Solid-phase chemistry, photolabile protecting groups, and photolithography have been combined to achieve light-directed, spatially addressable parallel chemical synthesis to yield a highly diverse set of chemical products. Binary masking, one of many possible combinatorial synthesis strategies, yields 2n compounds in n chemical steps. An array of 1024 peptides was synthesized in ten steps, and its interaction with a monoclonal antibody was assayed by epifluorescence microscopy. High-density arrays formed by light-directed synthesis are potentially rich sources of chemical diversity for discovering new ligands that bind to biological receptors and for elucidating principles governing molecular interactions. The generality of this approach is illustrated by the light-directed synthesis of a dinucleotide. Spatially directed synthesis of complex compounds could also be used for microfabrication of devices.

https://science.sciencemag.org/content/sci/251/4995/767.full.pdf

Light-directed, spatially addressable parallel chemical synthesis.

Single-crystal silicon is being increasingly employed in a variety of new commercial products not because of its well-established electronic properties, but rather because of its excellent mechanical properties. In addition, recent trends in the engineering literature indicate a growing interest in the use of silicon as a mechanical material with the ultimate goal of developing a broad range of inexpensive, batch-fabricated, high-performance sensors and transducers which are easily interfaced with the rapidly proliferating microprocessor. This review describes the advantages of employing silicon as a mechanical material, the relevant mechanical characteristics of silicon, and the processing techniques which are specific to micromechanical structures. Finally, the potentials of this new technology are illustrated by numerous detailed examples from the literature. It is clear that silicon will continue to be aggressively exploited in a wide variety of mechanical applications complementary to its traditional role as an electronic material. Furthermore, these multidisciplinary uses of silicon will significantly alter the way we think about all types of miniature mechanical devices and components.

Silicon as a mechanical material

Molecular self-assembly is the spontaneous association of molecules under equilibrium conditions into stable, structurally well-defined aggregates joined by noncovalent bonds. Molecular self-assembly is ubiquitous in biological systems and underlies the formation of a wide variety of complex biological structures. Understanding self-assembly and the associated noncovalent interactions that connect complementary interacting molecular surfaces in biological aggregates is a central concern in structural biochemistry. Self-assembly is also emerging as a new strategy in chemical synthesis, with the potential of generating nonbiological structures with dimensions of 1 to 10(2) nanometers (with molecular weights of 10(4) to 10(10) daltons). Structures in the upper part of this range of sizes are presently inaccessible through chemical synthesis, and the ability to prepare them would open a route to structures comparable in size (and perhaps complementary in function) to those that can be prepared by microlithography and other techniques of microfabrication.

Molecular self-assembly and nanochemistry: A chemical strategy for the synthesis of nanostructures

A high-throughput lithographic method with 25-nanometer resolution and smooth vertical sidewalls is proposed and demonstrated. The technique uses compression molding to create a thickness contrast pattern in a thin resist film carried on a substrate, followed by anisotropic etching to transfer the pattern through the entire resist thickness. Metal patterns with a feature size of 25 nanometers and a period of 70 nanometers were fabricated with the use of resist templates created by imprint lithography in combination with a lift-off process. With further development, imprint lithography should allow fabrication of sub-10-nanometer structures and may become a commercially viable technique for manufacturing integrated circuits and other nanodevices.

https://science.sciencemag.org/content/sci/272/5258/85.full.pdf

Imprint Lithography with 25-Nanometer Resolution

The problem of achieving compact, high-performance forced liquid cooling of planar integrated circuits has been investigated. The convective heat-transfer coefficient h between the substrate and the coolant was found to be the primary impediment to achieving low thermal resistance. For laminar flow in confined channels, h scales inversely with channel width, making microscopic channels desirable. The coolant viscosity determines the minimum practical channel width. The use of high-aspect ratio channels to increase surface area will, to an extent, further reduce thermal resistance. Based on these considerations, a new, very compact, water-cooled integral heat sink for silicon integrated circuits has been designed and tested. At a power density of 790 W/cm2, a maximum substrate temperature rise of 71°C above the input water temperature was measured, in good agreement with theory. By allowing such high power densities, the heat sink may greatly enhance the feasibility of ultrahigh-speed VLSI circuits.

High-performance heat sinking for VLSI

The molecular organization in ultrathin polymer films (thicknesses less than 1000 angstroms) and thin polymer films (thicknesses between 1000 and 10,000 angstroms) may differ substantially from that of bulk polymers, which can lead to important differences in resulting thermophysical properties. Such constrained geometry films have been fabricated from amorphous poly(3-methyl-4-hydroxy styrene) (PMHS) and semicrystalline poly(di-n-hexyl silane) (PD6S) by means of spin-casting. The residual solvent content is substantially greater in ultrathin PMHS films, which suggests a higher glass transition temperature that results from a stronger hydrogen-bonded network as compared with that in thicker films. Crystallization of PD6S is substantially hindered in ultrathin films, in which a critical thickness of 150 angstroms is needed for crystalline morphology to exist and in which the rate of crystallization is initially slow but increases rapidly as the film approaches 500 angstroms in thickness.

https://science.sciencemag.org/content/sci/273/5277/912.full.pdf

Structure in Thin and Ultrathin Spin-Cast Polymer Films

For all technologies, from flint arrowheads to DNA microarrays, patterning the functional material is crucial. For semiconductor integrated circuits (ICs), it is even more critical than for most technologies because enormous benefits accrue to going smaller, notably higher speed and much less energy consumed per computing function. The consensus is that ICs will continue to be manufactured until at least the ldquo22 nm noderdquo (the linewidth of an equal line-space pattern). Most patterning of ICs takes place on the wafer in two steps: (a) lithography, the patterning of a resist film on top of the functional material; and (b) transferring the resist pattern into the functional material, usually by etching. Here we concentrate on lithography. Optics has continued to be the chosen lithographic route despite its continually forecast demise. A combination of 193-nm radiation, immersion optics, and computer-intensive resolution enhancement technology will probably be used for the 45- and 32-nm nodes. Optical lithography usually requires that we first make a mask and then project the mask pattern onto a resist-coated wafer. Making a qualified mask, although originally dismissed as a ldquosupport technology,rdquo now represents a significant fraction of the total cost of patterning an IC largely because of the measures needed to push resolution so far beyond the normal limit of optical resolution. Thus, although optics has demonstrated features well below 22 nm, it is not clear that optics will be the most economical in this range; nanometer-scale mechanical printing is a strong contender, extreme ultraviolet is still the official front runner, and electron beam lithography, which has demonstrated minimum features less than 10 nm wide, continues to be developed both for mask making and for directly writing on the wafer (also known as ldquomaskless lithographyrdquo). Going from laboratory demonstration to manufacturing technology is enormously expensive ( $1 billion) and for good reason. Just in terms of data rate (mask pattern to resist pattern), today's exposure tools achieve about 10 Tb/s at an allowable error rate of about 1/h; this data rate will double with each generation. In addition, the edge placement precision required will soon be 30 parts per billion. There are so many opportunities for unacceptable performance that making the right decision goes far beyond understanding the underlying physical principles. But the benefits of continuing to be able to manufacture electronics at the 22-nm node and beyond appear to justify the investment, and there is no shortage of ideas on how to accomplish this.

Lithography and Other Patterning Techniques for Future Electronics

The ability to control structural dimensions below 5 nm is essential for a systematic study of the optical and electrical properties of Si nanostructures. A combination of electron beam lithography, NF3 reactive ion etching, and dry thermal oxidation has been successfully implemented to yield 2‐nm‐wide Si nanowires with aspect ratio of more than 100 to 1. With a sideview transmission electron microscopy technique, the oxidation progression of Si nanowires was characterized over a range of temperature from 800 to 1200 °C. A previously reported self‐limiting oxidation phenomenon was found to occur only for oxidation temperatures below 950 °C. A preliminary model suggests that increase in the activation energy of oxidant diffusivity in a highly stressed oxide may be the main mechanism for slowing down the oxidation rate in the self‐limiting regime.

Self‐limiting oxidation for fabricating sub‐5 nm silicon nanowires

Achieving tolerances of the order of 1 nm for sub‐10 nm structures is both challenging and necessary for controlled experiments on such structures. Here the use of a self‐limiting oxidation reaction to yield silicon (Si) wires of less than 10 nm diam with a tolerance of ±1 nm over 0.5 μm. The final self‐limiting diameters were found to be controlled by oxidation temperature. For 30 nm initial Si column diameters, the asymptotic diameters were found to be 11 and 6 nm for dry oxidation at 800 and 850 °C, respectively. The mechanism of the self‐limiting reaction is not yet fully understood but the tiny radius of curvature is obviously a factor. In addition, there appears to be an anomalous loss of Si; this may be due to sublimation of SiO.

Roger Fabian W. Pease

Papers

High-performance heat sinking for VLSI

Structure in Thin and Ultrathin Spin-Cast Polymer Films

Lithography and Other Patterning Techniques for Future Electronics

Self‐limiting oxidation for fabricating sub‐5 nm silicon nanowires

Self‐limiting oxidation of Si nanowires