Interferometrian ja valoakustisen spektroskopian soveltaminen taustavapaaseen hivenkaasuanalyysiin

A trace amount of a specific gas in air, breath, or an industrial process can profoundly affect the chemistry and properties of the medium. Therefore, an accurate measurement of the concentration of the trace gas can provide invaluable information. This thesis focuses on the development of trace gas detection methods based on background-free laser absorption spectroscopic techniques. Background-free techniques possess characteristics that greatly benefit the detection of minuscule amounts of gases. These include, for example, scalability with optical power and diminished sensitivity to optical power fluctuations. The thesis deals with two spectroscopic approaches: a novel interferometric method for broadband optical background suppression in absorption spectroscopy, and cantilever-enhanced photo-acoustic spectroscopy. We performed the spectroscopy mainly in the two atmospheric windows of 2000 to 3000 cm^(−1) and 800 to 1200 cm^(−1) found in the mid-infrared region. The employed light sources encompass various broadband and single mode laser devices, including optical parametric oscillators, optical frequency combs, and a quantum cascade laser. The presented results include a demonstration of the interferometric background suppression with a state-of-the-art mid-infrared dual-comb spectrometer. We used the setup to compare the signal-to-noise ratio in direct absorption spectroscopy with and without the background suppression technique. The novel method was found to improve the signal-to-noise ratio by approximately a factor of five. The improvement was limited by the available optical power, and is expected to increase considerably with high power laser light sources. In the cantilever-enhanced photo-acoustic experiments, we investigated the use of high optical power in improving the trace gas detection performance. Using a high power mid-infrared optical parametric oscillator as a laser light source, we reached a record level noise equivalent concentration of 2.5 ppt in 15 s measurement time for hydrogen fluoride. In another work, we reached a record normalised noise equivalent absorption of 1.75×10^(−12) W cm^(−1) Hz^(−1/2) by using an optical build-up cavity to enhance the optical power in the photo-acoustic cell. Lastly, we presented results on hyphenation of the cantilever-enhanced photo-acoustic detector and a gas chromatograph. With the hyphenation, we demonstrated the capability of quantitatively analysing a complex mixture of small to large molecular weight compounds, at a detection sensitivity far better than what can be obtained with a conventional Fourier-transform based infrared detector used in gas chromatography. Quantitative analysis of the sample would have been difficult for laser absorption spectroscopy without the chromatographic separation. The results show a great potential for laser absorption spectroscopy to be used as a detector for gas chromatography in the development of a field deployable multigas analyser.Hivenkaasuilla tarkoitetaan aineita, joita on vain hyvin vähän väliaineessa, kuten ilmassa. Pienistä pitoisuuksista huolimatta hivenkaasuilla voi olla merkittävä vaikutus kaasuseoksen kemiallisiin ominaisuuksiin. Siksi on tärkeää määrittää hivenkaasujen laatu ja pitoisuudet tarkasti. Väitöskirja keskittyy taustavapaiden laserabsorptiospektroskopiaan perustuvien hivenkaasumittausmenetelmien kehittämiseen. Taustavapaalla tarkoitan sitä, että muusta kuin mittauskohteesta tuleva signaali pyritään poistamaan, koska se häiritsee mittausta. Kyseisillä mittausmenetelmillä on erityispiirteitä, jotka sopivat hyvin erittäin pienten pitoisuuksien mittaamiseen. Näihin lukeutuu esimerkiksi havaittavan signaalin voimistuminen mittalaitteen optisen tehon suhteen sekä vähäisempi herkkyys optisen tehon vaihtelulle. Väitöskirjatyössäni hyödynsin kahta spektroskooppista mittausperiaatetta: uudenlaista interferometrista menetelmää laajakaistaisen taustavapaan absorptiospektrin mittaamiseksi sekä läppävahvisteista valoakustista spektroskopiaa. Suoritin mittaukset keski-infrapuna-alueella käyttäen useita erilaisia laservalon lähteitä, kuten optisia parametrivärähtelijöitä, optisia taajuuskampoja sekä kvanttikaskadilasereita. Tutkimustuloksiini lukeutuu kehittämäni uuden interferometrisen taustavapaan mittausmenetelmän havainnollistaminen tämän hetkistä huipputasoa edustavan keski-infrapunakaksoiskampaspektrometrin avulla. Mittauksilla osoitin, että uusi menetelmä parantaa absorptiomittauksen signaali-kohinasuhdetta noin kertoimella viisi verrattuna tavalliseen suoraan absorptiospektroskopiaan. Saavutettua etua rajoitti käytettyjen laserien pieni optinen teho, ja signaali-kohinasuhdetta onkin mahdollista parantaa tulevaisuudessa suurteholasereiden avulla. Tutkimuksissani läppävahvisteisen valoakustisen spektroskopian alalla saavutin ennätyksellisiä havaintoherkkyyksiä hyödyntämällä suuria lasertehoja. Ensimmäisessä tutkimuksessa mittauskohinaa vastaava pitoisuus erittäin haitalliselle fluorivedylle oli 2.5 ppt (2.5 biljoonasosaa) 15 s mittausajalla, kun käytin suuritehoista optista parametrivärähtelijää valonlähteenä. Vastaavasti toisessa tutkimuksessa lasertehoa vahvistavan optisen resonaattorin avulla saavutin 1.75×10^(-12) Wcm^(-1) Hz^(-1/2) suuruisen ennätyksellisen alhaisen normalisoitua mittauskohinaa vastaavan absorption. Erityisen herkkien mittauksien lisäksi kehitin uudenlaisen kaasukromatografian ja läppävahvisteisen valoakustisen spektroskopian yhdistävän menetelmän. Uuden menetelmän avulla on mahdollista analysoida aiempaa luotettavammin monimutkaisia kaasuseoksia, jotka sisältävät sekä pienen että suuren molekyylimassan yhdisteitä. Menetelmä osoittautui jo alustavissa tutkimustuloksissa selvästi herkemmäksi kuin verrattavissa oleva pitkään käytössä ollut kaasukromatografian ja Fourier-muunnos infrapunaspektrometrian yhdistelmä. Tulokset havainnollistavat laserabsorptiospektroskopian soveltuvuuden kehittyneeksi kaasukromatografian ilmaisimeksi etenkin kenttäsovelluksissa, joissa laserien pienestä koosta ja huoltovapaudesta on etua

Cavity-enhanced photoacoustic sensor based on a whispering-gallery-mode diode laser

A cavity-enhanced photoacoustic (CEPA) sensor was developed based on an ultra-narrow linewidth whispering-gallery-mode (WGM) diode laser. A cavity-enhanced photoacoustic module (CEPAM) was designed to match the output beam from the WGM-diode laser, resulting in an increase in the excitation light power, which, in turn, significantly enhanced the photoacoustic signal amplitude. The results show that a signal gain factor of 166 was achieved, which is in excellent agreement with the power enhancement factor of 175 after considering the power transmissivity. The performance of the sensor was evaluated in terms of the detection sensitivity and linearity. A 1σ detection limit of 0.45&thinsp;ppmV for C2H2 detection was obtained at atmospheric pressure with a 1&thinsp;s averaging time.</p

Wavelength modulation photoacoustic spectroscopy: Theoretical description and experimental results

A theoretical description of photoacoustic spectroscopy generated by wavelength modulation of a semiconductor laser source is reported for a Lorentzian absorption line. This model describes the first- and second-harmonic photoacoustic signals produced by a current-modulated semiconductor laser. Combined intensity- and wavelength-modulation is considered with arbitrary phase shift. Experimental results obtained when probing a CO2 absorption line with a 2-μm distributed feedback laser are presented and validate the relevance of the reported model. © 2005 Elsevier B.V. All rights reserved

Development, characterization and miniaturization of a trace gas detection system for NO₂ in air based on photoacoustic spectroscopy

This thesis provides a detailed theoretical discussion about common absorption spectroscopy (AS) and, in particular, about photoacoustic spectroscopy (PAS). The physical concepts of signal generation are illustrated in view of amplitude modulation (AM) and wavelength modulation (WM). Furthermore the advantages and disadvantages of the techniques are presented. As a result, PAS was identified to outclass AS, thus it turned out to be the method of choice in view of developing a miniaturized trace gas sensing application. The theoretical part of this work further outlines various approaches of signal enhancement, e.g. by acoustic and/or mechanical resonance amplification. Besides, several phenomena of signal attenuation are addressed, e.g. acoustic detuning, vibrational-translational (VT) relaxation and vibrational-vibrational (VV) energy transfer processes, which have to be considered with regard to the individual measuring conditions. Simulation and experimental chapters illustrate the pre-development and the practical implementation of a laboratory photoacoustic setup, a portable trace gas monitoring device and various photoacoustic cell (PAC) designs. These include a conventional bulky design, an optimized low-cost 3D printed PAC, a miniaturized quartz enhanced photoacoustic spectroscopic (QEPAS) scheme and a further integrated microelectromechanical system (MEMS) based sensor chip, respectively. Although several parts of this thesis also provide preparatory work for multi-component analysis, nitrogen dioxide (NO2) was used as primary analyte in order to characterize the above mentioned photoacoustic cell designs. This involves acoustic resonance and noise analysis, determination of optimal operating parameters (e.g. gas flow rate and lock-in time constant), performance evaluation (e.g. response behavior, optical performance, calibration characteristics and long-term signal stability) as well as interference studies towards oxygen (O2), carbon dioxide (CO2), humidity (H2O) and acoustic noise. In conclusion, NO2 detection by means of the low-cost 3D printed PAC and the QEPAS configuration even revealed two world record detection limits (1sigma) of 33 pptV and 600 pptV, respectively

Liquid-Phase and Evanescent-Wave Cavity Ring-Down Spectroscopy in Analytical Chemistry

Due to its simplicity, versatility, and straightforward interpretation into absolute concentrations, molecular absorbance detection is widely used in liquidphase analytical chemistry. Because this method is inherently less sensitive than zero-background techniques such as fluorescence detection, alternative, more sensitive measurement principles are being explored. This review discusses one of these: cavity ring-down spectroscopy (CRDS). Advantages of this technique include its long measurement pathlength and its insensitivity to light-source-intensity fluctuations. CRDS is already a wellestablished technique in the gas phase, so we focus on two new modes: liquidphase CRDS and evanescent-wave (EW)-CRDS. Applications of liquidphase CRDS in analytical chemistry focus on improving the sensitivity of absorbance detection in liquid chromatography. Currently, EW-CRDS is still in early stages: It is used to study basic interactions between molecules and silica surfaces. However, in the future this method may be used to develop, for instance, biosensors with high specificity. Copyright © 2009 by Annual Reviews

Novel sources of near- and mid-infrared femtosecond pulses for applications in gas sensing, pulse shaping and material processing

In this thesis the design, construction process and the performance of two femtosecond optical parametric oscillators and one second–harmonic generation femtosecond pulse shaper is described. One oscillator was applied to gas sensing while potential applications of other devices are outlined. ATi:sapphire oscillator was used to pump a periodically–poled lithium niobate– based optical parametric oscillator. This signal–resonant device was configured to produce broadband idler pulses tunable in the range of 2.7–3.4 μm. This wavelength coverage was matched to the ν3 optical absorption band of methane, and Fourier–transform spectroscopy of a CH4:N2 mixture was implemented by employing a mid–IR silica photonic bandgap fibre simultaneously as a gas cell and an optical waveguide. Methane sensing below a 1% concentration was demonstrated and the main limiting factors were identified and improvements suggested. Another optical parametric oscillator was demonstrated which was pumped by a commercial Yb:fibre master oscillator/power amplifier system and was based on a periodically–poled lithium niobate crystal. The signal was tunable between 1.42–1.57 μm and was intended as a source for a subsequent project for waveguide writing in silicon. The oscillator was a novel long–cavity device operating at 15 MHz. The 130 nJ pump pulse energies allowed for 21 nJ signal pulses at a pump power of 2 W. The performance of the oscillator was characterised via temporal and spectral measurements and the next steps of its development are outlined. Finally a pulse shaper based on second harmonic generation in a grating– engineered periodically–poled lithium niobate crystal was demonstrated. Pulses from a 1.53 μm femtosecond Er:fibre laser were compressed and then used as the input to the shaper. The performance of the shaper was tested by performing cross–correlation frequency–resolved optical gating measurements on the output second harmonic pulses and this confirmed the successful creation of multiple pulses and other tailored shapes including square and chirped pulses, agreeing well with theoretical calculations