As extreme ultraviolet lithography advances towards smaller feature sizes, controlling stochastics in resist materials is critical for maximizing performance. Most polymer photoresists have inherent chain-to-chain variations in molecular weight, composition, and sequence due to synthetic limitations. This, along with heterogeneities from the distribution of chemical additives, contributes to unacceptable levels of patterning defects. Polypeptoids are unique as a class of bio-inspired polymers that can be synthesized with perfectly defined sequence, composition, and molecular weight, yielding a uniform material. In this study, we present polypeptoid-based chemically amplified resists for EUVL and demonstrate the effects of sequence and functionality on patternability, as evaluated under DUV and electron-beam lithography.
One of the major challenges to lithography today is minimizing the consequences of stochastics, that is, the effect of statistical differences in photoresist structure and the distribution of additives, such as photo active compounds, in the photoresist. Most polymer photoresists due to their method of production will have large differences between polymer chains in molecular weight, composition, and sequence due to the nature of polymer synthesis. However, there exist methods of polymer formation that make uniform composition polymers such a homopolymers made using living polymerization. We discuss scissionable poly(phthalaldehyde)s as one example of a low stochastics photoresist. Using another method originally developed for the biological community we make polymers in which molecular weight, composition and sequence are identical in all polymer chains produced. Here we thus describe studies of polypeptoids, synthetic analogs of peptides, which have no chirality and in which the substituents are placed on the backbone nitrogen. The peptoids are produced as chemically amplified photoresists and are intended for study as EUV materials. To produce a CAR with aqueous base development using this hydrophilic backbone we have successfully learned how to make a more hydrophobic patterning system with Tg >100 °C. With our ability to control of sequence we have started to explore the effect that monomer placement has on lithographic performance and found that indeed sequence does play an important role. Sequences of solubility switch groups, adhesive, etch resistant and hydrophobic groups have been studied. Using e-beam lithography we have recently demonstrated sub-30 nm resolution.
Polymeric photoresists are limited in their sensitivity, resolution, and line-edge roughness due in large part to their molar mass distribution and variation in composition of single polymer chains. While most synthetic polymers, have monomer units distributed randomly along the polymer chain, polypeptoids are, however, characterized by low stochastics i.e., identical chains with extremely low chemical, structural, and molar mass variability with a widely adjustable length and composition. In this work we describe the synthesis of 10 repeat-unit polypeptoids designed as a photopolymer and demonstrate their potential as CARs evaluated by electron-beam, DUV and extreme-UV lithography, obtaining well defined line-space patterns of less than 30 nm half-pitch.
Achieving commercial viability for extreme ultraviolet lithography (EUVL) demands a homogeneous polymeric materials platform for fine pattern microelectronics. However, current polymer systems possess a heterogeneity length scale larger than the 13.5 nm range desired for EUVL leading to line-edge roughness close to the size of a single polymer molecule in less than a nanometer. In this report, we develop polypeptoids in a high-yielding polymer synthesis with low stochastics and enable a high sensitivity environmentally stable chemically amplified photoresist (ESCAP) for large-scale manufacturing using DUV/EUVL. Polypeptoids are bio-inspired, sequence-defined polymers that minimize molecular size and compositional and sequence statistics. Functional monomers, such as photosensitizers, solubility switches, etchresistant units, and Tg modulators, have been programmed to be precisely distributed into the polymer structure using a robotic synthesizer. Positive-tone polypeptoids ESCAPs can thus be tuned via chemical and sequence design. In particular, the arrangement of solubility-switch functional groups relative to adhesion-promoting groups influences synthetic yield and lithographic patternability. Other functional groups, such as phenolic and aromatic, promote a resist’s physical properties, film quality, adhesive characteristics, and pattern development by tuning the polymer’s polarity, depending on the sequence within the polymer chain. This work bridges the materials design of bioinspired polymers, high throughput manufacturing techniques, and nanolithography enabling polymer uses with high processing fidelity for nanotechnologies.
We identify and describe categories of fluorochemicals used to produce advanced semiconductors within the lithographic patterning manufacturing processes. Topics discussed include the per- and polyfluoroalkyl substance (PFAS) materials used and their necessary attributes for successful semiconductor manufacturing, consisting of photoacid generators, fluorinated polyimides, poly(benzoxazole)s, antireflection coatings, topcoats, and embedded barrier layers, fluorinated surfactants, and materials for nanoimprint lithography. In particular, an explanation is given of the particular function that these PFAS materials contribute. It is noted that in almost all cases fluorine-free alternatives are very unlikely to provide the essential properties present in PFAS systems. Nonfluorinated alternative compounds are discussed where available. Finally, a summary table is provided listing the families of materials discussed, the critical purpose served, what the PFAS compound provides, and the prospects for alternatives.
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