Mechanism of ablation of CdS at laser wavelengths in the visible and in the UV

The mechanisms of laser ablation of CdS targets at different laser wavelengths have been investigated. (CdS)_n⁺ cluster formation is only observed upon 532 nm ablation. The time and energy distributions of neutral S, S₂, Cd and CdS show significant dependence on laser wavelength. Bimodal distributions are observed at 266 and 308 nm. For the former, the average kinetic energy increases significantly with mass, taking values in the range of 0.3-1.7 eV. At 308 nm the slow component of the time distribution disappears at distances above the target larger than 1 cm. At this wavelength, the observed time distribution appears to reflect mainly the dynamics of the expansion. At 532 nm the time distribution is monomodal and the average kinetic energies are below 0.2 eV. Clear indications of the participation of thermal (at 532 nm) and non-thermal mechanisms (at 266 nm) have been found. It is tentatively concluded that the cluster formation observed upon ablation at 532 nm can be related to the thermal ablation mechanisms in which the low kinetic energy of the species in the plume and their similar velocities favor the aggregation processes.     

制备水溶性CdS量子点的一种物理方法：飞秒激光烧蚀法

用Ti/sapphire飞秒激光系统产生的100fs、800nm激光对置于水中的CdS体相材料进行烧蚀,得到了水溶性CdS纳米粒子。这种纯物理过程保证了无污染的制备环境,从而保证了所合成材料的纯洁性。通过透射电子显微镜、紫外/可见/近红外吸收光谱、室温光致发光谱的方法对CdS量子点的形貌及其光学性质进行了表征。结果表明:利用飞秒激光烧蚀法所制备的CdS量子点可直接分散在水中而且具有粒径小、分布均匀的特点;同时具有较好的胶体稳定性,可在空气中稳定存放6个月以上。飞秒激光烧蚀法所制备的CdS量子点所具有的这些性质使其在生物标记领域引起极大的兴趣,而且也为纳米材料的制备提供了新的思路。     

Raman characterization of localized CdS nanostructures synthesized by UV irradiation in sol–gel silica matrices

A new technique of UV irradiation has been used for the first time to create microstructures of CdS nanoparticles in bulk xerogels. Porous silica matrices, which were first soaked in a solution containing CdS precursors, were subjected to irradiation using a nanopulsed ArF laser with a wavelength of 193 nm and a repetition rate of 10 Hz. Resonant micro‐Raman spectra, recorded using the 325‐nm line of a He‐Cd laser (with a continuous power less than 0.5 mW so as to avoid the thermal formation of nanoparticles) made it possible to identify CdS nanoparticles within the inscribed yellow zones and also to estimate the average particle size (3.6 to 8.0 nm, depending on the number of UV pulses used). The emission of CdS particles embedded in the silica matrix under excitation at 351.1 nm was studied by photoluminescence spectroscopy. It was then possible to show the effect of the number of pulses on the electronic structure of the nanocrystals. Finally, Raman spectra were used to monitor the structural changes in the silica matrix caused by the irradiation. It was found that the pulsed UVirradiation resulted in a local densification of the matrix, which was compensated for by a depolymerization process of the Si O Si network. In spite of this pulsed irradiation and the resulting structural depolymerization, no apparent ablation or cracking of the samples was observed. Copyright © 2010 John Wiley & Sons, Ltd.     

Nanoparticle formation during laser ablation of solids in liquids

The experimental data on the generation of metal and semiconductor nanoparticles during their laser ablation in liquids is reviewed. The dependence of the morphology of noble metal nanoparticles on the liquid type and laser parameters is discussed. The data on the kinetics of the formation of alloyed Au-Ag nanoparticles under laser irradiation of a mixture of colloid solutions of individual nanoparticles are presented. The effect of femtosecond laser beam self-action during metal ablation in liquids via the second harmonic generation at Ag nanoclusters is discussed. The data on the generation of core-shell nanoparticles during laser ablation of alloys and in the presence of the chemical interaction of formed nanoparticles with surrounding liquid are presented. It was shown that laser ablation of CdS and ZnSe crystals leads to the formation of quantum dots of these semiconductors in solution. The parameters controlling the properties of nanoparticles during ablation in liquids and possible applications of the method are discussed.     

Gold Nanocages as Effective Photothermal Transducers in Killing Highly Tumorigenic Cancer Cells

Numerous gold nanostructures have the potential for photothermal therapy in cancers. Here, gold nanocages and gold nanoshells are synthesized, the sizes of which are fine‐tuned for a response at 750 nm wavelength. Their photothermal therapeutic efficiency is compared at gold concentration of 100 lg mL^?1 using a near‐infrared laser (750 nm). The biocompatibility for varying concentrations of gold (1 to 100 lg mL^?1) is performed in a normal cell line and laser‐mediated cell cytotoxicity for varying time intervals (7.5 and 10 min) is carried out in breast cancer cells. This study shows that when analyzed under similar conditions, the gold nanocages show better biocompatibility and are more efficient in near‐infrared absorption and photothermal conversion in comparison with conventional gold nanoshells. When subjected to photothermal laser ablation of breast cancer cell line for 7.5 min and 10 min, the nanocages are able to induce 62.92 ± 3.25% and 96.41 ± 3.04% reduction in cell viability, respectively, in comparison to nanoshells, in which a 43.35 ± 1.91% and 79.89 ± 4.74% reduction in cell viability is observed. The current study shows that the gold nanocages can outperform gold nanoshells and effectively kill cancer cells without any significant cytotoxic effect on normal cells.     

TEM and XPS studies on CdS/CIGS interfaces

Copper indium gallium selenide (CIGS) was deposited by metallic precursors sputtering and subsequently submitted to a selenization process. The upper CdS layers were deposited by chemical bath deposition (CBD) technique. The CdS/CIGS interfaces were investigated by Transmission Electron Microscopy (TEM) and X-ray Photoelectron Spectroscopy (XPS). As checked by XPS analysis, the CIGS surface exhibited a hydroxide-terminated CdSe layer when treated with Cd Partial Electrolyte solution (Cd PE). Its thickness was roughly estimated to several nanometers. A 100 nm thick CdS layer was deposited onto CIGS surface. The TEM images revealed a clear and sharp interface between CdS and CIGS. XPS analysis showed a CIGS surface covered by a pinhole free and homogeneous CdS layer. XPS depth profile measurement of the CdS/CIGS interface did not evidence elemental inter-diffusion between the CIGS and CdS layers, in very good agreement with TEM observations.     

基于双相延迟模型的飞秒激光烧蚀金属模型

为了分析飞秒激光烧蚀过程,在双相延迟模型的基础上建立了双曲型热传导模型.模型中考虑了靶材的加热、蒸发和相爆炸,还考虑了等离子体羽流的形成和膨胀及其与入射激光的相互作用,以及光学和热物性参数随温度的变化.研究结果表明:等离子体屏蔽对飞秒激光烧蚀过程有重要的影响,特别是在激光能量密度较高时;两个延迟时间的比值对飞秒激光烧蚀过程中靶材的温度特性和烧蚀深度有较大的影响;飞秒激光烧蚀机制主要以相爆炸为主.飞秒激光烧蚀的热影响区域较小,而且热影响区域的大小受激光能量密度的影响较小.计算结果与文献中实验结果的对比表明基于双相延迟模型的飞秒激光烧蚀模型能有效对飞秒激光烧蚀过程进行模拟.     

Optical investigation of the red band emission of CdS nanoparticles

Cadmium sulfide (CdS) nanoparticles, with different Cd/S molar ratios, were chemically produced and characterized in this study. High quality CdS nanoparticles were grown in the hexagonal phase, as indicated by X-ray diffraction data and Raman spectroscopy. Photoluminescence was used to investigate the surface effects caused by submitting the nanoparticle-based samples at different laser treatments and vacuum pressure.     

Improved thermal model and its application in UV high-power pulsed laser ablation of metal target

An improved thermal model describing UV high-power nanosecond laser ablation of metal target is presented. The vaporization effect, the plasma shielding effect, as well as the absorption coefficient and absorptivity dependence of temperature are considered in this model. Take iron target as an example, the numerical solutions are obtained from the heat flow equations (before and after melting) using a finite difference method. The space and time dependence of temperature of the target, the time dependence of temperature at two different positions for a certain laser fluence, and the ablation rate as a function of laser fluence are also presented. The numerical results that agreed well with the experimental data are much better than the one without, which indicates that the above two effects and the temperature dependence of absorption coefficient and absorptivity in UV high-power laser ablation of metal target should not be neglected. We hope the present model will be useful for further experimental investigation of metal thin films prepared by pulsed laser deposition.     

利用Cd(OH)_2选择性包覆与光分解腐蚀缩小CdS纳米微粒的尺寸分布的研究

提出结合Ｃｄ（ＯＨ）２ 选择性包覆与光分解腐蚀法缩小ＣｄＳ纳米微粒的尺寸分布, 并通过对ＣｄＳ纳米微粒发射光谱的研究证实了这一设计思想． 以多聚磷酸钠（ＨＭＰ）为稳定剂合成ＣｄＳ纳米微粒, 再通过Ｃｄ２＋ 与ＯＨ－ 的选择性包覆在大粒径的ＣｄＳ纳米微粒表面形成一层Ｃｄ（ＯＨ）２, 然后溶液置于日光下辐照处理, 数天后, 未经包覆的小粒径ＣｄＳ纳米微粒被日光腐蚀分解, 溶液中只剩下被Ｃｄ（ＯＨ）２ 包覆的大粒径ＣｄＳ纳米微粒, 这样即可达到缩小ＣｄＳ纳米微粒尺寸分布的目的．     

Laser ablation of a molten Ga target; comparison of experiments and simulation

The laser ablation mechanism of a molten Ga target was examined through comparison of experiments and simulation. The ablation was performed using an ArF excimer laser (193-nm wavelength and 20-ns duration) in vacuum. The observed existence of the threshold laser fluence (necessary for onset of the ablation) and linear increases in both the Ga deposition rate and the Ga emission (fluorescence) intensity with the laser fluence were satisfactorily explained by the simulation based on the thermal ablation model. In addition, it was found that most of the ablated particles are transferred to the substrate not in the form of an excited ion but an excited neutral atom, except at and near the target. Received: 3 September 2001 / Accepted: 7 November 2001 / Published online: 20 December 2001     

Graphene nanocomposites of CdS and ZnS in effective water purification

The present work deals with syntheses of CdS/graphene and ZnS/graphene nanocomposites by hydrothermal reaction of graphene oxide and morpholine-4-carbodithioate complex of Cd and Zn, respectively. The corresponding nanocomposites has been investigated separately as photocatalyst in the decomposition of methylene blue in the presence of UV light and also as adsorbents in the removal of Cd(II) and Pb(II) ions in contaminated water. These studies have established that CdS/graphene and ZnS/graphene are effective photocatalyst as well as effective adsorbents in the removal of Cd(II) and Pb(II) ions to an extent of 97 and 99 % by ZnS/graphene and CdS/graphene nanocomposite, respectively, under 1 g L^?1 of adsorption dose and at pH ~7. Further studies also established Langmuir model befitting for the adsorption of Pb(II) and Cd(II) ions on CdS/graphene and ZnS/graphene, respectively. The presence of interfering ions on extent of Cd(II) and Pb(II) removal has also been reported.     

纳秒激光烧蚀冲量耦合数值模拟

为研究激光烧蚀靶产生冲量过程和机理, 建立了一个复杂的一维热传导和流体动力学模型. 以空间碎片常见材料Al为例, 用建立的模型数值计算了纳秒脉宽激光烧蚀靶产生的冲量及冲量耦合系数随时间变化情况. 数值结果和已有的实验数据符合的较好. 数值计算表明: 激光脉冲时间内, 靶获得的冲量随时间迅速增加, 在脉冲时间结束后, 冲量变化随时间趋于稳定; 在冲量耦合过程中, 烧蚀等离子体向真空膨胀, 羽流尺度逐渐增大, 同时吸收入射激光能量, 导致激光与靶耦合的能量降低. 关键词： 激光烧蚀 冲量耦合 等离子体     

Observations on the influence of pH control on the properties of chemically deposited CdS films in an ammonia-free system

In this work we report on the properties of chemically deposited CdS thin films in an ammonia-free cadmium-sodium citrate system. We studied the influence on the properties of the films of the pH control of the reaction solution. For this, we deposited two types of CdS films employing two different types of reaction solutions. The only difference between both reaction solutions was the addition of a pH buffer in one of them in order to control its pH throughout the deposition process. Several sets of CdS films were deposited from growth solutions with different contents of Cd to determine also the influence of this parameter on the properties of the films. The CdS films were studied by X-ray diffraction, optical transmission and reflection spectroscopy and scanning electron microscopy measurements. We found that the properties of the films depend both on the amount of Cd in the growth solutions and on their pH control. The increase in Cd in the reaction solution yields to films with shorter lattice constant and then higher energy band gap. On the other hand, the pH control of the reaction produces higher deposition rate, larger final thickness and higher energy band gaps in the CdS films.     

Laser ablation and deposition of wide bandgap semiconductors: plasma and nanostructure of deposits diagnosis

Nanostructured CdS and ZnS films on Si (100) substrates were obtained by nanosecond pulsed laser deposition at the wavelengths of 266 and 532 nm. The effect of laser irradiation wavelength on the surface structure and crystallinity of deposits was characterized, together with the composition, expansion dynamics and thermodynamic parameters of the ablation plume. Deposits were analyzed by environmental scanning electron microscopy, atomic force microscopy and X-ray diffraction, while in situ monitoring of the plume was carried out with spectral, temporal and spatial resolution by optical emission spectroscopy. The deposits consist of 25–50 nm nanoparticle assembled films but ablation in the visible results in larger aggregates (150 nm) over imposed on the film surface. The aggregate free films grown at 266 nm on heated substrates are thicker than those grown at room temperature and in the former case they reveal a crystalline structure congruent with that of the initial target material. The observed trends are discussed in reference to the light absorption step, the plasma composition and the nucleation processes occurring on the substrate.     

Effect of vapor attenuation in surface ablation of cobalt by pulsed UV laser

Numerical calculations based on a thermal model were presented, which describe the process of target heating and ablation of cobalt during irradiation by 30-ns laser pulses at 308 nm. The attenuation of laser by vapor has been taken into account in this model. As results of the calculations, the temperature distribution beneath the target surface and the temporal evolution of surface temperature were given. The dependence of ablation rate on laser fluence was also studied based on this model. The surface ablation of cobalt with pulsed excimer laser was investigated experimentally. Our model considering proper vapor attenuation has shown to be in good agreement with the experimental results. Received: 20 January 2000 / Accepted: 13 March 2000 / Published online: 5 July 2000     

热阻塞效应对激光辐照靶材烧蚀过程的影响分析

研究了百兆瓦级激光烧蚀碳/碳复合材料靶材产生的等离子体吸收激光束能量引起的热阻塞效应。首先,基于逆轫致吸收理论,建立了激光在烧蚀靶材产生的等离子体中的传播模型;然后,基于磁流体理论,得到了等离子体在百兆瓦级激光形成的电磁场中的波动方程,建立了等离子体吸收激光能量引起热阻塞效应的模型。最后,对烧蚀过程中粒子的总密度、吸收系数、靶材表面等效热流随激光持续时间的变化规律以及是否考虑热阻塞效应时,靶面垂直方向的温度场进行了数值模拟。结果表明:等离子体的形成,对激光形成了明显的热阻塞效应,削弱了激光对靶材的烧蚀作用,使粒子总密度、吸收系数、靶材表面等效热流以及靶面垂直方向温度场的变化均呈现为非线性。     

Synthesis and characterization of Cr doped CdS nanoparticles stabilized with polyvinylpyrrolidone

Undoped and Cr (2 and 4 at.%) doped CdS nanoparticles were synthesized in aqueous solution by simple chemical co-precipitation method using polyvinylpyrrolidone (PVP) as stabilizer. The prepared nanoparticles were examined using X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDAX), transmission electron microscopy (TEM), UV-vis diffuse reflectance spectroscopy (DRS) and Fourier transform infrared spectroscopy (FTIR). XRD pattern of the nanoparticles showed cubic zincblende phase with the particle size of the order of 3-4 nm, which was in good agreement with the results obtained from TEM studies. The EDAX analysis confirmed that Cd, Cr and S elements were present in the samples and the variations between the target and actual compositions were microscopic. UV-vis DRS spectra of the samples exhibited decrease in the band gap which further attests the incorporation of Cr into CdS nanoparticles. FTIR studies revealed that the undoped as well as Cr doped CdS nanoparticles were capped by polyvinylpyrrolidone.     

Second-order optical nonlinearity of surface-capped CdS nanoparticles and effect of surface modification

Surface-capped CdS nanoparticles (5 nm mean diameter) with hexametaphosphate and CTAB (hexadecyltrimethyl-ammonium bromide) in chloroform were prepared by colloidal chemistry and phase transfer method. The second-order nonlinear optical response was measured by incoherent hyper-Rayleigh scattering (HRS) technique. Results show that the surface-capped CdS nanoparticles have a large first-order hyperpolarizability β value of 1.30×10⁻²⁶ esu per particle. Surface capping molecule modification was performed by adding pyridine to a chloroform sol of the surface-capped CdS nanoparticles where pyridine can be bound to the CdS nanoparticle surface through Cd–N chemical bonds. A reduction in HRS signal intensity was observed when increasing pyridine concentration. This is explained in terms of a two-level model approximation derived from molecular chromophores, when considering the influence of the formation of Cd–N coordinating bonds on the charge-transfer transition energy of surface molecule-like scatterers of Cd–S polar bonds.     

Laser ablation of energetic polymer solutions: effect of viscosity and fluence on the splashing behavior

Laser plasma thrusters are a new kind of propulsion system for small satellites, and work with the thrust created by the laser ablation of a target. Liquid polymer solutions are very promising fuels for such systems, provided that no splashing of the target occurs, because ejection of droplets strongly decreases the performances of the system. We have investigated the nanosecond infrared laser ablation of glycidyl azide polymer solutions containing carbon nanoparticles as absorber. Shadowgraphy imaging revealed two cases, namely splashing regime and solid-like behavior. The transition between both regimes depends on the viscosity of the solution and on the laser fluence, and is explained by the recoil force acting on the target. Appropriate conditions to avoid splashing were identified, showing that this liquid polymer solution is a suitable fuel for laser plasma thrusters.