The lithography community has studied EUV photoresists for nearly thirty years. Yet, some of the most basic details of the interaction of EUV photons with photoresists remain poorly understood. In a typical photochemical reaction using long-wavelength light ( = 157-1000 nm), photons create excited states in photoactive compounds, thereby creating known quantities of intermediates and photoproducts at measurable rates.The photochemical reactions occurring during EUV exposure are much more complex and, as yet, not fully explored. The 92 eV EUV photons ionize molecules in the resist, creating holes and free electrons, however, the numbers of these electrons created, their reaction mechanisms, lifetimes and reaction cross-sections are not well known. Here, we will discuss experimental results and provide insight into these poorly understood aspects of EUV exposure mechanisms.

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EUV photons expose photoresists by complex interactions starting with photoionization that create primary electrons (~80 eV), followed by ionization steps that create secondary electrons (10-60 eV).Ultimately, these lower energy electrons interact with specific molecules in the resist that cause the chemical reactions which are responsible for changes in solubility. The mechanisms by which these electrons interact with resist components are key to optimizing the performance of EUV resists. An electron exposure chamber was built to probe the behavior of electrons within photoresists. Upon exposure and development of a photoresist to an electron gun, ellipsometry was used to identify the dependence of electron penetration depth and number of reactions on dose and energy. Additionally, our group has updated a robust software that uses first-principles based Monte Carlo model called "LESiS", to track secondary electron production, penetration depth, and reaction mechanisms within materialsdefined environments. LESiS was used to model the thickness loss experiments to validate its performance with respect to simulated electron penetration depths to inform future modeling work.

Optimizing the photochemistry of extreme ultraviolet (EUV) photoresists should provide faster, more efficient resists which would lead to greater throughput in manufacturing. The fundamental reaction mechanisms in EUV resists are believed to be due to interactions with energetic electrons liberated by ionization. Identifying the likelihood (or cross section) of how these photoelectrons interact with resist components is critical to optimizing the performance of EUV resists. Chemically amplified resists utilize photoacid generators (PAGs) to improve sensitivity; measuring the cross section of electron induced decomposition of different PAGs will provide insight into developing new resist materials.To study the interactions of photoelectrons generated by EUV absorption, photoresists were exposed to electron beams at energies between 80 and 250 eV. The reactions between PAG molecules and electrons were measured using a mass spectrometer to monitor the levels of small molecules produced by PAG decomposition that outgassed from the film. Comparing the cross sections of a variety of PAG molecules can provide insight into the relationship between chemical structure and reactivity to the electrons in their environments. This research is a part of a larger SEMATECH research program to understand the fundamentals of resist exposures to help in the development of new, better performing EUV resists.