Self-Terminated Surface Monolayer Oxidation Induced Robust Degenerate Doping in MoTe2 for Low Contact Resistance.

We introduce an effective method to degenerately dope MoTe2 by oxidizing its surface into the p-dopant MoOx in oxygen plasma. As a self-terminated process, the oxidation is restricted only in the very top layer, therefore offering us an easy and efficient control. The degenerate p-doping with the hole concentration of 2.5 × 1013 cm-2 can be obtained by applying a ∼300 s O2 plasma treatment. Using the degenerately doped MoTe2, we demonstrate a record low contact resistance of 0.6 kΩ µm for MoTe2. Our measurement highlights an excellent stability for the plasma-doped MoTe2. The doped characteristics are robust with no significant degradation even after a one-year exposure to the air. The oxygen plasma doping technique is compatible with the conventional semiconductor processes, which can be utilized to realize high-performance MoTe2 field-effect transistors (FETs) or tunnel FETs in the future.

Large-area single-crystal AB-bilayer and ABA-trilayer graphene grown on a Cu/Ni(111) foil.

High-quality AB-stacked bilayer or multilayer graphene larger than a centimetre has not been reported. Here, we report the fabrication and use of single-crystal Cu/Ni(111) alloy foils with controllable concentrations of Ni for the growth of large-area, high-quality AB-stacked bilayer and ABA-stacked trilayer graphene films by chemical vapour deposition. The stacking order, coverage and uniformity of the graphene films were evaluated by Raman spectroscopy and transmission electron microscopy including selected area electron diffraction and atomic resolution imaging. Electrical transport (carrier mobility and band-gap tunability) and thermal conductivity (the bilayer graphene has a thermal conductivity value of about 2,300 W m-1 K-1) measurements indicated the superior quality of the films. The tensile loading response of centimetre-scale bilayer graphene films supported by a 260-nm thick polycarbonate film was measured and the average values of the Young's modulus (478 GPa) and fracture strength (3.31 GPa) were obtained.

Highly Oriented Monolayer Graphene Grown on a Cu/Ni(111) Alloy Foil.

Fast-growth of single crystal monolayer graphene by CVD using methane and hydrogen has been achieved on "homemade" single crystal Cu/Ni(111) alloy foils over large area. Full coverage was achieved in 5 min or less for a particular range of composition (1.3 at.% to 8.6 at.% Ni), as compared to 60 min for a pure Cu(111) foil under identical growth conditions. These are the bulk atomic percentages of Ni, as a superstructure at the surface of these foils with stoichiometry Cu6Ni1 (for 1.3 to 7.8 bulk at.% Ni in the Cu/Ni(111) foil) was discovered by low energy electron diffraction (LEED). Complete large area monolayer graphene films are either single crystal or close to single crystal, and include folded regions that are essentially parallel and that were likely wrinkles that "fell over" to bind to the surface; these folds are separated by large, wrinkle-free regions. The folds occur due to the buildup of interfacial compressive stress (and its release) during cooling of the foils from 1075 °C to room temperature. The fold heights measured by atomic force microscopy (AFM) and scanning tunneling microscopy (STM) prove them to all be 3 layers thick, and scanning electron microscopy (SEM) imaging shows them to be around 10 to 300 nm wide and separated by roughly 20 µm. These folds are always essentially perpendicular to the steps in this Cu/Ni(111) substrate. Joining of well-aligned graphene islands (in growths that were terminated prior to full film coverage) was investigated with high magnification SEM and aberration-corrected high-resolution transmission electron microscopy (TEM) as well as AFM, STM, and optical microscopy. These methods show that many of the "join regions" have folds, and these arise from interfacial adhesion mechanics (they are due to the buildup of compressive stress during cool-down, but these folds are different than for the continuous graphene films-they occur due to "weak links" in terms of the interface mechanics). Such Cu/Ni(111) alloy foils are promising substrates for the large-scale synthesis of single-crystal graphene film.

Modulation of Quantum Tunneling via a Vertical Two-Dimensional Black Phosphorus and Molybdenum Disulfide p-n Junction.

Diverse diode characteristics were observed in two-dimensional (2D) black phosphorus (BP) and molybdenum disulfide (MoS2) heterojunctions. The characteristics of a backward rectifying diode, a Zener diode, and a forward rectifying diode were obtained from the heterojunction through thickness modulation of the BP flake or back gate modulation. Moreover, a tunnel diode with a precursor to negative differential resistance can be realized by applying dual gating with a solid polymer electrolyte layer as a top gate dielectric material. Interestingly, a steep subthreshold swing of 55 mV/dec was achieved in a top-gated 2D BP-MoS2 junction. Our simple device architecture and chemical doping-free processing guaranteed the device quality. This work helps us understand the fundamentals of tunneling in 2D semiconductor heterostructures and shows great potential in future applications in integrated low-power circuits.

Carrier-Type Modulation and Mobility Improvement of Thin MoTe2.

A systematic modulation of the carrier type in molybdenum ditelluride (MoTe2 ) field-effect transistors (FETs) is described, through rapid thermal annealing (RTA) under a controlled O2 environment (p-type modulation) and benzyl viologen (BV) doping (n-type modulation). Al2 O3 capping is then introduced to improve the carrier mobilities and device stability. MoTe2 is found to be ultrasensitive to O2 at elevated temperatures (250 °C). Charge carriers of MoTe2 flakes annealed via RTA at various vacuum levels are tuned between predominantly pristine n-type ambipolar, symmetric ambipolar, unipolar p-type, and degenerate-like p-type. Changes in the MoTe2 -transistor performance are confirmed to originate from the physical and chemical absorption and dissociation of O2 , especially at tellurium vacancy sites. The electron branch is modulated by varying the BV dopant concentrations and annealing conditions. Unipolar n-type MoTe2 FETs with a high on-off ratio exceeding 106 are achieved under optimized doping conditions. By introducing Al2 O3 capping, carrier field effect mobilities (41 for holes and 80 cm2 V-1 s-1 for electrons) and device stability are improved due to the reduced trap densities and isolation from ambient air. Lateral MoTe2 p-n diodes with an ideality factor of 1.2 are fabricated using the p- and n-type doping technique to test the superb potential of the doping method in functional electronic device applications.

Controlled Folding of Single Crystal Graphene.

Folded graphene in which two layers are stacked with a twist angle between them has been predicted to exhibit unique electronic, thermal, and magnetic properties. We report the folding of a single crystal monolayer graphene film grown on a Cu(111) substrate by using a tailored substrate having a hydrophobic region and a hydrophilic region. Controlled film delamination from the hydrophilic region was used to prepare macroscopic folded graphene with good uniformity on the millimeter scale. This process was used to create many folded sheets each with a defined twist angle between the two sheets. By identifying the original lattice orientation of the monolayer graphene on Cu foil, or establishing the relation between the fold angle and twist angle, this folding technique allows for the preparation of twisted bilayer graphene films with defined stacking orientations and may also be extended to create folded structures of other two-dimensional nanomaterials.

P-Type Polar Transition of Chemically Doped Multilayer MoS2 Transistor.

A high-performance multilayer MoS2 p-type field-effect transistor is realized via controllable chemical doping, which shows an excellent on/off ratio of 10(9) and a maximum hole mobility of 132 cm(2) V(-1) s(-1) at 133 K. The developed technique will enable 2D materials to be used for future high-efficiency and low-power semiconductor device applications.

Self-screened high performance multi-layer MoS2 transistor formed by using a bottom graphene electrode.

We investigated the carrier transport in multi-layer MoS2 with consideration of the contact resistance (R(c)) and interlayer resistance (R(int)). A bottom graphene contact was suggested to overcome the degradation of I(d) modulation in a back gated multi-layer MoS2 field effect transistor (FET) due to the accumulated R(int) and increased R(c) with increasing thickness. As a result, non-degraded drain current (I(d)) modulation with increasing flake thickness was achieved due to the non-cumulative R(int). Benefiting from the low R(c) induced by the negligible Schottky barrier at the graphene/MoS2 interface, the intrinsic carrier transport properties immune to R(c) were investigated in the multi-layer MoS2 FET. ∼2 times the enhanced carrier mobility was attained from the self-screened channel in the bottom graphene contacted device, compared to those with top metal contacts.

Ultimate thin vertical p-n junction composed of two-dimensional layered molybdenum disulfide.

Semiconducting two-dimensional crystals are currently receiving significant attention because of their great potential to be an ultrathin body for efficient electrostatic modulation, which enables to overcome the limitations of silicon technology. Here we report that, as a key building block for two-dimensional semiconductor devices, vertical p-n junctions are fabricated in ultrathin MoS2 by introducing AuCl3 and benzyl viologen dopants. Unlike usual unipolar MoS2, the MoS2 p-n junctions show ambipolar carrier transport, current rectification via modulation of potential barrier in films thicker than 8 nm and reversed current rectification via tunnelling in films thinner than 8 nm. The ultimate thinness of the vertical p-n homogeneous junctions in MoS2 is experimentally found to be 3 nm, and the chemical doping depth is found to be 1.5 nm. The ultrathin MoS2 p-n junctions present a significant potential of the two-dimensional crystals for flexible, transparent, high-efficiency electronic and optoelectronic applications.

Lateral MoS2 p-n junction formed by chemical doping for use in high-performance optoelectronics.

This paper demonstrates a technique to form a lateral homogeneous 2D MoS2 p-n junction by partially stacking 2D h-BN as a mask to p-dope MoS2. The fabricated lateral MoS2 p-n junction with asymmetric electrodes of Pd and Cr/Au displayed a highly efficient photoresponse (maximum external quantum efficiency of ∼7000%, specific detectivity of ∼5 × 10(10) Jones, and light switching ratio of ∼10(3)) and ideal rectifying behavior. The enhanced photoresponse and generation of open-circuit voltage (VOC) and short-circuit current (ISC) were understood to originate from the formation of a p-n junction after chemical doping. Due to the high photoresponse at low VD and VG attributed to its built-in potential, our MoS2 p-n diode made progress toward the realization of low-power operating photodevices. Thus, this study suggests an effective way to form a lateral p-n junction by the h-BN hard masking technique and to improve the photoresponse of MoS2 by the chemical doping process.

Metal-semiconductor barrier modulation for high photoresponse in transition metal dichalcogenide field effect transistors.

A gate-controlled metal-semiconductor barrier modulation and its effect on carrier transport were investigated in two-dimensional (2D) transition metal dichalcogenide (TMDC) field effect transistors (FETs). A strong photoresponse was observed in both unipolar MoS2 and ambipolar WSe2 FETs (i) at the high drain voltage due to a high electric field along the channel for separating photo-excited charge carriers and (ii) at the certain gate voltage due to the optimized barriers for the collection of photo-excited charge carriers at metal contacts. The effective barrier height between Ti/Au and TMDCs was estimated by a low temperature measurement. An ohmic contact behavior and drain-induced barrier lowering (DIBL) were clearly observed in MoS2 FET. In contrast, a Schottky-to-ohmic contact transition was observed in WSe2 FET as the gate voltage increases, due to the change of majority carrier transport from holes to electrons. The gate-dependent barrier modulation effectively controls the carrier transport, demonstrating its great potential in 2D TMDCs for electronic and optoelectronic applications.