Synthesis and applications of graphene electrodes

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  • ABSTRACT

    The near explosion of attention given to graphene has attracted many to its research field. As new studies and findings about graphene synthesis, properties, electronic quality control, and possible applications simultaneous burgeon in the scientific community, it is quite hard to grasp the breadth of graphene history. At this stage, graphene’s many fascinating qualities have been amply reported and its potential for various electronic applications are increasing, pulling in ever more newcomers to the field of graphene. Thus it has become important as a community to have an equal understanding of how this material was discovered, why it is stirring up the scientific community and what sort of progress has been made and for what purposes. Since the first discovery, the hype has expediently led to near accomplishment of industrial-sized production of graphene. This review covers the progress and development of synthesis and transfer techniques with an emphasis on the most recent technique of chemical vapor deposition, and explores the potential applications of graphene that are made possible with the improved synthesis and transfer.

  • KEYWORD

    graphene , graphene synthesis , graphene applications , overview of graphene research development

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  • [Fig. 1.] Atomic force microscope images of various two-dimensional (2D) crystals discovered along with graphene. (a) NbSe2, (b) graphite, (c) MoS2, and (d) Bi2Sr2CaCu2Ox. The crystals are on 300 nm oxidized Si wafer except the MoS2, which is on holey carbon nulllm. (e) The graph shows the electric nulleld enullect in sheets of 2D crystals. The changes in electrical conductivity of NbSe2, MoS2, and graphene are shown as a function of gate voltage. It is clear that graphene has a distinct trend compared to other 2D crystals (inset is the device used to measure the conductivity) [5].
    Atomic force microscope images of various two-dimensional (2D) crystals discovered along with graphene. (a) NbSe2, (b) graphite, (c) MoS2, and (d) Bi2Sr2CaCu2Ox. The crystals are on 300 nm oxidized Si wafer except the MoS2, which is on holey carbon nulllm. (e) The graph shows the electric nulleld enullect in sheets of 2D crystals. The changes in electrical conductivity of NbSe2, MoS2, and graphene are shown as a function of gate voltage. It is clear that graphene has a distinct trend compared to other 2D crystals (inset is the device used to measure the conductivity) [5].
  • [Fig. 2.] Graphene micromechanical cleaving using atomic force microscope (AFM) tip. (a) Scanning electron microscope image of highly oriented pyrolytic graphite (HOPG) crystallite mounted on an AFM cantilever (inset is the bulk HOPG surface patterned by masked anisotropic oxygen plasma etching. (b) schematic drawing of the microleaving process using the modinulled AFM tip. (C) thin graphite nulllms obtained by the microcleaving process. (d) a mesoscoping device fabricated from the obtained graphite sample [6].
    Graphene micromechanical cleaving using atomic force microscope (AFM) tip. (a) Scanning electron microscope image of highly oriented pyrolytic graphite (HOPG) crystallite mounted on an AFM cantilever (inset is the bulk HOPG surface patterned by masked anisotropic oxygen plasma etching. (b) schematic drawing of the microleaving process using the modinulled AFM tip. (C) thin graphite nulllms obtained by the microcleaving process. (d) a mesoscoping device fabricated from the obtained graphite sample [6].
  • [Fig. 3.] Field enullect in a few layers of grapheme (FLG). (a) Relationship between FLG’s resistivity change and gate voltage for dinullerent temperatures at T = 5, 70, and 300 K, from top to bottom curves, respectively. (b) Example of changes in the nulllm’s conductivity obtained by inverting the 70 K curve. (c) Hall coenullcient as a function of gate voltage for the same FLG at T = 5 K [4].
    Field enullect in a few layers of grapheme (FLG). (a) Relationship between FLG’s resistivity change and gate voltage for dinullerent temperatures at T = 5, 70, and 300 K, from top to bottom curves, respectively. (b) Example of changes in the nulllm’s conductivity obtained by inverting the 70 K curve. (c) Hall coenullcient as a function of gate voltage for the same FLG at T = 5 K [4].
  • [Fig. 4.] Graphene oxide (GO) sheets. (a) General chemical structure of GO; (b and c) low- and medium-resolution scanning electron microscope side-view images of ~10 micron thick GO sample; (d-f) digital camera image of GO paper; (d) ~1 nullm-thick (the Northwestern University logo is beneath the paper); (e) folded ~5 nullm-thick semitransparent nulllm [13].
    Graphene oxide (GO) sheets. (a) General chemical structure of GO; (b and c) low- and medium-resolution scanning electron microscope side-view images of ~10 micron thick GO sample; (d-f) digital camera image of GO paper; (d) ~1 nullm-thick (the Northwestern University logo is beneath the paper); (e) folded ~5 nullm-thick semitransparent nulllm [13].
  • [Fig. 5.] Thin graphite grown epitaxially on SiC. (a-d) Low-energy electron dinullraction (LEED) patterns from graphite/SiC(0001). Each represents sample that was heated several times to successively higher temperatures. (a) 1050℃ for 10 min; shows SiC 1×1 pattern at 177 eV; (b) 1100℃ for 3 min; shows √3 ×√3 reconstruction at 171 eV; (c) 1250℃ for 20 min; shows 6√3 × 6√3 pattern at 109 eV; (c) 1400℃ for 8 min; shows LEED pattern at 98 eV; (e) scanning tunneling microscopy image of a surface region of graphite grown on SiC [26].
    Thin graphite grown epitaxially on SiC. (a-d) Low-energy electron dinullraction (LEED) patterns from graphite/SiC(0001). Each represents sample that was heated several times to successively higher temperatures. (a) 1050℃ for 10 min; shows SiC 1×1 pattern at 177 eV; (b) 1100℃ for 3 min; shows √3 ×√3 reconstruction at 171 eV; (c) 1250℃ for 20 min; shows 6√3 × 6√3 pattern at 109 eV; (c) 1400℃ for 8 min; shows LEED pattern at 98 eV; (e) scanning tunneling microscopy image of a surface region of graphite grown on SiC [26].
  • [Fig. 6.] Schematic illustration of the steps for transferring graphene grown on an SiC wafer to another substrate by using the Au peeling method [28].
    Schematic illustration of the steps for transferring graphene grown on an SiC wafer to another substrate by using the Au peeling method [28].
  • [Fig. 7.] Illustration of carbon segregation at metal surface such as Ni [39].
    Illustration of carbon segregation at metal surface such as Ni [39].
  • [Fig. 8.] Exploration of graphene growth mechanisms using dinullerent carbon isotopes. (a-f) Micro-Raman characterization of the isotope-labeled graphene grown on Cu foil and transferred onto an SiO2/Si wafer. (a) An optical micrograph of the identical region analyzed with micro-Raman spectroscopy; (b) Raman spectra from 12C-graphene (green), 13C-graphene (blue), and the junction of 12C- and 13C-graphene (red), respectively, marked with the corresponding colored circles in (a) and (e); (c) line scan of the dashed line in (d-f). integrated intensity Raman maps of (d) G13+12 (1500-1620 cm-1), (e) G13 (1500-1560 cm-1), (f ) G12 (1560-1620 cm-1) of the areas shown in (a). Scale bars are 5 nullm. (g-h) Schematic diagrams of the possible distribution of C isotopes in graphene nulllms based on dinullerent growth mechanisms for sequential input of C isotopes. (g) Graphene with randomly mixed carbon isotopes atoms such as might occur from surface segregation and precipitation (as expected for graphene growth on Ni); (h) graphene with carbon isotopes grown in the same sequence of input carbon source as might occur by surface adsorption (as expected for graphene growth on Cu) [43] .
    Exploration of graphene growth mechanisms using dinullerent carbon isotopes. (a-f) Micro-Raman characterization of the isotope-labeled graphene grown on Cu foil and transferred onto an SiO2/Si wafer. (a) An optical micrograph of the identical region analyzed with micro-Raman spectroscopy; (b) Raman spectra from 12C-graphene (green), 13C-graphene (blue), and the junction of 12C- and 13C-graphene (red), respectively, marked with the corresponding colored circles in (a) and (e); (c) line scan of the dashed line in (d-f). integrated intensity Raman maps of (d) G13+12 (1500-1620 cm-1), (e) G13 (1500-1560 cm-1), (f ) G12 (1560-1620 cm-1) of the areas shown in (a). Scale bars are 5 nullm. (g-h) Schematic diagrams of the possible distribution of C isotopes in graphene nulllms based on dinullerent growth mechanisms for sequential input of C isotopes. (g) Graphene with randomly mixed carbon isotopes atoms such as might occur from surface segregation and precipitation (as expected for graphene growth on Ni); (h) graphene with carbon isotopes grown in the same sequence of input carbon source as might occur by surface adsorption (as expected for graphene growth on Cu) [43] .
  • [Fig. 9.] Chemical vapor deposition (CVD) graphene and wafer-scale synthesis and transfer. (a) Scanning electron microscope images of CVD grown graphene nulllms on thin (300-nm) nickel layers and thick (1-mm) Ni foils (inset). (b) An optical microscope image of the graphene nulllm transferred to a 300 nm thick silicon dioxide layer. The inset atomic force microscope image shows a typical rippled structure. (c) Synthesis, etching, and transfer process of the large-scale patterned graphene nulllms. Etching is done using FeCl3 and the transfer is done using polydimethylsiloxane (PDMS) stamp. Etching can be done using bunullered oxide etchant (BOE) or hydrogen nulluoride solution and dry-transfer of the graphene nulllms at room temperature. (d) Schematic illustration for fast etching and transfer of wafer-size graphene nulllms. Transferring and patterning of graphene nulllms grown on a metal/SiO2/Si wafer. Graphene/metal layers supported by polymer nulllms are mechanically separated from an SiO2/Si wafer. After fast etching of metal, the graphene nulllms can be transferred to arbitrary substrates and then patterned using conventional lithography. (e-g) Photographs of wafer-scale graphene nulllms. (e-f) The graphene nulllms printed on a poly(ethylene terephthalate) and a stretchable rubber substrate. (g) The three-element rosette strain gauge pattern on rubber by pre-patterning method [42,52].
    Chemical vapor deposition (CVD) graphene and wafer-scale synthesis and transfer. (a) Scanning electron microscope images of CVD grown graphene nulllms on thin (300-nm) nickel layers and thick (1-mm) Ni foils (inset). (b) An optical microscope image of the graphene nulllm transferred to a 300 nm thick silicon dioxide layer. The inset atomic force microscope image shows a typical rippled structure. (c) Synthesis, etching, and transfer process of the large-scale patterned graphene nulllms. Etching is done using FeCl3 and the transfer is done using polydimethylsiloxane (PDMS) stamp. Etching can be done using bunullered oxide etchant (BOE) or hydrogen nulluoride solution and dry-transfer of the graphene nulllms at room temperature. (d) Schematic illustration for fast etching and transfer of wafer-size graphene nulllms. Transferring and patterning of graphene nulllms grown on a metal/SiO2/Si wafer. Graphene/metal layers supported by polymer nulllms are mechanically separated from an SiO2/Si wafer. After fast etching of metal, the graphene nulllms can be transferred to arbitrary substrates and then patterned using conventional lithography. (e-g) Photographs of wafer-scale graphene nulllms. (e-f) The graphene nulllms printed on a poly(ethylene terephthalate) and a stretchable rubber substrate. (g) The three-element rosette strain gauge pattern on rubber by pre-patterning method [42,52].
  • [Fig. 10.] Roll to roll production of graphene and touch screen application. (a) Schematic of the roll-based production of graphene nulllms grown on a copper foil. The process includes adhesion of polymer support such as thermal release tape, copper etching (rinsing) and dry-transfer-printing on a target substrate. (b-d) Photographs of application of graphene nulllm grown by roll-to-roll method. (b) Screen printing process of silver paste electrodes on graphene/ poly(ethylene terephthalate) (PET) nulllms. The inset shows 3.1-inch graphene/PET panels patterned with silver electrodes before assembly. (c) An assembled graphene/PET touch panel showing outstanding nullexibility. (f) A graphene-based touch-screen panel connected to a computer with control software [53].
    Roll to roll production of graphene and touch screen application. (a) Schematic of the roll-based production of graphene nulllms grown on a copper foil. The process includes adhesion of polymer support such as thermal release tape, copper etching (rinsing) and dry-transfer-printing on a target substrate. (b-d) Photographs of application of graphene nulllm grown by roll-to-roll method. (b) Screen printing process of silver paste electrodes on graphene/ poly(ethylene terephthalate) (PET) nulllms. The inset shows 3.1-inch graphene/PET panels patterned with silver electrodes before assembly. (c) An assembled graphene/PET touch panel showing outstanding nullexibility. (f) A graphene-based touch-screen panel connected to a computer with control software [53].
  • [Fig. 11.] Controlled growth of graphene domains. Scanning electron microscope images of partially grown graphene under dinullerent growth conditions: T (℃), JMe (sccm)/PMe (mTorr): (a) 985/35/460, (b) 1035/35/460, (c) 1035/7/460, (d) 1035/7/160. Scale bars are 10 nullm. As seen from the images, lower density of seed domain is achieved with higher temperature and lower methane nullow settings and large single crystal growth is achieved by lowering the methane partial pressure [44].
    Controlled growth of graphene domains. Scanning electron microscope images of partially grown graphene under dinullerent growth conditions: T (℃), JMe (sccm)/PMe (mTorr): (a) 985/35/460, (b) 1035/35/460, (c) 1035/7/460, (d) 1035/7/160. Scale bars are 10 nullm. As seen from the images, lower density of seed domain is achieved with higher temperature and lower methane nullow settings and large single crystal growth is achieved by lowering the methane partial pressure [44].
  • [Fig. 12.] Large single crystal growth of graphene. (a) Copper foil enclosure prior to insertion in the furnace for chemical vapor deposition (CVD) growth. (b) Schematics of the CVD system for graphene on copper. (c) Scanning electron microscope image of a large single crystal graphene on enclosed copper foil grown by CVD. The graphene domain is grown at 1035℃ on Cu at an average growth rate of ~6 nullm/min [55].
    Large single crystal growth of graphene. (a) Copper foil enclosure prior to insertion in the furnace for chemical vapor deposition (CVD) growth. (b) Schematics of the CVD system for graphene on copper. (c) Scanning electron microscope image of a large single crystal graphene on enclosed copper foil grown by CVD. The graphene domain is grown at 1035℃ on Cu at an average growth rate of ~6 nullm/min [55].
  • [Fig. 13.] Enullect of hydrogen on graphene grain (domain) shape. The average size of graphene grains grown for 30 min at 1000℃ on Cu foil using 30 ppm methane in Ar mixture at 1 atm, as a function of partial pressure of hydrogen. The nullgures illustrate scanning electron microscope images of the typical shapes under these dinullerent conditions. Note that perfect hexagons are observed only at higher hydrogen pressures. Irregularly shaped grains grown at low hydrogen pressure. Scale bars are 10 nullm (top two images) and 3 nullm (bottom two images) [56].
    Enullect of hydrogen on graphene grain (domain) shape. The average size of graphene grains grown for 30 min at 1000℃ on Cu foil using 30 ppm methane in Ar mixture at 1 atm, as a function of partial pressure of hydrogen. The nullgures illustrate scanning electron microscope images of the typical shapes under these dinullerent conditions. Note that perfect hexagons are observed only at higher hydrogen pressures. Irregularly shaped grains grown at low hydrogen pressure. Scale bars are 10 nullm (top two images) and 3 nullm (bottom two images) [56].
  • [Fig. 14.] Electronic transport cross a single grain boundary. (a) Optical image of a device with multiple electrodes (numbered 1-10) contacting two coalesced graphene grains (indicated by dashed lines). (b) Representative room-temperature I-V curves measured within each graphene grains and across the grain boundary. The measurements shown were performed at zero magnetic nulleld, and using four-probe connullgurations, with contacts ‘1’ and ‘6’ as current leads, and the 3 pairs of voltage leads labeled in the legend. (c) Four-terminal magnetoresistance (Rxx) measured at 4.3 K within each graphene grain
    Electronic transport cross a single grain boundary. (a) Optical image of a device with multiple electrodes (numbered 1-10) contacting two coalesced graphene grains (indicated by dashed lines). (b) Representative room-temperature I-V curves measured within each graphene grains and across the grain boundary. The measurements shown were performed at zero magnetic nulleld, and using four-probe connullgurations, with contacts ‘1’ and ‘6’ as current leads, and the 3 pairs of voltage leads labeled in the legend. (c) Four-terminal magnetoresistance (Rxx) measured at 4.3 K within each graphene grain
  • [Fig. 15.] Typical optical microscopy images, scanning electron microscope (SEM) images, and Raman spectroscopy of MLG and FLG grown on Ni (a-c), Fe (d-f), Co (g-i), and Cu (j-l) foil substrates using ethylene as the carbon source at 975℃. The growth time was 3 min, and the gas mixing ratio of C2H4/H2 was 5/500, and the cooling rate was 60℃/min. (a, d, g, and j) Optical microscope images of graphene. (b, e, h, and k) SEM images of graphene. (c, f, i, and l) Raman spectroscopy of graphene. Cu substrate background was subtracted. The spectra were normalized with the G- band [60].
    Typical optical microscopy images, scanning electron microscope (SEM) images, and Raman spectroscopy of MLG and FLG grown on Ni (a-c), Fe (d-f), Co (g-i), and Cu (j-l) foil substrates using ethylene as the carbon source at 975℃. The growth time was 3 min, and the gas mixing ratio of C2H4/H2 was 5/500, and the cooling rate was 60℃/min. (a, d, g, and j) Optical microscope images of graphene. (b, e, h, and k) SEM images of graphene. (c, f, i, and l) Raman spectroscopy of graphene. Cu substrate background was subtracted. The spectra were normalized with the G- band [60].
  • [Fig. 16.] Graphene application for nullexible transparent nulleld-enullect transistor (FET). (a) Schematic structure of the nullexible FETs on the plastic substrate and the change in the normalized enullective device mobility null/null0 for TTFTs as a function of the bending induced strain and bending radius. (b) Optical images of an array of ion gel gated graphene FET devices on a plastic substrate. Current density vs. voltage characteristics of chemical vapor deposition graphene (c) or indium tin oxide (ITO) (d) photovoltaic cells under 100 mW/cm2 AM1.5G spectral illumination for dinullerent bending angles. Insets in c and d show the experimental setup employed in the experiments [71].
    Graphene application for nullexible transparent nulleld-enullect transistor (FET). (a) Schematic structure of the nullexible FETs on the plastic substrate and the change in the normalized enullective device mobility null/null0 for TTFTs as a function of the bending induced strain and bending radius. (b) Optical images of an array of ion gel gated graphene FET devices on a plastic substrate. Current density vs. voltage characteristics of chemical vapor deposition graphene (c) or indium tin oxide (ITO) (d) photovoltaic cells under 100 mW/cm2 AM1.5G spectral illumination for dinullerent bending angles. Insets in c and d show the experimental setup employed in the experiments [71].
  • [Fig. 17.] Graphene for stretchable transparent transistor. (a) Schematic illustration of monolithically patterned graphene transistor. Ion gel is printed on channel region by aerosol printing method. (b) Photograph of stretchable ion gel gate dielectric graphene transistor array on PDMS substrate [80].
    Graphene for stretchable transparent transistor. (a) Schematic illustration of monolithically patterned graphene transistor. Ion gel is printed on channel region by aerosol printing method. (b) Photograph of stretchable ion gel gate dielectric graphene transistor array on PDMS substrate [80].