Beruflich Dokumente
Kultur Dokumente
Cinzia Casiraghi
Fachbereich Physik, Freie Universitt Berlin
RAMAN SCATTERING
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electron
phonon
electron
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incident photon
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MOLECULES: Raman spectroscopy probes excitation states of molecules and molecules structure CRYSTALS: Raman Spectroscopy probes PHONONS
GRAPHENE
RESONANT RAMAN
Non-resonant Raman Resonant Raman
RESONANCE PROFILE
i s k
Incident resonance
Scattered resonance
Raman in graphene is ALWAYS resonant Raman Spectroscopy is sensitive to the electronic structure
(q, -q)
(q=0)
2D PEAK
6
5 m
3 2 1
Graphene
*1 1
*2
K K
DOPED GRAPHENE
DOPED GRAPHENE
Das et al, Nature Nan. 2008; Casiraghi, RRL 3, 175 (2009); Casiraghi, PRB 80, 125422 (2009)
DEFECTS
GRAPHITIC SYSTEMS - Graphite - Pyrolitic graphite - Carbon fibers - Amorphous carbon & Diamond-like Carbon - Ribbons - Fullerenes - Carbon Nanotubes - Graphene TYPE OF DEFECTS - Stacking order - Crystalline size - Structural disorder (vacancy, topological defect, bond distortion, sp3 conversion) - EDGES
1. STACKING ORDER
Reflectivity measurement Glass Folded
GRAPHENE
Folded graphene
Turbostratic graphite
Lespade et al, Carbon 1984; Cancado et al, APL 2006; T. Moldt et al, in preparation
2. CRYSTALLINE SIZE
D PEAK
Tuinstra-Koenig relation
Lespade et al, Carbon 22, 375 (1984); Tuinstra & Koenig, J. Phys. Chem. 53, 1126 (1970)
3. STRUCTURAL DISORDER
D PEAK
DISORDERED Graphene
Exposure to UV light (244 nm, ~1mW)
GRAPHANE
(see Fluoro-graphene)
k K
OVERTONE : 2D PEAK (always active: q-q=0) DEFECT-activated peak: D PEAK: corresponds to a phonon far from (against selection rule)
Defect allows momentum conservation D and 2D peak frequency shifts with the excitation energy D and 2D peaks changes with the number of layers
Thomsen and Reich, PRL 2000
4. EDGES
- Nanoribbons technology - Localized states at Zigzag edges - High reactivity
The edges of exfoliated graphene seems to follow perfect crystallographic directions on the macroscopic scale
You et al. APL 93, 163112 (2008)
GRAPHITE EDGES
AFM
ARMCHAIR
STM
ZIGZAG
ARMCHAIR edge High I(D) ZIGZAG edge Low I(D) D peak intensity does not change for different edges
D PEAK
D PEAK
da
Edge direction
1. Meh ~ ein x k max: ein k 2. Backscattering from an ideal edge is possible only at normal incidence k || qa I(D)~ cos2 If we have incident and scattered polarized light: I(D)~ cos2in cos2sc
Basko, PRB 79, 205428 (2009); Casiraghi et al NL 9, 1433 (2009)
TYPE of EDGES
Momentum conservation upon reflection from an edge depends on the orientation and quality of the edge
(dedge >> e/2)
D PEAK
POLARIZATION
I(D) max for =0 I(D)=0 for =90 I(D) max for II average edge direction; I(D) min I(D) max & min depend on the number and orientation of the armchair segments
D PEAK- EDGE
Edge
La
Electron-phonon scattering rate at K is 40-60 meV (~60 ps-1) at 2.41 eV L~11-15 nm Attempts to extrapolate L from I(D) mapping at the edge give: L= 70-100 nm (upper limit)
Cancado et al, ArXiv 0802.3709; Gupta et al., ACS Nano, 3, 45 (2009)
Doping at EDGES
EDGE
I(D)
No smooth edges
Casiraghi et al NL 2009 Kobayashi et al. PRB 2006; Gupta et al., ACS Nano, 3, 45 (2009)
CONCLUSIONS
D peak intensity depends on: RELATIVE POSITION EDGE/LASER
(see scattering breaking length)
LIGHT POLARIZATION EDGE QUALITY 1. Perfect edge 2. Rough edge DOPING observed at the edge NO PERFECT EDGES observed in micro-mechanical exfoliated graphene, despite they seem to follow perfect crystallographic direction on a macroscopic scale
Acknowledgments
Alexander von Humboldt Foundation Oppenheimer Foundation P. Klar, T. Moldt, FU Berlin A. C. Ferrari, S. Piscanec, Cambridge University K. S. Novoselov, A. K. Geim, Manchester University A. Hartschuh and his group, LMU Munich D. Basko, CNR Grenoble L. G. Cancado, Belo Orizonte Brazil
THANKS !