15,527 research outputs found
Janus Monolayer Transition Metal Dichalcogenides
A novel crystal configuration of sandwiched S-Mo-Se structure (Janus SMoSe)
at the monolayer limit has been synthesized and carefully characterized in this
work. By controlled sulfurization of monolayer MoSe2 the top layer of selenium
atoms are substituted by sulfur atoms while the bottom selenium layer remains
intact. The peculiar structure of this new material is systematically
investigated by Raman, photoluminescence and X-ray photoelectron spectroscopy
and confirmed by transmission-electron microscopy and time-of-flight secondary
ion mass spectrometry. Density-functional theory calculations are performed to
better understand the Raman vibration modes and electronic structures of the
Janus SMoSe monolayer, which are found to correlate well with corresponding
experimental results. Finally, high basal plane hydrogen evolution reaction
(HER) activity is discovered for the Janus monolayer and DFT calculation
implies that the activity originates from the synergistic effect of the
intrinsic defects and structural strain inherent in the Janus structure.Comment: 22 pages, 12 figure
Defect Tolerant Monolayer Transition Metal Dichalcogenides
Localized electronic states formed inside the band gap of a semiconductor due
to crystal defects can be detrimental to the material's optoelectronic
properties. Semiconductors with lower tendency to form defect induced deep gap
states are termed defect tolerant. Here we provide a systematic first
principles investigation of defect tolerance in 29 monolayer transition metal
dichalcogenides (TMDs) of interest for nanoscale optoelectronics. We find that
the TMDs based on group VI and X metals form deep gap states upon creation of a
chalcogen (S, Se, Te) vacancy while the TMDs based on group IV metals form only
shallow defect levels and are thus predicted to be defect tolerant.
Interestingly, all the defect sensitive TMDs have valence and conduction bands
with very similar orbital composition. This indicates a bonding/anti-bonding
nature of the gap which in turn suggests that dangling bonds will fall inside
the gap. These ideas are made quantitative by introducing a descriptor that
measures the degree of similarity of the conduction and valence band manifolds.
Finally, the study is generalized to non-polar nanoribbons of the TMDs where we
find that only the defect sensitive materials form edge states within the band
gap
Janus monolayers of transition metal dichalcogenides.
Structural symmetry-breaking plays a crucial role in determining the electronic band structures of two-dimensional materials. Tremendous efforts have been devoted to breaking the in-plane symmetry of graphene with electric fields on AB-stacked bilayers or stacked van der Waals heterostructures. In contrast, transition metal dichalcogenide monolayers are semiconductors with intrinsic in-plane asymmetry, leading to direct electronic bandgaps, distinctive optical properties and great potential in optoelectronics. Apart from their in-plane inversion asymmetry, an additional degree of freedom allowing spin manipulation can be induced by breaking the out-of-plane mirror symmetry with external electric fields or, as theoretically proposed, with an asymmetric out-of-plane structural configuration. Here, we report a synthetic strategy to grow Janus monolayers of transition metal dichalcogenides breaking the out-of-plane structural symmetry. In particular, based on a MoS2 monolayer, we fully replace the top-layer S with Se atoms. We confirm the Janus structure of MoSSe directly by means of scanning transmission electron microscopy and energy-dependent X-ray photoelectron spectroscopy, and prove the existence of vertical dipoles by second harmonic generation and piezoresponse force microscopy measurements
Phonon Sidebands in Transition Metal Dichalcogenides
Excitons dominate the optical properties of monolayer transition metal
dichalcogenides (TMDs). Besides optically accessible bright exciton states,
TMDs exhibit also a multitude of optically forbidden dark excitons. Here, we
show that efficient exciton-phonon scattering couples bright and dark states
and gives rise to an asymmetric excitonic line shape. The observed asymmetry
can be traced back to phonon-induced sidebands that are accompanied by a
polaron redshift. We present a joint theory-experiment study investigating the
microscopic origin of these sidebands in different TMD materials taking into
account intra- and intervalley scattering channels opened by optical and
acoustic phonons. The gained insights contribute to a better understanding of
the optical fingerprint of these technologically promising nanomaterials
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