Zhengguang Lu

Magnetic brightening and control of dark excitons in monolayer WSe2

Monolayer transition metal dichalcogenide crystals, as direct-gap materials with strong light-matter interactions, have attracted much recent attention. Because of their spin-polarized valence bands and a predicted spin splitting at the conduction band edges, the lowest-lying excitons in WX2 (X = S, Se) are expected to be spin-forbidden and optically dark. To date, however, there has been no direct experimental probe of these dark excitons. Here, we show how an in-plane magnetic field can brighten the dark excitons in monolayer WSe2 and permit their properties to be observed experimentally. Precise energy levels for both the neutral and charged dark excitons are obtained and compared with ab initio calculations using the GW-BSE approach. As a result of their spin configuration, the brightened dark excitons exhibit much-increased emission and valley lifetimes. These studies directly probe the excitonic spin manifold and reveal the fine spin-splitting at the conduction band edges.

High Photoresponsivity and Short Photoresponse Times in Few-Layered WSe2 Transistors

Here, we report the photoconducting response of field-effect transistors based on three atomic layers of chemical vapor transport grown WSe2 crystals mechanically exfoliated onto SiO2. We find that trilayered WSe2 field-effect transistors, built with the simplest possible architecture, can display high hole mobilities ranging from 350 cm(2)/(V s) at room temperature (saturating at a value of ∼500 cm(2)/(V s) below 50 K) displaying a strong photocurrent response, which leads to exceptionally high photoresponsivities up to 7 A/W under white light illumination of the entire channel for power densities p < 10(2) W/m(2). Under a fixed wavelength of λ = 532 nm and a laser spot size smaller than the conducting channel area, we extract photoresponsitivities approaching 100 mA/W with concomitantly high external quantum efficiencies up to ∼40% at room temperature. These values surpass values recently reported from more complex architectures, such as graphene and transition metal dichalcogenides based heterostructures. Also, trilayered WSe2 phototransistors display photoresponse times on the order of 10 μs. Our results indicate that the addition of a few atomic layers considerably decreases the photoresponse times, probably by minimizing the interaction with the substrates, while maintaining a very high photoresponsivity.

Pronounced Photovoltaic Response from Multilayered Transition-Metal Dichalcogenides PN-Junctions

Transition metal dichalcogenides (TMDs) are layered semiconductors with indirect band gaps comparable to Si. These compounds can be grown in large area, while their gap(s) can be tuned by changing their chemical composition or by applying a gate voltage. The experimental evidence collected so far points toward a strong interaction with light, which contrasts with the small photovoltaic efficiencies η ≤ 1% extracted from bulk crystals or exfoliated monolayers. Here, we evaluate the potential of these compounds by studying the photovoltaic response of electrostatically generated PN-junctions composed of approximately 10 atomic layers of MoSe2 stacked onto the dielectric h-BN. In addition to ideal diode-like response, we find that these junctions can yield, under AM-1.5 illumination, photovoltaic efficiencies η exceeding 14%, with fill factors of ~70%. Given the available strategies for increasing η such as gap tuning, improving the quality of the electrical contacts, or the fabrication of tandem cells, our study suggests a remarkable potential for photovoltaic applications based on TMDs.

Spin–phonon couplings in transition metal complexes with slow magnetic relaxation

Spin–phonon coupling plays an important role in single-molecule magnets and molecular qubits. However, there have been few detailed studies of its nature. Here, we show for the first time distinct couplings of g phonons of CoII(acac)2(H2O)2 (acac = acetylacetonate) and its deuterated analogs with zero-field-split, excited magnetic/spin levels (Kramers doublet (KD)) of the S = 3/2 electronic ground state. The couplings are observed as avoided crossings in magnetic-field-dependent Raman spectra with coupling constants of 1–2 cm−1. Far-IR spectra reveal the magnetic-dipole-allowed, inter-KD transition, shifting to higher energy with increasing field. Density functional theory calculations are used to rationalize energies and symmetries of the phonons. A vibronic coupling model, supported by electronic structure calculations, is proposed to rationalize the behavior of the coupled Raman peaks. This work spectroscopically reveals and quantitates the spin–phonon couplings in typical transition metal complexes and sheds light on the origin of the spin–phonon entanglement.Transition metal complexes that display slow magnetic relaxation show promise for information storage, but our mechanistic understanding of the magnetic relaxation of such compounds remains limited. Here, the authors spectroscopically and computationally characterize the strength of spin–phonon couplings, which play an important role in the relaxation process.

Revealing the biexciton and trion-exciton complexes in BN encapsulated WSe 2

Strong Coulomb interactions in single-layer transition metal dichalcogenides (TMDs) result in the emergence of strongly bound excitons, trions, and biexcitons. These excitonic complexes possess the valley degree of freedom, which can be exploited for quantum optoelectronics. However, in contrast to the good understanding of the exciton and trion properties, the binding energy of the biexciton remains elusive, with theoretical calculations and experimental studies reporting discrepant results. In this work, we resolve the conflict by employing low-temperature photoluminescence spectroscopy to identify the biexciton state in BN-encapsulated single-layer WSe2. The biexciton state only exists in charge-neutral WSe2, which is realized through the control of efficient electrostatic gating. In the lightly electron-doped WSe2, one free electron binds to a biexciton and forms the trion–exciton complex. Improved understanding of the biexciton and trion–exciton complexes paves the way for exploiting the many-body physics in TMDs for novel optoelectronics applications.Owing to strong Coulomb interactions, atomically thin transition metal dichalcogenides host strongly bound excitonic complexes. Here, the authors report charge-neutral biexciton and negatively charged trion-exciton complexes in hBN encapsulated monolayer WSe2 by employing low-temperature photoluminescence spectroscopy.

Efficient generation of neutral and charged biexcitons in encapsulated WSe2 monolayers

Higher-order correlated excitonic states arise from the mutual interactions of excitons, which generally requires a significant exciton density and therefore high excitation levels. Here, we report the emergence of two biexcitons species, one neutral and one charged, in monolayer tungsten diselenide under moderate continuous-wave excitation. The efficient formation of biexcitons is facilitated by the long lifetime of the dark exciton state associated with a spin-forbidden transition, as well as improved sample quality from encapsulation between hexagonal boron nitride layers. From studies of the polarization and magnetic field dependence of the neutral biexciton, we conclude that this species is composed of a bright and a dark excitons residing in opposite valleys in momentum space. Our observations demonstrate that the distinctive features associated with biexciton states can be accessed at low light intensities and excitation densities.High-order correlated states in atomically thin transition metal dichalcogenides may be facilitated by long-lived optically dark excitons. Here, the authors report experimentally the emergence of neutral and charged biexciton species at low light intensities in encapsulated WSe2 monolayers.