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Cite this: Chem. Commun., 2011, 47, 12131–12133

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Acetic acid-confined synthesis of uniform three-dimensional (3D) bismuth
telluride nanocrystals consisting of few-quintuple-layer nanoplateletsw
Published on 13 October 2011. Downloaded by University of Windsor on 27/10/2014 12:36:31.

Qiang Yuan, Kelly Radar and Muhammad Mustafa Hussain*

Received 26th July 2011, Accepted 19th September 2011
DOI: 10.1039/c1cc14556h

High-selectivity, uniform three-dimensional (3D) flower-like bismuth In this paper, we report a facile small molecular organic acid
telluride (Bi2Te3) nanocrystals consisting of few-quintuple-layer (acetic acid) confined growth method to synthesize the uniform
nanoplatelets with a thickness down to 4.5 nm were synthesized 3D nanocrystals of Bi2Te3 consisting of ultrathin nanoplatelets
for the first time by a facile, one-pot polyol method with acetic with a controllable thickness down to 4.5 nm. The Raman
acid as the structure-director. Micrometre-sized 2D films and performance of the individual 3D Bi2Te3 nanocrystals was also
honeycomb-like spheres can be obtained using the uniform 3D studied.
Bi2Te3 nanocrystals as building blocks. Fig. 1a–b and Fig. S1a (ESIw) show the representative
transmission electron microscopy (TEM) images of the
Recently, the synthesis of nanostructured materials by colloidal as-synthesized bismuth telluride nanocrystals at 140 1C for
chemistry methods is of considerable interest because of the 1.0 h. The products display 100% selectivity, uniform flower-like
ability to control the size and shape of crystals, thus enabling an nanostructures lying flat on the TEM grid with hexagonal
investigation of the size/shape-dependent properties1,2 and
special properties of the individual nanocrystal,3,4 which is
very difficult to realize with conventional physical means or
CVD. Bismuth telluride (Bi2Te3) is considered to be one of most
promising TE materials for cooling and power generation
applications because its bulk alloys exhibit high room temperature
figures of merit, ZT = (S2sT)/k E 1.5 Both theoretical
simulations and experimental investigations have shown that
nanostructured materials can enhance the ZT by effectively
scattering phonons through the introduction of many internal
interfaces and quantum-confinement effects triggered by
decreasing size in any direction (x, y, or z).6–8 Furthermore,
the two-dimensional (2D) layers of Bi2Te3 were discovered to
be one of a new class of organizational quantum matter, referred
to as topological insulators, which has the potential application
for magnetic memory.9,10 All of the above-mentioned reasons
encourage the search for fabrication methods of Bi2Te3 nano-
structures. Very recently, ultrathin quasi-2D crystals of Bi2Te3
with one-dimensional quantum confinement were fabricated
by a ‘‘graphene-inspired’’ mechanical exfoliation procedure
from bulk Bi2Te3 because of the weak van der Waals inter-
actions existing in the Te1–Te1 bonds.11–13 However, to the
best of our knowledge, the synthesis of colloidal 3D nano-
crystals of Bi2Te3 with a thickness of only a few atomic layers
and high-quality interfaces has not been reported thus far.

Integrated Nanotechnology Lab, Division of Physical Science &
Engineering, King Abdullah University of Science & Technology,
Thuwal 23955-6900, Saudi Arabia.
E-mail: muhammad.hussain@kaust.edu.sa
w Electronic supplementary information (ESI) available: Experimental
details, TEM, HRTEM and SEM images and AFM results. See DOI:
10.1039/c1cc14556h
Fig. 1 TEM images of the as-synthesized Bi2Te3 nanocrystals (a) and
(b) (inset: corresponding electron diffraction (ED) pattern); HRTEM
images (c) top-down view; (inset: corresponding FT patterns) and
(d) side view (inset: the magnification of the selected area in the dotted
white rectangle); TEM images of self-assembled types (e) (2D film) and
(f) (honeycomb-like sphere).

This journal is c The Royal Society of Chemistry 2011 Chem. Commun., 2011, 47, 12131–12133 12131

platelets on the bottom, the average diameter, side-to-side, of
the bottom hexagonal platelets is 470  50 nm. The scanning
electron microscopy (SEM) images (Fig. S1b–d, ESIw) clearly
show that the products are 3D nanostructures consisted of
several different types of platelets, including well-defined
hexagonal platelets, curly, kilted and stand-up platelets, which
makes the particles look like 3D flower-like nanostructures.
The weak contrast of lying platelets relative to the background
indicates the thin character of the platelets (Fig. 1a–b and
Published on 13 October 2011. Downloaded by University of Windsor on 27/10/2014 12:36:31.
Fig. S1, ESIw). The electron diffraction (ED) patterns of one
single particle (Fig. 1b and Fig. S2, ESIw) can be indexed as
6-fold symmetry along the [0001] zone axis projection, which is
in agreement with the layered structure of Bi2Te3 along the
c axis (Fig. S3, ESIw). The ED patterns show that the bottom
hexagonal platelet is monocrystal and the monocrystal nature
was also identified by high-resolution TEM (HRTEM) images
and corresponding Fourier transform (FT) patterns (Fig. 1c
and Fig. S4, ESIw). The HRTEM image (Fig. 1c) indicates that
the h11 2% 0i is the growth direction for forming the hexagonal
platelets terminated by {0001} facets of the top-bottom surfaces
and {11 2% 0} facets of the six-side surfaces.14 The side-view
HRTEM image (Fig. 1d) of a stand-up platelet clearly displays
four intact quintuples with a thickness of 1.0 nm. The total
thickness of the platelet is about 4.5 nm, which equals the thickness
of 1.5 formula cells of Bi2Te3. Moreover, the as-synthesized
particles used as building blocks have the potential to self-assemble
into beyond 10-mm-sized 2D films (Fig. 1e and Fig. S1ew) and
honeycomb-like spheres (Fig. 1f), which can be used to
fabricate different types of nanodevices.
The thickness of the nanoplatelets was accurately measured
using atomic force microscopy (AFM). Fig. 2a–b and Fig. S5a
(ESIw) are the AFM topography images of one flower-like
nanocrystal. The AFM topography images (Fig. 2a–b) show
that the particles possess the structure of several small nano-
platelets. The nanoplatelets stack on the bottom well-defined
hexagonal platelet with obvious steps and interfaces and the
maximum vertical height reaches about 85.0 nm. The section
profiles (Fig. 2c and Fig. S4b, ESIw) along the red lines show
the thickness of the nanoplatelets at about 4.5  0.2 nm, which
is in agreement with the results of the HRTEM analysis
Fig. 2 An AFM image of a Bi2Te3 nanocystal (a), 3D topography
image (b) and the section profiles along the red lines shown in (a): (c)-1
and (d)-2.
12132 Chem. Commun., 2011, 47, 12131–12133
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(Fig. 1d). It indicates the nanoplatelets consist of 4–5 quintuple
layers of Bi2Te3. Furthermore, the height variation of the
section profiles also implies that the nanocrystals contain
many steps and interfaces (Fig. 2c–d).
The crystal structure and component distribution of the
as-synthesized nanocrystals were characterized using X-ray
diffraction (XRD), X-ray energy dispersive spectrometer
(EDS) line scanning and element mapping. The XRD pattern
of the as-synthesized products is shown in Fig. S6a (ESIw). All of
the detected peaks are consistent with that of a rhombohedral
Bi2Te3 crystal structure (JCPDS: 15-0863), which has a trigonal
structure and can be expressed in terms of a hexagonal cell of
lattice parameters a0 = 0.4385 nm and c0 = 3.0483 nm
containing three formula units. Each unit cell has five atoms
(Te1–Bi–Te2–Bi–Te1), referred to as quintuple layers with a
thickness of 1.0 nm along the C-axis (Fig. S3, ESIw). The result
of the side-view HRTEM image of one nanoplatelet is
consistent with the thickness of the quintuple layers, which
indicates that the nanoplatelets are composed of quintuples of
Bi2Te3. The peak of (0 0 15) is obviously enhanced. It implies
that the nanoplatelets are terminated by {0001} facets of the
top-bottom surfaces. The energy-dispersive X-ray spectro-
scopy (EDS) (Fig. S6b, ESIw) confirms that the particles are
composed of Bi and Te. Because Bi2Te3 and Te have a very
small lattice mismatch of only 1.67%, they can form the
heterostructured Bi2Te3–Te nanocrystals by epitaxial growth
in a solution phase method.14–16 Therefore, in order to verify
the component distribution of the flower-like nanocrystals, we
combined EDS line scanning with element analysis mapping to
analyze the compositions of one single particle. Fig. 3a–b show
the HAADF-STEM image and EDS line scanning profile of
the selected direction. The HAADF-STEM image also shows
the particle consists of well-defined hexagonal platelets, curly,
kilted and stand-up platelets, which is similar to the results of
SEM images (Fig. S1b-d, ESIw). The EDS line scanning profile
shows that the Te and Bi have the same variation tendency
along the scanning direction. Moreover, the element analysis
maps (Fig. 3c–d) show that the Te and Bi homogeneously
distribute throughout the whole particle. The EDS line
Fig. 3 The HAADF-STEM image of a typical flower-like nanocrystal
(a); (b) EDS line scanning profile along the red line shown in (a);
(c) Te (green) and (d) Bi (red) element maps.
This journal is c The Royal Society of Chemistry 2011

scanning and element mapping show that no Te- or Bi-rich
locations can be observed, which indicates the flower-like
nanocrystals are not Bi2Te3–Te heterostructured crystals, but
Bi2Te3 crystals.
In the bottom-up colloidal method, additives have often
been used to control the shape/size of nanocrystals.2,17 In our
synthetic system, the acetic acid played an essential role in the
synthesis of the flower-like nanocrystals. In the absence of
acetic acid, the products were made of uncontrollable size and
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mixed morphologies (e.g., particles, short rods and barbells)
(Fig. S7a–b, ESIw). Fig. S7c–f (ESIw) show the representative
TEM images of the samples synthesized with the addition
of different amounts of acetic acid. When a small amount
(0.2 mL) of acetic acid was added, the products (Figs S7c–d,
ESIw) were made of ill-defined particles containing sheets and
the morphology was more uniform than those prepared in the
absence of acetic acid. When the amount of acetic acid was
increased to 0.4 mL, the products (Fig. S7e–f, ESIw) were
made of well-defined flower-like nanocrystals consisting of
nanoplatelets with a particle size between 200–480 nm. When
the amount of acetic acid was increased to 0.6 mL, the small
flower-like particles disappeared, the size became more uniform
and the average size was 470  50 nm (Fig. 1a and Fig. S1,
ESIw). The products prepared in the absence of PVP were
composed of aggregates of irregular Bi2Te3 nanoplatelets
(Fig. S8, ESIw). It indicates that PVP mainly serves as a
coating reagent to stabilize the flower-like nanocrystals from
agglomeration in the synthesis process. These phenomena
imply that acetic acid acted the key role of structure-director
for the formation of the flower-like Bi2Te3 nanocrystals and
was conductive to the formation of few-atomic layers nano-
platelets of Bi2Te3 while inhibiting the crystal growth along the
c axis during the crystal growth process to avoid the formation
of particle- or rod-like crystals (Fig. S7a–b). Interestingly,
when the acetic acid was substituted by another small mole-
cular organic acid (i.e., formic acid and propionic acid), the
products also were composed of well-defined flower-like
nanocrystals (Fig. S9, ESIw).
The Raman properties of the single flower-like nanocrystals
were investigated by variation of excitation laser power
(Fig. S10, ESIw). When the excitation laser power was 0.4 mW,
two Raman shift peaks located at 123 cm1 and 141 cm1 were
observed respectively. When the excitation laser power was
increased to 0.8 mW, Raman shift peaks located at 60 cm1
and 107 cm1 occurred. The four peak positions are very
similar to the results acquired through testing the quasi-2D
bismuth telluride crystals by Balandin and coworkers.12 They
can be identified as A1g1, Eg2, A1u and A1g2 optical modes,
respectively.12,18 When the excitation laser power was increased
to over 1.6 mW, the shape of the Raman peak changed and
demonstrated big broadened peaks in the range 60–200 cm1,
which is ascribed to the local melting or oxidation of the
nanocrystal owing to their few-atomic layer thickness.12 It
indicates that the flower-like nanocrystals display energy-
sensitive Raman properties.
This journal is c The Royal Society of Chemistry 2011
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In conclusion, uniform 3D flower-like Bi2Te3 nanocrystals
were achieved by a simple one-pot polyol process with acetic
acid as the structure-director. The characterizations of
HRTEM and AFM show that the flower-like nanocrystals
consist of few-quintuple layer nanoplatelets with a thickness
down to 4.5 nm or so, which equals the thickness of 1.5 formula
cells of Bi2Te3. The as-synthesized nanocrystals used as building
blocks can self-assemble into a 2D film and honeycomb-like
spheres. Moreover, the individual flower-like Bi2Te3 nano-
crystals display energy-sensitive Raman properties. It is
believed that the uniform 3D flower-like Bi2Te3 nanocrystals
can serve not only as building blocks for nanodevice applications,
but also desired structures containing high-quality steps and
interfaces for thermoelectric applications.
This work is supported by the funds from Global Collaborative
Research, King Abdullah University of Science and Technology
(KAUST) under Special Academic Partner (SAP) and Academic
Excellence Award (AEA) grants. We also appreciate the useful
discussion with Prof. Hua Chun Zen of National University
Singapore about this work.
Notes and references
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