Quantum cascade laser-based spectrometer for high sensitive measurements of trace gases in air

A quantum cascade(QC)laser-based spectrometer is developed to measure trace gases in air.The proposed spectrometer is tested for N2O,and the results presented in this letter.This system takes advantage of recent technology in QC lasers by utilizing intra-pulse scan spectroscopy,which allows high sensitive measurement.Without calibration gases,the gas concentration can be calculated with scan integration and the corresponding values from the HITRAN04 database.By analyzing the Allan variance,a detection limit of 2 ppb is obtained.Continuous measurement of N2O sampled from ambient air shows the applicability of the proposed system for the field measurements of gases of environmental concern.     

Development of a compact quantum cascade laser spectrometer for field measurements of CO2 isotopes

We report the development of a field-deployable, pulsed quantum cascade laser spectrometer. The instrument is designed to measure the ¹³C/¹²C isotopic ratio in the CO₂ released from volcanic vents. Specific ¹²CO₂ and ¹³CO₂ absorption lines were selected around 4.3 m, where the P-branch of ¹²CO₂ overlaps the R-branch of ¹³CO₂ of the 00⁰1–00⁰0 vibrational transition. This particular selection makes the instrument insensitive to temperature variations. A dual-channel cell balances the two absorption signals. We provide details of the instrument design and a preliminary demonstration of its performance based on laboratory measurements of ¹⁶O¹²C¹⁶O and ¹⁶O¹²C¹⁸O. PACS 42.55.Px; 42.62.Fi; 07.88.+y     

Si/SiGe量子级联激光器的能带设计

详细论述Si/SiGe量子级联激光器的工作原理，通过对比找到一组合适的Si，Ge和SiGe合金的能带参数，进而应用6×6 k·p方法计算了不同阱宽、不同Ge组分Si/Si_1-xGe_x/Si量子阱价带量子化的空穴能级本征值及其色散关系，分析Si/Si_1-xGe_x/Si量子阱空穴态能级间距随阱宽和组分的变化规律，最后应用计算结果讨论了Si/SiGe量子级联激光器有源区的能带设计，有益于优化Si /SiGe量子级联激光器结构. 关键词： 硅锗材料 量子级联激光器 子带跃迁 k·p方法')" href="#">k·p方法     

InP基高功率短波长量子级联激光器设计

阐述了InP基高功率短波长量子级联激光器(QCL)的设计原理和设计方案。从有源区设计模型出发,介绍了器件的理想和实际载流子传输路径,进而指出有源区设计的发展趋势和方法。根据器件的发展进程,综述了双声子共振设计,非共振抽取式设计,超强耦合设计,深阱设计,浅阱设计,短注入区设计等先进设计方案,这些设计方案使得QCL在低温下的电光转换效率在50%以上,最大室温连续输出功率超过3 W,而器件的特征温度T₀和T₁的最大值分别达到383 K和645 K。针对量子级联激光器的短波长高功率提供的先进设计方案扩大了QCL在民用与军用领域的应用前景,该设计方案亦可为其它波段量子级联激光器实现室温高功率的设计提供借鉴。     

基于中红外量子级联激光器和石英增强光声光谱的CO超高灵敏度检测研究

采用石英增强光声光谱(QEPAS)技术对CO痕量气体展开检测研究. 为了实现超高灵敏度探测, 采用输出波长为4.6 μm的新颖中红外高功率分布反馈量子级联激光器为光源, 实现了对CO气体基频吸收带的激发与测量. 在优化了调制深度、气体压强和提高了CO分子的振动-转动弛豫速率后, 获得了1.95 ppbv的优异探测极限. 在分析检测结果的过程中, 讨论了能级寿命对信号强度的影响, 并对QEPAS信号强度的表达式进行了修正.     

Optimization of a compact photoacoustic quantum cascade laser spectrometer for atmospheric flux measurements: application to the detection of methane and nitrous oxide

Room temperature (RT) quantum cascade lasers (QCL) are now available even in continuous wave (cw) mode, which is very promising for in situ gas detectors. Ambient air monitoring requires high sensitivity with robust and simple apparatus. For that purpose, a compact photoacoustic setup was combined with two cw QCLs to measure ambient methane and nitrous oxide in the 8 μm range. The first laser had already been used to calibrate the sensitivity of the photoacoustic cell and a detection limit of 3 ppb of CH₄ with a 1s integration time per point was demonstrated. In situ monitoring with this laser was difficult because of liquid nitrogen cooling. The second laser is a new RT cw QCL with lower power, which enabled one to reach a detection limit of 34 ppb of methane in flow. The loss in sensitivity is mainly due to the weaker power as photoacoustic signal is proportional to light power. The calibration for methane detection leads to an estimated detection limit of 14 ppb for N₂O flux measurements. Various ways of modulation have been tested. The possibility to monitor ambient air CH₄ and N₂O at ground level with this PA spectrometer was demonstrated in flux with these QCLs. PACS 07.88; 92.60.Sz     

Chirped quantum cascade laser induced rapid passage signatures in an optically thick gas

We report observations of rapid passage signals induced in samples of N₂O and CH₄ present in a multipass cell with an optical path length of 5 m. The effect of laser power and chirp rate upon the signals has been studied by utilising two different chirped quantum cascade lasers operating around 8 μm. The rapid passage signals exhibit an increasing delay in the switch from absorption to emission as a function of increased gas pressure (up to 8 Torr of gas). By comparing a selection of transitions in N₂O and CH₄, we show that, unlike ammonia, this ‘pressure shift’ is independent of the transition dipole moment, spectroscopic branch probed and laser chirp rate. As the transition dipole moment is much larger in nitrous oxide than methane, we believe that this indicates that N₂O–N₂O collisions are more efficient at removing coherence from the polarised sample than CH₄–CH₄ collisions. We have also observed this pressure shift in a short path length of 40 cm, although with a much reduced value, indicating that propagation effects are important in this optically thick minimally damped system.     

Applications of quantum cascade lasers for sensitive trace gas measurements of CO, CH4, N2O and HCHO

We describe here a sensitive quantum cascade laser absorption spectrometer (QCLAS) employed for aircraft based measurements during the GABRIEL 2005 and HOOVER 2006 and 2007 campaigns. This 3-channel instrument measures CO, HCHO, CH₄ and N₂O using a 64-m path double corner cube White cell. Performance of the instrument was examined for the four species and precisions for CO, N₂O and CH₄ were measured in the field to be 0.5, 0.5 and 0.7% respectively (2σ). The 1σ detection limit for HCHO was ∼500 pptv for a 2 s average, while signal averaging of the HCHO over a 2 min time interval resulted in a 150 pptv detection limit with a duty cycle of 60%. PACS  82.80.Gk; 07.88.+y; 42.62.-b; 92.60.H-     

Real-time measurements of trace gases using a compact difference-frequency-based sensor operating at 3.5 μm

3 for on-line absorption measurements of H₂CO, CH₄, and H₂O near 3.5 μm is reported. Formaldehyde levels of 30 ppb, corresponding to absorptions of 2×10^-4 have been measured using absorption spectroscopy. In this paper we report specifically the performance of this sensor as part of the 1997 Lunar–Mars Life Support Test program at the NASA Johnson Space Center. Received: 1 April 1998     

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     

In-flight measurements of ambient methane, nitrous oxide and water using a quantum cascade laser based spectrometer

In-flight measurements of ambient methane, nitrous oxide and water have been made using frequency down-chirped radiation from a compact, pulsed, quantum-cascade laser spectrometer. In three flights from Oxford airport in October 2006 the variations of the concentration of these three trace gases could be measured and related to possible sources in the flight path. PACS 33.20.EA; 42.62.Fi; 42.68.Ca; 85.35.Be     

Spectroscopic detection of biological NO with a quantum cascade laser

Two configurations of a continuous wave quantum cascade distributed feedback laser-based gas sensor for the detection of NO at a parts per billion (ppb) concentration level, typical of biomedical applications, have been investigated. The laser was operated at liquid nitrogen temperature near λ=5.2 μm. In the first configuration, a 100 m optical path length multi-pass cell was employed to enhance the NO absorption. In the second configuration, a technique based on cavity-enhanced spectroscopy (CES) was utilized, with an effective path length of 670 m. Both sensors enabled simultaneous analysis of NO and CO₂ concentrations in exhaled air. The minimum detectable NO concentration was found to be 3 ppb with a multi-pass cell and 16 ppb when using CES. The two techniques are compared, and potential future developments are discussed. Received: 1 November 2000 / Revised version: 19 January 2001 / Published online: 20 April 2001     

Generation of tunable far-infrared radiation with a quantum cascade laser

We demonstrate the generation of cw tunable far-infrared radiation by mixing a quantum cascade laser and a CO>(2) laser in a W-Ni metal-insulator-metal diode. The first known spectroscopic application to the recording of an H(79)Br transition near 4.47 THz is reported.     

A high resolution ESCA instrument with X-ray monochromator for gases and solids

A new ESCA instrument with a fine-focussing X-ray monochromator, a high power electron gun, a rotating anode and a computerized multi-detector system is described. The instrument is suitable for the study of both solids and gases. The improved performance of the instrument is illustrated by a number of new spectra. Thus, spectra of gold, neon, methane, air, trifluoroacetate, thiophene and carbonyl sulphide, carbon monoxide, nitrogen, benzene and trithiapentalene are reported.     

Sub-part-per-billion detection of nitric oxide in air using a thermoelectrically cooled mid-infrared quantum cascade laser spectrometer

Non-cryogenic, laser-absorption spectroscopy in the mid-infrared has wide applications for practical detection of trace gases in the atmosphere. We report measurements of nitric oxide in air with a detection limit less than 1 nmole/mole (<1 ppbv) using a thermoelectrically cooled quantum cascade laser operated in pulsed mode at 5.26 μm and coupled to a 210-m path length multiple-pass absorption cell at reduced pressure (50 Torr). The sensitivity of the system is enhanced by operating under pulsing conditions which reduce the laser line width to 0.010 cm^-1 (300 MHz) HWHM, and by normalizing pulse-to-pulse intensity variations with temporal gating on a single HgCdTe detector. The system is demonstrated by detecting nitric oxide in outside air and comparing results to a conventional tunable diode laser spectrometer sampling from a common inlet. A detection precision of 0.12 ppb Hz^-1/2 is achieved with a liquid-nitrogen-cooled detector. This detection precision corresponds to an absorbance precision of 1×10^-5 Hz^-1/2 or an absorbance precision per unit path length of 5×10^-10 cm^-1 Hz^-1/2. A precision of 0.3 ppb Hz^-1/2 is obtained using a thermoelectrically cooled detector, which allows continuous unattended operation over extended time periods with a totally cryogen-free instrument. Received: 1 May 2002 / Revised version: 6 June 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +1-978/663-4918, E-mail: ddn@aerodyne.com     

A high resolution ESCA instrument with X-ray monochromator for gases and solids

A new ESCA instrument with a fine-focussing X-ray monochromator, a high power electron gun, a rotating anode and a computerized multi-detector system is described. The instrument is suitable for the study of both solids and gases. The improved performance of the instrument is illustrated by a number of new spectra. Thus, spectra of gold, neon, methane, air, trifluoroacetate, thiophene and carbonyl sulphide, carbon monoxide, nitrogen, benzene and trithiapentalene are reported.     

High power room-temperature design of terahertz quantum cascade laser based on difference frequency generation

Terahertz (THz) quantum cascade lasers (QCLs) are key elements for high-power terahertz beam generation for integrated applications. In this study, we design a highly nonlinear THz-QCL active region in order to increase the output power of the device especially at lower THz frequencies based on difference frequency generation (DFG) process. It has been shown that the output power increases for a 3.2 THz structure up to 1.2 μW at room temperature in comparison with the reported power of P = 0.3 μW in [1]. The mid-IR wavelengths associated with this laser are λ₁ = 12.12 μm and λ₂ = 13.93 μm, which are mixed in a medium with high second-order nonlinearity. A similar approach has been used to design an active region with THz frequency of 1.8 THz. The output power of this structure reaches to 1 μW at room temperature where the mid-IR wavelengths are λ₁ = 12.05 μm, λ₂ = 12.99 μm.     

Spice simulation of a large-signal model for quantum cascade laser

A large-signal spice model of QCL is described, which is based on a set of rate equations. This model can also perform both small- and large-signal simulations. The dynamic responses obtained by using Spice simulator are obviously different from those in the interband lasers. No resonance peak is presented in the modulation response and the 3-dB bandwidth would reach tens of GHz. The turn-on delay time is on the order of ps that accord with the carrier lifetime of QCL. In addition, the dependency of bias current on the dynamic response are investigated. Results indicates that the bias current has a significant effects on the QC laser.      

Photoacoustic spectroscopy for trace gas detection with cryogenic and room-temperature continuous-wave quantum cascade lasers

The main characteristics that a sensor must possess for trace gas detection and pollution monitoring are high sensitivity, high selectivity and the capability to perform in situ measurements. The photacoustic Helmholtz sensor developed in Reims, used in conjunction with powerful Quantum Cascade Lasers (QCLs), fulfils all these requirements. The best cell response is # 1200 V W⁻¹ cm and the corresponding ultimate sensitivity is j 3.3 × 10⁻¹⁰ W cm⁻¹¹ Hz^−11/2. This efficient sensor is used with mid-infrared QCLs from Alpes Lasers to reach the strong fundamental absorption bands of some atmospheric gases. A first cryogenic QCL emitting at 7.9 μm demonstrates the detection of methane in air with a detection limit of 3 ppb. A detection limit of 20 ppb of NO in air is demonstrated using another cryogenic QCL emitting in the 5.4 μm region. Real in-situ measurements can be achieved only with room-temperature QCLs. A room-temperature QCL emitting in the 7.9 μm region demonstrates the simultaneous detection of methane and nitrous oxide in air (17 and 7 ppb detection limit, respectively). All these reliable measurements allow the estimated detection limit for various atmospheric gases using quantum cascade lasers to be obtained. Each gas absorbing in the infrared may be detected at a detection limit in the ppb or low-ppb range.     

Design of surface emitting distributed feedback quantum cascade laser with single-lobe far-field pattern and high outcoupling efficiency

A 7.8-$\mu $m surface emitting second-order distributed feedback quantum cascade laser (DFB QCL) structure with metallized surface grating is studied. The modal property of this structure is described by utilizing coupled-mode theory where the coupling coefficients are derived from exact Floquet--Bloch solutions of infinite periodic structure. Based on this theory, the influence of waveguide structure and grating topography as well as device length on the laser performance is numerically investigated. The optimized surface emitting second-order DFB QCL structure design exhibits a high surface outcoupling efficiency of 22{\%} and a low threshold gain of 10~cm$^{ - 1}$. Using a {$\pi $} phase-shift in the centre of the grating, a high-quality single-lobe far-field radiation pattern is obtained.