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Over the past 30 years the world market for semiconductors has grown at an average annual rate of approximately 15%. This growth has been maintained by the industry's unique ability to consistently provide over this time frame higher device performance at lower cost (achieving a 25-30% per-year cost reduction per function). Microlithography is the key technological driving force for this; in large part, the overall rate of progress in microelectronics is controlled by the rate of advances in microlithographic tools, methods, and materials. Today, the photolithographic technologies that have served the microelectronics community since its inception are widely viewed to be nearing their limits of extendibility. If the historical growth rate is to be maintained in the future, new imaging technologies with the capability of forming features with sub-100 nm dimensions must be devised and refined. In this paper we provide an overview of the issues to be considered for patterning in the sub-100 nm regime and describe the imaging technologies which are currently being evaluated for such use.

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.

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We report novel strategies to integrate block copolymer self-assembly with 193 nm water immersion lithography. These strategies employ commercially available positive tone chemically amplified photoresists to spatially encode directing information into precise topographical or chemical prepatterns for the directed self-assembly of block copolymers. Each of these methods exploits the advantageous solubility and thermal properties of polarity-switched positive tone photoresist materials. Precisely registered, sublithographic self-assembled structures are fabricated using these versatile integration schemes which are fully compatible with current optical lithography patterning materials, processes, and tooling.

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Acid diffusion during postexposure baking is viewed to be a limiting factor in the extension of lithography using chemically amplified resists to formation of nanoscale features. Quantification of thermally activated reaction-diffusion kinetics in these materials is therefore an important step in understanding the extendability of this class of resist systems. Previous investigations have addressed this issue, however there is poor agreement among them, and too few data exist in the literature to allow the systematics of the effect of polymer, photoacid generator, added base or other resist components on the diffusion process to be understood. We describe in this article a combined experimental and modeling protocol that is designed to elucidate the chemistry and physics of the reaction-diffusion process. Because it is physically based, not phenomenological, it provides a means of developing a set of predictive, mutually comparable data that will allow new insights to be developed into the nanoscale behavior of chemically amplified resist materials. We apply the protocol to a p-t-butyloxycarbonyloxystyrene/bis͑t-butylphenyl͒iodonium perfluorobutanesulfonate positive-tone photoresist system. The resulting kinetics measurements show that diffusion is environment sensistive and describable with two limiting diffusion coefficients. The Arrhenius parameters for the coefficients in p-t-butyloxycarbonyloxystyrene are D 0 ϭ1.9ϫ10 8 cm 2 /s and E a ϭ36.5 kcal/mol; those for diffusion in the deprotected polymer product p-hydroxystyrene are D 0 ϭ9ϫ10 Ϫ3 cm 2 /s and E a ϭ22.1 kcal/mol. The coefficients are much smaller than previously reported, resulting in a very slow diffusion rate. The model indicates that the considerable image spreading observed during the postexposure bake process is attributable primarily to the efficiency of the catalytic chemistry. Our results suggest that numerical models currently used for prediction of imaging in chemically amplified resists may require refinement in order to be useful for feature sizes below 100 nm and for new classes of resist systems.

An accurate description of the evolution of organic aerosol in the Earth's atmosphere is essential for climate models. However, the complexity of multiphase chemical and physical transformations has been challenging to describe at the level required to predict aerosol lifetimes and changes in chemical composition. In this work a model is presented that reproduces experimental data for the early stages of oxidative aging of squalane aerosol by hydroxyl radical (OH), a process governed by reactive uptake of gas phase species onto the particle surface. Simulations coupling free radical reactions and Fickian diffusion are used to elucidate how the measured uptake coefficient reflects the elementary steps of sticking of OH to the aerosol as a result of a gas-surface collision, followed by very rapid abstraction of hydrogen and subsequent free radical reactions. It is found that the uptake coefficient is not equivalent to a sticking coefficient or an accommodation coefficient: it is an intrinsically emergent process that depends upon particle size, viscosity, and OH concentration. An expression is derived to examine how these factors control reactive uptake over a broad range of atmospheric and laboratory conditions, and is shown to be consistent with simulation results. Well-mixed, liquid behavior is found to depend on the reaction conditions in addition to the nature of the organic species in the aerosol particle.