Publications

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.

The strength and modulus of amorphous diamond, a new material for surface micromachined MEMS and sensors, was tested in uniaxial tension by pulling laterally with a flat tipped diamond in a nanoindenter. Several sample designs were attempted. Of those, only the single layer specimen with a 1 by 2 {micro}m gage cross section and a fixed end rigidly attached to the substrate was successful. Tensile load was calculated by resolving the measured lateral and normal forces into the applied tensile force and frictional losses. Displacement was corrected for machine compliance using the differential stiffness method. Post-mortem examination of the samples was performed to document the failure mode. The load-displacement data from those samples that failed in the gage section was converted to stress-strain curves using carefully measured gage cross section dimensions. Mean fracture strength was found to be 8.5 {+-} 1.4 GPa and the modulus was 831 {+-} 94 GPa. Tensile results are compared to hardness and modulus measurements made using a nanoindenter.

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.

The electronic defect density of native, anodic, and synthetic Al oxide layers on Al were studied by solid state electrical measurement as a function of hydration OF the oxide. The non-hydrated synthetic Al oxide layers, which included electron cyclotron resonance (ECR) plasma deposited oxides as well as ECR plasma grown oxides, were highly insulating with electrical transport dominated by thermal emission from deep traps within the oxide. Following hydration these oxides and the native oxides exhibited a large increase in electronic defect density as evidenced by increases in the DC leakage current, reduction in the breakdown field, and increase in AC conductance. Elastic recoil detection of hydrogen revealed that hydration leads to hydrogen incorporation in the oxide films and hydrogen injection through the films into the Al layer below. The increase in electronic defect concentration is related to this hydrogenation and may play a significant role in localized corrosion initiation.

The purpose of this laboratory-directed research and development (LDRD) project was to develop and assess novel low-permittivity dielectric materials for applications as interlevel dielectrics (ILDs) in Si-based microelectronics. There were three classes of materials investigated: (1) novel covalently-bonded ceramics containing carbon, boron, and/or nitrogen, (2) fluorinated SiO{sub 2} (SiOF), and (3) plasma polymerized fluorocarbon (PPFC). The specific advantages and disadvantages for each potential low k ILD material were evaluated. It was discovered that highly energetic deposition processes are required for the formation of thermally and environmentally stable carbon or boron nitride ceramics, and the resulting films may have many potentially valuable applications, such as diffusion barriers, tribological coatings, micro-sensor materials, etc. The films are not suitable as low k ILDs, however, because the highly energetic deposition process leads to films with high atomic density, and this leads to high dielectric constants. SiOF shows a promise as low k ILD material for near-term applications, but special passivation or encapsulation strategies may be required in order to reduce two instability problems that the authors have discovered: moisture absorption and thermal instability of the SiOF/Al interface. PPFC films offer promise for even lower dielectric constant ILDs than SiOF, but it will be necessary to develop new strategies to passivate the free radicals in the films generated during deposition. These free radicals lead to increase in dielectric loss over time when the films are exposed to room ambient conditions.

The thermal stability of fluorinated SiO2 films (SiOF) was found to be dependent on F content and the type of substrate upon which the film was deposited. SiOF films with a range of F concentrations were deposited using an electron cyclotron resonance (ECR) plasma upon Si, Al/Si, TiN/Al/Si, and Al/SiO2/Si substrates. Following deposition, the films were deliberately hydrated and/or annealed and their stability assessed. Hydration was found to only affect the high F content films. Capacitance changes with annealing in the high F content films were found to occur beginning at 200 °C. These changes, which were independent of substrate type, likely occurred due to desorption of H2O in the films. After annealing of the high F content films up to 400 °C, a reduction in F content was found for SiOF films on some substrates. Significant reductions were found for SiOF films on Al/Si substrates, while little or no change was found for films on TiN/Al/Si, Al/SiO2/Si, or Si substrates. Local chemical analysis of those films which showed F reduction indicated that the F profile was approximately uniform throughout the layer and did not pile-up at the interface. The substrate-dependent thermal instability exhibited by these films suggests the chemical nature or qualities of the substrate may play a role in the F reduction reaction.