Controllable Atomic Scale Patterning of Freestanding Monolayer Graphene at Elevated Temperature

Controllable Atomic Scale Patterning of Freestanding Monolayer Graphene at Elevated Temperature

Dr. Qiang Xu

Kavli Institute of Nanoscience, Delft University of Technology,The Netherlands Authors | Qiang Xu, Meng-Yue Wu, Grégory F. Schneider, Lothar Houben, Sairam K. Malladi, Cees Dekker, Emrah Yucelen, Rafal E. Dunin-Borkowski and Henny W. Zandbergen. Email |  h.w.zandbergen@tudelft.nl

Application Controllable Atomic Scale Patterning of Freestanding Monolayer Graphene at Elevated Temperature
Authors Qiang Xu, Meng-Yue Wu, Grégory F. Schneider, Lothar Houben, Sairam K. Malladi, Cees Dekker, Emrah Yucelen, Rafal E. Dunin-Borkowski and Henny W. Zandbergen.
Journal ACS Nano, 2013, 7 (2), pp 1566–1572
Sample Graphene
Topic Contamination Free, 2D Materials, Soft Matter, E-Beam Sensitive Imaging
Field Material Science, Chemistry, Electronics, Life Science
Techniques HRTEM, HRSTEM, EELS, Diffraction
Keywords Graphene; Controlled Sculpting; Nondestructive Imaging; Nanopatterning; Self-repair
Publication / D.O.I. Full Publication Here – DOI: 10.1021/nn3053582

Controllable Atomic Scale Patterning of Freestanding Monolayer Graphene at Elevated Temperature

ABSTRACT: In order to harvest the many promising properties of graphene in (electronic) applications, a technique is required to cut, shape, or sculpt the material on the nanoscale without inducing damage to its atomic structure, as this drastically influences the electronic properties of the nanostructure. Here, we reveal a temperature-dependent self-repair mechanism that allows near-damage-free atomic-scale sculpting of graphene using a focused electron beam. We demonstrate that by sculpting at temperatures above 600 C, an intrinsic self-repair mechanism keeps the graphene in a single-crystalline state during cutting, even though the electron beam induces considerable damage. Self-repair is mediated by mobile carbon ad-atoms that constantly repair the defects caused by the electron beam. Our technique allows reproducible fabrication and simultaneous imaging of single-crystalline free-standing nanoribbons, nanotubes, nanopores, and single carbon chains.

FIGURE ABOVE: Annular dark field STEM images of graphene ribbon arrays sculpted in a reproducible way by using a script-controlled electron beam at elevated temperature. After the first sculpting process, the patterns were imaged as shown in (a). Next, each ribbon was reduced in width precisely, and image (b) was acquired. Intensity line profiles across the ribbon outlined by the white frames in (a) and (b) are shown in (c) and (d), respectively. The width of the ribbon is estimated to be 4.0 nm after initial sculpting and 1.9 nm after final sculpting.

DENSsolutions Comments

Objective & Goal

Graphene, carbon nanotube and other soft-mater materials suffers irradiation damage caused by high energy electron beam during TEM characterization. The e-beam damage limits the observation time or observation electron beam condition, thus requiring a way to prevent. Moreover, application of graphene needs to patterning graphene into various functional devices with nano-size geometry. The e-beam induced damage can be utilized for creating a lithography method for graphene patterning. Achieving control of e-beam damage of graphene becomes an essential topic.

Benefit

DENSsolutions heating system provides the extreme high stability of sample at elevated temperature (sample spatial drift less than 0.5nm/min) At the elevated temperature, the e-beam induced defects of the sample can be repaired with a corresponding speed, therefore, provides an extra parameter for control of e-beam damage.

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Atomic Resolution Imaging and Spectroscopy of Barium Atoms and Functional Groups on Graphene Oxide

Atomic Resolution Imaging and Spectroscopy of Barium Atoms and Functional Groups on Graphene Oxide

Dr. Chris B. Boothroyd

Ernst Ruska-Centre for Microscopy and Spectroscopy with Electrons and Peter Grünberg Institute, Germany Authors | C.B. Boothroyda, M.S. Morenob, M. Duchampa, A. Kovácsa, N. Mongec, G.M. Moralesc, C.A. Barberoc, R.E. Dunin-Borkowskia Emailc.boothroyd@fz-juelich.de

Application Atomic Resolution Imaging and Spectroscopy of Barium Atoms and Functional Groups on Graphene Oxide
Authors C.B. Boothroyda, M.S. Morenob, M. Duchampa, A. Kovácsa, N. Mongec, G.M. Moralesc, C.A. Barberoc, R.E. Dunin-Borkowskia
Journal Ultramicroscopy Journal, 2014
Sample Graphene
Topic Contamination Free, 2D Materials, Soft Matter, E-Beam Sensitive Imaging
Techniques HRTEM, HRSTEM, EELS, Diffraction
Keywords Graphene oxide; Functional groups; Scanning transmission electron microscopy; Transmission electron microscopy; Spectrum imaging; Atomic resolution; Single atom imaging
Publication / D.O.I. Full Publication Here

Atomic Resolution Imaging and Spectroscopy of Barium Atoms and Functional Groups on Graphene Oxide

ABSTRACT: We present an atomic resolution transmission electron microscopy(TEM) and scanning TEM(STEM) study of the local structure and composition of graphene oxide modified with Ba2+. In our experiments, which are carried out at 80kV,the acquisition of contamination-free high-resolution STEM images is only possible while heating the sample above 400C using a highly stable heating holder. Ba atoms are identified spectroscopically in electron energy-loss spectrum images taken at 800C and are associated with bright contrast in high-angle annular dark-field STEM images. The spectrum images also show that Ca and O occur together and that Ba is not associated with a significant concentration of O. The electron dose used for spectrum imaging results in beam damage to the specimen, even at elevated temperature. It is also possible to identify Ba atoms in high-resolution TEM images acquired using shorter exposure times at room temperature, thereby allowing the structure of graphene oxide to be studied using complementary TEM and STEM techniques over a wide range of temperatures.
FIGURE ABOVE: HAADF STEM images acquired at a specimen temperature of 800 C (a) before and (b) after recording the spectrum image (the total time of spectrum imaging is 800s). The area of spectrum imaging is marked by the box. While the area surrounding the box is relatively unchanged after acquiring the spectrum image (except for a small drift and local distortion), the area from which the spectrum image was acquired has changed significantly.
FIGURE ABOVE: Color images created  from a selection of  the spectrum images which  were acquired  from graphene  oxide with  Ba  imaged at a temperature of 800 C by using STEM spectrum imaging method. The  images show the spatial relationships between the elements, corresponding to the following colours: (a)  Ba red and C cyan; (b)  O red and C cyan; (c) Ca red and C cyan; (d)  Ba red, Ca green and C blue. The  spectrum image shows that Ba, O and Ca are present mostly in the areas where the C is thinnest and that Ca and O have very similar distributions.

DENSsolutions Comments:

Graphene, graphene-like two dimensional and other soft-mater materials attract  increasing research efforts. Characterization of these type of materials in TEM, however, suffers contamination problems and e-beam damage.
Contamination, referring to the build-up of decomposed carbon on a specimen, heavily influences the quality of electron microscopy imaging. Graphene  and graphene-like two dimensional materials suffer contamination the most because of two reasons 1. these materials are ultrathin, with low image contrast,  the build up contamination contrast blur the original contrast easily; 2. these materials are with large surface area, easier to absorb hydrocarbon, water to form contamination under e-beam.
DENSsolutions heating system provides the opportunity to image these samples free of contamination at elevated temperature, without sacrificing the quality/resolution of imaging. The extreme high stability of DENSsolutions heating system (sample spatial drift less than 0.5nm/min) can even allow the researchers using a long exposure time (5s-8s) to  image the individual carbon atoms for improving the contrast. Furthermore, the low drift allows chemical sensitive spectrum imaging to be carried down to atomic level.

Download the full publication here at the Ultramicroscopy (2014) Journal

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Temperature Dependence of the Reconstruction of Zigzag Edges in Graphene

Temperature Dependence of the Reconstruction of Zigzag Edges in Graphene

Drs. Kuang He

Department of Materials, University of Oxford Authors | Kuang He, Alex W. Robertson, Ye Fan, Christopher S. Allen, Yung-Chang Lin, Kazu Suenaga, Angus I. Kirkland and Jamie H. Warner. Email |  jamie.warner@materials.ox.ac.uk

Application Temperature Dependence of the Reconstruction of Zigzag Edges in Graphene
Authors Kuang He, Alex W. Robertson, Ye Fan, Christopher S. Allen, Yung-Chang Lin, Kazu Suenaga, Angus I. Kirkland and Jamie H. Warner.
Journal ACS Nano, 2015
Publication Full Publication Here – DOI: 10.1021/acsnano.5b01130

Temperature Dependence of the Reconstruction of Zigzag Edges in Graphene

ABSTRACT: We examine the temperature dependence of graphene edge terminations at the atomic scale using an in situ heating holder within an aberration-corrected transmission electron microscope. The relative ratios of armchair, zigzag, and reconstructed zigzag edges from over 350 frames at each temperature are measured. Below 400 C, the edges are dominated by zigzag terminations, but above 600 C, this changes dramatically, with edges dominated by armchair and reconstructed zigzag edges.
We show that at low temperature chemical etching effects dominate and cause deviation to the thermodynamics of the system. At high temperatures (600 and 800 C), adsorbates are evaporated from the surface of graphene and chemical etching effects are significantly reduced, enabling the thermodynamic distribution of edge types to be observed. The growth rate of holes at high temperature is also shown to be slower than at room temperature, indicative of the reduced chemical etching process. These results provide important insights into hthe role of chemical etching effects in the hole formation, edge sputtering, and edge reconstruction in graphene.
Figure above: Edge behavior at room temperature (∼25 C). (ac) Three typical HRTEM images of graphene holes at that temperature. The edges are color-coded to differentiate the types of edge configurations. Red represents armchair; yellow is zigzag, and green is Rec. 57; white indicatesmixed or unidentified edge types. The inset in (a) and (b) shows typical long-ordered zigzag and armchair configurations at this temperature. The statistics for three examples are shown in (d); the percentages of edges occupied by different types of edges are ranked accordingly: black columns represent panel (a), red columns panel (b), and blue columns panel (c). (e,f) Long-ordered zigzag edge from both bulk of graphene and edge of a nanoribbon, respectively. (g) Representative long-ordered armchair edge found at this temperature. The o iginal image ofwhich (eg) are cropped fromthose shown in Figure S1ac of Supporting Information. All scale bars are 1 nm.

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Controlling Defects in Graphene for Optimizing the Electrical Properties of Graphene Nanodevices

Controlling Defects in Graphene for Optimizing the Electrical Properties of Graphene Nanodevices

Dr. Leonardo Vicarelli

Kavli Institute of Nanoscience, Delft University of Technology, 2628 CJ Delft, The Netherlands
Authors | Leonardo Vicarelli, Stephanie J. Heerema, Cees Dekker, and Henny W. Zandbergen Email | l.vicarelli@tudelft.nl

Application Controlling Defects in Graphene for Optimizing the Electrical Properties of Graphene Nanodevices
Authors Leonardo Vicarelli, Stephanie J. Heerema, Cees Dekker, and Henny W. Zandbergen
Journal ACS Nano, 2015
Publication Full Publication Here – DOI:10.1021/acsnano.5b01762

Controlling Defects in Graphene for Optimizing the Electrical Properties of Graphene Nanodevices

Abstract: Structural defects strongly impact the electrical transport properties of graphene nanostructures. In this Perspective, we give a brief overview of different types of defects in graphene and their effect on transport properties. We discuss recent experimental progress on graphene self-repair of defects, with a focus on in situ transmission electron microscopy studies. Finally, we present the outlook for graphene self-repair and in situ experiments.

Figure 1. Structural defects in graphene. (ad) High-resolution transmission electron microscopy (HRTEM) images of (a) StoneWales defect, (b) defect-free graphene, (c) single vacancy with 59 rings, (d) divacancy with 585 rings. Scale bar is 1 nm. (eh) HRTEM image sequence of divacancy migration observed at 80 keV. Scale bar is 1 nm. Reprinted with permission from ref 13. Copyright 2011 American Physical Society. (i) Scanning transmission microscopy image of a single N atom dopant in graphene on a copper foil substrate. (Inset) Line profile across the dopant shows atomic corrugation and apparent height of the dopant. Reprinted with permission from ref 15. Copyright 2011 American Association for the Advancement of Science. (l,m) HRTEM images of a Pt atom trapped in divacancy and (n) simulated HRTEM image for the Pt vacancy complex. Scale bar is 1 nm. Reprinted from ref 14. Copyright 2012 American Chemical Society.

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Graphene-Skeleton Heat-Coordinated and Nanoamorphous-Surface-State Controlled Pseudo-Negative-Photoconductivity of Tiny SnO2 Nanoparticles

Graphene-Skeleton Heat-Coordinated and Nanoamorphous-Surface-State Controlled Pseudo-Negative-Photoconductivity of Tiny SnO2 Nanoparticles

Drs. Longwei Ding

Center for Nanoscale Characterization and Devices, Wuhan National Laboratory for Optoelectronics, Huazhong University of Science and Technology, China
Authors | Longwei Ding , Nishuang Liu , Luying Li , Xing Wei , Xianghui Zhang , Jun Su , Jiangyu Rao , Congxing Yang , Wenzhi Li , Jianbo Wang , Haoshuang Gu , and Yihua Gao Email | gaoyihua@hust.edu.cn

Application Graphene-Skeleton Heat-Coordinated and Nanoamorphous- Surface-State Controlled Pseudo-Negative-Photoconductivity of Tiny SnO 2 Nanoparticles
Authors Longwei Ding , Nishuang Liu , Luying Li , Xing Wei , Xianghui Zhang , Jun Su , Jiangyu Rao , Congxing Yang , Wenzhi Li , Jianbo Wang , Haoshuang Gu , and Yihua Gao
Journal Advanced Materials. 2015
Publication Full Publication Here – DOI: 10.1002/adma.201500804

Graphene-Skeleton Heat-Coordinated and Nanoamorphous- Surface-State Controlled Pseudo-Negative-Photoconductivity of Tiny SnO 2 Nanoparticless

Abstract: SnO2 nanoparticles display a pseudo-negative-photoconductivity (PsdNPC) effect, which shows that their resistance increases under light irradiation via a heating effect. The PsdNPC originates from intensive electron scattering of the nanoamorphous surface state of the SnO2nanoparticles, resulting in a small inner current and a large absorption of moisture, leading to a large surface current. Graphene as the inner skeleton can shorten the response and recovery times.

IMAGE RIGHT: The schematic for working PsdNPC mechanism. a) The schematic for combining PPC effect by exciting electrons and the NPC effect by heating for an optoelectronic device. b) A thermodynamic 1D Fourier model for analyzing the heat transfer of the device under light irradiation heating. c) The schematic of shortening the response time of heating effect by decreasing the sizes of the device and the irradiation beam diameter, and increasing the thermal conductivity k of its substrate. d) Graphene can be used to decrease the response time because of its connected architectures, highest heat conductivity, and thus good heat coordination between different nanoparticles.
The SnO 2 nanoparticle has an amorphous surface shell yellow) and crystallized core (purple). e,f) The moisture molecules are released and absorbed with temperature increase and decrease, and surface conductivity becomes worse and better, respectively.

Download the full publication here at the Advanced Materials Journal

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