High-speed vertical-cavity surface-emitting laser (VCSEL) absorption spectroscopy of ammonia (NH<Subscript>3</Subscript>) near 1.54 μm

A single-frequency VCSEL has been used for the first time for high-resolution spectroscopy near 1.5 μm. The incorporated buried-tunnel-junction technology enabled the realization of a long-wavelength InGaAlAs/InP VCSEL with low threshold current (0.925 mA), high output powers (0.576 mW) and low series resistance (60 Ω). The high-speed tuning capability of the long-wavelength VCSEL was investigated and used to conduct high-speed absorption spectroscopy. The peak tuning speed was measured to be 3.4 cm^-1/μs and a 4.5-cm^-1-wide NH₃ spectrum was recorded in 2 μs. The VCSEL was used to measure highly resolved low-pressure spectra for pressures ranging from 9.6 mbar to 1 bar. The measured Doppler-broadened linewidth of 0.02 cm^-1 agrees within 3% with the theoretical calculations. The availability and various advantages of 1.3–2-μm single-frequency VCSELs as compared to edge-emitting diode lasers, such as a large current tuning range even at very high tuning frequencies, and low production costs, should significantly expand the application fields for near-infrared laser gas sensors. Received: 17 July 2002 / Revised version: 4 December 2002 / Published online: 12 May 2003 RID="*" ID="*"Corresponding author. Fax: +43-1/58801-15999, E-mail: Gerhard@Totschnig.com     

CH4/air/SO2 premixed flame spectroscopy with a 7.5-μm diode laser

As sulfur dioxide (SO₂) is often involved in combustion processes, we present here SO₂-concentration measurements in the post-flame region of a CH₄/air/SO₂ premixed flame. SO₂ concentrations were deduced from high-resolution absorption spectra recorded with a mid-infrared tunable diode-laser (TDL) source operating at liquid nitrogen temperature. Single-mode, continuous frequency tuning around 1384.5 cm^-1 (or 7.5 μm) is achieved by a fine TDL temperature ramp. These experiments lead us to develop in situ combustion-pollutant measurements with compact apparatus. We show that this non-intrusive method is efficient for detection and allows the retrieval of SO₂ concentration and temperature. Received: 19 February 2001 / Revised version: 18 April 2001 / Published online: 7 June 2001     

Mid-infrared trace gas detection using continuous-wave difference frequency generation in periodically poled RbTiOAsO4

A tunable mid-infrared continuous-wave (cw) spectroscopic source in the 3.4–4.5 μm region is reported, based on difference frequency generation (DFG) in a quasi-phase-matched periodically poled RbTiOAsO₄ (PPRTA) crystal, DFG power levels of 10 μW were generated at approximately 4 μm in a 20-mm long PPRTA crystal by mixing two cw single-frequency Ti:Al₂O₃ lasers operating near 713 nm and 871 nm, respectively, using a laser pump power of 300 mW. A quasi-phase-matched infrared wavelength-tuning bandwidth (FWHM) of ∼12 cm^-1 and a temperature tuning rate of 1.02 cm^-1/°C were achieved. Experimental details regarding the feasibility of trace gas detection based on absorption spectroscopy of CO₂ in ambient air using this DFG radiation source are also described. Received: 23 October 2000 / Revised version: 22 January 2001 / Published online: 27 April 2001     

Tunable diode laser spectroscopy of ethylene oxide near 1693 nm

We describe the application of the vertical-cavity surface-emitting laser (VCSEL) to absorption spectroscopy of the ethylene oxide (EO) Q-branch near 1693 nm. The VCSEL was electrically scanned over spectral intervals of up to ∼13 cm⁻¹ at a 1 kHz repetition rate. A methane absorption line at 5903.3 cm⁻¹ and Fabry–Pérot etalon with a free spectral range of 0.4 cm⁻¹ were used to calibrate frequency scale. The EO was mixed with ambient air, and total gas pressure and mixing ratios were varied from a few mbar to 1 bar and from ∼10² to 10⁵ parts per million, respectively. A rapid roll off of EO absorbance at 5903.7 cm⁻¹ was observed at gas pressures below ∼0.5 bar. A linear dependence of EO peak absorbance on mixing ratio was found at a total gas pressure of 1 bar. We conclude that monolithic VCSELs operating near 1693 nm could be used in EO sensors with a detection limit in the ppb range.     

High-resolution sum-frequency generation from alkylsiloxane monolayers

During the last decade, infrared optical sum-frequency generation (SFG) has been demonstrated to be a valuable technique for acquiring vibrational spectra of molecules at interfaces. However, the instrumentation that most frequently has been employed, which is based upon picosecond-scale pulse-width lasers, is fundamentally limited in the spectral resolution that can be achieved (typically ∼6 cm^-1). We have optimized an older technology, based on a nanosecond-scale pulse-width laser, which enables the infrared frequency to be specified to within 0.2 cm^-1. Exploiting this advantage, we have observed previously unrecognized features in the SFG spectrum of self-assembled monolayers. We demonstrate this through experiments performed on rubbed octadecylsiloxane (ODS) on glass, a system of considerable importance in liquid-crystal-display technology. Received: 14 August 2001 / Revised version: 15 January 2002 / Published online: 14 March 2002     

Mid-infrared generation and spectroscopy with a PPLN ridge waveguide

We have utilised a periodically poled LiNbO₃ crystal with a waveguide structure to produce up to 146 μW of mid-IR radiation around 2976 cm^-1 by difference frequency mixing of 1064 nm pump radiation with 1558 nm signal radiation. A conversion efficiency of 45% W^-1 is achieved within a crystal of length 50 mm, and temperature tuning curves are reported. The resultant idler radiation is exploited for high resolution absorption studies of both methane and methanethiol. The absorption cross-sections for methanethiol in the region of 2979 cm^-1 are measured and found to be ∼10^-19 cm², the relevance of these results to breath and headspace analysis of clinical samples containing volatile sulphur compounds is briefly discussed. PACS 42.62.Fi; 42.65.Ky     

Telecom-grade fiber laser-based difference-frequency generation and ppb-level detection of benzene vapor in air around 3 μm

We report on the development of a field deployable compact laser instrument tunable over ∼232 cm⁻¹ from 3.16 to 3.41 μm (2932.5–3164.5 cm⁻¹) for chemical species monitoring at the ppb-level. The laser instrument is based on widely tunable continuous-wave difference-frequency generation (DFG), pumped by two telecom-grade fiber lasers. DFG power of ∼0.3 mW near 3.3 μm with a spectral purity of ∼3.3 MHz was achieved by using moderate pumping powers: 408 mW at 1062 nm and 636 mW at 1570 nm. Spectroscopic performance of the developed DFG-based instrument was evaluated with direct absorption spectra of ethylene at 3.23 μm (∼3094.31 cm⁻¹). Absorption spectra of vapor-phase benzene near 3.28 μm (∼3043.82 cm⁻¹) were recorded with Doppler-limited resolution. Line intensities of the most intense absorption lines of the ν ₁₂ band near 3043.8 cm⁻¹ were determined to support development of sensitive mid-infrared trace gas detection of benzene vapor in the atmosphere. Detection of benzene vapor in air at different concentration levels has been performed for the first time using multi-pass cell enhanced direct absorption spectroscopy at ∼3.28 μm with a minimum detectable concentration of 50 ppb (1σ).     

Off-axis continuous-wave cavity-enhanced absorption spectroscopy of narrow-band and broadband absorbers using red diode lasers

We present an application of continuous-wave (cw) cavity-enhanced absorption spectroscopy (CEAS) with off-axis alignment geometry of the cavity and with time integration of the cavity output intensity for detection of narrow-band and broadband absorbers using single-mode red diode lasers at λ=687.1 nm and λ=662 nm, respectively. Off-axis cw CEAS was applied to kinetic studies of the nitrate radical using a broadband absorption line at λ=662 nm. A rate constant for the reaction between the nitrate radical and E-but-2-eneof (3.78±0.17)×10^-13 cm³ molecule^-1 s^-1 was measured using a discharge-flow system. A nitrate-radical noise-equivalent (1σ≡ root-mean-square variation of the signal) detection sensitivity of 5.5×10⁹ molecule cm^-3 was achieved in a flow tube with a diameter of 4 cm and for a mirror reflectivity of ∼99.9% and a lock-in amplifier time constant of 3 s. In this case, a noise-equivalent fractional absorption per one optical pass of 1.6×10^-6 was demonstrated at a detection bandwidth of 1 Hz. A wavelength-modulation technique (modulation frequency of 10 kHz) in conjunction with off-axis cw CEAS has also been used for recording 1f- and 2f-harmonic spectra of the ^RR(15) absorption of the b¹Σ_g ⁺-X³Σ_g ^- (1,0) band of molecular oxygen at =14553.947 cm^-1. Noise-equivalent fractional absorptions per one optical pass of 1.35×10^-5, 6.9×10^-7 and 1.9×10^-6 were obtained for direct detection of the time-integrated cavity output intensity, 1f- and 2f-harmonic detection, respectively, with a mirror reflectivity of ∼99.8%, a cavity length of 0.22 m and a detection bandwidth of 1 Hz. Received: 24 June 2002 / Revised version: 12 August 2002 / Published online: 15 November 2002 RID="*" ID="*"Corresponding author. Fax: +44-1865/275410, E-mail: vlk@physchem.ox.ac.uk     

Photoacoustic gas sensing employing fundamental and frequency-doubled radiation of a continuously tunable high-pressure CO2 laser

We present the first photoacoustic spectrometer for gas sensing employing both the fundamental and the frequency-doubled radiation of a continuously tunable high-pressure CO₂ laser with room temperature operation. A quasi-phase-matched diffusion-bonded GaAs crystal is used in the system for second-harmonic generation. A pulsed photoacoustic detection scheme with a non-resonant cell, equipped with an 80-microphone array, is employed. The wide continuous tuning range in the fundamental (9.2–10.7 μm) and the frequency-doubled (4.6–5.35 μm) regimes, together with the narrow linewidth of 540 MHz (0.018 cm^-1) for the 10-μm region and of 1050 MHz (0.0315 cm^-1) for the 5-μm region, allow the measurement of gas mixtures, individual species and isotope discrimination. This is illustrated with measurements on NO and CO₂. The measured isotope ratio ¹⁵ NO/¹⁴ NO=(3.58±0.55)×10^-3 agrees well with the literature (3.700×10^-3) and demonstrates the good selectivity of the system. Received: 30 April 2002 / Revised version: 10 June 2002 / Published online: 2 September 2002 RID="*" ID="*"Corresponding author. Fax: +41-1/633-1077, E-mail: sigrist@iqe.phys.ethz.ch     

Cavity-enhanced absorption: detection of nitrogen dioxide and iodine monoxide using a violet laser diode

We present an application of cavity-enhanced absorption spectroscopy with an off-axis alignment of the cavity formed by two spherical mirrors and with time integration of the cavity-output intensity for detection of nitrogen dioxide (NO₂) and iodine monoxide (IO) radicals using a violet laser diode at λ=404.278 nm. A noise-equivalent (1σ≡ root-mean-square variation of the signal) fractional absorption for one optical pass of 4.5×10^-8 was demonstrated with a mirror reflectivity of ∼0.99925, a cavity length of 0.22 m and a lock-in-amplifier time constant of 3 s. Noise-equivalent detection sensitivities towards nitrogen dioxide of 1.8×10¹⁰ molecule cm^-3 and towards the IO radical of 3.3×10⁹ molecule cm^-3 were achieved in flow tubes with an inner diameter of 4 cm for a lock-in-amplifier time constant of 3 s. Alkyl peroxy radicals were detected using chemical titration with excess nitric oxide (RO₂+NO→RO+NO₂). Measurement of oxygen-atom concentrations was accomplished by determining the depletion of NO₂ in the reaction NO₂+O→NO+O₂. Noise-equivalent concentrations of alkyl peroxy radicals and oxygen atoms were 3×10¹⁰ molecule cm^-3 in the discharge-flow-tube experiments. Received: 4 February 2003 / Revised version: 10 March 2003 / Published online: 12 May 2003 RID="*" ID="*"Corresponding author. Fax: +44-1865/275-410, E-mail: vlk@physchem.ox.ac.uk     

Simultaneous measurement of liquid water film thickness and vapor temperature using near-infrared tunable diode laser spectroscopy

A fiber-based multiplexed tunable diode-laser absorption sensor with three near-infrared distributed-feedback diode lasers at ∼1.4 μm is used for simultaneous nonintrusive measurements of liquid water film thickness and vapor-phase temperature. Water film thicknesses are derived from broad-band absorption determined at two fixed wavelengths while gas-phase temperature above the film is obtained via two-line thermometry using the fast wavelength tuning with line-integrating absorption. Probing the liquid film at two wavelengths with significantly different liquid-phase absorption cross sections allows discriminating against additional signal losses due to surface fowling, reflection, and beam steering. The technique is demonstrated for liquid layers of defined thicknesses and in time-resolved measurements of evaporating films.     

Nanocrystalline silicon thin-film transistors with 50-nm-thick deposited channel layer, 10 cm2V-1s-1 electron mobility and 108 on/off current ratio

Thin-film transistors were made using 50-nm-thick directly deposited nanocrystalline silicon channel layers. The transistors have a coplanar top gate structure. The nanocrystalline silicon was deposited from discharges in silane, hydrogen and silicon tetrafluoride. The transistors combine a high electron field effect mobility of ∼10 cm² V^-1s^-1 with a low ‘off’ current of ∼10^-14 A per μm of channel length and an ‘on’/‘off’ current ratio of ∼10⁸. This result shows that transistors made from directly deposited silicon can combine high mobility with low ‘off’ currents. Received: 28 May 2001 / Accepted: 30 May 2001 / Published online: 30 August 2001     

Efficient J=0-1 soft-X-ray lasing in neon-like ions at pump powers below 250 GW

2 . By using a 0.7% prepulse that precedes the main pulse by 5 ns and applying a total pump energy of 100 J or less, the J=0-1 lasing is at least one order of magnitude higher than the non-lasing background. For the 32.6-nm line of Ti, the 25.5-nm line of Fe, and the 23.1-nm line of Ni, gain coefficients of (±) 4.20.4cm^-1, (±) 3.90.3cm^-1, and (±) 3.60.6cm^-1, respectively, were measured for 2.4-cm-long curved targets, resulting in gain–length products of ∼10. Angle-resolved spectra indicate a beam divergence of 3 mrad (FWHM), typically. The space-resolved spectra show that the J=0-1 lasing lines are emitted from an approximately 60-μm-wide (FWHM) plasma region, whereas the nearby continuum emission is produced in a considerably broader plasma region of ∼250 μm. Lasing at 25.5 nm in neon-like iron was observed at a pump power as low as 180 GW (∼9 TW/cm²), with, however, considerable shot-to-shot scatter in the absolute laser output. Received: 5 September 1997/Revised version: 10 November 1997     

Application of a continuous-wave tunable erbium-doped fiber laser to molecular spectroscopy in the near infrared

Development of a continuous-wave tunable fiber laser-based spectrometer for applied spectroscopy is reported. Wide wavelength tunability of an erbium-doped fiber laser (EDFL) was investigated in the near-infrared region of 1543–1601 nm. Continuous mode-hop free fine frequency tuning has been accomplished by temperature tuning in conjunction with mechanical tuning. The overall spectroscopic performance of the EDFL was evaluated in terms of frequency tunability along with its suitability for molecular spectroscopy. High-resolution absorption spectra of acetylene (C₂H₂) were recorded near 1544 nm with a minimum measurable absorption coefficient of about 3.5×10^-7 cm^-1/Hz^1/2 for direct absorption spectroscopy associated with a 100-m long multipass cell. Detections of C₂H₂ at different concentration levels were performed as well with high dynamic detection range varying from 100% purity to sub ppmv using cavity ring down spectroscopy. A 3σ-detection-limited minimum detectable concentration (MDC) of 400 ppbv has been obtained by using the transition line P_e(22) of the ν₁+ν₃+ν₅ ¹(Π_g)-ν₅ ¹(Π_u) hot band near 1543.92 nm with a detection bandwidth of 2.3 Hz. This corresponds to a minimum detectable absorption coefficient of 6.6×10^-11 cm^-1/Hz^1/2. The sensitivity limit could be further improved by almost one order of magnitude (down to ∼60 ppbv) by use of the P_e(27) line of the ν₁+ν₃(Σ_u ⁺)-0(Σ_g ⁺)combination band near 1543.68 nm. PACS 42.55.Wd; 42.62.Fi; 07.57.Ty; 07.88.+y     

Nonlinear optical spectroscopy of electronic transitions in hexagonal manganites

The hexagonal rare-earth manganites RMnO₃ (R = Sc, Y, Ho, Er, Tm, Yb, Lu) are a group of materials with an unusual combination of magnetic, electric and optical properties. The electronic structure of these materials was studied by second harmonic (SH) spectroscopy in the range from 1.2 to 3.0 eV. Faraday rotation and absorption spectra were measured in the range from 1.0 to 1.6 eV. Broad bands at ∼1.7 eV and ∼2.7 eV are assigned to electronic transitions between Mn³⁺(3d⁴) levels. The SH spectra are discussed on the basis of a recently developed microscopic theory. Received: 26 April 2001 / Published online: 18 July 2001     

13CO2/12CO2 isotopic ratio measurements using a difference frequency-based sensor operating at 4.35 micrometers

A portable modular gas sensor for measuring the ¹³C/¹²C isotopic ratio in CO₂ with a precision of 0.8‰(±1σ) was developed for volcanic gas emission studies. This sensor employed a difference frequency generation (DFG)-based spectroscopic source operating at 4.35 μm (∼2300 cm^-1) in combination with a dual-chamber gas absorption cell. Direct absorption spectroscopy using this specially designed cell permitted rapid comparisons of isotopic ratios of a gas sample and a reference standard for appropriately selected CO₂ absorption lines. Special attention was given to minimizing undesirable precision degrading effects, in particular temperature and pressure fluctuations. Received: 16 April 2002 / Revised version: 28 May 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +1-713/5245237, E-mail: fkt@rice.edu     

Application of 940 nm high-power DFB lasers for line-broadening measurements at normal pressure using a robust and compact setup

High-power distributed-feedback (DFB) lasers for the wavelength range near 940 nm (i.e. about 10,600 cm⁻¹) were used for line-broadening measurements of individual rotational-vibrational absorption lines of water vapour at atmospheric pressure using a minimalist set-up. The laser has a maximum output power larger than 500 mW. Over the whole power range from threshold to maximum power, it operates in single mode operation with a tuning range of 4.7 nm, i.e. 50 cm⁻¹, at 20°C. With an emission line-width ≤2 MHz (0.66×10⁻⁴ cm⁻¹), the device is well suited for high-resolution spectroscopy.     

Influence of laser pulse width on absolute EUV-yield from Xe-clusters

Using 50 fs ( ∼ 2×10¹⁸ W/cm²) and 2 ps ( ∼ 5×10¹⁶ W/cm²) pulses from a Ti:Sa multi-TW laser at 800 nm wavelength large Xe-clusters ( 10⁵...10⁶ atoms per cluster) have been excited. Absolute yield measurements of EUV-emission in a wavelength range between 10 nm and 15 nm in combination with cluster target variation were carried out. The ps-laser pulse has resulted in about 30% enhanced and spatially more uniform EUV-emission compared to fs-laser excitation. Circularly polarized laser light instead of linear polarization results in enhanced emission which is probably caused by electrons gaining higher energies by the polarization dependent optical field ionization process. An absolute emission efficiency at 13.4 nm of up to 0.8% in 2π sr and 2.2% bandwidth has been obtained. Received 11 January 2001 and Received in final form 27 March 2001     

Measurement of the <Superscript>13</Superscript>CO<Subscript>2</Subscript>/<Superscript>12</Superscript>CO<Subscript>2</Subscript> concentration ratio in exhaled air by diode laser spectroscopy

A method for determining the relative concentration of ¹³C/₁₂C isotopes by the vibrational-rotational spectrum of CO₂ molecule absorption in the range near 2 μm was proposed. The use of the entire region of the diode laser tuning (∼7 cm⁻¹) and multivariate linear regression for spectrum approximation allow measurements at atmospheric pressure. The laser frequency is additionally stabilized by injection current variation. The ultimate sensitivity of the setup, determined by the plot of the squared Alan variance, is 0.03% for 2-min signal acquisition. The system does not contain elements cooled by liquid nitrogen and can be used in medical diagnostics.     

Widely tunable mode-hop free external cavity quantum cascade laser for high resolution spectroscopic applications

An external cavity (EC) quantum cascade laser (QCL) configuration with the thermoelectrically cooled gain medium fabricated using a bound-to-continuum design and operating in continuous wave at ∼5.2 μm is reported. The EC architecture employs a piezo-activated cavity mode tracking system for mode-hop free operation suitable for high resolution spectroscopic applications and multiple species trace-gas detection. The performance of the EC-QCL exhibits coarse single mode tuning over 35 cm^-1 and a continuous mode-hop free fine tuning range of ∼1.2 cm^-1. PACS 07.07.Df; 42.55.Px; 42.62.Fi; 42.60.Fc