Laser induced mechanisms controlling the size distribution of metallic nanoparticles

International audience

Dispersive liquid–liquid microextraction for metals enrichment: A useful strategy for improving sensitivity of laser-induced breakdown spectroscopy in liquid samples analysis

A rapid and efficient Dispersive Liquid–Liquid Microextraction (DLLME) followed by Laser-Induced Breakdown Spectroscopy detection (LIBS) was evaluated for simultaneous determination of Cr, Cu, Mn, Ni and Zn in water samples. Metals in the samples were extracted with tetrachloromethane as pyrrolidinedithiocarbamate (APDC) complexes, using vortex agitation to achieve dispersion of the extractant solvent. Several DLLME experimental factors affecting extraction efficiency were optimized with a multivariate approach. Under optimum DLLME conditions, DLLME-LIBS method was found to be of about 4.0–5.5 times more sensitive than LIBS, achieving limits of detection of about 3.7–5.6 times lower. To assess accuracy of the proposed DLLME-LIBS procedure, a certified reference material of estuarine water was analyzed.

Novel laser-induced luminescence resulting from benzophenone/O-propylated p-tert-butylcalix[4]arene complexes. A diffuse reflectance study

Laser-induced room temperature luminescence of air-equilibrated benzophenone/O-propylated p-tert-butylcalix[ 4] arene solid powdered samples revealed the existence of a novel emission, in contrast with benzophenone/p-tertbutylcalix[ 4] arene complexes, where only benzophenone emits. This novel emission was identified as phosphorescence of 1-phenyl-1,2-propanedione, which is formed as the result of an hydrogen atom abstraction reaction of the triplet excited benzophenone from the propoxy substituents of the calixarene. Room temperature phosphorescence was obtained in air-equilibrated samples in all propylated hosts. The decay times of the benzophenone emission vary greatly with the degree of propylation, the shortest lifetimes being obtained in the tri- and tetrapropylated calixarenes. Triplet - triplet absorption of benzophenone was detected in all cases, and is the predominant absorption in the p-tert-butylcalix[ 4] arene case, where an endo-calix complex is formed. Benzophenone ketyl radical formation occurs with the O-propylated p-tert-butylcalix[ 4] arenes hosts, suggesting a different type of host/guest molecular arrangement. Diffuse reflectance laser. ash photolysis and gas chromatography - mass spectrometry techniques provided complementary information, the former about transient species and the latter regarding the final products formed after light absorption. Product analysis and identification clearly show that the two main degradation photoproducts following laser excitation in the propylated substrates are 1-phenyl-1,2- propanedione and 2- hydroxybenzophenone, although several other minor photodegradation products were identified. A detailed mechanistic analysis is proposed. While the solution photochemistry of benzophenone is dominated by the hydrogen abstraction reaction from suitable hydrogen donors, in these solid powdered samples, the alpha-cleavage reaction also plays an important role. This finding occurs even with one single laser pulse which lasts only a few nanoseconds, and is apparently related to the fact that scattered radiation exists, due to multiple internal reflections possibly trapping light within non-absorbing microcrystals in the sample, and is detected until at least 20 mus after the laser pulse. This could explain how photoproducts thus formed could also be excited with only one laser pulse.

BARIUM CONCENTRATIONS IN ROCK SALT BY LASER INDUCED BREAKDOWN SPECTROSCOPY

Time-REsolved Laser Induced Breakdown Spectroscopy (TRELIBS) was used to determine the elemental concentration of barium in Texas Dome rock salt. TRELIBS allows for an efficient and in situ concentration analysis technique that detects a wide range of elements with no sample preparation. TRELIBS measurements were made in the 545nm to 594nm wavelength range. The proximity of a strong barium emission line (553.5481 nm) to the sodium doublet (588.9950 nm and 589.5924 nm) allowed for measurement within a single frame of the spectrograph. This barium emission line was compared to the sodium doublet for relative intensity. A homemade calibration sample containing known amounts of barium and sodium was used to determine the relative concentrations. By approximating the sodium content in the rock salt as 50%, we determined the absolute concentration of barium in the salt to be (0.13±0.03)%.

Elemental Analysis and Forensic Comparison of Soils by Laser-Induced Breakdown Spectroscopy (LIBS) and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS)

The elemental analysis of soil is useful in forensic and environmental sciences. Methods were developed and optimized for two laser-based multi-element analysis techniques: laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and laser-induced breakdown spectroscopy (LIBS). This work represents the first use of a 266 nm laser for forensic soil analysis by LIBS. Sample preparation methods were developed and optimized for a variety of sample types, including pellets for large bulk soil specimens (470 mg) and sediment-laden filters (47 mg), and tape-mounting for small transfer evidence specimens (10 mg). Analytical performance for sediment filter pellets and tape-mounted soils was similar to that achieved with bulk pellets. An inter-laboratory comparison exercise was designed to evaluate the performance of the LA-ICP-MS and LIBS methods, as well as for micro X-ray fluorescence (μXRF), across multiple laboratories. Limits of detection (LODs) were 0.01-23 ppm for LA-ICP-MS, 0.25-574 ppm for LIBS, 16-4400 ppm for µXRF, and well below the levels normally seen in soils. Good intra-laboratory precision (≤ 6 % relative standard deviation (RSD) for LA-ICP-MS; ≤ 8 % for µXRF; ≤ 17 % for LIBS) and inter-laboratory precision (≤ 19 % for LA-ICP-MS; ≤ 25 % for µXRF) were achieved for most elements, which is encouraging for a first inter-laboratory exercise. While LIBS generally has higher LODs and RSDs than LA-ICP-MS, both were capable of generating good quality multi-element data sufficient for discrimination purposes. Multivariate methods using principal components analysis (PCA) and linear discriminant analysis (LDA) were developed for discriminations of soils from different sources. Specimens from different sites that were indistinguishable by color alone were discriminated by elemental analysis. Correct classification rates of 94.5 % or better were achieved in a simulated forensic discrimination of three similar sites for both LIBS and LA-ICP-MS. Results for tape-mounted specimens were nearly identical to those achieved with pellets. Methods were tested on soils from USA, Canada and Tanzania. Within-site heterogeneity was site-specific. Elemental differences were greatest for specimens separated by large distances, even within the same lithology. Elemental profiles can be used to discriminate soils from different locations and narrow down locations even when mineralogy is similar.

Phosphorus quantification in fertilizers using laser induced breakdown spectroscopy (LIBS): a methodology of analysis to correct physical matrix effcts.

2016

Physical characterization of the organic nonlinear optical crystal � 3-methoxy 4-hydroxy benzaldehyde

We highlight our recent experimental work on an efficient molecular nonlinear optical crystal, 3-methoxy 4-hydroxy benzaldehyde (MHBA). Optical quality single crystals of MHBA were grown from mixtures of solvents and from melt. The overall absorption and transparency window were improved by growing them in a mixture of chloroform and acetone. The grown crystals were characterized for their optical transmission, mechanical hardness and laser damage. We have observed a strong correlation between mechanical properties and laser induced damage.

超短脉冲激光对透明材料的破坏

基于固体的能带理论和能量守恒原理建立了一个描述激光与非金属材料作用时载流子随时间空间变化的理论模型。讨论了材料的破坏阈值、烧蚀深度与激光脉宽、波长和强度之间的关系，同时也讨论了破坏阈值、烧蚀深度与材料禁带宽度等特性之间的关系。讨论了多光子电离、隧道电离和雪崩电离在激光对材料破坏过程中的不同地位，理论结果表明，光电离在超短脉冲激光对非金属材料破坏过程中对破坏阈值的影响最大。

电子束蒸发制备平板偏振膜激光损伤特性研究

采用电子束蒸发沉积技术制备了平板偏振膜。用Lambda900分光光度计测试了其光学性能。在中心波长1053nm处P偏振光的透过率Tp〉98％，S偏振光的透过率Ts〈0．5％，消光比T，／瓦〉200：1，带宽约为20nm。用波长1064nm，脉宽12ns的脉冲激光进行损伤阈值测试，获得P偏振光的损伤阈值为17．2J／cm^2，S偏振光的损伤阈值为19．6J／cm^2。用Nomarski显微镜对薄膜的损伤形貌进行观察，并用Alpha-500型台阶仪对损伤深度进行测试。结果表明，P偏振光的激光损伤为界面损伤与缺

多层介质膜光栅和介质膜反射镜抗激光损伤阈值研究

对多层介质膜光栅以及介质膜反射镜的激光损伤阈值进行了系统的研究。测试方法采用国际测试标准。测试结果表明，介质光栅的损伤阈值远低于未刻蚀的多层介质膜。对样品损伤形貌的扫描电镜照片分析发现，相比于未刻蚀的多层介质膜，介质膜光栅的初始损伤主要发生在光栅槽形的侧壁，且损伤主要是由驻波场的空间分布引起的本征吸收、制备过程中引入的杂质污染以及刻蚀过程中HfO2的化学计量机失衡引起的。

重复率激光作用下光学薄膜损伤的累积效应

使用脉宽12ns，频率10Hz的1064nm调Q Nd：YAG激光器，研究了高反射膜在重复率激光作用下的损伤的累积效应。实验发现，高反射膜的损伤阈值随辐照脉冲数增加而降低，表现出明显的累积效应。通过对损伤阈值和损伤概率以及辐照次数的统计性研究．并结合单脉冲辐照的结果，说明了存在于薄膜中微小的缺陷参与了多脉冲激光对薄膜的损伤过程。可用预损伤机制解释实验结果。得到了关于IBS制备的高反射膜的损伤阈值和照射次数的关系式，并用实验结果进行验证．发现具有很好的一致性。实验过程中样品的损伤形貌通过Nomarski偏光

多脉冲激光作用下光学薄膜损伤的累积效应

研究了高反射膜在多脉冲激光作用下损伤的累积效应．实验中使用1064nm调Q的Nd：YAG激光器，脉宽是12ns，频率为10Hz．实验发现：高反射膜的损伤阈值随辐照脉冲数增加而降低，表现出明显的累积效应．通过对损伤阈值和损伤概率以及辐照次数的统计性研究，并结合单脉冲辐照的结果，说明了存在于薄膜中微小的缺陷参与了多脉冲激光对薄膜的损伤过程，得到了制备IBS高反射膜的损伤闽值和照射次数的关系式，用Nomarski偏光显微镜观察了实验过程中样品的损伤形貌，发现是典型的缺陷损伤．

氧离子束辅助沉积氧化铪薄膜的激光损伤阈值研究

电子枪蒸发制备了氧化铪薄膜,对氧离子束辅助和未辅助两种情况下的样品进行了折射率、吸收、激光损伤阈值等属性的测试,结果表明,氧离子束辅助沉积的样品与未辅助沉积的样品相比具有高的折射率和高的吸收,以及稍低的激光损伤阈值.经过分析发现,薄膜的激光损伤阈值是影响薄膜抗激光特性的不利因素和有利因素竞争的结果,离子束辅助沉积技术在引入结构致密等有利因素的同时,也引入了吸收增加等不利因素.

沉积温度对LaF3薄膜性能的影响

abstract {LaF₃ single-layer coatings were prepared by thermal boat evaporation at the deposition temperatures of 189, 255, 277 and 321°C respectively. The crystal structures of the coatings were characterized by X-ray diffraction (XRD). A spectrophotometer was employed to measure its transmittance. Moreover, refractive index, extinction coefficient and cut-off wavelength were obtained from the measured transmittance spectral curve. The residual stress was evaluated by the Stoney's equation and optical interferometer. Laser induce damage threshold (LIDT) was performed by a tripled Nd:YAG laser system. The results show that the crystallization status becomes better with the deposition temperature increasing. Correspondingly, the grain size also gets larger. Meanwhile, the coatings become more compact and the refractive index increases. However, the absorption of coatings seriously rises and the cut-off wavelength drifts to the long wave. In addition, the residual stress also increases and the intrinsic stress plays a determinant role in the coating. The LIDT of the coating also enhances at high temperature.}