The SNR improvement for quartz-enhanced photoacoustic spectroscopy using wavelength calibration and fiber reflector

Wavelength calibration technique combined with a fiber reflector was used to improve the signal to noise ratio (SNR) of quartz-enhanced photoacoustic spectroscopy (QEPAS). A distributed feedback laser diode (DFB-LD), driven by sawtooth wave and high frequency sinusoidal wave, was used to excite the second harmonic signal of a quartz tuning fork (QTF) through laser-gas molecular interaction. Two collimators conducted the laser alignment through the spacing gap of QTF forks. Central wavelength of the DFB-LD was locked to the target gas absorption center by identifying the second harmonic signal maximum and applying calibration feedback on the driving current. The gas absorption center calibration and gas concentration measurements are conducted at a specific interval. The SNR of the photoacoustic signal was further acoustically enhanced by using a pair of on-beam acoustic resonators through increasing the photo-acoustic conversion efficient, and optically enhanced by using a fiber reflector to improve the laser power for photoacoustic signal excitation. The experimental results show that the SNR in wavelength calibration mode is 15 times higher than the conventional wavelength scanning mode and QEPAS signal with fiber reflector is 1.37 times stronger compared with that without a fiber reflector.     

石英晶振用于石英增强光声光谱系统的优化实验研究

研究了音叉式石英晶振的个体尺寸、安放角度、探测部位以及外部污染对整个石英增强光声光谱系统(QEPAS)的探测灵敏度影响。测试了国内外十种不同音,结果表明顶端为楔形构造的音叉式石英晶振比规则的长方体构造的音叉拥有更高的品质因数(Q值)。在相同的测试条件下探测水的吸收线(7 306 cm-1)时获得更高的灵敏度,探测信号的强度相差高达50%。在研究音叉安放角度对探测信号影响的实验中,发现音叉的旋转角度与俯仰角度对探测信号的强度几乎没有影响,但是当光束以角度φ斜入射时,更多的噪声被带入到测量中。在正入射的情况下音叉的最佳响应位置在距离音叉底部约3.1 mm。定性研究了外部杂物污染对音叉频率的影响,发现随着污染物的附着,石英音叉的频率会呈现降低的趋势,提供了一种改变音叉式石英晶振的共振频率的方法,为石英音叉用于较低调制频率的探测提供了一种理论可能,这对于石英增强光声光谱技术用于V-T弛豫率较慢的痕量气体检测有重要的意义。     

自建光声超声双模态成像系统的肿瘤成像分析

现有B超成像可以提供基于声阻抗差异的组织解剖结构信息,而近年来研究发现,光声成像可以提供标记组织成分的分布和功能信息。本文基于商用B超仪和脉冲激光系统建立了光声超声双模态成像系统,实现了超声组织结构成像和光声生物功能的同时成像。首先基于血红蛋白在某些波段的较强吸光性,实现了肿瘤内部组织血管灌注图像;其次用链接有靶向抗体的纳米颗粒作为靶向光声造影剂,对恶性肿瘤边缘和内部的血管以及血管附近的肿瘤组织进行了成像。最终,通过超声和光声的融合图像提供的肿瘤结构信息与光声图像提供的肿瘤功能信息,可以准确识别肿瘤组织。     

适用于ppb量级NO_2检测的低功率蓝光二极管光声技术研究

在405 nm处基于低功率蓝光二极管光声技术探测ppb量级NO_2浓度系统,获取了NO_2有效吸收截面,探讨了水蒸气等气体的测量干扰,通过频率扫描拟合得到了1.35 kHz的谐振频率.采用内部抛光的铝制圆柱空腔作为光声谐振腔(内径为8 mm,长为120 mm),系统优化了腔体、窗片和电源等影响因素,分析了降低本底噪声、提高信噪比的方法,噪声信号可降至0.02μV.设计了两级缓冲结构,显著抑制了流量噪声的影响,提高了系统的稳定性.系统的标定梯度曲线经过线性拟合后的斜率为0.016μV/ppb, R~2为0.998,在60 s平均时间下,系统NO_2探测限为3.67 ppb(3σ).为了证实系统的测量结果,将其与二极管激光腔衰荡光谱系统同步对比测量大气NO_2浓度,二者线性拟合后的斜率为0.94±0.009,截距为1.89±0.18,相关系数为0.87,一致性较好.实验结果表明,该系统实现了ppb量级NO_2浓度的低成本在线探测,可用于NO_2浓度外场的实时检测.     

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应用光声理论、相对论量子理论和电子与多光子集团非线性Compton散射模型,研究了Compton散射对掺杂固体中光声信号强度的影响。结果表明,当掺杂固体中发生电子与多光子集团之间的多光子非线性Compton散射时,在忽略光声转换效率的变化和基质晶格对介电函数贡献的情况下,耦合激光能量和磁感应强度是影响光声信号强度的两个主要因素,其中耦合磁感应强度起主导作用。Compton散射使光声信号强度随耦合光的磁感应强度和能量的增大而迅速增大。能量与光声信号声压之间存在对数线性关系,但它相对于Compton散射前的曲线下移。     

Compton散射对固体中激光能量与光声信号强度关系的影响

应用光声理论、相对论量子理论和电子与多光子集团非线性Compton散射模型,研究了Compton散射对掺杂固体中光声信号强度的影响。结果表明,当掺杂固体中发生电子与多光子集团之间的多光子非线性Compton散射时,在忽略光声转换效率的变化和基质晶格对介电函数贡献的情况下,耦合激光能量和磁感应强度是影响光声信号强度的两个主要因素,其中耦合磁感应强度起主导作用。Compton散射使光声信号强度随耦合光的磁感应强度和能量的增大而迅速增大。能量与光声信号声压之间存在对数线性关系,但它相对于Compton散射前的曲线下移。     

音叉式石英晶振共振频率对QEPAS传感器性能影响的研究

以标准商用石英音叉（QTF）为测声模块的石英增强光声光谱（QEPAS）技术是近年来发展迅速的一种痕量气体检测技术。标准商用QTF拥有的小体积,高Q值,高共振频率的特性使QEPAS技术具有结构紧凑且对环境噪声免疫的特性。但传统商用QTF狭窄的振臂间距以及较高的共振频率,使其无法在光源光束质量较差或被测气体弛豫率较低的情况下被很好的应用于QEPAS系统。为克服上述难题,非标准商用QTF（f₀≠32.7 kHz）被设计制作并越来越多的被装配于QEPAS系统中。因此,QTF共振频率对QEPAS系统信噪比的影响需要被详细研究。以水汽为目标气体,采用二次谐波调制解调技术研究了QTF共振频率对基于QEPAS技术传感器性能的影响。实验结果表明,QTF共振频率的变化对QEPAS系统的输出信号及噪声均有显著影响且QTF共振频率与QEPAS系统信噪比之间存在反比关系。上述结论对QEPAS系统中非标准QTF的设计及使用均具有重要的指导价值,对该类传感器的研发及应用意义重大。     

光纤倏逝波型石英增强光声光谱技术

采用块状光学准直聚焦透镜组的传统石英增强光声光谱(QEPAS)技术存在体积难以缩减,结构稳定性不佳,无法适应空间狭小、振动复杂的特殊环境等缺点.基于此,将光纤倏逝波技术与QEPAS技术相结合,提出了一种新型微纳结构光纤QEPAS痕量气体检测技术.实验中,为了提高QEPAS系统信号幅值,优化了石英音叉与激光束的空间位置、激光波长调制深度,同时对比了两种不同共振频率的石英音叉,最终采用共振频率较低的30.720 kHz石英音叉作为声波探测元件,获得的检测极限为6.25×10~(-4)(体积分数),归一化噪声等效吸收系数为4.18×10~(-7)cm~(-1).W·Hz~(-1/2).     

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应用多光子非线性Compton散射模型,研究了固体温度变化对光声信号强度的影响。结果表明,在Compton散射光和入射光形成的耦合光强度和频率不变时,随固体温度的升高,光声信号强度非线性迅速增强;固体温度不变时,随耦合激光强度和频率的增大,光声信号强度几乎趋于0。     

Compton散射下固体温度变化对光声信号强度的影响

应用多光子非线性Compton散射模型,研究了固体温度变化对光声信号强度的影响。结果表明,在Compton散射光和入射光形成的耦合光强度和频率不变时,随固体温度的升高,光声信号强度非线性迅速增强;固体温度不变时,随耦合激光强度和频率的增大,光声信号强度几乎趋于0。     

基于QEPAS技术的乙炔微量气体高灵敏度检测研究

石英增强光声光谱(QEPAS)是近年来发展起来的一种痕量气体探测技术,具有系统体积小、价格低廉、探测灵敏度高等优点。乙炔(C₂H₂)是一种化学性质活泼的有毒气体,对它进行高灵敏度检测在变压器故障诊断、环境监测等领域有着重要的意义,基于此,采用QEPAS技术对C₂H₂微量气体展开高灵敏度检测研究。采用输出波长为1.53 μm的连续波分布反馈半导体激光器作为激发光源。为了提高信噪比和简化数据处理过程,QEPAS传感器系统采用波长调制和2次谐波探测技术。为了提高QEPAS系统信号幅值,相比于常见的共振频率为32.768 kHz的石英音叉,采用了共振频率较低的30.72 kHz石英音叉作为声波传导器,同时还优化了石英音叉与激光束的空间位置、激光波长调制深度,并添加了声波微共振腔,选择的微共振腔长度为4 mm、内径为0.5 mm,最终获得了2.7 ppm的优异检测极限,归一化噪声等效吸收系数为1.3×10-8 cm-1·W·Hz-1/2。     

Determination of the ratio of soot refractive index function E(m) at the two wavelengths 532 and 1064 nm by laser induced incandescence

A new method is proposed to measure the ratio of the refractive index function of soot particles E(m) at the two fixed wavelengths: 532 and 1064 nm. Using a non-intrusive, in-situ laser based technique, the ratio E(m,1064 nm)/E(m,532 nm) can be determined by comparing laser induced incandescence (LII) intensities at 532 and 1064 nm excitation wavelengths. The method consists of selecting laser energies that insure the equality of the LII signals in the low fluence regime under given conditions. Such equality is consistent with the fact that the soot particle will have reached the same temperature independently of the laser wavelength, i.e. the soot particle has absorbed the same energy. As the absorbed energy is proportional to the laser irradiance times E(m), the measurement of the laser energies required to insure perfect concordance of the LII intensities (spatially and temporally) serves to deduce the ratio E(m,1064 nm)/E(m,532 nm). The method is demonstrated in an acetylene/air flame, validated against extinction measurements performed by cavity ring-down spectroscopy (CRDS) by using laser radiations at 532 nm and 1064 nm and finally applied to different flame conditions. PACS 78.20.Ci; 78.90.+t; 81.05.Uw; 42.62.-b     

石英音叉温度频率特性的温度传感器（英）

提出了一种基于石英晶体温度频率特性的石英音叉微谐振式温度传感器。通过理论分析的方法对传感器进行设计,并采用有限元仿真对传感器的结构参数进行优化。采用光刻和蚀刻微加工技术制造石英音叉谐振器,对石英音叉温度传感器样机的频率温度特性进行实验研究。实验结果表明:石英音叉温度传感器的标准谐振频率为36.545 kHz,灵敏度为-1.9 Hz/℃,在-20到100 ℃的温度范围内,其非线性误差小于0.18%,迟滞为0.02%,与理论研究相吻合。该传感器具有高精度、高灵敏度、低功耗和低成本的特点,为高性能温度测量提供较好的解决方案。     

呼吸性粉尘吸收系数的光声光谱探测

针对呼吸性粉尘浓度连续、可靠、低成本的实时检测需求,实现了光谱应用技术创新,提出了一种基于光声光谱的呼吸性粉尘探测系统,低功率二极管激光器光谱中心波长为403.56 nm及相应的NO₂有效吸收截面为5.948 5×10-19 cm2·mole-1;通过频率扫描拟合得到了1.35 kHz的谐振频率。开展了光声池结构的影响分析,得到了光声池长度参数对本底噪声影响较小但对激光信号影响较大、内径参数对本底噪声存在一定影响但对本底噪声影响较小的结论。在考虑品质因数、加工条件、使用场合和待测对象属性等影响情况下,选用120 mm的长度参数和8 mm的内径参数;基于长度为60 mm、内径为25 mm的缓冲腔结构,开展了缓冲隔板对系统稳定性的影响分析,通过在缓冲腔中设置缓冲隔板,降低了本底噪声、稳定了系统,其幅值及波动由(2.83±0.11) μv稳定为(1.26±0.03) μv。分析得到了NO₂的比吸收系数为195.28 Mm-1·(mg·m-3)-1,利用NO₂气体在405 nm处的吸收对系统进行了标定,得到了拟合斜率为0.0436 8 μv/Mm-1、相关系数为0.998、池常数为300.24 Pa·cm·W-1的结论。同时在1 min平均时间下,得到了系统探测浓度下限及吸收系数为2.30 μg·m-3和0.448 Mm-1。基于标准微球的聚苯乙烯作为气溶胶发生器对象开展了呼吸性粉尘的吸收系数影响分析,进行了5μm以下不同数浓度颗粒及同一数浓度下不同粒径颗粒吸收系数的测试,结果表明：呼吸性粉尘的吸收系数和数浓度成正比,线性拟合后的斜率为10.598±0.641 96,相关系数为0.993;吸收系数曲线的方差在3～4 Mm-1间,不同粒径的颗粒对吸收系数存在着一定的影响;随着粒径增加,吸收系数随之增加。开展了环境大气中NO₂的测量,选用0.2 μm的过滤膜滤除粉尘的干扰,实验结果表明大气NO₂浓度为16.4~61.6 μg·m-3,平均浓度为41.1 μg·m-3。为了证实测量系统的准确性,与课题组自行研发的长光程差分吸收光谱系统(LP-DOAS)进行了对比测试,测试结果显示了本光声光谱系统和LP-DOAS系统测量NO₂浓度的相关性较好,线性拟合后的斜率为1.011 78±0.040 13,相关系数为0.947 81。开展了环境大气中呼吸性粉尘的测量,选用5 μm过滤片过滤环境大气,通过“NO₂+5 μm粉尘”和“NO₂+0.2 μm粉尘”两路测量对象的差分测量,得到了呼吸性粉尘的变化趋势,可以满足自然悬浮状态下的呼吸性粉尘吸收系数实时测量。     

Cavity-enhanced optical feedback-assisted photo-acoustic spectroscopy with a 10.4 μm external cavity quantum cascade laser

An ultra-sensitive photo-acoustic spectrometer using a 10.4 μm broadly tunable mid-IR external cavity quantum cascade laser (EC-QCL) coupled with optical feedback to an optical power buildup cavity with high reflectivity mirrors was developed and tested. A laser optical power buildup factor of 181 was achieved, which corresponds to an intra-cavity power of 9.6 W at a wavelength of 10.4 μm. With a photo-acoustic resonance cell placed inside the cavity this resulted in the noise-equivalent absorption coefficient of 1.9 × 10^?10 cm^?1 Hz^?1/2, and a normalized noise-equivalent absorption of 1.1 × 10^?11 cm^?1 W Hz^?1/2. A novel photo-acoustic signal normalization technique makes the photo-acoustic spectrometer’s response immune to changes and drifts in the EC-QCL excitation power, EC-QCL to cavity coupling efficiency and cavity mirrors aging and contamination. An automatic lock of the EC-QCL to the cavity and optical feedback phase optimization permitted long wavelength scans within the entire EC-QCL spectral tuning range.     

Tunable erbium-doped fiber ring laser for applications of infrared absorption spectroscopy

We fabricate a low noise erbium-doped fiber ring laser that can be continuously tuned over 102 nm by insertion of the fiber Fabry-Perot tunable filter (FFP-TF) in the ring cavity with a novel cavity structure and the optimal gain medium length. As an application of this fiber ring laser, we performed the absorption spectroscopy of acetylene (¹³C₂H₂) and hydrogen cyanide (H¹³C¹⁴N) and measure the absorption spectra of more than 50 transition lines of these gases with an excellent signal to noise ratio (SNR). The pressure broadening coefficients of four acetylene transition lines are obtained using this fiber ring laser and an external cavity laser diode.     

Determinations of the transient thermal lensing effect in metal cluster Polymer {WS4Cu4I2(bpe)3}n solution by the use of the Z-scan

The nonlinear optical (NLO) properties of a novel cluster Polymer {WS₄Cu₄I₂(bpe)₃}_n solution are studied by using Z-scan technique with laser pulses of 4.5 ns pulse-width at a wavelength of 532 nm. The results show that the cluster solution possesses strong nonlinear absorption and refraction. Nonlinear refraction of the cluster is composed of third-order nonlinear refraction and transient thermal effect. The thermal effect is mainly due to the strong nonlinear absorption. Numerical simulations obtained by solving simultaneously photo-acoustic and electromagnetic wave equations, agrees basically with experimental results.     

A quartz-enhanced photoacoustic spectroscopy sensor for measurement of water vapor concentration in the air

A compact and highly linear quartz-enhanced photoacoustic spectroscopy(QEPAS)sensor for the measurement of water vapor concentration in the air is demonstrated.A cost-effective quartz tuning fork(QTF)is used as the sharp transducer to convert light energy into an electrical signal based on the piezoelectric effect,thereby removing the need for a photodetector.The short optical path featured by the proposed sensing system leads to a decreased size.Furthermore,a pair of microresonators is applied in the absorbance detection module(ADM)for QTF signal enhancement.Compared with the system without microresonators,the detected QTF signal is increased to approximately 7-fold.Using this optimized QEPAS sensor with the proper modulation frequency and depth,we measure the water vapor concentration in the air at atmospheric pressure and room temperature.The experimental result shows that the sensor has a high sensitivity of 1.058parts-per-million.     

Absorption line profile recovery based on TDLS and MEMS micro-mirror for photoacoustic gas sensing

A novel and efficient absorption line recovery technique is presented. A micro-electromechanical systems (MEMS) mirror driven by an electrothermal actuator is used to generate laser intensity modulation through the mirror reflection. Tunable diode laser spectroscopy (TDLS) and photoacoustic spectroscopy (PAS) are used to recover the target absorption line profile which is compared with the theoretical Voigt profile. The target gas is 0.01% acetylene (C2H2) in a nitrogen host gas. The laser diode wavelength is swept across the P17 absorption line of acetylene at 1535.4 nm by a current ramp, and an erbium-doped fibre amplifier (EDFA) is used to enhance the optical intensity and increase the signal-to-noise ratio (SNR). A SNR of about 35 is obtained with 100 mW laser power from the EDFA. Good agreement is achieved between the experimental results and the theoretical simulation for the P17 absorption line profile.     

灵敏的基于分布反馈式半导体激光波长调制光声光谱

利用室温下单模运行的近红外半导体二极管激光,报导了波长调制共振光声光谱结合二次谐波探测技术.实验系统应用到乙炔探测,在1个标准大气压和3毫瓦平均光功率以及3毫秒锁相积分时间条件下其探测灵敏度可达10ppm(体积比),归一化到激光功率和系统带宽最小可探测吸收为4.0×10-8Wcm-1/Hz,并且实验中发现系统最佳压力响应值在2.66×104Pa附近.本实验装置可有效的消除光声光谱系统中常见的窗片和光声腔壁吸收入射光而引起的背景噪声.此外,相对于其他方法我们描述的基于半导体激光共振光声光谱具有很大的优点,为进一步发展便利、实用、便携式环境监测仪器奠定了坚实的基础.