Thin film characterization vibrational spectroscopy

Although optical vibrational techniques are less sensitive than electron-based spectro-metric methods, these techniques are employed extensively for thin-film characterization because of the specific and characteristic vibrational spectrum shown by various functional groups and molecules present in the film. The most commonly used vibrational spectroscopic techniques are infrared (IR) and Raman spectroscopy. Because of the interference caused by absorption of IR by the underlying substrate, IR reflection-adsorption spectroscopy (IRRAS) and its polarization modulation (PM) analog, PM-IRRAS, which uses the polarization selectivity of surface adsorption, are typically employed to characterize thin films (Gregoriou and Rodman, 2006). 

As a probe of lattice vibrations, Raman spectroscopy is very sensitive to intrinsic crystal properties and extrinsic stimuli, especially in semiconductors. It may be employed to study crystal structure and quality, crystal orientation, optical interactions, chemical composition, phases, dopant concentration, surface and interface chemistry, and local temperatme or strain. As an optical technique, important sample information may be obtained rapidly and nondestructively with minimal sample preparation. Submicron lateral resolution is possible with the use of confo-cal lenses. These features have made it a vital tool for research labs studying semiconductor-based technologies. They also are increasingly important for the study of semiconductor NWs fabricated by both top-down and bottom-up approaches since many of the common characterization methods used with bulk crystals or thin films cannot be applied to NWs in a direct manner. 

Laser Raman spectroscopy has been applied to materials characterization studies over the past several years. Annual reviews discuss advances in the field and provide references for a number of specialized areas including thin film analysis (1). The attractive features for using Raman spectroscopy to evaluate thin films include a nondestructive j n situ measurement capability plus the ability to acquire both spatially and time-resolved vibrational data from which structural information can be inferred. 

Characterization of the Unmodified and PLL-g-PEG-Modified Surfaces. 3.2.1. RAIRS Measurements of the PLL(20)-g[3.5]-PEG(2) Monolayer. Reflection-absorption infrared spectroscopy (RAIRS) is well suited to study adsorbates on metallic surfaces, which are highly reflective. It relies on reflecting an infrared beam at near-grazing incidence from the metallic surface on which the thin film of interest has been deposited. Only the component of the vibrational transition dipole moments perpendicular to the surface plane contributes to the absorption spectra. The intensity of an absorption band is proportional to the squared cosine of the angle between the transition dipole moment and the surface normal. Therefore, RAIRS provides information not only on fimctional groups but also on orientation and conformation of adsorbed molecules or molecular entities. Metal oxides... 

Raman spectroscopy and Fourier Transform Raman spectroscopy (FTRS) [314,315] can detect vibrational motion in polymers but are less commonly employed in polymer blend characterization than FTIR nevertheless they offer utility in characterization of crystalline polymer morphology, conjugated polymers, thin film properties and surface modification as well as in... 

For iron oxides, IR spectroscopy is useful as a means of identification. Hematite crystals in films that were too thin (<70nm) to be characterized by XRD were shown by IR to be oriented with the c-axis perpendicular to the surface of the film (Yubero et al. 2000). This technique also provides information about crystal morphology, degree of crystallinity and the extent of metal (especially Al) substitution because these properties can induce shifts in some of the IR absorption bands. It is also widely used both to obtain information about the vibrational state of adsorbed molecules (particularly anions) and hence the nature of surface complexes (see Chap. 11) and to investigate the nature of surface hydroxyl groups and adsorbed water (see Chap. 10). Typical IR spectra of the various iron oxides are depicted in Figure 7.1. Impurities arising either from the method of preparation or from adsorption of atmospheric compounds can produce distinct bands in the spectra of these oxides -namely at 1700 cm (oxalate), 1400 cm (nitrate) and 1300 and 1500 cm (carbonate). 

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