Carbon 156 (2020) 470e487

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Carbon
journal homepage: www.elsevier.com/locate/carbon

Review article

A new twist in graphene research: Twisted graphene

Umesha Mogera a, 1, Giridhar U. Kulkarni a, b, *
a
Centre for Nano and Soft Matter Sciences, Jalahalli P.O., Bangalore, 560013, India
b
On lien from Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur P.O., Bangalore, 560064, India

a r t i c l e i n f o a b s t r a c t

Article history: Graphene is perhaps the most studied material around the globe in recent years. It has served as a classic
Received 27 April 2019 example of 2D material not just because of the historical reasons, but importantly, due to distinctly
Received in revised form observable dimensional crossover in it, from 2D to 3D, via Bernal stacked (AB) bilayer to multilayer finally
13 August 2019
culminating in graphite. The interlayer interactions that are thus responsible, however, tend to differ
Accepted 19 September 2019
Available online 23 September 2019
vastly in presence of defects or disorders. Of particular interest is the angular disorder causing the layers
to stack in a manner away from the conventional AB packing. The new class of graphene systems
involving an angular twist among otherwise highly crystalline 2D layers, is often termed as twisted
Keywords:
Graphene
graphene. Among these, twisted bilayer graphene, tBLG, has become archetypical. The twist as a new
Twisted graphene degree of freedom induces several angle dependent properties in tBLG, from visible absorption to su-
Twisted bilayer graphene perconductivity, unheard of in the case of graphene itself. This article overviews the recent developments
Twisted multilayer graphene in twisted graphene covering aspects related to its synthesis, the twist dependent properties and po-
Rotated graphene tential applications.
Turbostratic graphene © 2019 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 470
2. Methods of synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 471
3. Electronic structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 473
4. Raman spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 473
5. Optical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 474
6. Chemical reactivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 477
7. Electronic decoupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 479
8. Superconductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 479
9. Other properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 481
10. Conclusions and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 482
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 483
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 483

1. Introduction essentially a monolayer of sp2 bonded carbon atoms [1e3]. Its 2D

nature results in charge carriers that behave as relativistic massless
Graphene is a two-dimensional (2D) form of carbon allotrope, Dirac fermions [4e6], obeying a linear energy dispersion. Accord-
ingly, graphene exhibits exceptional properties such as very high
field mobility [7e9], anomalous quantum Hall effect [10e12],
* Corresponding author. Centre for Nano and Soft Matter Sciences, Jalahalli P.O., among many others [13e17], and new properties are still being
Bangalore, 560013, India. unearthed. However, these properties change drastically in case of
E-mail address: guk@cens.res.in (G.U. Kulkarni).
1 bilayer graphene (BLG) [18e22] due to the interlayer coupling. For
Present address: Samueli School of Engineering, University of California, Los
Angeles, CA, 90024, USA. example, energy dispersion becomes quadratic accompanied by the

https://doi.org/10.1016/j.carbon.2019.09.053
0008-6223/© 2019 Elsevier Ltd. All rights reserved.
 U. Mogera, G.U. Kulkarni / Carbon 156 (2020) 470e487
opening of a band gap that can be tuned by applying a perpen-
dicular electric field [19,20]. Similar are the scenarios with trilayer
(TLG) [23e25] and multilayer graphene (MLG) [26,27]. Thus with
increasing number of layers, the properties change continually and
finally converge into those of graphite.
In general, dimensionality crossover from 2D graphene to 3D
graphite assumes crystalline AB, also termed, Bernal packing
[25,28,29]. Any deviation from this packing, therefore, seriously
influences the dimensionality crossover and in turn the properties
themselves [23,30e32]. Deviations from AB packing can be ach-
ieved by varying the interlayer distance [33e35], strain [36e39],
translation [40,41], angular rotation [42e46] etc., between the
layers. It is not surprising that earlier studies on graphite were
aimed at expanding the lattice by foreign atoms or ions to form
insertion compounds [47e50]; however, the inserted species
would bring in its own properties and often adversely influence the
properties of the parent graphitic species. On the other hand, tur-
bostratic graphite, known for its random angular registry and
translation between layers [51e55] does look promising, but the
prevalent stacking faults and similar defects tend to destroy its
crystallinity [56,57], rendering it unworthy. With the advancing
studies on graphene, researchers have been mimicking the tur-
bostratic behavior in 2 or in 3-layer systems with controlled
angular mis-registry so as to retain the dimensionality close to 2
and achieve the properties of SLG in such virtually multilayered
systems. Indeed, recent studies have produced groundbreaking
results ranging from visible absorption to superconductivity, which
are simply outside the purview of pristine SLG [58e63]. These
interesting aspects form the subject matter of this review article.
2. Methods of synthesis
In this section, we review recent advances in the method of
preparation of twisted graphene systems. Earlier reports of making
twisted graphene involved accidental folding of SLG [71e73] during
mechanical exfoliation from highly oriented pyrolytic graphite
(HOPG) surface. As it was known that twisted graphene layers
occur naturally at the surface of crystalline graphite side by side of
the conventional AB stacking [74], one may find, by careful exam-
ination, regions of twisted graphene layers [75,76], albeit little
success. Poncharal et al. used controlled flux of water on the edge of
SLG to form folds of SLG [77]. Using AFM tip, Carozo et al. folded SLG
to selectively make twisted region along with single layer region
[78,79]. However, all the above methods are probabilistic,
cumbersome and produce low yield. More conventionally followed
method is based on stacking of two SLGs prepared by chemical
vapor deposition (CVD) [64] (see Fig. 1a). It typically involves
transfer of a SLG onto a substrate using the conventional procedure
of transfer [80e84] where SLG grown on Cu is coated with a
polymer (PMMA) followed by etching of Cu. SLG/PMMA is then
placed on the substrate, followed by removal of PMMA either by
acetone [85e88] or by thermal annealing [89e91]. On top, another
SLG/PMMA is brought in contact and then PMMA is removed. In
order to improve the adhesion between substrate-SLG and SLG-
SLG, it was found desirable to bake at 150
C for 2 h [64]. The
removal of PMMA from the bottom SLG is a key step as one has to
make sure that no PMMA residue remains on top as it may
adversely influence interlayer interaction between the two layers.
To avoid this, one may bring PMMA/SLG onto SLG/Cu so that the
two SLGs face each other directly. However, as CVD grown SLG
comes in random shapes with some degree of polycrystallinity, a
control over the twist angle seems rather difficult with this method.
To address this challenge, Tan et al. [92] developed CVD conditions
to grow square shaped single crystalline SLG. The SLGs were then
stacked by monitoring the directions associated with the edges
471
under an optical microscope so as to ensure a specific twist angle
between the two layers. Another method of stacking of SLGs with
defined twist angle is recently reported by Chen et al. employing a
cutting-rotation-stacking (SRS) sequential process [65]. The SLG
mechanically exfoliated onto SiO2/Si was divided into two pieces by
a femtosecond laser, resulting into a pair of straight and parallel cut
lines (Fig. 1b). With suitable transfer method, the first SLG was
transferred onto a glass substrate clamped to a micromanipulator
while the other was brought onto another SiO2/Si substrate and
placed on a rotation stage. Using the cut lines as reference, the two
SLGs were rotated with angle q and precisely (within 0.1
) stacked
together on the Si/SiO2 substrate.
In another method, Kin et al. introduced a transfer technique
with a better control on the fabrication and crystal axes alignment
to achieve the desired twist angle [66]. The technique relies on a
controlled flake pick-up technique, in which a micron size flake is
selectively detached from the substrate using a hemispherical
substrate with bulb-like handle that can be made using PVA-coated
epoxy. Fig. 1c describes the fabrication process flow of a hetero-
structure consisting of two rotationally aligned SLG on a hBN flake.
To create this, they first exfoliated monolayer graphene and hBN on
separate SiO2/Si substrates. Using the hemispherical handle, a flake
of hBN was initially picked and aligned partially with a SLG on SiO2/
Si under an optical microscope. The handle is then brought in
contact with the substrate, and the area making contact with the
hBN is selectively detached. Next, the hemispherical handle is
translated laterally, brought in contact with the substrate to pick up
the remaining graphene section. The resulting heterostructure
contained a region where the two SLGs overlapped. Due to the
single-crystal nature of the SLG, combined with the spatial trans-
lation of the transfer process, the two SLGs are expected to have
rotationally aligned crystal axes resulting in a well-defined tBLG.
More recently, Wang et al. [67] reported controlled folding of
single crystal SLG to form tBLG (see Fig. 1d). The method involves
selective modification of a SiO2/Si substrate to form hydrophobic
and hydrophilic regions with a clear interface between the two.
SLG/PMMA was then placed on the modified SiO2/Si substrate and
immersed in water. Delamination of the SLG from the substrate
occurs from the hydrophobic region which, with controlled and
careful pulling of the substrate from the hydrophobic region, leads
to self-folding of the SLG. The PMMA was then removed off. By
changing the angle between the hydrophilic/hydrophobic bound-
ary and the edge of the substrate used for folding (the fold angles),
an appropriate fold angle could be chosen resulting in the desired
twist angle. Liu et al. [68] have developed appropriate CVD condi-
tions to directly grow tBLG on Cu substrate (see Fig. 1e) using
decaborane as co-catalyst. At the initial growth stage, methane
molecules are catalytically decomposed on the surface of Cu foil
with the assistance of decaborane, and subsequently, BLG islands
(seeds) are formed. When the growth time is further increased, BLG
islands laterally grow and finally, these islands merge into a
continuous BLG film. Taking clue from previous literature [93e95]
that a high value of the surface diffusion coefficient aids the for-
mation of AB stacking order, authors stated that decaborane, being
the co-catalyzer for methane decomposition, hinders the diffusion
of active carbon species resulting in the formation of twisted BG
film. By this method, though large area tBLG can be grown,
controlled and uniform twist in the sample is not possible. In a
similar approach, single crystals of tBLG are grown under optimized
CVD conditions such as temperature, hydrogen partial pressure,
methane concentration, and copper surface conditions (Fig. 1e,
right) [69]. In another method by Mogera et al. [70,96], tMLG is
grown on a joule heated Ni foil using polyaromatic hydrocarbons
(PAHs) as the carbon source (see Fig. 1f). The angular rotations in
the grown tMLG are generated due to fast cooling of the metal foil,
472 U. Mogera, G.U. Kulkarni / Carbon 156 (2020) 470e487

Fig. 1. Different synthetic methods of twisted graphene.

(a) Schematic of process flow used in forming twisted bilayer graphene (tBLG) from stacking of two CVD grown single-layer graphene films. Optical microscopy image (right side) of
tBLG transferred onto SiO2/Si is shown. Adapted with permission [64]. Copyright 2013, American Chemical Society. (b) Schematic of the cutting-rotation-stacking (CRS) technique
used to fabricate tBLG and tTLG (twisted trilayer graphene) with precise control over the twist angle. It involves cutting of SLGs into two parts by a femtosecond laser beam to form a
pair of parallel edges. Using cutting lines as a reference, layers can be placed with precise rotation. Optical microscopy images with tBLG with 13
twist and tTLG with 7
and 13

twists are shown. Adapted with permission [65]. Copyright 2016, John Wiley and Sons. (c) Rotationally aligned tBLG achieved by successive transfers of a SLG. (i) Schematic of pickup
of SLG using a hemispherical handle substrate (red box). (iieiv) Schematics and corresponding optical micrographs of successive stacking steps. Adapted with permission [66].
Copyright 2016, American Chemical Society. (d) Schematic of controlled folding of a SLG involving substrate modification, folding driven by delamination from only the hydrophilic
region, and the removal of polymers. Optical microscopy images (right side) of transferred tBLGs onto SiO2/Si with twist angles. Adapted with permission [67]. Copyright 2017,
 U. Mogera, G.U. Kulkarni / Carbon 156 (2020) 470e487
but not compromising the 2D crystallinity of the individual layers.
This method is rapid and can produce large domains of tMLG
(~100 cm2), however, with little control over the twist angles.
3. Electronic structure
When two graphene layers are AB stacked, as in case of BLG, the
interlayer interactions between them destroy the relativistic nature
of charge carriers that are prevalent in SLG [18,21,100,101]. How-
ever, the scenario is quite different when graphene layers are
stacked with a certain rotation or twist, q (see Fig. 2a) [102e105]. As
a result, tBLG hosts two separate Brillouin zones shifted angularly
by the same twist, q (see Fig. 2b). Accordingly, the corresponding
Dirac cones shift by ‘DK’ with allowable overlap leading to a
reconstructed band structure shown in Fig. 2c. The energy bands at
the overlapping region tend to bend leading to logarithmic diver-
gence in the density of states (DOS), known as the van Hove sin-
gularity (vHS) [106e108]. While the SLG exhibits linearly increasing
DOS as one moves away from the neutrality point, tBLG presents
two vHSs in the DOS, one above and the other below the Fermi
level. The presence of vHSs in tBLG was first observed by Li et al.
[108] using STM (scanning tunneling microscopy) and STS (scan-
ning tunneling spectroscopy) measurements, which was later
extensively studied [106,107]. The most intriguing property of these
vHSs in tBLG is that the energy difference between vHSs varies
linearly with the twist angle [97], as also quantitatively measured
using STS technique (see Fig. 2d and e). The presence of vHS was
further confirmed by Yin et al. [98] using micro-ARPES where
overlapping of two Dirac cones is clearly seen (see Fig. 2f). Another
important property which interested many physicists is that the
Fermi velocity of tBLG varies sensitively at lower angles whereas at
higher angles, it follows that of SLG (see Fig. 1g) [99]. In other
words, when the twist angle is sufficiently large (>5
), the elec-
tronic properties of tBLG are identical to that of SLG. Further, there
exists a superlattice structure observed as a Moire
pattern (MP)
between two layers whose periodicity is different from that of SLG
and BLG [109e112]. Importantly, the periodicity, P, varies with the
varied twist angle as can be seen in STM images shown in Fig. 2h
and given by the equation sin(q/2) ¼ 0.123/P(nm) [97]. Using
continuum-based model, Dai et al. [113] demonstrated that tBLG
does not possess a perfect Moire
pattern, but rather a pattern with
bulges representing twisted dislocation structures.
4. Raman spectroscopy
Raman spectroscopy is a powerful technique to study the
properties of graphene [115e117]. Typical Raman spectrum of
graphene contains the G band at around 1580 cm1, originating
from first order Raman scattering of sp2 carbon atoms and the 2D
band, originating from a second-order Raman scattering involving
two phonons; the latter varies sensitively with the number of
graphene layers as well as the strength of the interlayer coupling.
SLG is characterized by single Lorentzian 2D band with FWHM
~30 cm1 and 2D/G integral intensity ratio (I2D/IG) between 2 and 5
[118e120]. However in high quality graphene samples, narrowest
FWHM, as low as 16 cm1, and high I2D/IG, up to 12, are seen
[121e123]. In BLG, the 2D band loses its single Lorentzian shape
American Chemical Society. (e) CVD growth of tBLG on Cu. The decaborane coated Cu foil was subjected to CVD conditions to grow twisted BG seeds which merge into a continuous
film upon increasing the growth time. Optical microscopy image of large area tBLG transferred onto SiO2/Si is shown along with electron diffraction patterns acquired at different
regions. Adapted with permission [68]. Copyright 2015, Nature Publishing Group. Right, a SEM image of tBLG array. Before the growth of BLG, an array of carbon seeds was made on
Cu foil, followed by the AP-CVD growth at optimized parameters. Adapted with permission [69]. Copyright 2017, American Chemical Society. (f) Schematic of synthesis of twisted
multilayer graphene (tMLG), involving drop coating of polyaromatic hydrocarbons (PAHs) on a Ni foil followed by Joule heating to red hot (~ 900
C) and rapid cooling. Electron
diffraction pattern (right side) is shown where spots representing differently rotated layers are marked with colored radial lines. Adapted with permission [70]. Copyright 2013,
American Chemical Society. (A colour version of this figure can be viewed online.)
473
with broadened FWHM (>50 cm1) and decreased I2D/IG (between
1 and 2) [124]. In case of MLG, the I2D/IG further decreases with a
left shoulder in the 2D band. In the context of twisted graphene
system, the I2D/IG value and the peak shapes become important, as
any twist among layers significantly influences the interlayer in-
teractions [125e127]. In this direction, Kim et al. [114] measured
Raman spectrum of tBLG with controllably varying the twist angle
from 0
to 30
with 1
steps and observed sensitive variations in
intensity, width (FWHM) and shift of G and 2D bands with
changing twist angle as summarized in Fig. 3. It is apparent that at
lower angles (<8
), the Raman spectra resemble that of MLG (low
I2D/IG and high 2D width), whereas at higher angles (>13
), the
spectra match closely that of SLG.
Although the position and width of the G band are unaffected,
the intensity tends to be highly angle dependent (see Fig. 3b). The
most striking observation is that there is a strong enhancement of
the G band at an intermediate twist angle (10
). As shown in Fig. 3c,
there is a 30-fold increase of G-band intensity at a twist of 10
,
compared to other angles where the intensity remains low and
similar. However, when lex is changed from 1.96 to 2.41 eV (see
Fig. 3d), the G-peak enhancement shifts to a higher angle (~13
).
The inset of Fig. 3d reveals a linear relation between the experi-
mental laser excitation energy and the twist angle at which the G-
band enhancement is observed (also called as critical angle). Fig. 3i
describes the Raman process involved in the G-band enhancement.
At the vHSs, there exist additional electron-hole excitations giving
rise to increased G-band intensity under the resonance conditions.
Since the energy difference between the vHSs is a function of the
twist angle and a resonance condition is essential, the varied twist
angle in tBLG demands that lex be varied to observe the G-band
enhancement (see Fig. 3d).
The behavior of the 2D band of tBLG is even more complex
associated with non-monotonic changes with respect to the twist
angle. Fig. 3e shows a magnified portion of the spectral region
where the 2D band is seen to be wide at small angles and appears
similar to that of SLG at larger angles. However, the variation in the
width is non-monotonous (see Fig. 3f) with an abrupt increase
around 8
. The peak position also shows a similar trend, blue-
shifted with reference to SLG (see Fig. 3g). The shift becomes
nearly angle independent only at higher angles (>17
). Interest-
ingly, the twist angle associated with the sharp changes, coincides
with the value at which the G-band enhancement is seen, thereby
implying that these features share a common origin. Going with
these observations, the intensity of 2D band (Fig. 3h) also shows
significant changes with respect to the twist angle. Interestingly at
higher angles, it is similar or even greater than the value found in
SLG. For noninteracting tBLG, one would expect a two-fold increase
in the 2D peak intensity as compared to the SLG (much the way the
G band does). This indicates that at higher angles, tBLG is essen-
tially a two noninteracting graphene layer system. Fig. 3j describes
the Raman processes involved in the 2D band of tBLG. When twist
angle is large, larger than critical angle, qC, the two Dirac cones of
tBLG are sufficiently distant. As a result, all the excitations effec-
tively occur in isolated Dirac cones (as shown by blue line) and
hence, tend to exhibit Raman features similar to SLG. Whereas at
lower angles, due to closeness of the Dirac cones of the two layers,
the scattering paths are significantly different from those of SLG (as
474 U. Mogera, G.U. Kulkarni / Carbon 156 (2020) 470e487

Fig. 2. Structural and unique properties of tBLG.

(a) Schematic of two graphene layers rotated with an angle ‘q’. (b) Brillouin zone (BZ) of tBLG with the separation between Dirac cones, DK. The circles represent the locations of
Dirac cones c) Energy dispersion relation in the vicinities of two Dirac cones where van Hove singularities (vHSs) are induced from band-overlap between the cones. Energy
dependence of density of states (DOS) near the Fermi level of tBLG are shown on the right. (d) Local DOS spectra acquired from tBLG with different twist angles. The curves are
shifted vertically for clarity. The arrows point to the vHSs. (e) Variation of separation of vHSs with twist angle. (aee) Adapted with permission [97]. Copyright 2012, American
Physical Society. (f) The ARPES spectrum confirming the presence of vHSs in tBLG (indicated by red arrows). The right curve is integrated energy spectrum density curve (EDC).
Adapted with permission from Ref. [98]. Copyright 2016 Nature Publishing Group. (g) Twist angle dependent Fermi velocity renormalization in tBLG. Red curve is the fit to the
theoretical equation. Adapted with permission [99]. Copyright 2011, American Physical Society. (h) STM images showing emergence of Moire
patterns (MP) in tBLG with varied twist
angles. Adapted with permission from Ref. [97]. Copyright 2012, American Physical Society. (A colour version of this figure can be viewed online.)

shown by black lines) and hence, behave differently.
In addition to D, G and 2D bands, Raman spectrum of tBLG
contains a new family of bands as shown in Fig. 4. The positions of
these bands vary with the twist angle suggesting that their origin
relates to overlapping of Dirac cones in the electronic structure.
Going from left to right in Fig. 4a, we see a set of bands (* marked)
whose positions drift with the twist angle. Solid lines in Fig. 4b is
the frequency variation of phonon branches with q (as derived from
q values) [79,128]. When twist-dependent Raman frequencies
(from Fig. 4a) are inserted in Fig. 4b (scatter points), each follows
one or the other phonon branch of tBLG, suggesting that all these
Raman frequencies are indeed related to phonon branches of tBLG.
Based on this observation, the Raman bands could be assigned to
different phonon branches of tBLG i.e. ZO0 , TA, LA, ZO, TO, LO where
Z stands for out of plane modes; T and L stand for transverse and
longitudinal whereas A and O stand for acoustic and optical
branches, respectively. In the recent literature, the bands appearing
from TO and LO branches also referred to as R and R’ bands
respectively [131]. These two bands are widely observed in tBLG
[78,79] and are used for assigning the twist angle in a given sample
[127,132].
Twisted graphene exhibits interplanar vibration modes
[133,134], shear (C) and layer breathing (LB) modes as well, whose
frequencies are governed by the strength of the interlayer coupling.
The C mode arises due to the relative motion of planes (layers) in a
direction perpendicular to the normal whereas the LB mode is due
to motion parallel to the normal. These modes are relatively weak
to be observed in untwisted BLG and MLGs due to weak electron-
phonon coupling [135,136]. However in case of tBLG, using reso-
nance conditions, such modes can be made as intense as the G
band. Fig. 4c shows the presence of C and LB modes in a twisted
multilayer graphene, t(1 þ 3)LG (one twisted layer with three
Bernal stacked TLG) at different twists where the C modes appear
at ~ 36 and 21 cm1 and the LB modes, at 116 and 93 cm1,
respectively. In each case, the resonance condition is matched by
correlating the twist angle and the excitation energy. Fig. 4d shows
different C modes and their positions for a given number of layers
in a tMLG. In general, for a t(mþn)LG, the total number of C modes
is given by m þ n-2 [130].
5. Optical properties
Following initial confirmation of vHS formation in tBLG [105],
various experimental and theoretical results followed dealing with
variations in the energy gap of vHSs with the twist angle
[79,97,126]. For example, dot-dashed and dashed lines in Fig. 5a are
theoretically calculated band gap values using the density func-
tional theory (DFT) [79,114,139] whereas solid triangles refer to
those from the extended tight binding method [126]. Interestingly,
the vHS band gap coincides with laser excitation energy (Elaser) at
which G-enhancement takes place i.e. EvHS ¼ Elaser. The EvHS vary
linearly at lower twist angles, up to 20
, beyond which it asymp-
totically saturates near 30
as evident in Fig. 5b. In the range of
30
e60
, EvHS follows a trend related by mirror symmetry to its
variation in 0
e30
range and at higher values, 60
e120
, the trend
is similar to the 0e60
variation due to the translational symmetry
[140,141]. The most striking observation is that the energy band gap
of vHS is found lying in the visible spectrum of electromagnetic
radiation which is absent in any other known form of graphene. An
empirical formula describing the EvHS and the twist angle is given
 U. Mogera, G.U. Kulkarni / Carbon 156 (2020) 470e487 475

Fig. 3. Raman spectroscopy of tBLG.

(a) Raman spectra of tBLG measured at different twist angles using laser excitation energy (lex) of 1.96 eV (633 nm). The spectra are shifted vertically for clarity. Raman spectrum of
SLG is shown for comparison. (b) Magnified G band of tBLG with twist angles. G band enhancement was seen at twist angle of 10
and referred to as critical angle (qc). Dependence
of G band intensity on the twist angle acquired with lex of (c) 1.96 and (d) 2.41 eV. The filled and unfilled symbols show experimental and theoretical values, respectively. The lines
are guides to the eye. The inset of (d) shows linear relation between of G-enhancement angle (critical angle) and lex. (e) Magnified 2D band of tBLG with twist angles along with the
2D band of SLG. The vertical dashed line represents the center of single-layer 2D band. Variation of (f) FWHM, (g) blueshift and (h) normalized intensity of 2D band with the twist
angles. The black squares and red circles are the experimental and theoretical values respectively. The grey (experiment) and red (calculation) areas serve as guide to the eye.
Intensity values of G and 2D bands were normalized to the SLG value. (i) Raman processes that contribute to the G band enhancement. (e) Intervalley 2D Raman scattering processes
for tBLG in which the laser excitation energy is smaller (blue lines) or larger (black lines) than the energy difference between van Hove singularities. (aei) Adapted with permission
[114]. Copyright 2012, American Physical Society. (A colour version of this figure can be viewed online.)

by EvHS ¼ Elaser ¼ E0|sin3q| where E0 ¼ 3.9 eV [141]. The maximum
energy absorption occurs at q ¼ 30
, coinciding with the largest
possible separation between the Dirac points. Carozo et al. [141]
theoretically extracted the optical absorption spectra of tBLG with
different twist angles which distinctly show an absorption
maximum in each spectrum (see Fig. 5c). Clearly, the wavelength
associated with the maximum increases with the twist angle (up to
30
) and decreases on further increase in the twist, much like the
trend seen in Fig. 5b. It is important to note that the appearance of
such absorption maxima which is a result of electronephoton
interaction, occurs independent of the G-band enhancement
although both processes occur at the same set of values of the laser
energy and the twist angle.
Although the occurrence of additional absorption bands had
been proposed on theoretical grounds, the experimental observa-
tion remained challenged, perhaps due to weak intensities associ-
ated with the features that merge with the large transmittance
background of BLG (~94%). Using hyperspectral microscopy imag-
ing technique, Havener et al. [137,139,142] extracted the absorption
spectra of tBLG from its optical conductivity (s) in UVeViseNIR
region (see Fig. 5d). The Bernal stacked BLG (top curve) possesses
constant s at IR and visible energies [16,137], and shows a peak
near 4.6 eV due to saddle point exciton (p-p* transition) whereas
tBLG exhibits an extra s peak whose energy increases from ~
2e4 eV with increasing q. Importantly, the position of this peak
with q varies in accordance with the theoretical prediction. On the
other hand, one can also identify tBLG regions, in the mixture of
SLG, BLG and MLG domains using optical colour contrast method
when these flakes are displayed on a SiO2/Si substrate [64]. Fig. 5e is
an optical microscopy image of a tBLG film with distinct regions
that appear red, yellow, and blue. Interestingly, thermal annealing
or solvent cleaning processes do not seem to change the distinct
coloration, suggesting that the observed colors are not related to
any surface residues but truly represent an intrinsic behavior of
tBLG. Using an imaging spectrometer, contrast spectra can be
derived selectively on the yellow, red and blue regions as shown in
Fig. 5f. Clearly, in each curve, there is a distinct peak indicating
enhanced absorption.
Using q-dependent enhanced absorption of tBLG, Patel et al.
[138] reported photoluminescence (PL) emission from a tBLG after
resonant 2-photon excitation. They spatially imaged the individual
tBLG domains at room-temperature and showed a five-fold reso-
nant PL-enhancement on selective tBLG domains over the back-
ground hot electron emission. Fig. 5g and h are absorption and PL
maps respectively, acquired on same tBLG region where 18.3
do-
mains are resonantly excited. The corresponding PL map collected
at 1.26 eV excitation, strikingly has two 17.5
domains with a ~5X
enhancement of PL intensity relative to the PL from the neighboring
tBLG domains. The twist angles assigned by 1-photon linear ab-
sorption spectra spectrally overlap with the corresponding 2-
photon PLE peaks with an energy difference of d.
The enhanced q-dependent optical absorption in tBLG provides
476 U. Mogera, G.U. Kulkarni / Carbon 156 (2020) 470e487

Fig. 4. Raman sub bands.

(a) Raman spectra of tBLG exhibiting sub bands whose positions change with the twist angle. Their variations with the twist angle is shown by a transparent green strip. Each band
is assigned to a phonon branch. Red, green and blue color stand for spectra obtained with Elaser ¼ 1.96, 2.41 and 2.54 eV, respectively whereas in a given color, different spectra are
related to different twist angles (angle increases going from top to bottom). (b) Variations of frequency of phonon branches (solid lines) with the twist angle where experimental
data (scatter points) of twist-dependent Raman frequencies are also given. The phonon branches are indicated alongside each curve. (aeb) Adapted with permission [128].
Copyright 2013, The Royal Society of Chemistry. (c) Twist dependent shear mode (C) and layer breathing (LB) modes of a t(1 þ 3)LG. Adapted with permission[ [129]. Copyright 2016,
Elsevier Ltd. (d) Layer position and number dependent C modes in tMLG. Adapted with permission [130]. Copyright 2014, Nature Publishing Group. (A colour version of this figure
can be viewed online.)

a new way to realize tunable optical devices with three adjustable
parameters, the twist angle, the laser energy and its polarization,
the latter assumes significance as absorption of graphene for s-
polarized light is substantially larger than that for p-polarized light
[143,144]. Recently, Chen et al. [67] defined four regions containing
different types of graphene films i.e. a SLG, Bernal stacked BLG and
tBLGs with twist angles 10
and 13
(see Fig. 6a) and demonstrated
enhancement of the optical absorption selectively. The total inter-
nal reflection (TIR) method which relies on the absorption differ-
ence for s and p-polarized lights, was employed as any
enhancement in absorption would reflect in increased absorption
difference for a given polarization. The latter measured along the
lines is shown in Fig. 6a, while the difference profiles for two laser
energies, 633 and 514 nm are in Fig. 6b. Clearly, around 35%
enhancement was observed in the case of 13
tBLG with 514 nm
light, whereas the 10
tBLG required 633 nm to show a similar
enhancement. These effects are seen vividly in the absorption maps
shown in Fig. 6c and d for the two laser energies. Thus, on a given
platform, pixelated regions with different optical properties can be
realized.
The photoconductivity of tBLG also depends on the polarization
of the light (Fig. 6e) and it follows the absorption; an enhanced
absorption leads to enhanced photocurrent in the device. The
dependence of the latter with the twist angle has been investigated
[67]. As shown in Fig. 6f, the photocurrent of tBLG could be
significantly and selectively enhanced by choosing a s-polarized
light of an appropriate wavelength for a given twist in the graphene
system. Similarly, Yin et al. [98] enhanced the photocurrent gen-
eration in tBLG device by tuning the twist angle and the laser en-
ergy. On a SiO2/Si substrate, two adjacent tBLG domains with twist
angles of 13
and 7
were defined to form two two-terminal devices
in parallel (see Fig. 6g and h). Below in the Raman spectral map, the
G-band intensity from the 13
domain, is seen 20-fold enhanced
compared to that from the 7
domain. Further, scanning
 U. Mogera, G.U. Kulkarni / Carbon 156 (2020) 470e487 477

Fig. 5. q-dependent optical properties of tBLG. Variations of EvHS of tBLG with the twist angle ‘q’ in the range of (a) 0
e30
and (b) 0
e120
. Symbols are experimental data whereas
the solid lines are fitted lines using equations. (c) Theoretical optical absorption spectra of a tBLG with different twist angles. (aec) Adapted with permission [79]. Copyright 2013,
American Physical Society. (d) Experimental optical absorption expressed as optical conductivity for BLG (top curve) and tBLG with varying twist angles. Dashed lines are the
features in the spectra of tBLG that are not found in BLG. Corresponding electron diffraction patterns are shown on the right, indicating q for each. Adapted with permission [137].
Copyright 2014, American Chemical Society (e) Optical microscopy image of a tBLG film transferred onto a SiO2/Si substrate showing “red”, “yellow”, and “blue” colored domains,
captured with no filters. (f) Contrast spectroscopy of red, yellow and blue regions measured with reference to large angle tBLG (q > qc). (eef) Adapted with permission [64].
Copyright 2013, American Chemical Society. (geh) q-tunable photoluminescence of tBLG. Linear absorption map (g) of a tBLG region taken at 2.9 eV excitation showing absorption
enhancement at 18.3
domains. Scanning PL map (h) of tBLG at 2-photon excitation (2  1.26 eV) showing PL emission enhancement at the 17.5
domains. Adapted with permission
[138]. Copyright 2019, Nature Publishing Group. (A colour version of this figure can be viewed online.)

photocurrent microscopy were performed by making use of inter- 6. Chemical reactivity

facial junctions at the tBLG-electrode contacts to separate the
photoexcited electrons from the holes. Accordingly, the sign of the
photocurrent was opposite at the two grapheneemetal electrode
interfaces [145e147]. Importantly, the intensity of photocurrent
generated at the 13
tBLG domain was 6.6 times higher than that at
the 7
tBLG domain (see Fig. 6i). As shown in IeV curves in Fig. 6j,
both tBLG domains produced pronounced photocurrent shifts and
again, thanks to the enhanced optical absorption with 532 nm, the
13
tBLG domain generated a much larger net photocurrent
(0.63 mA) than the 7
domain (0.097 mA). This twist angle-related
photocurrent enhancement holds a great promise in high-
selectivity (wavelength-dependent) photodetection applications.
The chemical reactivity of tBLG was recently studied. Liao et al.
[148] examined q-dependent photochemical reactivity of graphene
with benzoyl peroxide, via the formation of sp3 sites in graphene
(Fig. 7a). The reaction was triggered by the 514 nm laser beam from
the Raman spectrometer and the reaction rate was monitored
through the ‘D’ band intensity, the latter as a measure of the pop-
ulation of newly formed sp3 sites. In Fig. 7b, the D band intensity is
seen to rise with the reaction time; the rise is noticeably sharp in
the case of 13
tBLG compared to that observed for other angles
indicating that its chemical reactivity too is dependent on the twist
angle in tBLG. The reactivity is so dominant with 13
that the re-
action saturates within a few seconds since the onset (see the
478 U. Mogera, G.U. Kulkarni / Carbon 156 (2020) 470e487

Fig. 6. q-dependent enhanced absorption and photocurrent generation in tBLG.

a) Optical image of the graphene array with four different types of graphene films. b) The line scanning results of the sample for 633 and 514 nm lasers. The scanning route is marked
in (a). The horizontal strips refer to SLG and Bernard stacked BLG, respectively. Absorption mapping images obtained by the total internal reflection (TIR) method with laser energies
of c) 514 and d) 633 nm. e) The relationship between the photocurrent and incident light polarization. The upper inset shows the photocurrent obtained with varying laser power. It
was a s-polarized 633 nm light made incident on a region with a twist angle of 10
which is marked in the lower inset. f) Photocurrent response obtained for monolayer and tBLG of
the samples with 10
and 13
twist angles, with s- and p-polarized 514 and 633 nm lights. The scale bars in (a) and (e) are 50 mm. (aef) Adapted with permission [65]. Copyright
2016, John Wiley and Sons. (g) Schematic illustration of a tBLG photodetector device. The channel comprises of two adjacent tBLG domains with different twist angles of 7
and 13
,
respectively. (h) Optical image of the tBLG photodetector and its G-band intensity mapping (below) along the channel. Laser wavelength is 532 nm. Scale bar: 5 mm. (i) Scanning
photocurrent images and its 3D view (below) of the device. Scale bar, 5 mm. (j) IeV curves obtained with laser off (black curve) and while focusing on spots A (blue) and B (red). (g-j)
Adapted with permission [98]. Copyright 2016, Nature Publishing Group. (A colour version of this figure can be viewed online.)

intensity map in Fig. 7c), while at higher angles, the onset itself
appeared sluggish. The enhanced chemical reactivity of tBLG at 13

twist for 514 nm light can be explained by the hot electron transfer
mechanism [150e152]. BPO does not absorb significantly in the
UVevis region while tBLG [151] serves as a light absorbing material
producing hot electrons which tunnel into the unoccupied orbital
of the molecule. The probability of electron excitation in tBLG is
dependent on the DOS and the parallel band transition that occurs
under the resonance condition [139], the latter occurs when the
incident laser energy matches the energy interval of the vHSs of
tBLG. Thus, higher probability of both excitation and tunneling of
hot electrons lead to enhanced reactivity of tBLG when the twist
angle energetics tally with the incident laser energy.
While the previous example relates the reactivity of tBLG with
the twist angle, Ding et al. [149] compared the reactivity patterns of
BLG and tBLG (twist, 25.2
) while reacting with benzyl diazonium.
During the reaction (see Fig. 7e), an electron from graphene is
transferred to aryl diazonium cation forming an aryl radical [153].
This highly reactive radical forms a covalent bond with a previously
formed sp3 defect, the net reaction essentially stabilising the sp3
carbon sites. The sp2 conversion was monitored via the D band
intensity variations (Fig. 7f). In case of AB stacked BLG, the ID/IG
ratio increased gradually saturating at 0.15 whereas in the case of
tBLG, there was not only a sharp increase but a higher saturation
value (~0.55) as well. Accordingly, the characteristic time, t* (time
taken to attain 63% of the total change) was 3.87 and 1.84 h in BLG
and tBLG respectively. Further, Raman mapping acquired on the
BLG region showed negligible changes in the intensity before and
 U. Mogera, G.U. Kulkarni / Carbon 156 (2020) 470e487 479

Fig. 7. q-dependent chemical reactivity of tBLG.

(a) Schematic of photochemical reaction between tBLG and benzoyl peroxide (BPO). The evolution of the D band intensity from tBLG with different twist angles, with increasing
reaction times while being irradiated with 514 nm laser, shown in the form of a plot (b) and a map (c). (d) vHS induced hot electron transfer mechanism associated with the
dissociation of BPO. (a-d) Adapted with permission [148]. Copyright 2015, American Chemical Society. (e) Schematic of the diazonium modification reaction on tBLG and AB-stacked
bilayer graphene, causing the creation of sp3 defects in the top layers. (f) Evolution of ID/IG ratio, a measure of extent of reaction, for AB-stacked BLG and tBLG (twist, 25.2
) measured
after different reaction times. D-band mappings acquired on the same region of tBLG before (g) and after (h) 1.5 h reaction. (eeh) Adapted with permission [149]. Copyright 2016,
American Chemical Society. (A colour version of this figure can be viewed online.)

after the reaction whereas marked differences could be seen in the
tBLG region. The DOS associated with the vHS in tBLG leads to an
enhanced overlap with the unoccupied orbital of the diazonium
salt facilitating the electron transfer thereby increasing the overall
reaction rate.
7. Electronic decoupling
Can one realize most pristine nature of graphene in a twisted
system where the top layer(s) behave as though free from substrate
interference [9,154] akin to suspended graphene? Indeed, the twist
induced interlayer decoupling is expected to play such a role
[103,155,156]. There has been a discussion on this aspect with re-
gard to epitaxial grown graphene on SiC [157e159]. A recent study
has dealt with a twisted multilayer graphene (tMLG, instead of
tBLG) grown via Joule heating based modified CVD technique
[70,121]. Thus produced tMLG contained randomly rotated gra-
phene layers as shown in the schematic (Fig. 8a), derived from the
split yet sharp spots in the SAED pattern (inset of Fig. 8b). Although
multilayered, its Raman spectrum (Fig. 8b) contains a single narrow
Lorentzian 2D band with no ‘D’ band. The narrow width and high
I2D/IG ratio stand for the truly SLG nature of the layers [160]. A two
terminal device made of tMLG (Fig. 8c) showed large regions of
such graphene (Fig. 8d and e). On warming from low temperatures,
the conductivity exhibited a non-monotonous behavior (Fig. 8f)
marked by a transition from a Coulombic disorder dominated
semiconductor behavior to a metallic regime, where the phonon
scattering begins to make significant contribution [161,162]. The
trend in transition correlates with its photoresponse behavior
(Fig. 8g) with a positive photoresponse in the semiconducting re-
gion and a negative photoresponse in the metallic region.
Importantly, the density of charged impurities was low enough that
the crossover was observable below the ambient temperature.
Otherwise, for a SLG laid on a substrate, though of good quality, the
crossover may be at such high temperatures (>1000 K) that it
would be impractical to follow. Observing intrinsic conductivity of
SLG has therefore remained elusive [162] and it is not surprising
that only the semiconducting behavior is commonly seen
[154,163,164]. There have been alternate efforts to reduce disorder
for example, by current annealing of a suspended graphene [165].
8. Superconductivity
As mentioned earlier, the twist between two graphene layers in
tBLG brings out drastic changes in its properties, not prevalent
either in SLG or in BLG. Not surprisingly, tBLG continues to throw
new results, the latest being superconductivity! At a twist angle
~1.1
, referred to as the magic angle, tBLG tends to exhibit an
intrinsic superconductivity. It is known that at low twist angles,
Fermi velocity in tBLG drastically drops down from 106 m/s (see
Fig. 2g) and as a result, the charge carriers become localized [99],
leading to an insulating behavior [167,168]. However, by appro-
priately varying the charge carrier density by means of external
gating, Cao et al. [166] observed a sudden change to a super-
conducting state. The twist angle was tuned precisely to 1.1
and
using such tBLG and hBN film as dielectric, FETs were realized
(schematic in Fig. 9a). The four probe resistance values, Rxx, of the
two devices, M1 and M2, dropped to zero (Fig. 9b) as the temper-
ature was reduced below 2 K. The critical temperature Tc, calculated
using a resistance of 50% of the ‘normal’-state, was found to be 0.5
and 1.7 K respectively, for the two devices.
The authors further studied the gate-dependence conductance
480 U. Mogera, G.U. Kulkarni / Carbon 156 (2020) 470e487

Fig. 8. Interlayer electronic decoupling in tMLG.

(a) Schematic of rotation of graphene layers in twisted multilayer graphene (tMLG). The colored lines mark the edges of the rotated layers and the corresponding twist angles are
denoted. (b) Representative Raman spectrum (lex ¼ 532 nm) depicting narrow 2D band (FWHM ¼ 16.8 cm1) and high I2D/IG ratio (10.2). Inset is the SAED pattern of a tMLG
corresponding to the schematic shown in (a). (c) An optical image of a tMLG with Au metal contacts. The central region is the active tMLG whereas side bright regions are Au
contacts on tMLG. The dark colored features running across active tMLG are the wrinkles. Scale bar, 10 mm. Raman map of I2D/IG ratios (d) and FWHM of 2D band (e) acquired on the
same region. f) Variation of conductivity, s, of the tMLG device in the temperature range of 90e273 K. Red and blue lines are power law and linear fit to the curves in the sem-
iconducting and metallic regions, respectively. (g) Temporal changes in the photocurrent with the intermittent illumination of light source (365 nm) measured at 50 mV. (aeg)
Adapted with permission [121]. Copyright 2017, American Chemical Society. (A colour version of this figure can be viewed online.)

of the device M1 with zero and perpendicular magnetic fields at
70 mK (Fig. 9c). The device exhibited a typical V-shaped conduc-
tance at the charge neutrality point (n ¼ 0), identical to that of SLG.
The insulating states beyond ~ ±2.8  1012 cm2 are due to single-
particle bandgaps and the conductance minima observed in be-
tween may be associated with many-body gaps [169]. However, in
the range of n ~ 1.3 to 1.9  1012 cm2, the conductance is sub-
stantially higher at zero magnetic field than it is in a perpendicular
magnetic field of B⊥ ¼ 0.4 T and this is where the superconductivity
was observed. This region was further studied (Fig. 9d) with respect
to temperature. Four-probe resistance, Rxx, of device M1 exhibited
two superconducting domes on each side of Mott insulating region
and the dome features are similar to those associated with high-
temperature superconductivity in cuprate materials [169,170].
Upon heating with fixed n, the superconducting state turned into
the normal metallic state. As expected, the application of a
perpendicular magnetic field B⊥ gradually suppressed the super-
conductivity (Fig. 9e).
Indeed much earlier, it was realized that when two SLG sheets
are stacked on top of each other with a small relative twist, it leads
to the emergence of a “Moire
bands” [171,172] which become
increasingly flat with the twist angle. Later studies found that the
twist angle dependence is not monotonic: the bandwidth goes up
and down with twist angle, vanishing completely at a series of
discrete “magic” angles [173], the largest of which is slightly over 1

(see Fig. 10aed). This prediction promised that one could generate
flat bands with a small twist and therefore strong correlations [174].
Moreover, these strongly correlated electrons are easy to control in
graphene devices, thanks to its low charge carrier density, using an
external gate field. However, tBLG devices with accurate and pre-
cise twist angles remained a major challenge to realize the exact
behavior of the system experimentally, and none have predicted
the superconductivity in the system until the first experimental
observation from Cao et al.[ [166]].
The fact that the superconducting and insulating states are in
close proximity, a similar scenario observed in the cuprate super-
conductor, has brought huge interests in the graphene community
in general and in particular the correlated-electron physicists. Add
to it, the two phases are easily tunable with a gate field, unlike the
situation in cuprate where chemical doping brings structural dis-
tortions. These facts would make tBLG a simple system to under-
stand the electron behavior in high Tc superconductors. Therefore,
after the report of Cao et al. [166], there is a huge surge of publi-
cations, many are in preprints, confirming the experimental results
and various theories explaining the origin of superconductivity in
tBLG. Already significant progress has been made, though may
amount to finding just the tip of an iceberg, in understanding
behavior of tBLG as a function of twist angle [176], carrier-density
[177,178], magnetic-field [179], pressure [175,180], spin [181] etc.
For example, Yankowitz et al. [175], tuned the interlayer coupling
between graphene layers by applying external hydrostatic pressure
and induced superconductivity at a twist angle larger than 1.1
, i.e.
at 1.27
in which correlated phases are otherwise absent
(Fig. 10eeg). They also showed that increased Tc up to 3 K by tuning
the interlayer coupling between graphene layers with pressure. It is
important to note that superconductivity and related properties are
 U. Mogera, G.U. Kulkarni / Carbon 156 (2020) 470e487 481

Fig. 9. Superconductivity in tBLG (a) Schematic of the device configuration consisting of tBLG sandwiched between hexagonal boron nitride films. (b) Four probe resistance Rxx
measured in two devices M1 and M2 having with twist angle of q ¼ 1.16
and q ¼ 1.05
, respectively. The inset shows an optical image of device where the darker region is the
patterned tBLG. (c) Conductance of the device M1 with carrier density measured at zero (red curve) and perpendicular magnetic field (B⊥) (blue curve) and temperature of 70 mK.
The curves exhibit the typical V-shaped conductance near charge neutrality (n ¼ 0, purple dotted line) and the insulating states at both ends of n values (blue and red bars). Other
colored bars are intermittent conductance minima. In between the n values of 1 to 2 x1012 cm2, there is considerable conductance enhancement at zero field that is suppressed
in B⊥ ¼ 0.4 T. This enhancement signals the onset of superconductivity. (d) Map of four-probe resistance Rxx of the device M1, measured against carrier densities and temperatures.
Two asymmetric and overlapping superconducting domes are indicated along with metallic and Mott regions. (e) Effect of perpendicular magnetic field on Rxx vs T curves of the
device M1. (aee) Adapted with permission [166]. Copyright 2018, Nature Publishing Group. (A colour version of this figure can be viewed online.)

not just limited to twisted bilayer system but also observed in the
twisted multilayer (tMLG) system [182e184]. For example, Shen
et al. [185] observed the onset Tc as high as 12 K in a system of
twisted double bilayer graphene.
In spite of experimental confirmation and predicted correlated
behavior in such a superlattice, the understanding of the origin of
magic angles responsible for superconductivity is underway. Many
theories have been put forth to explain the phenomenon
[186e192]. Tarnopolsky et al. [186]. reported a fundamental con-
tinuum model for tBLG which covers not just the vanishing of the
Fermi velocity, but also the perfect flattening of the lowest band.
When parametrized q in terms of a ~ 1/q, the magic angles recur
with a periodicity of Da x 3/2. Gonza
lez et al. [ [188]] have
explained that superconductivity in tBLG is a consequence of the
Kohn-Luttinger (KL) instability which otherwise takes place at
extremely low energy scales. But in tBLG, due to strong coupling of
vHSs at magic angles, the instability becomes strong leading to an
effective attraction between electrons. Lian et al. [191] studied the
electron-phonon coupling in tBLG using ab initio calculations and
showed that the phonon-mediated electron attraction at the magic
angle is strong enough to induce an intervalley pairing between
graphene valleys. Apart from these reports, varieties of other pos-
sibilities have been studied, including electron assisted hoping
[187], phenomenological mean-field theory [192], Wannier pairs
formation [189], etc.
9. Other properties
Many other properties of tBLG are different from that of BLG
[193e197] or in some cases new properties are observed
482 U. Mogera, G.U. Kulkarni / Carbon 156 (2020) 470e487

Fig. 10. (aed) The low-energy DOS, calculated for four twist angles, 0.82
(a), 1.08
(b), 1.20
(c) and 1.79
. In (a) and (b), the DOS has a double-peak structure at lower energies, and
it is non-zero at zero energy. In (c), there is a finite DOS near-zero energy and the dispersion is no longer linear and in (d) the DOS has an almost linear dependence at lower
energies, consistent with the existence of Dirac cones. It is zero at zero energy. The solid (red) line is the DOS of the single-layer graphene. Adapted with permission [173]. Copyright
2012, American Physical Society (e) Conductance of a tBLG device with q ¼ 1.27
measured with charge density at two values of pressure: 0 GPa (gray) and 2.21 GPa (blue). (f)
Temperature dependent resistance at doping slightly larger than ns/2. (g) Temperature dependent resistance at 2.21 GPa at ns/2 (red) and at the optimal doping of the su-
perconductor (blue). Adapted with permission [175]. Copyright 2019, AAAS. (A colour version of this figure can be viewed online.)

[58,198e200]. For example, Li et al. [197] investigated the thermal
conductivity of tBLG using Raman spectroscopy and found that the
thermal conductivity of tBLG is lower than that of SLG and BLG.
(Fig. 11a). The decrease is attributed to the modification of the
Brillouin zone of the tBLG due to the twist and the emergence of
additional folded phonon branches that enhance the phonon
Umklapp and normal scattering. Nie et al. [196] theoretically
studied the thermal conductivity of tBLG and tMLGs with the twist
angles. The in-plane thermal conductivity of twisted bi, tri, and
four-layer follows a ‘W’ trend (Fig. 11b). In the range of 0e10
, the
thermal conductivity decreases significantly, whereas in the range
of 10e20
, the decrease becomes smaller. At the range of 20e30
,
the thermal conductivity increases and becomes a local maximum
at 30
. With the increase in the number of layers, the in-plane
thermal conductivity decreases. The interfacial thermal conduc-
tivity (Fig. 11c) also follows a similar decreasing trend as of in-plane
conductivity; however, the decrease is monotonic with a local
minimum at 30
.
In another study, Hu et al. [194] systematically studied plas-
monic behavior of tBLG with twist angles through real-space
nanoimaging and found that tBLG supports confined infrared
plasmons that are sensitively dependent on the twist angle.
Fig. 11d contains the near field amplitude responses which are
directly linked to the plasmons in tBLG and vary with the twist
angles. The amplitude images show bright fringe(s) close to the
SLG edge and the SLG-tBLG boundaries which are clear in the line
profiles (solid gray curves in Fig. 11e) taken perpendicular to the
edges. At small twist angles, tBLG has a plasmon wavelength
comparable to that of SLG, whereas, at larger twist angles, the
plasmon wavelength increases significantly (Fig. 11f). A similar
trend is observed for phases of the fringe (Fig. 11g). The under-
lining physics behind the observed twist angle dependence is
attributed to the Fermi velocity renormalization originating from
the interlayer electronic coupling.
10. Conclusions and outlook
Graphene has continued to throw surprises with new exotic
properties and kept the interest alive among researchers from
various branches even after 15 years since its isolation from
graphite. While doped graphene and other variations are well
studied, twisted graphene, which involves angular disorder be-
tween adjacent layers in a stack, has gained attention only recently
and already, the literature is abound with examples of precise
control of its varied properties with the twist angle. In this review
article, we have covered many literature studies pertaining to
twisted bilayer (tBLG) and multilayer (tMLG) graphene. Earlier
preparation of twisted bilayer graphene relied on accidental flip-
ping or folding of SLG during the transfer processes. Employing
nanomanipulators, stacking of CVD graphene layers with a well-
defined twist was then made possible. The fundamental physical
properties of tBLG such as vHSs and Moire
superlattices, were
initially the subject matter of study, supported by theoretical cal-
culations. It was realized that the decoupled nature of the layers in
tBLG is equivalent to graphene on graphene substrate and can be
treated as an ideal SLG sample much like SLG on hBN substrate.
Extensive angle dependent Raman study threw further light on the
electronic structure of tBLG. The angle dependent optical properties
have been investigated bringing out an absorption feature in the
visible spectrum, which otherwise is flat like in SLG. The usefulness
of this absorption has been demonstrated in pixelated color dis-
plays. Further, it has been shown that the inert surface of the gra-
phene can be made selectively reactive at certain twist angles. The
interest in twisted graphene took a new turn since the observation
of superconductivity in tBLG [166] and tMLG [201] systems.
However, there are challenges lying ahead before the properties
can be exploited in real life applications. Wafer scale production
and wide availability of tBLG and tMLG is still a distant dream.
There is hardly any progress in the chemical synthesis methods
which, in principle, should open-up and extend the application
 U. Mogera, G.U. Kulkarni / Carbon 156 (2020) 470e487 483

Fig. 11. (a) The thermal conductivity of suspended SLG, BLG and tBLG as a function of the measured temperature. Adapted with permission [197]. Copyright 2014, The Royal Society
of Chemistry. q-dependent in-plane (b) and inter-planar (c) thermal conductivity of twisted graphene layers. Adapted with permission [196]. Copyright 2019, Elsevier Ltd. (d) High-
resolution near-field amplitude images of tBLG with different twist angles. (e) Experimental (solid gray line) and modeled (red dashed line) amplitude profiles taken along the blue
dashed lines in corresponding near-field images above. Scale bar: 400 nm. The q-dependent near-field amplitude (f) and phase (g) from both experiment (squares) and modeling
(red curve). The vertical dashed lines in (e) is a mark q ¼ 3
. Adapted with permission [194]. Copyright 2012, American Physical Society. (A colour version of this figure can be viewed
online.)

space. Combining fine techniques of synthesis and faster litho-
graphic manipulation is therefore, the call of the hour. Once
addressed, coming years may be witnessing emergence of new
twisted families, some being heterostructures involving other types
of 2D systems, opening up new horizons in 2D materials and de-
vices, in general.
Acknowledgements
We thank Prof C N R Rao for his constant encouragement and
support. This research work is supported by Department of Science
and Technology (DST), New Delhi, India. UM acknowledges IGSTC
project for a fellowship.
References
[1] K.S. Novoselov, A.K. Geim, S.V. Morozov, D. Jiang, Y. Zhang, S.V. Dubonos,
I.V. Grigorieva, A.A. Firsov, Electric field effect in atomically thin carbon films,
Science 306 (2004) 666e669.
[2] A.H. Castro Neto, F. Guinea, N.M.R. Peres, K.S. Novoselov, A.K. Geim, The
electronic properties of graphene, Rev. Mod. Phys. 81 (2009) 109e162.
[3] A.K. Geim, K.S. Novoselov, The rise of graphene, Nat. Mater. 6 (2007) 183.
[4] K.S. Novoselov, A.K. Geim, S.V. Morozov, D. Jiang, M.I. Katsnelson,
I.V. Grigorieva, S.V. Dubonos, A.A. Firsov, Two-dimensional gas of massless
Dirac fermions in graphene, Nature 438 (2005) 197.
[5] C.-H. Park, L. Yang, Y.-W. Son, M.L. Cohen, S.G. Louie, New generation of
massless Dirac fermions in graphene under external periodic potentials,
Phys. Rev. Lett. 101 (2008), 126804.
[6] K. Nomura, A.H. MacDonald, Quantum transport of massless Dirac fermions,
Phys. Rev. Lett. 98 (2007), 076602.
[7] S.V. Morozov, K.S. Novoselov, M.I. Katsnelson, F. Schedin, D.C. Elias,
J.A. Jaszczak, A.K. Geim, Giant intrinsic carrier mobilities in graphene and its
bilayer, Phys. Rev. Lett. 100 (2008), 016602.
[8] R.S. Shishir, D.K. Ferry, Intrinsic mobility in graphene, J. Phys. Condens.
Matter 21 (2009), 232204.
[9] K.I. Bolotin, K.J. Sikes, Z. Jiang, M. Klima, G. Fudenberg, J. Hone, P. Kim,
H.L. Stormer, Ultrahigh electron mobility in suspended graphene, Solid State
Commun. 146 (2008) 351e355.
[10] K.S. Novoselov, Z. Jiang, Y. Zhang, S.V. Morozov, H.L. Stormer, U. Zeitler,
J.C. Maan, G.S. Boebinger, P. Kim, A.K. Geim, Room-temperature quantum
Hall effect in graphene, Science 315 (2007), 1379-1379.
[11] V.P. Gusynin, S.G. Sharapov, Unconventional integer quantum Hall effect in
graphene, Phys. Rev. Lett. 95 (2005), 146801.
[12] Y. Zhang, Y.-W. Tan, H.L. Stormer, P. Kim, Experimental observation of the
quantum Hall effect and Berry’s phase in graphene, Nature 438 (2005) 201.
[13] M.I. Katsnelson, K.S. Novoselov, A.K. Geim, Chiral tunnelling and the Klein
paradox in graphene, Nat. Phys. 2 (2006) 620.
[14] J.C. Meyer, A.K. Geim, M.I. Katsnelson, K.S. Novoselov, T.J. Booth, S. Roth, The
structure of suspended graphene sheets, Nature 446 (2007) 60.
[15] F. Schedin, A.K. Geim, S.V. Morozov, E.W. Hill, P. Blake, M.I. Katsnelson,
K.S. Novoselov, Detection of individual gas molecules adsorbed on graphene,
Nat. Mater. 6 (2007) 652.
[16] R.R. Nair, P. Blake, A.N. Grigorenko, K.S. Novoselov, T.J. Booth, T. Stauber,
N.M.R. Peres, A.K. Geim, Fine structure constant defines visual transparency
of graphene, Science 320 (2008), 1308-1308.
[17] A.A. Balandin, S. Ghosh, W. Bao, I. Calizo, D. Teweldebrhan, F. Miao, C.N. Lau,
Superior thermal conductivity of single-layer graphene, Nano Lett. 8 (2008)
902e907.
484 U. Mogera, G.U. Kulkarni / Carbon 156 (2020) 470e487
[18] M. Edward, K. Mikito, The electronic properties of bilayer graphene, Rep.
Prog. Phys. 76 (2013), 056503.
[19] V.C. Eduardo, K.S. Novoselov, S.V. Morozov, N.M.R. Peres, J.M.B.L.d. Santos,
N. Johan, F. Guinea, A.K. Geim, A.H.C. Neto, Electronic properties of a biased
graphene bilayer, J. Phys. Condens. Matter 22 (2010), 175503.
[20] E.V. Castro, K.S. Novoselov, S.V. Morozov, N.M.R. Peres, J.M.B.L. dos Santos,
J. Nilsson, F. Guinea, A.K. Geim, A.H.C. Neto, Biased bilayer graphene: semi-
conductor with a gap tunable by the electric field effect, Phys. Rev. Lett. 99
(2007), 216802.
[21] T. Ohta, A. Bostwick, T. Seyller, K. Horn, E. Rotenberg, Controlling the elec-
tronic structure of bilayer graphene, Science 313 (2006) 951e954.
[22] K.S. Novoselov, E. McCann, S.V. Morozov, V.I. Fal’ko, M.I. Katsnelson,
U. Zeitler, D. Jiang, F. Schedin, A.K. Geim, Unconventional quantum Hall effect
and Berry’s phase of 2p in bilayer graphene, Nat. Phys. 2 (2006) 177.
[23] W. Bao, L. Jing, J. Velasco Jr., Y. Lee, G. Liu, D. Tran, B. Standley, M. Aykol,
S.B. Cronin, D. Smirnov, M. Koshino, E. McCann, M. Bockrath, C.N. Lau,
Stacking-dependent band gap and quantum transport in trilayer graphene,
Nat. Phys. 7 (2011) 948.
[24] M.F. Craciun, S. Russo, M. Yamamoto, J.B. Oostinga, A.F. Morpurgo, S. Tarucha,
Trilayer graphene is a semimetal with a gate-tunable band overlap, Nat.
Nanotechnol. 4 (2009) 383.
[25] S. Ghosh, W. Bao, D.L. Nika, S. Subrina, E.P. Pokatilov, C.N. Lau, A.A. Balandin,
Dimensional crossover of thermal transport in few-layer graphene, Nat.
Mater. 9 (2010) 555.
[26] J. Nilsson, A.H. Castro Neto, F. Guinea, N.M.R. Peres, Electronic properties of
bilayer and multilayer graphene, Phys. Rev. B 78 (2008), 045405.
[27] J. Nilsson, A.H.C. Neto, F. Guinea, N.M.R. Peres, Electronic properties of gra-
phene multilayers, Phys. Rev. Lett. 97 (2006), 266801.
[28] C. Diaz-Pinto, D. De, V.G. Hadjiev, H. Peng, AB-stacked multilayer graphene
synthesized via chemical vapor deposition: a characterization by hot carrier
transport, ACS Nano 6 (2012) 1142e1148.
[29] J.D. Bernal, The structure of graphite, Proc. R. Soc. London, Ser. A 106 (1924)
749e773.
[30] K. Mikito, Stacking-dependent optical absorption in multilayer graphene,
New J. Phys. 15 (2013), 015010.
[31] M.P. Lima, J.E. Padilha, R.B. Pontes, A. Fazzio, A.J.R.d. Silva, Stacking-depen-
dent transport properties in few-layers graphene, Solid State Commun. 250
(2017) 70e74.
[32] C.-Y. Lin, J.-Y. Wu, Y.-H. Chiu, C.-P. Chang, M.-F. Lin, Stacking-dependent
magnetoelectronic properties in multilayer graphene, Phys. Rev. B 90 (2014),
205434.
[33] D. Loc Duong, G. Kim, H.-K. Jeong, Y. Hee Lee, Breaking AB stacking order in
graphite oxide: ab initio approach, Phys. Chem. Chem. Phys. 12 (2010)
1595e1599.
[34] J. Berashevich, T. Chakraborty, On the nature of interlayer interactions in a
system of two graphene fragments, J. Phys. Chem. C 115 (2011)
24666e24673.
[35] X. Chen, F. Tian, C. Persson, W. Duan, N.-x. Chen, Interlayer interactions in
graphites, Sci. Rep. 3 (2013) 3046.
[36] L. Huder, A. Artaud, T. Le Quang, G.T. de Laissardie re, A.G.M. Jansen,
G. Lapertot, C. Chapelier, V.T. Renard, Electronic spectrum of twisted gra-
phene layers under heterostrain, Phys. Rev. Lett. 120 (2018), 156405.
[37] L. Gong, R.J. Young, I.A. Kinloch, S.J. Haigh, J.H. Warner, J.A. Hinks, Z. Xu, L. Li,
F. Ding, I. Riaz, R. Jalil, K.S. Novoselov, Reversible loss of bernal stacking
during the deformation of few-layer graphene in nanocomposites, ACS Nano
7 (2013) 7287e7294.
[38] J.-H. Wong, B.-R. Wu, M.-F. Lin, Strain effect on the electronic properties of
single layer and bilayer graphene, J. Phys. Chem. C 116 (2012) 8271e8277.
[39] V.H. Nguyen, P. Dollfus, Strain-induced modulation of Dirac cones and van
Hove singularities in a twisted graphene bilayer, 2D Mater. 2 (2015), 035005.
[40] R. Bistritzer, A.H. MacDonald, Transport between twisted graphene layers,
Phys. Rev. B 81 (2010), 245412.
[41] R. Ishikawa, N.R. Lugg, K. Inoue, H. Sawada, T. Taniguchi, N. Shibata,
Y. Ikuhara, Interfacial atomic structure of twisted few-layer graphene, Sci.
Rep. 6 (2016), 21273.
[42] Y. Shibuta, J.A. Elliott, Interaction between two graphene sheets with a
turbostratic orientational relationship, Chem. Phys. Lett. 512 (2011)
146e150.
[43] J. Hicks, M. Sprinkle, K. Shepperd, F. Wang, A. Tejeda, A. Taleb-Ibrahimi,
F. Bertran, P. Le Fe vre, W.A. de Heer, C. Berger, E.H. Conrad, Symmetry
breaking in commensurate graphene rotational stacking: comparison of
theory and experiment, Phys. Rev. B 83 (2011), 205403.
[44] J.H. Warner, M.H. Rümmeli, T. Gemming, B. Büchner, G.A.D. Briggs, Direct
imaging of rotational stacking faults in few layer graphene, Nano Lett. 9
(2009) 102e106.
[45] L. Brown, R. Hovden, P. Huang, M. Wojcik, D.A. Muller, J. Park, Twinning and
twisting of tri- and bilayer graphene, Nano Lett. 12 (2012) 1609e1615.
[46] R. Zan, U. Bangert, Q. Ramasse, K.S. Novoselov, Imaging of Bernal stacked and
misoriented graphene and boron nitride: experiment and simulation,
J. Microsc. 244 (2011) 152e158.
[47] M.S. Dresselhaus, G. Dresselhaus, Intercalation compounds of graphite, Adv.
Phys. 30 (1981) 139e326.
[48] M. Inagaki, Applications of graphite intercalation compounds, J. Mater. Res. 4
(1989) 1560e1568.
[49] L. Pietronero, S. Str€assler, Bond-length change as a tool to determine charge
transfer and electron-phonon coupling in graphite intercalation compounds,
Phys. Rev. Lett. 47 (1981) 593e596.
[50] T.E. Weller, M. Ellerby, S.S. Saxena, R.P. Smith, N.T. Skipper, Superconducti-
vity in the intercalated graphite compounds C6Yb and C6Ca, Nat. Phys. 1
(2005) 39.
[51] S. Shallcross, S. Sharma, E. Kandelaki, O.A. Pankratov, Electronic structure of
turbostratic graphene, Phys. Rev. B 81 (2010), 165105.
[52] J.A. Garlow, L.K. Barrett, L. Wu, K. Kisslinger, Y. Zhu, J.F. Pulecio, Large-area
growth of turbostratic graphene on Ni(111) via physical vapor deposition,
Sci. Rep. 6 (2016), 19804.
[53] Z.Q. Li, C.J. Lu, Z.P. Xia, Y. Zhou, Z. Luo, X-ray diffraction patterns of graphite
and turbostratic carbon, Carbon 45 (2007) 1686e1695.
[54] M.A. Pimenta, G. Dresselhaus, M.S. Dresselhaus, L.G. Cançado, A. Jorio,
R. Saito, Studying disorder in graphite-based systems by Raman spectros-
copy, Phys. Chem. Chem. Phys. 9 (2007) 1276e1290.
[55] L.G. Cançado, A. Jorio, M.A. Pimenta, Measuring the absolute Raman cross
section of nanographites as a function of laser energy and crystallite size,
Phys. Rev. B 76 (2007), 064304.
[56] A. Wollbrink, K. Volgmann, J. Koch, K. Kanthasamy, C. Tegenkamp, Y. Li,
H. Richter, S. K€ amnitz, F. Steinbach, A. Feldhoff, J. Caro, Amorphous, tur-
bostratic and crystalline carbon membranes with hydrogen selectivity, Car-
bon 106 (2016) 93e105.
[57] Z. Zhou, W.G. Bouwman, H. Schut, C. Pappas, Interpretation of X-ray
diffraction patterns of (nuclear) graphite, Carbon 69 (2014) 17e24.
[58] J.C. Rode, D. Smirnov, H. Schmidt, R.J. Haug, Berry phase transition in twisted
bilayer graphene, 2D Mater. 3 (2016), 035005.
[59] C.-J. Kim, A. S
anchez-Castillo, Z. Ziegler, Y. Ogawa, C. Noguez, J. Park, Chiral
atomically thin films, Nat. Nanotechnol. 11 (2016) 520.
[60] F. Finocchiaro, F. Guinea, P. San-Jose, Quantum spin Hall effect in twisted
bilayer graphene, 2D Mater. 4 (2017), 025027.
[61] T. Stauber, T. Low, G. Go
mez-Santos, Chiral response of twisted bilayer
graphene, Phys. Rev. Lett. 120 (2018), 046801.
[62] E. Su
arez Morell, L. Chico, L. Brey, Twisting Dirac fermions: circular dichroism
in bilayer graphene, 2D Mater. 4 (2017), 035015.
[63] S. Simon, E. Voloshina, J. Tesch, F. Fo € rschner, V. Enenkel, C. Herbig, T. Knispel,
A. Tries, J. Kro€ ger, Y. Dedkov, M. Fonin, Layer-by-Layer decoupling of twisted
graphene sheets epitaxially grown on a metal substrate, Small 14 (2018),
1703701.
[64] J.T. Robinson, S.W. Schmucker, C.B. Diaconescu, J.P. Long, J.C. Culbertson,
T. Ohta, A.L. Friedman, T.E. Beechem, Electronic hybridization of large-area
stacked graphene films, ACS Nano 7 (2013) 637e644.
[65] X.-D. Chen, W. Xin, W.-S. Jiang, Z.-B. Liu, Y. Chen, J.-G. Tian, High-precision
twist-controlled bilayer and trilayer graphene, Adv. Mater. 28 (2016)
2563e2570.
[66] K. Kim, M. Yankowitz, B. Fallahazad, S. Kang, H.C.P. Movva, S. Huang,
S. Larentis, C.M. Corbet, T. Taniguchi, K. Watanabe, S.K. Banerjee, B.J. LeRoy,
E. Tutuc, van der Waals heterostructures with high accuracy rotational
alignment, Nano Lett. 16 (2016) 1989e1995.
[67] B. Wang, M. Huang, N.Y. Kim, B.V. Cunning, Y. Huang, D. Qu, X. Chen, S. Jin,
M. Biswal, X. Zhang, S.H. Lee, H. Lim, W.J. Yoo, Z. Lee, R.S. Ruoff, Controlled
folding of single crystal graphene, Nano Lett. 17 (2017) 1467e1473.
[68] J.-B. Liu, P.-J. Li, Y.-F. Chen, Z.-G. Wang, F. Qi, J.-R. He, B.-J. Zheng, J.-H. Zhou,
W.-L. Zhang, L. Gu, Y.-R. Li, Observation of tunable electrical bandgap in
large-area twisted bilayer graphene synthesized by chemical vapor deposi-
tion, Sci. Rep. 5 (2015) 15285.
[69] C.-C. Lu, Y.-C. Lin, Z. Liu, C.-H. Yeh, K. Suenaga, P.-W. Chiu, Twisting bilayer
graphene superlattices, ACS Nano 7 (2013) 2587e2594.
[70] U. Mogera, R. Dhanya, R. Pujar, C. Narayana, G.U. Kulkarni, Highly decoupled
graphene multilayers: turbostraticity at its best, J. Phys. Chem. Lett. 6 (2015)
4437e4443.
[71] Z. Ni, L. Liu, Y. Wang, Z. Zheng, L.-J. Li, T. Yu, Z. Shen, G-band Raman double
resonance in twisted bilayer graphene: evidence of band splitting and
folding, Phys. Rev. B 80 (2009), 125404.
[72] Z. Ni, Y. Wang, T. Yu, Y. You, Z. Shen, Reduction of Fermi velocity in folded
graphene observed by resonance Raman spectroscopy, Phys. Rev. B 77
(2008), 235403.
[73] A.K. Gupta, Y. Tang, V.H. Crespi, P.C. Eklund, Nondispersive Raman D band
activated by well-ordered interlayer interactions in rotationally stacked
bilayer graphene, Phys. Rev. B 82 (2010), 241406.
[74] P. Wing-Tat, D. Colm, A review and outlook for an anomaly of scanning
tunnelling microscopy (STM): superlattices on graphite, J. Phys. D Appl. Phys.
38 (2005) R329.
[75] T.N.D. Alpha, C. Johann, N.P. Tim, B. Carsten, M. Thomas, Structure of epitaxial
graphene on Ir(111), New J. Phys. 10 (2008), 043033.
[76] J. Campos-Delgado, G. Algara-Siller, C.N. Santos, U. Kaiser, J.P. Raskin, Twisted
Bi-layer graphene: microscopic rainbows, Small 9 (2013) 3247e3251.
[77] P. Poncharal, A. Ayari, T. Michel, J.L. Sauvajol, Raman spectra of misoriented
bilayer graphene, Phys. Rev. B 78 (2008), 113407.
[78] V. Carozo, C.M. Almeida, E.H.M. Ferreira, L.G. Cançado, C.A. Achete, A. Jorio,
Raman signature of graphene superlattices, Nano Lett. 11 (2011) 4527e4534.
[79] V. Carozo, C.M. Almeida, B. Fragneaud, P.M. Bede ^, M.V.O. Moutinho,
J. Ribeiro-Soares, N.F. Andrade, A.G. Souza Filho, M.J.S. Matos, B. Wang,
M. Terrones, R.B. Capaz, A. Jorio, C.A. Achete, L.G. Cançado, Resonance effects
on the Raman spectra of graphene superlattices, Phys. Rev. B 88 (2013),
085401.
 U. Mogera, G.U. Kulkarni / Carbon 156 (2020) 470e487
[80] Y. Wang, Y. Zheng, X. Xu, E. Dubuisson, Q. Bao, J. Lu, K.P. Loh, Electrochemical
delamination of CVD-grown graphene film: toward the recyclable use of
copper catalyst, ACS Nano 5 (2011) 9927e9933.
[81] J.W. Suk, A. Kitt, C.W. Magnuson, Y. Hao, S. Ahmed, J. An, A.K. Swan,
B.B. Goldberg, R.S. Ruoff, Transfer of CVD-grown monolayer graphene onto
arbitrary substrates, ACS Nano 5 (2011) 6916e6924.
[82] S. Bae, H. Kim, Y. Lee, X. Xu, J.-S. Park, Y. Zheng, J. Balakrishnan, T. Lei, H. Ri
€
Kim, Y.I. Song, Y.-J. Kim, K.S. Kim, B. Ozyilmaz, J.-H. Ahn, B.H. Hong, S. Iijima,
Roll-to-roll production of 30-inch graphene films for transparent electrodes,
Nat. Nanotechnol. 5 (2010) 574.
[83] C. Cai, F. Jia, A. Li, F. Huang, Z. Xu, L. Qiu, Y. Chen, G. Fei, M. Wang, Crackless
transfer of large-area graphene films for superior-performance transparent
electrodes, Carbon 98 (2016) 457e462.
[84] G.J.M. Fechine, I. Martin-Fernandez, G. Yiapanis, R. Bentini, E.S. Kulkarni,
€
R.V. Bof de Oliveira, X. Hu, I. Yarovsky, A.H. Castro Neto, B. Ozyilmaz, Direct
dry transfer of chemical vapor deposition graphene to polymeric substrates,
Carbon 83 (2015) 224e231.
[85] M. Her, R. Beams, L. Novotny, Graphene transfer with reduced residue, Phys.
Lett. A 377 (2013) 1455e1458.
[86] Z. Cheng, Q. Zhou, C. Wang, Q. Li, C. Wang, Y. Fang, Toward intrinsic graphene
surfaces: a systematic study on thermal annealing and wet-chemical treat-
ment of SiO2-supported graphene devices, Nano Lett. 11 (2011) 767e771.
[87] C. Gong, H.C. Floresca, D. Hinojos, S. McDonnell, X. Qin, Y. Hao, S. Jandhyala,
G. Mordi, J. Kim, L. Colombo, R.S. Ruoff, M.J. Kim, K. Cho, R.M. Wallace,
Y.J. Chabal, Rapid selective etching of PMMA residues from transferred
graphene by carbon dioxide, J. Phys. Chem. C 117 (2013) 23000e23008.
[88] Y. Chen, X.-L. Gong, J.-G. Gai, Progress and challenges in transfer of large-area
graphene films, Adv. Sci. 3 (2016), 1500343.
[89] A. Nourbakhsh, M. Cantoro, A. Klekachev, F. Clemente, B. Sore
e, M.H. van der
Veen, T. Vosch, A. Stesmans, B. Sels, S. De Gendt, Tuning the Fermi level of
SiO2-supported single-layer graphene by thermal annealing, J. Phys. Chem. C
114 (2010) 6894e6900.
[90] C.R. Dean, A.F. Young, I. Meric, C. Lee, L. Wang, S. Sorgenfrei, K. Watanabe,
T. Taniguchi, P. Kim, K.L. Shepard, J. Hone, Boron nitride substrates for high-
quality graphene electronics, Nat. Nanotechnol. 5 (2010) 722.
[91] K. Kumar, Y.-S. Kim, E.-H. Yang, The influence of thermal annealing to
remove polymeric residue on the electronic doping and morphological
characteristics of graphene, Carbon 65 (2013) 35e45.
[92] Z. Tan, J. Yin, C. Chen, H. Wang, L. Lin, L. Sun, J. Wu, X. Sun, H. Yang, Y. Chen,
H. Peng, Z. Liu, Building large-domain twisted bilayer graphene with van
Hove singularity, ACS Nano 10 (2016) 6725e6730.
[93] L. Liu, H. Zhou, R. Cheng, W.J. Yu, Y. Liu, Y. Chen, J. Shaw, X. Zhong, Y. Huang,
X. Duan, High-yield chemical vapor deposition growth of high-quality large-
area AB-stacked bilayer graphene, ACS Nano 6 (2012) 8241e8249.
[94] W. Liu, S. Kraemer, D. Sarkar, H. Li, P.M. Ajayan, K. Banerjee, Controllable and
rapid synthesis of high-quality and large-area bernal stacked bilayer gra-
phene using chemical vapor deposition, Chem. Mater. 26 (2014) 907e915.
[95] Z. Peng, Z. Yan, Z. Sun, J.M. Tour, Direct growth of bilayer graphene on SiO2
substrates by carbon diffusion through nickel, ACS Nano 5 (2011)
8241e8247.
[96] U. Mogera, N. Kurra, D. Radhakrishnan, C. Narayana, G.U. Kulkarni, Low cost,
rapid synthesis of graphene on Ni: an efficient barrier for corrosion and
thermal oxidation, Carbon 78 (2014) 384e391.
[97] I. Brihuega, P. Mallet, H. Gonza
lez-Herrero, G. Trambly de Laissardie re,
M.M. Ugeda, L. Magaud, J.M. Go
mez-Rodríguez, F. Yndura
in, J.Y. Veuillen,
Unraveling the intrinsic and robust nature of van Hove singularities in
twisted bilayer graphene by scanning tunneling microscopy and theoretical
analysis, Phys. Rev. Lett. 109 (2012), 196802.
[98] J. Yin, H. Wang, H. Peng, Z. Tan, L. Liao, L. Lin, X. Sun, A.L. Koh, Y. Chen,
H. Peng, Z. Liu, Selectively enhanced photocurrent generation in twisted
bilayer graphene with van Hove singularity, Nat. Commun. 7 (2016) 10699.
[99] A. Luican, G. Li, A. Reina, J. Kong, R.R. Nair, K.S. Novoselov, A.K. Geim,
E.Y. Andrei, Single-layer behavior and its breakdown in twisted graphene
layers, Phys. Rev. Lett. 106 (2011), 126802.
[100] Y. Zhang, T.-T. Tang, C. Girit, Z. Hao, M.C. Martin, A. Zettl, M.F. Crommie,
Y.R. Shen, F. Wang, Direct observation of a widely tunable bandgap in bilayer
graphene, Nature 459 (2009) 820.
[101] E. McCann, D.S.L. Abergel, V.I. Fal’ko, Electrons in bilayer graphene, Solid
State Commun. 143 (2007) 110e115.
[102] S. Latil, V. Meunier, L. Henrard, Massless fermions in multilayer graphitic
systems with misoriented layers: ab initio calculations and experimental
fingerprints, Phys. Rev. B 76 (2007), 201402.
[103] J. Hass, F. Varchon, J.E. Milla
n-Otoya, M. Sprinkle, N. Sharma, W.A. de Heer,
C. Berger, P.N. First, L. Magaud, E.H. Conrad, Why multilayer graphene on
4HSiC(0001) behaves like a single sheet of graphene, Phys. Rev. Lett. 100
(2008), 125504.
[104] J.M.B. Lopes dos Santos, N.M.R. Peres, A.H. Castro Neto, Graphene bilayer
with a twist: electronic structure, Phys. Rev. Lett. 99 (2007), 256802.
[105] S.K. Jain, V. Juri ci

c, G.T. Barkema, Structure of twisted and buckled bilayer
graphene, 2D Mater. 4 (2016), 015018.
[106] W. Yan, M. Liu, R.-F. Dou, L. Meng, L. Feng, Z.-D. Chu, Y. Zhang, Z. Liu, J.-C. Nie,
L. He, Angle-dependent van Hove singularities in a slightly twisted graphene
bilayer, Phys. Rev. Lett. 109 (2012), 126801.
[107] W. Yan, L. Meng, M. Liu, J.-B. Qiao, Z.-D. Chu, R.-F. Dou, Z. Liu, J.-C. Nie,
D.G. Naugle, L. He, Angle-dependent van Hove singularities and their
485
breakdown in twisted graphene bilayers, Phys. Rev. B 90 (2014), 115402.
[108] G. Li, A. Luican, J.M.B. Lopes dos Santos, A.H. Castro Neto, A. Reina, J. Kong,
E.Y. Andrei, Observation of Van Hove singularities in twisted graphene
layers, Nat. Phys. 6 (2009) 109.
[109] T. Ohta, J.T. Robinson, P.J. Feibelman, A. Bostwick, E. Rotenberg, T.E. Beechem,
Evidence for Interlayer Coupling and Moir\’e Periodic Potentials in Twisted
Bilayer Graphene, Phys. Rev. Lett. 109 (2012), 186807.
[110] K. Kim, A. DaSilva, S. Huang, B. Fallahazad, S. Larentis, T. Taniguchi,
K. Watanabe, B.J. LeRoy, A.H. MacDonald, E. Tutuc, Tunable moire
bands and
strong correlations in small-twist-angle bilayer graphene, Proc. Natl. Acad.
Sci. U.S.A. 114 (2017) 3364e3369.
[111] R. Bistritzer, A.H. MacDonald, Moire
bands in twisted double-layer graphene,
Proc. Natl. Acad. Sci. U.S.A. 108 (2011) 12233e12237.
[112] M.M.v. Wijk, A. Schuring, M.I. Katsnelson, A. Fasolino, Relaxation of moire

patterns for slightly misaligned identical lattices: graphene on graphite, 2D
Mater. 2 (2015), 034010.
[113] S. Dai, Y. Xiang, D.J. Srolovitz, Twisted bilayer graphene: Moire
with a twist,
Nano Lett. 16 (2016) 5923e5927.
[114] K. Kim, S. Coh, L.Z. Tan, W. Regan, J.M. Yuk, E. Chatterjee, M.F. Crommie,
M.L. Cohen, S.G. Louie, A. Zettl, Raman spectroscopy study of rotated double-
layer graphene: Misorientation-angle dependence of electronic structure,
Phys. Rev. Lett. 108 (2012), 246103.
[115] A.C. Ferrari, D.M. Basko, Raman spectroscopy as a versatile tool for studying
the properties of graphene, Nat. Nanotechnol. 8 (2013) 235.
[116] L.M. Malard, M.A. Pimenta, G. Dresselhaus, M.S. Dresselhaus, Raman spec-
troscopy in graphene, Phys. Rep. 473 (2009) 51e87.
[117] A.C. Ferrari, Raman spectroscopy of graphene and graphite: disorder,
electronephonon coupling, doping and nonadiabatic effects, Solid State
Commun. 143 (2007) 47e57.
[118] G. Ruan, Z. Sun, Z. Peng, J.M. Tour, Growth of graphene from food, insects,
and waste, ACS Nano 5 (2011) 7601e7607.
[119] A. Reina, X. Jia, J. Ho, D. Nezich, H. Son, V. Bulovic, M.S. Dresselhaus, J. Kong,
Large area, few-layer graphene films on arbitrary substrates by chemical
vapor deposition, Nano Lett. 9 (2009) 30e35.
[120] X. Li, C.W. Magnuson, A. Venugopal, R.M. Tromp, J.B. Hannon, E.M. Vogel,
L. Colombo, R.S. Ruoff, Large-area graphene single crystals grown by low-
pressure chemical vapor deposition of methane on copper, J. Am. Chem.
Soc. 133 (2011) 2816e2819.
[121] U. Mogera, S. Walia, B. Bannur, M. Gedda, G.U. Kulkarni, Intrinsic nature of
graphene revealed in temperature-dependent transport of twisted multi-
layer graphene, J. Phys. Chem. C 121 (2017) 13938e13943.
[122] L. Banszerus, M. Schmitz, S. Engels, J. Dauber, M. Oellers, F. Haupt,
K. Watanabe, T. Taniguchi, B. Beschoten, C. Stampfer, Ultrahigh-mobility
graphene devices from chemical vapor deposition on reusable copper, Sci.
Adv. 1 (2015).
[123] S. Berciaud, S. Ryu, L.E. Brus, T.F. Heinz, Probing the intrinsic properties of
exfoliated graphene: Raman spectroscopy of free-standing monolayers,
Nano Lett. 9 (2009) 346e352.
[124] A.C. Ferrari, J.C. Meyer, V. Scardaci, C. Casiraghi, M. Lazzeri, F. Mauri,
S. Piscanec, D. Jiang, K.S. Novoselov, S. Roth, A.K. Geim, Raman spectrum of
graphene and graphene layers, Phys. Rev. Lett. 97 (2006), 187401.
[125] W. Yanan, S. Zhihua, W. Wei, N. Shu, L. Xinghua, W. Haiyan, M. Kevin,
P. Shin-shem, R.-H. Francisco, G.H. Viktor, B. Jiming, Four-fold Raman
enhancement of 2D band in twisted bilayer graphene: evidence for a doubly
degenerate Dirac band and quantum interference, Nanotechnology 25
(2014), 335201.
[126] K. Sato, R. Saito, C. Cong, T. Yu, M.S. Dresselhaus, Zone folding effect in
Raman G-band intensity of twisted bilayer graphene, Phys. Rev. B 86 (2012),
125414.
[127] A. Jorio, L.G. Cançado, Raman spectroscopy of twisted bilayer graphene, Solid
State Commun. 175e176 (2013) 3e12.
[128] J. Campos-Delgado, L.G. Cançado, C.A. Achete, A. Jorio, J.-P. Raskin, Raman
scattering study of the phonon dispersion in twisted bilayer graphene, Nano
Res 6 (2013) 269e274.
[129] J.-B. Wu, H. Wang, X.-L. Li, H. Peng, P.-H. Tan, Raman spectroscopic charac-
terization of stacking configuration and interlayer coupling of twisted
multilayer graphene grown by chemical vapor deposition, Carbon 110
(2016) 225e231.
[130] J.-B. Wu, X. Zhang, M. Ij€ as, W.-P. Han, X.-F. Qiao, X.-L. Li, D.-S. Jiang,
A.C. Ferrari, P.-H. Tan, Resonant Raman spectroscopy of twisted multilayer
graphene, Nat. Commun. 5 (2014) 5309.
[131] R. He, T.-F. Chung, C. Delaney, C. Keiser, L.A. Jauregui, P.M. Shand,
C.C. Chancey, Y. Wang, J. Bao, Y.P. Chen, Observation of low energy Raman
modes in twisted bilayer graphene, Nano Lett. 13 (2013) 3594e3601.
[132] G.S.N. Eliel, M.V.O. Moutinho, A.C. Gadelha, A. Righi, L.C. Campos,
H.B. Ribeiro, P.-W. Chiu, K. Watanabe, T. Taniguchi, P. Puech, M. Paillet,
T. Michel, P. Venezuela, M.A. Pimenta, Intralayer and interlayer
electronephonon interactions in twisted graphene heterostructures, Nat.
Commun. 9 (2018) 1221.
[133] J.-B. Wu, Z.-X. Hu, X. Zhang, W.-P. Han, Y. Lu, W. Shi, X.-F. Qiao, M. Ijia €s,
S. Milana, W. Ji, A.C. Ferrari, P.-H. Tan, Interface coupling in twisted multi-
layer graphene by resonant Raman spectroscopy of layer breathing modes,
ACS Nano 9 (2015) 7440e7449.
[134] C. Cong, T. Yu, Enhanced ultra-low-frequency interlayer shear modes in
folded graphene layers, Nat. Commun. 5 (2014) 4709.
486 U. Mogera, G.U. Kulkarni / Carbon 156 (2020) 470e487
[135] M.-L. Lin, J.-B. Wu, X.-L. Liu, P.-H. Tan, Probing the shear and layer breathing
modes in multilayer graphene by Raman spectroscopy, J. Raman Spectrosc.
49 (2017) 19e30.
[136] P.H. Tan, W.P. Han, W.J. Zhao, Z.H. Wu, K. Chang, H. Wang, Y.F. Wang,
N. Bonini, N. Marzari, N. Pugno, G. Savini, A. Lombardo, A.C. Ferrari, The shear
mode of multilayer graphene, Nat. Mater. 11 (2012) 294.
[137] R.W. Havener, Y. Liang, L. Brown, L. Yang, J. Park, Van Hove Singularities and
excitonic effects in the optical conductivity of twisted bilayer graphene,
Nano Lett. 14 (2014) 3353e3357.
[138] H. Patel, L. Huang, C.-J. Kim, J. Park, M.W. Graham, Stacking angle-tunable
photoluminescence from interlayer exciton states in twisted bilayer gra-
phene, Nat. Commun. 10 (2019) 1445.
[139] R.W. Havener, H. Zhuang, L. Brown, R.G. Hennig, J. Park, Angle-resolved
Raman imaging of interlayer rotations and interactions in twisted bilayer
graphene, Nano Lett. 12 (2012) 3162e3167.
[140] V.I. Artyukhov, Y. Hao, R.S. Ruoff, B.I. Yakobson, Breaking of symmetry in
graphene growth on metal substrates, Phys. Rev. Lett. 114 (2015), 115502.
[141] P. Jadaun, D. Xiao, Q. Niu, S.K. Banerjee, Topological classification of crys-
talline insulators with space group symmetry, Phys. Rev. B 88 (2013),
085110.
[142] R.W. Havener, C.-J. Kim, L. Brown, J.W. Kevek, J.D. Sleppy, P.L. McEuen, J. Park,
Hyperspectral imaging of structure and composition in atomically thin
heterostructures, Nano Lett. 13 (2013) 3942e3946.
[143] Q. Ye, J. Wang, Z. Liu, Z.-C. Deng, X.-T. Kong, F. Xing, X.-D. Chen, W.-Y. Zhou,
C.-P. Zhang, J.-G. Tian, Polarization-dependent optical absorption of gra-
phene under total internal reflection, Appl. Phys. Lett. 102 (2013), 021912.
[144] P. Wang, Z.-B. Liu, X.-D. Chen, F. Xing, W.-S. Jiang, B. Dong, W. Xin, J.-G. Tian,
Accurate layers determination of graphene on transparent substrate based
on polarization-sensitive absorption effect, Appl. Phys. Lett. 103 (2013),
181902.
[145] T. Mueller, F. Xia, P. Avouris, Graphene photodetectors for high-speed optical
communications, Nat. Photonics 4 (2010) 297.
[146] K.J. Tielrooij, M. Massicotte, L. Piatkowski, A. Woessner, Q. Ma, P. Jarillo-
Herrero, N.F.v. Hulst, F.H.L. Koppens, Hot-carrier photocurrent effects at
grapheneemetal interfaces, J. Phys. Condens. Matter 27 (2015), 164207.
[147] F. Bonaccorso, Z. Sun, T. Hasan, A.C. Ferrari, Graphene photonics and opto-
electronics, Nat. Photonics 4 (2010) 611.
[148] L. Liao, H. Wang, H. Peng, J. Yin, A.L. Koh, Y. Chen, Q. Xie, H. Peng, Z. Liu, van
Hove singularity enhanced photochemical reactivity of twisted bilayer gra-
phene, Nano Lett. 15 (2015) 5585e5589.
[149] Y. Ding, Q. Peng, L. Gan, R. Wu, X. Ou, Q. Zhang, Z. Luo, Stacking-mode-
induced reactivity enhancement for twisted bilayer graphene, Chem. Mater.
28 (2016) 1034e1039.
[150] H. Liu, S. Ryu, Z. Chen, M.L. Steigerwald, C. Nuckolls, L.E. Brus, Photochemical
reactivity of graphene, J. Am. Chem. Soc. 131 (2009) 17099e17101.
[151] M. Cheng, A. Bakac, Kinetics and mechanism of the reaction of Cr(ii) aqua
ions with benzoylpyridine N-oxide, Dalton Trans. (2007) 2077e2082.
[152] L. Zhou, L. Zhou, M. Yang, D. Wu, L. Liao, K. Yan, Q. Xie, Z. Liu, H. Peng, Z. Liu,
Free radical reactions in two dimensions: a case study on photochlorination
of graphene, Small 9 (2013) 1388e1396.
[153] F.M. Koehler, A. Jacobsen, K. Ensslin, C. Stampfer, W.J. Stark, Selective
chemical modification of graphene surfaces: distinction between single- and
bilayer graphene, Small 6 (2010) 1125e1130.
[154] X. Du, I. Skachko, A. Barker, E.Y. Andrei, Approaching ballistic transport in
suspended graphene, Nat. Nanotechnol. 3 (2008) 491.
[155] F. Varchon, R. Feng, J. Hass, X. Li, B.N. Nguyen, C. Naud, P. Mallet, J.Y. Veuillen,
C. Berger, E.H. Conrad, L. Magaud, Electronic structure of epitaxial graphene
layers on SiC: effect of the substrate, Phys. Rev. Lett. 99 (2007), 126805.
[156] Z. Zhu, L. Zhan, T.-M. Shih, W. Wan, J. Lu, J. Huang, S. Guo, Y. Zhou, W. Cai,
Critical annealing temperature for stacking orientation of bilayer graphene,
Small 14 (2018) 1802498.
[157] N. Mishra, J. Boeckl, N. Motta, F. Iacopi, Graphene growth on silicon carbide:
a review, Phys. Status Solidi 213 (2016), 2269-2269.
[158] W.A. de Heer, C. Berger, X. Wu, P.N. First, E.H. Conrad, X. Li, T. Li, M. Sprinkle,
J. Hass, M.L. Sadowski, M. Potemski, G. Martinez, Epitaxial graphene, Solid
State Commun. 143 (2007) 92e100.
[159] J. Hass, W.A.d. Heer, E.H. Conrad, The growth and morphology of epitaxial
multilayer graphene, J. Phys. Condens. Matter 20 (2008), 323202.
[160] C.N. Lau, W. Bao, J. Velasco, Properties of suspended graphene membranes,
Mater. Today 15 (2012) 238e245.
[161] S. Adam, E.H. Hwang, V.M. Galitski, S. Das Sarma, A self-consistent theory for
graphene transport, Proc. Natl. Acad. Sci. U.S.A. 104 (2007) 18392e18397.
[162] S. Das Sarma, E.H. Hwang, Density-dependent electrical conductivity in
suspended graphene: approaching the Dirac point in transport, Phys. Rev. B
87 (2013), 035415.
[163] A.S. Mayorov, D.C. Elias, I.S. Mukhin, S.V. Morozov, L.A. Ponomarenko,
K.S. Novoselov, A.K. Geim, R.V. Gorbachev, How close can one approach the
Dirac point in graphene experimentally? Nano Lett. 12 (2012) 4629e4634.
[164] J.-H. Chen, C. Jang, S. Xiao, M. Ishigami, M.S. Fuhrer, Intrinsic and extrinsic
performance limits of graphene devices on SiO2, Nat. Nanotechnol. 3 (2008)
206.
[165] K.I. Bolotin, K.J. Sikes, J. Hone, H.L. Stormer, P. Kim, Temperature-dependent
transport in suspended graphene, Phys. Rev. Lett. 101 (2008), 096802.
[166] Y. Cao, V. Fatemi, S. Fang, K. Watanabe, T. Taniguchi, E. Kaxiras, P. Jarillo-
Herrero, Unconventional superconductivity in magic-angle graphene
superlattices, Nature 556 (2018) 43.
[167] Y. Cao, V. Fatemi, A. Demir, S. Fang, S.L. Tomarken, J.Y. Luo, J.D. Sanchez-
Yamagishi, K. Watanabe, T. Taniguchi, E. Kaxiras, R.C. Ashoori, P. Jarillo-
Herrero, Correlated insulator behaviour at half-filling in magic-angle gra-
phene superlattices, Nature 556 (2018) 80.
[168] Y. Cao, J.Y. Luo, V. Fatemi, S. Fang, J.D. Sanchez-Yamagishi, K. Watanabe,
T. Taniguchi, E. Kaxiras, P. Jarillo-Herrero, Superlattice-induced insulating
states and valley-protected orbits in twisted bilayer graphene, Phys. Rev.
Lett. 117 (2016), 116804.
[169] D. Tanmoy, P. Christos, Two types of superconducting domes in unconven-
tional superconductors, New J. Phys. 18 (2016), 103033.
[170] J.T. Ye, Y.J. Zhang, R. Akashi, M.S. Bahramy, R. Arita, Y. Iwasa, Super-
conducting dome in a gate-tuned band insulator, Science 338 (2012)
1193e1196.
[171] R. Bistritzer, A.H. MacDonald, Moire
bands in twisted double-layer graphene,
Proc. Natl. Acad. Sci. U.S.A. 108 (2011) 12233.
[172] G. Trambly de Laissardie re, D. Mayou, L. Magaud, Localization of Dirac
electrons in rotated graphene bilayers, Nano Lett. 10 (2010) 804e808.
[173] J.M.B. Lopes dos Santos, N.M.R. Peres, A.H. Castro Neto, Continuum model of
the twisted graphene bilayer, Phys. Rev. B 86 (2012), 155449.
[174] K. Kim, A. DaSilva, S. Huang, B. Fallahazad, S. Larentis, T. Taniguchi,
K. Watanabe, B.J. LeRoy, A.H. MacDonald, E. Tutuc, Tunable moire
bands and
strong correlations in small-twist-angle bilayer graphene, Proc. Natl. Acad.
Sci. U.S.A. 114 (2017) 3364.
[175] M. Yankowitz, S. Chen, H. Polshyn, Y. Zhang, K. Watanabe, T. Taniguchi,
D. Graf, A.F. Young, C.R. Dean, Tuning superconductivity in twisted bilayer
graphene, Science 363 (2019) 1059.
[176] N.R. Chebrolu, B.L. Chittari, J. Jung, Flat bands in twisted double bilayer
graphene, Phys. Rev. B 99 (2019), 235417.
[177] X. Lu, P. Stepanov, W. Yang, M. Xie, M.A. Aamir, I. Das, C. Urgell, K. Watanabe,
T. Taniguchi, G. Zhang, Superconductors, Orbital Magnets, and Correlated
States in Magic Angle Bilayer Graphene, 2019, 06513 arXiv preprint arXiv:
1903.
[178] Y. Cao, D. Rodan-Legrain, O. Rubies-Bigorda , J.M. Park, K. Watanabe,
T. Taniguchi, P. Jarillo-Herrero, Electric Field Tunable Correlated States and
Magnetic Phase Transitions in Twisted Bilayer-Bilayer Graphene, 2019,
08596 arXiv preprint arXiv:1903.
[179] A.L. Sharpe, E.J. Fox, A.W. Barnard, J. Finney, K. Watanabe, T. Taniguchi,
M.A. Kastner, D. Goldhaber-Gordon, Emergent ferromagnetism near three-
quarters filling in twisted bilayer graphene, Science 365 (2019) 605.
[180] S. Carr, S. Fang, P. Jarillo-Herrero, E. Kaxiras, Pressure dependence of the
magic twist angle in graphene superlattices, Phys. Rev. B 98 (2018), 085144.
[181] X. Liu, Z. Hao, E. Khalaf, J.Y. Lee, K. Watanabe, T. Taniguchi, A. Vishwanath,
P. Kim, Spin-polarized Correlated Insulator and Superconductor in Twisted
Double Bilayer Graphene, 2019, 08130 arXiv preprint arXiv:1903.
[182] C. Mora, N. Regnault, B.A. Bernevig, Flatbands and Perfect Metal in Trilayer
Moir\’e Graphene, Phys. Rev. Lett. 123 (2019), 026402.
[183] G. Chen, L. Jiang, S. Wu, B. Lyu, H. Li, B.L. Chittari, K. Watanabe, T. Taniguchi,
Z. Shi, J. Jung, Y. Zhang, F. Wang, Evidence of a gate-tunable Mott insulator in
a trilayer graphene moire
superlattice, Nat. Phys. 15 (2019) 237e241.
[184] G. Chen, A.L. Sharpe, P. Gallagher, I.T. Rosen, E.J. Fox, L. Jiang, B. Lyu, H. Li,
K. Watanabe, T. Taniguchi, J. Jung, Z. Shi, D. Goldhaber-Gordon, Y. Zhang,
F. Wang, Signatures of tunable superconductivity in a trilayer graphene
moire
superlattice, Nature 572 (2019) 215e219.
[185] C. Shen, N. Li, S. Wang, Y. Zhao, J. Tang, J. Liu, J. Tian, Y. Chu, K. Watanabe,
T. Taniguchi, Observation of Superconductivity with Tc Onset at 12K in
Electrically Tunable Twisted Double Bilayer Graphene, 2019, 06952 arXiv
preprint arXiv:1903.
[186] G. Tarnopolsky, A.J. Kruchkov, A. Vishwanath, Origin of magic angles in
twisted bilayer graphene, Phys. Rev. Lett. 122 (2019) 106405.
[187] F. Guinea, N.R. Walet, Electrostatic effects, band distortions, and supercon-
ductivity in twisted graphene bilayers, Proc. Natl. Acad. Sci. U.S.A. 115 (2018)
13174.
[188] J. Gonz
alez, T. Stauber, Kohn-luttinger superconductivity in twisted bilayer
graphene, Phys. Rev. Lett. 122 (2019), 026801.
[189] S. Ray, J. Jung, T. Das, Wannier pairs in superconducting twisted bilayer
graphene and related systems, Phys. Rev. B 99 (2019) 134515.
[190] F. Wu, A.H. MacDonald, I. Martin, Theory of phonon-mediated supercon-
ductivity in twisted bilayer graphene, Phys. Rev. Lett. 121 (2018) 257001.
[191] B. Lian, Z. Wang, B.A. Bernevig, Twisted bilayer graphene: a phonon-driven
superconductor, Phys. Rev. Lett. 122 (2019) 257002.
[192] J.F. Dodaro, S.A. Kivelson, Y. Schattner, X.Q. Sun, C. Wang, Phases of a
phenomenological model of twisted bilayer graphene, Phys. Rev. B 98
(2018), 075154.
[193] P.S. Mahapatra, K. Sarkar, H.R. Krishnamurthy, S. Mukerjee, A. Ghosh, See-
beck coefficient of a single van der Waals junction in twisted bilayer gra-
phene, Nano Lett. 17 (2017) 6822e6827.
[194] F. Hu, S.R. Das, Y. Luan, T.F. Chung, Y.P. Chen, Z. Fei, Real-space imaging of the
tailored plasmons in twisted bilayer graphene, Phys. Rev. Lett. 119 (2017),
247402.
[195] A.I. Cocemasov, D.L. Nika, A.A. Balandin, Phonons in twisted bilayer gra-
phene, Phys. Rev. B 88 (2013), 035428.
[196] X. Nie, L. Zhao, S. Deng, Y. Zhang, Z. Du, How interlayer twist angles affect in-
plane and cross-plane thermal conduction of multilayer graphene: a non-
equilibrium molecular dynamics study, Int. J. Heat Mass Transf. 137 (2019)
 U. Mogera, G.U. Kulkarni / Carbon 156 (2020) 470e487 487

161e173.
[197] H. Li, H. Ying, X. Chen, D.L. Nika, A.I. Cocemasov, W. Cai, A.A. Balandin,
S. Chen, Thermal conductivity of twisted bilayer graphene, Nanoscale 6
(2014) 13402e13408.
[198] J.S. Alden, A.W. Tsen, P.Y. Huang, R. Hovden, L. Brown, J. Park, D.A. Muller,
P.L. McEuen, Strain solitons and topological defects in bilayer graphene, Proc.
Natl. Acad. Sci. U.S.A. 110 (2013) 11256.
[199] L. Xian, Z.F. Wang, M.Y. Chou, Coupled Dirac fermions and neutrino-like
oscillations in twisted bilayer graphene, Nano Lett. 13 (2013) 5159e5164.
[200] Z.F. Wang, F. Liu, M.Y. Chou, Fractal landau-level spectra in twisted bilayer
graphene, Nano Lett. 12 (2012) 3833e3838.
[201] C. Xu, L. Balents, Topological superconductivity in twisted multilayer gra-
phene, Phys. Rev. Lett. 121 (2018), 087001.