Intracavity laser absorption spectroscopy and cavity ring-down spectroscopy in low-pressure flames

Intracavity laser absorption spectroscopy (ICLAS) and cavity ring-down spectroscopy (CRDS) have been used for measurement of the NH₂-radical spectrum near 643 nm. NH₂ was obtained in low-pressure methane/air flat flames doped with minor amounts of ammonia (as low as 0.023%). The NH₂ concentration was measured both by CRDS and ICLAS in the same conditions. This enables us to compare the practical sensitivity of the two methods. Both methods were also used for measurements in a sooting acetylene/air flame (ϕ = 2.6). The comparative advantages of the methods and their complementarities are discussed.     

高灵敏度光谱测量技术:腔振铃吸收光谱

腔振铃激光吸收光谱技术是近年快速发展的一项新颖的光谱技术,它不仅检测灵敏度高,而且结构简单,不需要高昂的光谱设备,特别适合于测量弱吸收物质,包括气体、固体、液体等稳态粒子和金属化合物、自由基、团簇等瞬态粒子.本文在介绍其基本原理的基础上,介绍了使用脉冲激光与连续激光光源的2种技术方案.     

Molecular oxygen detection in low pressure flames using cavity ring-down spectroscopy

Cavity ring down spectroscopy is used for measurement of the concentration profiles of oxygen in the low pressure (30 Torr) methane/nitrogen/oxygen flames. Three different equivalence ratios are used: 0.8, 1.0 and 1.17. Molecular oxygen concentration is monitored via rotational spectrum of b¹ Σ _g ⁺←X³ Σ _g ^- (v^′=0-v^′′=0) transition, also known as atmospheric A band, located near 750 nm. The P(15)P(15) line is used for concentration measurements. The sensitivity reached is 2.2×10^-8 cm^-1. The concentration profiles are in a good agreement with the ones calculated using GRI-3.0 mechanism. PACS 33.20.Kf; 33.70.Fd; 42.60.Da     

Direct detection of acetylene in air by continuous wave cavity ring-down spectroscopy

Diode laser-based continuous wave cavity ring-down spectroscopy (cw-CRDS) in the near-infrared region has been used to measure the mixing ratio of acetylene (C₂H₂) in ambient air. Detection limits of 120 parts per trillion by volume (pptv) for 20 min and 340 pptv for 70 s acquisition time were achieved without sample pre-concentration, measuring on a C₂H₂ absorption line at 6565.620 cm^?1 (～1523 nm). Several indoor and outdoor air samples were collected at different locations in the Helsinki metropolitan area and analyzed using static-cell measurements. In addition, flow measurements of indoor and outdoor air have been performed continuously over several days with a time resolution of down to one minute. Baseline acetylene levels in the range of 0.4 to 3 parts per billion by volume (ppbv), with a maximum around midday and a minimum during the night, were measured. Sudden high mixing ratios of up to 60 ppbv were observed in outdoor air during daytime on a minute time scale. In general, the indoor mixing ratios were found to be higher than those in outdoor air. The acetylene levels correlated with the ambient CO levels and with outdoor temperature.     

用光腔衰荡技术测量镜片的反射率

 根据光腔衰荡光谱技术原理,建立了测量镜片反射率的实验装置。利用该装置测定了一对反射率相等的高反射腔镜,反射率测试结果为（99.925±0.001）%;以22.5°将直腔变为折叠腔,测得的反射率为（99.992±0.003）％。重复测定反射镜样品的反射率,精度达到10^－5。该测量装置可用于超低损耗薄膜高反射镜反射率的精确测量。轻微移动探测器位置,对腔镜的测试结果影响不大。     

用光腔衰荡技术测量镜片的反射率

根据光腔衰荡光谱技术原理,建立了测量镜片反射率的实验装置。利用该装置测定了一对反射率相等的高反射腔镜,反射率测试结果为（99.925±0.001）%;以22.5°将直腔变为折叠腔,测得的反射率为（99.992±0.003）％。重复测定反射镜样品的反射率,精度达到10－5。该测量装置可用于超低损耗薄膜高反射镜反射率的精确测量。轻微移动探测器位置,对腔镜的测试结果影响不大。     

Investigation on an evanescent wave fiber-optic absorption sensor based on fiber loop cavity ring-down spectroscopy

An improved ring-down measurement principle for optical waveguides is presented. Fiber loop ring-down spectroscopy allows for measurement of minute optical losses in high-finesse fiber-optic cavities and immunity to the fluctuation of laser source. The evanescent wave absorption losses dependent on the absorption and the refractive index of ambient solution have been theoretically analyzed. The complex refractive index is introduced into our model and extinction coefficient can be calculated accurately through finite element analysis by setting the boundaries of the fiber and the ambient conditions. Using this method, the refractive index of environment can be taken into consideration. Our principle is validated by the highly-sensitive measurement of evanescent wave absorption loss. By chemically processing the surface of sensing segment along an extending ring-down cavity, the concentration of small volume Diethyl Sulphoxide solution where the etched fiber immersed into has been successfully measured and discussed.     

Theoretical analysis on two-photon absorption spectroscopy in a confined four-level atomic system

We investigate theoretically two-photon absorption spectroscopy modified by a control field in a confined Y-type four-level system. Dicke-narrowing effect occurs both in two-photon absorption lines and the dips of transparency against two-photon absorption due to enhanced contribution of slow atoms. We also find that the suppression and the enhancement of two-photon absorption can be modified by changing the strength of the control field and the detuning of three laser fields. This control of two-photon absorption may have some applications in information processing and optical devices.     

连续波腔衰荡光谱系统的电路设计与应用

 为实现连续波腔衰荡光谱系统的工程化,设计了一套集信号调理、高速采样及数据处理为一体的高集成度数字信号处理(DSP)系统。该系统被用于取代常规连续波腔衰荡光谱系统中由高速数据采集卡及计算机组成的腔衰荡信号测试系统,完成对腔衰荡信号的获取与拟合。该系统最高能实现16 bits/80 MHz的信号采样,并能准确地由腔衰荡信号反演出腔衰荡时间。实验结果表明：结合现有的光反馈式连续波腔衰荡光谱系统,该系统能实现等噪声测量灵敏度为1.0×10^-8 cm^-1的吸收光谱测量,其重复测量精度可达3‰。     

连续波腔衰荡光谱系统的电路设计与应用

为实现连续波腔衰荡光谱系统的工程化,设计了一套集信号调理、高速采样及数据处理为一体的高集成度数字信号处理(DSP)系统。该系统被用于取代常规连续波腔衰荡光谱系统中由高速数据采集卡及计算机组成的腔衰荡信号测试系统,完成对腔衰荡信号的获取与拟合。该系统最高能实现16 bits/80 MHz的信号采样,并能准确地由腔衰荡信号反演出腔衰荡时间。实验结果表明：结合现有的光反馈式连续波腔衰荡光谱系统,该系统能实现等噪声测量灵敏度为1.0×10-8 cm-1的吸收光谱测量,其重复测量精度可达3‰。     

Frequency-stabilized cavity ring-down spectroscopy measurements of carbon dioxide isotopic ratios

Carbon dioxide (CO₂) isotopic ratios on samples of pure CO₂ were measured in the 1.6 μm wavelength region using the frequency-stabilized cavity ring-down spectroscopy (FS-CRDS) technique. We present CO₂ absorption spectra with peak signal-to-noise ratios as high as 28,000:1. Measured single-spectrum signal-to-noise ratios were as high as 8900:1, 10,000:1, and 1700:1 for ¹³C/¹²C, ¹⁸O/¹⁶O, and ¹⁷O/¹⁶O, respectively. In addition, we demonstrate the importance of utilizing the Galatry line profile in the spectrum analysis. The use of the Voigt line profile, which neglects the observed collisional narrowing, leads to large systematic errors which are transition-dependent and vary with temperature and pressure. While the relatively low intensities of CO₂ transitions near λ=1.6 μm make this spectral region non-optimal, the sensitivity and stability of FS-CRDS enabled measurement precision of pure CO₂ samples which are comparable to those of other optical techniques which operate at far more propitious wavelengths. These results indicate that a FS-CRDS spectrometer designed to probe CO₂ bands near wavelengths of 2.0 μm or 4.3 μm could achieve significantly improved precision over the present instrument and likely be competitive with mass spectrometric methods.     

The effect of collisions with nitrogen on absorption by oxygen in the A-band using cavity ring-down spectroscopy.

This paper reports on the effect of collisions between nitrogen and oxygen on absorption in the A-band near 760?nm under atmospheric conditions relevant for satellite retrieval studies. We use pulsed laser cavity ring-down spectroscopy with a narrow bandwidth laser and use pressure scans to increase the accuracy of the measured oxygen extinction coefficients. We use the so-called Adjustable Branch Coupling model to describe line mixing in the magnetic allowed A-band dipole absorption and we retrieve the collision induced absorption spectrum due to N₂–O₂ collisions.     

Coherent two-photon absorption spectroscopy of the Raman-active KGd(WO4)2 crystal

We report on the systematic open-aperture Z-scan characterization of the two-photon absorption properties in one of the most efficient solid-state Raman frequency shifters, the crystal potassium gadolinium tungstate [KGd(WO4)2]. The two-photon absorption coefficient was determined in the 370-600-nm wavelength range, with the highest value found to be approximately 1.9 cm/GW at 370 nm. Nonlinear losses are crucial in determining the conversion efficiency of the stimulated Raman scattering process when it is excited with ultrashort laser pulses with photon energy exceeding half of the bandgap. In addition, the results were analyzed within the context of a simple two-parabolic-band theoretical model to yield an effective bandgap energy value for the crystal.     

光反馈腔衰荡光谱技术中纹波效应的测量及其特性分析（英）

为研究光反馈腔衰荡光谱技术中纹波效应的产生机理,基于所建立的腔长为49.1 cm的V型微晶玻璃衰荡腔在不同环境、不同光谱范围所测得的腔损耗谱,利用数据处理方法详细分析并讨论纹波效应的周期和振幅等典型特征。分析认为,纹波效应呈现出明显的部分干涉特点,光谱纹波的周期和振幅特性分别受折叠腔结构和折叠腔镜表面污染状态影响,而与光谱扫描区域关系不明显;这表明纹波效应主要来源于折叠腔镜表面散射场的部分干涉效应。     

光反馈腔衰荡光谱技术中纹波效应的测量及其特性分析（英）

为研究光反馈腔衰荡光谱技术中纹波效应的产生机理,基于所建立的腔长为49.1 cm的V型微晶玻璃衰荡腔在不同环境、不同光谱范围所测得的腔损耗谱,利用数据处理方法详细分析并讨论纹波效应的周期和振幅等典型特征。分析认为,纹波效应呈现出明显的部分干涉特点,光谱纹波的周期和振幅特性分别受折叠腔结构和折叠腔镜表面污染状态影响,而与光谱扫描区域关系不明显;这表明纹波效应主要来源于折叠腔镜表面散射场的部分干涉效应。     

Theoretical analysis on the dynamic absorption saturation in pulsed cavity ringdown spectroscopy

We perform a theoretical analysis on the transient dynamics of absorption saturation in pulsed cavity ringdown spectroscopy. Based on a coupled rate equation approach, modelling of the dynamic saturation is carried out to account for time-evolving intracavity photon density and absorbing population. Master equations are derived in terms of normalized system parameters, which enables one to systematically study the non-exponential feature of saturated cavity ringdown signals. Erroneous quantification of sample absorbance by the conventional ringdown time analysis is numerically simulated, and the saturated spectral feature showing a Lamb dip is obtained for a Doppler broadened sample. Finally a novel numerical recipe is proposed to handle saturated ringdown signals and retrieve unsaturated spectra, allowing relevant absorption parameters without degrading the measurement signal-to-noise ratio. PACS PACS 42.62.Fi; 42.60.Da     

Multi-species detection using multi-mode absorption spectroscopy (MUMAS)

The detection of multiple species using a single laser and single detector employing multi-mode absorption spectroscopy (MUMAS) is reported. An in-house constructed, diode-pumped, Er:Yb:glass micro-laser operating at 1,565 nm with 10 modes separated by 18 GHz was used to record MUMAS signals in a gas mixture containing C₂H₂, N₂O and CO. The components of the mixture were detected simultaneously by identifying multiple transitions in each of the species. By using temperature- and pressure-dependent modelled spectral fits to the data, partial pressures of each species in the mixture were determined with an uncertainty of ±2 %.     

Optical feedback cavity-enhanced absorption spectroscopy (OF-CEAS) in a ring cavity

Optical feedback cavity-enhanced absorption spectroscopy (OF-CEAS) has been demonstrated by coupling a distributed feedback diode laser to a ring cavity. Frequency-selected light decaying from the ring cavity is retro-reflected, inducing a counter-propagating intra-cavity beam, and providing optical feedback to the laser. At specific laser-to-cavity distances, all cavity mode frequencies return to the diode laser with the same phase, allowing spectra to be accumulated across the range of frequencies of the current-tuned laser. OF-CEAS has been used to measure very weak oxygen isotopologue (¹⁶O¹⁸O and ¹⁶O¹⁷O) absorptions in ambient air at wavelengths near 762 nm using the electric-dipole forbidden O₂ A-band. A bandwidth reduced minimum detectable absorption coefficient of 2.2×10⁻⁹ cm⁻¹ Hz^−1/2 is demonstrated.     

The evanescent-wave cavity ring-down spectroscopy technique applied to the investigation of thermally grown oxides on Si(100)

We report about the contribution of thermally grown SiO_x overlayer on the SiO_x/Si interface (with oxidation states Siⁿ⁺, where n = 1, 2, 3, 4) to the optical losses of a resonant spectroscopic cavity. The experiments on Si oxide thin films were performed in evanescent wave for Si samples in contact with a total internal reflection surface of a BK7 prism. The evanescent field can be exploited to investigate properties and processes such as the absorption of thin film or solid/air interface reactions. The results show that the oxide overlayer thickness grows with the thermal exposure time and is limited after more than 7 h of treatment. Transmission electron microscopy has been used for the native oxide thickness measurement and angle-resolved X-ray photoelectron spectroscopy used to determine the thermal oxide thickness. A change of absorption coefficient Δα in the range 100–200 cm^?1 is obtained by evanescent-wave cavity ring-down spectroscopy (EW-CRDS) for thermal silicon oxide overlayer, in agreement with the general trend from literature. The evaluation from the EW-CRDS experiments presents the used setup as a competitive method for measuring the absorption properties of thin overlayer.     

光在吸收介质中的传播速度对光腔衰荡测量精度的影响

利用光腔衰荡法测量吸收系数时,光在吸收介质中的传播速度和空腔是不同的,这种区别导致测量精度在一定程度上受到影响.为了考察吸收系数的测量精度受光速变化的影响程度,进行了相关的分析和推导,并根据实验及部分文献提供的数据进行了数值计算,得到了忽略光速变化将导致测量结果偏小的结论,偏差值与腔镜反射率有关.当腔镜反射率达到99.99%时,就有必要考虑该因素的影响,除非实际测量中存在其它因素使测量精度远不能达到最高值.