Carbon Nanotube Analysis                                           Particle Analysis: Jeffrey Bodycomb, Ph.D.             ...
Complementary Size and Aspect            Ratio Analysis of SWCNTs:          Photoluminescence Excitation-                E...
Me and My Wife© 2012 HORIBA, Ltd. All rights reserved.
© 2012 HORIBA, Ltd. All rights reserved.
SWCNTs are Graphene Roll-ups                                (0,0)                                               Ch = (10,5...
Why are SWCNTs Significant?2 Major SWCNT families: 2/3 =Semiconducting:               photo- and electro-luminescence (P...
SWCNTs Hot News Flashes Effects of Gamma radiation characterized, show  promise for medical apps and sterilization CNTs ...
SWCNTs: More Big News in 2012 Discovery of how sonication shortens and  damages SWCNTs Not all tubes are cylindrical the...
Photoluminescence: PLDef: Subsequent emission of light from a material caused by light it had previously absorbed.Semico...
Quantum Confinement Effect• The major principle defining the relationship between a  nanoparticles’ physical diameter and ...
5Conduction                                                    4                                                    3     ...
5          4                                                                   Conduction bands          3          2     ...
Suspension of SWNTs for PL                                           1. Nonfluorescent SWNT-SDS aggregates are sonicated  ...
PL Characterization of SWNTs     22                                                                                     ...
Photoluminescence: Steady State                                           Steady State White                              ...
The iHR-320Any 2 Detectors• CCDs• InGaAs Arrays• PIN Diodes• Photomultipliers     •Steady State- 10 ms     •TCSPC-50 ps   ...
Single Walled Carbon Nanotubes(SWCNTs)SWCNTs can be characterized using photoluminesence spectroscopy for:         Diame...
PL Yields Multidimensional Data Diameter:          absorbance and emission peaks correlate according to quantum         ...
Energy Transfer in Bundles                                           Energy Transfers from Narrow                         ...
Length Dependent SWCNT PL© 2012 HORIBA, Ltd. All rights reserved.
SWCNT Absorbance Spectra© 2012 HORIBA, Ltd. All rights reserved.
The Nanolog®-EXT    Deeper NIR Excitation and Emission ranges are     needed for larger diameter SWCNTs    Larger diamet...
Newport 3900S Power Ti-S Laser                                           •   Tuning from 700-1000 nm                      ...
3900S 5W Pump Power© 2012 HORIBA, Ltd. All rights reserved.
Ext IGA (3L dewar)                            Std IGA (3L dewar)                                             100 g x 800 n...
Large Dia. SWCNT Absorbance© 2012 HORIBA, Ltd. All rights reserved.
Large Diameter SWCNTs EEM© 2012 HORIBA, Ltd. All rights reserved.
© 2012 HORIBA, Ltd. All rights reserved.
Nanosizer®© 2012 HORIBA, Ltd. All rights reserved.
SWCNTs: TOP TEN STORIES          NEWSREEL 2011-2012© 2012 HORIBA, Ltd. All rights reserved.
© 2012 HORIBA, Ltd. All rights reserved.
© 2012 HORIBA, Ltd. All rights reserved.
© 2012 HORIBA, Ltd. All rights reserved.
© 2012 HORIBA, Ltd. All rights reserved.
© 2012 HORIBA, Ltd. All rights reserved.
© 2012 HORIBA, Ltd. All rights reserved.
© 2012 HORIBA, Ltd. All rights reserved.
© 2012 HORIBA, Ltd. All rights reserved.
© 2012 HORIBA, Ltd. All rights reserved.
© 2012 HORIBA, Ltd. All rights reserved.
Explore the Future of Nanotechnology                        with HORIBA!                                           Thank Y...
© 2012 HORIBA, Ltd. All rights reserved.© 2012 HORIBA, Ltd. All rights reserved.
Carbon Nanotube Analysis                                           Particle Analysis: Jeffrey Bodycomb, Ph.D.             ...
What is Dynamic Light Scattering?         Dynamic light scattering refers to          measurement and interpretation of l...
Other Light Scattering Techniques   Static Light Scattering: over a duration of    ~1 second. Used for determining partic...
Particle Diameter (m)          0.001                         0.01             0.1              1            10           ...
Brownian MotionParticles in suspension undergo Brownian motion due to solventmolecule bombardment in random thermal motion...
DLS signal    Random motion of particles leads to random     fluctuations in signal (due to changing     constructive/des...
Correlation Function          Random fluctuations are interpreted in terms           of the autocorrelation function (ACF...
Gamma to Size                     Dm q                       2    decay constant                                       ...
What is Hydrodynamic Size?         DLS gives the diameter of a sphere that          moves (diffuses) the same way as your...
Hydrodynamic Size   The instrument reports the size of sphere that    moves (diffuses) like your particle.   This size w...
Why DLS?         Non-invasive measurement         Requires only small quantities of          sample         Good for de...
New Nanoparticle Analyzer         Single compact unit that performs size,          zeta potential, and molecular weight  ...
Carbon Nanotubes         Nanotubes are not spheres….hence the          “tube” in the name.                               ...
Motion of Carbon Nanotubes         Two types of motion: Translation and          rotation         Here I ignore rotation...
What to do?         Recognize that big tubes diffuse slowly          and recognize that DLS is a fast, easy          size...
Measurement of Nanotubes Well characterized: We                                                                Z-avg.  kn...
How to Measure with DLS?         Ensure that the sample is well          dispersed         Ensure that the tubes are not...
Other NanoSamples         Nanometals                    Nanogold                    Nano Iron Oxide         Nanorods  ...
Questions?                                             labinfo@horiba.com                                           www.ho...
ありがとうございました                                                                              Cảm ơn                           ...
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Characterizing Carbon Nanotubes

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Dr. Adam Gilmore and Dr. Jeff Bodycomb from HORIBA Scientific discuss using particle size and photoluminescence measurements to characterize single-walled carbon nanotubes.

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Characterizing Carbon Nanotubes

  1. 1. Carbon Nanotube Analysis Particle Analysis: Jeffrey Bodycomb, Ph.D. Fluorescence: Adam Gilmore, Ph.D.© 2012 HORIBA, Ltd. All rights reserved.
  2. 2. Complementary Size and Aspect Ratio Analysis of SWCNTs: Photoluminescence Excitation- Emission Mapping Adam M. Gilmore, Fluorescence Product Manager© 2012 HORIBA, Ltd. All rights reserved.
  3. 3. Me and My Wife© 2012 HORIBA, Ltd. All rights reserved.
  4. 4. © 2012 HORIBA, Ltd. All rights reserved.
  5. 5. SWCNTs are Graphene Roll-ups (0,0) Ch = (10,5) y a1 a2 x© 2012 HORIBA, Ltd. All rights reserved.
  6. 6. Why are SWCNTs Significant?2 Major SWCNT families: 2/3 =Semiconducting:  photo- and electro-luminescence (PL/EL),  field-effect transistors (FETs)  Precise size and bandgap selection for device engineering  Bright, non-blinking PL/EL for chemical and biological sensing – NIR emission- fits ideally in biological window  Faciliate dense transistor networks 1/3 =Metallic:  high electric and thermal conductivity, efficient connectors  Faciliate transparent conductive films (TCFs)  Enhanced efficiency photovoltaic materials© 2012 HORIBA, Ltd. All rights reserved.
  7. 7. SWCNTs Hot News Flashes Effects of Gamma radiation characterized, show promise for medical apps and sterilization CNTs can divert heat from current flow in devices CNTs enhance photoacoustic imaging of tumours SWCNTs may replace ITO in solar cells Strain paint-stress changes shape and absorbance-emission spectra-aircraft etc.. Sub-10 nm SWCNT transistors more efficient than predicted by models© 2012 HORIBA, Ltd. All rights reserved.
  8. 8. SWCNTs: More Big News in 2012 Discovery of how sonication shortens and damages SWCNTs Not all tubes are cylindrical they can be flattened, like graphene, as long as their diameter is wide enough (> 2 nm) Chiral selection possible by growth on stainless steel wires Selective dispersion methods improved for chiral selection.© 2012 HORIBA, Ltd. All rights reserved.
  9. 9. Photoluminescence: PLDef: Subsequent emission of light from a material caused by light it had previously absorbed.Semiconductor PL: Light emission from around the semiconductor material’s bandgap energy level excited by absorption of light energy above the material’s bandgap energy level.© 2012 HORIBA, Ltd. All rights reserved.
  10. 10. Quantum Confinement Effect• The major principle defining the relationship between a nanoparticles’ physical diameter and it’s bandgap energy• The ‘Bohr-Exciton Radius’ for a bulk semiconductor material can be defined is the physical distance (in nm) between the electron and it’s hole across the bandgap.• When the diameter of a nanoparticle of a material is smaller than it’s ‘Bohr-Exciton Radius’ the nanoparticle’s bandgap is inversely related to the diameter of the nanoparticle due to ‘quantum confinement’.© 2012 HORIBA, Ltd. All rights reserved.
  11. 11. 5Conduction 4 3 2 Exciton Bohr Radius c2 1 + c1 Energy 0 Tuneable Bandgap -1 e- v1 -2 v2 -3 -4 Valence -5 0 2 4 6 8 10 Density of electron states dt Radius© 2012 HORIBA, Ltd. All rights reserved.
  12. 12. 5 4 Conduction bands 3 2 c2 NIR 1 fluorescence c1-v1 c1Energy 0 BAND GAP -1 e- e- v1 absorption v2-c2 -2 e- e- + v2 -3 e- e- Valence bands -4 -5 0 2 4 6 8 10 Density of electron states© 2012 HORIBA, Ltd. All rights reserved.
  13. 13. Suspension of SWNTs for PL 1. Nonfluorescent SWNT-SDS aggregates are sonicated 2. Single SWNTs are suspended 3. Centrifugation separates fluorescent SWCNTs M. J. O’Connell et al., Science 297 (2002) 593 S. M. Bachilo et al., Science 298 (2002) 2361.© 2012 HORIBA, Ltd. All rights reserved.
  14. 14. PL Characterization of SWNTs 22  Bachilo et al. (2002) Science 298:2361-2363 11© 2012 HORIBA, Ltd. All rights reserved.
  15. 15. Photoluminescence: Steady State Steady State White Light Source Dispersive Element for Exciting Light Double-grating monochromator Visible Detecor LN Cooled OE CCD Standard: 200-1000 nm NIR Detector InGaAs Array Standard: 800-1700 nm Sampling Optics Extended: 1100-2200 nm Right-angle Front-Face Dispersive Element for Sample Emission iHR-320 mm Spectrograph with Triple Kinematic Grating Turret© 2012 HORIBA, Ltd. All rights reserved.
  16. 16. The iHR-320Any 2 Detectors• CCDs• InGaAs Arrays• PIN Diodes• Photomultipliers •Steady State- 10 ms •TCSPC-50 ps •MCS-20 ns• Microchannel Plate PMTs •5 ps TCSPCKinematic Grating Turret 200 nm – 3000 nm © 2012 HORIBA, Ltd. All rights reserved.
  17. 17. Single Walled Carbon Nanotubes(SWCNTs)SWCNTs can be characterized using photoluminesence spectroscopy for: Diameter Helical twisting (chirality) Length Bundling-(SWCNT to SWCNT interactions)© 2012 HORIBA, Ltd. All rights reserved.
  18. 18. PL Yields Multidimensional Data Diameter:  absorbance and emission peaks correlate according to quantum confinement rules, smaller SWCNTs higher energy Helical twisting (chirality):  absorbance and emission peak energies are also influenced secondarily, and nonlinearly according to the SWCNT families Length:  intensity of absorbance extinciton and emisison intensity correlate. Bundling:  energy transfer from smaller (donor) to larger (acceptor) diameter SWCNTs influences relationship between absorbance and emission peak intensities.© 2012 HORIBA, Ltd. All rights reserved.
  19. 19. Energy Transfer in Bundles Energy Transfers from Narrow SWNTs (Wide-Bandgap) to Wider SWNTs (Narrow Bandgap)© 2012 HORIBA, Ltd. All rights reserved.
  20. 20. Length Dependent SWCNT PL© 2012 HORIBA, Ltd. All rights reserved.
  21. 21. SWCNT Absorbance Spectra© 2012 HORIBA, Ltd. All rights reserved.
  22. 22. The Nanolog®-EXT  Deeper NIR Excitation and Emission ranges are needed for larger diameter SWCNTs  Larger diameter SWCNTs with small bandgaps are important for device manufacturing. Essential Components: 1. Tunable Mainframe CW TiS Laser 2. Extended InGaAs Array (1100-2200 nm)© 2012 HORIBA, Ltd. All rights reserved.
  23. 23. Newport 3900S Power Ti-S Laser • Tuning from 700-1000 nm • Useful for SWCNTs from 1.3 – 2.2 nm • The only light source compatible with extended InGaAs array for large diameter SWCNTs • HORIBA Tuning Software with SMCC100 Stepper Motor Controller© 2012 HORIBA, Ltd. All rights reserved.
  24. 24. 3900S 5W Pump Power© 2012 HORIBA, Ltd. All rights reserved.
  25. 25. Ext IGA (3L dewar) Std IGA (3L dewar) 100 g x 800 nm 100 g x 800 nm 150 g x 2000 nm 600g x 1000 nm FF/RA FC-OP-LiO3 Laser interlock Attenuating /Beam expansion optics FL-1039 DM303 Si diode 180DF 1200 g x 500 nm 300 g x 750 nm 180F 3900S with SMCC100 1200 g x 500 nm iHR320 FAA R928P (290-850 nm)© 2012 HORIBA, Ltd. All rights reserved.
  26. 26. Large Dia. SWCNT Absorbance© 2012 HORIBA, Ltd. All rights reserved.
  27. 27. Large Diameter SWCNTs EEM© 2012 HORIBA, Ltd. All rights reserved.
  28. 28. © 2012 HORIBA, Ltd. All rights reserved.
  29. 29. Nanosizer®© 2012 HORIBA, Ltd. All rights reserved.
  30. 30. SWCNTs: TOP TEN STORIES NEWSREEL 2011-2012© 2012 HORIBA, Ltd. All rights reserved.
  31. 31. © 2012 HORIBA, Ltd. All rights reserved.
  32. 32. © 2012 HORIBA, Ltd. All rights reserved.
  33. 33. © 2012 HORIBA, Ltd. All rights reserved.
  34. 34. © 2012 HORIBA, Ltd. All rights reserved.
  35. 35. © 2012 HORIBA, Ltd. All rights reserved.
  36. 36. © 2012 HORIBA, Ltd. All rights reserved.
  37. 37. © 2012 HORIBA, Ltd. All rights reserved.
  38. 38. © 2012 HORIBA, Ltd. All rights reserved.
  39. 39. © 2012 HORIBA, Ltd. All rights reserved.
  40. 40. © 2012 HORIBA, Ltd. All rights reserved.
  41. 41. Explore the Future of Nanotechnology with HORIBA! Thank You for Your Attention! Please visit us at: www.horiba.com© 2012 HORIBA, Ltd. All rights reserved.
  42. 42. © 2012 HORIBA, Ltd. All rights reserved.© 2012 HORIBA, Ltd. All rights reserved.
  43. 43. Carbon Nanotube Analysis Particle Analysis: Jeffrey Bodycomb, Ph.D. Fluorescence: Adam Gilmore, Ph.D.© 2012 HORIBA, Ltd. All rights reserved.
  44. 44. What is Dynamic Light Scattering? Dynamic light scattering refers to measurement and interpretation of light scattering data on a microsecond time scale. Dynamic light scattering can be used to determine Particle/molecular size Size distribution Relaxations in complex fluids© 2012 HORIBA, Ltd. All rights reserved.
  45. 45. Other Light Scattering Techniques Static Light Scattering: over a duration of ~1 second. Used for determining particle size (diameters greater than 10 nm), polymer molecular weight, 2nd virial coefficient, Rg. Electrophoretic Light Scattering: use Doppler shift in scattered light to probe motion of particles due to an applied electric field. Used for determining electrophoretic mobility, zeta potential.© 2012 HORIBA, Ltd. All rights reserved.
  46. 46. Particle Diameter (m) 0.001 0.01 0.1 1 10 100 1000Sizes Nano-Metric Fine Coarse Colloidal MacromoleculesApps Powders Suspensions and Slurries Electron Microscope Acoustic Spectroscopy Light Obscuration Laser Diffraction - LA950Methods Electrozone Sensing DLS – SZ-100 Disc-Centrifuge (CPS) Microscopy CamSizer © 2012 HORIBA, Ltd. All rights reserved.
  47. 47. Brownian MotionParticles in suspension undergo Brownian motion due to solventmolecule bombardment in random thermal motion. Brownian Motion Random Related to Size Related to viscosity Related to temperature © 2012 HORIBA, Ltd. All rights reserved.
  48. 48. DLS signal  Random motion of particles leads to random fluctuations in signal (due to changing constructive/destructive interference of scattered light.© 2012 HORIBA, Ltd. All rights reserved.
  49. 49. Correlation Function  Random fluctuations are interpreted in terms of the autocorrelation function (ACF). T  I (t ) I (t   )dt C ( )  0 I (t ) I (t ) C ( )  1   exp(2 )© 2012 HORIBA, Ltd. All rights reserved.
  50. 50. Gamma to Size   Dm q 2  decay constant  2 Dt diffusion coefficient 4n q scattering vector q sin n refractive index  wavelength   scattering angle Dh hydrodynamic diameter  viscosity kB Boltzman’s constant k BT Dh  3 (T ) Dt Note effect of temperature!© 2012 HORIBA, Ltd. All rights reserved.
  51. 51. What is Hydrodynamic Size? DLS gives the diameter of a sphere that moves (diffuses) the same way as your sample. Dh Dh Dh© 2012 HORIBA, Ltd. All rights reserved.
  52. 52. Hydrodynamic Size  The instrument reports the size of sphere that moves (diffuses) like your particle.  This size will include any stabilizers bound to the molecule (even if they are not seen by TEM). Gold Colloids Technique Size nm Atomic Force Microscopy 8.5 ± 0.3 Scanning Electron Microscopy 9.9 ± 0.1 Transmission Electron Microscopy 8.9 ± 0.1 Dynamic Light Scattering 13.5 ± 0.1 SEM (above) and TEM (below) images for RM 8011© 2012 HORIBA, Ltd. All rights reserved.
  53. 53. Why DLS? Non-invasive measurement Requires only small quantities of sample Good for detecting trace amounts of aggregate Good technique for macro-molecular sizing© 2012 HORIBA, Ltd. All rights reserved.
  54. 54. New Nanoparticle Analyzer Single compact unit that performs size, zeta potential, and molecular weight measurements.© 2012 HORIBA, Ltd. All rights reserved.
  55. 55. Carbon Nanotubes Nanotubes are not spheres….hence the “tube” in the name. Nanotube Model for DLS© 2012 HORIBA, Ltd. All rights reserved.
  56. 56. Motion of Carbon Nanotubes Two types of motion: Translation and rotation Here I ignore rotation© 2012 HORIBA, Ltd. All rights reserved.
  57. 57. What to do? Recognize that big tubes diffuse slowly and recognize that DLS is a fast, easy size indicator. Try to match DLS data to model using some other information k BT ln( L / d )  0.32 L= length Dt  d=diameter 3L Nair, N., Kim, W., Braatz, R, and Strano, M. Langmuir 2008, 24, 1790- 1795.© 2012 HORIBA, Ltd. All rights reserved.
  58. 58. Measurement of Nanotubes Well characterized: We Z-avg. knew aspect ratio Diameter, (1000) and diameter nm (0.7 to 0.9 nm) in Repeat 1 115.0 advance Repeat 2 104.5 Well dispersed: few if Repeat 3 105.3 any aggregates Repeat 4 109.5 Repeat 5 115.2 Expect value between Repeat 6 106.2 97 and 125 nm using Average 109.3 equation on previous Standard Deviation 4.8 slide Coefficient of 4.4% Obtain a nice match. Variation© 2012 HORIBA, Ltd. All rights reserved.
  59. 59. How to Measure with DLS? Ensure that the sample is well dispersed Ensure that the tubes are not colliding (dilute sample) Use results as an indicator of tube size (or aggregation if you are thinking about dispersion quality) Don’t blindly turn Dh into L© 2012 HORIBA, Ltd. All rights reserved.
  60. 60. Other NanoSamples Nanometals Nanogold Nano Iron Oxide Nanorods Colloidal particles© 2012 HORIBA, Ltd. All rights reserved.
  61. 61. Questions? labinfo@horiba.com www.horiba.com/us/particle Adam.Gilmore@horiba.com Jeff.Bodycomb@horiba.com© 2012 HORIBA, Ltd. All rights reserved.
  62. 62. ありがとうございました Cảm ơn ขอบคุณครับ 谢谢 ُْ ‫اشكر‬ Gracias Grazie Σας ευχαριστούμε धन्यवादTacka dig நன்ற Danke Obrigado 감사합니다 Большое спасибо© 2012 HORIBA, Ltd. All rights reserved.

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