ARTICLES

PUBLISHED ONLINE: 10 JANUARY 2012 | DOI: 10.1038/NMAT3213

A new class of doped nanobulk high-figure-of-

merit thermoelectrics by scalable bottom-up
assembly
Rutvik J. Mehta1 , Yanliang Zhang2 , Chinnathambi Karthik1 , Binay Singh1 , Richard W. Siegel1 ,
Theodorian Borca-Tasciuc2 * and Ganpati Ramanath1 *

Obtaining thermoelectric materials with high figure of merit ZT is an exacting challenge because it requires the independent
control of electrical conductivity, thermal conductivity and Seebeck coefficient, which are often unfavourably coupled. Recent
works have devised strategies based on nanostructuring and alloying to address this challenge in thin films, and to obtain bulk
p-type alloys with ZT > 1. Here, we demonstrate a new class of both p- and n-type bulk nanomaterials with room-temperature
ZT as high as 1.1 using a combination of sub-atomic-per-cent doping and nanostructuring. Our nanomaterials were fabricated
by bottom-up assembly of sulphur-doped pnictogen chalcogenide nanoplates sculpted by a scalable microwave-stimulated
wet-chemical method. Bulk nanomaterials from single-component assemblies or nanoplate mixtures of different materials
exhibit 25–250% higher ZT than their non-nanostructured bulk counterparts and state-of-the-art alloys. Adapting our
synthesis and assembly approach should enable nanobulk thermoelectrics with further increases in ZT for transforming
thermoelectric refrigeration and power harvesting technologies.

H
igh-efficiency commercially viable thermoelectric materials
could revolutionize energy generation, usage and environ-
mental impact. However, achieving high-ZT thermoelectric
materials has been a challenge because it requires a combina-
tion of low thermal conductivity κ and high power factor α 2 σ ,
that is, high electrical conductivity σ and Seebeck coefficient
α, although these properties often follow unfavourably opposing
trends. To attack the problem, there is a great deal of interest
in nanostructuring bismuth- and antimony-based chalcogenides,
because these materials exhibit the highest room-temperature ZT
in bulk1–3 and restricting their characteristic dimensions to be-
low 10 nm offers the potential for obtaining further increases
in ZT (ref. 4). Factorial increases in ZT have been shown5–7
in nanostructured multilayer thin films by exploiting boundary-
scattering-induced κ decrease and high σ and α obtained from
quantum effects. However, this concept is yet to be successfully
adapted for scalably obtaining bulk quantities of both p- and
n-type nanomaterials with high ZT. Top-down approaches to
nanostructuring, such as ball-milling6 and melt-spinning8 , can
yield bulk quantities of high-ZT p-type alloys. These processes are
energy intensive, and adapting them for scalably obtaining high-ZT
n-type materials has been a challenge9 for bottom-up routes10–15 as
well16–19 . Devising low-energy-intensity scalable methods to obtain
high-ZT materials of both n and p type is crucial for fabricat-
ing commercially viable thermoelectric devices and modules for
transforming the fields of solid-state refrigeration and harvesting
electricity from heat.
Here, we report the first time realization of both p- and
n-type bulk nanomaterials (nanobulk) with ZT as high as 1.1
obtained by bottom-up assembly of rapidly synthesized single-
crystal nanoplates of sulphur-doped pnictogen chalcogenides
(Figs 1 and 2). Bulk pellets were prepared by cold compaction
and sintering of nanoplates synthesized by a scalable microwave-
stimulated, surfactant-directed, wet-chemical approach. We show
that the surfactants serve as sulphur doping agents and oxidation
inhibitors, in addition to guiding particle size and shape. Single-
component pellets made from pnictogen chalcogenide nanoplates
show twofold lower lattice thermal conductivity and high power
factors in the 1.5–4.5 mW m−1 K−2 range, comparable to state-
of-the-art bulk alloys1–3 . This remarkable charge-carrier-crystal
and phonon-glass behaviour without alloying is made possible
by combining nanostructuring and sub-atomic-per-cent sulphur
doping. We also report that multicomponent pellets fabricated
by mixing nanoplates of different chalcogenides show ultralow
thermal conductivities of 0.2 < κ ≤ 0.5 Wm−1 K−1 and large Seebeck
coefficients up to α ∼ 300 µV K−1 (Fig. 2c), and that the ZT is
a strong nonlinear function of the single-component nanoplate
fractions (Fig. 2d). Our scalable synthesis approach thus opens up
new pathways for producing bulk thermoelectric nanomaterials
for transformative technologies in solid-state refrigeration and
electricity generation from heat.
Synthesis and assembly of nanoplates
Our bottom-up wet-chemical synthesis method uses inexpensive
organic solvents and metal salts to rapidly sculpt large quantities
of sulphur-doped pnictogen chalcogenide (V2 VI3 ) nanocrystals
to create single- and multicomponent nanostructured bulk
(‘nanobulk’) thermoelectric materials (Fig. 1). In this method,
microwave stimulation activates the reaction between molecularly
ligated chalcogen and pnictogen complexes with thioglycolic
acid (TGA) in the presence of a high-boiling solvent. TGA
serves as a shape-directing, oxide-inhibiting and sulphur-dopant

1 Materials
Science and Engineering Department, Rensselaer Polytechnic Institute, 110 8th St., Troy, New York 12180, USA, 2 Department of Mechanical,
Aerospace and Nuclear Engineering, Rensselaer Polytechnic Institute, 110 8th St., Troy, New York 12180, USA. *e-mail: borcat@rpi.edu; Ramanath@rpi.edu.

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© 2012 Macmillan Publishers Limited. All rights reserved
ARTICLES NATURE MATERIALS DOI: 10.1038/NMAT3213

S
S
Doped Nanograins
nanoplates Nanopores
S

Bulk-nano
200 nm

1.2 Ours

Figure of merit ZT (300 K)

1.0 3 mm
0.8

p- and n-nano

p-nano
p- or n-bulk
0.6

n-nano
0.4

0.2
Microwave
0

Figure 1 | Schematic representation of the scalable synthesis used to obtain both n- and p-type bulk thermoelectric nanomaterials with high figures of
merit. Rapid (2–10 g min−1 ) microwave synthesis of sulphur-doped nanoplates followed by cold-compaction and sintering yields up to 92 ± 3% dense bulk
pellets with nanostructured grains. Sulphur doping provides control over the electrical conductivity, Seebeck coefficient and majority carrier type, while
nanostructuring results in very low thermal conductivity. The combined effect is applicable to multiple pnictogen chalcogenide systems and their
combinations. The graph compares the best ZT of our p- and n-type nanomaterials with those of the best p- and n-bulk materials, denoted as p- or
n-bulk1,2 , nanoparticle-dispersed n-bulk, referred to as n-nano33 , and a p-type ball-milled alloy, denoted as p-nano6 .

a b p-Bi0.5Sb1.5Te3
1.2 1.3

1.0 1.2
Figure of merit ZT (300 K)

Figure of merit ZT

0.8 p-Bi0.5Sb1.5Te3 1.1

n-Bi2Te3
1.0
0.6
0.9
0.4
n-Bi2Se3 0.8
n-Bi2Te3
0.2 p-Sb2Te3
0.7 p-Sb2Te3
0
0.6
20 40 60 80 100 120 140 160
Temperature (°C)
c d
300 p-type n-type p-type
1.2
Figure of merit ZT (300 K)

200 1.0
Seebeck coefficient α (μV K¬1)

0.8
100
0.6

0 0.4
0 20 40 60 80 100
0.2
Sb2Te3 nanoplate mole fraction
¬100
0
0 20 40 60 80 100
Sb2Te3 nanoplate mole fraction
¬200
n-type

Figure 2 | Figures of merit ZT for single-component and multicomponent bulk nanostructured pnictogen chalcogenides. a, Room-temperature ZT of the
best pellets of each pnictogen chalcogenide system. The ZT values of the corresponding bulk material of the same stoichiometry are indicated for
comparison. b, Temperature-dependent ZT of an n-type Bi2 Te3 , p-type Sb2 Te3 and p-type Bi0.5 Sb1.5 Te3 sintered pellet. c,d, Seebeck coefficient (c) and
room-temperature ZT (d) plotted as a function of Sb2 Te3 nanoplate mole fraction in Bi2 Te3 –Sb2 Te3 nanoplate mixtures. The dotted lines are to guide the
eye. The error bars denote the experimental measurement uncertainties for each sample; the spread in data points connotes sample-to-sample variations.

234 NATURE MATERIALS | VOL 11 | MARCH 2012 | www.nature.com/naturematerials

© 2012 Macmillan Publishers Limited. All rights reserved
NATURE MATERIALS DOI: 10.1038/NMAT3213 ARTICLES
a b c

2110
[01 10]
1 120 12 10
03 30
[21 10] 1120
1210
21 10
500 nm 200 nm [11 20]
[12 10]

d [11 20] e f

(0003)

200 nm 5 nm
200 nm

H
H
O H
O O O
g O h C O
C C
H C H
C 1s C H S 2s H C H
H
S
As prepared S H S

Se Bi
Annealed
As prepared
H Bi2Se3
O
Intensity (a.u.)

O
O C Annealed
Bi2Se3
H C H
C
As prepared
S Bi2Te3
O Te
Annealed
C Bi2Te3

Thioglycolic
acid

291 288 285 282 234 231 228 225 222

Binding energy (eV)

Figure 3 | Single-crystal hexagonal pnictogen chalcogenide nanoplates and mercaptan-mediated sulphur injection. a, Scanning electron micrograph
showing Bi2 Te3 nanoplates; more than 95% are hexagonal and less than 5% are triangular (see arrow). b, Bright-field TEM image of Bi2 Te3 nanoplate.
Inset: A high-resolution lattice image of the (0001) plane; the scale bar is 2 nm. c, Electron diffraction pattern from a nanoplate down the [0001] zone. The
faint spots (for an example see the arrow) are kinematically forbidden reflections arising from antisite defects. d, Bright-field TEM image from a Bi2 Se3
nanoplate with faceted islands (black arrows) that grow parallel to the parent plate face (white arrows). e, Edge-on bright-field image of a Bi2 Te3 nanoplate
showing ∼1 nm steps of (0003) planes. f, Moiré fringes and rotated spot patterns due to twist boundaries between overlapping Bi2 Se3 nanoplate crystals.
g,h, C 1s (g) and S 2s (h) core-level bands from annealed and unannealed pnictogen chalcogenide nanoplate films. A baseline spectrum from unligated
mercaptan groups is also shown for comparison.

delivery agent, whereas the use of tri-n-octylphosphine-chalcogen
complexes as microwave susceptors facilitates rapid high-
temperature (∼180–250◦ C) liquid-phase synthesis. The synthesis
can be carried out in either single-mode or off-the-shelf multimode
domestic microwave ovens, and yields a black precipitate in
∼10–15 s and completes the reaction in ∼30–60 s.
The precipitates consist of 5- to 20-nm-thick hexagonal
nanoplates (Fig. 3a,b) with bounding edge dimensions ranging
between 50 and 1,200 nm for all three pnictogen chalcogenides
investigated: Bi2 Te3 , Bi2 Se3 and Sb2 Te3 . Less than 5% of the
precipitates are truncated triangles, and the rod-like structures
seen in Fig. 3 are nanoplates oriented edge-on to the micrograph
plane. Increasing the microwave dose results in larger nanoplates
with little effect on plate thickness (Supplementary Fig. S1),
indicating that the nanoplate aspect ratio can be tuned by adjusting
the microwave dose. X-ray diffractometry and energy dispersive
X-ray spectroscopy reveal that the black precipitates consist
of phase-pure rhombohedral crystals of nearly stoichiometric
pnictogen chalcogenides doped with sulphur (Supplementary
Fig. S2). The near-100% yield of nanocrystals at 2–10 g min−1

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© 2012 Macmillan Publishers Limited. All rights reserved
ARTICLES
indicates that our method is quick, efficient and amenable to
scale-up and optimization.
Bright-field transmission electron microscopy (TEM) studies
of individual nanoplates reveal uniform contrast (Fig. 3b) and
spot diffraction patterns (Fig. 3c), indicating that each nanoplate
is a single crystal with the flat faces parallel to the (0001) basal
plane and the bounding prismatic edges consisting of {101̄0}
planes (Fig. 3b,d). Faint kinematically forbidden {101̄0} and {202̄0}
diffraction spots arise from antisite defects and/or incomplete
layers20 . Although stacking faults in the basal planes could also
give rise to such forbidden spots21 , no stacking faults were
observable in our microscopy studies. The relative crystal plane
orientations with respect to the bounding edges of the nanoplates
imply a higher growth rate along high charge-carrier mobility
h112̄0i and h101̄0i in-plane directions than along low thermal
conductivity [0001] directions. Surface steps and hexagonally
faceted islands with the bounding ledges aligned to the nanoplate
facets (Fig. 3d–f) indicate layer-by-layer growth of the nanoplates.
For example, the 1-nm-high ledges along h112̄0i parallel to the
bounding facets (Fig. 3e) correspond to (0003) planes consisting
of the five-layer stoichiometric stack of the rhombohedral crystal2 .
The atomic-level steps also manifest themselves as bend-contour
discontinuities, whereas Moiré fringes and rotated spot patterns
(Fig. 3f) arise from twist boundaries within each plate or between
adjacently stacked plates.
Nanostructured bulk pellets
We fabricated single- and multicomponent bulk pellets by the
assembly of nanoplates of a given pnictogen chalcogenide, or
mixtures of nanoplates of two different pnictogen chalcogenides,
respectively, by cold compaction and sintering 0.3–2 g of the
nanoplate powders. Our nanobulk pellets have up to 92 ± 3%
density of the respective bulk compounds after sintering. The
high density is attributed to the tendency of the nanoplates to
pack efficiently through stacking. Wavelength dispersive X-ray
spectroscopy reveals that the sintered single-component pellets
of Bi2 Te3 are 1–2 at.% bismuth rich and Bi2 Se3 is 1–5 at.%
bismuth deficient, whereas Sb2 Te3 is essentially stoichiometric,
all within experimental uncertainty of ±0.5 at.%. Pellets of all
three compounds contain 0.01–0.3 at.% sulphur (Supplementary
Fig. S2), which is controllable by adjusting the synthesis conditions.
The nanoscale grain size and porosity are controlled by the initial
nanoplate size and the compaction and sintering conditions. The
average dimensions of the sintered nanograins are a factor of two to
three larger than those of the as-synthesized nanoplates.
Figure-of-merit enhancement
The highest room-temperature ZT we obtain is 1.1 for bulk
nanostructured pellets of single-component n-type Bi2 Te3 and
multicomponent p-type Bi0.5 Sb1.5 Te pellets obtained from a 25:75
Bi2 Te3 :Sb2 Te3 mixture of nanoplates. Our measurements were
verified through independent measurements on blind and round-
robin samples with J. Sharp at Marlow Industries and Z. Ren’s
group at Boston College, MA. These results, summarized in Fig. 2a
and Table 1, represent a 25% improvement over conventional
alloys1–3 and are comparable to those of nanostructured ball-
milled alloys6 . Furthermore, our studies show that the ZT values
of bulk nanostructured materials of pnictogen chalcogenides, in
general, are two to four times higher than their corresponding
bulk counterparts of the same composition and stoichiometry, and
correspond to a 25–250% improvement over the highest values
reported for each material1,2 . This is perhaps best exemplified
by the p-type Sb2 Te3 case, where we obtain a room-temperature
ZT ∼ 0.75, compared with a polycrystalline bulk ZT of less
than 0.3. For Bi2 Te3 and Bi0.5 Sb1.5 Te, the ZT increases with
temperature and peaks between 70 and 90 ◦ C at values that are
236
© 2012 Macmillan Publishers Limited. All rights reserved
NATURE MATERIALS DOI: 10.1038/NMAT3213
10–15% higher than the room-temperature values (Fig. 2b). For
Sb2 Te3 , the ZT monotonically increases in the temperature range
studied. The temperature-induced ZT increase in all the samples
originates mainly owing to an increase in α, because σ decreases
with temperature, as expected in degenerate semiconductors,
and lattice thermal conductivity κL remains virtually unchanged
(Supplementary Fig. S3). The high ZT values arise from a
unique combination of bulk-like power factor α 2 σ enabled by
sulphur doping and very low κL due to nanostructuring, as
elaborated below.
Sulphur doping and inhibited oxidation by thioligation
Core-level spectra acquired by X-ray photoelectron spectroscopy
(XPS) from nanoplate assemblies (Fig. 3g,h) before sintering
reveal that TGA thioligation to the nanoplate surfaces results in
sulphur doping and inhibits oxidation. We observe two sulphur
2s sub-bands due to thioligated pnictogen and chalcogen states
(Fig. 3h) that are distinct from a central 229 eV sub-band from
unligated TGA. The C 1s ester peaks at 288 and 286 eV (Fig. 3g),
and infrared spectra showing C–S bands without detectable S–
H bands (Supplementary Fig. S4), corroborate TGA capping
of the nanoplates. Assuming that S diffusivity in Bi2 Te3 is
similar to that of Se (ref. 22), we expect that the S from the
adsorbed TGA is incorporated into the nanoplate crystal as
a substitutional impurity, thus providing a means for doping.
Such doping plays a pivotal role in determining the majority
carrier type and achieving a high power factor, as described
later below. The retention of thioligated pnictogen and chalcogen
signatures and the C 1s ester sub-bands, even on vacuum annealing
at 250 ◦ C, indicates robust molecular capping, responsible for
curtailed oxidation (Fig. 3g,h and Supplementary Fig. S5). As
a consequence, the nanoplate powders can be stored under
ambient conditions for more than two years, and do not require
oxygen-free processing.
Thermoelectric properties of n- and p-type nanomaterials
We measured the thermoelectric properties of the nanobulk
pnictogen chalcogenide pellets using well-established techniques23
that were calibrated using commercial samples. Our measure-
ments were verified by independent tests on several samples in
collaboration with Marlow Industries and Boston College. Our
measured values are within ±1% for α and σ , and ±5% for
κ, when compared with independent measurements. All values
reported here are the more conservative ones. The essentially
identical values (within experimental error) of α, σ and κ mea-
sured along mutually perpendicular axial and radial directions
of the same pellet, and X-ray pole figures showing a lack of
preferred grain orientation (Supplementary Fig. S6), indicate that
the pellets are isotropic.
Power-factor manipulation and sulphur doping
Our sulphur-doped single-component pellets exhibit power
factors comparable to those of bulk single crystals, which are
up to a hundred times higher than recently reported works on
nanocrystalline pnictogen chalcogenide materials17–19 . This result
combined with remarkably low thermal conductivity highlights
the heat-carrier glass charge-carrier crystal characteristics of
our nanobulk materials. The electrical conductivities are in
the 30 × 103 ≤ σ ≤ 250 × 103 1 m−1 range at room temperature
(Table 1; Fig. 4a,b), and the higher-end values are ∼2.5 times
higher than those of state-of-art alloys1,2 . Hall measurements
reveal carrier mobilities 60 ≤ µ ≤ 330 cm2 V−1 s−1 , corresponding
to 1018 –1020 cm−3 charge-carrier concentrations (Supplementary
Fig. S6), which are comparable to those of single-crystal
pnictogen chalcogenides1,2 . Our measurements reveal α < 0 for
the bismuth chalcogenides and α > 0 for antimony telluride:
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NATURE MATERIALS DOI: 10.1038/NMAT3213 ARTICLES
Table 1 | Thermoelectric properties and figures of merit of the best nanoplate bulk pellets measured.

Material and type σ α κ κL ZT at ZT increase

105 −1 m−1 (µV K−1 ) (W m−1 K−1 ) (W m−1 K−1 )* 300 K (%)†

n-Bi2 Te3 1.3 −185 1.23 0.59 1.1 26

n-Bi2 Te3 1.18 −140 0.80 0.38 0.87 148‡
n-Bi2 Te3 0.39 −193 0.51 0.38 0.86 146‡
p-Bi2 Te3 (no S) 0.01 40 - - - -
p-Sb2 Te3 2.5 116 1.36 0.35 0.74 51
p-Sb2 Te3 1.1 132 0.8 0.35 0.71 47
n-Bi2 Se3 0.77 −82 0.7 0.34 0.22 144
p-Bi0.5 Sb1.5 Te3 0.35 225 0.46 0.29 1.16 29
p-Bi0.5 Sb1.5 Te3 0.35 225 0.5 0.29 1.06 18

The measurement uncertainties in σ , α, κ and ZT are < ±1%, < ±1%, ∼ ±5% and ∼ ±7%, respectively, for each individual sample. All the values reported here are conservative ones, and are represented
in the graphs by the error bars. The spread in the data points connotes sample-to-sample variations. *Determined from the ordinate intercept of the plot of κ versus carrier concentration in Fig. 4a. † The
ZT increase cited is with respect to the highest ZT obtained in the pure bulk regardless of stoichiometry or anisotropy for each pnictogen chalcogenide material system1,2 . ‡ These percentage increases
are referenced to the pure bulk sample with the same stoichiometry.

a b 300
1.75 Bi2Te3

Bi2Te3 κ L = 0.59 W m¬1 K¬1 Sb2Te3

1.50 250
L Bi2Se3

1.25 Bi0.5Sb1.5Te3
κ (W m¬1 K¬1)

200
⎥α⎥ (μV K¬1)

1.00

α 2 σ (10¬3 W m¬1 K¬2)

150
5
0.75 4
Bi2Te3 κL = 0.38 W m¬1 K¬1 3
κL 100
0.50 2

Bi0.5Sb1.5Te3 κ L = 0.29 W m¬1 K¬1 1

0.25 50
0.5
0 0.5 1.0 1.5 2.0 2.5 0.5 1.0 1.5 2.0 2.5
σ (105 Ω¬1 m¬1) σ (105 Ω¬1 m¬1)
c 50 d
Undoped Bi2Te3
0 Sb2Te3

2.0
¬50
Intensity (a.u.)

α 2 σ (10¬3 W m¬1 K¬2)

α (μV K¬1)

¬100
1.3
Bi0.5Sb1.5Te3
¬150
S-doped Bi2Te3
1.8
¬200
1.3
¬250
¬0.1 0 0.1 0.2 0.3 0.4 2,460 2,470 2,480
Sulphur content (at.%) Binding energy (eV)

Figure 4 | Thermoelectric characterization of bulk-nanostructured pnictogen chalcogenides. a, Thermal conductivity κ of nanoplate pellets plotted as a
function of electrical conductivity σ . The slope is the Lorenz number L and the lattice thermal conductivity κL is the ordinate intercept. The error bars
denote the experimental uncertainties in the thermal conductivity measurements. b, Absolute value of the Seebeck coefficient α plotted as a function of σ .
Dotted curves denote different power factors α 2 σ . c, Seebeck coefficient versus the sulphur content for sulphur-doped and undoped Bi2 Te3 ; the error bars
for the sulphur content are the standard deviations for 10–12 wavelength-dispersive X-ray spectroscopy measurements from 10- to 15-µm-size regions on
each sample. d, Sulphur 1s core-level bands obtained using synchrotron radiation from sintered pellets of Sb2 Te3 and Bi0.5 Sb1.5 Te3 alloys, indicating a
correlation between high power factors and low-energy sulphur states.

−240 ≤ α ≤ −90 µV K−1 for Bi2 Te3 , −80 ≤ α ≤ −40 µV K−1 bismuth anti-site defects1,2 . This observed majority carrier reversal
for Bi2 Se3 and 105 ≤ α ≤ 135 µV K−1 for Sb2 Te3 (Fig. 4b). points to sulphur-doping-induced deviation from bulk defect
Although the Seebeck coefficient signs for Bi2 Se3 and Sb2 Te3 chemistry in Bi2 Te3 , as proposed earlier for 2 at.% sulphur
are consistent with the n- and p-type behaviours in the additions24 , except that in our case the sulphur levels are ten
respective bulk counterparts, that our Bi2 Te3 pellets show to a hundred times lower. Although sulphur doping regulates
α < 0 is significant because stoichiometric and bismuth-rich electronically active point-defect concentrations in pnictogen
Bi2 Te3 is known to be p-type owing to acceptor states from chalcogenides24,25 that can influence σ and α, further studies

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ARTICLES
are needed to reveal and exploit the nexus between processing
conditions, sulphur doping and dopant–defect interactions. The
high sensitivity of α to variations in sulphur doping (Fig. 4c)
suggests the alteration of density of states near the Fermi
level, which creates attractive possibilities to further increase
the power factor by controlling sulphur content and pnictogen
chalcogenide stoichiometry.
To verify the role of sulphur doping, we synthesized Bi2 Te3
nanoplates without TGA, by using bismuth neodecanoate—a
liquid organic compound acting both as bismuth precursor and
surfactant without sulphur. This microwave synthesis results in
bismuth telluride nanoplates of equivalent size and shape to
those obtained by TGA. However, the pellets fabricated from
these nanostructures without sulphur show p-type behaviour with
low α ∼ 40 µV K−1 and σ ∼ 103 −1 m−1 , yielding power factors
comparable to recent reports17–19 , but up to a hundred times
lower than our sulphur-doped pellets or state-of-the-art alloys.
Furthermore, core-level spectra obtained by synchrotron XPS reveal
that high power factor correlates with the appearance of low-
binding-energy sulphur 1s states at ∼2,471 eV and ∼2,468 keV
(Fig. 4d). These results underscore the importance of sulphur
doping for obtaining high power factors α 2 σ . By adjusting the
TGA concentration during Bi2 Te3 synthesis, we have been able to
obtain α 2 σ ∼ 4.5 mW m−1 K−2 , which is 5% higher than that of
polycrystalline bulk samples1–3 . Thus, our approach offers potential
opportunities for Fermi-level engineering26 of nanobulk materials
through controlled doping of the nanostructured building blocks.
We anticipate that further increases in power factor are possible
by refining our synthesis and processing procedures guided by
the connection between α 2 σ and sulphur-doping-induced defect-
chemistry and electronic-structure changes.
Thermal conductivity
Our pnictogen chalcogenide pellets exhibit thermal conductivities
in the 0.5 ≤ κ ≤ 1.4 W m−1 K−1 range (shown for Bi2 Te3 in Fig. 4a
and Table 1), representing a 40–75% diminution when compared
with their respective single-crystal bulk κ values1,2,27 . We deter-
mined the lattice thermal conductivity κL and Lorenz number L
from the ordinate intercept and slope of the linear fit to κ–σ
plots for pellets with similar microstructures (described below) and
different doping levels. The κL values are ∼60–75% lower (Fig. 4a)
than those of the bulk1–3 for the three single-component pnicto-
gen chalcogenides, and are similar to those of ball-milled nanos-
tructured alloys6 . The Lorenz number L = 1.66 × 10−8 W  K−2
is ∼15% lower than the value assumed in recent reports5,8,16 ,
indicating that our analysis yields a more conservative (higher)
estimate of κL because the electronic contribution of thermal
conductivity κe = Lσ T , and κL = κ − κe . We note that our direct
determination of κL and L from a κ–σ plot is possible because our
process enables the independent control of microstructure through
microwave dose and sintering treatments, and doping through
surfactant concentration.
Considering that the sulphur content is less than 0.5 at.%, the
low κL is largely attributable to nanostructuring, rather than to
alloying1–3 . This inference is corroborated by the tenfold variation in
σ for the sulphur doping range explored compared to only a twofold
variation in κ due to κe increase because our pellets have nearly
identical κL values owing to similar microstructures. The strong
dependence of κL on nanocrystal size enables κL tuning by adjusting
the microwave dose during synthesis. For example, for Bi2 Te3 κL
can be decreased from ∼0.59 to ∼0.38 W m−1 K−1 by decreasing the
dose from ∼ 50–80 to 5–10 kJ g−1 .
The κL decrease can be explained in terms of the 10–100 nm
grains and 5–50 nm inter- and intragranular pores (Fig. 5a–f)
revealed by our TEM measurements. The pellets consist of
stacks of 50- and 100-nm-thick plate-shaped grains (Fig. 5a,b),
238
© 2012 Macmillan Publishers Limited. All rights reserved
NATURE MATERIALS DOI: 10.1038/NMAT3213
and similar-size equiaxed grains forming high-angle boundaries
(Fig. 5c,d) with the stacks or nanopores (Fig. 5e), and 10–75 nm
grains dispersed inside the larger grains (Fig. 5d,f inset). The grain-
and pore-size distributions are shown in Fig. 5f. The intragranular
crystals are distinct from the 5–10 nm intragranular fringes (for
example, seen in Fig. 5a) due to strain-field modulations28 . The
plate-shaped grains are about five to ten times thicker and wider
than the as-synthesized nanoplates, suggesting sintering-induced
coalescence in assemblies of nanoplate building blocks. The
intragranular dispersions are probably a result of incomplete
coalescence. Although the observed stacking of plate-shaped
grains suggests texturing, X-ray pole figures (Supplementary
Fig. S6) show no observable preferred orientation, indicating
that our pellets consist of randomly oriented domains of
plate-shaped grain stacks with submicrometre-scale texture
restricted to each domain.
Simulations of κL using a modified Debye–Callaway29 model
combined with a modified effective-medium formulation30
(Fig. 5g) fitted best with our experimentally determined κL for
average grain and pore sizes of 30 nm and 10 nm, respectively,
consistent with the feature sizes determined by TEM (Fig. 5f). Thus,
equiaxed grains and porosity are the main contributors to the κL
decrease. Our simulations also reveal that phonon scattering at
grain boundaries and nanopores account for about 65% of the κL
decrease, with the rest attributable to ∼1020 cm−3 sulphur doping.
The weak temperature dependence of κL (Supplementary Fig. S3)
indicates the dominance of temperature-independent phonon
scattering at nanograin boundaries and nanopores. This inference is
supported by our model showing less than 10% change in κL for the
entire range of sulphur doping levels explored in our experiments.
Our ability to decrease κL mainly by nanostructuring enables us to
increase ZT by independently tailoring α and σ through sulphur
doping or alloying.
Multicomponent nanobulk pellets
We can also obtain κ in the 0.4–0.6 W m−1 K−1 range and ZT as high
as 1.1 by fabricating multicomponent pellets by mixing, compacting
and sintering nanoplates of different pnictogen chalcogenides.
For example, pellets fabricated from mixtures of n-Bi2 Te3 and
p-Sb2 Te3 nanoplates show up to ∼40% lower κL than single-
component pellets of either compound. The further κL decrease
is attributable to alloying, as supported by X-ray diffractograms
showing Bragg-reflection shifts when compared with that of the
pure pnictogen chalcogenide components (Supplementary Fig.
S7). Assuming that linear extrapolation is permitted, we obtain
κL ∼ 0.29 W m−1 K−1 from the ordinate intercept of the κ–σ
plot for the Bi0.5 Sb1.5 Te3 alloy (Fig. 4a). The ultralow κL is close
to the theoretical minimum for fully dense samples31 . Although
pellets obtained by mixing n-Bi2 Te3 and p-Sb2 Te3 nanoplates
decreases σ to ∼0.2–0.5 × 105 −1 m−1 , which is 40–50% lower
than those of their single-component counterparts, α is enhanced
significantly for certain single-component nanoplate fractions
(Fig. 2c). Consequently, the ZT increases substantially owing to the
quadratic contribution of α (Fig. 2d).
We also observe majority-carrier reversal in select component-
fraction ranges, opening a pathway for obtaining both n- and
p-type nanomaterials with high ZT. For example, we observe n-type
behaviour with peak α ∼ −200 µV cm−1 at ∼12–15% mole fractions
of Sb2 Te3 and p-type behaviour with peak α ∼ 298 µV cm−1
at ∼75–78% Sb2 Te3 (Fig. 2c), with a carrier-type crossover at
∼18–22% Sb2 Te3 . Further studies are needed to unveil the mecha-
nism of the nonlinear increase in Seebeck coefficient that may arise
from local compositional gradients or heterostructuring32 at certain
nanoplate fractions. We note that the baseline single-component
pellets made with either unoptimized n-Bi2 Te3 or p-Sb2 Te3
nanoplates exhibit ZT ∼ 0.5, underscoring the highly nonlinear
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NATURE MATERIALS DOI: 10.1038/NMAT3213 ARTICLES
a b d

c
e

[0001]

200 nm [1120]

f g 1.25
40
1.00
30

κ L (W m¬1 K¬1)
Frequency (%)

0.75 n-Bi2Te3

20
0.50

10
0.25
p-Bi0.5Sb1.5Te3
0
0
0 25 50 75 100 ¬150 ¬100 ¬50 0 50
Grain/pore size (nm) Temperature (°C)

Figure 5 | Diminution of lattice thermal conductivity in bulk-nanostructured chalcogenides due to nanoscale grain size and porosity. a–e, Bright-field
TEM micrographs from a Bi2 Te3 nanoplate pellet showing stacked plate-shaped grains, with intra-grain structural modulations observable at the
appropriate tilt angles28 with a [101̄0] zone electron diffraction from a grain (a); nanopores (red arrows) and stacked grains (b); equiaxed grains with
high-angle boundaries (c) and equiaxed grains containing smaller embedded nanograins and nanopores (d) (scale bars in b–d, 200 nm) and nanopores
(scale bar, 25 nm) (e). f, The overall grain-size (black circles) and pore-size (open green diamonds) distributions and the component distributions of
plate-shaped grains (blue circles) and equiaxed grains (red circles) measured by TEM image analyses. Inset: A bright-field TEM image of equiaxed
nanograins embedded in other grains; scale bar, 50 nm. g, Temperature dependence of the lattice thermal conductivity of the Bi2 Te3 pellets fitted to a
model combining a modified Debye–Callaway approach with a modified effective-medium formulation. The error bars denote the experimental
measurement uncertainties.

nature of ZT enhancement in pellets made with a mixture of the Methods

two types of nanoplates.
Summary and conclusions
We have demonstrated a readily scalable bottom-up approach to
create bulk thermoelectric nanomaterials of both n- and p-type
pnictogen chalcogenides with ZT > 1. Nanobulk thermoelectrics
were obtained by the assembly and sintering of nanoplate building
blocks synthesized by a microwave-stimulated wet-chemical
technique. The high power factor and low thermal conductivity
necessary for high ZT were realized through a combination of
nanostructuring and surfactant-induced doping. The shape- and
size-directing surfactants used for nanoplate synthesis inhibit oxi-
dation and serve as a means for doping the nanoplates with sulphur.
The doping-induced alteration of the electronic structure of the
pnictogen chalcogenides opens up an attractive new avenue for tun-
ing the thermoelectric power factor and charge-carrier mobilities
by simple chemical control during scalable synthesis. Bulk pellets
consisting of nanoscale grains obtained by assembly and sintering
of the nanoplates result in very low thermal conductivities. Mixing
doped nanoplates of different chalcogenides enables the adaptation
of this bottom-up approach to realize both n- and p-type alloys
and nanocomposites with ZT > 1. This unique set of features of our
scalable bottom-up nanostructure synthesis and assembly approach
makes it attractive for the manufacture of high-performance
thermoelectric devices and modules. Further understanding and
refinement of our approach holds promise for development and use
of high-ZT nanobulk thermoelectrics for transformative solid-state
refrigeration technologies and thermoelectric power harvesting.
Nanoplate synthesis. All chemicals were obtained from Sigma Aldrich and
used without further purification. In a typical small-scale synthesis, we added
∼0.08 mmol of tellurium or selenium shot to 2–5 ml tri-n-octylphosphine (TOP)
and heated it in a multimode 1,250 W domestic microwave oven for 90–120 s to
obtain a pale-yellow TOP–chalcogen complex. We added ∼0.04 mmol of BiCl3 or
SbCl3 to 2.5–10 ml of 1,5-pentanediol followed by sonication for 5 min to obtain
a pnictogen chloride solution. The bismuth chloride solution turns yellow on
addition of 100–350 µl of TGA owing to thioligated bismuth complex formation.
The solutions with TOP–chalcogen and thioligated bismuth (or antimony)
were mixed and exposed to microwaves for ∼30–60 s in a multimode domestic
microwave oven or a single-mode variable-power 300 W CEM microwave oven.
The whole procedure is simple and quick: it can be completed in ∼15 min.
The nanoplates were cleaned by repeated centrifugation and sonication with
isopropanol and acetone, and left to dry under ambient conditions, to obtain
powders consisting of single-crystal nanoparticles.
Pellet fabrication. We fabricated pellets from dried nanoplate aggregates
through cold-compaction using a hydraulic press. The ∼60–70% dense ‘green’
pellets were sintered in a 10−7 torr vacuum at 300–400 ◦ C for 60–120 min to
obtain up to ∼92 ± 3% density measured by the Archimedes method. For
thermoelectric measurements, we used 6-mm-diameter cylindrical pellets
with 2–5 mm thickness obtained by cutting and polishing using standard
metallography techniques.
Material characterization. Films formed by drop-casting the nanoplates on
to glass slides, silicon wafer or TEM grids, and green and sintered pellets were
characterized by X-ray diffractometry, scanning and transmission electron
microscopy and diffraction, and XPS. Fourier transform infrared spectra were
acquired from KBr-compacted pellets with the nanoplates. We measured the
sulphur content of the pellets by wavelength dispersive X-ray spectroscopy on an
electron microprobe. The reported values constitute an average of at least 10–12
measurements from 10- to 15-µm-sized regions. XPS spectra were acquired either
with a Mg Kα beam or by using a 3.028 keV synchrotron beam at Brookhaven
National Laboratory.

NATURE MATERIALS | VOL 11 | MARCH 2012 | www.nature.com/naturematerials 239

© 2012 Macmillan Publishers Limited. All rights reserved
ARTICLES
Thermoelectric transport characterization. The Seebeck coefficient α and
the thermal conductivity κ were simultaneously measured using a steady-state
instrumental setup23 (see Supplementary Fig. S8 for further details) calibrated
with commercial thermoelectric samples. The electrical conductivities σ of the
pellets were determined by four-probe switching methods using a.c. (6 kHz)
and d.c. techniques, van der Pauw for radial, and linear four-probe methods
for axial directions. All properties were measured on the same sample in two
mutually perpendicular, axial and radial pellet directions, and independently
verified by J. Sharp at Marlow Industries and Z. Ren’s group at Boston College.
Verification experiments included measurements of blind round-robin samples
and our nanostructured bulk samples by linear-probe (σ and α) and laser-flash
(κ) techniques. The measurement uncertainties for σ are less than ±1% (van der
Pauw) and ∼ ± 3% (linear four probe), less than ±1% for α and ∼ ± 5% for κ,
for each individual sample, and are represented in the graphs by the error bars
on the data points. The spread in the data points connotes sample-to-sample
variations. All values reported in the text are conservative ones, that is, the ones
that yield the lower ZT.
We determined α by measuring the temperature difference and Seebeck
voltage across the thickness of the pellets using E-type thermocouples and copper
wires (Supplementary Fig. S8). We polished the pellets and coated the top and
bottom surfaces with 150-µm-thick indium layers to minimize the contact
resistances Rc (kept at less than 3% of the measured thermal resistance R) and
uniformly spread the heat flux. The thermocouple and copper wires, all of 25 µm
diameter, were embedded in the indium layers. The lower indium piece is in
contact with the heat sink whereas the upper piece is in contact with a heater and
the sample is mechanically pressed between the two layers. To minimize heat
losses, we placed a thick Teflon block above the heater and gently fastened the
system before carrying out κ measurements in a 10−7 torr vacuum. With respect
to the total heater power, convection losses were less than 0.1% in the 10−7 torr
vacuum and conduction losses were restricted to less than 1% through the use
of fine thermocouples and copper wires, and Teflon insulation of the heater. We
determined the total heat losses from conduction and radiation, and accounted for
them in our data reduction. We extracted the pellet thermal conductivity κ from R.
For more details of the synthesis procedures and measurement techniques, please
refer to the sections in Supplementary Information.
Received 10 May 2011; accepted 23 November 2011;
published online 10 January 2012
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Acknowledgements
We gratefully acknowledge funding from the US Department of Energy, Office
of Basic Energy Sciences through the S3 TEC Energy Frontiers Research Center
at MIT under Award DE-SC0001299, National Science Foundation grants DMR
0519081, ECCS 1002282 and CBET 0348613, and a gift grant from IBM through the
Rensselaer Nanotechnology Center. We thank J. Woicik, B. Karlin and D. Fischer
for help with setting up the photoemission experiments carried out at the National
Synchrotron Light Source at Brookhaven National Laboratory, supported under the US
Department of Energy contract DE-AC02-98CH10886. We thank J. Sharp at Marlow
Industries and Z. Ren at Boston College for independently verifying our measured
thermoelectric property values.
Author contributions
R.J.M. carried out experiments, synthesized and characterized the materials and wrote
the paper with G.R. Thermoelectric measurements and modelling were carried out
by Y.Z. Data interpretation and analysis was carried out collaboratively by R.J.M.,
Y.Z., G.R. and T.B-T. C.K. and B.S. carried out transmission electron microscopy and
X-ray photoelectron spectroscopy measurements, respectively. G.R. directed the project
together with T.B-T. and R.W.S. All authors discussed the results and implications and
commented on the manuscript at all stages.
Additional information
The authors declare no competing financial interests. Supplementary information
accompanies this paper on www.nature.com/naturematerials. Reprints and permissions
information is available online at http://www.nature.com/reprints. Correspondence and
requests for materials should be addressed to T.B-T. or G.R.
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