Two-dimensional (2D) materials and heterostructures have recently gained wide attention due to potential applications in optoelectronic devices. However, the optical properties of the heterojunction have not been properly characterized due to the limited spatial resolution, requiring nano-optical characterization beyond the diffraction limit. Here, we investigate the lateral monolayer MoS2-WS2 heterostructure using tip-enhanced photoluminescence (TEPL) spectroscopy on a non-metallic substrate with picoscale tip-sample distance control. By placing a plasmonic Au-coated Ag tip at the heterojunction, we observed more than three orders of magnitude photoluminescence (PL) enhancement due to the classical near-field mechanism and charge transfer across the junction. The picoscale precision of the distance-dependent TEPL measurements allowed for investigating the classical and quantum tunneling regimes above and below the ~320 pm tip-sample distance, respectively. Quantum plasmonic effects usually limit the maximum signal enhancement due to the near-field depletion at the tip. We demonstrate a more complex behavior at the 2D lateral heterojunction, where hot electron tunneling leads to the quenching of the PL of MoS2, while simultaneously increasing the PL of WS2. Our simulations show agreement with the experiments, revealing the range of parameters and enhancement factors corresponding to various regimes. The controllable photoresponse of the lateral junction can be used in novel nanodevices.
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