Optimizing the photochemistry of extreme ultraviolet (EUV) photoresists can lead to faster, more efficient resists needed for implementation of EUV lithography into high volume manufacturing. EUV photoresists must simultaneously meet three requirements: improved resolution, low line edge roughness (LER), and high sensitivity. Common EUV photoresists utilize photoacid generators (PAGs) to improve sensitivity, which is affected by many variables, such as developer choice, developer concentration, PAG quantum yield, etc. Isolating one of these parameters will aid in the optimization of sensitivity. Prior work using alternate methods shows it is possible for resists to generate 5-6 acids per absorbed photon. However, the energy of the weakest bond in a typical PAG molecule is on the order of a few electron volts, it should be possible to reach much higher quantum yields with EUV (92 eV) photons. The photochemistry in EUV lithography is believed to be dominated by the energetic electrons generated from ionization. Investigating the acid generation efficiency for a variety of PAGs and concentrations upon electron exposure may lead to the development of resists with higher quantum yield, improving current EUV photoresist platforms. In this study, the reactions between PAG molecules and electrons were measured by using a mass spectrometer to monitor the levels of small molecules produced by PAG decomposition that outgassed from the film.
In extreme ultraviolet (EUV) lithography, 92 eV photons are used to expose photoresists. Typical EUV resists are organic-based and chemically amplified using photoacid generators (PAGs). Upon exposure, PAGs produce acids which catalyze reactions that result in changes in solubility. In EUV lithography, photo-and secondary electrons (energies of 10-80 eV) play a large role in PAG acid-production. Several mechanisms for electron-PAG interactions (e.g. electron trapping, and hole-initiated chemistry) have been proposed. The aim of this study is to explore another mechanism -internal excitation -in which a bound PAG electron can be excited by receiving energy from another energetic electron, causing a reaction that produces acid. This paper explores the mechanism of internal excitation through the analogous process of electron-induced fluorescence, in which an electron loses energy by transferring that energy to a molecule and that molecule emits a photon rather than decomposing. We will show and quantify electron-induced fluorescence of several fluorophores in polymer films to mimic resist materials, and use this information to refine our proposed mechanism. Relationships between the molecular structure of fluorophores and fluorescent quantum yield may aid in the development of novel PAGs for EUV lithography.
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