Phase-shift Cavity Ring-down Spectroscopy Research Articles

Lipoarabinomannan-based tuberculosis diagnosis using a fiber cavity ring down biosensor.

Despite existing for millennia, tuberculosis (TB) remains a persistent global health challenge. A significant obstacle in controlling TB spread is the need for a rapid, portable, sensitive, and accurate diagnostic test. Currently, sputum culture stands as a benchmark test for TB diagnosis. Although highly reliable, it necessitates advanced laboratory facilities and involves considerable testing time. In this context, we present a rapid, portable, and cost-effective optical fiber sensor designed to measure lipoarabinomannan (LAM), a TB biomarker found in patients' urine samples. Our sensing approach is based on the applications of phase shift-cavity ringdown spectroscopy (PS-CRDS) to an optical fiber cavity created by two fiber Bragg gratings. A tapered fiber is spliced inside the optical cavity to serve as the sensing head. We functionalize the tapered fiber surface with anti-LAM antigen CS-35 through a unique chemistry, creating a strong affinity for LAM molecules. We measure the phase difference between the cavity transmission and the reference modulating signal at the cavity output. The measured phase is directly proportional to the injected LAM concentrations in aqueous solutions over the sensing head. Our demonstrated sensor provides a detection limit of 10 pg/mL and a sensitivity of 0.026°/pg/mL. This sensor holds promise for numerous applications in the healthcare sector, particularly in low-resource settings.

Linear cavity tapered fiber sensor using amplified phase-shift cavity ring-down spectroscopy

Phase-shift cavity ring-down spectroscopy (PS-CRDS) enables the measurement of minute fluctuations in optical loss encountered by an intensity modulated laser beam via lock-in demodulation of the accumulated signal phase as the laser beam propagates through the cavity. A linear fiber cavity containing two highly reflective fiber Bragg gratings (FBGs) and a tapered fiber is a favorable cavity geometry for sensor applications due to its compact nature and wide availability of its components at telecom wavelengths. However, due to the optical absorption of water, usage of telecom wavelengths for sensing of aqueous solutions degrades the sensitivity. This problem can be worked around via an optical amplifier placed inside the fiber cavity, compensating for intrinsic cavity losses. In this work, we demonstrate amplified PS-CRDS using such a linear cavity tapered fiber sensor utilizing an optical amplifier that enables the use of thinner tapered fibers, thus achieving higher sensitivities. We also employ continuous laser wavelength sweeps and analyze peak-to-peak PSs of individual cavity modes instead of using laser-cavity mode locking with the Pound–Drever–Hall technique. This enables further simplification of the experimental arrangement without compromising sensor performance. To test the performance of the reported sensor, solutions of varying sucrose concentrations in deionized water were measured systematically by tracking the average peak-to-peak PS ⟨ ϕ pp ⟩ of the cavity modes. Tapered fibers with waist diameters ( D t a p e r ) around 2.2 µm were used during the experiment and limit of detection (LOD) values were measured down to 2.7 µM, corresponding to 1.01 × 10 − 7 R I U . The reported LOD values can be further improved by mechanical stabilization and thermal control of the device by the use of FBGs with higher reflectivity, by applying automatic optical gain control, and by spectral filtering to remove errors caused by amplified spontaneous emission. The presented concentration sensing device can be suitable for developing compact and highly sensitive, label-free optofluidic sensors.

Phase Shift-Cavity Ring Down Spectroscopy in Linear and Active Fiber Cavities for Sensing Applications at 1550 nm

Liquid phase sensing applications at 1550 nm are highly desirable due to widely available off-the-shelf components. Generally, liquids at 1550 nm induce a high absorption loss that limits the overall sensor’s sensitivity and detection limit. One solution is to use an active fiber loop in conjunction with cavity ring down spectroscopy to overcome these absorption losses. However, the amplifier inside the fiber loop suffers from inherent gain fluctuations that limit the sensing system’s overall performance. Here, we provide a novel sensor using the wavelength-scanned phase shift-cavity ring down spectroscopy (PS-CRDS) in conjunction with a linear active fiber cavity that potentially offers a more sensitive solution than traditional fiber loop sensors. We use a tapered fiber as a sensing head inside the active cavity built from fiber Bragg gratings. We derive a theoretical phase shift expression for our system and simulate it using the finite element method to determine optimum tapered fiber diameter for glucose sensing in DI water. Compared to a non-amplified system, we find that our amplified system can increase the sensitivity by fourteen times via the amplifier gain tuning. We also conduct experimental measurements using 0-15.5 mM glucose solutions and find them in excellent agreement with our theoretical predictions. Experimentally we obtain the sensor’s sensitivity of 0.768°/mM (1164°/RIU) and detection limit of 0.75 mM ( <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$4.5\times 10^{-4}$ </tex-math></inline-formula> RIU) without any temperature stabilization in the system. We anticipate that the present work will find a wide range of sensing applications in fiber cavities, ring resonators, and other microcavity structures.

Linear cavity tapered fiber sensor using mode-tracking phase-shift cavity ring-down spectroscopy

Phase-shift cavity ring-down spectroscopy (PS-CRDS) is an alternative CRDS approach that allows the detection of minute changes in cavity losses by measurement of the phase shift experienced by a modulated laser as it propagates through a high-quality factor cavity. Fiber loop resonators and microresonators have been employed in previous PS-CRDS demonstrations for liquid phase applications. Here we employ a tapered fiber-based linear fiber cavity for the demonstration of a highly sensitive sensor for sucrose concentration in water using PS-CRDS. Our linear fiber cavity has a small cavity length ( ∼ 1.25 m ) that enables the observation and tracking of individual cavity modes in transmission and phase spectra recorded during laser sweeps. Hence, we eliminate the need for Pound–Drever–Hall locking of the laser source to the cavity resonance and thus provide a simpler experimental scheme. We analyze the recorded data sets to track the changes in phase shifts observed only when the laser wavelength is in resonance with the cavity modes. Such a mode-tracking PS-CRDS approach reveals limit of detection values less than around 400 µM, better than the performance of previously demonstrated PS-CRDS sucrose concentration sensors employing fiber loop resonators. The sensitivity of our sensor critically depends on the fiber taper diameter and can reach up to around 6°/1 mM Suc. for 3.2 µm taper diameter at 6 MHz modulation frequency using fiber Bragg gratings (FBGs) with reflectivities around 86%. This value can be further increased by employing FBGs with higher reflectivities or fiber tapers with smaller diameters provided that the cavity loss due to water absorption is compensated with an amplifier.

Phase-shift feedback cavity ring-down spectroscopy.

Phase-shift cavity-enhanced techniques have been used to measure optical losses with relatively simple electronics. Instead of measuring the phase shift, in this work the intensity modulation frequency is varied using feedback to keep the phase shift locked to a target value. The modulation frequency then becomes a signal from which cavity losses can be estimated. The technique is applied with a super luminescent diode to measure losses resulting from the addition of acetylene to a cavity containing nitrogen at ambient temperature and pressure. The technique, phase-shift feedback cavity ring down, is compared to phase-shift cavity ring-down spectroscopy.

Analytical expressions for waveguide-coupled phase shift microcavity ring down spectroscopy

Phase shift cavity ring down spectroscopy (PS-CRDS) in conjunction with microcavities provides a highly sensitive approach for sensing applications. However, there have been no complete and accurate analytical expressions demonstrated so far for PS-CRDS based upon measurement of the transmitted waveguide signal only in a microcavity–waveguide system. For determining the ring down time of a microcavity, currently researchers employ PS-CRDS measurements either at multiple modulation frequencies or in the Rayleigh backscattered regime in conjunction with PS-CRDS measurements in the transmission mode of a microcavity–waveguide system. Here, we develop analytical expressions for PS-CRDS in waveguide-coupled microcavities by utilizing the coupled mode theory. Our mathematical treatment allows us to determine the ring down time of a microcavity by measuring a signal in the transmission mode (waveguide signal) only. The derived equations are also validated numerically and experimentally. The present work will find wide applications in sensors and modulators based upon microcavities.

English

A phase-shift cavity ring-down spectroscopy (PS-CRDS) experimental set-up has been established using a broadband diode laser for the measurement of phase shift due to absorption of NO 2 in a sealed off cavity ringdown cell. The PS-CRDS technique is verified by optimising various parameters of CRDS cavity and excitation laser. The PS-CRDS signals were measured on the first harmonics using a lock-in-amplifier. The square modulated laser pulses were used in the experiment to obtain the decay time. Measurements of the signal strengths at different CRDS cavity lengths wre also carried out to verify the detection sensitivity for ppm level concentration measurement of trace gases.

Absolute absorption cross-section measurement of a submonolayer film on a silica microresonator

Conventional absorption spectroscopy is not nearly sensitive enough for quantitative overtone measurements on submonolayer coatings. While cavity-enhanced absorption detection methods using microresonators have the potential to provide quantitative absorption cross sections of even weakly absorbing submonolayer films, this potential has not yet been fully realized. To determine the absorption cross section of a submonolayer film of ethylene diamine (EDA) on a silica microsphere resonator, we use phase-shift cavity ringdown spectroscopy simultaneously on near-IR radiation that is Rayleigh backscattered from the microsphere and transmitted through the coupling fiber taper. We then independently determine both the coupling coefficient and the optical loss within the resonator. Together with a coincident measurement of the wavelength frequency shift, an absolute overtone absorption cross section of adsorbed EDA, at submonolayer coverage, was obtained and was compared to the bulk value. The smallest quantifiable absorption cross section is σmin=2.7×10−12 cm2. This absorption cross section is comparable to the extinction coefficients of, e.g., single gold nanoparticles or aerosol particles. We therefore propose that the present method is also a viable route to absolute extinction measurements of single particles.

Erratum: Phase-shift cavity ring-down spectroscopy on a microsphere resonator by Rayleigh backscattering [Phys. Rev. A87, 053843 (2013)

Erratum: Phase-shift cavity ring-down spectroscopy on a microsphere resonator by Rayleigh backscattering [Phys. Rev. A<b>87</b>, 053843 (2013)

Publisher's Note: Phase-shift cavity ring-down spectroscopy on a microsphere resonator by Rayleigh backscattering [Phys. Rev. A87, 053843 (2013)

Publisher's Note: Phase-shift cavity ring-down spectroscopy on a microsphere resonator by Rayleigh backscattering [Phys. Rev. A<b>87</b>, 053843 (2013)

Phase-shift cavity ring-down spectroscopy on a microsphere resonator by Rayleigh backscattering

The optical ring-down time in a silica microsphere resonator is measured using phase-shift cavity ring-down spectroscopy. When detecting Rayleigh backscattered light that is coupled into the input waveguide it is found that the shift of the modulation phase angle, $\ensuremath{\Delta}\ensuremath{\phi}$, is approximately linearly dependent on the amplitude modulation frequency. The microresonator therefore behaves as if it was a delay line. A model involving two different time scales for the buildup of the Rayleigh backscattered light and the decay of the whispering gallery modes is used to explain the observations.

Accurate determination of the quality factor and tunneling distance of axisymmetric resonators for biosensing applications

Due to ultra high quality factor (10(6) - 10(9)), axisymmetric optical microcavities are popular platforms for biosensing applications. It has been recently demonstrated that a microcavity biosensor can track a biodetection event as a function of its quality factor by using phase shift cavity ring down spectroscopy (PS-CRDS). However, to achieve maximum sensitivity, it is necessary to optimize the microcavity parameters for a given sensing application. Here, we introduce an improved finite element model which allows us to determine the optimized geometry for the PS-CRDS sensor. The improved model not only provides fast and accurate determination of quality factors but also determines the tunneling distance of axisymmetric resonators. The improved model is validated numerically, analytically, and experimentally.

High sensitivity liquid phase measurements using broadband cavity enhanced absorption spectroscopy (BBCEAS) featuring a low cost webcam based prism spectrometer

Cavity enhanced techniques enable high sensitivity absorption measurements in the liquid phase but are typically more complex, and much more expensive, to perform than conventional absorption methods. The latter attributes have so far prevented a wide spread use of these methods in the analytical sciences. In this study we demonstrate a novel BBCEAS instrument that is sensitive, yet simple and economical to set up and operate. We use a prism spectrometer with a low cost webcam as the detector in conjunction with an optical cavity consisting of two R = 0.99 dielectric mirrors and a white light LED source for illumination. High sensitivity liquid phase measurements were made on samples contained in 1 cm quartz cuvettes placed at normal incidence to the light beam in the optical cavity. The cavity enhancement factor (CEF) with water as the solvent was determined directly by phase shift cavity ring down spectroscopy (PS-CRDS) and also by calibration with Rhodamine 6G solutions. Both methods yielded closely matching CEF values of ~60. The minimum detectable change in absorption (αmin) was determined to be 6.5 × 10(-5) cm(-1) at 527 nm and was limited only by the 8 bit resolution of the particular webcam detector used, thus offering scope for further improvement. The instrument was used to make representative measurements on dye solutions and in the determination of nitrite concentrations in a variation of the widely used Griess Assay. Limits of detection (LOD) were ~850 pM for Rhodamine 6G and 3.7 nM for nitrite, respectively. The sensitivity of the instrument compares favourably with previous cavity based liquid phase studies whilst being achieved at a small fraction of the cost hitherto reported, thus opening the door to widespread use in the community. Further means of improving sensitivity are discussed in the paper.

Derivation of New Equations for Phase-Shift Cavity Ring-Down Spectroscopy

Current phase-shift cavity ring-down spectroscopy (PS-CRDS) experiments make use of equations originally developed for fluorescence studies. As these equations fail to take the length of the optical cavity and the superposition of reflecting beams into account, they lose validity as the length of the cavity increases. A new set of equations, based solely on the principles of PS-CRDS, is developed for determining the ring-down time from either the phase shift or the intensity of the waveform exiting the cavity. It is shown that the PS-CRDS equations reduce to those developed for fluorescence study for short cavities. The new equations provide a more accurate method in determining the characteristic ring-down time and phase shift for long cavities, especially fiber optic cavities, which is promising in on-site chemical sensing.

A calibration method for broad-bandwidth cavity enhanced absorption spectroscopy performed with supercontinuum radiation

An efficient calibration method has been developed for broad-bandwidth cavity enhanced absorption spectroscopy. The calibration is performed using phase shift cavity ring-down spectroscopy, which is conveniently implemented through use of an acousto-optic tunable filter (AOTF). The AOTF permits a narrowband portion of the SC spectrum to be scanned over the full high-reflectivity bandwidth of the cavity mirrors. After calibration the AOTF is switched off and broad-bandwidth CEAS can be performed with the same light source without any loss of alignment to the set-up. We demonstrate the merits of the method by probing transitions of oxygen molecules O2 and collisional pairs of oxygen molecules (O2)2 in the visible spectral range.

Absorption detection using optical waveguide cavities

Cavity ring-down spectroscopy is a spectroscopic method that uses a high quality optical cavity to amplify the optical loss due to the light absorption by a sample. In this presentation we highlight two applications of phase-shift cavity ring-down spectroscopy that are suited for absorption measurements in the condensed phase and make use of waveguide cavities. In the first application, a fiber loop is used as an optical cavity and the sample is introduced in a gap in the loop to allow absorption measurements of nanoliters of solution at the micromolar level. A second application involves silica microspheres as high finesse cavities. Information on the refractive index and absorption of a thin film of ethylene diamine on the surface of the microresonator is obtained simultaneously by the measurements of the wavelength shift of the cavity mode spectrum and the change in optical decay time, respectively.

Phase-shift cavity ring-down spectroscopy using mid-IR light from a difference frequency generation PPLN waveguide

Approximately 200 microW of mid-infrared (mid-IR) light around 3081 cm(-1), produced by difference frequency generation (DFG) in a periodically poled lithium niobate crystal waveguide, has been used for phase-shift cavity ring-down spectroscopy measurements. The overlapping (12)C(2)H(4) (R)P(0)(14) and (P)R(6)(10) and (12)CH(2) (13)CH(2) (P)Q(3)(10) rotational lines of the nu(9) fundamental ethene vibrational band at 3081.0016 cm(-1) were probed in proof-of-principle experiments, and ethene detection was demonstrated with a minimum absorption coefficient of 1.4 x 10(-7) cm(-1) (approximately 4 min acquisition time). The compact DFG system, with a >35 cm(-1) tuning range, has a considerable potential for use in trace gas detection and in molecular spectroscopy.

Chemical sensing using a polymer coated long-period fiber grating interrogated by ring-down spectroscopy

An etched long-period grating was used as a refractive index sensor for vapours of four volatile organic compounds, i.e. m-xylene, cyclohexane, trichloroethylene and commercial gasoline. The sensitivity to the vapours was further increased by solid-phase microextraction into a coating made of polydimethylsiloxane (PDMS)/polymethyl-octylsiloxane (PMOS) co-polymer. By further amplification of the optical loss in an optical cavity made of two identical fiber-Bragg gratings and interrogation by phase-shift cavity ring-down spectroscopy we could detect and distinguish xylene (detection limit: 134ppm) from trichloroethylene (3300ppm), cyclohexane (1850ppm) and gasoline (10,500ppm).

Measurement of multi-exponential optical decay processes by phase-shift cavity ring-down

Multi-exponential decay waveforms are common occurrences in cavity ring-down spectroscopy and the respective ring-down times are typically obtained by fitting the ring-down waveform to the sum of exponential decay functions. In phase-shift cavity ring-down (CRD) spectroscopy the measurement of a single phase angle will not provide sufficient information and needs to be complemented by either intensity measurements or phase angle measurements at different modulation frequencies. Here, a formalism analogous to that developed for fluorescence lifetime spectroscopy is adapted to the phase-shift CRD technique and is tested for two types of waveguide CRD systems: (1) a single-mode fiber cavity in which light is confined by two identical Fiber Bragg Gratings and (2) a multimode fiber loop. By measuring the phase angle at different modulation frequencies, lifetimes for up to three different decay processes were obtained.

A broadband absorption spectrometer using light emitting diodes for ultrasensitive, in situ trace gas detection

A broadband absorption spectrometer has been developed for highly sensitive and target-selective in situ trace gas measurements. The instrument employs two distinct modes of operation: (i) broadband cavity enhanced absorption spectroscopy (BBCEAS) is used to quantify the concentration of gases in sample mixtures from their characteristic absorption features, and (ii) periodic measurements of the cavity mirrors' reflectivity are made using step-scan phase shift cavity ringdown spectroscopy (PSCRDS). The latter PSCRDS method provides a stand-alone alternative to the more usual method of determining mirror reflectivities by measuring BBCEAS absorption spectra for calibration samples of known composition. Moreover, the instrument's two modes of operation use light from the same light emitting diode transmitted through the cavity in the same optical alignment, hence minimizing the potential for systematic errors between mirror reflectivity determinations and concentration measurements. The ability of the instrument to quantify absorber concentrations is tested in instrument intercomparison exercises for NO(2) (versus a laser broadband cavity ringdown spectrometer) and for H(2)O (versus a commercial hygrometer). A method is also proposed for calculating effective absorption cross sections for fitting the differential structure in BBCEAS spectra due to strong, narrow absorption lines that are under-resolved and hence exhibit non-Beer-Lambert law behavior at the resolution of the BBCEAS measurements. This approach is tested on BBCEAS spectra of water vapor's 4v+delta absorption bands around 650 nm. The most immediate analytical application of the present instrument is in quantifying the concentration of reactive trace gases in the ambient atmosphere. The instrument's detection limits for NO(3) as a function of integration time are considered in detail using an Allan variance analysis. Experiments under laboratory conditions produce a 1sigma detection limit of 0.25 pptv for a 10 s acquisition time, which improves with further signal averaging to 0.09 pptv in 400 s. Finally, an example of the instrument's performance under field work conditions is presented, in this case of measurements of the sum of NO(3)+N(2)O(5) concentrations in the marine boundary layer acquired during the Reactive Halogens in the Marine Boundary Layer field campaign.