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Influence of nanoscale Ag2Te precipitates on the thermoelectric properties of the Sn

doped P-type AgSbTe2 compound


Rajeshkumar Mohanraman, Raman Sankar, Fang-Cheng Chou, Chih-Hao Lee, Yoshiyuki Iizuka, I. Panneer
Muthuselvam, and Yang-Yuan Chen
Citation: APL Materials 2, 096114 (2014); doi: 10.1063/1.4896435
View online: http://dx.doi.org/10.1063/1.4896435
View Table of Contents: http://scitation.aip.org/content/aip/journal/aplmater/2/9?ver=pdfcov
Published by the AIP Publishing
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APL MATERIALS 2, 096114 (2014)

Influence of nanoscale Ag2 Te precipitates on


the thermoelectric properties of the Sn doped
P-type AgSbTe2 compound
Rajeshkumar Mohanraman,1,2,3,a Raman Sankar,4 Fang-Cheng Chou,4
Chih-Hao Lee,1 Yoshiyuki Iizuka,5 I. Panneer Muthuselvam,4
and Yang-Yuan Chen2,a
1

Department of Engineering and System Science, National Tsing Hua University,


Hsinchu, Taiwan
2
Institute of Physics, Academia Sinica, Taipei, Taiwan
3
Nano Science and Technology, Taiwan International Graduate Program, Institute of
Physics, Academia Sinica, Taipei, Taiwan
4
Center for Condensed Matter Sciences, National Taiwan University, Taipei, Taiwan
5
Institute of Earth Sciences, Academia Sinica, Taipei, Taiwan
(Received 25 July 2014; accepted 15 September 2014; published online 25 September 2014)

We report a maximal figure of merit (ZT) value of 1.1 at 600 K was obtained for
the sample of which x = 0.03, representing an enhancement greater than 20% compared with a pristine AgSbTe2 sample. This favorable thermoelectric performance
originated from the optimal Sn2+ substitution for Sb3+ in AgSbTe2 , which not only
increased electrical conductivity but also led to a substantial reduction in thermal
conductivity that was likely caused by an enhanced phonon-scattering mechanism
through the combined effects of lattice defects and the presence of Ag2 Te nanoprecipitates dispersed in the matrix. 2014 Author(s). All article content, except where
otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported
License. [http://dx.doi.org/10.1063/1.4896435]

Thermoelectric (TE) systems have recently received an increasing amount of attention because
they facilitate direct and reversible conversion between heat and electrical energy, thus enabling
environmentally friendly refrigeration and electric power generation.1, 2 The performance of TE
materials is assessed using a dimensionless figure of merit (ZT) = 2 T/, where , , T, 2 ,
and are the Seebeck coefficient, electrical conductivity, absolute temperature, power factor (PF),
and total thermal conductivity, respectively. Therefore, optimal TE materials must feature a high
PF and low thermal conductivity.1 AgSbTe2 is a potential TE material because of its exceptionally
low thermal conductivity ( of approximately 0.7 W m1 K1 ).314 AgSbTe2 is a narrow bandgap
semiconductor that has a disordered NaCl-type structure (Fm-3m), with Ag+ and Sb3+ randomly
occupying the Na+ site.14 According to electronic structure calculations,15 the top of the valence
band is Ag(4d)Te(5p) hybridized anti-bonding states, therefore the formation energy of Ag-vacancy
V(Ag) is small and can easily be compensated by Sb anti-site defects Sb(Ag), double donor at Agsite, then following self-regeneration16 occurs: [2V(Ag) + Sb(Ag)]. When we doped Sn-acceptor
at Sb-site, this is p-type doping due to the Sn-acceptor, it reduces the formation energy of [2V(Ag)
+ Sb(Ag)], then increases the Sb2 Te3 and Ag2 Te, since 2[AgSbTe2 ] = Sb2 Te3 + Ag2 Te. This is
caused by the spinodal nano-decomposition17 of Ag and V(Ag). Numerous recent studies have
focused on the effects of nanostructures and nanoprecipitates on the TE properties of AgSbTe2
especially alloys with other cubic compounds such as PbTe, called lead antimony silver tellurium

a Authors to whom correspondence should be addressed. Electronic addresses: rajeshx@phys.sinica.edu.tw, Tel.: 886-2-

2817-5274 and cheny2@phys.sinica.edu.tw, Tel.: 886-2-2789-6725, Fax: 886-2-2783-4187.


2166-532X/2014/2(9)/096114/7

2, 096114-1

Author(s) 2014

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FIG. 1. (a) Photograph of synthesized crystals of Ag(Sb1x Snx )Te2 (x = 0.01, 0.03, 0.05, and 0.07) series. (b) disc and barshaped samples for thermal and electrical transport measurements, respectively. (c) Powder XRD patterns of Ag(Sb1x Snx )Te2
samples. The inset shows the composition dependence of lattice parameter fitted using the Rietveld refinement method.
(d) DSC curves of Ag(Sb1x Snx )Te2 samples.

(LAST)1821 and GeTe, called tellurium antimony germanium silver (TAGS)22, 23 and have successfully exhibited enhanced TE performance.
We have recently reported that doping with bismuth (Bi) and indium (In) in the AgSbTe2
system has improved TE performance.24, 25 In this paper, Sb3+ was substituted with Sn2+ in ptype Ag(Sb1x Snx )Te2 systems to optimize the charge-carrier concentration and simultaneously
reduce lattice thermal conductivity by enhancing phonon scattering through the naturally formed
fine dispersion of Ag2 Te nanoprecipitates in the matrix. When x = 0.03, the sample exhibited the
highest ZT value of 1.1 at 600 K; therefore, Ag(Sb0.97 Sn0.03 )Te2 can be used as a p-type TE material.
Samples with a nominal composition of AgSb1x Snx Te2 (x = 0.01, 0.03, 0.05, and 0.07) were
synthesized using the vertical Bridgman method. The synthesis procedures detailed in our previous
report24 were used to obtain highly dense crystalline ingots with a dark silvery metallic shine as
shown in Fig. 1(a). The crystalline ingots were cut into bar shapes of approximately 3 mm 3 mm
14 mm, formed into circular discs of 12 mm in diameter and 23 mm thick, and polished before
physical properties were measured (Fig. 1(b)).
The phases of the Ag(Sb1x Snx )Te2 samples were analyzed using powdered X-ray diffraction (XRD; XPert PRO-PANalytical, CuK radiation) and differential scanning calorimetry (DSC,
NETZSCH, STA 449, with a heating rate of 10 K min1 and a sample mass of 25 mg). The microstructure and quantitative chemical analysis of the bulk samples were determined by performing
field emission electron micro-probe analysis (FE-EPMA: JEOL JXA-8500F). The sample preparation procedure for the EPMA technique is shown in Fig. S2 of the supplementary material.28 The
thermal conductivity was calculated using the equation = D Cp d, where D is the thermal diffusivity coefficient measured using the laser flash method (NETZSCH, LFA 457), Cp is the specific
heat capacity obtained using DSC (NETZSCH, STA 449), and density d was determined using the
Archimedes method. The relative densities of all samples were greater than 99.9% (approximately
7.117.12 g/cm3 ). The temperature dependence of the electrical conductivity and Seebeck coefficient was measured simultaneously by using commercial equipment (ZEM-3, ULVAC-RIKO,
Japan) in a He atmosphere at temperatures ranging from 300 to 600 K. The Hall effect measurements
were performed using a five-probe configuration with the magnetic field sweeping between +5.0

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TABLE I. Carrier concentration nH , Hall mobility H , electrical conductivity , Seebeck coefficient , effective mass m /mo ,
occupancy (Sn/Sb site), and EPMA composition of Ag(Sb1x Snx )Te2 series.
Nominal
composition
AgSbTe2
Ag(Sb0.99 Sn0.01 )Te2
Ag(Sb0.97 Sn0.03 )Te2
Ag(Sb0.95 Sn0.05 )Te2
Ag(Sb0.93 Sn0.07 )Te2

Occupancy
(Sn/Sb site)

(EPMA)
composition

0
0.075 0.05
0.028 0.007
0.030 0.009
0.031 0.01

AgSb0.98 Te2.01
AgSb0.99 Sn0.01 Te2
Ag0.99 Sb0.98 Sn0.027 Te2
Ag0.97 Sb0.96 Sn0.048 Te1.99
Ag0.96 Sb0.94 Sn0.064 Te1.98

nH
H

m /
3
2
1
1
4
1
1
cm ) (cm V s ) (10 S m ) (V K ) m0

(1020

1.38
0.26
0.77
0.51
0.33

16.2
16.6
16.8
17.5
19.2

3.6
0.7
2.09
1.45
1.016

165
209
179
156
121

2.08
0.84
1.62
1.075
0.63

and 5.0 T (Quantum Design, PPMS Ever-cool II). The average measurement errors in , , and
were estimated to be approximately 2%, 3%, and 3%, respectively.
Fig. 1(c) shows the powder XRD patterns of the AgSb1x Snx Te2 (x = 0.01, 0.03, 0.05, and
0.07) samples at room temperature. All of the main peaks can be indexed into major-phase fcc
AgSbTe2 structures (reference code: 01-089-3671) except for a low-intensity peak corresponding to
the Ag2 Te secondary phases (reference code: 00-004-0795) that were observed in the sample of which
x = 0.05 and 0.07. The lattice parameter as a function of the Sn content x calculated using the Reitveld
refinement is shown in the inset of Fig. 1(c); the lattice parameter decreased substantially from x = 0
to 0.03 as expected because the ionic radii of the dopant Sn2+ (0.69 ) were slightly smaller than that
of the host Sb3+ (0.76 ). A slight upturn was observed in the specimens of which x 0.5 (deviation
from Vegards law-type behaviour, red dashed line). The site occupancy as a function of the Sn
composition for the Ag(Sb1x Snx )Te2 series is shown in Fig. S1 of the supplementary material28
and listed in Table I. Indeed, it is seen that the population of Sn atoms in Sb sites increases with
the Sn content, beyond that it almost remains constant. Therefore, the existence of a second phase
is highly likely for highly doped compositions. To determine the phase transition of the samples,
the DSC heat flows were plotted (Fig. 1(d)). We observed endothermic peaks at 422 K and 421.5 K
associated with structural phase transition of Ag2 Te10 in the samples for which x = 0.05 and
0.07, respectively. The experimental results of both DSC and XRD analyses implied that Sn doping
was nearly optimal in Ag(Sb1x Snx )Te2 samples of which x = 0.03.
Fig. 2 shows EPMA backscattered electron images of the AgSb1x Snx Te2 (x = 0.01, 0.03, 0.05,
and 0.07) samples. The surface of the sample of which x = 0.01 was homogeneous, exhibiting no
traces of secondary phases (Fig. 2(a)). Conversely, the surface of the sample of which x = 0.03 in Fig.
2(b) exhibited noticeable secondary phase precipitates Ag2 Te (dark area) embedded in the AgSbTe2
bulk matrix (light area). As shown in the upper right inset of Fig. 2(b), the Ag2 Te precipitates,
which had a feature size of 100500 nm, were dispersed in the matrix. The precipitates coarsened
in samples of which the Sn content was high (i.e., x > 0.03; Figs. 2(c) and 2(d)), as indicated by the
increased precipitate size and decreased number density. Fig. 3(a) shows the elemental distribution
of the AgSb0.97 Sn0.03 Te2 sample determined using EPMA confirming that the grain boundary areas
were rich in Ag and Te. The measurements were obtained at different locations on the matrix of
the sample and the average total Sn content (x = approximately 0.028) measured in the matrix
was close to that of the nominal composition x = 0.03 (Fig. 3(b) and Table I). However, when the
Sn content was further increased (x = 0.05 and 0.07), the samples exhibited coarsening of Ag2 Te
precipitates as observed using EPMA (see Figs. S3 and S4 of the supplementary material28 ), this
observation is consistent with the XRD and DSC data presented in this paper. That macro-scale
characterization technique, such as XRD and DSC, cannot detect the existence of a small fraction
of Ag2 Te precipitates in the AgSb0.97 Sn0.03 Te2 samples was expected.
Fig. 4 shows the temperature dependences of the TE transport properties of the AgSb1x Snx Te2
(x = 0.01, 0.03, 0.05, and 0.07) samples. Fig. 4(a) shows the electrical conductivity of the
Ag(Sb1x Snx )Te2 series in the temperature range of 300600 K. The electrical conductivity decreased as the temperature increased and then increased, indicating typical degenerate semiconductor
behavior. This behavior was observed in all samples except for the sample of which x = 0.03, which
exhibited conventional semiconductor behavior. The sample of which x = 0.03 exhibited an electrical

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FIG. 2. Backscattered electron images (BSEI) of Ag(Sb1x Snx )Te2 bulk samples. Light areas represent AgSbTe2 bulk matrix
and dark areas Ag2 Te precipitates. (a) x = 0.01 and (b) x = 0.03. The upper-right inset was taken from the grain boundary;
Ag2 Te nanosized precipitates were found, (c) x = 0.05 and (d) x = 0.07.

FIG. 3. (a) The elemental distribution determined using EPMA of AgSb0.97 Sn0.03 Te2 samples and (b) average Sn content in
AgSb0.97 Sn0.03 Te2 sample.

conductivity of value of 3 104 S m1 at 543 K, representing the highest value amongst all of the
samples. To explain the electrical transport behavior in this system (Sn-doped AgSbTe2 samples), the
Hall carrier concentration nH (see Fig S5 of the supplementary material28 ) and the mobility H were
measured on these samples, and the results are listed in Table I. Due to the carrier-carrier scattering,
the mobility exhibited contrary composition dependence with carrier concentration. According to
previous study, the p-type carriers in AgSbTe2 are mainly caused by Ag vacancies13 and tendency to
form Ag2 Te precipitates. So the maximum carrier concentration of 7.7 1019 cm3 was obtained
with the x = 0.03 because of the presence of nanoscale Ag2 Te precipitation6 in the bulk matrix.
With the further increase of x value from 0.05 to 0.07, the carrier concentration decreased while

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FIG. 4. Temperature dependence of the thermoelectric transport properties of Ag(Sb1x Snx )Te2 samples. (a) Electrical
conductivity , (b) Seebeck coefficient , (c) power factor 2 , (d) thermal diffusivity D, (e) total thermal conductivity ,
and (f) lattice thermal conductivity L .

the mobility increased due to the decrease of carrier concentrations. As shown in Fig. 4(b), the
Seebeck coefficients () of all samples were positive throughout the temperature range indicating
p-type electrical transport behavior. The substantial decrease in the Seebeck coefficient when the Sn
concentration increased was caused by the decrease in the calculated effective mass obtained from
the relationship between nH and (Table I; detailed calculations are provided in the supplementary
material28 ). The PF ( 2 ) was calculated based on the values of and , as shown in Fig. 4(c).
The sample of which x = 0.03 exhibited the maximal value of 1.38 mW m1 K2 at 600 K because
the value was enhanced at high temperatures. Overall, the electrical transport properties were
markedly improved by using the optimal Sn filling fraction probably because of the presence of the
nanostructural features in the bulk matrix. Fig. 4(d) shows the thermal diffusivity D measurements
of the Ag(Sb1x Snx )Te2 samples. The Cp measurements (Fig S6 of the supplementary material28 )
shows strong agreement with those reported in the literature12 regarding typical AgSbTe2 samples
(approximately 0.205 J g1 K1 ). Fig. 4(e) shows the total thermal conductivity values for the
Ag(Sb1x Snx )Te2 series in the temperature range of 300600 K. The Sn-doped AgSbTe2 samples
exhibited lower thermal conductivity compared than did pristine AgSbTe2 samples. The electronic
thermal conductivity e can be calculated by using the WiedmannFranz law ( e = L T), where
L is the Lorentz number. The lattice thermal conductivity L can be calculated by subtracting e from
, thus L = L T. As shown in Fig. 4(f), the sample of which x = 0.03 exhibited a low
L value of 0.35 W/m K at 510 K, which is lower than those of pristine AgSbTe2 (0.52 W m1 K1 ).
The L of samples of which x 0.03 decreased substantially as the Sn content increased; however,
the L value increased sharply when x > 0.03 because the Ag2 Te precipitate in the matrix coarsened,
indicating that x = 0.03 is the optimal doping amount. The low L achieved in the samples of which

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FIG. 5. (a) Temperature dependence of thermoelectric figure of merit ZT of Ag(Sb1x Snx )Te2 (x = 0.01, 0.03, 0.05, and
0.07) samples and (b) the three-dimensional plot of current state of art of various doped elements in AgSbTe2 system in the
temperature range from 300 to 700 K along with references.

x = 0.03 can be attributed to the combined effects of the lattice defects engendered by substituting
Sn into the Sb sites in AgSbTe2 systems24, 25 and the presence of nanometer-scale precipitates of
the Ag2 Te phase with a feature size as large as 100500 nm which was effective for enhancing
phonon scattering.9, 26, 27 Further studies like transmission electron microscope (TEM) analyses and
ultrafast dynamics of sample of which x = 0.03 by ultrafast laser spectroscopy in order to understand
nanoscale thermal transport will be subjected to future direction. The values of 2 and were
used to calculate the TE figure of merit ZT which is plotted in Fig. 5(a). The AgSb0.97 Sn0.03 Te2
sample exhibited a maximal ZT value of 1.1 is achieved at 600 K because of its enhanced PF and
reduced thermal conductivity at high temperatures. Fig. 5(b) shows a three-dimensional plot of
recently reported ZT values for various doping elements in AgSbTe2 systems in the temperature
range of 300700 K. This comparison shows that AgSbTe2 compounds featuring the optimal Sn
doping concentration are potential candidates for TE applications in the medium temperature range.
Thermal stability can be ensured because the TE measurement properties for AgSb0.97 Sn0.03 Te2
samples exhibited negligible change in repeated thermal cycles (heating and cooling cycles) within
a temperature range of 300600 K (Fig. S7 of the supplementary material28 ). The main finding
of this investigation is that doping an Ag(Sb1x Snx )Te2 system with an optimal amount of Sn
(x = 0.03) is the most effective method for controlling the morphology and size of nanoprecipitates
and achieving high ZT values, and that doping the system with amounts substantially higher than
the optimal amount yields adverse effects.
In summary, the microstructure and TE properties of Sn-doped AgSbTe2 compounds were investigated and thermal analysis was conducted. According to XRD, DSC, and EPMA analyses, the
filling limit of the Sn content in AgSbTe2 systems is approximately x = 0.03. The lattice thermal
conductivity of Ag(Sb1x Snx )Te2 (x = 0.01 and 0.03) decreased as Sn content increased. The compound AgSb0.97 Sn0.03 Te2 exhibited the lowest lattice thermal conductivity because of the enhanced
phonon scattering that is generated by substitutional effects and presence of Ag2 Te nanoprecipitates
in the matrix. The AgSb0.97 Sn0.03 Te2 sample exhibited a higher PF and low thermal conductivity,
resulting in a high ZT value of 1.1 at 600 K indicating that this sample is highly suitable for TE power
generation applications. Our subsequent study will focus on improving the ZT value of AgSbTe2
compounds by optimizing the doping concentration and calibrating nanoscale precipitates.
This work was supported by Academia Sinica and the National Science Council, Taiwan,
Republic of China, Grant No. NSC100-2112-M-001-019-MY3.
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