Electron transfer dynamics in nanocrystalline titanium dioxide solar cells sensitized with ruthenium or osmium polypyridyl complexes

Darius Kuciauskas, Michael S. Freund, Harry B. Gray, Jay R. Winkler, Nathan S Lewis

Research output: Contribution to journalArticle

253 Citations (Scopus)

Abstract

The electron transfer dynamics in solar cells that utilize sensitized nanocrystalline titanium dioxide photoelectrodes and the iodide/triiodide redpx couple have been studied on a nanosecond time scale. The . ruthenium and osmium bipyridyl complexes Ru(H2L′)2(CN)2, Os(H2L′)2(CN)2, Ru(H2L′)2(NCS)2, and Os(H2L′)2(NCS)2, where H2L′ is 4,4′-dicarboxylic acid 2,2′-bipyridine, inject electrons into the semiconductor with a rate constant >108 s-1. The effects of excitation intensity, temperature, and applied potential on the recombination reaction were analyzed using a second-order kinetics model. The rates of charge recombination decrease with increasing driving force to the oxidized sensitizer, indicating that charge recombination occurs in the Marcus inverted region. The electronic coupling factors between the oxidized sensitizer and the injected electrons in TiO2 and the reorganization energies for the recombination reaction vary significantly for the different metal complexes. The charge recombination rates are well described by semiclassical electron transfer theory with reorganization energies of 0.55-1.18 eV. Solar cells sensitized with Ru(H2L′)2(CN)2, Os(H2L′)2- (CN)2, and Ru(H2L′)2(NCS)2 have favorable photoelectrochemical characteristics, and iodide is oxidized efficiently. In contrast, iodide oxidation limits the efficiency of cells based on sensitization of TiO2 with Os(H2L′)2(NCS)2. The observation that charge recombination occurs in the Marcus inverted region has important implications for the design of molecular sensitizers in nanocrystalline solar cells operated under our experimental conditions.

Original languageEnglish
Pages (from-to)392-403
Number of pages12
JournalJournal of Physical Chemistry B
Volume105
Issue number2
Publication statusPublished - Jan 18 2001

Fingerprint

Osmium
Ruthenium
osmium
titanium oxides
Titanium dioxide
iodides
ruthenium
recombination reactions
Solar cells
electron transfer
Iodides
solar cells
Electrons
dicarboxylic acids
Dicarboxylic Acids
2,2'-Dipyridyl
Coordination Complexes
electrons
Metal complexes
Rate constants

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Engineering(all)

Cite this

Electron transfer dynamics in nanocrystalline titanium dioxide solar cells sensitized with ruthenium or osmium polypyridyl complexes. / Kuciauskas, Darius; Freund, Michael S.; Gray, Harry B.; Winkler, Jay R.; Lewis, Nathan S.

In: Journal of Physical Chemistry B, Vol. 105, No. 2, 18.01.2001, p. 392-403.

Research output: Contribution to journalArticle

Kuciauskas, Darius ; Freund, Michael S. ; Gray, Harry B. ; Winkler, Jay R. ; Lewis, Nathan S. / Electron transfer dynamics in nanocrystalline titanium dioxide solar cells sensitized with ruthenium or osmium polypyridyl complexes. In: Journal of Physical Chemistry B. 2001 ; Vol. 105, No. 2. pp. 392-403.
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