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Self-Assembly of Oriented Metal Bisphosphonate Multilayers with Potential Nonlinear Optical Properties

Published online by Cambridge University Press:  15 February 2011

Grace Ann Neff ,
Astrid C. Zeppenfeld ,
Bethany Klopfenstein  and
Catherine J. Page
Grace Ann Neff
Affiliation:
University of Oregon, Department of Chemistry, Eugene, Oregon 97403
Astrid C. Zeppenfeld
Affiliation:
University of Oregon, Department of Chemistry, Eugene, Oregon 97403
Bethany Klopfenstein
Affiliation:
University of Oregon, Department of Chemistry, Eugene, Oregon 97403
Catherine J. Page
Affiliation:
University of Oregon, Department of Chemistry, Eugene, Oregon 97403
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Abstract

We are investigating a method for synthesizing oriented layered thin film structures that exhibit nonlinear optical properties. This method involves self-assembly of metal bisphosphonate multilayers on gold and silicon substrates. Multilayers are characterized via optical ellipsometry, diffuse reflectance and attenuated total reflectance FTIR, and grazing angle X-ray diffraction.

To incorporate nonlinear optical activity into self-assembled films, we use a,w-bisphosphonates containing aromatic π systems sandwiched between donor and acceptor groups. In order to maximize the overall polarizability of the film, the polarizable bisphosphonate molecules must preferentially bind in only one orientation. To accomplish this, one of the terminal phosphonate groups of the molecule is protected (in ester form). After binding the free phosphonic acid end, the terminal ester is converted to a phosphonic acid group by hydrolysis with bromotrimethylsilane (BTMS). Layering is continued by binding a metal layer and repeating the cycle. Films prepared via this route do exhibit second harmonic generation, but apparently incomplete deprotection of each layer leads to increasing disorder with increasing number of layers.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 351: Symposium V – Molecularly Designed Ultrafine/Nanostructured Materials , 1994 , 269
Copyright
Copyright © Materials Research Society 1994

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References

REFERENCES

1. a) Lee, H., Kepley, L.J., Hong, H.-G., Mallouk, T.E., J. Am. Chem. Soc. 110, 618–620 (1988). b) H. Lee, L.J. Kepley, H.-G. Hong, S. Akhter, T.E. Mallouk, J. Phys. Chem., 92, 2597-2601 (1988).Google Scholar
2. Dines, M.B., DiGiacomo, P.M., Inorg. Chem., 20, 92–97 (1981)Google Scholar
3. Katz, H.E., Scheller, G., Putvinski, T.M., Schilling, M.L., Wilson, W.L., Chidsey, C.E.D., Science, 254, 1485–1487 (1991)Google Scholar
4. Neff, G.A., unpublished results.Google Scholar
5. a) Staring, E. G. J., Rikken, G. L. J. A., Seppen, C. J. E., Nijhuis, S., and Venhuizen, A. H. J., Adv. Mat., 3, 401 (1991). b) D. F. Eaton, G. R. Meredith, and J. S. Miller, Adv. Mat., 3, 564 (1991). c) Wenjiang Nie, Adv. Mat., 5, 520 (1993).Google Scholar
6. Morita, T., Okamoto, Y., and Sakurai, H., Bull. Chem. Soc. Japan, 51, 2169–2170 (1978)Google Scholar
7. Klopfenstein, B. and Page, C.J., in press.Google Scholar
8. Goss, C.A., Charych, D.H., and Majda, M., Anal. Chem. 63, 85 (1991).Google Scholar
9. Hong, H.-G., Sackett, D.D., Mallouk, T.E., Chem. Mater., 3, 521–527 (1991)Google Scholar
10. Tompkins, H.L., A User's Gude to Ellipsometry. (Academic Press, Inc., San Diego, CA, 1993), p. 36.Google Scholar
11. Zeppenfeld, A.C. and Page, C.J., in press.Google Scholar
12. Frey, B.L., Hanken, D.G., and Corn, R.M., Langmuir, 9, 1815–1820 (1993).Google Scholar
13. Porter, M.D., Bright, T. B., Allara, D. L, and Chidsey, C.E.D., J. Am. Chem. Soc., 109, 3559–3568 (1987)Google Scholar
14. Yang, H.C., Aoki, K., Hong, H., Sackett, D.D., Rendt, M.F., Yau, S., Bell, C.M., and Mallouk, T.E., J. Am. Chem. Soc., 115, 11855–11862 (1993).Google Scholar
15. We have observed SHG from these films, but experimental details and substrate inconsistencies limit our quantification of signal at this time.Google Scholar
16. Morita, T., Okamoto, Y., and Sakurai, H., Bull. Chem. Soc. Jpn., 54, 267–273 (1981)Google Scholar