Two-dimensional Atomic Sheets Research Articles

Microwave Synthesized 2D Gold and Its 2D-2D Hybrids.

Xenes, i.e., monoelemental two-dimensional atomic sheets, are promising for sensitive and ultrafast sensor applications owing to exceptional carrier mobility; however, most of them oxidize below 500 °C and therefore cannot be employed for high-temperature applications. 2D gold, an oxidation-resistant plasmonic Xene, is extremely promising. 2D gold was experimentally realized by both atomic layer deposition and chemical synthesis using sodium citrate. However, it is imperative to develop a new facile single-step method to synthesize 2D gold. Here, liquid-phase synthesis of 2D gold is demonstrated by microwave exposure to auric chloride dispersed in dimethylformamide. Microscopies (AFM and high-resolution TEM), spectroscopies (Raman, UV-vis, and X-ray photoelectron), and X-ray diffraction establish the formation of a hexagonal crystallographic phase for 2D gold. 2D-2D hybrids of 2D gold have also been synthesized and investigated for electronic/optoelectronic behaviors and SERS-based molecular sensing. DFT band structure calculation for 2D gold and its hybrids corroborates the experimental findings.

Abnormal Optoelectric Properties of Two-Dimensional Protonic Ruthenium Oxide with a Hexagonal Structure.

Two-dimensional structures can potentially lead to not only modulation of electron transport but also the variations of optical property. Protonic ruthenium oxide, a two-dimensional atomic sheet material, has been synthesized, and its optoelectric properties have been investigated. The results indicate that protonic ruthenium oxide is an excellent candidate for use as a flexible, transparent conducting material. A hydrated-ruthenium-oxide sheet has been first prepared via the chemical exfoliation of sodium intercalated ruthenium oxide (NaRuO2) and, subsequently, converted into a protonic ruthenium oxide sheet using thermal treatment. A thermally activated transport mechanism is dominant in hydrated ruthenium oxide but diminishes in protonic ruthenium oxide; this resulted in a high electrical conductivity of ∼200 S/cm of the protonic sheet. Because of the unique interband and intraband structure, protonic ruthenium oxide has a small optical absorption coefficient of ∼1.62%/L. Consequently, such high conductivity and low absorption coefficient of protonic ruthenium oxide results in excellent transparent conducting properties.

全反射高速陽電子回折法（TRHEPD）による最表面構造解析

Total-reflection high-energy positron diffraction (TRHEPD) is a surface-sensitive tool owing to the total reflection of positrons. Since the sign of the crystal potential energy for positrons is positive, opposite to that for electrons, the positron beam at a grazing incidence is totally reflected at a crystal surface. The penetration depth of the positron beam in the total reflection region is estimated to be about a few Å, which corresponds to the thickness of 1-2 atomic layers. Thus, the positron beam in the total reflection region sees only the topmost surface layer of the crystal. Slightly over the critical angle for the total reflection, the positon beam also sees the underlying surface layer. Adjusting the glancing angle of the incident positron beam, the diffraction intensity selectively contains information about the topmost and the underlying surface layers without any effect from the bulk. Therefore, the TRHEPD is very useful for structure determinations of crystal surface and two-dimensional atomic sheet adsorbed on the substrate. In this paper, we will show the surface-sensitivity of the TRHEPD. Shown is also the recent result of silicene, two-dimensional atomic sheet of silicon, using the TRHEPD.

Work function variation of MoS2 atomic layers grown with chemical vapor deposition: The effects of thickness and the adsorption of water/oxygen molecules

The electrical properties of two-dimensional atomic sheets exhibit remarkable dependences on layer thickness and surface chemistry. Here, we investigated the variation of the work function properties of MoS2 films prepared with chemical vapor deposition (CVD) on SiO2 substrates with the number of film layers. Wafer-scale CVD MoS2 films with 2, 4, and 12 layers were fabricated on SiO2, and their properties were evaluated by using Raman and photoluminescence spectroscopies. In accordance with our X-ray photoelectron spectroscopy results, our Kelvin probe force microscopy investigation found that the surface potential of the MoS2 films increases by ∼0.15 eV when the number of layers is increased from 2 to 12. Photoemission spectroscopy (PES) with in-situ annealing under ultra high vacuum conditions was used to directly demonstrate that this work function shift is associated with the screening effects of oxygen or water molecules adsorbed on the film surface. After annealing, it was found with PES that the surface potential decreases by ∼0.2 eV upon the removal of the adsorbed layers, which confirms that adsorbed species have a role in the variation in the work function.

Structure determination of two-dimensional atomic sheet of silicene using TRHEPD

This study reports determination of the atomic coordinates of a two-dimensional atomic sheet, silicene, by using total reflection high-energy positron diffraction (TRHEPD) [1]. TRHEPD method, formerly called as RHEPD, is a surface-sensitive tool owing to the total reflection of positrons. Since the sign of the potential energy for positrons in crystals is positive, opposite to that for the electrons, the positron beam at a grazing incidence are totally reflected at a crystal surface. The penetration depth of the positron beam in the total reflection region is estimated to be approximately a few Å, which corresponds to the thickness of 1-2 atomic layers. Thus, the positron beam selectively sees the topmost surface layer and hence the TRHEPD method is very useful for structure determinations of crystal surface and two-dimensional atomic sheet on the substrate. Silicene is a two-dimensional atomic sheet of silicon. Since the silicene has an intriguing property such as a Dirac cone like a graphene, it attracts increasing attention as a candidate for future devices. Recently, the synthesis of silicene on a Ag(111) surface was successfully performed [2]. Although the atomic coordinates of the silicene in this system was theoretically calculated, they were not confirmed experimentally. It is very important to experimentally determine the magnitude of the buckling in silicene and the spacing between the bottom of the silicene and the substrate because the dispersion of the Dirac cone is closely related to these structure parameters. We thus investigated the atomic positions of the silicene on the Ag(111) surface using the TRHEPD [3]. From the rocking curve analysis based on the dynamical diffraction theory of positrons (see figure), the existence of the buckling (0.83 Å) in silicene was verified experimentally. Moreover, the spacing between the silicene and the substrate was determined as 2.17 Å. The structural difference with the graphene will be also discussed.

Enhanced Chemical Reactivity of Graphene Induced by Mechanical Strain

Control over chemical reactivity is essential in the field of nanotechnology. Graphene is a two-dimensional atomic sheet of sp(2) hybridized carbon with exceptional properties that can be altered by chemical functionalization. Here, we transferred single-layer graphene onto a flexible substrate and investigated the functionalization using different aryl diazonium molecules while applying mechanical strain. We found that mechanical strain can alter the structure of graphene, and dramatically increase the reaction rate, by a factor of up to 10, as well as increase the final degree of functionalization. Furthermore, we demonstrate that mechanical strain enables functionalization of graphene for both p- and n-type dopants, where unstrained graphene showed negligible reactivity. Theoretical calculations were also performed to support the experimental findings. Our findings offer a simple approach to control the chemical reactivity of graphene through the application of mechanical strain, allowing for a tuning of the properties of graphene.

Graphene Field-Effect Transistors Based on Boron–Nitride Dielectrics

Two-dimensional atomic sheets of graphene represent a new class of nanoscale materials with potential applications in electronics. However, exploiting the intrinsic characteristics of graphene devices has been problematic due to impurities and disorder in the surrounding dielectric and graphene/dielectric interfaces. Recent advancements in fabricating graphene heterostructures by alternately layering graphene with crystalline hexagonal boron nitride (hBN), its insulating isomorph, have led to an order of magnitude improvement in graphene device quality. Here, recent developments in graphene devices utilizing boron-nitride dielectrics are reviewed. Field-effect transistor (FET) characteristics of these systems at high bias are examined. Additionally, existing challenges in material synthesis and fabrication and the potential of graphene/BN heterostructures for novel electronic applications are discussed.

Strain-Engineering of Band Gaps in Piezoelectric Boron Nitride Nanoribbons

Two-dimensional atomic sheets such as graphene and boron nitride monolayers represent a new class of nanostructured materials for a variety of applications. However, the intrinsic electronic structure of graphene and h-BN atomic sheets limits their direct application in electronic devices. By first-principles density functional theory calculations we demonstrate that band gap of zigzag BN nanoribbons can be significantly tuned under uniaxial tensile strain. The unexpected sensitivity of band gap results from reduced orbital hybridization upon elastic strain. Furthermore, sizable dipole moment and piezoelectric effect are found in these ribbons owing to structural asymmetry and hydrogen passivation. This will offer new opportunities to optimize two-dimensional nanoribbons for applications such as electronic, piezoelectric, photovoltaic, and opto-electronic devices.

Patterning of graphene

Two-dimensional atomic sheets of carbon (graphene, graphane, etc.) are amenable to unique patterning schemes such as cutting, bending, folding and fusion that are predicted to lead to interesting properties. In this review, we present theoretical understanding and processing routes for patterning graphene and highlight potential applications. With more precise and scalable patterning, the prospects of integrating flat carbon (graphene) with curved carbon (nanotubes and half nanotubes) and programmable graphene folding are envisioned.