Skip to main content Accessibility help

Excited State Charge Transfer in Dyads of ZnO Nanocrystals and Organic or Transition Metal Dyes

  • Julia E. Saunders (a1), Adam S. Huss (a2), Jon Bohnsack (a3), Kent R. Mann (a4), David A. Blank (a5) and Wayne L. L. Gladfelter (a6)...


To better understand the specific charge transfer events that occur within a dye-sensitized solar cell (DSSC), we synthesized well-defined ZnO:dye dyads. The ZnO nanocrystals were synthesized following literature procedures from zinc acetate and a hydroxide source in ethanol. The absorption onset of the ZnO nanocrystals was observed using UV-vis measurements, from which estimated nanocrystal diameters were determined. At room temperature, the synthesis yielded nanocrystals ranging in diameter from 2-4 nm. Dispersions of ZnO nanocrystals in ethanol were mixed with solutions containing 5΄΄-phenyl-3΄,4΄-di(nbutyl)-[2,2΄:5΄,2΄΄] terthiophene-5-carboxylic acid. Using FT-IR and fluorescence spectroscopy, it was verified that the dye molecules were adsorbed to the ZnO surface via their carboxylate groups while the number of dye molecules adsorbed to the surface was quantified using a combination of techniques. Adsorption isotherms were employed to probe surface coverage of the dye onto the nanocrystals to yield an adsorption equilibrium constant of 1.5 ± 0.2 x 105 M-1. The ability of ZnO nanocrystals to quench the emission of the dye by an electron transfer mechanism was observed and elucidated using ultra-fast laser spectroscopy where the time-scale for electron injection from the dye to the ZnO was determined to be 5.5 ps.



Hide All
1 O'Regan, B. and Gratzel, M., Nature 353 (6346), 737740 (1991).
2 Graetzel, M., Inorg. Chem. 44 (20), 68416851 (2005).
3 O'Regan, B. and Graetzel, M., Nature 353 (6346), 737740 (1991).
4 Ardo, S. and Meyer, G. J., Chem. Soc. Rev. 38 (1), 115164 (2009).
5 Anderson, N. A. and Lian, T., Annu. Rev. Phys. Chem. 56 (1), 491519 (2005).
6 Tachibana, Y., Nazeeruddin, M. K., Gratzel, M., Klug, D. R. and Durrant, J. R., Chemical Physics 285 (1), 127132 (2002).
7 Kallioinen, J., Benkoe, G., Myllyperkioe, P., Khriachtchev, L., Skrman, B., Wallenberg, R., Tuomikoski, M., Korppi-Tommola, J., Sundstroem, V. and Yartsev, A. P., J. Phys. Chem. B 108 (20), 63656373 (2004).
8 Wenger, B., Graetzel, M. and Moser, J.-E., Journal of the American Chemical Society 127 (35), 1215012151 (2005).
9 Law, M., Greene, L. E., Johnson, J. C., Saykally, R. and Yang, P., Nature Materials 4 (6), 455459 (2005).
10 Wolden, C. A., Barnes, T. M., Baxter, J. B. and Aydil, E. S., Journal of Applied Physics 97 (4), 043522/043521–043522/043527 (2005).
11 Baxter, J. B. and Aydil, E. S., Solar Energy Materials & Solar Cells 90 (5), 607622 (2006).
12 Ravirajan, P., Peiro, A. M., Nazeeruddin, M. K., Graetzel, M., Bradley, D. D. C., Durrant, J. R. and Nelson, J., J. Phys. Chem. B 110 (15), 76357639 (2006).
13 Bahnemann, D. W., Kormann, C. and Hoffmann, M. R., Journal of Physical Chemistry 91 (14), 37893798 (1987).
14 Spanhel, L. and Anderson, M. A., Journal of the American Chemical Society 113 (8), 28262833 (1991).
15 Meulenkamp, E. A., J. Phys. Chem. B 102 (29), 55665572 (1998).
16 Wong, E. M., Bonevich, J. E. and Searson, P. C., J. Phys. Chem. B 102 (40), 77707775 (1998).
17 Schwartz, D. A. and Gamelin, D. R., Proceedings of SPIE-The International Society for Optical Engineering 5224 (Nanomaterials and Their Optical Applications), 1–7 (2003).
18 Law, M., Goldberger, J. and Yang, P., Annual Review of Materials Research 34, 83122 (2004).
19 Yin, M., Gu, Y., Kuskovsky, I. L., Andelman, T., Zhu, Y., Neumark, G. F. and O'Brien, S., Journal of the American Chemical Society 126 (20), 62066207 (2004).
20 Kahn, M. L., Monge, M., Colliere, V., Senocq, F., Maisonnat, A. and Chaudret, B., Advanced Functional Materials 15 (3), 458468 (2005).
21 Andelman, T., Gong, Y., Polking, M., Yin, M., Kuskovsky, I., Neumark, G. and O'Brien, S., J. Phys. Chem. B 109 (30), 1431414318 (2005).
22 Greene, L. E., Yuhas, B. D., Law, M., Zitoun, D. and Yang, P., Inorganic Chemistry 45 (19), 75357543 (2006).
23 Luo, B., Rossini, J. E. and Gladfelter, W. L., Langmuir 25 (22), 1313313141 (2009).
24 Schwartz, D. A., Norberg, N. S., Nguyen, Q. P., Parker, J. M. and Gamelin, D. R., Journal of the American Chemical Society 125 (43), 1320513218 (2003).
25 Saunders, J. E., Huss, A. S., Mann, K. R., Blank, D. A. and Gladfelter, W. L., manuscript to be submitted.
26 Fillinger, A. and Parkinson, B. A., J. Electrochem. Soc. 146 (12), 45594564 (1999).
27 Fillinger, A., Soltz, D. and Parkinson, B. A., J. Electrochem. Soc. 149 (9), A1146–A1156 (2002).



Full text views

Total number of HTML views: 0
Total number of PDF views: 0 *
Loading metrics...

Abstract views

Total abstract views: 0 *
Loading metrics...

* Views captured on Cambridge Core between <date>. This data will be updated every 24 hours.

Usage data cannot currently be displayed