ELECTROCATALYSIS AT A MICRODISK ELECTRODE MODIFIED WITH A REDOX SPECIES

The current equation of the electrocatalytic reaction at a microdisk electrode modified with redox species has been described and verified experimentally. There exists a linear relationship between plateau limiting current and the radius of the microdisk electrode for a catalytic process. The influence of the dimensions of the microdisk electrode on catalytic efficiency is discussed. The polyvinylferrocene (PVFc)-modified microdisk electrode prepared by the coating method was taken as a typical example, on which the electrocatalytic oxidation of ascorbic acid could be studied. The catalytic reaction rate constants were determined as an average value of 1.5 X 10(-7) cm3/mol s by this method, and are consistent with those obtained at a conventional electrode.

Double potential step chronoamperometry at microdisk electrodes: simulating the case of unequal diffusion coefficients

An efficient approach to the simulation of the double potential step chronoamperometry at a microdisk electrode based on an exponentially expanding time grid and conformal mapping of the space is presented. The dimensionless second potential step flux data are included as a function of the first potential step duration and the ratio of the diffusion coefficients of the reacting species allowing instant analysis of the experimental double potential step chronoamperograms without a need for simulation. The values of the diffusion coefficients are determined for several test systems and found to be in good agreement with existing literature data. (C) 2004 Elsevier B.V. All rights reserved.

One-Electron Reduction of 2-Nitrotoluene, Nitrocyclopentane, and 1-Nitrobutane in Room Temperature Ionic Liquids: A Comparative Study of Butler–Volmer and Symmetric Marcus–Hush Theories Using Microdisk Electrodes

The voltammetry for the reduction of 2-nitrotoluene at a gold microdisk electrode is reported in two ionic liquids: trihexyltetradecylphosphonium tris(pentafluoroethyl)trifluorophosphate ([P-14,P-6,P-6,P-6][FAP]) and 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([Emim][NTf2]). The reduction of nitrocyclopentane (NCP) and 1-nitrobutane (BuN) was investigated using voltammetry at a gold microdisk electrode in the ionic liquid [P-14,P-6,P-6,P-6][FAP]. Simulated voltammograms, generated through the use of ButlerVolmer theory and symmetric MarcusHush theory, were compared to experimental data, with both theories parametrizing the data similarly well. An experimental value for the Marcusian parameter, 1 was also determined in all cases. For the reduction of 2-nitrotoluene, this was 0.5 +/- 0.1 eV in both solvents, while for NCP and BuN in [P-14,P-6,P-6,P-6][FAP], it was 2 +/- 0.1 and 5 +/- 0.1 eV, respectively. This is attributed to the localization of charge on the nitro group and the primary nitro alkyls increased interaction with the environment, resulting in a larger reorganization energy.

Nonlinear optics and wavelength translation via cavity-optomechanics

The field of cavity-optomechanics explores the interaction of light with sound in an ever increasing array of devices. This interaction allows the mechanical system to be both sensed and controlled by the optical system, opening up a wide variety of experiments including the cooling of the mechanical resonator to its quantum mechanical ground state and the squeezing of the optical field upon interaction with the mechanical resonator, to name two.

In this work we explore two very different systems with different types of optomechanical coupling. The first system consists of two microdisk optical resonators stacked on top of each other and separated by a very small slot. The interaction of the disks causes their optical resonance frequencies to be extremely sensitive to the gap between the disks. By careful control of the gap between the disks, the optomechanical coupling can be made to be quadratic to first order which is uncommon in optomechanical systems. With this quadratic coupling the light field is now sensitive to the energy of the mechanical resonator and can directly control the potential energy trapping the mechanical motion. This ability to directly control the spring constant without modifying the energy of the mechanical system, unlike in linear optomechanical coupling, is explored.

Next, the bulk of this thesis deals with a high mechanical frequency optomechanical crystal which is used to coherently convert photons between different frequencies. This is accomplished via the engineered linear optomechanical coupling in these devices. Both classical and quantum systems utilize the interaction of light and matter across a wide range of energies. These systems are often not naturally compatible with one another and require a means of converting photons of dissimilar wavelengths to combine and exploit their different strengths. Here we theoretically propose and experimentally demonstrate coherent wavelength conversion of optical photons using photon-phonon translation in a cavity-optomechanical system. For an engineered silicon optomechanical crystal nanocavity supporting a 4 GHz localized phonon mode, optical signals in a 1.5 MHz bandwidth are coherently converted over a 11.2 THz frequency span between one cavity mode at wavelength 1460 nm and a second cavity mode at 1545 nm with a 93% internal (2% external) peak efficiency. The thermal and quantum limiting noise involved in the conversion process is also analyzed and, in terms of an equivalent photon number signal level, are found to correspond to an internal noise level of only 6 and 4 times 10x^-3 quanta, respectively.

We begin by developing the requisite theoretical background to describe the system. A significant amount of time is then spent describing the fabrication of these silicon nanobeams, with an emphasis on understanding the specifics and motivation. The experimental demonstration of wavelength conversion is then described and analyzed. It is determined that the method of getting photons into the cavity and collected from the cavity is a fundamental limiting factor in the overall efficiency. Finally, a new coupling scheme is designed, fabricated, and tested that provides a means of coupling greater than 90% of photons into and out of the cavity, addressing one of the largest obstacles with the initial wavelength conversion experiment.

On-chip integrated label-free optical biosensing

This thesis investigates the design and implementation of a label-free optical biosensing system utilizing a robust on-chip integrated platform. The goal has been to transition optical micro-resonator based label-free biosensing from a laborious and delicate laboratory demonstration to a tool for the analytical life scientist. This has been pursued along four avenues: (1) the design and fabrication of high-$Q$ integrated planar microdisk optical resonators in silicon nitride on silica, (2) the demonstration of a high speed optoelectronic swept frequency laser source, (3) the development and integration of a microfluidic analyte delivery system, and (4) the introduction of a novel differential measurement technique for the reduction of environmental noise.

The optical part of this system combines the results of two major recent developments in the field of optical and laser physics: the high-$Q$ optical resonator and the phase-locked electronically controlled swept-frequency semiconductor laser. The laser operates at a wavelength relevant for aqueous sensing, and replaces expensive and fragile mechanically-tuned laser sources whose frequency sweeps have limited speed, accuracy and reliability. The high-$Q$ optical resonator is part of a monolithic unit with an integrated optical waveguide, and is fabricated using standard semiconductor lithography methods. Monolithic integration makes the system significantly more robust and flexible compared to current, fragile embodiments that rely on the precarious coupling of fragile optical fibers to resonators. The silicon nitride on silica material system allows for future manifestations at shorter wavelengths. The sensor also includes an integrated microfluidic flow cell for precise and low volume delivery of analytes to the resonator surface. We demonstrate the refractive index sensing action of the system as well as the specific and nonspecific adsorption of proteins onto the resonator surface with high sensitivity. Measurement challenges due to environmental noise that hamper system performance are discussed and a differential sensing measurement is proposed, implemented, and demonstrated resulting in the restoration of a high performance sensing measurement.

The instrument developed in this work represents an adaptable and cost-effective platform capable of various sensitive, label-free measurements relevant to the study of biophysics, biomolecular interactions, cell signaling, and a wide range of other life science fields. Further development is necessary for it to be capable of binding assays, or thermodynamic and kinetics measurements; however, this work has laid the foundation for the demonstration of these applications.

Frequency locked micro disk resonator for real time and precise monitoring of refractive index.

We experimentally demonstrate a frequency modulation locked servo loop, locked to a resonance line of an on-chip microdisk resonator in a silicon nitride platform. By using this approach, we demonstrate real-time monitoring of refractive index variations with a precision approaching 10(-7) RIU, using a moderate Q factor of 10(4). The approach can be applied for intensity independent, dynamic and precise index of refraction monitoring for biosensing applications.

Mode Simulation for Midinfrared Microsquare Resonators With Sloped Sidewalls and Confined Metals

EQUILATERAL-TRIANGLE; MU-M; LASERS; MICROLASERS; MICRODISK Abstract: Mode characteristics for midinfrared microsquare resonators with sloped sidewalls and confined metal layers are investigated by finite-difference time-domain (FDTD) techniques. For a microsquare with a side length of 10 mu m, the mode quality (Q)-factors of 8329, 4772, and 2053 are obtained for TM5,7 mode at wavelength 7.1 mu m by three-dimensional FDTD simulations, as the tilting angles of the side walls are 90 degrees, 88 degrees, and 86 degrees, respectively. Furthermore, microsquare resonators laterally surrounded by SiO2 and metal layers are investigated by the two-dimensional FDTD technique for the metal layers of Au, Ti-Au, Ag-Au, and Ti-Ag-Au, respectively.

Multimode resonances in metallically confined square-resonator microlasers

Directional emission InP/AlGaInAs square-resonator microlasers with a side length of 20 mu m are fabricated by standard photolithography and inductively coupled-plasma etching technique. Multimode resonances with about seven distinct mode peaks in a free-spectral range are observed from 1460 to 1560 nm with the free-spectral range of 12.1 nm near the wavelength of 1510 nm, and the mode refractive index versus the photon energy E (eV) as 3.07152+0.18304E are obtained by fitting the laser spectra with an analytical mode wavelength formula derived by light ray method. In addition, mode field pattern is simulated for cold cavity by two dimensional finite-difference time-domain technique.

Analysis of coupled microcircular resonators coupled to a bus waveguide with high output efficiency

Coupled microcircular resonators tangentially coupled to a bus waveguide, which is between the resonators, are numerically investigated by the finite-difference time-domain technique. For symmetrically coupled microcircular resonators with refractive index of 3.2, radius of 2 mu m, and width of the bus waveguide of 0.4 mu m, a mode Q factor of the order of 105 is obtained for a mode at the frequency of 243 THz. An output coupling efficiency of as high as 0.99 is calculated for a mode with a Q factor ranging from 10(3) to 10(4). The mode Q factor is 2 orders larger than that of the modes confined in a single circular resonator tangentially coupled to the same bus waveguide. Furthermore, the high Q traveling modes in the coupled microcircular resonators are suitable for optical single processing.

Design of quantum cascade microcavity lasers based on Q factor versus etching depth

The choice of the etching depth for semiconductor microcavities is a compromise between a high Q factor and a difficult technique in a practical fabricating process. In this paper, the influences of the etching depth on mode Q factors for mid-infrared quantum cascade microcylinder and microsquare lasers around 4.8 and 7.8 mu m are simulated by three-dimensional (3D) finite-difference time-domain (FDTD) techniques. For the microcylinder and the microsquare resonators, the mode Q factors of the whispering-gallery modes (WGMs) increase exponentially and linearly with the increase in the etching depth, respectively Furthermore, the mode Q factors of some higher order transverse WGMs may be larger than that of the fundamental transverse WGM in 3D microsquares. Based on the field distribution of the vertical multilayer slab waveguide and the mode Q factors versus the etching depth, the necessary etching depth is chosen at the position where the field amplitude is 1% of the peak value of the slab waveguide. In addition, the influences of sidewall roughness on the mode Q factors are simulated for microsquare resonators by 2D FDTD simulation. (C) 2009 Optical Society of America

Analysis of mode characteristics for equilateral-polygonal resonators with a center hole

Mode characteristics for equilateral triangles, squares, and hexagonal resonators with a center hole are numerically simulated by the finite-different time domain (FDTD) technique. The center hole does not break the symmetry behavior of the original resonators and can result in modification of the mode field patterns and mode Q factors. In an equilateral triangle resonator the center hole can suppress the symmetry state of degenerate states with the merit of single mode operation. In a square resonator, the Q factor can be enhanced for some modes with a suitable size of the hole. For a hexagonal resonator with a side length of 1 mu m and a refractive index of 3.2, the mode Q factors first gradually decrease with the increase of the hole diameter for modes at a wavelength of about 1500 nm, then the modes transform to that of a microdisk with a jump of the mode wavelength as the hole diameter approaches 0.7 mu m. Finally, the mode Q factors greatly enhance as the hole diameter reaches about 1 mu m. The results indicate that the center hole can greatly modify mode characteristics, especially that of the mode Q factor. (C) 2009 Optical Society of America

Investigation of mode characteristics for a square cavity with a pedestal by a three-dimensional finite-difference time-domain technique

Mode characteristics of a strongly confined square cavity suspended in air via a pedestal on the substrate are investigated by a three-dimensional finite-difference time-domain technique. The mode wavelengths and mode quality factors (Q factors) are calculated as the functions of the size of the pedestal and the slope angle 0 of the sidewalls of the square slab, respectively For the square slab with side length of 2 mu m, thickness of 0.2 mu m, and refractive index of 3.4, on a square pedestal with refractive index of 3.17, the Q factor of the whispering-gallery (WG)-like mode transverse-electric TE(3.5)o first increases with the side length b of the square pedestal and then quickly decreases as b > 0.4 mu m, but the Q factor of the WG-like mode TE(4.6)o drops down quickly as b > 0.2 mu m, owing to their different symmetries. The results indicate that the pedestal can also result in mode selection in the WG-like modes. In addition, the numerical results show that the Q factors decrease 50% as the slope angle of the sidewalls varies from 90 degrees to 80 degrees. The mode characteristics of WG-like modes in the square cavity with a rectangular pedestal are also discussed. The results show that the nonsquare pedestal largely degrades the WG-like modes. (c) 2006 Optical Society of America

Whispering-gallery-likel modes in square resonators

The mode frequencies and field distributions of whispering-gallery (WG)-like modes of square resonators are obtained analytically, which agree very well with the numerical results calculated by the FDTD technique and Pade approximation method. In the analysis, a perfect electric wall for the transverse magnetic mode or perfect magnetic wall for the transverse electric mode is assumed at the diagonals of the square resonators, which not only provides the transverse mode confinement, but also requires the longitudinal mode number to be an even integer. The WG-like modes of square resonators are nondegenerate modes with high-quality factors, which make them suitable for fabricating single-mode low-threshold semiconductor microcavity lasers.

Analysis of mode quality factors for equilateral triangle semiconductor microlasers with rough sidewalls

The eigenmode characteristics for equilateral triangle resonator (ETR) semiconductor microlasers are analysed by the finite-difference time-domain technique and the Pade approximation. The random Gaussian correlation function and sinusoidal function are used to model the side roughness of the ETR. The numerical results show that the roughness can cause the split of the degenerative modes, but the confined modes can still have a high quality factor. For the ETR with a 3 mum side length and the sinusoidal fluctuation, we can have a quality factor of 800 for the fundamental mode in the wavelength of 1500 nm, as the amplitude of roughness is 75 mn.

Influence of output waveguide on mode quality factor in semiconductor microlasers with an equilateral triangle resonator

Semiconductor microlasers with an equilateral triangle resonator (ETR) and an output waveguide are proposed and analyzed by the finite-difference time-domain technique and the Pade approximation. The numerical results show that microlasers with an output waveguide still have a high-quality factor (Q factor) and are suitable to realize directional emission. For the ETR with a 0.46-mum-width opening in one of the vertices connected to the output waveguide, we have the Q factor of 1.5x10(3) and 2.5x10(2) for the TM fundamental mode at the wavelength of 1.55 mum, as the side length of the ETR is 5 and 3 mum. The simulated intensity distributions are presented for the fundamental mode in the ETR with a side length of 3 mum and an opening of 0.23 mum. (C) 2000 American Institute of Physics. [S0003-6951(00)01749-6].