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Abstract Hybrid graphene (Gr)–quantum dot (QD) photodetectors have shown ultrahigh photoresponsivity combining the strong light absorption of QDs with the high mobility of Gr. QDs absorb light and generate photocarriers that are efficiently transported by Gr. Typically, hybrid PbS–QD/graphene photodetectors operate by transferring photogenerated holes from the QDs to Gr while photoelectrons stay in the QDs inducing a photogating mechanism that achieves a responsivity of 6 × 107A W−1. However, despite such high gain, these systems have poor charge collection with quantum efficiency below 25%. Herein, a ZnO intermediate layer (PbS‐QD/ZnO/Gr) is introduced to improve charge collection by forming an effective p‐n PbS‐ZnO junction driving the electrons to the ZnO layer and then to Gr. This improves the photoresponsivity of the devices by nearly an order of magnitude with respect to devices without ZnO. Charge transfer to Gr is demonstrated by monitoring the change in Fermi level under illumination for conventional PbS‐QD/Gr and for ZnO intermediate PbS‐QD/ZnO/Gr devices. These results improve the capabilities of hybrid QD/Gr configurations for optoelectronic devices.
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Systematic control of the rate of singlet fission within 6,13-diphenylpentacene aggregates with PbS quantum dot templates
Lead chalcogenide quantum dots (QDs) are promising acceptors for photovoltaic devices that harness the singlet fission (SF) mechanism. The rate of singlet fission of polyacenes in the presence of QDs is a critical parameter in determining the performance of such devices. The present study demonstrates that the rates of SF in a pentacene derivative, 6,13-diphenylanthracene (DPP), are modulated by forming coaggregates with PbS QDs in aqueous dispersions. PbS QDs generally accelerate SF within DPP aggregates, and the extent of acceleration depends on the size of the QD. The average rate of SF increases from 0.074 ps −1 for DPP-only aggregates to 0.37 ps −1 within DPP-D co-aggregates for QDs with radius 2.2 nm, whereas co-aggregation with the smallest ( r = 1.6 nm) and largest ( r = 2.7 nm) QDs we tried only slightly change the SF rate. The rate variation is associated with (i) the density of surface ligands, which is influenced by the faceting of the PbS surface, and (ii) the local dielectric constant for DPP. To accelerate SF, the ligands should be dense enough to provide sufficient affinity for DPP aggregates and effectively perturb the perpendicular alignment of DPP monomers within aggregates to increase the intermolecular coupling that promotes SF, but should not be too dense so as to form a low dielectric environment that disfavors SF. The study suggests that it is critical to consider the influence of the microenvironment of the QD surface on photophysical processes when fabricating QD/organic hybrid devices.
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- Award ID(s):
- 1664184
- PAR ID:
- 10192147
- Date Published:
- Journal Name:
- Faraday Discussions
- Volume:
- 216
- ISSN:
- 1359-6640
- Page Range / eLocation ID:
- 162 to 173
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/C8FD00157J
