Raman signatures of electron-phonon interactions and degree of commensurability in

artificially stacked twisted bilayer graphene superlattices

Vineet Pandey1*, Subhendu Mishra2, Abhishek Singh2, Vidya Kochat1

1
Materials Science Centre, Indian Institute of Technology, Kharagpur, West Bengal-721302,India
2
Materials Research Centre, Indian Institute of Science, Bengaluru-560012,India
*Email: vinpan2020@[Link]

Introduction Raman studies of Twisted Bilayer Graphene TBLG bandstructure evolution studies
• Two graphene layers vertically stacked with a relative twist comprises a 3 𝑎0 𝐸 𝐿 First-principles DFT calculations shows vHs points which play a major
twisted 2D system with superlattice-induced modified bandstructure G-peak resonant condition 𝜃𝐶 = role in determining the optical transitions. In TBLG, the allowed
4 𝜋 ℏ𝑣𝐹
and a playground of emergent phases. transitions are from 1-3 and 2-4, while 1-4 and 2-3 transitions are
When the Dirac cones of the top and bottom layers overlap, the DOS is forbidden. When the excitation laser energy EL matches the energy
• Moiré structures in Twisted Bilayer Graphene (TBLG) systems gives
modified due to the interactions leading to hybridization gap and vHs separation of allowed transition (transition 1-3 or 2-4), a large number of
rise to the van Hove singularity (vHs) as a consequence of the periodic
emerge in the conduction and valence bands of TBLG. When the excitations occur and give G-peak enhancement for particular twist angle.
modulation of the electronic potential landscape and the coupling
excitation laser energy EL matches this energy separation between the
between the Dirac cones.
conduction and valence band vHs, which in turn is dependent on the
• Raman spectroscopy to determine how twist angle determines the twist angle θ, resonance occurs for the G-peak transition.
fundamental properties such as mechanical coupling, elasticity,
electronic band structure and electron-phonon coupling in twisted 2D
systems.
θ
Moiré Pattern
AA M-band and combinational modes in TBLG

AB • The absence of M band indicates significant weakening of the

interlayer interactions as compared to Bernal stacked BLG which
M
TBLG PRL 109, 196802 (2012) renders the oTO phonon inactive. The observation of the M-band at
12.5°coinciding with the G-peak resonance enhancement, suggests its
Fabrication of Twisted Bilayer Graphene For 532 nm laser, 12.5O origin related to the resonant excitation between vHs and inelastic
scattering involving oTO phonons.
Tear and stack method
• Combinational Raman modes of TBLG occurs in the range of 1700
cm−1 to 2100 cm−1 shows transition from commensurate (C) to
(a) (b) (c)
2D band evolution as a function of twist angle incommensurate (I) TBLG systems , as LO-TO’@Γ (≈1860 cm-1 ) and
Stamp holder SLG
TOZO@K (≈ 2000 cm-1 ) disappears for twist angles 20°and 30°.
h-BN PPC/PDMS Si/SiO2
Substrate • 2D-peak for twist angles greater than 10°shows significant blueshift
• We also observe a significant blue shift of the phonon modes associated
65oC 35oC 55 C o
and maximum at θC when large number of optical transitions occur due
with LOTA and LOLA at higher twist angles when compared to that of
Substrate holder to the vHs which increases the joint DOS. There is also a transition SLG. This shows a stiffening of the phonon modes possibly due to a
(f) (e) (d)
from linear dispersion to a flat band dispersion, due to which the compressive strain in I-TBLG as opposed to the C-TBLG.
phonons giving rise to intervalley scattering have larger wavevectors
𝛉 which also explains the huge blue shift of the 2D peak at θC.
TBLG/h-BN

85oC 35oC • With increase in twist angle, the intensity ratio of the 2D peak to the G
TBLG on Si/SiO2
peak, I2D/IG increases to about 4 times that of SLG, while the FWHM
-rotation of the single Lorentzian reduces and becomes similar to that of SLG.

10 µm
8°

10 µm

Commensurate-incommensurate TBLG 4 µm

• For small values of twist angles, the atoms adjust with the
superlattice landscape forming an energetically favourable
commensurate system, by gaining van der Waals energy, but at Conclusion
the expense of elastic energy. 2 µm 2 µm

• As the Moiré period becomes smaller, the van der Waals energy • The changes in the interlayer interactions in TBLG and electron-
gain over the elastic energy loss is no longer compensated, phonon scattering pathways as the twist angle is varied from 0 to 30◦ is
leading to an incommensurate system of bilayers, where each probed using Raman spectroscopy.
layer is independent of the other.
• The long range Moiré potential of the superlattice gives rise to
7 µm 7 µm

30° additional intravalley and intervalley scattering of the electrons in

10° 12.5° TBLG which have been investigated through their Raman signatures.
• The density functional theory (DFT) calculations of the electronic band
structure of the TBLG superlattices was found to be in agreement with
the resonant Raman excitations across the van Hove singularities in the
valence and conduction bands predicted for TBLG due to hybridization
of bands from the two layers.
• We also observe that the relative rotation between the graphene layers
10° 12.5° has a marked influence on the second order overtone and combination
30° Raman modes signalling a commensurate-incommensurate transition in
TBLG as the twist angle increases.
• This serves as a convenient and rapid characterization tool to determine
Raman signatures of Moiré the degree of commensurability in TBLG systems.
potential – induced scattering
Short range moiré pattern
Preserve Long range moiré pattern &
Lack translational symmetry
Translational symmetry
(Incommensurate TBLG)
(Commensurate TBLG)

𝒒=𝒒𝟏 −𝒒 𝟐

1.5
𝒒
𝒒 𝟏θ
𝒒𝟐 Acknowledgements
Γ
Moiré Wavevector, (Å-1)

The authors acknowledge the funding from SERB

Startup Research Grant, DST Nanomission, India,
1.0 AOARD (Asian Office of Aerospace Research
𝑞 ( θ )=
8π
√3𝑎
sin ( )
𝜃
2
and Development) under Grant No. FA2386-21-
1-4014 and JSPS KAKENHI (Grant Nos.
19H05790, 20H00354, and 21H05233). We thank
0.5 • Rʹ-peak observed near 1625 cm-1 for 8°, arises due to the intravalley the Materials Research Centre (MRC) and Solid
. double resonance (DR) process elastically scattered with Moiré State and Structural Chemistry Unit (SSCU),
potential. Indian Institute of Science, Bangalore, for
5 10 15 20 25 30
Twist angle (º) • R-peak arises from the inter-valley DR scattering at ∼ 1375 cm −1 and providing the required computational facilities
∼1435 cm−1 for 30°and 20°respectively. and support from The Institute of Eminence (IoE)
scheme of MHRD, GoI.

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