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New First Order Raman-active Modes in Few Layered Transition Metal

Dichalcogenides

Article in Scientific Reports · February 2014

DOI: 10.1038/srep04215 · Source: PubMed

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 OPEN New First Order Raman-active Modes in
SUBJECT AREAS:
Few Layered Transition Metal
ELECTRONIC STRUCTURE
TWO-DIMENSIONAL MATERIALS
Dichalcogenides
H. Terrones1*, E. Del Corro2, S. Feng1, J. M. Poumirol3, D. Rhodes3, D. Smirnov3, N. R. Pradhan3, Z. Lin1,
Received M. A. T. Nguyen4, A. L. Elı́as1, T. E. Mallouk1,4, L. Balicas3, M. A. Pimenta2 & M. Terrones1,4,5
5 December 2013
Accepted 1
Department of Physics and Center for 2-Dimensional and Layered Materials, The Pennsylvania State University, 104 Davey Lab,
31 January 2014 University Park, PA 16802, USA, 2Universidade Federal de Minas Gerais, Departamento de Fı́sica, Av. Antônio Carlos, 6627
Caixa Postal 702 - cep 30.123-970 Belo Horizonte/MG – Brazil, 3National High Magnetic Field Laboratory, Florida State
Published University, Tallahassee-FL 32310, USA, 4Department of Chemistry, The Pennsylvania State University, University Park, PA 16802,
27 February 2014 United States, 5Department of Materials Science and Engineering, The Pennsylvania State University, University Park, PA 16802,
USA & Research Center for Exotic Nanocarbons (JST), Shinshu University, Wakasato 4-17-1, Nagano, 380-8553, Japan.

Correspondence and
Although the main Raman features of semiconducting transition metal dichalcogenides are well known for
requests for materials
the monolayer and bulk, there are important differences exhibited by few layered systems which have not
should be addressed to been fully addressed. WSe2 samples were synthesized and ab-initio calculations carried out. We calculated
H.T. ([email protected]) phonon dispersions and Raman-active modes in layered systems: WSe2, MoSe2, WS2 and MoS2 ranging
from monolayers to five-layers and the bulk. First, we confirmed that as the number of layers increase, the
E9, E0 and E2g modes shift to lower frequencies, and the A91 and A1g modes shift to higher frequencies.
* Current address: Second, new high frequency first order A91 and A1g modes appear, explaining recently reported
Department of Physics, experimental data for WSe2, MoSe2 and MoS2. Third, splitting of modes around A91 and A1g is found which
Applied Physics and explains those observed in MoSe2. Finally, exterior and interior layers possess different vibrational
frequencies. Therefore, it is now possible to precisely identify few-layered STMD.
Astronomy, Rensselaer
Polytechnic Institute,

T
IC25 Johnson-Rowland he field of 2-Dimensional semiconducting transition metal dichalcogenides (STMDs) is growing very fast
Science Center, 110 mainly due to: a) their moderate band gap which can be used for fabricating electronic devices such as field
Eighth Street, Troy, NY effect transistors (FETs)1–7; b) the presence of a direct band gap in monolayered STMDs, ideal for optoelec-
tronic devices8–11, and c) their unique valley polarization properties12–14. The direct band gap of monolayered
12180, USA.
SMTDs has been measured and it results in an intense photoluminescence (PL) signal9,11 which can be enhanced
at the edges possibly due to edge passivation15. The non-destructive technique of Raman spectroscopy has been
intensively used to characterize monolayered STMDs, and other than the first-order modes, double resonant and
triple resonant processes have been recently identified16,17. Recently, important efforts in understanding the
Raman spectroscopy of few layered systems have been carried out in WSe218,19. However, a careful, systematic
and deep study of the different Raman modes in few layered STMDs (FLSTMD) is needed since previous works
use either the monolayered or the bulk systems to explain Raman spectra of FLSTMDs. Unfortunately, this kind
of analysis might lead to an incorrect assignment of the active Raman modes20 since FLSTMDs exhibit different
symmetries depending on the number of layers. In this manuscript, using first principles density functional
perturbation theory (DFPT), we shed light on this subject and find that the particular symmetry in FLSTMD (e.g.
MoS2, WS2, WSe2, MoSe2) results in new Raman-active modes that are neither present in the monolayer nor in
the bulk spectra. In particular, we predict the existence of a new out-of-plane Raman-active mode, which is
expected to be intense in the spectra of FLSTMDs such as WSe2, MoSe2 and MoS2. This mode has already been
experimentally reported21–23, but neither fully understood nor studied in detail in different FLSTMDs. We present
here a polarized Raman study of this new mode, on synthesized chemical vapor transport samples24–26, which
supports our prediction. In our calculations, we additionally found a splitting in all Raman-active modes which
explains the recently observed double and triple modes in MoSe2 when L 5 3, L 5 4 and L 5 5 for the A91 and
A1g 22 (see table 1), in addition to other modes related to in-plane vibrations that differentiate between exterior
(surface) and interior (bulk) layer vibrations.
Bulk trigonal prismatic STMDs belong to P63/mmc (D6h4), which is a nonsymmorphic space group, and thus,
in order to analyze their vibrations in the unit cell, we need to consider that their unit cell exhibits D6h point group

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Table 1 | First order Raman-active modes in cm21 of few layered WSe2, MoSe2, MoS2 and WS2 (from L 5 1 to L 5 5 layers) and the bulk,
calculated using DFPT, and experimental results published in the literature (in yellow). The point symmetry of the unit cell is indicated in the
first row by its Shöenflies symbol. An asterisk * indicates the more intense calculated signals, ‘‘ir’’ indicates that the mode is also infrared-
active, ‘‘in’’ indicates that just the interior layers vibrate and ‘‘ex’’ represents that just the exterior layers vibrate. The lower frequency modes
have not been included since some of them do not appear in the most common Raman configurations
Structure L 5 1(cm21)D3h L 5 2 (cm21)D3d L 5 3(cm21)D3h L 5 4(cm21)D3d L 5 5(cm21)D3h Bulk(cm21)D6h
WSe2 175.75(E0) 176.20(Eg2) 175.01(E02) 175.22(Eg2) 174.69(E02) 175.01(E1g)
249.36(E9)*ir 176.26(Eg2)19 175.58(E92)ir 175.52(Eg2)19 175.07(E92)ir 177.5(E1g)46
250.23(A91*) 248.52(Eg1)* 175.84(E02)19 176.38(Eg2) 175.60(E02) 247.78(E2g)*
249.5(E9)21 250.83(A1g)* 176.33(E02) 247.66(Eg1)*In 176.01(E92)ir 251.61(A1g)*
249.5(A91)21 306.97(A1g2)* 247.83(E9)*ir,In 248.35(Eg1)*Ex 176.23(E02) 248.0(E2g)22
309.00(A1g2)22 248.32(E9)*ir,Ex 249.57(A1g) 247.55(E91)*ir,In 250.8(A1g)22
310.00(A1g2)21 248.31(E01)*Ex 251.30(A1g)* 247.65(E91)ir,In 247.00(E2g)30
249.16(A91) 305.57(A1g2) 248.55(E91)*ir,Ex 251.00(A1g)30
251.23(A91)* 306.62(A1g2)* 247.59(E01)In 250(E2g)46
306.57(A912)* 309.00(A1g2) 22 248.54(E01) Ex 253(A1g)46
309.00(A912)22 310.00(A1g2)21 248.83(A91)
310.00(A912)21 250.15(A91)
251.21(A91)*
305.29(A912)
306.84(A912)*
309.00(A912)22
310.00(A912)21
MoSe2 167.60(E0) 167.72(Eg2) 166.55(E02) 166.96(Eg2) 166.37(E02) 166.81(E1g)
240.27(A91)* 284.03(Eg1)* 167.51(E92)ir 167.94(Eg2) 166.80(E92)ir 168.00(E1g)30
240.5(A91)22 285.90(Eg1)22 168.00(E02) 239.49(A1g) 167.35(E02) 241.84(A1g)*
241.2(A91)34 240.68(A1g)* 238.74(A91)* 241.23(A1g)* 167.84(E92)ir 242.5(A1g)22
285.32(E9)*ir 348.04(A1g2)* 241.14(A91)* 282.64(Eg1)*In 168.10(E02) 243.00(A1g)34
287.2(E9)22 353.00(A1g2)22 282.69(E91)*ir,In 284.06(Eg1)*Ex 238.42(A91) 283.11(E2g)*
287.3(E9)34 284.18(E91)*ir,Ex 345.72(A1g2) 238.03(A91)22 283.7(E2g)34
284.17(E01)Ex 347.92(A1g2)* 240.02(A91)
348.07(A912)* 353.00(A1g2)22 240.12(A91)22
353.00(A912)22 241.40(A91)*
242.04(A91)22
282.63(E91)*ir,In
282.81(E91)ir,In
284.07(E91)*ir,Ex
282.73(E02)In
284.10(E02)Ex
345.54(A912)
347.90(A912)*
353.00(A912)22
WS2 298.54(E0) 299.08(Eg2) 297.22(E02) 297.73(Eg2) 297.10(E02) 299.20(E1g)
359.24(E9)ir 358.26(Eg1)* 298.22(E92)ir 298.94(Eg2) 297.83(E92)ir 357.21(E2g)*
356.00(E9)16 419.39(A1g)* 298.92(E02) 357.13(Eg1)*In 298.55(E02) 356.5(E2g)21
357.50(E9)21 437.61(A1g2) 357.17(E91)*ir,In 358.06(Eg1)*Ex 299.36(E92)ir 420.27(A1g)*
418.7(A91)* 358.13(E91)*ir,Ex 417.69(A1g) 299.47(E02) 421.00(A1g)21
417.50(A91)16 358.13(E02)Ex 419.81(A1g)* 357.09(E91)ir,In
418.0(A91)21 416.87(A91) 436.14(A1g2) 357.21(E91)*ir,In
419.63(A91)* 437.28(A1g2) 358.64(E91)*ir,Ex
437.09(A912) 357.23(E01)In
358.66(E01)Ex
416.73(A91)
418.49(A91)
420.14(A91)*
435.75(A912)
437.57(A912)
MoS2 284.00(E0) 283.78(Eg2) 281.91(E02) 281.79(Eg2) 281.84(E02) 282.05(E1g)
383.61(E9)*ir 381.65(Eg1)* 283.24(E92)ir 283.28(Eg2) 282.29(E92)ir 286.00(E1g)47
384.7(E9)34 402.86(A1g)* 283.83(E02) 379.57(Eg1)*In 282.95(E02) 287.00(E1g)48
384.0(E9)29 463.84(A1g2)* 379.89(E91)*ir,In 381.54(Eg1)*Ex 283.57(E92)ir 380.35(E2g)*
402.65(A91)* 381.75(E91)*ir,Ex 400.67(A1g) 284.01((E92)ir 383.00(E2g)48
406.1(A91)34 381.74(E01)Ex 402.80(A1g)* 380.14(E91)*ir,In 383.50(E2g)22
403.00(A91)29 400.00(A91) 461.12(A1g2) 380.50(E91)ir,In 383.7(E2g)34
403.05(A91)* 463.39(A1g2)* 381.46(E91)ir,Ex 405.02(A1g)*
463.62(A912)* 380.33(E01)In 408.6(A1g)22
381.47(E01)*Ex 408.7(A1g)34
399.73(A91)

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Table 1 | Continued
Structure L 5 1(cm21)D3h L 5 2 (cm21)D3d L 5 3(cm21)D3h L 5 4(cm21)D3d L 5 5(cm21)D3h Bulk(cm21)D6h
401.43(A91)
403.44(A91)*
461.28(A912)
463.18(A912)*
463.00(A912)23

symmetry; this is not the case for the monolayered or FLSTMDs, Raman-active modes involve the vibrations of the chalcogen and the
which are considered quasi 2-D systems in the ‘‘Z’’ direction. The transition metal atoms, belonging to the A91 or A1g irreducible repre-
monolayer in STMDs is non-centrosymmetric (no inversion sym- sentations (for odd and even number of layers, respectively), and do
metry) and its vibrational modes belong to the D3h point group. not appear in the monolayer. We propose to label these new modes
Therefore, in agreement with the irreducible representations of this A912 and A1g2 (See table 1 and figure 3). For the bi-layer
point group, one must use the symbols A91 and E9, for the out of (306.97 cm21) and tri-layer (306.57 cm21), only one Raman-active
plane and in-plane vibrations, respectively. For understanding the mode appears around this frequency, but for the tetra-layer
case of FLSTMDs (L 5 2,3,4,5…), their particular symmetries need (305.57 cm21 and 306.62 cm21) and penta-layer (305.29 cm21 and
to be analyzed since the symmetry changes when varying the number 306.84 cm21), two modes appear that are very close in frequency,
of layers from even to odd numbers. Systems with an odd number of corresponding to exterior and interior layer vibrations (See table 1
layers (L 5 1,3,5,…) exhibit D3h point-group symmetry, do not and figure 4).
possess a center of inversion, and the out-of-plane Raman-active In order to experimentally demonstrate that these first order high
modes belong to the A91 irreducible representation. For systems with frequency modes belong to vibrations perpendicular to the lattice
an even number of layers (L 5 2,4,…), the modes belong to the D3d plane, parallel and cross polarized Raman spectra were acquired
point group which exhibits a center of inversion, and the out-of- using a 514.5 nm laser, confirming that both the A1g and A91 signals
plane Raman-active modes possess the A1g irreducible representa- for systems with different number of layers vanish completely in the
tion. In this context, it is important to emphasize that the absence of cross-polarized Raman configuration (VH), as expected by group
inversion symmetry plays a crucial role in nonlinear optical prop- theory (See figure 3). In figure 3 it is also shown a signal around
erties such as the second harmonic generation27,28, and valley 260 cm21 for monolayer, bilayer and trilayer which under no strain
polarization12–14. could be regarded as a second order peak caused by a double re-
sonance effect involving the LA(M) phonon located around
Results 130 cm21 (See figure 3d) which will produce a peak circa
We synthesized crystals of the trigonal prismatic phase of WSe2 by 260 cm21; double resonance effects involving the LA(M) phonon
chemical vapor transport techniques24–26 (see methods section), and have already been reported in WS215.
by adhesive tape exfoliation we were able to produce few layered Interestingly, these new modes have also been reported experi-
WSe2 (See figure 1). Raman spectra were attained using four different mentally in MoSe2 at ca. 353 cm21 22, and appear in our calculations
laser lines (488 nm, 514.5 nm, 633 nm and 647 nm) to study their between 345.54 cm21 and 348.07 cm21, depending on the number of
vibrational properties depending on the number of layers (See layers (See table 1). For few-layered MoS2 and WS2, the high fre-
figure 2a–2d), and photoluminescence studies were carried out to quency out of plane modes, according to DFPT, are around 463 cm21
confirm the presence of the direct optical band gap at around 750 nm and 437 cm21, respectively. Unfortunately, these modes have not
(1.65 eV) for the monolayer22. It is noticed that as the number of been properly identified experimentally for several reasons. First,
layers increases, the PL intensity decreases, appearing two signals for MoS2 the mode at 464 cm21 is close to the 2LA(M) mode located
which shift to higher wavelengths (lower energies) agreeing with at 455 cm21 and it is often confused with it, and sometimes assigned
the work of Tonndorf et al22 (see figure 2e). to the Raman inactive mode in the bulk crystal, the A2u mode, but no
We first considered the case of monolayered WSe2, in which the further discussion has been made in the literature23,32. Second, for few
experimental Raman spectrum exhibits the presence of the perpen- layered WS2 the mode centered at 437 cm21 exhibits a very small
dicular mode A91 and the in-plane E9 almost degenerate at around intensity, probably due to the small polarizability of this mode (the
250 cm21 19,21,22; according to our calculations A91 is at 250.23 cm21 components of the Raman tensor are very small), thus making it
and the E9 at 249.36 cm21 (see table 1). By adding layers, we observed difficult to identify this mode experimentally.
that the out of plane modes A91 (A1g) shift to higher frequencies and In addition, our calculations in FLSTMDs reveal Raman-active
the E9 (Eg) displace to lower frequencies (see table 1), a behavior that splitting modes, both out of plane and in-plane; this can be seen
has been reported experimentally by different authors in WSe2 and for instance from the phonon dispersions of WSe2 at the C point
other STMDs15,19,21–23,29. Experimentally, these modes in the bulk 3-D (see figure 1S in supplementary information). While mono-layered
crystals are associated with the A1g (located at 251 cm21) and the E2g and bi-layered WSe2 exhibit only one perpendicular mode
(around 247 cm21) irreducible representations of the D6h point at 250.23 cm21 and 250.83 cm21, respectively, the tri-layer
group, exhibiting inversion symmetry (see table 1)22,30. (249.17 cm21 and 251.23 cm21) and tetra-layer (249.58 cm21 and
From the Raman spectra we noticed that with the laser line of 251.3 cm21) possess two branches, and the penta-layer reveals
514.5 nm a new peak located at 310.4 cm21 appears for the bilayer, three (248.83 cm21, 250.15 cm21 and 251.21 cm21) (See table 1
tri-layer, tetra-layer and penta-layer (see figure 2a–d). Other authors and figure 4). Recently, these three out of plane modes have been
have identified this peak at 308 cm21 21, 309 cm21 22 and 310 cm21 19. reported experimentally in five layered MoSe2 at 238.03 cm21,
One report assigned this peak to a combination of shear modes and 240.12 cm21 and 242.04 cm21 22; in our calculations, these modes
the E2g mode21, and another publication related this peak to the appear at 238.42 cm21, 240.02 cm21 and 241.4 cm21 and are in very
inactive B2g mode of bulk WSe222. Our calculations on FLSTMD good agreement with the experimental data (See table 1). The main
predicted Raman-active modes around 306 cm21 (See table 1) that reason why we cannot experimentally resolve them in WSe2 is
are close in frequency to the infrared-active A2u (305 cm21)31 and the because the in-plane modes are very close in frequency to the per-
Raman-inactive B2g mode of the bulk phase (301 cm21)30. These new pendicular modes, thus making this task very difficult and dependent

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Figure 1 | Optical and atomic force microscope images of exfoliated WSe2 crystals a) Monolayer; b) Bilayer; c)Tetra-layer; d) Penta-layer.

on the resolution of the instrument. In other FLSTMDs, such as WS2 representation for even numbers of layers, and to the E9 and E0 for
and MoS2, the in-plane and out of plane signals are separated by odd numbers of layers. In WSe2 the in plane modes are around
several wave numbers, around 60 cm21 for WS2 and 20 cm21 for 176 cm21 and 248 cm21 agreeing with the calculations presented
MoS2, thus making possible to identify the splitting when having a by Luo and co-workers for L 5 2 to L 5 419 (see table 1). In our
high resolution instrument working at low temperatures. For WS2, Raman spectra, despite using different laser lines, it is difficult to
our calculations depict that there should be two modes for both the observe a signal around 176 cm21 due to the small intensity of these
tri-layer and tetra-layer between 416.87 cm21 and 419.81 cm21 (see modes, however, around 248 cm21 we observe the signal of these
table 1), and for the penta-layer there should be three modes between modes which is mixed with the out of plane modes (see figure 2).
416.73 cm21 and 420.14 cm21. In the case of the MoS2 tri-layer and For the case of MoSe2 the in-plane modes are located circa 167 cm21
tetra-layer, the two splitting modes appear between 400 cm21 and and 283 cm21, in WS2 at about 298 cm21 and 357 cm21, and in MoS2
403 cm21, and for the penta-layer, three modes appear between are nearby 282 cm21 and 380 cm21 (to differentiate between these in
399.73 cm21 and 403.44 cm21 (See table 1). On the other hand, it plane modes a super index has been used in table 1). For example, in
might be interesting to try finding the splitting in other 2D materials. WSe2, two in-plane modes appear for the tri-layer (247.83 cm21 and
Our calculations indicate that the splitting of A91 (A1g), starting 248.33 cm21) and tetra-layer (247.66 cm21 and 248.35 cm21), and
from L 5 3, involves two main types of mode families: One, in which three modes appeared for the penta-layer (247.55 cm21, 247.65 cm21
all the Se or S atoms compress or expand at the same time, thus and 248.55 cm21. See figure 4). Further, it is worth noticing that
shifting to higher frequencies as the number of layers grows (reach- Raman-active E0 modes are also active for the tri-layer at
ing the maximum frequency in bulk), and another, in which the 248.32 cm21 and the penta-layer at 248.54 cm21, and only the exter-
chalcogen vibrations in each layer exhibit opposite directions in an ior layers are involved (See figure 4). In addition, the E9 in-plane
alternative way, resulting in lower frequencies (See table 1 and mode has its maximum frequency value for the monolayer, and when
figure 4). more layers are added, a splitting takes place in which the interior
It is also noteworthy that the new in-plane modes can differentiate layers (bulk-like) exhibit lower frequencies than the exterior ones
between interior and exterior layers, and belong to the Eg irreducible (surface layers). Therefore, when reaching the bulk phase (no

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Figure 2 | Raman spectra of few layered WSe2 with different excitation wavelengths; (a) 488 nm; (b) 514.5 nm; (c) 633 nm; (d) 647 nm; (e)
Photoluminescence (PL) spectra obtained with the 488 nm.

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Figure 3 | Experimental Raman spectra of WSe2 taken with a 514 nm laser under conventional geometry (VV) and cross polarization (VH). (a)
Monolayer (L 5 1). (b) Bilayer (L 5 2). (c) Trilayer (L 5 3). Insets show models of the out of plane vibrational modes present in each case. (d) Calculated
DFPT phonon dispersion of the WSe2 monolayer.

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Figure 4 | Models showing the vibrations of A91, E9 and E0 Raman-active modes for L 5 5 WSe2. A91(1) at 248.83 cm21; A91(2) at 250.15 cm21; A91(3) at
251.21 cm21; A912(1) at 305.29 cm21; A912(2) at 306.84 cm21;E91(1) at 247.55 cm21; E91(2) at 247.65 cm21; E91(3) at 248.55 cm21;
E01(1) at 247.59 cm21 and E01(2) at 248.54 cm21.

exterior layers), the E1g mode preserves the lower frequency values of samples, and confirming our observations by performing DFPT first
the interior layers, thus explaining the experimentally observed shift principles calculations. We find that there are novel, out of plane and
to lower frequencies as the number of layers is increased (See fig- in plane, Raman-active modes that are not present in the monolayer
ure 4). All the E9 modes in odd numbers of layers are also infrared- or in the bulk, and are capable of differentiating between the vibra-
active (See table 1), while for even numbers of layers the E1g modes, as tions of the outer and interior layers. Our results also explain recent
expected from the principle of mutual exclusion, are not infrared- observations reported for few layered WSe2, MoSe2 and MoS2. These
active since they are symmmetric with respect to inversion. The new modes reported here will be important when characterizing few-
calculated phonon dispersions of WSe2 for L 5 1 to L 5 5 and bulk layered systems as well as to identify monolayers. In addition, the
are shown in figure S1 (supplementary information) where the new new modes might play an important role in double resonance Raman
modes appear as new branches at the C point. These results can be processes in FLSTMDs.
extended to other FLSTMDs with trigonal prismatic layers (See
table 1). Methods
We also expect that the new modes mentioned above will appear in In order to study and understand the origin of the main features observed in Raman
hetero-bilayered systems formed by stacking different layers of spectra of FLSTMDs, ab-initio density functional theory (DFT) and density func-
STMDs. For example, for a bilayered system made of one layer of tional perturbation theory (DFPT) calculations were carried out in monolayers and
few-layered systems of WSe2, MoSe2, MoS2 and WS2 (from L 5 1 to L 5 5, and also
WSe2 and another layer of WS2, our calculations demonstrate that, the bulk), as implemented in the plane wave code CASTEP38 in the Materials Studio
besides the A1 (C3v symmetry) vibrational modes at 251.7 cm21 for package. Trigonal unit cells were considered under the local density approximation
WSe2 and at 415.4 cm21 for WS2, two other perpendicular Raman- (LDA) using the Ceperly-Alder-Perdew and Zunger (CA-PZ) functional39,40 with 9 3
active modes appear at different frequencies, one at 311.1 cm21 for 9 3 3 Monkhorst-Pack K-points and a plane waves cut off of 500 eV with a norm-
conserving pseudopotential. All the structures were relaxed, including the cells, until
WSe2 and another at 427.9 cm21 for WS2. Note that these modes are the forces became smaller than 0.01 eV/Å and with self- consistent energy tolerances
close in frequency to those present in the pure bilayered systems. less than 5 3 1027 eV/atom. A vacuum of 16 Å between the layers was considered.
However, the shift here is mainly due to an induced strain causing The electronic structure results obtained are in agreement with those reported by
the WS2 to expand and the WSe2 to contract to preserve an energy other groups within the LDA formalism41,42. In order to provide a reasonable
description of the van der Waals interaction, we have considered a dispersion cor-
local minimum33. Since our calculations consider free standing layers rection for both LDA (LDA-D)43 and for general gradient approximation (GGA-
of STMDs, the effect of the substrate has not been considered and PW91)44 finding that LDA provides a better description for the interlayer distance
could affect mainly the layer to which it has interaction depending on than LDA-D and corrected GGA-PW91, as described in a previous publication33. The
the particular substrate: Several experimental works, including ours, phonon dispersions and Raman scattering modes were calculated with the above
parameters, but extending the plane wave cut off to 720 eV with DFPT using the
use SiO2/Si substrates16,21–23,29,34, and the Raman modes exhibit little linear response methodology for insulators45.
change from those calculated here and by other authors when no The few layered WSe2 samples were obtained by mechanical exfoliation of WSe2
strain is considered18,19,35, indicating a weak interaction with the sub- crystals produced using the chemical vapor transport method with iodine as transport
strate. In addition, the photoluminescence results (See figure 2) show agent24–26. First, WSe2 powder was synthesized by heating a mixture containing
stoichiometric amounts of tungsten (Acros Organics 99.9%) and selenium (Acros
a clear signal at 750 nm which corresponds to the direct optical band Organics 99.51%) at 1000uC for 3 days in an evacuated and sealed quartz ampoule
gap of monolayer WSe2, thus no evident strain from the substrate or (10 mm ID, 12 mm OD, 150 mm length). The mixture was slowly heated from room
from the sample itself is detected since strain would alter the optical temperature to 1000uC for 12 hours, in order to avoid any explosion due to the strong
band gap35–37. Nevertheless, a careful study with different substrates is exothermic reaction. The WSe2 crystals were grown from that synthesized powder
using chemical vapor transport with iodine (Sigma-Aldrich, 99.81%) as the transport
required to address the role of a particular substrate with FLSTMDs. gas at 1.5 mg/cm3. The experiments ran for 10 days in an evacuated and sealed quartz
In summary, we have addressed Raman spectroscopic modes of ampoule (10 mm ID, 12 mm OD, 100 mm length). The source and growth zones
FLSTMDs by measuring directly few layered exfoliated WSe2 were kept at 950uC and 816uC, respectively. The resulted crystals were washed with

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hexane and dried in vacuo to remove any residual iodine. Both WSe2 powder and 27. Kumar, N. et al. Second harmonic microscopy of monolayer MoS2. Phys. Rev. B
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PhysRevB.88.195313 (2013). This work was supported by the U.S. Army Research Office MURI grant
20. Verble, J. L. & Wieting, T. J. Lattice Mode Degeneracy in MoS2 and Other Layer W911NF-11-1-0362, by the Materials Simulation Center of the Materials Research Institute
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support from the Penn State Center for Nanoscale Science for seed grant on 2-D Layered
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and Layered Materials at the Pennsylvania State University. M.A.P. and E.D.C.
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acknowledge the support of INCT Nanocarbono and the Brazilian agencies FAPEMIG and
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CNPq.
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Tungsten and of Their Dioxides and Sulfides. J. Solid State Chem. 8, 14–28, J.M.P., D.R., D.S. performed preliminary polarized Raman spectroscopy. N.R.P., S.F. and
doi:10.1016/0022-4596(73)90014-5 (1973). Z.L. exfoliated the WSe2 crystal samples. D.R., J.M.P., D.S., S.F. and Z.L. performed PL
26. Lieth, R. M. A. Preparation and Crystal Growth of Materials with Layered measurements. D.R. and M.A.T.N. worked on the synthesis of the WSe2 crystals. D.R.,
Structures. Vol. 1 (Springer Netherlands, 1977). N.R.P., S.F. and Z.L. performed optical microscopy and AFM measurements. T.E.M. and

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L.B. supervised the synthesis of crystals of WSe2, their exfoliation, optical, Raman and AFM How to cite this article: Terrones, H. et al. New First Order Raman-active Modes in Few
characterization, and discussed the results. M.T. coordinated and revised the theoretical and Layered Transition Metal Dichalcogenides. Sci. Rep. 4, 4215; DOI:10.1038/srep04215
experimental results, and wrote the manuscript. All authors revised the manuscript. (2014).

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