Study of Multiple Exciton Generation with New Multi-dimensional Spectroscopies
- Univ. of Colorado, Boulder, CO (United States)
Multiple exciton generation is a process that can occur in semiconductor nanocrystals small enough that their electronic properties deviate from that of the bulk semiconductor. Such small nanocrystals are known as quantum dots. At the time this project began, there were reports that multiple exciton generation in quantum dots was far more efficient than the analogous process of charge carrier multiplication in bulk semiconductors. In bulk semiconductors, this effect requires ultraviolet light, but is used for high energy photo-detectors. By exploiting enhanced photocurrent from photons with more than twice the bandgap energy, carrier multiplication is a potential route to more efficient photovoltaics using quantum dots with infrared bandgaps. The reports of enhanced multiple exciton generation in such materials motivated the fundamental investigations of the multiple exciton generation mechanism in this project. These experimental investigations showed that the initial charge carrier dynamics after exciting low bandgap quantum dots with photons far above bandgap are not those of the bound electron-hole pairs known as excitons, but rather those of the rapidly separating charge carriers found in the bulk semiconductor at similar excitation energies. This result was theoretically explained in terms of new fundamental criteria for size dependent changes in the optical properties of semiconductors. This result indicates that any new mechanism for multiple exciton generation must arise from the larger surface area to volume ratio of quantum dots. Several artifacts arising from repetitive excitation, poorly passivated quantum dot surfaces, and oxygen exposure were found. After eliminating these artifacts, investigations of the backward reaction have confirmed that its rate does increase as size decreases, in accord with theory, but were not able to isolate surface effects. Using two-dimensional electronic spectroscopy to investigate the influence of the surface upon excitation at the bandgap found no measurable effect. These studies indicate that better control of the quantum dot surface would be required to optimize multiple exciton generation for photovoltaics.
- Research Organization:
- Univ. of Colorado, Boulder, CO (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
- DOE Contract Number:
- FG02-07ER15912
- OSTI ID:
- 1439607
- Report Number(s):
- DOE-CUBoulder-ER15912
- Country of Publication:
- United States
- Language:
- English
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