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Chemical Modification of Graphene

Chemical Modification of Graphene. T obe lab M1 Kosuke HADA. Outline. Introduction Representative previous work about chemical modification of graphene My work Summary. Graphene. Graphite. Graphene. Graphene. Graphene was isolated by using adhesive tape.

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Chemical Modification of Graphene

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  1. Chemical Modification of Graphene Tobe lab M1 Kosuke HADA

  2. Outline • Introduction • Representative previous work about chemical modification of graphene • My work • Summary

  3. Graphene Graphite Graphene

  4. Graphene Graphene was isolated by using adhesive tape. Novoselov and Geim won the Nobel Prizein 2010. Graphene Novoselov, K. S. et al. Science2004, 306, 666-669.

  5. Graphene • Properties of Graphene • ・Strength • ・Zero bandgap • ・Ultrahigh carrier mobility Zboril, R. et al. Chem. Rev. 2012, 112, 6156−6214. Touch screens Sensor New Material Solar cell

  6. Chemical Modification (化学修飾) of Graphene Changing of sp2 Carbons to sp3 Carbons by Addition of Organic Molecules • sp2 carbon : conductive • sp3 carbon : non-conductive Graphene • Controllingconductivity of graphene • Functionalizingproperty of graphene

  7. Representative Previous Work onChemical Modification of Graphene Covalent chemistry for graphene electronics Niyogi, S.; Bekyarova, E.; Hong, J.; Khizroev, S.; Berger, C.; Heer, W.; Haddon, R. C. J. Phys. Chem. Lett. 2011, 2, 2487–2498. Nitrophenyl Radical

  8. Representative Previous Work onChemical Modification of Graphene Epitaxial Graphene (EG) 1100℃ Method of Chemical Modification Sic Nitrophenyl Radical Graphene Sic SiC

  9. Raman Spectrum Mechanism

  10. Raman Spectrum Functionalized by Nitrophenyl Epitaxial Graphene One or Two Layered Graphene vibration of lattice of graphene vibration of defects

  11. Tunneling current Scanning Tunneling Microscopy (STM) Mechanism 11

  12. Fast Fourier Transform(FFT) Mechanism lower-order filtered higher-order filtered 12

  13. STM Epitaxial Graphene removing graphene lattice higher-order filtered Nitrophenyl Functionalized Epitaxial Graphene

  14. STM Epitaxial Graphene superimpose (重ね合わせ) Nitrophenyl Functionalized Epitaxial Graphene superimpose (重ね合わせ)

  15. STM Epitaxial Graphene superimpose (重ね合わせ) Graphene Sic Moire pattern (モアレ模様)

  16. STM Nitrophenyl Functionalized Epitaxial Graphene superimpose (重ね合わせ)

  17. Resistance Epitaxial Graphene Nitrophenyl Functionalized Epitaxial Graphene 0.4kΩ at r.t. 3.2kΩ at r.t.

  18. Summary of the Work • Raman Spector • STM • Resistance ・Chemical modification change the conductivity of graphene ・Reaction positions and rate weren’t controlled My purpose is to control reaction positions and rate

  19. Construction of Nano Structure on Surfaces Top-down approach (photolithography) Bottom-up approach (molecular self-assembly) light = molecules = photoresist Self-assembly = substrate = substrate About 100 nm scale 1~10 nm scale

  20. Honeycomb Structureof Dehydrobenzo[12]annulene (DBA) at the Liquid/Graphite Interface DBA = STM Imageof DBA on Graphite Self-Assembly at the Liquid/Solid Interface

  21. Characters of DBA = DBA You can change the size of DBA and holes

  22. Purpose of MyWork Carbene Diazirine Diazirine • Chemical stability of diazirine • Precursor of carbene • Photo-reaction under long wavelength Carbene • High reactivity • Adding to graphene

  23. Purpose of MyWork = Diazirine Self-Assembly Graphene

  24. Purpose of MyWork hv Graphene

  25. Purpose of MyWork Graphene and DBA 1 before chemical modification

  26. Purpose of MyWork Graphene afterchemical modification

  27. Purpose of MyWork 14 carbons 12 carbons 10 carbons Graphene and DBA before chemical modification

  28. Purpose of MyWork 14 carbons 12 carbons 10 carbons 28units 36units 46 units Graphene afterchemical modification

  29. Purpose of My Work Protection from Light

  30. STM Image of DBA at the 1,2,4-trichlorobenzene/GraphiteInterface Solvent 1,2,4-trichlorobenzene STM Imageof DBA 1 on Graphite 2.9 × 10-6 mol/L

  31. STM Image of DBA at the 1,2,4-trichlorobenzene/GrapheneInterface Solvent 1,2,4-trichlorobenzene STM Imageof DBA 1 on Graphene 2.9 × 10-6 mol/L

  32. UVSpector after Photo Irradiation photo irradiation of 350~400 nm stable under photo irradiation photo irradiation generated carbene photo irradiation generated carbene

  33. Summary • Chemical modification changes the properties of graphene. • I designed DBA 1 and synthesized it. • DBA 1 formed honeycomb structures at solvent/graphite and solvent/graphene interfaces. • DBA 1 generates carbene by photo irradiation of about 350 nm.

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