Anisotropic Etching of Atomically Thin MoS₂

Exposure to oxygen at 300–340 °C results in triangular etch pits with uniform orientation on the surfaces of atomically thin molybdenum disulfide (MoS₂), indicating anisotropic etching terminating on lattice planes. The triangular pits grow laterally with oxidation time. The density of pits scarcely depends on oxidation time, temperature, and MoS₂ thickness but varies significantly from sample to sample, indicating that etching is initiated at native defect sites on the basal plane surface rather than activated by substrate effects such as charged impurities or surface roughness. Raman spectroscopy confirms that oxygen treatment produces no molybdenum oxide (MoO₃) below 340 °C. However, upon oxidation above 200 °C, the Raman A_1g mode upshifts and the linewidth decreases, indicating p-type doping of MoS₂. Oxidation at 400 °C results in complete conversion to MoO₃

Ambipolar Surface State Thermoelectric Power of Topological Insulator Bi₂Se₃

We measure gate-tuned thermoelectric power of mechanically exfoliated Bi₂Se₃ thin films in the topological insulator regime. The sign of the thermoelectric power changes across the charge neutrality point as the majority carrier type switches from electron to hole, consistent with the ambipolar electric field effect observed in conductivity and Hall effect measurements. Near the charge neutrality point and at low temperatures, the gate-dependent thermoelectric power follows the semiclassical Mott relation using the expected surface state density of states but is larger than expected at high electron doping, possibly reflecting a large density of states in the bulk gap. The thermoelectric power factor shows significant enhancement near the electron–hole puddle carrier density ∼0.5 × 10¹² cm^–2 per surface at all temperatures. Together with the expected reduction of lattice thermal conductivity in low-dimensional structures, the results demonstrate that nanostructuring and Fermi level tuning of three-dimensional topological insulators can be promising routes to realize efficient thermoelectric devices

Passivating Graphene and Suppressing Interfacial Phonon Scattering with Mechanically Transferred Large-Area Ga₂O₃

We demonstrate a large-area passivation layer for graphene by mechanical transfer of ultrathin amorphous Ga2O3 synthesized on liquid Ga metal. A comparison of temperature-dependent electrical measurements of millimeter-scale passivated and bare graphene on SiO2/Si indicates that the passivated graphene maintains its high field effect mobility desirable for applications. Surprisingly, the temperature-dependent resistivity is reduced in passivated graphene over a range of temperatures below 220 K, due to the interplay of screening of the surface optical phonon modes of the SiO2 by high-dielectric-constant Ga2O3 and the relatively high characteristic phonon frequencies of Ga2O3. Raman spectroscopy and electrical measurements indicate that Ga2O3 passivation also protects graphene from further processing such as plasma-enhanced atomic layer deposition of Al2O3

Self-Limiting Layer-by-Layer Oxidation of Atomically Thin WSe₂

Growth of a uniform oxide film with a tunable thickness on two-dimensional transition metal dichalcogenides is of great importance for electronic and optoelectronic applications. Here we demonstrate homogeneous surface oxidation of atomically thin WSe₂ with a self-limiting thickness from single- to trilayers. Exposure to ozone (O₃) below 100 °C leads to the lateral growth of tungsten oxide selectively along selenium zigzag-edge orientations on WSe₂. With further O₃ exposure, the oxide regions coalesce and oxidation terminates leaving a uniform thickness oxide film on top of unoxidized WSe₂. At higher temperatures, oxidation evolves in the layer-by-layer regime up to trilayers. The oxide films formed on WSe₂ are nearly atomically flat. Using photoluminescence and Raman spectroscopy, we find that the underlying single-layer WSe₂ is decoupled from the top oxide but hole-doped. Our findings offer a new strategy for creating atomically thin heterostructures of semiconductors and insulating oxides with potential for applications in electronic devices

Plasmon-Enhanced Terahertz Photodetection in Graphene

We report a large area terahertz detector utilizing a tunable plasmonic resonance in subwavelength graphene microribbons on SiC(0001) to increase the absorption efficiency. By tailoring the orientation of the graphene ribbons with respect to an array of subwavelength bimetallic electrodes, we achieve a condition in which the plasmonic mode can be efficiently excited by an incident wave polarized perpendicular to the electrode array, while the resulting photothermal voltage can be observed between the outermost electrodes

Effects of Floquet Engineering on the Coherent Exciton Dynamics in Monolayer WS2_2

Coherent optical manipulation of electronic bandstructures via Floquet Engineering is a promising means to control quantum systems on an ultrafast timescale. However, the ultrafast switching on/off of the driving field comes with questions regarding the limits of validity of the Floquet formalism, which is defined for an infinite periodic drive, and to what extent the transient changes can be driven adibatically. Experimentally addressing these questions has been difficult, in large part due to the absence of an established technique to measure coherent dynamics through the duration of the pulse. Here, using multidimensional coherent spectroscopy we explicitly excite, control, and probe a coherent superposition of excitons in the $K$ and $K^\prime$ valleys in monolayer WS$_2$. With a circularly polarized, red-detuned, pump pulse, the degeneracy of the $K$ and $K^\prime$ excitons can be lifted and the phase of the coherence rotated. We demonstrate phase rotations during the 100 fs driving pulse that exceed $\pi$, and show that this can be described by a combination of the AC-Stark shift of excitons in one valley and Bloch-Siegert shift of excitons in the opposite valley. Despite showing a smooth evolution of the phase that directly follows the intensity envelope of the pump pulse, the process is not perfectly adiabatic. By measuring the magnitude of the macroscopic coherence as it evolves before, during, and after the pump pulse we show that there is additional decoherence caused by power broadening in the presence of the pump. This non-adiabaticity may be a problem for many applications, such as manipulating q-bits in quantum information processing, however these measurements also suggest ways such effects can be minimised or eliminated

Plasmon-Enhanced Terahertz Photodetection in Graphene

We report a large area terahertz detector utilizing a tunable plasmonic resonance in subwavelength graphene microribbons on SiC(0001) to increase the absorption efficiency. By tailoring the orientation of the graphene ribbons with respect to an array of subwavelength bimetallic electrodes, we achieve a condition in which the plasmonic mode can be efficiently excited by an incident wave polarized perpendicular to the electrode array, while the resulting photothermal voltage can be observed between the outermost electrodes

Synthesis and Transfer of Large-Area Monolayer WS₂ Crystals: Moving Toward the Recyclable Use of Sapphire Substrates

Two-dimensional layered transition metal dichalcogenides (TMDs) show intriguing potential for optoelectronic devices due to their exotic electronic and optical properties. Only a few efforts have been dedicated to large-area growth of TMDs. Practical applications will require improving the efficiency and reducing the cost of production, through (1) new growth methods to produce large size TMD monolayer with less-stringent conditions, and (2) nondestructive transfer techniques that enable multiple reuse of growth substrate. In this work, we report to employ atmospheric pressure chemical vapor deposition (APCVD) for the synthesis of large size (>100 μm) single crystals of atomically thin tungsten disulfide (WS₂), a member of TMD family, on sapphire substrate. More importantly, we demonstrate a polystyrene (PS) mediated delamination process <i>via</i> capillary force in water which reduces the etching time in base solution and imposes only minor damage to the sapphire substrate. The transferred WS₂ flakes are of excellent continuity and exhibit comparable electron mobility after several growth cycles on the reused sapphire substrate. Interestingly, the photoluminescence emission from WS₂ grown on the recycled sapphire is much higher than that on fresh sapphire, possibly due to <i>p</i>-type doping of monolayer WS₂ flakes by a thin layer of water intercalated at the atomic steps of the recycled sapphire substrate. The growth and transfer techniques described here are expected to be applicable to other atomically thin TMD materials

Direct Observation of 2D Electrostatics and Ohmic Contacts in Template-Grown Graphene/WS₂ Heterostructures

Large-area two-dimensional (2D) heterojunctions are promising building blocks of 2D circuits. Understanding their intriguing electrostatics is pivotal but largely hindered by the lack of direct observations. Here graphene–WS₂ heterojunctions are prepared over large areas using a seedless ambient-pressure chemical vapor deposition technique. Kelvin probe force microscopy, photoluminescence spectroscopy, and scanning tunneling microscopy characterize the doping in graphene–WS₂ heterojunctions as-grown on sapphire and transferred to SiO₂ with and without thermal annealing. Both p–n and n–n junctions are observed, and a flat-band condition (zero Schottky barrier height) is found for lightly n-doped WS₂, promising low-resistance ohmic contacts. This indicates a more favorable band alignment for graphene–WS₂ than has been predicted, likely explaining the low barriers observed in transport experiments on similar heterojunctions. Electrostatic modeling demonstrates that the large depletion width of the graphene–WS₂ junction reflects the electrostatics of the one-dimensional junction between two-dimensional materials

High-Quality Uniform Dry Transfer of Graphene to Polymers

In this paper we demonstrate high-quality, uniform dry transfer of graphene grown by chemical vapor deposition on copper foil to polystyrene. The dry transfer exploits an azide linker molecule to establish a covalent bond to graphene and to generate greater graphene–polymer adhesion compared to that of the graphene–metal foil. Thus, this transfer approach provides a novel alternative route for graphene transfer, which allows for the metal foils to be reused