NIRT: Chemically Directed Surface Alignment and Wiring of Self-Assembled Nanoelectrical Circuits, CBET0708347 J. Liu‡, K. A. Nelson‡, E. Bird‡, J. Ashton‡, B. Mangold‡, E. Nelsen‡, H. Conley§, T. Pearson§, B. Davis§, D. Jones§, R. Ochoa§, F. Rivera§, E. Pound†, Y. Geng†, B. Cragun†, T. Wickard†, R. C. Davis§, A. T. Woolley†, M. R. Linford†, D. R. Wheeler‡, and J. N. Harb‡ of Chemical Engineering, § Department of Physics and Astronomy, † Department of Chemistry and Biochemistry, Brigham Young University, Provo, Utah 84602 Abstract High-resolution chemical surface patterning This poster describes nanofabrication efforts underway at BYU by an interdisciplinary research group, ASCENT (ASsembled nanoCircuit Elements by Nucleic acid Templating) under NIRT funding (2007). This group seeks to combine the complementary advantages of bottom-up selfassembly with top-down patterning, with the goal of providing a process for fabrication of nanoelectronic circuits. Efforts are focused on the development and refinement of four key technologies: (1) solution-phase assembly of structures and templates, (2) high-resolution chemical surface patterning, (3) high-precision metallization of molecular templates, and (4) chemically directed assembly and integration of nanostructures on surfaces. Molecular circuits are self-assembled in solution using customized DNA templates (“test-tube circuits”). DNA selfassembly is particularly powerful because of the large number of possible nucleic-acid sequences that enable highly selective bonding of DNA strands to each other and to other molecules. Chemical patterning will provide anchor points to attach and align the molecular circuits on the surface, as well as provide a means for local wiring to the anchored circuit, all with a resolution < 10 nm. Several patterning methods are being explored including polymer nanografting, chemomechanical patterning and self assembled layers. Metallization of both the exposed DNA and chemically templated lines is used to electrically connect active circuit elements to each other and to the larger-scale architecture. The net result will be DNA-templated molecular circuits that have been aligned and wired locally on an oxide surface. Interconnect technology similar to that used currently in the semiconductor industry can then be applied to create the larger global wiring needed for practical devices based on the molecular circuits under development. Metallization • Highly-selective metallization on DNA templates • Continuous deposition for metallization of interconnects between circuit elements Nanografting 1) 2) 3) 4) 5) Enables creation of direct, strong attachment to surfaces Able to pattern in a liquid environment Flexible for use with a range of surfaces and surface chemistries Low cost < 20 nm features Silane Glass Poly-L-lysine Electroless plating Vapor phase deposition CY3-tagged Poly-L-lysine Scribing away Poly-L-Lysine with AFM tip Replacing holes with fluorescently tagged Poly-L-Lysine • • Selective metallization of DNA with Ag (process modified from Yan et al., 2003) • Overview Selective Ni deposition on DNA templates via vapor phase deposition of Ni(acac)2 50min-Ni(acac)2 equilibration at 180 ºC, followed by 5min wafer exposure at 180 ºC Height of particles deposited on DNA: 10nm • Height of metallized DNA:14nm • Tasks 1.3K MPS COUNTS • Molecular circuit assembly • High-resolution chemical surface patterning • Chemically directed assembly and integration of MC’s on surfaces • High-selectivity, high-precision metallization 1.2K 1.1K 1K 900 COUNTS 800 200 195 190 185 180 175 170 165 160 155 150 145 140 135 130 125 120 115 110 105 100 700 PDS 348 347 346 345 344 343 342 341 COUNTS ‡ Department 340 339 338 337 BINDING ENERGY - EV 600 500 Pd peaks 400 300 200 100 950 8.5K 900 850 800 750 700 650 600 550 500 450 400 BINDING ENERGY - EV 350 300 250 200 150 100 50 0 Pd peaks 7.5K 7K 6.5K 6K COUNTS COUNTS 5.5K 5K 4.5K 4K 3.5K A 3K B 2.5K 2K 1.5K 1K 500 950 Solution based assembly molecular Chemical surface patterning including local wiring template circuit MC AFM (top) shows holes after scribing and optical fluorescence (bottom) verifies chemical functionality after grafting AFM of patterned lines and spaces with 12 nm half pitch created by scribing with a ~50 nm radius tip. D C MC Molecular Circuits 50 nm 1) 2) Contact hole for global wiring Chemically directed assembly • Micelle Self Assembly Local Wiring Rapid, high resolution patterning Can be combined with other patterning techniques for precise positioning and functionalization of gold particles < 10 nm features surface Metallization of wiring templates 3) • • • • • • • • • • Poly(styrene-b- 2-vinylpyridine) block copolymer forms micelles in toluene Gold salts enter micelle center Micelles deposited on silicon oxide surface Oxygen plasma etching leaving gold pattern on surface Gold particle diameter: 10-15nm Spacing: 60-70nm (process modified from Möller et al., 2000) Molecular circuit assembly Source Drain Current on a bundle of (7,6) carbon nanotubes Designing DNA origami rectangular motif 1). Build a model Source Drain current on a (7,6) nanotube bundle One turn is ~3.6 nm. 2). Fold DNA scaffold strand through model 1 10 -6 5 10 -7 Current (Amps) DNA is ~ 2 nm wide. There is ~1 nm between strands. 1.5 10 -6 Scaffold strand 0 -5 10 -7 -1 10 -6 -1.5 10 -6 -1 Origami from bead-separated scaffold 3). Design complementary staple strands that cross every 1.5 turns -0.5 0 0.5 1 1.5 2 VSD Chemically directed assembly and integration of MCs A high yield of individual properly aligned MCs at each site is desired. The assembly can be tuned using several molecular parameters including molecule flexibility, ligand length, induced steric constraints, and partial attachment binding affinity differences. Temperature cycling, selective ligation, and the use of multiple attach/rinse cycles will be explored to achieve the desired yield. Silicon dioxide surface modified with APTES PSS put on APTES layer Lines created by AFM tip scribing Lines then seeded with Pd Electroless plating with copper 1. 2. 3. 4. 5. e' 9. DNA-templated PMOS circuit Rectangle size: approx. 11 by 65 nm Carbon nanotubes placed between electrodes by dielectrophoresis f' 750 700 650 600 550 500 450 400 BINDING ENERGY - EV 350 300 250 200 150 100 50 0 340 330 320 310 300 290 280 270 260 250 240 230 220 210 200 190 180 170 160 150 140 333 900 332 331 850 330 800 329 750 700 650 600 550 500 450 400 BINDING ENERGY - EV 350 300 250 200 150 100 50 0 330 329 SA Pd peaks 348 347 346 345 344 343 342 341 340 339 338 337 BINDING ENERGY - EV 336 335 334 333 332 331 Application of additives in electroless Pd plating to enhance continuity and selectivity XPS results show additives facilitate Pd plating Sulfanilic acid showing best results References 8. g' 800 334 • Education of graduate students in a truly multidisciplinary environment. • Education of undergraduate students in a positive mentoring environment. • Involvement of local minority students in an outreach program focused on science and engineering. • Development of a method for producing wiring and metallization at a density unmatched by any present or near-future process. • Development, demonstration and dissemination of novel and transferable processes and enabling tools for nanotechnology. 6. 7. h' • • 850 335 Broader Impacts Summary Staple strands A program was developed to minimize the crossover strain and determine the DNA sequence needed for each of the staple strands • 900 PDS 950 SA 8K 4.2K 4K 3.8K 3.6K 3.4K 3.2K 3K 2.8K 2.6K 2.4K 336 2.2K 2K 1.8K 1.6K 1.4K 1.2K 1K 800 600 400 200 Becerril, H.A.; Woolley, A.T. DNA-Templated Nanofabrication. Chem. Soc. Rev. in press (2008). Stewart, J.T.; Becerril, H.A.; Yang, W.; Larsen, M.G.; Woolley, A.T. DNA-Templated Nanowires as Sacrificial Materials for Creating Nanocapillaries. Proceedings of SPIE (2008), 7035(Biosensing), 70350H/1-70350H/8. J. Liu, H.A. Becerril, M.V. Lee, K. Nelson, E. Bird, L. Hutchins, H. Conley, D.R. Wheeler, R.C. Davis, A.T. Woolley, M.R. Linford, J.N. Harb. Chemically Directed Surface Alignment and Wiring of SelfAssembled Nanoelectrical Circuits, In: Proceedings of 5th Annual Conference of Foundations of Nanoscience: Top-down Meets Bottom-up, p.12-16, FNANO08, Snowbird, UT, USA, April 2008. H.A. Becerril, R.M. Stoltenberg, D.R. Wheeler, R.C. Davis, J.N. Harb, and A.T. Woolley, "DNATemplated Three-Branched Nanostructures for Nanoelectronic Devices", JACS, vol. 127, (2005), p. 2828. K.A. Nelson, S.T. Cosby, J.C. Blood, M.V. Lee, D.R. Wheeler, R.C. Davis, A.T. Woolley, M.R. Linford, J.N. 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