Monolayer determination

The growth of Ni layers on W(llO) and (100) subsequent to the first monolayer, determined by the breaks in the AES vs. TPD area curves shown in Figs. 26 and 27, does not yield TPD areas that correspond to simple multiple of the TPD area found for the monolayer TPD feature. This result indicate that the second and successive Ni layers have significantly altered Ni atomic densities compared with the first Ni layer. On W(110) the ratio of the first to second monolayer TPD areas, 0.78, compares favorably with the ratio of the surface atomic densities of Ni(lll) and W(110X 0.79, using the value 1.81 X 10 and 1.43 x 10 for the atomic densitie of Ni(lll) and W(llO), respectively. On W(IOO) the ratio of Ni atoms in the first to the second layers. 

Laboratory research in this area is conducted by suspending a porous box of desiccant very close to the surface of a film balance. The rate of water uptake is determined by weighing at various times. This way the retardation of evaporation may be measured as a function of film pressure and correlated with other properties of the monolayer determined by the same method. As might be expected, the resistance to evaporation that a monolayer provides is enhanced by those conditions that promote the most coherent films, most notably high film pressures and straight-chain compounds. To see how this is quantified, consider the Example 7.3. 

Fig. 15 Average thickness of the monolayer (determined from the respective surface plasmon resonance spectra), (a) The dinitrospiropyran (31a) monolayer, (b) The (31a) mono-layer after binding of the anti-DNP-Ab. (c) After photoisomerization of the (31a)/DNP-Ab monolayerto the (31b) state, and washing off of the DNP-Ab.

R. Mendelsohn, J.W. Brauner, and A. Gericke, External Infrared Reflection Absorption Spectrometry of Monolayer Films at the Air-Water Interface, Ann. Rev. Phys. Chem. 46 (1995) 305. (Review theory and practice of IRRAS as applied to Langmuir monolayers determination of conformational states of hydrocarbon tails and H-bonding, ionization states of head groups, and molecular orientation illustrated with experimental results on monolayers of single-chain amphiphiles, phospholipids and proteins.)... 

Rubel, J. W., and Gentry, G. O. (1984) Measurement of the kinetics of solution droplets in the presence of adsorbed monolayers determination of water accommodation coefficients, J. Phys. Chem., 88,3142-3148. 

It is evident that if the physical adsorption capacity were limited to a close-packed monolayer, determination of the saturation limit from an experimental isotherm with a molecule of known size would provide a simple and straightforward method of estimating the specific area. The main difficulty is that in chemisorption the sites are usually widely spaced so that the saturation limit bears no obvious relationship to specific surface area while physical adsorption generally involves multilayer adsorption. The formation of the second and subsequent molecular layers commences at pressures well below that required for completion of the monolayer so it is not immediately obvious how to extract the monolayer capacity from the experimental isotherm. This problem was first solved by Brunauer, Emmett, and Teller (BET) who developed a simple model isotherm to account for multilayer adsorption and used this model to extract the monolayer capacity and hence the specific surface area. A number of refinements to the BET model and to the experimental method have been developed more recently but the basic BET method remains the most widely used technique for measurement of specific surface... 

Figure 5.2. Monolayers of the amphiphile 1-monopalmitoyl-( )-glycerol at the air-water interface assemble in domains in which the molecular tilt azimuth is organized in star-shaped patterns. It is possible to preserve this order during the transfer on to a solid support. LB monolayers of this material have been utilized for the anchoring of nematic liquid crystals. The order within the monolayer determines the order within the bulk phase of the nematic liquid crystal (LC). The image here shows the LC cell between crossed polarizers. (From J. Fang, U. Gehlert, R. Shashidar and C. Knobler, Langmuir (1999), 15, 297)...

A modification of the foregoing procedure is to suspend the plate so that it is partly immersed and to determine from the dry and immersed weights the meniscus weight. The procedure is especially useful in the study of surface adsorption or of monolayers, where a change in surface tension is to be measured. This application is discussed in some detail by Gaines [57]. Equation 11-28 also applies to a wire or fiber [58]. 

Neumann has adapted the pendant drop experiment (see Section II-7) to measure the surface pressure of insoluble monolayers [70]. By varying the droplet volume with a motor-driven syringe, they measure the surface pressure as a function of area in both expansion and compression. In tests with octadecanol monolayers, they found excellent agreement between axisymmetric drop shape analysis and a conventional film balance. Unlike the Wilhelmy plate and film balance, the pendant drop experiment can be readily adapted to studies in a pressure cell [70]. In studies of the rate dependence of the molecular area at collapse, Neumann and co-workers found more consistent and reproducible results with the actual area at collapse rather than that determined by conventional extrapolation to zero surface pressure [71]. The collapse pressure and shape of the pressure-area isotherm change with the compression rate [72]. 

The detailed examination of the behavior of light passing through or reflected by an interface can, in principle, allow the determination of the monolayer thickness, its index of refiraction and absorption coefficient as a function of wavelength. The subjects of ellipsometry, spectroscopy, and x-ray reflection deal with this goal we sketch these techniques here. 

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. 

Some further details are the following. Film nonideality may be allowed for [192]. There may be a chemical activation barrier to the transfer step from monolayer to subsurface solution and hence also for monolayer formation by adsorption from solution [294-296]. Dissolving rates may be determined with the use of the radioactive labeling technique of Section III-6A, although precautions are necessary [297]. 

Take the data from Fig. X-12 on the propyl monolayers and make a Zisman plot to determine the critical surface tension for the surface. 

There is a fair amount of work reported with films at the mercury-air interface. Rice and co-workers [107] used grazing incidence x-ray diffraction to determine that a crystalline stearic acid monolayer induces order in the Hg substrate. Quinone derivatives spread at the mercury-n-hexane interface form crystalline structures governed primarily by hydrogen bonding interactions [108]. 

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]. 

The monolayer amount adsorbed on an aluminum oxide sample was determined using a small molecule adsorbate and then molecular-weight polystyrenes (much as shown in Ref. 169). The results are shown in the table. Calculate the fractal dimension of the oxide. 

Heinz T F, Tom H W K and Shen Y R 1983 Determination of molecular orientation of monolayer adsorbates by optical second-harmonic generation Phys. Rev. A 28 1883-5... 

Harder P, Grunze M, Dahint R, Whitesides G M and Laibinis P E 1998 Molecular conformation in oligo(ethylene glycol)-terminated self-assembled monolayers on gold and silver surfaces determines their ability to resist protein adsorption J. Rhys. Chem. B 102 426-36... 

To obtain the monolayer capacity from the isotherm, it is necessary to interpret the (Type II) isotherm in quantitative terms. A number of theories have been advanced for this purpose from time to time, none with complete success. The best known of them, and perhaps the most useful in relation to surface area determination, is that of Brunauer, Emmett and Teller. Though based on a model which is admittedly over-simplified and open to criticism on a number of grounds, the theory leads to an expression—the BET equation —which, when applied with discrimination, has proved remarkably successful in evaluating the specific surface from a Type II isotherm. 

It follows therefore that the specific surface of a mesoporous solid can be determined by the BET method (or from Point B) in just the same way as that of a non-porous solid. It is interesting, though not really surprising, that monolayer formation occurs by the same mechanism whether the surface is wholly external (Type II isotherm) or is largely located on the walls of mesopores (Type IV isotherm). Since the adsorption field falls off fairly rapidly with distance from the surface, the building up of the monolayer should not be affected by the presence of a neighbouring surface which, as in a mesopore, is situated at a distance large compared with the size of a molecule. 

The strength of dispersion interaction of a solid with a gas molecule is determined not only by the chemical composition of the surface of the solid, but also by the surface density of the force centres. If therefore this surface density can be sufficiently reduced by the pre-adsorption of a suitable substance, the isotherm may be converted from Type II to Type III. An example is rutile, modified by the pre-adsorption of a monolayer of ethanol the isotherm of pentane, which is of Type II on the unmodified rutile (Fig. 5.3, curve A), changes to Type III on the treated sample (cf. Fig. 5.3 curve B). Similar results were found with hexane-l-ol as pre-adsorbate. Another example is the pre-adsorption of amyl alcohol on a quartz powder... 

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