Materials Letters 135 (2014) 87–91

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Annealing effect on the thermal conductivity of thermoelectric

ZnTe nanowires
Mehrdad Shaygan a,1, Nazli Kheirabi a,1, Keivan Davami a,n,1, Bohayra Mortazavi b,
Jeong-Soo Lee a,n, Gianaurelio Cuniberti b, M. Meyyappan c
a
Department of IT Convergence Engineering, Pohang University of Science and Technology (POSTECH), Pohang, South Korea
b
Institute for Materials Science and Max Bergmann Center of Biomaterials, TU Dresden, Dresden 01062, Germany
c
NASA Ames Research Center, Moffett Field, CA 94035, USA

art ic l e i nf o a b s t r a c t

Article history: We report here the effect of thermal annealing on the thermal conductivity of ZnTe nanowires measured
Received 12 June 2014 on a microfabricated suspended device. Molecular dynamics simulation was used to calculate the effect
Accepted 19 July 2014 of contacts on the measurements at different temperatures and to estimate the intrinsic nanowire
Available online 30 July 2014
thermal conductivity values. A decrease in thermal conductivity was observed after each thermal
Keywords: annealing step at all the measured temperatures. Thermal annealing can be a potential method to
Thermoelectric improve the thermoelectric efficiency of nanowires, not only by enhancing the electrical conduction as
ZnTe demonstrated before, but also by suppressing the thermal transport at the same time.
Nanowire & 2014 Elsevier B.V. All rights reserved.
Thermal conductivity

1. Introduction
Nanowires (NWs) have gained much attention as promising
materials in nanoscale electronics, photonics, optoelectronics and
others [1]. The nanowire form of thermoelectric (TE) materials
has been shown to overcome the limitations of bulk materials [2].
The efficiency of a TE material is measured by a figure of merit
ZT ¼ ðS2 σ =κ ÞT, where S is the intrinsic thermopower (Seebeck
coefficient) and T is the temperature. σ and κ are electrical and
thermal conductivities respectively; the latter can be rewritten as
κ ¼ κ e þ κ l since both electrons and phonons (lattice vibrations)
contribute to thermal conductivity. The challenge of simulta-
neously optimizing the above parameters and achieving ZT above
unity can be potentially resolved in nanoscale where the quantity
S2 σ increases due to higher density of states near the Fermi level
and κ l decreases due to phonon boundary scattering [3]. Theore-
tical and experimental studies have shown that the thermal
conductivity of semiconductor nanowires is different from their
bulk counterparts. Li et al. [4] reported two orders of magnitude
reduction in thermal conductivity of Si nanowires from bulk Si
due to altered phonon transport in nanowires, in total agreement
with theoretical predictions [5]. Thermal conductivity of ZnTe
n
Corresponding authors.
E-mail addresses: keivandavami@yahoo.com,
kdavami@seas.upenn.edu (K. Davami), ljs6951@postech.ac.kr (J.-S. Lee).
1
These authors contributed equally.
nanowires was shown to be size dependent and 3–10 times lower
than that of bulk ZnTe [6].
Thermal annealing can be used to eliminate crystal defects and
lattice imperfections in nanowires [7]. This enhancement in
crystallinity and decrease in defects and the subsequent improve-
ment in electrical conductivity was recognized [8] as the main
reason for the annealing-induced enhancement of thermopower
in nanostructured Bi2Te3. Thermal annealing induces enhanced
compositional heterogeneities in bulk materials by forming addi-
tional compositional phases and grain boundaries, which
improves phonon scattering and consequently decreases the
thermal conductivity; Ren et al. [9] noted a reduction in thermal
conductivity and increase in ZT of bulk SiGe by 10 to 400% through
thermal annealing. The interface between the outer shell and
inner core in core/shell nanowires can enhance the phonon
scattering and cause a reduction in thermal conductivity while
the electrical conductivity is less affected [10]. Thermal annealing
was also shown to increase the electrical conductivity of Bi2Te3
nanocrystals by modifying the mobility of charge carriers [11].
Liang et al. [12] observed a 14-fold increase in the electrical
conductance of PbSe nanowires after annealing due to enhanced
hole concentration from increased Pb vacancies. Annealing of ZnTe
NWs at 400 1C was shown to increase the electrical conductivity
by three orders of magnitude [13]. In this letter, we investigate the
effect of annealing on the thermal conductivity of ZnTe nanowires
and report a significant reduction as desired in thermoelectric
applications.

http://dx.doi.org/10.1016/j.matlet.2014.07.114
0167-577X/& 2014 Elsevier B.V. All rights reserved.
88 M. Shaygan et al. / Materials Letters 135 (2014) 87–91
2. Materials and methods
The ZnTe nanowires were synthesized on a silicon substrate
by an Au catalyzed vapor–liquid–solid approach using opti-
mized growth parameters reported previously [14,15]. The
microdevice for thermal conductance measurement consisted
of two adjacent suspended and thermally isolated silicon nitride
membranes, which were held suspended using six 420 μm long
SiNx beams. One serpentine-shaped Pt resistor  50 nm thick,
250 nm wide and 350 mm long was patterned on each of the
suspended membranes. Pt resistors were used as heater and
sensor interchangeably. A drop-cast method was used to place
one and only one NW on the measurement device bridging the
two suspended membranes. The device and nanowire were
placed into a cryostat under high vacuum to eliminate the
effects of heat transfer through the air on the measurement.
By passing a current through the heater, Joule heating increases
the temperature of the heating membrane and the heat was
transferred through the nanowire to the sensing membrane. The
temperature of each side can be calculated by measuring the
resistance of the heater and sensor. The thermal resistance of
the nanowire and the two contacts at the ends can be obtained
analytically. Details of the device fabrication and structure, the
measurement methodology and the calculations can be found in
Ref. [4]. Fig. 1(a) shows the scanning electron microscopy (SEM)
image of the fabricated microdevice with the nanowire con-
necting two thermally isolated heater structures. The nanowire
thermal conductivity was measured before and after Pt–C
deposition from room temperature to 450 K; the Pt–C pads
were deposited using a focused ion beam microscope to
improve the NW-electrode contacts.
The high-resolution transmission electron microscopy
(HRTEM) image in Fig. 1(b) reveals that the nanowire is single
crystal with FCC lattice structure, which is uniform without any
defects. The lattice spacing of 0.35 nm corresponds to the d-
spacing of the (1 1 1) plane of ZnTe structure. Selected area
diffraction pattern (not shown here) was indexed to the cubic
FCC structure, confirming that the ZnTe nanowires grew along the
〈1 1 1〉 direction. The formation of a native oxide layer on the
surface of the NWs is inevitable due to the residual oxygen in the
growth chamber as well as exposure to the ambient environment
after synthesis. The composition of this layer has been determined
as ZnO previously [16] and this amorphous oxide shell of 3 nm
covers the ZnTe nanowire surface uniformly as shown in Fig. 1(b).
3. Results and discussion
After measuring the thermal conductance of an as-grown
nanowire, the sample was annealed by placing it inside the
furnace under vacuum and keeping at room temperature first
for 1 h to purge oxygen completely from the furnace tube. Then
the heater was turned on to gradually increase the temperature
to 250 1C at a heating rate of 10 1C/min to anneal the sample for
4 h. The furnace was cooled down to room temperature before
sample removal, and the thermal conductance measurement
was performed again. The same sequence was repeated for a
subsequent annealing at 400 1C. HRTEM was utilized to measure
the oxide layer thickness to assess the impact of annealing on
the oxide shell of the NW. The oxide shell thickness increased
significantly from 3 nm to 5.4 nm and 11.8 nm after annealing at
250 and 400 1C under vacuum for four hours, respectively (Fig. 1
(c) and (d)) due to the residual oxygen molecules in the
annealing tube.
The fabricated microdevice along with the nanowire connecting
the two thermally isolated heater structures can be modeled as
three thermal resistors in series corresponding to the nanowire and
the nanowire-membrane contacts. The thermal resistance of the
nanowire and the contacts at the two ends are denoted as Rnw and
Rc , respectively in this model, while the as-measured total thermal
resistance of the sample can be written as Rt ¼ Rnw þ2Rc . We
denote the effective thermal conductivity derived from the sample
by κ ef f ¼ ðLnw =Anw :Rt Þ, where Anw and Lnw are the cross-sectional
area and length of the suspended nanowire, respectively. The
contact thermal resistance between the suspended nanowire and
membrane can be calculated as follows based on the fin heat
transfer model [17,18]:
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
Rc ¼ ½ κ nw Anw =R0c tanh ðLc = κ nw Anw R0c Þ  1 ð1Þ
where κ nw ¼ ðLnw =Anw  Rnw Þ is the intrinsic thermal conductivity
of the nanowire independent from the contacts, and R0c is the
thermal boundary resistance (TBR) of the contact between the
nanowire and the membrane per unit length. In the present
work, the TBR of the Pt contacts was estimated from the non-
equilibrium molecular dynamics (NEMD) simulation. Simulated
TBR values from along with measured Rt at different tempera-
tures allow to exclude the effect of contacts and estimate the
intrinsic thermal conductivity of the nanowire (κ nw ), as
described previously [6].
The molecular dynamics model for the evaluation of the
thermal contact resistance between ZnTe and Pt atoms and the
details of the simulation have been described previously
[6,15,19]. The simulations were performed for a minimum time
of 4 ns and the averaged temperatures at each slab were com-
puted. The average contact thermal resistance for the reference
nanowire with a diameter of 145 nm at different temperatures is
about 10% of the total measured value before Pt–C pad deposi-
tion, while this contribution reduces to about 3% after the Pt
deposition. Fig. 2 shows the thermal boundary resistance
between the nanowire and the surrounding platinum per unit
area and the corresponding thermal boundary conductance at
three different temperatures from the MD simulation. The esti-
mated thermal contact resistance decreases for higher tempera-
tures, which can be due to diffusion of Pt atoms into ZnTe and the
formation of an alloy material.
The thermal conductance between the ZnTe nanowire and the
electrodes increases significantly after Pt–C deposition (data not
shown here) mainly due to the increased contact area [6]. Fig. 3
(a) shows the measured effective thermal conductivity (κ ef f ) of
the reference nanowire (diameter of 145 nm), before and after Pt
pad deposition and after sequential thermal annealing steps. The
increase in measured κ ef f after Pt pad deposition is due to smaller
contact thermal resistance. However after the pad deposition,
each thermal annealing step resulted in a decrease in the
nanowire thermal conductivity. The same trend was observed
for the calculated κ nw (not shown here). Since the effects of
contacts have been excluded in the calculation of κ nw , the
decrease in thermal conductivity cannot be the result of a change
in thermal contact resistances.
A change in the surface roughness at the interface of the ZnTe
core and ZnO shell could not decrease the thermal conductivity
since no significant change was observed at the interface in the
HRTEM images of the nanowire at different stages of annealing
(Fig. 1(c) and (d)). The increase in oxide layer thickness could
affect κ nw negatively. This possibility is ruled out by estimating
the thermal conductivity of ZnTe core without the ZnO shell to
verify if the same decreasing trend is observable after the
annealing steps. Since the cross-section of the nanowires con-
sists of an outer ZnO shell (the native oxide layer) and an inner
ZnTe core, the calculated κ nw of the nanowire corresponds to
the whole ZnTe–ZnO core–shell system, which can be treated as
 M. Shaygan et al. / Materials Letters 135 (2014) 87–91 89

Fig. 1. (a) High magnification SEM image of the serpentine-shaped coils in the islands, ZnTe NW bridging two suspended microstructures and Pt pads deposited on the
contacts (shown by blue arrows). (b) HRTEM image of ZnTe nanowire. HRTEM images of annealed ZnTe nanowire (c) at 250 1C and (d) at 400 1C. (e) EDAX analysis of ZnTe
nanowire before and after annealing at 250 1C. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
90 M. Shaygan et al. / Materials Letters 135 (2014) 87–91
Fig. 2. Molecular dynamic simulation results, calculated thermal boundary resis-
tance (TBR) and thermal boundary conductance (TBC) at ZnTe and Pt interface at
different temperatures.
Fig. 3. (a) Effective thermal conductivity of the reference nanowire (diameter
145 nm) after annealing at different temperatures. (b) The calculated intrinsic
thermal conductivity of the ZnTe core (κ core ) of the reference nanowire with
Dnw ¼145 nm, at different temperatures, before and after the two sequential steps
of annealing.
two thermal resistors in parallel:
κ nw  Anw κ core  Acore κ shell  Ashell
Rnw  1 ¼ ¼ þ
Lnw Lnw Lnw
With the thermal conductivity of ZnO and the oxide layer
thickness, one can obtain the thermal conductance of the oxide
shell and consequently the intrinsic thermal conductivity of pure
ZnTe core denoted as κ core . The cross-sectional areas of the ZnTe
core and the ZnO shell of the NW denoted as Acore and Ashell
respectively, before and after each step of thermal annealing, were
calculated using the oxide layer thickness from the corresponding
TEM images. A previously reported MD simulation result for ZnO
nanowires was used for the thermal conductivity of ZnO shell
around the wire [20]. This value was used for the calculation of the
κ core at different temperatures for a reference nanowire with
diameter of 145 nm before and after sequential annealing steps at
250 and 400 1C (Fig. 3(b)). Each thermal annealing step led to a
considerable suppression in the thermal conductivity of ZnTe NW
core. Thus, a change in the oxide layer thickness cannot contribute
to the observed thermal conductivity suppression.
Another possible reason for the reduction in NW thermal
conductivity after annealing might be the change in the NW
crystal direction. Single crystal Bi nanowires of similar diameter
grown in different directions have shown different thermal con-
ductivities [21]. Bi nanowires with a growth direction of [1 0 2]
have four times the thermal conductivity of those with a growth
direction of [1 1 0]. A difference in the atomic distances in these
two directions causes discrepancies in their mobility, Fermi vector
and phonon group velocity, possibly causing the lower thermal
conductivity in [1 1 0] direction [21]. A similar observation was
reported for InAs nanowires [22] showing that NWs with a growth
direction of [1 1 0] have a thermal conductivity three times higher
compared to NWs with a [1 0 0] or [1 1 1] direction. We performed
XRD measurements of different samples before and after anneal-
ing to evaluate the crystallography change and Fig. 4 compares the
XRD results of ZnTe NW after the sequential annealing steps. No
significant change is seen in the places and shapes of the peaks for
different planes after annealing compared to the pristine samples.
This proves that the crystal direction in the nanowires does not
change during annealing and cannot cause the reduction in
thermal conductivity. Moreover, the interatomic distances in the
ZnTe nanowire were calculated using the corresponding lattice
constant of the sample in each annealing step. The interatomic
distances of Zn–Zn and Zn–Te are 0.4303, 0.2635 nm, and 0.4299,
0.2633 nm for annealing at 250 1C and 400 1C, respectively. Com-
pared to the calculated values for pristine ZnTe (0.4317,
0.2644 nm), only a slight variation was observed in the interatomic
distances of ZnTe during the thermal annealing steps, thus
eliminating it as a cause for the observed changes in thermal
conductivity.
An atomic rearrangement during thermal annealing may be a
possible reason for the reduced thermal conductivity of ZnTe
nanowires. Oxidation during annealing is likely if oxygen atoms
were available. Huang et al. [23] partially oxidized Bi NWs to
obtain core/shell nanowires by annealing at 250 1C for five hours.
The diffusion of oxygen atoms towards the core and the migration
of Bi atoms to the shell section led to a phase transformation in Bi
nanowires. To investigate a similar possibility of atomic rearrange-
ment in ZnTe nanowires, energy dispersive X-ray spectroscopy
(EDAX) and electron energy loss spectroscopy (EELS) were
employed. The EDAX results (Fig. 1(e)) confirm a significant change
in the atomic arrangement by annealing at 250 1C where Te atoms
are detected in the core part of the nanowire significantly after
ð2Þ
Fig. 4. XRD patterns of ZnTe nanowire after different annealing conditions.
 M. Shaygan et al. / Materials Letters 135 (2014) 87–91
annealing. This rearrangement might contribute to the reduction
in thermal conductivity, however, this needs further investigation.
Annealing temperatures higher than 400 1C were not attempted as
ZnTe NWs melt around 490 1C for a 165 nm diameter nanowire
(data not shown here).
The existence of oxygen atoms in the structure of ZnTe
nanowire acting as point defects may be a possible reason for
the observed thermal conductivity reduction in ZnTe nanowires
after annealing. Oxygen and carbon atoms as ionized impurities in
Bi nanowires have been reported to play a key role in the
reduction of lattice thermal conductivity by a nonisotope impurity
scattering of phonons and carriers, which can partially result in
the suppressed thermal conductivity [24]. Likewise, the existence
of oxygen atoms in the ZnTe nanowire as a result of annealing
treatment and probable impurity phonon scattering could be
ascribed to the reduced thermal conductivity.
4. Conclusion
In summary, we have studied the effect of thermal annealing
on the thermal conductivity of a single ZnTe nanowire and found it
to significantly decrease after sequential annealing at 250 and
400 1C. The results obtained from this work together with our
previous results on electrical conductivity [13] suggest that
annealing treatment reduces the thermal conductivity of ZnTe
nanowires while enhancing their electrical conductivity. These
simultaneous effects can boost the thermoelectric figure of merit
and increase the efficiency of ZnTe nanowires in TE applications.
Further work is needed to fully understand the mechanisms,
nanowire diameter dependency and extension to other thermo-
electric materials.
Acknowledgements
The World Class University program funded by the Ministry of
Education, Science and Technology through the National Research
91
Foundation of Korea (R31-10100) supported this research. Keivan
Davami did the measurement part of this work during his visit at
UT Austin and wishes to acknowledge Professor Shi and his group
for their helpful support during the visit. Dr. T. Gemming at IFW
Dresden is acknowledged for providing electron microscopy
facilities.
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