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Deepu Kumar et al

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 Journal of Physics: Condensed Matter

J. Phys.: Condens. Matter 32 (2020) 415702 (9pp) https://doi.org/10.1088/1361-648X/ab9a7a

Anisotropic electron–photon–phonon
coupling in layered MoS2
Deepu Kumar1,3 , Birender Singh1 , Rahul Kumar2 , Mahesh Kumar2
and Pradeep Kumar1,3
1
School of Basic Sciences, Indian Institute of Technology Mandi, Mandi-175005, India
2
Department of Electrical Engineering, Indian Institute of Technology Jodhpur, Jodhpur-342037, India

E-mail: [email protected] and [email protected]

Received 16 April 2020, revised 19 May 2020

Accepted for publication 8 June 2020
Published 20 July 2020

Abstract
Transition metal dichalcogenide, MoS2 has attracted a lot of attention recently owing to its
tunable visible range band gap, and anisotropic electronic and transport properties. Here, we
report comprehensive inelastic light scattering measurements on both chemical vapor
deposition grown (horizontally and vertically aligned) flakes, and mechanically exfoliated
flakes of single crystal MoS2 . We probe the anisotropic optical response by studying the
polarization dependence intensity of the Raman active phonon modes as a function of different
incident photon energy and flake thickness. Our polarization dependent Raman studies reveal
strong anisotropic behavior reflected in the anomalous renormalization of the modes intensity
as a function of flake thickness, phonons and photon energy. Our observations reflect the
strong anisotropic light–matter interaction in this high crystalline symmetric layered MoS2
system, especially for the in-plane vibrations, crucial for understanding as well as future
applications of these materials.
Keywords: Raman scattering, phonon, lattice-dynamics

S Supplementary material for this article is available online

(Some figures may appear in colour only in the online journal)

1. Introduction provide a tunable band gap that helps in overcoming the bot-
tleneck faced by graphene, and are thus promising materials
The journey of two-dimensional (2D) nano materials begins for the next generation electronic and optoelectronic appli-
with the discovery of graphene [1], the first 2D material that cations. In these systems, one may tune their properties as a
defied the Mermin–Wagner theorem. Since the discovery in function of layer thickness providing great leverage against
2004, these materials have been intensively probed both exper- the conventional 3D bulk systems [5]. Additionally, numer-
imentally as well as theoretically owing to their extraordi- ous properties of TMDCs such as electrical mobility, pho-
nary properties and rich physics [2]. Recently, they have been toluminescence, photo-responsivity and thermoelectric figure
joined by another large class of newly discovered 2D mate- of merit show strong dependence on the in-plane crystalline
rials, namely 2D transition metal dichalcogenides (TMDCs). orientation [6–9] as well as layer thickness. Interestingly, all
In the bulk form, TMDCs had been probed for decades [3, 4],
these properties may be linked with the underlying behavior
however the current interest lies in their atomically thin 2D
of the electrons, phonons and their coupling with the photons,
form. Although TMDCs have the properties which are com-
which may be investigated using light–matter interaction such
plementary to those of graphene, such as graphene being a
zero gap semiconductor, it cannot be switched off and as a as Raman spectroscopy. In these systems, reduced dielectric
result is not good for the semiconductor industry, TMDCs screening and significant quantum confinement also lead to
strong Coulomb interactions between electrons and holes, giv-
3
Authors to whom any correspondence should be addressed. ing rise to tightly bound excitons with a large binding energy

1361-648X/20/415702+9$33.00 1 © 2020 IOP Publishing Ltd Printed in the UK

J. Phys.: Condens. Matter 32 (2020) 415702 D Kumar et al

range [10]. Therefore, understand coupling of phonons and photon energies. We show how the electron–photon and elec-
photons with the electrons, which also controls the nature of tron–phonon interactions in MoS2 are related to its thickness
excitonic effects, is crucial for their applications. reflecting via the different polarization dependence behavior
MoS2 is one of first 2D TMDC systems being explored as of the phonon modes, as a function of layer thickness as well
an alternative to replace silicon in the semiconductor industry as phonons and incident photon energy.
owing to the tunable band gap, from ∼1.2 eV in bulk to 1.9 eV
in its monolayer [11]. In addition to the finite spin–orbit cou- 2. Experimental techniques
pling, broken inversion symmetry in MoS2 provides optical
access to the valley degrees of freedom suggesting its poten- Vertically and horizontally aligned MoS2 was synthesized
tial in future spintronic and valleytronic devices. Light–matter using CVD method as described in reference [28]. Single crys-
interaction in these 2D materials provides a deep insight into tal flakes were obtained using scotch tape method from the
the underlying interaction mechanism as photons may eas- bulk single crystal of MoS2 (2D semiconductors, USA) on 300
ily interact with electrons and phonons, which control their nm SiO2 /Si substrate, see figure S5(f) in the supplementary
electrical and thermal properties. The underlying mechanism information (http://stacks.iop.org/JPCM/32/415702/mmedia)
responsible for the stark difference in physical properties when for the steps used for exfoliation method. Polarization depen-
one moves from bulk to the monolayer may be linked with the dent measurements using Raman spectroscopy may be done
behavior of quasi-particles and coupling between them such as using different configurations based on the polarization of inci-
anisotropic coupling between electrons and phonons/photons dent, scattered light and rotation of the sample. In one possibil-
[12–15]. This anisotropy may be gauged via an indirect probe ity, polarization of the incident laser light is varied while the
by an external perturbation such as probing by light, in particu- analyzer is fixed. Second possibility is by keeping the polar-
lar Raman scattering. Raman scattering has proved to be a very ization of the incident beam fixed, while the polarization of
powerful technique to understand intricate coupling between the scattered light is varied using an analyzer. It is also pos-
different quasi-particles in both nano systems and bulk via cou- sible to combine the previous two configurations and control
pling of electrons and phonons with the incoming and outgoing the polarization of the incident and scattered lights simultane-
photons [16–23]. An anisotropy in the thermal conductivity ously. Another possibility is that by keeping the polarization of
was reported for the case of MoS2 , where in-plane conductiv- incident and scattered light fixed and only rotating the sample
ity is reported to be ∼5–6 times more than the out-of-plane around the laser beam. Here we followed the second configu-
conductivity [24] suggesting the more dominant role of the in- ration i.e. by fixing the direction of polarization of the incident
plane lattice vibrations such as E12g phonon mode as phonons beam and the rotation of the sample, we made use of the scat-
coupling controls the thermal behavior of a material. tered light polarization direction using analyzer (see figure 1
Phonon modes in TMDC are sensitive to the thickness of for the exp. geometry); and all the measurements were done
these materials. In case of MoS2 , as one moves from bulk to in backscattering geometry using 532 nm and 633 nm laser.
the monolayer, the out-of-plane phonon mode (A1g ) involv- The spectra were collected using a 100 x long working dis-
ing the vibration of S atom is red-shifted; on the other hand, tance objective and Peltier cooled charge couple device detec-
E12g mode involving the in-plane displacement of Mo and S tor. The laser power was kept very low (∼500 μW) to avoid
atoms shows blue-shift attributed to the dielectric screening any heating.
of long-range coulombic interaction [20]. Interestingly in 2D
materials, phonon modes may be tuned by varying the inci- 3. Result and discussions
dent photon energies if they fall within the resonance range
of optical transition [25]. In fact, close to the resonance condi- 3.1. Raman scattering and polarization dependence
tion, one may get additional modes including the forbidden one TMDCs have chemical formula MX2 , where two nearest layers
owing to the broken symmetry, and/or resonance effect which of X (chalcogen atom) are separated by a layer of M (transition
eases the momentum conservation rule. In case of MoS2 , exci- metal), which means the monolayer of MX2 system is com-
tation with 633 nm (1.96 eV) laser, which is close to A exciton posed of a trilayer i.e. X–M–X. For bulk MoS2 (point group
energy, gives rise to many multiphonon modes [26, 27]. These D46h ), Mo is sandwiched between two S atom layers form-
multimodes provide very rich information about phonons in ing a hexagonal plane, and is connected with S via a trigonal
the entire Brillouin zone (BZ) as opposed to the conventional prismatic coordination in 2H phase, where H stands for the
Raman process where observed phonon modes are confined hexagonal symmetry and prefix 2 for the number of layers in
only at the Γ point in the BZ. A detailed study focusing on each stacking order i.e. after two layer the pattern is repeated
the polarization dependence of phonon modes as a function [3]. As one moves from bulk to finite number of layers, then
of incident photon energy and layer thickness was lacking for symmetry reduces owing to a lack of translational symme-
high symmetric MoS2 . Focusing on the polarization depen- try in Z direction; 24 symmetry operation in bulk reduced to
dence of the phonon modes, here, we have undertaken such 12 in a few layers, and as a result, space group is different
a study and report comprehensive results in vertically and hor- for the few layered TMDC systems (see table S1). Mono-
izontally chemical vapor deposition (CVD) grown MoS2 as layer/odd number of layers of MoS2 belong to D13h point group
well as mechanically exfoliated flakes from MoS2 bulk single P6̄m2, #187, on the other hand bilayer/even number of layers
crystal as a function of flake thickness and different incident belongs to D33d (P3̄m1, #164) [29–31]. Details of the character

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J. Phys.: Condens. Matter 32 (2020) 415702 D Kumar et al

Figure 1. (a) and (b) Feynman diagram and schematic representation for the Stokes Raman scattering process, respectively. ω in /ω s and
ω ph correspond to the energy of incident/scattered photon and phonon energy, respectively. |i and |i  represent the intermediate states,
whereas |g stands for the ground state. i|Hop |g and g|Hop |i  are the matrix elements for the process of optical absorption and emission,
respectively; and i |Hel−ph |i is the electron–phonon matrix element. (c) Schematic representation of the experimental setup for the Raman
measurement. (d) Schematic showing the direction of polarization of the incident (êi ) and scattered light (ês ), making angle α and α + θ
with X-axis, respectively. ki and ks represents the direction of incident and scattered beam.

tables, Raman tensor of the phonon modes at the Γ point and intensity as a function of polar angle within the semi-classical
irreducible representation are given in detail in table S1 for all approach. As incident polarized light lies in the XY plane,
the three groups mentioned above [32–34]. polarized vector (êi ) of the incident beam may be decomposed
Figure 2 shows the Raman spectra of CVD grown hori- as (cos α, sin α, 0), where α is an arbitrary angle from the x-
zontally aligned MoS2 for two incident photon energies (i.e. axis (see figure 1(d)). We have fixed the direction of êi and
532 nm and 633 nm) with increasing thickness of the MoS2 rotated the analyzer at an interval of 10◦, polarization vec-
at four different flakes. Two first-order Raman active phonons tor (ês ) for the scattered light also lies within the XY plane
modes labeled as A1g and E12g are observed around 380 and 405 with decomposition as(cos(θ + α), sin(θ + α), 0), where θ =
cm−1 , respectively for all the flakes. Additionally, we observed 0◦ to 360◦. Within the semi-classical approach, Raman scat-
 2
few other modes for 633 nm incident photon energy attributed tering intensity is given as Iint = êts .R.êi  , where t denotes
to the higher-order overtone modes owing to the resonance the transpose of ês and R represents the Raman tensor [37].
effect. From the frequency difference (Δω = ωA1g − ωE1 ) of Using the above expression, the intensity of the A1g and E12g
2g
mode A1g and E12g , one may estimate the number of layers modes for our experimental setup is given as IA1g = a2 cos2 θ,
in these flakes [35, 36]. For monolayer, the frequency differ- IE1 = d2 (cos2 θ + sin2 θ), respectively. IA1g decreases to zero
ence (Δω) is ∼18 cm−1 for mechanically exfoliated one and
2g
when ês and êi are perpendicular to each other and is maximum
∼20 cm−1 for CVD grown sample, and difference increases for θ = 0◦ i.e., when ês and êi are parallel; on the other hand
by ∼2–3 cm−1 in the case of bilayer; and with further addi- IE1 remains constant. Solid lines in figure 3 (flake 1, 532 nm)
tion of layers it increases by ∼1 cm−1 per layer till six–seven 2g
are the fitted curves using the above functions, and the fitting
layers [35, 36]. We also measured thickness of the mechani-
is in a very good agreement with the theoretical prediction.
cally exfoliated layers of single crystal MoS2 using an AFM
As we changed the energy of the incident photon to 633 nm,
and using Raman compared the corresponding frequency dif-
and considering the data on the same flake and the same spot
ference in each layer (see figures S3 and S5 in supplementary
(see figure 3, 633 nm, flake 1), remarkably, the intensity of the
information), the observed frequency difference is found to be
commensurate with the measured thickness as stated above. E12g mode is no longer invariant under rotation and shows that
To understand the anisotropic coupling between electrons, the intensity is maximum around 0◦ and 180◦, similar to that
photons and phonons, compressive polarized Raman scatter- of IA1g . As we moved to the other flakes (flakes #2, 3 and 4)
ing measurements were carried out on CVD grown horizon- for 532 and 633 nm laser, intensity pattern of the A1g mode
tally aligned MoS2 flakes. Figure 3 shows the polarization remained constant. Interestingly for 532 nm laser, isotropic
dependence of A1g and E12g modes for both 532 and 633 nm nature of IE1 changes slightly with increasing thickness i.e.
2g
laser as a function of increasing thickness of horizontally the constant intensity shows the signature of minima around
aligned flakes of MoS2 . For flake 1 (532 nm laser), the intensity 90◦ and 270◦; on the other hand, as we changed the laser to
of E12g mode remains invariant with respect to the rotation of 633 nm, the intensity pattern for E12g mode shows remarkable
the analyzer, however the intensity of A1g mode shows a two- changes and becomes two-fold symmetric similar to that of
fold symmetric nature i.e. it has maximum intensity at both A1g mode. For 532 nm, as we move from flake 2 to flake 4 the
0◦ and 180◦. One may understand the observed variation in point of maxima for E12g mode showed a small variation; for

3
J. Phys.: Condens. Matter 32 (2020) 415702 D Kumar et al

Figure 2. Raman spectra for four different flakes of horizontally aligned CVD grown MoS2 under two different (a) 532 nm and (b) 633 nm
laser excitation energies. The solid red line shows the total sum of Lorentizan fit and thin blue lines show the individual fit of the phonon
modes. Flake numbering (from 1 to 4) is done in the increasing order of flakes thickness. Single layer thickness is ∼0.8–0.9 nm. Number of
layers and flake thickness mentioned in the left panel is estimated based on the frequency difference between A1g and E12g phonon modes.
Inset shows optical image of the region where Raman spectra were measured. Δω corresponds to the frequency difference between A1g and
E12g mode.

example, point of maxima for flake 4 is not at zero but slightly stark contrast to that predicted by the theory. This diametri-
above it. These features clearly reflect the anisotropic nature cally opposite behavior observed for E12g mode intensity under
of these phonon modes with respects to the layer thickness and different photon energy again point the anisotropic nature of
incident photon energy. For these flakes (#2, 3 and 4) we also these phonon modes.
notice that intensity of the E12g mode at zero and 360◦ is not Figure 5 shows the polarization dependence data for A1g
exactly same suggesting slight loss of periodicity in intensity and E12g modes for both 532 and 633 nm laser as a function
at these angles. Solid lines for A1g (both 532 and 633 nm) and of increasing thickness for four different flakes of vertically
E12g mode (for 633 nm) are fitted with the functions a2 cos2 θ aligned MoS2 . The intensity of the out of plane vibrational
and the fitting is very good. For E12g mode for 532 nm, where mode (A1g mode) shows consistent behavior irrespective of
the intensity pattern is deviating from constant value and form- the incident photon energy and layer thickness, except some
ing a semi-lobes kind of structure, we have fitted using the minor changes in the lobes sizes; for example, lobe size in
combined functions i.e., (d 2 + a2 )cos2 θ + d 2 sin2 θ, overall fit- the 2nd–3rd quadrant is more expanded for flake 1 and 4 (for
ting is modest. Figure 4 shows the intensity ratio (IE1 /IA1g ), 532 nm). On the other hand, the intensity of the in-plane vibra-
2g
which diverges as one moves closer to 90◦ (see figure 4(a), for tional mode (E12g ) changes drastically as we vary the incident
532 nm) on the expected lines within the theoretical predic- photon energy as well as layer thickness, similar to what we
tion. The intensity pattern is governed mainly by the intensity observed for the horizontally aligned MoS2 discussed above.
of A1g (IA1g ∝ cos2 θ) hence the ratio is expected to show diver- For example, for flake 1 intensity of the E12g mode is no not
gence as the angle closes to 90◦ . On the other hand, for 632 nm invariant under rotation instead it shows maxima around 0◦ and
(see figure 4(b)) intensity ratio no longer show any divergence 180◦ but without any nodes at 90◦ and 270◦. As we changed
rather it is constant with respect to the rotation of the ana- the incident photon energy to 633 nm (see flake #1), intensity
lyzer, completely in opposition to that observed for 532 nm of the E12g mode changes significantly and shows two nodes at
(see figure 4(a)). This constant intensity ratio observed for 90◦ and 270◦ similar to those of A1g mode. Analogous behavior
632 nm photon energy clearly reveal that both A1g and E12g is also observed for other flakes as well. The observed asym-
modes have same dependence on the polarization angle in metry reflected in the in-plane vibrational mode (E12g ) clearly

4
J. Phys.: Condens. Matter 32 (2020) 415702 D Kumar et al

Figure 3. Intensity polar plots for the Raman active phonon modes E12g and A1g with two different laser excitation energies (532 and
633 nm) in horizontally aligned CVD grown flakes of MoS2 . Black spheres are the experimental data points for different polarization angles
from θ = 0◦ to 360◦ and solid blue lines show fitted curves as described in the text. In plane vibrational mode E12g shows remarkable
anisotropic response when the incident photon energy is changed from 532 to 633 nm. Number of layers and flake thickness mentioned in
the left panel is estimated based on the frequency difference between A1g and E12g phonon modes.

suggests strong anisotropic nature of the phonon modes in 270◦. As soon as we changed the laser to 633 nm (see flake #1),
MoS2 , and weaker polarization dependence of out-of-plane intensity of the E12g mode changes significantly and shows two
vibrational mode (A1g ) as compared to the in-plane vibra- nodes at 90◦ and 270◦ similar to those of A1g mode. Intensity
tional mode (E12g ), suggesting that out-of-plane vibrations cou- ratio (i.e., IE1 /IA1g ) also shows similar behavior as for horizon-
2g
ple less anisotropically with the electronic states as compared tally and vertically aligned MoS2 (see figure S3 for the Raman
to the in-plane vibrations. Intensity ratio (see figure S1 for the spectra as a function of flake thickness and figure S4 for the
Raman spectra as a function of flake thickness and figure S2 for intensity ratio). The results shown in figures 3, 5 and 6 clearly
the intensity ratio) also shows similar changes as observed in suggest strong anisotropic optical response in this high crys-
the horizontally aligned MoS2 discussed above. To probe this talline symmetric layered MoS2 and its intricate dependence
anisotropic coupling further, we also did similar measurements on the incident photon energy, phonon energy as well as flake
using single crystal flakes of MoS2 on five different flakes thickness.
starting from monolayer of MoS2 (see figure 6). Interestingly,
3.2. Discussion
single crystals flakes also show similar polarization-dependent
behavior as that observed for the horizontally and vertically Our observations on these three different forms of MoS2 as
aligned flakes i.e. the intensity of the A1g mode shows two fold a function of layer thickness as well as incident photon ener-
symmetric nature irrespective of the incident photon energy gies evidently reflect the anisotropic nature of the phonons.
and layer thickness; while intensity of E12g changes as a func- They also make clear that the semi-classical approach can-
tion of layer thickness as well as incident photon energy. For not capture the complete picture with respect to the observed
example (see flake #1, 532 nm) intensity of the E12g is show- anisotropies especially for the case of in-plane vibrations. For
ing quasi-isotropic nature with maxima around 0◦ and 180◦ example, within this semi-classical approach, a phonon mode
and lowering of intensity around is observed around 90◦ and with the same symmetry would have the same polarization

5
J. Phys.: Condens. Matter 32 (2020) 415702 D Kumar et al

(c) Finally, the electron comes back to the initial state and
combines with the hole and emits the photon (elec-
tron–photon interaction; Hop ).
From this Raman scattering process, one may easily gauge
that Raman process can play a pivotal role in deciphering the
intricate coupling between photons, phonons and electrons.
The first-order Raman scattering process involves three steps,
as descried above, and quantum mechanical expression for the
Raman intensity, which uses the dipole selection rule for the
optical transition, is given as [37, 38]:
 2
 
 g|Hop |i  i |Hel−ph |i i|Hop |g 
Int· =  
 (1)
 g,i,i (EL − ΔEig )(EL − ωph − ΔEi g ) 

where, ΔEig = (Ei − Eg + iγ) and ΔEi g = (Ei − Eg + iγ),

|g is the ground state, |i and |i  are the intermediate states
(eigen or non-eigen ones), Hop and Hel – ph are the elec-
tron–photon and electron–phonon interactions, respectively.
EL is the incident photon energy and Eg , Ei and Ei are the
energies of the corresponding electronic states, and γ is the
broadening factor which is introduced phenomenologically for
the finite lifetime of the absorption/emission. Matrix elements
i|Hop |g and g|Hop |i  represent the process of optical absorp-
Figure 4. Intensity ratio of E12g with respect to A1g in horizontally tion and emission, respectively and i |Hel−ph |i is the elec-
aligned CVD grown flakes of MoS2 under two different (a) 532 nm tron–phonon matrix element. Treating the electron–photon
(b) 633 nm laser excitation energies. Solid blue lines are a guide to
the eye. interaction within the dipole approximation i.e. by neglect-
ing higher order multipole or non-linear effects, the elec-
tron–photon matrix element i|Hop |g is given as i|Hop |g ∝
dependence irrespective of the incident photon energy; what  ig , where êi is the polarization vector of the incident
êi .D
we observed for E12g mode (see figures 3, 5 and 6) is completely light and dipole vector D  ig is i|∇|g [39, 40]. From this
different from this prediction. This failure of semi-classical expression, it is clear that to have a non-zero contribution of
approach to explain the polarization dependence as a func- electron–photon, the matrix element D  ig should have a finite
tion of layer thickness and incident photon energy (EL ) may be component along the direction of light polarization êi . This
understood from the fact that the intensity of a Raman active may also explain which two states (|g, |i) from the energy
mode within this approach is independent of the EL as well bands be involved in this transition of an electron for a given
as the thickness of the materials. This independence of the EL and direction of êi , and the different possible values of the
intensity from EL and thickness comes from the fact that the matrix element i|Hop |g for varying incident light polariza-
optical dipole selection rule for the absorption and emission tion direction and incident photon energies. As there are three
of a photon is not included in this semi-classical theory. All matrix components involved (see equation (1) above), to get
it depends upon is the direction of polarization of the inci- the finite intensity for a mode each component should be non-
dent, scattered photons via ês , êi and Raman tensor (R), which zero and should be allowed by the symmetry. For example, to
is related to the rate of change of polarization for a given obtain non-vanishing electron–photon matrix elements for the
mode i.e. it depends on the symmetry of a vibration. To qual- optical transition from ground state to the intermediate state
itatively understand these anisotropies in the phonon modes |i, it should satisfy Γg ⊗ ΓD ⊂ Γi , where ΓD , Γg and Γi are
as a function of layer thickness and EL , quantum mechanical the irreducible representations of D  (i.e., the parallel compo-
picture needs to be invoked, which depends on the interac- nent of D  ig with respect to êi ), |g and |i, respectively. Sim-
tion between electron–photon–phonon. In a simplistic picture,
ilarly, g|Hop |i  ∝ ês .D
 gi , where ês is the polarization vector
stokes Raman scattering process may be understood via three
of the scattered light and D  gi = g|∇|i . Comparing quantum
steps as follows (also diagrammatically depicted in figures 1(a)
and (b)): expression (equation (1)) with the semi-classical approach,
one may write the XY component of Raman tensor, say
∂ 
(a) When a laser impinges on the system, the electronic sys- for E12g mode, as d ∝ [g| ∂y |i  i |Hel−ph |i i| ∂x
∂
|g]/[(EL −
tem absorbs a photon and an electron–hole pair is created ΔEig )(EL − ωph − ΔEi g )] êi ( X), ês ( Y). This suggests
that results in a finite electron–photon interaction (Hop ). that XY and similarly YX component of the Raman tensor
(b) Electron goes to the excited state and creates a phonon changes with the change in EL and this may give rise to a
(stokes process) into the system and results in an elec- change in a different polar dependence of the intensity. Also,
tron–phonon interaction (Hel – ph ). electron–phonon matrix element i |Hel−ph |i may also change.

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J. Phys.: Condens. Matter 32 (2020) 415702 D Kumar et al

Figure 5. Intensity polar plots for the Raman active phonon modes E12g and A1g with two different laser excitation energies (532 and
633 nm) in vertically aligned CVD grown flakes of MoS2 . Black spheres are experimental data points for different polarization angles from
θ = 0◦ to 360◦ and solid blue lines show fitted curves as described in the text. Number of layers and flake thickness mentioned in the left
panel is estimated based on the frequency difference between A1g and E12g phonon modes.

When the energy of the incident photon changes, the interme- have a large number of conduction bands with different sym-
diate states |i, |i  change to new states |inew , which may also metries at the Γ point in BZ. When incident photon energy or
change the denominator. In case of TMDCs, this renormal- layer thickness is changed, the intermediate states get modified
ization of the intermediate states may happen easily because and is reflected in the renormalized electron–photon matrix
of the existence of many energy bands with different sym- elements. To get the finite contribution for Raman intensity,
metries within a short range of energy. Importantly, as one both electron–photon matrix elements in equation (1) should
moves from bulk to single layer in TMDCs, band topology be finite, which constraints that symmetries of |i, |i  be linked
near the valance band and the bottom of the conduction band with |g state. Based on the group theory, one can find the
changes drastically, which may also give different polar plots allowed symmetries of the intermediate electronic states |i
for given Raman active phonon modes simply by changing the and |i . A detailed list of the intermediate states for a given
thickness. We note that similar anisotropic phonon modes as a polarization direction and phonon mode is given in tables S2
function of layer thickness and different EL have been reported and S3 (see supplementary information). Our observations,
in other class of 2D materials with low crystalline symmetry clearly reveal the strong in-plane anisotropic behavior in high
such as black phosphorus, GaTe, ReSe2 , ReS2 [41–45]. symmetric MoS2 . It has been observed that for many low-
Our observation of anisotropic polarization dependence for symmetry 2D systems [41–45], Raman active phonon modes
three different forms of MoS2 flakes as a function of thickness do show polarization dependence on the crystalline orienta-
and incident photon energy is attributed to the selection rule for tion. However, it was suggested that polarization dependence
optical transition, which can be expressed in quantum theory as well as anisotropic transport properties such as mobility,
of Raman scattering via electron–photon–phonon matrix ele- are also coupled to the underlying electronic symmetry along
ments as i|∇|g, g|Hop |i  and i |Hel−ph |i. Layered TMDCs with the crystalline symmetry of the material [41–46]. As

7
J. Phys.: Condens. Matter 32 (2020) 415702 D Kumar et al

Figure 6. Intensity polar plots for the Raman active phonon modes E12g and A1g with two different laser excitation energies (532 and
633 nm) in mechanically exfoliated flakes of MoS2 . Black spheres are experimental data points for different polarization angles from
θ = 0◦ to 360◦ and solid blue lines show fitted curves as described in the text. Number of layers and flake thickness mentioned in the left
panel is as per the thickness measured using AFM method (also see figure S5 in supplementary information) and it corroborate well with the
thickness estimated using the frequency difference between A1g and E12g phonon modes.

electron–phonon interaction is an important factor for tun- suggest that more theoretical as well experimental studies are
ing transport, thermal and superconductive properties in any required for the high crystalline symmetric 2D materials for
material, our findings provide crucial information for the study an understanding of their underlying properties for potential
of anisotropic 2D materials. For example, the out-of-plane future applications.
vibration (A1g ) shows much weaker polarization dependence
as compared to the in-plane vibration (E12g ), suggesting that
4. Summary and conclusions
the out-of-plane vibrations couple less anisotropically with
the in-plane electronic states. Also, the dependence of the In summary, we performed comprehensive Raman scattering
modes intensity on laser energy and flake thickness suggests studies on three different forms of layered MoS2 , probing
that electrons couple strongly to the E12g phonon. We note that the anisotropic behavior of the Raman active phonon modes
anisotropies in transport as well as electronic properties were revealing strong anisotropic electron–photon–phonon cou-
predicted and reported for the case of MoS2 [24, 47–49]. Our pling. The observed anisotropy in the Raman intensity depends
anisotropic results on this high crystalline symmetric material strongly on the incident photon energy, phonon energy as well

8
J. Phys.: Condens. Matter 32 (2020) 415702 D Kumar et al

as the thickness of MoS2 for all the three different forms [14] Wang G et al 2018 Rev. Mod. Phys. 90 021001
studied here. Our work cast a crucial light on understanding [15] Valagiannopoulos C A et al 2017 J. Phys. Commun. 1 045003
the anisotropic strong light–matter interactions in high sym- [16] Wang X et al 2017 Sci. Rep. 7 13539
[17] Singh B et al 2019 J. Phys.: Condens. Matter 31 485803
metric MoS2 , especially for the in-plane vibrations, and we [18] Yoon D et al 2011 Nano Lett. 11 3227
hope our studies also pave the way for the applications of this [19] Singh B et al 2019 J. Phys.: Condens. Matter 31 395701
system in electronic and optoelectronic devices. We believe [20] Lee C et al 2010 ACS Nano 4 2695
that our experimental findings will motivate other groups to [21] Singh B et al 2020 Phys. Rev. Research 2 013040
develop a comprehensive theoretical model for a quantitative [22] Grasset R et al 2019 Phys. Rev. Lett. 122 127001
[23] Wulferding D et al 2012 J. Phys.: Condens. Matter 24
understanding. 185602
[24] Muratore C et al 2014 Phys. Chem. Chem. Phys. 16 1008
Acknowledgments [25] Mitioglu A A et al 2014 Phys. Rev. B 89 245442
[26] Liu H L et al 2015 Phys. Chem. Chem. Phys. 17 14561
PK acknowledges DST Nano Mission, India, for the finan- [27] Saito R et al 2015 Phys. Status Solidi b 252 2363
[28] Kumar R et al 2018 Nanotechnology 29 464001
cial support. The authors at Mandi acknowledge IIT Mandi for
[29] Ribeiro-Soares J et al 2014 Phys. Rev. B 90 115438
providing the experimental facilities. [30] Yamamoto M et al 2014 ACS Nano 8 3895
[31] Zhao Y et al 2013 Nano Lett. 13 1007
[32] Verble J L and Wieting T J 1970 Phys. Rev. Lett. 25 362
ORCID iDs [33] Loudon R 1964 Adv. Phys. 13 423
[34] Cotton F A 2015 Chemical Applications of Group Theory (New
Deepu Kumar https://orcid.org/0000-0002-7900-6311 York: Wiley)
Birender Singh https://orcid.org/0000-0002-9640-0070 [35] Li H, Zhang Q et al 2012 Adv. Funct. Mater. 22 1385
Mahesh Kumar https://orcid.org/0000-0002-5357-7300 [36] Plechinger G et al 2014 Semicond. Sci. Technol. 29 064008
[37] Cardona M and Guntherodt G (ed) 1982 Light Scattering in
Solid II (Berlin: Springer)
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