Raman Spectroscopy of Graphene Edges

Cinzia Casiraghi
Fachbereich Physik, Freie Universitt Berlin

OPTICAL DETECTION TECHNIQUES

Optical detection is FAST, SENSITIVE AND NOTDESTRUCTIVE Light interaction with matter can be elastic or inelastic
RAYLEIGH SCATTERING RAMAN SCATTERING
0
atoms

RAMAN SPECTROSCOPY is a powerful metrology tool

(Resonant conditions; EPC effect)

RAYLEIGH SCATTERING is a perfect tool to quickly map large area substrates

RAMAN SCATTERING
Hep
electron

phonon
electron

|i
incident photon

Her

Her

|f

scattered photon hole

MOLECULES: Raman spectroscopy probes excitation states of molecules and molecules structure CRYSTALS: Raman Spectroscopy probes PHONONS
GRAPHENE

i-s= 0 ki-ks= q~0 RAMAN SELECTION RULE

Crystal lattice Brillouin zone

RESONANT RAMAN
Non-resonant Raman Resonant Raman

Resonant Raman Enhancement of the Intensity

RESONANCE PROFILE

M. Cardona & G. Guntherodt, Light Scattering in Solids II, Springer

Graphene- ALWAYS RESONANT

ph i s k ph

i s k

Incident resonance

Scattered resonance

Raman in graphene is ALWAYS resonant Raman Spectroscopy is sensitive to the electronic structure

RAMAN SPECTRUM OF GRAPHENE

(q, -q)

(q=0)

~K RAMAN SELECTION RULE

Ferrari, Meyer, Scardaci, Casiraghi et al PRL 2006

2D PEAK
6

5 m
3 2 1

2D PEAK SHAPE => IDENTIFICATION OF GRAPHENE

Electronic dispersion vs thickness

Bilayer Bilayer

Graphene

*1 1

*2
K K

2D PEAK shape probes changes in the electronic structure

DOPED GRAPHENE

A. Das et al. Nature Nanotech. 2008

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

Tuinstra-Koenig relation is NOT valid

Ferrari & Robertson PRB 2000; PRB 2001; Casiraghi, Ferrari, Robertson, PRB 2005

DISORDERED Graphene
Exposure to UV light (244 nm, ~1mW)

Casiraghi, RRL 3, 175 (2009)

Chemical derivatives of Graphene

GRAPHENE OXIDE

Gomez-Navarro et al, Nano Lett., 10, 1144 (2010)

Chemical derivatives of Graphene

On substrate Suspended

GRAPHANE

(see Fluoro-graphene)

D peak H content (sp3 content)

Elias et al, Science (2009)

DOUBLE RESONANCE (DR)

k K q
Defect d= -q

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

Sharma et al, NL 10, 398 (2010)

EDGES of exfoliated graphene

Geim, Novoselov, Nature Mat., 6, 183 (2007)

The edges of exfoliated graphene seems to follow perfect crystallographic directions on the macroscopic scale
You et al. APL 93, 163112 (2008)

We need a quick identification technique of graphene edges: RAMAN SPECTROSCOPY ?

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

Cancado et al. PRL 93, 247401 (2004)

RAMAN @edges: THEORY

D PEAK

D PEAK

da

da satisfies DR YES D peak dz does not satisfy DR NO D peak

Basko, PRB 79, 205428 (2009); Casiraghi et al NL 9, 1433 (2009)

LIGHT POLARIZATION dependence

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

Perfect ARMCHAIR Perfect ZIGZAG Atomically ROUGH edge Armchair + Zigzag

Basko, PRB 79, 205428 (2009)

D PEAK- EDGE

Casiraghi et al NL 9, 1433 (2009)

Raman mapping- SINGLE EDGE

Edge

TK relation is not valid!

La

Phase Breaking Length

L= average distance traveled by the electron before undergoing inelastic scattering by a phonon L depends on the quality of the edge For a ideal edge:

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)

EDGE- Polarization dependence

Incident light linearly polarized

Residual I(D) for =90 [I(D)/I(G)]90 > [I(D)/I(G)]bulk

From theory: - Edge composed mainly by armchair segments - Armchair segments oriented along the edge average direction

Doping at EDGES
EDGE

RAMAN ON GRAPHENE EDGES

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 !