Probing electronic properties of conjugated and saturated molecules in self-assembled monolayers

Annals of the New York Academy of Sciences

Volumn 852, Issue , 1998, Pages 145-168

  Weiss, P S ^a   Bumm, L A ^a   Dunbar, T D ^a   Burgin, T P ^b   Tour, J M ^b   Allara, D L ^a  

^a PENNSYLVANIA STATE UNIVERSITY   (United States)

^b UNIVERSITY OF SOUTH CAROLINA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

GOLD;

ALTERNATING CURRENT; CONDUCTANCE; CONFERENCE PAPER; ELECTRODE; ELECTRON TRANSPORT; SCANNING TUNNELING MICROSCOPY; SEMICONDUCTOR;

EID: 0031872667     PISSN: 00778923     EISSN: None     Source Type: Book Series    
DOI: 10.1111/j.1749-6632.1998.tb09869.x     Document Type: Conference Paper

References (92)

1. BARBARA, P.F., T.J. MEYER & M.A. RATNER. 1996. Contemporary issues in Electron Transfer Research. J. Phys. Chem. 100: 13148-13168.
2. ARNAUT L.G. & S.J. FORMOSINHO. 1996. Theoretical studies of intramolecular electron transfer reactions: Distance and free energy dependences. J. Photochem. Photobiol. A: Chem. 100: 15-34.
3. MOSER, C.C., J.M. KESKE, K. WARNCKE, R.S. FARID & J.P. DUTTON. 1992. Nature of biological electron transfer. Nature 355: 796-802.
4. HOLMLIN, R.E., P.J. DANDLIKER & J. K. BARTON. 1997. Charge transfer through the DNA base stack. Angew. Chem. Int. Ed. Engl. 36: 2714-2730.
5. GRATZEL, M. 1989. Heterogeneous Photochemical Electron Transfer. CRC Press. Boca Raton, FL. Fox, M.A. & M. Chanon, Eds. 1988. Photoinduced Electron Transfer. Elsevier Science Publishers. Amsterdam, The Netherlands.
6. GRAY, H.B. & J.R. WINKLER. 1996. Electron transfer in proteins. Ann. Rev. Biochem. 65: 537-561.
7. CLOSS, G.L. & J.R. MILLER. 1988. Intramolecular long-distance electron transfer in organic molecules. Science 240: 440-447.
8. PADDON-ROW M.N., A.M. OLIVER, J.M. WARMAN, K.J. SMIT, M.P. DE HAAS, H. OEVERING & J.W. VERHOEVEN. 1988. Factors affecting charge separation and recombination in photoexcited rigid donor-insulator-acceptor compounds. J. Phys. Chem. 92: 6958-6962.
9. PAULSON, B., K. PRAMOD, P. EATON, G. CLOSS & J.R. MILLER. 1993. Long-distance electron transfer through rodlike molecules with cubyl spacers. J. Phys. Chem. 97: 13042-13045.
10. CHIDSEY, C.E.D. 1991. Free energy and temperature dependence of electron transfer at the metal-electrolyte interface. Science 251: 919-922.
11. MILLER, C., P. CUENDET & M. GRATZEL. 1991. Adsorbed ω-hydroxy thiol monolayers on gold electrodes: Evidence for electron tunneling to redox species in solution. J. Phys. Chem. 95: 877-886.
12. FINKLEA, H.O., L. LIU, M.S. RAVENSCROFT & S. PUNTURI. 1996. Multiple electron tunneling paths across self-assembled monolayers of alkanethiols with attached ruthenium(II/III) redox centers. J. Phys. Chem. 100: 18852-18858.
13. LI, T.T.-T. & M.J. WEAVER. 1984. Intramolecular electron transfer at metal surfaces. 4. Dependence of tunneling probability upon donor-acceptor separation distance. J. Am. Chem. Soc. 106: 6107-6108.
14. SACHS, S.B., S.P. DUDEK, R.P. HSUNG, L.R. SITA, J.F. SMALLEY, M.D. NEWTON, S.W. FELDBERG & C.E.D. CHIDSEY. 1997. Rates of interfacial electron transfer through π-conjugated spacers. J. Am. Chem. Soc. 119: 10563-10564.
15. CARTER, M.T, G.K. ROWE, J.N. RICHARDSON, L.M. TENDER, R.H. TERRILL & R.W. MURRAY. 1995. Distance dependence of the low-temperature electron transfer kinetics of (ferrocenylcarboxy)-terminated alkanethiol monolayers. J. Am. Chem. Soc. 117: 2896-2899.
16. POYMEROPOULOS, E.E. & J. SAGIV. 1978. Electrical conduction through adsorbed monolayers. J. Chem. Phys. 69: 1836-1847.
17. REED, M.A., C. ZHOU, C.J. MULLER, T.P. BURGIN & J.M. TOUR. 1997. Conductance of a molecular junction. Science. 278: 252-253.
18. ZHOU, C., M.R. DESHPANDE, M.A. REED, L. JONES II & J.M. TOUR. 1997. Nanoscale metal/self-assembled monolayer/metal heterostructures. Appl. Phys. Lett. 71: 611-613.
19. ANDRES, R.P., J.I. HENDERSON, R.G. OSIFCHIN, W. MAHONEY, C.P. KUBIAK, R. REIFENBERGER, S. FENG, M. DOROGI & T. BEIN. 1996. "Coulomb staircase" at room temperature in a self-assembled molecular nanostructure. Science. 272: 1323-1324.
20. ANDRES, R.P., J.D. BIELEFELD, J.I. HENDERSON, D.B. JANES, V.R. KOLAGUNTA, C. P. KUBIAK, W.J. MAHONEY & R.G. OSIFCHIN. 1996. Self-assembly of a two-dimensional superlattice of molecularly linked metal clusters. Science 273: 1690-1691.
21. TANS, S.J., A. THESS, L.J. GEERLIGS & R.E. SMALLEY. 1997. Individual single-wall carbon nanotubes as quantum wires. Nature 386: 474-476.
22. LANGER, L., V. BAYOT, E. GRIVEI, J.-P. ISSI, J.P. HEREMANS, C.H. OLK, L. STOCK-MAN, C. VAN HAESENDONCK & Y. BRUYNSERAEDE. 1996. Quantum transport in a multiwalled carbon nanotube. Phys. Rev. Lett. 76: 479-482.
23. EBBESEN, T.W., H.J. LEZEC, H. HIURA, J.W. BENNETT, H.F GHAEMI & T. THIO. 1996. Electrical conductivity of individual carbon nanotubes. Nature 382: 54-56.
24. DAI, H., E.W. WONG & C.M. LIEBER. 1996. Probing electrical transport in nanomaterials: Conductivity of individual carbon nanontubes. Science 272: 523-526.
25. THESS, A., R. LEE, P. NIKOLAEV, H. DAI, P. PETIT, J. ROBERT, C. XU, Y.H. LEE, S.G. KIM, A.G. RINZLER, D.T. COLBERT, G.E. SCUSERIA, D. TOMÁNEK, J.E. FISCHER & R.E. SMALLEY 1996. Crystalline ropes of metallic carbon nanotubes. Science 273: 483-487.
26. BUMM, L.A., J.J. ARNOLD, M.T. CYGAN, I.D. DUNBAR, T.P. BURGIN, L. JONES II, D.L. ALLARA & P.S. WEISS. 1996. Are single molecular wires conducting? Science 271: 1705-1707.
27. CYGAN, M.T., T.D. DUNBAR, J.J. ARNOLD, L.A. BUMM, N.B. SHEDLOCK, T.P. BURGIN, L. JONES II, D.L. ALLARA, J.M. TOUR & P.S. WEISS. 1998. Insertion, conductivity, and structures of conjugated organic oligomers in self-assembled alkanethiol monolayers on Au{111}. J. Am. Chem. Soc. 120: 2721-2732.
28. BUMM, L.A., J.J. ARNOLD, T.D. DUNBAR, D.L. ALLARA & P.S. WEISS. Electron transport through organic molecules. Manuscript in preparation.
29. 60 molecule. Phys. Rev. Lett. 74: 2102-2105.
30. JOACHIM, C. & J.K. GIMZEWSKI. 1997. An electromechanical amplifier using a single molecule. Chem. Phys. Lett. 265: 353-357.
31. YAZDANI, A., D.M. EIGLER & N.D. LANG. 1996. Off-resonance conduction through atomic wires. Science 272: 1921-1924.
32. SALMERON, M., G. NEUBAUER, A. FOLCH, M. TOMITORI, D.F. OGLETREE & P. SAUTET. 1993. Viscoelastic and electrical properties of self-assembled monolayers on Au(111) films. Langmuir 9: 3600-3611.
33. DATTA, S., W. TIAN, S. HONG, R. REIFENBERGER, J.I. HENDERSON & C.P. KUBIAK. 1997. Current-voltage characteristics of self-assembled monolayers by scanning tunneling microscopy. Phys. Rev. Lett. 79: 2530-2533.
34. SAMANTA M.P., W. TIAN, S. DATTA, J.I. HENDERSON & C.P. KUBIAK. 1996. Electronic conduction through organic molecules. Phys. Rev. B. 53: R7626-R7629.
35. The height of the tip is measured in the laboratory frame, not relative to the sample surface.
36. SAUTET, P. 1997. Images of adsorbates with the scanning tunneling microscope: Theoretical approaches to the contrast mechanism. Chem. Rev. 97: 1097-1116.
37. VAN HOVE, M.A., J. CERDA, P. SAUTET, M.-L. BOCQUET & M. SALMERON. 1997. Surface structure determination by STM vs LEED. Prog. Surf. Sci. 54: 315-329.
38. PETTY, M.C., M.R. BRYCE & D. BLOOR, Eds. 1995. An Introduction to Molecular Electronics. Oxford University Press. New York.
39. AVIRAM, A. Ed. 1992. Molecular Electronics: Science and Technology, Conference Proceeding No. 262. American Institute of Physics. New York.
40. REED, M.A. & W.P. KIRK, Eds. 1989. Nanostructure Physics and Fabrication. Academic Press. New York.
41. REED, M.A. & W.P. KIRK, Eds. 1992. Nanostructures and Mesoscopic Systems. Academic Press. New York.
42. CARTER, F.L., Ed. 1987. Molecular Electronic Devices II. Marcel Dekker. New York.
43. MILLER, J.S. 1990. Molecular electronics? Adv. Mater. 2: 378-379, 495-497, 601-603.
44. JOACHIM, C. 1991. The conductance of a single molecule. New J. Chem. 15: 223-229.
45. TOUR, J.M. 1996. Conjugated macromolecules of precise length and constitution. Organic synthesis for the construction of nanoarchitectures. Chem. Rev. 96: 537-553.
46. TOUR, J.M., L. JONES II, D.L. PEARSON, J.J.S. LAMBA, T.P. BURGIN, G.M. WHITESIDES, D.L. ALLARA, A.N. PARIKH & S.V. ATRE. 1995. Self-assembled monolayers and multilayers of conjugated thiols, α,ω-dithiols, and thioacetyl-containing adsorbates. Understanding attachments between potential molecular wires and gold surfaces. J. Am. Chem. Soc. 117: 9529-9534.
47. PEARSON, D.L. & J.M. TOUR. 1997. Rapid syntheses of oligo(2,5-thiophene ethynylene)s with thioester termini: Potential molecular scale wires with alligator clips. J. Org. Chem. 62: 1376-1387.
48. JONES, L., II, J.S. SCHUMM & J.M. TOUR. 1997. Rapid solution and solid phase syntheses of oligo(1,4-phenylene ethynylene)s with thioester termini: Molecular scale wires with alligator clips. Derivation of iterative reaction efficiencies on a polymer support. J. Org. Chem. 62: 1388-1410.
49. MAGOGA, M. & C. JOACHIM. 1997. Conductance and transparence of long molecular wires. Phys. Rev. B 56: 4722-4729.
50. LANDAUER, R. 1987. Electrical transport in open and closed systems. Z. Phys. B. 68: 217-228.
51. LANDAUER, R. 1989. Conductance determined by transmission: Probes and quantized constriction resistance. J. Phys. Condens. Matter. 1: 8099-8110.
52. JOACHIM, C. & J.F. VINUESA. 1996. Length dependence of the electronic transparence (conductance) of a molecular wire. Europhys. Lett. 33: 635-640,
53. CHIDSEY, C.E.D., D.N. LOIACONO, T. SLEATOR & S. NAKAHARA. 1988. STM study of the surface morphology of gold on mica. Surf. Sci. 200: 45-66.
54. REFINING SYSTEMS, P.O. Box 72466, Las Vegas, NV 89170.
55. ASHVILLE-SCHOONMAKER MICA Co., 900 Jefferson Ave., P.O. Box 318, Newport News, VA 23607.
56. ALDRICH, 1001 W. St. Paul Ave., Milwaukee, WI 53233 (http://www.sial.com/).
57. BUMM, L.A., J.J. ARNOLD, L.F CHARLES, T.D. DUNBAR, D.L. ALLARA & P.S. WEISS. Creating molecular terraces with molecularly sharp boundaries in organic monolayers. Manuscript in preparation.
58. BESOCKE, K. 1987. An easily operable scanning tunneling microscope. Surf. Sci. 181: 145-153.
59. FROHN, J., J.F. WOLF, K. BESOCKE & M. TESKE. 1989. Coarse tip distance adjustment and positioner for a scanning tunneling microscope. Rev. Sci. Instrum. 60: 1200-1201.
60. KOCHANSKI, G.P. 1989. Nonlinear alternating-current tunneling microscopy. Phys. Rev. Lett. 62: 2285-2288.
61. MICHEL, B., W. MIZUTANI, R. SCHIERLE, A. JAROSCH, W. KNOP, H. BENEDIKTER, W. BACHTOLD & H. ROHRER. 1992. Scanning surface harmonic microscopy: Scanning probe microscopy based on microwave field-induced harmonic generation. Rev. Sci. Instrum. 63: 4080-4085.
62. SEIFERT, W., E. GERNER, M. STACHEL & K. DRANSFELD, 1992. Scanning tunneling microscopy at microwave frequencies. Ultramicroscopy 42-44: 379-387.
63. STRANICK, S.J. & P.S. WEISS. 1993. A versatile microwave frequency-compatible scanning tunneling microscope. Rev. Sci. Instrum. 64: 1232-1234.
64. BOURGOIN, J.-P., M.B. JOHNSON & B. MICHEL. 1994. Semiconductor characterization with the scanning surface harmonic microscope. Appl. Phys. Lett. 65: 2045-2047.
65. JOHNSON, M.B., J.-P. BOURGOIN & B. MICHEL. 1994. Doping profiling with scanning surface harmonic microscopy. Microelectronic Engineering. 27: 539-542.
66. BOURGOIN, J.-P., M.B. JOHNSON & B. MICHEL. 1994. Scanning surface harmonic microscopy: Application to silicon and Langmuir-Blodgett films on silicon. Microsc. Microanal. Microstruct. 5: 535-543.
67. STRANICK, S.J. & P.S. WEISS. 1994. A tunable microwave frequency alternating current scanning tunneling microscope. Rev. Sci. Instrum. 65: 918-921.
68. STRANICK, S.J. & P.S. WEISS. 1994. Alternating current scanning tunneling microscopy and nonlinear spectroscopy. J. Phys. Chem. 98: 1762-1764.
69. STRANICK, S.J., M.M. KAMNA & P.S. WEISS. 1994. A low temperature, ultrahigh vacuum, microwave-frequency-compatible scanning tunneling microscope. Rev. Sci. Instrum. 65: 3211-3215.
70. STRANICK, S.J., L.A. BUMM, M.M. KAMNA & P.S. WEISS. 1995. Linear and nonlinear spectroscopy with the tunable AC scanning tunneling microscope. In Photons and Local Probes. O. Marti & R. Moller, Eds. NATO ASI Series E: Applied Sciences. 300: 221-233. Kluwer Academic. Dordrecht, The Netherlands.
71. BUMM, L.A. & P.S. WEISS. 1995. Small cavity nonresonant tunable microwave-frequency alternating current scanning tunneling microscope. Rev. Sci. Instrum. 66: 4140-4145.
72. HEWLETT-PACKARD Co., P.O. Box 4026, Englewood, CO 80155-4026 (http:// www.hp.com/).
73. AXON INSTRUMENTS INC., 1101 Chess Dr., Foster City, CA 94404 (http:// www.axonet.com/).
74. DUNLOP, D., S. SMITH, C. BUSTAMANTE, J. TAMAYO & R. GARCIA. 1995. A very low current scanning tunneling microscope. Rev. Sci. Instrum. 66: 4876-4879.
75. We have limited the bandwidth of the CV4 signal used of STM feedback control with a 4 pole Bessel low pass filter. This gives us an excellent signal to noise for current feedback and also the ability to simultaneously use the frequencies above this band for other measurements.
76. STANFORD RESEARCH SYSTEMS, 1290 D Reamwood Ave., Sunnyvale, CA 94089 (http://www.srsys.com/srsys)
77. WEISENDANGER, R. 1994. Scanning Probe Microscopy and Spectroscopy. Cambridge University Press. New York.
78. POIRIER, G.E. 1997. Characterization of organosulfur molecular monolayers on Au(111) using scanning tunneling microscopy. Chem. Rev. 97: 1117-1127.
79. 80,83,84 This compares to -2.2-2.4 Å obtained from ellipsometry. Note that chain twist does not effect this value when the lengths differ by an even number of methylene units.
80. DUBOIS, L.H. & R.G. Nuzzo. 1992. Synthesis, structure, and properties of model organic surfaces. Annu. Rev. Phys. Chem. 43: 437-463.
81. ALLEN, F.H., O. KENNARD, D.G. WATSON, L. BRAMMER, A.G. ORPEN & R. TAYLOR. 1987. Tables of bond lengths determined by x-ray and neutron diffraction. Part I. Bond lengths in organic compounds. J. Chem. Soc. Perkin. Trans. II. 1987: S1-S19.
82. BURKERT, U. & N.L. ALLINGER. 1982. Molecular Mechanics, ACS monograph. Vol. 177. American Chemical Society. Washington, DC.
83. SHI, J., B. HONG, A.N. PARIKH, R.W. COLLINS & D.L. ALLARA. 1995. Optical characterization of electronic transitions arising from the Au/S interface of self-assembled n-alkanethiolate monolayers. Chem. Phys. Lett. 246: 90-94.
84. LAIBINIS, P.E., G.M. WHITESIDES, D.L. ALLARA, Y.-T. TAO, A.N. PARIKH & R.G. NUZZO. 1991. Comparison of the structures and wetting properties of self-assembled monolayers of n-alkanethiols on the coinage metal surfaces, Cu, Ag, Au. J. Am. Chem. Soc. 113: 7152-7167.
85. OLESEN, L., M. BRANDBYGE, M.R. SØRENSEN, K.W. JACOBSEN, E. LÆGSGAARD, I. STENSGAARD & F. BESENBACHER. 1996. Apparent barrier height in scanning tunneling microscopy revisited. Phys. Rev. Lett. 76: 1485-1488.
86. HSU, C.-P. & R.A. MARCUS. 1997. A sequential formula for electronic coupling in long range bridge-assisted electron transfer: Formulation of theory and application to alkanethiol monolayers. J. Chem. Phys. 106: 584-598.
87. STRANICK, S.J., A.N. PARIKH, D.L. ALLARA & P.S. WEISS. 1994. A new mechanism for surface diffusion: Motion of a substrate-adsorbate complex. J. Phys. Chem. 98: 11135-11142.
88. KROM K.R. 1997. Structural effects of alkanethiol monolayers on the gold surface studied by molecular dynamics. Ph.D. Thesis. The Pennsylvania State University. University Park, PA.
89. The actual figure of merit is the power generated at the difference frequency. Assigning the output as a voltage or as a current is purely arbitrary, usually chosen based by experimental convenience and/or by the system impedance.
90. SZE, S.M. 1981. Physics of Semiconductor Devices. John Wiley & Sons. New York, NY.
91. MILLER, R.C. 1964. Optical second harmonic generation in piezoelectric crystals. Appl. Phys. Lett. 5: 17-19.
92. It may be possible to observe the effects of dielectric relaxation of the host 12 matrix on the field-induced polarization of PE3.