Excimer laser surface treatment of bulk ceramics

Changes of surface morphology following excimer laser (KrF, ArF) irradiation were investigated for three technical ceramic materials (TZP, PSZ, Si₃N₄). Zirconia samples exhibit a smooth and glass-like surface at the low power density regime, while at higher power densities colour changes were observed due to changes in the chemical composition of the bulk material. In the silicon nitride samples new crystals of specific orientation are formed, which could be crystalline silicon.     

绝缘衬底上高密度均匀纳米硅量子点的形成与表面形貌

利用等离子体增强化学气相淀积技术，在绝缘氮化硅(SiNx)衬底上制备超薄非晶硅(aSi：H)薄膜，通过超短脉冲激光辐照与准静态常规热退火技术处理，制备出高密度、均匀纳米硅(ncSi)量子点.使用原子力显微镜对处理前后样品的表面形貌进行了研究，发现激光辐照能量密度增加的同时，所形成的ncSi尺寸也随之增加.在合适的能量密度范围内，可以得到面密度大于10.11cm^2、尺寸分布标准偏差小于20％的10 nm ncSi量子点薄膜，表明所制备的ncSi量子点具有较好的均匀性及较高的面密度.同时，对ncS i量子点 关键词： 纳米硅 激光诱导 尺寸分布     

The development of a portable line-shaping optical system for silicon surface treatment

This study proposes a beam shaper for converting a circle beam profile generated with a Gaussian intensity distribution by an 808 nm diode laser into a line beam profile for silicon surface treatment applications. To produce a hand-held and low-cost device with a large spot-size laser, this study uses a portable optical system consisting of a diode laser source, a collimator, a cylindrical lens, and a plano-convex lens to generate an approximately 40 × 3:5mm² line beam profile at a working distance of 200 mm. The silicon surface treated by the line-shaped laser beam has significantly reduced reflectance spectra. The proposed system is also suitable for the surface cleaning of materials.     

激光等离子体效应对硅表面损伤特征的影响

硅材料作为光电探测器的基础材料,研究其在强激光辐照下的损伤问题在激光探测、国防领域很有意义。对高强度纳秒激光作用下硅表面的损伤形貌特征进行了研究,结果表明:激光等离子体的热效应及冲击波效应,使激光作用区域内的物质迅速向外飞溅,形成点坑,并在点坑周围形成辐射状冷却物;散射光与入射激光干涉产生形成周期性分布的热应力使得硅材料表面张力发生变化,冷却后会在坑底表面产生周期性结构;从激光等离子体的光谱中可以发现N,O和Si的特征光谱,在重复激光脉冲作用下会在硅表面上覆盖一层导致色变的SiOx和SiNx复合薄膜,是激光等离子体的喷射产物。     

Ultraviolet laser microstructuring of silicon and the effect of laser pulse duration on the surface morphology

The study of the laser pulse duration effect on the silicon micro-spikes morphology is presented. The microcones were produced by ultraviolet (248 nm) laser irradiation of doped Si wafers in SF₆ environment. The laser pulse duration was adjusted at 450 fs, 5 ps and 15 ns. We have analyzed the statistical nature of the spikes’ morphological characteristics, such as periodicity and apex angle by exploiting image processing techniques, on SEM images of the irradiated samples. The correlation of the quantitative morphological characteristics with the laser parameters (pulse duration, laser fluence and number of pulses) provides new insight on the physical mechanisms, which are involved on the formation of Si microcones.     

ArF laser surface modification of polyethersulfone film: Effect of laser fluence in improving surface biocompatibility

ArF laser treatment of polyethersulfone (PES) films was performed to improve biocompatibility of surfaces. For this purpose, the threshold fluence for laser ablation of PES was obtained from experimental measurements and then samples were irradiated at 2 separate ranges of fluences, i.e. below and above the ablation threshold. In order to investigate the physico-chemical changes, the modified surfaces were characterized by attenuated total reflectance (ATR) infrared spectroscopy and contact-angle measurements. The biocompatibility of the treated samples in comparison to those untreated was examined in vitro using a platelet adhesion test. The number of adhered platelets was obtained using the lactate dehydrogenase (LDH) method. For surfaces irradiated below the ablation threshold, a high reduction in the number of the adhered platelets was observed; while this number increased in samples treated at the fluence above the ablation threshold. The change in platelet adhesion was attributed to the change in chemistry and roughness of the irradiated surfaces.     

Fabrication of black multicrystalline silicon surface by nanosecond laser ablation

The optimal regimes for uniform texturing of a multicrystalline silicon (mc-Si) surface by pulsed laser radiation have been determined. The morphology and reflectance spectra of the texturized mc-Si have been studied. The laser-texturized mc-Si samples with reflectance of 2?C3% over a wide spectral region have been produced. The influence of subsequent chemical etching on the reflective properties of the texturized surface has been analyzed.     

飞秒激光烧蚀硅表面产生微纳结构过程中激光脉冲数目的影响

为了研究飞秒激光脉冲数目与硅表面形貌之间的关系,在相同的SF6气体氛围下,改变照射硅表面的飞秒激光脉冲数,发现在飞秒激光照射下由硅表面形成的微型锥状尖峰的高度与飞秒激光脉冲数呈现一种非线性关系.通过对该关系的研究有利于找出在制造具有较高吸收效率的高微型锥状尖峰的"黑硅"的实验条件,有利于基于"黑硅"材料的光电器件转化效...     

不同气氛下飞秒激光诱导硅表面微结构

利用钛宝石飞秒激光脉冲对单晶硅在SF6、空气和真空环境中进行了累积脉冲辐照,研究了硅表面微结构的演化。在SF6气氛中,在激光辐照的初始阶段,硅表面形成了1维的波纹结构,随着辐照脉冲数的增加,波纹结构演化成了2维凹凸结构。累积600个脉冲后,硅表面产生了准规则排列且具有大纵横比的锥形尖峰结构。该结构呈现高度相对较低、锥形尖端小球不明显的特征,分析认为主要与环境气压的大小有关。对比空气、SF6和真空中的微结构发现,尖峰的数密度依次减小;SF6中形成的尖峰高度最大,其次为真空,再次为空气。研究结果表明,真空、SF6和空气3种环境下微结构的形成及表面形貌主要由激光烧蚀、化学刻蚀和氧化决定。     

Protons’ generation by laser irradiation at 5 × 10 W/cm from silicon dielectric targets containing an excess of hydrogen

A study of silicon plasma generated in vacuum by 532 nm Nd:YAG laser at intensities of about 5 × 10⁹ W/cm² from dielectric targets containing a relatively huge quantity of hydrogen was presented.Time-of-flight technique was employed to measure the particles’ energy and the relative yield with respect to other ion species. Plasma-accelerated ions show Coulomb-Boltzmann-shifted distributions depending on their charge state.Mass quadrupole spectrometry allowed the estimation of the relative hydrogen amount inside the different samples considered: silicon (Si), silicon nitride (Si₃N₄) and hydrogenated annealed silicon (Si(H)) as a function of the ablation depth and irradiation time.Depth profiles of the laser craters permit to calculate the ablation yield at the used laser fluence. The plasma temperature and density was evaluated by the experimental data. A special regard is given to the protons’ generation process occurring inside the plasma, due to the possible influence of the hydrogen excess on the treated samples in comparison to the not-hydrogenated silicon ones.     

Silicon surface morphology study after exposure to tailored femtosecond pulses

Temporal pulse shaping of ultrashort laser pulses has been used for laser ablation of semiconductors. Even the simplest double pulse sequence with a delay of several picoseconds shows remarkable differences in the interaction process, compared to a single pulse of the same total energy. We discuss the interaction of double pulses with single crystal silicon sample in the context of crater morphology for multiple pulses on the same spot. The growth of the typical columnar structures in helium at atmospheric pressure is suppressed and the crater bottom is flat despite the Gaussian beam profile. The influence of the temporal pulse shape has to be treated in conjunction with the influence of the other ablation parameters.     

The interaction and the surface crack of single-crystal silicon induced by a millisecond laser

When the silicon material is irradiated by laser, it absorbs the laser energy leading to the temperature rise and the thermal stress. The damage effect includes melting, vaporation and thermal stress damage. Once the thermal stress exceeds the stress strength the crack will initiate. The silicon surface cracks induced by a millisecond laser are investigated. The experimental results show that three types of cracks are generated including cleavage crack, radial crack and circumferential crack. The cleavage crack is located within the laser spot. The radial crack and circumferential crack are located outside the laser spot. A two-dimensional spatial axisymmetric model of silicon irradiated by a 1064 nm millisecond laser is established. To assess what stresses generate and explain the generation mechanism of the different cracks, the thermal stress fields during laser irradiation and the cooling process are obtained using finite element method. The radial stress and hoop stress within the laser spot are tensile stress after the laser irradiation. The temperature in the center is the highest but the thermal stress in the center is not always highest during the laser irradiation. The cleavage cracks are induced by the tensile stress after the laser irradiation. The radial crack and the circumferential crack are generated during the laser irradiation.     

Effect of polarization on femtosecond laser pulses structuring silicon surface

Arrays of conical-like spikes can be formed on silicon surface after irradiated with femtosecond laser pulses in ambient of SF₆ or N₂. In this article, we report our observations on how the shape of the spikes formed on silicon surface varies with the polarization of laser beam. The experimental results show that, with circular polarized laser irradiation, the shape of the spikes is conical; however, with linearly polarized laser irradiation, the spikes show elliptic conical shape, and the long-axes are perpendicular to the direction of the polarization of laser beam. The asymmetric shape of spikes produced by linearly polarized laser beam can be explained by considering the polarization dependence of Fresnel-refraction.     

基于激光诱导击穿光谱技术检测分析原铝中硅、铁元素含量

利用自行搭建的LIBS装置对原铝中硅铁含量进行了分析测试，测试前对原铝试样进行了微观形貌分析，研究发现原铝中硅元素除有个别区域聚团现象外，其分布相对较为均匀；铁元素多以团状汇聚形态出现，且无明显的分布规律。实验分别考察了激光脉冲能量对激光诱导原铝等离子体光谱的影响，发现随着激光脉冲能量的增大，硅、铁元素信噪比先增加后减小，硅、铁谱线信噪比最大值均出现在160 mJ处，实验选取的激光脉冲能量为160 mJ。在上述较为合理的实验条件下，以内标法为基础，分别采用两种标样（纯铝标样与自选标样）建立了定标模型；结果表明：相比于纯铝标准试样，采用自选试样建立的定标模型不够理想，且数据的离散程度较大，铁元素直线拟合优度仅为0.921 3，相对标准偏差也较大。采用纯铝标样时，在试样不旋转的情况下，硅、铁元素定标曲线拟合优度分别为0.961 1与0.974 1，相对标准偏差分别为8.85%与9.43%，且误差棒显示误差随定标试样的硅、铁含量升高而增大。当试样台保持转速50 r·min-1条件下进行实验，发现硅、铁元素定标曲线的拟合优度分别为0.978 5与0.988，相对标准偏差分别为3.78%与3.4%，相比于试样平台固定情况下的定标结果，拟合优度明显改善，相对标准偏差也有所降低，定标模型明显优于自选试样建立的模型。使用两种定标模型对25个测试样进行了分析测试，比较了两种测试结果的相对误差，纯铝定标试样由于含量梯度较大，跨度较宽，采用该标样建立的定标模型对低铁原铝试样测试适应性相对较差，而自选试样建立的定标模型虽然不够理想，但针对低铁原铝试样的测试适应性相对较好。对激光诱导原铝产生的等离子体进行了诊断，通过镁元素几条离子谱线的玻耳兹曼图，计算出了等离子体温度约为9 163.63 K，利用镁元素一条谱线的Stark展宽估算出等离子体电子密度为1.69×1017 cm-3，验证了激光诱导原铝等离子体处于局部热力学平衡状态的假设是成立的。     

Femtosecond laser-induced mesoporous structures on silicon surface

By femtosecond laser line-by-line scanning irradiating, large-scale microstructures were formed on the surface of silicon with dimensions of 1 × 1 mm². Scanning electron microscope investigations exhibited that homogeneous surface microstructures, such as directional-arranged bacilliform mesoporous structures, have been successfully prepared. The dependence of the surface morphology on laser pulse energy was analyzed, and the results indicated that the bacilliform mesoporous structures only can be textured within a certain energy range. The optical reflective spectrum measurement revealed that the presence of bacilliform mesoporous structures can significantly enhance the absorptivity of silicon at visible light range. This work would help to control the formation of surface micro/nanostructures on silicon and other materials, which has potential applications in solar energy, photoelectronics, biology and material science.     

Transmission electron microscopy investigation of crystalline silicon surface irradiated by femtosecond laser pulses in different background atmospheres

This article aims to obtain structural and compositional characteristics of a crystalline silicon surface irradiated by femtosecond laser pulses in SF₆, N₂, air, and vacuum background atmospheres by performing transmission electron microscopy observation of ??110?? cross-sectional specimens. Conical microstructures covered with defective outer layers were formed in SF₆ gas. The elemental sulfur dopants in the surface microstructure, which located in close proximity to defects, were mainly concentrated at the tip region of the microcones, and about several hundred nanometers thick. In N₂ atmosphere, the defects produced regularly on the silicon surface were of the same types with those formed in SF₆ gas and confirmed to be stacking faults and overlapped twins. Furthermore, silicon crystalline grains with different orientations were observed on the silicon surface irradiated in N₂, air, and vacuum atmospheres. Especially, ??-Si₃N₄ crystalline grains were found to be formed in N₂ and air as chemical products when elemental nitrogen exists, and the SiO₂ amorphous phase was formed in air by the oxidation effect. Based on these experimental results, the relevant interaction mechanisms between pulsed laser and crystalline silicon were suggested to be mainly attributed to laser-assisted chemical etching and laser ablation, i.e., if volatile silicon compounds can be produced in a reactive gas atmosphere (e.g., SF₆), the strong laser-assisted chemical etching dominates over the laser irradiation process. Otherwise, laser ablation is the dominant mechanism such as in N₂, air, and vacuum.     

单脉冲纳秒激光诱导硅表面微结构

利用Nd:YAG纳秒脉冲激光(波长532nm)在空气中对单晶硅表面进行单脉冲辐照,研究了激光能量密度和光斑面积变化对微结构的影响。通过场发射扫描电子显微镜和原子力显微镜(AFM)对样品表征,并对纳秒激光辐照硅的热力学过程进行分析。结果显示:当脉冲激光的能量密度接近硅的熔融阈值且光斑直径小于8μm时,形成尖峰微结构;随着能量密度或光斑面积增大,尖峰结构消失,形成边缘隆起和弹坑微结构。通过流体动力学模型得到微结构形貌的解析解,模拟得到的微结构形貌与实验测得的AFM数据一致。研究表明微结构的形成主要是由于表面张力引起的熔融硅流动。表面张力与表面温度和表面活性剂的质量浓度有关。温度梯度引起的热毛细流作用和表面活性剂浓度引起的毛细作用共同影响下形成尖峰、边缘隆起和弹坑微结构。     

飞秒激光改性6H-碳化硅晶体表面光电导增益现象研究

半绝缘6H型碳化硅(6H-SiC)具有高电阻率性质,在可见光照射下进行光电导测量时,通常光生电流很小;然而经过飞秒激光辐照改性之后,发现在可见光波段的光电导有明显的增益.本文利用紫外-可见-近红外吸收谱、X射线光电子能谱和发光光谱测量分析了激光改性之后碳化硅样品的光谱吸收、发射和晶体元素比例变化情况.分析认为碳化硅光电导增益的原因是飞秒激光辐照过程改变了碳化硅表面的硅碳元素的原子浓度比,形成新的物质结构形式,从而导致了表面光电导性能的提高.     

Laser-induced etching of silicon

Conventional fabrication method of porous silicon is anodisation of single crystal silicon in hydrofluoric acid. In this report, we show that it is possible to fabricate porous silicon by laser-induced etching. An earlier report by us has demonstrated the dependence of porous silicon photoluminescence characteristic on the etching laser wavelength [1]. Here we used 780 nm line from a diode laser as the etching source, and the optimum etching conditions were obtained. A simple model was proposed to explain the etching process. Scanning Electron Microscope (SEM) images of the samples support the proposed process.     

Stabilization of porous silicon surface by low temperature photoassisted reaction with acetylene

A hybrid approach of forming a stabilizing layer of bonded carbon on porous silicon (PSi) surface by photoassisted reaction of acetylene gas at low temperatures is described. The PSi samples were made by anodization in a HF/H₂O₂ electrolyte at a current density of 80 mA/cm². Samples show a strong luminescence with a peak at 644±4 nm. The photoluminescence (PL) intensity shows a very strong quenching under the influence of continuous laser illumination (∼0.25 W/cm², 488 nm). The PSi samples were subjected to flowing acetylene under optical illumination from quartz halogen lamp (20 mW/cm²). The PL intensity is initially quenched to very low values (less than 5% of initial value) and then recovers on further exposure to acetylene to a final value ∼30% of the initial value. No quenching is observed on further exposure to laser illumination in ambient air instead an improvement of 15–25% in PL intensity is observed. This behaviour is a good indicator of the formation of a practically stable PSi surface.