Chain Length Dependence of the Structuee and Wetting Properties in Binary Composition Monolayers of OH- and CH3-Terminated Alkanethiolates on Gold

Langmuir

Volumn 11, Issue 10, 1995, Pages 3882-3893

  Atre, Sundar V ^a,b   Liedberg, Bo ^a,b   Allara, David L ^a,b  

^a PENNSYLVANIA STATE UNIVERSITY   (United States)

^b LINKÖPING UNIVERSITY   (Sweden)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000097939     PISSN: 07437463     EISSN: 15205827     Source Type: Journal    
DOI: 10.1021/la00010a045     Document Type: Article

References (111)

1. Bain, C. D.; Whitesides, G. M. J. Am. Chem. Soc. 1988, 110, 6560-6561.
2. Bain, C. D.; Whitesides, G. M. J. Am. Chem. Soc. 1988, 110, 3665-3666.
3. Bain, C. D.; Whitesides, G. M. Science 1988, 240 62-63.
4. Bain, C. D.; Biebuyck, H. A.; Whitesides, G. M. Langmuir 1989, 5, 723-727.
5. Laibinis, P. E.; Fox, M. A.; Folkers, J. P.; Whitesides, G. M. Langmuir 1991, 7, 3167-3173.
6. Evans, S. D.; Sharma, R.; Ulman, A. Langmuir 1991, 7, 156-161.
7. Siepmann, J. I.; McDonald, I. R. Molec. Phys. 1992, 75, 255-259.
8. Overney, R. M.; Frommer, J.; Brodbeck, D.; Lüthi, R.; Howald, L.; Güntherodt, H. J.; Fujhira, M.; Takano, H.; Gotoh, Y. Nature 1992, 359, 133-135.
9. Möhwald, H. J. Mol. Electron. 1988, 4, 47-55.
10. Biebuyck, H. A.; Whitesides, G. M. Langmuir 1993, 9, 1766-1770.
11. Troughton, E. B.; Bain, C. D.; Whitesides, G. M.; Nuzzo, R. G.; Allara, D. L.; Porter, D. L. Langmuir 1988, 4, 365-385.
12. Laibinis, P. E.; Whitesides, G. M. J. Am. Chem. Soc. 1992, 114, 1990-1995.
13. Silberzan, P.; Léger, L.; Ausserré, D.; Benattar, J. Langmuir 1991, 7, 1647-1651.
14. Dubois, L. H.; Nuzzo, R. G. Annu. Rev. Phys. Chem. 1992, 43, 437-463.
15. Bain, C. D.; Evall, J.; Whitesides, G. M. J. Am. Chem. Soc. 1989, 111, 7155-7164.
16. Bain, C. D.; Whitesides, G. M. J. Am. Chem. Soc. 1989, 111, 7164-7175.
17. Chidsey, C. E. D.; Bertozzi, C. R.; Putvinski, T. M.; Mujsce, A. M. J. Am. Chem. Soc. 1990, 112, 4301-4306.
18. Chidsey, C. E. D. Science 1991, 251, 919-922.
19. Collard, D. M.; Fox, M. A. Langmuir 1991, 7, 1192-1197.
20. Rowe, G. K.; Creager, S. E. Langmuir 1991, 7, 2307-2312.
21. Hickman, J. J.; Ofer, D.; Laibinis, P. E.; Whitesides, G. M.; Wrighton, M. S. Science 1991, 252, 688-691.
22. Bain, C. D.; Whitesides, G. M. Langmuir 1989, 5, 1370-1378.
23. Ulman, A.; Evans, S. D.; Shnidman, Y.; Sharma, R.; Eilers, J. E.; Chang, J. C. J. Am. Chem. Soc. 1991, 113, 1499-1506.
24. Prime, K. L.; Whitesides, G. M. Science 1991, 252, 1164-1167.
25. Pale-Grosdemange, C.; Simon, E. S.; Prime, K. L.; Whitesides, G. M. J. Am. Chem. Soc. 1991, 113, 12-20.
26. Haussling, L.; Michel, B.; Ringsdorf, H.; Rohrer, H. Angew. Chem., Int. Ed. Engl. 1991, 30, 569-572.
27. Sanassy, P.; Evans, S. D. Langmuir 1993, 9, 1024-1027.
28. Parikh, A. N.; Liedberg, B.; Atre, S. V.; Ho, M.; Allara, D. L. J. Phys. Chem. 1995, 99, 9996-10008
29. Strong, L.; Whitesides, G. M. Langmuir 1988, 4, 546-558.
30. Chidsey, C. E. D.; Loicano, D. N. Langmuir 1990, 6, 682-691.
31. X-ray diffraction (XRD): Fenter, P.; Eisenberger, P.; Liang, K. S. Phys. Rev. Lett. 1993, 70, 437-447.
32. IRS: Nuzzo, R. G.; Dubois, L. H.; Allara, D. L. J. Am. Chem. Soc. 1990, 112, 558-569.
33. Raman spectroscopy: Bryant, M. E.; Pemberton, J. E. J. Am. Chem. Soc. 1991, 113, 8284-8293.
34. Molecular dynamics simulations: Hautman, J.; Klein, M. L. J. Chem. Phys. 1989, 91, 4994-5001. Low-energy He atom diffraction studies:
35. Chidsey, C. E. D.; Liu, G.-Y.; Rowntree, P.; Scoles, G. J. Chem. Phys. 1989, 91, 4421-4423.
36. Camillone, N., III; Chidsey, C. E. D.; Liu, G.-Y.; Scoles, G. J. Chem. Phys. 1991, 94, 8493-8502.
37. Scanning tunneling microscopy (STM): Widrig, C. A.; Alves, C. A.; Porter, M. D. J. Am. Chem. Soc. 1991, 113, 2805-2810.
38. Kim, Y.-T.; Bard, A. J. Langmuir 1992, 8, 1096-1102.
39. Sun, L.; Crooks, R. M. Langmuir 1993, 9, 1951-1954.
40. Edinger, K.; Gölzhäuser, A.; Demota, K.; W611, C.; Grunze, M. Langmuir 1993, 9, 4-8.
41. Poirier, G. E.; Tarlov, M. J. Langmuir 1994, 10, 2853-2856.
42. Laibims, P. E.; Whitesides, G. M.; Allara, D. L.; Tao, Y.-T.; Parikh, A. N.; Nuzzo, R. G. J. Am. Chem. Soc. 1991, 113, 7152-7167.
43. Bain, C. D.; Troughton, E. B.; Tao, Y.-T.; Evall, J.; Whitesides, G. M.; Nuzzo, R. G. J. Am. Chem. Soc. 1989, 111, 321-335.
44. Folkers, J. P.; Laibims, P. E.; Whitesides, G. M. Langmuir 1992, 8, 1330-1341.
45. Folkers, J. P.; Laibinis, P. E.; Whitesides, G. M. J. Adhesion Sci. Technol. 1992, 6, 1397-1410.
46. For example, it has been noted in electron-transfer studies involving ferrocenyl- and CH3-terminated alkanethiolate SAMs on Au that the electroactive ferrocenyl groups need to be well-separated from each other by the n-alkyl component in order to ensuee observation of identical, isolated electrochemical events.9 On the other hand, in order to mimic domains of receptor sites such as coated pits on cell surfaces, lateral distributions of the order of about 100 nm would be typically required (Goldstein, J. L.; Anderson, R. G. W.; Brown, M. S. Nature 1979, 279, 679-685). Finally, the extension of functional groups away from a surface is relevant to biological interfaces where functional group mobilities are thought to be important
47. Brier-Russell, D.; Salzman, E. W.; Lindon, J.; Handin, R.; Merrill, E. W.; Dincer, A. K.; Wu, J.-S. J. Colloid Interface Sci. 1981, 87, 311-318.
48. Reichert, W.M.; Filisko, F. E.; Barenburg, S. A. J. Biomed. Mater. Res. 1982, 16, 301-312.
49. Merrill, E. VI. Ann. N. Y. Acad. Sci. 1987, 516, 196-203.
50. Hausslmg, L.; Knoll, W.; Ringsdorf, H.; Schmitt, F.-J.; Yang, J. Makromol. Chem. Macromol. Symp. 1991, 46, 145-1551
51. Creighton, T. E. Prog. Biophys. Mol. Biol. 1978, 33, 231-297.
52. Hanein, D.; Sabanay, H.; Addadi, L.; Geiger, B. J. Cell Sci. 1993, 104, 275-288.
53. Hanein, D.; Geiger, B.; Addadi, L. Langmuir 1993, 9, 1058-1065.
54. Bertilsson, L.; Liedberg, B. Langmuir 1993, 9, 141-149.
55. Groth, P. Acta Chem. Scand. 1979, A33, 199-201.
56. Kay, H. F.; Newman, B. A. Acta Crystallogr. 1968, B24, 615-624.
57. Sheen, C. W.; Martensson, J.; Shi, J.; Parikh, A. N.; Allara, D. L. J. Am. Chem. Soc. 1992, 114, 1524-1525.
58. Sheen, C. W.; Allara, D. L. Unpublished results.
59. Folkers, J. P.; Laibinis, P. E.; Whitesides, G. M.; Deutch, J. J Phys. Chem. 1994, 98, 563-571.
60. Allara, D. L.; Nuzzo, R. G. Langmuir 1985, 1, 45-52.
61. Porter, M. D.; Bright, T. B.; Allara, D. L.; Chidsey, C. E. D. J. Am. Chem. Soc. 1987, 109, 3559-3568.
62. Bain, C. D.; Whitesides, G. M. J. Phys. Chem. 1989, 93, 1670-1673.
63. Laibinis., P. E.; Bain, C. D.; Whitesides, G. M. J. Phys. Chem. 1991, 95, 7017-7021.
64. Israelachvili, J. N. Intermoleular and Surface Forces; Academic: New York, 1985.
65. Cassie, A. B. D. Discuss. Faraday Soc. 1948, 3, 11-16.
66. Adamson, A. W. Physical Chemistry of Surfaces, 5th ed.; John Wiley & Sons: New York, 1990; pp 385-389.
67. Israelachvili, J. N.; Gee, M. L. Langmuir 1989, 5, 288-289.
68. For general experimental examples of wetting-induced redis tribution of chain conformations and wetting-induced reorientation of functional groups, see: Holmes-Farley, S. R.; Reamey, R. H.; Nuzzo, R. G.; McCarthy, T. J.; Whitesides, G. M. Langmuir 1967, 3, 799-815.
69. Cross, E. M.; McCarthy, T. J. Macromolecules 1990, 53, 3916-3922.
70. Wilson, M.D.; Whitesides, G. M. J. Am. Chem. Soc. 1988, 110, 8718-8719.
71. Holmes-Farley, S. R.; Whitesides, G. M. Langmuir 1987, 3, 62.
72. Snyder, R. H.; Schachtschneider, J. H. Spectrochim. Acta 1963, 19, 83-116.
73. Stuart, A. V.; Sutherland, G. B. B. M. J. Chem. Phys. 1956, 24, 559-570.
74. Snyder, R. G., J. Mol. Spectrosc. 1961, 7, 116-144.
75. MacPhail, R. A.; Strauss, H. L.; Snyder, R. G.; Elliger, C. A. J. Phys. Chem. 1984, 88, 334-341.
76. Snyder, R. G.; Strauss, H. L.; Elliger, C. A. J. Chem. Phys. 1982, 86, 5145-5150.
77. Snyder, R. G.; Maroncelli, M.; Strauss, H. L.; Hallmark, V. M. J. Chem. Phys. 1986, 90, 5623-5630.
78. Laibinis, P. E.; Nuzzo, R. G.; Whitesides, G. M. J. Phys. Chem. 1992, 96, 5097-5105.
79. Atre, S. V.; Allara, D. L.; Snyder, R. G.; Elliger, C. A. Manuscript in preparation.
80. Parikh, A. N.; Allara, D. L. J. Chem. Phys. 1992, 96, 927-945.
81. Snyder, R. G. Macromolecules 1990, 23, 2081-2087.
82. Calculations weee carried out using effective medium theory [generalized Maxwell-Garnett model: Maxwell-Garnett, J. C. Phil. Trans. 1904, 203, 385.
83. Maxwell-Garnett, J. C. Phil. Trans. 1906, 205, 237] in which the infrared optical functions for islanded and isotropic distributions of the protruding chains weee determined starting from independently known values of the optical function spectra of the pure compounds (Shi, J.-X. M.S. Thesis, The Pennsylvania State University, University Park, PA). The calculations show that the d intensities for equal coverage mixed 1:1 films of long and short chains increase with increased islanding of the long chains. Details will be published elsewhere (Parikh, A. N., Allara, D. L. Manuscript in preparation).
84. The r spectra of alkyl chains depend upon both spatial and temporal effects and ared strongly temperature and orientationally dependent (MacPhail, R. A.; Snyder, R. G.; Strauss, H. L. J. Chem. Phys. 1982, 86, 1118-1137).
85. 3 plane are broadened near room temperature to form an asymmetric singlet peak, typically at ∼2956 cm-1, for isotropic samples such as polycrystalline n-alkanes (MacPhail, R. A.; Snyder, R. G.; Strauss, H. L. J. Chem. Phys. 1982, 86, 1118-1137) and a variety of alkyl compounds. Shifts of the ra'/rb intensity ratio can arise for a variety of reasons, including structural and orientational50 effects, leading to apparent shifts in the average r” peak position.
86. Allara, D. L.; Nuzzo, R. G. Langmuir 1985, 1, 52-66.
87. Schlotter, N. E.; Porter, M. D.; Bright, T. B.; Allara, D. L. Chem. Phys. Lett. 1986, 132, 93-98.
88. Tao, Y.-T. J. Am. Chem. Soc. 1993, 115, 4350-4358.
89. Sondag, A. H. M.; Raas, M. C. J. Chem. Phys. 1989, 91, 4926-4931.
90. Dunbar, T. E.; Sheen, C. W.; Allara, D. L. Unpublished results.
91. Saperstein, D. J. Phys. Chem. 1986, 90, 1408-1412.
92. 3-terminated SAMs/Au with liquids such as water and methanol (IRS: Stole, S. M.; Porter, M. D. Langmuir 1990, 6, 1199-1202.
93. Sum frequency generation spectra: Ong, T. H.; Ward, R. N.; Davies, P. B.; Bain, C. D. J. Am. Chem. Soc. 1992, 114, 6243-6245).
94. -1 in going from the liquid to the vapor phase at room temperature (Cameron, D. G.; Hsi, S. C.; Umemura, J.; Mantsch, H. H. Can. J. Chem. 1981, 59, 1357-1360), an observation attributed to increased rotational motion and reduced intermolecular interactions upon vaporization. While this shift is similar to that observed with the emergence of CH3 groups from the mixed SAM surface (increasing m), one must use caution since the average CH3-CH3 spacing (volume density) in the mixed SAMs is ∼2 orders of magnitude higher than for an ideal gas at room temperature.
95. Bellamy, L. J. The Infrared Spectra of Complex Molecules, Chapman and Hall: London, 1975.
96. Allara, D. L.; Parikh, A. N.; Judge, E. J. Chem. Phys. 1994, 100, 1714-1717.
97. Stranick, S.; Parikh, A. N.; Tao, Y.-T.; Allara, D. L.; Weiss, P. S. J. Phys. Chem. 1994, 98, 7636-7646.
98. Recent time-of-flight secondary ion mass spectrometry investigations of RAuR' cluster peaks from equal chain length OH/CH3 mixed SAMs indicate the existence of phase segregated domains on a nanometer scale (Wood, M.; Atre, S. V.; Liedberg, B.; Zhou, Y.; Allara, D. L.; Winograd, N. Manuscript in preparation).
99. Bhatia, R.; Garrison, B. J. Personal communication.
100. The mechanism(s) by which phase segregation in SAMs arises remains unclear. Published STM experiments (ref 63) show that the surface motion of alkanethiolate chains on a Au{111} substrate appears insufficient to significantly alter the distribution of a once-formed mixed SAM at room temperature. On this basis, it appears that phase segregation must arise during the deposition process and that solvation effects may be important. Experiments centering on solvent effects in the formation of mixed SAM structures using scanning tip microscopies are in progress and will be reported elsewhere [Dunbar, T. E.; Cygan, M.; Allara, D. L.; Weiss, P. S. Unpublished results.
101. Coulman, D.; Parikh, A. N.; Allara, D. L. Unpublished results]
102. de Gennes, P. G. Rev. Mod. Phys. 1985, 57, 827-863.
103. Billmeyer, F. W. Textbook of Polymer Science; John Wiley and Sons: New York, 1994.
104. Frommer, J. Angew. Chem., Int. Ed. Engl. 1992, 31, 1298-1328.
105. Wilson, M. D.; Ferguson, G. S.; Whitesides, G. M. J. Am. Chem. Soc. 1990, 112, 1244-1245.
106. Smith, A. E. Acta Crystallogr. 1952, 5, 224-235.
107. Relevant to this point, it has been reported Bain, C.D.; Whitesides, G. M. J. Am. Chem. Soc. 1988, 110, 5897-5898.
108. 20 molecules) would be given by those at tilt-phase boundaries, ∼19 Å for the above mercapto ether given a 60° (=2 x 30°) chain-chain angle along the phase boundary.
109. Laibinis, P. E.; Bain, C. D.; Nuzzo, R. G.; Whitesides, G. M. J. Phys. Chem. 1995, 99, 7663-7676.
110. 3 groups rather than OH groups, further comparisons with the mixed SAM data are difficult at this point.
111. Experiments involving in situ analyses of the liquid/SAM interface are underway using spectroscopic ellipsometry (SE) Shi, J.; Hong, B.; Parikh, A. N.; Collins, R. W.; Allara, D. L. Chem. Phys. Lett, in press.