Singlet Fission and Electron Injection from the Triplet Excited State in Diphenylisobenzofuran–Semiconductor Assemblies : Effects of Solvent Polarity and Driving Force
| Autor: | Victor Gray, Fredrik D. Johansson, Elin Sundin, Jerker Mårtensson, Rasmus Ringström, Andreas Ekebergh, Maria Abrahamsson, Bo Albinsson, Betül Küçüköz |
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| Jazyk: | angličtina |
| Rok vydání: | 2020 |
| Předmět: |
Fysikalisk kemi
Materials science business.industry 02 engineering and technology 010402 general chemistry 021001 nanoscience & nanotechnology 01 natural sciences Physical Chemistry 0104 chemical sciences Surfaces Coatings and Films Electronic Optical and Magnetic Materials General Energy Semiconductor Chemical physics Excited state Singlet fission Molecule Singlet state Physical and Theoretical Chemistry Thin film 0210 nano-technology Mesoporous material business Excitation |
| Popis: | Singlet fission has emerged as a promising way to overcome the Shockley-Queisser limit in solar energy conversion devices, and a few studies have claimed proof-of-principle results using dye-sensitized photoelectrodes. However, a detailed understanding of what factors govern the fate of the excited state on mesoporous surfaces is still lacking. Here, we have studied how the excitation progresses into singlet fission, electron injection, or formation of molecular charge separated states in diphenylisobenzofuran derivatives with flexible carbon linkers attached to nanocrystalline mesoporous ZrO2, TiO2, and SnO2 thin films. We show that singlet fission occurs for the molecule attached to ZrO2 films when the assembly is immersed in nonpolar solvents, and that singlet fission is hampered by the formation of a molecular charge separated state in more polar solvents. On TiO2 surfaces, direct electron injection from the singlet excited state outcompetes the singlet fission. Instead, triplet formation occurs via charge recombination from the conduction band of TiO2 in nonpolar solvents. When the molecule is attached to SnO2 films, singlet fission partly outcompetes electron injection from the singlet excited state and the two processes occur in parallel. Subsequent to singlet fission on SnO2, triplet injection into the conduction band of SnO2 is observed. The results presented here provide a detailed picture of the singlet fission dynamics in molecules attached to mesoporous semiconductor surfaces, demonstrating that both the semiconductor substrate as well as the environment around the molecules have a large impact, which can be useful in the design of future devices. |
| Databáze: | OpenAIRE |
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