Andrew C. R. Pipino

Evanescent wave cavity ring-down spectroscopy with a total-internal-reflection minicavity

A miniature-cavity realization of the cavity ring-down concept, which permits extension of the technique to spectroscopy of surfaces, thin films, liquids, and, potentially, solids, is explored using a wave-optics model. The novel spectrometer design incorporates a monolithic, total-internal-reflection-ring cavity of regular polygonal geometry with at least one convex facet to induce stability. Evanescent waves generated by total-internal reflection probe absorption by matter in the vicinity of the cavity. Optical radiation enters or exits the resonator by photon tunneling, which permits precise control of input and output coupling. The broadband nature of total-internal reflection circumvents the narrow bandwidth restriction imposed by dielectric mirrors in conventional gas-phase cavity ring-down spectroscopy. Following a general discussion of design criteria, calculations are presented for square and octagonal cavity geometries that quantify intrinsic losses and reveal an optimal cavity size for each geo...

EVANESCENT WAVE CAVITY RING-DOWN SPECTROSCOPY FOR PROBING SURFACE PROCESSES

Abstract Sub-monolayer detection of adsorbed I 2 is demonstrated with the cavity ring-down technique by using intra-cavity total-internal reflection to generate an evanescent field that probes the adsorption process. A precision, fused-silica Pellin-Broca prism with ultra-smooth facets (surface roughness ∼0.05 nm r.m.s) is employed to provide the intra-cavity TIR. The known cross-section for the 1 Σ g + → 3 Π u transition of I 2 , which is largely invariant between pressure-broadened gaseous, weakly chemisorbed, and liquid states, provides quantification of sensitivity. A minimum detectable coverage of ∼0.04 monolayer is determined at a weakly absorbed probe wavelength.

Monolithic folded resonator for evanescent wave cavity ringdown spectroscopy

An optical resonator is characterized that employs both ultrahigh-reflective coated surfaces and total internal reflection to enable cavity ringdown spectroscopy of surfaces, films, and liquids. The monolithic folded design possesses a polarization-independent finesse that allows polarization-dependent phenomena, such as molecular orientation, to be probed. Although a restricted bandwidth (~15% of the design wavelength) results from use of reflective coatings, the resonator provides high sensitivity and facile operation. A minimum detectable absorption of 2.2 x 10(-6) was obtained for single laser shots by use of multimode excitation at 530 nm with an excimer-pumped, pulsed dye laser.

Absolute surface coverage measurement using a vibrational overtone

Determination of absolute surface coverage with sub-monolayer sensitivity is demonstrated using evanescent-wave cavity ring-down spectroscopy (EW-CRDS) and conventional CRDS by employing conservation of the absolute integrated absorption intensity between gas and adsorbed phases. The first C-H stretching overtones of trichloroethylene (TCE), cis-dichloroethylene, and trans-dichloroethylene are probed using the idler of a seeded optical parametric amplifier having a 0.075 cm(-1) line width. Polarized absolute adsorbate spectra are obtained by EW-CRDS using a fused-silica monolithic folded resonator having a finesse of 28 500 at 6050 cm(-1), while absolute absorption cross sections for the gas-phase species are determined by conventional CRDS. A measure of the average transition moment orientation on the surface, which is utilized for the coverage determination, is derived from the polarization anisotropy of the surface spectra. Coverage measurement by EW-CRDS is compared to a mass-spectrometer-based surface-uptake technique, which we also employ for coverage measurements of TCE on thermally grown SiO(2) surfaces. To assess the potential for environmental sensing, we also compare EW-CRDS to optical waveguide techniques developed previously for TCE detection.

Surface-plasmon-resonance-enhanced cavity ring-down detection.

The cavity ring-down technique is used to probe the absolute optical response of the localized surface plasmon resonance (SPR) of a gold nanoparticle distribution to adsorption of trichloroethylene (TCE) and perchloroethylene (PCE) from the gas phase. Extended Mie theory for a coated sphere with a particle-size-dependent dielectric function is used to elucidate size-dispersion effects, the size-dependence of the SPR sensitivity to adsorption, and the kinetics of adsorption. An approximate Gaussian distribution of nanospheres with a mean diameter of 4.5 nm and a standard deviation of 1.1 nm, as determined by atomic force microscopy, is provided by the intrinsic granularity of an ultrathin, gold film, having a nominal thickness of approximately 0.18 nm. The cavity ring-down measurements employ a linear resonator with an intracavity flow cell, which is formed by a pair of ultrasmooth, fused-silica optical flats at Brewsters angle, where the Au film is present on a single flat. The total system intrinsic loss is dominated by the film extinction, while the angled flats alone contribute only approximately 5 x 10(-5)/flat to the total loss. Based on a relative ring-down time precision of 0.1% for ensembles averages of 25 laser shots from a pulsed optical parametric oscillator, the minimum detectable concentrations of PCE and TCE obtained by probing the SPR response are found to be 2 and 7 x 10(-8) mol/L, respectively, based on a 30 s integration time.

Evanescent-wave cavity ring-down spectroscopy: a new platform for thin-film chemical sensors

A new optical technique is described that permits extension of cavity ring-down spectroscopy (CRDS) to surfaces, films, and liquids. As in conventional CRDS, the photon intensity decay time in a low loss optical cavity is utilized to probe optical absorption. Extension to condensed matter is achieved by employing intra-cavity total internal reflection (TIR) to generate an evanescent wave that is especially well suited for thin film chemical sensing. Tow general monolithic cavity designs are discussed: (1) a broadband, TIR-ring cavity that employs photon tunneling to excite and monitor cavity modes, and (2) a narrow bandwidth cavity that utilizes a combination of TIR and highly reflective coatings. Following a qualitative description of design features, a beam transfer matrix analysis is given which yields stability criteria and mode properties as a function of cavity length and mirror radius of curvature. A signal- to-noise ratio calculation is given to demonstrate the evaluation of sensitivity.

Atomic hydrogen induced defect kinetics in amorphous silicon

Near-infrared evanescent-wave cavity ring-down spectroscopy (CRDS) has been applied to study the defect evolution in an amorphous silicon (a-Si:H) thin film subjected to a directed beam of atomic H with a flux of (0.4–2) × 1014 cm−2 s−1. To this end, a 42 ± 2 nm a-Si:H film was grown on the total internal reflection surface of a folded miniature optical resonator by hot-wire chemical vapor deposition. A fully reversible defect creation process is observed, with a nonlinear dependence on H flux, with a time resolution of 33 ms and a relative sensitivity of 10−7. Using polarizing optics, the CRDS signal was split into s- and p-polarized components, which, combined with E-field calculations, provides depth sensitivity. Extensive kinetic modeling of the observed process is used to determine rate constants for the hydrogen–material interactions and defect formation in a-Si:H, as well as revealing a high diffusion coefficient for atomic H on the order of 10−11 cm2 s−1. A novel reaction pathway is proposed, wher...

Nano-scale spectroscopy with ultra-high-Q monolithic optical resonators

A unique and challenging new direction in spectroscopy is realized by using an ultra-low-loss monolithic optical resonator to probe monolayers, thin films, and nano-scale materials. Achievements, optical designs, and future challenges will be discussed.

Recent advances in evanescent-wave cavity ring-down spectroscopy

Evanescent wave cavity ring-down spectroscopy (EW-CRDS) is used to probe surface silanols (SiOH) and hydrogen-bonded water on an amorphous silica surface, revealing considerable ordering. A novel resonator for EW-CRDS of liquids is also described.

Evanescent wave cavity ring-down spectroscopy for trace water detection

We explore the use of evanescent wave cavity ring-down spectroscopy (BW-CRDS) for water detection through a signal-to-noise ratio analysis. Cavity ring-down spectroscopy (CRDS) is an emerging optical absorption technique that employs the mean photon decay time ofa high-finesse optical cavity as the absorption-sensitive observable. EW-CRDS is a novel implementation of CRDS that extends the technique to surfaces, films, and liquids by employing optical cavities which incorporate at least one total-internal-reflection (TIR) mirror. The concomitant evanescent wave is then used to probe the absorption ofan ambient medium at the TIR surface also through a change in the photon decay time. By employing miniature monolithic cavities with ultra-smooth surfaces that are fabricated from ultra-high transmission materials, extreme sub-monolayer detection sensitivity is readily achieved. The detection of water by EW-CRDS with a fused-silica resonator provides an interesting and important application, since the nascent hydroxylated Si02 surface is expected to show a high natural affinity for adsorption ofwater through hydrogen-bonding interactions. Furthermore, in the 13 80 nm spectral region where water absorbs strongly, low-OH-content fused silica has extremely high bulk transmission. These factors potentially provide the basis for a novel water sensor.