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.

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.

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.

Configurable multifunctional integrated circuits based on carbon nanotube dual-material gate devices.

Nanoelectronic devices with specifically designed structures for performance promotion or function expansion are of great interest, aiming for diversified advanced nanoelectronic systems. In this work, we report a dual-material gate (DMG) carbon nanotube (CNT) device with multiple functions, which can be configured either as a high-performance p-type field-effect transistor (FET) or a diode by changing the input manners of the device. When operating as a FET, the device exhibits a large current on/off ratio of more than 108 and a drain-induced barrier lowering of 97.3 mV V-1. When configured as a diode, the rectification ratio of the device can be greater than 105. We then demonstrate configurable analog and digital integrated circuits that are enabled by utilizing these devices. The configurability enables the realization of transformable functions in a single device or circuits, which gives future electronic systems the flexibility to adapt to the diverse requirements of their applications and/or ever-changing operating environments.

Constant-rate dissolution of InAs nanowires in radiolytic water observed by in situ liquid cell TEM.

Understanding the dissolution process and mechanism of materials in a liquid at the nanoscale is very important for both science and technology in many fields. Although the dissolution process of nanoparticles has been studied by many groups, the dissolution of one-dimensional (1D) nanomaterials with a high aspect ratio has seldom been directly observed with a high spatial resolution. In this paper, the dissolution process of 1D nanowires (NWs), InAs NWs as an example, in radiolytic water is studied by in situ liquid cell transmission electron microscopy. Different from most size-dependent dissolutions of nanoparticles, the dissolution rate of InAs NWs is found to be constant with reducing size down to ∼5 nm in diameter. The kinetics of InAs NW dissolution in radiolytic water is investigated by analyzing the source supply, surface reaction and product diffusion steps in the dissolution process. We find surface reaction limited dissolution fits well with our experimental results and the activation energy should be constant during the whole dissolution process even when the diameter of InAs NWs is as small as 5 nm. The present results are significant for a quantitative understanding of liquid phase reactions for 1D systems and for design and optimization of dissolution processes.

Interlayer electrical resistivity of rotated graphene layers studied by in-situ scanning electron microscopy.

Interlayer electrical transport between two-dimensional atomic crystals can be strongly modulated by the rotational misalignment between them. However, the experimental study on the interlayer electrical transport between rotated two-dimensional atomic crystals with variable rotation angles is challenging. Here, an in-situ scanning electron microscopy method is developed to study the interlayer electrical transport between rotated graphene layers. We employ nanoprobes installed in a scanning electron microscope to function as both "fingers" to induce interlayer rotation of a microfabricated metal-graphite-metal sandwiched island and also electrical probes to measure interlayer electrical resistivity of the rotated graphene layers. Interlayer electrical resistivity of the rotated graphene layers is found to increase monotonically by three orders of magnitude from ∼0.1 to ∼100 Ω cm when the rotational misalignment angle increases from 0° to 30°. This phenomenon can be well described by phonon-mediated electrical transport model. The large-magnitude tunability of interlayer electrical resistivity by mechanical rotation implies the potential applications of rotated graphene layers in nanoelectromechanical systems. Our results also provide a method for studying and tuning interlayer electrical transport between rotated two-dimensional atomic crystals.

1D Piezoelectric Material Based Nanogenerators: Methods, Materials and Property Optimization.

Due to the enhanced piezoelectric properties, excellent mechanical properties and tunable electric properties, one-dimensional (1D) piezoelectric materials have shown their promising applications in nanogenerators (NG), sensors, actuators, electronic devices etc. To present a clear view about 1D piezoelectric materials, this review mainly focuses on the characterization and optimization of the piezoelectric properties of 1D nanomaterials, including semiconducting nanowires (NWs) with wurtzite and/or zinc blend phases, perovskite NWs and 1D polymers. Specifically, the piezoelectric coefficients, performance of single NW-based NG and structure-dependent electromechanical properties of 1D nanostructured materials can be respectively investigated through piezoresponse force microscopy, atomic force microscopy and the in-situ scanning/transmission electron microcopy. Along with the introduction of the mechanism and piezoelectric properties of 1D semiconductor, perovskite materials and polymers, their performance improvement strategies are summarized from the view of microstructures, including size-effect, crystal structure, orientation and defects. Finally, the extension of 1D piezoelectric materials in field effect transistors and optoelectronic devices are simply introduced.

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.

Single-walled carbon nanotube thermionic electron emitters with dense, efficient and reproducible electron emission.

Thermionic electron emitters have recently been scaled down to the microscale using microfabrication technologies and graphene as the filament. While possessing several advantages over field emitters, graphene-based thermionic micro-emitters still exhibit low emission current density and efficiency. Here, we report nanoscale thermionic electron emitters (NTEEs) fabricated using microfabrication technologies and single-walled carbon nanotubes (SWCNTs), the thinnest conducting filament we can use. The SWCNT NTEEs exhibit an emission current density as high as 0.45 × 105 A cm-2, which is superior to that of traditional thermionic emitters and five orders of magnitude higher than that of graphene-based thermionic emitters. The emission characteristics of SWCNT NTEEs are found to strongly depend on the electrical properties of the SWCNTs, with metallic SWCNT NTEEs showing a substantially lower turn-on voltage and more reproducible emission performances than those based on semiconducting SWCNTs. Our results indicate that SWCNT NTEEs are promising for electron source applications.

Superlubricity between MoS2 Monolayers.

The ultralow friction between atomic layers of hexagonal MoS2 , an important solid lubricant and additive of lubricating oil, is thought to be responsible for its excellent lubricating performances. However, the quantitative frictional properties between MoS2 atomic layers have not been directly tested in experiments due to the lack of conventional tools to characterize the frictional properties between 2D atomic layers. Herein, a versatile method for studying the frictional properties between atomic-layered materials is developed by combining the in situ scanning electron microscope technique with a Si nanowire force sensor, and the friction tests on the sliding between atomic-layered materials down to monolayers are reported. The friction tests on the sliding between incommensurate MoS2 monolayers give a friction coefficient of ≈10-4 in the regime of superlubricity. The results provide the first direct experimental evidence for superlubricity between MoS2 atomic layers and open a new route to investigate frictional properties of broad 2D materials.

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.

Direct Observation of the Layer-by-Layer Growth of ZnO Nanopillar by In situ High Resolution Transmission Electron Microscopy.

Catalyst-free methods are important for the fabrication of pure nanowires (NWs). However, the growth mechanism remains elusive due to the lack of crucial information on the growth dynamics at atomic level. Here, the noncatalytic growth process of ZnO NWs is studied through in situ high resolution transmission electron microscopy. We observe the layer-by-layer growth of ZnO nanopillars along the polar [0001] direction under electron beam irradiation, while no growth is observed along the radial directions, indicating an anisotropic growth mechanism. The source atoms are mainly from the electron beam induced damage of the sample and the growth is assisted by subsequent absorption and then diffusion of atoms along the side surface to the top (0002) surface. The different binding energy on different ZnO surface is the main origin for the anisotropic growth. Additionally, the coalescence of ZnO nanocrystals related to the nucleation stage is uncovered to realize through the rotational motions and recrystallization. Our in situ results provide atomic-level detailed information about the dynamic growth and coalescence processes in the noncatalytic synthesis of ZnO NW and are helpful for understanding the vapor-solid mechanism of catalyst-free NW growth.

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.

Tunable graphene micro-emitters with fast temporal response and controllable electron emission.

Microfabricated electron emitters have been studied for half a century for their promising applications in vacuum electronics. However, tunable microfabricated electron emitters with fast temporal response and controllable electron emission still proves challenging. Here, we report the scaling down of thermionic emitters to the microscale using microfabrication technologies and a Joule-heated microscale graphene film as the filament. The emission current of the graphene micro-emitters exhibits a tunability of up to six orders by a modest gate voltage. A turn-on/off time of less than 1 µs is demonstrated for the graphene micro-emitters, indicating a switching speed about five orders of magnitude faster than their bulky counterparts. Importantly, emission performances of graphene micro-emitters are controllable and reproducible through engineering graphene dimensions by microfabrication technologies, which enables us to fabricate graphene micro-emitter arrays with uniform emission performances. Graphene micro-emitters offer an opportunity of realizing large-scale addressable micro-emitter arrays for vacuum electronics applications.

Remarkable influence of slack on the vibration of a single-walled carbon nanotube resonator.

We for the first time quantitatively investigate experimentally the remarkable influence of slack on the vibration of a single-walled carbon nanotube (SWCNT) resonator with a changeable channel length fabricated in situ inside a scanning electron microscope, compare the experimental results with the theoretical predictions calculated from the measured geometric and mechanical parameters of the same SWCNT, and find the following novel points. We demonstrate experimentally that as the slack s is increased from about zero to 1.8%, the detected vibration transforms from single-mode to multimode vibration, and the gate-tuning ability gradually attenuates for all the vibration modes. The quadratic tuning coefficient α decreases linearly with 1/√s when the gate voltage V(g)dc is small and the nanotube resonator operates in the beam regime. The linear tuning coefficient γ decreases linearly with 1/ (4√S) when V(g)dc has an intermediate value and the nanotube resonator operates in the catenary regime. The calculated α and γ fit the experimental values of the even in-plane mode reasonably well. As the slack is increased, the quality factor Q of the resonator linearly goes up, but the increase is far less steep than that predicted by the previous theoretical study. Our results are important to understand and design resonators based on CNT and other nanomaterials.

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.

The intrinsic origin of hysteresis in MoS2 field effect transistors.

We investigate the hysteresis and gate voltage stress effect in MoS2 field effect transistors (FETs). We observe that both the suspended and the SiO2-supported FETs have large hysteresis in their transfer curves under vacuum which cannot be attributed to the traps at the interface between the MoS2 and the SiO2 or in the SiO2 substrate or the gas adsorption/desorption effect. Our findings indicate that the hysteresis we observe comes from the MoS2 itself, revealing an intrinsic origin of the hysteresis besides some extrinsic factors. The fact that the FETs based on thinner MoS2 have larger hysteresis than that with thicker MoS2 suggests that the surface of MoS2 plays a key role in the hysteresis. The gate voltage sweep range, sweep direction, sweep time and loading history all affect the hysteresis observed in the transfer curves.