Electrical Transport Properties Driven by Unique Bonding Configuration in γ-GeSe.

Group IV monochalcogenides have recently shown great potential for their thermoelectric, ferroelectric, and other intriguing properties. The electrical properties of group IV monochalcogenides exhibit a strong dependence on the chalcogen type. For example, GeTe exhibits high doping concentration, whereas S/Se-based chalcogenides are semiconductors with sizable bandgaps. Here, we investigate the electrical and thermoelectric properties of γ-GeSe, a recently identified polymorph of GeSe. γ-GeSe exhibits high electrical conductivity (∼106 S/m) and a relatively low Seebeck coefficient (9.4 µV/K at room temperature) owing to its high p-doping level (5 × 1021 cm-3), which is in stark contrast to other known GeSe polymorphs. Elemental analysis and first-principles calculations confirm that the abundant formation of Ge vacancies leads to the high p-doping concentration. The magnetoresistance measurements also reveal weak antilocalization because of spin-orbit coupling in the crystal. Our results demonstrate that γ-GeSe is a unique polymorph in which the modified local bonding configuration leads to substantially different physical properties.

Capacitive Heart-Rate Sensing on Touch Screen Panel with Laterally Interspaced Electrodes.

It is demonstrated that the heart-rate can be sensed capacitively on a touch screen panel (TSP) together with touch signals. The existing heart-rate sensing systems measure blood pulses by tracing the amount of light reflected from blood vessels during a number of cardiac cycles. This type of sensing system requires a considerable amount of power and space to be implemented in multi-functional mobile devices such as smart phones. It is found that the variation of the effective dielectric constant of finger stemming from the difference of systolic and diastolic blood flows can be measured with laterally interspaced top electrodes of TSP. The spacing between a pair of non-adjacent top electrodes turns out to be wide enough to distinguish heart-rate signals from noises. With the aid of fast Fourier transform, the heart-rate can be extracted reliably, which matches with the one obtained by actually counting heart beats on the wrist.

One-Dimensional Assembly on Two-Dimensions: AuCN Nanowire Epitaxy on Graphene for Hybrid Phototransistors.

The van der Waals epitaxy of functional materials provides an interesting and efficient way to manipulate the electrical properties of various hybrid two-dimensional (2D) systems. Here we show the controlled epitaxial assembly of semiconducting one-dimensional (1D) atomic chains, AuCN, on graphene and investigate the electrical properties of 1D/2D van der Waals heterostructures. AuCN nanowire assembly is tuned by different growth conditions, although the epitaxial alignment between AuCN chains and graphene remains unchanged. The switching of the preferred nanowire growth axis indicates that diffusion kinetics affects the nanowire formation process. Semiconducting AuCN chains endow the 1D/2D hybrid system with a strong responsivity to photons with an energy above 2.7 eV, which is consistent with the bandgap of AuCN. A large UV response (responsivity ∼104 A/W) was observed under illumination using 3.1 eV (400 nm) photons. Our study clearly demonstrates that 1D chain-structured semiconductors can play a crucial role as a component in multifunctional van der Waals heterostructures.

Strong Fermi-Level Pinning at Metal/n-Si(001) Interface Ensured by Forming an Intact Schottky Contact with a Graphene Insertion Layer.

We report the systematic experimental studies demonstrating that a graphene layer inserted at metal/n-Si(001) interface is efficient to explore interface Fermi-level pinning effect. It is confirmed that an inserted graphene layer prevents atomic interdiffusion to form an atomically abrupt Schottky contact. The Schottky barriers of metal/graphene/n-Si(001) junctions show a very weak dependence on metal work-function, implying that the metal Fermi-level is almost completely pinned at charge neutrality level close to the valence band edge of Si. The atomically impermeable and electronically transparent properties of graphene can be used generally to form an intact Schottky contact for all semiconductors.

In situ observations of gas phase dynamics during graphene growth using solid-state carbon sources.

A single-layer graphene has been uniformly grown on a Cu surface at elevated temperatures by thermal processing of a poly(methyl methacrylate) (PMMA) film in a rapid thermal annealing (RTA) system under vacuum. The detailed chemistry of the transition from solid-state carbon to graphene on the catalytic Cu surface was investigated by performing in situ residual gas analysis while PMMA/Cu-foil samples were being heated, in conjunction with interrupted growth studies to reconstruct ex situ the heating process. The data clearly show that the formation of graphene occurs by vaporizing hydrocarbon molecules from PMMA, such as methane and/or methyl radicals, which act as precursors, rather than by the direct graphitization of solid-state carbon. We also found that the temperature for vaporizing hydrocarbon molecules from PMMA and the length of time the gaseous hydrocarbon atmosphere is maintained, which are dependent on both the heating temperature profile and the amount of a solid carbon feedstock, are the dominant factors that determine the crystalline quality of the resulting graphene film. Under optimal growth conditions, the PMMA-derived graphene was found to have a carrier (hole) mobility as high as ∼2700 cm(2) V(-1) s(-1) at room temperature, which is superior to common graphene converted from solid carbon.

One-step graphene coating of heteroepitaxial GaN films.

Today, state-of-the-art III-Ns technology has been focused on the growth of c-plane nitrides by metal-organic chemical vapor deposition (MOCVD) using a conventional two-step growth process. Here we show that the use of graphene as a coating layer allows the one-step growth of heteroepitaxial GaN films on sapphire in a MOCVD reactor, simplifying the GaN growth process. It is found that the graphene coating improves the wetting between GaN and sapphire, and, with as little as ~0.6 nm of graphene coating, the overgrown GaN layer on sapphire becomes continuous and flat. With increasing thickness of the graphene coating, the structural and optical properties of one-step grown GaN films gradually transition towards those of GaN films grown by a conventional two-step growth method. The InGaN/GaN multiple quantum well structure grown on a GaN/graphene/sapphire heterosystem shows a high internal quantum efficiency, allowing the use of one-step grown GaN films as 'pseudo-substrates' in optoelectronic devices. The introduction of graphene as a coating layer provides an atomic playground for metal adatoms and simplifies the III-Ns growth process, making it potentially very useful as a means to grow other heteroepitaxial films on arbitrary substrates with lattice and thermal mismatch.

Reversibly Controlled Ternary Polar States and Ferroelectric Bias Promoted by Boosting Square-Tensile-Strain.

Interaction between dipoles often emerges intriguing physical phenomena, such as exchange bias in the magnetic heterostructures and magnetoelectric effect in multiferroics, which lead to advances in multifunctional heterostructures. However, the defect-dipole tends to be considered the undesired to deteriorate the electronic functionality. Here, deterministic switching between the ferroelectric and the pinched states by exploiting a new substrate of cubic perovskite, BaZrO3 is reported, which boosts the square-tensile-strain to BaTiO3 and promotes four-variants in-plane spontaneous polarization with oxygen vacancy creation. First-principles calculations propose a complex of an oxygen vacancy and two Ti3+ ions coins a charge-neutral defect-dipole. Cooperative control of the defect-dipole and the spontaneous polarization reveals ternary in-plane polar states characterized by biased/pinched hysteresis loops. Furthermore, it is experimentally demonstrated that three electrically controlled polar-ordering states lead to switchable and nonvolatile dielectric states for application of nondestructive electro-dielectric memory. This discovery opens a new route to develop functional materials via manipulating defect-dipoles and offers a novel platform to advance heteroepitaxy beyond the prevalent perovskite substrates.

Negative Fermi-Level Pinning Effect of Metal/n-GaAs(001) Junction Induced by a Graphene Interlayer.

It is demonstrated that the electric dipole layer due to the overlapping of electron wave functions at the metal/graphene contact results in a negative Fermi-level pinning effect on the region of the GaAs surface with low interface-trap density in the metal/graphene/n-GaAs(001) junction. The graphene interlayer plays the role of a diffusion barrier, preventing the atomic intermixing at the interface and preserving the low interface-trap density region. The negative Fermi-level pinning effect is supported by the decrease of the Schottky barrier with the increase of the metal work function. Our work shows that the graphene interlayer can invert the effective work function of the metal between high and low, making it possible to form both Schottky and Ohmic-like contacts with identical (particularly high work function) metal electrodes on a semiconductor substrate possessing low surface-state density.

Stretchable Dual-Capacitor Multi-Sensor for Touch-Curvature-Pressure-Strain Sensing.

We introduce a new type of multi-functional capacitive sensor that can sense several different external stimuli. It is fabricated only with polydimethylsiloxane (PDMS) films and silver nanowire electrodes by using selective oxygen plasma treatment method without photolithography and etching processes. Differently from the conventional single-capacitor multi-functional sensors, our new multi-functional sensor is composed of two vertically-stacked capacitors (dual-capacitor). The unique dual-capacitor structure can detect the type and strength of external stimuli including curvature, pressure, strain, and touch with clear distinction, and it can also detect the surface-normal directionality of curvature, pressure, and touch. Meanwhile, the conventional single-capacitor sensor has ambiguity in distinguishing curvature and pressure and it can detect only the strength of external stimulus. The type, directionality, and strength of external stimulus can be determined based on the relative capacitance changes of the two stacked capacitors. Additionally, the logical flow reflected on a tree structure with its branches reaching the direction and strength of the corresponding external stimulus unambiguously is devised. This logical flow can be readily implemented in the sensor driving circuit if the dual-capacitor sensor is commercialized actually in the future.

Highly-Sensitive Thin Film THz Detector Based on Edge Metal-Semiconductor-Metal Junction.

Terahertz (THz) detectors have been extensively studied for various applications such as security, wireless communication, and medical imaging. In case of metal-insulator-metal (MIM) tunnel junction THz detector, a small junction area is desirable because the detector response time can be shortened by reducing it. An edge metal-semiconductor-metal (EMSM) junction has been developed with a small junction area controlled precisely by the thicknesses of metal and semiconductor films. The voltage response of the EMSM THz detector shows the clear dependence on the polarization angle of incident THz wave and the responsivity is found to be very high (~2,169 V/W) at 0.4 THz without any antenna and signal amplifier. The EMSM junction structure can be a new and efficient way of fabricating the nonlinear device THz detector with high cut-off frequency relying on extremely small junction area.

Growth and Simultaneous Valleys Manipulation of Two-Dimensional MoSe2-WSe2 Lateral Heterostructure.

The covalently bonded in-plane heterostructure (HS) of monolayer transition-metal dichalcogenides (TMDCs) possesses huge potential for high-speed electronic devices in terms of valleytronics. In this study, high-quality monolayer MoSe2-WSe2 lateral HSs are grown by pulsed-laser-deposition-assisted selenization method. The sharp interface of the lateral HS is verified by morphological and optical characterizations. Intriguingly, photoluminescence spectra acquired from the interface show rather clear signatures of pristine MoSe2 and WSe2 with no intermediate energy peak related to intralayer excitonic matter or formation of MoxW(1-x)Se2 alloys, thereby confirming the sharp interface. Furthermore, the discrete nature of laterally attached TMDC monolayers, each with doubly degenerated but nonequivalent energy valleys marked by (KM, K'M) for MoSe2 and (KW, K'W) for WSe2 in k space, allows simultaneous control of the four valleys within the excitation area without any crosstalk effect over the interface. As an example, KM and KW valleys or K'M and K'W valleys are simultaneously polarized by controlling the helicity of circularly polarized optical pumping, where the maximum degree of polarization is achieved at their respective band edges. The current work provides the growth mechanism of laterally sharp HSs and highlights their potential use in valleytronics.

Giant Electroresistance in Edge Metal-Insulator-Metal Tunnel Junctions Induced by Ferroelectric Fringe Fields.

An enormous amount of research activities has been devoted to developing new types of non-volatile memory devices as the potential replacements of current flash memory devices. Theoretical device modeling was performed to demonstrate that a huge change of tunnel resistance in an Edge Metal-Insulator-Metal (EMIM) junction of metal crossbar structure can be induced by the modulation of electric fringe field, associated with the polarization reversal of an underlying ferroelectric layer. It is demonstrated that single three-terminal EMIM/Ferroelectric structure could form an active memory cell without any additional selection devices. This new structure can open up a way of fabricating all-thin-film-based, high-density, high-speed, and low-power non-volatile memory devices that are stackable to realize 3D memory architecture.

Enhanced crystallinity of epitaxial graphene grown on hexagonal SiC surface with molybdenum plate capping.

The crystallinity of epitaxial graphene (EG) grown on a Hexagonal-SiC substrate is found to be enhanced greatly by capping the substrate with a molybdenum plate (Mo-plate) during vacuum annealing. The crystallinity enhancement of EG layer grown with Mo-plate capping is confirmed by the significant change of measured Raman spectra, compared to the spectra for no capping. Mo-plate capping is considered to induce heat accumulation on SiC surface by thermal radiation mirroring and raise Si partial pressure near surface by confining the sublimated Si atoms between SiC substrate and Mo-plate, which would be the essential contributors of crystallinity enhancement.

Growth of wrinkle-free graphene on texture-controlled platinum films and thermal-assisted transfer of large-scale patterned graphene.

Growth of large-scale patterned, wrinkle-free graphene and the gentle transfer technique without further damage are most important requirements for the practical use of graphene. Here we report the growth of wrinkle-free, strictly uniform monolayer graphene films by chemical vapor deposition on a platinum (Pt) substrate with texture-controlled giant grains and the thermal-assisted transfer of large-scale patterned graphene onto arbitrary substrates. The designed Pt surfaces with limited numbers of grain boundaries and improved surface perfectness as well as small thermal expansion coefficient difference to graphene provide a venue for uniform growth of monolayer graphene with wrinkle-free characteristic. The thermal-assisted transfer technique allows the complete transfer of large-scale patterned graphene films onto arbitrary substrates without any ripples, tears, or folds. The transferred graphene shows high crystalline quality with an average carrier mobility of ∼ 5500 cm(2) V(-1) s(-1) at room temperature. Furthermore, this transfer technique shows a high tolerance to variations in types and morphologies of underlying substrates.

Negative Poisson's ratios in metal nanoplates.

The Poisson's ratio is a fundamental measure of the elastic-deformation behaviour of materials. Although negative Poisson's ratios are theoretically possible, they were believed to be rare in nature. In particular, while some studies have focused on finding or producing materials with a negative Poisson's ratio in bulk form, there has been no such study for nanoscale materials. Here we provide numerical and theoretical evidence that negative Poisson's ratios are found in several nanoscale metal plates under finite strains. Furthermore, under the same conditions of crystal orientation and loading direction, materials with a positive Poisson's ratio in bulk form can display a negative Poisson's ratio when the material's thickness approaches the nanometer scale. We show that this behaviour originates from a unique surface effect that induces a finite compressive stress inside the nanoplates, and from a phase transformation that causes the Poisson's ratio to depend strongly on the amount of stretch.

Monolithic graphene oxide sheets with controllable composition.

Graphene oxide potentially has multiple applications and is typically prepared by solution-based chemical means. To date, the synthesis of a monolithic form of graphene oxide that is crucial to the precision assembly of graphene-based devices has not been achieved. Here we report the physical approach to produce monolithic graphene oxide sheets on copper foil using solid carbon, with tunable oxygen-to-carbon composition. Experimental and theoretical studies show that the copper foil provides an effective pathway for carbon diffusion, trapping the oxygen species dissolved in copper and enabling the formation of monolithic graphene oxide sheets. Unlike chemically derived graphene oxide, the as-synthesized graphene oxide sheets are electrically active, and the oxygen-to-carbon composition can be tuned during the synthesis process. As a result, the resulting graphene oxide sheets exhibit tunable bandgap energy and electronic properties. Our solution-free, physical approach may provide a path to a new class of monolithic, two-dimensional chemically modified carbon sheets.

Facile synthesis of few-layer graphene with a controllable thickness using rapid thermal annealing.

Few-layer graphene films with a controllable thickness were grown on a nickel surface by rapid thermal annealing (RTA) under vacuum. The instability of nickel films in air facilitates the spontaneous formation of ultrathin (<2-3 nm) carbon- and oxygen-containing compounds on a nickel surface; thus, the high-temperature annealing of the nickel samples without the introduction of intentional carbon-containing precursors results in the formation of graphene films. From annealing temperature and ambient studies during RTA, it was found that the evaporation of oxygen atoms from the surface is the dominant factor affecting the formation of graphene films. The thickness of the graphene layers is strongly dependent on the RTA temperature and time, and the resulting films have a limited thickness (<2 nm), even for an extended RTA time. The transferred films have a low sheet resistance of ~0.9 ± 0.4 kΩ/sq, with ~94% ± 2% optical transparency, making them useful for applications as flexible transparent conductors.

Near room-temperature synthesis of transfer-free graphene films.

Large-area graphene films are best synthesized via chemical vapour and/or solid deposition methods at elevated temperatures (~1,000 °C) on polycrystalline metal surfaces and later transferred onto other substrates for device applications. Here we report a new method for the synthesis of graphene films directly on SiO(2)/Si substrates, even plastics and glass at close to room temperature (25-160 °C). In contrast to other approaches, where graphene is deposited on top of a metal substrate, our method invokes diffusion of carbon through a diffusion couple made up of carbon-nickel/substrate to form graphene underneath the nickel film at the nickel-substrate interface. The resulting graphene layers exhibit tunable structural and optoelectronic properties by nickel grain boundary engineering and show micrometre-sized grains on SiO(2) surfaces and nanometre-sized grains on plastic and glass surfaces. The ability to synthesize graphene directly on non-conducting substrates at low temperatures opens up new possibilities for the fabrication of multiple nanoelectronic devices.

Precursor polar clusters in the paraelectric phase of ferroelectric Ba0.80Ca0.20TiO3 single crystals studied by Brillouin light scattering.

A strong relaxation mode was observed in the gigahertz frequency window in the paraelectric phase of Ba0.80Ca0.20TiO3 single crystals by using Brillouin light scattering. The appearance and growth of this relaxation mode were accompanied by substantial softening of the longitudinal acoustic mode as well as a remarkable increase in the hypersonic damping. Similar to BaTiO3, the temperature dependence of the relaxation time of Ba0.80Ca0.20TiO3 displayed a slowing-down behavior near the Curie temperature, indicating the order-disorder nature of the paraelectric-ferroelectric phase transition in this substance. The dynamics of precursor polar clusters observed in this work was discussed in relation with recent theoretical studies and found to be consistent with their predictions.