Polarization-Modulation Infrared Reflection-Absorption Spectroscopy PM-IRRAS

During this work, we analyzed the organization, the morphology, and the preferential adsorption of these copolymers and how these properties would be influenced by the interfacial interactions that could be established between the polymer and the chemical functionalities grafted onto the adsorption substrate. Our results were mainly based on two surface techniques polarization-modulation infrared reflection-absorption spectroscopy (PM-IRRAS) and atomic force microscopy (AFM). 

Two PCL-b-PMMA diblocks with different compositions were the subject of this study (see Table 4.1) [17]  

Thin films of PCL-b-PMMA were spin-coated from 2 g L solutions in toluene on gold-coated glass slides and then on OH-functionalized gold substrates (by grafting of OH-terminated thiols). 

For OH grafting, gold substrates were cleaned by UV radiation before being immersed for about 12 h in 11-mercapto-l-undecanol (97% from Sigma-Aldrich) solution (in 99.99% ethanol). A typical concentration of 3 mM was chosen for the grafting solution. 

The thickness, as obtained from elhpsometric measurements, ranged between 10 and 14 nm for Diblock 1 and Diblock 2 thin films on gold substrates and between 5 and 8 nm on OH substrates. 

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The three most commonly applied external reflectance techniques can be considered in terms of the means employed to overcome the sensitivity problem. Both electrically modulated infrared spectroscopy (EMIRS) and in situ FTIR use potential modulation while polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) takes advantage of the surface selection rule to enhance surface sensitivity. 

Polarization-Modulation Infrared Reflection-Absorption Spectroscopy (PM-IRRAS)... 

The second means of increasing the S/N ratio, which has also been employed with FTIR spectrometers, involves modulating the polarization state of the light, a technique termed polarization modulation infrared reflection-absorption spectroscopy (PM-IRRAS). This technique relies on a subsidiary selection rule, valid... 

A second lock-in detection method that was employed is polarization modulation, which involves modulating the polarization state of the incident infrared beam, and is again an extension of an approach developed for the study of the gas-solid interface [80]. Polarization modulation infrared reflection-absorption spectroscopy (PM-IRRAS) relies upon the principles underlying the surface selection rule... 

The complexation of PABA with nucleotides was further studied using polarization modulated infrared reflection absorption spectroscopy (PM-IRRAS). PM-IRRAS spectra of PABA films exhibit all the characteristic vibrations of polyaniline and boronic acid (Figure 3.27) [93, 94]. After complexation with NAD+ (Figure 3.27, b) and NADH (Figure 3.27, c), the disappearance of the free B-OH group vibration at 986 cm and increase in the intensity of the asymmetric B-O bond vibration at 1330 cm indicate the formation of boronate ester. The new vibrations at 1080 and 1470 cm have been attributed to ribose and adenine moieties, respectively [153]. The vibrations at 1218 (NAD+), 1245... 

Infrared Spectroscopy. Polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) data were collected using a Nicolet MAGNA-IR 860 Fourier transform spectrometer equipped with a liquid nitrogen-cooled mercury-cadmium-telluride (MCT) detector and a Hinds Instruments PEM-90 photoelastic modulator. The p-polarized light was incident at 80° from the surface normal. The spectra were collected for 1000 scans at a spectral resolution of 4 cm . ... 

Polarization-modulation infrared reflection-absorption spectroscopy (PM-IRRAS) is a surface-sensitive technique that can determine surface structures, chemical states of surface species, and their orientation relative to the surface [9,26]. The polarized parallel (p) component of the... 

Polarization-modulation infrared reflection-absorption spectroscopy (PM-IR-RAS) spectra were recorded with a Bruker ITS 66/S Fourier transform infrared spectrometer equipped with a PMA 37 polarization modulation module and a ititrogen-cooled MCT detector. The infrared beam was first p-polarized with a ZnSe wire grid polarizer (Specac) before passing through a photoelastic modulator (Hinds Instruments, PEM-90), which modulated at a frequency of 74 kHz. A lock-in ampHfier (Stanford model SR-830) was used to obtain the PM-IRRAS spectra. The half-wave retardation frequency was set at 4000 cm . The PM-IR-RAS spectra were recorded as S= R -Rs)/(R +Rg). A total of 250 scans at a resolution of 4 cm were collected for each measurement at an angle of incidence of 82.5° with respect to the normal to the sample surface. 

A prerequisite for the development indicated above to occur, is a parallel development in instrumentation to facilitate both physical and chemical characterization. TEM and SPM based methods will continue to play a central role in this development, since they possess the required nanometer (and subnanometer) spatial resolution. Optical spectroscopy using reflection adsorption infrared spectroscopy (RAIRS), polarization modulation infrared adsorption reflection spectroscopy (PM-IRRAS), second harmonic generation (SFIG), sum frequency generation (SFG), various in situ X-ray absorption (XAFS) and X-ray diffraction spectroscopies (XRD), and maybe also surface enhanced Raman scattering (SERS), etc., will play an important role when characterizing adsorbates on catalyst surfaces under reaction conditions. Few other methods fulfill the requirements of being able to operate over a wide pressure gap (to several atmospheres) and to be nondestructive. 

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). 

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