Ellipsometry, described

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. 

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... 

Wasserman [186] has described the use of both low-angle X-ray reflectivity and ellipsometry for the determination of thickness of Cio-Cig SAMs prepared on surface silanol groups of silicon plates. Ellipsometry is based on the reflection of polarized light from a sample and depends on the sample s thickness and refractive index. X-ray reflectivity measures the intensity of X-rays reflected from a surface (or interference pattern) that is characteristic of the distance between interfaces. The thickness of the SAMs was consistent with fully extended alkyl chains with all-trans conformations and excellent agreement was observed between the two methods. 

The SiC Schottky diodes and capacitors that have been processed by the authors were processed on either 6H or 4H substrates (n-type, about 1 x 10 cm ) with a 5-10- m n-type epilayer (2-6 x lO cm" ) [123, 124]. A thermal oxide was grown and holes were etched for the metal contacts. In the case of the Schottky sensors, the SiC surface was exposed to ozone for 10 minutes before deposition of the contact metal. This ozone treatment produces a native silicon dioxide of 10 1 A, as measured by ellipsometry [74, 75]. The MISiC-FET sensors (Figure 2.9) were processed on 4H-SiC, as previously described [125]. The catalytic metal contacts consisted of 10-nm TaSiyiOO-nm Pt, porous Pt, or porous Ir deposited by sputtering or by e-gun. 

Adsorption of putidaredoxin on gold electrodes has been studied using dynamic spectroscopic ellipsometry and differential capacitance measurements [307]. In Ref. 307, a method for the measurement of metal surface optical perturbation during protein adsorption at a constant potential has been described. The method is based on the concept that the charged transition layer develops between the electrode substrate and the adsorbate. 

The heart of the polarization-modulated nephelometer is a photoelastic modulator, developed by Kemp (1969) and by Jasperson and Schnatterly (1969). The latter used their instrument for ellipsometry of light reflected by solid surfaces (the application described here could be considered as ellipsometry of scattered light). Kemp first used the modulation technique in laboratory studies but soon found a fertile field of application in astrophysics the modulator, coupled with a telescope, allowed circular polarization from astronomical objects to be detected at much lower levels than previously possible. 

The main experimental technique applied in this chapter is SE. Several textbooks were written on SE [73,114-118], Therefore, only some basic concepts are described. SE examines the relative phase change of a polarized light beam upon reflection (or transmission) at a sample surface. In Fig. 3.4 the setup of an ellipsometry experiment is shown. Upon model analysis of the experimental data, the DFs and thicknesses of the sample constituents can be extracted. Two different experimental approaches have to be distinguished, standard and generalized ellipsometry. 

Ellipsometry. Determination of h(u>) by KK analysis and coupled measurements of 1Z and T are affected, respectively, by the problem of the tails added to the experimental R(u>) spectra and by the need to perform 7Z and T measurements separately These problems, which introduce some uncertainty, can be solved by spectroscopic ellipsometry. The technique involves analyzing the polarization of a light beam reflected by a surface. The incident beam must be linearly polarized and its polarization should be allowed to rotate. A second linear polarizer then analyzes the reflected beam. The roles of polarizer and analyzer can be exchanged. The amplitudes of the s and p components of the reflected radiation are affected in a different way by reflection at the surface. The important function describing the process is the ellipsometric ratio p, which is defined as the polarization of the reflected wave with respect to the incident wave, expressed as the ratio between the Fresnel coefficients for p and s polarizations ... 

From the data reported in Fig. 2.2 and from spectroscopic ellipsometry measurements, the anisotropic complex optical constants of oriented PPV have been determined [32,69]. Several different data analyses, described previously, were carried out on the 7Z and T spectra in order to extract n, both below and above the HOMO-LUMO transition (transparent free-standing film and bulk material, respectively). In order to evaluate n below 1.6 eV, where the sum of 1Z and T is equal to 1 within experimental error, a numerical inversion of the 7Z and T spectra was performed by assuming k = 0... 

Ellipsometry measures the orientation of polarized light undergoing oblique reflection from a sample surface. Linearly polarized light, when reflected from a surface, will become elliptically polarized, because of presence of the thin layer of the boundary surface between two media. Dependence between optical constants of a layer and parameters of elliptically polarized light can be found on basis of the Fresnel formulas described above. 

Polyimide surface modification by a wet chemical process is described. Poly(pyromellitic dianhydride-oxydianiline) (PMDA-ODA) and poly(bisphenyl dianhydride-para-phenylenediamine) (BPDA-PDA) polyimide film surfaces are initially modified with KOH aqueous solution. These modified surfaces are further treated with aqueous HC1 solution to protonate the ionic molecules. Modified surfaces are identified with X-ray photoelectron spectroscopy (XPS), external reflectance infrared (ER IR) spectroscopy, gravimetric analysis, contact angle and thickness measurement. Initial reaction with KOH transforms the polyimide surface to a potassium polyamate surface. The reaction of the polyamate surface with HC1 yields a polyamic acid surface. Upon curing the modified surface, the starting polyimide surface is produced. The depth of modification, which is measured by a method using an absorbance-thickness relationship established with ellipsometry and ER IR, is controlled by the KOH reaction temperature and the reaction time. Surface topography and film thickness can be maintained while a strong polyimide-polyimide adhesion is achieved. Relationship between surface structure and adhesion is discussed. 

Among the large variety of in situ experiments that have been described one can distinguish (1) those whose purpose is investigation of the electrochemical doping process itself cyclic voltammetry, quartz balance [17], mirage effect [18], and ellipsometry [19], and (2) those developed for studies of the properties of the CP UV-near-IR spectroscopy [20], IR [21], ESR [22], conductivity [23], impedence [24], and so on. 

In all ranges of the infrared, the near, middle, and far infrared (NIR, MIR, and FIR) mainly the absorption of radiation by a sample is evaluated. Emission spectra are only rarely recorded, even though they are a powerful tool for solving problems which cannot be investigated by other methods investigations of remote samples (in astronomy and for environmental analysis), of reactions of substances on catalysts, and of layers on surfaces (Mink and Keresztury, 1988) (Sec. 3.3.1). Other techniques of investigating surface layers, e.g., ATR technique and ellipsometry in the infrared range, are described in Sec. 6.4. 

Ellipsometry grants the independent determination of two results per resolution element without changing the experimental geometry this technique is described in Sec. 6.4.4.2. More often however, the information on the phase shift is abandoned and just the reflectance is determined. Usually it is measured by comparing the signal caused by the reflected intensity with the one obtained when the sample is replaced by a mirror. Even without correcting for its reflectance such results can often be used for further mathematical evaluation. The Fresnel reflection coefficient r in the form given by Eq. 

Ellipsometry quantification and rapid visual detection of DNA hybridization, using biotinylated target sequences, on amorphous sihcon and diamond-like carbon deposited on a porous polycarbonate membrane, creating a gold-coloured reflective test surface coated with immobihzed ssDNA capture probe were described by Ostroif et al. [38]. 

Several techniques have been developed to measure the electro-optic susceptibility of single crystals or thin films. All are based on the measurement of variation of the refractive index of a material induced by the applied external field. We will shortly describe the modulation ellipsometry technique [18,19], which is relatively simple in use and can be applied to thin films, provided that some precautions are undertaken [20]. 

Several other techniques have been appHed for the measurement of foam films, including ellipsometry, Fourier transform-infrared (FT-IR) spectroscopy. X-ray reflection, and the measurement of gas permeabihty through the film. These techniques are described in detail in the text by Exerowa and Kruglyakov [4] to which the reader is referred. 

Ellipsometry, a classical technique that is commonly employed in the study of thin films on solid supports, has long been used to investigate Langmuir monolayers. The relative ease with which such measurements can now be carried out, and their high sensitivity and high spatial resolution, has led to renewed interest in the method. Rasing et al. have recently described studies on PDA in which the phase retardation was measured as a function of the surface pressure. Fluctuations in the signal can be correlated with the texture of the monolayer, and estimates of the sizes of the domains and their character can be obtained from quantitative analysis of the data. 

For comparison, the open circle of Fig. 10b is the single data point found by the most direct method of Hugoniot determination (as described above - ultrafast dynamic ellipsometry) the fit of the interferometric data from two incidence angles and two polarizations allows s, p> and therefore P= u,UpP, to be determined directly, and the P- Up point plotted clearly agrees with bulk PMMA Hugoniot. 

In this section, we describe how combined QCM-D and optical (e.g., SPR, ellipsometry etc.) analysis can be used to determine (i) the water content, and hence the effective density, (ii) changes in effective thickness, 5f, and... 

In-situ spectroelectrochemical techniques are covered by chapters on infrared, Raman EPR, ellipsometry, electroreflectance, and photocurrent spectroscopy. Ex-situ UHV experiments are treated in a separate chapter. New electrochemical directions are described in chapters on hydrodynamic methods, channel electrodes, and microelectrodes. A final chapter covers computing strategies for the on-line accumulation and processing of elec-trochemial data. 

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