Top notch design for fiber-loop cavity ring-down spectroscopy

Fiber-loop cavity ring-down spectroscopy (CRDS) is a highly sensitive spectroscopic absorption technique which has shown considerable promise for the analysis of small-volume liquid samples. We have developed a new light coupling method for fiber-loop CRDS, which overcomes two disadvantages of the technique: low efficiency light coupling into the cavity and high loss per pass. The coupler is based on a 45° reflective notch polished between 10 and 30 μm into the core of a large-core-diameter (365 μm) optical fiber, and allows for nearly 100% light coupling into the cavity, with a low loss per pass (<4%). The coupler has the additional advantage that the input and output light is spatially separated on opposite sides of the fiber. The detection sensitivity of a fiber-loop CRD spectrometer employing the new coupling method is established from ring-down measurements on aqueous rhodamine 6G (Rh6G) at 532 nm. The results are compared with data obtained using the same light source and detector, but a conventional bend-coupled small-core-diameter (50 μm) optical fiber loop. With our new coupler, a detection limit of 0.11 cm(-1) is found, which corresponds to detection of 0.93 μM Rh6G in a volume of only 19 nL. This is an improvement of over an order of magnitude on our bend-coupled small-core optical fiber results, in which a detection limit of 5.3 cm(-1) was found, corresponding to a detection of 43 μM Rh6G in a volume of 20 pL.     

Capillary electrophoresis absorption detection using fiber-loop ring-down spectroscopy

The application of phase-shift, fiber-loop, ring-down spectroscopy (PS-FLRDS) as an on-line detector for capillary electrophoresis (CE) of biomolecules is demonstrated. CE was conducted using a custom-designed capillary/fiber interface coupled to an absorption detector, which is based on the ring-down of an optical signal in a closed fiber waveguide loop. The ring-down times were obtained by measuring the phase difference between intensity modulated light entering and exiting the fiber loop. The incorporation of a microlens to enhance transmission through the sample gap led to an improvement of the sensitivity by up to 80% compared to the square-cut fiber and a reduction in the detection limit. The performance of the PS-FLRDS absorption technique as an online detector was characterized by flow injection through a capillary. Good repeatability and linear response were obtained, and the detection limit using the lensed fiber/capillary interface system was determined to be alpha(min) = 1.6 cm(-1) for an absorption path of approximately 30 microm. PS-FLRDS coupled to CE was also applied to the analysis of human serum albumin (HSA) by using a NIR dye as a noncovalent label. The excess free dye and the dye/protein complex were resolved. The labeling coefficient was determined to be approximately 6, and good repeatability of peak areas (RSD = 8.7%) was obtained for the analysis of HSA. Furthermore, an excellent linear response (R2 > 0.99) was obtained between the peak areas and concentrations of HSA. The detection limit of labeled HSA was determined to be 1.67 microM.     

Direct monitoring of absorption in solution by cavity ring-down spectroscopy

Cavity ring-down spectroscopy is applied to the liquid phase by placing the target solution directly into the optical cavity. We demonstrate that solutions in the cavity can be stirred and more importantly monitored in a flow. We report a minimum detectable absorption of 10(-6) cm(-1) for a range of organic solvents. This detection limit corresponds to picomolar concentrations for strong absorbers.     

Moving beyond traditional UV-visible absorption detection: cavity ring-down spectroscopy for HPLC

We describe the use of liquid-phase continuous-wave cavity ring-down spectroscopy for the detection of an HPLC separation. This technique builds on earlier work by Snyder and Zare using pulsed laser sources and improves upon commercially available UV-visible detectors by a factor of up to 50. The system employs a compact doubled-diode single-mode continuous-wave laser operating at 488 nm and a previously described Brewster's-angle flow cell. Ring-down time constants as long as 5.8 micros were observed with liquid samples in a 0.3-mm path length cell. The baseline noise during an HPLC separation was only 2 x 10(-7) absorbance units (AU) peak to peak, as compared to 1 x 10(-5) AU for a state-of-the-art commercial UV-visible detector.     

Integrated fiber optic incoherent broadband cavity enhanced absorption spectroscopy detector for near-IR absorption measurements of nanoliter samples

An integrated fiber-optic sensor is described that uses incoherent broadband cavity enhanced absorption spectroscopy for sensitive detection of aqueous samples in nanoliter volumes. Absorption was measured in a 100 μm gap between the ends of two short segments of multimode graded-index fiber that were integrated into a capillary using a precision machined V-grooved fixture that allowed for passive fiber alignment. The other ends of the fibers were coated with dielectric mirrors to form a 9.5 cm optical resonator. Light from a fiber-coupled superluminescent diode was directly coupled into one end of the cavity, and transmission was measured using a fiber-coupled silicon photodiode. Dilute aqueous solutions of near infrared dye were used to determine the minimum detectable absorption change of 2.4×10(-4) under experimental conditions in which pressure fluctuations limited performance. We also determined that the absolute minimum detectable absorption change would be 1.6×10(-5) for conditions of constant pressure in which absorption measurement is limited by electronic and optical noise. Tolerance requirements for alignment are also presented.     

基于光纤光栅的波分复用系统设计

设计了两种基于光纤布拉格光栅的波分复用(WDM)系统,一种为基于光纤光栅的四路波分复用系统,另一种为结合光分插复用器(OADM)的四路波分复用系统。给出了基于Opti System的波分复用光传输系统仿真模型,对复用及解复用后的光信号进行仿真得出了光谱图,对传输性能及Q因子、误码率、眼图等参数进行分析。在第二种结构中光纤光栅作为色散补偿器、光反射器和滤波器使用,可以实现任一波长的上载和下路。两种波分复用系统眼图张开良好,误码率均低于10e-9。证明了波分复用系统的正确性和设计方案的可行性。     

Effects of linear birefringence and polarization-dependent loss of supermirrors in cavity ring-down spectroscopy

In cavity ring-down spectroscopy (CRDS), residual or stress-induced birefringence (10(-7)-10(-6) rad) of supermirrors will lift the polarization degeneracy of TEM(00) modes and generate two new polarization eigenstates in the cavity with small resonant frequency splitting (approximately 0.1 kHz); the new eigenstates are nearly linearly polarized. When both modes are excited simultaneously, the intracavity polarization state will evolve as the energy decays in the cavity. Without polarization analysis, such mode beating would not be observable. However, real supermirrors have a linear polarization-dependent loss (dichroism) that leads to a change in the loss rate as the polarization state evolves and thus to deviation from the expected single-exponential decay. We develop a model for the evolution of the intracavity polarization state and intensity for a cavity with both birefringence and polarization-dependent loss in the mirrors. We demonstrate, experimentally, that these parameters (both magnitudes and directions) can be extracted from a series of measurements of the cavity decay and depolarization of the transmitted light.     

Characterization of two types of silanol groups on fused-silica surfaces using evanescent-wave cavity ring-down spectroscopy

Evanescent-wave cavity ring-down spectroscopy has been applied to a planar fused-silica surface covered with crystal violet (CV+) cations to characterize the silanol groups indirectly. A radiation-polarization dependence of the adsorption isotherm of CV+ at the CH3CN/silica interface is measured and fit to a two-site Langmuir equation to determine the relative populations of two different types of isolated silanol groups. CV+ binding at type I sites yields a free energy of adsorption of -29.9 +/- 0.2 kJ/mol and a saturation surface density of (7.4 +/- 0.5) x 10(12) cm(-2), whereas the values of -17.9 +/- 0.4 kJ/mol and (3.1 +/- 0.4) x 10(13) cm(-2) are obtained for the type II sites. The CV+ cations, each with a planar area of approximately 120 A2, seem to be aligned randomly while lying over the SiO- type I sites, thereby suggesting that this type of site may be surrounded by a large empty surface area (>480 A2). In contrast, the CV+ cations on a type II sites are restricted with an average angle of approximately 40 degrees tilted off the surface normal, suggesting that the CV+ cations on these sites are grouped closely together. The average tilt angle increases with increasing concentration of crystal violet so that CV+ cations may be separated from each other to minimize the repulsion of nearby CV+ and SiOH sites.     

Molecular adsorption at silica/CH3CN interface probed by using evanescent wave cavity ring-down absorption spectroscopy: determination of thermodynamic properties

Evanescent wave cavity ring-down absorption spectroscopy is applied to measure the thermodynamic properties of the surface adsorption for neutral trans-4-[4-(dibutylamino)styryl]-1-(3-sulfopropyl) pyridinium (DP) and charged trans-4-[4-(dibutylamino)styryl]-1-methylpyridinium iodide (DMP+ I-) at the silica/CH3CN interface, where the interfacial density is determined by measurement of absorbance. The bulk concentration dependence of the surface density may be characterized with a Langmuir isotherm model, which yields saturated surface density, equilibrium constant, and free energy of adsorption of (7.0 +/- 0.3) x 10(13) cm(-2), (1.3 +/- 0.2) x 10(4) M(-1), and -23.5 +/- 0.4 kJ/mol for DP and (8.9 +/- 0.3) x 10(12) cm(-2), (2.6 +/- 0.7) x 10(4) M(-1), and -25.2 +/- 0.6 kJ/mol for DMP+ I-, respectively. The surface density of the isolated silanol groups may then be estimated in terms of the molecular probe results. The absorption contribution from the bulk solution is a factor of approximately 10(1)-10(2) smaller than the total absorbance measured such that subtraction of the bulk contribution leads to negligible change of the thermodynamic properties. The DP is adsorbed to the SiOH sites by forming hydrogen bonds, while the DMP+ cation is bound to the SiO- sites by electrostatic attraction. Surface forces are also probed by addition of triethylamine (TEA), which is competitive with DP for the silanol sites. When the TEA concentration is increased, the DP surface density is found to decrease, whereas the DMP+ surface density increases. The obtained thermodynamic properties are generally consistent with those measured by second harmonic generation spectroscopy. However, when a tetramethylammonium ((CH3)4N+ Cl-) salt is added, the DMP+ cation behaves differently between these two methods. Formation of an electrical double layer may account for the difference.     

Fiber-optic Fabry-Perot sensors based on a combination of spatial-frequency division multiplexing and wavelength division multiplexing formed by chirped fiber Bragg grating pairs

Effective multiplexing for a very large number of fiber-optic fiber-Bragg-grating-based Fabry-Perot (FBGFP) sensors is proposed that is based on wavelength division multiplexing (WDM) and spatial-frequency division multiplexing (SFDM). For WDM, FBGFP sensors are arranged in different wavelength domains formed by a series of chirped fiber Bragg gratings with different central wavelengths while the sensors with different cavity lengths within the same wavelength domain are multiplexed by use of SFDM because they have different spatial frequencies as a result of their different cavity lengths. In principle, a thousand FBGFP sensors could be multiplexed with such an approach. The experimental results show that a strain accuracy of better than +/-10 microepsilon has been achieved with little cross talk.     

Ultrasensitive absorption spectroscopy with a high-finesse optical cavity and off-axis alignment

A simple and easy to use method that allows high-finesse optical cavities to be used as absorption cells for spectroscopic purposes is presented. This method introduces a single-mode continuous-wave laser into the cavity by use of an off-axis cavity alignment geometry to eliminate systematically the resonances commonly associated with optical cavities, while preserving the absorption signal amplifying properties of such cavities. This considerably reduces the complexity of the apparatus compared with other high-resolution cavity-based absorption methods. Application of this technique in conjunction with either cavity ringdown spectroscopy or integrated cavity output spectroscopy produced absorption sensitivities of 1.5 x 10(-9) cm(-1) Hz(-1/2) and 1.8 x 10(-10) cm(-1) Hz(-1/2), respectively.     

Antireflection-coated blue GaN laser diodes in an external cavity and Doppler-free indium absorption spectroscopy

Commercially available GaN-based laser diodes were antireflection coated in our laboratory and operated in an external cavity in a Littrow configuration. A total tuning range of typically 4 nm and an optical output power of up to 30 mW were observed after optimization of the external cavity. The linewidth was measured with a beterodyne technique, and 0.8 MHz at a sweep time of 50 ms was obtained. The mode-hop-free tuning range was more than 50 GHz. We demonstrated the performance of the laser by detecting the saturated absorption spectrum of atomic indium at 410 nm, allowing observation of well-resolved Lamb dips.     

Isotope 18O/16O ratio measurements of water vapor by use of the 950-nm wavelength region with cavity ring-down and photoacoustic spectroscopic techniques

Two optical methods, cavity ring-down spectroscopy and photoacoustic spectroscopy, are applied to the measurement of the isotope ratio 18O/16O in water-vapor samples with a Nd3+:YAG pumped-dye laser. The combination band of (2v1 + v3) in the 960-nm region of water molecules is investigated for two standard water samples, the Vienna Standard Mean Ocean Water and the Standard Light Antarctic Precipitation. The results demonstrate that the two methods have the potential of compact systems for in-situ measurements of H2O isotope ratio in the environment.     

Measurements of absolute CH concentrations by cavity ring-down spectroscopy and linear laser-induced fluorescence in laminar, counterflow partially premixed and nonpremixed flames at atmospheric pressure

We report quantitative, spatially resolved measurements of methylidyne concentration ([CH]) in laminar, counterflow partially premixed and nonpremixed flames at atmospheric pressure by using both cavity ring-down spectroscopy (CRDS) and linear laser-induced fluorescence (LIF) in the A-X (0, 0) band. Three partially premixed (phiB = 1.45, 1.6, 2.0) flames plus a single nonpremixed methane-air flame are investigated at a global strain rate of 20 s(-1). These quantitative measurements are compared with predictions from an opposed-flow flame code when utilizing two GRI chemical kinetic mechanisms (versions 2.11 and 3.0). The LIF measurements of [CH] are corrected for variations in the electronic quenching rate coefficient by using predicted major species concentrations and temperatures along with quenching cross sections for CH that are available in the literature. The peak CH concentration obtained by CRDS is used to calibrate the quenching-corrected LIF measurements. Excellent agreement is obtained between CH concentration profiles measured by using the CRDS and LIF techniques. The spatial location of the CH layer is very well predicted by GRI 3.0; moreover, the measured and predicted CH concentrations are in good agreement for all the flames of this study.     

Design of differential optical absorption spectroscopy long-path telescopes based on fiber optics

We present a new design principle of telescopes for use in the spectral investigation of the atmosphere and the detection of atmospheric trace gases with the long-path differential optical absorption spectroscopy (DOAS) technique. A combination of emitting and receiving fibers in a single bundle replaces the commonly used coaxial-Newton-type combination of receiving and transmitting telescope. This very simplified setup offers a higher light throughput and simpler adjustment and allows smaller instruments, which are easier to handle and more portable. The higher transmittance was verified by ray-tracing calculations, which result in a theoretical factor threefold improvement in signal intensity compared with the old setup. In practice, due to the easier alignment and higher stability, up to factor of 10 higher signal intensities were found. In addition, the use of a fiber optic light source provides a better spectral characterization of the light source, which results in a lower detection limit for trace gases studied with this instrument. This new design will greatly enhance the usability and the range of applications of active DOAS instruments.     

Acoustically steered and rotated true-time-delay generator based on wavelength-division multiplexing

The acoustically steered and rotated (ASTRO) true-time-delay (TTD) generator, capable of two-dimensional (2D) multiple beam generation without causing extraneous beams, is described. It is based on wavelength-division multiplexing to encode and decode various linear chirp time delays with wavelengths. An array of equally spaced light stripes with linear chirp time delays among them is formed and is subsequently rotated to a desired angle by use of our nonmechanical acousto-optic dove prism, believed to be novel. Our architecture reduces hardware complexity significantly by avoiding redundancy in conventional TTD generators. Experimental results to prove the concept of 2D multiple beam generation are shown. Also, an extension of the system for bidirectional communications is proposed. Various technical issues for practical applications are discussed.     

Off-axis cavity enhanced spectroscopy based on a pulsed quantum cascade laser for sensitive detection of ammonia and ethylene

A pulsed, distributed feedback (DFB) quantum cascade (QC) laser centered at 970 cm(-1) was used in combination with an off-axis cavity enhanced absorption (CEA) spectroscopic technique for the detection of ammonia and ethylene. Here, the laser is coupled into a high-finesse cavity with an optical path length of ～76 m. The cavity is installed into a 53 cm long sample cell with a volume of 0.12 L. The laser is excited with short current pulses (5-10 ns), and the pulse amplitude is modulated with an external current ramp, resulting in a ～0.3 cm(-1) frequency scan. A demodulation approach followed by numerical filtering was utilized to improve the signal-to-noise ratio. We demonstrated detection limits of ~15 ppb and ～20 ppb for ammonia and ethylene, respectively, with less than 5 s averaging time.     

Ultracompact wavelength and polarization directional coupler based on nanowire waveguides

In this paper, we numerically study and propose a wavelength and polarization selective directional coupler based on nanowire waveguides. The plane wave expansion method is used to design the structures and the finite-difference time–domain method is used to evaluate the device performance, which agrees well with each other. The results show that the proposed directional coupler can realize functions of the wavelength and polarization splitters simultaneously without changing the structure parameters. The crosstalks for both wavelength and polarization splitters are lower than ?17 dB at telecommunication wavelengths. The proposed structure has the advantages of small foot print, fabrication without complex nanostructures and complementary metal-oxide-semiconductor compatibility, which is promising for highly dense photonic integration.     

Light profile microscopy based on Raman and wavelength resolved luminescence contrast

Light profile microscopy based on contrast from wavelength resolved Raman and luminescence measurements is demonstrated experimentally for the first time. A Raman/multispectral light profile microscope (RMSLPM) has been constructed based on a line profiling geometry in which the sample is irradiated with a tightly focused laser beam (of ten micrometers radius or less) behind a polished view surface and the resulting line image is dispersed over the wavelength using an imaging spectrograph. The instrumentation developed in this laboratory has a spectral resolution approaching 10 cm(-1) and an (actual) depth independent spatial resolution of 6-8 times the Rayleigh diffraction limit, limited at present by optical aberrations and alignment. The technique has the potential to image at approximately twice the Rayleigh diffraction limit. The spectral signatures reconstructed from a variety of common industrial polymers show excellent agreement with reference spectra from the literature, and may be used to identify individual layers in depth images of unknown materials. RMS-LPM image data based on luminescence contrast have also been used to provide concentration depth profiles of additives and degradation products in injection molded samples of high-density poly(ethylene) (HDPE).     

Determination of inlet transmission and conversion efficiencies for in situ measurements of the nocturnal nitrogen oxides, NO3, N2O5 and NO2, via pulsed cavity ring-down spectroscopy

Pulsed cavity ring-down spectroscopy is a highly sensitive method for direct absorption spectroscopy that has been applied to in situ detection of NO3, N2O5 and NO2 in the atmosphere from a variety of platforms, including ships, aircraft, and towers. In this paper, we report the development of schemes to significantly improve the accuracy of these measurements. This includes the following: (1) an overall improvement in the inlet transmission efficiencies (92 +/- 2% for NO3 and 97 +/- 1% for N2O5) achieved primarily through a reduction in the inlet residence time; and (2) the development of a calibration procedure that allows regular determination of these efficiencies in the field by addition of NO3 or N2O5 to the inlet from a portable source followed by conversion of NO3 to NO2. In addition, the dependence of the instrument's sensitivity and accuracy to a variety of conditions encountered in the field, including variations in relative humidity, aerosol loading, and VOC levels, was systematically investigated. The rate of degradation of N2O5 transmission efficiency on the inlet and filter system due to the accumulation of inorganic aerosol was determined, such that the frequency of filter changes required for accurate measurements could be defined. In the absence of aerosol, the presence of varying levels of relative humidity and reactive VOC were found to be unimportant factors in the instrument's performance. The 1 sigma accuracy of the NO3, N2O5, and NO2 measured with this instrument are -9/+12, -8/+11, +/- 6%, respectively, where the -/+ signs indicate that the actual value is low/high relative to the measurement. The largest contribution to the overall uncertainty is now due to the NO3 absorption cross section rather than the inlet transmission efficiency.