Merging Intellectual Merit and Broader Impact of University Research Activities Through Industrial Collaborations

1. Merging Intellectual Merit and Broader Impact of University Research Activities Through Industrial Collaborations Nicholas J. Turro Columbia University Professor Nicholas J. Turro of Columbia University has sought to design research that attacks important problems of the chemical industry and also possesses a high level of intellectual merit. This highlight describes the research of a network of collaborations with Columbia University and industrial scientists that are of high importance to the chemical industry and also possess a high level of intellectual merit as evidenced by publications described in this Highlight. . A strategy for success in industrial collaborations has been to develop partnerships for which both the academic and industrial partners are stakeholders in the execution and success of the projects. Inherent in this strategy is the gratification that both sides enjoy participating in effective team work, the sharing of cultural and scientific diversity and the continuous quality and intellectual improvement through collaboration. Alcatel-Lucent The support of the National Science Foundation with the following grants is gratefully acknowledged: Beyond a Supramolecular Approach to Structure and Reactivity of Organic Molecules (CHE 0415516) Understanding Chemical Complexity and Diversity Through Collaboration and Integration (CHE 0717518)

2. Energy efficient “Green” diaper manufacturing, tracking molecules adsorbed on porous catalytic solids and application of a universal ligand concept for the manufacture of flexible electronic materials. Industrial collaborator: Dr. Andreas Flohr, Proctor & Gamble, Schwalbach, Germany. A novel method for the surface cross-linking (Figure left) of superabsorbent polymer particles used for manufacturing diapers has been developed. Polymer materials produced have superior properties such as liquid flow thought the fluid particle bed and capacity. In addition, the process is projected to be more energy efficient (through green chemistry) than the current thermal method for cross-linking. Reference: J. Appl. Polymer Sci., 111, 2163-2170 (2009). Industrial collaborator: Dr. Lloyd Abrams, DuPont, Wilmington, DE. An understanding of the supramolecular structure and dynamics of absorption of molecules on the external and internal surface of porous solids is of critical importance in a range of solid state catalysis. Electron spin resonance (Figure right) has been employed to quantitatively determine the surface structure and dynamics of organic molecules adsorbed on the external surface of the important MFI family of zeolite catalysts. Reference: J. Am. Chem. Soc., 130, 11344-11354 (2008). Industrial collaborator: Dr. Ashok Maliakal, Alcatel-Lucent, Murray Hill, NJ A “universal ligand” concept incorporating a phosphonate surface anchor and a terminal alkyne moiety that binds to TiO2 was employed as a method to synthesize TiO2 nanoparticles with organic polystyrene and poly(s-butyl acrylate) polymer shells. The resulting materials (Figure left) were incorporated as high dielectric films in capacitor and organic thin film transistor devices as promising candidate materials for flexible electronics applications. Reference: Molecular Rapid Comm., 29, 1544-1547 (2008).

3. The manufacture of computer chips by photolithography: understanding photochemistry at 157 nm, producing immersion fluids with high refractive index and inventing novel two photon acid producing materials. This research was performed in collaboration with International SEMATECH, a consortium of USA industries whose members make up 50% of the worldwide chip market. Industrial collaborator: Dr. Paul Zimmerman, Intel, Portland, Oregon. Theory predicts that photolithography performed on current 193 nm tools can achieve smaller features in the production of computer chips through the use of materials that produced acid in a sequential two photon sequence. The existence of such materials was demonstrated (Figure left). A naphthalene dimer was cleaved by the first photon to produce a naphthalene monomer that produced an acid upon absorption of a second photon. Reference: Chem. Materials, 20, 7374-7376 (2008) Industrial collaborator: Dr. Will Conley, Freescale Semiconductor, Austin, TX Producing immersion fluids that are transparent at 193 nm and that possess a high refractive index is an important goal for producing smaller features in making computer chips by photolithography. An empirical correlation (Figure right) was developed that allows an accurate prediction of the best candidates for such immersion fluids. Importantly, the correlation revealed that cyclic saturated hydrocarbons possess a significantly higher refractive index than linear hydrocarbons of comparable molecular weight. Reference: Chem. Matter, 19, 3641-3647 (2007). Industrial collaborator: Dr. Roger French, DuPont, Wilmington, Delaware. The photolithographic industry has considered the use of 157 nm lasers as a means of making smaller features in the manufacture of computer chips. The only materials that are suitably transparent at 157 nm are perfluorocarbons whose photochemistry was elucidated by our investigations (Figure left) Reference: J. Am. Chem. Soc., 127, 8320-8327 (2005).

4. Industrial collaborator Dr. K. P. Ananthapadmanabhan, Unilever Research, Trumbull, CT. Hydrophobically modified polelectrolytes are important in a range of applications due to their ability to associate with materials that are important in cosmetics, paints and foods. The mechanism of association/dissociation of a hydrophobically modified anionic polymer with a cationic surfactant was elucidated by a multi-pronged battery of techniques. Reference: Langmuir, 23, 5906-5913 (2007). A novel method to make smaller computer chips, increasing the applications of water soluble polymers through structural modifications and a probing investigation of mechanism of radical-radical combination inefficiency in free radical polymer syntheses. Industrial collaborator: Dr. Igor Khudyakov, Bomar Specialties, Winsted, CT The mechanism of radical-radical recombination reactions is critical in determining the efficiency of radical polymerization reactions which are at the heart of the manufacture of many industrially important materials. We have determined for the first time the basis of the inefficiency of the reactions of reactive radicals with inert diradicals. Reference: J. Am. Chem. Soc, 129, 7785-7792 (2007). Industrial collaborator: Dr. Paul Zimmerman, Intel, Portland, Oregon. .A novel method to produce smaller features in computer chips by double exposure lithography has been designed. The double exposure method has the potential to produced chips through a much cheaper pathway than alternatives. However, this technology requires the development of new methods and new materials whose feasibility are analyzed. Reference: Optical Microlithography XXI, Ed. H. J. Levinson and M. V. Dusa, Proc. SPIE, 6924, 6924A 1-11 (2008)

5. Senior industrial collaborators Summary NSF’s Broader Impact review criteria encourage its university research force to consider activities that are “outside of the box” of the traditional aspects of research that emphasize academic training and intellectual merit. Activities that enhance the training of students and postdoctoral associates through partnering and collaborations with industrial partners are an effective means to expose researchers to the critical aspects of translating ideas and discoveries into practical applications. Dr. Paul Zimmerman Intel Portland, OR Dr. Roger French DuPont Wilmington, DE Dr. Ashok Maliakal Alcatel•Lucent Murray Hill, NJ Attacking important industrial projects while maintaining a high level of intellectual merit is a demanding challenge, but one that can be quite gratifying when the effective merging of high intellectual merit and industrial needs can be achieved. Dr. Will Conley Freescale Semiconductor Austin, TX Dr. Lloyd Abrams DuPont Wilmington, DE Dr. K. Ananthapadmanabhan Unilever Trumbull, CT Dr. Andreas Flohr Proctor & Gamble Schwalbach, Germany Dr. Forrest Blackburn PPG Industries Pittsburg, PA Dr.Igor Khudyakov Bomar Specialties Winsted, CT The outstanding assistance of Prof. Tom Poon and Dr. Steffen Jockusch in preparing this Highlight is gratefully acknowledged.