Monolayer film

In the case of Langmuir monolayers, film thickness and index of refraction have not been given much attention. While several groups have measured A versus a, [143-145], calculations by Knoll and co-workers [146] call into question the ability of ellipsometry to unambiguously determine thickness and refractive index of a Langmuir monolayer. A small error in the chosen index of refraction produces a large error in thickness. A new microscopic imaging technique described in section IV-3E uses ellipsometric contrast but does not require absolute determination of thickness and refractive index. Ellipsometry is routinely used to successfully characterize thin films on solid supports as described in Sections X-7, XI-2, and XV-7. 

Surface Micelles. The possibility of forming clusters of molecules or micelles in monolayer films was first proposed by Langmuir [59]. The matter of surface micelles and the issue of equilibration has been the subject of considerable discussion [191,201,205-209]. Nevertheless, many ir-a isotherms exhibit nonhorizontal lines unexplained by equations of state or phase models. To address this, Israelachvili [210] developed a model for ir-u curves where the amphiphiles form surface micelles of N chains. The isotherm... 

Adechanical stahility. ChemisoriDtion to tire surface, intennolecular interactions and crosslinking between adjacent compounds—if possible—all contribute to tire resulting stability of tire monolayer film. Lateral force microscopy investigations revealed tliat tire mechanical stability towards lateral forces on tire nanometre scale is likely to be detennined by tire defect density and tire domain size on a nano- to micrometre scale [163, 1731. 

Bain C D, Troughton, E B Tao Y T, Evall J and Whitesides G M 1989 Formation of monolayer films by the spontaneous assembly of organic thiols from solution onto gold J. Am. Chem. Soc. Ill 321-35... 

There are three advantages to study molecular recognition on surfaces and interfaces (monolayers, films, membranes or soHds) (175) (/) rigid receptor sites can be designed (2) the synthetic chemistry may be simplified (J) the surface can be attached to transducers which makes analysis easier and may transform the molecular recognition interface to a chemical sensor. And, which is also a typical fact, this kind of molecular recognition involves outside directed interaction sites, ie, exo-receptor function (9) (see Fig. 5b). 

Films or membranes of silkworm silk have been produced by air-drying aqueous solutions prepared from the concentrated salts, followed by dialysis (11,28). The films, which are water soluble, generally contain silk in the silk I conformation with a significant content of random coil. Many different treatments have been used to modify these films to decrease their water solubiUty by converting silk I to silk II in a process found usehil for enzyme entrapment (28). Silk membranes have also been cast from fibroin solutions and characterized for permeation properties. Oxygen and water vapor transmission rates were dependent on the exposure conditions to methanol to faciUtate the conversion to silk II (29). Thin monolayer films have been formed from solubilized silkworm silk using Langmuir techniques to faciUtate stmctural characterization of the protein (30). ResolubiLized silkworm cocoon silk has been spun into fibers (31), as have recombinant silkworm silks (32). 

LB films of 1,4,8,11,15,18-hexaoctyl-22,25-bis-(carboxypropyl)-phthalocyanine (2), an asymmetrically substituted phthalocyanine, were stable monolayers formed at the water—air interface that could be transferred onto hydrophilic siUca substrates (32—34). When a monolayer film of the phthalocyanine derivative was heated, there was a remarkable change in the optical spectmm. This, by comparison to the spectmm of the bulk material, indicated a phase transition from the low temperature herringbone packing, to a high temperature hexagonal packing. 

For ultrathin epitaxial films (less than "100 A), Grazingincidence X-ray Diffraction (GrXD) is the preferred method and has been used to characterize monolayer films. Here the incidence angle is small ("0.5°) and the X rays penetrate only "100-200 A into the specimen (see below). The exit angle of the diffracted X rays is also small and structural information is obtained about (hkl) planes perpendicular to the specimen sur e. Thus, GIXD complements those methods where structural information is obtained about planes parallel to the surface (e.g., Bra -Brentano and DCD). 

In a separate study using the JKR technique, Chaudhury and Owen [48,49] attempted to understand the correlation between the contact adhesion hysteresis and the phase state of the monolayers films. In these studies, Chaudhury and Owen prepared self-assembled layers of hydrolyzed hexadecyltrichlorosilane (HTS) on oxidized PDMS surfaces at varying degrees of coverage by vapor phase adsorption. The phase state of the monolayers changes from crystalline (solidlike) to amoiphous (liquid-like) as the surface coverage (0s) decreases. It was found that contact adhesion hysteresis was the highest for the most closely packed... 

For a monolayer film, the stress-strain curve from Eqs. (103) and (106) is plotted in Fig. 15. For small shear strains (or stress) the stress-strain curve is linear (Hookean limit). At larger strains the stress-strain curve is increasingly nonlinear, eventually reaching a maximum stress at the yield point defined by = dT Id oLx x) = 0 or equivalently by c (q x4) = 0- The stress = where is the (experimentally accessible) static friction force [138]. By plotting T /Tlx versus o-x/o x shear-stress curves for various loads T x can be mapped onto a universal master curve irrespective of the number of strata [148]. Thus, for stresses (or strains) lower than those at the yield point the substrate sticks to the confined film while it can slip across the surface of the film otherwise so that the yield point separates the sticking from the slipping regime. By comparison with Eq. (106) it is also clear that at the yield point oo. 

In order to demonstrate that the systems in question exhibit nonzero wetting temperature, we have displayed the results of calculations for one of the systems (with =1 at T = 0.7). Fig. 12 testifies that only a thin (monolayer) film develops even at densities extremely close to the bulk coexistence density (p/,(T — 0.7) — 0.001 664). In Fig. 13(a) we show the density profiles obtained at temperature 0.9 evaluated for = 7. Part (b) of this figure presents the fraction of nonassociated particles, x( )- We... 

III. SURFACE HETEROGENEITY AND PHASE TRANSITIONS IN MONOLAYER FILMS... 

FIG. 8 Phase diagrams for monolayer films on surfaces with boundary potential equal to 0.25 (a), 0.50 (b), and 0.75 (c). (Reprinted with permission from Langmuir 9 2562-2568, October 1993. 1993, American Chemical Society.)... 

On the other hand, whenever AV exceeds the value of AVq the formation of a dense monolayer film appears to be the continuous process. It has been demonstrated that the observed crossover between those two regimes is due to the changes in the mechanism of the adsorbate nucleation, as determined by the calculation of the nucleated cluster size distribution functions. For... 

FIG. 9 Changes of the monolayer film critical temperature with the concentration of impurities obtained from the Monte Carlo simulations (open circles) and resulting from the mean field theory (solid line). (Reprinted from A. Patrykiejew. Monte Carlo studies of adsorption. II Localized monolayers on randomly heterogeneous surfaces. Thin Solid Films, 205 189-196, with permision from Elsevier Science.)... 

Chidsey and coworkers made pioneering works in preparing covalently bonded monolayer films on silicon surfaces by the radical-initiated reaction of 1-alkenes with the H-Si(lll) surfaces. Reactions were carried out in neat deoxygenated alkenes using thermal decomposition of diacyl peroxides as the... 

Reactions on the surface are interesting. The adsorptions of unsaturated organic molecules on the surface provide a means for fabricating well-ordered monolayer films. Thin film organic layers can be used for diverse applications such as chemical and biological sensors, computer displays, and molecular electronics. 

The second way of preparing L-B monolayer structures, the horizontal lifting method, was introduced by Langmuir and Schaefer. In this method, a compressed monolayer first is formed at the water-air interface, and a flat substrate is then placed horizontally on the monolayer film. When the substrate is lifted and separated from the water surface, the monolayer is transferred onto the substrate, as depicted in Fig. 15(d). 

Studies of the Frictional Properties of Monolayer Films A Systematic Comparison of CF3-, (CH3)2CH-, and... 

Fig. 18—Friction force images of L-B monolayer film, normal force 1 nN (scan range 2 /u.m). (a) Monolayer L-B film, (b) four-layer L-B films.

AFM is used in the surface analysis. Figure 16 is the AFM topography of the monolayer and the multilayer L-B films. It shows that the monolayer L-B film is well packed and highly ordered on the mica surface. The surface of the monolayer film (shown in Fig. 16(a)) has a higher packing density than that of the four-layer L-B film (shown in Fig. 16(b)). This is because the molecules form the different structures in the monolayer film from those in four-layer... 

The popular applications of the adsorption potential measurements are those dealing with the surface potential changes at the water/air and water/hydrocarbon interface when a monolayer film is formed by an adsorbed substance. " " " Phospholipid monolayers, for instance, formed at such interfaces have been extensively used to study the surface properties of the monolayers. These are expected to represent, to some extent, the surface properties of bilayers and biological as well as various artificial membranes. An interest in a number of applications of ordered thin organic films (e.g., Langmuir and Blodgett layers) dominated research on the insoluble monolayer during the past decade. 

Further modification of the above nanostructures is useful for obtaining new functional materials. Thirdly, we apply the dopant-induced laser ablation technique to site-selectively doped thin diblock copolymer films with spheres (sea-island), cylinders (hole-network), and wormlike structures on the nanoscale [19, 20]. When the dye-doped component parts are ablated away by laser light, the films are modified selectively. Concerning the laser ablation of diblock copolymer films, Lengl et al. carried out the excimer laser ablation of diblock copolymer monolayer films, forming spherical micelles loaded with an Au salt to obtain metallic Au nanodots [21]. They used the laser ablation to remove the polymer matrix. In our experiment, however, the laser ablation is used to remove one component of block copolymers. Thereby, we can expect to obtain new functional materials with novel nanostmctures. 

Efl s of Magnetic Processing on the Luminescence Properties of Monolayer Films with Mn -Doped ZnS Nanoparticles... 

We prepared monolayered films with Q-Zni xMnxS and examined the effects of magnetic processing during their preparation on their luminescence properties [59]. 

Monolayer films with the alkanethiol-capped ZnS Mn nanoparticles were fabricated on quartz substrates by the layer-by-layer method using a self-assembled monolayer of 1,6-hexanedithiol. 

Figure 15.8 Experimental set-up for magnetic processing in the preparation of monolayer films consisting of Q-Zni flVln fS.

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