Julio A Rodríguez-Manzo

University of Strasbourg, Strasburg, Alsace, France

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Publications (41)307.16 Total impact

  • [Show abstract] [Hide abstract]
    ABSTRACT: Graphene nanoribbons (GNRs) are promising candidates for next generation integrated circuit (IC) components; this fact motivates exploration of the relationship between crystallographic structure and transport of graphene patterned at IC-relevant length scales (< 10 nm). We report on the controlled fabrication of pristine, freestanding GNRs with widths as small as 0.7 nm, paired with simultaneous lattice-resolution imaging and electrical transport characterization, all conducted within an aberration-corrected transmission electron microscope. Few-layer GNRs very frequently formed bonded-bilayers and were remarkably robust, sustaining currents in excess of 1.5 μA per carbon bond across a 5 atom-wide ribbon. We found that the intrinsic conductance of a sub-10 nm bonded bilayer GNR scaled with width as GBL(w) ≈ ¾(e2/h)w, where w is the width in nm, while a monolayer GNR was roughly five times less conductive. Nanosculpted, crystalline monolayer GNRs exhibited armchair-terminated edges after current annealing, presenting a pathway for the controlled fabrication of semiconducting GNRs with known edge geometry. Finally, we report on simulations of quantum transport in GNRs that are in qualitative agreement with the observations.
    Nano Letters 06/2014; · 12.94 Impact Factor
  • Matthew Puster, Julio A Rodríguez-Manzo, Adrian Balan, Marija Drndic
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    ABSTRACT: Graphene-based nanopore devices are promising candidates for next-generation DNA sequencing. Here we fabricated graphene nanoribbon-nanopore (GNR-NP) sensors for DNA detection. Nanopores with diameters in the range of 2-10 nm were formed at the edge or in the center of graphene nanoribbons (GNRs), with widths between 20 and 250 nm and a length of 600 nm, on 40 nm thick silicon nitride (SiNx) membranes. GNR conductance was monitored in situ during electron irradiation-induced nanopore formation inside a transmission electron microscope (TEM) operating at 200 kV. We show that GNR resistance increases linearly with electron dose and that GNR conductance and mobility decrease by a factor of ten or more when GNRs are imaged at relatively high magnification with a broad beam prior to making a nanopore. By operating the TEM in scanning TEM (STEM) mode, in which the position of the converged electron beam can be controlled with high spatial precision via automated feedback, we were able to prevent electron beam-induced damage and make nanopores in highly conducting GNR sensors. This method minimizes the exposure of the GNRs to the beam before and during nanopore formation. The resulting GNRs with unchanged resistances after nanopore formation can sustain microampere currents at low voltages (∼ 50 mV) in buffered electrolyte solution and exhibit high sensitivity, with a large relative change of resistance upon changes of gate voltage, similar to pristine GNRs without nanopores.
    ACS Nano 11/2013; · 12.03 Impact Factor
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    ABSTRACT: Graphene-boron nitride monolayer heterostructures contain adjacent electrically active and insulating regions in a continuous, single-atom thick layer. To date structures were grown at low pressure, resulting in irregular shapes and edge direction, so studies of the graphene-boron nitride interface were restricted to microscopy of nano-domains. Here we report templated growth of single crystalline hexagonal boron nitride directly from the oriented edge of hexagonal graphene flakes by atmospheric pressure chemical vapor deposition, and physical property measurements that inform the design of in-plane hybrid electronics. Ribbons of boron nitride monolayer were grown from the edge of a graphene template and inherited its crystallographic orientation. The relative sharpness of the interface was tuned through control of growth conditions. Frequent tearing at the graphene-boron nitride interface was observed, so density functional theory was used to determine that the nitrogen-terminated interface was prone to instability during cool down. The electronic functionality of monolayer heterostructures was demonstrated through fabrication of field effect transistors with boron nitride as an in-plane gate dielectric.
    ACS Nano 11/2013; · 12.03 Impact Factor
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    ABSTRACT: Crystalline hexagonally ordered silicon oxide layers with a thickness of less than a nanometer are grown on transition metal surfaces in an in-situ electron microscopy experiment. The nucleation and growth of silica bilayers and monolayers, which represent the thinnest possible ordered structures of silicon oxide, are monitored in real time. The emerging layers show structural defects reminiscent of those in graphene, and can also be vitreous. First-principles calculations provide atomistic insight into the energetics of the growth process. The interplay between the gain in silica-metal interaction energy due to their epitaxial match and energy loss associated with the mechanical strain of silica network is addressed. The results of calculations indicate that both ordered and vitreous mono/bilayer structures are possible so that the actual morphology of the layer is defined by the kinetics of the growth process.
    ACS Nano 05/2013; · 12.03 Impact Factor
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    ABSTRACT: In the last two decades, new techniques that monitor ionic current modulations as single molecules pass through a nanoscale pore have enabled numerous single-molecule studies. While biological nanopores have recently shown the ability to resolve single nucleotides within individual DNA molecules, similar developments with solid-state nanopores have lagged, due to challenges both in fabricating stable nanopores of similar dimensions as biological nanopores and in achieving sufficiently low-noise and high-bandwidth recordings. Here we show that small silicon nitride nanopores (0.8 to 2-nm-diameter in 5 to 8-nm-thick membranes) can resolve differences between ionic current signals produced by short (30 base) ssDNA homopolymers (poly(dA), poly(dC), poly(dT)), when combined with measurement electronics that allow a signal-to-noise ratio of better than 10 to be achieved at 1 MHz bandwidth. While identifying intramolecular DNA sequences with silicon nitride nanopores will require further improvements in nanopore sensitivity and noise levels, homopolymer differentiation represents an important milestone in the development of solid-state nanopores.
    ACS Nano 04/2013; · 12.03 Impact Factor
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    ABSTRACT: The industry's march towards higher transistor density has called for an ever-increasing number of interconnect levels in logic devices. The historic transition from aluminum to copper was necessary in reducing timing delays while future technology nodes presents an opportunity for new materials and patterning techniques. One material for consideration is graphene, a single atomic layer of carbon atoms. Graphene is known to have excellent electrical properties [1], driving strong interest in its integration into the wafer fabrication processes for future electronics [2], and its ballistic transport properties give promise for use in on-chip interconnects [3]. This study demonstrates the feasibility of a direct electron beam lithography technique to pattern sub-5nm metallic graphene ribbons, without using a mask or photoresist, to act as next generation interconnects. Sub-5nm monolayer and multilayer graphene ribbons were patterned using a focused electron beam in a transmission electron microscope (TEM) through direct knock-on ejection of carbon atoms. These ribbons were measured during fabrication to quantify their electrical performance. Multilayered graphene nanoribbons were found to sustain current densities in excess of 109 A/cm2, orders of magnitude higher than copper, while monolayer graphene provides comparable performance to copper but at the level of a single atomic layer. High volume manufacturing could utilize wafer-size chemical vapor deposition (CVD) graphene [4] transferred directly onto the substrate paired with a direct write multi-beam tool to knock off carbon atoms for patterning of nanometer sized interconnects. The patterning technique introduced here allows for the fabrication of small foot-print high performance next generation graphene interconnects that bypass the use of a mask and resist process.
    Proceedings of SPIE - The International Society for Optical Engineering 03/2013; · 0.20 Impact Factor
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    ABSTRACT: We report electronic measurements on high quality single layer junction-confined graphene nanoribbons fabricated in a transmission electron microscope (TEM). In this work, a process is demonstrated for the fabrication and confirmation of pristine single layer graphene nanoribbons using high vacuum current annealing and precision nano-sculpting, both conducted within the vacuum chamber of a TEM. Briefly, CVD-grown graphene is patterned into a freely-suspended nanoribbon connected to large area contacts. The sample is then mounted on a TEM holder with electrical feedthroughs to allow for simultaneous imaging and in-situ electrical transport measurements within the TEM. A focused electron beam is used to progressively narrow the ribbon, providing a platform to controllably sculpt and define the device geometry while characterizing its electrical properties. In-situ electrical measurements and TEM imaging with sub-nm resolution revealed the dependence of the nanoribbon resistance as a function of width in the range 17 -- 280 nm. Monolayer graphene were found to sustain current densities in excess of 5 x 10^9 A/cm^2, orders of magnitude higher than copper while the conductance varied approximately as w^0.75, where w is the ribbon width in nanometers. These results demonstrates graphene's potential as a next generation, high performance interconnects material with the ability to reach single-digit technology nodes at the level of a single atomic layer.
  • Kimberly Venta, Gabriel Shemer, Julio A. Rodríguez-Manzo, Marija Drndić
    Biophysical Journal 01/2013; 104(2):523-. · 3.83 Impact Factor
  • J. A. Rodríguez-Manzo, F. Banhart
    Microscopy and Microanalysis 07/2012; 18(S2):1492-1493. · 1.76 Impact Factor
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    Julio A Rodríguez-Manzo, Arkady V Krasheninnikov, Florian Banhart
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    ABSTRACT: Carbon atoms are displaced in pre-selected locations of carbon nanotubes by using a focused electron beam in a scanning transmission electron microscope. Sub-nanometer-sized holes are created that change the morphology of double and triple-walled carbon nanotubes and connect the shells in a unique way. By combining in situ transmission electron microscopy experiments with atomistic simulations, we study the bonding between defective shells in the new structures which are reminiscent of the shape of a flute. We demonstrate that in double-walled nanotubes the shells locally merge by forming nanoarches while atoms with dangling bonds can be preserved in triple-walled carbon nanotubes. In the latter system, nanoarches are formed between the inner- and outermost shells, shielding small graphenic islands with open edges between the neighboring shells. Our results indicate that arrays of quantum dots may be produced in carbon nanotubes by spatially localized electron irradiation, generating atoms with dangling bonds that may give rise to localized magnetic moments.
    ChemPhysChem 03/2012; 13(10):2596-600. · 3.36 Impact Factor
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    ABSTRACT: Single-walled carbon nanotubes (SWCNTs) containing traces of iron oxide were functionalized by noncovalent lipid-PEG or covalent carboxylic acid function to supply new efficient MRI contrast agents for in vitro and in vivo applications. Longitudinal (r(1)) and transversal (r(2)) water proton relaxivities were measured at 300 MHz, showing a stronger T(2) feature as an MRI contrast agent (r(2)/r(1)  = 190 for CO(2) H functionalisation). The r(2) relaxivity was demonstrated to be correlated to the presence of iron oxide in the SWNT-carboxylic function COOH, in comparison to iron-free ones. Biodistribution studies on mice after a systemic injection showed a negative MRI contrast in liver, suggesting the presence of the nanotubes in this organ until 48 h after i.v. injection. The presence of carbon nanotubes in liver was confirmed after ex vivo carbon extraction. Finally, cytotoxicity studies showed no apparent effect owing to the presence of the carbon nanotubes. The functionalized carbon nanotubes were well tolerated by the animals at the dose of 10 µg g(-1) body weight.
    Contrast Media & Molecular Imaging 03/2012; 7(2):153-9. · 2.87 Impact Factor
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    O Cretu, J A Rodríguez-Manzo, A Demortière, F Banhart
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    ABSTRACT: Nanocrystals of different metals with sizes of 2–6 nm are deposited on graphene, carbon nanotubes, or amorphous carbon films. Irradiation with a highly focused electron beam is used to split clusters of a few metal atoms (<1 nm in diameter) from the crystals. The metal clusters follow the electron beam spot on the graphitic surface when the beam is slowly deflected away from the clusters. This unusual behaviour of metals on graphitic sur-faces is explained in terms of electron beam-induced activation of the graphitic surfaces and covalent bonding between metal and carbon atoms. The technique might be applicable in (sub-)nanometre structuring of graphene with metal dots.
    Carbon 09/2011; 50(1). · 6.16 Impact Factor
  • Julio A. Rodríguez-Manzo, Florian Banhart
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    ABSTRACT: Thin Co and Ni lamellae grow under electron irradiation of metal crystals supported on multilayer graphene or amorphous carbon films. The lateral growth of a lamella from a source crystal is achieved by directing an electron beam to the periphery of the metal crystal and moving the beam over the surrounding carbon. Patterns of linear, branched, or ringlike metal lamellae can be created. The patterning is carried out in situ in a transmission electron microscope, allowing simultaneous structuring and imaging. The process is driven by the metal-carbon interaction at a beam-activated carbon surface.
    Applied Physics Letters 05/2011; 98(18):183105-183105-3. · 3.52 Impact Factor
  • Julio A Rodríguez-Manzo, Cuong Pham-Huu, Florian Banhart
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    ABSTRACT: Single and few-layer graphene is grown by a solid-state transformation of amorphous carbon on a catalytically active metal. The process is carried out and monitored in situ in an electron microscope. It is observed that an amorphous carbon film is taken up by Fe, Co, or Ni crystals at temperatures above 600 °C. The nucleation and growth of graphene layers on the metal surfaces happen after the amorphous carbon film has been dissolved. It is shown that the transformation of the energetically less favorable amorphous carbon to the more favorable phase of graphene occurs by diffusion of carbon atoms through the catalytically active metal.
    ACS Nano 02/2011; 5(2):1529-34. · 12.03 Impact Factor
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    ABSTRACT: Reconstructed point defects in graphene are created by electron irradiation and annealing. By applying electron microscopy and density functional theory, it is shown that the strain field around these defects reaches far into the unperturbed hexagonal network and that metal atoms have a high affinity to the nonperfect and strained regions of graphene. Metal atoms are attracted by reconstructed defects and bonded with energies of about 2 eV. The increased reactivity of the distorted π-electron system in strained graphene allows us to attach metal atoms and to tailor the properties of graphene.
    Physical Review Letters 11/2010; 105(19):196102. · 7.73 Impact Factor
  • Julio A Rodríguez-Manzo, Ovidiu Cretu, Florian Banhart
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    ABSTRACT: Lattice defects in carbon nanotubes and graphene are created by focusing an electron beam in a scanning transmission electron microscope onto a 0.1 nm spot on the objects. Metal atoms migrating on the graphenic surfaces are observed to be trapped by these defects. Depending on the size of the defect, single metal atoms or clusters of several atoms can be localized in or on nanotubes or graphene layers. Subsequent escape of the metal atoms from the trapping centers gives information about the bonding between the metal atom and the defect. The process of trapping and detrapping is studied in a temperature range of 20-670 degrees C. The technique allows one to place metal atoms with almost atomic precision in graphenic structures and to create a predefined pattern of foreign atoms in graphene or carbon nanotubes.
    ACS Nano 06/2010; 4(6):3422-8. · 12.03 Impact Factor
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    ABSTRACT: Interfaces between the ends of single- or double-wall carbon nanotubes and metal crystals (Fe, Co, Pd, and Pt) are established by electron irradiation with nanometre precision at metal-nanotube contact areas. Calculations of the bonding energies at the metal-nanotube interfaces confirm that the formation of these covalent junctions is energetically favourable in the presence of a certain concentration of structural defects in the nanotubes. The process may be endothermic or exothermic in comparison with the unconnected configuration, but in either case atomic defects in carbon nanotubes are a necessary condition for joining them with metals.
    Nanoscale 06/2010; 2(6):901-5. · 6.74 Impact Factor
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    ABSTRACT: The nucleation and growth of single-walled carbon nanotubes is observed in situ in a transmission electron microscope. Carbon atoms are implanted into catalytically active metal particles by electron-beam sputtering. The metal particles are then shaped with a focused electron beam. Once the particles have a region of high surface curvature, spontaneous nucleation and growth of single-walled carbon nanotubes occurs on the metal particles. It is shown that the local solubility of carbon in the metal determines the nucleation of nanotubes. This is confirmed by atomistic computer simulations treating the solubility of carbon in a metal particle as a function of the size of the system.
    Small 10/2009; 5(23):2710-5. · 7.51 Impact Factor
  • Advanced Materials 09/2009; 21(44):4477 - 4482. · 15.41 Impact Factor
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    ABSTRACT: New methods of processing multiwall carbon nanotubes (CNTs) are demonstrated in experiments in the transmission electron microscope (TEM). These include precisely controllable cutting, repairing, and interconnecting of different CNTs with the assistance of an encapsulated Co particle. All processes involve the interactions between the metal and graphitic shells that are driven by combined electrical biasing [using a scanning-tunneling microscope (STM)-TEM setup] of the CNT and focused electron-beam irradiation of a Co-containing region. In particular, we present two CNT soldering processes, that is, Co-joined and Co-catalytic connections. The former process uses a Co particle as the central node to which two CNTs are covalently attached on the opposite sides, and the latter makes use of the segregation of new graphitic shells from the metal at the connecting site, resulting in CNT plumbing. We compare the mechanical robustness of both connection types by direct force measurements in the TEM using an integrated atomic force microscope (AFM) setup. They reveal a tensile strength of 4.2 and 31 GPa, respectively, thus demonstrating the superiority of the Co-catalytic connection whose strength is already comparable to standard CNTs. In addition, all connected nanotubes show metallic conduction. The developed methods could be of particular importance in future nanoelectronic device technology.
    ACS Nano 09/2009; 3(9):2632-8. · 12.03 Impact Factor

Publication Stats

727 Citations
307.16 Total Impact Points


  • 2012
    • University of Strasbourg
      Strasburg, Alsace, France
  • 2009–2012
    • Institut de Physique et Chimie des Matériaux de Strasbourg
      Strasburg, Alsace, France
    • National Institute for Materials Science
      • International Center for Materials Nanoarchitectonics (MANA)
      Tsukuba, Ibaraki-ken, Japan
  • 2004–2007
    • Instituto Potosino de Investigación Científica y Tecnológica
      • Department of Advanced Materials
      San Luis, San Luis Potosí, Mexico
  • 2006
    • Johannes Gutenberg-Universität Mainz
      • Institute of Physical Chemistry
      Mainz, Rhineland-Palatinate, Germany