Ultrathin 2D Photodetectors Utilizing Chemical Vapor Deposition Grown WS₂ With Graphene Electrodes

In this report, graphene (Gr) is used as a 2D electrode and monolayer WS₂ as the active semiconductor in ultrathin photodetector devices. All of the 2D materials are grown by chemical vapor deposition (CVD) and thus pose as a viable route to scalability. The monolayer thickness of both electrode and semiconductor gives these photodetectors ∼2 nm thickness. We show that graphene is different to conventional metal (Au) electrodes due to the finite density of states from the Dirac cones of the valence and conduction bands, which enables the photoresponsivity to be modulated by electrostatic gating and light input control. We demonstrate lateral Gr–WS₂–Gr photodetectors with photoresponsivities reaching 3.5 A/W under illumination power densities of 2.5 × 10⁷ mW/cm². The performance of monolayer WS₂ is compared to bilayer WS₂ in photodetectors and we show that increased photoresponsivity is achieved in the thicker bilayer WS₂ crystals due to increased optical absorption. This approach of incorporating graphene electrodes in lateral TMD based devices provides insights on the contact engineering in 2D optoelectronics, which is crucial for the development of high performing ultrathin photodetector arrays for versatile applications

Separation of Hydrogen Gas from Coal Gas by Graphene Nanopores

We designed a series of porous graphene as the separation membrane for hydrogen gas in coal gas. The permeation process of different gas molecules (H₂, CO, CH₄, and H₂S) in porous graphene was evaluated under the atmospheric pressure and high pressure conditions. Our results indicate the hydrogen permeability and selectivity could be tuned by the size and the shape of the porous graphene. For graphene with bigger pores, the selectivity for hydrogen gas could decrease. In the porous graphene with same pore area, the hydrogen gas selectivity could be affected by the shape of the pore. The potential of mean force (PMF) of different gases to pass through a good separation candidate was calculated. The order of PMF for different gases to pass through the good separation candidate is H₂ < CO < CH₄ ≈ H₂S, which is also confirmed by the first-principle density function theory (DFT) calculation

<i>In Situ</i> Atomic Level Dynamics of Heterogeneous Nucleation and Growth of Graphene from Inorganic Nanoparticle Seeds

An <i>in situ</i> heating holder inside an aberration-corrected transmission electron microscope (AC-TEM) is used to investigate the real-time atomic level dynamics associated with heterogeneous nucleation and growth of graphene from Au nanoparticle seeds. Heating monolayer graphene to an elevated temperature of 800 °C removes the majority of amorphous carbon adsorbates and leaves a clean surface. The aggregation of Au impurity atoms into nanoparticle clusters that are bound to the surface of monolayer graphene causes nucleation of secondary graphene layers from carbon feedstock present within the microscope chamber. This enables the <i>in situ</i> study of heterogeneous nucleation and growth of graphene at the atomic level. We show that the growth mechanism consists of alternating C cluster attachment and indentation filling to maintain a uniform growth front of lowest energy. Back-folding of the graphene growth front is observed, followed by a process that involves flipping back and attaching to the surrounding region. We show how the highly polycrystalline graphene seed evolves with time into a higher order crystalline structure using a combination of AC-TEM and tight-binding molecular dynamics (TBMD) simulations. This helps understand the detailed lowest-energy step-by-step pathways associated with grain boundaries (GB) migration and crystallization processes. We find the motion of the GB is discontinuous and mediated by both bond rotation and atom evaporation, supported by density functional theory calculations and TBMD. These results provide insights into the formation of crystalline seed domains that are generated during bottom-up graphene synthesis

Europa und das Meer. Deutsches Historisches Museum, Berlin 13 June 2018 &#8211; 06 January 2019

The atomic structure of subnanometer pores in graphene, of interest due to graphene’s potential as a desalination and gas filtration membrane, is demonstrated by atomic resolution aberration corrected transmission electron microscopy. High temperatures of 500 °C and over are used to prevent self-healing of the pores, permitting the successful imaging of open pore geometries consisting of between −4 to −13 atoms, all exhibiting subnanometer diameters. Picometer resolution bond length measurements are used to confirm reconstruction of five-membered ring projections that often decorate the pore perimeter, knowledge which is used to explore the viability of completely self-passivated subnanometer pore structures; bonding configurations where the pore would not require external passivation by, for example, hydrogen to be chemically inert

<i>In Situ</i> Atomic Level Dynamics of Heterogeneous Nucleation and Growth of Graphene from Inorganic Nanoparticle Seeds

An <i>in situ</i> heating holder inside an aberration-corrected transmission electron microscope (AC-TEM) is used to investigate the real-time atomic level dynamics associated with heterogeneous nucleation and growth of graphene from Au nanoparticle seeds. Heating monolayer graphene to an elevated temperature of 800 °C removes the majority of amorphous carbon adsorbates and leaves a clean surface. The aggregation of Au impurity atoms into nanoparticle clusters that are bound to the surface of monolayer graphene causes nucleation of secondary graphene layers from carbon feedstock present within the microscope chamber. This enables the <i>in situ</i> study of heterogeneous nucleation and growth of graphene at the atomic level. We show that the growth mechanism consists of alternating C cluster attachment and indentation filling to maintain a uniform growth front of lowest energy. Back-folding of the graphene growth front is observed, followed by a process that involves flipping back and attaching to the surrounding region. We show how the highly polycrystalline graphene seed evolves with time into a higher order crystalline structure using a combination of AC-TEM and tight-binding molecular dynamics (TBMD) simulations. This helps understand the detailed lowest-energy step-by-step pathways associated with grain boundaries (GB) migration and crystallization processes. We find the motion of the GB is discontinuous and mediated by both bond rotation and atom evaporation, supported by density functional theory calculations and TBMD. These results provide insights into the formation of crystalline seed domains that are generated during bottom-up graphene synthesis

<i>In Situ</i> Atomic Level Dynamics of Heterogeneous Nucleation and Growth of Graphene from Inorganic Nanoparticle Seeds

An <i>in situ</i> heating holder inside an aberration-corrected transmission electron microscope (AC-TEM) is used to investigate the real-time atomic level dynamics associated with heterogeneous nucleation and growth of graphene from Au nanoparticle seeds. Heating monolayer graphene to an elevated temperature of 800 °C removes the majority of amorphous carbon adsorbates and leaves a clean surface. The aggregation of Au impurity atoms into nanoparticle clusters that are bound to the surface of monolayer graphene causes nucleation of secondary graphene layers from carbon feedstock present within the microscope chamber. This enables the <i>in situ</i> study of heterogeneous nucleation and growth of graphene at the atomic level. We show that the growth mechanism consists of alternating C cluster attachment and indentation filling to maintain a uniform growth front of lowest energy. Back-folding of the graphene growth front is observed, followed by a process that involves flipping back and attaching to the surrounding region. We show how the highly polycrystalline graphene seed evolves with time into a higher order crystalline structure using a combination of AC-TEM and tight-binding molecular dynamics (TBMD) simulations. This helps understand the detailed lowest-energy step-by-step pathways associated with grain boundaries (GB) migration and crystallization processes. We find the motion of the GB is discontinuous and mediated by both bond rotation and atom evaporation, supported by density functional theory calculations and TBMD. These results provide insights into the formation of crystalline seed domains that are generated during bottom-up graphene synthesis

Elongated Silicon–Carbon Bonds at Graphene Edges

We study the bond lengths of silicon (Si) atoms attached to both armchair and zigzag edges using aberration corrected transmission electron microscopy with monochromation of the electron beam. An <i>in situ</i> heating holder is used to perform imaging of samples at 800 °C in order to reduce chemical etching effects that cause rapid structure changes of graphene edges at room temperature under the electron beam. We provide detailed bond length measurements for Si atoms both attached to edges and also as near edge substitutional dopants. Edge reconstruction is also involved with the addition of Si dopants. Si atoms bonded to the edge of graphene are compared to substitutional dopants in the bulk lattice and reveal reduced out-of-plane distortion and bond elongation. An extended linear array of Si atoms at the edge is found to be energy-favorable due to inter-Si interactions. These results provide detailed structural information about the Si–C bonds in graphene, which may have importance in future catalytic and electronic applications

Atomically Flat Zigzag Edges in Monolayer MoS₂ by Thermal Annealing

The edges of 2D materials show novel electronic, magnetic, and optical properties, especially when reduced to nanoribbon widths. Therefore, methods to create atomically flat edges in 2D materials are essential for future exploitation. Atomically flat edges in 2D materials are found after brittle fracture or when electrically biasing, but a simple scalable approach for creating atomically flat periodic edges in monolayer 2D transition metal dichalcogenides has yet to be realized. Here, we show how heating monolayer MoS₂ to 800 °C in vacuum produces atomically flat Mo terminated zigzag edges in nanoribbons. We study this at the atomic level using an ultrastable in situ heating holder in an aberration-corrected transmission electron microscope and discriminating Mo from S at the edge, revealing unique Mo terminations for all zigzag orientations that remain stable and atomically flat when cooling back to room temperature. Highly faceted MoS₂ nanoribbon constrictions are produced with Mo rich edge structures that have theoretically predicted spin separated transport channels, which are promising for spin logic applications

Atomically Flat Zigzag Edges in Monolayer MoS₂ by Thermal Annealing

The edges of 2D materials show novel electronic, magnetic, and optical properties, especially when reduced to nanoribbon widths. Therefore, methods to create atomically flat edges in 2D materials are essential for future exploitation. Atomically flat edges in 2D materials are found after brittle fracture or when electrically biasing, but a simple scalable approach for creating atomically flat periodic edges in monolayer 2D transition metal dichalcogenides has yet to be realized. Here, we show how heating monolayer MoS₂ to 800 °C in vacuum produces atomically flat Mo terminated zigzag edges in nanoribbons. We study this at the atomic level using an ultrastable in situ heating holder in an aberration-corrected transmission electron microscope and discriminating Mo from S at the edge, revealing unique Mo terminations for all zigzag orientations that remain stable and atomically flat when cooling back to room temperature. Highly faceted MoS₂ nanoribbon constrictions are produced with Mo rich edge structures that have theoretically predicted spin separated transport channels, which are promising for spin logic applications

Atomically Flat Zigzag Edges in Monolayer MoS₂ by Thermal Annealing

The edges of 2D materials show novel electronic, magnetic, and optical properties, especially when reduced to nanoribbon widths. Therefore, methods to create atomically flat edges in 2D materials are essential for future exploitation. Atomically flat edges in 2D materials are found after brittle fracture or when electrically biasing, but a simple scalable approach for creating atomically flat periodic edges in monolayer 2D transition metal dichalcogenides has yet to be realized. Here, we show how heating monolayer MoS₂ to 800 °C in vacuum produces atomically flat Mo terminated zigzag edges in nanoribbons. We study this at the atomic level using an ultrastable in situ heating holder in an aberration-corrected transmission electron microscope and discriminating Mo from S at the edge, revealing unique Mo terminations for all zigzag orientations that remain stable and atomically flat when cooling back to room temperature. Highly faceted MoS₂ nanoribbon constrictions are produced with Mo rich edge structures that have theoretically predicted spin separated transport channels, which are promising for spin logic applications