Applied Surface Science 531 (2020) 147303

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Applied Surface Science

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Anomalous vibrational behavior of two dimensional tellurium: Layer T

thickness and temperature dependent Raman spectroscopic study
⁎
Ram Ashish Yadava, N. Padmab,c, , Shashwati Senb,c, K.R.S. Chandrakumarc,d, H. Donthulae,
⁎
Rekha Raoc,f,
a
Government Girls’ College Vidisha, 464001 Madhya Pradesh, India
b
Technical Physics Division, Bhabha Atomic Research Centre, Mumbai 400085, India
c
Homi Bhabha National Institute, Anushaktinagar, Mumbai 400094, India
d
Theoretical Chemistry Section, Bhabha Atomic Research Centre, Mumbai 400085, India
e
Material Science Division, Bhabha Atomic Research Centre, Mumbai 400085, India
f
Solid State Physics Division, Bhabha Atomic Research Centre, Mumbai 400085, India

A R T I C LE I N FO A B S T R A C T

Keywords: A few layer/multilayer two-dimensional (2D) Tellurium (Te) nanoflakes were mechanically exfoliated and their
Tellurene structural and vibrational properties were probed. Layer thickness reduction was confirmed using optical mi-
Exfoliation croscopy, atomic force microscopy and kelvin probe force microscopy. Raman spectroscopy measurements re-
Raman spectroscopy vealed anomalous shift in the frequencies of their intrachain vibrational modes, where, after an initial increasing
Inter-chain and intra-chain interaction
trend (blue shift) with thickness reduction from bulk, they changed to decreasing trend (red shift) on further
layer thinning. Such unusual vibrational behaviour of 2D Te, exhibiting reversal from blue shift to red shift, is
attributed mainly to the deformations occurring in the Te chains on layer thinning, followed by modifications in
the local structures and bondlengths of the corresponding Te atoms. The deformation under relaxed conditions
are also confirmed from first principle calculations. Red shift can also be correlated to lesser hole concentration
for thinner flakes, as revealed by work function changes measured on the nanoflakes surfaces. Interestingly, in
spite of such anomalous behavior, the difference in frequencies of both modes showed initial increase with
thickness and saturation beyond a certain thickness, as generally observed in other 2D materials. Temperature
dependent Raman spectroscopic measurements further confirmed anomalous behaviour for thinner flakes.

1. Introduction same for another class of 2D materials, namely Xenes or mono-ele-

The discovery of graphene in 2004 and its exotic material properties
that ensured its success in various application fields, has directed the
interest of the researchers towards other two dimensional (2D) mate-
rials [1]. Most of the 2D materials are generally layered materials
having covalent bonding in the plane of the layers with the individual
layers held together by Van der Waals bonding. These materials have
electronic properties different from their bulk counterparts because of
quantum confinements of carriers in one dimension, varying from
metallic to semiconducting to insulating [2–4]. Therefore, for applica-
tions of these 2D materials in various technologies, it is imperative to
explore their intrinsic properties. Though vast literature is available on
the material properties of mono/multilayers of transition metal di-
chalcogenides (TMDs), nitrides and carbides etc. studies exploring the
mental 2D materials, are scarce [5–9]. While graphene and group VI A
materials like silicene, germanene etc. are reported to be semi-metals
and borophene to be metallic, only phosphorene, arsenene and anti-
monene were suggested to be semiconducting, with their band gap
opening when thinned down to a monolayer [6,10]. Among these, only
phosphorene has been widely explored as a p-type semiconductor in
various applications due to its layer dependent direct band gap from
0.3 eV (bulk) to 1.5 eV (monolayer) [7,11–14]. But the major dis-
advantage of phosphorene is that it reacts strongly with moisture and
oxygen from the ambient, thereby forming phosphoric acid and other
related species, leading to degradation of the devices within hours of
fabrication [8,13]. Focus was shifted to antimonene whose isolation
into thin layers is still at an infant stage and the attempts to fabricate
gated devices using antimonene has not yet been successful [6,8,12].

⁎
Corresponding authors at: Technical Physics Division, Bhabha Atomic Reserach Centre, Mumbai 400094 India (N. Padma). Solid State Physics Division, Bhabha
Atomic Research Centre, Mumbai 400094, India (R. Rao).
E-mail addresses: padman@barc.gov.in (N. Padma), rekhar@barc.gov.in (R. Rao).

https://doi.org/10.1016/j.apsusc.2020.147303
Received 20 April 2020; Received in revised form 26 June 2020; Accepted 16 July 2020
Available online 21 July 2020
0169-4332/ © 2020 Elsevier B.V. All rights reserved.
R.A. Yadav, et al.
Other Xenes like silicene, germanene and borophene are reported to be
substrate dependent 2D materials that are unstable in free standing
form [15]. Therefore, the hunt for other mono-elemental 2D materials
is still being pursued and, in this context, 2D form of Tellurium (Te) has
caught the attention of researchers recently.
Tellurium belongs to the family of chalcogens and has trigonal
crystal lattice, where the bulk Te is an indirect band gap p type semi-
conductor with a band gap of 0.35 eV. Due to the small spin orbit
coupling, bulk Te has high hole mobility and small effective mass
[16,17]. It is basically a one-dimensional van der Waals solid con-
taining helical chains of Te atoms bonded by strong covalent bond
along the chain and each of the neighbouring chains bonded by weak
van der Waals interaction [15,18]. The large structural anisotropy of Te
favours the formation of one dimensional nanostructures which has
been explored in a number of studies where such nanostructures are
synthesised using different methods [19–24]. Bulk Te was not con-
sidered to be a layered material, until recently, when some groups have
predicted this one- dimensional van der Waals solid to be also stable in
2D form, called as tellurene and have convincingly included the same in
the family of 2D materials [25–27]. These groups theoretically pre-
dicted tellurene to be existing in three forms [25]. The α-Te phase,
which is energetically most stable, is suggested to be having 1 T MoS2
like structure with three Te atoms per unit cell and two Te atoms having
different coordination. The metastable β phase of tellurene was pre-
dicted to be composed of planar four members and chair like six
member rings arranged alternately. The metastable γ tellurene has 2H
MoS2 like structure. The α and β phases are suggested to be semi-
conducting and γ phase to be metallic. Since then, the promising
properties of Te such as thermoelectricity, piezoelectricity, photo-
conductivity, etc. have motivated the research community to begin
exploring the isolation/synthesis of 2D tellurene and ultrathin Te films
[15,18,19,25,28–32]. Huang et al and Chen et al have reported the
growth of epitaxial β-Te films on the surface of graphene and highly
oriented pyrolytic graphite (HOPG) respectively, by molecular beam
epitaxy (MBE) [28,31]. Wang et al have reported successful synthesis of
tellurene by substrate free solution process [15]. They demonstrated
fabrication of tellurene based field effect transistors (FETs) exhibiting
ON/OFF ratio of the order of 106 charge carrier mobility of the order of
700 cm2 V−1s−1 and improved stability. Apte et al have grown ultra-
thin Te films on MgO and SiO2 substrates using pulsed laser deposition
(PLD) and physical vapour deposition (PVD) respectively [32].
The feasibility of isolation of these layered materials into mono/
multi layers allow them to exhibit layer thickness dependent band gap/
electronic properties, which are well exploited in the applications like
optoelectronics. Tellurium has also been reported to exhibit layer
thickness dependent band gap ranging from that corresponding to mid
infra-red region for the bulk to near infra-red region for monolayer
(~1.13 eV) [15,18,28]. As the thickness of the layers plays an im-
portant role in many applications like FETs, solar cells etc., it is ne-
cessary to identify the thickness of the layers for each of the 2D ma-
terials. The layer thickness dependent vibrational properties have
enabled the use of Raman spectroscopy as a successful tool to determine
the thickness of the layers in these materials, with the difference in the
peak positions of in-plane and out-of-plane vibration modes being used
as the markers [33]. Though layer thickness dependent studies and
markers are almost identified for most of the materials, such studies for
tellurene are sparse [15,34]. Churchill et al have isolated Te sheets by
mechanical exfoliation and have shown hardening of the Raman modes
of an isolated flake as compared to that of the bulk Te [18]. Apte et al
have also reported a systematic hardening of the A1 and E(2) Raman
modes with reduction in thickness of PLD deposited Te films [32].
Wang et al [15] and Peng et al [34] have reported systematic thickness
dependent Raman shifts for solution processed tellurene, in this study,
we have attempted to isolate the layers from the bulk by mechanical
exfoliation, as reported by Churchill et al [18] and have investigated the
thickness dependent vibrational behavior of the same. While the
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Applied Surface Science 531 (2020) 147303
previous reports have shown continuous blue shift of both A1 and E(2)
peaks with reduction in thickness of tellurene flakes, our study shows
an anomalous behavior of the same, which is discussed here.
2. Experimental methods
2.1. Exfoliation and characterization of 2D Te flakes
The SiO2 (270 nm)/Si substrates were cleaned by ultra-sonication in
trichloroethylene, acetone and methanol for 10 min each. A single
crystal whisker of tellurium, synthesized as reported earlier [35], was
initially slid on cleaned SiO2 (270 nm)/Si substrate to exfoliate flakes
[18]. Fresh SiO2/Si substrates were subsequently slid on the first sub-
strate with exfoliated flakes. This process was repeated two to three
times in order to reduce the thickness of flakes each time. As different
colored flakes have different thicknesses, the exfoliated flakes were first
observed using Olympus optical microscope with different objectives to
identify the optical colour contrast of these flakes. Atomic force mi-
croscopy (AFM) images and kelvin probe force microscopy (KPFM)
measurements were recorded by Asylum Research Oxford Instrument
(MFP3D) in non-contact mode. The WSxM software was used for the
roughness analysis of AFM images and contact potential difference
(CPD) analysis of KPFM images of tellurium flakes. For recording TEM
images the nanolayers were prepared by initially exfoliating Te flakes
on sapphire substrates and subsequently sonicating these substrates in
isopropyl alcohol for 10 min. A few μL of the sonicated dispersion was
drop cast on carbon coated copper grid. Field emission scanning elec-
tron microscopy (FESEM) was further used to verify the morphology
and the size of the nanoflakes. TEM investigation was carried out under
Tecnai T20 microscope having LaB6 filament and images were recorded
digitally using 2Kx2K camera. For the analysis of the images DM soft-
ware freely provided by Gatan was used. The Raman spectra of colored
tellurium flakes were recorded by Jobin Yvon HR-800 evolution Raman
spectrometer calibrated with first order silicon peak (520.9 cm−1).
Raman spectroscopic measurements were carried out at room tem-
perature and pressure using 632.8 nm laser and a grating of 1800 l/mm
to get a dispersion of 0.35 cm−1/pixel. The laser power was kept at 0.3
mW in order to avoid any sample heating. To identify the orientation of
the c-axis in a tellurium flake, angle resolved polarized Raman spec-
troscopic measurements were carried out by rotating the incident po-
larization using a half-wave plate. Low temperature Raman spectro-
scopic measurements were carried out using Linkam THMS 600
temperature stage with a temperature stability ± 0.5 K on the sample.
2.2. Theoretical methods and models
The total energy calculations were performed at the first-principles
density functional theory (DFT) level by employing the Perdew-Burke-
Erzerhoff (PBE) exchange–correlation functional as implemented in the
ORCA suits of electronic structure theory based program package. Full
geometry optimizations of the Te layers have been performed without
any symmetry constraints with the Los Alamos National Laboratory
based valence double-zeta (LANL2DZ) basis set and in this calculation,
for each tellurium atom, the Hay-Wadt based effective core potential
with the associated basis set is used for the core electrons. All the atoms
were allowed to relax during the geometry optimization until a self-
consistent-field convergence criterion of 10-8 hartree on total energy is
achieved. The grid based DFT has been used as present in ORCA, that
employs a typical grid quadrature to compute the integrals. During the
SCF procedure, the grid consists of 96 radial shells with 36 and 72
angular points. This level of theory has been employed for the de-
termination of energy, geometries and properties of variety of systems
and the calculated properties have been found to be reliable within
2–5% error. Since these layered structured are known to be stabilized
by the weak van der Waals forces, the atom-pairwise dispersion cor-
rections to the DFT energy with Becke-Johnson damping has been
R.A. Yadav, et al.
Fig. 1. (a) Helical chains of Te forming a layered structure, (b) Projection of Te chains forming a hexagonal structure, (c-e) optical images of Te flakes with different
thicknesses and optical contrast, (f-h) Atomic force microscopy images of Te flakes with different thicknesses and (i-k) corresponding height profiles along the lines
across the flakes.
employed.
The bulk Te geometries have been initially generated using the
single crystal X-ray data and the corresponding layered structures were
formed by aligning c-lattice of the bulk structures. Herein, the first
monolayer is generated by combining three single chains orienting to-
wards the a and b lattice axis. Subsequently, the second and other layers
up to 5 were initially generated in the similar way. For the multi-
layered cases, each layer is arranged with respect to the bulk unit cell
dimension along the a or b axis.
3. Results and discussion
As mentioned before, Te is a one-dimensional van der Waals solid
containing helical chain of Te atoms bonded by strong covalent bond
along the chain, with each of the neighbouring chains bonded by weak
van der Waals interaction (Fig. 1a). The projection of each of the chain
forms a hexagonal lattice in the ab plane, as shown in Fig. 1b. The
monolayer form of Te has been predicted to be stable in three phases (α,
β and γ) with α Te to be most stable having 1 T-MoS2 like structure and
semiconducting in nature [25]. The β and γ Te are suggested to be
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Applied Surface Science 531 (2020) 147303
metastable tetragonal and 2H-MoS2 type structures with semi-
conducting and metallic behavior respectively. While most of the stu-
dies have focussed on synthesis and applications of 1D nanostructures
of Te [36,37], only a few studies have reported preparation of 2D Te
films and flakes.
Wang et al [19] have demonstrated first the formation of 2D hex-
agonal Te nanoplates when deposited on mica substrate by van der
Waals epitaxial technique, with c axis perpendicular to the substrate.
Though Zhu et al [25] have suggested α Te to be more stable, they have
confirmed the epitaxially grown Te nanolayers on HOPG by MBE
method in their study to be in β phase, with c-axis lying parallel to the
substrate. Many other groups that have also prepared/synthesized Te
films/flakes through different methods like MBE, physical vapour de-
position, mechanical exfoliation, substrate free solution process, liquid
phase exfoliation (LPE) etc. have also reported c-axis to be parallel to
the substrate [15,18,19,25,28–31]. In the present study, the mechani-
cally exfoliated Te flakes, similar to that adapted by Churchill et al [18],
are also expected to have c-axis parallel to the SiO2 substrate, as
mentioned in the above studies. Fig. 1c-e shows the optical images of
some of those exfoliated Te flakes with different colours. It has been
R.A. Yadav, et al.
Fig. 2. FESEM images of (a) Nanoflake 1 and (b) nanoflake 2, EDX intensity mapping of nanoflake 1 at (c) and (d) Te and O elements respectively, EDX intensity
mapping of nanoflake 2 at (e) Te element.
well established that the flakes with different thickness exhibit different
colours and varying optical contrast with the SiO2 substrate [33,38].
Therefore, the dark coloured flakes can be expected to represent thicker
flakes while those with colours close to that of the substrate could be
due to thinner flakes. Hence, the flake in Fig. 1e is suggested to be
thinner than those shown in Fig. 1c and d.
The layer thickness of Te flakes was estimated using AFM images,
where the step height produced by the different layers of these mate-
rials on the substrate was measured. Fig. 1f-h show the images of Te
flake with different thicknesses and Fig. 1i-k show their corresponding
height profiles along the lines drawn across the flakes in each of these
figures. The height profiles show the thickness of the flake in Fig. 1f to
be around 80 nm while those shown in Fig. 1g and h are found to be
about 23 and 7 nm respectively. As the thickness of the flakes decreases,
the lateral sizes of most of the flakes are also observed to generally
decrease, ranging from about 6–8 µm for thicker flakes (also seen from
optical microscopy images) to less than 1 µm for thinner flakes.
The morphology of the exfoliated Te flakes of different lateral di-
mensions was verified using FESEM imaging, as shown in Fig. 2a (na-
noflake 1) and b (nanoflake 2). The EDX elemental mapping displayed
in Fig. 2 c and d represents the distribution profile of Te and O for
nanoflake 1 (Fig. 2a) and that in Fig. 2e shows the distribution profile of
Te for nanoflake 2 (Fig. 2b). It can be seen that while nanoflake 1 has
length around 2 µm, the other has dimensions of around 500 nm. As
seen in optical and AFM images, the images of the flakes further con-
firm the growth direction or the c-axis to be parallel to the substrate and
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Applied Surface Science 531 (2020) 147303
are found to be of good crystallinity. It can be seen that the elemental
intensity mapping shows uniform distribution of Te atoms in both
thinner and thicker flakes, and the absence of TeO, TeO2 etc.
Kelvin Probe Force Microscopy (KPFM) can be used for quantitative
mapping of contact potential difference (CPD) and work function dis-
tribution of 2D materials surfaces by mapping the local surface poten-
tials. It has been shown in earlier reports that the thickness variation in
2D materials reflects as change in the work function, as measured using
KPFM [39]. The present study uses KPFM as another tool to identify the
change in thickness of the Te flakes by estimating the change in work
function of the same. For this purpose, the topography and surface
potentials of tellurium flakes were simultaneously recorded. Fig. 3a
shows the KPFM image of Te flakes that were seen with different col-
ours, using optical microscopy as shown in Fig. 1. In this image, the
dark points correspond to the Te flakes having larger negative contact
potential difference. The work function of Te flakes were determined
using the formula
∅sample = ∅tip − exCPD (1)
where∅sample and∅tip represent the work functions of sample and tip re-
spectively, e is the electronic charge. The work function of the flakes is
determined with respect to work function of Titanium Iridium tip
(4.9 eV). Fig. 3b shows the variations in work function of Te flakes with
layer thickness that is observed to be increasing with thickness of the
flakes by about 0.1 eV. Increase in work function by about 0.15 eV was
also made in an earlier study on MoS2 which attributes it to the
R.A. Yadav, et al.
Fig. 3. (a) KPFM image of the tellurium flake on SiO2/Si substrate and (inset) CPD variation of this flake along the line drawn across the flake, (b) Variation of work
function of tellurium flakes with thickness. Continuous line is a guide to eye. (c) TEM image of one of the flakes and (d) corresponding HRTEM image, inset- top left-
SAED pattern, top right- FFT of the selected area shown in white box, bottom right- inverse FFT of selected area.
increasing hole doping with layer thickness [39]. In the present study
also, increase in hole doping could be causing the increase in work
function. Since Te is reported to be a p type semiconductor, such in-
crease in work function clearly indicates the increase in layer thickness.
Transmission electron microscopy (TEM) has been successfully used
for lattice parameter and crystal system determination of 2D materials.
Fig. 3c shows a TEM image of one of the typical Te flakes. The high
resolution TEM (HRTEM) image of the flake is shown in Fig. 3d and
corresponding SAED pattern of the flake, with planes indexed, is shown
as the top left inset of Fig. 3d. The HRTEM image shows presence of
fringe patterns at certain places; where one of those areas is selected as
shown in white box in Fig. 3d. The corresponding Fast Fourier trans-
form (FFT) and the inverse FFT of the selected area are shown as top
right and bottom right insets respectively. Both SAED pattern and FFT
show bright diffraction spots, indicating that the exfoliated Te flake is
single crystalline. The spacing between the fringes as seen from inverse
FFT was estimated to be about 0.39 nm which is close to the interplanar
spacing of (1 0 0) planes of Te. The inverse FFT image also shows mild
deformations in Te chains and hence local structure variations.
Layer thickness dependent vibrational behavior of these mechani-
cally isolated Te flakes were investigated using Raman spectroscopy.
Tellurium crystallizes in trigonal structure (space group D34 ) containing
three atoms per unit cell arranged helically about the c-axis [40]. Group
theory predicts 9 normal vibrational modes of which three are acous-
tical modes and six are zone centred optic modes having irreducible
5
Applied Surface Science 531 (2020) 147303
representation Γ = A1 + A2 + 2E [41]. A1 is a Raman active mode, A2
is an infrared active mode and doubly degenerate E mode is both
Raman and infrared active mode. Generally, in 2D layered materials
like TMDs, Ag mode is the out of plane vibrational and Eg modes are the
in plane vibrational modes. In the case of tellurium, A1 mode is an intra-
chain vibrational mode (Fig. 4a) with eigen vectors along a axis in the
ab basal plane [15,36]. E modes are the two doubly degenerate modes
with E(1) consisting of rotation around a and b -axis and E(2) is an intra-
chain asymmetric stretching vibrational mode within a single layer of
tellurium (tellurene) with eigenvectors mainly along c- axis (Fig. 4b).
Fig. 4c shows the unpolarized Raman spectra of bulk Te crystal at
ambient temperature and pressure, which reveals one Raman active
non-degenerate A1 mode at 121.5 cm−1 and two degenerate E modes at
92 cm−1 (E(1)) and 141.3 cm−1 (E(2)) as reported earlier [15,36]. The
A1 mode was found to have higher intensity in comparison to E(2)
mode. Fig. 5a shows the Raman spectra of tellurium flakes having
different thicknesses. With reduction in the thickness of Te flakes,
Raman spectra were found to clearly exhibit changes in peak fre-
quencies, intensity and the full width at half maximum (FWHM) as
compared to that of the bulk Te. The Raman spectra clearly show the
thickness dependent shift in the frequencies for both A1 and E(2)
modes.
In the Raman spectra of Te flakes with lower thicknesses only A1
mode and one of the E modes, around 141 cm−1, is visible with de-
creasing intensities. As described earlier, optical microscopy, FESEM
R.A. Yadav, et al. Applied Surface Science 531 (2020) 147303

Fig. 4. (a, b) Vibration of Te atoms in A1 and E(2) modes in the basal plane of tellurium respectively, (c) Raman spectra of bulk Te crystal.

and AFM images show the flakes to be elongated in the direction par-
allel to the substrate. The orientation of c-axis was further verified using
angle resolved polarized Raman spectroscopy measurement of a typical
flake (Fig. 5b). The polarization of the excitation wavelength was ro-
tated and the total integrated intensity of the Raman modes over the
entire range shown in Fig. 5a is plotted in Fig. 5b. The Raman mode
intensity showed two maxima at 0° and 180° within one full rotation.
This implies that the flakes in the present study have c-axis parallel to
the substrate as also reported by Churchill et al [18]. The measured
polarization dependence of Raman intensity is fitted with expected
polarization dependence of Raman intensity from Raman tensor cal-
culation as provided in the Supporting Information.
Fig. 6a shows the shifts in the frequencies of A1 and E(2) modes as a
function of thickness of tellurium flakes (with a maximum error of ±
0.3 cm−1 for A1 and ± 0.4 cm−1 for E(2) modes considering all the
thicknesses) revealing an anomalous behavior. It can be seen from this
figure that for initial reduction in layer thickness from the bulk, both A1
and E(2) modes of nano-layered flakes exhibit hardening. E(2) mode at
141 cm−1 showed a maximum hardening of about 3.1 cm−1 for a
thickness of around 35 nm. Beyond this thickness, E(2) mode is found to
revert to decreasing trend with the shift of about 5 cm−1 for 7 nm thick
flakes, from the maximum value. In the case of A1 mode also, such
anomalous behavior is observed with layer thinning, where the max-
imum blue shift is observed to occur at around 23 nm thickness beyond
which the peaks show a red shift. In the case of TMDs like MoS2, Ag
mode is reported to decrease in frequency and Eg mode to harden as
they are thinned from bulk to monolayer [33,42,43]. While decrease of
Ag mode is attributed to the reduced van der Waals force and hence
easier vibration of the Mo atoms out of plane, stiffening of Eg mode is
suggested to be due to the effective long range coulombic interactions
and to changes in the intralayer structure causing increase in the
strength of the covalent bonding between the atoms [38,42]. In the case
of mono-elemental 2D materials like antimonene, both Ag and Eg modes
were reported to show a large shift to high frequency for reduction in
thickness from bulk to monolayer, as also observed for initial reduction
in the thickness in the present study [6]. In all these 2D materials, the
modes either shift to higher or lower frequencies throughout, on re-
ducing from bulk to monolayer, unlike the anomalous reverting of the
direction of shift observed in the present study. To the best of our
knowledge, this anomalous behavior of A1 and E(2) modes are not

Fig. 5. (a) Raman spectra of different thicknesses of Te flakes, dotted lines are guide to eye, (b) Polar plot of total integrated Raman intensity for flake of thickness
80 nm of the range shown in (a), lines with symbol represent experimental data and the solid line represents the fitting.

6
R.A. Yadav, et al.
Fig. 6. Variation with thickness of Te flakes- (a) peak positions of A1 and E(2) modes, with error of a maximum of ± 0.3 cm−1 for A1 and ± 0.4 cm−1 for E(2)
modes, (b) difference in peak positions of E(2) and A1 modes (E(2)-A1), (c and d) FWHM of A1 and E(2) modes respectively. Continuous lines are guide to eye.
reported in any 2D materials.
As mentioned before, there are only three studies showing the effect
of layer thinning of Te on Raman shift, with two of them discussing
systematically about the layer thickness dependent Raman shift
[15,34]. Wang et al and Peng et al have carried out systematic studies
on the effect of thickness on Raman peaks using Te flakes synthesized
by solution route [15,34]. Wang et al [15] have reported an increase of
A1 and E(2) mode frequencies by about 14 and 6 cm−1 respectively and
Peng et al [34] have also shown similar results. Churchill et al have
isolated thin layers of Te by mechanical exfoliation as also exfoliated in
the present study and have also shown a hardening of both the modes
for a 30 nm flake as compared to that of the bulk [18]. Apte et al have
also reported blue shift in the Raman modes of PLD deposited ultrathin
Te films, with reduction in thickness [32]. Though their study suggests
the c-axis to be orthogonal to the substrate surface, it should be noted
that the flakes synthesized in most of the studies are reported to have c-
axis parallel to the substrate, as in the present study. It can be pointed
out that all these studies have shown stiffening of both E(2) and A1
modes with thinning down of bulk Te. Churchill et al attributed the
stiffening of E(2) modes of 30 nm thick Te flakes to mainly substrate
flake interaction [18]. Wang et al and Apte et al have attributed hard-
ening of E(2) mode to enhancement of long-range interlayer coulombic
interactions on thinning down, similar to the cases for other 2D mate-
rials like TMDs, phosphorene etc. [15,32]. Peng et al have attributed
high frequency shift of E(2) modes to laminating induced structural
changes [34]. The blue shift/stiffening of A1 mode in thin layers of Te,
which is unlike that observed for other 2D materials like MoS2, have
also been attributed to increased intra chain forces, in these studies. It
should be mentioned here that while the method of exfoliation in the
present study is similar to that of Churchill et al [18], such an anom-
alous behavior is not reported by them. In the reports of Churchill et al,
Raman spectrum of nanoflakes of around 30 nm are compared with that
7
Applied Surface Science 531 (2020) 147303
of bulk Te, which show hardening of A1 and E(2) modes to higher
frequency, as also seen in the present study around that thickness range.
It has to be pointed out that Churchill et al have not shown Raman
spectrum of flakes of lower thicknesses, whereas anomaly in the vi-
brational behaviour, showing softening of both the modes, is observed
for thicknesses below ~ 23 nm in the present study.
In the present study also, the initial high frequency shift of both the
modes when reduced from bulk, could be due to reduced dielectric
screening of long-range coulomb interaction and structural changes in
Te-Te bonds. As the A1 and E(2) modes in Te are due to intrachain
vibrations of same Te atoms in different directions respectively, (Fig. 4a
and b), hardening of A1 could also be attributed to increased intra chain
interaction, as also reported in the above mentioned studies. The shift
to lower frequencies of both the modes, after a maximum hardening as
shown in Fig. 6a, cannot be connected to increased intra chain inter-
actions. Though the substrate–layer interaction may be expected to
become prominent below a certain layer thickness, it is also mostly
suggested to stiffen the A1 and E(2) modes, unlike that observed in the
present study [18]. It can be suggested at this point that the attenuated
van der Waals interaction between the Te chains belonging to different
layers, brought about by layer thinning, can be expected to create de-
formation in the chains of Te. This deformation or the local structure
variations could be dominating over the increased intra chain interac-
tion suggested for initial thickness reduction from bulk (blue shift re-
gions), altering the bond length randomly. Irregularity in the fringes
observed in the HRTEM image (Fig. 3d) could be taken as corroborative
evidence of the deformation of the chains. It may be noted that KPFM
studies (Fig. 3b) indicated a drastic variation of charge carrier con-
centration below about 30 nm thickness. It is well known that inter-
action of charge carriers with phonons results in modification of
phonon frequency as well as FWHM [44]. The change in carrier con-
centration in thinner flakes, as noted from the lesser work function seen
R.A. Yadav, et al.
in KPFM analysis (Fig. 3b), could be resulting in variation in phonon
spectra and could be further contributing to red shift of Raman modes.
Hence, the resultant reduction in Raman mode frequencies could be a
combined effect of changes in the structure of the chains as well as due
to changes in charge carrier concentration.
As the difference in peak positions of A1 and E(2) modes are gen-
erally used as a facile tool to estimate the layer thickness of 2D mate-
rials, a plot of the difference in A1 and E(2) peak positions of Te flakes,
against the layer thickness is shown in Fig. 6b. While this frequency
difference remains constant upto about 30 nm as reduced from the bulk,
it shows a clear reducing trend below this thickness. A similar variation
is also observed for other 2D materials like MoS2, antimonene etc. while
opposing trend is also reported for phosphorene [6,33,45]. Therefore,
this study shows that even though the peak shifts of E(2) and A1 show
an anomalous behavior, the frequency difference follows a common
trend and hence can be used to determine the thickness of Te layers.
The FWHM of Raman modes were also systematically studied with
layer thickness, as shown in Fig. 6c and d for A1 and E(2) modes re-
spectively. The FWHM of Raman mode is reported to be affected by
many factors including defects and disorder. The electron phonon
coupling has been suggested to play a role in the broadening of Raman
modes in 2D materials [46]. The thickness of the flakes also is reported
to affect the FWHM of two dimensional materials [34]. Lee et al have
reported increase in the line-width of both Ag and Eg modes with de-
creasing layer thickness of MoS2, as also observed in the present study.
Reduction in layer thickness could result in varying structural changes
for the outer and inner layers of Te flakes, leading to varying force
constants. This could be giving rise to increase in FWHM. Deformation
in chains or random variations in local structure can also be causing
larger FWHM.
To gain further insight into these changes taking place in the chains,
which are suggested to be leading to anomalous layer thickness de-
pendent shift in Raman mode positions, first principles calculations
were carried out for systems with monolayer to five layers thickness,
with each layer containing three adjacent chains. As is well known,
bulk Te has helical chain like structure with nearest neighbouring
atoms covalently bonded to each other. The three Te atoms in the he-
lical cycle, marked as Te1, Te2 and Te3 in Fig. 4a are separated with the
bond lengths l1, l2 and l3, which are found to be equal (2.91 Ả) [25]. A
typical three layers structure used in our calculations in unrelaxed
condition is shown in Fig. 7a. The calculations show that on thinning
down to 5 layers or below and the system allowed to relax, these bond
lengths become different with l1 and l2 increasing above 3.0 Ả and l3
decreasing below that in the bulk. These changes in bond lengths or the
random variations in the local structures, also reported by Zhu et al
[25], could be attributed to the deformation occurring in the chains
(Fig. 7b). The remaining one, two, four and five layered structures, and
the cross-sectional view of all the layered structures under relaxed
condition, are shown in Fig. S1 and S2 respectively, in the Supporting
Information.
While Zhu et al [25] have reported l1 and l2 to be equal, our results
show slight variations between the same that are also found to be
slightly different for different chains. Since the Raman modes A1 and E
(2) mainly depend on vibrations involving l1 and l2, we have ignored l3
in further discussions. The average of l1 and l2 (l) for all the chains in
each layered structure is shown as a function of layer thickness (number
of layers) in Fig. 7c. It can be seen that l exhibits a tendency to increase
slightly from 5 layers to 3 layered structure, and to decrease sharply
below this thickness, exhibiting a maximum at certain layer thickness.
The observed trend of increasing bond length would result in lowering
of frequency of A1 and E(2) modes in the Raman spectra. Such a trend
matches with the decrease in frequency of these Raman modes with
thinning down, observed for lower thickness flakes (after reversal of
direction from blue shift to red shift) as shown in Fig. 6a. It can also be
noted from Fig. 7c that the bond length l shows a value larger than that
of the bulk (which is about 2.91 Å) for upto bilayer structures, resulting
8
Applied Surface Science 531 (2020) 147303
in Raman frequency of A1 and E(2) modes to be lower than that of the
bulk. Though the lowest thickness of the exfoliated flake for which
Raman modes could be measured in the present study is around 5 nm
(about10 layered systems), the obtained E(2) mode peak frequency in
Fig. 6a, falling below that of the bulk, is found to correlate well with the
above mentioned theoretically observed increase in bond length.
For bulk Te, similar to intra-chain covalent bonds, interchain dis-
tances are also observed to be with two different sets of values such as
3.3 Å and 4.3 Å. The first set with lower value (3.3 Å), which is the next
nearest distance d1, corresponds to that between two Te atoms be-
longing to two neighbouring chains that come closer to each other in
their spiralling process [47]. The other set with higher value (4.3 Å) is
the distance d2 between two similar Te atoms, for example, between Te1
atoms (Fig. 4a) belonging to the neighbouring chains. The variations in
the average values of these distances d1 and d2 as a function of number
of layers, are shown in Fig. 7d and e respectively. As mentioned before,
since covalent interactions and the bond lengths between the same Te
atoms are responsible for both A1 and E(2) Raman modes, changes
observed in A1 and E(2) modes should also be in similar direction, with
additional contributions from d1 and d2. Since d1 and d2 are also found
to increase with decrease in thickness upto 2 or 3 layers respectively,
they would further support reduction of A1 as well as E(2) peak fre-
quencies with reduction in layer thickness, as observed in this study in
the lower thickness regions. The initial increase of A1 and E(2) modes
frequencies and reverting below a certain thickness, results in the ex-
istence of a maximum in both cases. To our knowledge, this behavior
has not been reported in other 2D materials and can be attributed to the
chain like structure of Te and deformation in the same.
To additionally verify the effect of layer thinning on temperature
dependent behaviour of Raman modes, measurements were carried out
on bulk and two exfoliated Te nanoflakes with thicknesses around 80
and 23 nm. The A1 mode intensity mapping of these two nanoflakes,
along with their respective optical images in the inset, are shown in
Fig. 8a and b respectively. Fig. 8c shows the Raman spectra of one of
the exfoliated thin tellurium flakes (thickness ~ 23 nm) at four different
temperatures during cooling cycle. Similarly, Raman spectra of the
thicker nanoflake (~80 nm) and the bulk, at different temperatures are
shown in Fig. 8d and e respectively. The corresponding plots for the
temperature dependence of the Raman mode frequencies for all the
three are given in Supporting Information (Fig. S3). From Fig. 8c, it can
be seen that the Raman intensity of both A1 and E(2) modes of the
nanoflake with thickness ~ 23 nm, shows enormous increase with de-
creasing temperatures. It may be noted that this enormous increase in
integrated intensity with decreasing temperature is not observed for
bulk or thicker flakes. In all the three cases, Raman modes hardened
with lowering of temperature regardless of thickness as seen in Fig. S3.
But we have observed thickness dependent variation in the integrated
total intensity of the two prominent modes, i.e., A1 and E(2) modes. In
the case of thin flake, there in an increase in integrated total intensity of
the Raman modes about 6 times with cooling whereas it increases only
marginally (by a factor of about 1.3) in the case of bulk/thick flakes.
Apte et al reported increase in Raman intensity at low temperatures
for PVD grown Te flakes during both heating (100 K-350 K) and cooling
cycles (RT-100 K). They found the A1 mode intensity to be affected
more than the E mode and attributed the increase in intensity to lattice
strain relaxation at lower temperatures. They also suggested that this
relaxation is more for in-plane mode than the out-of-plane mode. In the
present study, larger increase in intensity with decreasing temperature
is observed for thinner nanoflake, than that for the thicker nanoflake
and the bulk. This anomalous behaviour could be due to the stronger
effect of local structure variation/deformation in the thin flake than in
the thicker nanoflake and the bulk, as also observed for thickness de-
pendent Raman measurements (Fig. 5a). Unlike the observation made
by Apte et al, we observe both A1 and E(2) modes exhibit similar in-
crease in intensity with lowering of temperature. This reaffirms our
earlier observation from polarized Raman and thickness dependent
R.A. Yadav, et al.
Fig. 7. Three layered structure of Te under–(a) unrelaxed and (b) relaxed conditions, variations of- (c) average bond length l, (d) average interchain distance d1 and
(e) average interchain distance d2, as a function of layer thickness. Black solid lines in c, d and e are guide to eye.
Raman measurements, along with imaging techniques, that c-axis is
parallel to the substrate in exfoliated flakes and hence, both the modes
are affected by deformation in similar fashion.
Therefore, it can be mentioned that the low temperature Raman
spectroscopic measurements further show the significant influence of
layer thinning on temperature dependent behaviour of Raman modes
and hence add to the suggestion of increased local structure variations/
deformation in thinner flakes, resulting in the anomalous thickness
dependent vibrational behaviour of Te flakes. These results are similar
to that reported by Hussain et al wherein they observe stronger effect of
lattice strain on the Raman spectra of thinner flakes [48].
4. Conclusions
In summary, a few layered flakes of tellurium were successfully
isolated by mechanical exfoliation of single crystals of Te on SiO2/Si
substrates. The thinning down of Te flakes from bulk was identified
using optical microscopy and further confirmed using AFM and KPFM
techniques, from the changes in the height profile in the former and the
work function in the latter. The peak frequencies and FWHM of Raman
active A1 and E(2) modes were found to be varying with thickness of Te
flakes. Though frequencies of both A1 and E(2) modes were found to be
increasing initially on thinning from bulk, they exhibited an anomalous
behavior by reverting to decreasing trend beyond a certain layer
thickness, which has not been reported in any 2D materials. While the
initial increase was attributed to reduced dielectric screening of long-
9
Applied Surface Science 531 (2020) 147303
range coulomb interaction and restructuring of covalently interacting
Te atoms, the subsequent decrease was attributed to deformation that
could be occurring in Te chains with further reduction in the layer
thickness, leading to local structure variations. The trend in shifting of
both A1 and E(2) modes in same directions, was suggested to be due to
the involvement of the same Te atoms vibrating along and perpendi-
cular to the chains respectively. The decreasing trend of these modes
frequencies at low thickness region was also confirmed by the corre-
sponding changes in bond lengths and inter-chain distances observed by
first principle calculations. Additionally, it is also suggested that the
change in carrier concentration for thinner flakes could further be
contributing for the red shift in the Raman modes. Our study also shows
that though the vibrational modes individually show anomalous be-
havior, the difference in their peak positions shows an increase with
increase in layer thickness at low thickness region, tending to exhibit a
saturation beyond a certain thickness. Such a behavior is also reported
for 2D materials like MoS2, and is suggested to be useful for de-
termining 2D Te layer thickness. Temperature dependent Raman mea-
surements also showed variations with respect to layer thickness, ex-
hibiting anomalous behaviour for thinner flakes.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
R.A. Yadav, et al. Applied Surface Science 531 (2020) 147303

Fig. 8. A1 mode intensity mapping of the nanoflakes with thickness –(a) ~ 80 nm and (b) ~ 23 nm, along with their respective optical images in the inset, Raman
spectra at different temperatures - of (c) exfoliated thinner nanoflake (~23 nm), (d) thicker nanoflake (~80 nm) and (e) bulk. Raman spectra have been vertically
shifted for clarity.

Acknowledgements Funding sources

The authors would like to thank Central Facility, CAFM, IIT
Bombay, Mumbai, India, for providing AFM and KPFM data for the
exfoliated Te samples. The authors would also like to thank Dr. R.
Tewari, Materials Science Division, Bhabha Atomic Research Centre,
Mumbai, for helping in the analysis of TEM data. The authors ac-
knowledge Dr. D. Sen and Dr. J. Bahadur, Solid State Physics Division,
Bhabha Atomic Research Centre, Mumbai, for FESEM and EDX mapping
data.
This research did not receive any specific grant from funding
agencies in the public, commercial, or not-for-profit sectors.
Data availability
The raw/processed data required to reproduce these findings cannot
be shared at this time as the data also forms part of an ongoing study.

10
R.A. Yadav, et al. Applied Surface Science 531 (2020) 147303

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