Large and Pressure-Dependent c-Axis Piezoresistivity of Highly Oriented Pyrolytic Graphite near Zero Pressure.

The c-axis piezoresistivity is a fundamental and important parameter of graphite, but its value near zero pressure has not been well determined. Herein, a new method for studying the c-axis piezoresistivity of van der Waals materials near zero pressure is developed on the basis of in situ scanning electron microscopy and finite element simulation. The c-axis piezoresistivity of microscale highly oriented pyrolytic graphite (HOPG) is found to show a large value of 5.68 × 10-5 kPa-1 near zero pressure and decreases by 2 orders of magnitude to the established value of ∼10-7 kPa-1 when the pressure increases to 200 MPa. By modulating the serial tunneling barrier model on the basis of the stacking faults, we describe the c-axis electrical transport of HOPG under compression. The large c-axis piezoresistivity near zero pressure and its large decrease in magnitude with pressure are attributed to the rapid stiffening of the electromechanical properties under compression.

Pull-to-Peel of Two-Dimensional Materials for the Simultaneous Determination of Elasticity and Adhesion.

The flexible and clinging nature of ultrathin films requires an understanding of their elastic and adhesive properties in a wide range of circumstances from fabrications to applications. Simultaneously measuring both properties, however, is extremely difficult as the film thickness diminishes to the nanoscale. Here we address such difficulties through peeling by pulling thin films off from the substrates (we thus refer to it as "pull-to-peel"). Particularly, we perform in situ pull-to-peel of graphene and MoS2 films in a scanning electron microscope and achieve simultaneous determination of their Young's moduli and adhesions to gold substrates. This is in striking contrast to other conceptually similar tests available in the literature, including indentation tests (only measuring elasticity) and spontaneous blisters (only measuring adhesion). Furthermore, we show a weakly nonlinear Hooke's relation for the pull-to-peel response of two-dimensional materials, which may be harnessed for the design of nanoscale force sensors or exploited in other thin-film systems.

Efficient and Dense Electron Emission from a SiO2 Tunneling Diode with Low Poisoning Sensitivity.

We report a tunneling diode enabling efficient and dense electron emission from SiO2 with low poisoning sensitivity. Benefiting from the shallow SiO2 channel exposed to vacuum and the low electron affinity of SiO2 (0.9 eV), hot electrons tunneling into the SiO2 channel from the cathode of the diode are efficiently emitted into vacuum with much less restriction in both space and energy than those in previous tunneling electron sources. Monte Carlo simulations on the device performance show an emission efficiency as high as 87.0% and an emission density up to 3.0 × 105 A/cm2. By construction of a tunneling diode based on Si conducting filaments in electroformed SiO2, an emission efficiency up to 83.7% and an emission density up to 4.4 × 105 A/cm2 are experimentally realized. Electron emission from the devices is demonstrated to be independent of vacuum pressure from 10-4 to 10-1 Pa without poisoning.

Controlling the Facet of ZnO during Wet Chemical Etching Its (000 1 ¯ ) O-Terminated Surface.

Special surface plays a crucial role in nature as well as in industry. Here, the surface morphology evolution of ZnO during wet etching is studied by in situ liquid cell transmission electron microscopy and ex situ wet chemical etching. Many hillocks are observed on the (000 1 ¯ ) O-terminated surface of ZnO nano/micro belts during in situ etching. Nanoparticles on the apex of the hillocks are observed to be essential for the formation of the hillocks, providing direct experimental evidence of the micromasking mechanism. The surfaces of the hillocks are identified to be {01 1 ¯ 3 ¯ } crystal facets, which is different from the known fact that {01 1 ¯ 1 ¯ } crystal facets appear on the (000 1 ¯ ) O-terminated surface of ZnO after wet chemical etching. O2 plasma treatment is found to be the key factor for the appearance of {01 1 ¯ 3 ¯ } instead of {01 1 ¯ 1 ¯ } crystal facets after etching for both ZnO nano/micro belts and bulk materials. The synergistic effect of acidic etching and O-rich surface caused by O2 plasma treatment is proposed to be the cause of the appearance of {01 1 ¯ 3 ¯ } crystal facets. This method can be extended to control the surface morphology of other materials during wet chemical etching.

Deterministic Line-Shape Programming of Silicon Nanowires for Extremely Stretchable Springs and Electronics.

Line-shape engineering is a key strategy to endow extra stretchability to 1D silicon nanowires (SiNWs) grown with self-assembly processes. We here demonstrate a deterministic line-shape programming of in-plane SiNWs into extremely stretchable springs or arbitrary 2D patterns with the aid of indium droplets that absorb amorphous Si precursor thin film to produce ultralong c-Si NWs along programmed step edges. A reliable and faithful single run growth of c-SiNWs over turning tracks with different local curvatures has been established, while high resolution transmission electron microscopy analysis reveals a high quality monolike crystallinity in the line-shaped engineered SiNW springs. Excitingly, in situ scanning electron microscopy stretching and current-voltage characterizations also demonstrate a superelastic and robust electric transport carried by the SiNW springs even under large stretching of more than 200%. We suggest that this highly reliable line-shape programming approach holds a strong promise to extend the mature c-Si technology into the development of a new generation of high performance biofriendly and stretchable electronics.

Influence of water vapor on the electronic property of MoS2 field effect transistors.

The influence of water vapor on the electronic property of MoS2 field effect transistors (FETs) is studied through controlled experiments. We fabricate supported and suspended FETs on the same piece of MoS2 to figure out the role of SiO2 substrate on the water sensing property of MoS2. The two kinds of devices show similar response to water vapor and to different treatments, such as pumping in the vacuum, annealing at 500 K and current annealing, indicating the substrate does not play an important role in the MoS2 water sensor. Water adsorption is found to decrease the carrier mobility probably through introducing a scattering center on the surface of MoS2. The threshold voltage and subthreshold swing of the FETs do not change obviously after introducing water vapor, indicating there is no obvious doping and trap introducing effects. Long time pumping in a high vacuum and 500 K annealing show negligible effects on removing the water adsorption on the devices. Current annealing at high source-drain bias is found to be able to remove the water adsorption and set the FETs to their initial states. The mechanism is proposed to be through the hot carriers at high bias.

Crystal Phase- and Orientation-Dependent Electrical Transport Properties of InAs Nanowires.

We report a systematic study on the correlation of the electrical transport properties with the crystal phase and orientation of single-crystal InAs nanowires (NWs) grown by molecular-beam epitaxy. A new method is developed to allow the same InAs NW to be used for both the electrical measurements and transmission electron microscopy characterization. We find both the crystal phase, wurtzite (WZ) or zinc-blende (ZB), and the orientation of the InAs NWs remarkably affect the electronic properties of the field-effect transistors based on these NWs, such as the threshold voltage (VT), ON-OFF ratio, subthreshold swing (SS) and effective barrier height at the off-state (ΦOFF). The SS increases while VT, ON-OFF ratio, and ΦOFF decrease one by one in the sequence of WZ ⟨0001⟩, ZB ⟨131⟩, ZB ⟨332⟩, ZB ⟨121⟩, and ZB ⟨011⟩. The WZ InAs NWs have obvious smaller field-effect mobility, conductivities, and electron concentration at VBG = 0 V than the ZB InAs NWs, while these parameters are not sensitive to the orientation of the ZB InAs NWs. We also find the diameter ranging from 12 to 33 nm shows much less effect than the crystal phase and orientation on the electrical transport properties of the InAs NWs. The good ohmic contact between InAs NWs and metal remains regardless of the variation of the crystal phase and orientation through temperature-dependent measurements. Our work deepens the understanding of the structure-dependent electrical transport properties of InAs NWs and provides a potential way to tailor the device properties by controlling the crystal phase and orientation of the NWs.

Whole-journey nanomaterial research in an electron microscope: from material synthesis, composition characterization, property measurements to device construction and tests.

The whole-journey nanomaterial research from material synthesis, composition and structure characterizations, property measurements to device construction and tests in one equipment chamber provides a quick and unambiguous way of establishing the relationships between synthesis conditions, composition and structures, physical properties and nanodevice performances of nanomaterials; however, it still proves challenging. Herein, we report the whole-journey research of tungsten oxide nanowires in an environmental scanning electron microscope (ESEM) equipped with an x-ray energy dispersive spectrometer (EDS) and a multifunctional nanoprobe system. Tungsten oxide nanowires are synthesized by irradiating a tungsten filament using a high-energy laser in O2 atmosphere with the dynamic growth processes of nanowires being directly visualized under ESEM observation. The as-synthesized nanowires are then characterized to be monoclinic W18O49 nanowires by combing in situ EDS and ex situ transmission electron microscopy. Important physical parameters, i.e. Young's modulus, breaking strength, and electrical conductivity, of W18O49 nanowires are determined based on in situ property measurements. Two-terminal electronic devices employing single W18O49 nanowires as the channel are in situ constructed and their performances as near-infrared photodetectors and water vapor sensors are studied. The whole-journey research establishes the relationships between synthesis conditions, composition and structures, physical properties and nanodevice performances of tungsten oxide nanowires, and can be applied to other nanomaterials.

Comparative fracture toughness of multilayer graphenes and boronitrenes.

We report the comparative in situ fracture toughness testing on single-edge V/U-notched multilayer graphenes and boronitrenes in a high-resolution transmission electron microscope (HRTEM). The nanostructures of notch tips and fracture edges of the tested specimens are unambiguously resolved using HRTEM. By analyzing the notch tip stresses using finite element method, the fracture toughness of multilayer graphenes and boronitrenes is determined to be 12.0 ± 3.9 and 5.5 ± 0.7 MPa√m, respectively, taking into account the notch tip blunting effects.

Amorphization and Directional Crystallization of Metals Confined in Carbon Nanotubes Investigated by in Situ Transmission Electron Microscopy.

The hollow core of a carbon nanotube (CNT) provides a unique opportunity to explore the physics, chemistry, biology, and metallurgy of different materials confined in such nanospace. Here, we investigate the nonequilibrium metallurgical processes taking place inside CNTs by in situ transmission electron microscopy using CNTs as nanoscale resistively heated crucibles having encapsulated metal nanowires/crystals in their channels. Because of nanometer size of the system and intimate contact between the CNTs and confined metals, an efficient heat transfer and high cooling rates (∼10(13) K/s) were achieved as a result of a flash bias pulse followed by system natural quenching, leading to the formation of disordered amorphous-like structures in iron, cobalt, and gold. An intermediate state between crystalline and amorphous phases was discovered, revealing a memory effect of local short-to-medium range order during these phase transitions. Furthermore, subsequent directional crystallization of an amorphous iron nanowire formed by this method was realized under controlled Joule heating. High-density crystalline defects were generated during crystallization due to a confinement effect from the CNT and severe plastic deformation involved.

New insight in understanding oxygen reduction and evolution in solid-state lithium-oxygen batteries using an in situ environmental scanning electron microscope.

Via designing a facile microscale all-solid-state lithium-oxygen battery system constructed in an environmental scanning electron microscope, direct visualization of discharge and charge processes of the lithium-oxygen battery is achieved. Different morphologies of the discharge product are observed, including a sphere, conformal film, and red-blood-cell-like shape, with a particle size up to 1.5 µm; whereas upon charge, the decomposition initiates at their surface and continues along a certain direction, instead of from the contact point at the electrode. These new findings indicate that the electron and lithium ion conductivities of Li2O2 could support the growth and decomposition of the discharge product in our system. In addition, our results indicate that various morphologies of Li2O2 arise from the different current density and surface chemistry of CNT, and the growth and decomposition of the particle are related to the uneven distribution of the ionic and electronic conductivities of Li2O2.

Effect of electrochemical dissolution and deposition order on lithium dendrite formation: a top view investigation.

Rechargeable metallic lithium batteries are the ultimate solution to electrochemical storage due to their high theoretical energy densities. One of the key technological challenges is to control the morphology of metallic lithium electrode during electrochemical dissolution and deposition. Here we have investigated the morphology change of metallic lithium electrode after charging and discharging in nonaqueous batteries by ex situ SEM techniques from a top view. Formation of the hole structure after lithium dissolution and the filling of dendrite-like lithium into the holes has been observed for the first time. In addition, an in situ SEM investigation using an all-solid Li/Li(2)O/super aligned carbon nanotube set-up indicates that lithium ions could diffuse across through the surface oxide layer and grow lithium dendrites after applying an external electric field. The growth of lithium dendrites can be guided by electron flow when the formed lithium dendrite touches the carbon nanotube.

Revealing the anomalous tensile properties of WS2 nanotubes by in situ transmission electron microscopy.

Mechanical properties and fracture behaviors of multiwalled WS2 nanotubes produced by large scale fluidized bed method were investigated under uniaxial tension using in situ transmission electron microscopy probing; these were directly correlated to the nanotube atomic structures. The tubes with the average outer diameter ∼40 nm sustained tensile force of ∼2949 nN and revealed fracture strength of ∼11.8 GPa. Surprisingly, these rather thick WS2 nanotubes could bear much higher loadings than the thin WS2 nanotubes with almost "defect-free" structures studied previously. In addition, the fracture strength of the "thick" nanotubes did not show common size dependent degradation when the tube diameters increased from ∼20 to ∼60 nm. HRTEM characterizations and real time observations revealed that the anomalous tensile properties are related to the intershell cross-linking and geometric constraints from the inverted cone-shaped tube cap structures, which resulted in the multishell loading and fracturing.

Mechanical properties of Si nanowires as revealed by in situ transmission electron microscopy and molecular dynamics simulations.

Deformation and fracture mechanisms of ultrathin Si nanowires (NWs), with diameters of down to ~9 nm, under uniaxial tension and bending were investigated by using in situ transmission electron microscopy and molecular dynamics simulations. It was revealed that the mechanical behavior of Si NWs had been closely related to the wire diameter, loading conditions, and stress states. Under tension, Si NWs deformed elastically until abrupt brittle fracture. The tensile strength showed a clear size dependence, and the greatest strength was up to 11.3 GPa. In contrast, under bending, the Si NWs demonstrated considerable plasticity. Under a bending strain of <14%, they could repeatedly be bent without cracking along with a crystalline-to-amorphous phase transition. Under a larger strain of >20%, the cracks nucleated on the tensed side and propagated from the wire surface, whereas on the compressed side a plastic deformation took place because of dislocation activities and an amorphous transition.

Nanoscale bending of multilayered boron nitride and graphene ribbons: experiment and objective molecular dynamics calculations.

By combining experiments performed on nanoribbons in situ within a high-resolution TEM with objective molecular dynamics simulations, we reveal common mechanisms in the bending response of few-layer-thick hexagonal boron nitride and graphene nanoribbons. Both materials are observed forming localized kinks in the fully reversible bending experiments. Microscopic simulations and theoretical analysis indicate platelike bending behavior prior to kinking, in spite of the possibility of interlayer sliding, and give the critical curvature for the kinking onset. This behavior is distinct from the rippling and kinking of multi- and single-wall nanotubes under bending. Our findings have implications for future study of nanoscale layered materials, including nanomechanical device design.

Phonon-assisted electron emission from individual carbon nanotubes.

A question of how electrons can escape from one-atom-thick surfaces has seldom been studied and is still not properly answered. Herein, lateral electron emission from a one-atom-thick surface is thoroughly studied for the first time. We study electron emission from side surface of individual electrically biased carbon nanotubes (CNTs) both experimentally and theoretically and discover a new electron emission mechanism named phonon-assisted electron emission. A kinetic model based on coupled Boltzmann equations of electrons and optical phonons is proposed and well describes experimentally measured lateral electron emission from CNTs. It is shown that the electrons moving along a biased CNT can overflow from the one-atom-thick surface due to the absorption of hot forward-scattering optical phonons. A low working voltage, high emission density, and side emission character make phonon-assisted electron emission primarily promising in electron source applications.

An On-Chip Microscale Vacuum Chamber with High Sealing Performance Using Graphene as Lateral Feedthrough.

On-chip microscale vacuum chambers with high sealing performance and electrical feedthroughs are highly desired for microscale vacuum electronic devices and other MEMS devices. In this paper, we report an on-chip microscale vacuum chamber which achieves a high sealing performance by using monolayer graphene as lateral electrical feedthrough. A vacuum chamber with the dimensions of π × 2 mm × 2 mm × 0.5 mm is fabricated by anodically bonding a glass chip with a through-hole between two Si chips in a vacuum, after monolayer graphene electrodes have been transferred to the surface of one of the Si chips. Benefiting from the atomic thickness of monolayer graphene, the leak rate of Si-glass bonding interface with a monolayer graphene feedthrough is measured at less than 2 × 10-11 Pa·m3/s. The monolayer graphene feedthrough exhibits a minor resistance increase from 22.5 Ω to 31 Ω after anodic bonding, showing good electrical conductance. The pressure of the vacuum chamber is estimated to be 185 Pa by measuring the breakdown voltage. Such a vacuum is found to maintain for more than 50 days without obvious degradation, implying a high sealing performance with a leak rate of less than 1.02 × 10-16 Pa·m3/s.

Local temperature measurements on nanoscale materials using a movable nanothermocouple assembled in a transmission electron microscope.

A nanoscale thermocouple consisting of merged Cu and Cu-Ni tips is developed for local temperature measurements on advanced nanomaterials by using a probing technique in a high-resolution transmission electron microscope (TEM) equipped with a double probe scanning tunneling microcopy (STM) unit. The fabricated nanothermocouple works as the so-called T-type thermocouple and displays a quick response and high spatial and thermal resolutions. A generated thermoelectromotive force which reflects rapid temperature changes controlled by electron beam intensity alternations on a metal nanoelectrode proves the technique's usefulness for high-precision local temperature measurements. The developed method demonstrates the effectiveness while also measuring temperature changes in Joule heated multi-walled carbon nanotubes (CNTs) and in a modeled electrical conductive composite nanosystem.

Thermal stability of carbon nanotubes probed by anchored tungsten nanoparticles.

The thermal stability of multiwalled carbon nanotubes (CNTs) was studied in high vacuum using tungsten nanoparticles as miniaturized thermal probes. The particles were placed on CNTs inside a high-resolution transmission electron microscope equipped with a scanning tunneling microscope unit. The setup allowed manipulating individual nanoparticles and heating individual CNTs by applying current to them. CNTs were found to withstand high temperatures, up to the melting point of 60-nm-diameter W particles (∼3400 K). The dynamics of W particles on a hot CNT, including particle crystallization, quasimelting, melting, sublimation and intradiffusion, were observed in real time and recorded as a video. Graphite layers reel off CNTs when melted or premelted W particles revolve along the tube axis.