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Ultrafast Energy Transfer of Both Bright and Dark Excitons in 2D Van Der Waals Heterostructures Beyond Dipolar Coupling Lingling Wu, Yuzhong Chen, Hongzhi Zhou, and Haiming Zhu ACS Nano, Just Accepted Manuscript • DOI: 10.1021/acsnano.8b09059 • Publication Date (Web): 04 Feb 2019 Downloaded from http://pubs.acs.org on February 4, 2019
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ACS Nano
Ultrafast Energy Transfer of Both Bright and Dark Excitons in 2D Van Der Waals Heterostructures Beyond Dipolar Coupling Lingling Wu1†, Yuzhong Chen1†, Hongzhi Zhou1, Haiming Zhu1,2* 1. Centre for Chemistry of High-Performance & Novel Materials, Department of Chemistry, Zhejiang University, Hangzhou, Zhejiang, 310027, China 2. State Key Laboratory of Modern Optical Instrumentation, Zhejiang University, Hangzhou, Zhejiang, 310027, China. * Email:
[email protected] Abstract Two-dimensional (2D) transition metal dichalcogenides (TMDs) have shown great potential in ultrathin and flexible optoelectronic and photonics devices. Besides emissive bright excitons, they also possess rich non-emissive dark excitons including momentum-forbidden indirect excitons and spin-forbidden triplet-like excitons, which could be dominant species under optical or electrical excitation in 2D optoelectronic and photonic devices. Efficient harvesting of both bright and dark excitons from TMDs and understanding the exciton transfer mechanism consequently is of not only 1
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fundamental interests but technological challenges. Here, by combining steady state photoluminescence spectroscopy and ultrafast transient reflectance spectroscopy, we show efficient exciton harvesting by ultrafast energy transfer in WSe2/MoTe2 van der Waals heterostructures, leading to the PL enhancement of MoTe2. The energy transfer occurs with near-unity yield and in ultrafast (~ 200 fs) manner for both bright and dark excitons, suggesting dominant Dexter-type energy transfer process consisting of simultaneous transfer of both electron and hole in van der Waals coupled 2D layers at ultimate proximity. This result is beyond the conventional dipole-dipole coupling mechanism typically assumed at 2D interface and offers a path to high speed and enhanced light harvesting and emission applications based on 2D heterostructures. KEYWORDS: energy transfer, ultrafast spectroscopy, 2D dan der Waals heterostructures, type I band alignment, PL enhancement
Energy transfer (EnT) across nanoscale hetero-interface plays a key role in low dimensional
optoelectronic
devices,
including
light
emitting
diodes,
solar
concentrators, photodetectors and lasers.1-5 EnT process depends on various factors including spectral overlap, spatial separation and dielectric environment between donor and acceptor.6-8 Recently, two-dimensional (2D) van der Waals (vdW) heterostructures, by rationally combining individual layered materials e.g. transition metal dichalcogenides (TMDs) with atomic sharpness and precision, allow exploring new 2
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ACS Nano
fundamental physical process as well as next generation electronic and optoelectronic applications.9-11 Due to reduced dielectric screening, the optical properties and elementary excitations in TMDs are governed by strongly bound electron-hole pairs (i.e. excitons). Besides bright emissive exciton states, recent experimental and theoretical studies confirm the existence of energetically lower non-emissive exciton states in TMDs, including momentum-forbidden indirect excitons in multilayer AX2 (A = Mo, W; X = S, Se) and spin-forbidden (triplet-like) dark excitons in WX2.12-15 The tunable electronic structure, sub-nanometer separation, together with rich excitonic states in 2D vdW heterostructures provide an ideal platform to investigate nanoscale EnT process at ultimate proximity. To date, interfacial photoexcitation dynamics on 2D vdW heterostructures mostly focus on the charge transfer process with type II band alignment, where electron and hole are spatially separated spatially.16-26 Ultrafast (
