Journal
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
Volume 5, Issue 19, Pages 3354-3359Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jz501740n
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Funding
- National Science Foundation (NSF) [1152250, 1133099]
- Direct For Mathematical & Physical Scien [1152250] Funding Source: National Science Foundation
- Division Of Chemistry [1152250] Funding Source: National Science Foundation
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The Shockley-Queisser analysis provides a theoretical limit for the maximum energy conversion efficiency of single junction photovoltaic cells. But besides the semiconductor bandgap no other semiconductor properties are considered in the analysis. Here, we show that the maximum conversion efficiency is limited further by the excited state entropy of the semiconductors. The entropy loss can be estimated with the modified Sackur-Tetrode equation as a function of the curvature of the bands, the degeneracy of states near the band edges, the illumination intensity, the temperature, and the band gap. The application of the second law of thermodynamics to semiconductors provides a simple explanation for the observed high performance of group IV, III-V, and II-VI materials with strong covalent bonding and for the lower efficiency of transition metal oxides containing weakly interacting metal d orbitals. The model also predicts efficient energy conversion with quantum confined and molecular structures in the presence of a light harvesting mechanism.
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