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Fig. 1 – Raman Spectroscopy
• TERS was not supported by results, but it still exists
• Proved the necessity of TERS because:
1. ~5nm bundle was measured ~400nm using Far-field
2. D-band was indiscernible from noise after defect
• RBM peak shift could indicate a shift in the orientation of
the bundled CNTs or change in CNT band structure
Spincoated and then baked
CoMoCAT SWCNT onto glass slides
Far-field (as in step 2) and near-field (using the setup
of Fig. 4 with the tip constantly over the focal point)
images of the manipulated SWCNT were taken
• Work with a single CNT strand instead of bundle
• Obtain data showcasing TERS enhancement
• Develop new opto-electric devices using the SWCNT
structural deformation relation to electronic structure
• Far-field Raman Spectroscopy has low spatial resolution
~300nm – (due to diffraction limit of propagating light d = λ/2)
Tip-Enhanced Raman Spectroscopy (TERS) can
achieve a spatial resolution of less than 30nm
• Raman Scattering is very weak compared to Rayleigh Sct.
(~1 in 10 million photons in a scattering event are Raman!)
• Manipulation of CNTs could cause loss in Raman intensity
TERS increases the Raman Scattering response
by a factor of 100 - 104
The Study of Tip-Induced Deformations in Single-Walled Carbon
Nanotubes Using Tip-Enhanced Near-Field Raman Spectroscopy
http://nanojapan.rice.edu
This material is based upon work supported
by the National Science Foundation under
Grant No. OISE‐0530220.
Warren Cheng1,2, Shota Kuwahara2, and Satoshi Kawata2
1.NanoJapan Program, Rice University and Columbia Laboratory for Unconventional
Electronics, Department of Electrical Engineering, Columbia University, NYC, USA
2. Laboratory for Scientific Instrumentation and Engineering, Department of Applied Physics, Osaka University, Osaka, Japan
CONCLUSION
Raman Spectroscopy
Elastic Rayleigh
Scattering
Monochromatic
Excitation
Source
Before After
Inelastic Raman
Scattering
Filter
Diffraction
Grating
Detector
Sample Molecules
• Possess electronic and
vibrational properties which
are dependent on the CNTs’
chirality (detected with Raman
spectroscopy)
Significance
Future Work
1
• Evanescent illumination decreases the spot size
of the laser confining the illuminated region of the sample
• High NA p-polarized component of the laser increases
the electromagnetic field along the metallized tip
• Propagating photons are captured and confined at the
apex of the hovering conical silver coated silicon tip due
to coupling with localized surface plasmon polaritons
How does TERS work?
G+
G-
D
RBM
Fig. 2 - Active Phonon Modes in CNT
Carbon Nanotubes (CNT)
Acknowledgements
I would like to sincerely thank Prof. J. Kono, Dr. C. Matherly, K. Packard, S. Phillips, and Prof. C. Stanton of NanoJapan 2010 for
developing such an amazing program that enabled me to achieve this dream. Thanks to Prof. S. Kawata for giving me the
opportunity to work at LaSIE, to Y. Okuno for his helpful lessons, to the members of LaSIE and to last but certainly not least
Dr. S. Kuwahara for his endless patience and guidance for without whom I could not have accomplished such a project.
Fig. 4 – TERS
Schematic
Fig. 3 – Deformations in CNT
• Deformations alter the CNTs’
energy band structure thereby
altering their characteristics
• Shifts in the phonon modes
result from these alterations
2
• Used an AFM-Raman System comprised of a SII AFM
system and Nikon Optical Microscope
• Far-field image of the SWCNT was taken by raster
scanning the sample with the setup in Fig. 4 but with
the tip and evanescent mask removed
Using a silicon Dynamic
Force Microscopy (DFM)
tip, a ~430 nm horizontal
defect was introducedFig. 5 – AFM Image of Tip-Induced
Deformation in CNT
BEFORE AFTER
3
Process
Raman
Spectrometer
Beam Profile
(High NA)
Evanescent
Mask
Expander
Objective Lens
(60x, NA = 1.4)
Beam
Splitter
Near Field Probe
(Silver Coated AFM Tip)
Sample
Longpass
Filter
Raman
Signal
Confined Field
Focus Spot
(~300nm)
Diode
Pumped
Laser
532nm,10mW
Expanded
Laser Beam
Carbon Nanotube
Mirror
G+
G-
D
RBM
Fig. 2 – Raman Spectrum of CNT
1. Mono. Source
Excites Sample
2. Molecules Vibrate
& Scatters Light
3. Rayleigh
Removed
4. Raman Spectra
Detected
METHOD
4
Before
AFMRaman
Manipulation
AfterManipulation
Raman AFM
Intensity
Profile at
Manipulation
Point
CNT manipulation could not be discerned from TERS Image
Raman SpectrumNear-field TERS Image
1μm
Manipulation region was about 5 nm wide - determined with DFM
Indicates a bundled structure containing 4 or 5 SWCNT
Raman Spectra At Manipulation Point
ΔG+ = 1.7 cm-1
ΔG- = 1.3 cm-1
ΔD = N/A
(Low SNR)
ΔRBM = 8 cm-1
Peak
Shift
Far-field
Bundle
Width~400nm
RBM
G+
G-
D
Intensity
Decreases
Raman at
brightest point
Raman Image
Centered at G+
1584 cm-1
Raman Image
Centered at G+
1586 cm-1
Manipulated
SWCNT Bundle
AFM
1
2
3
Measurement
Taken Within
RESULTSBACKGROUND
Z. Liu, et. al., Chem. Comm.2009, 6902 (2009).

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Cheng, Warren_Final Poster

  • 1. Fig. 1 – Raman Spectroscopy • TERS was not supported by results, but it still exists • Proved the necessity of TERS because: 1. ~5nm bundle was measured ~400nm using Far-field 2. D-band was indiscernible from noise after defect • RBM peak shift could indicate a shift in the orientation of the bundled CNTs or change in CNT band structure Spincoated and then baked CoMoCAT SWCNT onto glass slides Far-field (as in step 2) and near-field (using the setup of Fig. 4 with the tip constantly over the focal point) images of the manipulated SWCNT were taken • Work with a single CNT strand instead of bundle • Obtain data showcasing TERS enhancement • Develop new opto-electric devices using the SWCNT structural deformation relation to electronic structure • Far-field Raman Spectroscopy has low spatial resolution ~300nm – (due to diffraction limit of propagating light d = λ/2) Tip-Enhanced Raman Spectroscopy (TERS) can achieve a spatial resolution of less than 30nm • Raman Scattering is very weak compared to Rayleigh Sct. (~1 in 10 million photons in a scattering event are Raman!) • Manipulation of CNTs could cause loss in Raman intensity TERS increases the Raman Scattering response by a factor of 100 - 104 The Study of Tip-Induced Deformations in Single-Walled Carbon Nanotubes Using Tip-Enhanced Near-Field Raman Spectroscopy http://nanojapan.rice.edu This material is based upon work supported by the National Science Foundation under Grant No. OISE‐0530220. Warren Cheng1,2, Shota Kuwahara2, and Satoshi Kawata2 1.NanoJapan Program, Rice University and Columbia Laboratory for Unconventional Electronics, Department of Electrical Engineering, Columbia University, NYC, USA 2. Laboratory for Scientific Instrumentation and Engineering, Department of Applied Physics, Osaka University, Osaka, Japan CONCLUSION Raman Spectroscopy Elastic Rayleigh Scattering Monochromatic Excitation Source Before After Inelastic Raman Scattering Filter Diffraction Grating Detector Sample Molecules • Possess electronic and vibrational properties which are dependent on the CNTs’ chirality (detected with Raman spectroscopy) Significance Future Work 1 • Evanescent illumination decreases the spot size of the laser confining the illuminated region of the sample • High NA p-polarized component of the laser increases the electromagnetic field along the metallized tip • Propagating photons are captured and confined at the apex of the hovering conical silver coated silicon tip due to coupling with localized surface plasmon polaritons How does TERS work? G+ G- D RBM Fig. 2 - Active Phonon Modes in CNT Carbon Nanotubes (CNT) Acknowledgements I would like to sincerely thank Prof. J. Kono, Dr. C. Matherly, K. Packard, S. Phillips, and Prof. C. Stanton of NanoJapan 2010 for developing such an amazing program that enabled me to achieve this dream. Thanks to Prof. S. Kawata for giving me the opportunity to work at LaSIE, to Y. Okuno for his helpful lessons, to the members of LaSIE and to last but certainly not least Dr. S. Kuwahara for his endless patience and guidance for without whom I could not have accomplished such a project. Fig. 4 – TERS Schematic Fig. 3 – Deformations in CNT • Deformations alter the CNTs’ energy band structure thereby altering their characteristics • Shifts in the phonon modes result from these alterations 2 • Used an AFM-Raman System comprised of a SII AFM system and Nikon Optical Microscope • Far-field image of the SWCNT was taken by raster scanning the sample with the setup in Fig. 4 but with the tip and evanescent mask removed Using a silicon Dynamic Force Microscopy (DFM) tip, a ~430 nm horizontal defect was introducedFig. 5 – AFM Image of Tip-Induced Deformation in CNT BEFORE AFTER 3 Process Raman Spectrometer Beam Profile (High NA) Evanescent Mask Expander Objective Lens (60x, NA = 1.4) Beam Splitter Near Field Probe (Silver Coated AFM Tip) Sample Longpass Filter Raman Signal Confined Field Focus Spot (~300nm) Diode Pumped Laser 532nm,10mW Expanded Laser Beam Carbon Nanotube Mirror G+ G- D RBM Fig. 2 – Raman Spectrum of CNT 1. Mono. Source Excites Sample 2. Molecules Vibrate & Scatters Light 3. Rayleigh Removed 4. Raman Spectra Detected METHOD 4 Before AFMRaman Manipulation AfterManipulation Raman AFM Intensity Profile at Manipulation Point CNT manipulation could not be discerned from TERS Image Raman SpectrumNear-field TERS Image 1μm Manipulation region was about 5 nm wide - determined with DFM Indicates a bundled structure containing 4 or 5 SWCNT Raman Spectra At Manipulation Point ΔG+ = 1.7 cm-1 ΔG- = 1.3 cm-1 ΔD = N/A (Low SNR) ΔRBM = 8 cm-1 Peak Shift Far-field Bundle Width~400nm RBM G+ G- D Intensity Decreases Raman at brightest point Raman Image Centered at G+ 1584 cm-1 Raman Image Centered at G+ 1586 cm-1 Manipulated SWCNT Bundle AFM 1 2 3 Measurement Taken Within RESULTSBACKGROUND Z. Liu, et. al., Chem. Comm.2009, 6902 (2009).