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     

Oxygen measurements at high pressures with vertical cavity surface-emitting lasers

Measurements of oxygen concentration at high pressures (to 10.9 bar) were made using diode-laser absorption of oxygen A-band transitions near 760 nm. The wide current-tuning frequency range (>30 cm^-1) of vertical cavity surface-emitting lasers (VCSELs) was exploited to enable the first scanned-wavelength demonstration of diode-laser absorption at high pressures; this strategy is more robust than fixed-wavelength strategies, particularly in hostile environments. The wide tuning range and rapid frequency response of the current tuning were further exploited to demonstrate wavelength-modulation absorption spectroscopy in a high-pressure environment. The minimum detectable absorbance demonstrated, ∼1×10^-4, corresponds to ∼800 ppm-m oxygen detectivity at room temperature and is limited by etalon noise. The rapid- and wide-frequency tunability of VCSELs should significantly expand the application domain of absorption-based sensors limited in the past by the small current-tuning frequency range (typically <2 cm^-1) of conventional edge-emitting diode lasers. Received: 26 July 2000 / Revised version: 2 January 2001 / Published online: 20 April 2001     

Optically stabilized tunable diode-laser system for saturation spectroscopy

We present an optically stabilized lead-salt diode-laser system which is the nucleus of a very-high-resolution instrument for sub-Doppler molecular spectroscopy in the mid-infrared. By application of external optical feedback, we have narrowed the diode-laser linewidth by two orders of magnitude, yielding a spectral width of less than 200 kHz. The diode- laser frequency is stabilized and controlled via the external reflector by variable-frequency offset-locking the diode-laser to a CO laser frequency. This substantial improvement in the spectral properties enabled us to perform a Lamb-dip experiment on a carbonyl sulfide (OCS) absorption line near 1985 cm^–1. We were able to detect a saturated dispersion signal at low pressure (5 Pa) with a signal-to-noise ratio of several thousand. The present paper describes the unique features of the optically stabilized tunable diode-laser system and its use as a spectroscopic tool for sub-Doppler applications.     

A tunable light source in the 370 nm range based on an optically stabilized,frequency-doubled semiconductor laser

A tunable harmonic output power of 18 W at a wavelength of =370 nm is obtained by resonance-enhanced frequency doubling of an optically-stabilized semiconductor laser. A commercially available AlGaAs laser diode which emits a maximum power of 10 mW at =740 nm is operated in an extended-cavity configuration. Dispersion prisms are used in the extended cavity to obtain longitudinal-mode selection with low loss of optical power. The output is focussed into an optically isolated high-finesse ring resonator which contains a LiIO₃ crystal for second-harmonic generation. One potential application of this laser source is the optical excitation and laser cooling of ytterbium in an ion trap. In a related demonstration experiment, the frequency-doubled diode laser is applied to excite the =369.5 nm ² S _1/2-² P _1/2 transition of ytterbium ions in a hollow-cathode discharge.     

Fast, low-noise, mode-by-mode, cavity-enhanced absorption spectroscopy by diode-laser self-locking

A new technique of cavity enhanced absorption spectroscopy is described. Molecular absorption spectra are obtained by recording the transmission maxima of the successive TEM_oo resonances of a high-finesse optical cavity when a Distributed Feedback Diode Laser is tuned across them. A noisy cavity output is usually observed in such a measurement since the resonances are spectrally narrower than the laser. We show that a folded (V-shaped) cavity can be used to obtain selective optical feedback from the intracavity field which builds up at resonance. This induces laser linewidth reduction and frequency locking. The linewidth narrowing eliminates the noisy cavity output, and allows measuring the maximum mode transmissions accurately. The frequency locking permits the laser to scan stepwise through the successive cavity modes. Frequency tuning is thus tightly optimized for cavity mode injection. Our setup for this technique of Optical-Feedback Cavity-Enhanced Absorption Spectroscopy (OF-CEAS) includes a 50 cm folded cavity with finesse ∼20 000 (ringdown time ∼20 μs) and allows recording spectra of up to 200 cavity modes (2 cm⁻¹) using 100 ms laser scans. We obtain a noise equivalent absorption coefficient of ∼5×10⁻¹⁰ cm⁻¹ for 1 s averaging over scans, with a dynamic range of four orders of magnitude.     

Multiple frequency stabilization of lasers using double saturation spectroscopy

We have developed a method of stabilizing multiple lasers based on double saturation spectroscopy. Compared with other laser-stabilization methods based on conventional saturation spectroscopy, ours provides numerous reference spectra constructed with several velocity groups of atoms. Two independent laser sources can be simultaneously stabilized by using combined optical-pumping processes associated with a single Rb reference. We analyzed the stability of the feedback loop taking the correlation effect of the saturation spectra into consideration. We experimentally demonstrated two stabilized laser sources with a frequency difference of 6,109 MHz in the ⁸⁷Rb D₂ line. The results were in good agreement with theory within errors in measurement.     

Practical optical frequency measurement system around 1.5 μm based on an acetylene-stabilized laser-locked optical frequency comb

We have developed a practical and precise frequency measurement system at 1.5 μm telecommunication band. An electro-optic-modulator based optical frequency comb is phase-locked to a dither-free acetylene-stabilized laser to realize an optical frequency comb with frequency uncertainty of 10 kHz (5 × 10⁻¹¹) and the linewidth of 15 kHz. The present frequency comb can be also used as an optical frequency reference grid defined by ITU-T (International Telecommunication Union, Telecommunication Standardization Sector). Using the present frequency measurement system, we have demonstrated the first optical frequency measurement of ¹²C¹⁶O overtone absorption lines around 1.56 μm with the uncertainty of lower than 900 kHz.     

Wavelength-modulation spectroscopy using a frequency-doubled current-modulated diode laser

We have studied atomic absorption in an argon discharge by wavelength-modulation spectroscopy with a frequency-doubled diode laser. The tunable wavelength-modulated radiation at 430 nm was generated by frequency doubling a current-modulated 860-nm diode laser in a KNbO₃ crystal. 2f-, 4f- and 6f-harmonic spectra as a function of diode laser modulation depth were measured on a Doppler-broadened sample of excited argon atoms produced in a capacitively coupled plasma chamber. Characterisation of the harmonic signals was accomplished. Minimum detectable absorbances of 7.7×10^-5 and 1.9×10^-4 based on a 3σ criterion (σ being the standard deviation of the noise) were estimated for 2f- and 4f-harmonic detection of the frequency-doubled radiation with a time constant of 0.1 s. The concentrations of argon in the 1s₄ state were found to be in the range of 3×10⁸ to 1.2×10¹¹ cm^-3 for the experimental conditions studied. Received: 25 February 2002 / Revised version: 4 April 2002 / Published online: 14 May 2002     

Fundamental noise sources in a high-sensitivity two-tone frequency modulation spectrometer and detection of CO2 at 1.6 μm and 2 μm

2 , and its sensitivity is 7(2)×10^-8 in a 1-Hz bandwidth. The corresponding minimum detectable concentration of CO₂ in air has been estimated to be 1 ppm · m. This opens the possibility of a detection at ppb levels at 2 μm, where a two orders of magnitude increase in the CO₂ absorption signal is demonstrated. Received: 06 April 1998/Revised version: 02 July 1998     

Cavity-enhanced absorption spectroscopy with a rapidly swept diode laser

Cavity-enhanced absorption spectroscopy is explained in terms of the transmission function of a rapidly swept interferometer, and the integrated transmission is shown to be proportional to the cavity ringdown time. The technique is demonstrated on the b¹Σ_g ⁺-X³Σ_g ^-  (1,0) band in molecular oxygen at 687 nm using a tunable diode laser and a relative-ly high-Q optical cavity (finesse ≈4000). A detection limit of 3×10^-8 cm^-1 s^1/2 is achieved for a 0.8 cm^-1 scanning range. Received: 24 June 2002 / Revised version: 5 August 2002 / Published online: 15 November 2002 RID="*" ID="*"Corresponding author. Fax: +44-1865/275410, E-mail: peverall@physchem.ox.ac.uk     

Simultaneous detection of methane, oxygen and water vapour utilising near-infrared diode lasers in conjunction with difference-frequency generation

An all-diode-laser-based spectrometer is used for the simultaneous detection of methane, oxygen and water vapour. This is accomplished using a 760-nm diode laser and a 980-nm diode laser in conjunction with difference-frequency generation to 3.4 μm in a periodically poled lithium niobate crystal. Each of the output wavelengths is resonant with one of the molecular species. Simultaneous recordings over a 15-m open path of laboratory air are demonstrated. The recording scheme shows the wide applicability of a diode-laser-based difference-frequency spectrometer for the detection of molecular species in different wavelength ranges. By increasing the frequency of the 760-nm diode laser and decreasing the frequency of the 980-nm diode laser, a maximum continuous tuning range in the mid infrared of 3.6 cm^-1 is achieved. This enables the recording of several methane lines at atmospheric pressure. Pressure-dependence studies of methane lineshapes are also performed in an absorption cell. An indoor-air methane background level of 3 ppm is measured. The signal-to-noise ratio in the recorded methane spectra indicates that sub-ppm detection of methane at atmospheric pressure is feasible. Received: 6 March 2000 / Revised version: 19 June 2000 / Published online: 11 October 2000     

Blue up-conversion with excitation into Tm ions at 808 nm in YVO4 crystals co-doped with thulium and ytterbium

The up-conversion of infrared radiation at 808 nm, emitted by a diode laser, into blue emission centered at 480 nm in 1 at.% Tm, 5 at.% Yb: YVO₄; 1 at.% Tm, 8 at.% Yb: YVO₄ and 2 at.% Tm, 5 at.% Yb: YVO₄ has been studied. The highest intensity of blue emission is found for the 1 at.% Tm, 8 at.%Yb: YVO₄ system. The power dependence of up-converted emission upon continuous-wave excitation as well as the time evolution of its intensity upon short-pulse excitation were found to be consistent with a two-step excitation mechanism in which the forward Tm³⁺–Yb³⁺ energy transfer is followed by the back Yb³⁺–Tm³⁺ energy transfer. The effect of dopant concentrations on the up-conversion process is interpreted taking into account dynamics of the excited states involved.     

Sensitive birefringence measurement in a high-finesse resonator using diode laser optical self-locking

We demonstrate a new method to measure weak birefringence of dielectric mirrors with excellent spatial resolution and sensitivity (<10^-7 radians). We exploit a well-known optical feedback scheme for line-width narrowing and frequency locking of a diode laser to a high-finesse cavity. Feedback comes from the intracavity field which builds up at resonance, selected by its change in polarization with respect to the incident field. This change, due to the residual birefringence of the cavity mirror coatings, was already exploited for birefringence measurements using an active laser-locking scheme. Here we measure the optical feedback rate as a function of rotation angle of one of the cavity mirrors (around the cavity axis). A stable feedback signal is obtained since the laser, as soon as it locks to a cavity resonance, effectively behaves as a monochromatic source. By fitting the data with a theoretical expression, we determine quantitatively the local birefringence vectors of both mirrors, which are around 10^-6 radians. Our scheme is simple, works with cavities of very high finesse (F∼10⁵), and is promising for measuring birefringence in gases induced by external fields. Received: 18 July 2001 / Final version: 14 March 2002 / Published online: 8 May 2002     

Intra-cavity spectroscopy with diode lasers

A multi-mode diode laser with an external cavity is studied experimentally and theoretically for its application to intra-cavity spectroscopy. One facet of a typical Ga_0.89Al_0.11As laser diode was antireflection-coated by deposition of HfO₂ such that 10^–3 residual reflectivity was left over. This diode was placed in an external optical cavity. The emission spectrum of this diode laser is highly sensitive to any frequency-dependent loss in the cavity, and the detectivity of such a loss grows with the pump rate. Even close to threshold, the absorption at 780 nm of Rb atoms with a density of 5×10¹⁰ cm^–3 has been detected. An adequate model for diode lasers based on rate equations and including frequency-dependent gain saturation is developed and applied to the calculations of output spectra. The sensitivity of these spectra to intra-cavity absorption is determined by the overall cavity loss — which is rather high — and the fraction of spontaneous emission in the total emission, in contrast with dye lasers where it is limited by nonlinear mode coupling. Various criteria for the sensitivity are suggested. The smallest detectable absorption with a perfectly antireflection-coated laser is 10^–6 cm^–1. Improvement of the characteristics of the laser diode would increase the sensitivity.     

Spectroscopic trace-gas sensor with rapidly scanned wavelengths of a pulsed quantum cascade laser for in situ NO monitoring of industrial exhaust systems

Development of a pulsed quantum cascade laser (QCL)-based spectroscopic trace-gas sensor for sub-part-per-million detection of nitric oxide (NO) and capable of monitoring other molecular species such as CO₂, H₂O, and NH₃ in industrial combustion exhaust systems is reported. Rapid frequency modulation is applied to the QCL to minimize the influence of fluctuating non-selective absorption. A novel method utilizes only a few laser pulses within a single wavelength scan to probe an absorption spectrum at precisely selected optical frequencies. A high-temperature gas cell was used for laboratory evaluation of the NO sensor performance. A noise-equivalent sensitivity (1) of 100 ppb × m/ at room temperature and 200 ppb × m/ at 630 K was achieved by measuring the NO R(6.5) absorption doublet at 1900.075 cm^–1.     

Wide bandwidth phase-locked diode laser with an intra-cavity electro-optic modulator

Two extended cavity laser diodes are phase-locked, thanks to an intra-cavity electro-optical modulator. The phase-locked loop bandwidth is on the order of 10 MHz, which is about twice larger than when the feedback correction is applied on the laser current. The phase noise reaches −120 dBrad²/Hz at 10 kHz. This new scheme reduces the residual laser phase noise, which constitutes one of the dominant contributions in the sensitivity limit of atom interferometers using two-photon transitions.     

Intracavity photoacoustic gas detection with an external cavity diode laser

The first use of an external cavity diode-laser light source in combination with a photoacoustic detector for high-sensitivity gas detection is described. This combined system is applicable for detecting gases with absorption coefficients as low as 5 x 10^–8 cm^–1 by operating the photoacoustic cell in an intracavity mode. Measurements were made on the 1.13 m absorption lines of water vapour. For quantitative measurements, it was found to be necessary to introduce a reference cell into the system.     

All-diode-laser ultraviolet absorption spectroscopy for sulfur dioxide detection

Ultraviolet radiation around 302 nm was produced by sum-frequency generation in beta-barium borate employing a blue and a near-infrared diode laser. The diode-laser-based spectrometer has a mode-hop-free tuning range of 50 GHz and was used for high-resolution spectroscopic detection of sulfur dioxide. Differential measurements of several gas concentrations, at low pressure as well as at ambient atmospheric pressure, were demonstrated. The detection limit in the first implementation of the instrument was about 20 ppm m at atmospheric pressure, essentially limited by interference fringes. Methods for greatly improving this limit are suggested.     

Luminescence spectroscopy of Er-doped and Er, Yb-codoped LaPO4 single crystals

LaPO₄ single crystals lightly doped with Er³⁺, and codoped with Er³⁺ and Yb³⁺ have been grown by spontaneous nucleation in a lead phosphate flux. Absorption and luminescence spectra have been measured in the visible and near-IR regions and the excited state dynamics has been studied upon pulsed laser excitation. The obtained results have allowed the evaluation of the effective emission cross-sections around 1.5 μm, that have been found to be similar to important oxide laser crystals doped with Er³⁺. Efficient visible upconversion has been observed upon excitation at 980 nm in the codoped crystals. This behaviour is attributed to Yb³⁺-Er³⁺ energy transfer processes.