Second harmonic generation applications

Unlike linear optical effects such as absorption, reflection, and scattering, second order non-linear optical effects are inherently specific for surfaces and interfaces. These effects, namely second harmonic generation (SHG) and sum frequency generation (SFG), are dipole-forbidden in the bulk of centrosymmetric media. In the investigation of isotropic phases such as liquids, gases, and amorphous solids, in particular, signals arise exclusively from the surface or interface region, where the symmetry is disrupted. Non-linear optics are applicable in-situ without the need for a vacuum, and the time response is rapid. 

The development of hydrodynamic techniques which allow the direct measurement of interfacial fluxes and interfacial concentrations is likely to be a key trend of future work in this area. Suitable detectors for local interfacial or near-interfacial measurements include spectroscopic probes, such as total internal reflection fluorometry [88-90], surface second-harmonic generation [91], probe beam deflection [92], and spatially resolved UV-visible absorption spectroscopy [93]. Additionally, building on the ideas in MEMED, submicrometer or nanometer scale electrodes may prove to be relatively noninvasive probes of interfacial concentrations in other hydrodynamic systems. The construction and application of electrodes of this size is now becoming more widespread and general [94-96]. 

In the following sections we will first in Section 2 briefly discuss the necessary background to understand optical activity effects in linear and nonlinear optics and to illustrate the similarities and differences between both types. In Section 3 we present a more thorough analysis of nonlinear optical effects in second-harmonic generation, both from a theoretical and an experimental point of view. Section 4 deals with experimental examples that illustrate the usefulness of nonlinear optical activity in the study of chiral thin films and surfaces. Finally, in Section 5 we give an overview of the role of chirality in the field of second-order nonlinear optics and show that chiral molecules can be useful for applications in this field. 

In addition to the indirect experimental evidence coming from work function measurements, information about water orientation at metal surfaces is beginning to emerge from recent applications of a number of in situ vibrational spectroscopic techniques. Infrared reflection-absorption spectroscopy, surface-enhanced Raman scattering, and second harmonic generation have been used to investigate the structure of water at different metal surfaces, but the pictures emerging from all these studies are not always consistent, partially because of surface modification and chemical adsorption, which complicate the analysis. 

The same equipment, which is used for time-resolved Ivuninescence application is suitable for other laser-based spectroscopies. Thus several spectroscopic methods may be applied simultaneously. The most important techniques, which may be used together with time-resolved luminescence, are laser-induced breakdown spectroscopy, Raman spectroscopy and Second Harmonics Generation spectroscopy. 

The Applications of Laser-induced Time-resolved Spectroscopic Techniques chapter starts with a short description of laser-induced spectroscopies, which may be used in combination with laser-induced luminescence, namely Breakdown, Raman and Second Harmonic Generation. The chapter contains several examples of the application of laser-based spectroscopies in remote sensing and radiometric sorting of minerals. The proljlem of minerals as geomaterials for radioactive waste storage is also considered. 

B. Pettinger, C. Bdger, J. Lipkowski, Second harmonic generation anisotropy from single crystalline electrode surfaces in Interfacial Electrochemistry. Theory, Experiment and Applications (Ed. A. Wifckowski), Marcel Dekker, New York-Basel, 1999, p. 373. 

A number of special optical techniques such as the study of second harmonic generation by irradiation of non-centrosymmetric systems by high intensity laser light will be discussed in relation to particular materials and problems. However, one optical technique having a general applicability, namely ellipsometry, must be discussed here. It is one of the best techniques available to determine the thickness of a thin organic film. Such determinations are important as they allow one to have an independent check on the number of layers deposited, given that the thickness of one layer has been determined by X-ray diffraction. 

Application of metal alkoxides for the preparation of niobates and tanta-lates in the form of both powders and films has been first performed by Dand-liker [475]. In our study of hydrolysis of LiOEt andNb(OEt)5 solutions in anhydrous EtOH, it was demonstrated that although the freshly prepared powder is amorphous for X-ray, it already contains microcrystallites of LiNb03 [1778]. In addition to conventional techniques, the properties ofthe powder in the course of thermal treatment were studied by the second harmonic generation ofthe laser beam, which is a sensitive technique for detection ofnoncen-trosymmetric phase the first signal was registered at 350°C. 

Table 2. Second harmonic generation figures of merit relative to LiNb03 (d13 coefficient) for materials with potential for waveguide applications...

Figure 2 shows the tradeoffs between crystal and polymer organic NLO materials for device applications. Although cither type of materials could in principle be used for both applications, crystals are best for second harmonic generation, and poled polymers are best for electro-optic waveguide devices such as modulators and switches. 

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