Intracavity laser absorption measurements at ultrahigh spectral resolution

Intracavity laser absorption spectroscopy with ultrahigh sensitivity and enhanced spectral resolution is demonstrated. It entails use of an intracavity étalon that selects equally spaced modes of the cavity. These modes are reduced in intensity when they occur at spectral locations where absorption that is due to intracavity species also occurs. We obtained absorption spectra by tuning the étalon in small steps across its free spectral range, recording intracavity spectra at each step, and summing the result. The maximum resolution is determined by the width of the étalon peaks, which was ~0.01 cm(-1). When the finesse of the étalon is increased, the resolution equal to the width of a single laser mode can be achieved. With this technique, spectra at Doppler-free resolution such as that required for studies of high vibrational-overtone transitions of molecules in supersonic jets are possible.     

Spectral control of an alexandrite laser for an airborne water-vapor differential absorption lidar system

A narrow-linewidth pulsed alexandrite laser has been greatly modified for improved spectral stability in an aircraft environment, and its operation has been evaluated in the laboratory for making water-vapor differential absorption lidar measurements. An alignment technique is described to achieve the optimum free spectral range ratio for the two étalons inserted in the alexandrite laser cavity, and the sensitivity of this ratio is analyzed. This technique drastically decreases the occurrence of mode hopping, which is commonly observed in a tunable, two-intracavity-étalon laser system. High spectral purity (> 99.85%) at 730 nm is demonstrated by the use of a water-vapor absorption line as a notch filter. The effective cross sections of 760-nm oxygen and 730-nm water-vapor absorption lines are measured at different pressures by usingthis laser, which has a finite linewidth of 0.02 cm(-1) (FWHM). It is found that for water-vapor absorption linewidths greater than 0.04 cm(-1) (HWHM), or for altitudes below 10 km, the laser line can be considered monochromatic because the measured effective absorption cross section is within 1% of the calculated monochromatic cross section. An analysis of the environmental sensitivity of the two intracavity étalons is presented, and a closed-loop computer control for active stabilization of the two intracavity étalons in the alexandrite laser is described. Using a water-vapor absorption line as a wavelength reference, we measure a long-term frequency drift (≈ 1.5 h) of less than 0.7 pm in the laboratory.     

Intracavity absorption spectroscopy with a tunable multimode traveling-wave ring Ti:sapphire laser

A tunable multimode unidirectional traveling-wave Ti:sapphire laser was developed to measure in situ the atmospheric absorption spectra using intracavity absorption spectroscopy. The effective absorption path length was 2100 km. O2 and H2O vapor lines in atmosphere with absorption coefficients of 10(-6)-10(-8) cm(-1) were measured with uncertainties <5%, and the absorption coefficients were in agreement with those estimated from the HITRAN database. By tuning the wavelength, a weak absorption line with an absorption coefficient of 10(-9) cm(-1) was measured with a sensitivity of 2×10(-10) cm(-1). The sensitivity was limited by the residual parasitic variation that appeared in the spectrum.     

Trace gas detection by laser intracavity photothermal spectroscopy

A novel laser intracavity photothermal detector is described. In this scheme, sample absorption of the pump laser power takes place within the cavity of a probe He-Ne laser causing modulation in the gain and in turn the output power. Comparison of this intracavity detector with two other photothermal techniques, namely, phase fluctuation optical heterodyne spectroscopy and thermal beam deflection, is made in terms of practicality and sensitivity. For in situ measurements, sensitivity of 0.5 x 10(-7) cm(-1) for a probe length of 3 cm has been achieved.     

Ultrasensitive absorption spectroscopy with a high-finesse optical cavity and off-axis alignment

A simple and easy to use method that allows high-finesse optical cavities to be used as absorption cells for spectroscopic purposes is presented. This method introduces a single-mode continuous-wave laser into the cavity by use of an off-axis cavity alignment geometry to eliminate systematically the resonances commonly associated with optical cavities, while preserving the absorption signal amplifying properties of such cavities. This considerably reduces the complexity of the apparatus compared with other high-resolution cavity-based absorption methods. Application of this technique in conjunction with either cavity ringdown spectroscopy or integrated cavity output spectroscopy produced absorption sensitivities of 1.5 x 10(-9) cm(-1) Hz(-1/2) and 1.8 x 10(-10) cm(-1) Hz(-1/2), respectively.     

Injection-seeded pulsed alexandrite laser for differential absorption lidar application

We describe a Q-switched alexandrite laser injection seeded with a cw single-mode titanium-sapphire laser. The reported experimental results show that this system meets the frequency stabilization required for differential absorption lidar measurement of humidity, pressure, and temperature. The emission of the cw titanium-sapphire master oscillator is locked to an atmospheric absorption line by means of a servoloop with derivative spectroscopy. The spectral position is stabilized within ±3.5 × 10(-4) cm(-1) (10 MHz) of the peak of the line over 1 hr. The alexandrite laser emits pulses of 30 mJ in 500 ns, with a spectral linewidth of ≈ 3.3 × 10(-3) cm(-1) (100 MHz). The position of the centroid of the emitted spectrum has a standard deviation of 6 × 10(-4) cm(-1) (18 MHz) and is held within ±1.3 × 10(-3) cm(-1) (40 MHz) of the peak of the absorption line over 1 h.     

Tunable diode-laser absorption measurements of NO(2) near 670 and 395 nm

Two single-mode diode lasers were used to record high-resolution absorption spectra of NO(2) (dilute in Ar) near 670.2 and 394.5 nm over a range of temperatures (296 to 774 K) and total pressures (2.4 × 10(-2) to 1 atm). A commercial InGaAsP laser was tuned 1.3 cm(-1) at a repetition rate of 1 kHz to record the absorption spectra near 670.2 nm. In separate experiments with a prototype system, an external-cavity GaAlAs laser was frequency doubled with a quasi-phase-matched LiNbO(3) waveguide and tuned 3.5 cm(-1) to record absorption spectra near 394.5 nm. Variations of the spectral absorption coefficients with temperature and pressure were determined from measured spectra.     

Measurement of tissue absorption coefficients by use of interferometric photothermal spectroscopy

We describe a spectroscopic technique called interferometric photothermal spectroscopy (IPTS) that can measure the absorption coefficient of pulsed laser radiation in nonscattering tissue samples. The technique is suitable for measuring effective absorption coefficients from 10(3) to 10(5) cm(-1). IPTS is particularly attractive because it requires minimal disturbance of the sample. These features indicate potential use for in vivo measurements of tissue absorption coefficients. To validate the technique, the absorption coefficient of pulsed Q-switched Er:YSGG (2.79-microm) radiation in pure water was measured to be 5200 (+/-500) cm(-1) when IPTS was used, in agreement with other published values. IPTS was also used to measure the absorption coefficient of pulsed ArF excimer laser radiation (193 nm) in bovine corneal stroma (in vitro), giving a value of 1.9 (+/-0.4) x 10(4) cm(-1).     

Multipass grating interferometer applied to line narrowing in excimer lasers

The line narrowing of excimer lasers is discussed. The theory for an optical two-effect intracavity line narrowing device, the multipass grating interferometer (MGI), is presented. An MGI contains a grating aligned in its second-order Littrow configuration and a mirror aligned parallel to the grating surface reflecting back the beam normal to the grating corresponding to the first-order diffraction. The Littrow grating is doing the coarse line narrowing, and the mirror aligned parallel to the grating has similar line narrowing properties as tilted intracavity Fabry-Perot etalons. An MGI is applied to a KrF laser cavity to achieve a linewidth of 0.03 cm(-1).     

Fully reflective external-cavity setup for quantum-cascade lasers as a local oscillator in mid-infrared wavelength heterodyne spectroscopy

To our knowledge we present the first experiments with a fully reflective external-cavity quantum-cascade laser system at mid-infrared wavelengths for use as a local oscillator in a heterodyne receiver. The performance of the presented setup was investigated using absorption spectroscopy as well as heterodyne techniques. Tunability over approximately 30 cm(-1) at 1130 cm(-1) was demonstrated using a grating spectrometer. A continuous tuning range of 0.28 cm(-1) was verified by observing the spectra of an internally coupled confocal Fabry-Pérot interferometer and the absorption lines of gas phase SO(2). In a second step the output from the system was used as a local oscillator signal for a heterodyne setup. We show that spectral stability and side mode suppression are excellent and that a compact external-cavity quantum-cascade laser system is well suited to be used as a local oscillator in infrared heterodyne spectrometers.     

Wavelength-modulation laser hygrometer for ultrasensitive detection of water vapor in semiconductor gases

Water vapor is measured by use of a near-infrared diode laser and wavelength-modulation absorption spectroscopy. Humidity levels as low as 5 nmol/mol [1 nmol/mol = 1 ppb (1 ppb equals 1 part in 10(9))] of water vapor in air are measured with a sensitivity of better than 0.2 nmol/mol (3varsigma). The sensitivity, linearity, and stability of the technique are determined in experiments conducted at the National Institute of Standards and Technology, Gaithersburg, Maryland, by use of the low frost-point humidity generator over the range from 5 nmol/mol to 2.5 mumol/mol of water vapor in air. The pressure-broadening coefficients for water broadened by helium [0.0199(6) cm(-1) atm(-1) HWHM] and by hydrogen chloride [0.268(6) cm(-1) atm(-1) HWHM] are reported for the water line at 1392.5 nm.     

Transmission fourier transform Raman spectroscopy of pharmaceutical tablet cores

Transmission Fourier transform (FT) Raman spectroscopy of pharmaceutical tablet cores is demonstrated using traditional, unmodified commercial instrumentation. The benefits of improved precision over backscattering Raman spectroscopy due to increased sample volume are demonstrated. Self-absorption effects on analyte band ratios and sample probe volume are apparent, however. A survey of near-infrared (NIR) absorption spectra in the FT-Raman spectral range (approximately 0 to 3500 wavenumber shift from 1064 nm, or 1064 to 1700 nm) of molecules with a wide range of NIR-active functional groups shows that although absorption at the laser wavelength (1064 nm) is relatively small, some regions of the Raman spectrum coincide with NIR absorbances of 0.5 per cm or greater. Fortunately, the pharmaceutically important regions of the Raman shift spectrum from 0 to 600 cm(-1) and from 1400 to 1900 cm(-1) exhibit low self-absorption for most organic materials. A statistical analysis of transmission FT-Raman noise in spectra collected from different regions of a pharmaceutical tablet provides insight into both spectral distortion and reduced sampling volume caused by self-absorption.     

Shock-tube study of high-pressure H2O spectroscopy

Water-vapor absorption features near 7117, 7185, and 7462 cm(-1) were probed at pressures to 65 atm (1 atm = 760 Torr) and temperatures to 1800 K in shock-heated mixtures of H(2)O in N(2) and Ar with a diode-laser source. Calculated absorbances based on Voigt line shapes and measured line parameters were in good agreement, within 10%, with measured absorbances at 7185.4 and 7117.4 cm(-1). We obtained temperature-dependent N(2) and Ar shift parameters for H(2)O absorption features by shifting the calculated spectra to match the recorded absorption scan. Absorbance simulations based on line parameters from HITRAN and HITEMP were found to be similar over the range of temperatures 600-1800 K and were within 25% of the measurements. The combined use of Toth's [Appl. Opt. 36, 4851 (1994)] line positions and strengths and HITRAN broadening parameters resulted in calculated absorption coefficients that were within 15% of the measurements at all three probed wavelengths.     

In situ measurements of H2O from a stratospheric balloon by diode laser direct-differential absorption spectroscopy at 1.39 microm

A distributed-feedback InGaAs laser diode emitting near 1.393 mum is used in conjunction with an optical multipass cell that is open to the atmosphere to yield ambient water-vapor measurements by infrared absorption spectroscopy. To obtain the high dynamic range for the measurements that is required for continuous water-vapor monitoring in the upper troposphere and the lower stratosphere, we used a simple circuit that combined differential and direct detection. Furthermore, the laser emission wavelength was tuned to balance the steep decrease in H(2)O concentration with altitude by sweeping molecular transitions of stronger line strengths. The technique was implemented by use of the Spectromètre à Diodes Laser Accordables (SDLA), a tunable diode laser spectrometer operated from a stratospheric balloon. Absorption spectra of H(2)O in the 5-30-km altitude range obtained at 1-s intervals during recent balloon flights are reported. Water-vapor mixing ratios were retrieved from the absorption spectra by a fit to the full molecular line shape in conjunction with in situ pressure and temperature measurements, with a precision error ranging from 5% to 10%.     

Etch rate and spectroscopic ablation studies of Er:YAG laser-irradiated dentine

The interaction of a 200-mus Er:YAG laser at 2.94 mum with human molar dentine has been studied by ablation depth rate measurements as well as time-resolved and optical multichannel analyzer emission spectroscopy. Ablation rates indicate a threshold fluence of ~5.2 J cm(-2) for significant material removal with a low-fluence (<20 J cm(-2)) effective optical absorption coefficient of ~700 cm(-1). Deviation from a Beer's law dependence is significant in the range ~20 to ~60 J cm(-2) and indicates a maximum effective plume absorption of ~1200 cm(-1) at ~40 J cm(-2), coinciding with the appearance of strong line and broadband optical emission in the visible region. Time-of-flight emission measurements yield maximum species-resolved ablation velocities of up to ~1.2 x 10(6) cm s(-1), enabling calculation of plasma temperatures. The results suggest that etch-rate characteristics are driven by changes in plume absorption dynamics, which have a strong dependency on incident laser fluence.     

808-nm diode-pumped continuous-wave Tm:GdVO4 laser at room temperature

A high-quality gadolinium vanadate (GdVO4) crystal with 7-at. % thulium as the starting material was grown by the Czochralski technique. The measured absorption spectra exhibited sufficient absorption coefficients for laser diodes (LDs) for neodymium laser pumping: 6.0 cm(-1) for pi polarization and 6.2 cm(-1) for sigma polarization at 808 nm. Laser oscillation was carried out with single-stripe 808-nm LDs in an end-pumping configuration. A slope efficiency of 28% and a threshold of 750 mW were exhibited with respect to the absorbed pump power. An output power of 420 mW was achieved at an absorbed power of 2.4 W. It was demonstrated that Tm:GdVO4 is a useful material for 2-microm lasers, particularly in a compact LD-pumped system.     

Ultrabroadband operation of a cr(4+): forsterite laser by use of a spatially dispersed resonator

Ultrabroadband (half-width of 88 nm) nanosecond Cr(4+):forsterite oscillation was achieved simultaneously in the 1170-1340-nm range (1085 cm(-1)) by use of a spatially dispersed resonator with an intracavity prism pair. The laser demonstrates 4.8% real pump-to-laser efficiency. The oscillation build-up time for different spectral components is around 20 ns and varies by only 2.5 ns in the 1190-1260-nm region, which indicates that the ultrabroadband laser represents a complex multifrequency laser system with nonlinear spectral mode interaction.     

Molecular iodine fluorescence spectra generated with helium-neon lasers for spectrometer calibration

Gas-phase molecular iodine laser-induced fluorescence (LIF) spectra were recorded out to 815 nm at 1 cm(-1) resolution using green, yellow, and red helium-neon (HeNe) lasers as excitation sources. Nine previously unreported I(2) B←X absorption transitions accessed by these lasers were identified, and specific rovibronic transition assignments were made for two hundred LIF peaks--more than sixty per laser. These I(2) LIF peaks can be used to calibrate the vacuum wavenumber coordinate of spectrometers to better than 0.1 cm(-1) accuracy. In particular, green HeNe excitation of the I(2) R(106) 28-0 transition leads to strong fluorescence well suited for calibration, with a rotational doublet spacing of 15 cm(-1) and a doublet-to-doublet spacing of 190 cm(-1). Calibration by HeNe I(2) LIF may be an especially valuable technique for Raman spectroscopy applications.     

Anti-Stokes Raman spectrometry with 1064-nm excitation: an effective instrumental approach for field detection of explosives

Anti-Stokes Raman spectra of 28 explosive materials were obtained with 1064-nm excitation using fiber-optic sampling and a dispersive spectrograph equipped with a charge-coupled device (CCD) array detector. By using a silicon CCD detector, anti-Stokes features could clearly be observed for the majority of samples from -250 to -1650 cm(-1). Using the fiber-optic probe, spectra were routinely obtained from samples positioned up to twelve meters from the spectrograph within 240 s. The utility of an anti-Stokes correction routine is demonstrated, which routine allowed anti-Stokes spectra measured with 1064-nm excitation to be successfully searched and identified against libraries of Stokes spectra obtained using a Fourier transform (FT) Raman system equipped with a 1064-nm Nd:YAG laser.     

A developed optical-feedback cavity ring-down spectrometer and its application

A developed spectrometer based on optical-feedback cavity ring-down spectroscopy (OF-CRDS) has been demonstrated with a distributed feedback laser diode and a V-shaped glass ceramic cavity. The laser is coupled to the V-shaped cavity, which creates an absorption path length greater than 2.8 km, and resonance between the laser frequency and the cavity modes is realized by modulating the cavity length instead of tuning the laser wavelength to obtain a higher resolution. A noise-equivalent absorption coefficient of ~2.6 × 10(-8) cm(-1)Hz(-1/2) (1σ) is determined with spectral resolution of ~0.003 cm(-1) and spectral range of 1.2 cm(-1). As an application example, the absorption spectrum measurement of water vapor in the spectral range of 6590.3~6591.5 cm(-1) is demonstrated with this spectrometer.