Abstract
The ability to control the placement of molecules is essential for the patterning and fabrication of nanoscale electronic devices. We apply selective chemistry and self-assembly in combination with conventional nanolithographic techniques to reach higher resolution, greater precision, and chemical versatility in the nanostructures that we create. We illustrate three successful approaches: (1) phase separation of self-assembled monolayers (SAMs) by terminal and internal functionalization, (2) phase separation of SAMs induced by post-adsorption processing and (3) control of molecular placement by insertion into a self-assembled monolayer. These methods demonstrate the possibilities of patterning films by exploiting the intrinsic properties of the molecules. We then employ these self-assembled monolayers as a means to isolate molecules with electronic function to determine the mechanisms of function, and the relationships between molecular structure, environment, connection, coupling, and function. Using self-assembly techniques in combination with scanning tunneling microscopy (STM) we are able to study candidate molecular switches individually and in small bundles. Alkanethiolate SAMs on gold are used as a host two-dimensional matrix to isolate and to insulate electrically the molecular switches. We then individually address and electronically probeeach moleculeusing STM. The conjugated molecules exhibit reversible conductance switching, manifested as a change in the topographic height in the STM images. The origins of switching and the relevant aspects of the molecular structure and environment required will be discussed.
This is a preview of subscription content, log in via an institution.
Buying options
Tax calculation will be finalised at checkout
Purchases are for personal use only
Learn about institutional subscriptionsPreview
Unable to display preview. Download preview PDF.
References
Rai-Chaudhury, P. (1997) Handbook of Microlithography, Micromachining, and Microfabrication; SPIE: London.
Xia, Y.N. and Whitesides, G.M. (1998) Soft lithography, Angewandte Chemie, International Edition, 37, 551–575.
Zhao, X.M., Xia, Y.N., and Whitesides, G.M. (1997) Soft lithographic methods for nano-fabrication, J. Mater. Chem. 7, 1069–1074.
Becker, R.S., Golovchenko, J.A., and Swartzentruber, B. S. (1987) Atomic-scale surface modifications using a tunneling microscope, Nature 325, 419–421.
Eigler, D.M. and Schweizer, E.K. (1990) Positioning single atoms with a scanning tunneling microscope, Nature 344, 524–526.
Weiss, P.S. and Eigler, D.M. (1993) NATO ASI Series E: Applied Sciences, 235, 213–217.
Gimzewski, J. K. and Joachim, C. (1999) Nanoscale science of single molecules using local probes, Science 283, 1683–1688.
Hla, S.-W., Bartels, L., Meyer, G., and Rieder, K.-H. (2000) Inducing all steps of a chemical reaction with a scanning tunneling microscope tip: Towards single molecule engineering, Phys. Rev. Lett. 85, 2777–2780.
Ulman, A. (1991) An Introduction to Ultrathin Organic Films: From Langmuir-Blodgett to Self-Assembly, Academic, San Diego.
Ulman, A. (1996) Formation and Structure of Self-Assembled Monolayers, Chem. Rev. 96, 1533–1554.
Nuzzo, R.G. and Allara, D.L. (1983) Adsorption of bifunctional organic disulfides on gold surfaces, J. Amer. Chem. Soc. 105, 4481–4483.
Allara, D.L. (1995) Critical issues in applications of self-assembled monolayers, Biosensors and Bioelectronics 10, 771–783.
Bain, C.D. and Whitesides, G.M. (1989) Formation of monolayers by the adsorption of thiols on gold: Variation in the length of the alkyl chain, J. Amer. Chem. Soc. 111, 7164–7175.
Bain, C.D. and Whitesides, G.M. (1989) A study by contact angle of the acid-base behavior of monolayers containing Ω-mercaptocarboxylic acids adsorbed on gold: An example of reactive spreading, Langmuir 5, 1370–1378.
Dubois, L.H. and Nuzzo, R.G. (1992) Synthesis, structure, and properties of model organic surfaces, Annu. Rev.Phys. Chem. 43, 437–463.
Poirier, G.E. (1997) Characterization of organosulfur molecular monolayers on Au(111) using scanning tunneling microscopy, Chem. Rev. 97, 1117–1127.
Hong, S., Zhu, J., and Mirkin, C.A. (1999) Multiple ink nanolithography: Toward a multiple pen nanoplotter, Science 286, 523–525.
Liu, G.-Y., Xu, S., and Qian, Y.L. (2000) Nanofabrication of self-assembled monolayers using scanning probe lithography, Acc. Chem. Res. 33, 457–466.
Zharnikov, M., Frey, S., Heister, K., and Grunze, M. (2000) Modification of alkanethiolate monolayers by low energy electron irradiation: Dependence on the substrate material and on the length and isotopic composition of the alkyl chains, Langmuir 16, 2697–2705.
Gölzhäuser, A., Geyer, W., Stadler, V., Eck, W., Grunze, M., Edinger, K., Weimann, T., and Hinze, P. (2000) Nanoscale patterning of self-assembled monolayers with electrons, Journal of Vacuum Science & Technology B 18, 3414–3418.
Heister, K., Zharnikov, M., Grunze, M., Johansson, L.S.O., and Ulman, A. (2001) Characterization of X-ray induced damage in alkanethiol monolayers by high-resolution photoelectron spectroscopy, Langmuir 17, 8–11.
Collet, J., Tharaud, O., Chapoton, A., and Vuillaume, D. (2000) Low-voltage, 30 nm channel length, organic transistors with a self-assembled as gate insulating films, Appl. Phys. Lett. 76, 1941–1943.
Collet, J. and Vuillaume, D. (1998) Nano-field effect transistor with an organic self-assembled monolayer as gate insulator, Appl. Phys. Lett. 73, 2681–2683.
Boulas, C., Davidovits, J.V., Rondelez, F., and Vuillaume, D. (1996) Suppression of charge carrier tunneling through organic self-assembled monolayers, Phys. Rev. Lett. 76, 4797–4800.
Lee, S.A., Yoshida, Y., Fukuyama, M., and Hotta, S. (1999) Phenyl-capped oligothiophenes: novel lightemitting materials with different molecular alignments in thin films, Synthetic Metals, 106, 39–43.
Bain, C.D. and Whitesides, G.M. (1988) Formation of 2-component surfaces by the spontaneous assembly of monolayers on gold from solutions containing mixtures of organic thiols, J. Amer. Chem. Soc. 110, 6560–6561.
Bain, C.D., Evall, J., and Whitesides, G.M. (1989) Formation of monolayers by the coadsorption of thiols on gold: Variation in the head group, tail group, and solvent, J. Amer. Chem. Soc. 111, 7155–7164.
Folkers, J.P., Laibinis, P.E., Whitesides, G.M., and Deutch, J. (1994) Phase behavior of two-component self-assembled monolayers of alkanethiolates on gold, J. Phys. Chem. 98, 563–571.
Smith, R.K., Reed, S.M., Lewis, P.A., Monnell, J.D., Clegg, R.S., Kelly, K.F., Bumm, L.A., Hutchison, J.E., and Weiss, P.S. (2001) Phase separation within a binary self-assembled monolayer on Au{111} driven by an amide-containing alkanethiol, J. Phys. Chem. B 105, 1119–1122.
Stranick, S.J., Parikh, A.N., Tao, Y.-T., Allara, D.L., and Weiss, P.S. (1994) Phase-separation of mixed-composition self-assembled monolayers into nanometer-scale molecular domains, J. Phys. Chem. 98, 7636–7646.
Stranick, S.J., Atre, S.V., Parikh, A.N., Wood, M.C., Allara, D.L., Winograd, N., and Weiss, P.S. (1996) Nanometer-scale phase separation in mixed composition self-assembled monolayers, Nanotechnology 7, 438–442.
Binnig, G., Rohrer, H., Gerber, C., and Weibel, E. (1982) Tunneling through a controllable vacuum gap, Appl. Phys. Lett. 40, 178–180.
Binnig, G., Quate, C.F., and Gerber, C. (1986) Atomic force microscope, Phys. Rev. Lett. 56, 930–933.
Delamarche, E., Michel, B., Gerber, C., Anselmetti, D., Güntherodt, H.-J., Wolf, H., and Ringsdorf, H. (1994) Real-space observation of nanoscale molecular domains in self-assembled monolayers, Langmuir 10, 2869–2871.
Anselmetti, D., Baratoff, A., Güntherodt, H.-J., Delamarche, E., Michel, B., Gerber, C., Kang, H., Wolf, H., and Ringsdorf, H. (1994) Domain and molecular superlattice structure of dodecanethiol self-assembled On Au(111), Europhys. Lett. 27, 365–370.
Camillone, N., Eisenberger, P., Leung, T.Y.B., Schwartz, P., Scoles, G., Poirier, G.E., and Tarlov, M.J. (1994) New monolayer phases of n-alkanethiols self-assembled on Au(111): Preparation, surface characterization, and imaging, J. Chem. Phys. 101, 11031–11036.
Bumm, L.A., Arnold, J.J., Charles, L.F., Dunbar, T.D., Allara, D.L., and Weiss, P.S. (1999) Directed self-assembly to create molecular terraces with molecularly sharp boundaries in organic monolayers, J. Amer. Chem. Soc. 121, 8017–8021.
Clegg, R.S. and Hutchison, J.E. (1996) Hydrogen-bonding, self-assembled monolayers: Ordered molecular films for study of through-peptide electron transfer, Langmuir 12, 5239–5243.
Clegg, R.S. and Hutchison, J.E. (1999) Control of monolayer assembly structure by hydrogen bonding rather than by adsorbate-substrate templating, J. Amer. Chem. Soc. 121, 5319–5327.
Clegg, R.S., Reed, S.M., Smith, R.K., Barron, B.L., Rear, J.A., and Hutchison, J.E. (1999) The interplay of lateral and tiered interactions in stratified self-organized molecular assemblies, Langmuir 15, 8876–8883.
Lewis, P.A., Smith, R.K., Kelly, K.F., Bumm, L.A., Reed, S.M., Clegg, R.S., Gunderson, J.D., Hutchison, J.E., and Weiss, P.S. (2001) The role of buried hydrogen bonds in self-assembled mixed composition thiols on Au{111}, J. Phys. Chem. B 105, 10630–10636.
Finklea, H.O., Ravenscroft, M.S., and Snider, D.A. (1993) Electrolyte and temperature effects on long-range electron-transfer across self-assembled monolayers, Langmuir 9, 223–227.
Bumm, L.A., Arnold, J.J., Dunbar, T.D., Allara, D.L., and Weiss, P.S. (1999) Electron transfer through organic molecules, J. Phys. Chem. B 103, 8122–8127.
Weiss, P.S., Bumm, L.A., Dunbar, T.D., Burgin, T.P., Tour, J.M., and Allara, D.L. (1998) Molecular Electronics: Science and Technology 852, 145–168.
Arnold, J.J. (1997) Masters thesis, The Pennsylvania State University, University Park.
Tour, J.M. (2000) Molecular electronics: Synthesis and testing of components, Acc. Chem. Res. 33, 791–804.
Cygan, M.T., Dunbar, T.D., Arnold, J.J., Bumm, L.A., Shedlock, N.F., Burgin, T.P., Jones, L., Allara, D.L., Tour, J.M., and Weiss, P.S. (1998) Insertion, conductivity, and structures of conjugated organic oligomers in self-assembled alkanethiol monolayers on Au{111}, J. Amer. Chem. Soc. 120, 2721–2732.
Bumm, L.A., Arnold, J.J., Cygan, M.T., Dunbar, T.D., Burgin, T.P., Jones II, L., Allara, D.L., Tour, J.M., and Weiss, P.S. (1996) Are single molecular wires conducting?, Science 271, 1705–1707.
Langlais, V.J., Schlittler, R.R., Tang, H., Gourdon, A., Joachim, C., and Gimzewski, J.K. (1999) Spatially resolved tunneling along a molecular wire, Phys. Rev. Lett. 83, 2809–2812.
Moresco, F., Meyer, G., Rieder, K.-H., Tang, H., Gourdon, A., and Joachim, C. (2001) Conformational changes of single molecules induced by scanning tunneling microscopy manipulation: A route to molecular switching, Phys. Rev. Lett. 86, 672–675.
Donhauser, Z.J., Mantooth, B.A., Kelly, K.F., Bumm, L.A., Monnell, J.D., Stapleton, J.J., Price, D.W., Rawlett, A.M., Allara, D.L., Tour, J.M., and Weiss, P.S. (2001) Conductance switching in single molecules through conformational changes, Science 292, 2303–2307.
Joachim, C., Gimzewski, J.K., Schlittler, R.R., and Chavy, C. (1995) Electronic transparency of a single C60 molecule, Phys. Rev. Lett. 74, 2102–2105.
Reed, M.A., Chen, J., Rawlett, A.M., Price, D.W., and Tour, J.M. (2001) Molecular random access memory cell, Appl. Phys. Lett. 78, 3735–3737.
Chen, J., Wang, W., Reed, M.A., Rawlett, A.M., Price, D.W., and Tour, J.M. (2000) Room-temperature negative differential resistance in nanoscale molecular junctions, Appl. Phys. Lett. 77, 1224–1226.
Chen, J., Reed, M.A., Rawlett, A.M., and Tour, J.M. (1999) Large on—off ratios and negative differential resistance in a molecular electronic device, Science 286, 1550–1552.
Seminario, J.M., Zacarias, A.G., and Tour, J.M. (2000) Theoretical study of a molecular resonant tunneling diode, J. Amer. Chem. Soc. 122, 3015–3020.
Seminario, J.M., Zacarias, A.G., and Tour, J.M. (1998) Molecular current-voltage characteristics, J. Amer. Chem. Soc. 120, 3970–3397.
Tour, J.M. (1996) Conjugated macromolecules of precise length and constitution. Organic synthesis for the construction of nanoarchitectures`, Chem. Rev. 96, 537–553.
Tour, J.M., Kozaki, M., and Seminario, J.M. (1998) Molecular scale electronics: A synthetic/computational approach to digital computing, J. Amer. Chem. Soc. 120, 8486–8493.
Tour, J.M., Reinerth, W.A., Jones II, L., Burgin, T.P., Zhou, C.W., Muller, C.J., Deshpande, M.R., and Reed, M.A. (1998) Molecular Electronics: Science and Technology, 852, 197–204.
Di Ventra, M., Kim, S.G., Pantelides, S.T., and Lang, N.D. (2001) Temperature effects on the transport properties of molecules, Phys. Rev. Lett. 86, 288–291.
Weck, M., Jackiw, J.J., Weiss, P.S., and Grubbs, R.H. (1998) Ring-opening metathesis polymerization from surfaces, Proceedings of Polymers, Materials Science, and Engineering 79, 72–73.
Weck, M., Jackiw, J.J., Rossi, R.R., Weiss, P.S., and Grubbs, R.H. (1999) Ring-opening metathesis polymerization from surfaces, J. Amer. Chem. Soc. 121, 4088–4089.
Charles, L.F. (1999) Masters thesis, The Pennsylvania State University: University Park.
Sakaguchi, H., Kelly, K.F., Donhauser, Z.J., Lewis, P.A., and Weiss, P.S., manuscript in preparation.
Donhauser, Z.J., Price II, D.W., Tour, J.M., and Weiss, P.S. (2003) Control of alkanethiolate monolayer structure using vapor-phase annealing, J. Amer. Chem. Soc. 125, 11462–11463.
Molecular Imaging Corp., Phoenix, AZ, USA.
Mantooth, B.A., Donhauser, Z.J., Kelly, K.F., and Weiss, P.S. (2002) Cross-correlation image tracking for drift correction and adsorbate analysis, Review of Scientific Instruments 73, 313–317.
Herrmann, C.F. and Boland, J.J. (1999) Probing repulsive interactions on the Si(100)(2x1) surface by local tip-induced excitation, J. Phys. Chem. B 103, 4207–4211.
Akpati, H.C., Norlander, P., Lou, L., and Avouris, P. (1997) The effects of an external electric field on the adatom-surface bond: H and Al adsorbed on Si(111), Surface Science 372, 9–20.
Tao, Y.-T., Wu, C.C., Eu, J.Y., Lin, W.L., and Wu, K.C. (1997) Structure evolution of aromatic-derivatized thiol monolayers on evaporated gold, Langmuir 13, 4018–4023.
Sellers, H., Ulman, A., Shnidman, Y., and Eilers, J.E. (1993) Structure and bonding of alkanethiolates on gold and silver surfaces: Implications for self-assembled monolayers, J. Amer. Chem. Soc. 115, 9389–9401.
Kornilovitch, P.E. and Bratkovsky, A.M. (2001) Orientational dependence of current through molecular films, Phys. Rev. B 64, 5413–5417.
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2005 Kluwer Academic Publishers
About this paper
Cite this paper
Kelly, K., Donhauser, Z., Lewis, P., Smith, R., Weiss, P. (2005). Nanometer-Scale Electronics and Storage. In: Vilarinho, P.M., Rosenwaks, Y., Kingon, A. (eds) Scanning Probe Microscopy: Characterization, Nanofabrication and Device Application of Functional Materials. NATO Science Series II: Mathematics, Physics and Chemistry, vol 186. Springer, Dordrecht. https://doi.org/10.1007/1-4020-3019-3_15
Download citation
DOI: https://doi.org/10.1007/1-4020-3019-3_15
Publisher Name: Springer, Dordrecht
Print ISBN: 978-1-4020-3017-8
Online ISBN: 978-1-4020-3019-2
eBook Packages: Physics and AstronomyPhysics and Astronomy (R0)