Gate-tunable contact-induced Fermi-level shift in semimetal.

Low-dimensional semimetal­semiconductor (Sm-S) van der Waals (vdW) heterostructures have shown their potentials in nanoelectronics and nano-optoelectronics recently. It is an important scientific issue to study the interfacial charge transfer as well as the corresponding Fermi-level shift in Sm-S systems. Here we investigated the gate-tunable contact-induced Fermi-level shift (CIFS) behavior in a semimetal single-walled carbon nanotube (SWCNT) that formed a heterojunction with a transition-metal dichalcogenide (TMD) flake. A resistivity comparison methodology and a Fermi-level catch-up model have been developed to measure and analyze the CIFS, whose value is determined by the resistivity difference between the naked SWCNT segment and the segment in contact with the TMD. Moreover, the relative Fermi-level positions of SWCNT and two-dimensional (2D) semiconductors can be efficiently reflected by the gate-tunable resistivity difference. The work function change of the semimetal, as a result of CIFS, will naturally introduce a modified form of the Schottky­Mott rule, so that a modified Schottky barrier height can be obtained for the Sm-S junction. The methodology and physical model should be useful for low-dimensional reconfigurable nanodevices based on Sm-S building blocks.

Engineering van der Waals Contacts by Interlayer Dipoles.

Tuning the interfacial Schottky barrier with van der Waals (vdW) contacts is an important solution for two-dimensional (2D) electronics. Here we report that the interlayer dipoles of 2D vdW superlattices (vdWSLs) can be used to engineer vdW contacts to 2D semiconductors. A bipolar WSe2 with Ba6Ta11S28 (BTS) vdW contact was employed to exhibit this strategy. Strong interlayer dipoles can be formed due to charge transfer between the Ba3TaS5 and TaS2 layers. Mechanical exfoliation breaks the superlattice and produces two distinguished surfaces with TaS2 and Ba3TaS5 terminations. The surfaces thus have opposite surface dipoles and consequently different work functions. Therefore, all the devices fall into two categories in accordance with the rectifying direction, which were verified by electrical measurements and scanning photocurrent microscopy. The growing vdWSL family along with the addition surface dipoles enables prospective vdW contact designs and have practical application in nanoelectronics and nano optoelectronics.

Highly Efficient Visible-Blind Ultraviolet Photodetector Based on Scalably Produced Titanium Dioxide Nanowire Arrays.

Here, we report a novel, feasible, and cost-effective method for the preparation of one-dimensional TiO2 nanowire arrays using a super-aligned carbon nanotube film as a template. Pure-anatase-phase TiO2 nanowires were scalably prepared in a suspended manner, and a high-performance ultraviolet (UV) photodetector was realized on a flexible substrate. The large surface area and one-dimensional nanostructure of the TiO2 nanowire array led to a high detectivity (1.35 × 1016 Jones) and an ultrahigh photo gain (2.6 × 104), respectively. A high photoresponsivity of 7.7 × 103 A/W was achieved under 7 µW/cm2 UV (λ = 365 nm) illumination at a 10 V bias voltage, which is much higher than those of commercial UV photodetectors. Additionally, by taking advantage of its anisotropic geometry, we found the TiO2 nanowire array showed polarized photodetection. The concept of using nanomaterial systems shows the potential for realization of nanostructured photodetectors for practical applications.

Graphene Microheater Chips for In Situ TEM.

Low-dimensional materials are bringing significant innovations to in situ TEM characterization. Here a new graphene microheater chip for TEM was developed by stacking graphene on a suspended SiNx membrane as the Joule heating element. It could be heated up to 800 °C within 26.31 ms with a low power consumption of 0.025 mW/1000 µm2. The bulging was only ∼50 nm at 650 °C, which is 2 orders of magnitude smaller than those of conventional MEMS heaters at similar temperatures. The performances benefit from the employment of graphene, since its monolayer structure greatly reduces the heat capacity, and the vdW contact significantly reduces the interfacial interaction. The TEM observation on the Sn melting process verifies its great potential in resolving thermodynamic processes. Moreover, more multifunctional in situ chips could be developed by integrating other stimuli to such chips. This work opens a new frontier for both graphene and in situ characterization techniques.

Direct Monitoring of Li2 S2 Evolution and Its Influence on the Reversible Capacities of Lithium-Sulfur Batteries.

The polysulfide (PS) dissolution and low conductivity of lithium sulfides (Li2 S) are generally considered the main reasons for limiting the reversible capacity of the lithium-sulfur (Li-S) system. However, as the inevitable intermediate between PSs and Li2 S, lithium disulfide (Li2 S2 ) evolutions are always overlooked. Herein, Li2 S2 evolutions are monitored from the operando measurements on the pouch cell level. Results indicate that Li2 S2 undergoes slow electrochemical reduction and chemical disproportionation simultaneously during the discharging process, leading to further PS dissolution and Li2 S generation without capacity contribution. Compared with the fully oxidized Li2 S, Li2 S2 still residues at the end of the charging state. Therefore, instead of the considered Li2 S and PSs, slow electrochemical conversions and side chemical reactions of Li2 S2 are the determining factors in limiting the sulfur utilization, corresponding to the poor reversible capacity of Li-S batteries.

Lithium Storage Mechanism and Application of Micron-Sized Lattice-Reversible Binary Intermetallic Compounds as High-Performance Flexible Lithium-Ion Battery Anodes.

A strategy of lattice-reversible binary intermetallic compounds of metallic elements is proposed for applications in flexible lithium-ion battery (LIB) anode with high capacity and cycling stability. First, the use of metallic elements can ensure excellent electronic conductivity and high capacity of the active anode substance. Second, binary intermetallic compounds possess a larger initial lattice volume than metallic monomers, so that the problem of volume expansion can be alleviated. Finally, the design of binary intermetallic compounds with lattice reversibility further improves the cycle stability. In this work, the feasibility of this strategy is verified using an indium antimonide (InSb) system. The volumetric expansion and lithium storage mechanism of InSb are investigated by in situ Raman characterization and theoretical calculations. The active material utilization is significantly improved and the growth of In whiskers is inhibited in the micron-sized ball-milled and carbon coated InSb (bInSb@C) anode, which exhibits a reversible capacity of 733.8 mAh g-1 at 0.2 C, and provides a capacity of 411.5 mAh g-1 after 200 cycles at 3 C with an average Coulombic efficiency of 99.95%. This strategy is validated in pouch cells, illustrating the great potential of lattice-reversible binary intermetallic compounds for use as commercial flexible LIB anodes.

Electrical control of spatial resolution in mixed-dimensional heterostructured photodetectors.

Low-dimensional nanomaterials, such as one-dimensional (1D) nanomaterials and layered 2D materials, have exhibited significance for their respective unique electronic and optoelectronic properties. Here we show that a mixed-dimensional heterostructure with building blocks from multiple dimensions will present a synergistic effect on photodetection. A carbon nanotube (CNT)-[Formula: see text]-graphene photodetector is representative on this issue. Its spatial resolution can be electrically switched between high-resolution mode (HRM) and low-resolution mode (LRM) revealed by scanning photocurrent microscopy (SPCM). The reconfigurable spatial resolution can be attributed to the asymmetric geometry and the gate-tunable Fermi levels of these low-dimensional materials. Significantly, an interference fringe with 334 nm in period was successfully discriminated by the device working at HRM, confirming the efficient electrical control. Electrical control of spatial resolution in CNT-[Formula: see text]-graphene devices reveals the potential of the mixed-dimensional architectures in future nanoelectronics and nano-optoelectronics.

Reconfigurable Tunneling Transistors Heterostructured by an Individual Carbon Nanotube and MoS2.

Low-dimensional semiconductors have shown great potential in switches for their atomically thin geometries and unique properties. It is significant to achieve new tunneling transistors by the efficient stacking methodology with low-dimensional building blocks. Here, we report a one-dimensional (1D)-two-dimensional (2D) mixed-dimensional van der Waals (vdW) heterostructure, which was efficiently fabricated by stacking an individual semiconducting carbon nanotube (CNT) and 2D MoS2. The CNT-MoS2 heterostructure shows specific reconfigurable electrical transport behaviors and can be set as a nn junction, pn diode, and band-to-band tunneling (BTBT) transistor by gate voltage. The transport properties, especially BTBT, could be attributed to the electron transfer from MoS2 to CNT through the ideal vdW interface and the 1D nature of the CNT. The progress suggests a new solution for tunneling transistors by making 1D-2D heterostructures from the rich library of low-dimensional nanomaterials. Furthermore, the reconfigurable functions and nanoscaled junction show that it is prospective to apply CNT-MoS2 heterostructures in future nanoelectronics and nano-optoelectronics.

Toward an Intelligent Synthesis: Monitoring and Intervening in the Catalytic Growth of Carbon Nanotubes.

The bottom-up approach to directly synthesizing low-dimensional materials with outstanding performance has extended the material basis for the next generation integrated circuit industry. All the low-dimensional semiconductors, metals, dielectrics, and their heterojunctions are very promising bricks to build faster and more efficient chips because of their atomically smooth surface and interfaces. The greatest challenge in the synthesis of nanomaterials is how to precisely control the structure, crystalline orientation, defects, dimensions, etc. In past decades, both the methodology and the mechanism of synthesis have been systematically investigated to improve the controllability. However, few studies focused on sensing the synthesis processes in situ and responding to the synthesis immediately. Here, we propose the concept of intelligent synthesis in which the final product can be automatically fine-controlled by a closed loop including in situ monitoring and real-time interventions. As a model system, a high-temperature-tolerant circuit is fabricated on the single-walled carbon nanotube (SWCNT) growth substrate for sensing and responding to the synthesis processes. As a result, either highly pure semiconducting (s-) SWCNT arrays or metallic-semiconducting (m-s) junction arrays with different junction positions is simply synthesized by programming the responding signal. The intelligent synthesis shows much higher efficiency and controllability compared to conventional methods and will lead to the next leap in nanotechnology.

Macroscopic Carbon Nanotube Structures for Lithium Batteries.

Carbon nanotubes (CNTs) are regarded as one of the most promising materials to manufacture high-performance lithium batteries. This prospect is closely related to the construction of macroscopic architectures of CNTs. The superaligned CNT (SACNT) array is a unique kind of vertically aligned CNT array. Its highly oriented feature and strong intertube force facilitate the fabrication of macroscopic SACNT structures with various forms, including unidirectional films, buckypapers, and aerogels, etc. The as-produced SACNT macroscopic architectures are successfully introduced into lithium batteries due to their outstanding electrical and mechanical properties. Herein, an overview of the functions of macroscopic SACNTs in lithium batteries is proposed, including their applications in composite electrodes, current collectors, interlayers, and flexible full cells.

Continuous, Ultra-lightweight, and Multipurpose Super-aligned Carbon Nanotube Tapes Viable over a Wide Range of Temperatures.

In extreme environments, such as at ultrahigh or ultralow temperatures, the amount of tape used should be minimal so as to reduce system contamination and unwanted residues. However, tapes made from conventional materials typically lose their adhesiveness or leave residues difficult to remove under such conditions. Thus, the development of more versatile, lightweight, and easily removable tapes for applications in such extreme environments has received considerable attention. Here, we report that horizontally superaligned carbon nanotube (SACNT) tapes can be used to provide perfect van der Waals (vdW) interface contacts over a wide range of temperatures (from -196 to 1000 °C), yielding outstanding adhesiveness with specific adhesion strengths up to ∼1.1 N/µg. With a surface density of only 0.5-5 µg/cm2, hundreds of times lighter than the vertically aligned CNT adhesives, the SACNT tapes can be cost-effectively provided in hundreds of meters. They have multipurpose adhesive abilities for versatile materials and are also easily separated from samples even after exposure to extreme temperature regimes. First-principles calculations confirm the mechanism of vdW adhesion and reveal that ultraflat and nanometer-thick SACNT tapes may yield far greater adhesive abilities. These SACNT tapes show great potential for use in mechanical bonding, electrical bonding, and thermal dissipation in electronic devices.

Carbon Nanotube Film Gate in Vacuum Electronic Devices.

A superaligned carbon nanotube (SACNT) film can act as an ideal gate electrode in vacuum electronics due to its low secondary electron emission, high electron transparency, ultrasmall thickness, highly uniform electric field, high melting point, and high mechanical strength. We used a SACNT film as the gate electrode in a thermionic emission electron tube and field emission display prototype. The SACNT film gate in a thermionic emission electron tube shows a larger amplification factor. A triode tube with the SACNT film gate is used in an audio amplification circuit. The SACNT film gate electrode in field emission devices shows better field uniformity. The field emission display prototype is demonstrated to dynamically display Chinese characters.

Self-Expansion Construction of Ultralight Carbon Nanotube Aerogels with a 3D and Hierarchical Cellular Structure.

A novel and simple strategy is developed to construct ultralight and 3D pure carbon nanotube (CNT) aerogels by the spontaneous expansion of superaligned CNT films soaked in a piranha (mixed H2 SO4 and H2 O2 ) solution, followed by cryodesiccation. The macroscopic CNT aerogels have an extremely low apparent density (0.12 mg cm-3 ), ultrahigh porosity (99.95%), high specific surface area (298 m2 g-1 ), and a hierarchical cellular structure with giant and ultrathin CNT sheets as cell walls. The pure CNT aerogels show high adsorption abilities for various kinds of solvents, and have great potential in widespread applications such as energy storage, catalysis, and bioengineering.

Observation of Charge Generation and Transfer during CVD Growth of Carbon Nanotubes.

Carbon nanotube (CNT) is believed to be the most promising material for next generation IC industries with the prerequisite of chirality specific growth. For various approaches to controlling the chiral indices of CNTs, the key is to deepen the understanding of the catalytic growth mechanism in chemical vapor deposition (CVD). Here we show our discovery that the as-grown CNTs are all negatively charged after Fe-catalyzed CVD process. The extra electrons come from the charge generation and transfer during the growth of CNTs, which indicates that an electrochemical process happens in the surface reaction step. We then designed an in situ measurement equipment, verifying that the CVD growth of CNTs can be regarded as a primary battery system. Furthermore, we found that the variation of the Fermi level in Fe catalysts have a significant impact on the chirality of CNTs when different external electric fields are applied. These findings not only provide a new perspective on the growth of CNTs but also open up new possibilities for controlling the growth of CNTs by electrochemical methods.

Cross-stacked carbon nanotube film as an additional built-in current collector and adsorption layer for high-performance lithium sulfur batteries.

Cross-stacked carbon nanotube (CNT) film is proposed as an additional built-in current collector and adsorption layer in sulfur cathodes for advanced lithium sulfur (Li-S) batteries. On one hand, the CNT film with high conductivity, microstructural rough surface, high flexibility and mechanical durability retains stable and direct electronic contact with the sulfur cathode materials, therefore decreasing internal resistivity and suppressing polarization of the cathode. On the other hand, the highly porous structure and the high surface area of the CNT film provide abundant adsorption points to support and confine sulfur cathode materials, alleviate their aggregation and promote high sulfur utilization. Moreover, the lightweight and compact structure of the CNT film adds no extra weight or volume to the sulfur cathode, benefitting the improvement of energy densities. Based on these characteristics, the sulfur cathode with a 100-layer cross-stacked CNT film presents excellent rate performances with capacities of 986, 922 and 874 mAh g(-1) at cycling rates of 0.2C, 0.5C and 1C for sulfur loading of 60 wt%, corresponding to an improvement of 52%, 109% and 146% compared to that without a CNT film. Promising cycling performances are also demonstrated, offering great potential for scaled-up production of sulfur cathodes for Li-S batteries.

Linearly polarized light emission from quantum dots with plasmonic nanoantenna arrays.

Polarizers provide convenience in generating polarized light, meanwhile their adoption raises problems of extra weight, cost, and energy loss. Aiming to realize polarizer-free polarized light sources, herein, we present a plasmonic approach to achieve direct generation of linearly polarized optical waves at the nanometer scale. Periodic slot nanoantenna arrays are fabricated, which are driven by the transition dipole moments of luminescent semiconductor quantum dots. By harnessing interactions between quantum dots and scattered fields from the nanoantennas, spontaneous emission with a high degree of linear polarization is achieved from such hybrid antenna system with polarization perpendicular to antenna slot. We also demonstrate that the polarization is engineerable in aspects of both spectrum and magnitude by tailoring plasmonic resonance of the antenna arrays. Our findings will establish a basis for the development of innovative polarized light-emitting devices, which are useful in optical displays, spectroscopic techniques, optical telecommunications, and so forth.

Study of Carbon Nanotubes as Etching Masks and Related Applications in the Surface Modification of GaAs-based Light-Emitting Diodes.

The surface modification of LEDs based on GaAs is realized by super-aligned multiwalled carbon nanotube (SACNT) networks as etching masks. The surface morphology of SACNT networks is transferred to the GaAs. It is found that the light output power of LEDs based on GaAs with a nanostructured surface morphology is greatly enhanced with the electrical power unchanged.

Vapor-condensation-assisted optical microscopy for ultralong carbon nanotubes and other nanostructures.

Here we present a simple yet powerful approach for the imaging of nanostructures under an optical microscope with the help of vapor condensation on their surfaces. Supersaturated water vapor will first form a nanometer-sized water droplet on the condensation nuclei on the surface of nanostructures, and then the water droplet will grow bigger and scatter more light to make the outline of the nanostructure be visible under dark-field optical microscope. This vapor-condensation-assisted (VCA) optical microscopy is applicable to a variety of nanostructures from ultralong carbon nanotubes to functional groups, generating images with contrast coming from the difference in density of the condensation sites, and does not induce any impurities to the specimens. Moreover, this low-cost and efficient technique can be conveniently integrated with other facilities, such as Raman spectroscope and so forth, which will pave the way for widespread applications.

M-shaped grating by nanoimprinting: a replicable, large-area, highly active plasmonic surface-enhanced Raman scattering substrate with nanogaps.

Plasmonic nanostructures separated by nanogaps enable strong electromagnetic-field confinement on the nanoscale for enhancing light-matter interactions, which are in great demand in many applications such as surface-enhanced Raman scattering (SERS). A simple M-shaped nanograting with narrow V-shaped grooves is proposed. Both theoretical and experimental studies reveal that the electromagnetic field on the surface of the M grating can be pronouncedly enhanced over that of a grating without such grooves, due to field localization in the nanogaps formed by the narrow V grooves. A technique based on room-temperature nanoimprinting lithography and anisotropic reactive-ion etching is developed to fabricate this device, which is cost-effective, reliable, and suitable for fabricating large-area nanostructures. As a demonstration of the potential application of this device, the M grating is used as a SERS substrate for probing Rhodamine 6G molecules. Experimentally, an average SERS enhancement factor as high as 5×108 has been achieved, which verifies the greatly enhanced light-matter interaction on the surface of the M grating over that of traditional SERS surfaces.

Thermoacoustic chips with carbon nanotube thin yarn arrays.

Aligned carbon nanotube (CNT) films drawn from CNT arrays have shown the potential as thermoacoustic loudspeakers. CNT thermoacoustic chips with robust structures are proposed to promote the applications. The silicon-based chips can play sound and fascinating rhythms by feeding alternating currents and audio signal to the suspending CNT thin yarn arrays across grooves in them. In additional to the thin yarns, experiments further revealed more essential elements of the chips, the groove depth and the interdigital electrodes. The sound pressure depends on the depth of the grooves, and the thermal wavelength can be introduced to define the influence-free depth. The interdigital fingers can effectively reduce the driving voltage, making the chips safe and easy to use. The chips were successfully assembled into earphones and have been working stably for about one year. The thermoacoustic chips can find many applications in consumer electronics and possibly improve the audiovisual experience.