Photoacoustic detection of two photon absorption in formaldehyde using pulsed dye laser

Absorption spectra of formaldehyde molecule in the gas phase have been recorded using photoacoustic (PA) technique with pulsed dye laser at various power levels. The spectral profiles at higher power levels are found to be different from that obtained at lower laser powers. Two photon absorption (TPA) is found to be responsible for the photoacoustic signal at higher laser power while the absorption at lower laser power level is attributed to one photon absorption (OPA) process. Probable assignments for the different transitions are given in this paper.     

单光子波长调制吸收光谱用于1.5 μm激光器的波长锁定

提出了一种kHz调制频率量级的单光子调制技术,实现对激光器的实时锁定. 通过探测乙炔气体的单光子吸收光谱,对离散的单光子响应脉冲进行锁定放大, 获得激光器频率锁定的鉴频曲线.将1.5 μm分布反馈半导体激光器的输出频率稳定在乙炔气体 ν₁ + ν ₃带P5e支吸收峰上,在175 s内典型激光频率起伏小于25 MHz. 这种基于单光子波长高频调制吸收光谱的稳频技术消除了低频段较高背景的噪声, 可应用于单光子量级的量子保密通讯系统以及光学波分复用系统.     

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.     

In Vivo Monitoring of Neovascularization in Tumour Angiogenesis by Photoacoustic Tomography

Photoacoustic tomography （PAT） is presented to in vivo monitor neovascularization in tumour angiogenesis with high resolution and high contrast images in a rat. With a circular scan system, the photoacoustic signal, generated by laser pulses at a wavelength of 532nm from a Q-switched Nd：YAG laser is captured by a hydrophone with a diameter of 1 mm and a sensitivity of 850nV/Pa. The vascular structure around the rat tumour is imaged clearly, with optimal contrast, because blood has strong absorption near this wavelength. Serial noninvasive photoacoustic images of neovascularization in tumour angiogenesis are also obtained consecutively from a growing tumour implanted under the skin of a rat over a period of two weeks. This work demonstrates that PAT can potentially provide a powerful tool for tumour angiogenesis detection in cancer research. It will bring us closer to clinical applications for tumour diagnosis and treatment monitoring.     

基于OPO脉冲激发的血糖光声检测影响因素研究

构建了一套基于侧向模式的光学参数振荡(optical parameter oscillator,OPO)脉冲激光激发-超声传感的血糖光声检测系统,并且将激发波长、激光能量、探测频率和温度等对血糖光声检测的影响,在系统结构上进行了有效融合。然后,以不同浓度的葡萄糖溶液作为测试样品,实验研究了几个因素(激发波长、激光能量、探测频率和温度等)对葡萄糖光声检测和浓度预测的影响。实验得到了不同浓度葡萄糖溶液在不同影响因素条件下的葡萄糖实时光声信号和光声峰峰值,同时,为了得到不同因素对葡萄糖光声值和浓度预测的影响规律,通过线性回归算法建立了葡萄糖光声峰峰值与各因素变化,以及不同因素下光声峰峰值与浓度梯度的映射关系模型。实验和模型预测结果表明：相比1 200和1 300 nm波长而言,1 064 nm波长下的葡萄糖光声峰峰值与浓度梯度模型预测效果最好,模型相关系数达到0.986;葡萄糖光声峰峰值随着脉冲激光输出能量的增大呈线性增大趋势,且葡萄糖浓度预测准确度随着激光输出能量增大有所提高;根据不同探测频率的超声探测器捕获的葡萄糖光声峰峰值与浓度梯度建模效果来看,响应频率为1 MHz的超声探测器相比2.5和10 MHz的超声探测器,在葡萄糖光声信号探测上具有更好的探测效果;最后,实验发现,葡萄糖光声峰峰值随着温度和浓度的增大均呈线性增大趋势,且浓度预测误差随着温度的升高逐渐增大。     

Experimental and theoretical investigation of photoacoustic-signal generation by wavelength-modulated diode lasers

The dependence of photoacoustic spectra on different experimental parameters was investigated by both theoretical and experimental means. The experiments were carried out with an inexpensive resonant optoacoustic system based on near-infrared laser diodes, which allowed photoacoustic and direct absorption spectra to be recorded simultaneously. The experimental observations were compared to theoretical predictions. It was also demonstrated that source-frequency (wavelength) modulation at the resonance frequency of the cell provides superior signal to noise ratio compared to amplitude modulation and eliminates background drifts and fluctuations.     

双光程光声光谱甲烷传感器

利用甲烷(CH₄)气体分子在1.6 μm的吸收特性,使用中心波数为6 046.96 cm-1的蝶形分布反馈式(DFB)激光器和自制的大内径光声池,设计了一款紧凑高灵敏的CH₄气体传感器。为了进一步增强输出光声信号强度,一个具有高反射率的平面镜放置在光声池后,使透射光束被反射后,二次通过光声池,增强了光与被测气体的作用距离,使光声信号提高了1.9倍。传感器各项参数,包括调制频率、调制深度及气体流速被优化。在标准大气压和1 s的积分时间下,该传感器最终获得的探测灵敏度为0.21 ppm,1σ归一化等效噪声系数(NNEA)为2.1×10-8 cm-1·W·Hz-1/2。该甲烷传感器使用性价比高的DFB近红外激光二极管作为激发光源,装置简单,成本低廉可以满足大气环境检测、矿井瓦斯监测、工业过程控制及无创伤医疗诊断等领域的需求。     

水溶性CdTe:Mn量子点的双光子吸收

采用激发波长800 nm、脉宽50 fs、重复频率1 kHz的Ti:sapphire放大飞秒激光器作为激发光源,利用开孔Z扫描技术研究了不同粒径的CdTe:Mn量子点的非线性吸收性质。理论计算结果表明,同一生长时间CdTe:Mn量子点的双光子吸收系数是CdTe量子点的1.1倍,其双光子吸收系数随量子点尺寸的减小而增大,这是由于CdTe:Mn量子点非线性吸收属于反饱和吸收,掺杂了Mn元素,减小了表面缺陷浓度,表明掺杂量子点具有很好的双光子吸收现象。     

Co-laser photoacoustic spectroscopy of gases and vapours for trace gas analysis

This comprehensive study reviews the sensitive and selective detection of trace gases by laser photoacoustic spectroscopy. A computer controlled CO-laser photoacoustic system is presented. The wavelength range between 5.0 and 6.5 μm is of great interest because it coincides with specific absorption bands of various gases and vapours of environmental concern. However, since water-vapour, which is present in most samples, absorbs rather strongly in this wavelength region, its contribution to the total absorption has to be determined with high accuracy. For this purpose, we developed a dual-beam setup with sample- and reference cell. The novel design of these resonant photoacoustic cells is based on a new matrix formalism with distributed acoustic impedances and sources.Our photoacoustic system is calibrated with certified gas mixtures and vapours. In total, the absorption cross sections of 18 gases and vapours have been derived for all CO-laser lines. In addition to the absorption, the relaxation time of vibrationally excited nitric oxide (NO) could be deduced by measuring the phase shift of the photoacoustic signal for a sample of nitrogen containing traces of NO and water-vapour.The main application concerns the detection of multiple components in gas mixtures, particularly in exhaust gases. The high sensitivity achieved permits the detection of trace gases at ppbv concentrations. The problem of interfering absorptions occurring for multicomponent mixtures is studied in detail. We discuss measurements and results on exhausts of various vehicles. The photoacoustic spectra of the exhaust samples are analyzed on the basis of the calibration spectra with the aid of an iterative mathematical procedure.The individual concentrations of 12 of the most important components including nitric oxide, olefines, aromatic hydrocarbons and aldehydes could be derived. In particular, the selective detection of the different isomers of xylene is emphasized.     

Quartz enhanced photoacoustic spectroscopy with a 3.38 μm antimonide distributed feedback laser

A system for gas sensing based on the quartz-enhanced photoacoustic spectroscopy technique has been developed. It makes use of a quantum well distributed feedback (DFB) laser diode emitting at 3.38 μm. This laser emits near room temperature in the continuous wave regime. A spectrophone, consisting of a quartz tuning fork and two steel microresonators were used. Second derivative wavelength modulation detection is used to perform low concentration measurements. The sensitivity and the linearity of the Quartz enhanced photoacoustic spectroscopy (QEPAS) sensor were studied. A normalized noise equivalent absorption coefficient of 4.06×10(-9) cm(-1)·W/Hz(1/2) was achieved.     

CdSe/ZnS核-壳结构量子点的非线性光学吸收

利用开孔Z扫描技术研究了吸收峰分别为553 nm和503 nm的两种尺寸CdSe/ZnS核-壳结构量子点溶液的非线性吸收性质.对于532 nm,6 ns激光脉冲,两种材料均表现出饱和吸收向反饱和吸收转化的现象.数值模拟结果表明：当吸收峰波长大于激光波长时,饱和吸收过程由快、慢两种机制组成,分别对应基态载流子被激发至不同的激发态,而强光下的反饱和吸收与快过程相关;当吸收峰波长小于激光波长时,饱和吸收主要由快过程机制引起,强光下的反饱和吸收源自激发态吸收和双光子吸收.我们的研究结果表明半导体量子点是研制光开关和光限制器件的理想候选材料.     

Absorption line profile recovery based on residual amplitude modulation and first harmonic integration methods in photoacoustic gas sensing

Two methods for recovery of gas absorption line profiles are presented in this paper using photoacoustic spectroscopy and tunable diode laser spectroscopy (TDLS) with wavelength modulation (WM). A theoretical analysis based on Fourier coefficients is given in order to describe the various components that arise under simultaneous intensity and frequency modulation. The first method makes use of the residual amplitude modulation (RAM) signal which is always present in current modulation of distributed feedback (DFB) tunable diode lasers. The second method involves integration of a near-pure first harmonic derivative signal, separated from other distorting components by appropriate choice of the lock-in detection phase in the case of low modulation index. Good agreement is obtained with both methods between the experimental results and the theoretical simulation for the P17 absorption line of acetylene at 1535.39 nm but the second method gives a much improved accuracy and signal-to-noise ratio in lineshape recovery with photoacoustic spectroscopy.     

双光子吸收光谱

本文报道以皮秒脉冲激光抽运的光参量放大器为宽带可调谐激发光源，直接测量非线性光学材料的双光子吸收谱的方法。光参量放大器不但可调谐谱带很宽，而且可用一对尼科尔棱镜很容易地实现全波段功率足够强和相等，使此方法的测量结果准确可靠。用此方法研究了一个新有机化合物的双光子吸收谱。实验结果表明所测的新有机化合物在很宽的波长范围内呈现出很大的双光子吸收截面。     

Photoacoustic flow measurements by use of laser-induced shape transitions of gold nanorods

A quantitative technique for flow measurements based on a wash-in analysis is proposed. The technique makes use of the shape dependence of the optical absorption of gold nanorods and the transitions in their shape induced by pulsed laser irradiation. The photon-induced shape transition of gold nanorods involves mainly a rod-to-sphere conversion and a shift in the peak optical absorption wavelength. The application of a series of laser pulses will induce shape changes in gold nanorods as they flow through a region of interest, with quantitative flow information being derived from the photoacoustic signals from the irradiated gold nanorods measured as a function of time. To demonstrate the feasibility of the technique, a Nd:YAG laser operating at 1064 nm was used for irradiation and a 1 MHz ultrasonic transducer was used for acoustic detection. The flow velocity ranged from 0.35 to 2.83 mm/s. Excellent agreement between the measured velocities and the actual velocities was demonstrated, with a linear regression correlation coefficient of 0.93. This study is a pioneer work on wash-in flow estimation in photoacoustic imaging.     

单波长光声光谱血氧饱和度检测技术研究

血氧饱和度(SO₂)为临床观察病情变化提供了有意义的指标。传统血氧饱和度检测研究工作多采用双光源和多光源光电容积脉搏波描记法实现无创检测来减少病人痛苦。通过研究生物组织对光的吸收和散射特性,将光谱学和光声技术相结合提出了一种无创式单光源检测血氧饱和度(SO₂)、脱氧血红蛋白浓度[HBR]和氧合血红蛋白浓度[HbO₂]的新方法。该方法基于血液对光信号的吸收和散射理论基础和光声信号呈现吸收线形关系建立单波长光声光谱血氧饱和度检测技术,不仅可以进行指标性参数分析还可以对组织成像。为了验证该技术可行性,在实验中采用单波长激光脉冲光源,以绿色和红色墨水的混合液体作为含有脱氧血红蛋白和氧合血红蛋白的血液模型注入软管模拟人体血液环境。其中红色墨水的含量类比于血液中含氧血红蛋白含量,从而可通过测量计算出红色和绿色墨水浓度来表征伪血氧饱和度(poseudo-SO₂)。实验结果表明,所测的伪血氧饱和度与实际浓度误差不超过6.97%,采用该方法量化血氧饱和度是可行的;同时利用实验结果,结合光声成像技术完成了对伪血液中单圆管截面成像。该方法替代多波长光谱分析的方法能显著降低激光系统和便携式实现成本。     

Intravascular photoacoustic imaging of lipid in atherosclerotic plaques in the presence of luminal blood

Intravascular photoacoustic (IVPA) imaging can characterize atherosclerotic plaque composition on the basis of the optical absorption contrast between different tissue types. Given the high optical absorption of lipid at 1720 nm wavelength, an atherosclerotic rabbit aorta was imaged at this wavelength ex vivo using an integrated intravascular ultrasound (IVUS) and IVPA imaging catheter in the presence of luminal blood. Strong optical absorption of lipid combined with low background signal from other tissues provides a high-contrast, depth-resolved IVPA image of lipid. The ability to image lipid at a single wavelength without removing luminal blood suggests that in vivo detection of lipid in atherosclerotic plaques using combined IVUS/IVPA imaging is possible.     

基于光声光谱技术的1.5 μm波段 NH3吸收谱线测量与分析

NH₃的检测具有广泛的应用,采用光声法检测NH₃是当前研究的热点,而确定NH₃的吸收谱线则是实现光声法检测NH₃的前提。采用外腔可调谐半导体激光器构造了光声气体检测系统,检测了NH₃的近红外吸收谱线,获得了常温常压下NH₃在1 515~1 532 nm范围内的吸收光谱。实验确认了NH₃在1 515.2,1 516.0,1 518.0,1 519.9,1 522.4,1 527.0,1 531.7 nm处存在强吸收。HITRAN 2004光谱数据库在近红外1.5 μm波段NH₃的吸收谱线数据未见报道,该结果为研究光声法检测NH₃提供了更多可选择的吸收谱线。     

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.     

Laser ablation and desorption from calcite from ultraviolet to mid-infrared wavelengths

3 ) at wavelengths ranging from the ultraviolet to the mid-infrared, including a Nd:YAG laser operated at the fundamental, second and third harmonics, and a tunable infrared free-electron laser (wavelength range 2.5–8 μm). The threshold for ablation and the topography of the irradiated spot were characterized by scanning electron microscopy. A clear indication of two distinct excitation mechanisms was observed, namely, cracks and fractures followed by exfoliation at ultraviolet to near-infrared wavelengths, in contrast to evaporative holes and scattered droplets in the mid-infrared. Plume emission/absorption spectroscopy, plume transmission and photoacoustic beam deflection were used to characterize the ablation plasma. The composition of atoms, molecules, or particles in the ablation plumes also has a distinctive variation as a function of the wavelength. The excitation mechanisms leading to ablation appear to be defect activation at ultraviolet to near-infrared wavelengths, molecular impurity absorption and resonant vibrational absorption of the calcite at mid-infrared. Received: 5 December 1996/Accepted: 6 January 1997