ONRRep99

OFFICE OF NAVAL RESEARCH

END-OF-THE-YEAR REPORT

PUBLICATIONS/PATENTS/PRESENTATIONS/HONORS/STUDENTS REPORT

for

GRANT or CONTRACT: N00014-91-J-1630

PR Number 96PR00670

Creation and Measurement of Components for Nanometer-Scale and Hybrid-Function Devices

Paul S. Weiss

Department of Chemistry
The Pennsylvania State University

152 Davey Laboratory
University Park, PA 16802-6300

Date Submitted
30 June 1999

Reproduction in whole, or in part, is permitted for any purpose of the United States Government.

This document has been approved for public release and sale, its distribution is unlimited.

Office of Naval Research End-of-the-Year (EOY) Report

Reporting period:
1 June 1998 to 31 May 1999
PR Number: 96PR00670

EOY Report - PART I

a. Papers submitted to refereed journals, but not yet published:

TR 35. Directed Self-Assembly to Create Molecular Terraces with Molecularly Sharp Boundaries in Organic Monolayers, L. A. Bumm, J. J. Arnold, T. D. Dunbar, D. L. Allara, and P. S. Weiss, Journal of the American Chemical Society, in press.

TR 36. Electron Transport through Organic Molecules, L. A. Bumm, J. J. Arnold, T. D. Dunbar, D. L. Allara, and P. S. Weiss, submitted for publication.

TR 43. Molecular Motion to Step Edges, J. H. Ferris, J. G. Kushmerick, and P. S. Weiss, submitted for publication. (ABSTRACT)

TR 44. Spatially Resolved Spectroscopic Analysis: Scanning Probe Microscopies, J. G. Kushmerick and P. S. Weiss, Encyclopedia of Spectroscopy and Spectrometry, G. Tranter and J. Holmes, eds. (Academic Press, London, 1999), in press.

TR 45. Scanning Probe Studies of Single Nanostructures, G. S. McCarty and P. S. Weiss, Chemical Reviews, in press.

TR 48. Formation of Nanoscale Polarized Domains in Organic Ferroelectric Thin Films by Scanning Force Microscopy, X. Q. Chen, H. Yamada, T. Horiuchi, K. Matsushige, and P. S. Weiss, Molecular Crystals and Liquid Crystals, in press. Collaborative research with Kyoto University.

TR 49. Scanning Tunneling Microscopy and Spectroscopies of Nanometer-Scale Particles, G. S. McCarty, J. C. Love, J. G. Kushmerick, L. F. Charles, C. D. Keating, B. J. Toleno, M. E. Lyn, A. W. Castleman, Jr., M. J. Natan, and P. S. Weiss, Journal of Nanoparticle Research 1 (1999), in press.

TR 51. Strong Substrate Effect in Local Poling of Ultrathin Ferroelectric Polymer Films, X. Q. Chen, Y. Terai, T. Horiuchi, H. Yamada, K. Matsushige, and P. S. Weiss, Thin Solid Films, in press. Collaborative research with Kyoto University.

TR 52. Surface Potential of Ferroelectric Thin Films Investigated by Scanning Probe Microscopy, X. Q. Chen, H. Yamada, T. Horiuchi, K. Matsushige, S. Watanabe, M. Kawai, and P. S. Weiss, Journal of Vacuum Science and Technology B, in press. Collaborative research with Kyoto University, RIKEN, and Nikon.

b. Papers published in refereed journals:

TR 33. Design, Operation, and Housing of an Ultrastable, Low Temperature, Ultrahigh Vacuum Scanning Tunneling Microscope, J. H. Ferris, J. G. Kushmerick, J. A. Johnson, R. B. Kessinger, H. F. Kingsbury, M. G. Yoshikawa Youngquist, and P. S. Weiss, Review of Scientific Instruments 69, 2691 (1998).

TR 34. Creating, Tailoring and Using One-Dimensional Interfaces in Two-Dimensional Films, P. S. Weiss, H. Yokota, R. Aebersold, G. van den Engh, L. A. Bumm, J. J. Arnold, T. D. Dunbar, and D. L. Allara, manuscript in preparation for Journal of Physics: Condensed Matter 10, 7703 (1998).

TR 38. Probing Electronic Properties of Conjugated and Saturated Molecules in Self-Assembled Monolayers, P. S. Weiss, L. A. Bumm, T. D. Dunbar, T. P. Burgin, J. M. Tour, and D. L. Allara, Annals of the New York Academy of Sciences 852, 145 (1998). Collaborative work with the University of South Carolina.

TR 39. Evolution of Strategies for Self-Assembly and Hookup of Molecule-Based Devices, D. L. Allara, T. D. Dunbar, P. S. Weiss, L. A. Bumm, M. T. Cygan, J. M. Tour, T. P. Burgin, L. Jones, II, Annals of the New York Academy of Sciences 852, 349 (1998). Collaborative work with the University of South Carolina.

TR 41. Strong Electronic Perturbation of the Cu{111} Surface by 7,7',8,8'-Tetracyanoquinonedimethane, M. M. Kamna, T. M. Graham, J. C. Love, and P. S. Weiss, Surface Science 419, 12 (1998).

TR 42. Mobile Promoters on Anisotropic Catalysts: Ni on MoS₂, J. G. Kushmerick and P. S. Weiss, Journal of Physical Chemistry B 102, 10094 (1998).

TR 46. Observations of Anisotropic Electron Scattering on Graphite with a Low Temperature Scanning Tunneling Microscope, J. G. Kushmerick, K. F. Kelly, N. J. Halas, H. P. Rust, and P. S. Weiss, Journal of Physical Chemistry B 103, 1619 (1999). Collaborative research with Rice University and the Fritz-Haber-Institut der Max-Planck-Gesellschaft.

TR 47. Ring-Opening Metathesis Polymerization from Surfaces, M. Weck, J. J. Jackiw, R. R. Rossi, P. S. Weiss, and R. H. Grubbs, Journal of the American Chemical Society 121, 4088 (1999). Collaborative research with Cal Tech.

TR 50. Surface Characterization, G. E. McGuire, D. J. Fuchs, P. Han, J. G. Kushmerick, P. S. Weiss, R. J. Nemanich, N. R. Parikh, and D. R. Chopra, Analytical Chemistry 71, 373R (1999).

c. Books or chapters submitted, but not yet published:

None.

d. Books or chapters published:

None.

e. Printed technical reports/non-refereed papers:

TR 40. Ring-Opening Metathesis Polymerization from Surfaces, M. Weck, J. J. Jackiw, P. S. Weiss, and R. H. Grubbs, Polymer Preprints (American Chemical Society, Division of Polymer Chemistry) 79, 72 (1998). Collaborative work with Cal Tech.

f. Patents filed:

None.

g. Patents granted:

None.

h. Invited presentations:

Kyoto University, Venture Business Laboratory, Department of Electronic Science and Engineering, "Exploring and Controlling the Atomic-Scale World," P. S. Weiss, Kyoto, Japan, August 5, 1998.

MITRE/DARPA Annual Meeting on Nanometer-Scale Control and Devices, "Current and Future Experimental Developments in Molecular Electronics," J. C. Love, G. S. McCarty, C. D. Keating, M. J. Natan, and P. S. Weiss, Reston, VA, August 13, 1998. Presented by J. C. Love.

216th Meeting of the American Chemical Society, "Measuring and Understanding Electron Transport Through Molecules Isolated or Organized in Monomolecular Films," P. S. Weiss, Boston, MA, August 23, 1998.

Tohoku University, Institute for Materials Research, "Electrons In, Around, and Through Molecules on Surfaces," P. S. Weiss, Sendai, Japan, September 5, 1998.

Osaka University, Institute for Scientific and Industrial Research, "Electrons In, Around, and Through Molecules on Surfaces," P. S. Weiss, Osaka, Japan, September 8, 1998.

RIKEN, Institute for Physical and Chemical Research, "Exploring and Controlling the Atomic-Scale World," P. S. Weiss, Wako-shi, Saitama, Japan, September 21, 1998.

Joint Research Center for Atom Technology and the National Institute for Advanced Interdisciplinary Research, "Exploring and Controlling the Atomic-Scale World," P. S. Weiss, Tsukuba, Ibaraki, Japan, September 22, 1998.

25th Annual Conference of the Federation of Analytical Chemistry & Spectroscopy Societies, P. S. Weiss, Austin, TX, October 12, 1998.

University of California at San Diego, Department of Chemistry, "Electrons In, Around, and Through Molecules on Surfaces," P. S. Weiss, La Jolla, CA, October 13, 1998.

The Pennsylvania State University, Department of Physics, "Electrons In, Around, and Through Molecules on Surfaces," P. S. Weiss, University Park, PA, October 29, 1998.

IBM T. J. Watson Research Center, Nanotechnology Seminar, "Electrons In, Around, and Through Molecules on Surfaces," P. S. Weiss, Yorktown Heights, NY, November 18, 1998.

Lucent Technologies, Bell Laboratories, "Exploring and Controlling the Atomic-Scale World," P. S. Weiss, Murray Hill, NJ, November 19, 1998.

Yale University, Department of Electrical Engineering, "Exploring and Controlling the Atomic-Scale World," P. S. Weiss, New Haven, CT, November 20, 1998.

National Institute of Standards and Technology, "Probing the Atomic-Scale Chemistry and Physics of Anisotropic Surfaces," J. G. Kushmerick, December 15, 1998.

International Workshop on Electron Transmission through Molecular Interfaces, "Electrons In, Around, and Through Adsorbed Molecules," P. S. Weiss, Sea of Galilee, Israel, December 16, 1998.

JRCAT Workshop on Technology for Identifying and Manipulating Atoms & Molecules, The 2nd Workshop on Scanning Probe and Nanoelectronics (SP-Nano '99), and the 3rd Asian Conference on Scanning Tunneling Microscopy (Asian STM '99) "Selectively Placing Molecules in Monolayer Films through Self-Assembly and Directed Assembly," P. S. Weiss, Tsukuba, Ibaraki, Japan, January 13, 1999.

University of Delaware, Department of Chemistry, "Probing the Atomic-Scale Chemistry and Physics of Anisotropic Surfaces," J. G. Kushmerick, Newark, DE, February 12, 1999.

Holy Cross, Department of Chemistry, "Molecular Measurements with Scanning Tunneling Microscopy," Lloyd A. Bumm, Worcester, MA, February 19, 1999.

University of California at Berkeley, Department of Chemistry and the Lawrence Berkeley Laboratory, "Exploring and Controlling the Atomic-Scale World," P. S. Weiss, Berkeley, CA, March 4, 1999.

IBM Almaden Research Center, "Exploring and Controlling the Atomic-Scale World," P. S. Weiss, San Jose, CA, March 5, 1999.

University of California at Santa Barbara, Department of Chemistry, "Exploring and Controlling the Atomic-Scale World," P. S. Weiss, Santa Barbara, CA, March 8, 1999.

Sandia National Laboratory, "Probing the Atomic-Scale Chemistry and Physics of Anisotropic Surfaces," J. G. Kushmerick, Albuquerque, NM, April 12, 1998.

Los Alamos National Laboratory, "Probing the Atomic-Scale Chemistry and Physics of Anisotropic Surfaces," J. G. Kushmerick, Los Alamos, NM, April 14, 1998.

i. Submitted presentations:

58th Conference on Physical Electronics, "Control of Self-Assembled Monolayer Film Structure and Properties," L. F. Charles, L. A. Bumm, J. J. Jackiw, J. A. Johnson, E. H. Muth, T. D. Dunbar, D. L. Allara, and P. S. Weiss, University Park, PA, June 16, 1998. Poster presented by Lyndon Charles.

58th Conference on Physical Electronics, "Atomic-Scale Insight into Catalytic Promoters," J. G. Kushmerick and P. S. Weiss, University Park, PA, June 16, 1998. Poster presented by James Kushmerick.

American Chemical Society, Colloid and Surface Section Meeting, "Patterning Molecules on the Nanometer Scale," L. A. Bumm, J. J. Arnold, L. F. Charles, M. T. Cygan, T. D. Dunbar, D. L. Allara, and P. S. Weiss, University Park, PA, June, 1998. Presented by L. A. Bumm.

216th Meeting of the American Chemical Society, "Atomic-Scale Insight into the Catalytic Properties of Nickel-Promoted Molybdenum Disulfide," J. G. Kushmerick and P. S. Weiss, Boston, MA, August 21, 1998 and August 22, 1998. Poster and Sci-Mix poster presented by J. G. Kushmerick.

American Vacuum Society 45th International Symposium, "Phenyl-Containing Radicals on Cu{111}," G. S. McCarty, M. M. Kamna, and P. S. Weiss, Baltimore, MD, November 2, 1998. Poster presented by G. S. McCarty.

American Vacuum Society 45th International Symposium, "Control of Self-Assembled Monolayer Film Structure and Properties," P. S. Weiss, L. F. Charles, L. A. Bumm, T. D. Dunbar, and D. L. Allara, Baltimore, MD, November 3, 1998. Presented by L. F. Charles.

American Vacuum Society 45th International Symposium, "Growth, Modification, and Control of the Structures of Mixed Composition Organic Monolayers," T. D. Dunbar, T. P. Burgin, J. M. Tour, D. L. Allara, and L. A. Bumm, Baltimore, MD, November 3, 1998. Presented by L. A. Bumm.

American Vacuum Society 45th International Symposium, "Controlling Defects in Self-Assembled Monolayers," J. J. Jackiw, J. J. Arnold, J. A. Johnson, T. D. Dunbar, T. L. Spiva, D. L. Allara, and P. S. Weiss, Baltimore, MD, November 4, 1998. Presented by J. J. Jackiw.

American Vacuum Society 45th International Symposium, "Tunneling and Photon Emission of Colloidal Particles," G. S. McCarty, C. D. Keating, P. S. Weiss, and M. J. Natan, Baltimore, MD, November 5, 1998. Poster presented by G. S. McCarty.

American Vacuum Society 45th International Symposium, "Anisotropic Electron Scattering from Point Defects on Graphite at Low Temperature," K. F. Kelly, J. G. Kushmerick, H. P. Rust, N. J. Halas, and P. S. Weiss, Baltimore, MD, November 5, 1998. Poster presented by J. G. Kushmerick.

1999 Centennial American Physical Society Meeting, "Electron Transport Through Organic Molecules," L. A. Bumm, L. F. Charles, J. J. Arnold, T. D. Dunbar, D. L. Allara, and P. S. Weiss, Atlanta, GA, March 24, 1999. Presented by L. A. Bumm.

j. Honors/Awards/Prizes for contract/grant employees:

Aimee L. Bross
Eberly College of Science John and Elizabeth Teas Scholarship.
American Chemical Society, Analytical Chemistry Division I. M. Kolthoff Undergraduate Research Award.

James G. Kushmerick
Braddock Graduate Fellowship of the Eberly College of Science.

Greg S. McCarty
American Vacuum Society, Nanometer Science and Technology Division Travel Award.

Elizabeth Muth
Eberly College of Science John and Elizabeth Teas Scholarship.

Roger Wang
College of Engineering H. Thomas and Dorothy Willits Hallowell Scholarship.
The Pennsylvania State University Presidential Freshman Award.

Paul S. Weiss
Visiting Professor, Department of Electronic Science and Engineering and the Venture Business Laboratory, Kyoto University.

l. Other funding:

Date: September 15, 1994 - October 31, 1999.
Title: Surface Chemistry and Spectroscopy: From Model to Real Systems.
Agency: National Science Foundation. Includes supplements and Creativity Award
Extension.
Amount: $633,500.

Date: April 1, 1997 - August 31, 1999.
Title: The Chemistry of Catalyst Surfaces.
Agency: Petroleum Research Fund administered by the American Chemical Society.
Amount: $55,000.

Date: July 1, 1999 - June 30, 2000.
Title: Control of Structure and Properties in Monomolecular Films.
Agency: Army Research Office.
Amount: $75,000.

Date: September 30, 1998 - September 29, 2001.
Title: New DNA Microarray Detection Techniques in the Study of Stress-Induced
Changes in Plant Gene Expression.
Submitted to: National Science Foundation.
Amount: $1,801,988.
Participation: $564,264 PSW. Co-investigator with two others.

Date: February 15, 1999 - February 14, 2001.
Title: Moleware and the Molecular Computer.
Submitted to: Defense Advanced Research Projects Agency.
Amount: $1,998,871.
Participation: $372,000 PSW. Co-investigator with six others.

EOY Report - PART II

a. Principal Investigator
Paul S. Weiss
b. Current telephone number
(814) 865-3693 voice
(814) 863-5516 fax
c. Cognizant ONR Program Officer
Dr. John C. Pazik
d. Program objective

The objective of this program is to examine the electronic and physico-chemical properties, the stability, and the dynamics of nanometer-scale structures and of components that may be used in such structures. These structures and components may play key roles in evolving or even revolutionizing devices for communications, sensors, and detectors. Our understanding of these structures is developed using unique scanning tunneling microscopy instrumentation which gives us the ability to work at low temperatures, to manipulate surface structures, and to work at microwave and optical frequencies. We collaborate with key developers of molecules, films, and devices to screen and to advance the properties of the components, structures, and films they create. This work serves as the backbone of the technological advances in the related DARPA Moletronics work and in a wide range of other technologies.

e. Most significant results during the last year

We have made substantial progress in manipulating desorption, exchange, and deposition kinetics to advantage in monolayers in order to manipulate film structures and to insert molecules for study and use. We have mapped this replacement strategy using scanning tunneling microscopy and infrared spectroscopy.¹

We have obtained significant understanding of induced and local polarization in ferroelectric films.^2-4 Nearby substrate poles both organic and inorganic ultrathin films. We find that the resolution obtainable in storing charge varies substantially depending upon whether we pole with or against the induced polarization. These films are currently in use as nonvolatile RAMs, but we find that the 2D storage density could be increased by 10,000-fold. We anticipate measurements to still smaller scales. We expect to exploit our ability to functionalize the substrate and to grow or to place nanometer-scale structures to increase the storage density further.^2,5

We have enhanced our abilities to measure with sub-nanometer resolution across a broad spectral range.^6,7 We have demonstrated our ability to discriminate between different materials in nanostructures. We have proposed using this capability to develop selective "stains" for scanning probe microscopy in analogy to those employed in conventional light microscopy. The difference here is that much higher spatial resolution will be possible.

_______________________

^{1This work will first be presented at the Fall ACS Meeting and is currently being written up for publication. The student involved won the ACS Analytical Division I. M. Kolthoff Award for the work.
^{2 Strong Substrate Effect in Local Poling of Ultrathin Ferroelectric Polymer Films, X. Q. Chen, Y. Terai, T. Horiuchi, H. Yamada, K. Matsushige, and P. S. Weiss, Thin Solid Films, in press.
^{3Surface Potential of Ferroelectric Thin Films Investigated by Scanning Probe Microscopy, X. Q. Chen, H. Yamada, T. Horiuchi, K. Matsushige, S. Watanabe, M. Kawai, and P. S. Weiss, Journal of Vacuum Science and Technology B, in press.
^{4Formation of Nanoscale Polarized Domains in Organic Ferroelectric Thin Films by Scanning Force Microscopy, X. Q. Chen, H. Yamada, T. Horiuchi, K. Matsushige, and P. S. Weiss, Molecular Crystals and Liquid Crystals, in press.
^{5Ring-Opening Metathesis Polymerization from Surfaces, M. Weck, J. J. Jackiw, R. R. Rossi, P. S. Weiss, and R. H. Grubbs, Journal of the American Chemical Society 121, 4088 (1999).
^{6Scanning Probe Studies of Single Nanostructures, G. S. McCarty and P. S. Weiss, Chemical Reviews, in press.
^{7Scanning Tunneling Microscopy and Spectroscopies of Nanometer-Scale Particles, G. S. McCarty, J. C. Love, J. G. Kushmerick, L. F. Charles, C. D. Keating, B. J. Toleno, M. E. Lyn, A. W. Castleman, Jr., M. J. Natan, and P. S. Weiss, Journal of Nanoparticle Research 1 (1999), in press.}}}}}}}

f. Brief summary of plans for next year's work

We will examine the electronic and optical properties of a variety of molecules, assemblies, and nanostructures to understand the effects of functionalization, surface attachment, chemical environment, etc. We will continue to expand the repertoire of molecular-scale tools and techniques in order to access and to control molecular properties with increasing precision and resolution.

g. List of names of graduate students and post-doctoral(s) currently working on the project

Jennifer J. Jackiw, Greg S. McCarty, Dr. Lloyd A. Bumm

EOY Report - PART III

Provides the Division with material to defend and support current and future research in the field.

a. An introductory 5 - part viewgraph (or full size GIF version)
We are able to target specific structures with desired properties. These structures include molecular switches attached to nanoparticles, which are of interest for charge storage. These structures are specific goals in our related DARPA Moletronics program.

We need to develop the means:
1) to test whether the structures produced match the targets, and
2) whether the targeted (or other) structures have the desired properties.
This is particularly exciting as we are able to move beyond the level of the single synthesized molecules and yet we can retain much, if not all, of the specificity of chemical syntheses and preparations. Our abilities to measure extend to sub-nanometer length scales, at frequencies from dc to the microwave, as well as to the visible and near visible optical frequencies.

The inset shows a piezoelectric image of an ultrathin poled ferroelectric copolymer film. It is poled using a conducting AFM tip. Poling produces no change in the film topography, but substantial structure in the surface charge, film orientation, and local piezoelectric properties. We discovered that the film could be substantially poled by the underlying substrate. We hypothesize that the exposed substrate surface could be used to control the poling. Such films are targeted for use as nonvolatile RAMs. The resolution obtainable is easily 10,000x higher density than commercial ferroelectric nonvolatile RAM.

b. Supporting viewgraph #1 (or full size GIF version)
Nanostructures show very different nonlinearities as a function of frequency.
The left frame shows adsorbed gold nanoparticles measured at 9 MHz. Topography is shown as contours and microwave difference frequency signal is shown as color. The right frame shows the same film at 10 GHz. Note that contrast is inverted between the two frequencies! We are currently exploring this phenomenon more thoroughly. Such contrast inversion may well prove relevant in our molecular electronic studies, particularly when coupled to control of the materials and assemblies under test.

c. Supporting viewgraph #2 (or full size GIF version)
We have developed the means to record optical signals over part of a nanostructure. Here the upper frame shows topography and the lower frame shows photon emission.

We have found that our ability to measure emitted photons gives us the ability to distinguish between different materials. This has direct application in the current program in identifying nanoparticles within assemblies and in using nanoparticles to "stain" exposed functional groups. We are pursuing both of these aspects in current work.

OFFICE OF NAVAL RESEARCH
PUBLICATIONS/PATENTS/PRESENTATIONS/HONORS REPORT

PR Number: 96PR00670
Contract/Grant Number: N00014-91-J-1630
Contract/Grant Title: Creation and Measurement of Components for Nanometer-Scale and Hybrid-Function Devices
Principal Investigator: Paul S. Weiss
Mailing Address:
152 Davey Laboratory
The Pennsylvania State University
University Park, PA 16802-6300
Phone Number: (814) 865-3693
Fax Number: (814) 863-5516
E-mail Address: stm@psu.edu
http address: http://stm1.chem.psu.edu/

a. Number of papers submitted to refereed journals, but not published: 9
b. + Number of papers published in refereed journals: 9
c. + Number of books or chapters submitted, but not yet published: 0
d. + Number of books or chapters published: 0
e. + Number of printed technical reports/non-refereed papers: 1
f. Number of patents filed: 0
g. + Number of patents granted: 0
h. + Number of invited presentations: 23
i. + Number of submitted presentations: 12
j. + Honors/Awards/Prizes for contract/grant employees: 8
k. Total number of Full-time equivalent Graduate Students and Post-Doctoral associates supported during this period, under this R&T project number: 3
Graduate Students: 2
Post-Doctoral Associates: 1
including the number of,
Female Graduate Students: 0.5
Female Post-Doctoral Associates: 0
Minority* Graduate Students: 0.5
Minority* Post-Doctoral Associates: 0
Asian Graduate Students: 0
Asian Post-Doctoral Associates: 0