Angular laser cleaning for effective removal of particles. from a solid surface

Laser removal of small particles from a metal surface is carried out by changing the incident angle of the laser beam. It has been found that a dramatic improvement of cleaning efficiency in terms of area and energy is observed when using the laser at glancing angle of incidence as compared to perpendicular. Furthermore substrate damage is greatly reduced and probably eliminated at glancing angles. The process mechanism is discussed by considering the adhesion and the laser-induced cleaning forces for different incident angles. It is shown that there are different laser–matter interactions operating. Received: 25 April 2000 / Accepted: 9 May 2000 / Published online: 5 October 2000     

Laser surface cleaning of organic contaminants

Laser surface cleaning process has been a useful and efficient technique for various industrial applications. The removal of photoresist contaminants on silicon wafers was investigated with a krypton fluoride (KrF) excimer laser, and the irradiated area was characterized using a profilometer, a scanning electronic microscopy (SEM), an Auger electron spectroscopy (AES) and a Fourier transition infrared spectroscopy (FT-IR). It was found that there exist an optimal number of pulses to remove the contaminant from the substrate surface without any laser-induced damage, depending on the laser density on the surface. A model to predict the optimal number of pulses, which agrees well with Beer–Lambert's law, is proposed and proved to be operable.     

Laser removal of copper particles from silicon wafers using UV, visible and IR radiation

Laser removal of small copper particles from silicon wafer surfaces was carried out using Nd:YAG laser radiation from near-infrared (1064 nm) through visible (532 nm) to ultraviolet (266 nm). It has been found that both 266 nm and 532 nm are successful in removing the particles from the surface whereas 1064 nm was shown to be ineffective in the removal of particles. The damage-threshold laser fluence at 266 nm was much higher than other wavelengths which provides a much wider regime for safe cleaning of the surface without causing any substrate damage. The cleaning efficiency was increased with a shorter wavelength. The effect of laser wavelength in the removal process is discussed by considering the adhesion force of the particle on the surface and the laser-induced cleaning forces for the three wavelengths. Received: 31 May 2000 / Accepted: 14 July 2000 / Published online: 20 June 2001     

Formation of charged defects during the nitridation of a metal particle

A model explaining and predicting generation of a temporal electric potential during nitridation of a single metal pellet has been developed. The model takes into account the kinetics of defects formation and assumes that the rate of the chemical reaction can be described by the shrinking-core process. The model simulations have shown that time scale of the generated electric potential depends on both the initial nitride shell thickness and heat removal from the particle surface. At thin initial shell and low rate of heat removal the maximum of the surface electric potential is attained before the temperature and surface nitrogen concentration have reached their maximums but after the maximum of nitridation has appeared. Quasi-neutral distributions of metal vacancies and electron holes are formed at the maximum temperature. At thick initial shell and/or high rates of heat removal from the particle surface the potential maximum may be observed much later: after the maximum temperature has been achieved. Correspondingly, non-equilibrium concentrations of the charged defects exist till the end of nitridation. In contrast to oxidation the nitrogen adsorption rate constants (the activation energy and pre-exponent) have negligible effect on the surface potential form and amplitude. At the ignition limit the rate of nitridation is proportional to the power of −1/2 for the ambient nitrogen pressure in the proposed scheme of defects formation. Metal vacancies and electron holes are the main charged defects in nitrides during nitrogen combustion. The nitride formation is limited by transfer of the vacancies in nitride.     

Observation of oxygen contamination at ZnSe/GaAs interfaces using SIMS

ZnSe epilayers were grown on GaAs (1 0 0) substrates using MBE. The native contamination (oxide and carbon) was removed in situ from the substrate surfaces by conventional thermal cleaning and by exposure to atomic hydrogen. A maximum substrate temperature of 600 °C was required for the thermal cleaning process, while a substrate temperature of 450 °C was sufficient to clean the substrate using hydrogen. ZnSe epilayers were also grown on As capped GaAs epilayers, which were decapped at a maximum temperature of 350 °C. SIMS profiles showed the existence of oxygen at the interface for all of the substrate preparation methods. The oxygen surface coverage at the interface was found to be 0.03% for the atomic hydrogen cleaned substrate and 0.7% for the thermally cleaned substrate.     

Ultraviolet laser removal of small metallic particles from silicon wafers

Laser removal of small 1 μm sized copper, gold and tungsten particles from silicon wafer surfaces was carried out using ultraviolet radiation at 266 nm generated by Nd:YAG harmonic generation. Successful removal of both copper and gold particles from the surface was achieved whereas tungsten particles proved to be difficult to remove. The cleaning efficiency was increased with an increase of laser fluence. The optimum processing window for safe cleaning of the surface without any substrate damage was determined by measuring the damage threshold laser fluence on the silicon substrate and the required fluence for complete removal of the particles. The different cleaning efficiencies with particle type are discussed by considering the adhesion force of the particle on the surface and the laser-induced cleaning force for the three different particles.     

Influence of surface orientation and defects on early-stage oxidation and ultrathin oxide growth on pure copper

We investigate oxidation and oxide growth on single-crystal copper surfaces using reactive molecular dynamics simulation. The kinetics of surface oxide growth are strongly correlated with the microstructure of the metal substrates. Simulating oxide layer growth along the (100), (110), and (111) orientations of crystalline copper, oxidation characteristics are investigated at temperatures of 300?K and 600?K. The oxidation kinetics are found to strongly depend on the surface orientation, ambient temperature, and surface defects. The effect of surface morphology on oxidation characteristics is analyzed by comparing oxygen adsorption on various sites and the structure factor. The surface oxide formed on (100) retains the initial crystal structure in the 300–600?K range. The (100) surface shows the highest oxidation rate at both temperature conditions but saturates, facilitating oxygen adsorption on hollow sites. The oxidation kinetics of the (100) orientation are found to be not significantly affected by surface defects. (110) shows modest oxidation at 300?K but the highest oxidation is observed at 600?K. By surface disorder and reconstruction, the oxide layer is produced continuously. The (111) surface is sensitive to ambient temperature and surface defects, showing that surface reconstruction is a key element for further oxidation. The charge distribution of oxidized Cu atoms indicates multiple groups of stoichiometric oxides, while the fraction of CuO-like characteristics increases significantly on the (110) and (111) orientations at higher temperature (600?K). The energetics and mechanisms of oxidation on Cu metal substrates at the nanoscale are discussed in detail, and comparisons with available experimental and other theoretical studies are presented wherever possible.     

Surface cleaning of metals by pulsed-laser irradiation in air

The surface-cleaning effect of metals was investigated using KrF-excimer-laser irradiation of metal surfaces in air. The laser-induced cleaning of copper, stainless steel and aluminum surfaces was studied. It is found that laser cleaning is an effective cleaning process for metals even if the metal surfaces are heavily contaminated. It is also found that short wavelength and pulse duration are necessary for laser surface-cleaning. The energy density of the laser pulse is an important parameter in the cleaning process. Low energy density results in a cleaner surface but a larger pulse number is required, whereas high energy density can achieve higher cleaning efficiency but the temperature rise can cause surface oxidation and secondary contamination. In contrast to the KrF-excimer-laser, the pulsed CO₂ laser is not effective in surface-cleaning. The mechanisms of laser cleaning may include laser photodecomposition, laser ablation and surface vibration due to the impact of the laser pulse. Laser cleaning provides a new dry process to clean different substrate surfaces and can replace the conventional wet cleaning processes such as ultrasonic cleaning with CFC and other organic solvents.     

HfO2顶层多层介质膜脉宽压缩光栅的Piranha溶液清洗

为了提高HfO2顶层多层介质膜脉宽压缩光栅(PCG)的抗激光损伤性能,使用Piranha溶液(浓硫酸和双氧水的混合液)清洗PCG去除其制作工艺和使用过程中残留在表面的污染物,包括CHF3作为工作气体对HfO2进行反应离子束刻蚀生成的碳氟化合物及金属氟化物.对Piranha溶液的清洗温度、组成成分、清洗时间、清洗遍数等参...     

Approximation of transformation media-based reshaping action by genetic optimization

The aim of this paper is to study the laser-induced backside wet cleaning techniques for glass substrates. Two kinds of laser cleaning techniques are proposed in this study. The first involves applying an Nd:YAG laser to the backside of the substrate which is submerged in water. A metal plate is placed below the glass substrate. Most of the laser energy will be absorbed by the metal plate. The metal then vaporizes the water and generates a turbulent bubble flow. The bubble flow removes the alumina particles from the surface of the glass substrate. The second involves using a CO₂ laser to generate turbulent bubble flow to remove the particles. Both methods were successfully demonstrated for the removal of submicron particles of 0.5 μm in size. The phenomena of bubble generation and diffusion are presented in the paper. Because the laser is applied to the backside of the substrate, the damage due to the laser heat can be significantly reduced. The quality and efficient of the backside processing is better than those of the front side processing. The proposed techniques have great potential to provide an improved solution for glass cleaning.     

离子束清洗在激光薄膜中的应用

介绍了在激光薄膜中End Hall型离子源离子束清洗的应用。通过实验验证了基片的二次污染和离子束的清洗效果,观测了离子束清洗前后基片的表面形貌变化。研究了用离子束清洗基片时对薄膜抗激光损伤阈值的作用。分析了用离子束清洗基片时其基片表面的性质,如清洁度、表面能、接触角、表面形貌的变化机理。指出了杂质微粒的去除和附着力的增加是如何使薄膜抗激光损伤阈值显著提高的。     

Enhanced cleaning of photoresist film on a transparent substrate by backward irradiation of a Nd:YAG laser

Laser cleaning of a photoresist (PR) on a glass substrate using ns-pulsed Nd:YAG laser was studied. The direction of the substrate facing the laser beam was varied as a main parameter as well as the power of the laser beam. The backward irradiation (BWI) of the third harmonic beam (355 nm) completely removed 1.2 μm thick PR layer with three pulses at 1.5 J/cm² leaving no residues behind; while the forward irradiation (FWI) at the same condition just partially cleaned it. To investigate the difference of removal mechanisms between irradiation directions, the size distributions of particulates generated during laser cleaning were observed using an optical particle counter. The concentration of micron-sized particulates increased with increasing laser fluence up to 1 J/cm² for FWI and 0.5 J/cm² for BWI and then decreased at higher fluences because the target was a very thin film. The concentration of larger particulates for BWI was much higher than that for FWI implying the difference in removal mechanisms. In consideration of the size characteristics of the particulates and the temperature profiles of the PR layer, the most probable distinct mechanism for the BWI would be a blasting due to high temperature at the PR/glass interface. The particulate number concentration decreased rapidly after the completion of cleaning, suggesting that the measurement of the particulate concentration could detect the progress of the cleaning. Our results demonstrated that the backward irradiation will be useful for the laser cleaning of film-type contaminants on an optically transparent substrate.     

Comparison of mechanisms and effects of Nd:YAG and CO2 laser cleaning of titanium alloys

The paper compares laser cleaning trials performed using a Q-switched Nd:YAG laser, λ = 1.064 μm and a continuous wave (CW) CO₂ laser, λ = 10.6 μm, applied to aerospace-grade, contaminated titanium alloys. The mechanisms for cleaning using each laser system are modelled to determine the mode and extent of contaminant removal. The model results are then compared with the surface chemistry and micro-structural results from the cleaning trials performed. The results show the dominant cleaning process for Nd:YAG cleaning to be by evaporation of the contaminant via conduction through surface heating, while for CO₂ laser cleaning the small fraction of the beam coupling directly with the contaminant is sufficient for direct heating and selective evaporation. The results for experimental cleaning, electron beam (EB) welding and diffusion bonding align well with the model, particularly when secondary reactions are taken into account.     

Formation of microtower structures on nanosecond laser ablation of liquid metals

We report the formation of microtower structures, observed on multishot nanosecond laser irradiation of liquid metals (Ga, In, Sn–Pb alloy, Wood’s metal). Ablation in a reactive ambient gas (air, nitrogen, sulfur hexafluoride, nitrogen trifluoride) is shown to lead to a tower-like structure growing on the irradiated surface at a rate of 3–20 μm per pulse depending on laser fluence and the types of metal and ambient gas. The interplay between different processes in the heat-affected zone of the irradiated samples is analyzed, including ablation, thermal expansion, temperature variations of viscosity, surface tension, thermal stresses, capillary effects, and surface chemistry. A clear picture of microtower origin has been established, and qualitative modeling can explain the formation mechanism.     

Hot-electron induced impact-ionisation damage at the interface of sub-micron silicon MOS devices: Model and monitor

It is well known that hot-carriers can cause damage to the interface of silicon MOS devices. Sub-micron and nano-channel nMOS devices have a higher electron temperature in the channel leading to increased impact-ionisation and enhanced interface degradation and damage. During dynamic operation of the nMOS device, hot-electron and hot-hole injections may take place giving rise to greater interface damage. Hot electrons produced due to impact ionisation also generate secondary electron-hole pairs in Si substrate. The visible light is generated by radiative recombination between the secondary hot electrons and hot holes. An optimised substrate current model was developed, the model was used to plot substrate current for a sub-micron nMOS transistor and was compared with the actual measurements carried out on similar device. It was found that the substrate current model can be used as a reliable monitor for impact ionisation damage in MOS devices.     

Numerical investigation of the microstructure of a clad layer produced via laser cladding with coaxial metal powder injection

The microstructure of a clad layer produced via selective laser cladding with coaxial metal powder injection is studied numerically. The Johnson–Mehl–Avrami–Kolmogorov equation for condensed systems with inhomogeneous rates of nucleation is used to model the phase change kinetics. The impact of the substrate boundary along with interconnected heat transfer and phase change processes on the final microstructure of a built-up layer is demonstrated. The qualitative difference between the behavior of the temperature on the built-up layer’s surface and at the depth of the substrate is established, revealing the inhomogeneous microstructure of the final layer.     

制备工艺对HfO2薄膜抗激光损伤能力的影响

采用反应蒸镀法镀制了单层HfO2薄膜,观察了薄膜表面主要的微结构缺陷,研究了基片清洗工艺对薄膜损伤阈值的影响。测量了薄膜沉积前后表面粗糙度变化。结果表明：沉积工艺可以改变粗糙度,并对薄膜抗激光损伤能力有较大的影响。     

KrF excimer laser dry and steam cleaning of silicon surfaces with metallic particulate contaminants

KrF excimer laser-assisted dry and steam cleaning of single-crystal silicon wafers contaminated with three different types of metallic particles was studied. The laser fluence used was 0.3 J/cm². In the dry process, for samples cleaned with 100 laser pulses the cleaning efficiency was 91, 71 and 59% for Au, Cu and W particles, respectively, whilst in steam cleaning the efficiency is about 100% after 5 laser pulses, independently of the type of contaminant. The effects of laser irradiation on the Si surface are investigated by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Laser processing at 0.3 J/cm² does not deteriorate the Si-wafer surface, either in dry or steam cleaning. However, the measured XPS intensity coming from the metallic component is greater on the cleaned surfaces than in the initial condition. Quantification of the XPS results, assuming a stratified overlayer model for the detected species and accounting for the presence of the metallic particles on the surface, showed that the obtained results can be explained by the formation of a fractional metallic monolayer on the cleaned surfaces, due to partial vaporisation of small particles initially present on the sample surface. This contamination of the substrate could be considered excessive for some applications and it shows that the process requires careful optimisation for the required efficiency to be achieved without degradation of the substrate. Received: 14 January 2001 / Accepted: 19 February 2001 / Published online: 20 June 2001     

制备工艺对HfO_2薄膜抗激光损伤能力的影响

采用反应蒸镀法镀制了单层ＨｉＯ２薄膜,观察了薄膜表面主要的微结构缺陷, 研究了基片清洗工艺对薄膜损伤阈值的影响。测量了薄膜沉积前后表面粗糙度变化。结果表 明：沉积工艺可以改变粗糙度,并对薄膜抗激光损伤能力有较大的影响。     

Removal mechanisms of micro-scale particles by surface wave in laser cleaning

This paper is to investigate the mechanisms of micro-scale particle removal by surface wave, which was induced by a short pulse laser in a cleaning process. The authors analyzed the adhesive forces of particles on substrate surface and the clearance force produced by surface wave in laser cleaning. The physical model of particle removal by laser-induced surface wave was established to predict the removal area and the processing conditions of laser cleaning. In this research, a KrF excimer laser was applied to irradiate 304 stainless steel specimen distributed with copper particles to generate surface wave for copper particle removal. Considering that a time-varying and uniformly distributed heat source irradiates on material surface with thermao-elastic behavior, the displacement and acceleration of substrate induced by a pulsed laser were solved by an uncoupled thermal–mechanical analysis based on the finite element method. The processing parameters such as laser energy, laser spot size are discussed, respectively. A series of laser cleaning experiments were designed to compare with computation results. The results show that the removal area by surface wave beyond the laser spot increases with the laser energy and that, the surface acceleration decreases with the increase of the laser spot size.