The Outstanding Achievement Award
The Photopolymer Science and Technology Award No.191100
Robert D. Allen
IBM Research, Almaden
The Photopolymer Science and Technology Award No. 191100, the Outstanding Achievement Award 2019, was presented to Dr. Robert D. Allen (IBM Research, Almaden) for his outstanding achievements in photopolymer science and technology, “Pioneering semiconductor patterning technology using water immersion ArF lithography with the originally designed photoresist”.
Robert (Bob) Allen is Senior Department Manager of the Materials Innovation and Discovery Department at the IBM Almaden Research Center in San Jose, California, USA. He is Polymer Division Fellow of ACS (2015), was elected to the United States National Academy of Engineering (2012), SPIE Fellow (2010), currently serving on Virginia Tech Macromolecular Innovation Institute Industrial Advisory Board and Virginia Tech Chemistry Department External Advisory Board, and serves on the Program Committee Member of Conference of Photopolymer Science and Technology. He received the Virginia Tech Alumni Achievement Award (2017), Industrial Polymer Science Award from the American Chemical Society (2014), an Outstanding Technical Achievement Award from IBM Research for Photoresist Materials Innovations Impact on the Implementation of 193nm Lithography in IBM Manufacturing (2002) and an IBM Corporate Award for his Leadership in 193nm Patterning Materials Innovation (2012). He was awarded the Mahboob Khan SRC Mentor of the Year Award (2000) for work with Professor Ober’s group at Cornell.
The design of advanced photoresists for next generation lithography offers immense materials challenges and an innovation opportunity for polymer designers. Once the revolutionary lithographic imaging mechanistic change of Chemical Amplification was invented with Ito, Willson and Fréchet , the initial design target became polymers that could support optical transparency at the imaging wavelength and with the requisite functional requirements of dissolution in developer with easily installable dissolution switching.
The transition from DUV (248nm) lithography to ArF (193nm) lithography represented a complete redesign of photoresist polymers. About 25 years ago, the photoresist team at IBM Almaden led by Bob Allen published on the importance of a terpolymer approach to separate functions required to prepare aqueous base solubility in a phenolic-free methacrylate-based chemically amplified resist polymer . This approach became the timetested design strategy and remains in use today for photoresists for ArF lithography.
Allen and the IBM team extended this approach to improve dry-etching resistance collaborated with MIT Lincoln Laboratory . They also reported the influence of photoacid structure , comparison of acrylic resists with cyclic olefins resists  and anhydride-containing resist materials  for photoresists for ArF lithography. He also led the IBM team on the studies of diffusion and distributions of photoacid generators , supercritical processing , non-polymeric macromolecular resists , and polymer-bond PAGs .
Allen and the IBM team collaborated with several leading chemical companies, JSR and Central Glass to explore, develop and ultimately manufacture water immersion-specific materials. Possibly the most important material type developed to enable worldwide volume manufacturing of semiconductors using water immersion lithography were the invention and development of aqueous base-soluble polymers via the HFA (hexafluoro-alcohol) functional group . Methacrylate monomers were developed with varying “spacer” groups that gave tremendous control over desirable properties . These materials importantly combine clean aqueous development with solubility in hydrophobic solvents and high transparency at 193nm, making them ideal for use in immersion lithography topcoats. This concept has been extended to the resists for immersion  and organic bottom antireflective coating  Allen gave several presentations at the Photopolymer Conference about this topic  including extensions of HFA polymer technology to the challenge of water purification .
Recently, Dr. Allen is focused broadly on polymer chemistry for future electronic technologies and to help solve global challenges in sustainability and the lower carbon circular economy. And he is intrigued by the potential of digital manufacturing using 3D printing. This is one of the next frontiers for photopolymers. As such, he has organized a 3D Printing Session at the Photopolymer Conference since 2015.
Allen is a pioneer of the resist design for ArF 193nm photoresist platform and materials specific or extending semiconductor patterning technology using water immersion lithography.
His work was far ahead of its time and the contribution and originality are outstanding. With these achievements, the Outstanding Achievement Award 2019 was presented to Dr. Robert Allen.
1. H. Ito, C. G. Willson and J. M. J. Fréchet, “New UV Resists with Negative or Positive Tone”, Digest of Technical Papers of 1982 Symposium on VLSI Technology, (1982) 86.
2. R. D. Allen, G. M. Wallraff, W. D. Hinsberg, and L. L. Simpson, “High performance acrylic polymer for chemically amplified photoresist applications”, J. Vac. Sci. Technol. B, 9 (1991) 3357; R. D. Allen, G. M. Wallraff, W. D. Hinsberg, W. E. Conley, R. R. Kunz, “Designing High Performance KrF and ArF Single Layer Resists with Methacrylate Polymers”, J. Photopolym. Sci. Technol., 6 (1993) 575.
3. R. D. Allen, G. M. Wallraff, R. A. DiPietro, D. C. Hofer, R. R. Kunz, “Single layer resists with enhanced etch resistance for 193nm lithography”, J. Photopolym. Sci. Technol., 7 (1994) 507.
4. R. D. Allen, J. Opitz, C. E. Larson, T. I. Wallow, R. A. DiPietro, G. Breyta, R. Sooriyakumaran, D. C. Hofer, “The Influence of Photoacid Structure on the Design and Performance of 193-nm Resists”, J. Photopolym. Sci. Technol., 10 (1997) 503.
5. R. D. Allen, T. I. Wallow, J. Opitz, C. Larson, R. A. DiPietro, R. Sooriyakumaran, P. Brock, G. Breyta, D. C. Hofer, S. Jayaraman, R. Vicari, K. A. Hullihen, L. F. Rhodes, B. L. Goodall, R. A. Shick, “Platform-Dependent Properties of 193nm Single Layer Resists”, J. Photopolym. Sci. Technol., 11 (1998) 475.
6. R. D. Allen, C. E. Larson, H. D. Truong, P. J. Brock, H. Ito, “Progress in 193nm Resists: Impact of the Development Process on Anhydride-Containing Resist Materials”, J. Photopolym. Sci. Technol., 13 (2000) 595.
7. N. Sundararajan, C. F. Keimel, N. Bhargava, C. K. Ober, J. Opitz, R. D. Allen, G. Barclay, G. Xu, “Diffusion and Distribution Studies of Photoacid Generators: Ion Beam Analysis in Lithography”, J. Photopolym. Sci. Technol., 12 (1999) 457.
8. N. Sundararajan, S. Yang, K. Ogino, S. Valiyaveettil, J. Wang, X. Zhou, C. K. Ober, S. K. Obendorf, R. D. Allen, “Supercritical CO2 Processing for Submicron Imaging of Fluoropolymers”, Chem. Mater., 12 (2000) 41.
9. R. Sooriyakumaran, T. Hoa, L. Sundberg, M. Morris, B. Hinsberg, H. Ito, R. Allen, Wu-Song Huang, D. Goldfarb, S. Burns, D. Pfeiffer, “Positive Resists Based on Non-polymeric Macromolecules”, J. Photopolym. Sci. Technol., 18 (2005) 425.
10. R. D. Allen, P. J. Brock, Young-Hye Na, M. H. Sherwood, H. D. Truong, G. M. Wallraff, M. Fujiwara, K. Maeda, “Investigation of Polymerbound PAGs: Synthesis, Characterization and Initial Structure/ Property Relationships of Anion-bound Resists”, J. Photopolym. Sci. Technol., 22 (2009) 25.
11. R. D. Allen, P. J. Brock, L. Sundberg, C. E. Larson, G. M. Wallraff, W. D. Hinsberg, J. Meute, T. Shimokawa, T. Chiba, M. Slezak, “Design of Protective Topcoats for Immersion Lithography”, J. Photopolym. Sci. Technol., 18 (2005) 615.
12. R. D. Allen, G. Breyta, P. Brock, R. DiPietro, D. Sanders, R. Sooriyakumaran, L. K. Sundberg, “Fundamental Properties of Fluoroalcoholmethacrylate Polymers for use in 193nm Lithography”, J. Photopolym. Sci. Technol., 19 (2006) 569.
13. D. P. Sanders, L. K. Sundberga, R. Sooriyakumarana, P. J. Brocka, R. A. DiPietroa, H. D. Truonga, D. C. Millera, M. C. Lawsonb, R. D. Allen, “Fluoroalcohol Materials with Tailored Interfacial Properties for Immersion Lithography”, Proc. SPIE, 6519 (2007) 651904.
14. D. L. Goldfarb, L. Vyklicky, S. D. Burns, K. Petrillo, J. Arnold, A. Lisi, D. Pfeiffer, D. D. Sanders, R. D. Allen, D. R. Medeiros, D. Chung Owe-Yang, K. Noda, S. Tachiban, S. Shirai, “Graded Spin-on Organic Bottom Antireflective Coating for High NA Immersion Lithography”, J. Photopolym. Sci. Technol., 21 (2008) 397.
15. R. D. Allen, “Trends in Patterning Materials for Advanced Lithography”, J. Photopolym. Sci. Technol., 20 (2007) 453.
16. R. D. Allen, Y.-H. Na, R. Sooriyakumaran, M. Fujiwara, K. Yamanaka, “Leveraging Resist
Chemistry Research for Water Purification Membrane Technology”, J. Photopolym. Sci. Technol., 23 (2010) 741.
Takumi Ueno, Shinshu University
The Best Paper Award 2019
The Photopolymer Science and Technology Award 192100
Hiroaki Takehara, Yukihiro Kanda, and Takanori Ichiki
The University of Tokyo, Japan
The Photopolymer Science and Technology Award No. 182100, the Best Paper Award 2018, was presented to Hiroaki Takehara, Yukihiro Kanda, and
Takanori Ichiki (Department of Materials Engineering, School of Engineering, The University of Tokyo) for their outstanding contribution published in Journal of Photopolymer Science and
Technology, 31, (2018) 59–63, entitled “Microfluidic Model for Optical Detection of Nanoparticles in Whole Blood”.
Microfabrication technology has played an important role in the advancement of bio-analysis methods. Microfluidic device technologies started from devices for molecular analysis in early 1990s [1,2], and Prof. Ichiki contributed to drive its advancement in early stage by applying microfabrication technology for LSI devices [3-8]. Furthermore, remarkable progress in polymer technology has also played a pivotal role in the development of biomedical devices and drug delivery systems because of their biocompatibility and functionality [9-12]. In the technological advancement as mentioned above, the combined use of microfabrication technology and functional polymer materials can be a promising approach to bestow effective measurement methods in biological environment (in situ) and even inside the living body (in vivo). In situ and in vivo measurements of molecules, cells, biological tissues, and living animals, are highly attractive for both powerful tools to obtain new insights in fundamental biological studies and medical applications to provide information in diagnostics [13,14].
Dr. Takehara, Prof. Ichiki and their collaborative researchers have been proposed novel device technology focusing on “in vivo” and “in situ” measurements towards biomedical applications. Recently, they developed in vivo measurement method of living mouse brain using microfluidic device platform (named as lab-onbrain) [15-17], and implantable semiconductor devices [18,19]. They also developed in situ monitoring method of temperature of liquids , cellular oxygen metabolism , and cellular response to cytokines , based on the materials technology and microfabrication technology.
In this article, they investigated optical measurement methods of therapeutic polymer nanoparticles in the blood stream. Light has shown great potential as a safe energy source for sensing, owing to unique photon energy range of light around 0.53 eV that allows effective yet safe interactions with polymer materials and biological tissues . The core challenge in the optical measurement of polymer nanoparticles in blood is absorption of light by complex interferents. The absorbed photon energy can be converted into heat by the photothermal effect and re-emitted through luminescence as autofluorescence. Thus, in the present study, they studied photothermal effect and the autofluorescence by using a microfluidic model. The photothermal effect was evaluated by observing temperature increases in whole blood with laser-induced fluorescence spectroscopy. The detection limit of fluorescent nanoparticles was elucidated in the presence of autofluorescence as the background noise in the whole blood.
As described above, the authors have investigated the role of the photothermal effect and autofluorescence in the measurement of fluorescence from polymer nanoparticles in the blood by using a specially designed experimental model based on microfluidic chip technology and fluorescence microspectroscopy. These results provide valuable insights to pave the way for the development of optical sensing methods for monitoring biological molecules or therapeutic drugs inside the body.
These important research results were presented at the International Conference of Photopolymer Science and Technology in 2018 and the paper was published in the Journal of Photopolymer Science and Technology. These contributions give the advancement of photopolymer science and technology in the field of biomedical engineering.
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Kohei Soga Tokyo University of Science
The Best Paper Award 2019
The Photopolymer Science and Technology Award 192200
Satoshi Takei, Makoto Hanabata, Kento Mizui, Kazuho Kurematsu, and Shinya Nakajima
Toyama Prefectural University, Japan
The Photopolymer Science and Technology Award No. 182200, the Best Paper Award 2018, was presented to Satoshi Takei, Makoto Hanabata, Kento Mizui, Kazuho Kurematsu, and Shinya Nakajima (Departments of Mechanical Systems Engineering and Pharmaceutical Engineering, Toyama Prefectural University) for their outstanding contribution published in Journal of Photopolymer Science and Technology, 31, (2018) 289–294, entitled “Reduction of Defect for Imprinted UV Curable Resin including Volatile Solvents using Gas Permeable Mold Derived from Cellulose”.
The mainstream of microfabrication technology is a photolithography [1,2]. Photolithography is a suitable process that can transfer geometric patterns to a film or substrate. However, due to the increasing cost to achieve high resolution, it reaches to the limitations. In this situation, imprint lithography (IL) has drawn much attention because of its high productivity and low cost. The IL is a processing method [3,4]. It was reported that it is possible in transcription of 10 nm . This technique has a high resolution, high throughput, high aspect ratio patterning, cost reduction, and large area patterning [6-10]. The applicability of IL has wide varieties of biosensor, optical materials, and compact discs. [11-13]. It is promising as the next generation microfabrication technologies. A gas impermeable quartz mold used in conventional processes often causes air trapping and out gas accumulation between the mold and the transfer material. To solve the air trapping problem, the use of pentafluoropropane was suggested . In previous studies, we reported a gas permeable mold derived from cellulose reduces the void caused by the outgas from acrylic material including acetone [15-17]. The pattern failures caused by the air trapping and the outgassing between the mold and the UV curing liquid material were removed because these gasses easily passed outside through the gas permeable mold.
This paper reports a new family of imprint mold that the authors have recently developed. Mass productivity of the gas permeable mold from quartz master mold was confirmed by replicating a large amount of gas permeable mold. Defects in line and space patterns of the UV-cross-linkable materials including 10 wt% of acetone, 10 wt% of 1-methoxy2-propyl acetate and 10 wt% of cyclopentane as volatile solvents were greatly eliminated by using the developed gas permeable mold derived from biomass.
These results were also presented at the International Conference of Photopolymer Science and Technology in 2018. The work on the imprint lithography has recently greatly progressed, providing novel structures of gas permeable molds derived from biomass. This approach is expected to expand the utility of non-liquid materials which need solvents that are currently not suitable for imprint lithography. The progress will be presented at the International Conference of Photopolymer Science and Technology in 2018 .
The results presented in this paper provide a new useful family of imprint molds with unprecedented advantages, and hence deserves the Photopolymer Science and Technology Award.
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Yoshihiko Hirai, Osaka Prefecture University