High-Performance WSe2 Top-Gate Devices with Strong Spacer Doping.

Because of the lack of contact and spacer doping techniques for two-dimensional (2D) transistors, most high-performance 2D devices have been produced with nontypical structures that contain electrical gating in the contact regions. In the present study, we used chloroauric acid (HAuCl4) as a strong p-dopant for WSe2 monolayers used in transistors. The HAuCl4-doped devices exhibited a record-low contact resistance of 0.7 kΩ·µm under a doping concentration of 1.76 × 1013 cm-2. In addition, an extrinsic carrier diffusion phenomenon was discovered in the HAuCl4-WSe2 system. With a suitably designed spacer length for doping, a normally off, high-performance underlap top-gate device can be produced without the application of additional gating in the contact and spacer regions.

Electrically Driven Hyperbolic Nanophotonic Resonators as High Speed, Spectrally Selective Thermal Radiators.

We introduce and experimentally demonstrate electrically driven, spectrally selective thermal emitters based on globally aligned carbon nanotube metamaterials. The self-assembled metamaterial supports a high degree of nanotube ordering, enabling nanoscale ribbons patterned in the metamaterial to function both as Joule-heated incandescent filaments and as infrared hyperbolic resonators imparting spectral selectivity to the thermal radiation. Devices batch-fabricated on a single chip emit polarized thermal radiation with peak wavelengths dictated by their hyperbolic resonances, and their nanoscale heated dimensions yield modulation rates as high as 1 MHz. As a proof of concept, we show that two sets of thermal emitters on the same chip, operating with different peak wavelengths and modulation rates, can be used to sense carbon dioxide with one detector. We anticipate that the combination of batch fabrication, modulation bandwidth, and spectral tuning with chip-based nanotube thermal emitters will enable new modalities in multiplexed infrared sources.

Intrinsically ultrastrong plasmon-exciton interactions in crystallized films of carbon nanotubes.

In cavity quantum electrodynamics, optical emitters that are strongly coupled to cavities give rise to polaritons with characteristics of both the emitters and the cavity excitations. We show that carbon nanotubes can be crystallized into chip-scale, two-dimensionally ordered films and that this material enables intrinsically ultrastrong emitter-cavity interactions: Rather than interacting with external cavities, nanotube excitons couple to the near-infrared plasmon resonances of the nanotubes themselves. Our polycrystalline nanotube films have a hexagonal crystal structure, ∼25-nm domains, and a 1.74-nm lattice constant. With this extremely high nanotube density and nearly ideal plasmon-exciton spatial overlap, plasmon-exciton coupling strengths reach 0.5 eV, which is 75% of the bare exciton energy and a near record for room-temperature ultrastrong coupling. Crystallized nanotube films represent a milestone in nanomaterials assembly and provide a compelling foundation for high-ampacity conductors, low-power optical switches, and tunable optical antennas.

Tunable Hyperbolic Metamaterials Based on Self-Assembled Carbon Nanotubes.

We show that packed, horizontally aligned films of single-walled carbon nanotubes are hyperbolic metamaterials with ultrasubwavelength unit cells and dynamic tunability. Using Mueller matrix ellipsometry, we characterize the films' optical properties, which are doping level dependent, and find a broadband hyperbolic region tunable in the mid-infrared. To characterize the dispersion of in-plane hyperbolic plasmon modes, we etch the nanotube films into nanoribbons with differing widths and orientations relative to the nanotube axis, and we observe that the hyperbolic modes support strong light localization. An agreement between the experiments and theoretical models using the ellipsometry data indicates that the packed carbon nanotubes support bulk anisotropic responses at the nanoscale. Self-assembled films of carbon nanotubes are well-suited for applications in thermal emission and photodetection, and they serve as model systems for studying light-matter interactions in the deep subwavelength regime.

Strong and Broadly Tunable Plasmon Resonances in Thick Films of Aligned Carbon Nanotubes.

Low-dimensional plasmonic materials can function as high quality terahertz and infrared antennas at deep subwavelength scales. Despite these antennas' strong coupling to electromagnetic fields, there is a pressing need to further strengthen their absorption. We address this problem by fabricating thick films of aligned, uniformly sized semiconducting carbon nanotubes and showing that their plasmon resonances are strong, narrow, and broadly tunable. With thicknesses ranging from 25 to 250 nm, our films exhibit peak attenuation reaching 70%, ensemble quality factors reaching 9, and electrostatically tunable peak frequencies by a factor of 2.3. Excellent nanotube alignment leads to the attenuation being 99% linearly polarized along the nanotube axis. Increasing the film thickness blueshifts the plasmon resonators down to peak wavelengths as low as 1.4 µm, a new near-infrared regime in which they can both overlap the S11 nanotube exciton energy and access the technologically important infrared telecom band.

Transport/magnetotransport of high-performance graphene transistors on organic molecule-functionalized substrates.

In this article, we present the transport and magnetotransport of high-quality graphene transistors on conventional SiO(2)/Si substrates by modification with organic molecule octadecyltrichlorosilane (OTS) self-assembled monolayers (SAMs). Graphene devices on OTS SAM-functionalized substrates with high carrier mobility, low intrinsic doping, suppressed carrier scattering, and reduced thermal activation of resistivity at room temperature were observed. Most interestingly, the remarkable magnetotransport of graphene devices with pronounced quantum Hall effect, strong Shubnikov-de Haas oscillations, a nonzero Berry's phase, and a short carrier scattering time also confirms the high quality of graphene on this ultrasmooth organic SAM-modified platform. The high-performance graphene transistors on the solution-processable OTS SAM-functionalized SiO(2)/Si substrates are promising for the future development of large-area and low-cost fabrications of graphene-based nanoelectronics.

Hysteresis-Free Contact Doping for High-Performance Two-Dimensional Electronics.

Contact doping is considered crucial for reducing the contact resistance of two-dimensional (2D) transistors. However, a process for achieving robust contact doping for 2D electronics is lacking. Here, we developed a two-step doping method for effectively doping 2D materials through a defect-repairing process. The method achieves strong and hysteresis-free doping and is suitable for use with the most widely used transition-metal dichalcogenides. Through our method, we achieved a record-high sheet conductance (0.16 mS·sq-1 without gating) of monolayer MoS2 and a high mobility and carrier concentration (4.1 × 1013 cm-2). We employed our robust method for the successful contact doping of a monolayer MoS2 Au-contact device, obtaining a contact resistance as low as 1.2 kΩ·µm. Our method represents an effective means of fabricating high-performance 2D transistors.

High-Performance Two-Dimensional Electronics with a Noncontact Remote Doping Method.

Because of the intrinsic low carrier density of monolayer two-dimensional (2D) materials, doping is crucial for the performance of underlap top-gated 2D devices. However, wet etching of a high-k (dielectric constant) dielectric layer is difficult to implement without causing performance deterioration on the devices; therefore, finding a suitable spacer doping technique for 2D devices is indispensable. In this study, we developed a remote doping (RD) method in which defective SiOx can remotely dope the underlying high-k capped 2D regions without directly contacting these materials. This method achieved a doping density as high as 1.4 × 1013 cm-2 without reducing the mobility of the doped materials; after 1 month, the doping concentration remained as high as 1.2 × 1013 cm-2. Defective SiOx can be used to dope most popular 2D transition-metal dichalcogenides. The low-k properties of SiOx render it ideal for spacer doping, which is very attractive from the perspective of circuit operation. In our experiments, MoS2 and WS2 underlap top-gate devices exhibited 10× and 200× increases in their on-currents, respectively, after being doped with SiOx. These results indicate that SiOx doping can be conducted to manufacture high-performance 2D devices.

Ambiphilicity of a mononuclear cobalt(III) superoxo complex.

Addition of HOTf to a mixture of CoIII(BDPP)(O2˙) (1, H2BDPP = 2,6-bis((2-(S)-diphenylhydroxylmethyl-1-pyrrolidinyl)methyl)pyridine) and Cp*2Fe produced H2O2 in high yield implying formation of CoIII(BDPP)(OOH) (3), and reaction of Sc(OTf)3 with the same mixture gave a peroxo-bridged CoIII/ScIII5. These findings demonstrate the ambiphilic property of CoIII-superoxo 1.

Fast growth of large-grain and continuous MoS2 films through a self-capping vapor-liquid-solid method.

Most chemical vapor deposition methods for transition metal dichalcogenides use an extremely small amount of precursor to render large single-crystal flakes, which usually causes low coverage of the materials on the substrate. In this study, a self-capping vapor-liquid-solid reaction is proposed to fabricate large-grain, continuous MoS2 films. An intermediate liquid phase-Na2Mo2O7 is formed through a eutectic reaction of MoO3 and NaF, followed by being sulfurized into MoS2. The as-formed MoS2 seeds function as a capping layer that reduces the nucleation density and promotes lateral growth. By tuning the driving force of the reaction, large mono/bilayer (1.1 mm/200 µm) flakes or full-coverage films (with a record-high average grain size of 450 µm) can be grown on centimeter-scale substrates. The field-effect transistors fabricated from the full-coverage films show high mobility (33 and 49 cm2 V-1 s-1 for the mono and bilayer regions) and on/off ratio (1 ~ 5 × 108) across a 1.5 cm × 1.5 cm region.

High-Mobility InSe Transistors: The Nature of Charge Transport.

InSe is a high-mobility layered semiconductor with mobility being highly sensitive to any surrounding media that could act as a source of extrinsic scattering. However, little effort has been made to understand electronic transport in thin InSe layers with native surface oxide formed spontaneously upon exposure to an ambient environment. Here, we explore the influence of InOx/InSe interfacial trap states on electronic transport in thin InSe layers. We show that wet oxidation (processed in an ambient environment) causes massive deep-lying band-tail states, through which electrons conduct via 2D variable-range hopping with a short localization length of 1-3 nm. In contrast, a high-quality InOx/InSe interface can be formed in dry oxidation (processed in pure oxygen), with a low trap density of 1012 eV-1 cm-2. Metal-insulator transition can be thus observed in the gate sweep of the field-effect transistors (FETs), indicative of band transport predominated by extended states above the mobility edge. A room-temperature band mobility of 103 cm2/V s is obtained. The profound difference in the transport behavior between the wet and dry InSe FETs suggests that fluctuating Coulomb potential arising from trapped charges at the InOx/InSe interface is the dominant source of disorders in thin InSe channels.

Spatially and Precisely Controlled Large-Scale and Persistent Optical Gating in a TiO x-MoS2 Heterostructure.

Optical gating derived from persistent photodoping is a promising technique that can control the transport behavior of two-dimensional (2D) materials through light modulation. The advantage of photoinduced doping is that the doping can be controlled precisely and spatially by tuning the light intensity and position. As most photoinduced doping methods suffer from a low doping level, persistent, strong photodoping was conducted in this study in TiO x-MoS2 heterostructures under ultraviolet (UV) illumination, which precisely controlled the doping to a high level (1.5 × 1013 cm-2) with a trap-mediated mechanism. This mechanism was confirmed by controlling the doping level with various UV pretreatment doses. After photodoping, devices displayed superior mobility, which is a characteristic of the modulation doping used in high-electron-mobility transistors. The modulation doping sites in the inner TiO x layer were far from the channel surface (MoS2); thus, the channel was able to preserve its high-mobility property even after doping. This dose-dependent, strong, and persistent photodoping phenomenon can render the TiO x-MoS2 heterostructure suitable for use in UV detectors and in nonvolatile light-driven memory products. Moreover, by using spatially controlled light scans, selective photodoping at the contact edges can dramatically reduce the contact resistance without destroying the on-off ratio of the device by forming an n+-n-n+ channel. Because TiO x-MoS2 heterostructures are versatile, they provide a compelling platform for high-performance 2D optoelectronic devices.

High-Mobility InSe Transistors: The Role of Surface Oxides.

In search of high-performance field-effect transistors (FETs) made of atomic thin semiconductors, indium selenide (InSe) has held great promise because of its high intrinsic mobility and moderate electronic band gap (1.26 eV). Yet the performance of InSe FETs is decisively determined by the surface oxidation of InSe taking place spontaneously in ambient conditions, setting up a mobility ceiling and causing an uncontrollable current hysteresis. Encapsulation by hexagonal boron nitride (h-BN) has been currently used to cope with this deterioration. Here, we provide insights into the role of surface oxides played in device performance and introduce a dry-oxidation process that forms a dense capping layer on top, where InSe FETs exhibit a record-high two-probe mobility of 423 cm2/V·s at room temperature and 1006 cm2/V·s at liquid nitrogen temperature without the use of h-BN encapsulation or high-κ dielectric screening. Ultrahigh on/off current ratio of >108 and current density of 365 µA/µm can be readily achieved without elaborate engineering of drain/source contacts or gating technique. Thickness-dependent device properties are also studied, with optimized performance shown in FETs comprising of 13 nm thick InSe. The high performance of InSe FETs with ultrathin dry oxide is attributed to the effective unpinning of the Fermi level at the metal contacts, resulting in a low Schottky barrier height of 40 meV in an optimized channel thickness.

Environment-insensitive and gate-controllable photocurrent enabled by bandgap engineering of MoS2 junctions.

Two-dimensional (2D) materials are composed of atomically thin crystals with an enormous surface-to-volume ratio, and their physical properties can be easily subjected to the change of the chemical environment. Encapsulation with other layered materials, such as hexagonal boron nitride, is a common practice; however, this approach often requires inextricable fabrication processes. Alternatively, it is intriguing to explore methods to control transport properties in the circumstance of no encapsulated layer. This is very challenging because of the ubiquitous presence of adsorbents, which can lead to charged-impurity scattering sites, charge traps, and recombination centers. Here, we show that the short-circuit photocurrent originated from the built-in electric field at the MoS2 junction is surprisingly insensitive to the gaseous environment over the range from a vacuum of 1 × 10-6 Torr to ambient condition. The environmental insensitivity of the short-circuit photocurrent is attributed to the characteristic of the diffusion current that is associated with the gradient of carrier density. Conversely, the photocurrent with bias exhibits typical persistent photoconductivity and greatly depends on the gaseous environment. The observation of environment-insensitive short-circuit photocurrent demonstrates an alternative method to design device structure for 2D-material-based optoelectronic applications.

Wavelength-selective dual p- and n-type carrier transport of an organic/graphene/inorganic heterostructure.

A novel organic/graphene/inorganic -heterostructure, consisting of a graphene layer encapsulated by n- and p-type photoactive materials with complementary absorptions, enables the control of dual n- and p-typed transport behaviors of a graphene transistor under selective UV or visible light illumination. A graphene-based p-n junction created by spatially patterned wavelength-selective illumination using the organic/graphene/inorganic heterostructure is also demonstrated.

Extrinsic Origin of Persistent Photoconductivity in Monolayer MoS2 Field Effect Transistors.

Recent discoveries of the photoresponse of molybdenum disulfide (MoS2) have shown the considerable potential of these two-dimensional transition metal dichalcogenides for optoelectronic applications. Among the various types of photoresponses of MoS2, persistent photoconductivity (PPC) at different levels has been reported. However, a detailed study of the PPC effect and its mechanism in MoS2 is still not available, despite the importance of this effect on the photoresponse of the material. Here, we present a systematic study of the PPC effect in monolayer MoS2 and conclude that the effect can be attributed to random localized potential fluctuations in the devices. Notably, the potential fluctuations originate from extrinsic sources based on the substrate effect of the PPC. Moreover, we point out a correlation between the PPC effect in MoS2 and the percolation transport behavior of MoS2. We demonstrate a unique and efficient means of controlling the PPC effect in monolayer MoS2, which may offer novel functionalities for MoS2-based optoelectronic applications in the future.

Self-crack-filled graphene films by metallic nanoparticles for high-performance graphene heterojunction solar cells.

Graphene, with cracks filled with gold nanoparticles, is grown by chemical vapor deposition on a Cu substrate. The crack-filled graphene not only exhibits superior electrical properties but also forms a better junction with other semiconductors. A high-quality crack-filled graphene/Si Schottky junction solar cell is achieved, demonstrating the highest fill factor (0.79) and best efficiency (12.3%).

Precisely Controlled Ultrastrong Photoinduced Doping at Graphene-Heterostructures Assisted by Trap-State-Mediated Charge Transfer.

Ultrastrong and precisely controllable n-type photoinduced doping at a graphene/TiOx heterostructure as a result of trap-state-mediated charge transfer is demonstrated, which is much higher than any other reported photodoping techniques. Based on the strong light-matter interactions at the graphene/TiOx heterostructure, precisely controlled photoinduced bandgap opening of a bilayer graphene device is demonstrated.

Clean-lifting transfer of large-area residual-free graphene films.

A unique "clean-lifting transfer" (CLT) technique that applies a controllable electrostatic force to transfer large-area and high-quality CVD-grown graphene onto various rigid or flexible substrates is reported. The CLT technique without using any organic support or adhesives can produce residual-free graphene films with large-area processability, and has great potential for future industrial production of graphene-based electronics or optoelectronics.

Self-encapsulated doping of n-type graphene transistors with extended air stability.

This paper presents an innovative approach to fabricating controllable n-type doping graphene transistors with extended air stability by using self-encapsulated doping layers of titanium suboxide (TiOx) thin films, which are an amorphous phase of crystalline TiO(2) and can be solution processed. The nonstoichiometry TiOx thin films consisting of a large number of oxygen vacancies exhibit several unique functions simultaneously in the n-type doping of graphene as an efficient electron-donating agent, an effective dielectric screening medium, and also an encapsulated layer. A novel device structure consisting of both top and bottom coverage of TiOx thin layers on a graphene transistor exhibited strong n-type transport characteristics with its Dirac point shifted up to -80 V and an enhanced electron mobility with doping. Most interestingly, an extended stability of the device without rapid degradation after doping was observed when it was exposed to ambient air for several days, which is not usually observed in other n-type doping methods in graphene. Density functional theory calculations were also employed to explain the observed unique n-type doping characteristics of graphene using TiOx thin films. The technique of using an "active" encapsulated layer with controllable and substantial electron doping on graphene provides a new route to modulate electronic transport behavior of graphene and has considerable potential for the future development of air-stable and large-area graphene-based nanoelectronics.