The high oxygen-ion conductivity over wide ranges of temperature and oxygen pressure in stabilized cubic zirconia has led to its use as a solid-oxide electrolyte in a variety of electrochemical applications. Zirconia-based oxygen sensors are widely used for combustion control, especially in automobiles, for atmosphere control in furnaces, and as monitors of oxygen concentration in molten metals. Other applications include electrochemical pumps for control of oxygen potential, steam electrolyzers, and high-temperature solidoxide fuel cells (SOFCs). High-temperature SOFCs offer a clean, pollution-free technology to electrochemically generate electricity at high efficiencies. These fuel cells provide many advantages over traditional energy-conversion systems, including high efficiency, reliability, modularity, fuel adaptability, and very low levels of NOx and SOx emissions. The quiet, vibrationfree operation of SOFCs also eliminates the noise usually associated with conventional power-generation systems. Furthermore, because of the high temperature of operation (~1000°C) of SOFCs, naturalgas fuel can be reformed within the cell stack, eliminating the need for an expensive external reformer system. Also, pressurized SOFCs can be successfully used as replacements for combustors in gas turbines; such hybrid SOFC/gas-turbine power systems are expected to reach efficiencies approaching 70%.

High-purity silicon used for the growth of single crystals is a material with a high resistivity. Small traces of foreign atoms, which are mainly substitutionally dissolved on lattice sites, make the material highly conductive and therefore suitable for electronic applications. The controlled incorporation of extrinsic point defects in silicon is the main task for the production of electronic devices. Homogeneous doping is generally achieved by adding a controlled amount of the dopant element to the silicon melt. However, the fabrication of electronic devices like diodes, transistors, and complex integrated circuits requires spatially inhomogeneous dopant distributions. Control of the inhomogeneous doping profiles demanded by the considerations outlined in the article by Packan in this issue requires a detailed knowledge of the atomic mechanisms of dopant diffusion in silicon, the properties of intrinsic point defects like vacancies (V) and self-interstitials (I), and the interactions among different point defects.

Although research in and the development of visible light-emitting diodes (LEDs) began nearly 100 years ago, recent developments have made the field truly revolutionary. In this article, I will discuss the evolution of LEDs, provide a little history, describe some recent developments and emerging applications, and finally speculate as to where this technology might lead us in the future.

Silicon produced for the microelectronics industry is far and away the purest and most perfect crystalline material manufactured today. It is fabricated routinely and in very large volumes. Many of the advances in integrated-circuit (IC) manufacturing achieved in recent years would not have been possible without parallel advances in silicon-crystal quality and defect engineering. Transition-metal contamination is a case in point. Essentially all practical problems (minority carrier lifetime, metal precipitation, stacking faults, etc.) associated with metal contaminants have largely been solved through advances in crystal purity.

Fine powders of semiconducting oxides loaded with deposited metal and/or metaloxide particles have been widely used as heterogeneous photocatalysts for innumerable chemical reactions. Among the many photocatalytic reactions, the splitting of water assisted by light has become one of the most active areas in heterogeneous photocatalysis, since it can be a promising chemical route for energy renewal and energy storage. The photocatalytic splitting of water on TiO2 electrodes, discovered by Fujishima and Honda in 1972, is a prototypic example of this technique, and there is a vast body of literature describing the potential application of TiO2-based photocatalysts for water decomposition. This has brought about a burst of research related to the development of many other photocatalytic systems.

Chocolate is a common confectionery material throughout the world that has seen generally increasing production trends over the last 10 years. Making chocolate requires an understanding of how the consumer perceives it. The preferred type of chocolate varies from country to country; for example, common U.S. and U.K. chocolate tastes are mutually incomprehensible, while the rest of Europe hates both of them! The different tastes and uses for chocolate reflect the histories of the industry in different places.

The design of inorganic and organic solids with novel structures and properties has long been the object of materials research. The classical examples of porous materials (i.e., involving reversible guest passage) are zeolites. First discovered in the mid-1700s, zeolites are hydrated, crystalline aluminosilicates that organize into stable, discrete frameworks. Basic structures employ tetrahedral atoms (silicon or aluminum) bridged by oxygen atoms, where each oxygen is shared between two metalloid tetrahedra. Resulting covalent lattices can be neutral or negatively charged (as a result of bridging oxides) and often employ alkali metal or alkalineearth counterions. As a consequence of this ordered structure, zeolites both benefit from and are limited by their highly geometrical nature: their rigid structures are inherently robust, yet they are difficult to process. In addition, while natural and unnatural zeolites have been characterized, harsh synthetic conditions are common to both and lead to limitations in design and processability. Even so, these impediments have not prevented constructing a myriad of architectures on zeolite host lattices. Strengths and weaknesses aside, zeolites demonstrate a major objective of materials chemistry: the ability to manifest macroscopic physical properties based on embedded microscopic structure.

Inorganic solids with wide bandgaps are usually classified as electrical insulators and are used in industry as insulators, dielectrics, and optical materials. Many metallic oxides have wide bandgaps because of the significant contribution of ionic character to the chemical bonds between metallic cations and oxide ions. Their ionic nature simultaneously suppresses the formation of easily ionizable shallow donors or acceptors and enhances the localization of electrons and positive holes. Thus it is understandable that interest in these wide-gap oxides as conductive materials has not been strong.

The beta-alumina family of materials has played a central role in the field of solid-state ionics. β- and β-alumina have been a principal theme in the field ever since Yao and Kummer reported the extraordinarily high conductivity for sodium β-alumina. The material “came of age” at a time when there was great interest in the science and technology of highconductivity solid electrolytes. A previous MRS Bulletin review introduced this broad family of materials, examining the range of compositions and the two major structures. The beta-alumina family emerged as almost an ideal system in which to explore structure-property relations, as its unusual structure is responsible for its remarkable ion-transport properties. Although the initial interest in this material, and the one which endures to this day, is its rapid sodium-ion transport, the rich ion-exchange chemistry added a dimension to this material that few inorganic systems can match, let alone exceed. β-alumina, in particular, is an almost universal solid electrolyte for cations. It constitutes a broad family of solid electrolytes whose properties are dependent upon the nature of the ion inserted into the conduction plane. As a result, the β-aluminas have served as model systems for a wide range of studies: proton transport and mixed-ion diffusion, order-disorder reactions, and superlattice phenomena. Moreover, these β-alumina compositions demonstrated that fast-ion transport was not limited to a few monovalentions, but could be extended to divalent and even trivalent cations. With the latter materials, the interest was not necessarily ion transport, but optical properties instead. The presence of trivalent cations in this unusual structure, coupled with the ability to control the chemistry of the local environment, enabled the β-aluminas to exhibit a number of novel optical properties.

Thermal spray is a continuous, directed, melt-spray process in which particles (e.g., 1–50 μm in diameter) of virtually any material are melted and accelerated to high velocities, through either a combustion flame or a dc or rf nontransferred thermal-plasma arc. The molten or semimolten droplets impinge on a substrate and rapidly solidify to form a thin “splat.” The deposit is built up by successive impingement and interbonding among the splats. The splats accumulate into a wellbonded deposit, generally > 10 μm thick.

That fracture is governed by processes occurring over a wide range of length scales has been recognized since the earliest developments of modern fracture mechanics. Griffitha's study of the strength of cracked solids 1,2 is perhaps the earliest example of such multiscale thinking, predating by several decades the first attempts to apply atomistically grounded traction-separation laws to fracture (e.g., the Orowan-Gilman model3,4). Griffith recognized the critical condition for crack extension to be a statement of thermodynamic equilibrium of a cracked solid, representing a balance between the mechanical energy decrease upon crack extension and the corresponding increase in energy due to the newly created crack surface. Griffith determined the elastic strain energy of the cracked body using the continuum solution of the stress field about an ellipse5 and recognized that the potential energy associated with the cleavage surfaces of the crack was directly proportional to the surface energy, the latter deriving from the cohesive molecular forces of the solid. The Irwin-Orowan extension of Griffith mechanics to include plastic dissipation,6-9 which is known to occur on the mesoscopic length scale (~1–100 μm), provides yet a further example of multiscale thinking in the early community of fracture researchers. In fact, the interaction of length scales is of central importance in most problems of fracture.

The notion of organic molecular materials showing metallic properties, such as electric conductivity or ferromagnetism, started several decades ago as a mere dream of some members of the chemical community. The goal was to create an assembly of organic molecules or macromolecules containing only light elements (C, H, N, O, S, etc.) and yet possessing the electron/hole mobility or spin alignment that is inherent in typical metals or their oxides and different from the isolated molecular materials. Organic molecular conductors initially were developed during the 1960s, but the first examples of organic molecular magnets took several more decades to be discovered, owing to the more subtle and complex structural and electronic aspects of these materials. The flurry of activity in this field can be traced to the widely held belief that even the most sophisticated properties can be rationally designed by a systematic modification of organic molecular structures. This motivation was further fueled by increased synthetic capabilities, especially for obtaining large organic molecules with suitable structures and topologies, and also by the spectacular progress of supramolecular chemistry for materials development witnessed in recent years. Also noteworthy is the pioneering work performed in the 1960s by several physical organic chemists who unraveled different ways of aligning spins within open-shell molecules (i.e., triplet diradicals, carbenes, etc.), working against nature's tendency to align them in an antiparallel manner. Magnetic interactions between unpaired electrons, located on the singly occupied molecular orbitals (SOMOs) of di- and polyradicals, or between the adjacent open-shell molecules in crystals, are a crucial issue in this evolving field. Thus, depending upon the symmetry, degeneracy,and topological characteristics of SOMOs and also on the mode of arrangement of the molecules in a crystal, the resulting interaction can align the neighboring spins parallel or antiparallel (see the introductory article by Miller and Epstein in this issue of MRS Bulletin).

The construction of more and more complex systems starting from elemental molecular units used as building blocks is propelling several disciplines of burgeoning interest, such as supramolecular chemistry, molecular electronics, and molecular magnetism. In the particular context of magnetic molecular materials, an attractive possibility for adding complexity to the material is to use a hybrid approach in which an organic component is combined with an inorganic one. Both purely organic and purely inorganic approaches (see the articles in this issue by Veciana and Iwamura and by Miller, respectively) have been used extensively to obtain molecule-based magnets. The combination of these two kinds of magnetic molecular components has also been successfully explored to design polymeric magnets of different dimensionalities (the metal-radical approach). In this last case, both components play a magnetic role. A step forward in achieving multifunctionality is to design hybrid molecular materials formed by two independent molecular networks, such as anion/cation salts or host/guest solids, whereby each network furnishes distinct physical properties to the solid. This novel class of materials is interesting because it can give rise to the development of materials in which two properties in the same crystal lattice coexist, or materials that exhibit improved properties over those of the individual networks, or to new, unexpected properties due to the mutual interactions between them. One can imagine, for example, the combination of an extended inorganic magnetic layer opening the pathway to cooperative magnetism, with an organic or organometallic molecule that acts as a structural component controlling the interlayer separation. If the molecule inserted between the layers has unpaired electrons, a hybrid compound is produced that combines cooperative magnetism and paramagnetism. Other suitable combinations, such as electronic conductivity and magnetism, or nonlinear optics and magnetism, can also be achieved by wisely choosing the constituent molecules. In this article, we report some relevant examples that illustrate the potential of this hybrid approach in the context of molecule-based magnetic materials.

Progress in silicon technology has been phenomenal since the invention of the transistor some 50 years ago. Device performance has improved by at least a factor of a million in every respect. As the minimum feature size on chips decreases toward 0.1 μm, which should be reached on a mass-production scale in a few years, the device yield is becoming ever more sensitive to defects and impurities. Transition metals, particularly iron, nickel, and copper, are the most common and most detrimental contaminants on a process line, and they can be unintentionally introduced in nearly every process step, including ingot growth, wafer handling, ion implantation, wet-chemical cleaning, high-temperature anneals, or oxidation. To avoid yield losses, the silicon industry has to be very strict with respect to metal-contamination levels on the production line. For instance, for iron, the Semiconductor Industry Association (SIA) Roadmap presently specifies 2.5 ϗ 1010 cm−2 as the maximum tolerable surface concentration, decreasing to 5 ϗ 109 cm−2 by 2004.

Recently, inorganic/inorganic and organic/inorganic heterostructured materials have attracted considerable research interest, due to their unusual physicochemical properties, which cannot be achieved by conventional solid-state reactions. In order to develop new hybrid materials, various synthetic approaches, such as vacuum deposition, Langmuir–Blodgett films, selfassembly, and intercalation techniques, have been explored. Among them, the intercalation reaction technique—that is, the reversible insertion of guest species into the two-dimensional host lattice—is expected to be one of the most effective tools for preparing new layered heterostructures because this process can provide a soft chemical way of hybridizing inorganic/inorganic, organic/inorganic, or biological/inorganic compounds. In fact, the intercalation/deintercalation process allows us to design high-performance materials in a solution at ambient temperature and pressure, just as “soft solution processing” provides a simple and economical route for advanced inorganic materials by means of an environmentally benign, lowenergy method. These unique advantages of the intercalation technique have led to its wide application to diverse fields of the solid-state sciences, namely, secondary (rechargeable) batteries, electrochromic systems, oxidation–reduction catalysts, separating agents, sorbents, and so on. Through these extensive studies, many kinds of low-dimensional compounds have been developed as host materials for the intercalation reaction, including graphite, transition-metal chalcogenides, transitionmetal oxides, aluminosilicates, metal phosphates, metal chalcogenohalides, and so on. Recently, the area of intercalation chemistry has been extended to high-Tc superconducting copper oxides, resulting in remarkable structural anisotropy.