Bingchen Cao

Observation of Excitonic Fine Structure in a 2D Transition-Metal Dichalcogenide Semiconductor

Two-dimensional (2D) semiconductors, such as transition-metal dichalcogenide monolayers (TMD 1Ls), have attracted increasing attention owing to the underlying fundamental physics (e.g., many body effects) and the promising optoelectronic applications such as light-emitting diodes. Though much progress has been made, intrinsic excitonic states of TMD 1Ls are still highly debated in theory, which thirsts for direct experimental determination. Here, we report unconventional emission and excitonic fine structure in 1L WS2 revealed by electrical doping and photoexcitation, which reflects the interplay of exciton, trion, and other excitonic states. Tunable excitonic emission has been realized in a controllable manner via electrical and/or optical injection of charge carriers. Remarkably enough, the superlinear (i.e., quadratic) emission is unambiguously observed which is attributed to biexciton states, indicating the strong Coulomb interactions in such a 2D material. In a nearly neutral 1L WS2, trions and biexcitons possess large binding energies of ∼ 10-15 and 45 meV, respectively. Moreover, our finding of electrically induced robust emission opens up a possibility to boost the luminous efficiency of emerging 1L TMD light emitting diodes.

Electrically Tunable Valley-Light Emitting Diode (vLED) Based on CVD-Grown Monolayer WS2

Owing to direct band gap and strong spin-orbit coupling, monolayer transition-metal dichalcogenides (TMDs) exhibit rich new physics and great applicable potentials. The remarkable valley contrast and light emission promise such two-dimensional (2D) semiconductors a bright future of valleytronics and light-emitting diodes (LEDs). Though the electroluminescence (EL) has been observed in mechanically exfoliated small flakes of TMDs, considering real applications, a strategy that could offer mass-product and high compatibility is greatly demanded. Large-area and high-quality samples prepared by chemical vapor deposition (CVD) are perfect candidates toward such goal. Here, we report the first demonstration of electrically tunable chiral EL from CVD-grown monolayer WS2 by constructing a p-i-n heterojunction. The chirality contrast of the overall EL reaches as high as 81% and can be effectively modulated by forward current. The success of fabricating valley LEDs based on CVD WS2 opens up many opportunities for developing large-scale production of unconventional 2D optoelectronic devices.

Dichroic spin-valley photocurrent in monolayer molybdenum disulphide

The aim of valleytronics is to exploit confinement of charge carriers in local valleys of the energy bands of semiconductors as an additional degree of freedom in optoelectronic devices. Thanks to strong direct excitonic transitions in spin-coupled K valleys, monolayer molybdenum disulphide is a rapidly emerging valleytronic material, with high valley polarization in photoluminescence. Here we elucidate the excitonic physics of this material by light helicity-dependent photocurrent studies of phototransistors. We demonstrate that large photocurrent dichroism (up to 60%) can also be achieved in high-quality molybdenum disulphide monolayers grown by chemical vapour deposition, due to the circular photogalvanic effect on resonant excitations. This opens up new opportunities for valleytonic applications in which selective control of spin–valley-coupled photocurrents can be used to implement polarization-sensitive light-detection schemes or integrated spintronic devices, as well as biochemical sensors operating at visible frequencies.

Remarkable anisotropic phonon response in uniaxially strained few-layer black phosphorus

Black phosphorus (BP) is a good candidate for studying strain effects on twodimensional (2D) materials beyond graphene and transition-metal dichalcogenides. This is because of its particular ability to sustain high strain and remarkably anisotropic mechanical properties resulting from its unique puckered structure. We here investigate the dependence of lattice vibrational frequencies on crystallographic orientations in uniaxially strained few-layer BP by in-situ strained Raman spectroscopy. The out-of-plane A1g mode is sensitive to uniaxial strain along the near-armchair direction whereas the in-plane B2g and A2g modes are sensitive to strain in the near-zigzag direction. For uniaxial strains applied away from these directions, all three phonon modes are linearly redshifted. Our experimental observation is explained by the anisotropic influence of uniaxial tensile strain on structural properties of BP using density functional theory. This study demonstrates the possibility of selective tuning of in-plane and out-of-plane phonon modes in BP by uniaxial strain and makes strain engineering a promising avenue for extensively modulating the optical and mechanical properties of 2D materials.

Magnetic oscillation of optical phonon in ABA- and ABC-stacked trilayer graphene

We present a comparative measurement of the G-peak oscillations of phonon frequency, Raman intensity and linewidth in the Magneto-Raman scattering of optical E2g phonons in mechanically exfoliated ABA- and ABC-stacked trilayer graphene (TLG). Whereas in ABA-stacked TLG, we observe magnetophonon oscillations consistent with single-bilayer chiral band doublets, the features are flat for ABC-stacked TLG up to magnetic fields of 9 T. This suppression can be attributed to the enhancement of band chirality that compactifies the spectrum of Landau levels and modifies the magnetophonon resonance properties. The drastically different coupling behaviour between the electronic excitations and the E2g phonons in ABA- and ABC-stacked TLG reflects their different electronic band structures and the electronic Landau level transitions and thus can be another way to determine the stacking orders and to probe the stacking-order-dependent electronic structures. In addition, the sensitivity of the magneto-Raman scattering to the particular stacking order in few layers graphene highlights the important role of interlayer coupling in modifying the optical response properties in van der Waals layered materials.

Electrical field tuning of magneto-Raman scattering in monolayer graphene

In this work, we report the electrical field tuning of magneto-phonon resonance in monolayer graphene under magnetic fields up to 9 T. It is found that the carrier concentration can drastically affect the G (E2g) phonon response to a varying magnetic field through a pronounced magneto-phonon resonance (MPR). In charge neutral or slightly doped monolayer graphene, both the energy and the line width of the E2g phonon show clear variation with magnetic fields. This is attributed to magneto-phonon resonance between magnetoexcitations and the E2g phonons. In contrast, when the Fermi level of the monolayer graphene is far away from the Dirac point, the G band shows weak magnetic dependence and exhibits a symmetric line-shape. This suggests that the magneto-phonon coupling around 4 T has been switched off due to the Pauli blocking of the inter-Landau level excitations. Moreover, the G band asymmetry caused by Fano resonance between excitonic many-body states and the E2g phonons is observed. This work offers a way to study the magnetoexcitation phonon interaction of materials through magneto-Raman spectroscopy with an external electrical field.

Low temperature photoresponse of monolayer tungsten disulphide

High photoresponse can be achieved in monolayers of transition metal dichalcogenides. However, the response times are inconveniently limited by defects. Here, we report low temperature photoresponse of monolayer tungsten disulphide prepared by exfoliation and chemical vapour deposition (CVD) method. The exfoliated device exhibits n-type behaviour; while the CVD device exhibits intrinsic behaviour. In off state, the CVD device has four times larger ratio of photoresponse for laser on/off and photoresponse decay–rise times are 0.1 s (limited by our setup), while the exfoliated device has few seconds. These findings are discussed in terms of charge trapping and localization.

Tunable excitonic emission of monolayer WS2 for the optical detection of DNA nucleobases

Two-dimensional transition metal dichalcogenides (2D TMDs) possess a tunable excitonic light emission that is sensitive to external conditions such as electric field, strain, and chemical doping. In this work, we reveal the interactions between DNA nucleobases, i.e., adenine (A), guanine (G), cytosine (C), and thymine (T) and monolayer WS2 by investigating the changes in the photoluminescence (PL) emissions of the monolayer WS2 after coating with nucleobase solutions. We found that adenine and guanine exert a clear effect on the PL profile of the monolayer WS2 and cause different PL evolution trends. In contrast, cytosine and thymine have little effect on the PL behavior. To obtain information on the interactions between the DNA bases and WS2, a series of measurements were conducted on adenine-coated WS2 monolayers, as a demonstration. The p-type doping of the WS2 monolayers on the introduction of adenine is clearly shown by both the evolution of the PL spectra and the electrical transport response. Our findings open the door for the development of label-free optical sensing approaches in which the detection signals arise from the tunable excitonic emission of the TMD itself rather than the fluorescence signals of label molecules. This dopant-selective optical response to the DNA nucleobases fills the gaps in previously reported optical biosensing methods and indicates a potential new strategy for DNA sequencing.

Magnetic Modes in Rare Earth Perovskites: A Magnetic-Field-Dependent Inelastic Light Scattering study

Here, we report the presence of defect-related states with magnetic degrees of freedom in crystals of LaAlO3 and several other rare-earth based perovskite oxides using inelastic light scattering (Raman spectroscopy) at low temperatures in applied magnetic fields of up to 9 T. Some of these states are at about 140 meV above the valence band maximum while others are mid-gap states at about 2.3 eV. No magnetic impurity could be detected in LaAlO3 by Proton-Induced X-ray Emission Spectroscopy. We, therefore, attribute the angular momentum-like states in LaAlO3 to cationic/anionic vacancies or anti-site defects. Comparison with the other rare earth perovskites leads to the empirical rule that the magnetic-field-sensitive transitions require planes of heavy elements (e.g. lanthanum) and oxygen without any other light cations in the same plane. These magnetic degrees of freedom in rare earth perovskites with useful dielectric properties may be tunable by appropriate defect engineering for magneto-optic applications.

Intrinsic excitonic emission and valley Zeeman splitting in epitaxial MS2 (M = Mo and W) monolayers on hexagonal boron nitride

Two-dimensional (2D) semiconductors, represented by 2D transition metal dichalcogenides (TMDs), exhibit rich valley physics due to strong spin-orbit/spin-valley coupling. The most common way to probe such 2D systems is to utilize optical methods, which can monitor light emissions from various excitonic states and further help in understanding the physics behind such phenomena. Therefore, 2D TMDs with good optical quality are in great demand. Here, we report a method to directly grow epitaxial WS2 and MoS2 monolayers on hexagonal boron nitride (hBN) flakes with a high yield and high optical quality; these monolayers show better intrinsic light emission features than exfoliated monolayers from natural crystals. For the first time, the valley Zeeman splitting of WS2 and MoS2 monolayers on hBN has been visualized and systematically investigated. This study paves a new way to produce high optical quality WS2 and MoS2 monolayers and to exploit their intrinsic properties in a multitude of applications.