It has been recently postulated that sub-22 nm photolithography with polymeric photoresists has reached a materials design barrier due to its large molecular mass and distribution. In this argument, the "pixel" size, which is related to the smallest molecular unit, determines the feature fidelity and resolution of the lithographic process. This hypothesis remains unproven, but molecular glass photoresists can provide a test because they can share similar chemical functionality to polymer resists, but with low molecular mass and a monodisperse molecular mass distribution. The low molecular mass leads to the smaller pixel size compared to the radius of gyration of the polymer photoresist. In this work, we compare the deprotection reaction-diffusion kinetics of a common photoacid generator in a polymer and molecular glass resist with similar resist chemistry to elucidate effects of molecular architecture on photoresist performance. We determine the mechanism of reaction, photoacid trapping behavior, and diffusivity by measuring and comparing the reaction kinetics parameters as a function of temperature and exposure dose. These results permit an analysis of the latent image formation which is a crucial factor in resolution and line-edge roughness. Further, knowledge of the reaction-diffusion parameters of each type of resist provides a quantitative approach to predict line-space features, crucial for design for resolution-enhancement features.
Current extreme ultraviolet (EUV) photoresist materials do not yet meet performance requirements on exposure-dose sensitivity, line-width roughness, and resolution. In order to quantify how these trade-offs are related to the materials properties of the resist and processing conditions, advanced measurements and fundamental studies are required that consider EUV-resist specific problems. In this paper, we focus on the correlations between the latent image and developed image in EUV exposed line/space features. The latent images of isolated lines produced by EUV lithography are characterized by atomic force microscopy through the change in topology caused by change in film thickness that occurs upon deprotection. The resulting latent-image deprotection gradient (DGL), based on line cross-sections, and latent-image line-width roughness (LWRL) provide metrics and insight into ways to optimize the lithographic process. The results from a model poly(hydroxystyrene-co-tert-butylacrylate) resist and a model calixresorcinarene molecular glass type resist show the general applicability of the metric before development.
Current extreme ultraviolet (EUV) photoresist materials do not yet meet requirements on exposure-dose sensitivity,
line-width roughness (LWR), and resolution. Fundamental studies are required to quantify the trade-offs in materials
properties and processing steps for EUV photoresist specific problems such as high photoacid generator (PAG) loadings
and the use of very thin films. Furthermore, new processing strategies such as changes in the developer strength and
composition may enable increased resolution. In this work, model photoresists are used to investigate the influence of
photoacid generator loading and developer strength on EUV lithographically printed images. Measurements of line
width roughness and developed line-space patterns were performed and highlight a combined PAG loading and
developer strength dependence that reduce LWR in a non-optimized photoresist.
More demanding requirements are being made of photoresist materials for fabrication of nanostructures as the feature critical dimensions (CD) decrease. For extreme ultraviolet (EUV) resists, control of line width roughness (LWR) and high resist sensitivity are key requirements for their success. The observed LWR and CD values result from many factors in interdependent processing steps. One of these factors is the deprotection interface formed during the post-exposure bake (PEB) step. We use model EUV photoresist polymers to systematically address the influence of exposure-dose on the spatial evolution of the deprotection reaction at a model line edge for fixed PEB time using neutron reflectivity. The bilayer consists of an acid feeder layer containing photoacid generator (PAG) and a model photoresist polymer, poly(hydroxystyrene-co-<i>tert</i>-butylacrylate) with perdeuterated <i>t</i>-butyl protecting group. The deuterium labeling allows the protection profile to be measured with nanometer resolution. The evolution of two length scales that contribute to the compositional profile is discussed.