Engineering Valley Polarization of Monolayer WS2 : A Physical Doping Approach.

The emerging field of valleytronics has boosted intensive interests in investigating and controlling valley polarized light emission of monolayer transition metal dichalcogenides (1L TMDs). However, so far, the effective control of valley polarization degree in monolayer TMDs semiconductors is mostly achieved at liquid helium cryogenic temperature (4.2 K), with the requirements of high magnetic field and on-resonance laser, which are of high cost and unwelcome for applications. To overcome this obstacle, it is depicted that by electrostatic and optical doping, even at temperatures far above liquid helium cryogenic temperature (80 K) and under off-resonance laser excitation, a competitive valley polarization degree of monolayer WS2 can be achieved (more than threefold enhancement). The enhanced polarization is understood by a general doping dependent valley relaxation mechanism, which agrees well with the unified theory of carrier screening effects on intervalley scattering process. These results demonstrate that the tunability corresponds to an effective magnet field of ≈10 T at 4.2 K. This work not only serves as a reference to future valleytronic studies based on monolayer TMDs with various external or native carrier densities, but also provides an alternative approach toward enhanced polarization degree, which denotes an essential step toward practical valleytronic applications.

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.

Doping density, not valency, influences catalytic metal-assisted plasma etching of silicon.

Metal-assisted plasma etching (MAPE) of silicon (Si) is an etching technique driven by the catalytic activity of metals such as gold in fluorine-based plasma environments. In this work, the role of the Si substrate was investigated by examining the effects of the dopant concentration in both n- and p-type Si and the dopant atom type in n-type Si in SF6/O2 mixed gas plasma. At the highest dopant concentrations, both n- and p-type Si initially exhibit inhibition of the MAPE-enhanced etching. As the etch progresses, MAPE initiates, resulting in catalytic etching of the underlying Si at the metal-Si interface. Interestingly, MAPE-enhanced etching increases with decreasing doping concentrations for both n- and p-type Si substrates, distinct from results for the similar but divergent, metal-assisted chemical etching of silicon in liquid. Our findings show that the metal-Si interface remains essential to MAPE, and surface enrichment of the dopant atoms or other surface chemistries and the size of metal nanoparticles play roles in modulating catalytic activity.

Electrical tuning of optically active interlayer excitons in bilayer MoS2.

Interlayer (IL) excitons, comprising electrons and holes residing in different layers of van der Waals bonded two-dimensional semiconductors, have opened new opportunities for room-temperature excitonic devices. So far, two-dimensional IL excitons have been realized in heterobilayers with type-II band alignment. However, the small oscillator strength of the resulting IL excitons and difficulties with producing heterostructures with definite crystal orientation over large areas have challenged the practical applicability of this design. Here, following the theoretical prediction and recent experimental confirmation of the existence of IL excitons in bilayer MoS2, we demonstrate the electrical control of such excitons up to room temperature. We find that the IL excitonic states preserve their large oscillator strength as their energies are manipulated by the electric field. We attribute this effect to the mixing of the pure IL excitons with intralayer excitons localized in a single layer. By applying an electric field perpendicular to the bilayer MoS2 crystal plane, excitons with IL character split into two peaks with an X-shaped field dependence as a clear fingerprint of the shift of the monolayer bands with respect to each other. Finally, we demonstrate the full control of the energies of IL excitons distributed homogeneously over a large area of our device.

Engineering Dielectric Screening for Potential-well Arrays of Excitons in 2D Materials.

Tailoring of the band gap in semiconductors is essential for the development of novel devices. In standard semiconductors, this modulation is generally achieved through highly energetic ion implantation. In two-dimensional (2D) materials, the photophysical properties are strongly sensitive to the surrounding dielectric environment presenting novel opportunities through van der Waals heterostructures encompassing atomically thin high-κ dielectrics. Here, we demonstrate a giant tuning of the exciton binding energy of the monolayer WSe2 as a function of the dielectric environment. Upon increasing the average dielectric constant from 2.4 to 15, the exciton binding energy is reduced by as much as 300 meV in ambient conditions. The experimentally determined exciton binding energies are in excellent agreement with the theoretical values predicted from a Mott-Wannier exciton model with parameters derived from first-principles calculations. Finally, we show how texturing of the dielectric environment can be used to realize potential-well arrays for excitons in 2D materials, which is a first step toward exciton metamaterials.

Unveiling exceptionally robust valley contrast in AA- and AB-stacked bilayer WS2.

Valleytronics is a particularly interesting field that employs the valley degree of freedom for information manipulation. The fascinating prospects for realizing valleytronic devices have inspired persistent efforts towards exploring material systems with robust valley polarization. Monolayer transition metal dichalcogenides (TMDs) obey the well-known valley-dependent selection rule as a result of their inversion asymmetry. However, for inversion-symmetric bilayer tungsten-based TMDs, highly selective valley polarization has been surprisingly observed and is not yet fully understood. Here we systematically study the origin of the anomalously high valley polarization in bilayer WS2 by temperature-dependent polarization-resolved photoluminescence measurements. It is found that acoustic phonons play a critical role in the valley polarization of bilayer WS2. For some WS2 bilayers with relatively small intensity ratios of indirect to direct bandgap emission, acoustic phonons could remarkably assist the intervalley scattering process and smear the valley contrast. On the other hand, in other bilayers, which show obvious indirect band gap emission, the indirect optical transition process depletes the phonon mode at the Λ point dramatically and results in anomalously robust valley polarization in bilayer WS2. These results help recognize the crucial role of electron-phonon coupling in intervalley relaxation in bilayer WS2 and provide new insights into the future design of valleytronic devices based on two-dimensional TMDs.

Room-temperature 2D semiconductor activated vertical-cavity surface-emitting lasers.

Two-dimensional (2D) semiconductors are opening a new platform for revitalizing widely spread optoelectronic applications. The realisation of room-temperature vertical 2D lasing from monolayer semiconductors is fundamentally interesting and highly desired for appealing on-chip laser applications such as optical interconnects and supercomputing. Here, we present room-temperature low-threshold lasing from 2D semiconductor activated vertical-cavity surface-emitting lasers (VCSELs) under continuous-wave pumping. 2D lasing is achieved from a 2D semiconductor. Structurally, dielectric oxides were used to construct the half-wavelength-thick cavity and distributed Bragg reflectors, in favour of single-mode operation and ultralow optical loss; in the cavity centre, the direct-bandgap monolayer WS2 was embedded as the gain medium, compatible with the planar VCSEL configuration and the monolithic integration technology. This work demonstrates 2D semiconductor activated VCSELs with desirable emission characteristics, which represents a major step towards practical optoelectronic applications of 2D semiconductor lasers.Two-dimensional materials have recently emerged as interesting materials for optoelectronic applications. Here, Shang et al. demonstrate two-dimensional semiconductor activated vertical-cavity surface-emitting lasers where both the gain material and the lasing characteristics are two-dimensional.

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.

Chemically driven tunable light emission of charged and neutral excitons in monolayer WS2.

Monolayer (1L) semiconducting transition metal dichacogenides (TMDs) possess remarkable physical and optical properties, promising for a wide range of applications from nanoelectronics to optoelectronics such as light-emitting and sensing devices. Here we report how the molecular adsorption can modulate the light emission and electrical properties of 1L WS2. The dependences of trion and exciton emission on chemical doping are investigated in 1L WS2 by microphotoluminescence (µPL) measurements, where different responses are observed and simulated theoretically. The total PL is strongly enhanced when electron-withdrawing molecules adsorb on 1L WS2, which is attributed to the increase of the exciton formation due to charge transfer. The electrical transport measurements of a 1L WS2 field effect transistor elucidate the effect of the adsorbates on the conductivity, which give evidence for charge transfer between molecules and 1L WS2. These findings open up many opportunities to manipulate the electrical and optical properties of two-dimensional TMDs, which are particularly important for developing optoelectronic devices for chemical and biochemical sensing applications.

Nonblinking, intense two-dimensional light emitter: monolayer WS2 triangles.

Monolayer WS2 (1L-WS2), with a direct band gap, provides an ideal platform to investigate unique properties of two-dimensional semiconductors. In this work, light emission of a 1L-WS2 triangle has been studied by using steady-state, time-resolved, and temperature-dependent photoluminescence (PL) spectroscopy. Two groups of 1L-WS2 triangles have been grown by chemical vapor deposition, which exhibit nonuniform and uniform PL, respectively. Observed nonuniform PL features, i.e., quenching and blue-shift in certain areas, are caused by structural imperfection and n-doping induced by charged defects. Uniform PL is found to be intrinsic, intense, and nonblinking, which are attributed to high crystalline quality. The binding energy of the A-exciton is extracted experimentally, which gives direct evidence for the large excitonic effect in 1L-WS2. These superior photon emission features make 1L-WS2 an appealing material for optoelectronic applications such as novel light-emitting and biosensing devices.

Photocontrolled molecular structural transition and doping in graphene.

We studied chemical doping of trans- and cis-azobenzene on graphene by Raman spectroscopy. It was found that the molecule induces hole-doping in graphene through charge transfer. Moreover, the doping level in graphene can be reversibly modulated by a photocontrolled molecular conformation change. As trans-azobenzene isomerizes to the cis configuration under UV irradiation, we probe the dynamic molecular structural evolution of azobenzene on graphene by Raman spectroscopy. Raman analysis indicates the precise orientation of cis-azobenzene on the graphene surface, which brings us further comprehension of the effect of conformation change on the electronic properties of graphene. In particular, the substantial decreases of the doping level and chemical enhancement of the molecular signal are attributed to the weakening of hole transfer from molecule to graphene, owing to the lifting of the electron-withdrawing group away from the graphene. Moreover, the calculation results exhibit the favorable configuration of cis-azobenzene, which is in good agreement with Raman spectroscopic analysis. Our results highlight an approach for employing graphene as a promising platform for probing molecular conformation transition at the submolecular level by Raman spectroscopy.