WO2008118799A1 - Procédé de formation de nanotubes - Google Patents

Procédé de formation de nanotubes Download PDF

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Publication number
WO2008118799A1
WO2008118799A1 PCT/US2008/057885 US2008057885W WO2008118799A1 WO 2008118799 A1 WO2008118799 A1 WO 2008118799A1 US 2008057885 W US2008057885 W US 2008057885W WO 2008118799 A1 WO2008118799 A1 WO 2008118799A1
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WO
WIPO (PCT)
Prior art keywords
atoms
films
thin films
nanotube
thin film
Prior art date
Application number
PCT/US2008/057885
Other languages
English (en)
Inventor
Feng Liu
Decai Yu
Original Assignee
The University Of Utah Research Foundation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The University Of Utah Research Foundation filed Critical The University Of Utah Research Foundation
Priority to US12/593,125 priority Critical patent/US20100119434A1/en
Publication of WO2008118799A1 publication Critical patent/WO2008118799A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/02—Single-walled nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/36—Diameter

Definitions

  • This invention pertains generally to the formation of nanotubes from thin films, such as graphene sheets and silicon films, using atomic adsorption.
  • the present invention provides methods for forming nanotubes from thin films using atomic adsorption to induce bending of the films.
  • the films comprises a single graphene sheet (i.e., a "graphene nanoribbon")
  • the methods may be used to form single-walled carbon nanotubes (SWNTs).
  • SWNTs single-walled carbon nanotubes
  • the methods of the present invention eliminate the need for any post-synthesis steps, allow mass production of nanotubes of uniform size and chirality and offer easy integration of the nanotubes into nanodevices on a substrate.
  • One embodiment of the invention provides a method for forming the nanotubes.
  • a thin film is patterned onto a substrate.
  • Atoms such as hydrogen (H) and fluorine (F) atoms, are adsorbed to the surface of the film, inducing surface stress that bends the film downward, away from the adsorbed atoms.
  • the radius of curvature of the nanotubes may be controlled through the selection of appropriate adsorbants and surface coverages.
  • chemical bond such as covalent bond
  • FIG. 1 shows the formation of SWNTs using first-principles molecular dynamics ("MD") simulations.
  • a 1.7 nm wide graphene nanoribbon is patterned onto a graphite substrate (a(l)). H atoms are adsorbed to a surface coverage of 50% (a(2)). The adsorbed atoms cause the nanoribbon to bend into a SWNT (a(3)-(5)).
  • FIGs. lb(l)-(5) show the formation of a SWNT from a 2.0 nm wide graphene nanoribbon and adsorption of F atoms to a surface coverage of 45%.
  • FIG. 2 shows the formation of SWNTs using classical MD simulations.
  • a 1.6-nm-wide (3.5, 3.5) graphene nanoribbon is patterned onto a graphite substrate and H atoms are adsorbed to a surface coverage of 50% (a(l)).
  • the adsorbed atoms cause the nanoribbon to bend into a (4,4) armchair SWNT (a(2)-(3)).
  • the adsorbed atoms are Atty. Dkt. No.: 083404-0140 desorbed at high temperature (a(4)-(6)).
  • FIG. 2c shows a sideview of the resulting armchair SWNT.
  • FIG. 2b(l)-(6) show the formation of a (14,0) zigzag SWNT from a 3.3-nm-wide (13,0) graphene nanoribbon and adsorption of H atoms to a surface coverage of 45%.
  • FIG. 2d is a sideview of the resulting zigzag SWNT.
  • FIG. 3 shows the formation of SWNTs from two layers of graphene nanoribbons using classical MD simulations.
  • Two 1.6-nm-wide and 1.1-nm-wide graphene nanoribbons are patterned onto a graphite substrate and H atoms are adsorbed to the top layer graphene nanoribbon to a surface coverage of 50% (a(l)).
  • the adsorbed atoms cause the nanoribbons to bend until the carbon atoms at the edges of the two graphene sheets covalently bond together into a SWNT (a(2)).
  • Atoms are desorbed at high temperature (a(3)).
  • FIGs. 3b(l)-(3) show the formation of a larger SWNT from two 3.1-nm-wide and 2.6-nm-wide graphene nanoribbons and adsorption of H atoms to a surface coverage of 50%.
  • FIG. 4 includes schematics of H adsorption on graphene nanoribbons (a, b, and d), and theoretical calculations relating to the adsorption of H atoms on graphene nanoribbons (c, e).
  • FIG. 5 depicts the bending of a graphene nanoribbon where the nanoribbon width W is much greater than the circumference 2 ⁇ R of the SWNT.
  • the present invention provides methods for forming nanotubes from thin films.
  • the films are desirably a single atom thick, as in the case of graphene nanoribbons, or only a few (e.g., 2-10) atomic layers thick, as in the case of semiconductor, metal, or other material films.
  • the methods involve the adsorption of atoms onto the surface of the films.
  • the adsorbed atoms introduce a surface stress, inducing a curvature in the films.
  • edges of the thin films are brought into contact with each other, or with edges of other thin films. Covalent bonds form between the edges, resulting in nanotube formation.
  • the method for forming a nanotube comprises three steps.
  • a first step a thin film is patterned onto a substrate.
  • Various substrate materials may be used, including graphite.
  • the film may comprise a variety of different shapes having different dimensions.
  • the width of the thin films will depend on the desired diameter of the nanotubes. In some embodiments, the width is in the range of 1 to 20 run. In other embodiments, the width is in the range of 1 to 10 nm. In yet other embodiments, the width is in the range of 1 to 2 nm.
  • the length of the films, while not critical to the method, is generally many times greater than the width of the nanoribbon.
  • the films may be defined using semiconductor processing techniques, such as lithography, patterning and etching. This is advantageous because it provides an inexpensive parallel process capable of making many identical, or different, sized films in a single run.
  • semiconductor processing techniques such as lithography, patterning and etching. This is advantageous because it provides an inexpensive parallel process capable of making many identical, or different, sized films in a single run.
  • stacks of many layers of graphene may be defined in the substrate.
  • each graphene layer in the stack provides a separate thin film.
  • atoms are adsorbed to its surface. Atoms or combinations of atoms may be adsorbed onto the films. Many different atoms may be used for this purpose. The only requirement is that the selected atoms introduce a surface stress on the thin film that induces a curvature in the film when they are absorbed onto the film. As a result, film edges are brought together, where they undergo covalent or other chemical bonding to form nanotubes.
  • the adsorbed atoms are selected from the group consisting of H atoms, F atoms, and combinations thereof.
  • the adsorption step can provide different surface coverages of adsorbed atoms. Because the degree of surface coverage will affect the radius of curvature, the degree of surface coverage will depend on the desired diameter of the nanotubes. In some embodiments, the surface coverage is in the range of about 40% to 60%.
  • the adsorption step may be accomplished at room temperature.
  • the adsorbed atoms are desorbed from the surface of the film.
  • Desorption may be accomplished at a high temperature.
  • the desorption of H atoms from a graphene sheet may be carried out at 600 K or higher. Atty. Dkt. No.: 083404-0140
  • the nanotubes are formed from a single thin film, whereby the adsorbent-induced curvature causes opposing edges of the film to meet and form covalent or other chemical bonds. Examples 1 and 2, below, illustrate this variation of the method.
  • a nanotube is formed from a plurality (e.g., two) of layered thin films.
  • atoms are adsorbed onto the surface of one or more of the films, causing the edges of the films to contact and form covalent and other chemical bonds, resulting in the formation of a closed tube.
  • the widths of the two nanoribbons are substantially the same, while in other embodiments the widths are different.
  • the driving force for the formation of nanotubes from films according to the present invention is the stress induced by the adsorption of atoms on the surface of the films.
  • the thinner the film the larger the bending curvature, and the smaller the radius of the bending curvature.
  • the magnitude of the bending curvature can be controlled by adjusting the coverage of adsorbed atoms to tune the magnitude of the surface-adsorption- induced stress. This is illustrated for the case of a graphene nanoribbon in FIG. 4. As illustrated in FIG. 4a, first-principle MD calculations show that the preferred H adsorption site on a graphene nanoribbon is on top of a carbon atom. As depicted in FIG. 4b, H adsorption leads to a transition of the bonding configuration of the underlying carbon atom from sp 2 to sp 3 .
  • the appropriate surface coverage will determine the width of the patterned nanoribbon.
  • W should approximate 2 ⁇ R, where R is the radius of bending curvature as defined by the surface coverage of adsorbed atoms.
  • R is the radius of bending curvature as defined by the surface coverage of adsorbed atoms.
  • the patterned graphene nanoribbon is not a free-standing film, but is weakly bonded to the underlying substrate through van der Waals attractive forces.
  • the surface stress induced by atomic adsorption should be large enough to overcome this attraction in order for the graphene nanoribbon to detach from the underlying substrate during the bending process.
  • Example 1 Simulation of SWNTs using first-principles MD simulations
  • FIG. la(2) shows the graphene nanoribbon detaching from the underlying graphite substrate.
  • FIG. la(5) shows the opposite edges of the graphene nanoribbon bonded together to form an SWNT.
  • FIGs. lb(l)-(5) illustrate the simulation of an SWNT using a 2.0 nm wide graphene nanoribbon and adsorption of F atoms to a surface coverage of 45%.
  • FIG. 2a shows snapshots of the formation of a 0.5-nm-diameter (4,4) armchair SWNT.
  • a 1.6-nm-wide, (3.5,3.5) graphene nanoribbon was patterned onto a graphite substrate comprised of two graphite layers.
  • H atoms were adsorbed to the surface of the graphene nanoribbon at room temperature to a coverage of 50% (FIG. 2a(l)).
  • Tube formation is shown in FIG. 2a(2)-(3).
  • the SWNT was heated to 1800 K to desorb the surface H atoms (FIG. 2a(4)-(6)).
  • FIG. 2(c) A sideview of the armchair SWNT is shown in FIG. 2(c).
  • FIGs. 2b(l)-(6) illustrate the formation of a 0.9-nm-diameter (14,0) zigzag SWNT, using a 3.3-nm-wide, (13,0) graphene nanoribbon and adsorption of H atoms to 45% surface coverage.
  • FIG. 2(d) shows a sideview of the zigzag SWNT.
  • Example 3 Simulation of SWNTs from two layers of graphene nanoribbons
  • FIG. 3a(3) illustrates the formation of a 2.2-nm-diameter SWNT using a 3.1-nm-wide, top-layer graphene nanoribbon and a 2.6-nm-wide, bottom-layer graphene nanoribbon and adsorption of H atoms to 50% coverage.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

L'invention concerne des procédés de formation d'un nanotube à partir de films minces. Le procédé implique l'absorption d'atomes à la surface des films. Les atomes absorbés introduisent une contrainte de surface, induisant une courbure dans les films. La courbure est suffisante pour amener des atomes au niveau des bords et à proximité suffisamment étroite pour former des liaisons covalentes. D'autres procédés comporte une étape de désorption des atomes de la surface du film. Les films peuvent inclure une variété de nanomatériaux, y compris des feuilles de graphène et des films minces de semi-conducteur.
PCT/US2008/057885 2007-03-26 2008-03-21 Procédé de formation de nanotubes WO2008118799A1 (fr)

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US12/593,125 US20100119434A1 (en) 2007-03-26 2008-03-21 Method of forming nanotubes

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US90803907P 2007-03-26 2007-03-26
US60/908,039 2007-03-26

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WO2016201101A1 (fr) * 2015-06-09 2016-12-15 William Marsh Rice University Réseaux de nanotubes de carbone contenant du soufre utilisés en tant qu'électrodes

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040247516A1 (en) * 2001-12-18 2004-12-09 Lisa Pfefferle Growth of nanostructures with controlled diameter
US6949237B2 (en) * 1997-03-07 2005-09-27 William Marsh Rice University Method for growing single-wall carbon nanotubes utlizing seed molecules
US20050238565A1 (en) * 2004-04-27 2005-10-27 Steven Sullivan Systems and methods of manufacturing nanotube structures

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US7595111B2 (en) * 2002-02-20 2009-09-29 Joseph Dale Udy Methods to continuous, monoatomic thick structures
GB2385864A (en) * 2002-02-28 2003-09-03 Qinetiq Ltd Production of nanocarbons
WO2005019104A2 (fr) * 2003-08-18 2005-03-03 President And Fellows Of Harvard College Fabrication controlee de nanotubes et utilisations des nanotubes
EP1724380B1 (fr) * 2004-03-11 2016-06-15 Teijin Limited Fibre de carbone
US7858876B2 (en) * 2007-03-13 2010-12-28 Wisconsin Alumni Research Foundation Graphite-based photovoltaic cells

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6949237B2 (en) * 1997-03-07 2005-09-27 William Marsh Rice University Method for growing single-wall carbon nanotubes utlizing seed molecules
US7108841B2 (en) * 1997-03-07 2006-09-19 William Marsh Rice University Method for forming a patterned array of single-wall carbon nanotubes
US20040247516A1 (en) * 2001-12-18 2004-12-09 Lisa Pfefferle Growth of nanostructures with controlled diameter
US20050238565A1 (en) * 2004-04-27 2005-10-27 Steven Sullivan Systems and methods of manufacturing nanotube structures

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