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Raman Characterization of the Charge Density

Wave Phase of 1T-TiSe2: From Bulk to
Atomically Thin Layers
Dinh Loc Duong,† Gihun Ryu,† Alexander Hoyer,† Chengtian Lin,† Marko Burghard,*,†
and Klaus Kern†,‡
†
Max Planck Institute for Solid State Research, Heisenbergstrasse 1, D-70569 Stuttgart, Germany
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‡
Institut de Physique, École Polytechnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland
*
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S Supporting Information

ABSTRACT: Raman scattering is a powerful tool for investigating the vibrational properties
of two-dimensional materials. Unlike the 2H phase of many transition metal dichalcogenides,
the 1T phase of TiSe2 features a Raman-active shearing and breathing mode, both of which
shift toward lower energy with increasing number of layers. By systematically studying the
Raman signal of 1T-TiSe2 in dependence of the sheet thickness, we demonstrate that the
charge density wave transition of this compound can be reliably determined from the
temperature dependence of the peak position of the Eg mode near 136 cm−1. The phase
transition temperature is found to first increase with decreasing thickness of the sheets,
followed by a decrease due to the effect of surface oxidation. The Raman spectroscopy-based
method is expected to be applicable also to other 1T-phase transition metal dichalcogenides
featuring a charge density wave transition and represents a valuable complement to electrical
transport-based approaches.

KEYWORDS: 2D transition metal dichalcogenides, 1T-TiSe2, charge density wave transition, low-frequency Raman modes,
shearing mode

T he charge density wave (CDW), or distorted charge

wave phase, has been extensively studied for many
decades.1,2 It comprises a structural transition from a
normal to a distorted phase, driven by the competition between
the energy gain due to the formation of an electronic energy
is almost independent of the number of layers, while the
transition from the nearly commensurate to the commensurate
CDW phase is shifted toward lower temperature with
decreasing sample thickness.14,15 The detailed origin of this
behavior has yet to be identified. Particularly interesting is the
gap, which redistributes the electronic levels to lower energies, possibility to tune the CDW transition temperature of a thin
and the energy cost associated with the distortion of the crystal TMDC sample through electrostatic gating or strain engineer-
structure.2 The CDW transition occurs in many different types ing.9,14,15 This might enable controlling the quantum phase
of materials, a prominent example being the metallic transition transition in a manner compatible with semiconductor
metal dichalcogenides (TMDCs) such as 2H-NbSe2 or 1T- technology.16,17
TiSe2, wherein the cohesive bonding between metal and Bulk 1T-TiSe2 undergoes a CDW transition from the 1 × 1
chalcogenide is quite weak.3 The nonlinear electrical character- × 1 normal phase to the 2 × 2 × 2 CDW phase at 200 K.18
istics of the CDW phase, which can be controlled by While the underlying mechanism is still under debate, it has
electrostatic gating, open up potential applications of CDW
been suggested to involve Fermi surface nesting, the Jahn−
materials in electronic devices.2,4 Furthermore, the competition
Teller effect or a periodic lattice distortion (PLD), or
of CDW and superconducting phases, leading to a dome shape
excitons.17,19−21 A recent study using ultrabroadband THz
like in case of high-Tc superconductivity, is currently only little
understood.5−8 pulses points toward PLD as the main driving force for the
Two-dimensional (2D) TMDCs are attracting great formation of the CDW phase in TiSe2.20 Similar conclusions
attention due to the dimensional dependence of their have been drawn from density functional theory (DFT)-based
properties, including the CDW phase transition.9−15 It has simulations.17,19 The existence of a superconductivity dome has
been shown that the transition temperature of the CDW phase
of 2H-NbSe2 increases upon decreasing the thickness of the Received: November 16, 2016
exfoliated sheets.11 In 1T-TaS2, by contrast, the transition from Accepted: January 3, 2017
the incommensurate to the nearly commensurate CDW phase Published: January 3, 2017

© 2017 American Chemical Society 1034 DOI: 10.1021/acsnano.6b07737

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Figure 1. Symmetry analysis of a 1T-TiSe2 (a) mono- and (b) bilayer. The space group D33d, with the corresponding C3, C2, σd, S6, and i
symmetry operators, is preserved down to the thinnest sheets. The representation of the lattice modes depends on whether the thin sheets
comprise an odd or even number of layers.

Figure 2. (a) Optical micrograph and (b) AFM image of exfoliated TiSe2 sheets (corresponding to the region marked by the red rectangle in
panel (a)). (c) Height profiles taken along the two dashed, horizontal lines in panel (b). (d) Room-temperature Raman spectra (λ = 633 nm)
recorded from regions of different thickness of the sheet in panel (b). While the low-frequency shearing and breathing modes are absent in
bulk TiSe2, they are clearly visible in the thin sheets.

been experimentally confirmed by subjecting bulk TiSe2 to Here, we experimentally and theoretically investigate the
pressure or compositional doping.8,5 Angle-resolved photo- dependence of the low-frequency Raman modes and CDW
emission spectroscopy (ARPES) has revealed the CDW transition of TiSe2 on the number of layers. Our density
transition in TiSe2 monolayers on graphene, although different functional perturbation theory (DFPT) simulations predict an
values of Tc have been obtained in these experiments.10,12 Thus, enhancement of the CDW phase upon decreasing the thickness
the question of whether the CDW is enhanced or suppressed of the sheets. This trend is experimentally confirmed for sheet
upon thinning the samples down to atomic thickness has not thicknesses down to 10 nm, reaching a value of 210 K, whereas
yet been resolved. Moreover, only very little has been reported for thinner sheets the substrate influence and oxidation under
on the possible use of the low-frequency Raman modes of the ambient conditions cause a reduction of Tc. In particular, we
1T-phase of TiSe2 for determining the number of layers.22 present a Raman spectroscopy-based approach to determine
1035 DOI: 10.1021/acsnano.6b07737
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Figure 3. Room-temperature Raman spectra of thin TiSe2 sheets, acquired with λ = 633 nm in (a) XX and (b) XY polarization configuration.
Atomic displacements associated with the (c) shearing and (d) breathing mode in TiSe2 sheets of different thickness, as calculated by DFT-
LDA. (*) Raman signal contribution from the adjacent, three-layer-thick region.

the CDW transition temperature (Tc) of 1T-TiSe2, which different thickness can be readily distinguished by their
exploits the peak position of the Eg mode (around 136 cm−1). contrast. The corresponding topographic AFM image (Figure
2b) and height profiles (Figure 2c) signify the layered structure
RESULTS AND DISCUSSION of TiSe2 with many step edges and an interlayer distance of
approximately 0.6 ± 0.2 nm. In Figure 2d, the Raman spectrum
The crystal structure of 1T-TiSe2 belongs to the symmorphic
of bulk TiSe2 is compared to spectra collected from sheet
P3m1 (D33d) space group with one Ti and two Se atoms in the
regions of different thickness. The two main Raman peaks in
unit cell.18,23−25 The corresponding factor group at the gamma
point is isomorphic to the point group D3d (see the irreducible the bulk spectrum at 136 and 200 cm−1 correspond to the Eg
representation in Table S1). The representation of the lattice and A1g mode, respectively. The Raman data in Figure 2d are
vibration is decomposed as Γlat.mod. = A1g + Eg + 2A2u + 2E2u. consistent with previous reports.18,22−24 The peaks at 233 and
Unlike the 2H-phase of TMDCs (like 2H-MoS2), the crystal 316 cm−1, which can be attributed to defect-enabled phonons at
symmetry of bulk TiSe2 is preserved for the thinnest sheets, as the L and M points24 according to previous theoretical work,
shown in Figure 1 for the mono- and bilayer.26−28 However, are absent for the clean (freshly cleaved) surface at both high
the lattice mode representation depends on whether the and low temperature in our measurements (Figure S1).29
number of TiSe2 layers n is odd or even. For an odd number of Moreover, the peak at 233 cm−1 occurs after longer exposure to
layers, the Ti atom is located on three C2 axes, whose crossing the ambient environment. Raman signals below 50 cm−1
point represents a center of inversion, whereas for an even emerge for TiSe2 sheets with a thickness of less than 10 nm.
number there is no atom at this location. Accordingly, the As the unit cell of bulk TiSe2 consists of only one layer, no low-
number of equivalent atoms is different in the two cases (Table frequency modes corresponding to the shearing and breathing
S1). The lattice vibrational modes in sheets with an odd and mode are observed in bulk TiSe2. However, these two
even number of layers are designated as (interlayer) modes appear for thin sheets, due to breaking of
3n − 1 3n + 1
Γlat.mod.(odd) = 2 (A1g + Eg) + 2 (A 2u + E u) and the translation symmetry along the z-axis. The actual number of
3n
TiSe2 layers cannot be determined from AFM data alone.
Γlat.mod.(even) = 2 (A1g + Eg + A 2u + E u), r e s p e c t i v e l y . However, step edges can easily be identified in the AFM images
Among these, the modes belonging to A1g and Eg are Raman (as exemplified by Figure 2d, where the height increase from
active. Our symmetry analysis is in accordance with previous 3.5 nm to 4.2 nm corresponds to a TiSe2 monolayer). In order
reports on 1T-PtS2, which has a similar lattice structure.22 to identify a monolayer region, the Raman spectrum provides
Figure 2a shows an optical micrograph of mechanically additional valuable information. Specifically, the thinnest areas
exfoliated TiSe2 sheets on a Si/SiO2 substrate. Sheets of displaying Raman features at 136 and 200 cm−1 without peaks
1036 DOI: 10.1021/acsnano.6b07737
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in the low-frequency range can be assigned to a monolayer. For composed of more than four layers display multiple Raman
the sheet in Figure 2b, this is the case for the 3.1 nm thick peaks, which can be assigned to higher frequency branches of
region (see spectrum in Figure 2d). In principle, the intensity of the shearing and breathing modes. The low-frequency modes
the Raman peaks would be expected to gradually increase with are useful to determine the number of layers within different
increasing TiSe2 sheet thickness, as it is indeed observed for the regions of extended TiSe2 sheets from Raman maps (Figure
two peaks at 136 and 200 cm−1, respectively. However, this is S3). The interlayer shear and breathing force constants
not the case for the peaks in the low-frequency range (below extracted using the linear chain model (Figure S4) are listed
∼60 cm−1), where pronounced peaks suddenly emerge starting in Table 1.
from a sheet thickness of 3.5 nm. This observation supports the
assignment of the 3.1 nm thick region to an effective monolayer Table 1. Position of Shearing and Breathing Modes
that is surrounded by oxidized material. Another indication for
oxidation under ambient conditions is the fact that the 1.4 nm force constant
(1019 N m−3)
thick region within the sheet of Figure 2b does not display any
Raman signal (black line in Figure 2d). As shown in Figure S2, quadruple
bilayer trilayer layer exptl DFT(LDA)
the low-frequency modes undergo a notable change upon
increasing sample exposure to air. In fact, after keeping the shearing mode 21 15 12 2.2 3.8
(cm−1)
sample for 3 h in air, the main peak at 12 cm−1 has changed breathing mode 37 26 21 6.6 9.4
into two peaks located at 14 and 10 cm−1, respectively. Thus, (cm−1)
the oxidation of thin TiSe2 sheets can be monitored using the
low-energy peaks, whereas the Raman modes at 136 and 200
cm−1 remain essentially unaffected by the air. The normal phase of TiSe2 changes to the distorted phase
The shearing mode involves vibration in the xy-plane, while below the transition temperature, Tc. The CDW phase
the breathing mode is associated with out-of-plane vibration transition can be monitored by changes in the Raman spectrum
along the perpendicular (z) direction. Hence, the shearing as well as in the electrical transport characteristics. Figure 4a
(breathing) mode is 2-fold degenerate (nondegenerate) and shows the evolution of the Raman spectrum of bulk TiSe2 with
belongs to the Eg (A1g) irreducible representation. This renders temperature. Upon cooling, there appear two new peaks at 70
the Raman tensors of the two types of modes different (Table (Eg) and 110 (A1g) cm−1, respectively, indicating the transition
S2). While Eg modes can be detected in both XX and XY to the CDW phase.18,23,25 These two peaks are associated with
polarization configuration, A1g modes appear only in the XX the transverse acoustic phonon mode at the L and M points,
configuration.26−28 Thus, the shearing and breathing mode can which folds to the gamma point in the 2 × 2 × 2 CDW
be distinguished with the aid of polarized Raman spectroscopy. reciprocal lattice.23,25 Here, we term these two peaks “softened
Figure 3a and b show the Raman modes below 50 cm−1, modes”. One option to determine the transition temperature
acquired from various thin TiSe2 sheets in XX and XY relies upon the temperature dependence of the softened mode
configuration, respectively. In the case of the monolayer, no intensity (Figure 4b), analogous to the phase transition of
Raman peaks are observed in this range. By contrast, the sheets NbSe2.11 In this manner, the transition temperature of bulk
composed of two, three, or four layers display two well-defined TiSe2 is estimated to be 180 K, somewhat lower than the Tc of
peaks in the XX configuration, with one of them disappearing 200 K derived from electrical transport measurements (Figure
in the XY configuration. On the basis of the above symmetry S5). This discrepancy arises from the weak temperature
analysis, we assign the peaks in Figure 3b to the shearing mode, dependence of the softened modes in TiSe2, due to which
while the additional peaks visible in XX configuration (Figure clear peaks are observable only at temperatures below Tc, and
3a) are attributed to the breathing mode. The shearing mode is accordingly the peak intensities are difficult to determine.
shifted to lower energy with increasing number of layers, a Although it is possible to minimize the error by increasing the
trend that is opposite that of 2H-stacked layered materials, such spectral acquisition time and the laser power, this is time
as 2H-MoS226,28,29 but similar to the 1T-like structures such as intensive and involves the risk of sample heating. These
PtSe2 and Bi2Se3.22,30 This difference can be rationalized by a problems can be avoided by evaluating the Eg Raman peak at
linear chain model.31 The frequency ωi of the ith shearing 136 cm−1, relating to the in-plane vibration of two Se atoms
vibration is given by ωi 2 = 2π 2c 2 μ 1 − cos⎡⎣ N ⎤⎦ , where c
around the Ti atom. This vibrational mode exists in both the
1 α
{ }
(i − 1)π
normal and the CDW phase of 1T-TiSe2. As apparent from
is the velocity of light, α is the interlayer shearing force, and μ is Figure 4c, upon cooling, this mode initially shifts to higher
the mass per unit area of one layer. In the case of the 2H energy. Such behavior is expected due to phonon hardening
structure, the highest frequency branch (i = N) vibration is with decreasing temperature. However, upon further cooling
detected.31 In 1T-TiSe2, the lowest frequency branch is below 195 K, the peak position reverses back to that at room
observed with i = 2. Therefore, the shearing mode frequency temperature. Importantly, the transition temperature of 195 K
in the T-phase is ω2 2 = 2π 2c 2 μ ⎡⎣1 − cos N ⎤⎦. It follows that
1 α π coincides with Tc of the CDW phase, establishing a reliable and
( ) straightforward means to experimentally determine Tc. This
upon increasing the number of layers N, the shearing mode method is much easier and more accurate than tracing the
shifts to lower energy. We could gain further support for this softened mode intensities. By contrast, the A1g peak near 200
trend from DFPT-based simulations of the shearing and cm−1 is not suitable for this purpose, as it monotonically
breathing mode, as illustrated in Figure 3c and d, where the increases upon cooling (Figure S6). In fact, the A1g mode is
lowest energy modes (wavenumbers in red) belong to the associated with the out-of-plane vibration of Se atoms around a
measured Raman peaks.32,33 The theoretical values slightly Ti atom and is therefore insensitive to the CDW phase
exceed the experimental ones, as the local density approx- transition accompanied by a strong in-plane distortion. It is
imation overestimates the interlayer interaction. Sheets noteworthy that the corresponding peak in 1T-TaS2 displays a
1037 DOI: 10.1021/acsnano.6b07737
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Figure 4. (a) Evolution of the Raman spectrum (λ = 633 nm) of bulk TiSe2 with temperature. (b) Averaged intensity of the softened mode at
100 cm−1 as a function of temperature. The mean intensity corresponds to the average within the range of 60 to 110 cm−1. (c) Peak position
of the Eg mode near 136 cm−1 in dependence of temperature.

Figure 5. (a, b) Evolution of the phonon spectrum of monolayer (a) and bilayer (b) TiSe2 with electronic temperature. (c) Fits of the
electronic (smearing) temperature dependence of the frequency of the softened phonon mode at the M point, together with the extracted Tc
values.

sharp, temperature-dependent change due to the first-order end, Figure 5a,b display the evolution of the phonon spectrum
transition behavior of this compound.34 of monolayer and bilayer TiSe2 with electronic temperature.
Of particular interest is the dependence of the CDW The phonon softening observed at the M point is associated
transition on the sheet thickness. In the case of 2H-NbSe2 the with the 2 × 2 × 1 CDW phase structure. Fitting the
Tc is higher for thin sheets as compared to the bulk material, dependence with the equation ωL = ω0*(T − Tc)δ yields a Tc of
whereas an opposite trend is observed for 1T-TaS2.11,14,15 1000 and 1050 K for the bilayer and monolayer TiSe2,
Toward predicting the thickness dependence of Tc for TiSe2, it respectively, as shown in Figure 5c. Comparison with the bulk
is relevant that the CDW phase transition is driven by the value on the order of 600 K, as predicted by theory, signifies
redistribution of the electronic states, and accordingly a rough that Tc increases upon decreasing the TiSe2 sample thickness.19
estimate can be made by investigating the change of the In order to determine the dependence of Tc on the thickness
phonon spectrum with the electronic temperature.19 To this of TiSe2 sheets experimentally, we evaluate the Eg peak position
1038 DOI: 10.1021/acsnano.6b07737
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Figure 6. (a) Peak position of the Eg mode near 136 cm−1 as a function of temperature for three TiSe2 sheets of different thickness (2L
denotes a bilayer). (b) Temperature dependence of electrical resistance (top plot) and the temperature derivative of resistance (bottom plot)
for three TiSe2 sheets of different thickness.

as a function of temperature for sheets with a thickness of 25 METHODS

nm, 10 nm, and bilayer TiSe2, respectively (see Figure 6a).35 Bulk TiSe2 crystals were exfoliated by the Scotch tape method onto Si
For the 25 nm thick sheet, Tc is 210 K, notably above the bulk substrates covered by 300 nm of thermal SiO2. Standard e-beam
value of 195 K. This increase can be attributed to enhanced lithography and subsequent metal evaporation were used to define Ti/
electron−phonon interaction, in close correspondence to the Au (2/40 nm) electrodes on top of the exfoliated sheets. Raman
behavior of 2H-NbSe2 and our theoretical simulation.11 spectroscopy was performed in air (unless otherwise noted) with a
However, Tc decreases upon further decreasing the sheet laser wavelength of 633 nm combined with an 1800 g/mm grating,
thickness, reaching 200 K for a thickness of 10 nm and 180 K with a resolution of 0.34 cm−1. In order to access the Stokes and anti-
for bilayer TiSe2. The same trend is apparent from the Stokes Raman modes at low frequency, a Bragg filter was used (±10
cm−1 cutoff around the laser line). The laser power was kept below 0.1
resistance vs temperature plots in Figure 6b. It is most likely mW to minimize sample heating. The samples were cooled inside a
due to surface oxidation, similar to the effect of defects within Linkam THMS600 cryostat using liquid N2. Electrical transport
bulk TiSe2, which have been documented to reduce the Tc of measurements were carried out in four-probe configuration down to
this compound.18 As the highest Tc thus far reported for 1.5 K in a liquid helium cryostat. The energy of the vibrational modes
monolayer TiSe2 is 230 K, observed on a monolayer grown on was calculated by the Quantum Espresso code.36 The exchange−
a graphene substrate by molecular epitaxy,10,12 additional correlation interaction was calculated by the local density approx-
influence may arise from the substrate or intrinsic defects imation.37 The 24 × 24 × 12 k-point grid with the projector
that are already present in the bulk18 but whose density is augmented wave (PAW) potential was implemented by a cutoff energy
further enhanced in the thin TiSe2 sheets. of 80 Ry for all calculations.38 The phonon dispersion was calculated
as previously reported.19 The transition temperature was determined
from the maximum peak position of the Eg mode around 136 cm−1. As
CONCLUSIONS the temperature difference between two measurements is 10 K, the
error of Tc is ±5 K.
In summary, we have studied the temperature-dependent
Raman modes of 1T-TiSe2 down to monolayer thickness. The
low-frequency shearing and breathing modes, which do not ASSOCIATED CONTENT
exist in the bulk form, are shown to be suitable for determining *
S Supporting Information
the number of layers in thin TiSe2 sheets. In addition, we The Supporting Information is available free of charge on the
demonstrate a straightforward method to monitor the CDW ACS Publications website at DOI: 10.1021/acsnano.6b07737.
transition in 1T-TiSe2 via the temperature-dependent position
of the Eg peak around 136 cm−1. Thus derived transition Supporting Information detailing supplementary text and
temperatures agree well with values gained from electrical Figures S1 to S7 (PDF)
transport measurements. Major factors that limit the accuracy
of the method are surface oxidation effects, the substrate AUTHOR INFORMATION
influence, and intrinsic defects. Our findings suggest that the
low-energy Raman modes in ultrathin 2D transition metal Corresponding Author
dichalcogenide layers could prove useful as more general *Tel: +49-(0711) 689-1448. Fax: +49-(0711) 689-1662. E-
probes such as for magnetic or electron−hole interactions. mail: m.burghard@fkf.mpg.de.
1039 DOI: 10.1021/acsnano.6b07737
ACS Nano 2017, 11, 1034−1040
ACS Nano Article

ORCID K.; Huber, R. Non-Thermal Separation of Electronic and Structural

Dinh Loc Duong: 0000-0002-4118-9589 Orders in a Persisting Charge Density Wave. Nat. Mater. 2014, 13, 1−
19.
Notes (21) Monney, C.; Battaglia, C.; Cercellier, H.; Aebi, P.; Beck, H.
The authors declare no competing financial interest. Exciton Condensation Driving the Periodic Lattice Distortion of 1T-
TiSe2. Phys. Rev. Lett. 2011, 106, 1−4.
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The DFPT calculations were performed in Karlsruhe Institute W.; Chai, Y. Extraordinarily Strong Interlayer Interaction in 2D
of Technology (KIT) within the ELCPHON project. Layered PtS2. Adv. Mater. 2016, 28, 2399−2407.
(23) Holy, J. A.; Woo, K. C.; Klein, M. V.; Brown, F. C. Raman and
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1040 DOI: 10.1021/acsnano.6b07737

ACS Nano 2017, 11, 1034−1040