3- LB films

The following part of this review article consists of four sections. Section 2 is concerned with infrared and AFM studies of Langmuir-Blodgett (LB) films. This section contains introductory parts for infrared and AFM studies of monolayers. This section also emphasizes the importance of combined use of infrared spectroscopy and AFM. LB films of 2-alkyl-7,7,8,8-tetracyanoqui-nodimethane (alkyl-TCNQ) are taken up as examples. Section 3 outlines SERS studies of monolayers. This section describes the usefulness and uniqueness of SERS in the investigations of LB and self-assembled monolayer (SAM) films. Following this section, we present other AFM studies on monolayers in Section 4. In Section 5 infrared and visible spectroscopy studies on J- and H-aggregates in LB films of mecrocyanine dye are reported. 

INFRARED AND ATOMIC FORCE MICROSCOPY STUDIES OF LB FILMS 

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Chemical properties of deposited monolayers have been studied in various ways. The degree of ionization of a substituted coumarin film deposited on quartz was determined as a function of the pH of a solution in contact with the film, from which comparison with Gouy-Chapman theory (see Section V-2) could be made [151]. Several studies have been made of the UV-induced polymerization of monolayers (as well as of multilayers) of diacetylene amphiphiles (see Refs. 168, 169). Excitation energy transfer has been observed in a mixed monolayer of donor and acceptor molecules in stearic acid [170]. Electrical properties have been of interest, particularly the possibility that a suitably asymmetric film might be a unidirectional conductor, that is, a rectifier (see Refs. 171, 172). Optical properties of interest include the ability to make planar optical waveguides of thick LB films [173, 174]. 

Most LB-forming amphiphiles have hydrophobic tails, leaving a very hydrophobic surface. In order to introduce polarity to the final surface, one needs to incorporate bipolar components that would not normally form LB films on their own. Berg and co-workers have partly surmounted this problem with two- and three-component mixtures of fatty acids, amines, and bipolar alcohols [175, 176]. Interestingly, the type of deposition depends on the contact angle of the substrate, and, thus, when relatively polar monolayers are formed, they are deposited as Z-type multilayers. Phase-separated LB films of hydrocarbon-fluorocarbon mixtures provide selective adsorption sites for macromolecules, due to the formation of a step site at the domain boundary [177]. 

Film stability is a primary concern for applications. LB films of photopoly-merizable polymeric amphiphiles can be made to crosslink under UV radiation to greatly enhance their thermal stability while retaining the ordered layered structure [178]. Low-molecular-weight perfluoropolyethers are important industrial lubricants for computer disk heads. These small polymers attached to a polar head form continuous films of uniform thickness on LB deposi-... 

Fig. XV-16. A schematic drawing of the arrangement of polyglutamates having alkyl side chains in an LB film. The circles represent the rodlike polyglutamate backbone oriented perpendicular to the page the wiggly lines are the alkyl sidechains. (From Ref. 182.)...

A unique but widely studied polymeric LB system are the polyglutamates or hairy rod polymers. These polymers have a hydrophilic rod of helical polyglutamate with hydrophobic alkyl side chains. Their rigidity and amphiphilic-ity imparts order (lyotropic and thermotropic) in LB films and they take on a F-type stmcture such as that illustrated in Fig. XV-16 [182]. These LB films are useful for waveguides, photoresists, and chemical sensors. LB films of these polymers are very thermally stable, as was indicated by the lack of interdiffusion up to 414 K shown by neutron reflectivity of alternating hydrogenated and deuterated layers [183]. AFM measurements have shown that these films take on different stmctures if directly deposited onto silicon or onto LB films of cadmium arachidate [184]. 

Among the many applications of LB films, the creation or arrangement of colloidal particles in these films is a unique one. On one hand, colloidal particles such as 10-nm silver sols stabilized by oleic acid can be spread at the air-water interface and LB deposited to create unique optical and electrooptical properties for devices [185]. 

Another approach is to use the LB film as a template to limit the size of growing colloids such as the Q-state semiconductors that have applications in nonlinear optical devices. Furlong and co-workers have successfully synthesized CdSe [186] and CdS [187] nanoparticles (<5 nm in radius) in Cd arachidate LB films. Finally, as a low-temperature ceramic process, LB films can be converted to oxide layers by UV and ozone treatment examples are polydimethylsiloxane films to make SiO [188] and Cd arachidate to make CdOjt [189]. 

Investigate the differences between LB films and self-assembled monolayer SAMs (Chapter XI). Which are finding more practical use, and what are the potential applications of each ... 

Demand for temperature controlled troughs came from the material scientists who worked witli large molecules and polymers tliat establish viscous films. Such troughs allow a deeper understanding of tire distinct phases and tire transitions in LB films and give more complete pressure-area isotlienns (see d) below). 

In general, extreme care has to be taken when LB films are prepared, since tire quality of the resulting films depends cmcially on tire preparation conditions. The best place for an LB trough is a laboratory where tire surroundings, i.e. temperature, humidity and atmosphere, are completely controlled. Often it is placed in a laminar flow box. Also, tire trough should be installed in a shock-free environment. 

Apart from fatty acids, straight-chain molecules containing other hydrophilic end groups have been employed in numerous studies. In order to stabilize LB films chemical entities such as tlie alcohol group and tlie metliyl ester group have been introduced, botli of which are less hydrophilic tlian carboxylic acids and are largely unaffected by tlie pH of tlie subphase. 

New factors for tlie establislmient of multilayer stmctures are, for example, tire replacement of tire hydrocarbon chain by a perfluorinated chain and tire use of a subphase containing multivalent ions [29]. The latter can become incoriDorated into an LB film during deposition. The amount depends on tire pH of tire subphase and tire individual ion. The replacement of tire hydrocarbon by a rodlike fluorocarbon chain is one way to increase van der Waals interaction and tlierefore enlrance order and stability in molecular assemblies [431. 

Thermal stahility. Yor applications of LB films, temperature stability is an important parameter. Different teclmiques have been employed to study tliis property for mono- and multilayers of arachidate LB films. In general, an increase in temperature is connected witli a confonnational disorder in tire films and above 390 K tire order present in tire films seems to vanish completely [45, 46 and 45] However, a comprehensive picture for order-disorder transitions in mono- and multilayer systems cannot be given. Nevertlieless, some general properties are found in all systems [47]. Gauche confonnations mostly reside at tire ends of tire chains at room temperature, but are also present inside tire... 

Many workers have used the cis-to-trans stmctural change referred to above and brought about by UV irradiation to change some physical parameter of the LB films fonned from azobenzene derivatives [55, 56, 57, 58, 59 and 60],... 

LB films of porjDhyrin and phtlialocyanine derivatives ean be made in different ways. 

In summary, a vast number of materials has been used to fonn LB films. However, in the majority of cases an effort to characterize the film stmcture or even to show that a regular layer stmcture has been achieved is lacking. Work on the stmcture of films of disc-like molecules such as porjDhyrins and phthalocyanines is especially limited. Some references can be found in [29]. 

The generally low chemical, mechanical and thennal stability of LB films hinders their use in a wide range of applications. Two approaches have been studied to solve this problem. One is to spread a polymerizable monomer on the subphase and to polymerize it either before or following transfer to the substrate. The second is to employ prefonned polymers containing hydrophilic and hydrophobic groups. 

LB films made of more complex stmctures such as polymers can be divided into different classes [841. 

A summary of the studies perfonned on symmetrical compounds having a diacetylene group at the centre is given in [94]. Most of the materials studied in the context of LB films have been diyonic acids (figure C2.4.8). 

Figure C2.4.8 Diacetylene stmcture employed to prepare polymeric LB films (a) and principle in diacetylene polymerization (b).

Unwanted stmctures in the film plane—often found within LB films fonned from simple rodlike molecules or from molecules polymerized after deposition—can be problematic, since many possible applications of such films require a unifonn stmcture within the plane. On the other hand, however, the production of a system in which the stmcture within the plane is so disordered that there exist no stmctural features large enough to cause problems would also render applications possible. In tliree-dimensional materials, for example, both inorganic glasses and many polymers are capable of transmitting light without any appreciable scattering for substantial distances. 

Another approach to the fabrication of LB films from prefonned polymers is to fonn a hydrophobic main chain by reacting monomers tenninated by a vinyl group [102, 103, 104, 105 and 106]. The side groups studied also included perfluorinated hydrocarbon chains, which tilt with respect to the nonnal to the plane of the film, whereas the analogous ordinary hydrocarbon chains do not [105]. 

The variety of molecules used to prepare LB films is enonnous. and only a small selection of examples can be presented here. Liquid crystals and biomolecules such as phospholipids, for example, can also be used to prepare LB films. The reader is referred to tire literature for infonnation about individual species. 

In contrast to tire preparation of LB films, tliat of SAMs is fairly simple and no special equipment is required. The inorganic substrate is simply immersed into a dilute solution of tire surface active material in an organic solvent (typically in tire mM range) and removed after an extended period ( 24 h). Subsequently, tire sample is rinsed extensively witli tire solvent to remove any excess material (wet chemical preparation). 

Chemical stability. The chemical stability of SA films is of interest in many areas. However, tliere is no general mle for it. The chemical stability of silane films is remarkable, due to tlieir intennolecular crosslinking. Therefore, tliey are found to be more stable tlian LB films. Alkyltrichlorosilane monolayers provide stmctures tliat are stable to chemical conditions tliat most LB films could not stand. However, photopolymerized LB films also show considerable stability in organic solvents. 

Thermal stability. The tliennal stability of SAMs is, similarly to LB films, an important parameter for potential applications. It was found tliat SA films containing alkyl chains show some stability before an increase in tire number of gauche confonnations occurs, resulting in melting and irreversible changes in tire film. The disordering of tire... 

Similarly to LB films, the order of alkanetliiols on gold depending on temperature has been studied witli NEXAFS. It was observed tliat tire barrier for a gauche confonnation in a densely packed film is an order of magnitude higher tlian tliat of a free chain [48]. 

The examples described above are only a small selection out of a tremendous number of investigations of LB films aird SAMs. This number is still increasing aird it is expected tlrat ultrathin orgairic films will play a central role in botlr fundamental aird applied sciences in tire future. 

Nishiyama Kand Fujihira M 1988 Cis-trans reversible photoisomerization of an amphiphilio azobenzene derivative in its pure LB film prepared as polyion oomplexes with polyallylamine Chem. Lett. 1257-60... 

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