure, consistent with out of plane scans. Monitoring the surface morphology in real time during growth, we find relatively smooth films (surface roughness sigma below approximately 15 A for thicknesses up to at least 600 A) and a significant delay before the onset of roughening. This anomalous roughening in the beginning and crossover to normal roughening later during growth may be related to conformational changes of rubrene in the early stages of growth.     

Picosecond acoustic transmission measurements. I. Transient grating generation and detection of acoustic responses in thin metal films

The technique of impulsive stimulated thermal scattering is extended to backside measurement of acoustic wave packets that have propagated through thin metal films following their generation by pulsed optical excitation, heating, and thermal expansion at the front side. The acoustic transmission measurement at the backside substantially isolates the acoustic responses from thermal and electronic responses of the metal film that often dominate acoustic reflection signals measured from the front side, and permits straightforward measurement of the acoustic response generated by optical excitation at a substrate-thin film interface. It can thus better distinguish among different factors that limit the bandwidth of the acoustic wave packet, an issue of concern in the measurement of high frequency responses. The paper that follows demonstrates the application of the backside measurement to a study of high frequency structural relaxation in the glass-forming liquid glycerol.     

Electrodeposition and characterization of CdSex-Te1-x semiconducting thin films

Thin polycrystalline films of cadmium chalcogenides CdSe_xTe_1-x ( 0 ≤ x ≤ 1) have been prepared by electrochemical plating on ITO (indium tin oxide) coated glass substrates from an acid sulfate solution at 90 °C. Structural, morphological and compositional studies of the deposited films are reported as a function of the x coefficient. XRD analysis shows that all deposits have a cubic structure with a preferred orientation along the (111) direction. The composition in the films is found to vary linearly with the composition in the solution. The increase in the selenium content x in the CdSe_xTe_1-x films decreases the lattice constant and increases the band gap. Nevertheless this latter presents a minimum for x = 0.27.     

Recognition of the carbon thin films sub-structures: thermo-optical measurements

Carbon thin films oxidation was investigated on-line by high-sensitivity optical transmission (OT) method. The films have been prepared by common vacuum arc discharge and subsequently air oxidized at linear heating rates until temperatures of their complete gasification. The shape of the optical curves acquired was interpreted in light of deduced partial optical changes, each of them being ascribed by simple sigmoidal dependence. The dependencies converted to their derivative form ordered respective to the temperature scale conveniently represent an inter-relationship among the sequentially evolved films’ optical events, considered as being closely related to the individual carbon-replenishing steps. The dependencies correspond well to the ones obtained on thicker films by means of the thermogravimetry (TG) measurements.     

Fluorescence in thin liquid films: a simple model

A model is proposed to account for the effect of various parameters on the fluorescence characteristics of dyestuffs in thin films during drainage of the films.     

Proton mobility in thin ice films: a revisit

We have examined proton transport through an ice film in the temperature range 73-140 K by initially adding hydronium ions into the interior of the film and then monitoring the build-up of hydronium ion population at the film surface. The result confirms that the proton exhibits limited mobility in the ice film at low temperature, but it becomes highly mobile at temperature above 130 K. Based on this result we suggest an explanation of the anomalous experimental observations in the literature for the proton mobility in ice films.     

Advances in smart materials: Stimuli-responsive hydrogel thin films

This review highlights recent developments in the field of stimuli-responsive hydrogels, focusing primarily on thin films, with a thickness range between 100 nm to 10 μm. The theory and dynamics of hydrogel swelling is reviewed, followed by specific applications. Gels are classified based on the active stimulus—mechanical, chemical, pH, heat, and light—and fabrication methods, design constraints, and novel stimuli-responses are discussed. Often, these materials display large physiochemical reactions to a relatively small stimulus. Noteworthy materials larger than 10 μm, but with response times on the order of seconds to minutes are also discussed. Hydrogels have the potential to advance the fields of medicine and polymer science as useful substrates for “smart” devices. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1084–1099     

Photoactive additives for cross-linking polymer films: Inhibition of dewetting in thin polymer films

In this report, we describe a versatile photochemical method for cross-linking polymer films and demonstrate that this method can be used to inhibit thin polymer films from dewetting. A bifunctional photoactive molecule featuring two benzophenone chromophores capable of abstracting hydrogen atoms from various donors, including C-H groups, is mixed into PS films. Upon exposure to UV light, the bis-benzophenone molecule cross-links the chains presumably by hydrogen abstraction followed by radical recombination. Photoinduced cross-linking is characterized by infrared spectroscopy and gel permeation chromatography. Optical and atomic force microscopy images show that photocrosslinked polystyrene (PS) thin films resist dewetting when heated above the glass transition temperature or exposed to solvent vapor. PS films are inhibited from dewetting on both solid and liquid substrates. The effectiveness of the method to inhibit dewetting is studied as a function of the ratio of cross-linker to macromolecule, duration of exposure to UV light, film thickness, the driving force for dewetting, and the thermodynamic nature of the substrate.     

Optical induced modifications in thin films of Fe:PVA

The ferric chloride doped polymers change their refractive index under UV irradiation. The Fe:PVA is sensitive to ferric chloride concentration, molecular weight of PVA, and recording beam power. By Mössbauer investigations we tried to correlate the Fe²⁺/Fe³⁺ ratio, as well as the temperature dependence of the energetical parameters with the assumed mechanisms which involve both the valence state of iron and a cross-linking reaction of PVA matrix.     

Mesoporous hybrid thin films: the physics and chemistry beneath

Mesoporous films containing organic or biological functions within an organised array of cavities are produced by combining sol-gel, self-assembly of supramolecular templates and surface chemistry. This paper reviews the essential physics and chemical concepts behind the synthesis of these complex multifunctional materials.     

Challenges in the structural characterization of thin organic films

This review addresses the special problems associated with the micro-structural characterization of thin and ultrathin organic films, primarily by optical spectroscopies. Films which are deposited by Langmuir-Blodgett techniques, self-assembly chemistry, and bulk film deposition techniques are considered. The use of enhanced optical excitation using surface phasma resonances and integrated optical structures is discussed extensively, as is the use of ellipsometry. Discussion of the spectroscopies used is broken into a section on electronic spectroscopies and an extensive discussion of vibrational spectroscopies. Vibrational information may be obtained with photons (absorption or scattering) or electrons (loss spectra), and the types of experimental systems amenable to each, along with the advantages and disadvantages of each are explored.     

Thermoanalytical methods in the study of inorganic thin films

Thermoanalytical (TA) methods are relatively seldom applied for assessing the physical and chemical proeprties of thin films, but they can be used in studies of composition, phase transitions and film—substrate interactions. In the present paper the possibilities of TA methods in thin film studies are reviewed. The thermoanalytical methods considered are the classical TG and DTA/DSC methods but some complementary methods will also be briefly mentioned. The main emphasis is given to true thin films. Details of sample preparation are also given. An important application of TA methods is characterization of precursors for the CVD growth of thin films, and this is also discussed.     

Stability of thin polymer films: influence of solvents

The interface and surface properties and the wetting behavior of polymer-solvent mixtures are investigated using Monte Carlo simulations and self-consistent field calculations. We carry out Monte Carlo simulations in the framework of a coarse-grained bead-spring model using short chains (oligomers) of N(P)=5 beads and a monomeric solvent, N(S)=1. The self-consistent field calculations are based on a simple phenomenological equation of state for compressible binary mixtures and we employ Gaussian chain model. The bulk behavior of the polymer-solvent mixture belongs to type III in the classification of van Konynenburg and Scott [Phil. Trans. R. Soc. London, Ser. A 298, 495 (1980)]. It is characterized by a triple line on which the polymer-liquid coexists with solvent-vapor and a solvent-rich liquid. The solvent is not homogeneously distributed across the dense polymer film but tends to accumulate at the surface and the polymer-vapor interface. This solvent enrichment at the interface and surface becomes more pronounced upon increasing the vapor pressure and alters the surface and interface tensions. This effect gives rise to a nonmonotonic dependence of the contact angle on the vapor pressure and one might observe reentrant wetting. The results of the Monte Carlo simulations and the self-consistent field calculations qualitatively agree. The profiles of drops are investigated by Monte Carlo simulations and a pronounced solvent enrichment is observed at the wedge formed by the substrate and the liquid-vapor interface at the three-phase contact line.