Molecular rectification in a metal-insulator-metal junction based on self-assembled monolayers

Journal of the American Chemical Society

Volumn 124, Issue 39, 2002, Pages 11730-11736

  Chabinyc, Michael L ^a   Chen, Xiaoxi ^a   Holmlin, R Erik ^a   Jacobs, Heiko ^a   Skulason, Hjalti ^b   Frisbie, C Daniel ^b   Mujica, Vladimiro ^c   Ratner, Mark A ^c   Rampi, Maria Anita ^d   Whitesides, George M ^a  

^a HARVARD UNIVERSITY   (United States)

^b University of Minnesota ^*  (United States)

^c NORTHWESTERN UNIVERSITY   (United States)

^d UNIVERSITY OF FERRARA   (Italy)

Author keywords

[No Author keywords available]

Indexed keywords

ELECTRIC JUNCTIONS;

ELECTRIC CONDUCTIVITY; ELECTRIC CURRENTS; ELECTRIC INSULATORS; ELECTRIC POTENTIAL; ELECTRIC PROPERTIES;

MONOLAYERS;

ALKYL GROUP; GOLD; MERCURY; METAL; NITRILE; SILVER;

ARTICLE; COVALENT BOND; DIPOLE; ELECTRIC CONDUCTIVITY; ELECTRIC CURRENT; ELECTRIC POTENTIAL; MOLECULAR INTERACTION; OXIDATION REDUCTION REACTION;

DISULFIDES; ELECTRIC CONDUCTIVITY; ELECTROCHEMISTRY; ELECTROSTATICS; GOLD; MERCURY; NITRILES; SILVER;

EID: 0037010021     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja020506c     Document Type: Article

References (50)

1. Aviram, A. J. Am. Soc. 1988, 110, 5687-92.
2. Metzger, R. M. Acc. Chem. Res. 1999, 32, 950-957.
3. Joachim, C.; Gimzewski, J. K.; Aviram, A. Nature (London) 2000, 408 541-548.
4. Ellenbogen, J. C.; Ratner, M. A. Proc. IEEE 2000, 88, 386-426.
5. Aviram, A.; Ratner, M. A. Chem. Phys. Lett. 1974, 29, 277-83.
6. Martin, A. S.; Sambles, J. R.; Ashwell, G. J. Phys. Rev. Lett. 1993, 70, 218-221.
7. A number of workers have demonstrated rectification by organic monolayers using scanning probe microscopy. We focus here on results obtained from measurements on ensembles of molecules. For example, see: Pomerantz, M.; A. Aviram, McCorkle, R. A.; Li, L.; Schrott, A. G. Science 1992, 255, 1115-1118; Dhirani, A.; Lin, P.-H.; Guyot-Sionnest, P.; Zehner R. W.; Sita, L. R. J. Chem. Phys. 1997, 106, 5249-5253.
8. A number of workers have demonstrated rectification by organic monolayers using scanning probe microscopy. We focus here on results obtained from measurements on ensembles of molecules. For example, see: Pomerantz, M.; A. Aviram, McCorkle, R. A.; Li, L.; Schrott, A. G. Science 1992, 255, 1115-1118; Dhirani, A.; Lin, P.-H.; Guyot-Sionnest, P.; Zehner R. W.; Sita, L. R. J. Chem. Phys. 1997, 106, 5249-5253.
9. Xu, T.; Peterson, I. R.; Lakshmikantham, M. V.; Metzger, R. M. Angew. Chem., Int. Ed. 2001, 40, 1749-1752.
10. Vuillaume, D.; Chen, B.; Metzger, R. M. Langmuir 1999, 15, 4011-4017.
11. Wong, E. W.; Collier, C. P.; Behloradsky, M.; Raymo, F. M.; Stoddart, J. F.; Heath, J. R. J. Am. Chem. Soc. 2000, 122, 5831-5840.
12. Zhou, C.; Deshpande, M. R.; Reed, M. A.; Jones L., II; Tour, J. M. Appl. Phys. Lett. 1997, 71, 611-613.
13. Konstantine, K.; Zhang, P.; Opila, R. L.; Allara, D. L. Surf. Sci. 1995, 338, 300-312.
14. Haag, R.; Rampi, M. A.; Holmlin, R. E.; Whitesides, G. M. J. Am. Chem. Soc. 1999, 121, 7895-7906.
15. Rampi, M. A.; Schueller, O. J. A.; Whitesides, G. M. Appl. Phys. Lett. 1998, 72, 1781-1783.
16. Holmlin, R. E.; Haag, R.; Chabinyc, M. L.; Ismagilov, R. F.; Cohen, A. E.; Terfort, A.; Rampi, M.; Whitesides, G. M. J. Am. Chem. Soc. 2001, 123, 5075-5085.
17. Holmlin, R. E.; Ismagilov, R. F.; Haag, R.; Mujica, V.; Ratner, M. A.; Rampi, M.; Whitesides, G. M. Angew. Chem., Int. Ed. 2001, 40, 2316-2320.
18. Slowinski, K.; Fong, H. K. Y.; Majda, M. J. Am. Chem. Soc. 1999, 121, 7257-7261.
19. Slowinski, K.; Majda, M. J. Electroanal. Chem. 2000, 491, 139-147.
20. Porter, J. D.; Zinn-Warner, A. S. Phys. Rev. Lett. 1994, 73, 2879-82.
21. Porter, J. D.; Zinn, A. S. J. Phys. Chem. 1993, 97, 1190-203.
22. The refractive index of the SAM was assumed to be the same as that for a SAM of an alkanethiolate (1.45). We do not believe that the assumption of this value of the refractive index will create a substantial error in the derived value of the thickness.
23. Metzger, R. M.; Xu, T.; Peterson, I. R. J. Phys. Chem. B 2001, 105, 7280-7290.
24. Ashwell, G. J.; Gandolfo, D. S. J. Mater. Chem. 2001, 11, 246-248. Ashwell and co-workers have observed rectification using different donor acceptor systems in a MIM jumnction: Ashwell, G. J.; Gandolfo, D. S. J. Mater. Chem. 2002, 12, 411-415. Ashwell, G. J.; Gandolfo, D. S.; Hamilton, R. J. Mater. Chem. 2002, 12, 416-419.
25. Ashwell, G. J.; Gandolfo, D. S. J. Mater. Chem. 2001, 11, 246-248. Ashwell and co-workers have observed rectification using different donor acceptor systems in a MIM jumnction: Ashwell, G. J.; Gandolfo, D. S. J. Mater. Chem. 2002, 12, 411-415. Ashwell, G. J.; Gandolfo, D. S.; Hamilton, R. J. Mater. Chem. 2002, 12, 416-419.
26. Ashwell and co-workers have observed rectification using different donor acceptor systems in a MIM jumnction: Ashwell, G. J.; Gandolfo, D. S. J. Mater. Chem. 2002, 12, 411-415. Ashwell, G. J.; Gandolfo, D. S.; Hamilton, R. J. Mater. Chem. 2002, 12, 416-419.
27. Skulason, H.; Frisbie, C. D. Langmuir 1998, 14, 5834-5840.
28. Majda and co-workers have observed this behavior in a similar MIM junction where both metal electrodes are formed from liquid mercury. Ref 17, 18.
29. The refractive index of the SAM was assumed to be the same as that for a SAM of an alkanethiolate (1.45). We do not believe that the assumption of this value of the refractive index will create a substantial error in the derived value of the thickness.
30. Porter, M. D.; Bright, T. B.; Allara, D. L.; Chidsey, C. E. D. J. Am. Chem. Soc. 1987, 109, 3559-3568.
31. Smalley, J. F.; Feldberg, S. W.; Chidsey, C. E. D.; Linford, M. R.; Newton, M. D.; Liu, Y.-P. J. Phys. Chem. 1995, 99, 13141-13149.
32. Metzger has shown that the rectification in MIM junctions formed with HQ-TCNQ is not caused by electrodes containing a metal oxide as well: Xu, T.; Peterson, I. R.; Lakshmikantham, M. V.; Metzger, R. M. Angew. Chem., Int. Ed. 2001, 40, 1749-1752.
33. Weast, R. C., Ed. CRC Handbook of Chemistry and Physics; CRC Press: Boca Raton, FL, 1987.
34. We base our discussion on a valence orbital representation and treat the orbitals of TCNQ separately from those of the alkyl chain. The π symmetry states of TCNQ are unlikely to mix strongly with the alkyl chain due to symmetry and difference in energy.
35. Bartmess, J. E. In NIST Chemistry WebBook, NIST Standard Reference Database 69; Mallard, W. G., Linstrom, P. J., Eds.; National Institute of Standards and Technology: Gaithersburg, MD, 1998.
36. Datta, S.; Tian, W.; Hong, S.; Reifenberger, R.; Henderson, J. I.; Kubiak, C. P. Phys. Rev. Lett. 1997, 79, 2530-2533.
37. Mujica, V.; Roitberg, A. E.; Ratner, M. J. Chem. Phys. 2000, 112, 6834-6839.
38. Mujica, V.; Ratner, M. A. Chem. Phys. 2001, 264, 365-370.
39. Ratner, M. A. J. Phys. Chem. 1990, 94, 4877-4883.
40. Ag-(Cn)II(C16)-Hg where the insulating layer contains only one type of functional group). See ref 16.
41. Gonzalez, C.; Mujica, V.; Ratner, M. Ann. New York Acad. Sci. 2002, 960, 161-176.
42. Mujica, V.; Nitzan, A.; Ratner, M. A. Chem. Phys. 2002, 281, 147-150.
43. Ratner, M. A.; Davis, B.; Kemp, M.; Mujica, V.; Roitberg, A.; Yaliraki, S. Ann. N. Y. Acad. Sci. 1998, 852, 22-37.
44. Tian, W.; Datta, S.; Hong, S.; Reifenberger, R.; Henderson, J. I.; Kubiak, C. P. J. Chem. Phys. 1998, 109, 2874-2882.
45. Samanta, M. P.; Tian, W.; Datta, S.; Henderson, J. I.; Kubiak, C. P. Phys. Rev. B: Condens. Matter 1996, 53, R7626-R7629.
46. Hall, L. E.; Reimers, J. R.; Hush, N. S.; Silverbrook, K. J. Chem. Phys. 2000, 112, 1510-1521.
47. It is difficult to determine whether this assumption is valid for the junctions studied here. We assume that the qualitative predictions of the model are valid, but a more detailed analysis of the system will require testing of this assumption.
48. Experimental evidence and model theoretical calculations indicate that, for many homogeneous molecular MIM junctions, the voltage drops at the two metal-molecule interfaces and also across the molecular bridge: Samanta, M. P.; Tian, W.; Datta, S.; Henderson, J. I.; Kubiak, C. P. Phys. Rev. B 1996, 53, R7626-R7629. Damle, P. S.; Ghosh, A. W.; Datta, S. Phys. Rev. B 2001, 64, 201403-1.
49. Experimental evidence and model theoretical calculations indicate that, for many homogeneous molecular MIM junctions, the voltage drops at the two metal-molecule interfaces and also across the molecular bridge: Samanta, M. P.; Tian, W.; Datta, S.; Henderson, J. I.; Kubiak, C. P. Phys. Rev. B 1996, 53, R7626-R7629. Damle, P. S.; Ghosh, A. W.; Datta, S. Phys. Rev. B 2001, 64, 201403-1.
50. Krzeminski, C.; Delerue, C.; Allan, G.; Vuillaume, D.; Metzger, R. M. Phys. Rev. B 2001, 64, 085405-1.