Thin-Film Fluorescence

6 Electronic Structure and Energy Transfer in Solid a-Sexithienyl 

In retrospect, by inspecting the literature, we find a confirmation of this variance (see for instance Ref. [67]). Peak intensities of bands originally assigned to Franck-Condon components of the excitonic emission have random relative intensities. This would not be possible if the bands were intrinsically vibronic. Since we know that the excitonic emission, as it is observed in single crystals, is rather sharp at low temperatures, we were forced to reconsider the assignment of the fluorescence of thin films. From the temperature dependence of the fluores- 

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Perhaps best known of Perrin s work is his spirited defense of kinetic theory and physical atomism entitled Les atomes (1913), in which he made use of his own work on Brownian motion, in combination with studies of cathode rays and x-rays, ionization, radioactivity, radiation, and quantum theory.72 About the time of the 1911 Solvay physics conference, Perrin shifted from Brownian motion to work on thin films, fluorescence, and photochemistry, partly to test the early quantum theory and especially to study individual atom-based fluctuations. 

In the above-described set-up (Fig. 8.16), the physical absorption of oxygen in water was used to measure the gas to liquid mass transfer. Thin-film fluorescence quenching-based sensors were installed to determine the oxygen concentration at the inlet and exit of the reactor. From the measured oxygen concentrations, the mass transfer coefficient was calculated based on the reactor-based liquid velocity ... 

Fig. 2 Room temperature and well resolved 20 K thin film fluorescence spectra of PF2/6...

In X-Ray Fluorescence (XRF), an X-ray beam is used to irradiate a specimen, and the emitted fluorescent X rays are analyzed with a crystal spectrometer and scintillation or proportional counter. The fluorescent radiation normally is diffracted by a crystal at different angles to separate the X-ray wavelengths and therefore to identify the elements concentrations are determined from the peak intensities. For thin films XRF intensity-composition-thickness equations derived from first principles are used for the precision determination of composition and thickness. This can be done also for each individual layer of multiple-layer films. 

In another approach, which was previously mentioned, the mass thickness, or depth distribution of characteristic X-ray generation and the subsequent absorption are calculated using models developed from experimental data into a < )(p2) function. Secondary fluorescence is corrected using the same i flictors as in ZAP. The (pz) formulation is very flexible and allows for multiple boundary conditions to be included easily. It has been used successfully in the study of thin films on substrates and for multilayer thin films. 

In addition to qualitative identification of the elements present, XRF can be used to determine quantitative elemental compositions and layer thicknesses of thin films. In quantitative analysis the observed intensities must be corrected for various factors, including the spectral intensity distribution of the incident X rays, fluorescent yields, matrix enhancements and absorptions, etc. Two general methods used for making these corrections are the empirical parameters method and the fimdamen-tal parameters methods. 

Both XRF and EPMA are used for elemental analysis of thin films. XRF uses a nonfocusing X-ray source, while EPMA uses a focusing electron beam to generate fluorescent X rays. XRF gives information over a large area, up to cm in diameter, while EPMA samples small spots, (om in size. An important use of EPMA is in point-to-point analysis of elemental distribution. Microanalysis on a sub- lm scale can be done with electron microscopes. The penetration depth for an X-ray beam is normally in the 10-(om range, while it is around 1 (om for an electron beam. There is, therefore, also a difference in the depth of material analyzed by XRF and EPMA... 

Fig. 4.10. Fluorescence signal from small particles or thin films deposited on a silicon substrate used as sample carrier. The intensity was calculated for particles, thin films, or sections ofdiffe-rent thickness but equal mass of analyte, and plotted against the glancing angle f. A Mo-Ka beam was assumed for excitation. Particles or films more than 100 nm thick show double intensity below the critical angle of0.1° [4.21].

For an electron-transparent specimen the absorption and fluorescence correction parts can often be neglected, this is the so-called thin-film criterion introduced by Cliff and Lorimer [4.118]. Thus, for a thin specimen containing two elements A and B yielding the net X-ray intensities I a and 1b, the concentration ratio reduces to ... 

Experiments on transport, injection, electroluminescence, and fluorescence probe the spatial correlation within the film, therefore we expect that their response will be sensitive to the self-affinity of the film. This approach, which we proved useful in the analysis of AFM data of conjugated molecular thin films grown in high vacuum, has never been applied to optical and electrical techniques on these systems and might be an interesting route to explore. We have started to assess the influence of different spatial correlations in thin films on the optical and the electro-optical properties, as it will be described in the next section. 

Figure 6-21. Site-selective fluorescence measurements of a T thin film. Starting from the top spectrum the excitation energies were at 17860. 17700, 17390, 17240, 17095, and 16950 cur, respectively. The reminiscence of the exciting laser lines is shown by the sharp peak on the left.

Figure 6-22. Fluorescence exciuuon spectrum of a T() thin film detected at energies spanning from 15380 to 17300 cm-1. In this energy range the spectrum is unchanged.

Only 6% of the iifitial total lycopene prepared as a thin film on the surface of each vial remained after 144 hr under fluorescent light (2000 to 3000 lux) at 25°C under N2. Lycopene degradation occurred as a first-order reaction at 2.93 x 10" /min, and the concentration of aU lycopene mono-c isomers already present in the sample, 5-cis-, 9-cis-, l3-cis- and 15-d5 -, showed an inconsistent change in this period. Nevertheless, formation of lycopene di-c isomers was observed after 32 hr of light exposure and when considering relative percentage, loss of 13% of all-trani-lycopene occurred while an increase of 11% for total cis isomers was found after 144 hr. ... 

For the investigation of polymer systems under spatial confinement, fluorescence microscopy is a powerful method providing valuable information with high sensitivity. A fluorescence microscopy technique with nanometric spatial resolution and nanosecond temporal resolution has been developed, and was used to study the structure and dynamics of polymer chains under spatial confinement a polymer chain in an ultra-thin film and a chain grafted on a solid substrate. Studies on the conformation of the single polymer chain in a thin film and the local segmental motion of the graft polymer chain are described herein. 

We prepared thin film Pt alloy electrodes by Ar-sputtering Pt and the second metal targets simultaneously onto a disk substrate at room temperature (thickness approximately 200 nm). The resulting alloy composition was determined by gravimetry and X-ray fluorescent analysis (EDX). Grazing incidence (i7= 1°) X-ray diffraction patterns of these alloys indicated the formation of a solid solution with a face-centered cubic (fee) crystal stmeture. 

The Thin Film Approximation. If absorption and X-ray fluorescence are neglected (i.e. the film is assumed to be infinitely thin ), then the measured X-ray intensity from element A in a thin specimen of unit thickness, generated by a current i is given by... 

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