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Exfoliation of Layered Topological Insulators

Bi2Se3 and Bi2Te3 via Electrochemistry
Adriano Ambrosi,† Zdeněk Sofer,‡ Jan Luxa,‡ and Martin Pumera*,†
†
Division of Chemistry & Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University,
Singapore 637371
‡
Department of Inorganic Chemistry, University of Chemistry and Technology Prague, Technická 5, 166 28 Prague 6, Czech
Republic
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*
S Supporting Information

ABSTRACT: Among layered materials, topological insu-

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lators such as Bi2Se3 and Bi2Te3 are lately attracting much

attention due to particular electronic properties and,
especially with Bi2Te3, excellent thermoelectric properties.
Methods of preparation of few-layered nanosheets of Bi2Se3
and Bi2Te3 range from the bottom-up chemical vapor
deposition or hydrothermal synthesis from oxide precursors
to the top-down mechanical exfoliation and liquid-based
exfoliation supported by sonication from the natural bulk
crystals. Here, we propose a simple and rapid electro-
chemical approach to exfoliate natural Bi2Se3 and Bi2Te3
crystals in aqueous media to single/few-layer sheets. The exfoliated materials have been characterized by scanning
transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray powder diffraction, high-resolution
transmission electron microscopy, and Raman spectroscopy in addition to evaluation of their electrochemical properties.
This electrochemical procedure represents a simple, reagent-free, and scalable method for the fabrication of single/few-
layer sheets of these materials.
KEYWORDS: topological insulator, exfoliation, layered compound, electrochemistry, hydrogen evolution reaction

L ayered materials have recently gained much interest due

to the interesting properties emerging when single- or
few-layer thick sheets are produced and which are
different from the bulk multilayered material.1,2 Graphene
represents the most recognized example of this phenomenon,
which triggered an explosion of scientific research toward
several other 2D materials such as transition metal
dichalcogenides (TMDs),3,4 black phosphorus,5−8 antimo-
nene,9,10 boron nitride,11,12 etc. Another class of materials
possessing interesting thermal, optical, and electrical properties
when down-sized to single- or few-layer sheets is represented
by the topological insulators (TIs).13,14 These materials have
anisotropic electrical properties which include an insulator
along the c-axis in the bulk state but with the metallic phase
along the layer surface.15 Antimony and bismuth chalcogenides
(with sulfur and tellurium chalcogen) with general structure
A2B3 (where A = Bi, Sb; B = Se, Te) represent the most studied
materials among the TIs because they are among the best
thermoelectric materials.16 Different preparation methods have
been proposed to fabricate single sheets of this class of
materials in order to study their properties. Similarly to
graphene, mechanical exfoliation has been proposed to split
apart the crystal layers of Bi2Te3 and to study the thermal and
electrical properties of single- and few-layer sheets.17 Liquid
exfoliation has also been achieved in polyvinyl pyrrolidone
(PVP) with the assistance of ultrasonication18 and also via a
preliminary Li intercalation process at 200 °C in ethylene glycol
(EG) followed by spontaneous exfoliation in water.19 Bottom-
up approaches consisted of the growth of few-layer nanoplates
using a vapor−solid20 or chemical vapor deposition (CVD)21
method onto oxidized silicon wafers or by solvothermal
synthesis using oxide precursors.22
Electrochemical exfoliation methods are being considered
lately with enormous interest due to the easy procedure, high
controllability, mild conditions, and good efficiencies. They
have already been applied with good results to exfoliate
graphene23−25 and MoS2.26,27
We propose here a convenient top-down electrochemical
exfoliation approach in aqueous solutions to obtain few-layered
sheets of Bi2Se3 and Bi2Te3 crystals grown from melt. The
materials have been characterized by scanning transmission
electron microscopy (STEM), X-ray photoelectron spectrosco-
py (XPS), X-ray diffraction, high-resolution transmission
Received: October 20, 2016
Accepted: December 7, 2016
Published: December 12, 2016

© 2016 American Chemical Society 11442 DOI: 10.1021/acsnano.6b07096

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electron microscopy (HR-TEM), and Raman spectroscopy
methods in addition to electrochemical studies involving the
inherent redox behavior and catalysis toward hydrogen
evolution reaction (HER) and oxygen evolution reaction
(OER).
RESULTS AND DISCUSSION
Bi2Se3 and Bi2Te3 are layered materials with rhombohedral
crystal structure of the space group D3d (R3m). Each layer is
formed by five monatomic sheets called quintuple layer (QL) in
which atoms are covalently bonded in the sequence X−Bi−X−
Bi−X where X = Se or Te (Figure 1). Weak van der Waals
Figure 1. Layered crystal structure of Bi2Se3 and Bi2Te3 showing
quintuple layers with the Te(Se)−Bi−Te(Se)−Bi−Te(Se) sequence
along the c-axis. Weak van der Waals interactions hold together the
quintuple layers.
(vdW) interactions held together the QLs, and therefore,
single- or few-quintuple layers can be obtained upon exfoliation
of the bulk crystal. The energy of vdW forces is not
experimentally known for most of the compounds; however,
theoretical calculations were recently performed for several
Figure 2. Raman spectra of bulk (A) Bi2Se3 and (B) Bi2Te3.
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layered materials, which revealed that the energy of vdW forces
of Bi2Se3 and Bi2Te3 are, on the basis of method used, in the
range of 13−26 meV/Å2.28
Raman spectroscopy was employed to characterize the Bi2Se3
and Bi2Te3 crystals (Figure 2). Typical Raman-active modes
1
A1g, 2Eg, and 2A1g were recorded for Bi2Se3 at about 72, 132,
and 174 cm−1, respectively, and about 62, 102, and 135 cm−1
for Bi2Te3. Similarly to the graphene experience, different
exfoliation procedures were proposed for Bi2Se3 and Bi2Te3
such as Li intercalation,19 mechanical exfoliation,17 and liquid-
phase exfoliation supported by sonication.18 To the best of our
knowledge, no attempt has been done to exfoliate crystals of
Bi2Se3 and Bi2Te3 using electrochemical methods. We
previously developed a controllable electrochemical exfoliation
of graphite foils to obtain graphene sheets with different
structural and chemical composition depending on the
electrolyte employed.25 Here, we propose a modified procedure
to exfoliate natural crystals of Bi2Se3 and Bi2Te3.
The phase purity of Bi2Se3 and Bi2Te3 crystals was proven by
X-ray diffraction. Both samples show single-phase composition
of rhombohedral phases (symmetry R3̅m) with preferential
orientation of the crystallites due to its layered structure. The
X-ray diffractograms with diffraction patterns of corresponding
PDF card 01-089-2009 for Bi2Se3 and 01-089-2008 for Bi2Te3
are shown in Figure 3.
Using small flakes of Bi2Se3 and Bi2Te3 crystals (see Figure
4G,H) we set up a two-electrode system in combination with a
Pt foil as the counter electrode, which is separated from the
solution through a dialysis membrane in order to avoid direct
contact of exfoliated material with the electrode surface while
ensuring electrical and ionic current to flow (Figure 4A,D). We
employed aqueous Na2SO4 electrolyte for the experiment.
Applying to the working electrode (crystal) positive DC
voltages up to +10 V resulted with no exfoliation process being
observed. This is different from the exfoliation of graphite
because exfoliation was obtained in only anodic conditions.25
We noticed, however, that by inverting the electrode polarity
and applying negative voltages to the working electrode,
materials were released in solution (Figure 4B,E) in about 2
min. This phenomenon repeated only when a combination of
preliminary anodic potential followed by a cathodic potential
was applied. We therefore optimized the procedure alternating
anodic voltages of +10 V to cathodic voltages of −10 V, both
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Figure 3. X-ray diffractograms of Bi2Se3 and Bi2Te3 and corresponding PDF cards. Unmatched diffraction patterns originate from Kβ lines.
Figure 4. Process of electrochemical exfoliation of Bi2Se3 (A−C)
and Bi2Te3 (D−F). (G) Bi2Se3 and Bi2Te3 crystals used for
exfoliation. (H) Electrical connection of the crystal using copper
tape. Colloidal suspension of Bi2Se3 (I) and Bi2Te3 (J) obtained
after the electrochemical exfoliation.
for the duration of 2 min. When this two-step procedure was
repeated, abundant material release was observed for both
Bi2Se3 and Bi2Te3 (Figure 4C,F). After a series of washing steps
to eliminate the electrolyte, both exfoliated materials were
resuspended in distilled water and sonicated for 1 h, obtaining a
stable dispersion (Figure 4I,J).
Representative STEM images of the exfoliated materials can
be seen in Figure 5. It can be noticed that exfoliated sheets of
materials were obtained, although material debris was also
visible. The morphology was further characterized by TEM.
The exfoliated sheet of Bi2Se3 is shown on Figure 6A together
with the HR-TEM image (Figure 6B), and the exfoliated sheet
of Bi2Te3 is shown on Figure 6C with corresponding HR-TEM
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Figure 5. Scanning transmission electron microscopy images of (A)
electrochemical exfoliated Bi2Se3 and (B) electrochemical ex-
foliated Bi2Te3. Scale bar corresponds to 1 μm.
Figure 6. (A) Low-resolution TEM and (B) HR-TEM images of
Bi2Se3. (C) Low-resolution TEM and (D) HR-TEM images of
Bi2Te3.
image (Figure 6D). EDS analysis of sheets shows the
composition of sheets from bismuth, selenium, and tellurium
(Figure S1 of Supporting Information). The EDS mapping
shows the main origin of debris from elemental tellurium in the
case of Bi2Te3 and elemental selenium in the case of Bi2Se3.
These particles are formed by oxidation of selenides and
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Figure 7. XPS spectra of Bi2Se3 crystal (upper) and electrochemically exfoliated Bi2Se3 nanosheets (lower). (A) Survey spectra. High
resolution spectra of (B) Bi 4f signal and (C) Se 3d signal.
tellurides during electrochemical exfoliation. HR-TEM images
are also provided with simulated figures showing orientation of
observed planes (Figure S2 of Supporting Information).
XPS is a useful characterization tool able to analyze the
surface composition of solid materials as well as the atomic
oxidation state of the elements. Figure 7A summarizes the XPS
survey spectra of the bulk Bi2Se3 crystal and the exfoliated
material. The presence of intense oxygen and Si signals for the
exfoliated material is due to the SiO2 wafer onto which the
exfoliated dispersed material was deposited. It can be noticed
that a more intense C 1s signal resulted for the exfoliated
material, which should be due to contamination. Survey spectra
are particularly useful to determine the relative atomic
composition of the material analyzed. The Bi/Se atomic ratio
for the bulk crystal material was 0.69, close to the theoretical
0.66, confirming the composition of Bi2Se3. The exfoliated
material resulted in a Bi/Se ratio of 0.49, which suggests a ratio
1:2 and is likely due to the formation of oxides. The high-
resolution XPS spectra of Bi 4f and Se 3d signals (Figure 7B,C)
confirm such a hypothesis because both signals are shifted to
higher binding energies.
Similarly, the survey XPS spectrum of the bulk Bi2Te3
enables the evaluation of the relative atomic composition. A
Bi/Te ratio of 0.68 resulted, which confirms the composition of
Bi2Te3. After the exfoliation, the Bi/Te ratio changed to 0.37,
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which is close to the 1:3 ratio (Figure 8A). The formation of
the oxide species of Bi and Te altering the natural Bi2Te3
composition could be the reason, as also demonstrated by the
high-resolution XPS spectra of Bi 4f and Te 3d (Figure 8B,C).
Clearly, both Bi and Te present oxidation states higher than
that of natural Bi2Te3, producing signals at higher binding
energy.
An electrochemical study was performed in order to
investigate inherent electrochemical behavior of the materials
and possible catalytic properties toward the HER and OER.
Figure 9A shows the cyclic voltammogram recorded in buffered
solution for exfoliated Bi2Se3 drop-casted onto glassy carbon
(GC) electrodes. It can be noticed that oxidative and reductive
signals resulted at about 0 V and −0.75 V, respectively,
suggesting a common redox process. Since both signals
persisted for several scans, the redox process can be considered
pseudoreversible. Bi2Te3 presented a similar electrochemical
behavior indicated by oxidative signals at about −0.1 and 0.1 V
and reduction signals at about −0.8 and −1.2 V. Again, as can
be seen from Figure 9B, the redox process persisted over
several voltammetric scans, suggesting reversible behavior. The
redox signals to the oxidation and reduction potential of Bi
oxide species are consistent with oxidation of Bi0 films and
reduction of Bi3+.29,30
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Figure 8. XPS spectra of Bi2Te3 crystal (upper) and electrochemically exfoliated Bi2Te3 nanosheets (lower). (A) Survey spectra. High
resolution spectra of (B) Bi 4f signal and (C) Te 3d signal.
Probing the catalytic properties of both exfoliated Bi2Se3 and
Bi2Te3, we noticed that only Bi2Te3 was catalytically active for
HER, showing a reduced overpotential of about 150 mV (at
current density of −10 mA cm−2) compared to that of the bare
GC electrode. Bi2Se3 presented an almost overlapping polar-
ization curve with that of GC (Figure 10). Both materials were
catalytically inactive toward OER, presenting overlapping
curves with that of GC (Figure S3 of Supporting Information).
CONCLUSIONS
A fast, reagent-less, glovebox-free, and controllable exfoliation
method is presented here to prepare single- and few-layer thick
Bi2Se3 and Bi2Te3 nanosheets starting from natural crystals. The
exfoliated materials present interesting electrochemical proper-
ties, particularly a pseudoreversible inherent redox behavior
which needs to be taken into account when electrochemical
sensing or energy-related applications are the intended
applications for these materials. This method has great
potential for exfoliation of Bi2Se3 and Bi2Te3.
EXPERIMENTAL SECTION
Materials. Bismuth (99.999%), selenium (99.999%), and tellurium
(99.999%) were obtained from MaTecK, Germany. N,N-Dimethyl-
formamide, potassium sulfate, potassium ferricyanide, and potassium
hydroxide were purchased from Sigma-Aldrich, Singapore. Glassy
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carbon (GC) with a diameter of 3 mm was obtained from CH
Instruments, USA.
Synthesis. For the synthesis of Bi2Se3 crystals, a stoichiometric
amount of bismuth and selenium forming 10 g of Bi2Se3 was placed in
a quartz glass ampule (15 × 100 mm) and evacuated at pressure below
1 × 10−3 Pa. The evacuated ampule was melt-sealed by an oxygen−
hydrogen torch. The ampule was heated at 750 °C at a heating rate of
5 °C/min. After 1 h dwell time at 750 °C, the ampule was cooled to
650 °C at a cooling rate of 0.3 °C/min and finally cooled to room
temperature at a cooling rate of 1 °C/min.
Similarly, Bi2Te3 crystals were prepared by introducing a
stoichiometric amount of bismuth and tellurium forming 10 g of
Bi2Te3 into a quartz glass ampule (15 × 100 mm) evacuated at
pressure below 1 × 10−3 Pa. This was then melt-sealed by an oxygen−
hydrogen torch at 620 °C at a heating rate of 5 °C/min. After 1 h
dwell at 620 °C, the ampule was first cooled to 500 °C at a cooling rate
of 0.3 °C/min and finally cooled to room temperature at cooling rate
of 1 °C/min.
Apparatus. STEM images were obtained by using JEOL 7600F
SEM (JEOL, Japan) operating at 30 kV. XPS was performed with a
Phoibos 100 spectrometer and a monochromatic Mg X-ray radiation
source (SPECS, Germany). Raman spectroscopy analysis was
performed using a confocal micro-Raman LabRam HR instrument
(Horiba Scientific, Japan) in backscattering geometry with a CCD
detector, a 514.5 nm Ar laser, and a 100× objective mounted on a
Olympus optical microscope. X-ray diffraction (XRD) was done with a
Bruker D8 Discoverer diffractometer in Bragg−Brentano parafocusing
geometry. A Cu Kα radiation was used. Diffraction patterns were
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Figure 9. Cyclic voltammograms of (A) exfoliated Bi2Se3 and (B)
exfoliated Bi2Te3. The scan rate is 100 mV/s; 0.05 M PBS; pH =
7.2.
Figure 10. Hydrogen evolution reaction in 0.5 M sulfuric acid for
exfoliated Bi2Se3 (blue line), exfoliated Bi2Te3 (red line), and glassy
carbon (GC) electrode (black line). Scan rate is 5 mV/s.
collected between 10° and 80° of 2θ. The obtained data were
evaluated using HighScore Plus 3.0e software. High resolution
transmission electron microscopy (HR-TEM) was performed using
an EFTEM Jeol 2200 FS microscope (Jeol, Japan). A 200 keV
acceleration voltage was used for measurement. Sample preparation
was attained by drop casting the suspension (1 mg mL−1 in water) on
a TEM grid (Cu; 200 mesh; Formvar/carbon) and drying at 60 °C for
12 h. The simulation of HR-TEM images was performed with JEMS
software (version 4.4631U2016) using Blochwave method. The noise
level used for the simulation was 1%, astigmatism of 21.51 nm, and
sample drift of 0.075 nm.s−1.
Procedures. Electrochemical Exfoliation. Small flakes from the
natural crystal of Bi2Se3 and Bi2Te3 were electrically connected to the
high-voltage device through a copper tape. Parafilm protection was
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employed to avoid contamination from copper, leaving only the
crystals exposed to the solution. A Pt foil was used as the counter
electrode. Exfoliation proceeded by applying a preliminary DC voltage
of +2 V to the anode for 2 min. This can facilitate a proper wetting of
the crystal with the intercalation of the electrolyte anions. This was
followed by the application of +10 V for a further 2 min. Exfoliation
occurred by alternating anodic (+10 V) and cathodic (−10 V) voltages
to the crystal. Exfoliation was carried out in 0.5 M Na2SO4 electrolyte.
Upon completion of the electrochemical exfoliation, the exfoliated
materials were washed several times with ultrapure water using
centrifugation and dried in a vacuum oven for 2 days at 40 °C.
Electrochemical Characterizations. Electrochemical experiments
were performed at room temperature by using a three-electrode
configuration on a Autolab PGSTAT101 electrochemical analyzer
(Methrom Autolab B.V., The Netherlands) connected to a personal
computer and controlled by NOVA software, version 1.9 (Methrom
Autolab B.V.). A platinum electrode (Autolab) served as an auxiliary
electrode, and a Ag/AgCl electrode (CH Instruments, USA) served as
a reference electrode. The exfoliated materials were drop-casted onto a
previously polished working electrode (GC) from 1 mg/mL water
dispersions. Cyclic voltammograms were recorded in 0.1 M phosphate
buffer solution (pH 7.2) with scan rate of 0.1 V/s. Polarization curves
for HER were recorded in 0.5 M H2SO4 solution at scan rate of 5 mV/
s. All potentials are considered versus the relative hydrogen electrode
(RHE) using the conversion relation: E(RHE) = E(Ag/AgCl) + 0.059pH +
°
E(Ag/AgCl) . Polarization curves for OER were recorded in 0.1 M KOH at
a scan rate of 5 mV/s.
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsnano.6b07096.
EDS mapping, HR-TEM images with simulated
orientation planes and OER measurements (PDF)
AUTHOR INFORMATION
Corresponding Author
*E-mail: pumera.research@gmail.com.
ORCID
Martin Pumera: 0000-0001-5846-2951
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
M.P. acknowledges a Tier 2 grant (MOE2013-T2-1-056; ARC
35/13) from the Ministry of Education, Singapore. Z.S. and J.L.
were supported by Czech Science Foundation (GACR No. 16-
05167S) and by specific university research (MSMT No. 20-
SVV/2016).
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11448 DOI: 10.1021/acsnano.6b07096

ACS Nano 2016, 10, 11442−11448