Stacking-Order-Driven Optical Properties and Carrier Dynamics in ReS2.

Two distinct stacking orders in ReS2 are identified without ambiguity and their influence on vibrational, optical properties and carrier dynamics are investigated. With atomic resolution scanning transmission electron microscopy (STEM), two stacking orders are determined as AA stacking with negligible displacement across layers, and AB stacking with about a one-unit cell displacement along the a axis. First-principles calculations confirm that these two stacking orders correspond to two local energy minima. Raman spectra inform a consistent difference of modes I & III, about 13 cm-1 for AA stacking, and 20 cm-1 for AB stacking, making a simple tool for determining the stacking orders in ReS2 . Polarized photoluminescence (PL) reveals that AB stacking possesses blueshifted PL peak positions, and broader peak widths, compared with AA stacking, indicating stronger interlayer interaction. Transient transmission measured with femtosecond pump-probe spectroscopy suggests exciton dynamics being more anisotropic in AB stacking, where excited state absorption related to Exc. III mode disappears when probe polarization aligns perpendicular to b axis. The findings underscore the stacking-order driven optical properties and carrier dynamics of ReS2 , mediate many seemingly contradictory results in the literature, and open up an opportunity to engineer electronic devices with new functionalities by manipulating the stacking order.

Band Structure Engineering of Layered WSe2 via One-Step Chemical Functionalization.

Chemical functionalization is demonstrated to enhance the p-type electrical performance of two-dimensional (2D) layered tungsten diselenide (WSe2) field-effect transistors (FETs) using a one-step dipping process in an aqueous solution of ammonium sulfide [(NH4)2S(aq)]. Molecularly resolved scanning tunneling microscopy and spectroscopy reveal that molecular adsorption on a monolayer WSe2 surface induces a reduction of the electronic band gap from 2.1 to 1.1 eV and a Fermi level shift toward the WSe2 valence band edge (VBE), consistent with an increase in the density of positive charge carriers. The mechanism of electronic transformation of WSe2 by (NH4)2S(aq) chemical treatment is elucidated using density functional theory calculations which reveal that molecular "SH" adsorption on the WSe2 surface introduces additional in-gap states near the VBE, thereby, inducing a Fermi level shift toward the VBE along with a reduction in the electronic band gap. As a result of the (NH4)2S(aq) chemical treatment, the p-branch ON-currents (ION) of back-gated few-layer ambipolar WSe2 FETs are enhanced by about 2 orders of magnitude, and a ∼6× increase in the hole field-effect mobility is observed, the latter primarily resulting from the p-doping-induced narrowing of the Schottky barrier width leading to an enhanced hole injection at the WSe2/contact metal interface. This (NH4)2S(aq) chemical functionalization technique can serve as a model method to control the electronic band structure and enhance the performance of devices based on 2D layered transition-metal dichalcogenides.

Evidence for moiré excitons in van der Waals heterostructures.

Recent advances in the isolation and stacking of monolayers of van der Waals materials have provided approaches for the preparation of quantum materials in the ultimate two-dimensional limit1,2. In van der Waals heterostructures formed by stacking two monolayer semiconductors, lattice mismatch or rotational misalignment introduces an in-plane moiré superlattice3. It is widely recognized that the moiré superlattice can modulate the electronic band structure of the material and lead to transport properties such as unconventional superconductivity4 and insulating behaviour driven by correlations5-7; however, the influence of the moiré superlattice on optical properties has not been investigated experimentally. Here we report the observation of multiple interlayer exciton resonances with either positive or negative circularly polarized emission in a molybdenum diselenide/tungsten diselenide (MoSe2/WSe2) heterobilayer with a small twist angle. We attribute these resonances to excitonic ground and excited states confined within the moiré potential. This interpretation is supported by recombination dynamics and by the dependence of these interlayer exciton resonances on twist angle and temperature. These results suggest the feasibility of engineering artificial excitonic crystals using van der Waals heterostructures for nanophotonics and quantum information applications.

Visualization of Local Conductance in MoS2/WSe2 Heterostructure Transistors.

The vertical stacking of van der Waals (vdW) materials introduces a new degree of freedom to the research of two-dimensional (2D) systems. The interlayer coupling strongly influences the band structure of the heterostructures, resulting in novel properties that can be utilized for electronic and optoelectronic applications. Based on microwave microscopy studies, we report quantitative electrical imaging on gated molybdenum disulfide (MoS2)/tungsten diselenide (WSe2) heterostructure devices, which exhibit an intriguing antiambipolar effect in their transfer characteristics. Interestingly, in the region with significant source-drain current, electrons in the n-type MoS2 and holes in the p-type WSe2 segments are nearly balanced, whereas the heterostructure area is depleted of mobile charges. The spatial evolution of local conductance can be ascribed to the lateral band bending and formation of depletion regions along the line of MoS2-heterostructure-WSe2. Our work vividly demonstrates the microscopic origin of novel transport behaviors, which is important for the vibrant field of vdW heterojunction research.

Carrier Trapping by Oxygen Impurities in Molybdenum Diselenide.

Understanding defect effect on carrier dynamics is essential for both fundamental physics and potential applications of transition metal dichalcogenides (TMDs). Here, the phenomenon of oxygen impurities trapping photoexcited carriers has been studied with ultrafast pump-probe spectroscopy. Oxygen impurities are intentionally created in exfoliated multilayer MoSe2 with Ar+ plasma irradiation and air exposure. After plasma treatment, the signal of transient absorption first increases and then decreases, which is a signature of defect-capturing carriers. With larger density of oxygen defects, the trapping effect becomes more prominent. The trapping defect densities are estimated from the transient absorption signal, and its increasing trend in the longer-irradiated sample agrees with the results from X-ray photoelectron spectroscopy. First-principle calculations with density functional theory reveal that oxygen atoms occupying Mo vacancies create mid-gap defect states, which are responsible for carrier trapping. Our findings shed light on the important role of oxygen defects as carrier trappers in TMDs, and facilitate defect engineering in relevant materials and device applications.

Activation of a Nickel-Based Oxygen Evolution Reaction Catalyst on a Hematite Photoanode via Incorporation of Cerium for Photoelectrochemical Water Oxidation.

There has been debate on whether Ni(OH)2 is truly catalytically active for the photo/electrocatalytic oxygen evolution reaction. In this report, we synthesized a Ni(OH)2 cocatalyst on a hematite photoanode and showed that, as has been proposed in other studies, the current density varies as a function of scan rate, which arises due to a photoinduced capacitive charging effect. We discovered that this photoinduced charging of Ni2+/3+ can be overcome by mixing cerium nitrate into the Ni precursor solution. Under illumination, the NiCeOx cocatalyst on a hematite photoanode exhibited an approximately 200 mV cathodic shift in onset potential and a ∼53% enhancement in photocurrent at 1.23 V vs RHE. Material characterization by electrochemical impedance spectroscopy revealed that the Ni species create a p-n junction across the charge space region, which facilitates collection of the photogenerated holes by the cocatalyst layer, and core level X-ray photoelectron spectroscopy showed that Ce incorporated into the Ni-based cocatalyst layer may possibly induce the oxidation of the Ni species. In addition, we observed a reduction in binding energies of Ni after photoelectrochemical water splitting reactions, which suggests that the lattice oxygen of the NiCeOx is consumed in the catalytic cycle, forming oxygen vacancies. The NiCeOx cocatalyst, however, was incapable of passivating the surface recombination centers of the hematite photoanode, as indicated by the unaltered flat-band potential determined with Mott-Schottky analysis.

Reconfigurable Complementary Monolayer MoTe2 Field-Effect Transistors for Integrated Circuits.

Transition metal dichalcogenides are of interest for next generation switches, but the lack of low resistance electron and hole contacts in the same material has hindered the development of complementary field-effect transistors and circuits. We demonstrate an air-stable, reconfigurable, complementary monolayer MoTe2 field-effect transistor encapsulated in hexagonal boron nitride, using electrostatically doped contacts. The introduction of a multigate design with prepatterned bottom contacts allows us to independently achieve low contact resistance and threshold voltage tuning, while also decoupling the Schottky contacts and channel gating. We illustrate a complementary inverter and a p-i-n diode as potential applications.

Effects of Electrode Layer Band Structure on the Performance of Multilayer Graphene-hBN-Graphene Interlayer Tunnel Field Effect Transistors.

Interlayer tunnel field-effect transistors based on graphene and hexagonal boron nitride (hBN) have recently attracted much interest for their potential as beyond-CMOS devices. Using a recently developed method for fabricating rotationally aligned two-dimensional heterostructures, we show experimental results for devices with varying thicknesses and stacking order of the graphene electrode layers and also model the current-voltage behavior. We show that an increase in the graphene layer thickness results in narrower resonance. However, due to a simultaneous increase in the number of sub-bands and decrease of sub-band separation with an increase in thickness, the negative differential resistance peaks becomes less prominent and do not appear for certain conditions at room temperature. Also, we show that due to the unique band structure of odd number of layer Bernal-stacked graphene, the number of closely spaced resonance conditions increase, causing interference between neighboring resonance peaks. Although this can be avoided with even number of layer graphene, we find that in this case the bandgap opening present at high biases tend to broaden the resonance peaks.

Structural and Electrical Properties of MoTe2 and MoSe2 Grown by Molecular Beam Epitaxy.

We demonstrate the growth of thin films of molybdenum ditelluride and molybdenum diselenide on sapphire substrates by molecular beam epitaxy. In situ structural and chemical analyses reveal stoichiometric layered film growth with atomically smooth surface morphologies. Film growth along the (001) direction is confirmed by X-ray diffraction, and the crystalline nature of growth in the 2H phase is evident from Raman spectroscopy. Transmission electron microscopy is used to confirm the layered film structure and hexagonal arrangement of surface atoms. Temperature-dependent electrical measurements show an insulating behavior that agrees well with a two-dimensional variable-range hopping model, suggesting that transport in these films is dominated by localized charge-carrier states.

Large-Area Monolayer MoS2 for Flexible Low-Power RF Nanoelectronics in the GHz Regime.

Flexible synthesized MoS2 transistors are advanced to perform at GHz speeds. An intrinsic cutoff frequency of 5.6 GHz is achieved and analog circuits are realized. Devices are mechanically robust for 10,000 bending cycles.

High-Mobility Holes in Dual-Gated WSe2 Field-Effect Transistors.

We demonstrate dual-gated p-type field-effect transistors (FETs) based on few-layer tungsten diselenide (WSe2) using high work-function platinum source/drain contacts and a hexagonal boron nitride top-gate dielectric. A device topology with contacts underneath the WSe2 results in p-FETs with ION/IOFF ratios exceeding 10(7) and contacts that remain ohmic down to cryogenic temperatures. The output characteristics show current saturation and gate tunable negative differential resistance. The devices show intrinsic hole mobilities around 140 cm(2)/(V s) at room temperature and approaching 4000 cm(2)/(V s) at 2 K. Temperature-dependent transport measurements show a metal-insulator transition, with an insulating phase at low densities and a metallic phase at high densities. The mobility shows a strong temperature dependence consistent with phonon scattering, and saturates at low temperatures, possibly limited by Coulomb scattering or defects.

Radio Frequency Transistors and Circuits Based on CVD MoS2.

We report on the gigahertz radio frequency (RF) performance of chemical vapor deposited (CVD) monolayer MoS2 field-effect transistors (FETs). Initial DC characterizations of fabricated MoS2 FETs yielded current densities exceeding 200 µA/µm and maximum transconductance of 38 µS/µm. A contact resistance corrected low-field mobility of 55 cm(2)/(V s) was achieved. Radio frequency FETs were fabricated in the ground-signal-ground (GSG) layout, and standard de-embedding techniques were applied. Operating at the peak transconductance, we obtain short-circuit current-gain intrinsic cutoff frequency, fT, of 6.7 GHz and maximum intrinsic oscillation frequency, fmax, of 5.3 GHz for a device with a gate length of 250 nm. The MoS2 device afforded an extrinsic voltage gain Av of 6 dB at 100 MHz with voltage amplification until 3 GHz. With the as-measured frequency performance of CVD MoS2, we provide the first demonstration of a common-source (CS) amplifier with voltage gain of 14 dB and an active frequency mixer with conversion gain of -15 dB. Our results of gigahertz frequency performance as well as analog circuit operation show that large area CVD MoS2 may be suitable for industrial-scale electronic applications.

Air Stable Doping and Intrinsic Mobility Enhancement in Monolayer Molybdenum Disulfide by Amorphous Titanium Suboxide Encapsulation.

To reduce Schottky-barrier-induced contact and access resistance, and the impact of charged impurity and phonon scattering on mobility in devices based on 2D transition metal dichalcogenides (TMDs), considerable effort has been put into exploring various doping techniques and dielectric engineering using high-κ oxides, respectively. The goal of this work is to demonstrate a high-κ dielectric that serves as an effective n-type charge transfer dopant on monolayer (ML) molybdenum disulfide (MoS2). Utilizing amorphous titanium suboxide (ATO) as the "high-κ dopant", we achieved a contact resistance of ∼180 Ω·µm that is the lowest reported value for ML MoS2. An ON current as high as 240 µA/µm and field effect mobility as high as 83 cm(2)/V-s were realized using this doping technique. Moreover, intrinsic mobility as high as 102 cm(2)/V-s at 300 K and 501 cm(2)/V-s at 77 K were achieved after ATO encapsulation that are among the highest mobility values reported on ML MoS2. We also analyzed the doping effect of ATO films on ML MoS2, a phenomenon that is absent when stoichiometric TiO2 is used, using ab initio density functional theory (DFT) calculations that shows excellent agreement with our experimental findings. On the basis of the interfacial-oxygen-vacancy mediated doping as seen in the case of high-κ ATO-ML MoS2, we propose a mechanism for the mobility enhancement effect observed in TMD-based devices after encapsulation in a high-κ dielectric environment.

Perpendicular Magnetic Anisotropy and Spin Glass-like Behavior in Molecular Beam Epitaxy Grown Chromium Telluride Thin Films.

Reflection high-energy electron diffraction (RHEED), scanning tunneling microscopy (STM), vibrating sample magnetometry, and other physical property measurements are used to investigate the structure, morphology, magnetic, and magnetotransport properties of (001)-oriented Cr2Te3 thin films grown on Al2O3(0001) and Si(111)-(7×7) surfaces by molecular beam epitaxy. Streaky RHEED patterns indicate flat smooth film growth on both substrates. STM studies show the hexagonal arrangements of surface atoms. Determination of the lattice parameter from the atomically resolved STM image is consistent with the bulk crystal structures. Magnetic measurements show the film is ferromagnetic, having a Curie temperature of about 180 K, and a spin glass-like behavior was observed below 35 K. Magnetotransport measurements show the metallic nature of the film with a perpendicular magnetic anisotropy along the c-axis.

Field effect transistors with current saturation and voltage gain in ultrathin ReS2.

We report the fabrication and device characteristics of exfoliated, few-layer, dual-gated ReS2 field effect transistors (FETs). The ReS2 FETs display n-type behavior with a room temperature Ion/I(off) of 10(5). Many devices were studied with a maximum intrinsic mobility of 12 cm(2) · V(-1) · s(-1) at room temperature and 26 cm(2) · V(-1) · s(-1) at 77 K. The Cr/Au-ReS2 contact resistance determined using the transfer length method is gate-bias dependent and ranges from 175 kΩ · µm to 5 kΩ · µm, and shows an exponential dependence on back-gate voltage indicating Schottky barriers at the source and drain contacts. Dual-gated ReS2 FETs demonstrate current saturation, voltage gain, and a subthreshold swing of 148 mV/decade.