Tunable spin injection and detection across a van der Waals interface.

Van der Waals heterostructures with two-dimensional magnets offer a magnetic junction with an atomically sharp and clean interface. This attribute ensures that the magnetic layers maintain their intrinsic spin-polarized electronic states and spin-flipping scattering processes at a minimum level, a trait that can expand spintronic device functionalities. Here, using a van der Waals assembly of ferromagnetic Fe3GeTe2 with non-magnetic hexagonal boron nitride and WSe2 layers, we demonstrate electrically tunable, highly transparent spin injection and detection across the van der Waals interfaces. By varying an electrical bias, the net spin polarization of the injected carriers can be modulated and reversed in polarity, which leads to sign changes of the tunnelling magnetoresistance. We attribute the spin polarization reversals to sizable contributions from high-energy localized spin states in the metallic ferromagnet, so far inaccessible in conventional magnetic junctions. Such tunability of the spin-valve operations opens a promising route for the electronic control of next-generation low-dimensional spintronic device applications.

Harvesting electrical energy using plasmon-enhanced light pressure in a platinum cut cone.

We have designed a method of harvesting electrical energy using plasmon-enhanced light pressure. A device was fabricated as a cut cone structure that optimizes light collection so that the weak incident light pressure can be sufficiently enhanced inside the cut cone to generate electrical energy. An increase in the device's current output is a strong indication that the pressure of incident light has been enhanced by the surface plasmons on a platinum layer inside the cut cone. The electrical energy harvested in a few minutes by irradiating pulsed laser light on a single micro device was possible to illuminate a blue LED.

Tunneling Spectroscopy for Electronic Bands in Multi-Walled Carbon Nanotubes with Van Der Waals Gap.

Various intriguing quantum transport measurements for carbon nanotubes (CNTs) based on their unique electronic band structures have been performed adopting a field-effect transistor (FET), where the contact resistance represents the interaction between the one-dimensional and three-dimensional systems. Recently, van der Waals (vdW) gap tunneling spectroscopy for single-walled CNTs with indium-metal contacts was performed adopting an FET device, providing the direct assignment of the subband location in terms of the current-voltage characteristic. Here, we extend the vdW gap tunneling spectroscopy to multi-walled CNTs, which provides transport spectroscopy in a tunneling regime of ~1 eV, directly reflecting the electronic density of states. This new quantum transport regime may allow the development of novel quantum devices by selective electron (or hole) injection to specific subbands.

Direct Probing of the Electronic Structures of Single-Layer and Bilayer Graphene with a Hexagonal Boron Nitride Tunneling Barrier.

The chemical and mechanical stability of hexagonal boron nitride (h-BN) thin films and their compatibility with other free-standing two-dimensional (2D) crystals to form van der Waals heterostructures make the h-BN-2D tunnel junction an intriguing experimental platform not only for the engineering of specific device functionalities but also for the promotion of quantum measurement capabilities. Here, we exploit the h-BN-graphene tunnel junction to directly probe the electronic structures of single-layer and bilayer graphene in the presence and the absence of external magnetic fields with unprecedented high signal-to-noise ratios. At a zero magnetic field, we identify the tunneling spectra related to the charge neutrality point and the opening of the electric-field-induced bilayer energy gap. In the quantum Hall regime, the quantization of 2D electron gas into Landau levels (LL) is seen as early as 0.2 T, and as many as 30 well-separated LL tunneling conductance oscillations are observed for both electron- and hole-doped regions. Our device simulations successfully reproduce the experimental observations. Additionally, we extract the relative permittivity of three-to-five layer h-BN and find that the screening capability of thin h-BN films is as much as 60% weaker than bulk h-BN.

Mapping of the atomic lattice orientation of a graphite flake using macroscopic liquid crystal texture.

The electronic properties of graphene depend critically on its lattice orientation and edge type. However, it is very difficult to identify them, and they are accessible only using sophisticated tools. In this paper, we show an easy and reliable way to reveal the lattice orientation and edge type of graphene and graphite flakes, i.e. multi-layered graphene. Nematic liquid crystals have the potential to align themselves into three symmetric and equivalent orientations on crystalline graphite. The director of macroscopic texture due to the elasticity indicates the lattice orientation of the top graphite layer. By analyzing the director orientation using a polarizing optical microscope, we were able to show the lattice orientation, chiral angle and edge type of graphene and graphite flakes on the macroscopic scale. As liquid crystals are soft and easily removable, our technique has little chance of influencing the following processes for graphene manipulation.

Nano-engineered optimal templates for surface-plasmon enhanced Raman scattering.

We investigated the critical conditions to realize reliable and nano-engineered templates for surface-plasmon enhanced Raman scattering (SERS). Ultra-sensitive SERSs of thymine oligonucleotides were successfully realized on the template of Au nanoparticle arrays which were prepared by the combination of electron-beam lithography and post-chemical modification techniques. Drastic enhancement of Raman signal from the thymine oligonucleotides was only observed on the optimized templates, where the tuning of the plasmon resonance condition and the formation of the hot spots were both critical. Our results suggest that the artificial generation of reproducible and controlled hot spots can be achieved by our approach.

Tuning photoluminescence spectra of MoS2 with liquid crystals.

The photoluminescence (PL) and Raman spectra of molybdenum disulfide (MoS2) can be tuned with liquid crystals. A nematic liquid crystal, 5CB, was aligned in a zigzag direction on an MoS2 monolayer flake. The PL and A1g Raman mode peaks of the MoS2 monolayer were shifted by 46 meV and 2 cm-1, respectively, owing to the interaction between MoS2 and the liquid crystal. Based on Lorentzian fitting analysis, it was confirmed that the peak positions and intensity ratios of the trion PL and exciton PL varied with the phase transition of the liquid crystal. This phenomenon was possibly caused by the transfer of electrons from MoS2 to the liquid crystal. This electron transfer varies with the temperature-dependent change in the liquid crystal phase. Therefore, the PL spectra of MoS2 can be tuned simply by controlling the phase, without changing the type of added material.

Changes in the Photoluminescence of Monolayer and Bilayer Molybdenum Disulfide during Laser Irradiation.

Various postsynthesis processes for transition metal dichalcogenides have been attempted to control the layer number and defect concentration, on which electrical and optical properties strongly depend. In this work, we monitored changes in the photoluminescence (PL) of molybdenum disulfide (MoS2) until laser irradiation generated defects on the sample flake and completely etched it away. Higher laser power was required to etch bilayer MoS2 compared to monolayer MoS2. When the laser power was 270 µW with a full width at half-maximum of 1.8 µm on bilayer MoS2, the change in PL intensity over time showed a double maximum during laser irradiation due to a layer-by-layer etching of the flake. When the laser power was increased to 405 µW, however, both layers of bilayer MoS2 were etched all at once, which resulted in a single maximum in the change of PL intensity over time, as in the case of monolayer MoS2. The dependence of the etching pattern for bilayer MoS2 on laser power was also reflected in position changes of both exciton and trion PL peaks. The subtle changes in the PL spectra of MoS2 as a result of laser irradiation found here are discussed in terms of PL quantum efficiency, conversion between trions and excitons, mean interatomic spacing, and the screening of Coulomb interaction.

Plasmon resonance changes of gold nanoparticle arrays upon modification.

Periodic Au nanoparticle arrays, fabricated using electron beam lithography, have been modified by chemical reaction in solutions having various concentrations of a reducing agent. As the nanoparticles enlarge due to the formation of additional Au nanolumps on the surface, both the position and intensity of plasmon absorbance of Au nanoparticle arrays change in proportion to the concentration of the reducing agent. Moreover, the plasmon absorbance is split into dipole and quadrupole modes as conductive connections form between the particles. Our results demonstrate that the changes in both the position and intensity of plasmon absorbance can be employed together as complementary readout values of nanosensors.

Formation of (111)-oriented nickel nanocrystals by thermal annealing of nickel thin films.

We have produced Ni nanocrystals with face centered cubic structure by thermally annealing Ni films deposited on SiO2-covered Si(001) substrates in a flow of mixed hydrogen and argon gas. Ni films thicker than 5 nm self-assemble into highly (111)-oriented Ni nanocrystals on a flat and continuous SiO2 interlayer during the thermal annealing, while Ni films of 5 nm thickness aggregate to the irregularly shaped nanoparticles. The lateral width of the nanocrystals ranges from tens of nanometers to hundreds of nanometers, and the crystal height is under 100 nm. The nanocrystals have wide (111) top facets of hexagonal shape and narrow (100) sidewalls of truncated pyramidal shape, as a result of each crystal minimizing its total surface energy. Our results demonstrate that the formation of nanocrystals during thermal annealing is strongly affected by the morphology of the SiO2 interlayer, the Ni film thickness, the annealing temperature, and the partial pressure of hydrogen gas.

Cellular organization of three germ layer cells on different types of noncovalent functionalized graphene substrates.

Graphene and its derivatives have seen a rapid rise in interest as promising biomaterials especially in the field of tissue engineering, regenerative medicine, and cell biology of late. Despite its proven potential in numerous biological applications, information regarding the relationship between the different forms of graphene and cell lineages is still lacking partly due to its topical emergence in cellular studies. Herein, we explore the biocompatibility of four types of graphene substrates (chemical vapor deposition grown graphene, mechanically exfoliated graphene, chemically exfoliated graphene oxide, and reduced graphene oxide) with three types of somatic cells (keratinocytes, hepatocytes, endothelial cells) derived from the three germ layers in relation to cell adhesion, proliferation, morphology, and gene expression. The results revealed exceptional cell adhesion for all tested groups but enhanced proliferation and cytoskeletal interconnectivity in graphene oxide and reduced graphene oxide substrates. We were unable to detect any adverse effects in gene expression and survivability during a week of culture. We further show topographic changes to graphene substrates under fetal bovine serum adsorption to better illustrate the actual microenvironment of inhabitant cells. This study highlights the extraordinary synergy between graphene and somatic cells, suggesting the discretionary use of extracellular matrix components for in vitro cultivation.

Characteristics of localized surface plasmon resonance of nanostructured Au patterns for biosensing.

Periodic arrays of pseudotetrahedal-shaped gold nanoparticles were fabricated using nanosphere lithography (NSL) and examined for localized surface plasmon resonance (LSPR). The dependence of the LSPR on particle size of the periodic gold nanostructures was explored for potential application as a new biosensor. With increasing size and height of the Au nanoparticles, the absorption peak of the LSPR shifts to the longer wavelength and becomes relatively sharper. With thinner metal deposition or finer Au nanostructure, the absorption signal varies more sensitively for the changes in the Au particle size. The binding affinity study for biotin-streptavidine system on the Au nanopat-terns resulted in blue-shifted absorption signal, opening up the possibility of the nanostructured Au pattern as a new LSPR biosensor.

Highly stretchable, mechanically stable, and weavable reduced graphene oxide yarn with high NO2 sensitivity for wearable gas sensors.

Stretchable gas sensors are important components of wearable electronic devices used for human safety and healthcare applications. However, the current low stretchability and poor stability of the materials limit their use. Here, we report a highly stretchable, stable, and sensitive NO2 gas sensor composed of reduced graphene oxide (RGO) sheets and highly elastic commercial yarns. To achieve high stretchability and good stability, the RGO sensors were fabricated using a pre-strain strategy (strain-release assembly). The fabricated stretchable RGO gas sensors showed high NO2 sensitivity (55% at 5.0 ppm) under 200% strain and outstanding mechanical stability (even up to 5000 cycles at 400% applied strain), making them ideal for wearable electronic applications. In addition, our elastic graphene gas sensors can also be woven into fabrics and clothes for the creation of smart textiles. Finally, we successfully fabricated wearable gas-sensing wrist-bands from superelastic graphene yarns and stretchable knits to demonstrate a wearable electronic device.

Homogeneity and tolerance to heat of monolayer MoS2 on SiO2 and h-BN.

We investigated the homogeneity and tolerance to heat of monolayer MoS2 using photoluminescence (PL) spectroscopy. For MoS2 on SiO2, the PL spectra of the basal plane differ from those of the edge, but MoS2 on hexagonal boron nitride (h-BN) was electron-depleted with a homogeneous PL spectra over the entire area. Annealing at 450 °C rendered MoS2 on SiO2 homogeneously electron-depleted over the entire area by creating numerous defects; moreover, annealing at 550 °C and subsequent laser irradiation on the MoS2 monolayer caused a loss of its inherent crystal structure. On the other hand, monolayer MoS2 on h-BN was preserved up to 550 °C with its PL spectra not much changed compared with MoS2 on SiO2. We performed an experiment to qualitatively compare the binding energies between various layers, and discuss the tolerance of monolayer MoS2 to heat on the basis of interlayer/interfacial binding energy.

Graphene bubbles and their role in graphene quantum transport.

Graphene bubbles are often formed when graphene and other layered two-dimensional materials are vertically stacked as van der Waals heterostructures. Here, we investigate how graphene bubbles and their related disorder impact the quantum transport behavior of graphene in the absence and presence of external magnetic fields. By combining experimental observations and numerical simulations, we find that the disorder induced by the graphene bubbles is mainly from p-type dopants and the charge transport in pristine graphene can be severely influenced by the presence of bubbles via long- and short-range scattering even with a small bubble-coverage of 2% and below. Upon bubble density increase, we observe an overall decrease in carrier mobility, and the appearance of a second Dirac point on the electron carrier side. At high magnetic fields, the disorder from graphene bubbles primarily impacts the quantization of the lowest Landau level, resulting in quantum Hall features associated with a new Dirac cone at high charge carrier density.

Vibrational Properties of h-BN and h-BN-Graphene Heterostructures Probed by Inelastic Electron Tunneling Spectroscopy.

Inelastic electron tunneling spectroscopy is a powerful technique for investigating lattice dynamics of nanoscale systems including graphene and small molecules, but establishing a stable tunnel junction is considered as a major hurdle in expanding the scope of tunneling experiments. Hexagonal boron nitride is a pivotal component in two-dimensional Van der Waals heterostructures as a high-quality insulating material due to its large energy gap and chemical-mechanical stability. Here we present planar graphene/h-BN-heterostructure tunneling devices utilizing thin h-BN as a tunneling insulator. With much improved h-BN-tunneling-junction stability, we are able to probe all possible phonon modes of h-BN and graphite/graphene at Γ and K high symmetry points by inelastic tunneling spectroscopy. Additionally, we observe that low-frequency out-of-plane vibrations of h-BN and graphene lattices are significantly modified at heterostructure interfaces. Equipped with an external back gate, we can also detect high-order coupling phenomena between phonons and plasmons, demonstrating that h-BN-based tunneling device is a wonderful playground for investigating electron-phonon couplings in low-dimensional systems.