Moisture absorption in model photoresist films of poly(4-hydroxystryene) (PHOSt) and poly(tert-butoxycarboxystyrene) (PBOCSt) supported on silicon wafers was measured by X-ray and neutron reflectivity. The overall thickness change in the films upon moisture exposure was found to be dependent upon the initial film thickness. As the film becomes thinner, the swelling is enhanced. The enhanced swelling in the thin films is due to the attractive nature of the hydrophilic substrate, leading to an accumulation of water at the silicon/polymer interface and subsequently a gradient in concentration from the enhancement at the interface to the bulk concentration. As films become thinner, this interfacial excess dominates the swelling response of the film. This accumulation was confirmed experimentally using neutron reflectivity. The water rich layer extends 25 +/- 10 A into the film with a maximum water concentration of approximately 30 vol %. The excess layer was found to be polymer independent despite the order of magnitude difference in the water solubility in the bulk of the film. To test if the source of the thickness dependent behavior was the enhanced swelling at the interface, a simple, zero adjustable parameter model consisting of a fixed water rich layer at the interface and bulk swelling through the remainder of the film was developed and found to reasonably correspond to the measured thickness dependent swelling.

The continuing drive by the semiconductor industry to fabricate smaller structures using photolithography will soon require dimensional control at length scales comparable to the size of the polymeric molecules in the materials used to pattern them. The current technology, chemically amplified photoresists, uses a complex reaction-diffusion process to delineate patterned areas with high spatial resolution. However, nanometer-level control of this critical process is limited by the lack of direct measurements of the reaction front. We demonstrate the use of x-ray and neutron reflectometry as a general method to measure the spatial evolution of the reaction-diffusion process with nanometer resolution. Measuring compositional profiles, provided by deuterium-labeled reactant groups for neutron scattering contrast, we show that the reaction front within the material is broad rather than sharply defined and the compositional profile is altered during development. Measuring the density profile, we directly correlate the developed film structure with that of the reaction front.

A supercritical drying process was developed to eliminate the capillary forces naturally present during normal drying of photoresist materials. Supercritical carbon dioxide (scCO2), organic solvents and surfactants were used to prevent the collapse of high-aspect-ratio structures fabricated from aqueous-based photoresist. Nondistorted resist lines were patterned with this process with aspect ratios of at least 6.8. Water rinsed resist structures cannot be dried directly with scCO2 due to the low solubility of water in the supercritical phase. In our process we introduced the replacement of the aqueous rinse by n-hexane mediated by a compatible surfactant. The surfactant allowed to incorporate the aqueous phase into micellar microdomains in the organic phase while keeping the interfacial tension at values close to zero. Noncollapsed supercritically dried structures were rewet in n-hexane or water and dried using nitrogen at atmospheric pressure. Under these conditions, the patterns were collapsed as a result of capillary forces acting on the resist walls. The effect of capillary forces on pattern stability were qualitatively compared to the relative surface tension values between n-hexane and water. The advantage of using supercritical CO2 in the drying stage of resists compared to normal drying highlights the importance of eliminating the surface (or interfacial) tension forces created by the rinse fluid, if a reduction of linewidth and spacing between resist lines is pursued, while keeping the aspect ratio constant.

For the patterning of sub-100 nm features, a clear understanding of the origin and control of line edge roughness (LER) is extremely desirable, from a fundamental as well as a manufacturing perspective. With the migration to thin photoresists coupled with bottom antireflective coating (ARC)-hardmask underlayers, LER analysis of the developed resist structures is perhaps an inaccurate representation of the substrate roughness after the etch process, since those underlayers can play a significant role in increasing/decreasing linewidth variations during the image transfer process and hence can impact the device performance. In this article, atomic force microscopy is used to investigate the contribution of the imaging resist sidewall topography to the sidewall roughness of the final etched feature in thin photoresists, ARC, and hardmasks. Resist systems suitable for 248 and 193 nm lithography as well as fluorine-containing resists were processed using N2-H2 or fluorocarbon plasma etch. It is shown that the interaction of different etch chemistries with existing sidewall profiles can result in loss of the original morphological information and creation of new spatial frequency domains that act as physical templates for subsequent image transfer processes. Excessive roughness transfer into the hardmask layer due to insufficient resist thickness or inadequate etch resistance originates from striation propagation from the resist layer into the hardmask layer. In the case of fluorine-containing materials, a decreased etch resistance and reduced initial film thickness values give rise to critical underlayer roughening during plasma etch. Based on the results shown, it is predicted that advanced resist systems for 157 nm lithography and beyond will require the use of ARC layers with built-in hardmask properties in those particular cases in which patterning of deep trenches is needed, in order to maintain LER values within acceptable levels.

The demand to print increasingly smaller microelectronic device features means that the thickness of the polymer films used in the lithographic processes must decrease. The thickness of these films is rapidly approaching the unperturbed dimensions of the polymer, length scales at which confinement deviations and dewetting are a significant concern. We combine specular x-ray reflectivity ͑SXR͒ and incoherent neutron scattering ͑INS͒ to probe the thermal stability and dynamical effects of thin film confinement in poly͑hydroxy styrene͒ ͑PHS͒, a polymer used in a majority of the 248 nm deep UV photoresists. PHS forms stable thin films ͑down to 5 nm͒ that do not dewet over a wide temperature range on Si surfaces ranging from hydrophilic to hydrophobic. The surface energy has a profound influence on the magnitude of the thin film expansion coefficient, especially above the glass transition, in films as thick as 100 nm. Confinement also appears to suppress the mean-square atomic displacements and the level of anharmonicity in the dynamics, primarily above the bulk glass transition.