Removal of Tin from Extreme Ultraviolet Collector Optics by <Emphasis Type="Italic">In</Emphasis>-<Emphasis Type="Italic">Situ</Emphasis> Hydrogen Plasma Etching

Extreme ultraviolet (EUV) lithography produces 13.5 nm light by irradiating a droplet of molten Sn with a laser, creating a dense, hot laser-produced plasma and ionizing the Sn to the + 8 through + 12 states. An unwanted by-product is deposition of Sn debris on the collector optic, which focuses the EUV light emitting from the plasma. Consequently, collector reflectivity is degraded. Reflectivity restoration can be accomplished by means of Sn etching by hydrogen radicals, which can be produced by an H₂ plasma and etch the Sn as SnH₄. It has previously been shown that plasma cleaning can successfully create radicals and restore EUV reflectivity but that the Sn removal rate is not necessarily limited by the radical density. Additionally, while Sn etching by hydrogen radicals has been shown by multiple investigators, quantification of the mechanisms behind Sn removal has never been undertaken. This paper explores the processes behind Sn removal. Experiments and modeling show that, within the parameter space explored, the limiting factor in Sn etching is not radical flux or SnH₄ decomposition, but ion energy flux. Thus the removal is akin to reactive ion etching.     

Study of Spark Discharge Assisted to Enhancement of Laser-Induced Breakdown Spectroscopic Detection for Metal Materials

In this work, laser triggered spark discharge was combined with laser-ablation under Air and Ar gases to investigate the characteristics of laser-ablated plasma emission. The experimental results show that the optical emission intensity is significantly enhanced by electric discharge compared to without discharge and the spectral emission time of plasma is much longer than that without discharge. The enhancement effect is more apparent in the presence of Ar ambient. In addition, the plasma temperature and electron density as well as limits of detections (LOD) have been determined. The better LOD can be attributed to the improvement of plasma. The higher plasma temperature and electron density indicate that the enhanced mechanism in emission intensity is predominated by the further excitation/ionization of the laser-ablated material by the spark discharge due to the energy deposition in the plasma.     

Depth profiling of tungsten coating layer on CuCrZr alloy using LIBS approach

Laser induced breakdown spectroscopy (LIBS) was employed to find the depth profile of W-coated CuCrZr alloy. Cathodic arc deposition method was applied to produce tungsten coating on the CuCrZr alloy. The LIBS measurements were carried out by using a Nd:YAG laser at its fundamental wavelength (1064 nm) with various fluences. The spectral intensity emitted from laser induced plasma of the coating material was investigated for both elemental and depth-profile analyses in terms of linear correlation coefficient. Other surface characterization techniques (scanning electron microscopy and energy dispersive X-ray) were also used to determine morphology and elemental composition. It is observed that nonuniform radial energy distribution of Gaussian laser beam caused gradual decay of spectral lines of the coating and rise of substrate lines. The results indicate that the spectral intensity from W coating was higher than that from the bulk material at same laser fluence. The high-resolution in-depth profile was achieved at low fluence. This study demonstrates that LIBS is a promising technique for the depth-profiling analysis of W coating of EAST-like material and can be used to determine the material erosion and impurity deposition on plasma facing components.     

Study of the morphology of a laser-produced aerosol plume by cavity ringdown laser absorption spectroscopy

Cavity ring-down laser absorption spectroscopy (CRLAS) was applied for the first time to detection and characterization of laser breakdown generated aerosols. The method provided time-resolved morphological information on the aerosol plume, which is of importance in laser ablation (LA) and deposition, in laser-induced breakdown spectroscopy (LIBS) analysis, and in laser ablation inductively coupled plasma (LA-ICP) methods. This method provides sensitive detection of a variety of aerosols produced under ambient conditions. The morphological investigation revealed that the aerosol density has a reproducible pattern as a function of distance from the surface, although its details depend on time, on geometrical parameters and on the surface characteristics.     

等离子体聚合成膜中的活性粒子模拟分析

针对等离子体聚合成膜实验中的活性粒子的能量及空间分布问题,运用电磁场理论和Ｍｏｎｔｅ Ｃａｒｌｏ方法模拟分析氢、氧、氮直流辉光放电等离子体中的活性粒子的运动,得出其能量分布图和空间密度分布图,并与离子活性能量范围相比较,从而得出结论：在氢、氧等离子体中有足够多的活性离子可以参与和单体分子的物理化学反应,成膜较快;在氮等离子体中,达到活性粒子能量范围的离子相当少,成膜较慢。     

不同进气方式对热等离子体应用于CH4-CO2重整的影响

采用大功率双阳极热等离子体装置, 对CH4-CO2重整制合成气进行实验研究. 实验采用两种不同的原料气输入方式: 一种是使原料气(CH4和CO2的混合气体)作为等离子体放电气体全部通入第1阳极与第2阳极间的放电区, 直接参与放电; 另一种是保持前述状态, 再附加另一部分原料气通入从等离子体发生器喷出的等离子体射流区. 实验表明: 第1种方式下, CH4和CO2同时具有很高的单程转化率和反应选择性, 但能量转化效率较低; 第2种方式下, 尽管CH4和CO2单程转化率和选择性有所降低, 但由于进料量增加, 所得合成气摩尔量较大, 因此能量转化效率高于第1种进气方式所得结果. 实验还发现, 保持放电电流恒定的情况下, 等离子体放电电压随通入第1阳极与第2阳极间放电区的原料气流量增加而增加, 与通入等离子体射流区的流量无关, 同时实验未发现等离子体发生器阴极和阳极被氧化或出现碳沉积现象.     

Laser Based Optical Emission Studies of Zinc Oxide (ZnO) Plasma

We present the optical emission characteristics of the zinc oxide (ZnO) plasma produced by the first (1,064 nm) and second (532 nm) harmonics of a Q switched Nd: YAG laser. The target material was placed in front of laser beam in air (at atmospheric pressure).The experimentally observed line profiles of neutral zinc (Zn I) have been used to extract the electron temperature using the Boltzmann plot method, whereas, the electron number density has been determined from the Stark broadening. The electron temperature is calculated by varying distance from the target surface along the line of propagation of plasma plume and also by varying the laser irradiance. Beside we have studied the variation of number density as a function of laser irradiance as well as its variation with distance from the target surface. It is observed that electron temperature and electron number density increases as laser energy is increased.     

Study of deposition offset in plasma spray of zirconia

Numerical modeling and experimental measurements have been performed to study the effects of powder carrier gas flow rates and powder sizes on the deposition offset in a plasma spray of yttria-stablized zirconia. The mathematical model involved simultaneous solution of the continuity, momentum and energy equations of the plasma gas, the dynamics and heat transfer of powder particles in the plasma, and the coupling effects between the plasma and panicles. Experiments included measurement of particle velocities by laser strobe technique and measurement of deposition offset. Calculated plasma temperatures and velocities are greater than 13,000 K and 2,000 m/s, respectively, in the vicinity of nozzle exit. For the plasma-particle momentum transfer, the drag coefficient was computed in two ways- with corrections accounting for the strongly varying plasma properties, and without these corrections. Calculated and experimental results, in respect to deposition offset, are in agreement to within 25% when calculated without varying properties corrections, and within about 40% with corrections; agreement in respect to average particle velocities is within 20% when calculated without varying properties corrections, and within the range 30–50% with corrections.     

The influence of laser-particle interaction in laser induced breakdown spectroscopy and laser ablation inductively coupled plasma spectrometry

Particles produced by previous laser shots may have significant influence on the analytical signal in laser-induced breakdown spectroscopy (LIBS) and laser ablation inductively coupled plasma (LA-ICP) spectrometry if they remain close to the position of laser sampling. The effects of these particles on the laser-induced breakdown event are demonstrated in several ways. LIBS-experiments were conducted in an ablation cell at atmospheric conditions in argon or air applying a dual-pulse arrangement with orthogonal pre-pulse, i.e., plasma breakdown in a gas generated by a focussed laser beam parallel and close to the sample surface followed by a delayed crossing laser pulse in orthogonal direction which actually ablates material from the sample and produces the LIBS plasma. The optical emission of the LIBS plasma as well as the absorption of the pre-pulse laser was measured. In the presence of particles in the focus of the pre-pulse laser, the plasma breakdown is affected and more energy of the pre-pulse laser is absorbed than without particles. As a result, the analyte line emission from the LIBS plasma of the second laser is enhanced. It is assumed that the enhancement is not only due to an increase of mass ablated by the second laser but also to better atomization and excitation conditions favored by a reduced gas density in the pre-pulse plasma. Higher laser pulse frequencies increase the probability of particle-laser interaction and, therefore, reduce the shot-to-shot line intensity variation as compared to lower particle loadings in the cell. Additional experiments using an aerosol chamber were performed to further quantify the laser absorption by the plasma in dependence on time both with and without the presence of particles. The overall implication of laser-particle interactions for LIBS and LA-ICP-MS/OES are discussed.     

Spatial Transition of the Electron Gas from the Active to the Remote Plasma State

Starting from the active region of a weakly ionized plasma the spatial transition of the electron gas through an adjacent field decay region into the field-free remote plasma is studied in neon on a rigorous basis by using two independent kinetic approaches. The main objective of the analysis concerns the complex features of the electron gas in its transition process from a field-driven active plasma to a purely diffusion-driven remote plasma. In addition to the energy resolved characterization of the velocity distribution, in particular, the spatial decay behavior of important, energy space averaged transport and dissipation properties of the electrons, as the density, the particle and energy fluxes and the power transfer rates to the gas particles in electron collisions, is elaborated and interpreted. Moreover, the influence of a variation of the active plasma conditions and of the spread of the field decay region on the resultant transition behavior of the electron gas is evaluated. A particular finding is that the spatial field decay is generally accompanied by a large density increase in order to allow the continuation of the electron flux by a pure diffusion process in the adjacent remote plasma. This finding could be completely confirmed by the almost perfect coincidence of corresponding results obtained by two independent kinetic approaches.     

Optical emission studies of plasma induced by single and double femtosecond laser pulses

Double-pulse femtosecond laser ablation has been shown to lead to significant increase of the intensity and reproducibility of the optical emission signal compared to single-pulse ablation particularly when an appropriate interpulse delay is selected, that is typically in the range of 50–1000 ps. This effect can be especially advantageous in the context of femtosecond laser-induced breakdown spectroscopy analysis of materials. A detailed comparative study of collinear double- over single-pulse femtosecond laser-induced breakdown spectroscopy has been carried out, based on measurements of emission lifetime, temperature and electronic density of plasmas, produced during laser ablation of brass with 450 fs laser pulses at 248 nm. The results obtained show a distinct increase of plasma temperature and electronic density as well as a longer decay time in the double-pulse case. The plasma temperature increase is in agreement with the observed dependence of the emission intensity enhancement on the upper energy level of the corresponding spectral line. Namely, intensity enhancement of emission lines originating from higher lying levels is more profound compared to that of lines arising from lower energy levels. Finally, a substantial decrease of the plasma threshold fluence was observed in the double-pulse arrangement; this enables sensitive analysis with minimal damage on the sample surface.     

Influence of Gas Entry Point on Plasma Chemistry,Ion Energy and Deposited Alumina Thin Films in Filtered Cathodic Arc

The effect of gas entry point on the plasma chemistry, ion energy distributions and resulting alumina thin film growth have been investigated for a d.c. cathodic arc with an aluminum cathode operated in an oxygen/argon atmosphere. Ions of aluminum, oxygen and argon, as well as ions originating from the residual gas are investigated, and measurements for gas entry at both the cathode and close to the substrate are compared. The latter was shown to result in higher ion flux, lower levels of ionised residual gas, and lower ion energies, as compared to gas inlet at the cathode. These plasma conditions that apply when gas entry at the substrate is used result in a higher film deposition rate, less residual gas incorporation, and more stoichiometric alumina films. The results show that the choice of gas entry point is a crucial parameter in thin film growth using reactive PVD processes such as reactive cathodic arc deposition.     

Optical emission spectroscopy of nitrogen species and plasma plume induced by laser ablation combined with pulse modulated radio-frequency discharge

Combined laser ablation and pulse modulated radio-frequency (RF) discharge for deposition of CNalpha films was studied by the use of optical emission spectroscopy. Chemically active nitrogen was produced by RF discharge, concentrated between two small electrodes. Influence of RF power, nitrogen pressure, modulation frequency and pulse rate on nitrogen species production was researched. For the same system plasma expansion rate, kinetic energy and concentration of carbon ions emitted by laser from graphite target were determined by Langmuir probes measurement.     

Time-resolved investigations of laser-induced plasmas generated by nanosecond bursts in the millijoule burst energy regime

Laser-induced plasmas are investigated during laser micro structuring of a C 75 steel alloy using laser bursts that consist of nanosecond laser pulses under atmospheric pressure. The influence of the laser burst mode — single and collinear double pulses — on plasma dynamics and ablation efficiency is investigated for burst energies in the millijoule regime. Electron density and excitation temperatures measured as a function of time. The results are compared with published data looking for changes of the plasma parameters scaling with the burst energy over two orders of magnitude. For collinear double pulses at burst energies of 1–2 mJ an increase of the ablation rate by a factor of three to four compared to single pulses was observed.     

Optical measurements of ion density in the second vacuum stage of an inductively coupled plasma mass spectrometer

A portion of the ion beam in the second stage of an inductively coupled plasma mass spectrometer was mapped using laser induced fluorescence (LIF). With LIF relative density measurements are made in real time with minimal interference to the ion beam. We report axial measurements of Ba and Sc ion density from 22 to 45 mm behind the tip of the skimmer cone. Additionally, maps of radial ion density with and without Pb and Mg matrices are given for the same two analyte species. The results reveal that earlier ion deposition experiments dramatically underestimated the extent of the radial spread of the ion beam and the influence of matrix on the ion beam.     

SNMS and XRD investigations of laser deposited YSZ buffer layers

Summary Secondary Neutral Mass Spectrometry (SNMS) and X-Ray Diffraction (XRD) were used to find optimum parameters for the in-situ pulsed laser deposition of ZrO₂/Y₂O₃ (YSZ) buffer layers on silicon (100) substrates. Homogeneous and nearly stoichiometric concentration depth profiles were found by SNMS for the laser deposited YSZ films. A peak of the SiO intensity during profiling of the YSZ/Si interface points to a SiO₂ intermediate layer. An increasing Y-deficit of the YSZ films was found by decreasing the laser energy density at the target. Epitaxial growth of the YSZ thin films was observed at an oxygen partial pressure lower than 10^–3 mbar, a substrate temperature of 600–800°C and a laser energy density at the target of about 8 J/cm².     

Role of positive ions in determining the deposition rate and film chemistry of continuous wave hexamethyl disiloxane plasmas

New data shed light on the mechanisms of film growth from low power, low pressure plasmas of organic compounds. These data rebalance the widely held view that plasma polymer formation is due to radical/neutral reactions only and that ions play no direct role in contributing mass at the surface. Ion reactions are shown to play an important role in both the plasma phase and at the surface. The mass deposition rate and ion flux in continuous wave hexamethyl disiloxane (HMDSO) plasmas have been studied as a function of pressure and applied RF power. Both the deposition rate and ion flux were shown to increase with applied power; however, the deposition rate increased with pressure while the ion flux decreased. Positive ion mass spectrometry of the plasma phase demonstrates that the dominant ionic species is the (HMDSO-CH(3))(+) ion at m/z 147, but significant fragmentation and subsequent oligomerization was also observed. Chemical analysis of the deposits by X-ray photoelectron spectroscopy and secondary ion mass spectrometry show that the deposits were consistent with deposits reported by previous workers grown from plasma and hyperthermal (HMDSO-CH(3))(+) ions. Increasing coordination of silicon with oxygen in the plasma deposits reveals the role of ions in the growth of plasma polymers. Comparing the calculated film thicknesses after a fixed total fluence of 1.5 × 10(19) ions/m(2) to results for hyperthermal ions shows that ions can contribute significantly to the total absorbed mass in the deposits.     

A comparison of single and double pulse laser-induced breakdown spectroscopy of aluminum samples

Single and double pulse laser-induced breakdown spectroscopy (LIBS) was carried out on aluminum samples in air. In the case of double pulse excitation, experiments were conducted by using the same laser source operated at the same wavelength (1064 nm in most cases here presented). A lowering of the second pulse plasma threshold was observed, together with an overall enhancement in line emission for the investigated time delay between the two pulses (40–60 μs). The laser-induced plasma originated by a single and double pulse was investigated near ignition threshold with the aim to study possible dynamical mechanisms in different regimes. Currently available spectroscopic diagnostics of plasma, such as the line broadening and shift due Stark effects, have been used in the characterization in order to retrieve electron densities, while standard temperature measurements were based on Boltzmann plot. Plasma relevant parameters, such as temperature and electron density, have been measured in the plasma decay on a long time scale, and compared with crater shape (diameter and inferred volume). The comparison of double with single pulse laser excitation was carried out while keeping constant the energy per pulse; the influence of laser energy was investigated as well. Results here obtained suggest that use of the double pulse technique could significantly improve the analytical capabilities of LIBS technique in routine laboratory experiments.     

Thermophoretic force acting on an evaporating particle suspended in a rarefied plasma

Analytical results of the thermophoretic force on an evaporating spherical particle immersed in a rarefied plasma with a large temperature gradient are presented for the extreme case of free-molecule regime and thin plasma sheath. It has been shown that the existence of a temperature gradient in the plasma causes a nonuniform distribution of the local heat flux density on the sphere surface with its maximum value at the fore-stagnation point of the sphere, although the total heal flux to the whole particle is independent of the temperature gradient existing in the plasma. This nonuniform-distribution of the local heat flux density causes a nonuniform distribution of the. local evaporated-mass flux and related reaction force around the surface of an evaporating particle, and thus causes an additional force on the particle. Calculated results show that the thermophoretic force on an evaporating particle may substantially exceed that on a nonevaporating one, especially for the case of a metallic particle (with infinite electric conductivity). The effect of evaporation on the thermophoretic force is more pronounced as the evaporation latent heat of the particle material is comparatively low and as high plasma temperatures are involved.     

The effect of positive ion energy on plasma polymerization: a comparison between acrylic and propionic acids

Using a novel RF biasing technique, the energy of positive ions at a depositing substrate is controlled, independently of other parameters. Under bias conditions which gave the maximum and minimum ion energies, plasmas of propionic and acrylic acid were investigated using mass spectrometry, an ion flux probe, quartz crystal microbalance, and X-ray photoelectron spectroscopy (XPS). For both compounds investigated, the ion energy affects the deposition rate but leaves the neutral gas-phase chemistry and positive ion fluxes unchanged. The chemistry of the polymer deposit for acrylic acid is unaffected by the change in ion energy, but the chemistry of the propionic acid plasma polymer changes markedly. We argue that the results presented are consistent with the hypothesis that, under the plasma conditions explored, the carbon-carbon double bond present in acrylic acid plays a significant role in the formation of the polymer. Conversely, the absence of this bond in propionic acid leads us to conclude that positive ions contribute significantly to film formation for this compound.