Uncovering edge states and electrical inhomogeneity in MoS2 field-effect transistors.

The understanding of various types of disorders in atomically thin transition metal dichalcogenides (TMDs), including dangling bonds at the edges, chalcogen deficiencies in the bulk, and charges in the substrate, is of fundamental importance for TMD applications in electronics and photonics. Because of the imperfections, electrons moving on these 2D crystals experience a spatially nonuniform Coulomb environment, whose effect on the charge transport has not been microscopically studied. Here, we report the mesoscopic conductance mapping in monolayer and few-layer MoS2 field-effect transistors by microwave impedance microscopy (MIM). The spatial evolution of the insulator-to-metal transition is clearly resolved. Interestingly, as the transistors are gradually turned on, electrical conduction emerges initially at the edges before appearing in the bulk of MoS2 flakes, which can be explained by our first-principles calculations. The results unambiguously confirm that the contribution of edge states to the channel conductance is significant under the threshold voltage but negligible once the bulk of the TMD device becomes conductive. Strong conductance inhomogeneity, which is associated with the fluctuations of disorder potential in the 2D sheets, is also observed in the MIM images, providing a guideline for future improvement of the device performance.

Out-of-Plane Electromechanical Response of Monolayer Molybdenum Disulfide Measured by Piezoresponse Force Microscopy.

Two-dimensional (2D) materials have recently been theoretically predicted and experimentally confirmed to exhibit electromechanical coupling. Specifically, monolayer and few-layer molybdenum disulfide (MoS2) have been measured to be piezoelectric within the plane of their atoms. This work demonstrates and quantifies a nonzero out-of-plane electromechanical response of monolayer MoS2 and discusses its possible origins. A piezoresponse force microscope was used to measure the out-of-plane deformation of monolayer MoS2 on Au/Si and Al2O3/Si substrates. Using a vectorial background subtraction technique, we estimate the effective out-of-plane piezoelectric coefficient, d33eff, for monolayer MoS2 to be 1.03 ± 0.22 pm/V when measured on the Au/Si substrate and 1.35 ± 0.24 pm/V when measured on Al2O3/Si. This is on the same order as the in-plane coefficient d11 reported for monolayer MoS2. Interpreting the out-of-plane response as a flexoelectric response, the effective flexoelectric coefficient, µeff*, is estimated to be 0.10 nC/m. Analysis has ruled out the possibility of elastic and electrostatic forces contributing to the measured electromechanical response. X-ray photoelectron spectroscopy detected some contaminants on both MoS2 and its substrate, but the background subtraction technique is expected to remove major contributions from the unwanted contaminants. These measurements provide evidence that monolayer MoS2 exhibits an out-of-plane electromechanical response and our analysis offers estimates of the effective piezoelectric and flexoelectric coefficients.

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.

Thermal Oxidation of WSe2 Nanosheets Adhered on SiO2/Si Substrates.

Because of the drastically different intralayer versus interlayer bonding strengths, the mechanical, thermal, and electrical properties of two-dimensional (2D) materials are highly anisotropic between the in-plane and out-of-plane directions. The structural anisotropy may also play a role in chemical reactions, such as oxidation, reduction, and etching. Here, the composition, structure, and electrical properties of mechanically exfoliated WSe2 nanosheets on SiO2/Si substrates were studied as a function of the extent of thermal oxidation. A major component of the oxidation, as indicated from optical and Raman data, starts from the nanosheet edges and propagates laterally toward the center. Partial oxidation also occurs in certain areas at the surface of the flakes, which are shown to be highly conductive by microwave impedance microscopy. Using secondary ion mass spectroscopy, we also observed extensive oxidation at the WSe2-SiO2 interface. The combination of multiple microcopy methods can thus provide vital information on the spatial evolution of chemical reactions on 2D materials and the nanoscale electrical properties of the reaction products.

Mesoscale imperfections in MoS2 atomic layers grown by a vapor transport technique.

The success of isolating small flakes of atomically thin layers through mechanical exfoliation has triggered enormous research interest in graphene and other two-dimensional materials. For device applications, however, controlled large-area synthesis of highly crystalline monolayers with a low density of electronically active defects is imperative. Here, we demonstrate the electrical imaging of dendritic ad-layers and grain boundaries in monolayer molybdenum disulfide (MoS2) grown by a vapor transport technique using microwave impedance microscopy. The micrometer-sized precipitates in our films, which appear as a second layer of MoS2 in conventional height and optical measurements, show ∼ 2 orders of magnitude higher conductivity than that of the single layer. The zigzag grain boundaries, on the other hand, are shown to be more resistive than the crystalline grains, consistent with previous studies. Our ability to map the local electrical properties in a rapid and nondestructive manner is highly desirable for optimizing the growth process of large-scale MoS2 atomic layers.

Two-Step Growth of Uniform Monolayer MoS2 Nanosheets by Metal-Organic Chemical Vapor Deposition.

To achieve large area growth of transition metal dichalcogenides of uniform monolayer thickness, we demonstrate metal-organic chemical vapor deposition (MOCVD) growth under low pressure followed by a high-temperature sulfurization process under atmospheric pressure (AP). Following sulfurization, the MOCVD-grown continuous MoS2 film transforms into compact triangular crystals of uniform monolayer thickness as confirmed from the sharp distinct photoluminescence peak at 1.8 eV. Raman and X-ray photoelectron spectroscopies confirm that the structural disorders and chalcogen vacancies inherent to the as-grown MOCVD film are substantially healed and carbon/oxygen contaminations are heavily suppressed. The as-grown MOCVD film has a Mo/S ratio of 1:1.6 and an average defect length of ∼1.56 nm, which improve to 1:1.97 and ∼21 nm, respectively, upon sulfurization. The effect of temperature and duration of the sulfurization process on the morphology and stoichiometry of the grown film is investigated in detail. Compared to the APCVD growth, this two-step growth process shows more homogenous distribution of the triangular monolayer MoS2 domains across the entire substrate, while demonstrating comparable electrical performance.

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.

Effects of Uniaxial and Biaxial Strain on Few-Layered Terrace Structures of MoS2 Grown by Vapor Transport.

One of the most fascinating properties of molybdenum disulfide (MoS2) is its ability to be subjected to large amounts of strain without experiencing degradation. The potential of MoS2 mono- and few-layers in electronics, optoelectronics, and flexible devices requires the fundamental understanding of their properties as a function of strain. While previous reports have studied mechanically exfoliated flakes, tensile strain experiments on chemical vapor deposition (CVD)-grown few-layered MoS2 have not been examined hitherto, although CVD is a state of the art synthesis technique with clear potential for scale-up processes. In this report, we used CVD-grown terrace MoS2 layers to study how the number and size of the layers affected the physical properties under uniaxial and biaxial tensile strain. Interestingly, we observed significant shifts in both the Raman in-plane mode (as high as -5.2 cm(-1)) and photoluminescence (PL) energy (as high as -88 meV) for the few-layered MoS2 under ∼1.5% applied uniaxial tensile strain when compared to monolayers and few-layers of MoS2 studied previously. We also observed slippage between the layers which resulted in a hysteresis of the Raman and PL spectra during further applications of strain. Through DFT calculations, we contended that this random layer slippage was due to defects present in CVD-grown materials. This work demonstrates that CVD-grown few-layered MoS2 is a realistic, exciting material for tuning its properties under tensile strain.

Revealing the planar chemistry of two-dimensional heterostructures at the atomic level.

Two-dimensional (2D) atomic crystals and their heterostructures are an intense area of study owing to their unique properties that result from structural planar confinement. Intrinsically, the performance of a planar vertical device is linked to the quality of its 2D components and their interfaces, therefore requiring characterization tools that can reveal both its planar chemistry and morphology. Here, we propose a characterization methodology combining (micro-) Raman spectroscopy, atomic force microscopy and time-of-flight secondary ion mass spectrometry to provide structural information, morphology and planar chemical composition at virtually the atomic level, aimed specifically at studying 2D vertical heterostructures. As an example system, a graphene-on-h-BN heterostructure is analysed to reveal, with an unprecedented level of detail, the subtle chemistry and interactions within its layer structure that can be assigned to specific fabrication steps. Such detailed chemical information is of crucial importance for the complete integration of 2D heterostructures into functional devices.

Controlled seeding of laser deposited Ta:TiO2 nanobrushes and their performance as photoanode for dye sensitized solar cells.

Hexagonal patterned indium tin oxide (ITO) with a height of 1.5 µm was fabricated on fluorinated SnO2 (FTO) substrate via nanoimprint lithography and pulsed laser deposition (PLD). Tantalum doped TiO2 was deposited on the patterned substrate by PLD. The film of Ta:TiO2 grew vertically and separately on the patterned ITO and formed a brush-like structure. Dye-sensitized solar cells with the Ta:TiO2 film deposited on the patterned substrate as well as flat FTO substrate for comparison were fabricated and tested. The device with the patterned substrate showed a 25% increase in short circuit current (Jsc) compared to the one with flat FTO substrate. Optical and photoelectrochemical characterization techniques were performed to investigate the improvement. The increase of Jsc was attributed to the enhancements of light absorption in the 600-750 nm range and collection of excited electrons by the brush-like structure and the patterned ITO, respectively.

Surface patterning of mesoporous niobium oxide films for solar energy conversion.

An array of periodic surface features were patterned on mesoporous niobium oxide films by a soft-lithographic technique with the goal of constructing a photonic crystal (PC) structure on the back side of the oxide. The oxide films, fabricated by mixing sol-gel derived niobium oxide nanoparticles and hydroxypropyl cellulose, were employed as photoelectrodes in dye-sensitized solar cells (DSSCs), and their performance evaluated against their flat counterparts. The surface patterns were imprinted using a photocurable perfluoropolyether (PFPE) soft-replica of a silicon master with a two-dimensional array of cylindrical posts (200 nm (D) × 200 nm (H)) in hexagonal geometry. The PC on the niobium oxide surface caused large changes in optical measurements, particularly in the blue wavelengths. To evaluate the optical effect on solar energy conversion, the incident photon-to-current conversion efficiency (IPCE) was measured in the patterned devices and the control group. The IPCE of patterned niobium oxide anodes exhibited a relative enhancement in photocurrent generation over the wavelength range corresponding to the higher absorption in optical measurements.

Increasing photocurrents in dye sensitized solar cells with tantalum-doped titanium oxide photoanodes obtained by laser ablation.

Laser ablation is employed to produce vertically aligned nanostructured films of undoped and tantalum-doped TiO(2) nanoparticles. Dye-sensitized solar cells using the two different materials are compared. Tantalum-doped TiO(2) photoanode show 65% increase in photocurrents and around 39% improvement in overall cell efficiency compared to undoped TiO(2). Electrochemical impedance spectroscopy, Mott-Schottky analysis and open circuit voltage decay is used to investigate the cause of this improved performance. The enhanced performance is attributed to a combination of increased electron concentration in the semiconductor and a reduced electron recombination rate.

Nanoforest Nb2O5 photoanodes for dye-sensitized solar cells by pulsed laser deposition.

Vertically aligned bundles of Nb(2)O(5) nanocrystals were fabricated by pulsed laser deposition (PLD) and tested as a photoanode material in dye-sensitized solar cells (DSSC). They were characterized using scanning and transmission electron microscopies, optical absorption spectroscopy (UV-vis), and incident-photon-to-current efficiency (IPCE) experiments. The background gas composition and the thickness of the films were varied to determine the influence of those parameters in the photoanode behavior. An optimal background pressure of oxygen during deposition was found to produce a photoanode structure that both achieves high dye loading and enhanced photoelectrochemical performance. For optimal structures, IPCE values up to 40% and APCE values around 90% were obtained with the N(3) dye and I(3)(-)/I(-) couple in acetonitrile with open circuit voltage of 0.71 V and 2.41% power conversion efficiency.