Charged Exciton Generation by Curvature-Induced Band Gap Fluctuations in Structurally Disordered Two-Dimensional Semiconductors.

Curvature is a general factor for various two-dimensional (2D) materials due to their flexibility, which is not yet fully unveiled to control their physical properties. In particular, the effect of structural disorder with random curvature formation on excitons in 2D semiconductors is not fully understood. Here, the correlation between structural disorder and exciton formation in monolayer MoS2 on SiO2 was investigated by using photoluminescence (PL) and Raman spectroscopy. We found that the curvature-induced charge localization along with band gap fluctuations aid the formation of the localized charged excitons (such as trions). In the substrate-supported region, the trion population is enhanced by a localized charge due to the microscopic random bending strain, while the trion is suppressed in the suspended region which exhibits negligible bending strain, anomalously even though the dielectric screening effect is lower than that of the supported region. The redistribution of each exciton by the bending strain leads to a huge variation (∼100-fold) in PL intensity between the supported and suspended regions, which cannot be fully comprehended by external potential disorders such as a random distribution of charged impurities. The peak position of PL in MoS2/SiO2 is inversely proportional to the Raman peak position of E12g, indicating that the bending strain is correlated with PL. The supported regions exhibit an indirect portion that was not shown in the suspended regions or atomically flat substrates. The understanding of the structural disorder effect on excitons provides a fundamental path for optoelectronics and strain engineering of 2D semiconductors.

Anomalous Conductance near Percolative Metal-Insulator Transition in Monolayer MoS2 at Low Voltage Regime.

Conductivity of the insulating phase increases generally at an elevated drain-source voltage due to the field-enhanced hopping or heating effect. Meanwhile, a transport mechanism governed by percolation in a low compensated semiconductor gives rise to the reduced conductivity at a low-field regime. Here, in addition to this behavior, we report the anomalous conductivity behavior to transform from a percolative metallic to an insulating phase at the low voltage regime in monolayer molybdenum disulfide (MoS2). Percolation transport at low source-drain voltage is governed by inhomogeneously distributed potential in strongly interacting monolayer MoS2 with a substrate, distinct from the quantum phase transition in multilayer MoS2. At a high source-drain voltage regime, the insulating phase is transformed further to a metallic phase, exhibiting multiphases of metallic-insulating-metallic transitions in monolayer MoS2. These behaviors highlight MoS2 as a model system to study various classical and quantum transports as well as metal-insulator transition in two-dimensional systems.

Correction: Thickness-dependent in-plane thermal conductivity of suspended MoS2 grown by chemical vapor deposition.

Correction for 'Thickness-dependent in-plane thermal conductivity of suspended MoS2 grown by chemical vapor deposition' by Jung Jun Bae et al., Nanoscale, 2017, 9, 2541-2547.

Electrothermal Local Annealing via Graphite Joule Heating on Two-Dimensional Layered Transistors.

A simple but powerful device platform for electrothermal local annealing (ELA) via graphite Joule heating on the surface of transition-metal dichalcogenide, is suggested here to sustainably restore intrinsic electrical properties of atomically thin layered materials. Such two-dimensional materials are easily deteriorated by undesirable surface/interface adsorbates and are screened by a high metal-to-semiconductor contact resistance. The proposed ELA allows one to expect a better electrical performance such as an excess electron doping, an enhanced carrier mobility, and a reduced surface traps in a monolayer molybdenum disulfide (MoS2)/graphite heterostructure. The thermal distribution of local heating measured by an infrared thermal microscope and estimated by a finite element calculation shows that the annealing temperature reaches up to >400 K at ambient condition and the high efficiency of site-specific annealing is demonstrated unlike the case of conventional global thermal annealing. This ELA platform can be further promoted as a practical gas sensor application. From an O2 cycling test and a low-frequency noise spectroscopy, the graphite on top of the MoS2 continuously recovers its initial condition from surface adsorbates. This ELA technique significantly improves the stability and reliability of its gas sensing capability, which can be expanded in various nanoscale device applications.

Soft Coulomb gap and asymmetric scaling towards metal-insulator quantum criticality in multilayer MoS2.

Quantum localization-delocalization of carriers are well described by either carrier-carrier interaction or disorder. When both effects come into play, however, a comprehensive understanding is not well established mainly due to complexity and sparse experimental data. Recently developed two-dimensional layered materials are ideal in describing such mesoscopic critical phenomena as they have both strong interactions and disorder. The transport in the insulating phase is well described by the soft Coulomb gap picture, which demonstrates the contribution of both interactions and disorder. Using this picture, we demonstrate the critical power law behavior of the localization length, supporting quantum criticality. We observe asymmetric critical exponents around the metal-insulator transition through temperature scaling analysis, which originates from poor screening in insulating regime and conversely strong screening in metallic regime due to free carriers. The effect of asymmetric scaling behavior is weakened in monolayer MoS2 due to a dominating disorder.

Junction-Structure-Dependent Schottky Barrier Inhomogeneity and Device Ideality of Monolayer MoS2 Field-Effect Transistors.

Although monolayer transition metal dichalcogenides (TMDs) exhibit superior optical and electrical characteristics, their use in digital switching devices is limited by incomplete understanding of the metal contact. Comparative studies of Au top and edge contacts with monolayer MoS2 reveal a temperature-dependent ideality factor and Schottky barrier height (SBH). The latter originates from inhomogeneities in MoS2 caused by defects, charge puddles, and grain boundaries, which cause local variation in the work function at Au-MoS2 junctions and thus different activation temperatures for thermionic emission. However, the effect of inhomogeneities due to impurities on the SBH varies with the junction structure. The weak Au-MoS2 interaction in the top contact, which yields a higher SBH and ideality factor, is more affected by inhomogeneities than the strong interaction in the edge contact. Observed differences in the SBH and ideality factor in different junction structures clarify how the SBH and inhomogeneities can be controlled in devices containing TMD materials.

Thickness-dependent in-plane thermal conductivity of suspended MoS2 grown by chemical vapor deposition.

The in-plane thermal conductivities of suspended monolayer, bilayer, and multilayer MoS2 films were measured in vacuum by using non-invasive Raman spectroscopy. The samples were prepared by chemical vapor deposition (CVD) and transferred onto preformed cavities on a Au-coated SiO2/Si substrate. The measured thermal conductivity (13.3 ± 1.4 W m-1 K-1) of the suspended monolayer MoS2 was below the previously reported value of 34.5 ± 4 W m-1 K-1. We demonstrate that this discrepancy arises from the experimental conditions that differ from vacuum conditions and small absorbance. The measured in-plane thermal conductivity of the suspended MoS2 films increased in proportion to the number of layers, reaching 43.4 ± 9.1 W m-1 K-1 for the multilayer MoS2, which explicitly follows the Fuchs-Sondheimer suppression function. The increase in the thermal conductivity with the number of MoS2 layers is explained by the reduced phonon boundary scattering. We also observe that the Fuchs-Sondheimer model works for the thickness-dependent thermal conductivity of MoS2 down to 10 nm in thickness at room temperature, yielding a phonon mean free path of 17 nm for bulk.

Indirect Bandgap Puddles in Monolayer MoS2 by Substrate-Induced Local Strain.

An unusually large bandgap modulation of 1.23-2.65 eV in monolayer MoS2 on a SiO2 /Si substrate is found due to the inherent local bending strain induced by the surface roughness of the substrate, reaching the direct-to-indirect bandgap transition. Approximately 80% of the surface area reveals an indirect bandgap, which is confirmed further by the degraded photoluminescence compared to that from suspended MoS2 .

Electrical Transport Properties of Polymorphic MoS2.

The engineering of polymorphs in two-dimensional layered materials has recently attracted significant interest. Although the semiconducting (2H) and metallic (1T) phases are known to be stable in thin-film MoTe2, semiconducting 2H-MoS2 is locally converted into metallic 1T-MoS2 through chemical lithiation. In this paper, we describe the observation of the 2H, 1T, and 1T' phases coexisting in Li-treated MoS2, which result in unusual transport phenomena. Although multiphase MoS2 shows no transistor-gating response, the channel resistance decreases in proportion to the temperature, similar to the behavior of a typical semiconductor. Transmission electron microscopy images clearly show that the 1T and 1T' phases are randomly distributed and intervened with 2H-MoS2, which is referred to as the 1T and 1T' puddling phenomenon. The resistance curve fits well with 2D-variable range-hopping transport behavior, where electrons hop over 1T domains that are bounded by semiconducting 2H phases. However, near 30 K, electrons hop over charge puddles. The large temperature coefficient of resistance (TCR) of multiphase MoS2, -2.0 × 10(-2) K(-1) at 300 K, allows for efficient IR detection at room temperature by means of the photothermal effect.

Photochemical Reaction in Monolayer MoS2 via Correlated Photoluminescence, Raman Spectroscopy, and Atomic Force Microscopy.

Photoluminescence (PL) from monolayer MoS2 has been modulated using plasma treatment or thermal annealing. However, a systematic way of understanding the underlying PL modulation mechanism has not yet been achieved. By introducing PL and Raman spectroscopy, we analyze that the PL modulation by laser irradiation is associated with structural damage and associated oxygen adsorption on the sample in ambient conditions. Three distinct behaviors were observed according to the laser irradiation time: (i) slow photo-oxidation at the initial stage, where the physisorption of ambient gases gradually increases the PL intensity; (ii) fast photo-oxidation at a later stage, where chemisorption increases the PL intensity abruptly; and (iii) photoquenching, with complete reduction of PL intensity. The correlated confocal Raman spectroscopy confirms that no structural deformation is involved in slow photo-oxidation stage; however, the structural disorder is invoked during the fast photo-oxidation stage, and severe structural degradation is generated during the photoquenching stage. The effect of oxidation is further verified by repeating experiments in vacuum, where the PL intensity is simply degraded with laser irradiation in a vacuum due to a simple structural degradation without involving oxygen functional groups. The charge scattering by oxidation is further explained by the emergence/disappearance of neutral excitons and multiexcitons during each stage.

Sensitive photo-thermal response of graphene oxide for mid-infrared detection.

This study characterizes the effects of incident infrared (IR) radiation on the electrical conductivity of graphene oxide (GO) and examines its potential for mid-IR detection. Analysis of the mildly reduced GO (m-GO) transport mechanism near room temperature reveals variable range hopping (VRH) for the conduction of electrons. This VRH behavior causes the m-GO resistance to exhibit a strong temperature dependence, with a large negative temperature coefficient of resistance of approximately -2 to -4% K(-1). In addition to this hopping transport, the presence of various oxygen-related functional groups within GO enhances the absorption of IR radiation significantly. These two GO material properties are synergically coupled and provoke a remarkable photothermal effect within this material; specifically, a large resistance drop is exhibited by m-GO in response to the increase in temperature caused by the IR absorption. The m-GO bolometer effect identified in this study is different from that exhibited in vanadium oxides, which require added gold-black films that function as IR absorbers owing to their limited IR absorption capability.

Hollow carbon nanospheres/silicon/alumina core-shell film as an anode for lithium-ion batteries.

Hollow carbon nanospheres/silicon/alumina (CNS/Si/Al2O3) core-shell films obtained by the deposition of Si and Al2O3 on hollow CNS interconnected films are used as the anode materials for lithium-ion batteries. The hollow CNS film acts as a three dimensional conductive substrate and provides void space for silicon volume expansion during electrochemical cycling. The Al2O3 thin layer is beneficial to the reduction of solid-electrolyte interphase (SEI) formation. Moreover, as-designed structure holds the robust surface-to-surface contact between Si and CNSs, which facilitates the fast electron transport. As a consequence, the electrode exhibits high specific capacity and remarkable capacity retention simultaneously: 1560 mA h g(-1) after 100 cycles at a current density of 1 A g(-1) with the capacity retention of 85% and an average decay rate of 0.16% per cycle. The superior battery properties are further confirmed by cyclic voltammetry (CV) and impedance measurement.

Transition from direct to Fowler-Nordheim tunneling in chemically reduced graphene oxide film.

We investigate charge transport in a chemically reduced graphene oxide (RGO) film of sub-micron thickness. The I-V curve of RGO film shows current switching of the order of ∼10(5) above the threshold voltage. We found that the observed I-V curve is consistent with quantum tunnelling based charge transport. The quantum tunnelling based Simmons generalized theory was used to interpret the charge transport mechanism which shows that the current switching phenomenon is associated with transition from direct to Fowler-Nordheim (F-N) tunneling. The absence of current switching in the I-V curve after stripping away the oxygen functional groups from chemically RGO film confirms that the presence of these groups and reduced interaction between adjacent layers of RGO play a key role in charge transport. Such metal-based current switching devices may find applications in graphene-based electronic devices such as high voltage resistive switching devices.

TLM-PSD model for optimization of energy and power density of vertically aligned carbon nanotube supercapacitor.

Electrochemical capacitors with fast charging-discharging rates are very promising for hybrid electric vehicle industries including portable electronics. Complicated pore structures have been implemented in active materials to increase energy storage capacity, which often leads to degrade dynamic response of ions. In order to understand this trade-off phenomenon, we report a theoretical model based on transmission line model which is further combined with pore size distribution function. The model successfully explained how pores length, and pore radius of active materials and electrolyte conductivity can affect capacitance and dynamic performance of different capacitors. The powerfulness of the model was confirmed by comparing with experimental results of a micro-supercapacitor consisted of vertically aligned multiwalled carbon nanotubes (v-MWCNTs), which revealed a linear current increase up to 600 Vs(-1) scan rate demonstrating an ultrafast dynamic behavior, superior to randomly entangled singlewalled carbon nanotube device, which is clearly explained by the theoretical model.

Transferred wrinkled Al2O3 for highly stretchable and transparent graphene-carbon nanotube transistors.

Despite recent progress in producing transparent and bendable thin-film transistors using graphene and carbon nanotubes, the development of stretchable devices remains limited either by fragile inorganic oxides or polymer dielectrics with high leakage current. Here we report the fabrication of highly stretchable and transparent field-effect transistors combining graphene/single-walled carbon nanotube (SWCNT) electrodes and a SWCNT-network channel with a geometrically wrinkled inorganic dielectric layer. The wrinkled Al2O3 layer contained effective built-in air gaps with a small gate leakage current of 10(-13) A. The resulting devices exhibited an excellent on/off ratio of ~10(5), a high mobility of ~40 cm(2) V(-1) s(-1) and a low operating voltage of less than 1 V. Importantly, because of the wrinkled dielectric layer, the transistors retained performance under strains as high as 20% without appreciable leakage current increases or physical degradation. No significant performance loss was observed after stretching and releasing the devices for over 1,000 times. The sustainability and performance advances demonstrated here are promising for the adoption of stretchable electronics in a wide variety of future applications.

Synthesis of multilayer graphene balls by carbon segregation from nickel nanoparticles.

Three-dimensional (3D) structured graphene is a material of great interest due to its diverse applications in electronics, catalytic electrodes, and sensors. However, the preparation of 3D structured graphene is still challenging. Here, we report the fabrication of multilayer graphene balls (GBs) by template-directed carbon segregation using nickel nanoparticles (Ni-NPs) as template materials. To maintain the ball shape of the template Ni-NPs, we used a carburization process using polyol solution as the carbon source and a thermal annealing process to synthesize graphene layers via carbon segregation on the outer surface of the Ni-NPs. The resulting GBs were hollow structures composed of multilayer graphene after the removal of core Ni-NPs, and the thickness of the graphene layers and the size of GBs were tunable by controlling the graphene synthesis conditions. X-ray diffraction analysis and in situ transmission electron microscope characterization revealed that carbon atoms diffused effectively into the Ni-NPs during the carburization step, and that the diffused carbon atoms in Ni-NPs segregated and successfully formed a graphene layer on the surface of the Ni-NPs during thermal annealing. We also performed further heat treatment at high temperature to improve the quality of the graphene layer, resulting in highly crystalline GBs. The unique hollow GBs synthesized here will be useful as excellent high-rate electrode materials for electrochemical lithium storage devices.

Influence of copper morphology in forming nucleation seeds for graphene growth.

We report that highly crystalline graphene can be obtained from well-controlled surface morphology of the copper substrate. Flat copper surface was prepared by using a chemical mechanical polishing method. At early growth stage, the density of graphene nucleation seeds from polished Cu film was much lower and the domain sizes of graphene flakes were larger than those from unpolished Cu film. At later growth stage, these domains were stitched together to form monolayer graphene, where the orientation of each domain crystal was unexpectedly not much different from each other. We also found that grain boundaries and intentionally formed scratched area play an important role for nucleation seeds. Although the best monolayer graphene was grown from polished Cu with a low sheet resistance of 260 Ω/sq, a small portion of multilayers were also formed near the impurity particles or locally protruded parts.

Graphene/carbon nanotube hybrid-based transparent 2D optical array.

Graphene/carbon nanotube (CNT) hybrid structures are fabricated for use as optical arrays. Vertically aligned CNTs are directly synthesized on a graphene/quartz substrate using plasma-enhanced chemical vapor deposition (PECVD). Graphene preserves the transparency and resistance during CNT growth. Highly aligned single-walled CNTs show a better performance for the diffraction intensity.

Reduction-controlled viologen in bisolvent as an environmentally stable n-type dopant for carbon nanotubes.

Various viologens have been used to control the doping of single-walled carbon nanotubes (SWCNTs) via direct redox reactions. A new method of extracting neutral viologen (V(0)) was introduced using a biphase of toluene and viologen-dissolved water. A reductant of sodium borohydride transferred positively charged viologen (V(2+)) into V(0), where the reduced V(0) was separated into toluene with high separation yield. This separated V(0) solution was dropped on carbon nanotube transistors to investigate the doping effect of CNTs. With a viologen concentration of 3 mM, all the p-type CNT transistors were converted to n-type with improved on/off ratios. This was achieved by donating electrons spontaneously to CNTs from neutral V(0), leaving energetically stable V(2+) on the nanotube surface again. The doped CNTs were stable in water due to the presence of hydrophobic V(0) at the outermost CNT transistors, which may act as a protecting layer to prevent further oxidation from water.

Fermi level engineering of single-walled carbon nanotubes by AuCl3 doping.

We investigated the modulation of optical properties of single-walled carbon nanotubes (SWCNTs) by AuCl 3 doping. The van Hove singularity transitions (E 11 (S), E 22 (S), E 11 (M)) in absorption spectroscopy disappeared gradually with an increasing doping concentration and a new peak appeared at a high doping concentration. The work function was downshifted up to 0.42 eV by a strong charge transfer from the SWCNTs to AuCl 3 by a high level of p-doping. We propose that this large work function shift forces the Fermi level of the SWCNTs to be located deep in the valence band, i.e., highly degenerate, creating empty van Hove singularity states, and hence the work function shift invokes a new asymmetric transition in the absorption spectroscopy from a deeper level to newly generated empty states.