Anomalous luminescence from perylene in thin polymer films

Perylene dispersed in thin polystyrene films can exhibit a structureless fluorescence with a maximum at 527 nm. It is assigned to dimer sites featuring perylene molecules that are close enough to interact upon excitation.     

Wetting-Dewetting oscillations of liquid films during solution-mediated vacuum deposition of rubrene

We found a novel oscillating phenomenon associated with surface wetting during the vacuum deposition of an organic semiconductor (rubrene) on a liquid film (bis(2-ethylhexyl)sebacate, B2EHS). In-situ observations by an optical microscope revealed that the oscillation was associated with the growth of the rubrene crystals. The oscillation frequency was proportional to the evaporation rate of rubrene. On the basis of the contact angle measurements, it was concluded that the oscillation is probably due to the change in the contact angle of the liquid caused by the formation of ultrathin rubrene films on the liquid surface.     

Anomalous sorption of supercritical fluids on polymer thin films

Unusual sorption has been reported in thin polymer films exposed to near-critical CO2. When the supercritical fluid approaches the critical point, the film appears to thicken, but it is not clear whether the film swells or there is an adsorption layer on the film surface. A combination of the gradient theory of inhomogeneous systems and the Sanchez-Lacombe equation of state has been used to investigate this phenomenon. It is shown analytically that surface adsorption on an attractive surface is proportional to the compressibility of the fluid. We have also investigated numerically the sorption of supercritical CO2 on poly(dimethylsiloxane) and polyisobutylene, and supercritical 1,1-difluoroethane on polystyrene. By calculating the Gibbs adsorption and adsorption layer thickness of the supercritical fluids, we found in all cases (different substrates, different supercritical fluids) that maximum adsorption occurs when the supercritical fluid is near its compressibility maximum.     

Crystalline morphology evolution in PCL thin films

The transition of crystalline morphology is revealed in poly(?‐caprolactone) (PCL) thin films as the polymer film thickness changes from hundreds of nanometers to several nanometers. The PCL can crystallize into spherulites, dense‐branching morphology (DBM), or dendrites, depending on the polymer film thickness. It was found that when the polymer film thickness approaches 2Rg (radius of gyration of polymer), there is a remarkable change in crystalline morphology. Under this condition, the polymer crystallization is a diffusion‐controlled process. When the value of polymer film thickness closes to Rg, PCL cannot crystallize, and a dewetting phenomenon will take place. Moreover, polymer morphology can be controlled by varying supercooling. The effect of molecular weight on polymer morphology has been investigated. The main factors that affected pattern formation in nonequilibrium crystallization are also discussed. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1303–1309, 2005     

Surface structural evolution in iron oxide thin films

Ordered iron oxide ultrathin films were fabricated on a single-crystal Mo(110) substrate under ultrahigh vacuum conditions by either depositing Fe in ambient oxygen or oxidizing preprepared Fe(110) films. The surface structure and electronic structure of the iron oxide films were investigated by various surface analytical techniques. The results indicate surface structural transformations from metastable FeO(111) and O-terminated Fe(2)O(3)(0001) to Fe(3)O(4)(111) films, respectively. The former depends strongly on the oxygen pressure and substrate temperature, and the latter relies mostly upon the annealing temperature. Our experimental observations are helpful in understanding the mechanisms of surface structural evolution in iron oxides. The model surfaces of Fe-oxide films, particularly O-terminated surfaces, can be used for further investigation in chemical reactions (e.g., in catalysis).     

Growth of crystalline rubrene films with enhanced stability

The growth of well-oriented crystalline films of rubrene (C42H28) on SiO2 and Au111 substrates is achieved by employing "hot wall" deposition whereas organic molecular beam deposition (OMBD) only yields rather amorphous layers or poly-crystalline dendritic networks at elevated temperature. This pronounced difference in film growth is related to the conformational change of rubrene molecules involving a loss of chirality upon crystallization and the enhanced diffusion which becomes possible at high temperature and large vapor pressure. Moreover, it is demonstrated that the crystalline rubrene films reveal an enhanced thermal and chemical stability as compared to the OMBD grown films.     

Structural evolution in amorphous silicon and germanium thin films.

The structural evolution in amorphous silicon and germanium thin films has been investigated by high-resolution transmission electron microscopy (HRTEM) in conjunction with autocorrelation function (ACF) analysis. The results established that the structure of as-deposited semiconductor films is of a high density of nanocrystallites embedded in the amorphous matrix. In addition, from ACF analysis, the structure of a-Ge is more ordered than that of a-Si. The density of embedded nanocrystallites in amorphous films was found to diminish with annealing temperature first, then to increase. The conclusions also corroborate well with the results of diminished medium-range order in annealed amorphous films determined previously by a variable coherence microscopy method.     

Heterogeneous diffusion in thin polymer films as observed by high-temperature single-molecule fluorescence microscopy

Single-molecule fluorescence microscopy was used to investigate the dynamics of perylene diimide (PDI) molecules in thin supported polystyrene (PS) films at temperatures up to 135 °C. Such high temperatures, so far unreached in single-molecule spectroscopy studies, were achieved using a custom-built setup which allows for restricting the heated mass to a minimum. This enables temperature-dependent single-molecule fluorescence studies of structural dynamics in the temperature range most relevant to the processing and to applications of thermoplastic materials. In order to ensure that polymer chains were relaxed, a molecular weight of 3000 g/mol, clearly below the entanglement length of PS, was chosen. We found significant heterogeneities in the motion of single PDI probe molecules near T(g). An analysis of the track radius of the recorded single-probe molecule tracks allowed for a distinction between mobile and immobile molecules. Up to the glass transition temperature in bulk, T(g,bulk), probe molecules were immobile; at temperatures higher than T(g,bulk) + 40 K, all probe molecules were mobile. In the range between 0 and 40 K above T(g,bulk) the fraction of mobile probe molecules strongly depends on film thickness. In 30-nm thin films mobility is observed at lower temperatures than in thick films. The fractions of mobile probe molecules were compared and rationalized using Monte Carlo random walk simulations. Results of these simulations indicate that the observed heterogeneities can be explained by a model which assumes a T(g) profile and an increased probability of probe molecules remaining at the surface, both effects caused by a density profile with decreasing polymer density at the polymer-air interface.     

Crystal growth kinetics in GeS2 amorphous thin films

The crystal growth kinetics of germanium disulfide in undercooled melts has been studied by optical microscopy under isothermal conditions. The linear growth kinetics of GeS₂ has been observed in the temperature range 672 ≤ T ≤ 711 K in thin film samples. The activation energy of crystal growth assuming Arrhenius behavior has been determined as E _G = 166 ± 8 kJ mol^?1 for thin film samples. From the dependence of reduced growth rate on undercooling, the interface driven 2-D surface nucleated model was estimated.     

Ordering evolution of block copolymer thin films upon solvent-annealing process

Morphologies of polystyrene-block-poly(2-vinylpyridine) copolymer (S2VP) thin films, which are forming poly(2-vinylpyridine) cylinders in bulk phase, were investigated by atomic force microscopy (AFM) and transmission electron microscopy (TEM) to account for their ordering behavior induced by solvent annealing. Initially, when the copolymer was dissolved in toluene, which is selective solvent for majority polystyrene (PS) blocks, and was spin-coated on Si substrates, dimple-type micellar structures of S2VP were formed. After the film was placed in a solvent-annealing chamber covered with a lid under the existence of chloroform, surface morphologies of S2VP were measured as a function of annealing time. In this study, it was found that the morphologies of S2VP thin film repeated the cycle of the creation and extinction of various morphologies on ordering process. Namely, S2VP exhibited the various transformations between different morphologies, including highly disordered state, cylinders normal to the plane, and cylinders parallel to the plane. Each of the morphologies observed here was employed as a template to synthesize gold (Au) nanoparticles or nanowires. The arrays of Au nano-objects were used to tune a surface plasmon resonance.     

Defect evolution in block copolymer thin films via temporal phase transitions

We study the details of the defect dynamics in thin films of a cylinder-forming polystyrene-block-polybutadiene (SB) diblock copolymer melt. The high temporal resolution of in-situ scanning force microscopy (SFM) uncovers elementary dynamic processes of structural rearrangements on time scales not accessible so far. Short-term interfacial undulations and the formation of transient phases (spheres, perforated lamellae, and lamellae) are observed. We demonstrate that the well-known structural defects are annihilated by short-term phase transitions into what may be considered excited states. These temporary phase transitions are reproduced in simulations based on dynamic self-consistent field theory. We discuss the role of the observed structural evolution in the context of the equilibrium phase behavior in SB thin films.     

Micro-morphological investigations on wettability of Al-incorporated c-Si thin films using statistical surface roughness parameters

The tunable surface properties of Al-incorporated c-Si and/or homogeneous c-Si (i.e., absorber layer) thin films are investigated with the help of 3D surface topography, statistical analysis, and contact angle measurement. The absorber layers are developed by ion irradiation on c-Al/a-Si films, which results the crystallization of Si in bilayer films, and the top unreacted Al layers were chemically etched off by wet selective etching. The 3D surface topography and statistical analysis is performed on the atomic force microscopy images of the absorber film surface. The analyses suggest that the surfaces are highly complex and irregular isotropic. The surface roughness and irregularity is found to be decreasing with increasing ion fluence. Variation of contact angle with statistical parameters suggest that the wettability of the absorber surface strongly depends on the surface statistical parameters. The surfaces are hydrophobic in nature, and hydrophobicity is found to decrease with increasing ion fluence. The hydrophobic nature of low reflective absorber surface suggests that the film may be useful as a photon absorber layer for advance solar cell applications.     

Thermally activated mechanisms of hydrogen abstraction by growth precursors during plasma deposition of silicon thin films

Hydrogen abstraction by growth precursors is the dominant process responsible for reducing the hydrogen content of amorphous silicon thin films grown from SiH(4) discharges at low temperatures. Besides direct (Eley-Rideal) abstraction, gas-phase radicals may first adsorb on the growth surface and abstract hydrogen in a subsequent process, giving rise to thermally activated precursor-mediated (PM) and Langmuir-Hinshelwood (LH) abstraction mechanisms. Using results of first-principles density functional theory (DFT) calculations on the interaction of SiH(3) radicals with the hydrogen-terminated Si(001)-(2x1) surface, we show that precursor-mediated abstraction mechanisms can be described by a chemisorbed SiH(3) radical hopping between overcoordinated surface Si atoms while being weakly bonded to the surface before encountering a favorable site for hydrogen abstraction. The calculated energy barrier of 0.39 eV for the PM abstraction reaction is commensurate with the calculated barrier of 0.43-0.47 eV for diffusion of SiH(3) on the hydrogen-terminated Si(001)-(2x1) surface, which allows the radical to sample the entire surface for hydrogen atoms to abstract. In addition, using the same type of DFT analysis we have found that LH reaction pathways involve bond breaking between the silicon atoms of the chemisorbed SiH(3) radical and the film prior to hydrogen abstraction. The LH reaction pathways exhibit energy barriers of 0.76 eV or higher, confining the abstraction only to nearest-neighbor hydrogens. Furthermore, we have found that LH processes compete with radical desorption from the hydrogen-terminated Si(001)-(2x1) surface and may be suppressed by the dissociation of chemisorbed SiH(3) radicals into lower surface hydrides. Analysis of molecular-dynamics simulations of the growth process of plasma deposited silicon films have revealed that qualitatively similar pathways for thermally activated hydrogen abstraction also occur commonly on the amorphous silicon growth surface.     

Nonlinear evolution of thin liquid films dewetting near soft elastomeric layers

The nonlinear evolution of thin liquid films dewetting near soft elastomeric layers is examined in this work. Evolution equations are derived by applying the lubrication approximation and assuming that van der Waals forces in the liquid cause the dewetting and that the solid can be described as a linear viscoelastic material. Two cases are examined: (i) a liquid layer resting on an elastomer bounded from below by a rigid substrate, and (ii) an elastomer overlying a thin liquid film bounded from below by a rigid substrate. Linear stability analysis is carried out to obtain asymptotic relations which are then compared against solutions of the full characteristic equations. In the liquid-on-solid case, numerical solutions of the evolution equations show that van der Waals forces cause thinning of the liquid film and thickening of the elastomeric solid beneath film depressions. Inclusion of a short-range repulsive force suggests that regular patterns may form in which ridges of fluid rest on depressions in the solid. In the solid-on-liquid case, the van der Waals forces cause the solid layer to break up before the liquid film can dewet. The results presented here support the idea that the dewetting of thin liquid films might be exploited to create topographically patterned surfaces on soft polymeric solids.     

Structural evolution of cylindrical‐phase diblock copolymer thin films

We have measured the time evolution of the self‐assembly process in perpendicular‐oriented cylindrical‐phase diblock copolymer thin films using statistical analysis of high‐resolution scanning electron microscope (SEM) images. Within minutes of annealing above the polymer glass‐transition temperature, microphase separation between polymer blocks results in formation of uniform nanometer‐scale domains whose relative position is initially largely uncorrelated. On further annealing, the cylindrical polymer domains organize into a two‐dimensional hexagonal lattice whose characteristic grain size increases slowly with time (～t^1/4). © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1970–1975, 2004     

Instabilities during the formation of electroactive polymer thin films

The solvent-induced film structure of poly(n-vinyl carbazole) (PVK) thin films on indium tin oxide (ITO)-coated glass was examined. PVK thin films were prepared via spin-coating using five different solvents. We investigated the relationship between the solvent characteristics and film properties, including surface roughness and structure, film thickness, and density. The spin-coated polymer thin films are not in thermodynamic equilibrium; rather, the film properties are affected by the dynamics of the spin-coating process. We found that water present in tetrahydrofuran (THF) induces dewetting of PVK films during the spin-coating process. Solvents with a high evaporation rate lead to high surface roughness due to Marangoni convection. The results show that the surface roughness and structure of the films are dominated by the dynamics of the film formation process, rather than thermodynamic interactions between the polymer and solvents.     

Chemical surface deposition and growth rate of thin CdSe films

Chemical surface deposition of thin CdSe films was studied. The conditions for preparing thin films were examined, the degrees of Cd conversion in the starting compounds were determined, and the film thicknesses were measured.