Mid-infrared photoacoustic spectroscopy of solids using an external-cavity quantum-cascade laser

We describe the use of a pulsed external-cavity quantum-cascade laser (EC-QCL) for the acquisition of mid-IR photoacoustic (PA) spectra of solids. The EC-QCL employed in this work operates from 990 to 1075 cm(-1) (9.30-10.10 microm). A gas-microphone PA cell was used as the detector, and the signal was demodulated using a lock-in amplifier. PA EC-QCL spectra of solids display bands significantly narrower than those in corresponding PA Fourier transform infrared spectra.     

Cavity ringdown spectroscopy using mid-infrared quantum-cascade lasers

Cavity ringdown spectra of ammonia at 10 parts in 10(9) by volume (ppbv) and higher concentrations were recorded by use of a 16-mW continuous-wave quantum-casacde distributed-feedback laser at 8.5 mum whose wavelength was continuously temperature tuned over 15 nm. A sensitivity (noise-equivalent absorbance) of 3.4x10(-9) cm(-1) Hz(-1/2) was achieved for ammonia in nitrogen at standard temperature and pressure, which corresponds to a detection limit of 0.25 ppbv.     

Longitudinal resonant spectrophone for CO-laser photoacoustic spectroscopy

A photoacoustic (PA) system for monitoring gaseous air pollutants absorbing in the CO-laser range is presented. The characteristics of the CO laser and the interference caused by water-vapor absorption demand a special design of the PA cell and experimental setup. The optimum cell design was found by numerical simulation of the acoustic properties of various cell geometries. For this purpose a model using infinitesimal analogue acoustic impedances was developed. Based on a matrix formalism for fourterminals, a computer program was applied that permits the calculation of the frequency response of the PA signal amplitude at any position within a one-dimensional PA cell. Excellent agreement with experimental data is obtained. As a result, a new design for an acoustically resonant spectrophone with improved properties is presented. The response of the cell with aQ-factor of 52, operated at 555 Hz, is 2000 Pa cm/W.     

Sensitive harmonic detection of ammonia trace using a compact photoacoustic resonator at double-pass configuration and a wavelength-modulated distributed feedback diode laser

A sensitive detection of ammonia in parts per billion by volume is described. The system based on photoacoustic spectroscopy (PAS) consists of distributed feedback laser diode emitting near 1,531.7 nm and a compact PA cell at double-pass configuration. In order to optimize the signal background ratio of the system, two types of modulations were tested, amplitude and wavelength modulations (WM). Using a digital lock-in amplifier, the 1f and 2f detection in WM could be investigated. A detection limit of 470 parts per million by volume could be achieved at WM-2f. In the sense of quantifing the adsorption–desorption process, the response time of the system and detection accuracy was performed in different flows. Response times between 10 and 49 s, depending on the flow rate, were obtained which enables the PA system to measure low concentrations of ammonia with high accuracy in real time.     

1.531μm附近NH_3分子痕量探测

基于离轴积分腔输出光谱技术(OA-ICOS)的小型集成系统以工作在近红外1.531 μm附近的分布反馈式(DFB)二极管激光器为光源,测量了窒温下各种低浓度NH_3与空气的混合气.首先利用标准浓度的CO_2气体校准得到腔镜的有效反射率R为0.996 9,在此条件下,基长35.8 cm的光学谐振腔作为吸收池可得到115.46 m的吸收光程.NH_3在6 528.764cm~(-1)位置的强吸收谱线被选择用于痕最探测,在100 torr的总压力下,实验测得NH_3的探测极限为2.66 ppmv(S/N～3),之后结合波长调制技术,在信号检测通路中采用锁丰兀放大技术来实现调制信号的二次谐波检测,这可以更好地抑制背景噪声而提高探测信号的信噪比,最终将NH_3的探测极限进一步提高到0.274 ppmv(S/N～3).     

A sensitivity comparison of three photoacoustic cells containing a single microphone,a differential dual microphone or a cantilever pressure sensor

Three photoacoustic (PA) cells designed for trace-gas sensing were compared by measuring absorption by the P(15) rotational line of the vibrational combination band of acetylene using a distributed-feedback diode laser. Normalised sensitivities were determined for each cell by analysis of the signal to noise ratios of acquired spectra. The first cell was constructed in-house, and contained a single electret microphone held in a stainless steel tube. The second cell was a differential PA cell that contained two microphones housed in identical flow tubes, with one microphone to detect the PA signal and the other to determine background noise levels. The third cell contained a novel cantilever pressure sensor, movement of which was measured by a compact laser interferometer. Normalised sensitivities (2σ) of 3.1×10^-7, 1.7×10^-7 and 2.2×10^-9 cm^-1 W Hz^-1/2, respectively, were obtained. An erbium-doped fibre amplifier was used to amplify the laser power, and a detection limit of 9.8×10¹⁰ molecule cm^-3 was obtained using the cantilever pressure sensor PA cell, with a laser power of 1.17 W. This detection limit corresponded to a mixing ratio of 14.5 parts per billion by volume at 277 mbar. PACS 82.80.Kq; 42.62.Fi; 82.80.Gk     

Sub-part-per-billion monitoring of nitric oxide by use of wavelength modulation spectroscopy in combination with a thermoelectrically cooled, continuous-wave quantum cascade laser

We used a thermoelectrically cooled, continuous-wave, quantum cascade laser operating between 1847 and 1854 cm(-1) in combination with wavelength modulation spectroscopy for the detection of nitric oxide (NO) at the sub-part-per-billion by volume (ppbv) level. The laser emission overlaps the P7.5 doublet of NO centered around 1850.18 cm(-1). Using an astigmatic multiple-pass absorption cell with an optical path length of 76 m, we achieved a detection limit of 0.2 ppbv at 10 kPa, with a total acquisition time of 30 s. The corresponding minimal detectable absorption is 8.8 x 10(-9) cm(-1) Hz(-1/2).     

1.315 μm波长附近实际大气高分辨率吸收光谱

 用窄线宽、脉冲可调谐光参量振荡器（OPO）作光源，使用光程长达1 097m的怀特池，采用单探测器分时复用的探测方法，首次在吸收池中精确测量了实际大气中1.315 μm波长附近高分辨率吸收光谱，实验验证了实际大气中水汽是该波段的主要吸收气体；得到了实际大气中吸收分子在氧碘激光波长（7 603.14cm^-11）处的吸收截面为 (1.05±0.09)×10^-24 cm²(标准大气条件下）以及在该波段主要吸收谱线的参数，包括吸收线的位置、线强度、压力加宽半宽度等。利用实测的线参数计算了在氧碘激光波长附近大气分子的吸收截面，发现吸收最小的波长分别位于7 603.31和7 603.93cm^-1，其值约为(8.9±0.8)×10^-25 cm²，比氧碘激光波长处的吸收截面约小15%。     

CO2的腔增强吸收与高灵敏吸收光谱研究

腔增强吸收光谱(CEAS)是在衰荡吸收光谱的基础上发展起来的一种新型的直接吸收光谱技术.文章报道了用中心输出波长为1.573μm的窄线宽连续可调谐半导体激光器(DFB封装)作光源,用两块高反射率平凹透镜(在1.573μm附近,凹面反射率R～99.4%,曲率半径r～1 m)组成对称共焦腔作吸收池的腔增强吸收光谱系统.采用扫描腔长的方法改变谐振腔的模式,当激光器的输出频率与谐振腔的某一腔模之间满足共振匹配关系时,激光被耦合到谐振腔内,用探测器接收透过谐振腔的光信号,同时用波长计精确测量激光器的输出波长.在33.5 cm长的吸收池内测量了吸收强度为1.816×10-23cm-1·(molecule·cm-2)-1的二氧化碳分子的弱吸收谱线,探测灵敏度达到了6.78×10-7 cm-1.实验结果表明,腔增强吸收光谱具有灵敏度高,装置简单,易于操作等优点.     

Photoacoustic spectroscopy for fast and sensitive ammonia detection

A photoacoustic (PA) spectrometer with H-type first longitudinal resonant cells for ammonia detection is developed. A new PA cell structure is designed to accelerate the drift velocity of the sample gas near the cell surface, so that the short response time at the flow rate of 100 sccm (standard cubic centimeter per minute) is achieved. The response time of 5 min and detection limit of 0.86 ppbv is reached for ammonia concentration measurement with a Teflon polytetrafluoroethylene (PTFE) cell. Further improvement could be expected when using a brass cell with a high quality Teflon fluorinated ethylene propylene (FEP) coating.     

Evaluation of ammonia absorption coefficients by photoacoustic spectroscopy for detection of ammonia levels in human breath

Photoacoustic spectroscopy represents a powerful technique for measuring extremely low absorptions independent of the path length and offers a degree of parameter control that cannot be attained by other methods. We report precise measurements of the ammonia absorption coefficients at the CO₂ laser wavelengths by using a photoacoustic (PA) cell in an extracavity configuration and we compare our results with other values reported in the literature. Ammonia presents a clear fingerprint spectrum and high absorption strengths in the CO₂ wavelengths region. Because more than 250 molecular gases of environmental concern for atmospheric, industrial, medical, military, and scientific spheres exhibit strong absorption bands in the region 9.2–10.8 μm, we have chosen a frequency tunable CO₂ laser. In the present work, ammonia absorption coefficients were measured at both branches of the CO₂ laser lines by using a calibrated mixture of 10 ppm NH₃ in N₂. We found the maximum absorption in the 9 μm region, at 9R(30) line of the CO₂ laser. One of the applications based on the ammonia absorption coefficients is used to measure the ammonia levels in exhaled human breath. This can be used to determine the exact time necessary at every session for an optimal degree of dialysis at patients with end-stage renal disease.     

Tunable fiber laser based photoacoustic spectrometer for breath ammonia analysis during hemodialysis1

A photoacoustic (PA) spectrometer based on a near-IR tunable fiber laser is developed and used for breath ammonia analysis. We successfully measured the breath ammonia level variation of six patients with end-stage renal disease while they were undergoing hemodialysis in the hospital. The measurement results showed that the initial concentration level of the breath ammonia were from 1600 to 2200 ppb before dialysis treatment, the levels decreased to 200–600 ppb in the end stage of dialysis, which close to the levels of healthy persons. Further improvement and applications of this PA spectrometer are discussed.     

Continuous-wave operation of a broadly tunable thermoelectrically cooled external cavity quantum-cascade laser

Continuous-wave operation of an external cavity quantum-cascade laser on a thermoelectric cooler is reported. The active region of the gain element was based on a bound-to-continuum design emitting near 5.15 microm. The external cavity setup was arranged in a Littrow configuration. The front facet of the gain chip was antireflection coated. The laser could be tuned over more than 170 cm(-1) from 4.94 to 5.4 microm and was single mode over more than 140 cm(-1). The output power was in excess of 10 mW over approximately 100 cm(-1) and in excess of 5 mW over approximately 130 cm(-1) at -30 degrees C.     

Demonstration of a transient-gain nickel-like xenon-ion x-ray laser

We demonstrate a high-gain nickel-like xenon-ion x-ray laser, using a picosecond-laser-irradiated gas-puff target. The elongated x-ray laser plasma column was produced by irradiation of the gas-puff target with line-focused double picosecond laser pulses with a total energy of 18 J in a traveling-wave excitation scheme. Strong lasing at 9.98 nm was observed, and a high gain coefficient of 17.4 cm(-1) was measured on the transient collisionally excited 4d-4p , J=0-1 transition for nickel-like xenon ions with target lengths as great as 0.45 cm. A weak nickel-like lasing line at a shorter wavelength of 9.64 nm was also observed, with a gain coefficient of 5.9 cm(-1) .     

Highly efficient 1.3-microm second-stokes PbWO4 Raman laser

A second-Stokes Raman laser based on PbWO4 with a 1.316-microm wavelength pumped by an approximately 120-ps Nd:YAG laser at 1.06415 microm scattered at 901 cm(-1) phonon was developed. High-reflection mirrors for the Stokes wavelength were used. The maximum output energy was 0.85 mJ. The conversion efficiency increased with crystal length of 40-100 mm up to 30%. The spatial beam profile was smooth, and the Raman laser emission lasted for approximately 18 ns. New stimulated Raman scattering lines from a phonon at 323 cm(-1) were observed.     

High-resolution (Doppler-limited) spectroscopy using quantum-cascade distributed-feedback lasers

Lasing characteristics were evaluated for distributed-feedback quantum-cascade (QC) lasers operating in a continuous mode at cryogenic temperatures. These tests were performed to determine the QC lasers' suitability for use in high-resolution spectroscopic applications, including Doppler-limited molecular absorption and pressure-limited lidar applications. By use of a rapid-scan technique, direct absorbance measurements of nitric oxide (NO) and ammonia (NH>(3)) were performed with several QC lasers, operating at either 5.2 or 8.5 microm. Results include time-averaged linewidths of better than 40 MHz and long-term laser frequency reproducibility, even after numerous temperature cycles, of 80 MHz or better. Tuning rates of 2.5 cm(-1) in 0.6 ms can be easily achieved. Noise-equivalent absorbance of 3 x 10(-6) was also obtained without optimizing the optical arrangement.     

Photoacoustic spectroscopy using quantum-cascade lasers

Photoacoustic spectra of ammonia and water vapor were recorded by use of a continuous-wave quantum-cascade distributed-feedback (QC-DFB) laser at 8.5 mum with a 16-mW power output. The gases were flowed through a cell that was resonant at 1.6 kHz, and the QC-DFB source was temperature tuned over 35 nm for generation of spectra or was temperature stabilized on an absorption feature peak to permit real-time concentration measurements. A detection limit of 100 parts in 10(9) by volume ammonia at standard temperature and pressure was obtained for a 1-Hz bandwidth in a measurement time of 10 min.     

Absorption spectroscopy of ammonia between 6526 and 6538 cm−1

The spectral measurements of ammonia absorption lines from 6526 to 6538 cm^?1 have been performed at room temperature by using fiber-coupled distributed feedback (DFB) diode laser operating at 1.531 μm. As many as 152 lines of ammonia and its line intensities, self-broadening and air-broadening coefficients were obtained, which include many weak lines not previously reported. The 20 strongest lines were obtained using the traditional direct absorption spectroscopy technology with a 30 cm single-path cell and the other 132 lines were acquired using a compact system based on off-axis integrated-cavity output spectroscopy (OA-ICOS) with an effective optical path of 36.62 m.     

Z-scan analytical theories for characterizing multiphoton absorbers

The open-aperture Gaussian-beam Z-scan measurements for characterizing an optically thin multiphoton-absorbing material were systematically investigated. Two widely used temporal profiles of the laser pulses on Z-scan traces were considered as well. The analytical polynomial expressions of Z-scan traces were presented for a thin sample with only one nonlinear process at a time [two-, three-, four-, or five-photon absorption (2PA, 3PA, 4PA, or 5PA)] and concurrence of two different processes (e.g., 2PA and 3PA, 3PA and 4PA, or 4PA and 5PA), respectively. A simple yet highly efficient approach was presented for identifying and evaluating the simultaneous n- and (n+1)-photon absorption coefficients.     

Demonstration of a Ni-like Kr optical-field-ionization collisional soft x-ray laser at 32.8 nm

We report the first experimental demonstration of a Ni-like optical-field ionization collisional soft x-ray laser. The amplifying medium is generated by focusing a circularly polarized 760 mJ, 30 fs, 10-Hz Ti:sapphire laser beam in a few mm cell filled with krypton. We have measured a gain coefficient of 78 cm(-1) on the 3d(9)4d 1S0-3d(9)4p(1)P1 transition at 32.8 nm, which is here amplified for the first time. This radiation source represents the shortest wavelength optical-field ionization collisional soft x-ray laser ever produced. The influence of the gas pressure and the pumping energy on the lasing output are also presented.