Simulation of sputter-induced roughness for depth profiling of thin film structures

Sputtering induced surface roughening is the dominant factor that degrades depth resolution in sputter profiling of polycrystalline film samples. Due to the dependence of the sputtering yield on the crystallographic orientation, ion beam incidence angle and composition, the local sputtering rate differs from grain to grain. A simple computer program based on a model of Marton and Fine can simulate such a roughness development within one layer, an improved version can even be applied for interfaces. A further extension of the program using a model of Hauffe includes effects like shadowing and enhanced peak erosion leading to surface smoothing.     

溅射功率对氧化锡薄膜结构和电化学性能的影响

应用射频磁控溅射技术在硅基底上制备氧化锡薄膜,着重研究溅射功率对薄膜结构和电化学性能的影响.XRD,SEM分析及恒电流充放电测试表明,随着溅射功率的增大,薄膜的结晶程度提高;生长速率和晶粒尺寸增大;电池的贮锂容量减少,且首圈不可逆容量损失增大.溅射功率对薄膜的电化学性能有较大的影响.     

On the origin of the lattice constant anomaly in nanocrystalline ceria

The lattice parameter of nanocrystalline ceria films prepared by sputtering was monitored as a function of annealing temperature. Within the temperature range of 150-420 degrees C, an equilibrium with atmospheric oxygen is established within a few hours, whereas grain growth does not occur. On the basis of the experimental results and analysis of literature data, we present a model that posits the formation of a non-uniform grain structure with stoichiometric interiors and oxygen deficient boundaries. This model, based on defect thermodynamics, correctly describes the dependence of the lattice parameter of nanocrystalline ceria on annealing temperature and grain size and can be extended to other materials as well.     

Sputtering of aluminium alloys in the grimm glow lamp for emission spectrochemical analysis

The effects of surface roughness, grain size and target thickness on the cathodic sputtering and emission intensities of spectral lines in the Grimm glow lamp have been investigated for samples of aluminium alloys. The intensities of the alloying elements changed with discharge time because the θ phase (Al²Cu) and β phase (Si) are sputtered selectively. The selective sputtering of the θ phase in an Al—8% Cu alloy can be decreased and the intensities can be made constant during discharge by polishing the target surface with coarse sand paper before discharge. When a fine-grained Al—4.9% Cu—7.2% Si alloy sample was used as a target, the intensities remained nearly constant during discharge. The sample preparation for obtaining fine-grained samples involves casting the melt in a metal mould. The thickness of disk samples influences not only the sample temperature but the current, sputtering and intensities. Special attention should be paid to the thickness for the determination of copper in aluminium alloys.     

Surface analytical investigation of the electrochemical and corrosion behaviour of nanocrystalline FeAl8

From the higher fraction of grain boundaries in nanocrystalline substances a different corrosion behaviour in comparison to the conventional polycrystalline material can be expected, which may be utilised for the development of new corrosion resistant alloys. Therefore, the oxidation behaviour of these two different crystallisation states of FeAl8 was compared by means of electrochemical and surface analytical experiments. The oxide films formed after electrochemical passivation were investigated by Auger Electron Spectroscopy. The application of inelastic peak shape analysis by the method of Tougaard showed, that for both materials the oxide layer may be described by a model of a (below the contamination) buried layer with a thickness of only a few nanometers depending on the preparation conditions. Factor Analysis was applied for the evaluation of the differentiated low energy Auger electron spectra (20–100 eV) as a function of depth profiling sputtering time. For both, the nanocrystalline and the polycrystalline material, the inner part of the oxide layer was enriched in Al, whereas the very outer part (surface region) was enriched in Fe. No differences concerning the sputtering time for removal of the oxide layers were found for the two alloys.     

Description of sputter removal during auger depth profiling of rough oxide layers

A model for describing sputter depth profiles on rough surfaces is presented; this is based on the assumption that sputter removal occurs at preferred sites due to the intrinsically rough surface. The progress of sputtering is described by the growth and overlap of statistically distributed holes in the surface layer. Within this assumption the variation of the Auger signal intensity during sputtering is described by simple functions. The model is applied to the sputter removal of oxide layers formed on INCOLOY 800 in hot water.     

Atomistic surface erosion and thin film growth modelled over realistic time scales

We present results of atomistic modelling of surface growth and sputtering using a multi-time scale molecular dynamics-on-the-fly kinetic Monte Carlo scheme which allows simulations to be carried out over realistic experimental times. The method uses molecular dynamics to model the fast processes and then calculates the diffusion barriers for the slow processes on-the-fly, without any preconceptions about what transitions might occur. The method is applied to the growth of metal and oxide materials at impact energies typical for both vapour deposition and magnetron sputtering. The method can be used to explain growth processes, such as the filling of vacancies and the formation of stacking faults. By tuning the variable experimental parameters on the computer, a parameter set for optimum crystalline growth can be determined. The method can also be used to model sputtering where the particle interactions with the surface occur at a higher energy. It is shown how a steady state can arise in which interstitial clusters are continuously being formed below the surface during an atom impact event which also recombine or diffuse to the surface between impact events. For fcc metals the near surface region remains basically crystalline during the erosion process with a pitted topography which soon attains a steady state roughness.     

Classical Cascade Calculations on the Analysis of Surface Bonding Structures by Secondary Particle Mass Spectrometry

The application of secondary particle mass spectrometry to analyze the atomic bonding configuration on a surface was investigated with computer calculations of particle sputtering from an Ar-bombarded surface of Ag{111}. In contrast to the prediction from the present sputtering theory, better resolved structure in the angular distribution was not observed for particles of high energy sputtered from the surface. These particles ejected to a wide angle and their angular distribution may not reflect well the atomic bonding geometry on the surface. The analytical capability of secondary particle mass spectrometry to determine surface structures can be significantly improved by selecting for detection only those particles that have prolonged collisions. The preferred directions of ejection and the relative sputtering intensity in the distribution of azimuthal angle between major open channels on the surface vary insignificantly with the duration of collision in the regime of long collisions. The results provide the first evidence that at small energies of sputtering the particles emitted from the surface may contain information about only the top two surface layers. Secondary particle mass spectrometry can thus be extremely surface sensitive for analysis of properties of solid surfaces.     

Sputtering induced recombination of nitrogen isotopes on tungsten

Adsorbed isotopic mixtures of ¹⁴N₂ and ¹⁵N₂ at low coverages on polycrystalline tungsten have been used as model systems for studying sputtering induced recombination during secondary ion mass spectrometry (SIMS). Earlier studies have shown that N₂ is completely dissociated on a W surface at low coverage. Thermal desorption spectroscopy (TDS) has been employed here to confirm this fact; our results show that complete isotopic mixing occurs. Adsorbed nitrogen can be sputtered as both atoms and molecules and sputtering induced recombination of adsorbate atoms increases as primary ion energy increases. Sputtering induced recombination is detected through isotopic mixing in SIMS. The data show that the dominant mechanism for sputtering of dimers (N₂) is not direct emission from the surface but rather a sputtering induced recombination mechanism.     

Rotational and vibrational state population distributions in excited CH radicals sputtered from a chemisorption layer on silicon

Using a computer-generated spectrum synthesis program, the upper state rotational and vibrational population distributions in the A ²Δ-X²Π transition of the CH radical sputtered with 10 keV Kr⁺ ions from an acetone chemisorption layer on silicon have been studied. Both the rotational and the vibrational populations can be adequately described by a Boltzmann distribution with a temperature near 4500 K. The significance of these results with respect to the local termodynamic equilibrium model of excited and ionized particle generation during sputtering is discussed.     

Modeling of the sputtering process of cubic silver halide microcrystals and its relevance in depth profiling by secondary-ion mass spectrometry (SIMS)

Secondary-ion mass spectrometry is frequently used for concentration–depth profiling of macroscopic samples, but it is certainly not a common analytical technique for the analysis of sub-micrometer-size particles. This is because of the additional ion-bombardment-induced artifacts which can occur when a three-dimensional microvolume is sputtered, instead of a flat surface. This paper presents a model of how small cubic photographic Ag(Cl,Br) crystals are eroded under primary-ion bombardment, and the extent to which secondary ions generated at different faces are extracted. The latter is studied by means of the program SIMION, which simulates ion trajectories in complex electrical field systems. It is shown that up to 90% of the secondary ions originating from the side face of a cubic crystal are unable to reach the detector, in contrast with most secondary ions originating from the top face. The angular dependence of the sputtering yield and the elemental ratio of Br/Cl sputtered particles have been calculated by using the well-known computer code TRIM (transport of ions in matter) under some limiting assumptions (possible preferential sputtering is disregarded and a steady-state sputtering process is assumed). The validity of the theoretical model and the calculated results were checked with experimental data. On the basis of the depth profiles presented it is explained why it is still possible to measure an interface inside a cubic volume, even though a group of several hundred crystals is sputtered simultaneously, and even though the orientations of the distinct faces of the cubes relative to the angle of incidence of the primary-ion beam are different.     

Modeling of the sputtering process of cubic silver halide microcrystals and its relevance in depth profiling by secondary-ion mass spectrometry (SIMS)

Secondary-ion mass spectrometry is frequently used for concentration-depth profiling of macroscopic samples, but it is certainly not a common analytical technique for the analysis of sub-micrometer-size particles. This is because of the additional ion-bombardment-induced artifacts which can occur when a three-dimensional microvolume is sputtered, instead of a flat surface. This paper presents a model of how small cubic photographic Ag(Cl,Br) crystals are eroded under primary-ion bombardment, and the extent to which secondary ions generated at different faces are extracted. The latter is studied by means of the program SIMION, which simulates ion trajectories in complex electrical field systems. It is shown that up to 90% of the secondary ions originating from the side face of a cubic crystal are unable to reach the detector, in contrast with most secondary ions originating from the top face. The angular dependence of the sputtering yield and the elemental ratio of Br/Cl sputtered particles have been calculated by using the well-known computer code TRIM (transport of ions in matter) under some limiting assumptions (possible preferential sputtering is disregarded and a steady-state sputtering process is assumed). The validity of the theoretical model and the calculated results were checked with experimental data. On the basis of the depth profiles presented it is explained why it is still possible to measure an interface inside a cubic volume, even though a group of several hundred crystals is sputtered simultaneously, and even though the orientations of the distinct faces of the cubes relative to the angle of incidence of the primary-ion beam are different.     

The influence of grain size on the overall kinetics of surface-induced glass crystallization

A simple kinetic model of surface-induced glass crystallization is proposed. The grain size of glass powders, a constant density of surface nuclei and a steadily increasing temperature throughout the reaction are taken into account. The crystal growth rate and the density of surface nuclei can be estimated easily from overall kinetic curves (e.g. DTA curves) of powder of different grain size.The usefulness of the model is demonstrated in the case of the primary surface-induced crystallization of cordierite glass powders.     

Microstructure and Magnetic Properties of Ag/Fe/Ag Pseudo-Sandwich Nanogranular Films

"Nanogranular Ag/Fe/Ag films were prepared by magnetron sputtering from a silver and an iron target onto glass substrates at room temperature and subsequent in situ annealing. The structural and magnetic properties of the films were investigated as a function of silver layer thickness and annealing temperature. X-ray diffraction shows the Fe(110) peak is formed in all the samples. Vibrating sample magnetometer measurements indicate that the magnetic moments lie well perpendicular to the film plane. Coercivityreaches the maximum in the sample annealed at 500 oC for 30 min with 3 nm Ag layer. A scanning probemicroscope was used to scan surface morphology and magnetic domain structures. In as-deposited samplesthe average grain size and the average roughness is smaller than that the annealing samples. After annealing,the grain size is larger and the contrast of domains increases, but the domain size becomes smaller."     

Dynamics of GDOES-induced surface roughening in metal interfaces

The roughness induced during glow-discharge optical-emission spectroscopy (GDOES) measurements has been reported to cause a loss of resolution during GDOES depth-profiling analysis. In this paper, we undertake for the first time a study of the dynamics of the surface morphology of chromium and titanium thin films (designed in mono and multilayer structures) under the impinging of GDOES incoming ions. We performed this study under the theoretical framework of the dynamic scaling theory, by analysing surface morphology changes, as measured ex-situ by AFM, with irradiation time. For single metal layers it was found that, after an initial surface smoothening, the surface undergoes a rapid steep roughening for both systems, with quite similar quantitative dynamics. Once this roughening ends a second temporal scaling regime arises, operating for long length scales with dynamics depending on the sputtering rate of the material. For the chromium layer, with a very high sputtering rate of 5.5 μm min^?1, this regime is consistent with the KPZ model, whereas for the titanium layer an EW scaling regime is indicated. These different scaling regimes are consistent with the development of larger surface slopes for the Cr system. In the multilayer systems, the initial roughness induced on the top Cr layer by GDOES has similar dynamics to that for single-layer Cr. However, a clear decrease in the roughness was observed once the underlying Ti layer, with a lower sputtering rate, was reached. This decrease in the induced roughness is maintained while the Ti layer is eroded. Therefore, choice of appropriate material (i.e. sputtering yield values) combinations and of their depth of location can enable tuning of GDOES-induced roughness and achieve substantial control over the depth profiling process.     

MoO3在Al2O3薄膜表面扩散的研究

氧化物和盐类在高比表面载体上的单层分散现象已被大量实验所证实［１］．ＭｏＯ_３在γ－Ａｌ_２Ｏ_３等高比表面载体上的分散已经研究很多,近来的研究证实ＭｏＯ３等在α－Ａｌ２Ｏ３等小比表面载体上也能自发单层分散［２］,但是分散的过程仍然缺乏直接的观察研究．本工作通过多种表面分析方法首次研究了ＭｏＯ３在平整无定形的Ａｌ２Ｏ３薄膜上的扩散过程以及影响因素．发现除温度升高外、水汽的存在对该扩散过程也有促进作用．１实验部分１．１样品的制备采用ＳＳ－３２００真空磁控溅射镀膜机,通入Ａｒ－Ｏ２作为反应气,直流磁控…     

A study of theoretical depth resolution of GaAs/AlAs reference material with low energy inert‐gas ions by Monte Carlo simulation

A Monte Carlo (MC) simulation program written in C++ has been newly developed to describe the dynamic processes of depth profiling with low energy ions. This MC simulation was applied to the depth profiling of GaAs/AlAs reference material for Ne⁺, Ar⁺, and Xe⁺ ions to elucidate the depth resolution attained by surface analytical techniques. The result clearly predicts that there is a considerable difference between the depth resolutions estimated from the leading and trailing edges of Ne⁺ and Xe⁺ ions, whereas the difference is quite small for Ar⁺ ions. Systematic investigation of the dependence of theoretical depth resolution on primary ion energy has revealed that the preferential sputtering primarily caused by the difference in energy transfer to target atoms through elastic collisions between incident ions and target atoms results in the difference between the leading and trailing edges. The inclusion of other factors, e.g. preferential sputtering effect caused by the metallization of Al atoms on the topmost surface, etc. for further improvement of the MC simulation modeling before accommodating quantitative arguments on the depth resolution is strongly recommended. Copyright © 2006 John Wiley & Sons, Ltd.     

Impedance of metal hydride electrodes. Rate of phase transformation limited by nucleation and growth mechanisms

A mathematical model for the electrochemical impedance spectroscopy of a metal hydride electrode was developed. Ac impedance data of phase transformation were derived by considering a nucleation and growth mechanism based on the theory developed by Johnson–Mehl–Avramy. Different mechanisms such as grain edge and grain boundary preferential nucleation sites are discussed. Global Nyquist plots of the metal hydride electrode are obtained by adding a surface charge transfer reaction and a double-layer capacitance to the model.     

XPS研究等离子体处理的聚苯乙烯表面结构

采用不同功率(10、20、60、100、150W)、时间(0.5、1、3、6、15和30分),在Ar、N_2、O_2、H_2和空气中,对聚苯乙烯(PS)片基进行了等离子体处理。 通过XPS技术、谱图的拟合、差谱分析和Ar~+小功率剖面处理,研究了PS表面组成与结构变化,指出处理的聚苯乙烯表面有C—O、C—NH_2、C=O、COOH和基团嵌入,因而改变了材料特性。     

The effect of glow discharge sputtering on the analysis of metal oxide films

The potential of radiofrequency glow discharge optical emission spectrometry (rf-GD-OES) for the quantification and the solid-state speciation of metal oxide films has been investigated in this work. Two types of oxide coatings, an iron oxide film deposited on silicon and a chromate conversion coating (CCC), were studied at 700 Pa of pressure and 30 W of forward power. The metal to oxygen ratios in the quantitative depth profiles (Fe/O and Cr/O, respectively) were used to evaluate the oxidation states of iron and chromium in the oxide films, demonstrating the capability of GD-OES technique for depth-resolved solid-state speciation. Furthermore, the effect of glow discharge sputtering on the samples surface in terms of modifications in the surface morphology and species transformations, were investigated by using atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The iron and chromium oxidation states were carefully studied by XPS at the original samples surface and at the bottom of GD craters, and a systematic reduction of metal elements was observed after rf-GD-OES analysis. In the case of thin oxide films, preferential sputtering can be considered as a critical factor since oxygen atoms can be preferentially sputtered, leaving a metal-enriched surface and, therefore, promoting the reduction of metal elements. In the present study preferential sputtering was found to be sample dependent, changing the proportion of the metal reduction in the oxide film with its composition. Additionally, alternative sputter-depth-profiling techniques such as secondary ion mass spectrometry (SIMS), femtosecond laser ablation (fs-LA), and XPS ion gun were used for the analysis of the CCC in order to evaluate the reduction of Cr⁶⁺ to Cr³⁺ depending on the sputtering mechanism.