Development and Application of Ultrafast Circular Dichroism Spectroscopy Techniques

Chirality hold broad applications in life sciences,quantum devices,and various other areas.Traditionally,molecular chirality can be characterized by using steady-state circular dichroism spectroscopy.However,the techniques that can characterize excited state chirality are progressively capturing the public interest as it can provide the dynamic information for chirality generation and transfer.In this review,we focus on the theoretical background and the developmental history of femtosecond time-resolved circular dichroism spectroscopy(TRCD)techniques around the world.Additionally,we provide examples to showcase the utility of these techniques in the analysis of the dynamical molecular chemical structures,the investigation of molecular chirality generation,and the detection of electron spin dynamics in semiconductor quantum dots.

Determination of Iron in Water Solution by Time-Resolved Femtosecond Laser-Induced Breakdown Spectroscopy

The influence of the energy of femtosecond laser pulses on the intensity of Fe I （371.99 nm） emission line and the continuous spectrum of the plasma generated on the surface of Fe^3＋ water solution by a Ti： sapphire laser radiation with pulse duration 〈45 fs and energies up to 7 mJ is determined. A calibration curve was obtained for Fe3＋ concentration range from 0.5 g/L to the limit of detection in water solution, and its saturation was detected for concentrations above 0.25 g/L, which is ascribed to self-absorption. The 3σ- limit of detection obtained for Fe in water solution is 2.6 mg/L in the case of 7 mJ laser pulse energy. It is found that an increase of laser pulse energy insignificantly affects on LOD in the time-resolved LIBS and leads to a slight improvement of the limit of detection.

A comparison of single shot nanosecond and femtosecond polarization-resolved laser-induced breakdown spectroscopy of Al

Aluminum samples have been analyzed by femtosecond polarization-resolved laser-induced breakdown spectroscopy （fs-PRLIBS）. We compare the obtained spectra with those obtained from nanosecond PRLIBS （ns-PRLIBS）. The main specific features of fs-PRLIBS are that a lower plasma temperature leads to a low level of continuum and no species are detected from the ambient gas. Furthermore, signals obtained by fs-PRLIBS show a higher stability than those of ns-PRLIBS. However, more elements are detected in the ns-PRLIBS spectra.

Investigation of ultrafast dynamics of CdTe quantum dots by femtosecond fluorescence up-conversion spectroscopy

The ultrafast carrier relaxation processes in CdTe quantum dots are investigated by femtosecond fluorescence upconversion spectroscopy.Photo-excited hole relaxing to the edge of the forbidden gap takes a maximal time of ～ 1.6 ps with exciting at 400 nm,depending on the state of the photo-excited hole.The shallow trapped states and deep trap states in the forbidden gap are confirmed for CdTe quantum dots.In addition,Auger relaxation of trapped carriers is observed to occur with a time constant of ～ 5 ps.A schematic model of photodynamics is established based on the results of the spectroscopy studies.Our work demonstrates that femtosecond fluorescence up-conversion spectroscopy is a suitable and effective tool in studying the transportation and conversion dynamics of photon energy in a nanosystem.

Time-resolved spectroscopy of femtosecond laser-induced Cu plasma with spark discharge

The combination of spark discharge and laser-induced breakdown spectroscopy (LIBS) is called spark discharge assisted LIBS.It works under laser-plasma triggered spark discharge mode,and shows its ability to enhance spectral emission intensity.This work uses a femtosecond laser as the light souuce,since femtosecond laser has many advantages in laser-induced plasma compared with nanosecond laser,meanwhile,the study on femtosecond LIBS with spark discharge is rare.Time-resolved spectroscopy of spark discharge assisted femtosecond LIBS was investigated under different discharge voltages and laser energies.The results showed that the spectral intensity was significantly enhanced by using spark discharge compared with LIBS alone.And,the spectral emission intensity using spark discharge assisted LIBS increased with the increase in the laser energy.In addition,at low laser energy,there was an obvious delay on the discharge time compared with high laser energy,and the discharge time with positive voltage was different from that with negative voltage.

A Highly Sensitive Femtosecond Time-Resolved Sum Frequency Generation Vibrational Spectroscopy System with Simultaneous Measurement of Multiple Polarization Combinations

Characterization of real-time and ultrafast motions of the complex molecules at surface and interface is critical to understand how interracial molecules function. It requires to develop surface-sensitive, fast-identification, and time-resolved techniques. In this study, we employ several key technical procedures and successfully develop a highly sensitive femtosecond time-resolved sum frequency generation vibrational spectroscopy （SFG-VS） system. This system is able to measure the spectra with two polarization combinations （ssp and ppp, or psp and ssp） simultaneously. It takes less than several seconds to collect one spectrum. To the best of our knowledge, it is the fastest speed of collecting SFG spectra reported by now. Using the time-resolved measurement, ultrafast vibrational dynamics of the N-H mode of α-helical peptide at water interface is determined. It is found that the membrane environment does not affect the N-H vibrational relaxation dynamics. It is expected that the time-resolved SFG system will play a vital role in the deep understanding of the dynamics and interaction of the complex molecules at surface and interface. Our method may also provide an important technical proposal for the people who plan to develop time-resolved SFG systems with simultaneous measurement of multiple polarization combinations.

Influence of target temperature on femtosecond laser-ablated brass plasma spectroscopy

Spectral intensity,electron temperature and density of laser-induced plasma(LIP) are important parameters for affecting sensitivity of laser-induced breakdown spectroscopy(LIBS).Increasing target temperature is an easy and feasible method to improve the sensitivity.In this paper,a brass target in a temperature range from 25℃ to 200℃ was ablated to generate the LIP using femtosecond pulse.Time-resolved spectral emission of the femtosecond LIBS was measured under different target temperatures.The results showed that,compared with the experimental condition of 25℃,the spectral intensity of the femtosecond LIP was enhanced with more temperature target.In addition,the electron temperature and density were calculated by Boltzmann equation and Stark broadening,indicating that the changes in the electron temperature and density of femtosecond LIP with the increase of the target temperature were different from each other.By increasing the target temperature,the electron temperature increased while the electron density decreased.Therefore,in femtosecond LIBS,a hightemperature and low-density plasma with high emission can be generated by increasing the target temperature.The increase in the target temperature can improve the resolution and sensitivity of femtosecond LIBS.

Ultrafast Investigation of Excited-State Dynamics in Trans-4-methoxyazobenzene Studied by Femtosecond Transient Absorption Spectroscopy

The ultrafast photoisomerization and excited-state dynamics of trans-4-methoxyazobenzene (trans-4-MAB) in solutions were investigated by femtosecond transient absorption spectroscopy and quantum chemistry calculations. After being excited to the S2 state, the two-dimensional transient absorptions spectra show that cis-4-MAB is produced and witnessed by the permanent positive absorption in 400-480 nm. Three decay components are determined to be 0.11, 1.4 and 2.9 ps in ethanol, and 0.16, 1.5 and 7.5 ps in ethylene glycol, respectively. The fast component is assigned to the internal conversion from the S2 to S1 state. The other relaxation pathways are correlated with the decay of the S1 state via internal conversion and isomerization, and the vibrational cooling of the hot S0 state of the cis-isomer. Comparing of the dynamics in different solvents, it is demonstrated that the photoisomerization pathway undergoes the inversion mechanism rather than the rotation mechanism.

Comparison of sample temperature effect on femtosecond and nanosecond laser-induced breakdown spectroscopy

In this paper,we investigated the emission spectra of plasmas produced from femtosecond and nanosecond laser ablations at different target temperatures in air.A brass was selected as ablated target of the experiment.The results indicated that spectral emission intensity and plasma temperature showed similar trend for femtosecond and nanosecond lasers,and the two parameters were improved by increasing the sample temperature in both cases.Moreover,the temperature of nanosecond laser-excited plasma was higher compared with that of femtosecond laser-excited plasma,and the increase of the plasma temperature in the case of nanosecond laser was more evident.In addition,there was a significant difference in electron density between femtosecond and nanosecond laser-induced plasmas.The electron density for femtosecond laser decreased with increasing the target temperature,while for nanosecond laser,the electron density was almost unchanged at different sample temperatures.

High-Resolution Rb Two-Photon Transition Spectroscopy by a Femtosecond Frequency Comb via Pulses Control

We experimentally observe the high resolution direct frequency comb spectroscopy using counter-propagating broadband femtosecond pulses on two-photon transitions in room-temperature ^87 Rb atoms. The Doppler broad- ened background is effectively eliminated with the pulse shaping method and the spectrum modulation technique. The combination of the pulse shaping method and the spectra modulation technique provides a potential approachto reduce background of at least 99%.

Comparison of emission signals for different polarizations in femtosecond laser-induced breakdown spectroscopy

In this study, a femtosecond laser was focused to ablate brass target and generate plasma emission in air. The influence of lens to sample distance(LTSD) on spectral emission of brass plasma under linearly and circularly polarized pulses with different pulse energies was investigated. The results indicated that the position with the strongest spectral emission moved toward focusing lens with increasing the energy. At the same laser energy, the line emission under circularly polarized pulse was stronger compared with linearly polarized pulse for different LTSDs. Next, electron temperature and density of the plasma were obtained with Cu(Ⅰ) lines,indicating that the electron temperature and density under circularly polarized pulse were higher compared to that under linearly polarized pulse. Therefore, changing the laser polarization is a simple and effective way to improve the spectral emission intensity of femtosecond laserinduced plasma.

Development of new diagnostics based on LiF detector for pump-probe experiments

We present new diagnostics for use in optical laser pump-X-ray Free Electron Laser(XFEL)probe experiments to monitor dimensions,intensity profile and focusability of the XFEL beam and to control initial quality and homogeneity of targets to be driven by optical laser pulse.By developing X-ray imaging,based on the use of an LiF crystal detector,we were able to measure the distribution of energy inside a hard X-ray beam with unprecedented high spatial resolution(~1 mm)and across a field of view larger than some millimetres.This diagnostic can be used in situ,provides a very high dynamic range,has an extremely limited cost,and is relatively easy to be implemented in pump-probe experiments.The proposed methods were successfully applied in pump-probe experiments at the SPring-8 Angstrom Compact free electron LAser(SACLA)XFEL facility and its potential was demonstrated for current and future High Energy Density Science experiments.

飞秒相干反斯托克斯拉曼散射光谱测温研究进展

当今世界大约90%的能量供应都是由燃烧生成的。在燃烧场中,火焰的温度影响着场中各种组分链式反应的途径和浓度,获取燃烧场温度信息可以为提高燃料燃烧效率,改进燃烧装置的设计提供重要的支撑依据。随着我国在航空、航天和航海这类高端制造业领域的不断发展,各种大型燃气轮机和超声速发动机的研发进入加速期,此类燃烧装置产生的火焰具有高温、高压、湍流超声速和持续时间短等特点。传统的接触式测温法难以对这类湍流燃烧场进行温度测量,近年以激光光谱法为代表的非接触式测温技术逐渐走向成熟,并获得了广泛地应用。与超短脉冲相结合的飞秒相干反斯托克斯拉曼散射光谱测温技术凭借可提供高时间分辨率(每秒可提供上千个测温数据)、高测温精度和高测温灵敏度等优势而被应用到各种高温、湍流等复杂燃烧场景温度诊断中。文章概述了飞秒相干反斯托克斯拉曼散射测温技术的基本原理,综述了该技术在稳态火焰、加热气体、模拟燃气轮机等燃烧环境中测温工作的研究进展,简要介绍了飞秒时间分辨相干反斯托克斯拉曼光谱的研究和应用,着重介绍了可以实现毫秒量级时间分辨率的飞秒啁啾探测脉冲相干反斯托克斯拉曼散射测温技术和混合飞秒/皮秒相干反斯托克斯拉曼散射测温技术的基本原理和应用进展。指出了三种测温技术的优缺点,并提出飞秒相干反斯托克斯拉曼散射测温技术目前需要关注并解决的技术问题,主要为在高温高压湍流燃烧等极端条件下实现高精度CARS光谱高保真反演出温度信息,以及高温高压湍流燃烧场极端条件下如何获得高信噪比CARS信号的问题。展望了今后的发展趋势:通过高时间分辨的测量,获得湍流火焰中温度的瞬时演化规律,并建立各种复杂火焰的温度演化信息数据库,为研究各种发动机机理提供支撑。

飞秒-纳秒双脉冲激光诱导击穿光谱(LIBS)技术对合金的定量分析

激光诱导击穿光谱(Laser-induced breakdown spectroscopy,LIBS)技术几乎不受聚变环境中的强磁场影响,是一种最有希望实现托卡马克装置中面向等离子体材料(Plasma facing materials,PFMs)原位在线诊断的技术,已被用于多个托卡马克PFMs壁诊断。然而,LIBS技术对PFMs表面元素的探测限、定量分析以及PFMs的服役状态判定依旧面临很大挑战。采用同轴飞秒-纳秒激光协同技术,建立了飞秒-纳秒双脉冲激光诱导击穿光谱(fs-ns-DP-LIBS)技术,通过高峰值功率、低激光能量的飞秒激光诱导等离子体,再用纳秒激光增强常规单脉冲LIBS技术信号发射强度,进而提升常规单脉冲LIBS的探测灵敏度,同时结合6种合金标准样品,采用fs-ns-DP-LIBS技术对样品中的主要元素进行了定量分析,并进一步结合机器学习方法对6种合金进行种类判别。结果显示:在纳秒单脉冲和飞秒单脉冲LIBS检测中,Ni、Fe和Mo在400~800 nm波段没有观察到明显特征峰,仅观察到Cr的特征峰;在飞秒-纳秒脉冲间2μs延时,NiⅠ498.02 nm、FeⅠ517.16 nm、FeⅠ523.85 nm、MoⅠ588.83 nm和MoⅠ603.07 nm均被激发,且Cr的特征峰强度增强明显;并且相比对纳秒单脉冲LIBS技术,Cr的信号强度提高约7倍。定量分析结果显示,fs-ns-DP-LIBS技术绘制的定标曲线拟合度(R ^(2))更高,且Cr的探测限提高约3.5倍。进一步采用决策树、最近邻、线性判别和支持向量机等算法对6种合金进行了分类研究,线性判别和支持向量机的分类预测准确率大于99%。研究有望为原位LIBS技术诊断PFMs壁表面元素、定量分析及其服役状态判定提供检测方法。

金属微结构表面增强激光诱导击穿光谱的强度与稳定性

在金属铝表面用飞秒激光分别刻蚀了四种形状的微结构,对比分析了周期不同的矩形、圆形、三角形和六边形微结构对沉积在其表面Cr元素水溶液的表面增强激光诱导击穿光谱(LIBS)光谱强度和稳定性的影响。研究结果表明微结构的周期越小,光谱增强效果越显著,其中矩形微结构在相同周期下表现出最优光谱增强效果,相比于未处理的金属铝,其光谱强度增强了4倍左右。此外,六边形微结构的光谱稳定性最佳,具有良好的可重复性。研究结果为今后采用表面增强LIBS法检测水溶液中的重金属元素提供了一种可行的基底制备方法。

跨入X射线波段:超快和非线性光谱学的研究进展

超快非线性光谱技术(远红外至近紫外波段)是探测物质动力学过程及对称性的有效手段。近年来X射线自由电子激光技术的发展使超快光谱学测量拓展至X射线波段成为可能。文章对相关的研究进展进行了评述,并着重强调X射线波段的超快非线性光谱技术对于加深人们对物理和化学现象以及材料性质等的理解具有重要意义。

Frequency doubled femtosecond Ti:sapphire laser with an assisted enhancement cavity

We report an enhancement cavity for femtosecond Ti：sapphire laser at the repetition rate of 170 MHz. An enhancement factor of 24 is obtained when the injecting pulses have an average power of 1 W and a pulse duration of 80 fs. By placing a BBO crystal at the focus of the cavity, we obtain a 392-mW intracavity doubled-frequency laser, corresponding to a conversion efficiency of 43%. The output power has a long-term stability with a root mean square （RMS） of 0.036%.

The high dependence of polarization resolved laser-induced breakdown spectroscopy on experimental conditions

It is shown that the continuum emission produced by an A1 alloy ablated by femtosecond laser pulses is much more polarized than the characteristic lines of elements. A Glan-Thomson polarizer is used in the laser-induced breakdown spectroscopy experiment to investigate the polarization effect. The use of the polarizer at its minimal transmission increases the signal-to-noise ratio. The effects of angle of detection, focal position, and pulse energy on the signal-to- noise ratio are also studied.

Phase transformation and nanograting structure on TiO2 rutile single crystal induced by infrared femtosecond laser

In this paper, TitaiJum dioxide （TiO2） rutile single crystal was irradiated by infrared femtosecond laser pulses with repetition rate of 250 kHz. For a P-polarized femtosecond laser, the periodic nanograting structure on the ablation crater surface was formed . The periodicity is much less than the laser wavelength. The direction of nanograting alignment depends on the polarization laser beam. Micro-Raman spectra show that the intensity of Eg Raman vibrating mode of rutile phase increases and that of Alg Raman vibrating mode decreases apparently within the ablation crater. With the increase of irradiation time and laser average power, the Raman vibrating modes of anatase phase emerged. Rutile phase of TiO2 single crystal is partly transformed into anatase phase.

Ultrafast dynamics observation during femtosecond laser-material interaction

Femtosecond laser technology has attracted significant attention from the viewpoints of fundamental and application;especially femtosecond laser processing materials present the unique mechanism of laser-material interaction.Under the extreme nonequilibrium conditions imposed by femtosecond laser irradiation,many fundamental questions concerning the physical origin of the material removal process remain unanswered.In this review,cutting-edge ultrafast dynamic observation techniques for investigating the fundamental questions,including timeresolved pump-probe shadowgraphy,ultrafast continuous optical imaging,and four-dimensional ultrafast scanning electron microscopy,are comprehensively surveyed.Each technique is described in depth,beginning with its basic principle,followed by a description of its representative applications in laser-material interaction and its strengths and limitations.The consideration of temporal and spatial resolutions and panoramic measurement at different scales are two major challenges.Hence,the prospects for technical advancement in this field are discussed finally.