DOI: 10.1073/pnas.1011972107. Photoinduced electron transfer from semiconductor quantum dots to metal oxide nanoparticles

Photoinduced electron transfer from semiconductor quantum dots to metal oxide nanoparticles

10.1073/pnas.1011972107

Crossref journal-article

Proceedings of the National Academy of Sciences

Proceedings of the National Academy of Sciences (341)

Abstract

Quantum dot-metal oxide junctions are an integral part of next-generation solar cells, light emitting diodes, and nanostructured electronic arrays. Here we present a comprehensive examination of electron transfer at these junctions, using a series of CdSe quantum dot donors (sizes 2.8, 3.3, 4.0, and 4.2 nm in diameter) and metal oxide nanoparticle acceptors (SnO2, TiO2, and ZnO). Apparent electron transfer rate constants showed strong dependence on change in system free energy, exhibiting a sharp rise at small driving forces followed by a modest rise further away from the characteristic reorganization energy. The observed trend mimics the predicted behavior of electron transfer from a single quantum state to a continuum of electron accepting states, such as those present in the conduction band of a metal oxide nanoparticle. In contrast with dye-sensitized metal oxide electron transfer studies, our systems did not exhibit unthermalized hot-electron injection due to relatively large ratios of electron cooling rate to electron transfer rate. To investigate the implications of these findings in photovoltaic cells, quantum dot-metal oxide working electrodes were constructed in an identical fashion to the films used for the electron transfer portion of the study. Interestingly, the films which exhibited the fastest electron transfer rates (SnO2) were not the same as those which showed the highest photocurrent (TiO2). These findings suggest that, in addition to electron transfer at the quantum dot-metal oxide interface, other electron transfer reactions play key roles in the determination of overall device efficiency.

Bibliography

Tvrdy, K., Frantsuzov, P. A., & Kamat, P. V. (2010). Photoinduced electron transfer from semiconductor quantum dots to metal oxide nanoparticles. Proceedings of the National Academy of Sciences, 108(1), 29â34.

Authors 3

Kevin Tvrdy (first)
Pavel A. Frantsuzov (additional)
Prashant V. Kamat (additional)

References 47 Referenced 617

10.1126/science.271.5251.933
10.1126/science.290.5490.314
10.1103/PhysRevB.53.16338
10.1038/nmat1390
10.1021/cr900137k
10.1038/nphoton.2009.83
10.1021/jp806791s
10.1021/jz100863b
10.1021/ja100106z
10.1021/ja8003683
10.1063/1.1742723
10.1021/j100370a056
10.1021/jp912133r
10.1063/1.480918
10.1021/jp046037d
10.1021/jp003485m
10.1146/annurev.physchem.55.091602.094347
10.1021/jp0483977
10.1021/jp077492n
10.1021/jp053948u
10.1021/cr00033a003
10.1146/annurev.matsci.30.1.475
10.1021/jp9944132
10.1021/ja070099a
10.1021/ja0782706
10.1021/ja00256a012
10.1021/jp0366771
10.1021/jp020453l
10.1021/nl9011744
10.1021/jp046781y
10.1021/jp808562x
10.1021/j100324a046
10.1021/jp0754583
10.1021/jp0652291
10.1103/PhysRevB.75.245311
10.1021/jp055795g
10.1103/PhysRevB.60.13740
10.1021/ja016561n
JE Moser, M Gratzel, Excitation-wavelength dependence of photoinduced charge injection at the semiconductor-dye interface: Evidence for electron transfer from vibrationally hot excited states. Chimia 52, 160–162 (1998). (10.2533/chimia.1998.160) / Chimia / Excitation-wavelength dependence of photoinduced charge injection at the semiconductor-dye interface: Evidence for electron transfer from vibrationally hot excited states by Moser JE (1998)
10.1021/jp962227f
MM Martin, P Plaza, YH Meyer, Ultrafast intramolecular charge-transfer in the merocyanine dye DCM. J Chem Phys 192, 367–377 (1995). / J Chem Phys / Ultrafast intramolecular charge-transfer in the merocyanine dye DCM by Martin MM (1995)
10.1126/science.1185509
10.1063/1.331124
10.1021/jp050145y
10.1088/0957-4484/18/14/145708
10.1021/nl062000o
10.1002/adfm.200801173

Dates

Type	When
Created	14 years, 8 months ago (Dec. 13, 2010, 11:49 p.m.)
Deposited	2 years, 2 months ago (June 4, 2023, 9:33 a.m.)
Indexed	1 week, 6 days ago (Aug. 20, 2025, 9:21 a.m.)
Issued	14 years, 8 months ago (Dec. 13, 2010)
Published	14 years, 8 months ago (Dec. 13, 2010)
Published Online	14 years, 8 months ago (Dec. 13, 2010)
Published Print	14 years, 7 months ago (Jan. 4, 2011)

Funders 0

None

BibTeX

@article{Tvrdy_2010, title={Photoinduced electron transfer from semiconductor quantum dots to metal oxide nanoparticles}, volume={108}, ISSN={1091-6490}, url={http://dx.doi.org/10.1073/pnas.1011972107}, DOI={10.1073/pnas.1011972107}, number={1}, journal={Proceedings of the National Academy of Sciences}, publisher={Proceedings of the National Academy of Sciences}, author={Tvrdy, Kevin and Frantsuzov, Pavel A. and Kamat, Prashant V.}, year={2010}, month=dec, pages={29–34} }

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