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.

Reconfigurable Two-Dimensional Air-Gap Barristors.

Reconfigurable logic circuits implemented by two-dimensional (2D) ambipolar semiconductors provide a prospective solution for the post-Moore era. It is still a challenge for ambipolar nanomaterials to realize reconfigurable polarity control and rectification with a simplified device structure. Here, an air-gap barristor based on an asymmetric stacking sequence of the electrode contacts was developed to resolve these issues. For the 2D ambipolar channel of WSe2, the barristor can not only be reconfigured as an n- or p-type unipolar transistor but also work as a switchable diode. The air gap around the bottom electrode dominates the reconfigurable behaviors by widening the Schottky barrier here, thus blocking the injection of both electrons and holes. The electrical performances can be improved by optimizing the electrode materials, which achieve an on/off ratio of 104 for the transistor and a rectifying ratio of 105 for the diode. A complementary inverter and a switchable AND/OR logic gate were constructed by using the air-gap barristors as building blocks. This work provides an efficient approach with great potential for low-dimensional reconfigurable electronics.

One-dimensional semimetal contacts to two-dimensional semiconductors.

Two-dimensional (2D) semiconductors are promising in channel length scaling of field-effect transistors (FETs) due to their excellent gate electrostatics. However, scaling of their contact length still remains a significant challenge because of the sharply raised contact resistance and the deteriorated metal conductivity at nanoscale. Here, we construct a 1D semimetal-2D semiconductor contact by employing single-walled carbon nanotube electrodes, which can push the contact length into the sub-2 nm region. Such 1D-2D heterostructures exhibit smaller van der Waals gaps than the 2D-2D ones, while the Schottky barrier height can be effectively tuned via gate potential to achieve Ohmic contact. We propose a longitudinal transmission line model for analyzing the potential and current distribution of devices in short contact limit, and use it to extract the 1D-2D contact resistivity which is as low as 10-6 Ω·cm2 for the ultra-short contacts. We further demonstrate that the semimetal nanotubes with gate-tunable work function could form good contacts to various 2D semiconductors including MoS2, WS2 and WSe2. The study on 1D semimetal contact provides a basis for further miniaturization of nanoelectronics in the future.

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.

Super broadband mid-infrared absorbers with ultrathin folded highly-lossy films.

Super broadband optical absorbers with ultrathin films have been keenly pursued for a long time. Although highly lossy materials with sharp light attenuation have the potential to become super absorbers, a large percent of light from free space is inevitably reflected back for the distinct impedance mismatch. Here, a simple strategy, of which reducing the thickness of highly-lossy thin films to minish reflectance and simultaneously folding the ultrathin films to make light multiple pass through, is proposed to obtain super broadband mid-infrared absorbers with ultrathin films. Along this line, the absorbers were prepared by depositing Al-doped ZnO film on scaffolds consisted of alumina spherical shells, whose substrates were opaque. When the thickness of Al-doped ZnO is 43 nm and the layer number of scaffolds is three, a maximum average absorptance was achieved as 97.6% over the wavelength range from 3 to 15 µm. Applying this strategy on polished Al foil, excellent infrared camouflage performance on human-body background was demonstrated. Featured by the strong broadband optical absorption with ultrathin films, flexible access to multiple substrates and low-cost procedures, this approach has the potential in widespread applications of infrared thermal emitters and optoelectronic devices.

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.

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.

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.

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.

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.

Boosting the Oxidative Potential of Polyethylene Glycol-Based Polymer Electrolyte to 4.36 V by Spatially Restricting Hydroxyl Groups for High-Voltage Flexible Lithium-Ion Battery Applications.

Cross-linked polyethylene glycol-based resin (c-PEGR) is constructed by a ring-opening reaction of polyethylene glycol diglycidyl ether (PEGDE) with epoxy groups and polyether amine (PEA) with amino groups. By confining the hydroxyl groups with inferior oxidative stability to the c-PEGR backbone, the oxidation potential of the PEG-based polymer material with reduced reactivity is boosted to 4.36 V. The c-PEGR based gel electrolyte shows excellent flexibility, lithium-ion transport, lithium compatibility, and enhanced oxidation stability, and is successfully applied to a 4.35 V lithium cobaltate (LCO)||lithium (Li) battery system. A quasi-static linear scanning voltammetry (QS-LSV) method is proposed for the first time to accurately measure the oxidation potential and electrochemical stability window of materials with low conductivities such as polymers, which possesses the advantages of high accuracy and short test time. This work provides new insights and research techniques for selecting polymer electrolytes for high-voltage flexible lithium-ion batteries (LIBs).

Interfacial Gated Graphene Photodetector with Broadband Response.

A much stronger interfacial gating effect was observed in the graphene/HfO2/Si photodetector when compared with that in the graphene/SiO2/Si photodetector. We found that this improvement was due to the higher interface state density at the HfO2/Si interface and the higher dielectric constant of the HfO2 layer. The photoresponsivity of the graphene/HfO2/Si photodetector is as high as 45.8 A W-1. Germanium and amorphous MoS2 (a-MoS2) were used to prepare graphene/HfO2/Ge and graphene/HfO2/a-MoS2 photodetectors, further demonstrating the high efficiency of the interfacial gating mechanism for photodetection. Because of the 0.196 eV bandgap of a-MoS2, which was verified in our previous report, the graphene/HfO2/a-MoS2 photodetector realized ultrabroadband photodetection over the range from 473 nm (visible) to 2712 nm (mid-infrared) at room temperature with photoresponsivity as high as 5.36 A W-1 and response time as fast as 68 µs, which represent significant improvements from the corresponding properties of the pure a-MoS2 photodetectors in our previous report and are comparable with those of state-of-the-art broadband photodetectors. By taking full advantage of the interfacial gating mechanism, a fast response, high photoresponsivity and ultrabroadband photodetection were achieved simultaneously. These interfacial gated graphene photodetectors also offer simple fabrication and full semiconductor process compatibility. The advantages described here indicate that the proposed photodetectors have significant potential for use in electronic and optoelectronic applications and offer a new path toward the development of ultrabroadband photodetectors.

Efficient polysulfide trapping in lithium-sulfur batteries using ultrathin and flexible BaTiO3/graphene oxide/carbon nanotube layers.

Ultrathin and flexible layers containing BaTiO3 (BTO) nanoparticles, graphene oxide (GO) sheets, and carbon nanotube (CNT) films (BTO/GO@CNT) are used to trap solvated polysulfides and alleviate the shuttle effect in lithium-sulfur (Li-S) batteries. In the functional layers, the CNT films build a conductive framework, and the GO sheets form a support membrane for the uniform dispersion of BTO nanoparticles. BTO nanoparticles without ferroelectricity (nfBTO) can trap polysulfides more effectively by chemical interaction compared to BTO nanoparticles with ferroelectricity (fBTO). A Li-S cell with the nfBTO/GO@CNT functional layer exhibits a reversible capacity of 824.5 mA h g-1 over 100 cycles at 0.2 C. At a high sulfur loading of 5.49 mg cm-2, an electrode with the functional layer shows an areal capacity of 5.15 mA h cm-2 at 0.1 C, demonstrating the nfBTO/GO@CNT functional layer's potential in developing high-performance Li-S batteries.

On-chip torsion balances with femtonewton force resolution at room temperature enabled by carbon nanotube and graphene.

The torsion balance, consisting of a rigid balance beam suspended by a fine thread, is an ancient scientific instrument, yet it is still a very sensitive force sensor to date. As the force sensitivity is proportional to the lengths of the beam and thread, but inversely proportional to the fourth power of the diameter of the thread, nanomaterials should be ideal building blocks for torsion balances. Here, we report a torsional balance array on a chip with the highest sensitivity level enabled by using a carbon nanotube as the thread and a monolayer graphene coated with Al nanofilms as the beam and mirror. It is demonstrated that the femtonewton force exerted by a weak laser can be easily measured. The balances on the chip should serve as an ideal platform for investigating fundamental interactions up to zeptonewton in accuracy in the near future.

Ultra-stretchable supercapacitors based on biaxially pre-strained super-aligned carbon nanotube films.

Super-aligned carbon nanotube (SACNT) films with wrinkled structures are prepared by a biaxial pre-strain method and can withstand repetitive stretching of large strains in multiple directions. Ultra-stretchable supercapacitors were fabricated with the SACNT film and active carbon (AC) powders. The initial specific capacitance without strain and with 150% strains in the X, Y and 45° axes was 91, 88, 89 and 90 F g-1, respectively. Moreover, the capacitance retentions were 97%, 98.5% and 98.6% after 2000 tensile cycles at 0-150% strain in the X, Y and 45° axes, respectively, demonstrating the excellent strain durability of the SACNT/AC supercapacitors. The stretchable circuit with the combination of stretchable SACNT/AC supercapacitors and SACNT conductors demonstrates a promising method in developing self-contained stretchable functional devices for a variety of applications. The low-cost and scalable biaxial pre-strain process presents a potential route for designing high performance stretchable electronic and energy storage devices.

Mixed-Dimensional Vertical Point p-n Junctions.

Mixed-dimensional van der Waals (vdW) heterostructures composed of one-dimensional (1D) and two-dimensional (2D) materials have exhibited great potential in nanoelectronics and nano-optoelectronics. In this study, we present a vertical point p-n junction (VPpnJ), in which a vertical stacked molybdenum disulfide/tungsten diselenide p-n junction is sandwiched between two cross-stacked metallic carbon nanotubes (CNTs). The device can be transformed from p-n junction to n-n junction via gate modulation. As a photodetector, the VPpnJ device can work in three different modes by setting the appropriate gating voltages. The photosensitive areas are localized around the top CNT, bottom CNT, and the cross point at VG = -10 V, 10 V, and ∼0 V, respectively. In the p-n regime at the negative gate voltage, the VPpnJ device showed an obvious photovoltaic effect. The external quantum efficiency of the VPpnJ can reach 42.7%. The electrical control of the electronic and optoelectronic characteristics can be mainly attributed to the gate-tunable interfacial built-in electric fields in the heterostructures. The progress also reveals the functional diversity of such 1D/2D mixed-dimensional heterostructures, which will be prospects for future nanoelectronics and nano-optoelectronics.

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.

Emission Enhancement from CdSe/ZnS Quantum Dots Induced by Strong Localized Surface Plasmonic Resonances without Damping.

A high-performance exciton-localized surface plasmon (LSP) coupling system consisting of well-designed plasmonic nanostructures and CdSe/ZnS quantum dots (QDs) was fabricated by first introducing a Ta2O5 layer as both an adhesive coating and coupling medium. It is shown that a larger emission enhancement factor of 6 from CdSe/ZnS QDs can be obtained from the strong coupling effect between QDs and triprism Au nanoarrays and the high scattering efficiency of LSPs without damping. This can be attributed to the matching conditions and a low extinction coefficient with little damping absorption of the Ta2O5 layer in the system. The radiative scattering rate of ΓLSPs can make a contribution to the spontaneous emission rate Γ and thus improve the internal quantum yield of the QDs. This strategy could be promising for practical application of metal-modified fluorescence enhancement.