Measurement of Non-Stationary Gas Flow Parameters Using Diode Laser Absorption Spectroscopy at High Temperatures and Pressures

The layout of an absorption spectrometer with diode lasers for contactless measurement of the temperature and water-vapor concentration in gas flows with mixture pressures of up to 3 atm and temperatures of 300–2000 K has been designed. The technique is based on the rapid tuning of the radiation wavelength of two lasers, the registration of the absorption lines of water molecules that are located in the tuning range, and the fitting of the experimental absorption spectra by theoretical ones that have been simulated using spectroscopic databases. The original components of the spectrometer and different algorithms of the processing of experimental spectra are described. The performance of the spectrometer and processing methods were tested in the laboratory with a cuvette at a pressure of 1 atm and temperatures of 300–1500 K. The different processing algorithms give a reasonable coincidence of data on hot zone parameters that were obtained by the method of diode laser absorption spectrometry, and the temperature that was measured using standard sensors. The designed layout of the spectrometer passed the first tests on the T-131 experimental stand at the TsAGI (Central Aerohydrodynamics Institute).     

High-sensitivity mid-infrared heterodyne spectrometer with a tunable diode laser as a local oscillator

A new mid-IR heterodyne spectrometer, which is intended to be applied for atmospheric and astrophysical studies, is presented. The spectrometer uses a frequency-stabilized tunable diode laser as a local oscillator. Owing to the low output power of available single-mode diode lasers, a newly developed confocal-ring resonator, the diplexer, is used to superimpose the source signal efficiently with that of the local oscillator. Additionally, the diplexer serves as an optical filter that establishes controlled optical feedback between the laser diode and the detector, which allows stable laser operation with linewidths of the order of 1 MHz. The heterodyne signal from the HgCdTe detector is analyzed by means of a 1.4-GHz acousto-optical spectrometer. With this setup we find system temperatures as low as 4400 K (double sideband), that is, approximately a factor of 6 of the quantum limit.     

Widely tunable rapid-scanning mid-infrared laser spectrometer for industrial gas process stream analysis

A mid-infrared spectrometer with a tuning range of >400 cm(-1) in the C-H stretching region of the spectrum has been designed and constructed. The spectrometer is based on the difference-frequency generation of two tunable diode lasers in periodically poled lithium niobate waveguides. Tuning is achieved by varying a single parameter, the wavelength of one of the near-infrared input lasers. The instrument can be tuned over the entire tuning range in less than 1 s. By taking advantage of the wide tuning range, the instrument has been used to analyze a mixture of methane, ethylene, and propylene. Each of these major components was measured with an accuracy of better than 2% (where the error is defined as a percentage of the measured value) in a single 30 s long scan. When optimized, the spectrometer has the potential to meet both the performance requirements and the practical requirements for real-time process control in petrochemical manufacturing. The general principles for the design of mid-infrared spectrometers with wide tuning ranges are explained, including the use of variable waveguide fabrication recipes to create broad phase-matching resonances (which lead to broad tuning) in the desired location.     

Sensitive absorption spectroscopy by use of an asymmetric multiple-quantum-well diode laser in an external cavity

We have developed a broadly tunable diode laser system by employing custom-designed asymmetric multiple-quantum-well (AMQW) InGaAsP lasers in an external cavity configuration. Feedback is provided by a diffractive optical element with high coupling efficiency and wavelength selectivity, allowing for single-mode tuning of the output wavelength by varying the external cavity length. This tunable laser system was used experimentally to perform absorption spectroscopy on weak CO(2) lines over a broad wavelength region in the near infrared. An experimental tuning range of 80 nm has been observed for a laser cavity length of 600 mum, which is double the tuning range found with conventional, uncoated quantum-well lasers. We achieved a detection sensitivity of 5 x 10(-6) at 95% confidence over the wavelength range of 1.54-1.62 mum by employing a second-harmonic detection technique. The theoretical predictions of a broad gain profile from an ambipolar rate equation model are found to correspond to the experimentally observed increased tunability of the uncoated AMQW lasers.     

Tuning of external-cavity semiconductor lasers with chirped diffraction gratings

We present a novel scheme of tunable semiconductor laser based on the use of a chirped grating in an external cavity. The chirped grating is fabricated using a simple holographic technique: two Gaussian beams having wavefronts with different radii of curvature are brought to interfere on a photoresist layer. The tuning properties of chirped gratings have been investigated with semiconductor lasers operated with an external cavity. With this type of grating positioned in Littrow configuration, the wavelength selection can be done by translating the grating without any need to rotate it. This cavity configuration provides a tunable output beam with an angle of propagation that is independent of the wavelength. The translation of chirped gratings was shown to tune a visible diode laser and an infrared diode laser over the same spectral band as the conventional tuning scheme where an unchirped grating is rotated.     

Power-scalable system of phase-locked single-mode diode lasers

The direct use of diode lasers for high-power applications in material processing is limited to applications with relatively low beam quality and power density requirements. To achieve high beam quality one must use single-mode diode lasers, however with the drawback of relatively low optical output powers from these components. To realize a high-power system while conserving the high beam quality of the individual emitters requires coherent coupling of the emitters. Such a power-scalable system consisting of 19 slave lasers that are injection locked by one master laser has been built and investigated, with low-power diode lasers used for system demonstration. The optical power of the 19 injection-locked lasers is coupled into polarization-maintaining single-mode fibers and geometrically superimposed by a lens array and a focusing lens. The phase of each emitter is controlled by a simple electronic phase-control loop. The coherence of each slave laser is stabilized by computer control of the laser current and guarantees a stable degree of coherence of the whole system of 0.7. An enhancement factor of 13.2 in peak power density compared with that which was achievable with the incoherent superposition of the diode lasers was observed.     

Tunable Diode Laser Absorption Spectroscopy of Carbon Monoxide Around 2.35 microm

Novel GaInSbAs/GaSb multiple-quantum-well lasers operating near room temperature have been successfully used for tunable diode laser absorption spectroscopy in the vicinity of 2.35 mum. Continuous current tuning over a more than 150-GHz frequency range has been realized. Direct absorption measurements have been carried out on the R, R, R, and R lines of carbon monoxide. Traces of carbon monoxide at the level of 0.3 part in 10(6) in volume at 100 Torr could be detected by the low-frequency wavelength-modulation technique and an astigmatic multipass cell. These results show a potential use of these diode lasers in portable low-cost trace-pollutant sensors.     

Development of a near-infrared/mid-infrared dual-region spectrometer for online process analysis

A near-infrared (NIR) and mid-infrared (mid-IR) dual-region spectrometer having two immersion probes, a transmission probe for NIR, and an attenuated total reflection (ATR) probe for mid-IR has been developed for highly reliable process monitoring and deep process understanding. This spectrometer facilitates sequential acquisition of both NIR (10,000-4000 cm(-1)) and mid-IR (5000-1200 cm(-1)) spectra by switching the light path leading to the probes without the need for probe replacement. The use of a single light source and a single beam splitter enables achievement of a permanent alignment of the optical system and sequential data acquisition. The transmission NIR and ATR mid-IR probes designed and developed in the present study facilitate the acquisition of NIR/mid-IR spectra with optimized absorption intensities in both regions by simply placing the probes into a sample solution. The performance of the developed spectrometer was demonstrated in monitoring the ethanol fermentation process. NIR/mid-IR spectra of the fermentation solution with multiplicative scatter correction (MSC) represent the relative changes in the concentrations of glucose and ethanol in both regions. Principal component analysis (PCA) was performed on the MSC-treated spectra in the regions 6300-5650 cm(-1), 4850-4300 cm(-1), and 3500-2880 cm(-1) to detect the end-point of the fermentation as an example of process monitoring. For all the regions, the score plot of the first principal component (PC) indicates that the fermentation progresses with the fermentation time and stops after 210 minutes and thus the end-point of the fermentation exists at around 210 minutes. The loading plot indicates that all of the first PCs are the relative changes in the concentrations of glucose and ethanol. This result reveals that the same chemical changes are observed in both transmission NIR and ATR mid-IR spectra. Multiple and simultaneous analysis was also performed, and intensity change in light scattering relating the growth of yeasts was monitored by the NIR spectra.     

Single-frequency Sb-based distributed-feedback lasers emitting at 2.3 microm above room temperature for application in tunable diode laser absorption spectroscopy

GaInAsSb/GaAlAsSb/GaSb distributed-feedback (DFB) laser diodes based on a type I active region were fabricated by molecular beam epitaxy at the Centre d'Electronique et de Micro-Optoélectronique de Montpellier (CEM2). The DFB processing was done by Nanoplus Nanosystems and Technologies GmbH. The devices work in the continuous-wave regime above room temperature around an emission wavelength of 2.3 microm with a side-mode suppression ratio greater than 25 dB and as great as 10 mW of output power. The laser devices are fully characterized in terms of optical and electrical properties. Their tuning properties made them adaptable to tunable diode laser absorption spectroscopy because they exhibit more than 220 GHz of continuous tuning by temperature or current. The direct absorption of CH4 is demonstrated to be possible with high spectral selectivity.     

Wavelength tuning and spectral properties of distributed feedback diode lasers with a short external optical cavity

We report on the wavelength tuning and spectral properties of distributed feedback (DFB) diode lasers operated with a plane external cavity (XC) mirror positioned as close as possible to the diode-laser front facet. These lasers generate single-frequency near IR radiation at wavelengths of 1392, 1580, 1602, and 1653 nm. A piezoelectric variation of the XC length provided continuous single-frequency tuning to as high as 19 GHz. A further benefit of XC DFB lasers is a residual amplitude modulation per gigahertz tuning of less than 10(-3). The XC feedback also suppresses residual side-mode oscillations to less than 60 dB. The laser's total intensity noise is close to the shot noise limit. The laser linewidth (measured in a beat note experiment) is less than 90 kHz within an acquisition time of 40 ms. The advantageous properties of XC DFB lasers for molecular spectroscopy are demonstrated by recording R(3) 2nu(3) overtone spectra of methane by single-scan single-pass absorption or frequency-modulation spectroscopy.     

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.     

Stable isotopic analysis of atmospheric methane by infrared spectroscopy by use of diode laser difference-frequency generation

An infrared absorption spectrometer has been constructed to measure the stable isotopic composition of atmospheric methane samples. The spectrometer employs periodically poled lithium niobate to generate 15 microW of tunable difference-frequency radiation from two near-infrared diode lasers that probe the nu3 rotational-vibrational band of methane at 3.4 microm. To enhance the signal, methane is extracted from 25 l of air by use of a cryogenic chromatographic column and is expanded into the multipass cell for analysis. A measurement precision of 12 per thousand is demonstrated for both delta13C and deltaD.     

Wide-bandwidth mode-hop-free tuning of extended-cavity GaN diode lasers

We present a new approach for extended-cavity diode-laser tuning to achieve wide mode-hop-free tuning ranges. By using a multiple piezoactuated grating mount, the cavity length and grating angle in the laser can be adjusted independently, allowing mode-hop-free tuning without the need for a mechanically optimized pivot-point mount. Furthermore, synchronized diode injection-current tuning allows diode lasers without antireflection coatings to be employed. In combination these two techniques make the construction of a cheap, efficient, and easily optimized extended-cavity diode laser possible. A theoretical analysis is presented for optimal control of piezoactuator displacements and injection current to achieve the widest possible mode-hop-free tuning ranges, and a comparison is made with measurements. The scheme is demonstrated for blue and violet GaN lasers operating at approximately 450 nm and approximately 410 nm, for which continuous tuning ranges exceeding 90 GHz have been achieved. Examples of applications of these lasers are also given.     

On-line multicomponent trace-gas analysis with a broadly tunable pulsed difference-frequency laser spectrometer

The design and application of a novel automated room-temperature laser spectrometer are reported. The compact instrument is based on difference-frequency generation in bulk LiNbO(3). The instrument employs a tunable cw external-cavity diode laser (795-825 nm) and a pulsed diode-pumped Nd:YAG laser (1064 nm). The generated mid-IR nanosecond pulses of 50-muW peak power and 6.5-kHz repetition rate, continuously tunable from 3.16 to 3.67 mum, are coupled into a 36-m multipass cell for spectroscopic studies. On-line measurements of methane are performed at concentrations between 200 ppb (parts in 10(9) by mole fraction) and approximately 1%, demonstrating a large dynamic range of 7 orders of magnitude. Furthermore computer-controlled multicomponent analysis of a mixture containing five trace gases and water vapor with an overall response time of 90 s at an averaging time of only approximately 30 s is reported. A minimum detectable absorption coefficient of 1.1 x 10(-7) cm(-1) has been achieved in an averaging time of 60 s, enabling detection limits in the ppb range for many important trace gases, such as CH(4), C(2)H(6), H(2)CO, NO(2), N(2)O, HCl, HBr, CO, and OCS.     

室温准连续多量子阱二极管激光器调谐特性

为了将应变补偿多量子阱（SC-MQW）激光器用于调谐激光吸收光谱（TDLAS）技术进行气体分子检测,研究了SC-MQW激光器在室温、准连续工作模式下的调谐特性.从半导体激光器的速率方程出发,分析了SC-MQW激光器输出波长与温度和注入电流的关系;使用傅里叶变换红外光谱仪（FT-IR）测量了激光器分别在不同电流、温度条件下的调谐特性,得到SC-MQW激光器在允许工作电流范围内的调谐范围接近20nm,电流调谐率约为0.03nm/mA;温度调谐率约为0.25nm/℃;电流和温度联合调谐的波长覆盖范围达50nm.结果表明,该激光器在带状吸收谱的挥发性有机物气体检测方面有很好的应用前景.     

Application of Balanced Detection to Absorption Measurements of Trace Gases with Room-Temperature, Quasi-cw Quantum-Cascade Lasers

Distributed-feedback quantum-cascade (QC) lasers are expected to form the heart of the next-generation mid-IR laser absorption spectrometers, especially as they are applied to measurements of trace gases in a variety of environments. The incorporation of room-temperature-operable, single-mode QC lasers should result in highly compact and rugged sensors for real-world applications. We report preliminary results on the performance of a laser absorption spectrometer that uses a QC laser operating at room temperature in a quasi-cw mode in conjunction with balanced ratiometric detection. We have demonstrated sensitivities for N(2)O [10 parts in 10(6) volume-mixing ratio for a 1-m path (ppmv-m)] and NO [520 parts in 10(9) volume-mixing ratio for a 1-m path (ppbv-m)] at 5.4 mum. System improvements are described that are expected to result in a 2 orders of magnitude increase in sensitivity.     

Diffractive optical element used in an external feedback configuration to tune the wavelength of uncoated Fabry-Pérot diode lasers

Abstract

A diffractive optical element (DOE) has been designed, fabricated and used in an external feedback configuration to set the wavelength of operation of uncoated Fabry-Pérot diode lasers. The DOE was designed to replace the conventional elements of an external feedback system, which are a collimating lens and grating in the Littrow configuration. The goal was to simplify use of the external cavity laser by replacing the lens and grating with a single optical element while maintaining the performance that is achieved with a grating and lens. Four DOEs were fabricated with two different focal lengths and two different reflectivities. DOE external cavity lasers were tested for maximum tunable range and stability of the wavelength of operation and compared with an external cavity laser based on a lens and grating in the Littrow configuration. A 40 nm tuning range was achieved with the DOE external cavity laser and this is comparable with the tuning range of the external cavity lasers based on a grating and collimating lens in the Littrow configuration.     

Measurements of (12)CH4 nu4 band halfwidths using a tunable diode laser system and a Fourier transform spectrometer

Air-broadened and N2-broadened halfwidths at room temperature for twenty-five transitions in the 4 fundamental band of '2CH4 have been determined from IR absorption spectra recorded with a tunable diode laser spectrometer. Two tunable diode lasers operating in the 1250-1380-cm(-1) region were used to obtain these data. Air-broadened halfwidths for twenty of these lines were also determined from additional spectra recorded at 0.01-cm(-1) resolution with the Fourier transform spectrometer in the McMath solar telescope complex on Kitt Peak. The air-broadened halfwidths obtained from these two techniques are very consistent with agreement better than 3% in most cases.     

Real-time diode laser measurements of vapor-phase benzene

An absorption spectrometer equipped with a IV-VI semiconductor tunable mid-IR diode laser was used to make sensitive measurements of benzene (C(6)H(6)) gas in the 5.1-microm spectral range. Wavelength modulation coupled with second-harmonic detection achieved accurate real-time quantification of benzene concentrations down to a minimum detection limit of 1 ppmv with an integration time of 4 s. A variety of calibrated benzene-sensing measurements were made, including the determination of the benzene concentrations in vehicle exhaust and headspace vapors from unleaded gasoline and other liquids. Kinetic phenomena, including the monitoring of benzene evaporation and absorption/desorption by granulated activated carbon were observed with the instrument. Measurements were performed that allowed experimental determination of the activation energy for desorption of benzene from activated carbon, which was found to be 198 meV/molecule (19.0 kJ/mol).     

Extension of wavelength-modulation spectroscopy to large modulation depth for diode laser absorption measurements in high-pressure gases

Tunable diode laser absorption measurements at high pressures by use of wavelength-modulation spectroscopy (WMS) require large modulation depths for optimum detection of molecular absorption spectra blended by collisional broadening or dense spacing of the rovibrational transitions. Diode lasers have a large and nonlinear intensity modulation when the wavelength is modulated over a large range by injection-current tuning. In addition to this intensity modulation, other laser performance parameters are measured, including the phase shift between the frequency modulation and the intensity modulation. Following published theory, these parameters are incorporated into an improved model of the WMS signal. The influence of these nonideal laser effects is investigated by means of wavelength-scanned WMS measurements as a function of bath gas pressure on rovibrational transitions of water vapor near 1388 nm. Lock-in detection of the magnitude of the 2f signal is performed to remove the dependence on detection phase. We find good agreement between measurements and the improved model developed for the 2f component of the WMS signal. The effects of the nonideal performance parameters of commercial diode lasers are especially important away from the line center of discrete spectra, and these contributions become more pronounced for 2f signals with the large modulation depths needed for WMS at elevated pressures.