More Like this

1. Proximity-enhanced valley Zeeman splitting at the WS ₂ /graphene interface

   https://doi.org/10.1088/2053-1583/acd5df  

   Faria Junior, Paulo E. ; Naimer, Thomas ; McCreary, Kathleen M. ; Jonker, Berend T. ; Finley, Jonathan J. ; Crooker, Scott A. ; Fabian, Jaroslav ; Stier, Andreas V. ( May 2023 , 2D Materials)

   The valley Zeeman physics of excitons in monolayer transition metal dichalcogenides provides valuable insight into the spin and orbital degrees of freedom inherent to these materials. Being atomically-thin materials, these degrees of freedom can be influenced by the presence of adjacent layers, due to proximity interactions that arise from wave function overlap across the 2D interface. Here, we report 60 T magnetoreflection spectroscopy of the A- and B- excitons in monolayer WS₂, systematically encapsulated in monolayer graphene. While the observed variations of the valley Zeeman effect for the A- exciton are qualitatively in accord with expectations from the bandgap reduction and modification of the exciton binding energy due to the graphene-induced dielectric screening, the valley Zeeman effect for the B- exciton behaves markedly different. We investigate prototypical WS₂/graphene stacks employing first-principles calculations and find that the lower conduction band of WS₂at the$K/K^{\mathrm{\prime }}$valleys (the${\mathrm{C}\mathrm{B}}^{-}$band) is strongly influenced by the graphene layer on the orbital level. Specifically, our detailed microscopic analysis reveals that the conduction band at theQpoint of WS₂mediates the coupling between${\mathrm{C}\mathrm{B}}^{-}$and graphene due to resonant energy conditions and strong coupling to the Dirac cone. Thismore »leads to variations in the valley Zeeman physics of the B- exciton, consistent with the experimental observations. Our results therefore expand the consequences of proximity effects in multilayer semiconductor stacks, showing that wave function hybridization can be a multi-step energetically resonant process, with different bands mediating the interlayer interactions. Such effects can be further exploited to resonantly engineer the spin-valley degrees of freedom in van der Waals and moiré heterostructures.

   « less
2. Controlling exciton transport in monolayer MoSe ₂ by dielectric screening

   https://doi.org/10.1039/C9NH00462A  

   Hao, Shengcai ; Bellus, Matthew Z. ; He, Dawei ; Wang, Yongsheng ; Zhao, Hui ( January 2020 , Nanoscale Horizons)

   Due to their atomic thinness with reduced dielectric screening, two-dimensional materials can possess a stable excitonic population at room temperature. This is attractive for future excitonic devices, where excitons are used to carry energy or information. In excitonic devices, controlling transport of the charge-neutral excitons is a key element. Here we show that exciton transport in a MoSe 2 monolayer semiconductor can be effectively controlled by dielectric screening. A MoSe 2 monolayer was partially covered with a hexagonal boron nitride flake. Photoluminescence measurements showed that the exciton energy in the covered region is about 12 meV higher than that in the uncovered region. Spatiotemporally resolved differential reflection measurements performed at the junction between the two regions revealed that this energy offset is sufficient to drive excitons across the junction for about 50 ps over a distance of about 200 nm. These results illustrate the feasibility of using van der Waals dielectric engineering to control exciton transport and contribute to understanding the effects of the dielectric environment on the electronic and optical properties of two-dimensional semiconductors.
3. Tuning the Electronic and Photonic Properties of Monolayer MoS ₂ via In Situ Rhenium Substitutional Doping

   https://doi.org/10.1002/adfm.201706950  

   Zhang, Kehao ; Bersch, Brian M. ; Joshi, Jaydeep ; Addou, Rafik ; Cormier, Christopher R. ; Zhang, Chenxi ; Xu, Ke ; Briggs, Natalie C. ; Wang, Ke ; Subramanian, Shruti ; et al ( February 2018 , Advanced Functional Materials)

   Doping is a fundamental requirement for tuning and improving the properties of conventional semiconductors. Recent doping studies including niobium (Nb) doping of molybdenum disulfide (MoS₂) and tungsten (W) doping of molybdenum diselenide (MoSe₂) have suggested that substitutional doping may provide an efficient route to tune the doping type and suppress deep trap levels of 2D materials. To date, the impact of the doping on the structural, electronic, and photonic properties of in situ‐doped monolayers remains unanswered due to challenges including strong film substrate charge transfer, and difficulty achieving doping concentrations greater than 0.3 at%. Here, in situ rhenium (Re) doping of synthetic monolayer MoS₂with ≈1 at% Re is demonstrated. To limit substrate film charge transfer,r‐plane sapphire is used. Electronic measurements demonstrate that 1 at% Re doping achieves nearly degenerate n‐type doping, which agrees with density functional theory calculations. Moreover, low‐temperature photoluminescence indicates a significant quench of the defect‐bound emission when Re is introduced, which is attributed to the MoO bond and sulfur vacancies passivation and reduction in gap states due to the presence of Re. The work presented here demonstrates that Re doping of MoS₂is a promising route toward electronic and photonic engineering of 2D materials.
4. Synthesis of Co‐Doped MoS ₂ Monolayers with Enhanced Valley Splitting

   https://doi.org/10.1002/adma.201906536  

   Zhou, Jiadong ; Lin, Junhao ; Sims, Hunter ; Jiang, Chongyun ; Cong, Chunxiao ; Brehm, John A. ; Zhang, Zhaowei ; Niu, Lin ; Chen, Yu ; Zhou, Yao ; et al ( February 2020 , Advanced Materials)

   Internal magnetic moments induced by magnetic dopants in MoS₂monolayers are shown to serve as a new means to engineer valley Zeeman splitting (VZS). Specifically, successful synthesis of monolayer MoS₂doped with the magnetic element Co is reported, and the magnitude of the valley splitting is engineered by manipulating the dopant concentration. Valley splittings of 3.9, 5.2, and 6.15 meV at 7 T in Co‐doped MoS₂with Co concentrations of 0.8%, 1.7%, and 2.5%, respectively, are achieved as revealed by polarization‐resolved photoluminescence (PL) spectroscopy. Atomic‐resolution electron microscopy studies clearly identify the magnetic sites of Co substitution in the MoS₂lattice, forming two distinct types of configurations, namely isolated single dopants and tridopant clusters. Density functional theory (DFT) and model calculations reveal that the observed enhanced VZS arises from an internal magnetic field induced by the tridopant clusters, which couples to the spin, atomic orbital, and valley magnetic moment of carriers from the conduction and valence bands. The present study demonstrates a new method to control the valley pseudospin via magnetic dopants in layered semiconducting materials, paving the way toward magneto‐optical and spintronic devices.
5. Reaction mechanism – explored with the unified reaction valley approach

   https://doi.org/10.1039/D3CC01576A  

   Kraka, Elfi ; Antonio, Juliana J. ; Freindorf, Marek ( June 2023 , Chemical Communications)

   One of the ultimate goals of chemistry is to understand and manipulate chemical reactions, which implies the ability to monitor the reaction and its underlying mechanism at an atomic scale. In this article, we introduce the Unified Reaction Valley Approach (URVA) as a tool for elucidating reaction mechanisms, complementing existing computational procedures. URVA combines the concept of the potential energy surface with vibrational spectroscopy and describes a chemical reaction via the reaction path and the surrounding reaction valley traced out by the reacting species on the potential energy surface on their way from the entrance to the exit channel, where the products are located. The key feature of URVA is the focus on the curving of the reaction path. Moving along the reaction path, any electronic structure change of the reacting species is registered by a change in the normal vibrational modes spanning the reaction valley and their coupling with the path, which recovers the curvature of the reaction path. This leads to a unique curvature profile for each chemical reaction, with curvature minima reflecting minimal change and curvature maxima indicating the location of important chemical events such as bond breaking/formation, charge polarization and transfer, rehybridization, etc. A decomposition ofmore »the path curvature into internal coordinate components or other coordinates of relevance for the reaction under consideration, provides comprehensive insight into the origin of the chemical changes taking place. After giving an overview of current experimental and computational efforts to gain insight into the mechanism of a chemical reaction and presenting the theoretical background of URVA, we illustrate how URVA works for three diverse processes, (i) [1,3] hydrogen transfer reactions; (ii) α-keto-amino inhibitor for SARS-CoV-2 M pro ; (iii) Rh-catalyzed cyanation. We hope that this article will inspire our computational colleagues to add URVA to their repertoire and will serve as an incubator for new reaction mechanisms to be studied in collaboration with our experimental experts in the field.« less