Hybrid graphene and quantum dots (QDs) photodetectors merge the excellent conductivity and ambipolar electric field sensitivity of graphene, with the unique properties of QDs. The photoresponsivity of these devices depends strongly on the charge transfer at the graphene/QDs interface. Here 1‐pyrene butyric acid (PBA)‐coated PbS QDs with single layer graphene (SLG) are used to investigate the effect of pyrene as a π–π mediator to enhance charge transfer at the SLG/QDs junction under illumination. The surface chemistry at the QD–QD and SLG/QD interface is studied with the conventional tetrabutylammonium iodide (TBAI) QD linker. The hybrid SLG/QD photodetectors with PBA as a SLG‐QD linker demonstrate a photoresponse up to 30% higher than that recorded for devices where only TBAI is used, due to the strong electron coupling between SLG and QDs. Transconductance measurements show that PBA provokes electron depletion in SLG ascribed to the tendency to delocalize the QDs holes, favoring their transfer to SLG. This surface ligand is found to improve the interaction between the QDs light absorbers and the SLG charge collector, leading to an increased photodetection response. This demonstrates that ligand engineering can enhance charge dynamics and boost the performance of the hybrid device.
Ab initio calculations of through-space and through-bond charge-transfer properties of interacting Janus-like PbSe and CdSe quantum dot heterostructures
Heterostructure quantum dots (QDs) are composed of two QD nanocrystals (NCs) conjoined at an interface. They are useful in applications such as photovoltaic solar cells. The properties of the interface between the NCs determine the efficiency of electron–hole recombination rates and charge transfer. Therefore, a fundamental understanding of how this interface works between the two materials is useful. To contribute to this understanding, we simulated two isolated heterostructure QD models with Janus-like geometry composed of Cd33Se33 + Pb68Se68 NCs. The first Janus-like model has a bond connection between the two NCs and is approximately 16 × 17 × 29 Å3 in size. The second model has a through-space connection between the NCs and is approximately 16 × 17 × 31 Å3. We use density functional theory to simulate the ground state properties of these models. Nonadiabatic on-the-fly couplings calculations were then used to construct the Redfield Tensor, which described the excited state dynamics due to nonradiative relaxation. From our results, we identified a qualitative trend which shows that having a bond connecting the two NCs reduces hole relaxation time. We also identified for a sample of electron–hole excitations pairs that the through-bond model allows for a net positive or negative numerical net charge transfer, depending on the excitation pair.
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- PAR ID:
- 10528769
- Publisher / Repository:
- Taylor and Francis
- Date Published:
- Journal Name:
- Molecular Physics
- ISSN:
- 0026-8976
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Two-dimensional electron gas or hole gas (2DEG or 2DHG) and their functionalities at artificial heterostructure interfaces have attracted extensive attention in recent years. Many theoretical calculations and recent experimental studies have shown the formation of alternating 2DEG and 2DHG at ferroelectric/insulator interfaces, such as BiFeO3/TbScO3, depending on the different polarization states. However, a direct observation based on the local charge distribution at the BiFeO3/TbScO3interface has yet to be explored. Herein we demonstrate the direct observation of 2DHG and 2DEG at BiFeO3/TbScO3interface using four-dimensional scanning transmission electron microscopy and Bader charge analysis. The results show that the measured charge state of each Fe/O columns at the interface undergoes a significant increase/reduction for the polarization state pointing away/toward the interface, indicating the existence of 2DHG/2DEG. This method opens up a path of directly observing charge at atomic scale and provides new insights into the design of future electronic nanodevices.
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1080/00268976.2023.2273415
