Publications

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An analytical capability is being developed that can be used to predict the effect of corrosion on the performance of electrical circuits and systems. The availability of this ''toolset'' will dramatically improve our ability to influence device and circuit design, address and remediate field occurrences, and determine real limits for circuit service life. In pursuit of this objective, we have defined and adopted an iterative, statistical-based, top-down approach that will permit very formidable and real obstacles related to both the development and use of the toolset to be resolved as effectively as possible. An important component of this approach is the direct incorporation of expert opinion. Some of the complicating factors to be addressed involve the code/model complexity, the existence of large number of possible degradation processes, and an incompatibility between the length scales associated with device dimensions and the corrosion processes. Two of the key aspects of the desired predictive toolset are (1) a direct linkage of an electrical-system performance model with mechanistic-based, deterministic corrosion models, and (2) the explicit incorporation of a computational framework to quantify the effects of non-deterministic parameters (uncertainty). The selected approach and key elements of the toolset are first described in this paper. These descriptions are followed by some examples of how this toolset development process is being implemented.

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.

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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 methodology has been established to predict the effect of atmospheric corrosion on the reliability of plastic encapsulated microelectronic (PEM) devices. New experimental techniques were developed to directly characterize the Al/Au wirebond interface where corrosion primarily occurs. A deterministic empirical model describing wirebond degradation as a function of environmental conditions was generated. To demonstrate how this model can be used to determine corrosion effects on device reliability, a numerical simulation was performed on a three-lead voltage reference device. Surface reaction rate constants, environmental variables and the defect characteristics of the encapsulant were treated as distributed parameters. A Sandia-developed analytical framework (CRAX{trademark}) was used to include uncertainty in the analysis and directly calculate reliability.

Many types of integrated and discrete microelectronic devices exist in the enduring stockpile. In the past, most of these devices have used conventional ceramic hermetic packaging (CHP) technology. Sometime in the future, plastic encapsulated microelectronic (PEM) devices will almost certainly enter the inventory. In the presence of moisture, several of the aluminum-containing metallization features common to both types of packaging become susceptible to atmospheric corrosion (Figure 1). A breach in hermeticity (e.g., due to a crack in the ceramic body or lid seal) could allow moisture and/or contamination to enter the interior of a CHP device. For PEM components, the epoxy encapsulant material is inherently permeable to moisture. A multi-year project is now underway at Sandia to develop the knowledge base and analytical tools needed to quantitatively predict the effect of corrosion on microelectronic performance and reliability. The issue of corrosion-induced failure surfaced twice during the past year because cracks were found in their ceramic bodies of two different CHP devices: the SA371 1/3712 MOSFET and the SA3935 ASIC (acronym for A Simple Integrated Circuit). Because of our inability to perform a model-based prediction at that time, the decision was made to determine the validity of the corrosion concern for these specific situations by characterizing the expected environment and assessing its relative degree of corrosivity. The results of this study are briefly described in this paper along with some of the advancements made with the predictive model development.

Corrosion is a leading material degradation mode observed in many military systems. This report contains a description of a small project that was performed to allow some of the important electrochemical aspects of two distinct and potentially relevant degradation modes to be better understood: environmentally assisted cracking (EAC) of aluminum alloys and corrosion in moist salt. Two specific and respective tasks were completed: (A) the characterization of the effect of aluminum microstructural variability on its susceptibility to EAC, and (B) the development of experimental and analytical techniques that can be used to identify the factors and processes that influence the corrosivity of moist salt mixtures. The resultant information constitutes part of the basis needed to ultimately predict component reliability and/or possibly to identify techniques that could be used to control corrosion in critical components. In Task A, a physical model and related understanding for the relevant degradation processes were formulated. The primary result from Task B included the identification and qualitative validation of a methodology for determining the corrosivity of salt mixtures. A detailed compilation of the results obtained from each of these two diverse tasks is presented separately in the body of this report.

The primary current-collector materials being used in lithium-ion cells are susceptible to environmental degradation: aluminum to pitting corrosion and copper to environmentally assisted cracking. Pitting occurs at the highly oxidizing potentials associated with the positive-electrode charge condition. However, the pitting mechanism is more complex than that typically observed in aqueous systems in that the pits are filled with a mixed metal/oxide product and exist as mounds or nodules on the surface. Electrochemical impedance spectroscopy was shown to be an effective analytical tool for quantifying and verifying aluminum corrosion behavior. Two fluorocarbon-based coatings were shown to improve the resistance of Al to pitting attack. Detailed x-ray photoelectron spectroscopy (XPS) surface analyses showed that there was very little difference in the films observed after simple immersion in either PC:DEC or EC:DMC electrolytes versus those following electrical cycling. Li and P are the predominant surface species. Finally, environmental cracking of copper can occur at or near the lithium potential and only if specific metallurgical conditions exist (work-hardening and large grain size).

The primary current-collector materials being used in lithium-ion cells are susceptible to environmental degradation: aluminum to pitting corrosion and copper to environmentally assisted cracking. Pitting occurs at the highly oxidizing potentials associated with the positive-electrode charge condition. However, the pitting mechanism is more complex than that typically observed in aqueous systems in that the pits are filled with a mixed metal/oxide product and exist as mounds or nodules on the surface. Electrochemical impedance was shown to be an effective analytical tool for quantification and verification of visual observations and trends. Two fluorocarbon-based coatings were shown to improve the resistance of Al to localized pitting. Finally, environmental cracking of copper can occur at or near the lithium potential and only if specific metallurgical conditions exist (work hardening and large grain size).

The use of modular systems to distribute power using batteries to store off-peak energy and a state of the art power inverter is envisioned to offer important national benefits. A 4-year, cost- shared contract was performed to design and develop a modular, 300kVA/300-kWh system for utility and customer applications. Called Nas-P{sub AC}, this system uses advanced sodium/sulfur batteries and requires only about 20% of the space of a lead-acid-based system with a smaller energy content. Ten, 300-VDC, 40-kWh sodium/sulfur battery packs are accommodated behind a power conversion system envelope with integrated digital control. The resulting design facilities transportation, site selection, and deployment because the system is quiet and non-polluting, and can be located in proximity to the load. This report contains a detailed description of the design and supporting hardware development performed under this contract.

The US Department of Energy is sponsoring the development of battery energy storage systems for electric utilities. An important part of this DOE program is the engineering of the battery subsystem. Because lower costs are possible and less space is required compared with conventional battery technologies, two advanced battery systems are being developed: sodium/sulfur and zinc/bromine. A brief description of the development approach being followed along with the current status of the sodium/sulfur technology is described in this paper. Of immediate relevance, a factory integrated modular sodium/sulfur system has been designed that incorporates many of the advantages of this technology. Each module (designated as NAS-P{sub AC}) combines a 600-kWh sodium/sulfur battery, a 300 kW power converter and a control system. In addition to the potential for low life-cycle cost, other specific benefits include excellent portability and an installed system-level footprint that is about 20% of an equivalent system using lead-acid batteries. The sodium/sulfur battery is designed to deliver its rated energy for 1500 cycles or 5 years of maintenance-free operation.

Over the past decade, Sandia National Laboratories has managed the Department of Energy (DOE)-sponsored programs for the development of the sodium/sulfur battery technology. Two DOE offices have provided support for these programs: the Office of Energy Storage and Distribution (OESD) and the Office of Transportation Systems (OTS). The ultimate goal of these ongoing efforts is to develop and demonstrate high performance, cost-effective systems suitable for both stationary and mobile applications. A part of Sandia's responsibility is to evaluate the status of the technologies and to address specific problems that are encountered during the development process. The number and level of effort devoted to these tasks are scaled such that the funding emphasis is given to the contracted engineering development programs. Two of the major safety-related concerns with sodium/sulfur EV batteries are the potential consequences associated with large temperature increases and vehicle accidents. The first three tasks represent Sandia's initial effort to help identify effective methods to limit the temperature rise in the battery during both expected and unexpected conditions and to assess one possible result of a vehicle accident. Descriptions of each task along with selected results are given in the following sections. 4 figs., 2 tabs.