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Title: Observation of site-controlled localized charged excitons in CrI3/WSe2 heterostructures

Isolated spins are the focus of intense scientific exploration due to their potential role as qubits for quantum information science. Optical access to single spins, demonstrated in III-V semiconducting quantum dots, has fueled research aimed at realizing quantum networks. More recently, quantum emitters in atomically thin materials such as tungsten diselenide have been demonstrated to host optically addressable single spins by means of electrostatic doping the localized excitons. Electrostatic doping is not the only route to charging localized quantum emitters and another path forward is through band structure engineering using van der Waals heterojunctions. Critical to this second approach is to interface tungsten diselenide with other van der Waals materials with relative band-alignments conducive to the phenomenon of charge transfer. In this work we show that the Type-II band-alignment between tungsten diselenide and chromium triiodide can be exploited to excite localized charged excitons in tungsten diselenide. Leveraging spin-dependent charge transfer in the device, we demonstrate spin selectivity in the preparation of the spin-valley state of localized single holes. Combined with the use of strain-inducing nanopillars to coordinate the spatial location of tungsten diselenide quantum emitters, we uncover the possibility of realizing large-scale deterministic arrays of optically addressable spin-valley holes more » in a solid state platform.

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Publication Date:
Journal Name:
Nature Communications
Nature Publishing Group
Sponsoring Org:
National Science Foundation
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  1. Strain engineering is a natural route to control the electronic and optical properties of two-dimensional (2D) materials. Recently, 2D semiconductors have also been demonstrated as an intriguing host of strain-induced quantum-confined emitters with unique valley properties inherited from the host semiconductor. Here, we study the continuous and reversible tuning of the light emitted by such localized emitters in a monolayer tungsten diselenide embedded in a van der Waals heterostructure. Biaxial strain is applied on the emitters via strain transfer from a lead magnesium niobate–lead titanate (PMN-PT) piezoelectric substrate. Efficient modulation of the emission energy of several localized emitters up to 10 meV has been demonstrated on application of a voltage on the piezoelectric substrate. Further, we also find that the emission axis rotates by∼<#comment/>40∘<#comment/>as the magnitude of the biaxial strain is varied on these emitters. These results elevate the prospect of using all electrically controlled devices where the property of the localized emitters in a 2D host can be engineered with elastic fields for an integrated opto-electronics and nano-photonics platform.

  2. Abstract

    As hosts for tightly-bound electron-hole pairs carrying quantized angular momentum, atomically-thin semiconductors of transition metal dichalcogenides (TMDCs) provide an appealing platform for optically addressing the valley degree of freedom. In particular, the valleytronic properties of neutral and charged excitons in these systems have been widely investigated. Meanwhile, correlated quantum states involving more particles are still elusive and controversial despite recent efforts. Here, we present experimental evidence for four-particle biexcitons and five-particle exciton-trions in high-quality monolayer tungsten diselenide. Through charge doping, thermal activation, and magnetic-field tuning measurements, we determine that the biexciton and the exciton-trion are bound with respect to the bright exciton and the trion, respectively. Further, both the biexciton and the exciton-trion are intervalley complexes involving dark excitons, giving rise to emissions with large, negative valley polarization in contrast to that of the two-particle excitons. Our studies provide opportunities for building valleytronic quantum devices harnessing high-order TMDC excitations.

  3. Time-dependent density functional theory (TDDFT) based approaches have been developed in recent years to model the excited-state properties and transition processes of the molecules in the gas-phase and in a condensed medium, such as in a solution and protein microenvironment or near semiconductor and metal surfaces. In the latter case, usually, classical embedding models have been adopted to account for the molecular environmental effects, leading to the multi-scale approaches of TDDFT/polarizable continuum model (PCM) and TDDFT/molecular mechanics (MM), where a molecular system of interest is designated as the quantum mechanical region and treated with TDDFT, while the environment is usually described using either a PCM or (non-polarizable or polarizable) MM force fields. In this Perspective, we briefly review these TDDFT-related multi-scale models with a specific emphasis on the implementation of analytical energy derivatives, such as the energy gradient and Hessian, the nonadiabatic coupling, the spin–orbit coupling, and the transition dipole moment as well as their nuclear derivatives for various radiative and radiativeless transition processes among electronic states. Three variations of the TDDFT method, the Tamm–Dancoff approximation to TDDFT, spin–flip DFT, and spin-adiabatic TDDFT, are discussed. Moreover, using a model system (pyridine–Ag 20 complex), we emphasize that caution is needed tomore »properly account for system–environment interactions within the TDDFT/MM models. Specifically, one should appropriately damp the electrostatic embedding potential from MM atoms and carefully tune the van der Waals interaction potential between the system and the environment. We also highlight the lack of proper treatment of charge transfer between the quantum mechanics and MM regions as well as the need for accelerated TDDFT modelings and interpretability, which calls for new method developments.« less
  4. We fabricated a van der Waals heterostructure of WS 2 –ReSe 2 and studied its charge-transfer properties. Monolayers of WS 2 and ReSe 2 were obtained by mechanical exfoliation and chemical vapor deposition, respectively. The heterostructure sample was fabricated by transferring the WS 2 monolayer on top of ReSe 2 by a dry transfer process. Photoluminescence quenching was observed in the heterostructure, indicating efficient interlayer charge transfer. Transient absorption measurements show that holes can efficiently transfer from WS 2 to ReSe 2 on an ultrafast timescale. Meanwhile, electron transfer from ReSe 2 to WS 2 was also observed. The charge-transfer properties show that monolayers of ReSe 2 and WS 2 form a type-II band alignment, instead of type-I as predicted by theory. The type-II alignment is further confirmed by the observation of extended photocarrier lifetimes in the heterostructure. These results provide useful information for developing van der Waals heterostructure involving ReSe 2 for novel electronic and optoelectronic applications and introduce ReSe 2 to the family of two-dimensional materials to construct van der Waals heterostructures.
  5. The newly developed van der Waals materials allow fabrication of multilayer heterostructures. Early efforts have mostly focused on heterostructures formed by similar materials. More recently, however, attempts have been made to expand the types of materials, such as topological insulators and organic semiconductors. Here we introduce an amorphous semiconductor to the material library for constructing van der Waals heterostructures. Samples composed of 2 nm amorphous black phosphorus synthesized by pulsed laser deposition and monolayer WS 2 obtained by mechanical exfoliation were fabricated by dry transfer. Photoluminescence measurements revealed that photocarriers excited in WS 2 of the heterostructure transfer to amorphous black phosphorus, in the form of either energy or charge transfer, on a time scale shorter than the exciton lifetime in WS 2 . Transient absorption measurements further indicate that holes can efficiently transfer from WS 2 to amorphous black phosphorus. However, interlayer electron transfer in either direction was found to be absent. The lack of electron transfer from amorphous black phosphorus to WS 2 is attributed to the localized electronic states in the amorphous semiconductor. Furthermore, we show that a hexagonal BN bilayer can effectively change the hole transfer process.