Universality of periodicity as revealed from interlayer-mediated cracks.

A crack and its propagation is a challenging multiscale materials phenomenon of broad interest, from nanoscience to exogeology. Particularly in fracture mechanics, periodicities are of high scientific interest. However, a full understanding of this phenomenon across various physical scales is lacking. Here, we demonstrate periodic interlayer-mediated thin film crack propagation and discuss the governing conditions resulting in their periodicity as being universal. We show strong confinement of thin film cracks and arbitrary steering of their propagation by inserting a predefined thin interlayer, composed of either a polymer, metal, or even atomically thin graphene, between the substrate and the brittle thin film. The thin interlayer-mediated controllability arises from local modification of the effective mechanical properties of the crack medium. Numerical calculations incorporating basic fracture mechanics principles well model our experimental results. We believe that previous studies of periodic cracks in SiN films, self-de-bonding sol-gel films, and even drying colloidal films, along with this study, share the same physical origins but with differing physical boundary conditions. This finding provides a simple analogy for various periodic crack systems that exist in nature, not only for thin film cracks but also for cracks ranging in scale.

Tunnelling current-voltage characteristics of Angstrom gaps measured with terahertz time-domain spectroscopy.

Quantum tunnelling becomes inevitable as gap dimensions in metal structures approach the atomic length scale, and light passing through these gaps can be used to examine the quantum processes at optical frequencies. Here, we report on the measurement of the tunnelling current through a 3-Å-wide metal-graphene-metal gap using terahertz time-domain spectroscopy. By analysing the waveforms of the incident and transmitted terahertz pulses, we obtain the tunnelling resistivity and the time evolution of the induced current and electric fields in the gap and show that the ratio of the applied voltage to the tunnelling current is constant, i.e., the gap shows ohmic behaviour for the strength of the incident electric field up to 30 kV/cm. We further show that our method can be extended and applied to different types of nanogap tunnel junctions using suitable equivalent RLC circuits for the corresponding structures by taking an array of ring-shaped nanoslots as an example.

Electromagnetic Saturation of Angstrom-Sized Quantum Barriers at Terahertz Frequencies.

Metal-graphene-metal hybrid structures allow angstrom-scale van der Waals gaps, across which electron tunneling occurs. We squeeze terahertz electromagnetic waves through these λ/10 000 000 gaps, accompanied by giant field enhancements. Unprecedented transmission reduction of 97% is achieved with the transient voltage across the gap saturating at 5 V. Electron tunneling facilitated by the transient electric field strongly modifies the gap index, starting a self-limiting process related to the barrier height. Our work enables greater interplay between classical optics and quantum tunneling, and provides optical indices to the van der Waals gaps.

Bright visible light emission from graphene.

Graphene and related two-dimensional materials are promising candidates for atomically thin, flexible and transparent optoelectronics. In particular, the strong light-matter interaction in graphene has allowed for the development of state-of-the-art photodetectors, optical modulators and plasmonic devices. In addition, electrically biased graphene on SiO2 substrates can be used as a low-efficiency emitter in the mid-infrared range. However, emission in the visible range has remained elusive. Here, we report the observation of bright visible light emission from electrically biased suspended graphene devices. In these devices, heat transport is greatly reduced. Hot electrons (∼2,800 K) therefore become spatially localized at the centre of the graphene layer, resulting in a 1,000-fold enhancement in thermal radiation efficiency. Moreover, strong optical interference between the suspended graphene and substrate can be used to tune the emission spectrum. We also demonstrate the scalability of this technique by realizing arrays of chemical-vapour-deposited graphene light emitters. These results pave the way towards the realization of commercially viable large-scale, atomically thin, flexible and transparent light emitters and displays with low operation voltage and graphene-based on-chip ultrafast optical communications.

Polarized Raman spectroscopy with differing angles of laser incidence on single-layer graphene.

Chemical vapor deposition (CVD)-grown single-layer graphene samples, transferred onto a transmission electron microscope (TEM) grid and onto a quartz plate, were studied using polarized Raman spectroscopy with differing angles of laser incidence (θ). Two different polarization configurations are used. In an in-plane configuration, the polarization direction of both incident and scattered light is parallel to the graphene plane. In an out-of-plane configuration, the angle between the polarization vector and the graphene plane is the same as the angle of laser incidence (θ). The normalized Raman intensity of the G-band measured in the out-of-plane configuration, with respect to that in the in-plane configuration, was analyzed as a function of θ. The normalized Raman intensity showed approximately cos(2) θ-dependence up to θ = 70°, which can be explained by the fact that only the electric field component of the incident and the scattered photon in the out-of-plane configuration projected onto the graphene plane can contribute to the Raman scattering process because of the perfect confinement of the electrons to the graphene plane.

Direct growth of patterned graphene on SiO2 substrates without the use of catalysts or lithography.

We demonstrate a one-step fabrication of patterned graphene on SiO2 substrates through a process free from catalysts, transfer, and lithography. By simply placing a shadow mask during the plasma enhanced chemical vapor deposition (PECVD) of graphene, an arbitrary shape of graphene can be obtained on SiO2 substrate. The formation of graphene underneath the shadow mask was effectively prevented by the low-temperature, catalyst-free process. Growth conditions were optimized to form polycrystalline graphene on SiO2 substrates and the crystalline structure was characterized by Raman spectroscopy and transmission electron microscopy (TEM). Patterned graphene on SiO2 functions as a field-effect device by itself. Our method is compatible with present device processing techniques, and should be highly desirable for the proliferation of graphene applications.

Direct integration of polycrystalline graphene into light emitting diodes by plasma-assisted metal-catalyst-free synthesis.

The integration of graphene into devices is a challenging task because the preparation of a graphene-based device usually includes graphene growth on a metal surface at elevated temperatures (∼1000 °C) and a complicated postgrowth transfer process of graphene from the metal catalyst. Here we report a direct integration approach for incorporating polycrystalline graphene into light emitting diodes (LEDs) at low temperature by plasma-assisted metal-catalyst-free synthesis. Thermal degradation of the active layer in LEDs is negligible at our growth temperature, and LEDs could be fabricated without a transfer process. Moreover, in situ ohmic contact formation is observed between DG and p-GaN resulting from carbon diffusion into the p-GaN surface during the growth process. As a result, the contact resistance is reduced and the electrical properties of directly integrated LEDs outperform those of LEDs with transferred graphene electrodes. This relatively simple method of graphene integration will be easily adoptable in the industrialization of graphene-based devices.

Ordered growth of topological insulator Bi2Se3 thin films on dielectric amorphous SiO2 by MBE.

Topological insulators (TIs) are exotic materials which have topologically protected states on the surface due to strong spin-orbit coupling. However, a lack of ordered growth of TI thin films on amorphous dielectrics and/or insulators presents a challenge for applications of TI-junctions. We report the growth of topological insulator Bi2Se3 thin films on amorphous SiO2 by molecular beam epitaxy (MBE). To achieve the ordered growth of Bi2Se3 on an amorphous surface, the formation of other phases at the interface is suppressed by Se passivation. Structural characterizations reveal that Bi2Se3 films are grown along the [001] direction with a good periodicity by the van der Waals epitaxy mechanism. A weak anti-localization effect of Bi2Se3 films grown on amorphous SiO2 shows a modulated electrical property by the gating response. Our approach for ordered growth of Bi2Se3 on an amorphous dielectric surface presents considerable advantages for TI-junctions with amorphous insulator or dielectric thin films.

Focused-laser-enabled p-n junctions in graphene field-effect transistors.

With its electrical carrier type as well as carrier densities highly sensitive to light, graphene is potentially an ideal candidate for many optoelectronic applications. Beyond the direct light-graphene interactions, indirect effects arising from induced charge traps underneath the photoactive graphene arising from light-substrate interactions must be better understood and harnessed. Here, we study the local doping effect in graphene using focused-laser irradiation, which governs the trapping and ejecting behavior of the charge trap sites in the gate oxide. The local doping effect in graphene is manifested by large Dirac voltage shifts and/or double Dirac peaks from the electrical measurements and a strong photocurrent response due to the formation of a p-n-p junction in gate-dependent scanning photocurrent microscopy. The technique of focused-laser irradiation on a graphene device suggests a new method to control the charge-carrier type and carrier concentration in graphene in a nonintrusive manner as well as elucidate strong light-substrate interactions in the ultimate performance of graphene devices.

Graphitic carbon grown on fluorides by molecular beam epitaxy.

We study the growth mechanism of carbon molecules supplied by molecular beam epitaxy on fluoride substrates (MgF2, CaF2, and BaF2). All the carbon layers form graphitic carbon with different crystallinities depending on the cation. Especially, the growth on MgF2 results in the formation of nanocrystalline graphite (NCG). Such dependence on the cation is a new observation and calls for further systematic studies with other series of substrates. At the same growth temperature, the NCG on MgF2 has larger clusters than those on oxides. This is contrary to the general expectation because the bond strength of the carbon-fluorine bond is larger than that of the carbon-oxygen bond. Our results show that the growth of graphitic carbon does not simply depend on the chemical bonding between the carbon and the anion in the substrate.

Methane as an effective hydrogen source for single-layer graphene synthesis on Cu foil by plasma enhanced chemical vapor deposition.

A single-layer graphene is synthesized on Cu foil in the absence of H(2) flow by plasma enhanced chemical vapor deposition (PECVD). In lieu of an explicit H(2) flow, hydrogen species are produced during the methane decomposition process into their active species (CH(x<4)), assisted with the plasma. Notably, the early stage of growth depends strongly on the plasma power. The resulting grain size (the nucleation density) has a maximum (minimum) at 50 W and saturates when the plasma power is higher than 120 W because hydrogen partial pressures are effectively tuned by a simple control of the plasma power. Raman spectroscopy and transport measurements show that decomposed methane alone can provide a sufficient amount of hydrogen species for high-quality graphene synthesis by PECVD.

Reduction of graphene damages during the fabrication of InGaN/GaN light emitting diodes with graphene electrodes.

Although graphene looks attractive to replace indium tin oxide (ITO) in optoelectronic devices, the luminous efficiency of light emitting diodes (LEDs) with graphene transparent conducting electrodes has been limited by degradation in graphene taking place during device fabrication. In this study, it was found that the quality of graphene after the device fabrication was a critical factor affecting the performance of GaN-based LEDs. In this paper, the qualities of graphene after two different device fabrication processes were evaluated by Raman spectroscopy and atomic force microscopy. It was found that graphene was severely damaged and split into submicrometer-scale islands bounded by less conducting boundaries when graphene was transferred onto LED structures prior to the GaN etching process for p-contact formation. On the other hand, when graphene was transferred after the GaN etch and p-contact metallization, graphene remained intact and the resulting InGaN/GaN LEDs showed electrical and optical properties that were very close to those of LEDs with 200 nm thick ITO films. The forward-voltages and light output powers of LEDs were 3.03 V and 9.36 mW at an injection current of 20 mA, respectively.

Thickness-independent transport channels in topological insulator Bi(2)Se(3) thin films.

With high quality topological insulator Bi(2)Se(3) thin films, we report thickness-independent transport properties over wide thickness ranges. Conductance remained nominally constant as the sample thickness changed from 256 to ∼8 QL (where QL refers to quintuple layer, 1 QL≈1 nm). Two surface channels of very different behaviors were identified. The sheet carrier density of one channel remained constant at ∼3.0×10(13) cm(-2) down to 2 QL, while the other, which exhibited quantum oscillations, remained constant at ∼8×10(12) cm(-2) only down to ∼8 QL. The weak antilocalization parameters also exhibited similar thickness independence. These two channels are most consistent with the topological surface states and the surface accumulation layers, respectively.

Nanoscale investigation of charge transport at the grain boundaries and wrinkles in graphene film.

The influence of grain boundaries and mechanical deformations in graphene film on the electric charge transport is investigated at nanoscale with conductive atomic force microscopy. Large area monolayer graphene samples were prepared by the chemical vapor deposition technique. Field emission scanning electron microscopy confirmed the formation of grain boundaries and the presence of wrinkles. The presence of the D-band in the Raman spectrum also indicated the existence of sharp defects such as grain boundaries. Extremely low conductivity was found at the grain boundaries and the wrinkled surface was also more resistive in comparison to the plain graphene surface. Many samples were experimented with to justify our findings by selecting different areas on the graphene surface. Uniform conductivity was found on grain boundary and wrinkle free graphene surfaces. We made channels of varied lengths by local anodic oxidation to confine the charge carrier to the smallest dimensions to better confirm the alteration in current due to grain boundaries and wrinkles. The experimental findings are discussed with reference to the implementation of graphene as transparent conductive electrode.

Unusual flexibility of 2,5-bis(4-pyridylethynyl)thiophene self-assembled with Co(NCS)2 in a novel coordination polymer.

A novel coordination polymer containing Co(NCS)2 and a rigid ligand, 2,5-bis(4-pyridylethynyl)-thiophene showing unusual flexibility was synthesized.