The frequency dependent hyperpolarizability of typical donor–acceptor organic nonlinear optical molecules is commonly represented by a nonresonant two-level model, first presented by Oudar and Chemla. We discuss how this model can be extended into the resonant regime, including cases where the molecular transition is described by an inhomogeneously broadened peak. A resonant measurement of hyperpolarizability by electric field induced second harmonic generation (EFISH) is demonstrated, as well as the more conventional off-resonance EFISH. The theoretical model correctly predicts both the amplitude and phase of the resonant hyperpolarizability measured by EFISH. We also show that both on-resonance and off-resonance EFISH yield the same hyperpolarizability extrapolated to the zero frequency limit.
The secondary electron emission flux in a scanning electron microscope is a powerful tool for delineation of electrically active dopant concentration, built-in potentials, and surface electric fields in semiconductor junctions. In all the secondary electron images of p-n junctions, the p-doped regions appear brighter than n-doped regions. We present a theory for the doping contrast in p-n junctions that is based on the secondary electron emission yield and surface band bending extracted from Kelvin probe force microscopy measurements. We show that the contrast is governed by the secondary electron escape depth, and their escape probability which is related to the secondary electron energy distribution and the effective electron affinity. It is found that the escape depth is the main factor determining the dopant contrast, and the escape probability has a smaller effect. In addition, our theory explains the logarithmic dependence of the measured contrast on the acceptor concentration in silicon reported by many groups.
Electron donor−π−acceptor chromophores 5, 9, 11, 18−20, 21, 22, 27, 28a, 28c, 31, 32, 34−36, 38a−c, 41a, 41c, and 42 have been synthesised. The donor units are 1,3-dithiole and ferrocene; conjugated ethylenic, phenyl, phenylenevinylene, thienyl, bithienyl, terthienyl, or thienylenevinylene linkers act as a central π-electron relay unit, and dicyanomethylene and polynitrofluorene groups as the acceptor unit. The electronic absorption spectra display a broad low-energy intramolecular charge transfer band in the visible region (500−700 nm) the energy (hν ICT ഠ 1.7−2.5 eV) and intensity (ε ഠ 5000−50000 m −1 cm −1 ) of which depend substantially on the nature of both D and A moieties and on the structure of the linker unit. Nonlinear optical properties have been evaluated using the EFISH technique: the highest µβ (0) values are observed for 38b [(900±300)×10 −48 esu] and 42
A new form of biomineralization has been studied in the pineal gland of the human brain. It consists of small crystals that are less than 20 microm in length and that are completely distinct from the often observed mulberry-type hydroxyapatite concretions. A special procedure was developed for isolation of the crystals from the organic matter in the pineal gland. Cubic, hexagonal, and cylindrical morphologies have been identified using scanning electron microscopy. The crystal edges were sharp whereas their surfaces were very rough. Energy dispersive spectroscopy showed that the crystals contained only the elements calcium, carbon, and oxygen. Selected area electron diffraction and near infrared Raman spectroscopy established that the crystals were calcite. With the exception of the otoconia structure of the inner ear, this is the only known nonpathological occurrence of calcite in the human body. The calcite microcrystals are probably responsible for the previously observed second harmonic generation in pineal tissue sections. The complex texture structure of the microcrystals may lead to crystallographic symmetry breaking and possible piezoelectricity, as is the case with otoconia. It is believed that the presence of two different crystalline compounds in the pineal gland is biologically significant, suggesting two entirely different mechanisms of formation and biological functions. Studies directed toward the elucidation of the formation and functions, and possible nonthermal interaction with external electromagnetic fields are currently in progress.
We study 2-(p-N-hexadecyl-N-methylamino)benzylidene-1,3-indandione (1a) as a model compound for the preparation of nonlinear optically (NLO) active Langmuir-Blodgett (LB) layers. The pressure-area (π-A) isotherm of (1a) at the air-water interface is investigated. A limiting area of 0.60 ( 0.02 nm 2 per molecule is found. The alternate-layer LB deposition of compound (1a) and an inert spacer, cadmium stearate, at different surface pressures is performed. The effects of temperature and delay time between spreading of the Langmuir film and the deposition of the LB films are studied. An increase of collapse pressure from 20 to 30 mN/m is observed as the delay time increases. UV-vis spectra indicate a uniform transfer of (1a) and show compressioninduced changes as a function of the deposition conditions. A split of the absorption maximum is observed for LB films deposited at higher pressures and lower temperatures. The two bands can result from two different molecular electronic transitions, affected by the aligning influence of the surface, and the different environments in the film compared to solution. Alternatively, these two bands can be associated with (at least) two different conformers. The orientation of the transition moments is evaluated on the basis of polarized UV-vis spectra at different angles of incidence, and found to be 40-44°. Significant second harmonic (SH) generation by the LB films is observed. Analysis of the SH response gives a tilt angle of 44°, in agreement with the finding from UV absorbance.
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