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Crystal structure and mechanical properties of


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Solid State Communications 207 (2015) 2125

Contents lists available at ScienceDirect

Solid State Communications


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

Crystal structure and mechanical properties of spark plasma sintered


Cu2Se: An efcient photovoltaic and thermoelectric material
Kriti Tyagi a, Bhasker Gahtori a, Sivaiah Bathula a,b, M. Jayasimhadri b, Sakshi Sharma a,
Niraj Kumar Singh a, D. Haranath a, A.K. Srivastava a, Ajay Dhar a,n
a
CSIR-Network of Institutes for Solar Energy, CSIR-National Physical Laboratory, Dr. K. S. Krishnan Road, New Delhi 110012, India
b
Department of Applied Physics, Delhi Technological University, Delhi, India

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

Article history: Copper selenide (Cu2Se) based materials are currently being investigated globally for efcient photo-
Received 13 December 2014 voltaic and thermoelectric (TE) device applications. Despite having enormous device potential its crystal
Received in revised form structure and mechanical properties are still not fully explored owing to its complex behavior.
23 December 2014
Stereographic projection is one of such useful tools to estimate the crystallography of the material
Accepted 5 February 2015
conclusively. In the current study, the crystal structure of and -phases of Cu2Se was determined by its
Communicated by T. Kimura
Available online 12 February 2015 stereographic projections in reciprocal space. Further, mechanical properties of Cu2Se are highly
important to avoid catastrophic failure and ensure longevity of the TE devices made out of these
Keywords: materials. Cu2Se exhibited the compressive strength of  45 MPa with  3% of plastic strain and a
A. Semiconductor
fracture toughness value of  2 70.02 MPam, the latter being signicantly higher than that of the
C. Scanning and transmission electron
other known TE materials. Finally, thermal shock resistance, which is one of the crucial parameters for
microscopy
D. Mechanical properties the stability and longevity of the device applications, was calculated to be  281 712 W m  1. Superior
D. Phase transitions mechanical properties coupled with highly reported thermoelectric behavior makes Cu2Se as a potential
candidate for green energy generation.
& 2015 Elsevier Ltd. All rights reserved.

1. Introduction all the available literature on Cu2Se unanimously conrms that the
high temperature phase exists as [3,9,10], while quandary still
The development of promising power generation methods that exists over the low temperature -phase of Cu2Se. Various groups
are eco-friendly in nature require special attention to meet the [2,3,9] have already reported different crystal structures for Cu2Se
global needs of large power usage [1]. The direct conversion of predicting that the low temperature phase is either monoclinic,
heat into electrical energy based on thermoelectric (TE) effect orthorhombic or tetragonal at room temperature (  25 1C). But
without moving parts in the device is an attractive alternative for still there are many debates unresolved over the crystal structure
power generation [2]. The performance of a thermoelectric device of Cu2Se. Hence, there is a need to address the existence of
depends on its gure-of-merit (ZT), a dimensionless quantity of the -phase in Cu2Se at low temperature with suitable supporting
material dened as ZT (2), where , , T and are Seebeck characterization techniques. Moreover, in the -phase of Cu2Se,
coefcient, electrical conductivity, temperature and thermal con- the surface migration of Cu ions as well as evaporation of
ductivity, respectively. The optimization of ZT clearly demands elemental Se limits the precise control over the nal composition.
high TE power and electrical conductivity but having low thermal Furthermore, it is desired to have complete crystallographic
conductivity values. It is known that these three physical quan- information of state-of-art TE materials prior to device fabrication
tities (, and T) of materials are correlated in such a way that the to ensure that these materials are strong enough to operate in the
optimization of one adversely affects the other. Among several temperature range 500600 K useful for automobiles. Conse-
other available TE materials, Cu2Se has been designated as one of quently, these materials have to withstand high internal thermal
the most promising materials for TE power generation, due to its stresses created due to rapid temperature cycling gradients of two
high ZT value [28] in spite of its complex crystal structure. ends of the same TE element. Many of the existing TE materials are
Further, it has been reported in literature that phase transition in strong enough in thermoelectric performance, but poor at their
Cu2Se occurs from monoclinic ()-cubic () at  413 K [2,9]. But, mechanical strength. Hence, the mechanical facets of these TE
materials are also to be addressed properly. Very few reports are
available on mechanical properties of other state-of-the art TE
n
Corresponding author. Tel.: 91 11 4560 9455x9456; fax: 91 11 4560 9310. materials, such as, n-type nanostructured SiGe alloys [11], Co4Sb12
E-mail address: adhar@nplindia.org (A. Dhar). [12], In0.1Co4Sb12 [12] and Bi2Te3 0.1 vol% SiC [13]. But for Cu2Se,

http://dx.doi.org/10.1016/j.ssc.2015.02.004
0038-1098/& 2015 Elsevier Ltd. All rights reserved.
22 K. Tyagi et al. / Solid State Communications 207 (2015) 2125

there is no comprehensive study available in the literature either


on stereographic microstructural interpretations of its crystal
structure or mechanical properties. Therefore, in the current study,
we report the crystal structure determination employing stereo-
graphic projections in reciprocal space for Cu2Se with respect to
temperature dependent - phase transformations. The current
study will surely be a guideline for other researchers in the
photovoltaic and thermoelectric elds to interpret the crystal-
lographic information for other novel TE materials. Additionally,
mechanical properties, such as, fracture toughness; thermal shock
resistance and compressive strength have also been investigated
in the context of TE device fabrication.

2. Experimental details

Cu2Se samples were synthesized by thorough grinding of Copper


(Cu, 99.99%, Alfa Aesar) and Selenium (Se, 99.99%, Alfa Aesar)
powders in respective chemical stoichiometric ratio in a glove box,
under a high-purity argon atmosphere and these powders were
subsequently pelletized and vacuum-sealed (10  5 Torr) in quartz
tubes. The sealed quartz ampoules were heat-treated at 1000 1C for
24 h, and then naturally cooled to room temperature. The powder
samples of Cu2Se were subsequently consolidated and sintered under
vacuum ( 4 Pa) using spark plasma sintering (SPS Syntex, 725)
technique at identical optimized process parameters of pressure
60 MPa and temperature 600 1C for 3 min (soaking time) at a heating
rate of 400 1C/min using graphite die and punches. Mechanical
properties such as fracture toughness measurements were carried
out employing the indentation-crack technique using Vickers micro- Fig. 1. X-ray diffraction pattern for (a) low temperature monoclinic () phase and
hardness tester (FM-e7) with a load of 4.9 N for 10 s of indentation (b) high temperature cubic () phase.
time. Also, compression tests at room temperature were performed as
per ASTM standard (ASTM: E9-09) with an aspect ratio of  2.5 under (space group: Fm3m, a5.787 ) are recalled from the litera-
uniaxial loading with a strain rate of 2  10  5 s  1 (INSTRON 4204). ture [15]. The stereographic projection along (010) for monoclinic
(-phase) crystal with space group C2/c has been displayed in Fig. 2.
The stereogram shows the presence of important planes in the
3. Results and discussion structure located with respect to the angular distances between the
two planes. It is important to mention that a section of 451 (as
3.1. Crystal structure determination by stereographic projections marked with a white dotted line) is sufcient to exhibit the entire
crystal symmetry of a given structure. Keeping this in view the
The microscopy results in conjunction with X-ray diffraction pat- repeatability of 451 section of the stereogram, a zone axes map has
terns clearly shown in Fig. 1(a,b). It is evident from the Fig. 1(a) - been plotted and the reciprocal space calculated diffraction patterns
transition takes place as the system loses its monoclinic structure and are appended with stereographic projection as shown in Fig. 3. In a
begins to behave as cubic after  413 K, which is supported by similar way stereographic projection along (010) for cubic (-phase)
disappearance of (090) peak in the XRD pattern Fig. 1(b). It has been crystal with space group Fm3m has been displayed in Fig. 4. Further,
reported in literature [3] that - phase transition is reversible in the stereogram of -phase (lattice constants: a5.787 ) has been
Cu2Se around 413 K. In the current study, we have observed that Cu2Se calculated and plotted for a 451 section along 010 zone axis of face
has a structural metamorphosis at about 400 (710) K. Moreover, it centered cubic lattice. Correspondingly the reciprocal space calcu-
could be noted that, this is a reversible phase transformation. There are lated diffraction patterns are appended with stereographic projection
several reports on different crystal structures of Cu2Se [9,14,15]. A as shown in Fig. 5. The idea of putting the important diffraction
review on literature pertaining to various crystalline phases delineates patterns of both and -phases together to realize about the
that presumably the composition and also the processing conditions important planes that are probably involved in thermally reversible
inuence the nal crystal symmetry of the product. A few crystalline transformations during cyclic low to high between these crystalline
phases, including the current investigation, are summarized in Table 1. structures. The structure of Cu2Se makes a reversible phase transfor-
However, it is to be noted that there exists no evidence about the mation around 413 K. Based on the understanding of crystal structure
formation of different crystalline phases and their phase transforma- employing stereographic interpretations and XRD experiments [2,3],
tions. Hence, we have employed stereographic interpretations in the nal structure is classied in terms of the sub-lattice of selenium,
reciprocal space to determine the structural transitions. for the reason that copper sub-lattice turns into a super-ionic state at
With these stereographic projections, the -phase (monoclinic) high temperature. However, the structure of copper in the low
and -phase (cubic) have been drawn to understand the important temperature regime has ever been considered to be random [2,3].
zone axes of two different crystal structures in reciprocal space. This
methodology has been opted to give an idea of movement of atoms 3.2. Mechanical properties
(crystallographic planes) during reversible transformation between
- and vice versa in case of Cu2Se. For this symmetry elements 3.2.1. Fracture toughness analysis
and lattice constants for -phase (space group: C2/c, lattice con- It is well known that, most of the research has been focused on
stants: a7.14 , b 12.39 , c27.33 , 94.401) and -phase thermal and electrical transport properties of Cu2Se, primarily
K. Tyagi et al. / Solid State Communications 207 (2015) 2125 23

Table 1
Lattice parameters and space groups of Cu2Se available in literature are compared to the current study.

Materials Phase Space group Unit cell details Reference

Cu2Se Monoclinic (low temperature) C2/c a 14.087 , b 20.481 , c 4.145 , 90.381 Murray et al. [14]
Cu2Se Cubic (high temperature) Fm 3m a 5.787 Milat et al. [15]
Cu2Se Monoclinic C2/c a 7.1379 , b 12.3823 , c 27.3904 , 94.3081 Gulay et al. [9]
Cu2Se Monoclinic C2/c a 7.14 , b 12.39 , c 27.33 , 94.401 This work

Fig. 2. Stereographic projection along 010 for a monoclinic crystal with space
group C2/c.
Fig. 5. Reciprocal space along different UVW for a face centered cubic crystal
structure.

aimed towards enhancing their thermoelectric performance and


efciencies of state-of-art novel TE materials [1,1619]. However,
their mechanical properties are equally important for the long term
reliability of TE modules, as these materials are known to be brittle
with low fracture toughness. Further, there is no comprehensive
report available for the mechanical properties of this material,
which is equally important, for the in-service application of TE
modules to avoid catastrophic failure. Hence, in the current study,
we report some of the mechanical properties of Cu2Se samples.
Fracture toughness (KIC) of TE materials is often estimated
using Vicker's indentation-Crack (VIF) technique as this method
was outlined by Antis et al. [20] for brittle solids for radial mean
crack systems, as described:
 1=2
E P
K IC 0:016  3=2 1
H l
Fig. 3. Reciprocal space along different UVW for a monoclinic crystal structure.

where P is the load in Newton's, a is the half-diagonal of Vicker's


indentation mark in meters, E is Young's modulus in GPa [21] and H
is Vickers hardness  0.43 GPa. As sintered Cu2Se samples exhibited
near theoretical density and these samples were indented with a
Vicker's diamond shaped indenter at a load of 4.9 N with a dwell
time of 10 s, enough to generate cracks without any spill out of
material, as shown in Fig. 6. Subsequently, the observed cracks were
in radial mean type cracks as it was reported for other brittle solids
[22]. Crack lengths were measured using eld emission scanning
electron microscope (FESEM) for estimating the fracture strength.
The radial mean crack length (c) on the material surface has been
measured to be 46 m after removal of indenter. The calculated
fracture toughness of Cu2Se alloy after spark plasma sintering (SPS)
was found to be  2.070.02 MPam by VIF method employing
Eq. (1). It has been reported that low temperature (o500 K)
operating applications of Bi2Te3 0.1 vol% SiC exhibited a fracture
toughness of 1.35 MPam [13]. Whereas Co4Sb12, and In0.1Co4Sb12 at
Fig. 4. Stereographic projection along 010 for a face centered cubic crystal structure high operating temperatures (4500 K) exhibited a fracture tough-
with space group Fm3m. ness of 0.8270.11, 0.4670.13 and 170.02 MPam, respectively
24 K. Tyagi et al. / Solid State Communications 207 (2015) 2125

Fig. 7. Stressstrain curve of bulk p-type Cu2Se tested under uniaxial compression
mode with a strain rate of 2  10  5 s  1.

3.2.3. Thermal shock resistance


Fig. 6. FESEM image of Vickers-indentation cracks developed at a load of 4.9 N, a is
the half-diagonal of indentation mark and c is the radial-median crack length. Many of the novel TE materials are sensitive to thermal shock in-
service TE devices applications [3840]. Thermal shock resistance
parameter can be dened as a sudden temperature change between
[12]. Recently, for nanostructured SiGe alloys a fracture toughness hot and cold ends of the TE device legs that can lead to failure due
value of 1.670.05 MPam has been reported by our group [11]. to internal mechanical stress induced by temperature gradients
However, these SiGe materials can be operated only at high [4143]. Moreover, structural reliability of TE modules become
(Z1173 K) temperature. In the current study, Cu2Se sample nds important and should possess high thermal shock resistance in
applications in the temperature range of 500600 K and most of the order to seize resistance to different kinds of thermal stresses under
automobile exhaust systems fall in this category. Further from the actual operating conditions [23,4446]. The thermal shock resis-
literature, it is to be noted that the ne grain size in nanostructured tance parameter (RT), is given by the expression [41],
alloys help to minimize the dislocation pile-up stresses resulting in
1 
improvement in fracture toughness [23,24]. Moreover, nanostruc- RT 2
E
tured materials containing low crystallite size is expected to enhance
the localized fracture processes [25], which generally occur during where is Poisson's ratio, is thermal conductivity and is the
crack extension [26,27]. On the other hand, the ne nanocrystallites coefcient of thermal expansion. The value of RT for Cu2Se has been
in nanostructured materials would certainly enhance the fracture calculated using Eq. (2) with experimentally determined values of
toughness [28] because during the steady state of crack initiation 0.045 GPa, 2.6 W/m K and [2], [47] and E [21] from the
[29,30], work done by an applied stress is considered to be dissipated literature. Thermal shock resistance of current Cu2Se sample was
as heat by specic rotational deformation, grain boundary sliding and found to be  281712 W m  1. This value a bit higher than the other
diffusion process [28,31,32]. Hence, the fracture toughness of Cu2Se state-of-art TE materials such as, PbTe alloy, which exhibited a value
could be improved by nanostructuring the Cu2Se sample. of 140 W m  1 [48]. This suggests that Cu2Se sample prepared in the
current study has a very high resistance to thermal shock without
compromising their thermoelectric performance. Also, the high value
3.2.2. Compressive strength analysis of RT is attributed to high compressive strength and thermal con-
Compressive strength test of as-sintered Cu2Se (-phase) has ductivities for Cu2Se sample. In general, many of the known TE
been conducted at room temperature (25 1C) under uniaxial com- materials represent high ZT due to their low thermal conductivities
pressive loading and a typical stressstrain curve is plotted as [4951]. But, for higher RT, the materials should have high thermal
shown in Fig. 7. Further, it has been observed that compressive conductivity to reduce sudden failure in practical applications. Hence,
strength of the p-type Cu2Se found to be 45 MPa with almost 3% of there is need to optimize these transport properties and RT to get
plastic strain, which is signicantly higher than other reported longer life periods for TE materials in device applications. Further,
values of nearly similar alloy composition [33]. Micro-hardness of substantial improvement in RT may be realized through better control
the bulk Cu2Se measured to be 0.43 GPa and these values are and understanding of the microstructure at high temperatures. Also,
comparable with the existing state-of-the art materials, such as temperature dependence of the mechanical properties of TE materials
Bi2Te3 and PbTe, which have the hardness values of 0.62 and has to be evaluated thoroughly since these materials are highly prone
0.23 GPa, respectively [34]. Also, it has been reported in literature to changes in their microstructure with change in temperature.
that high temperature -phase (cubic) of Cu2Se shows the super
plastic deformation behavior after - phase transition at 413 K,
which in turn resulted a lower (0.0325 GPa) values of compressive 4. Conclusions
strength [33]. However, higher compressive strength values asso-
ciating with moderate ductility of the Cu2Se assumes that this could In summary, we have successfully demonstrated the crystal struc-
be a reliable TE candidate material in the temperature range of ture determination for both and -phases of spark plasma sintered
500800 K, whereas this material also possesses highest ZT among Cu2Se in reciprocal space by stereographic projections. Further, fracture
all the available polycrystalline bulk TE materials [3]. It is also to be toughness of Cu2Se exhibited a value of  270.02 MPam, which is
noted that, strength and ductility of these alloys could also be signicantly higher than that of other existing thermoelectric materials
improved further by nanostructuring approach, where dislocation at similar operating temperature. Consequently, the compressive
pinning for slip movement and grain boundary strengthening result strength was found to be 45 MPa with 3% of plastic strain. Moreover,
the enhancement of compressive strength [3537]. thermal shock resistance of Cu2Se was found to be  281712 W m  1
K. Tyagi et al. / Solid State Communications 207 (2015) 2125 25

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