Xiao-Fen Qiao

Epitaxial Monolayer MoS2 on Mica with Novel Photoluminescence

Molybdenum disulfide (MoS2) is back in the spotlight because of the indirect-to-direct bandgap tunability and valley related physics emerging in the monolayer regime. However, rigorous control of the monolayer thickness is still a huge challenge for commonly utilized physical exfoliation and chemical synthesis methods. Herein, we have successfully grown predominantly monolayer MoS2 on an inert and nearly lattice-matching mica substrate by using a low-pressure chemical vapor deposition method. The growth is proposed to be mediated by an epitaxial mechanism, and the epitaxial monolayer MoS2 is intrinsically strained on mica due to a small adlayer-substrate lattice mismatch (~2.7%). Photoluminescence (PL) measurements indicate strong single-exciton emission in as-grown MoS2 and room-temperature PL helicity (circular polarization ~0.35) on transferred samples, providing straightforward proof of the high quality of the prepared monolayer crystals. The homogeneously strained high-quality monolayer MoS2 prepared in this study could competitively be exploited for a variety of future applications.

Resonant Raman spectroscopy of twisted multilayer graphene

Graphene and other two-dimensional crystals can be combined to form various hybrids and heterostructures, creating materials on demand, in which the interlayer coupling at the interface leads to modified physical properties as compared to their constituents. Here, by measuring Raman spectra of shear modes, we probe the coupling at the interface between two artificially-stacked few-layer graphenes rotated with respect to each other. The strength of interlayer coupling between the two interface layers is found to be only 20% of that between Bernal-stacked layers. Nevertheless, this weak coupling manifests itself in a Davydov splitting of the shear mode frequencies in systems consisting of two equivalent graphene multilayers, and in the intensity enhancement of shear modes due to the optical resonance with several optically allowed electronic transitions between conduction and valence bands in the band structures. This study paves way for fundamental understanding into the interface coupling of two-dimensional hybrids and heterostructures.Graphene and other two-dimensional crystals can be combined to form various hybrids and heterostructures, creating materials on demand with properties determined by the interlayer interaction. This is the case even for a single material, where multilayer stacks with different relative orientation have different optical and electronic properties. Probing and understanding the interface coupling is thus of primary importance for fundamental science and applications. Here we study twisted multilayer graphene flakes with multi-wavelength Raman spectroscopy. We find a significant intensity enhancement of the interlayer coupling modes (C peaks) due to resonance with new optically allowed electronic transitions, determined by the relative orientation of the layers. The interlayer coupling results in a Davydov splitting of the C peak in systems consisting of two equivalent graphene multilayers. This allows us to directly quantify the interlayer interaction, which is much smaller compared with Bernal-stacked interfaces. This paves the way to the use of Raman spectroscopy to uncover the interface coupling of two-dimensional hybrids and heterostructures.

Highly sensitive phototransistors based on two-dimensional GaTe nanosheets with direct bandgap

Highly sensitive phototransistors based on two-dimensional (2D) GaTe nanosheet have been demonstrated. The performance (photoresponsivity, detectivity) of the GaTe nanosheet phototransistor can be efficiently adjusted by using the applied gate voltage. The devices exhibit an ultrahigh photoresponsivity of 274.3 AW−1. The detectivity of 2D GaTe devices is ∼1012 Jones, which surpasses that of currently-exploited InGaAs photodetectors (1011−1012 Jones). To reveal the origin of the enhanced photocurrent in GaTe nanosheets, theoretical modeling of the electronic structures was performed to show that GaTe nanosheets also have a direct bandgap structure, which contributes to the promotion of photon absorption and generation of excitons. This work shows that GaTe nanosheets are promising materials for high performance photodetectors.

Interface Coupling in Twisted Multilayer Graphene by Resonant Raman Spectroscopy of Layer Breathing Modes

Raman spectroscopy is the prime nondestructive characterization tool for graphene and related layered materials. The shear (C) and layer breathing modes (LBMs) are due to relative motions of the planes, either perpendicular or parallel to their normal. This allows one to directly probe the interlayer interactions in multilayer samples. Graphene and other two-dimensional (2d) crystals can be combined to form various hybrids and heterostructures, creating materials on demand with properties determined by the interlayer interaction. This is the case even for a single material, where multilayer stacks with different relative orientations have different optical and electronic properties. In twisted multilayer graphene there is a significant enhancement of the C modes due to resonance with new optically allowed electronic transitions, determined by the relative orientation of the layers. Here we show that this applies also to the LBMs, which can be now directly measured at room temperature. We find that twisting has a small effect on LBMs, quite different from the case of the C modes. This implies that the periodicity mismatch between two twisted layers mostly affects shear interactions. Our work shows that ultralow-frequency Raman spectroscopy is an ideal tool to uncover the interface coupling of 2d hybrids and heterostructures.

Photoluminescence properties and exciton dynamics in monolayer WSe2

In this work, comprehensive temperature and excitation power dependent photoluminescence and time-resolved photoluminescence studies are carried out on monolayer WSe2 to reveal its properties of exciton emissions and related excitonic dynamics. Competitions between the localized and delocalized exciton emissions, as well as the exciton and trion emissions are observed, respectively. These competitions are suggested to be responsible for the abnormal temperature and excitation intensity dependent photoluminescence properties. The radiative lifetimes of both excitons and trions exhibit linear dependence on temperature within the temperature regime below 260 K, providing further evidence for two-dimensional nature of monolayer material.

Coherent Longitudinal Acoustic Phonon Approaching THz Frequency in Multilayer Molybdenum Disulphide

Coherent longitudinal acoustic phonon is generated and detected in multilayer Molybdenum Disulphide (MoS2) with number of layers ranging from 10 to over 1300 by femtosecond laser pulse. For thin MoS2, the excited phonon frequency exhibits a standing wave nature and shows linear dependence on the sample thickness. The frequency varies from 40 GHz to 0.2 THz (10 layers), which promises possible application in THz frequency mechanical resonators. This linear thickness dependence gradually disappears in thicker samples above about 150 layers, and the oscillation period shows linear dependence on the probe wavelength. From both the oscillation period of the coherent phonon and the delay time of acoustic echo, we can deduce a consistent sound velocity of 7.11*103 m/s in MoS2. The generation mechanisms of the coherent acoustic phonon are also discussed through pump power dependent measurement.

Substrate-free layer-number identification of two-dimensional materials: A case of Mo0.5W0.5S2 alloy

Any of two or more two-dimensional (2D) materials with similar properties can be alloyed into a new layered material, namely, 2D alloy. Individual monolayer in 2D alloys is kept together by van der Waals interactions. The property of multilayer alloys is a function of their layer number. Here, we studied the shear (C) and layer-breathing (LB) modes of Mo0.5W0.5S2 alloy flakes and their link to the layer number. The study reveals that the disorder effect is absent in the C and LB modes of 2D alloys, and the monatomic chain model can be used to estimate the frequencies of the C and LB modes. We demonstrated how to use the frequencies of C and LB modes to identify the layer number of alloy flakes deposited on different substrates. This technique is independent of the substrate, stoichiometry, monolayer thickness, and complex refractive index of 2D materials, offering a robust and substrate-free approach for layer-number identification of ultrathin flakes of 2D materials, such as 2D crystals and 2D alloys.

Nonlinear saturable absorption of vertically stood WS2 nanoplates

We report the nonlinear optical (NLO) properties of vertically stood WS2 nanoplates excited by 532-nm picosecond laser light. The nanoplates were synthesized by a no-catalyst thermal evaporation process. Raman spectroscopy and x-ray diffraction pattern indicate that the nanoplates are of high crystal quality. The nanoplates exhibit large nonlinear saturable absorption but negligible nonlinear refraction. Mechanisms of the NLO response are proposed.

Raman and photoluminescence spectra of two-dimensional nanocrystallites of monolayer WS2 and WSe2

Defects strongly modify optical properties in pristine and nanostructured two-dimensional (2D) materials. The ion implantation technique can be used to gradually introduce defects in semiconductor to obtain nanocrystallites (NCs) with different domain sizes. Here, we present a detailed study on the Raman and photoluminescence spectra of 2D NCs of monolayer WS2 (1L WS2) and 1L WSe2 prepared by ion implantation. With increasing ion dosages, both and modes of 1L WS2 exhibit a downshift in frequency and an asymmetrical broadening toward lower frequency, while the mode in 1L WSe2 NCs exhibits an opposite behavior, showing asymmetrical broadening and peak shift toward higher frequency. This behavior is well understood by phonon quantum confinement of the out-of-plane optical branch whose frequency displays a minimum at Γ in pristine 1L WSe2. After the ion implantation, phonons from the Brillouin zone boundary are revealed in the Raman spectra, and the corresponding assignments are identified by resonant Raman spectra at low temperature. The defects can act as trapping centers of free carriers, which result in a sharp decrease of photoluminescence (PL) emission from A exciton with increasing ion dosage. The PL peak from A-exciton in both 1L WS2 and 1L WSe2 NCs blueshifts with increasing the ion dosage due to the quantum confinement effect of smaller NC size. The ion-implantation results in a new emission peak of defect-bound neutral excitons below the A-exciton peak in both 1L WS2 and 1L WSe2 NCs. Its relative intensity to the A exciton increases with increasing the ion dosage and finally vanishes along with the A exciton. These results offer a route toward tailoring the optical properties of 2D materials by controlling the size of 2D NCs.

Valley depolarization in monolayer WSe2

We have systematically examined the circular polarization of monolayer WSe2 at different temperature, excitation energy and exciton density. The valley depolarization in WSe2 is experimentally confirmed to be governed by the intervalley electron-hole exchange interaction. More importantly, a non-monotonic dependence of valley circular polarization on the excitation power density has been observed, providing the experimental evidence for the non-monotonic dependence of exciton intervalley scattering rate on the excited exciton density. The physical origination of our experimental observations has been proposed to be in analogy to the D′yakonov-Perel′ mechanism that is operative in conventional GaAs quantum well systems. Our experimental results are fundamentally important for well understanding the valley pseudospin relaxation in atomically thin transition metal dichalcogenides.