Spectroscopy ellipsometry

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 this chapter we review some of the most important developments in recent years in connection with the use of optical teclmiques for the characterization of surfaces. We start with an overview of the different approaches available to tire use of IR spectroscopy. Next, we briefly introduce some new optical characterization methods that rely on the use of lasers, including nonlinear spectroscopies. The following section addresses the use of x-rays for diffraction studies aimed at structural detenninations. Lastly, passing reference is made to other optical teclmiques such as ellipsometry and NMR, and to spectroscopies that only partly depend on photons. 

Amongst other spectroscopic teclmiques which have successfiilly been employed in situ in electrochemical investigations are ESR, which is used to investigate electrochemical processes involving paramagnetic molecules, Raman spectroscopy and ellipsometry. 

Monolayers of alkanetliiols adsorbed on gold, prepared by immersing tire substrate into solution, have been characterized by a large number of different surface analytical teclmiques. The lateral order in such layers has been investigated using electron [1431, helium [144, 1451 and x-ray [146, 1471 diffraction, as well as witli scanning probe microscopies [122, 1481. Infonnation about tire orientation of tire alkyl chains has been obtained by ellipsometry [149], infrared (IR) spectroscopy [150, 151] and NEXAFS [152]. 

Porter M D, Bright T B, Allara D L and Chidsey C E D 1987 Spontaneously organized molecular assemblies. 4. Structural characterization of normal-alkyl thiol monolayers on gold by optical ellipsometry, infrared-spectroscopy, and electrochemistry J. Am. Chem. Soc. 109 3559-68... 

The most recently introduced optical teclmique is based on the retardation of light guided in an optical waveguide when biomolecules of a polarizability different from that of the solvent they displace are adsorbed at the waveguide surface (optical waveguide lightmode spectroscopy, OWLS) [H]. It is even more sensitive than ellipsometry, and the mode... 

Band gaps in semiconductors can be investigated by other optical methods, such as photoluminescence, cathodoluminescence, photoluminescence excitation spectroscopy, absorption, spectral ellipsometry, photocurrent spectroscopy, and resonant Raman spectroscopy. Photoluminescence and cathodoluminescence involve an emission process and hence can be used to evaluate only features near the fundamental band gap. The other methods are related to the absorption process or its derivative (resonant Raman scattering). Most of these methods require cryogenic temperatures. 

RAIRS spectra contain absorption band structures related to electronic transitions and vibrations of the bulk, the surface, or adsorbed molecules. In reflectance spectroscopy the ahsorhance is usually determined hy calculating -log(Rs/Ro), where Rs represents the reflectance from the adsorhate-covered substrate and Rq is the reflectance from the bare substrate. For thin films with strong dipole oscillators, the Berre-man effect, which can lead to an additional feature in the reflectance spectrum, must also be considered (Sect. 4.9 Ellipsometry). The frequencies, intensities, full widths at half maximum, and band line-shapes in the absorption spectrum yield information about adsorption states, chemical environment, ordering effects, and vibrational coupling. 

Electrochemical techniques have been developed into very powerful tools for research and technology. However, decades ago, researchers started to understand that even more insight could be obtained if electrochemical techniques were combined with additional spectroscopic tools. Among these it is sufficient to mention infrared spectroscopy, Raman spectroscopy, luminescence techniques, electroreflection or ellipsometry. 

Infrared (IR) spectroscopy and elUpsometry are used to measure the thickness of thin films with angstrom resolution. Ellipsometry has proven to be very useful in studies of dy-... 

The film thickness and retractive index were calculated using spectroscopic ellipsometry. X-ray photoelectron spectroscopy (XPS) was used for composition analysis. Auger electron spectroscopy (AES) and secondary ion mass spectroscopy (SIMS) was used to investigate the depth profiles of the film. 

Optical Methods Reflectance and ellipsometry snffer from lack of a theory at the molecnlar level. The same is true for SERS and SHG. The main advances will be in the nse of far-IR spectroscopy and SFG. SFG measurements performed with femtosecond lasers open np new possibilities for time-resolved adsorbate stndies. 

Pleith, W., W. Kozlowski, and T. Twomey, Reflectance spectroscopy and ellipsometry of organic monolayers, in Adsorption of Molecules at Metal Electrodes, 3. Lipkowski and P. N. Ross, Eds., VCH, New York, 1992, p. 285. 

In order to relate material properties with plasma properties, several plasma diagnostic techniques are used. The main techniques for the characterization of silane-hydrogen deposition plasmas are optical spectroscopy, electrostatic probes, mass spectrometry, and ellipsometry [117, 286]. Optical emission spectroscopy (OES) is a noninvasive technique and has been developed for identification of Si, SiH, Si+, and species in the plasma. Active spectroscopy, such as laser induced fluorescence (LIF), also allows for the detection of radicals in the plasma. Mass spectrometry enables the study of ion and radical chemistry in the discharge, either ex situ or in situ. The Langmuir probe technique is simple and very suitable for measuring plasma characteristics in nonreactive plasmas. In case of silane plasma it can be used, but it is difficult. Ellipsometry is used to follow the deposition process in situ. 

The evidence for two reasonably well defined layers comes primarily from electrochemical studies, ellipsometry and Raman spectroscopy, The ellipsometric studies of Ord and DeSmet (1976) show good evidence of an abrupt... 

Until quite recently the very initial stages of metal deposition were difficult to characterize in detail by structure- and morphology-sensitive techniques. As a consequence and for practical purposes - multilayers were more useful for applications than monolayers - the main interest was focussed onto thick deposits. Optical and electron microscopy, ellipsometry and specular or diffuse reflectance spectroscopy were the classic tools, by which the emerging shape of the deposit was monitored [4-7],... 

Several experimental parameters have been used to describe the conformation of a polymer adsorbed at the solid-solution interface these include the thickness of the adsorbed layer (photon correlation spectroscopy(J ) (p.c.s.), small angle neutron scattering (2) (s.a.n.s.), ellipsometry (3) and force-distance measurements between adsorbed layers (A), and the surface bound fraction (e.s.r. (5), n.m.r. ( 6), calorimetry (7) and i.r. (8)). However, it is very difficult to describe the adsorbed layer with a single parameter and ideally the segment density profile of the adsorbed chain is required. Recently s.a.n.s. (9) has been used to obtain segment density profiles for polyethylene oxide (PEO) and partially hydrolysed polyvinyl alcohol adsorbed on polystyrene latex. For PEO, two types of system were examined one where the chains were terminally-anchored and the other where the polymer was physically adsorbed from solution. The profiles for these two... 

Spectroscopic ellipsometry is a non-destructive, interface sensitive, in situ technique for interface characterization. Time resolved ellipsometric spectroscopy was used to determine the mechanism of electrochemical deposition of photoresists on copper electrodes under potentiostatic, anodic conditions. Nucleation of photoresist deposition occurs randomly. During the early stages of nucleation the semi-spherical particles are separated by about 100 A. The deposits tend to grow like "pillars" up to 50 A. Further growth of the "pillars" lead to coalescence of the photopolymer deposits. 

The monotonic increase of immobilized material vith the number of deposition cycles in the LbL technique is vhat allo vs control over film thickness on the nanometric scale. Eilm growth in LbL has been very well characterized by several complementary experimental techniques such as UV-visible spectroscopy [66, 67], quartz crystal microbalance (QCM) [68-70], X-ray [63] and neutron reflectometry [3], Fourier transform infrared spectroscopy (ETIR) [71], ellipsometry [68-70], cyclic voltammetry (CV) [67, 72], electrochemical impedance spectroscopy (EIS) [73], -potential [74] and so on. The complement of these techniques can be appreciated, for example, in the integrated charge in cyclic voltammetry experiments or the redox capacitance in EIS for redox PEMs The charge or redox capacitance is not necessarily that expected for the complete oxidation/reduction of all the redox-active groups that can be estimated by other techniques because of the experimental timescale and charge-transport limitations. 

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