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Stability of PPV Derivatives: The Effect of Side Group Functionalities

Published online by Cambridge University Press:  10 February 2011

B. H. Cumpston ,
K. F. Jensen ,
F. Klavettert ,
E. G. J. Staring  and
R. C. J. E. Demand
B. H. Cumpston
Affiliation:
Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, MA
K. F. Jensen
Affiliation:
Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, MA
F. Klavettert
Affiliation:
Uniax Corporation, Santa Barbara, CA, and
E. G. J. Staring
Affiliation:
Philips Research Labs, Eindhoven, The Neth0erlands
R. C. J. E. Demand
Affiliation:
Philips Research Labs, Eindhoven, The Neth0erlands
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Abstract

We have identified excited-state singlet oxygen as a reactive intermediate in the solid state photo-oxidation of two poly(p-phenylene vinylene) (PPV) derivatives, poly(2,5-bis(5,6- cholestanoxy)-1,4-phenylene vinylene) (BCHA-PPV) and poly(2-methoxy,5-(2'-ethyl-hexoxy)- 1,4-phenylene vinylene) (MEH-PPV). Singlet oxygen is photosensitized via energy transfer from the polymer and undergoes 1,2-cycloaddition across the electron-rich vinyl double bond in the backbone of the polymer resulting in the formation of highly oxidized species such as esters. Volatile carbonyl species are also formed, and, consequently, the film thins. This degradation pathway occurs when the polymer film is exposed in air to light having energy above the bandgap of the polymer, from either a low-pressure UV mercury lamp or an Ar+ laser operating at 514 or 457 nm. Interestingly, the singlet oxygen reaction does not take place in model compounds with similar structures such as trans-stilbene. In an effort to understand which properties of the polymer make it susceptible to singlet oxygen attack, we have studied the effect of conjugation length and side groups on the reactivity of thin polymer films. Specifically, the role of electron withdrawing groups, steric protection of the vinyl double bond, and conjugation length effects have been investigated using both FrIR spectroscopy and semi-empirical computational chemistry calculations.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 413: Symposium W – Electrical, Optical, and Magnetic Properties of Organic Solid State Materials III , 1995 , 35
Copyright
Copyright © Materials Research Society 1996

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References

REFERENCES

1. Burroughes, I. J.H., Bradley, D.D.C., Brown, A.R., Marks, R.N., Mackay, K., Friend, R.H., Burns, P.L., and Holmes, A.B., Nature, 347, 539 (1990).Google Scholar
2. Baignet, D.R., Grünham, N.C., Groiner, J., Marks, R.N., Friend, R.H., Moratti, S.C., and Holmes, A.B., Synthetic Metals, 67, 3 (1994).Google Scholar
3. Greenham, N.C., Moratti, S.C., Bradley, D.D.C., Friend, R.H., and Holmes, A.B., Nature, 365, 628 (1993).Google Scholar
4. Aratani, S., Zhang, C., Pakbaz, K., Hiöger, S., Wudl, F., and Heeger, A.J., J. Electronic Materials, 22, 745 (1993).Google Scholar
5. Scott, J.C., Kaufman, J.H., Brock, P.J., DiPietro, R., Salem, J., and Goitia, J.A., J. Appl. Phys., submitted, (1995).Google Scholar
6. Bradley, D.D.C., Synthetic Metals, 54, 401 (1993).Google Scholar
7. Staring, E.G.J., Demandt, R.C.J.E., Braun, D., Rikken, G.L.J., Kessener, Y.A.R.R., Venhuizen, T.H.J., Wynberg, H., ten Hoeve, W., and Spoelstra, K.J., Advanced Materials, 6, 934 (1994).Google Scholar
8. Lu, J.P., Nagarkar, P.V., Volfson, D., Trusell, F., Jensen, K.F., and Senturia, S.D., J. Vac. Sci. Technol., in press, (1995).Google Scholar
9. Carter, R.O., Gierczak, C.A., and Dickie, R.A., Applied Spectroscopy, 40, 649 (1986).Google Scholar
10. Greenler, R.G., J. Chem. Phys., 44, 310 (1966).Google Scholar
11. Dilks, A., in Photon, Electron, and Ion Properties of Polymer Structure and Properties, Dwight, D.W., Fabish, T.J., and Thomas, H.R., Editors, American Chemical Society, Washington, D.C., 293, (1981).Google Scholar
12. Brédas, J., Advanced Materials, 7, 263 (1995).Google Scholar
13. Cumpston, B.H. and Jensen, K.F., Synthetic Metals, 73, 195 (1995).Google Scholar
14. Yan, M., Rothberg, L.J., Papadimitrakopoulos, F., Galvin, M.E., and Miller, T.M., Physical Review Letters, 73, 744 (1994).Google Scholar
15. Scurlock, R.D., Wang, B., Ogilby, P.R., Sheats, J.R., and Clough, R.L., J. Am. Chem. Soc., in press, (1995).Google Scholar
16. Papadimitrakopoulos, F., Yan, M., Rothberg, L.J., Katz, H.E., Chandross, E.A., and Galvin, M.E., Mol. Cryst. Liq. Cryst., 6, 1563 (1994).Google Scholar
17. Gollnick, K., La Chimica E L'Industria, 64, 156 (1982).Google Scholar
18. Inamoto, N. and Masuda, S., Chemistry Letters, 1003 (1982).Google Scholar