Tunable single-frequency diode laser at wavelength λ=1.65 μm for methane concentration measurements

This paper deals with the development of a novel single-frequency tunable diode laser with fiber-optic output for gas-analysis applications. The approach we propose is a convenient, simple and cheap solution for spectroscopy of single absorption lines of any gases having absorption bands in the optical fiber transparency window (0.7 microm/1.7 microm). The presence of fiber-optic output is an additional advantage for remote sensing applications. The laser operation is demonstrated as applied to R7 line of 2 nu(3) methane absorption band at lambda = 1.645 microm. The mode-hop-free tuning range of 35 GHz (1.2 cm(-1)) has been achieved.     

Fiber-optic evanescent-field laser sensor for in-situ gas diagnostics

A compact, rugged and portable fiber-optic evanescent-field laser sensor is developed for the detection of gaseous species in harsh environments such as volcano fumaroles or industrial combustion of glass furnaces. The sensor consists of an optical multi-mode fused silica fiber with jacket and cladding removed and the bare fiber core in direct contact with the surrounding molecules. The beam of a single-mode DFB diode laser with an emission wavelength centered at 1.5705 microm is coupled into the fiber. At the other end of the fiber an infrared detector is used to record the transmitted infrared laser light intensity. Due to the frustrated total reflection (FTR) and the attenuated total reflection (ATR) the laser intensity is attenuated when passing through the fiber. The FTR is related to a change of the index of refraction while the latter one is related to a change of the absorption coefficient. While tuning the DFB laser wavelength across absorption lines of molecules surrounding the fiber a spectral intensity profile is measured. Voigt functions are fitted to the recorded intensity profiles to estimate relative molecule concentrations. In this paper results from first field measurements at the volcano site 'Solfatara' in Italy are reported that use such a sensor device for simultaneous detection of H2S, CO2 and H2O directly in the gas stream of a volcano fumarole.     

Spectroscopic gas analyzers based on indium-phosphide,antimonide and lead-salt diode-lasers

Currently available semiconductor lasers for spectroscopy in the near- and mid-infrared region based on direct band-to-band transitions as gallium-arsenide, indium-phosphide, antimonides and lead-salt containing compounds will be discussed together with the main features of different tunable diode-laser absorption spectrometers for trace gas analysis. Measurements of atmospheric carbon dioxide with a room-temperature 2 microm indium-phosphide laser, applications of antimonide lasers for methane and formaldehyde sensing in the 3-4 microm range and a fast chemical sensor for methane flux measurements based on lead-salt diode-lasers operating near 7.8 microm will be presented.     

Spectroscopic tests of a 2.3 microm tunable diode laser

A 2.3 microm near-room temperature tunable diode laser was tested for applications in high-resolution laboratory spectroscopy. It was mounted using a simple adaptor in a spectrometer usually used with lead-salt diode lasers, and was found to be electrically and optically compatible with the system. Good output power (several milliwatts) was observed, and a tuning range of 4460-4150 cm(-1) was achieved for laser temperatures of 210-310 K. Some spectra of N(2)O and NH(3) were recorded in the 4300-4430 cm(-1) region. However, the laser was not generally useful due to noisy and unstable output and high sensitivity to optical feedback.     

DFB laser diodes in the wavelength range from 760 nm to 2.5 μm

We present a novel device technology to produce DFB laser diodes which are suitable for tunable diode laser spectroscopy. The new technological approach employs lateral metal distributed feedback (DFB) gratings in close proximity to the laser ridge which results in single mode emission with high spectral purity and output powers as required for most spectroscopic applications. Over the entire wavelength range from the visible (760 nm) up to the near-infrared (2.5 microm) single mode emission can be obtained for devices based on different semiconductor systems such as GaAs, InP and GaSb. Typical side mode suppression ratios are better than 35 dB for cw-room temperature operation and narrow linewidths ensure high spectroscopic resolution.     

DFB laser diodes in the wavelength range from 760 nm to 2.5 microm

We present a novel device technology to produce DFB laser diodes which are suitable for tunable diode laser spectroscopy. The new technological approach employs lateral metal distributed feedback (DFB) gratings in close proximity to the laser ridge which results in single mode emission with high spectral purity and output powers as required for most spectroscopic applications. Over the entire wavelength range from the visible (760 nm) up to the near-infrared (2.5 microm) single mode emission can be obtained for devices based on different semiconductor systems such as GaAs, InP and GaSb. Typical side mode suppression ratios are better than 35 dB for cw-room temperature operation and narrow linewidths ensure high spectroscopic resolution.     

Physical properties of organic particulate UV-absorbers used in sunscreens. I. Determination of particle size with fiber-optic quasi-elastic light scattering (FOQELS), disc centrifugation, and laser diffractometry

In this study microparticles consisting of a benzotriazole derivative, which are used as absorbers for UV radiation in cosmetic sunscreens, were investigated. The particles were micronized in presence of a dispersing agent by means of a ball milling process. According to the energy input different particle sizes were produced in the range of 0.16 to 4 microm. The particle sizes obtained after different stages of the micronization process were measured using fiber-optic quasi-elastic light scattering (FOQELS), disc centrifugation, and laser diffractometry. All methods showed satisfactory agreement over the whole range of sizes. With the FOQELS technique the particle size distribution could be resolved to sizes well below 0.1 microm.     

Infrared (1.2-1.6 microm) luminescence in Cr4+:Yb3Al5O12 single crystal with 940 nm diode pumping

Infrared (1.2-1.6 microm) luminescence in a ytterbium aluminium garnet (YbAG) crystal, doped with Cr (0.05at.%) ions, was investigated under CW laser diode pumping (lambda=940 nm). The Cr4+ emission band was observed with its peak at 1.34 microm and measured to be about 1.3 times with respect to Yb3+ IR luminescence (lambda=1.03 microm). We demonstrate that for the excitation wavelength of 940 nm Yb3+ ions act as sensitizers of the 3B2(3T2)-3B1(3A2) emission of Cr4+ ions. This crystal is promising as a high-efficient system for tunable laser (1.2-1.6 microm) output.     

Diode laser emission linewidth determination: application to H2O line profile studies in the 5 and 1.4 microm regions

In order to study absorption line profiles using the stabilized diode laser spectrometer of Laboratoire de Physique Moléculaire et Applications (LPMA), a reliable determination of the emission line shape of different diodes laser is needed. In the near infrared region (1.39 and 1.66 microm) we used Distributed Feed Back diode lasers which operate around room temperature and in the middle infrared (5 and 8 microm) we used lead salt diode lasers cooled in a helium closed cycle cryostat or in a liquid nitrogen dewar. Some results obtained in H2O line profile studies in the 1.39 and 5 microm regions are presented as examples demonstrating how absorption line profile measurements can lead to erroneous values of the spectroscopic parameters when the contribution of the diode laser emission line width is neglected.     

Methodology for fiber-optic Raman mapping and FTIR imaging of metastases in mouse brains

The objectives of this study were to optimize the preparation of pristine brain tissue to obtain reference information, to optimize the conditions for introducing a fiber-optic probe to acquire Raman maps, and to transfer previous results obtained from human brain tumors to an animal model. Brain metastases of malignant melanomas were induced by injecting tumor cells into the carotid artery of mice. The procedure mimicked hematogenous tumor spread in one brain hemisphere while the other hemisphere remained tumor free. Three series of sections were prepared consecutively from whole mouse brains: dried, thin sections for FTIR imaging, hematoxylin and eosin-stained thin sections for histopathological assessment, and pristine, 2-mm thick sections for Raman mapping. FTIR images were recorded using a spectrometer with a multi-channel detector. Raman maps were collected serially using a spectrometer coupled to a fiber-optic probe. The FTIR images and the Raman maps were segmented by cluster analysis. The color-coded cluster memberships coincided well with the morphology of mouse brains in stained tissue sections. More details in less time were resolved in FTIR images with a nominal resolution of 25 microm than in Raman maps collected with a laser focus 60 microm in diameter. The spectral contributions of melanin in tumor cells were resonance enhanced in Raman spectra on excitation at 785 nm which enabled their sensitive detection in Raman maps. Possible reasons why metastatic cells of malignant melanomas were not identified in FTIR images are discussed.     

Detection and spectroscopy of the v1 + v3 band of N2O by difference-frequency spectrometer at 3 microm

We report the realisation of a laser spectrometer in the mid-infrared spectral region based on difference-frequency generation in a periodically poled LiNbO3 crystal. Tunable coherent radiation around 3 microm was produced by mixing a diode-pumped monolithic cw Nd-YAG laser and an injection-locked diode laser at 0.785 microm. High sensitivity N2O detection was demonstrated by observing pure absorption spectra of lines in the v1 + v3 combination band. We estimate a minimum detectable pressure of pure N2O of 1 x 10(-2) Pa with 0.9 m absorption path-length, corresponding to an absorbance of 3 x 10(-4). Nitrous oxide was also detected in presence of O2, N2 and air. Collisional broadening coefficients for the P(33) line at 3447.678 per cm are reported for N2O-N2 and N2O-O2 mixtures.     

Spectroscopic studies of a near-infrared absorbing pH sensitive carbocyanine dye

Near-infrared dyes can be derivatized with appropriate functional groups for use as analytical probes for numerous applications. A dye derivatized with pH-sensitive functional groups may show spectral changes when the pH of its environment is changed. These dyes are valuable to the researcher since they absorb and fluoresce at long wavelengths where interference is minimal and their absorption maxima permit the use of semiconductor lasers. In this paper we have evaluated the sensitivity to pH of a bis-carboxylic acid derivative of a near infrared dye to illustrate its potential as a probe for determining pH. The dye has an absorption maximum at 795 nm in aqueous solution, a region where several commercially available laser diodes have their output maximum. The analytical utility of near-infrared laser diodes for pH determination has also been evaluated.     

A compact NIR fiber-optic diode laser spectrometer for CO and CO(2): analysis of observed 2f wavelength modulation spectroscopy line shapes

A compact fiber-optic diode laser spectrometer for the measurement of CO and CO(2) gas concentrations in the near infrared around 1580 nm is described. By use of a balanced receiver to suppress diode laser intensity noise a sensitivity of 6.4 x 10(-7) at 1 Hz system bandwidth was achieved. At a reduced pressure of 80 hPa this equals to a detection limit of 5.1 ppm CO and 9.1 ppm CO(2) with 1m absorption path length. The observed line shapes of the 2f wavelength modulation spectroscopy (WMS) scheme are analyzed theoretically and experimentally. Accurate measurements of magnitude and phase of the diode laser frequency and intensity modulation responses were found critically for modeling the observed line shapes. In situ measurements of gas dissociation processes inside of a medium-power carbon dioxide laser are presented as an application example.     

Depth profile analysis of various titanium based coatings on steel and tungsten carbide using laser ablation inductively coupled plasma--"time of flight" mass spectrometry

A homogenized 193 nm ArF* laser ablation system coupled to an inductively coupled plasma-"Time of Flight"-mass spectrometer (LA-ICP-TOFMS) was tested for depth profiling analysis on different single-layer Ti based coatings on steel and W carbides. Laser parameters, such as repetition rate, pulse energy and spatial resolution were tested to allow optimum depth related calibration curves. The ablation process using a laser repetition rate of 3 Hz, 120 microm crater diameter, and 100 mJ output energy, leads to linear calibration curves independent of the drill time or peak area used for calibrating the thickness of the layer. The best depth resolution obtained (without beam splitter) was 0.20 microm per laser shot. The time resolution of the ICP-TOFMS of 102 ms integration time per isotope was sufficient for the determination of the drill time of the laser through the coatings into the matrix with better than 2.6% RSD (about 7 microm coating thickness, n = 7). Variation of the volume of the ablation cell was not influencing the depth resolution, which suggests that the depth resolution is governed by the ablation process. However, the application on the Ti(N,C) based single layer shows the potential of LA-ICP-TOFMS as a complementary technique for fast depth determinations on various coatings in the low to medium microm region.     

Resonant infrared laser-induced desorption of methane condensed on NaCl(100): isotope mixture experiments

Resonantly enhanced infrared laser-induced desorption of methane condensed on a single-crystal NaCl(100) surface is observed after excitation with the widely tunable infrared laser output of the free-electron laser at the free-electron laser for infrared experiments facility using mass spectroscopic detection and time-of-flight analysis. Desorption of methane is observed only when the exciting light is in resonance with an internal vibrational mode of the molecule. Different intramolecular modes of the three methane isotopologues under study--CH(4), CD(4), and CD(3)H--are excited; the degenerate deformation mode nu(4) is observed for CH(4) and CD(4) at 7.69 and 10.11 microm, respectively, as well as the nu(2) and nu(4) modes of CD(3)H at 7.79, 9.75, and 9.98 microm. The desorption signals for the pure layers of these different methane isotopologues as well as for different mixtures of two of these are investigated as a function of the infrared wavelength and the laser fluence. The desorption behavior for pure and mixed layers is compared and the underlying desorption mechanism is discussed.     

Ethylene spectroscopy using a quasi-room-temperature quantum cascade laser

Spectroscopic measurements on ethylene were performed using a quasi-room-temperature quantum cascade (QC) laser operated in pulsed mode in the 10.3 microm range. Using transmission spectroscopy, a broadening of the ethylene absorption spectrum was observed with increasing laser pulse duration, due to an increase of the laser linewidth. This linewidth was determined from the measured absorption spectra, showing a value of 0.04 cm(-1) for a 20 ns pulse duration and an enhancement coefficient of 6.5 x 10(-3) cm(-1) per ns in the 20-50 ns pulse length range. Photoacoustic (PA) detection of ethylene was also performed using the QC laser and a resonant PA cell, with a detection limit of 60 ppm.     

Determination of the 2H/1H, 17O/16O,and 18O/16O isotope ratios in water by means of tunable diode laser spectroscopy at 1.39 microm

We demonstrate the feasibility of the accurate and simultaneous measurement of the 2H/1H, 17O/16O, and 18O/16O isotope ratios in water vapor by means of tunable diode laser spectroscopy. The absorptions are due to the v1 + v3 combination band, observed using a room temperature, distributed feedback (DFB) diode laser at 1.39 microm. The precision of the instrument is approximately 3, 1, and 0.5/1000 for the 2H, 17O, and 18O isotope ratios, respectively, and is at present limited by residual optical feedback to the laser. The signal-to-noise, however, is superior to that obtained in a similar experiment using a color center laser at 2.7 microm. Replacing the current laser with a better unit, we are confident that a precision well below 1/1000 is attainable for all three isotope ratios. The diode laser apparatus is ideally suited for applications demanding a reliable, cheap, and/or portable instrument, such as the biomedical doubly labeled water method and atmospheric sensing.     

Infrared laser desorption and ionization of polypeptides from a polyacrylamide gel

We observed direct desorption and ionization of angiotensin II and bovine insulin from a frozen polyacrylamide gel without the addition of an exogenous matrix, using picosecond pulses from a tunable, mid-infrared free-electron laser tuned to strong absorption bands of the gel. At 5.7, 5.9, 6.1 and 6.3 microm we were able to desorb and ionize both analyte molecules, with the strongest analyte signal generated at 5.9 microm. However, no analyte signal was observed at 5.5 microm. Consistent with a previous report, we did not observe ions of either polypeptide at 2.9 microm, in spite of strong overall absorption. We discuss the implications of this wavelength-dependent ionization, including possible ablation mechanisms and energy partitioning between competing vibrational modes.     

Soft lithography: masters on demand

We report an ultra-rapid prototyping technique for forming microchannel networks for lab-on-a-chip applications, called masters on-demand. Channels are produced by replica molding on masters formed by laser printing on flexible copper printed circuit board (PCB) substrates. Masters of various designs and dimensions can be individually or mass produced in less than 10 minutes. Using this technique, we have fabricated channels as narrow as 100 microm with heights ranging between 9 microm and 70 microm. Multi-depth channel fabrication is also reported, using a two-step printing process. The functionality of devices formed in this manner is verified by performing in-channel electrophoretic separations and culture and analysis of primary mammalian cells.     

Quantum cascade laser-based photoacoustic spectroscopy of volatile chemicals: application to hexamethyldisilazane

The use of photoacoustic spectroscopy and mid-infrared quantum-cascade lasers (QCLs) for the detection of hexamethyldisilazane (HMDS) is reported. A detection limit of 200 parts in 10(9) is found using a Fabry-Perot QCL operated at 8.4 microm in pulsed mode and a photoacoustic cell equipped with four electret microphones. The laser multimode spectrum matches the range of the N-H bending absorption band of HMDS. Further improvements to reach lower detection limits are discussed.