Per- and polyfluoroalkyl substances (PFAS) have been identified by various regulatory bodies as substances of concern. In line with the objective of safer and sustainable by design, a comprehensive program has been initiated to address these concerns. Part of this program includes the development of non -fluorinated photoacid generators (PAGs) without introducing new chemicals with unintended consequences. Using computational chemistry and synthetic organic chemistry , several scaffolds amenable to PAG library design have been realized. These novel PAGs offer facile tunability and advantages in many critical design parameters such as pKa, diffusion, absorption, shelf-life stability, and scalability. These early generation non-fluorinated PAGs show competitive and similar lithographic performance compared to fluorinated PAGs in i-line, krypton fluoride (KrF) laser, argon fluoride (ArF) laser and extreme ultraviolet (EUV) lithography.
Conventional chemically amplified resists for extreme ultraviolet (EUV) lithography are comprised of three fundamental components: a photoreactive, acid-generating species (PAG), an acid reactive polymer for solubility switching, and a basic component for acid diffusion control. The PAG component is typically derived from an organic onium salt, wherein the cation’s capacity to capture secondary electrons generated upon EUV irradiation of the resist underscores their reactivity in lithographic applications. Thus, effective rational design of these materials is critical for controlling both sensitivity of the resist and feature regularity. Herein, we describe a robust method for in silico prediction of fundamental properties of onium cations including electron affinity, LUMO energy, and relative charge distribution. We correlate these theoretical values to experimental measurements and further to the influence of PAG cation properties on resist performance under EUV exposure. In addition to the reactive properties of these cations, we analyze these lithographic data in the context of the physicochemical properties of the cations, particularly polarity. In all, the results of this study suggest that while electron affinity of the PAG cation may drive reactivity in response to EUV exposure, multiple factors must be considered in the design of cations for optimal overall resist performance.
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