Polymer bilayer thin films

The boundary between cases I-II has been explored by Flexer et al. [69] with LbL self-assembled GOx multilayers and poly(bipyridine-pyridine) redox polymer (PAH-Os). Figure 2.29 shows the catalytic response in excess glucose as a function of the number ofself-assembled polymer-enzyme bilayers. For the first bilayers (thin films)... 

The photophysics of jt-conjugated polymers are reviewed in detail in other chapters of this book. (See, for example, Chapter 3.) Here, we focus on the electronic and photophysical phenomena that occur at the heterojunction between two different semiconductor polymers. The heteroj unctions are formed by combining four different polyfluorene copolymers in blend or bilayer thin films and are investigated using time-resolved and steady-state, temperature- and elec-tric-field-dependent photoluminescence measurements as well as electroluminescence and time-resolved spectroscopy. We review a body of work carried out in our laboratories over the last few years, and published in numerous journal articles (see refs. [13-17]). 

The simplest recording medium is a bilayer structure. It is constructed by first evaporating a highly reflective aluminum layer onto a suitable disk substrate. Next, a thin film (15-50 nm thick) of a metal, such as tellurium, is vacuum deposited on top of the aluminum layer. The laser power required to form the mark is dependent on the thermal characteristics of the metal film. Tellurium, for example, has a low thermal diffusivity and a melting point of 452 °C which make it an attractive recording material. The thermal diffusivity of the substrate material should also be as low as possible, since a significant fraction of the heat generated in the metal layer can be conducted to the substrate. For this reason, low cost polymer substrates such as poly (methylmethacrylate) or poly (vinyl chloride) are ideal. 

In the past, mica has been the material of choice for the interacting surfaces because of the ease of handling and since molecularly smooth surfaces can be fabricated mica surface coated with a thin film of other materials (e.g., lipid monolayers or bilayers, metal films, polymer films, or other macromolecules such as proteins) can also be used. The use of alternative materials such as molecularly smooth sapphire and silica sheets and carbon and metal oxide surfaces is also being explored. 

The bilayer morphology of thin asymmetric films of may be unstable. A regularly corrugated surface structure of the films was ascribed to spinodal transition into a laterally phase separated structure, where the surface morphology depended on the polymer incompatibility and the interfacial interactions [347, 348]. Recently, the phase separation and dewetting of thin films of a weakly incompatible blend of deuterated PS and poly(p-methylstyrene) have been monitored by SFM [349, 350]. Starting from a bilayer structure, after 454 h at T= 154 °C the film came to the final dewetting state where mesoscopic drops of... 

Similar polymer/Au nanoparticle multilayer thin films were made by Wu et al. in a study of pH-sensitive dissociation behavior of poly (3-thiophene acetic acid) (PTA A) and PAA in a LbL film (of 8 bilayers).50 Unlike the pure polymer LbL film, the Au nanoparticles-containing LbL films were difficult to be released from the substrate by varying the pH. It was suggested that the gold particles act as a cross-linker in between the multilayers, thus further enhancing the stability of the LbL films. 

Coexistence conditions of high polymer mixtures may be determined directly with the advent of the novel approach [74,75] focused on two coexisting phases confined in a thin film geometry and forming a bilayer morphology. Such equilibrium situation is obtained in the course of relaxation of an interface between pure blend components or in late stages of surface induced spinodal decomposition. It is shown that both methods lead to equivalent results [107] (Sect. 2.2.1). 

A mean field theory has recently been developed to describe polymer blend confined in a thin film (Sect. 3.2.1). This theory includes both surface fields exerted by two external interfaces bounding thin film. A clear picture of this situation is obtained within a Cahn plot, topologically equivalent to the profile s phase portrait d( >/dz vs < >. It predicts two equilibrium morphologies for blends with separated coexisting phases a bilayer structure for antisymmetric surfaces (each attracting different blend component, Fig. 32) and two-dimensional domains for symmetric surfaces (Fig. 31), both observed [94,114,115,117] experimentally. Four finite size effects are predicted by the theory and observed in pioneer experiments [92,121,130,172,220] (see Sect. 3.2.2) focused on (i) surface segregation (ii) the shape of an intrinsic bilayer profile (iii) coexistence conditions (iv) interfacial width. The size effects (i)-(iii) are closely related, while (i) and (ii) are expected to occur for film thickness D smaller than 6-10 times the value of the intrinsic (mean field) interfacial width w. This cross-over D/w ratio is an approximate evaluation, as the exact value depends strongly on the... 

Furthermore, in addition to the bulk thermal properties of polymers and resists, determination of Tg of film interfaces and of ultrathin films has become an important issue in thin film imaging (bilayer, 157 nm, and EUV). Various techniques have been employed, which include ellipsometry [481,482], positron annihilation spectroscopy (PALS) [483], QCM [484], scanning viscoelasticity microscope (SVM) [485],x-ray reflectivity [486,487], and thermal probe [488]. 

J. S. Sharp, K. R. Thomas, and M. P. Weir, mechanically driven wrinkling instability in thin film polymer bilayers. Phys. Rev. E 75, 011601 (2007). 

It should be pointed out that a specific modification of Ti(0)Pc 1 (R = -H) in organic polymers is the most widely used photoconductor in bilayer photoreceptor copiers and laser printers [19]. A thin film containing ethylene-bridged silicon phthalocyanine polymer dispersed in poly(vinylidene fluoride) (1 4 by weight) obtained by casting from a DMF slurry on quartz was orientated in an electrical field [20], A double-layered receptor device for measuring the... 

Sample preparation In order to measure the interfacial thickness, always bilayer specimens were prepared containing a thick substrate (about 1mm) and a thin film on top (in the range from 15 to 100 nm). The substrates were melt-pressed between two silicon wafers at 200 °C. The thin films were prepared by spin-casting of the polymer solutions onto a silicon wafer and the resulting films were floated off onto a water surface. The floating films were then picked up with the substrate and dried at elevated temperatures in a vacuum oven. 

Electrostatic layer-by-layer (LBL) self-assembly techniques based on oppositely charged poipelectrolytes can be useful to create stable noncentrosymmetric order in thin films. Using this interesting technique, thermodynamically stable noncentrosymmetric multilayer films can be prepared without any need for poling. Tripathy et al. reported the fabrication stable multilayer films of epoxy-based side chain azo polymers for second-order nonlinear optics.The second-order NLO coefficients of the five-bilayer LBL films of these polymers were found to be comparable to those of spin-coated poled films. A schematic view of the procedure to fabricate polyelectrolyte-based LBL films is shown in Fig. 7. 

Two complementary amphiphilic polymers woe alternatively deposited by Y-type deposition. In Polymer A, the chromophore s electron accepting end is connected to a hydrophobic bridging unit, and its electron donating end is connected to a hydrophilic bridging unit The converse is true for Polymer B. These multilayer thin films have second order nonlinear optical properties which are stable at ambient temperature in the absence of oxygen. Microstructural information on a 92-bilayer polymer film was obtained fix)m polarized optical measurements. 

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