Graphene growth from polymers

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  • ABSTRACT

    Graphene is a fascinating material with excellent electrical, optical, mechanical, and chemical properties. Remarkable progress has been made in the development of methods for synthesizing large-area, high-quality graphene. Recently, the chemical vapor deposition method has opened up the possibility of using graphene for electronic devices and other applications. This review covers simple and inexpensive methods to grow graphene using polymers as solid carbon sources; which do not require an additional process to transfer graphene from the growth substrate to the receiver substrate.

  • KEYWORD

    graphene , graphene synthesis , solid carbon sources , polymers

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  • [Fig. 1.] (a) Monolayer graphene is made by spin-coating and annealing solid poly(methyl methacrylate) (PMMA) films on Cu substrates at 800 to 1000℃ under an Ar-H2 gas mix; (b) Raman spectrum (514-nm excitation) of PMMA-derived graphene annealed at 1000℃; (c) IDS-VG curve of a PMMA-derived, graphenebased, back-gated field-effect transistor device (at room temperature). The top inset shows the IDS-VDS characteristics; VG changes from 0 V to -40 V. The bottom inset shows a scanning electron microscopy (JEOL-6500 microscope) image of the device in which the PMMA-derived graphene is perpendicular to the Pt leads. (IDS: drain-source current; VG: gate voltage; VDS: drain-source voltage); (d) Raman spectra varied by the number of sheets of PMMA-derived graphene with controllable thicknesses derived from different flow rates of H2 [26] (Reprinted with permission. Copyright 2010, Macmillan Publishers Limited).
    (a) Monolayer graphene is made by spin-coating and annealing solid poly(methyl methacrylate) (PMMA) films on Cu substrates at 800 to 1000℃ under an Ar-H2 gas mix; (b) Raman spectrum (514-nm excitation) of PMMA-derived graphene annealed at 1000℃; (c) IDS-VG curve of a PMMA-derived, graphenebased, back-gated field-effect transistor device (at room temperature). The top inset shows the IDS-VDS characteristics; VG changes from 0 V to -40 V. The bottom inset shows a scanning electron microscopy (JEOL-6500 microscope) image of the device in which the PMMA-derived graphene is perpendicular to the Pt leads. (IDS: drain-source current; VG: gate voltage; VDS: drain-source voltage); (d) Raman spectra varied by the number of sheets of PMMA-derived graphene with controllable thicknesses derived from different flow rates of H2 [26] (Reprinted with permission. Copyright 2010, Macmillan Publishers Limited).
  • [Fig. 2.] (a) Chemical structure of polymers used as graphene precursors; (b) graphene growth process; (c) Raman spectra of PAN-derived graphene film with a 50-nm-thick Ni capping layer annealed at 1000℃ (the capping layer is subsequently removed); (d) cross-sectional high-resolution transmission electron microscopy (HRTEM) image of graphenes formed on a SiO2/Si substrate outside the agglomerated Ni islands; (e) magnified HRTEM image and intensity profile across the graphenes; (f) Raman spectra of PAN-derived graphene with polymer layers of different thickness after removing the capping layer [29] (Reprinted with permission. Copyright 2011, American Chemical Society). PS: polystyrene, PAN: polyacrylonitrile, PMMA: poly(methyl methacrylate).
    (a) Chemical structure of polymers used as graphene precursors; (b) graphene growth process; (c) Raman spectra of PAN-derived graphene film with a 50-nm-thick Ni capping layer annealed at 1000℃ (the capping layer is subsequently removed); (d) cross-sectional high-resolution transmission electron microscopy (HRTEM) image of graphenes formed on a SiO2/Si substrate outside the agglomerated Ni islands; (e) magnified HRTEM image and intensity profile across the graphenes; (f) Raman spectra of PAN-derived graphene with polymer layers of different thickness after removing the capping layer [29] (Reprinted with permission. Copyright 2011, American Chemical Society). PS: polystyrene, PAN: polyacrylonitrile, PMMA: poly(methyl methacrylate).
  • [Fig. 3.] (a) Bilayer graphene grown directly on a SiO2/Si substrate from a solid polymer or self-assembled monolayer (SAM) film by annealing the sample under an Ar-H2 gas mix at 1000℃ for 15 min; (b) Raman spectrum (514-nm excitation) of PPMS-derived bilayer graphene; two-dimensional (2D) Raman (514 nm) mapping of the bilayer graphene film (112 × 112 μm2): (c) D/G peak ratio; (d) G/2D peak ratio. The color gradient bar is to the right of each map, and the scale bars are equivalent to 20 μm in (c) and (d) [38] (Reprinted with permission. Copyright 2011, American Chemical Society). PPMS: poly(2-phenylpropyl)methylsiloxane.
    (a) Bilayer graphene grown directly on a SiO2/Si substrate from a solid polymer or self-assembled monolayer (SAM) film by annealing the sample under an Ar-H2 gas mix at 1000℃ for 15 min; (b) Raman spectrum (514-nm excitation) of PPMS-derived bilayer graphene; two-dimensional (2D) Raman (514 nm) mapping of the bilayer graphene film (112 × 112 μm2): (c) D/G peak ratio; (d) G/2D peak ratio. The color gradient bar is to the right of each map, and the scale bars are equivalent to 20 μm in (c) and (d) [38] (Reprinted with permission. Copyright 2011, American Chemical Society). PPMS: poly(2-phenylpropyl)methylsiloxane.
  • [Fig. 4.] (a) IDS-VG curve for a PPMS-derived, graphene-based, back-gated field-effect transistor device (room temperature); (b) Raman spectra of graphene converted from polymers (PS, PMMA, ABS) and an self-assembled monolayer (SAM) prepared from butyltriethoxysilane; (c) Raman spectra of graphene derived from PPMS on h-BN, Si3N4, and Al2O3 (sapphire) [38] (Reprinted with permission. Copyright 2011, American Chemical Society). PS: polystyrene, PMMA: poly(methyl methacrylate), ABS: poly(acrylonitrile-co-butadiene-co-styrene), PPMS: poly(2-phenylpropyl)methylsiloxane.
    (a) IDS-VG curve for a PPMS-derived, graphene-based, back-gated field-effect transistor device (room temperature); (b) Raman spectra of graphene converted from polymers (PS, PMMA, ABS) and an self-assembled monolayer (SAM) prepared from butyltriethoxysilane; (c) Raman spectra of graphene derived from PPMS on h-BN, Si3N4, and Al2O3 (sapphire) [38] (Reprinted with permission. Copyright 2011, American Chemical Society). PS: polystyrene, PMMA: poly(methyl methacrylate), ABS: poly(acrylonitrile-co-butadiene-co-styrene), PPMS: poly(2-phenylpropyl)methylsiloxane.
  • [Fig. 5.] (a) Schematic of the growth of bilayer graphene from polymer films; bilayer graphene is grown directly on a SiO2/Si substrate by spin-coating a polymer film on a Ni layer and annealing the sample under an Ar-H2 gas mix at 1000℃ for 10 min; (b) Raman spectrum of PMMA-derived bilayer graphene; Raman mapping of the PMMA-derived bilayer graphene film (100 × 100 μm2): (c) D/G peak ratio; (d) G/2D peak ratio [40] (Reprinted with permission. Copyright 2011, American Chemical Society). PMMA: poly(methyl methacrylate).
    (a) Schematic of the growth of bilayer graphene from polymer films; bilayer graphene is grown directly on a SiO2/Si substrate by spin-coating a polymer film on a Ni layer and annealing the sample under an Ar-H2 gas mix at 1000℃ for 10 min; (b) Raman spectrum of PMMA-derived bilayer graphene; Raman mapping of the PMMA-derived bilayer graphene film (100 × 100 μm2): (c) D/G peak ratio; (d) G/2D peak ratio [40] (Reprinted with permission. Copyright 2011, American Chemical Society). PMMA: poly(methyl methacrylate).
  • [Fig. 6.] (a) Low-resolution transmission electron microscopy (TEM) image of bilayer graphene films on a TEM grid; (b) high-resolution TEM image of bilayer graphene edges showing two carbon layers; (c) Raman spectra of graphene: from the top of the Ni layer before and after UV-ozone exposure; on the substrate after UV-ozone exposure and removal of the Ni layer [40] (Reprinted with permission. Copyright 2011, American Chemical Society).
    (a) Low-resolution transmission electron microscopy (TEM) image of bilayer graphene films on a TEM grid; (b) high-resolution TEM image of bilayer graphene edges showing two carbon layers; (c) Raman spectra of graphene: from the top of the Ni layer before and after UV-ozone exposure; on the substrate after UV-ozone exposure and removal of the Ni layer [40] (Reprinted with permission. Copyright 2011, American Chemical Society).