This issue of the MRS Bulletin provides an up-to-date look at ongoing research activities within the field of functionally gradient materials (FGM). The term FGM, now widely used by the materials community, originated in Japan in the late 1980s as a description for a class of engineering materials exhibiting spatially inhomogeneous microstructures and properties. Of course, gradient materials are not something new. It must be recognized that humans have extensively utilized materials containing microstructural gradients (either those found in nature or those created through processing) since the earliest days of craftsmanship and engineering construction. Indeed, there are examples of graded materials developed long ago, such as case-hardened steel, which are still in common use today. Contemporary examples of these materials serve in technologically significant applications, as, for example, in thermal-barrier coatings for gas turbines. Nevertheless, what is new and exciting about FGMs is the realization that gradients can be designed at the microstructural level to tailor a material for the specific functional and performance requirements of an intended application. In addition, recent advances in processing are opening the possibility for the extension of the gradient materials concept to new materials systems and engineering problems.

The recent resurgence of interest in gradient materials has been driven by the need for improved materials, capable of meeting the demanding performance requirements established by emerging technologies such as the aerospace plane, ceramic engines, and nuclear fusion.

The current interest in the wide bandgap II-VI semiconductor compounds can be traced back to the initial developments in semiconductor optoelectronic device physics that occurred in the early 1960s. The II-VI semiconductors were the object of intense research in both industrial and university laboratories for many years. The motivation for their exploration was the expectation that, possessing direct bandgaps from infrared to ultraviolet, the wide bandgap II-VI compound semiconductors could be the basis for a variety of efficient light-emitting devices spanning the entire range of the visible spectrum.

During the past thirty years or so, development of the narrower gap III-V compound semiconductors, such as gallium arsenide and related III-V alloys, has progressed quite rapidly. A striking example of the current maturity reached by the III-V semiconductor materials is the infrared semiconductor laser that provides the optical source for fiber communication links and compact-disk players. Despite the fact that the direct bandgap II-VI semiconductors offered the most promise for realizing diode lasers and efficient light-emitting-diode (LED) displays over the green and blue portions of the visible spectrum, major obstacles soon emerged with these materials, broadly defined in terms of the structural and electronic quality of the material. As a result of these persistent problems, by the late 1970s the II-VI semiconductors were largely relegated to academic research among a small community of workers, primarily in university research laboratories.

It is anticipated that a new generation of advanced electronic and optical devices will involve the synthesis of diverse materials in single or multielement thin-film form, or in layered heterostructures. These devices will most likely involve diverse materials such as high-temperature superconductors, ferroelectric, electrooptic, and optical materials; diamond; nitrides; semiconductors; insulators; and metals in the form of ultra-thin layers with sharp interfaces in which the layer thickness may reach atomic dimensions. Therefore, it becomes increasingly important to be able to monitor the deposition process in situ and in real time, particularly for complex multicomponent oxides or nitrides, in which the production of the desired phase is a highly sensitive function of the growth conditions, often requiring relatively high-pressure oxygen or nitrogen environments up to several hundred mTorr, and in some cases, several Torr. Consequently, the growth environment for many of these materials is incompatible with conventional surface-analytic methods, which are typically restricted to high-or ultrahigh-vacuum conditions. New deposition and analytical methods, or adaptation of those already established, will be required.

Since thin-film growth occurs at the surface, the analytical methods should be highly surface-specific, although sub-surface diffusion and chemical processes also affect film properties. Sampling depth and ambient-gas compatibility are key factors which must be considered when choosing in situ probes of thin-film growth phenomena. In most cases, the sampling depth depends on the mean range of the exit species (ion, photon, or electron) in the sample.

A few years ago, I surprised my wife by asking for a guitar for Christmas. Our budget was limited in those days, so I started at the low-cost end and remember being disappointed with the tone quality of the guitar we purchased. Even with my poorly trained ear, I could tell the difference between a $50 guitar and a $100 instrument. The jump from $100 to $200 was also easily detectable. I could even make out the difference in tone quality between a $200 and a $500 guitar. One hand-crafted instrument with a $1000 price tag had a lovely tone. However, the limitations of my ear made it difficult to detect significant improvement in tone quality beyond that stage. At any rate, I realized that an instrument manufacturer would clearly not waste precious select woods on a “cigar-box” instrument. Since then, while trying to unlock the secrets of fine tone quality, the importance of materials in crafting fine musical instruments has become apparent during my investigations of various musical instruments in the laboratory.

We know from experience that ceramic materials are brittle and easily broken. This is one reason why ceramics have not been used as engineering materials. Fracture is the result of crack growth through the microstructure. It was Griffith who proposed that ceramics have intrinsic cracks which grow under applied stress. The concentration of the applied stress at the crack tip decreases the strength to a level of about 1% or less of the theoretical strength. If the crack starts to grow, strength decreases so sharply that a catastrophic fracture occurs.

In spite of the brittle nature of ceramics, their application as engineering materials was proposed in the 1960s because ceramic materials made of silicon nitride or carbide have higher strength at high temperatures than metals and oxide ceramics. Non-oxide ceramics have lower thermal-expansion-coefficients than oxides, resulting in better thermal shock resistance, which is one of the most important requirements for engineering ceramics.

Low-energy (5–15 keV) ion scattering spectroscopy (ISS) and direct recoil spectroscopy (DRS) are well-established analysis techniques that have been used for several years to characterize surfaces of materials. ISS utilizes a beam of ions in the 1–15 keV range which are scattered by a surface atom at an angle θ1 relative to the direction of incidence. In this energy range, the collisions are elastic and are described by classical two-body collision kinematics. The kinetic energy E1 of the scattered primary ion is given by

where E0 is the primary ion kinetic energy and α = M2/M1. Note that Equation 1 has real values only if M2 > M1, and ISS is not able to detect surface atoms which are lighter than the primary ion beam.

The kinetic energy of the backscattered primary particle may be measured either by using an electrostatic energy analyzer (ESA) or by pulsing the beam and using a time-of-flight (TOF) detection scheme. The ESA only detects the ion fraction (typically 10 2−10−4) of the scattered primary beam and transmits only a narrow portion of the energy distribution of these ions, whereas the TOF detection scheme simultaneously detects the full energy range of both ions and neutrals. Consequently, the required beam dose for TOF detection is 3–4 orders of magnitude smaller than that required by the ESA. A typical analysis beam dose for TOF detection is ∼1011−1012 ions/cm2, removing or displacing one part in 103−104 of the near-surface atoms and making the TOF scheme essentially nondestructive.

The six articles comprising this issue of the MRS Bulletin deal with ultrathin films formed from organic molecules by a variety of techniques. In each case the component molecule forming the film is a relatively simple, single molecule which may or may not have important self-organizing properties that facilitate the formation of a film or related ordered molecular assembly. Taken together, the series of articles offer a concise look at the remarkable diversity and complexity of molecular thin films in terms of preparation and their properties.

This issue of the MRS Bulletin focuses on current interconnect metallurgies practiced in the manufacturing of integrated circuits (ICs). The issue should serve as a reference for researchers, scientists, engineers, and those who are not familiar with the IC arena.

Al-metallization requires special attention due to its wide usage in logic and memory circuits. Logic requirements drive technology toward improved circuit performance while memory improvements require high device and wiring densities. As the dynamic random access memory (DRAM) evolves from 64 Mbits to 256 Mbits, ultralarge-scale integrated (ULSI) wiring will decrease to below sub-0.3 μm in dimensions. Such circuits require robust, reliable back end of the line (BEOL) technology that meets high-performance, low-cost, stringent electromigration requirements. We feel that several of these emerging interconnect fabrication techniques have reached a sufficient level of maturity to warrant a reasonable exposition. We will concentrate on metallization systems in this issue, leaving a discussion of dielectrics for the future, due to space limitations.

The semiconductor industry has relied on aluminum technology since the 1960s because it is a well-established, low-cost technology. Early improvements in the electromigration resistance of Al lines by the addition of Cu impurities after 1971 helped this metallurgy to endure further feature size reductions, without degradation of reliability. However, the relentless reduction in via and line size once again may bring into question the limitation of Al reliability. As a result, work on alternate low-resistivity and high-electromigration-resistant metals like Cu is continuing in parallel.

The development of early knowledge about crystals of flexible macromolecules (usually called simply “polymers”) and their defects was reviewed in Reference. Much of the initial research followed the information gathered on crystals of small molecules, metals, salts, and ceramics. Very quickly, however, the special nature of polymers became obvious. It was suggested some time ago to describe semicrystalline polymers with the help of zero- to three-dimensional defects. The present status of this scheme is summarized in this article.

Crystallized polymers are rarely in equilibrium. Therefore, the phase rule, which permits the presence of only one phase with two degrees of freedom (temperature and pressure) for a onecomponent material, does not apply. This nonequilibrium state is kept metastable by restrictions caused by the molecules that cross the interfaces (two-dimensional defects). The strain propagated to the noncrystalline areas produces three-dimensional defects of limited mobility. The overall structure can also be described as being microphase-separated.

Often the sizes of the different phases can be as small as the nanometer scale. One-dimensional or line defects, also called dislocations, became obvious in polymers with the first observations of solution-grown crystals of polyethylene that showed frequent growth spirals. Because of the molecular chain struc ture, many of these dislocations are sessile (immobile) and cannot participate for example, in deformation mecha nisms. Until recently, zero-dimensiona or point defects were understood largely because of molecular-mechanics calculations.

Space planes require high-performance heat-resistant materials which can withstand ultrahigh temperatures and extremely large temperature gradients. To meet these needs, functionally gradient materials (FGMs) were proposed about 10 years ago in Japan.

Figure 1 shows a conceptual diagram of functionally gradient materials, taking into account the relaxation of thermal stress. For the surface that contacts high-temperature gases at thousands of degrees, ceramics are used to provide adequate heat resistance. For the surface that provides cooling, metallic materials are used to furnish the necessary thermal conductivity and mechanical strength. In addition, the composition of these materials is formulated to provide optimum distribution of composition, structure, and porosity to effectively relax thermal stress.

Since fiscal 1987, an R&D project entitled “Research on Fundamental Techniques to Develop Functionally Gradient Materials for Relaxation of Thermal Stress,” which aimed to develop ultra heat-resistant materials, had been carried out with special coordination funds from the Science and Technology Agency. The five-year project had two phases; Phase I was carried out from 1987 to 1989, and Phase II from 1990 to 1991.