A physics-based understanding of material aging mechanisms helps to increase reliability when predicting the lifetime of mechanical and electrical components. This report examines in detail the mechanisms of atmospheric copper sulfidation and evaluates new methods of parallel experimentation for high-throughput corrosion analysis. Often our knowledge of aging mechanisms is limited because coupled chemical reactions and physical processes are involved that depend on complex interactions with the environment and component functionality. Atmospheric corrosion is one of the most complex aging phenomena and it has profound consequences for the nation's economy and safety. Therefore, copper sulfidation was used as a test-case to examine the utility of parallel experimentation. Through the use of parallel and conventional experimentation, we measured: (1) the sulfidation rate as a function of humidity, light, temperature and O{sub 2} concentration; (2) the primary moving species in solid state transport; (3) the diffusivity of Cu vacancies through Cu{sub 2}S; (4) the sulfidation activation energies as a function of relative humidity (RH); (5) the sulfidation induction times at low humidities; and (6) the effect of light on the sulfidation rate. Also, the importance of various sulfidation mechanisms was determined as a function of RH and sulfide thickness. Different models for sulfidation-reactor geometries and the sulfidation reaction process are presented.
The relative electronic defect densities and oxide interface potentials were determined for naturally-occurring and synthetic Al oxides on Al. In addition, the effect of electrochemical treatment on the oxide electrical properties was assessed. The measurements revealed (1) that the open circuit potential of Al in aqueous solution is inversely correlated with the oxide electronic defect density (viz., lower oxide conductivities are correlated with higher open circuit potentials), and (2) the electronic defect density within the Al oxide is increased upon exposure to an aqueous electrolyte at open circuit or applied cathodic potentials, while the electronic defect density is reduced upon exposure to slight anodic potentials in solution. This last result, combined with recent theoretical predictions, suggests that hydrogen may be associated with electronic defects within the Al oxide, and that this H may be a mobile species, diffusing as H{sup +}. The potential drop across the oxide layer when immersed in solution at open circuit conditions was also estimated and found to be 0.3 V, with the field direction attracting positive charge towards the Al/oxide interface.
Nanostructural characterization of amorphous diamondlike carbon (a-C) films grown on silicon using pulsed-laser deposition (PLD) is correlated to both growth energetic and film thickness. Raman spectroscopy and x-ray reflectivity probe both the topological nature of 3- and 4-fold coordinated carbon atom bonding and the topographical clustering of their distributions within a given film. In general, increasing the energetic of PLD growth results in films becoming more ``diamondlike'', i.e. increasing mass density and decreasing optical absorbance. However, these same properties decrease appreciably with thickness. The topology of carbon atom bonding is different for material near the substrate interface compared to material within the bulk portion of an a-C film. A simple model balancing the energy of residual stress and the free energies of resulting carbon topologies is proposed to provide an explanation of the evolution of topographical bonding clusters in a growing a-C film.
Al{sub 2}Cu thin films ({approx} 382 nm) are fabricated by melting and resolidifying Al/Cu bilayers in the presence of a {micro} 3 nm Al{sub 2}O{sub 3} passivating layer. X-ray Photoelectron Spectroscopy (XPS) measures a 1.0 eV shift of the Cu2p{sub 3/2} peak and a 1.6 eV shift of the valence band relative to metallic Cu upon Al{sub 2}Cu formation. Scanning Electron microscopy (SEM) and Electron Back-Scattered Diffraction (EBSD) show that the Al{sub 2}Cu film is composed of 30-70 {micro}m wide and 10-25 mm long cellular grains with (110) orientation. The atomic composition of the film as estimated by Energy Dispersive Spectroscopy (EDS) is 67 {+-} 2% Al and 33 {+-} 2% Cu. XPS scans of Al{sub 2}O{sub 3}/Al{sub 2}Cu taken before and after air exposure indicate that the upper Al{sub 2}Cu layers undergo further oxidation to Al{sub 2}O{sub 3} even in the presence of {approx} 5 nm Al{sub 2}O{sub 3}. The majority of Cu produced from oxidation is believed to migrate below the Al{sub 2}O{sub 3} layers, based upon the lack of evidence for metallic Cu in the XPS scans. In contrast to Al/Cu passivated with Al{sub 2}O{sub 3}, melting/resolidifying the Al/Cu bilayer without Al{sub 2}O{sub 3} results in phase-segregated dendritic film growth.
The authors have used ion channeling to examine the lattice configuration of deuterium in Mg doped GaN grown by MOCVD. The deuterium is introduced both by exposure to deuterium gas and to ECR plasmas. A density functional approach including lattice relaxation, was used to calculate total energies for various locations and charge states of hydrogen in the wurtzite Mg doped GaN lattice. Computer simulations of channeling yields were used to compare results of channeling measurements with calculated yields for various predicted deuterium lattice configurations.
Al{sub 2}Cu thin films ({approximately}382 nm) are fabricated by melting and resolidifying Al/Cu bilayers in the presence of a {approximately}3 nm Al{sub 2}O{sub 3} passivating layer. X-ray Photoelectron Spectroscopy (XPS) measures a 1.0 eV shift of the Cu2p{sub 3/2} peak and a 1.6 eV shift of the valence band relative to metallic Cu upon Al{sub 2}Cu formation. Scanning Electron Microscopy (SEM) and Electron Back-Scattered Diffraction (EBSD) show that the Al{sub 2}Cu film is composed of 30--70 {mu}m wide and 10--25 mm long cellular grains with (110) orientation. The atomic composition of the film as estimated by Energy Dispersive Spectroscopy (EDS) is 67{+-}2% Al and 33{+-}2% Cu. XPS scans of Al{sub 2}O{sub 3}/Al{sub 2}Cu taken before and after air exposure indicate that the upper Al{sub 2}Cu layers undergo further oxidation to Al{sub 2}O{sub 3} even in the presence of {approximately}5 nm Al{sub 2}O{sub 3}. The majority of Cu produced from oxidation is believed to migrate below the Al{sub 2}O{sub 3} layers, based upon the lack of evidence for metallic Cu in the XPS scans. In contrast to Al/Cu passivated with Al{sub 2}O{sub 3}, melting/resolidifying the Al/Cu bilayer without Al{sub 2}O{sub 3} results in phase-segregated dendritic film growth.
Engineered Cu-rich islands were fabricated on an Al thin film to investigate pit initiation mechanisms at noble particles. X-ray photoelectron spectroscopy confirms that the thin film Cu-rich islands interdiffuse with the underlying Al substrate to form Al{sub 2}Cu islands. The defect arrays exhibit open circuit potential fluctuations whose magnitude and frequency increase as defect spacing decreases for constant island size and cathode/anode ratio. Post-exposure examination by energy dispersive spectroscopy (EDS) shows that the Al beneath the Cu-rich island dissolves with a crevice geometry. Engineered Al islands fabricated under identical conditions do not induce crevice corrosion in the vicinity of the Al defects. These results suggest that the Al dissolution is driven by the galvanic coupling between the noble island and matrix, and/or by a local change in chemistry, rather than by the presence of a defective oxide in the vicinity of the island.
Parallel microscopic experimentation (the combinatorial approach often used in solid-state science) was applied to characterize atmospheric copper corrosion behavior. Specifically, this technique permitted relative sulfidation rates to be determined for copper containing different levels of point defects and impurities (In, Al, O, and D). Corrosion studies are inherently difficult because of complex interactions between material interfaces and the environment. The combinatorial approach was demonstrated using micron-scale Cu lines that were exposed to a humid air environment containing sub-ppm levels of H{sub 2}S. The relative rate of Cu{sub 2}S growth was determined by measuring the change in resistance of the line. The data suggest that vacancy trapping by In and Al impurities slow the sulfidation rate. Increased sulfidation rates were found for samples containing excess point defects or deuterium. Furthermore, the sulfidation rate of 14 {micro}m wide Cu lines was increased above that for planar films.
A new approach is being pursued to study corrosion in Cu alloy systems by using combinatorial analysis combined with microscopic experimentation (the Combinatorial Microlab) to determine mechanisms for copper corrosion in air. Corrosion studies are inherently difficult because of complex interactions between materials and environment, forming a multidimensional phase space of corrosion variables. The Combinatorial Microlab was specifically developed to address the mechanism of Cu sulfidation, which is an important reliability issue for electronic components. This approach differs from convention by focusing on microscopic length scales, the relevant scale for corrosion. During accelerated aging, copper is exposed to a variety of corrosive environments containing sulfidizing species that cause corrosion. A matrix experiment was done to determine independent and synergistic effects of initial Cu oxide thickness and point defect density. The CuO{sub x} was controlled by oxidizing Cu in an electron cyclotron resonance (ECR) O{sub 2} plasma, and the point defect density was modified by Cu ion irradiation. The matrix was exposed to 600 ppb H{sub 2}S in 65% relative humidity air atmosphere. This combination revealed the importance of oxide quality in passivating Cu and prevention of the sulfidizing reaction. A native oxide and a defect-laden ECR oxide both react at 20 C to form a thick Cu{sub 2}S layer after exposure to H{sub 2}S, while different thicknesses of as-grown ECR oxide stop the formation of Cu{sub 2}S. The species present in the ECR oxide will be compared to that of an air oxide, and the sulfide layer growth rate will be presented.
The role of hydrogen in enhancing the photoluminescence (PL) yield observed from Si nanocrystals embedded in SiO{sub 2} has been studied. SiO{sub 2} thermal oxides and bulk fused silica samples have been implanted with Si and subsequently annealed in various ambients including hydrogen or deuterium forming gases (Ar+4%H{sub 2} or Ar+4%D{sub 2}) or pure Ar. Results are presented for annealing at temperatures between 200 and 1100 C. Depth and concentration profiles of H and D at various stages of processing have been measured using elastic recoil detection. Hydrogen or deuterium is observed in the bulk after annealing in forming gas but not after high temperature (1100 C) anneals in Ar. The presence of hydrogen dramatically increases the broad PL band centered in the near-infrared after annealing at 1100 C but has almost no effect on the PL spectral distribution. Hydrogen is found to selectively trap in the region where Si nanocrystals are formed, consistent with a model of H passivating surface states at the Si/SiO{sub 2} interface that leads to enhanced PL. The thermal stability of the trapped H and the PL yield observed after a high temperature anneal have been studied. The hydrogen concentration and PL yield are unchanged for subsequent anneals up to 400 C. However, above 400 C the PL decreases and a more complicated H chemistry is evident. Similar concentrations of H or D are trapped after annealing in H{sub 2} or D{sub 2} forming gas; however, no differences in the PL yield or spectral distribution are observed, indicating that the electronic transitions resulting in luminescence are not dependent on the mass of the hydrogen species.
This report summarizes a two-year Laboratory-Directed Research and Development (LDRD) program to gain understanding and control of the important parameters which govern the optical performance of rare-earth (RE) doped ceramics. This LDRD developed the capability to determine stable atomic arrangements in RE doped alumina using local density functional theory, and to model the luminescence from RE-doped alumina using molecular dynamic simulations combined with crystal-field calculations. Local structural features for different phases of alumina were examined experimentally by comparing their photoluminescence spectra and the atomic arrangement of the amorphous phase was determined to be similar to that of the gamma phase. The luminescence lifetimes were correlated to these differences in the local structure. The design of both high and low-phonon energy host materials was demonstrated through the growth of Er-doped aluminum oxide and lanthanum oxide. Multicomponent structures of rare-earth doped telluride glass in an alumina and silica matrix were also prepared. Finally, the optical performance of Er-doped alumina was determined as a function of hydrogen content in the host matrix. This LDRD is the groundwork for future experimentation to understand the effects of ionizing radiation on the optical properties of RE-doped ceramic materials used in space and other radiation environments.
The authors have developed a radiation-hard, charged particle spectrometer, consisting of thin parallel conducting foils as current collectors. Prototype detectors have been tested in accelerator bombardments and at the fusion plasma facilities TFTR and JET. In the case of the accelerator bombardments, a detector consisting of 6 Al foils, each of thickness about 6 {micro}m, demonstrated an energy resolution of about 7% for 7 MeV alpha particles. The prototype tested immediately outside TFTR demonstrated the expected insensitivity to moderately high levels of fast neutrons and hard gamma rays. The prototype tested inside JET similarly indicated operational capability at elevated temperatures as a lost alpha particle detector for d-t tokamak fusion plasmas. The robustness and moderately good energy resolution of these detectors should permit the application to tasks such as the first wall measurement of lost alpha particles from tokamak fusion plasmas, the real time measurement of light ion fission fragments from fission reactor experiments and the in-beam measurement of accelerator beam energies as a control diagnostic.
Low dielectric constant insulating films, such as SiO2 and fluorine doped SiOx, are an important class of materials in semiconductor manufacturing. Evaluation of a new process to grow low temperature SiOxFy films using an electron cyclotron resonance plasma (ECR) was done. Ion beam analysis techniques were used to characterize the compositions of the insulating films and correlate this with their physical and electrical properties. Since Si, O, F and H are of primary interest in these films, three different techniques were utilized in order to get a more thorough analysis. 2.8 MeV He Rutherford Backscattering Spectrometery (RBS) revealed the Si and O content, but because of the low fluorine concentrations (2-10 at.%) RBS proved difficult for analysis of the F content. Instead, Nuclear Reaction Analysis (NRA), which used 872 keV protons in the 19F(p, αγ)16O reaction, was employed. Finally, 30 MeV Si Elastic Recoil Detection (ERD) was used to obtain the H concentration and supplement the O analysis. The dielectric constant decreased from ε = 4 to ε = 3.55 as the F concentration increased from 0 to 10%.
The growth of polycrystalline and amorphous aluminum-oxygen alloy films using electron-beam evaporation of Al in the presence of an O{sub 2} electron-cyclotron-resonance (ECR) plasma was investigated for film compositions varying from 40% Al (Al{sub 2}O{sub 3}) to near 100% Al (AlO{sub x}). Processing parameters such as deposition temperature and ion energy were varied to study their effects on surface texture and film microstructure. The Al-rich films (AlO{sub x}) contain polycrystalline fcc Al grains with finely dispersed second-phase particles of {gamma}-Al{sub 2}O{sub 3} (1-2 nm in size). The surface roughness of these films was measured by atomic force microscopy and found to increase with sample bias and deposition temperature. Stoichiometric Al{sub 2}O{sub 3} films grown at 100{degrees}C and 400{degrees}C without an applied bias were amorphous, while an applied bias of -140 V formed a nanocrystalline {gamma}-Al{sub 2}O{sub 3} film at 400{degrees}C. The surface roughness of the Al{sub 2}O{sub 3} increased with temperature while ion irradiation produced a smoother surface.
Low-energy deposition of Al(O) alloys from an electron cyclotron resonance (ECR) plasma offers a scaleable method for the synthesis of thick, high-strength Al layers. This work compares alloy layers formed by an ECR-0{sub 2} plasma in conjunction with Al evaporation to 0-implanted Al (ion energies 25-200 keV); and it examines the effects of volume fraction of A1{sub 2}0{sub 3} phase and deposition temperature on the yield stress of the material. TEM showed the Al(O) alloys contain a dense dispersion of small {gamma}-Al{sub 2}0{sub 3} precipitates ({approximately}l nm) in a fine-grain (10-100 nm) fcc Al matrix when deposited at a temperature of {approximately}100C, similar to the microstructure for gigapascal-strength 0-implanted Al. Nanoindentation gave hardnesses for ECR films from 1.1 to 3.2 GPa, and finite-element modeling gave yield stresses up to 1.3 {plus_minus} 0.2 GPa with an elastic modulus of 66 GPa {plus_minus} 6 GPa (similar to pure bulk Al). The yield stress of a polycrystalline pure Al layer was only 0.19 {plus_minus} 0.02 GPa, which was increased to 0.87 {plus_minus} 0.15 GPa by implantation with 5 at. % 0.
A description of ion-irradiation-induced reduction in the photoluminescence (PL) signal from porous silicon is given and a simple model which is consistent with a nanocrystalline Si structure is presented. Ion irradiation with 250 keV Ne is used to controllably reduce the integrated PL signal by 20% after a fluence of 4*1012 Ne cm-2 and completely eliminate the PL signal after a fluence of 4*1013 Ne cm-2. The use of vacuum and air annealing to recover ion-induced damage is also described, but the high temperatures for annealing cause elimination of the PL signal.
Good quality, low temperature silicon nitride and oxynitride films were deposited downstream from an electron cyclotron resonance (ECR) plasma source using SiH{sub 4} and N{sub 2} gas mixtures. The Si/N ratio and H content in the deposited films were determined using Rutherford backscattering spectrometry (RBS)and elastic recoil detection (ERD). The H concentration was minimum for films with compositions closest to that of stoichiometric Si{sub 3}N{sub 4}. The optimum conditions for producing a stoichiometric Si{sub 3}N{sub 4}were: a SiH{sub 4}/N{sub 2} flow ratio between 0.1 and 0.2, and an electrically isolated sample far from the ECR source. Infrared absorption spectra showed that as the film composition changed from N rich to Si rich the dominant bonds associated with H changed from N-H to Si-H. The addition of O{sub 2} to the background gas formed an oxynitride with a low H content similar to the stoichiometric Si{sub 3}N{sub 4} 10 refs., 4 figs., 2 tabs.
Nuclear microprobe analysis (NMA) is a unique form of microbeam analysis in that it combines high lateral resolution with the high depth resolution techniques of conventional ion beam analysis (IBA) to nondestructively determine sample composition in three dimensions. By using depth sensitive IBA techniques (e.g., Rutherford Backscattering Spectrometry (RBS), Enhanced Backscattering Spectrometry (EBS) or Elastic Recoil Detection (ERD)), NMA finds its greatest utility in analyses requiring the following information: (1) 1--100 ppM sensitivity, (2) nondestructive three-dimensional depth profiling, and (3) quantitative light element analysis (e.g., the first two rows of the periodic table). This paper demonstrates the continuing evolution of NMA capabilities through two examples. First, the unique capabilities afforded NMA are shown in a simple yet accurate method to measure both oxygen and metal atom concentrations in Y-Ba-Cu-O alloys with micro-area ion beam analysis. Second, a NMA of buried tungsten lines in a silicon wafer demonstrates the complementary nature of information determined by NMA and scanning electron microscopy (SEM). 9 refs., 2 figs.