Laser spectroscopy imaging technique coupled withnanomaterials for cancer diagnosis: A review

Laser spectroscopic imaging techniques have received tremendous attention in the-eld of cancer diagnosis due to their high sensitivity,high temporal resolution,and short acquisition time.However,the limited tissue penetration of the laser is still a challenge for the in vivo diagnosis of deep-seated lesions.Nanomaterials have been universally integrated with spectroscopic imaging techniques for deeper cancer diagnosis in vivo.The components,morphology,and sizes of nanomaterials are delicately designed,which could realize cancer diagnosis in vivo or in situ.Considering the enhanced signal emitting from the nanomaterials,we emphasized their combination with spectroscopic imaging techniques for cancer diagnosis,like the surface-enhanced Raman scattering(SERS),photoacoustic,fluorescence,and laser-induced breakdown spectroscopy(LIBS).Applications ofthe above spectroscopic techniques offer new prospectsfor cancer diagnosis.

Measurement of residual stress in a multi-layer semiconductor heterostructure by micro-Raman spectroscopy

Si-based multilayer structures are widely used in current microelectronics. During their preparation, some inhomogeneous residual stress is induced, resulting in competition between interface mismatching and surface energy and even leading to structure failure. This work presents a methodological study on the measurement of residual stress in a multi-layer semiconductor heterostructure. Scanning electron microscopy（SEM）, micro-Raman spectroscopy（MRS）, and transmission electron microscopy（TEM） were applied to measure the geometric parameters of the multilayer structure. The relationship between the Raman spectrum and the stress/strain on the [100] and [110] crystal orientations was determined to enable surface and crosssection residual stress analyses, respectively. Based on the Raman mapping results, the distribution of residual stress along the depth of the multi-layer heterostructure was successfully obtained.

Influence of laser intensity in second-harmonic detection with tunable diode laser multi-pass absorption spectroscopy

Tunable diode laser absorption spectroscopy （TDLAS） has been widely employed in atmospheric trace gases detection. The ratio of the second-harmonic signal to the intensity of laser beam incident to the multi-pass cell is proved to be proportional to the product of the path length and the gas concentration under any condition. A new calibration method based on this relation in TDLAS system for the measurement of trace gas concentration is proposed for the first time. The detection limit and the sensitivity of the system are below 110 and 31ppbv （parts-per-billion in volume）, respectively.

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.

Heavy Metal Detection in Soils by Laser Induced Breakdown Spectroscopy Using Hemispherical Spatial Confinement

Spatial confinement has great potential for Laser Induced Breakdown Spectroscopy （LIBS） instruments after it has been proven that it has the ability to enhance the LIBS signal strength and repeatability. In order to achieve in-situ measurement of heavy metals in farmland soils by LIBS, a hemispherical spatial confinement device is designed and used to collect plasma spectra, in which the optical fibers directly collect the breakdown spectroscopy of the soil samples. This device could effectively increase the stability of the spectrum intensity of soil. It also has other advantages, such as ease of installation, and its small and compact size. The relationship between the spectrum intensity and the laser pulse energy is studied for this device. It is found that the breakdown threshold is 160 cm-2, and when the laser fluence increases to 250 J/cm2, the spectrum intensity reaches its maximum. Four different kinds of laser pulse energy were set up and in each case the limits of detection of Cd, Cu, Ni, Pb and Zn were calculated. The results show that when the laser pulse fluence was 2.12 GW/cm2, we obtained the smallest limits of detection of these heavy metals, which are all under 10 mg/kg. This device can satisfy the needs of heavy metal in-situ detection, and in the next step it will be integrated into a portable LIBS instrument.

Laser frequency stabilization and shifting by using modulation transfer spectroscopy

The stabilizing and shifting of laser frequency are very important for the interaction between the laser and atoms. The modulation transfer spectroscopy for the 87Rb atom with D2 line transition F = 2 →F＇ = 3 is used for stabilizing and shifting the frequency of the external cavity grating feedback diode laser. The resonant phase modulator with electro-optical effect is used to generate frequency sideband to lock the laser frequency. In the locking scheme, circularly polarized pump- and probe-beams are used. By optimizing the temperature of the vapor, the pump- and probe-beam intensity, the laser linewidth of 280 kHz is obtained. Furthermore, the magnetic field generated by a solenoid is added into the system. Therefore the system can achieve the frequency locking at any point in a range of hundreds of megahertz frequency shifting with very low power loss.

Quantitative analysis of C, Si, Mn, Ni, Cr and Cu in low-alloy steel under ambient conditions via laser-induced breakdown spectroscopy

A diode-pumped solid-state laser （DPSSL） with a high energetic stability and long service life is applied to ablate the steel samples instead of traditional Nd：YAG laser pumped by a xenon lamp, and several factors, such as laser pulse energy, repetition rate and argon flow rate, that influence laser-induced breakdown spectroscopy （LIBS） analytical performance are investigated in detail. Under the optimal experiment conditions, the relative standard deviations for C, Si, Mn, Ni, Cr and Cu are 3.3%-8.9%, 0.9%-2.8%, 1.2%-4.1%, 1.7%-3.0%, 1.1%-3.4% and 2.5%-8.5%, respectively, with the corresponding relative errors of 1.1%-7.9%, 1.0%-6.3%, 0.4%-3.9%, 1.5%-6.3%, 1.2%-4.0% and 1.2%-6.4%. Compared with the results of the traditional spark discharge optical emission spectrometry technique, the analytical performance of LIBS is just a little inferior due to the less stable laser-induced plasma and smaller amount of ablated sample by the laser. However, the precision, detection limits and accuracy of LIBS obtained in our present work were sufficient to meet the requirements for process analysis. These technical performances of higher stability of output energy and longer service life for DPSSL, in comparison to the Q-switch laser pumped by xeon lamp, qualify it well for the real time online analysis for different industrial applications.

Improvement of quantitative analysis of molybdenum element using PLS-based approaches for laser-induced breakdown spectroscopy in various pressure environments

An experimental setup has been designed and realized in order to optimize the characteristics of laser-induced breakdown spectroscopy system working in various pressure environments. An approach combined the normalization methods with the partial least squares(PLS) method are developed for quantitative analysis of molybdenum(Mo) element in the multi-component alloy,which is the first wall material in the Experimental Advanced Superconducting Tokamak. In this study, the different spectral normalization methods(total spectral area normalization,background normalization, and reference line normalization) are investigated for reducing the uncertainty and improving the accuracy of spectral measurement. The results indicates that the approach of PLS based on inter-element interference is significantly better than the conventional PLS methods as well as the univariate linear methods in the various pressure for molybdenum element analysis.

Spectral Enhancement of Laser-Induced Breakdown Spectroscopy in External Magnetic Field

In this paper the spectral enhancement of laser-induced breakdown spectroscopy （LIBS） for copper plasma in the presence of a magnetic field is investigated and the temporal- and spatial-resolved plasma emission spectra are analyzed. Experimental results show that the copper plasma atomic and ion spectra have been enhanced in the presence of the external magnetic field. In addition, the Cu I 521.82 nm spectral intensity evolution with delay time appears to have a double peak around the delay time of 2 μs, but that of Cu II 507.57 nm has a sharp decrease because of the electron-atom three body recombination process. The plasma temperature with magnetic confinement is lower than that of the case in the absence of magnetic fields. Finally, the spectral enhancement mechanisms of laser induced breakdown spectroscopy with magnetic confinement are analyzed.

Frequency stabilization of a 399-nm laser by modulation transfer spectroscopy in an ytterbium hollow cathode lamp

The modulation transfer spectroscopy in an ytterbium hollow cathode lamp at 399 nm is measured. The error signal for frequency locking is optimized by measuring the dependences of its slope, linewidth and magnitude on various parameters. Under the optimum condition, the laser frequency at 399 nm can be stabilized. The long-term stability of laser frequency is measured by monitoring the fluorescence signal of the ytterbium atomic beam induced by the locked laser. The laser frequency is shown to be tightly locked, and the stabilized laser is successfully applied to the cooling of ytterbium atoms.

Commissioning of a high-resolution collinear laser spectroscopy apparatus with a laser ablation ion source

Collinear laser spectroscopy is a powerful tool for studying the nuclear spins,electromagnetic moments,and charge radii of exotic nuclei.To study the nuclear properties of unstable nuclei at the Beijing Radioactive Ion-beam Facility(BRIF)and the future High Intensity Heavy-ion Accelerator Facility(HIAF),we developed a collinear laser spectroscopy apparatus integrated with an offline laser ablation ion source and a laser system.The overall performance of this state-of-the-art technique was evaluated,and the system was commissioned using a bunched stable ion beam.The high-resolution optical spectra for the 4s ^(2)S_(1/2)→4p^(2)P_(3/2)(D2)ionic transition of ^(40;42;44;48)Ca isotopes were successfully measured.The extracted isotope shifts relative to ^(40)Ca showed excellent agreement with the literature values.This system is now ready for use at radioactive ion beam facilities such as the BRIF and paves the way for the further development of higher-sensitivity collinear resonance ionization spectroscopy techniques.

Flexible control of semiconductor laser with frequency tunable modulation transfer spectroscopy

We introduce a new method of simultaneously implementing frequency stabilization and frequency shift for semiconductor lasers. We name this method the frequency tunable modulation transfer spectroscopy （FTMTS）. To realize a stable output of 780 nm semiconductor laser, an FTMTS optical heterodyne frequency stabilization system is constructed. Before entering into the frequency stabilization system, the probe laser passes through an acousto-optical modulator （AOM） twice in advance to achieve tunable frequency while keeping the light path stable. According to the experimental results, the frequency changes from 120 MHz to 190 MHz after the double-pass AOM, and the intensity of laser entering into the system is greatly changed, but there is almost no change in the error signal of the FTMTS spectrum. Using this signal to lock the laser frequency, we can ensure that the frequency of the laser changes with the amount of AOM shift. Therefore, the magneto-optical trap （MOT）-molasses process can be implemented smoothly.

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.

Measurement of electron density and electron temperature of a cascaded arc plasma using laser Thomson scattering compared to an optical emission spectroscopic approach

As advanced linear plasma sources, cascaded arc plasma devices have been used to generate steady plasma with high electron density, high particle flux and low electron temperature. To measure electron density and electron temperature of the plasma device accurately, a laser Thomson scattering（LTS） system, which is generally recognized as the most precise plasma diagnostic method, has been established in our lab in Dalian University of Technology. The electron density has been measured successfully in the region of 4.5？×10^19m^-3 to7.1？×10^20m^-3 and electron temperature in the region of 0.18 eV to 0.58 eV. For comparison,an optical emission spectroscopy（OES） system was established as well. The results showed that the electron excitation temperature（configuration temperature） measured by OES is significantly higher than the electron temperature（kinetic electron temperature） measured by LTS by up to 40% in the given discharge conditions. The results indicate that the cascaded arc plasma is recombining plasma and it is not in local thermodynamic equilibrium（LTE）. This leads to significant error using OES when characterizing the electron temperature in a non-LTE plasma.

Time-Resolved Optical Emission Spectroscopy Diagnosis of CO_2 Laser-Produced SnO_2 Plasma

The spectral emission and plasma parameters of SnO2 plasmas have been investigated. A planar ceramic SnO2 target was irradiated by a CO2 laser with a full width at half maximmn of 80 ns. The temporal behavior of the specific emission lines from the SnO2 plasma was characterized. The intensities of Sn I and Sn Ⅱ lines first increased, and then decreased with the delay time. The results also showed a faster decay of Sn I atoms than that of Sn II ionic species. The temporal evolutions of the SnO2 plasma parameters （electron temperature and density） were deduced. The measured temperature and density of SnO2 plasma are 4.38 eV to 0.5 eV and 11.38×1017 cm 3 to 1.1×1017^ cm-3, for delay times between 0.1 μs and 2.2 #s. We also investigated the effect of the laser pulse energy on Sn02 plasma.

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.

Laser Induced Breakdown Spectroscopy for Comparative Quantitative Analysis of Betel Leaves from Pakistan

Laser induced breakdown Spectroscopy(LIBS)was applied for the elemental analysis and exposure of the heavy metals in betel leaves in air.Pulsed Nd∶YAG(1064 nm)in conjunction with a suitable detector(LIBS 2000+,Ocean Optics,Inc)having the optical resolution of 0.06 nm was used to record the emission spectra from 220 to 720 nm.Elements like Al,Ba,Ca,Cr,Cu,P,Fe,K,Mg,Mn,Na,P,S,Sr,and Zn were found to present in the samples.The relative abundances of the observed elements were calculated through standard calibration curve method,integrated intensity ratio method,and weight percentage LIBS approach.LIBS findings were validated by comparing its results with the results obtained using a typical analytical technique of Inductively Coupled plasma-optical emission spectroscopy(ICP-OES).Limit of detection(LOD)of the LIBS system was also estimated for heavy metals.The experience gain through this work implies that LIBS could be highly applicable for testing the quality and purity of food products.

Investigation on plasma characteristics in a laser ablation pulsed plasma thruster by optical emission spectroscopy

In order to further improve the propulsion performance of pulsed plasma thrusters for space micro propulsion,a novel laser ablation pulsed plasma thruster is proposed,which separated the laser ablation and electromagnetic acceleration.Optical emission spectroscopy is utilized to investigate the plasma characteristics in the thruster.The spectral lines at different times,positions and discharge intensities are experimentally recorded,and the plasma characteristics in the discharge channel are concluded through analyzing the variation of spectral lines.With the discharge energy of 24 J,laser energy of 0.6 J and the use of aluminum propellant,the specific impulse and thrust efficiency reach 6808 s and 70.6%,respectively.

Effect of parameter setting and spectral normalization approach on study of matrix effect by laser induced breakdown spectroscopy of Ag–Zn binary composites

The complex nature of laser-material interaction causes non-stoichiometric ablation of alloy samples.This is attributed to matrix effect, which reduces analyzing capability. To address this issue, the analytical performance of three different normalization methods, namely normalization with background, internal normalization and three point smoothing techniques at different parameter settings is studied for quantification of Ag and Zn by Laser induced breakdown spectroscopy(LIBS).The LIBS spectra of five known concentration of silver zinc binary composites have been investigated at various laser irradiances(LIs). Calibration curves for both Ag(I) line(4d^(10)5s^2S_(1/2)→4d^(10)5p^2P_(1/2) at 338.28 nm) and Zn(I) line(4s5s^3S_1→4s4p^3P_2 at 481.053 nm) have been determined at LI of 5.86?×?10^(10)W cm^(-2). Slopes of these calibration curves provide the valuation of matrix effect in the Ag–Zn composites. With careful sample preparation and normalization after smoothing at optimum parameter setting(OPS), the minimization of sample matrix effect has been successfully achieved. A good linearity has been obtained in Ag and Zn calibration curve at OPS when normalized the whole area of spectrum after smoothing and the obtained coefficients of determination values were R^2?=?0.995 and 0.998 closer to 1. The results of matrix effect have been further verified by analysis of plasma parameters. Both plasma parameters showed no change with varying concentration at OPS. However, at high concentration of Ag, the observed significant changes in both plasma parameters at common parameter setting PS-1 and PS-2 were the gesture of matrix effect. In our case, the better analytical results were obtained at smoothing function with optimized parameter setting that indicates it is more efficient than normalization with background and internal normalization method.

The polarization characteristics of single shot nanosecond laser-induced breakdown spectroscopy of Al

The polarization-resolved laser-induced breakdown spectroscopy （PRLIBS） technique, which can significantly reduce the polarized emission from laser plasma by placing a polarizer in front of the detector, is a powerful tool to improve the line-to-continuum ratio in LIBS applications. It is shown that the continuum emission from the plasma produced through ablating an Al sample by nanosecond laser pulses is much more polarized than the discrete line emission with the singlepulse PRLIBS technique. The effects of laser fluence and detection angle on the Al polarization spectrum are systematically explored experimentally. The calculated result of the polarization spectrum as a function of laser fluence shows that it is in agreement with the experimental observations.