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Scripta Materialia 127 (2017) 6367

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Scripta Materialia

journal homepage: www.elsevier.com/locate/scriptamat

Regular Article

Enhanced thermoelectric gure of merit of p-type Si0.8Ge0.2


nanostructured spark plasma sintered alloys with embedded
SiO2 nanoinclusions
Andrey Usenko a,, Dmitriy Moskovskikh a, Mikhail Gorshenkov a, Andrey Voronin a,b, Andrey Stepashkin a,
Sergey Kaloshkin a, Dmitriy Arkhipov a, Vladimir Khovaylo a
a
National University of Science and Technology MISiS, Moscow 119049, Russia
b
National Research South Ural State University, Chelyabinsk 454080, Russia

a r t i c l e i n f o a b s t r a c t

Article history: We report on thermoelectric properties of p-type boron doped nanostructured bulk Si80Ge20 synthesized via
Received 27 June 2016 spark plasma technique. We demonstrate that the presence of a limited amount of nanometer-sized SiO2 inclu-
Received in revised form 2 September 2016 sions, resulting from the oxidation during processing stages is an effective way to further thermal conductivity
Accepted 8 September 2016
reduction in the nanostructured Si80Ge20 alloys. Signicant reduction of thermal conductivity and high values
Available online xxxx
of Seebeck coefcient allowed us to reach a peak ZT value of about 0.72 at 800 C in boron doped Si80Ge20.
Keywords:
2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Thermoelectric materials
Spark plasma sintering
Mechanical alloying
Silicon germanium
Nanocomposite

Sustainable supply of energy to the worldwide population is one of a merit which is determined as ZT k, where is Seebeck coefcient,
2

major societal problem in the 21st century as fossil fuel supplies de- is electrical conductivity and k is thermal conductivity [13].
crease. It is obvious now that the energy production has been switching During the last decades, many research groups have demonstrated a
away from oil to alternative sources. The dynamic of oil and natural gas signicant enhancement of ZT in various material systems via
price on the world market conrms the last statement. Thermoelectric nanostructuring approach. For instance, this approach has allowed one
effects are expected to play an important role in meeting the energy to improve ZT of n-type SiGe alloys up to 1 at 800900 C [1416]. How-
challenge in future [1]. Many of the recent advances in enhancing ther- ever, ZT of p-type SiGe bulk materials has remained rather a low,
moelectric efciency have been connected to nanoscale phenomena ZT ~ 0.4. It has been shown recently that p-type SiGe-based thermoelec-
found in the bulk samples containing nanoscale elements [2]. In the tric materials prepared by mechanical alloying followed by different
last decades, advances in the eld of hightemperature thermoelectrics consolidation methods can demonstrate a large enhancement of the g-
have mostly been connected with such materials as boron rich cluster ure of merit ZT [17,18]. The increase in ZT has been attributed to the
compounds and oxide thermoelectrics [37]. However, the well- thermal conductivity reduction while maintaining electron transport
known silicon germanium alloys have still been considered as one of properties. If the crystallite sizes in the nanostructured material are
the most promising thermoelectrics for applications in a temperature compared with the phonon mean free path and are larger than the
range from 600 C to 1000 C. High mechanical strength and resistance charge carrier mean free path, the thermal conductivity can be reduced
to atmospheric oxidation makes SiGe alloys suitable for various applica- more than the electrical conductivity. Nanostructuring-induced en-
tions [8,9]. Silicon germanium alloys have also been studied as a per- hancement of the gure of merit has been demonstrated for a group
spective material for the design of segmented and cascaded of the well-known thermoelectric materials [1921]. It has been
thermoelectric generators (TEG) [1012]. The large-scale thermoelec- shown theoretically that nanoinclusions in a semiconducting matrix
tric applications of SiGe are limited due to several reasons. The most can lead to a signicant increase of Seebeck coefcient due to the energy
important of them is the high price and a low thermoelectric gure of ltering effect [22]. This effect was experimentally veried for nano-
crystalline CrSi composites [23], Pt-doped Sb2Te3 [24], half-Heusler al-
loys [25], Nb-doped SrTiO3 [26], nanocrystalline silicon with the
Corresponding author. inclusion of a secondary phase and nano-porous silicon [27,28]. The
E-mail address: usenko@misis.ru (A. Usenko). presence of nanometer-sized inclusions of amorphous silica dispersed

http://dx.doi.org/10.1016/j.scriptamat.2016.09.010
1359-6462/ 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
64 A. Usenko et al. / Scripta Materialia 127 (2017) 6367

in a polycrystalline matrix has experimentally been demonstrated in Table 2


previous works for n-type SiGe alloys [14,19]. It has been shown that Sintering parameters and volume density of p-type SiGe nanostructured alloys.

the presence of such nodules can positively inuence thermoelectric Sample Temperature, Soaking time, Density, Density,
properties. We also found silica nanoinclusions in our samples but C min g cm3 (% of theoretical)
they were determined as crystalline randomly oriented nodules. The (ser.1)1050 1000 5 2.73 90.8
nanoscale structural elements investigated in our study can evidently (ser.1)1100 1100 5 2.82 93.8
explain the enhanced ZT value in our SiGe alloys due to a considerable (ser.1)1150 1150 5 2.91 96.8
(ser.2)1050 1050 5 2.86 95.5
reduction of the thermal conductivity and an enhancement of the
(ser.2)1100 1100 5 2.95 98.1
Seebeck coefcient which is presumably due to the energy ltering (ser.2)1150 1150 5 2.99 99.3
effect. (ser.3)1050 1050 5 2.44 80.9
Powders of Si, Ge and B of at least 99.99% purity were used for fabri- (ser.3)1100 1100 30 2.79 92.6
cation of Si80Ge20 samples doped with 2 at.% of boron. The powders
were mixed in desired proportions and then milled by Fritsch
Pulverisette-5 (F5) and Fritsch Pulverisette-7 (F7) ball mills for 1 h. [15] which demonstrated the possibility of rapid alloying of SiGe in
For the F5 mill we used stainless steel vials (500 ml) and the milling b1 h. When preparing the rst series (ser.1), the ball milling media
media with the ball-to-powder weight ratio 30:1 for series 1 (ser.1) ratio was chosen 30:1 in order to increase the collision energy in the
samples and 20:1 for series 2 (ser.2) samples; the milling process was bowl. Unfortunately, this also led to a signicant contamination of the
performed in argon atmosphere at a speed of 350 rpm. The third series sample from the milling media and the bowl. In ser.2 we used 20:1
of samples (ser.3) was fabricated in the F7 mill. The vials (45 ml) and ball-to-powder weight ratio and new ball milling media. We succeeded
the milling media of the F7 mill were made of zirconium dioxide. The in decreasing contamination down to b 1% at., according to EDS data col-
milling process was also performed in argon atmosphere but with at a lected from many spectra.
speed of 700 rpm. A 1 wt.% anti-friction and re-welding control agent In the current study, we used spark plasma sintering method accord-
(alcohol) was added to the vials. The samples were sintered from the ing to accumulated experimental data [1519] which showed that the
as-milled powders by Spark Plasma Sintering (SPS) method (Labox SPS method does not lead to a signicant grain growth and allows the
650, Sinter Land, Japan). The powders were put into a cylindrical graph- nanocrystallite structure to be retained. The sintering parameters and
ite die, which was placed in a camera evacuated to a vacuum ~5 Pa. Uni- volume density of p-type SiGe nanostructured alloys are presented in
axial pressure was then applied through top and bottom plungers. Each Table 2. The theoretical density of Si80Ge20 was calculated from the fol-
plunger has a diameter of 12.7 mm and a length of 23 mm. The samples lowing equation: (2.329 + 3.4930.499 2) g cm3 [29].
were prepared using the following sintering protocol. Initially, the sam- Fig. 1 shows XRD spectra of the as-prepared nanopowder (top spec-
ples were pre-compressed at room temperature for 2 min then the pres- trum), the as-sintered dense bulk sample (middle spectrum) and the
sure was increased and reached the peak of 60 MPa. After that the same sample annealed at 1000 C for 48 h in argon atmosphere (bottom
samples were gradually heated to 100 C and then the temperature spectrum). It is seen from Fig. 1 that all powder XRD peaks have a shoul-
was raised either to 1050, or to 1100, or to 1150 C with a heating der that is attributed to an incomplete alloying during the short-time
rate 10 C/s. After 5 min soaking time the pressure was reduced to ball milling. The calculation of the average grain size (AGS) was made
10 MPa, and the samples were cooled to room temperature during by Rietveld method [30]. The average crystallite size was found to signif-
20 min. The sintered disc samples have a dimension of 12.7 mm icantly grow from 9 to 68 nm during sintering process and then slightly
(diameter) 2 mm (height). The samples were annealed at 1000 C increase to 75 nm after the annealing at 1000 C for 48 h.
for 48 h in vacuum. Structure of the samples was examined by Trans- The low magnication TEM image (Fig. 2a) showed that the nano-
mission Electron Microscopy (TEM). TEM sample was prepared by ion structured sample consists of grains with the size ranging from 20 to
polishing installation on the JEOL ION Slicer with the energy of Ar ions 200 nm. These post-sintering nanoscale features were attributed to
4 keV. X-ray diffraction (XRD) study of the nanostructured SiGe was car- the rapid heating rates achieved by DC pulsated current employed dur-
ried out at room temperature by a Difrey-401 X-ray diffractometer with ing SPS which considerably inhibited the grain growth [1517]. It is
Cr-K radiation ( = 2,2909 ). Energy dispersive X-ray spectroscopy seen from Fig. 2a that the grains have numerous twin defects. Moreover,
(EDS) was used to analyze contaminations of the powders by ball mill-
ing media and to determine chemical composition and homogeneity of
the sintered samples. Density of the samples was measured using a con-
ventional Archimedes principle. Thermal conductivity measurements
were carried out using a laser ash analysis system (Netzsch LFA 457)
from room temperature to 900 C. Specic heat measurements were
performed by a Netzsch differential scanning calorimeter (DSC 204
F1). Electrical conductivity and Seebeck coefcient were measured si-
multaneously on 1 3 12 mm3 bars using a homemade transport
measuring system (Cryotel Ltd.). The accuracy of these measurements
was checked against a silver sample of 99.99% purity.
Parameters of the mechanical alloying are presented in Table 1.
Grinding time was selected followed the results of our previous work

Table 1
Mechanical alloying parameters of p-type SiGe powders.

Powder Ball mill Ball-powder Speed, Bowl Contamination,


weight ratio rpm volume, ml % at.

(ser.1) Fritsch 5 30:1 350 500 2.5 (Fe)


0.6 (Cr)
(ser.2) Fritsch 5 20:1 350 500 0.7 (Fe)
Fig. 1. XRD patterns of powder (ser.2), SPS-sintered sample (ser.2)1150 and the same
(ser.3) Fritsch 7 20:1 700 45 0.3 (Zr)
sample after annealing at 1000 C for 48 h in vacuum.
A. Usenko et al. / Scripta Materialia 127 (2017) 6367 65

Fig. 2. (a) TEM image of spark plasma sintered p-type Si80Ge20 nanostructured alloy showing randomly oriented nanograins and EDS spectrum of a typical SiGe grain (Spectrum 1) and a
SiO2 nanoinclusion (Spectrum 2); (b) HRTEM image of a SiO2 nanoinclusion and its polycrystalline electron diffraction pattern.

nanoinclusions of SiO2 with the size ranging from 5 to 30 nm were Detailed study of some of those dark inclusions inside the SiGe ma-
found inside the SiGe grains. Similar SiO2 nodules were found in previ- trix showed no difference in the dark regions and in the background.
ous works [14,19]. Unlike the authors of the previous works, we found The observed nonuniformity of the contrast may be due to the segrega-
that the SiO2 nanoinclusions are actually crystalline, as can be seen tion of the dopant (boron). However, the EDS detector was not sensitive
from the high-resolution TEM (HRTEM) image and its polycrystalline enough to distinguish such low boron concentration.
electron diffraction pattern (Fig. 2b). Presence of the rings with inter- The bright eld scanning TEM (STEM) image coupled with the EDS
planar spacing close to those of Ge (marked by arrows in the lower analysis is shown in Fig. 3. The bright area on the STEM image corre-
inset in Fig. 2b) points to the existence of Ge-rich nanocrystals in the sponds to the region with a low average atomic number Z. The chemical
SiGe grains. The inhomogeneity in the element distributions is also evi- mapping indicates that this area is oxygen-rich and Ge-poor. This im-
dent from the EDS spectra analysis (Fig. 3). plies that comparatively large areas of SiO2 exist in the main matrix. It

Fig. 3. STEM image of a SiO2 grain inside the main matrix of the spark plasma sintered (ser.2)1100 sample (a) and EDS mapping of Si (b), Ge (c), and O (d) corresponding to the host image (a).
66 A. Usenko et al. / Scripta Materialia 127 (2017) 6367

is clearly seen from the image that the large SiO2 region is inhomoge- carriers to the total thermal conductivity due to the bipolar effect [2].
neous and contains Ge-rich inclusions randomly distributed in the The fact that this contribution overcomes a decrease of the lattice ther-
SiO2 phase. On the basis of collected low magnication STEM data, vol- mal conductivity with increasing temperature presumably means that
ume fraction of the SiO2 phase can be estimated to be below 2% (vol.). the lattice component of the thermal conductivity is small in such nano-
Despite the fact that the large silica particles are rather rare, they can in- structured materials.
uence transport properties of the nanostructured material. It can be Thermoelectric materials are usually very highly doped and/or de-
suggested that the large SiO2 regions are formed during mechanical generate semiconductors. However, their electrical properties are
alloying because the argon atmosphere does not provide the complete sometimes closer to those of metals than semiconductors. That is why
protection and some oxygen may get into the vials. Speaking about electrical conductivity of SiGe can decrease with increasing tempera-
the SiO2 nanosized inclusions inside the SiGe matrix, they could be in- ture, as is shown in Fig. 4b. It is also seen from Fig. 2b that the electrical
troduced via internal oxidation during the SPS process due to the conductivity of the studied nanostructured samples is sometimes signif-
presence of soluted oxygen in the SiGe powder. Indeed, it has been icantly lower than in the bulk crystalline SiGe RTG sample. There were
demonstrated previously that the vacancy agglomerated Si crystals several possible reasons for this. First, the volume density of some sam-
could be lled by the silica phase with actual size from 100 to 150 nm ples was small as presented in Table 2. Concurrently, the presence of the
via internal oxidation during annealing at temperatures higher than SiO2 oxide phase on grain boundaries of the main matrix and inside the
1100 C for a few hours [31]. We suppose therefore that the internal ox- SiGe grains (Figs. 2, 3) could also signicantly inuence the electrical
idation of the same nature took place in the nanostructured SiGe alloys conductivity. Finally, contaminations from the milling media introduced
during SPS process followed by annealing at 1000 C. into the SiGe samples during mechanical alloying can also affect the
As compared to the radioisotope thermoelectric generator (RTG) electrical transport by adding minority n-type carriers. Theoretical cal-
sample, a signicant decrease of the thermal conductivity is attained culations showed that the electron mean free path in Si80Ge20 is of
in our samples (Fig. 4a). The drop of the thermal conductivity down to about 5 to 10 nm [32,33], while the grain size in our samples ranges
b2.5 W m1 K1 is mainly due to a decrease in the lattice thermal con- from 10 to 200 nm. Thus, it can be suggested that the nanostructuring
ductivity. According to the XRD data and microscopy study (Figs. 1, 2), affects the electrical conductivity to a lesser extent than the thermal
the mean grain size is in the range from 20 to 200 nm. It means that conductivity.
our nanostructured materials are able to scatter phonons with different Fig. 3c shows temperature dependencies of the Seebeck coefcient.
wavelength. A slight upturn in the thermal conductivity seen at T N 700 Except the (ser.3)1050 sample, Seebeck coefcient in the studied
C can be explained as caused by a growing contribution of the charge samples increases almost linearly with temperature up to 800 C. The

Fig. 4. Temperature dependence of thermoelectric properties of nanostructured p-type SiGe and the reference RTG sample (solid line) [17]: (a) thermal conductivity, (b) electrical
conductivity, (c) Seebeck coefcient and (d) calculated ZT.
A. Usenko et al. / Scripta Materialia 127 (2017) 6367 67

fact that the temperature dependence of Seebeck coefcient in the References


(ser.3)1050 sample is quite different from that seen in the rest samples
[1] M.S. Dresselhaus, G. Chen, M.Y. Tang, R.G. Yang, H. Lee, D.Z. Wang, Z.F. Ren, NASA
could be explained by the absence of the complete SiGe solid solution in Rep. (2005).
this sample. It has to be noted in this context that such a high Seebeck [2] A. Minnich, M. Dresselhaus, Z. Ren, G. Chen, Energy Environ. Sci. 2 (5) (2009)
coefcient as in the (ser.3)1050 sample is typical for pure silicon. As 466479.
[3] A. Kikuchi, N. Okinaka, T. Akiyama, Scr. Mater. 63 (2010) 407410.
compared to the RTG reference sample, Seebeck coefcient of the [4] M.G. Kang, K.H. Cho, J.S. Kim, S. Nahm, S.J. Yoon, C.Y. Kang, Acta Mater. 73 (2014)
sintered samples is larger by about 2030% in the high temperature 251258.
range. This result can be explained by the energy ltering effect, previ- [5] A.P. Novitskii, A.I. Voronin, A.A. Usenko, M.V. Gorshenkov, V.V. Khovaylo, L.V.
Shvanskaya, A.T. Burkov, A.N. Vasiliev, J. Electron. Mater. 45 (2016) 17051710.
ously demonstrated for InGaAs/InGaAlAs superlattice [34], bulk nano- [6] T. Mori, T. Nishimura, J. Solid State, Chemistry 179 (2006) 29082915.
structured PbTe-based materials [35] and many other nanostructured [7] M.A. Hossain, I. Tanaka, T. Tanaka, A.U. Khan, T. Mori, J. Phys, Chem. Solids 87 (2015)
compounds. The chemical composition inhomogeneity detected by 221227.
[8] D.M. Rowe, Thermoelectr. Handb. Macro to Nano, CRC Press, Boka Raton, FL, 2006.
the EDS analysis (Fig. 3) also inuenced Seebeck coefcient. The role
[9] K. Romanjek, S. Vesin, L. Aixala, T. Bafe, G. Bernard-Granger, J. Dufourcq, J. Electron.
of Ge-rich nanoinclusions can be described by so-called modulation Mater. 44 (2015) 21922202.
doping effect. By using the modulation doping concept, the ionized im- [10] A. Vargas-Almeida, M.A. Olivares-Robles, F.M. Lavielle, Entropy 17 (2015)
purity scattering rate can be decreased, leading to increased carrier mo- 73847405.
[11] G.J. Snyder, Appl. Phys. Lett. 84 (2004) 24362438.
bility and a larger power factor [36,37]. We expected that further [12] L. Chen, J. Lee, Appl. Energy 150 (2015) 138149.
improvement of the power factor of SiGe materials would be possible [13] G.S. Nolas, J. Sharp, H.J. Goldsmid, Thermoelectrics: Basic Principles and New Mate-
via the conceptual hybrid effect theory demonstrated for higher boride rials Developments, Marlow Industries, Dallas, 2010.
[14] G. Bernard-Granger, K. Favier, M. Soulier, C. Navone, M. Boidot, B. Deniau, P.
composites [38]. Grondin, J. Leforestier, J. Simon, Scr. Mater. 93 (2014) 4043.
Fig. 4d shows ZT as a function of temperature for the studied nano- [15] A.A. Usenko, D.O. Moskovskikh, M.V. Gorshenkov, A.V. Korotitskiy, S.D. Kaloshkin,
structured samples and the bulk crystalline RTG reference sample. For A.I. Voronin, V.V. Khovaylo, Scr. Mater. 96 (2015) 912.
[16] X.W. Wang, H. Lee, Y.C. Lan, G.H. Zhu, G. Joshi, D.Z. Wang, J. Yang, A.J. Muto, M.Y.
each series of the samples, it is clearly seen that ZT correlates with the Tang, J. Klatsky, S. Song, M.S. Dresselhaus, G. Chen, Z.F. Ren, Appl. Phys. Lett. 93
sintering temperature, i.e., the higher the sintering temperature, the larg- (2008), 193121.
er ZT. It is also obvious that the ser.2 is the most promising due to the [17] Z. Zamanipour, X. Shi, A.M. Dehkordi, J.S. Krasinski, D. Vashaee, Phys. Status Solidi A
209 (2012) 20492058.
highest volume density and a low contamination from the milling media.
[18] G. Joshi, H. Lee, Y. Lan, X. Wang, G. Zhu, D. Wang, R.W. Gould, D.C. Cuff, M.Y. Tang,
The signicant enhancement of ZT value is mainly attributed to the M.S. Dresselhaus, G. Chen, Z. Ren, Nano Lett. 8 (2008) 46704674.
thermal conductivity reduction and enhancement of the Seebeck coef- [19] N. Petermann, N. Stein, G. Schierning, R. Theissmann, B. Stoib, M.S. Brandt, C. Hecht,
C. Schulz, H. Wiggers, J. Phys. D. Appl. Phys. 44 (2011) 174034.
cient. High electrical conductivity which is also a necessary condition for
[20] L.P. Bulat, I.A. Drabkin, V.B. Osvenskii, Y.N. Parkhomenko, D.A. Pshenay-Severin, A.I.
attaining high ZT value, was achieved in the p-type SiGe sample sintered Sorokin, A.A. Igonina, V.T. Bublik, M.G. Lavrentev, J. Electron. Mater. 44 (2015)
at 1150 C. The largest value of ZT = 0.72 was achieved for the 18461850.
(ser.2)1150 sample at 800 C. A long term annealing and thermal cy- [21] A.U. Khan, N.V. Vlachos, E. Hatzikraniotis, G.S. Polymeris, C.B. Lioutas, E.C. Stefanaki,
K.M. Paraskevopoulos, I. Giapintzakis, T. Kyratsi, Acta Mater. 77 (2014) 4353.
cling in the high temperature range determined thermal stability of [22] S.V. Faleev, F. Lonard, Phys. Rev. B 77 (2008) 214304.
the sintered samples. The results of the thermal cycling were similar [23] A.T. Burkov, S.V. Novikov, V.V. Khovaylo, J. Schumann, J. Alloys, Compounds 691
to those previously reported for n-type SiGe [15]. We found that the (2017) 8994.
[24] D.K. Ko, Y. Kang, C.B. Murray, Nano Lett. 11 (2011) 28412844.
role of sintering temperature is very important in the case of a rapid [25] S. Chen, Z. Ren, Mater. Today 16 (2013) 387395.
sintering process with a short soaking time. It was demonstrated that [26] J. Wang, X. Ye, X. Yaer, B. Zhang, W. Ma, L. Miao, Scr. Mater. 99 (2015) 2528.
the solid solution formation was incomplete after mechanical alloying [27] D. Narducci, S. Frabboni, X. Zianni, J. Mater, Chem. C 3 (2015) 1217612185.
[28] T. Zhang, S. Wu, J. Xu, R. Zheng, G. Cheng, Nano Energy 13 (2015) 433441.
and sintering process but subsequent annealing at 1000 C for 48 h [29] M.E. Levinshtein, S.L. Rumyantsev, M. Shur, Properties of Advanced Semiconductor
was sufcient to complete the solid solution formation. Thus, the use Materials: GaN, AlN, InN, BN, SiC, SiGe, John Wiley & Sons, 2001.
of short milling time and the rapid sintering followed by the thermal [30] E.V. Shelekhov, T.A. Sviridova, Met. Sci. Heat Treat. 42 (2000) 309313.
[31] G. Kissinger, G. Morgenstern, J. Vanhellemont, D. Grf, U. Lambert, H. Richter, Appl.
treatment can be recommended for the large-scale manufacturing of Phys. Lett. 72 (1998) 223225.
the p-type SiGe alloys. We demonstrated the presence of randomly ori- [32] M. Lundstrom, Meas. Sci. Technol. 13 (2002) 230.
ented SiO2 nodules in the SiGe matrix, which could be an efcient [33] J. Singh, Physics of Semiconductors and Their Heterostructures, McGraw-Hill, New
York, 1993.
source of phonon scattering. Probably, the low oxygen concentration
[34] J.M.O. Zide, D. Vashaee, Z.X. Bian, G. Zeng, J.E. Bowers, A. Shakouri, A.C. Gossard,
in SiGe material can positively inuence the thermoelectric properties Phys. Rev. B 74 (2006) 205335.
until nanosized SiO2 nodules are growing inside the SiGe grains rather [35] J.P. Heremans, C.M. Thrush, D.T. Morelli, J. Appl. Phys. 98 (2005) 063703.
than on their boundaries. [36] B. Yu, M. Zebarjadi, H. Wang, K. Lukas, H. Wang, D. Wang, C. Opeil, M. Dresselhaus,
G. Chen, Z. Ren, Nano Lett. 12 (2012) 20772082.
The authors gratefully acknowledge the nancial support of the [37] M. Zebarjadi, G. Joshi, G. Zhu, B. Yu, A. Minnich, Y. Lan, X. Wang, M. Dresselhaus, Z.
Ministry of Education and Science of the Russian Federation in the Ren, G. Chen, Nano Lett. 11 (2011) 22252230.
framework of Increase Competitiveness Program of NUST MISiS. [38] T. Mori, T. Hara, Scr. Mater. 111 (2016) 4448.

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