Chiral π-conjugated molecules provide new materials with outstanding features for current and perspective applications, especially in the field of optoelectronic devices. In thin films, processes s...

Chiroptical Properties in Thin Films of π-Conjugated Systems.

Characterization of plasmonic effects in thin films and metamaterials using spectroscopic ellipsometry

A large number of inorganic materials form crystals with chiral symmetry groups. Enantioselectively synthesizing nanostructures of such materials should lead to interesting optical activity effects. Here we report the synthesis of colloidal tellurium and selenium nanostructures using thiolated chiral biomolecules. The synthesis conditions are tuned to obtain tellurium nanostructures with chiral shapes and large optical activity. These nanostructures exhibit visible optical and chiroptical responses that shift with size and are successfully simulated by an electromagnetic model. The model shows that they behave as chiral optical resonators. The chiral tellurium nanostructures are transformed into chiral gold and silver telluride nanostructures with very large chiroptical activity, demonstrating a simple colloidal chemistry path to chiral plasmonic and semiconductor metamaterials. These materials are natural candidates for studies related to interactions of chiral (bio)molecules with chiral inorganic surfaces, with relevance to asymmetric catalysis, chiral crystallization and the evolution of homochirality in biomolecules.

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Enantioselective control of lattice and shape chirality in inorganic nanostructures using chiral biomolecules

We report that the π-stacking direction in poly(3-hexylthiophene) (P3HT) films can be made to orient strongly out-of plane by uniaxially straining films in orthogonal directions, providing a valuable opportunity to evaluate charge transport in a very unusual microstructure for this material. The structure of the films was characterized using UV–visible spectroscopy, X-ray diffraction, and near-edge X-ray absorption fine structure spectroscopy, showing that unstrained films have a weakly edge-on stacking character with a large orientation distribution, whereas films strained biaxially by 100% in orthogonal directions have highly face-on stacking. In the biaxially strained films the face-on packing occurs while the P3HT long axis orientation is found to be only weakly anisotropic in-plane. Charge transport is characterized in an organic thin-film transistor (OTFT) configuration, showing that the saturated field effect mobility in the biaxially strained films is greater than that for unstrained films for cha...

Charge Transport in Highly Face-On Poly(3-hexylthiophene) Films

In this paper we describe a new Mueller matrix (MM) microscope that generalizes and makes quantitative the polarized light microscopy technique. In this instrument all the elements of the MU are simultaneously determined from the analysis in the frequency domain of the time-dependent intensity of the light beam at every pixel of the camera. The variations in intensity are created by the two compensators continuously rotating at different angular frequencies. A typical measurement is completed in a little over one minute and it can be applied to any visible wavelength. Some examples are presented to demonstrate the capabilities of the instrument.

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Mueller matrix microscope with a dual continuous rotating compensator setup and digital demodulation

Imaging chiroptical artifacts.

D-sorbitol forms so-called spherulites from under-cooled melts. These polycrystalline formations have optically uniaxial radii. Melts pressed between glasses crystallize as plane sections of spheres. Dyes that are soluble in molten sorbitol become oriented as the crystallization front passes through the melt so as to form disks with large linear dichroism in the absorption bands of the dyes. The dyeing of spherulites is thus a general method of solute alignment. The linear optical properties of sorbitol spherulites containing the azo dye amaranth were analyzed in detail so as to correct a persistent confusion in the literature regarding the orientational dependence of linear dichroism. In cases involving thin film dichroism of multilayered samples requiring many corrections of intensity data in non-normal incidence, some authors have taken transmittance and others absorbance as having a cosine-squared angular dependence on the plane of the electric vector of linearly polarized light. Plane sections of doped spherulites present all orientations of an electric dipole oscillator in spatially localized region in normal incidence. As such, the samples described herein are ideally suited to resolving this confusion. Images of transmittance of dyed spherulites in polarized light were recorded with a CCD camera and simulated under the assumption that both absorbance and transmittance show a cosine-squared angular dependence but with respect to different angles. Transmittance with a cosine-squared dependence follows azimuthal rotations of the spherulite radii around the wave vector, while absorbance with a cosine-squared dependence follows rotations about axes perpendicular to the wave vector, natural consequences of the properties of the optical indicatrix that are often overlooked. Spherulites obviate the substantial experimental complexities that are engendered in non-normal incidence by sample reorientation. Thus, the principles of anisotropic absorption are given in a complete and intuitive fashion.

Eva Hollis

Papers

Imaging chiroptical artifacts.

Orientational dependence of linear dichroism exemplified by dyed spherulites.