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Backbone Degradable Poly(aryl acetal) Photoresist Polymers: Synthesis, Acid Sensitivity, and Extreme Ultraviolet Lithography Performance
摘要： A new class of acid labile poly(aryl acetal) polymers has been developed that can be used in photoresist formulations for next-generation microlithography techniques including extreme ultraviolet (EUV) or electron beam lithography. Example polymers have been synthesized by an optimized Suzuki polycondensation protocol. They are soluble in common photoresist solvents but are insoluble in water or aqueous bases that are used to develop positive photoresists. The structural design includes further elements that are aimed at improving photoresist resolution, stability, and etch resistance. Upon acid exposure, the acetal linkages are cleaved, and the polymers degrade into phenolic terphenyl fragments, which are readily soluble in a photoresist developer. Polymer degradation has been studied by NMR and LC-MS. Lithographic formulations have been developed and tested in line-and-space patterning experiments using EUV photolithography. Optimized resist formulations achieved 22 nm resolution with line width roughness values of 5.7 nm.
关键词： poly(aryl acetal),resolution,EUV lithography,acid degradation,photoresist,line width roughness,Suzuki polycondensation
更新于2025-09-23 15:22:29
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Fundamental understanding of chemical processes in extreme ultraviolet resist materials
摘要： New photoresists are needed to advance extreme ultraviolet (EUV) lithography. The tailored design of efficient photoresists is enabled by a fundamental understanding of EUV induced chemistry. Processes that occur in the resist film after absorption of an EUV photon are discussed, and a new approach to study these processes on a fundamental level is described. The processes of photoabsorption, electron emission, and molecular fragmentation were studied experimentally in the gas-phase on analogs of the monomer units employed in chemically amplified EUV resists. To demonstrate the dependence of the EUV absorption cross section on selective light harvesting substituents, halogenated methylphenols were characterized employing the following techniques. Photoelectron spectroscopy was utilized to investigate kinetic energies and yield of electrons emitted by a molecule. The emission of Auger electrons was detected following photoionization in the case of iodo-methylphenol. Mass-spectrometry was used to deduce the molecular fragmentation pathways following electron emission and atomic relaxation. To gain insight on the interaction of emitted electrons with neutral molecules in a condensed film, the fragmentation pattern of neutral gas-phase molecules, interacting with an electron beam, was studied and observed to be similar to EUV photon fragmentation. Below the ionization threshold, electrons were confirmed to dissociate iodo-methylphenol by resonant electron attachment.
关键词： photoabsorption,molecular fragmentation,electron emission,photoresists,mass-spectrometry,Auger electrons,photoelectron spectroscopy,EUV lithography,resonant electron attachment,halogenated methylphenols
更新于2025-09-23 15:21:01
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Prominent radiative contributions from multiply-excited states in laser-produced tin plasma for nanolithography
摘要： Extreme ultraviolet (EUV) lithography is currently entering high-volume manufacturing to enable the continued miniaturization of semiconductor devices. The required EUV light, at 13.5 nm wavelength, is produced in a hot and dense laser-driven tin plasma. The atomic origins of this light are demonstrably poorly understood. Here we calculate detailed tin opacity spectra using the Los Alamos atomic physics suite ATOMIC and validate these calculations with experimental comparisons. Our key finding is that EUV light largely originates from transitions between multiply-excited states, and not from the singly-excited states decaying to the ground state as is the current paradigm. Moreover, we find that transitions between these multiply-excited states also contribute in the same narrow window around 13.5 nm as those originating from singly-excited states, and this striking property holds over a wide range of charge states. We thus reveal the doubly magic behavior of tin and the origins of the EUV light.
关键词： multiply-excited states,tin plasma,EUV lithography,atomic physics,opacity spectra
更新于2025-09-23 15:21:01
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Tuning photoionization mechanisms of molecular hybrid materials for EUV lithography applications
摘要： The investigation of the photoionization processes of a series of titanium oxo clusters evidenced that doping their organic shell with extended aromatic structures decreases their ionization energy and stabilises the resulting radical cations. Such tunability of their photochemistry arising from ligand exchange gives these hybrid compounds great potential as EUV photoresists.
关键词： photoionization,titanium oxo clusters,EUV lithography,ligand exchange,photoresists
更新于2025-09-23 15:19:57