Gain versus tuning issues to Q-switch with Yb<Superscript>3+</Superscript>:LSO and amplify broad-bandwidth pulses

We report on the development of Incoherent Broadband Cavity Enhanced Absorption Spectroscopy (IBBCEAS) using a blue light emitting diode (LED) for the detection of NO₂ in laboratory ambient air. Absorption of the oxygen collisional pair in the atmosphere was also detected in the same spectral range. The mirror reflectivity was determined using a standard gas sample mixture of NO₂, and calibrated with the help of the absorption spectrum of the oxygen collisional pair in pure oxygen at atmospheric pressure. Optimization of the experimental parameters was investigated and is discussed in detail. For the first time in IBBCEAS involving broadband absorption spectra, averaging time for signal-to-noise ratio enhancement has been optimized using Allan variance plot. 18.1 ppbv NO₂ in laboratory ambient air has been retrieved from the absorption spectra using differential fitting method over a 40 nm spectral region centered at 470 nm. A minimum detection sensitivity of about 2.2 ppbv (1σ) for NO₂ at atmospheric pressure has been achieved using the optimal averaging time of 100 s by means of a high finesse optical cavity formed with two moderate reflectivity (∼99.55%) mirrors. No purging of the cavity mirrors by high purity He or N₂ gas streams was necessary to prevent contamination of the mirror faces for the in situ measurements.     

Deposition and microstructure characterization of atmospheric plasma-sprayed ZnO coatings for NO2 detection

This work studied the possibility of using a sensor based on plasma-sprayed zinc oxide (ZnO) sensitive layer for NO₂ detection. The atmospheric plasma spray process was employed to deposit ZnO gas sensing layer and the obtained coating structure was characterized by scanning electron microscopy and X-ray diffraction analysis. The influences of gas concentration, working temperature, water vapor in testing air on NO₂ sensing performance of the ZnO sensors were studied. ZnO sensors showed a good sensor response and selectivity to NO₂ at an optimal working temperature.     

Simultaneous measurements of atmospheric HONO and NO<Subscript>2</Subscript> via absorption spectroscopy using tunable mid-infrared continuous-wave quantum cascade lasers

Nitrous acid (HONO) is important as a significant source of hydroxyl radical (OH) in the troposphere and as a potent indoor air pollutant. It is thought to be generated in both environments via heterogeneous reactions involving nitrogen dioxide (NO₂). In order to enable fast-response HONO detection suitable for eddy-covariance flux measurements and to provide a direct method that avoids interferences associated with derivatization, we have developed a 2-channel tunable infrared laser differential absorption spectrometer (TILDAS) capable of simultaneous high-frequency measurements of HONO and NO₂. Beams from two mid-infrared continuous-wave mode quantum cascade lasers (cw-QCLs) traverse separate 210 m paths through a multi-pass astigmatic sampling cell at reduced pressure for the direct detection of HONO (1660 cm⁻¹) and NO₂ (1604 cm⁻¹). The resulting one-second detection limits (S/N=3) are 300 and 30 ppt (pmol/mol) for HONO and NO₂, respectively. Our HONO quantification is based on revised line-strengths and peak positions for cis-HONO in the 6-micron spectral region that were derived from laboratory measurements. An essential component of ambient HONO measurements is the inlet system and we demonstrate that heated surfaces and reduced pressure minimize sampling artifacts.     

Laser-based systems for trace gas detection in life sciences

Infrared gas phase spectroscopy is becoming very common in many life science applications. Here we present three types of trace gas detection systems based on CO₂ laser and continuous wave (cw) optical parametric oscillator (OPO) in combination with photoacoustic spectroscopy and cw quantum cascade laser (QCL) in combination with wavelength modulation spectroscopy. Examples are included to illustrate the suitability of CO₂ laser system to monitor in real time ethylene emission from various dynamic processes in plants and microorganisms as well as from car exhausts. The versatility of an OPO-based detector is demonstrated by simultaneous detection of ¹³C-methane and ¹²C-methane (at 3240 nm) at similar detection limits of 0.1 parts per billion by volume. Recent progress on a QCL-based spectrometer using a continuous wave QCL (output power 25 mW, tuning range of 1891–1908 cm^-1) is presented and a comparison is made to a standard chemiluminescence instrument for analysis of NO in exhaled breath. PACS  42.62 Be; 42.62 Fi     

Time-resolved time-dependent photo-acoustic spectroscopy of NO2 in a high frequency multi-resonant cavity

The paper reports the pulsed laser-based time-resolved time-dependent Photo-acoustic (PA) spectroscopy of NO₂ gas in a specially designed multi mode-Resonant PA Cell which is made of Stainless Steel and has a “Q” value of the order of 79. Furthermore the designed cell allows us to excite some of the longitudinal, radial and azimuthal resonance modes of the photo-acoustic signals simultaneously in a very efficient manner. The presence of many newly excited modes occur at 7050 Hz, 10350 Hz and 14650 Hz frequencies is observed for the first time in NO₂ at room temperature. These results are obtained by employing second harmonics i.e. λ=532 nm pulses from Q-switched Nd:YAG laser having 7 ns pulse duration. Some of the new acoustic spectrum lines at higher frequencies are recorded between 0.5–10 ms data acquisition time, which also extends the frequency monitoring range of our system. The study also highlights some of the important aspects such as the decaying behavior of some of these resonant acoustic spectrum lines occur on the expense of others as well as the saturation behavior of some other modes in the NO₂ gas sample. The estimated low level detection limit of NO₂ buffered in air is of the order of 17.9 ppbV.     

Incoherent broad-band cavity-enhanced absorption spectroscopy for simultaneous trace measurements of NO2 and NO3 with a LED source

In the past decade, due to a growing awareness of the importance of air quality and air pollution control, many diagnostic tools and techniques have been developed to detect and quantify the concentration of pollutants such as NO _x , SO _x , CO, and CO₂. We present here an Incoherent Broad-Band Cavity-Enhanced Spectroscopy (IBB-CEAS) set-up which uses a LED emitting around 625 nm for the simultaneous detection of NO₂ and NO₃. The LED light transmitted through a high-finesse optical cavity filled with a gas sample is detected by a low resolution spectrometer. After calibration of the spectrometer with a NO₂ reference sample, a linear multicomponent fit analysis of the absorption spectra allows for simultaneous measurements of NO₂ and NO₃ concentrations in a flow of ambient air. The optimal averaging time is found to be on the order of 400 s and appears to be limited by the drift of the spectrometer. At this averaging time the smallest detectable absorption is 2×10⁻¹⁰ cm⁻¹, which corresponds to detection limits of 600 pptv for NO₂ and 2 pptv for NO₃. This compact and low cost instrument is a promising diagnostic tool for air quality control in urban environments.     

Performance evaluation of a near infrared QEPAS based ethylene sensor

A sensor based on quartz-enhanced photoacoustic spectroscopy (QEPAS) was evaluated for the detection of trace levels of ethylene at atmospheric pressure using a fiber coupled DFB diode laser emitting in the 1.62 μm spectral range. A noise-equivalent QEPAS signal of ∼4 ppm C₂H₄ was achieved for a 0.7 s data acquisition time using wavelength-modulation with a second-harmonic detection scheme on the strongest C₂H₄ absorption peak at 6177.14 cm⁻¹ with an average optical power of ∼15 mW. Improved detection sensitivity of 0.5 and 0.3 ppm C₂H₄ (1σ) was demonstrated using longer averaging time of 70 and 700 s, respectively. Important characteristics for the QEPAS based sensor operation in real-world conditions are presented, particularly the influence of external temperature variations. Furthermore, the response time of the ethylene sensor was measured in different configurations and it is shown that the QEPAS technique can provide a response time in a few seconds range even without active gas flow.     

Optical characterization of CuIn5S8 crystals by ellipsometry measurements

Optical properties of CuIn₅S₈ crystals grown by Bridgman method were investigated by ellipsometry measurements. Spectral dependence of optical parameters; real and imaginary parts of the pseudodielectric function, pseudorefractive index, pseudoextinction coefficient, reflectivity and absorption coefficients were obtained from the analysis of ellipsometry experiments performed in the 1.2–6.2 eV spectral region. Analysis of spectral dependence of the absorption coefficient revealed the existence of direct band gap transitions with energy 1.53 eV. Wemple–DiDomenico and Spitzer–Fan models were used to find the oscillator energy, dispersion energy, zero-frequency refractive index and high-frequency dielectric constant values. Structural properties of the CuIn₅S₈ crystals were investigated using X-ray diffraction and energy dispersive spectroscopy analysis.     

Real-time measurement of nitrogen dioxide in vehicle exhaust gas by mid-infrared cavity ring-down spectroscopy

The application of pulsed cavity ring-down spectroscopy (CRDS) was demonstrated for the measurement of nitrogen dioxide (NO₂) in automotive exhaust gas. The transition of the ν ₃ vibrational band assigned to the antisymmetric stretching mode of NO₂ was probed with a thermoelectrically cooled, pulsed, mid-infrared, distributed feedback, quantum cascade laser (QCL) at 6.13 μm. The measurement of NO₂ in the exhaust gas from two diesel vehicles equipped with different aftertreatment devices was demonstrated using a CRDS-based NO₂ sensor, which employs a HEPA filter and a membrane gas dryer to remove interference from water as well as particulates in the exhaust gas. Stable and sensitive measurement of NO₂ in the exhaust gas was achieved for more than 30 minutes with a time resolution of 1 s.     

Cell viability and measurement of reactive species in gas- and liquid-phase exposed by a microwave-excited atmospheric pressure argon plasma jet

A microwave-excited atmospheric pressure plasma jet (ME-APPJ) was generated utilizing coaxial transmission line resonators with the resonance frequency of 788 MHz. We investigated the effects of the operating parameters such as input power and gas flow rate on the electron excitation temperature and electron density using optical emission spectroscopy. The amounts of various reactive species in the plasma-activated media (PAM) exposed by the ME-APPJ were estimated using colorimetric methods. The PAM was applied to A549 cultured cells and subsequently incubated for a given duration. The concentrations of NO₂⁻ and H₂O₂ in the PAM incubating A549 cells were monitored until 24 h. The reduced cell viability rate was observed on A549 cells incubated in the PAM. The concentrations of NO₂⁻ and H₂O₂ and the viability of A549 cells depended on the operating conditions of ME-APPJ. The cell viability rate exhibited a decrease with increasing power and decreasing gas flow rate. Correlation between the concentrations of gaseous reactive species in the plasma and in the PAM and the cell viability is discussed.     

Facile synthesis of nanostructured CuO for low temperature NO2 sensing

Detection of environmental pollutant and health hazardous, nitrogen dioxide (NO₂) is reported using nanostructured CuO particulates (NPs). Powder X-ray diffraction and field emission scanning electron microscopy were used to probe crystalline phase and morphological details, respectively. Small crystallites of ∼10–12 nm and a strain of 4% were found in the leafy structure of CuO. Raman studies further supported the presence of nanosized CuO phase. This is the first instance of utilizing CuO NPs to detect 5 ppm of NO₂ even at a low operating temperature of 50 °C. The highest sensitivity for NO₂ was observed at 150 °C, for the first time, in CuO NPs. A low activation energy of 0.18 eV was found for sensing process. The CuO NPs sensor responded to NO₂ within a few seconds and recovered totally under a minute. The kinetics of the NO₂ gas adsorption on the CuO film surface was described following the Elovich model.     

Effect of substitution group variation on the optical functions of -5-sulfono-7-(4-x phenyl azo)-8-hydroxy quinoline thin films

-5-Sulfono-7-(4-x phenyl azo)-8-hydroxy quinoline (SAHQ)-x ligands, x = NO₂ or CH₃ or Cl have polycrystalline structure in as synthesized condition. Thermally evaporated thin films of SAHQ-x have crystal structure depending on the substitution group; SAHQ-NO₂ and SAHQ-Cl films have nano-crystalline structure with different degree of crystallinity and SAHQ-CH₃ film has amorphous structure. The changes in optical functions and therefore optical constants with substitution group variation have been calculated by using spectrophotometer measurements of the transmittance and reflectance at nearly normal incidence of light in the wavelength range 200–2500 nm. Substitution group variation influences the refractive index, dispersion parameters, optical functions and bond length of SAHQ. It has no influence on mobility, relaxation time and plasma frequency of charge carriers. The obtained optical energy gaps for SAHQ-x ligands, x = NO₂ or CH₃ or Cl are 1.89, 2 and 2eV, respectively.     

Effect of solution concentration on physicochemical and gas sensing properties of sprayed WO3 thin films

Sub-stoichiometric tungsten trioxide (WO₃) thin films are deposited onto the glass substrates by spray pyrolysis technique using ammonium metatungstate. Effect of solution concentration on structural, morphological, optical, electrical and NO₂ sensing properties of WO₃ thin films is studied. Films are polycrystalline with monoclinic crystal structure and sub-stoichiometric as observed form the XRD and XPS studies, respectively. The SEM and AFM images show micro grained structure and surface roughness increases with increase in solution concentration. The PL studies revealed that the majority of the defects are the oxygen vacancies. From XPS and PL studies it is observed that, oxygen vacancies decrease with increase in solution concentration. The dielectric constant of the films as a function of frequency is in concurrence with resistivity measurements. Films show reproducible and reversible gas response at various operating temperatures and gas concentrations. Highest sensor response (38%) towards 200 ppm NO₂ concentration is observed for the film with 15 mM solution concentration at moderate operating temperature (200 °C). Pd sensitization enhanced gas response to 68% and improved kinetics of the sensor. Films are highly selective towards NO₂ as compared with the various gases such as SO₂, LPG, NH₃ and H₂S.     

Tuning fork enhanced interferometric photoacoustic spectroscopy: a new method for trace gas analysis

A photoacoustic trace gas sensor based on an optical read-out method of a quartz tuning fork is shown. Instead of conventional piezoelectric signal read-out, as applied in well-known quartz-enhanced photoacoustic spectroscopy (QEPAS), an interferometric read-out method for measurement of the tuning fork’s oscillation is presented. To demonstrate the potential of the optical read-out of tuning forks in photoacoustics, a comparison between the performances of a sensor with interferometric read-out and conventional QEPAS with piezoelectric read-out is reported. The two sensors show similar characteristics. The detection limit (L) for the optical read-out is determined to be L _opt=(2598±84) ppm (1σ) compared to L _elec=(2579±78) ppm (1σ) for piezoelectric read-out. In both cases the detection limit is defined by the thermal noise of the tuning fork.     

Mid-infrared dual-comb spectroscopy with 2.4 μm Cr2+:ZnSe femtosecond lasers

The mid-infrared part of the electromagnetic spectrum is the so-called molecular fingerprint region because gases have tell-tale absorption features associated with molecular rovibrations. This region can be for instance exploited to detect small traces of environmental and toxic vapors in atmospheric and industrial applications. Novel Fourier-transform spectroscopy without moving parts, based on time-domain interferences between two comb sources, can in particular benefit optical diagnostics and precision spectroscopy. To date, high-resolution and -sensitivity proof-of-principle experiments have only been reported in the near-infrared region where frequency-comb oscillators are conveniently available. However, as most of the molecular transitions in this region are due to weak overtone bands, this spectral domain is not ideal for sensitive and rapid detection. Here we present a proof-of-principle experiment of frequency-comb Fourier-transform spectroscopy with two Cr²⁺:ZnSe femtosecond oscillators directly emitting in the 2.4 μm mid-infrared region. The acetylene absorption spectrum in the region of the n₁+n₅¹\nu_{1}+\nu_{5}^{1} band, extending from 2370 to 2525 nm, could be recorded within a 10 μs acquisition time without averaging with 12 GHz resolution.     

Simultaneous removal of nitrogen oxides and diesel soot particulate in nano-structured electrochemical reactor

Simultaneous decomposition of nitrogen oxides (NO_x) and solid state graphite particles were carried out using a 8 mol% Y₂O₃ doped ZrO₂ (YSZ) based electrochemical reactor with a nano-structured NO_x selective multilayer cathode and an oxidative porous anode. The ceramic electrochemical cell was prepared by screen-printing a Pt and a NiO–YSZ pastes as cathode layers and a 12 CaO7Al₂O₃–Pt paste as an anode layer on the YSZ electrolyte, respectively. Simultaneous decomposition of NO_x and graphite particles was investigated using the cell with coated graphite particles on the surface of the 12 CaO7Al₂O₃–Pt composite anode in 1000 ppm NO_x–He gas flow under applying DC voltage at 475 °C. The coated graphite particles at the anode were removed completely with 80% NO_x decomposition by electrochemical reactions.     

NO trace gas sensor based on quartz-enhanced photoacoustic spectroscopy and external cavity quantum cascade laser

A gas sensor based on quartz-enhanced photoacoustic detection and an external cavity quantum cascade laser was realized and characterized for trace nitric oxide monitoring using the NO R(6.5) absorption doublet at 1900.075 cm⁻¹. Signal and noise dependence on gas pressure were studied to optimize sensor performance. The NO concentration resulting in a noise-equivalent signal was found to be 15 parts per billion by volume, with 100 mW optical excitation power and a data acquisition time of 5 s.     

Laser ablation of AsxSe100−x chalcogenide glasses: Plume investigations

The use of amorphous chalcogenides offers advantages such as remarkable optical properties like a wide transmission window (∼1-20 μm) depending upon composition, making them suitable for sensitive detection of clinical or environmental changes. They also present interesting high (non)linear refractive indices, photorefractive effects, and other properties interesting for wavelength conversion, all-optical switching or modulation, Raman and parametric amplification, laser sources for mid-IR, etc.Slab waveguides based on chalcogenide amorphous films with good adherence and controlled composition can be obtained using pulsed laser deposition allowing to design and to manufacture complex optical functions on waveguides within a small and compact chip. The aim of this work is to characterize the ejection plume obtained by laser ablation of As_xSe_100−x samples in order to get some insight on the process involved for optimizing the pulsed laser deposition process. The dynamics of the plume has been systematically investigated by ICCD camera fast imaging and space- and time-resolved optical emission spectroscopy for samples of various compositions.     

Structural and electrical properties of fluorine-doped zinc tin oxide thin films prepared by radio-frequency magnetron sputtering

Transparent and conductive thin films of fluorine doped zinc tin oxide (FZTO) were deposited on glass substrates by radio-frequency (RF) magnetron sputtering using a 30 wt% ZnO with 70 wt% SnO₂ ceramic targets. The F-doping was carried out by introducing a mixed gas of pure Ar, CF₄, and O₂ forming gas into the sputtering chamber while sputtering ZTO target. The effect of annealing temperature on the structural, electrical and optical performances of FZTO thin films has been studied. FZTO thin film annealed at 600 °C shows the decrease in resistivity 5.47 × 10⁻³ Ω cm, carrier concentration ∼10¹⁹ cm⁻³, mobility ∼20 cm² V⁻¹ s⁻¹ and an increase in optical band gap from 3.41 to 3.60 eV with increasing the annealing temperatures which is well explained by Burstein–Moss effect. The optical transmittance of FZTO films was higher than 80% in all specimens. Work function (ϕ) of the FZTO films increase from 3.80 eV to 4.10 eV through annealing and are largely dependent on the amounts of incorporated F. FZTO is a possible potential transparent conducting oxide (TCO) alternative for application in optoelectronics.