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Journal Reference
ACS Appl Mater Interfaces. 2015 Aug 5;7(30):16348-56.
Chagas GR1, Satyanarayana VS2, Kessler F3, Belmonte GK1, Gonsalves KE2, Weibel DE1.
[expand title=”Show Affiliations”]- Department of Chemical Physics, Chemical Institute, UFRGS, Porto Alegre, Postal Code 91501-970, Rio Grande do Sul, Brazil.
- School of Basic Sciences, Indian Institute of Technology Mandi, Mandi-175001, Himachal Pradesh, India.
- School of Chemistry and Food, Federal University of Rio Grande, Avenida Itália km 8, Postal Code 96.201-900, Rio Grande, Rio Grande do Sul, Brazil
Abstract
Two key concepts in extreme ultraviolet lithography (EUVL) are important for it to be a candidate for the mass production of future integrated circuits: the polymer formulation and the photofragmentation process. In this work, both concepts were carefully studied. The design and synthesis of radiation-sensitive organic polymeric materials based on the inclusion of a radiation-sensitive tetrahydrothiophenium functional group are outlined. A 1-(4-methacryloyoxy)naphthalene-1-yl)tetrahydro-1H-thiophenium trifluoromethanesulfonate (MANTMS) monomer containing the tetrahydrothiophenium group undergoes homo- and copolymerizations using free-radical polymerization with a 2,2′-azobis(isobutyronitrile) initiator. The surface photodegradation and oxidation of these novel polymeric materials were investigated using highly monochromatized soft X-rays from synchrotron radiation at the carbon K-edge excitation region. An efficient functionalization was observed when the excitation energy was tuned to C 1s → π*C═C. A high rate of defluorination and a loss of sulfonated groups as a result of an increase in the irradiation time for the MANTMS homopolymer thin films were mainly observed under the π*C═C excitation of the naphthyl functional groups. On the contrary, excitation similar to C 1s → π*C═O or C 1s → σ*C-F did not produce important degradation, showing a highly selective process of bond breaking. Additionally, the presence of methyl methacrylate copolymer in the original MANTMS yielded a much higher degree of stability against inner-shell radiation damage. Our results highlight the importance of choosing the right polymer formulation and excitation energy to produce a sensitive material for EUVL without using the concept of chemical amplification.
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About the Authors
Gabriela Ramos Chagas holds a degree in Chemistry and a master’s degree in Materials Science from the Federal University of Rio Grande do Sul (UFRGS). Now she is working towards a PhD in Chemistry at the University of Nice Sophia Antipolis, France. She has experience in polymer and physical chemistry of surfaces.”
Dr. V. S. V. Satyanarayana received his PhD in the field of “Synthetic Organic Chemistry” from VIT University, Vellore, India in 2011. He has good hands-on experience in Organic Synthesis and Materials synthesis. He worked for a project entitled “Design and synthesis of non-chemically amplified resists for EUVL at sub-20 nm half pitch” funded by INTEL Crop, USA as a Research Scientist (PDF) at Indian Institute of Technology Mandi (IIT Mandi), Himachal Pradesh. His present research interest includes Organic synthesis, Hybrid materials and Medicinal chemistry.
Felipe Kessler holds a degree in chemistry from Regional Integrated University of High Uruguay and Missions, a master’s degree in chemistry from the Federal University of Rio Grande do Sul (UFRGS), and a PhD in chemistry from UFRGS. He carried out a one-year doctoral period in the University of Manchester, United Kingdom, and postdoctoral period at Mackenzie Presbyterian University, Brazil. Currently, he is an adjunct professor at School of Chemistry and Food in the Federal University of Rio Grande (FURG), Brazil. He has experience in the fields of chemistry, physical chemistry of surfaces, and photochemistry. His present research interests includes photochemistry, materials science and surface science.
Guilherme Kretzmann Belmonte holds a degree in Chemistry and a master’s degree in Materials Science from the Federal University of Rio Grande do Sul (UFRGS). Now he is working towards a PhD in Material Science at the UFRGS. He has experience in surface characterization and modification of polymeric materials, with particular interest in the use of biopolymers as biomaterials.
Kenneth E. Gonsalves is a visiting Distinguished Professor at IIT Mandi. He is the PI of an Intel contract for the development of resists for the 15 nm node and beyond following the ITRS 2013 roadmap. Through his initiatives and in collaboration with his colleagues at UFRGS Brazil, seminal basic research in the photodynamics of novel resist architectures developed under his Intellectual property portfolio have been obtained. Prof. Gonsalves was the Celanese Acetate Distinguished Professor at the University of North Carolina at Charlotte (UNCC) from 2001-2014. He was also a faculty member of the Center for Optoelectronics and Optical Communications at UNCC. His research has focused on materials synthesis: organic Polymer Chemistry, organometallic polymers, polymer and molecular precursors for ceramics and intermetallics; nanostructured materials/composites; biomaterials; novel resists for nanolithography; nanofabrication and nanopatterning of biomaterials; organic and hybrid nanomaterials for energy harvesting, nanoscale drug delivery devices
Daniel E. Weibel studied chemistry (diploma) at the Nacional University of Córdoba (UNC) and obtained a PhD in physical chemistry from UNC. He spent postdoctoral periods at the University of Gakushuin, Japan, Munster University, Germany, and Manchester University, United Kingdom. He is currently associate professor at UFGRS, Brazil and Head of the Material Science graduation Program, UFRGS. He has experience in the field of physical-chemistry and, in particular, in surface science acting on the following topics: TOF-SIMS, X-ray photoelectron spectroscopy, AES, NEXAFS, synchrotron radiation, polymers, and photochemistry.
