Among solution-processed nanocrystals containing environmentally benign elements, bismuth sulfide (Bi2S3) is a very promising n-type semiconductor for solar energy conversion. Despite the prompt success in the fabrication of optoelectronic devices deploying Bi2S3 nanocrystals, the limited understanding of electronic properties represents a hurdle for further materials developments. Here, two key materials science issues for light-energy conversion are addressed: bandgap tunability via the quantum size effect, and photocarrier trapping. Nanocrystals are synthesized with controlled sizes varying from 3 to 30 nm. In this size range, bandgap tunability is found to be very small, a few tens of meV. First principles calculations show that a useful blueshift, in the range of hundreds of meV, is achieved in ultra-small nanocrystals, below 1.5 nm in size. Similar conclusions are envisaged for the class of pnictide chalcogenides with a ribbon-like structure [Pn4Ch6]n (Pn = Bi, Sb; Ch = S, Se). Time-resolved differential transmission spectroscopy demonstrates that only photoexcited holes are quickly captured by intragap states. Photoexcitation dynamics are consistent with the scenario emerging in other metal–chalcogenide nanocrystals: traps are created in metal-rich nanocrystal surfaces by incomplete passivation by long fatty acid ligands. In large nanocrystals, a lower bound to surface trap density of one trap every sixteen Bi2S3 units is found.

Colloidal Bi2S3 nanocrystals: Quantum size effects and midgap states

ARESTI, MAURO;SABA, MICHELE;PIRAS, ROBERTO;MARONGIU, DANIELA;MULA, GUIDO;QUOCHI, FRANCESCO;MURA, ANTONIO ANDREA;CANNAS, CARLA;ARDU, ANDREA;ENNAS, GUIDO;MUSINU, ANNA MARIA GIOVANNA;BONGIOVANNI, GIOVANNI LUIGI CARLO
2014-01-01

Abstract

Among solution-processed nanocrystals containing environmentally benign elements, bismuth sulfide (Bi2S3) is a very promising n-type semiconductor for solar energy conversion. Despite the prompt success in the fabrication of optoelectronic devices deploying Bi2S3 nanocrystals, the limited understanding of electronic properties represents a hurdle for further materials developments. Here, two key materials science issues for light-energy conversion are addressed: bandgap tunability via the quantum size effect, and photocarrier trapping. Nanocrystals are synthesized with controlled sizes varying from 3 to 30 nm. In this size range, bandgap tunability is found to be very small, a few tens of meV. First principles calculations show that a useful blueshift, in the range of hundreds of meV, is achieved in ultra-small nanocrystals, below 1.5 nm in size. Similar conclusions are envisaged for the class of pnictide chalcogenides with a ribbon-like structure [Pn4Ch6]n (Pn = Bi, Sb; Ch = S, Se). Time-resolved differential transmission spectroscopy demonstrates that only photoexcited holes are quickly captured by intragap states. Photoexcitation dynamics are consistent with the scenario emerging in other metal–chalcogenide nanocrystals: traps are created in metal-rich nanocrystal surfaces by incomplete passivation by long fatty acid ligands. In large nanocrystals, a lower bound to surface trap density of one trap every sixteen Bi2S3 units is found.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11584/110123
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