Sergio B. Mendes

The Electroactive Integrated Optical Waveguide: Ultrasensitive Spectroelectrochemistry of Submonolayer Adsorbates

Highly sensitive spectroelectrochemistry of adsorbed films on ITO is demonstrated with the electroactive integrated optical waveguide (EA-IOW). The EA-IOW, a single-mode planar waveguide coated with an ITO layer, is ∼10(4)-fold more sensitive to changes in absorbance occurring during electrochemical events versus a single-pass transmission spectroelectrochemical experiment, as demonstrated by reduction of surface-adsorbed methylene blue. Furthermore, the EA-IOW is selective to near-surface events, as it is relatively insensitive to absorbance by solutions of dissolved chromophores at <1 mM. The EA-IOW is also used to monitor the formation of Prussian Blue during the reduction of ferricyanide, an event that is not easily followed using current-detected cyclic voltammetry, due to interfering faradaic and non-faradaic electrochemical events. The optical background of the EA-IOW is potential-dependent and is explained by ion diffusion into the ITO and by voltage-dependent changes in optical constants for the material. Finally, the high sensitivity of the EA-IOW (relative to other evanescent-field-based spectroelectrochemical techniques) is discussed in terms of its design.

Sol-gel-based, planar waveguide sensor for water vapor

A water vapor sensor based on a combination of sol-gel processing and planar optical waveguide technologies has been developed. The indicator erythrosin B was entrapped in a thin sol-gel film (thickness ∼100 nm) prepared from methyltriethoxysilane, dimethyldiethoxysilane, and tetraethoxysilane. This dye exhibits an increase in absorbance in the presence of liquid or gaseous water. The sol-gel layer containing the dye was deposited onto a sol-gel-derived, single-mode planar waveguide. Outcoupled light intensity measurements (at 514.5 nm) over a range of water vapor concentrations (in a nitrogen gas stream) yielded a response over a wide range of relative humidity (<1-∼70%) at room temperature. Response and reversal times were less than 1 min, which may make this sensor attractive for real-time monitoring applications.

Near diffraction-limited laser emission from a polymer in a high finesse planar cavity

We report near diffraction-limited laser emission from the conjugated polymer BEH:PPV in a cavity made with two dielectric mirrors providing a high finesse planar cavity. The laser has a sharp intensity threshold, a strong directionality, and a high degree of polarization. These emission characteristics are compared with those of a single polymer layer without optical feedback.

Diffraction gratings in sol-gel films by direct contact printing using a UV-mercury lamp

Abstract We report on the fabrication of diffraction gratings in photosensitive sol–gel thin films by direct contact printing using a UV-mercury lamp. Titanium amplitude masks were used to replicate diffraction gratings into photosensitive sol–gel films by contact printing with an incoherent UV-light source. Gratings with 1-μm period were fabricated in sol–gel films. The diffraction efficiencies of each diffracted order were measured and compared to theoretical values. The demonstrated process of contact printing using a regular UV-light source in the optically compatible sol–gel material has potential for large-scale fabrication of submicrometer gratings at very low cost.

Compact multimode pumped erbium-doped phosphate fiber amplifiers

The performance of compact multimode pumped erbium-doped phosphate fiber amplifiers is presented. A fiber amplifier with a small signal net gain of 41 dB at 1535 nm and 21 dB over the full C-band is demonstrated using a newly developed 8-cm-long erbium-doped phosphate fiber excited with a 1-W, 975-nm multimode laser diode. A theoretical model is developed for the multimode pumped amplifier based on modified rate equations and an effective beam propagation method. Close agreement between experimental and modeling results is observed.

Static tester for characterization of phase-change, dye-polymer, and magneto-optical media for optical data storage.

We have designed and built a static tester around a commercially available polarized light microscope. This device employs two semiconductor laser diodes (at 643- and 680-nm wavelengths) for the purpose of recording small marks on various media for optical data storage and for the simultaneous monitoring of the recording process. We use one of the lasers in the single-pulse mode to write a mark on the sample and operate the other laser in the cw mode to monitor the recording process. The two laser beams are brought to coincident focus on the sample through the objective lens of the microscope. The reflected beams are sent through a polarizing beam splitter and thus divided into two branches, depending on whether they are p or s polarized. In each branch the beam is further divided into two according to the wavelength. The four beams thus produced are sent to four high-speed photodetectors, and the resulting signals are used to monitor the reflectance as well as the polarization state of the beam on reflection from the sample. We provide a comprehensive description of the testers design and operating principles. We also report preliminary results of measurements of phase-change, dye-polymer, and magneto-optical samples, which are currently of interest in the areas of writable and rewritable optical data storage.

Integrated optical biosensor for detection of multivalent proteins.

We have developed a simple, highly sensitive and specific optical waveguide sensor for the detection of multivalent proteins. The optical biosensor is based on optically tagged glycolipid receptors embedded within a fluid phospholipid bilayer membrane formed upon the surface of a planar optical waveguide. Binding of multivalent cholera toxin triggers a fluorescence resonance energy transfer that results in a two-color optical change that is monitored by measurement of emitted luminescence above the waveguide surface. The sensor approach is highly sensitive and specific and requires no additional reagents and washing steps. Demonstration of protein-receptor recognition by use of planar optical waveguides provides a path forward for the development of fieldable miniaturized biosensor arrays.

Voltammetric and waveguide spectroelectrochemical characterization of ultrathin poly(aniline)/poly(acrylic acid) films self-assembled on indium-tin oxide

We report on the spectroelectrochemical characterization of conducting polymer (CP) films, composed of alternating layers of poly(aniline) (PANI) and poly(acrylic acid) (PAA), deposited on ITO-coated, planar glass substrates using layer-by-layer self-assembly. Absorbance changes associated with voltammetrically induced redox changes in ultrathin films composed of only two bilayers (ITO/PANI/PAA/PANI/PAA) were monitored in real time using a unique multiple reflection, broadband attenuated total reflection (ATR) spectrometer. CP films in contact with pH 7 buffer undergo a single oxidation/reduction process, with ca. 12.5% of the aniline centers in the film being oxidized and reduced. The ATR spectra indicate that during an anodic sweep, the leucoemeraldine form of PANI in these films is oxidized to generate both the emeraldine and pernigraniline forms simultaneously. A comparison of the behavior observed during anodic and cathodic sweeps suggests that the rate of oxidation is limited by structural changes in the polymer film originating in electrostatic repulsion between positively charged PANI chains.

Comparative analysis of absorbance calculations for integrated optical waveguide configurations by use of the ray optics model and the electromagnetic wave theory

Focusing on the use of planar waveguides as platforms for highly sensitive attenuated total reflection spectroscopy of organic thin films, we extend the ray optics model to provide absorbance expressions for the case of dichroic layers immobilized on the waveguide surface. Straightforward expressions are derived for the limiting case of weakly absorbing, anisotropically oriented molecules in the waveguide-cladding region. The second major focus is on the accuracy of the ray optics model. This model assumes that the introduction of absorbing species, either in the bulk cladding or as an adlayer on the waveguide surface, only causes a small perturbation to the original waveguide-mode profile. We investigate the accuracy of this assumption and the conditions under which it is valid. A comparison to an exact calculation by use of the electromagnetic wave theory is implemented, and the discrepancy of the ray optics model is determined for various waveguide configurations. We find that in typical situations in which waveguide-absorbance measurements are used to study organic thin films (k(l)/n(l) <or= (-1), h/lambda approximately (-2)) the discrepancy between the ray optics and the exact calculations is only a few percent (2-3%).

Technique for determining the angular orientation of molecules bound to the surface of an arbitrary planar optical waveguide

A technique to determine the angular orientation of a molecular assembly bound to the surface of a planar optical waveguide of arbitrary structure is described. The approach is based on measuring the absorption dichroic ratio by using the waveguide evanescent fields with orthogonal polarizations (TE, TM) and the same mode order to probe two molecular assemblies, (i) a reference sample composed of an isotropic orientation distribution of dipoles and (ii) a sample of interest. The isotropic sample is used to characterize the waveguide structure, which then allows the orientation parameters of a molecular assembly under investigation to be determined from a measured dichroic ratio. The method developed here is particularly important for applications in gradient-index and multilayer planar waveguide platforms because in those cases the extension of previously reported approaches would require a full experimental characterization of the guiding structure, which would be problematic and may yield inaccurate results.