Interface Properties of MoS2 van der Waals Heterojunctions with GaN.

The combination of the unique physical properties of molybdenum disulfide (MoS2) with those of gallium nitride (GaN) and related group-III nitride semiconductors have recently attracted increasing scientific interest for the realization of innovative electronic and optoelectronic devices. A deep understanding of MoS2/GaN interface properties represents the key to properly tailor the electronic and optical behavior of devices based on this heterostructure. In this study, monolayer (1L) MoS2 was grown on GaN-on-sapphire substrates by chemical vapor deposition (CVD) at 700 °C. The structural, chemical, vibrational, and light emission properties of the MoS2/GaN heterostructure were investigated in detail by the combination of microscopic/spectroscopic techniques and ab initio calculations. XPS analyses on as-grown samples showed the formation of stoichiometric MoS2. According to micro-Raman spectroscopy, monolayer MoS2 domains on GaN exhibit an average n-type doping of (0.11 ± 0.12) × 1013 cm-2 and a small tensile strain (ε ≈ 0.25%), whereas an intense light emission at 1.87 eV was revealed by PL analyses. Furthermore, a gap at the interface was shown by cross-sectional TEM analysis, confirming the van der Waals (vdW) bond between MoS2 and GaN. Finally, density functional theory (DFT) calculations of the heterostructure were carried out, considering three different configurations of the interface, i.e., (i) an ideal Ga-terminated GaN surface, (ii) the passivation of Ga surface by a monolayer of oxygen (O), and (iii) the presence of an ultrathin Ga2O3 layer. This latter model predicts the formation of a vdW interface and a strong n-type doping of MoS2, in closer agreement with the experimental observations.

Large-Area MoS2 Films Grown on Sapphire and GaN Substrates by Pulsed Laser Deposition.

In this paper, we present the preparation of few-layer MoS2 films on single-crystal sapphire, as well as on heteroepitaxial GaN templates on sapphire substrates, using the pulsed laser deposition (PLD) technique. Detailed structural and chemical characterization of the films were performed using Raman spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction measurements, and high-resolution transmission electron microscopy. According to X-ray diffraction studies, the films exhibit epitaxial growth, indicating a good in-plane alignment. Furthermore, the films demonstrate uniform thickness on large areas, as confirmed by Raman spectroscopy. The lateral electrical current transport of the MoS2 grown on sapphire was investigated by temperature (T)-dependent sheet resistance and Hall effect measurements, showing a high n-type doping of the semiconducting films (ns from ~1 × 1013 to ~3.4 × 1013 cm-2 from T = 300 K to 500 K), with a donor ionization energy of Ei = 93 ± 8 meV and a mobility decreasing with T. Finally, the vertical current injection across the MoS2/GaN heterojunction was investigated by means of conductive atomic force microscopy, showing the rectifying behavior of the I-V characteristics with a Schottky barrier height of ϕB ≈ 0.36 eV. The obtained results pave the way for the scalable application of PLD-grown MoS2 on GaN in electronics/optoelectronics.

Multiscale Investigation of the Structural, Electrical and Photoluminescence Properties of MoS2 Obtained by MoO3 Sulfurization.

In this paper, we report a multiscale investigation of the compositional, morphological, structural, electrical, and optical emission properties of 2H-MoS2 obtained by sulfurization at 800 °C of very thin MoO3 films (with thickness ranging from ~2.8 nm to ~4.2 nm) on a SiO2/Si substrate. XPS analyses confirmed that the sulfurization was very effective in the reduction of the oxide to MoS2, with only a small percentage of residual MoO3 present in the final film. High-resolution TEM/STEM analyses revealed the formation of few (i.e., 2-3 layers) of MoS2 nearly aligned with the SiO2 surface in the case of the thinnest (~2.8 nm) MoO3 film, whereas multilayers of MoS2 partially standing up with respect to the substrate were observed for the ~4.2 nm one. Such different configurations indicate the prevalence of different mechanisms (i.e., vapour-solid surface reaction or S diffusion within the film) as a function of the thickness. The uniform thickness distribution of the few-layer and multilayer MoS2 was confirmed by Raman mapping. Furthermore, the correlative plot of the characteristic A1g-E2g Raman modes revealed a compressive strain (ε ≈ -0.78 ± 0.18%) and the coexistence of n- and p-type doped areas in the few-layer MoS2 on SiO2, where the p-type doping is probably due to the presence of residual MoO3. Nanoscale resolution current mapping by C-AFM showed local inhomogeneities in the conductivity of the few-layer MoS2, which are well correlated to the lateral changes in the strain detected by Raman. Finally, characteristic spectroscopic signatures of the defects/disorder in MoS2 films produced by sulfurization were identified by a comparative analysis of Raman and photoluminescence (PL) spectra with CVD grown MoS2 flakes.

Indium Nitride at the 2D Limit.

The properties of 2D InN are predicted to substantially differ from the bulk crystal. The predicted appealing properties relate to strong in- and out-of-plane excitons, high electron mobility, efficient strain engineering of their electronic and optical properties, and strong application potential in gas sensing. Until now, the realization of 2D InN remained elusive. In this work, the formation of 2D InN and measurements of its bandgap are reported. Bilayer InN is formed between graphene and SiC by an intercalation process in metal-organic chemical vapor deposition (MOCVD). The thickness uniformity of the intercalated structure is investigated by conductive atomic force microscopy (C-AFM) and the structural properties by atomic resolution transmission electron microscopy (TEM). The coverage of the SiC surface is very high, above 90%, and a major part of the intercalated structure is represented by two sub-layers of indium (In) bonded to nitrogen (N). Scanning tunneling spectroscopy (STS) measurements give a bandgap value of 2 ± 0.1 eV for the 2D InN. The stabilization of 2D InN with a pragmatic wide bandgap and high lateral uniformity of intercalation is demonstrated.

Dynamic strain in gold nanoparticle supported graphene induced by focused laser irradiation.

Graphene on noble-metal nanostructures constitutes an attractive nanocomposite with possible applications in sensors or energy conversion. In this work we study the properties of hybrid graphene/gold nanoparticle structures by Raman spectroscopy and scanning probe methods. The nanoparticles (NPs) were prepared by local annealing of gold thin films using a focused laser beam. The method resulted in a patterned surface, with NPs formed at arbitrarily chosen microscale areas. Graphene grown by chemical vapour deposition was transferred onto the prepared, closely spaced gold NPs. While we found that successive higher intensity (6 mW) laser irradiation increased gradually the doping and the defect concentration in SiO2 supported graphene, the same irradiation procedure did not induce such irreversible effects in the graphene supported by gold NPs. Moreover, the laser irradiation induced a dynamic hydrostatic strain in the graphene on Au NPs, which turned out to be completely reversible. These results can have implications in the development of graphene/plasmonic nanoparticle based high temperature sensors operating in dynamic regimes.

The Only Blue Mimeresia (Lepidoptera: Lycaenidae: Lipteninae) Uses a Color-Generating Mechanism Widely Applied by Butterflies.

The butterfly Mimeresia neavei (Joicey & Talbot, 1921) is the only species in the exclusively African subtribal clade Mimacraeina (Lipteninae: Lycaenidae: Lepidoptera) having sexual dimorphism expressed by structurally blue-colored male and pigmentary colored orange-red female phenotypes. We investigated the optical mechanism generating the male blue color by various microscopic and experimental methods. It was found that the blue color is produced by the lower lamina of the scale acting as a thin film. This kind of color production is not rare in day-flying Lepidoptera, or in other insect orders. The biological role of the blue color of M. neavei is not yet well understood, as all the other species in the clade lack structural coloration, and have less pronounced sexual dimorphism, and are involved in mimicry-rings.

Time dependent decomposition of ammonia borane for the controlled production of 2D hexagonal boron nitride.

Ammonia borane (AB) is among the most promising precursors for the large-scale synthesis of hexagonal boron nitride (h-BN) by chemical vapour deposition (CVD). Its non-toxic and non-flammable properties make AB particularly attractive for industry. AB decomposition under CVD conditions, however, is complex and hence has hindered tailored h-BN production and its exploitation. To overcome this challenge, we report in-depth decomposition studies of AB under industrially safe growth conditions. In situ mass spectrometry revealed a time and temperature-dependent release of a plethora of NxBy-containing species and, as a result, significant changes of the N:B ratio during h-BN synthesis. Such fluctuations strongly influence the formation and morphology of 2D h-BN. By means of in situ gas monitoring and regulating the precursor temperature over time we achieve uniform release of volatile chemical species over many hours for the first time, paving the way towards the controlled, industrially viable production of h-BN.

Publisher Correction: Time dependent decomposition of ammonia borane for the controlled production of 2D hexagonal boron nitride.

A correction to this article has been published and is linked from the HTML version of this paper. The error has been fixed in the paper.

Rapid epitaxy-free graphene synthesis on silicidated polycrystalline platinum.

Large-area synthesis of high-quality graphene by chemical vapour deposition on metallic substrates requires polishing or substrate grain enlargement followed by a lengthy growth period. Here we demonstrate a novel substrate processing method for facile synthesis of mm-sized, single-crystal graphene by coating polycrystalline platinum foils with a silicon-containing film. The film reacts with platinum on heating, resulting in the formation of a liquid platinum silicide layer that screens the platinum lattice and fills topographic defects. This reduces the dependence on the surface properties of the catalytic substrate, improving the crystallinity, uniformity and size of graphene domains. At elevated temperatures growth rates of more than an order of magnitude higher (120 µm min(-1)) than typically reported are achieved, allowing savings in costs for consumable materials, energy and time. This generic technique paves the way for using a whole new range of eutectic substrates for the large-area synthesis of 2D materials.

Morphology--composition correlations in carbon nanotubes synthesised with nitrogen and phosphorus containing precursors.

We have correlated the elemental composition with the structure of multi-wall carbon nanotubes synthesised with nitrogen and phosphorus containing precursors and identified two chemically distinct dominant morphologies. The first type are cone-structured tubes and the second are nanotubes with fewer walls which can accommodate N2 gas along their inner channel and contain up to ten times more nitrogen than the cone-structured nanotubes. Phosphorus was present in the catalyst particles but was not detected within the walls of either type of nanotube. Elemental analysis combined with in situ electrical measurements has allowed us to monitor the evolution of the doped nanotubes when current is passed. The N2 gas becomes bonded immediately when current flows and the gas-containing nanotubes restructure more easily than the cone-structured ones. Since the inclusion of heteroatoms in multi-wall carbon nanotubes is generally inhomogeneous, understanding the distribution of elements across the sample is an important step towards the optimization of devices including gas sensors and components in electrical applications.

WS2 2D nanosheets in 3D nanoflowers.

In this work it has been established that 3D nanoflowers of WS2 synthesised by chemical vapour deposition are composed of few layer WS2 along the edges of the petals. An experimental study in order to understand the evolution of these nanostructures shows the nucleation and growth along with the compositional changes they undergo.

A graphene surface force balance.

We report a method for transferring graphene, grown by chemical vapor deposition, which produces ultraflat graphene surfaces (root-mean-square roughness of 0.19 nm) free from polymer residues over macroscopic areas (>1 cm(2)). The critical step in preparing such surfaces involves the use of an intermediate mica template, which itself is atomically smooth. We demonstrate the compatibility of these model surfaces with the surface force balance, opening up the possibility of measuring normal and lateral forces, including friction and adhesion, between two graphene sheets either in contact or across a liquid medium. The conductivity of the graphene surfaces allows forces to be measured while controlling the surface potential. This new apparatus, the graphene surface force balance, is expected to be of importance to the future understanding of graphene in applications from lubrication to electrochemical energy storage systems.

In situ engineering of NanoBud geometries.

NanoBuds exist in a variety of stable structures. Our studies show that engineering NanoBud geometries is indeed possible and we visualise the transformation of one Nanobud geometry to another using in situ aberration corrected imaging techniques. Such NanoBuds are precursors for generating nanotube junctions which could be used in composite and electronic applications.

Probing the bonding in nitrogen-doped graphene using electron energy loss spectroscopy.

Precise control of graphene properties is an essential step toward the realization of future graphene devices. Defects, such as individual nitrogen atoms, can strongly influence the electronic structure of graphene. Therefore, state-of-the-art characterization techniques, in conjunction with modern modeling tools, are necessary to identify these defects and fully understand the synthesized material. We have directly visualized individual substitutional nitrogen dopant atoms in graphene using scanning transmission electron microscopy and conducted complementary electron energy loss spectroscopy experiments and modeling which demonstrates the influence of the nitrogen atom on the carbon K-edge.

Controlled growth of Ni nanocrystals on SrTiO(3) and their application in the catalytic synthesis of carbon nanotubes.

Truncated pyramid-shaped Ni nanocrystals were epitaxially grown on SrTiO(3)(001) surfaces and characterised by scanning tunneling microscopy (STM). These nanocrystals were shown to be catalytically active for the synthesis of carbon nanotubes (CNTs). The narrow size distribution of the Ni nanocrystals results in a similar narrow distribution of CNT diameters.

Controlling the orientation, edge geometry, and thickness of chemical vapor deposition graphene.

We report that the shape, orientation, edge geometry, and thickness of chemical vapor deposition graphene domains can be controlled by the crystallographic orientations of Cu substrates. Under low-pressure conditions, single-layer graphene domains align with zigzag edges parallel to a single <101> direction on Cu(111) and Cu(101), while bilayer domains align to two directions on Cu(001). Under atmospheric pressure conditions, hexagonal domains also preferentially align. This discovery can be exploited to generate high-quality, tailored graphene with controlled domain thickness, orientations, edge geometries, and grain boundaries.

Boron-mediated nanotube morphologies.

The "doping" of carbon nanotubes with heteroatoms is an established method of controlling their properties. However, variations in heteroatom concentration in multiwalled carbon nanotubes (MWCNTs) tend to produce nanotubes with different morphologies, and hence varying properties, within the same sample. Electron energy loss spectroscopy in conjunction with imaging using a scanning transmission electron microscope (STEM) is a powerful tool to precisely map the spatial variation and bonding state of heteroatoms, e.g., B, N, P, Si, or combinations of these, present in carbon nanotubes exhibiting different structures. TEM analysis revealed that B incorporation during MWCNT growth (B-MWCNTs) results in nanotube morphologies that can be divided into three different types. These include core-shell structures possessing a B-rich core of cones and a C outer layer, B-containing cone structures, and MWCNTs with an irregular inner channel. In situ studies were carried out using Nanofactory() holder experiments in order to investigate the properties of individual B-MWCNTs and to show that the three types of nanotubes undergo different current-induced breakdown. The inhomogeneity in composition, structure, and properties of B-MWCNTs could result from the variation in chemical composition and temperature within the furnace, and this work highlights the importance of developing synthesis techniques that can control the inclusion of heteroatoms into nanotubes.

Facile, fast, and inexpensive synthesis of monodisperse amorphous nickel-phosphide nanoparticles of predefined size.

Monodisperse, size-controlled Ni-P nanoparticles were synthesised in a single step process using triphenyl-phosphane (TPP), oleylamine (OA), and Ni(II)acetyl-acetonate. The nanoparticles were amorphous, contained ~30 at% P and their size was controlled between 7-21 nm simply by varying the amount of TPP. They are catalytically active for tailored carbon nanotube growth.

Interconnecting carbon nanotubes with an inorganic metal complex.

Intermolecular carbon nanotube junctions were formed through amide linkage of amino functionalized multiwall carbon nanotubes and [Ru (dcbpy)(bpy)2](PF6)2, an inorganic metal complex. Nanotube interconnects were visualized using atomic force microscopy. Absorption and emission spectroscopy showed significant changes between starting products and the resulting ruthenium nanotube complex, indicative of successful chemical modification.