Inelastic Light Scattering in Carbon Nanostructures: From Micro to Nano
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This document provides an overview of inelastic light scattering in carbon nanostructures from the micro to the nanoscale. It begins with a discussion of Raman spectroscopy and vibrational modes in sp2 carbons like nanotubes and graphene. It then reviews the development of carbon nanostructures from graphite to fullerenes to nanotubes to graphene. The rest of the document discusses techniques like tip-enhanced Raman spectroscopy that allow single-nanotube spectroscopy at the nanoscale. It also covers applications of carbon nanostructures in areas like bioengineering and discusses methods for characterizing structures and interactions.
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Inelastic Light Scattering in Carbon Nanostructures: From Micro to Nano
- 1. Innelastic Light Scattering in Carbon Nanostructures: From the micro do the nanoscale Ado JORIO Departamento de Física Universidade Federal de Minas Gerais BRAZIL 27 September 2016
- 2. INNELASTIC LIGHT SCATTERING RAMAN SPECTROSCOPY
- 3. Vibrational modes in sp2 carbons... 3 ... nanotubes and graphene RBM G band D band RBM = C/dt
- 4. “Toy-model” sp2 carbon nanostructures Time line Graphite Fullerene Nanotube Graphene 1960 1985 1991 2004 Moore et al. Kroto et al. Iijima et al. Novoselov et al. C – 1s2 2s2 2p2
- 6. C nanostructures in the market Carbon blackC fibers GIC Amorphous carbon
- 7. Terras Pretas de Índios (TIPs) da Amazonia Indian black earth in Amazon B. Glaser et al. Naturwis 88, 31-41 (2001) B. Glaser et al. Org Geochem. (31), 669-678 (2000) Highly stable carbon in the soil improve fertility
- 8. G and D band imaging of a nano-graphite Confocal G band and D band imaging 2005 - Experiment performed with Achim Hartschuh in the laboratory of Prof. A. J. Meixner (Tuebingen) 2m Published in PCCP 9, 1276–1291 (2007)
- 9. Near-Field Imaging of a graphene step? D band optical image AFM D band image with 20nm resolution Umpublished AFM
- 10. AFM Image J. H. Hafner, C. L. Cheung, T. H. Oosterkamp, and C. M. Lieber, J. Phys. Chem. B 105, 743 (2001) Single carbon nanotube spectroscopy “in micro”
- 11. RBM (cm-1) Raman spectrum Si AFM Image A. Jorio et al., PRL 86, 1118 (2001) Also Duesberg et al., PRL 85, 5436 (2000) Single nanotube spectroscopy
- 12. Marked Sample Resonant Raman Intensity with Tunable Laser A. Jorio et al., Phys. Rev. B 63, 245416 (2001) Anti-Stokes Raman CNT JDOS RBM spectra changing laser line Resonance window LaserEnergy
- 13. 0.44 0.88 1.32 1/dt (nm-1) E11 S E22 S E11 ME33 SE44 SE22 M The Kataura plot Optics addresses (n,m)-dependent physics SWNT optical transitions Single nanotube spectroscopy Physical Properties of Carbon Nanotubes Riichiro Saito, G. Dresselhaus, M. S. Dresselhaus Imperial College Press 1998 RBM
- 14. Raman spectra AFM Image A. Jorio et al., Phys. Rev. Letters 86, 1118 (2001) Single nanotube spectroscopy Si Kataura plot
- 15. RBM Raman spectra from SWNTs bundles Araujo et al. PRB 77, 241403(R) (2008)
- 16. (Eii, RBM) (n, m) E11 S E22 S E11 ME33 S E44 S E22 M 0.44 1.32 E11 S E22 S E11 ME33 SE44 SE22 M 0.88 1/dt (nm-1) Many laser lines probe the Kataura plot Araujo et al. PRL 98, 067401 (2007) Araujo et al. Physica E 42, 1251 (2010)
- 17. The density of states and dimensionality DOS E 0 Dimensional
- 18. The density of states and dimensionality DOS E 1 Dimensional dE dE
- 19. 19 Excitons
- 20. Characterization of CNT structures The gray scale gives the G band frequency or strain Study of intertube interactions @ carbon nanotube superloops Shadmi et al. Nano Lett. 2016, 16, 2152−2158 Araujo et al. Nano Lett. 2012, 12, 4110−4116 Soares and Jorio, J. of Nanotech 2012, ID 512738 Soares et al Nano Letters 10, 5043–5048, 2010 Study of tube-substrate interactions @ Carbon nanotube serpentines
- 21. Bioengineering Applications Carbon Nanotubes “inside the body” Biocompatibility assessment of fibrous nanomaterials in mammalian embryos Nanomedicine: Nanotechnology, Biology, and Medicine 12 (2016) 1151– 1159 Efficient delivery of DNA into bovine preimplantation embryos by multiwall carbon nanotubes Scientific Reports | 6:33588 | DOI: 10.1038/srep33588 Highly efficient siRNA delivery system into human and murine cells using single-wall carbon nanotubes Nanotechnology 21, 385101 (2010)
- 22. Single nanotube spectroscopy “in nano“ Tip enhanced Raman Spectroscopy (TERS) of Carbon nanotubes AFM TERS Achim Hartschuh et al. Phys. Rev. Lett. 90, 095503 (2003)
- 23. Local G' (2D) emission at the defect location Localized light emission Red-shifted G´ (2D) at the defect site: n-type doping I. O. Maciel et al. Nat. Materials 7, 878 (2008)
- 24. OPTICAL MICROSCOPY THE PINHOLE CAMERA PARADIGM
- 25. OPTICAL MICROSCOPY THE PINHOLE CAMERA PARADIGM
- 26. Tip Enhanced Raman Spectroscopy special resolution beyond the diffraction limit Conventional microscope “Near-field” microscope Abbé, Arch. Mikrosk., Anat.,(1873). Wessel, JOSA B, (1985). Novotny et al., Ultramicroscopy, (1998).
- 27. TIP UP AND TIP DOWN IN CARBONO NANOTUBES Jorio & Cancado PCCP 14, 15246 (2012)Cancado et al. PRL 103, 186101 (2009)
- 28. TERS VS. AFM – CHEMICAL SELECTIVITY TOPOGRAPHY TERS
- 29. Oil Objective 60x NA 1.4 XY STAGE Gold Tip Raman Spectro meter Dichroic mirror Laser Source Sample Tunning fork Gold tip • “Home-built” We can do AFM, STM… and optical spectroscopy (Raman, Rayleigh, photoluminecence…) in situ. • Our best resolution is 10nm The system
- 30. The system • “Home-built” We can do AFM, STM… and optical spectroscopy (Raman, Rayleigh, photoluminecence…) in situ.
- 31. 31
- 32. NUMERICAL APERTURE OPTICAL MICROSCOPY RESOLVING POWER DEPENDS ON THE INCIDENCE ANGLE AND NUMERICAL APERTURE
- 33. NUMERICAL APERTURE OPTICAL MICROSCOPY 1086420 10 8 6 4 2 0 X[µm] Y[µm] PL FROM NYON BLUE
- 34. Oil Objective 60x NA 1.4 XY STAGE Gold Tip Sample Tunning fork
- 36. TERS SYSTEM
- 37. ESQUEMA DO FILTRO NOTCH (Z), CENTRADO NA FREQUÊNCIA DE 32, 7 KHZ
- 40. PI 1105968-0 BR 1020120333040 BR 1020120269732 lhos 93 MEV de uma nanoponteira estruturada por desbaste de íons Tip fabrication and control BR1020150103522 BR1020150312032 14.12.2015 BR1020150312032 DISPOSITIVO METÁLICO PARA MICROSCOPIA POR VARREDURA POR SONDA E MÉTODO DE FABRICAÇÃO DO MESMO 07.05.2015 BR1020150103522 DISPOSITIVO METÁLICO PARA MICROSCOPIA E ESPECTROSCOPIA ÓPTICA DE CAMPO PRÓXIMO E MÉTODO DE FABRICAÇÃO DO MESMO 27.12.2012 BR 1020120333040 DISPOSITIVO MACIÇO COM EXTREMIDADE UNIDIMENSIONAL PARA MICROSCOPIA E ESPECTROSCOPIA ÓPTICA DE CAMPO PRÓXIMO 22.10.2012 BR 1020120269732 DISPOSITIVO MACIÇO ENCAPADO COM NANOCONE DE CARBONO PARA MICROSCOPIA E ESPECTROSCOPIA POR VARREDURA DE SONDA 29.12.2011 PI 1105972-9 DISPOSITIVO DE FIBRA ÓPTICA COM ELEMENTO UNIDIMENSIONAL PARA MICROSCOPIA E ESPECTROSCOPIA ÓPTICA DE CAMPO PRÓXIMO 29.12.2011 PI 1107185-0 DISPOSITIVO VAZADO COM EXTREMIDADE UNIDIMENSIONAL PARA MICROSCOPIA E ESPECTROSCOPIA ÓPTICA DE CAMPO PRÓXIMO 29.12.2011 PI 1105968-0 DISPOSITIVO MACIÇO COM EXTREMIDADE UNIDIMENSIONAL PARA MICROSCOPIA E ESPECTROSCOPIA ÓPTICA DE CAMPO PRÓXIMO
- 41. Tungsten wire 0.1mm diameter LARGE SCALE PRODUCTION OF PIRAMID TIPS 15.05.2015 BR1020150112335 MÉTODO E EQUIPAMENTO DE POSICIONAMENTO AUTOMÁTICO PARA MICROSCOPIA POR VARREDURA DE SONDA E ESPECTROSCOPIA ÓPTICA IN SITU
- 42. A. Cano Marques et al. Scientific Reports |5:10408 | DOI: 10.1038/srep10408 Carbon nanocone@gold nanotip
- 43. A. Cano Marques et al. Scientific Reports | 5:10408 | DOI: 10.1038/srep10408 Carbon nanocone@gold nanotip
- 44. Gold nanotip with plasmonic confinement Vasconcelos et al. ACSNano 9(6) 6297 (2015) Schematics SEM EELS
- 45. Gold nanotip with plasmonic confinement Vasconcelos et al. ACSNano 9(6) 6297 (2015) TIP UP TIP DOWNTIP
- 46. Symmetry dependence for coherent near-field Raman Maximiano et al. PRB 85, 235434 (2012); Cancado et al. PRX 4, 031054 (2014)
- 47. Calculation for spatially coherent near-field Raman D G G’ (2D) Tip approach curves Distance (nm) Distance (nm) Distance Beams et al. PRL 113, 186101 (2014); Cancado et al. PRX 4, 031054 (2014) Phonon coherence length lC = 30nm
- 48. 1 10 100 1000 0 20 40 60 80 100 120 La (nm) A G (cm -1 ) 1.96 eV 2.33 eV 2.71 eV Phonon coherence length (lC) and crystallite size (La) 1000 1200 1400 1600 1800 2800°C 2600°C 2400°C 2300°C 2200°C 2000°C 1800°C 1600°C 1400°C 1200°C Intensity(arb.units) Raman shift (cm-1 ) 3.8 nm 4.6 nm 10 nm 17 nm 30 nm 58 nm 140 nm 217 nm 526 nm 2300 nm J. Ribeiro Soares et al. Carbon 95 646-652 (2015) The G band width STM D G La lC = 30nm
- 51. http://www.globalccsinstitute.com/publications/global-status-beccs-projects-2010/online/27026 (2010) Carbon release in the atmosphere With and without CCS With CCS (carbon capture storage)
- 52. M. W. I. Schmidt et al., NATURE 478, 49 (2011) Data from surface horizons of 20 long- term field experiments (up to 23 years) in temperate climate, using 13C labeling to trace the residence time of bulk SOM and of individual molecular compounds The persistence of soil organic matter
- 53. Tropical soils (google images)
- 54. Terras Pretas de Índios (TIPs) da Amazonia Indian black earth in Amazon B. Glaser et al. Naturwis 88, 31-41 (2001) B. Glaser et al. Org Geochem. (31), 669-678 (2000) Highly stable carbon in the soil improve fertility Researchers are trying to reproduce this soil in laboratory TPI form Balbina Presidente Figueiredo, AM Lat. 1º 54’ sul Long. 59º 28’ O altitude 60 m.
- 55. The role of carbon on soil cation exchange capacity Liang et al. Soil Sci. Am. J. 70, September-October (2006). DS: Dona Stella ACU: Acutuba LG: Lago Grande HAT: Hatahara
- 56. The nanocrystallite size have special dimensions 2 to 8 nanometers Stable Inert Unstable Reactive Jorio et al. Soil & Tillage Research 122 (2012) 61–66
- 57. Comparison of grain size between different types of biochar Jorio et al. Soil & Tillage Research (2012) G La -1 G band Raman FWHM
- 58. Acknowledgements UFMG Luiz Gustavo Cançado Cassiano Rabelo Douglas S. Ribeiro Mateus G. da Silva João Luiz E. Campos Marcela Pagano Sugandha Pandei Jenaina Ribeiro-Soares Rodolfo Maximiano Indhira Maciel Jaqueline S. Ribeiro Paulo T. Araujo INMETRO Carlos Alberto Achete Marcia Lucchese Braulio Archanjo Thiago Vasconcelos Erlon Ferreira Soares UFRJ Rodrogo Barbosa Capaz ETH Zurich Lukas Novotny Mark Kasperczik Univ. Basel Patrick Maletinsky Univ. Manchester Aravind Vijayaraghavan NIST Ryan Beams FINEPFINEP INPA Newton Falcão Aalto J. Riikonen Weitzman Inst Ernesto Joselevich UNICAMP Pedro A.S. Autreto R. Paupitz Douglas S. Galvão U. Munich Achim Hartschuh CNRS Alain Penicaud