Molecular multilayer films

Molecular Multilayer Films The Quest for Order, Orientation, and Optical Properties... 

During the remainder of the 1930s, Langmuir and Blodgett carried out a brilliant series of studies on multilayer films of a variety of chemicals, supplemented by studies in Britain, especially at the ill-fated Department of Colloid Science in Cambridge (Section 2.1.4). Then the War came, and momentum was lost for a couple of decades. After that, L-B films came back as a major topic of research and have been so ever since (Mort 1980). It is current practice to refer to molecular films, made by various techniques (Swalen 1991), but the L-B approach remains central. 

Molecular calculations provide approaches to supramolecular structure and to the dynamics of self-assembly by extending atomic-molecular physics. Alternatively, the tools of finite element analysis can be used to approach the simulation of self-assembled film properties. The voxel4 size in finite element analysis needs be small compared to significant variation in structure-property relationships for self-assembled structures, this implies use of voxels of nanometer dimensions. However, the continuum constitutive relationships utilized for macroscopic-system calculations will be difficult to extend at this scale because nanostructure properties are expected to differ from microstructural properties. In addition, in structures with a high density of boundaries (such as thin multilayer films), poorly understood boundary conditions may contribute to inaccuracies. 

Fabrication of organic thin films based on sponfaneous molecular assembly has been considered as one of fhe powerful approaches to create novel supramolecular systems. In this context, multilayer films were fabricated by layer-by-layer electrostatic deposition techniques based on the electrostatic interaction between dsDNA and the positively charged polymer poly(diallyldimethylammonium chloride) (PDDA) on GC surfaces. A uniform assembly of PDDA/DNA multilayer films was achieved, based on the adsorption of the negatively charged DNA molecules on the positively charged substrate [55]. 

No direct method exists by which monolayer film structures on water can be studied. Therefore, the LB method has been used to study molecular structures in past decades. The most useful method for investigating the detailed LB-deposited film structure is the well-known electron diffraction technique (or the scanning probe microscope [Birdi, 2002a]). The molecular arrangements of deposited mono-and multilayer films of fatty acids and their salts, using this technique, have been reported. The analyses showed that the molecules were almost perpendicular to the solid surface in the first monolayer. It was also reported that Ba-stearate molecules have a more precise normal alignment compared to stearic-acid monolayers. In some investigations, the thermal stability of these films has been found to be remarkably stable up to 90°C. 

Electron-Induced Reactions—HREELS Measurements. Novel LEE-induced chemistry has also been observed in HREEL measurements of molecular solids and molecules physisorbed on the surface of RGS. For example, Lepage et ah, building on the initial observations of Jay-Gerin et al. [141], have employed HREELS to measure in situ, neutral dissociation products arising from the impact of low-energy electrons on thin multilayer films of methanol [37] and acetone [38]. The technique is similar to that developed earlier by Martel et al. [258] for chemisorbed systems, in that the same electron beam is used for both the production and the detection of the neutral fragments. However, in the work of Lepage... 

Electron beam damage effects followed the general rule that molecular groups in intimate contact with the metal substrate and aromatic groups appear relatively stable. Thus in the monolayer, alanine, with a methyl group likely sticking out from the surface, was the only molecule found to be unstable. In multilayer films, only tryptophan with the aromatic indole group to stabilize the molecule was found to yield multilayers stable under electron beam irradiation. 

Methods for preparing and using compositions containing poly(4-methyl-l-pentene) having a controlled molecular weight distribution are described by Patel et al. (3). Methods for preparing multilayer films and film layers are also described. 

Molecular organization and self-assembly into layers, membranes, vesicles etc., construction of multilayer films [7.1-7.5], generation of defined aggregate morphologies [4.74, 4.75, 7.6-7.8J etc., make it possible to build up specific supramolecular architectures. The polymerization of the molecular components has been a major step in increasing control over the structural properties of such assemblies [7.9-7.13]. 

A detailed transport model for resist dissolution has been developed (169). In conjunction with standard ellipsometric equations describing multilayer films, the model provides quantitative agreement with the observed traces from the in situ ellipsometer. Model parameters are thus extracted, and their significance in terms of molecular structures of the system can be established. This model can then be extended for predictive purposes in the design and selection of resist materials. 

They have observed linear growth of the film thickness, which is consistent with multilayer ordering. The thickness of an individual molecular layer for the generation G4 is about 5 nm, which indicates preservation of the globular shape of the dendritic macromolecules within the multilayer films (Fig. 4.13c). 

Haynie DT, Balkundi S, Palath N et al (2004) Polypeptide multilayer films role of molecular structure and charge. Langmuir 20 4540-4547... 

For monolayer films, the temperature dependence of reactivity was somewhat more complicated than that for the multilayer films. Three temperature ranges could be distinguished. Below 20°C and above 60°C, the reactivity dependence on the temperature was similar to that observed for the multilayer films. However, between 20°C and 60°C, no dependence of reactivity on temperature was observed. This observation was rationalized by considering the two opposing effects that the temperature increase has on the molecular vibrations. On one hand, the increase in temperature causes an increase of the reaction cross-section on the other hand, increase in temperature causes an increase of the amount of defects in the chains, such as kinks and bends. These defects are responsible for the decrease in the free space between the chains and for the increased repulsion between the chains, which cause an increase of the force constant f This effect was not observed in the multilayer films, since they are more organized than monolayers, and the defects such as kinks and bends occur in multilayers only at significantly higher temperatures. 

However, in an attempt to integrate the SFA and spectroscopic techniques, the use of silver for optical interferometry has been seen as a drawback due to the fact that it precluded sufficient excitation source intensity to illuminate the buried interface. In order to circumvent this problem Mukhopadhyay and co-workers in an experimental set-up where the SFA was combined with fluorescence correlation spectroscopy (FCS) used, instead of silver, multilayer dielectric coatings that allowed simultaneous interferometry and fluorescence measurements in different regions of the optical spectrum [75]. Using this set-up they succeeded in measuring diffusion in molecularly thin films with singlemolecule sensitivity. 

---