J Mater Sci (2022) 57:18178–18194

Innovation
I N N O V A T I O N Iin
N MMaterials
A T E R I A L S P RProcessing
OCESSING

Development of a self-consistent thermodynamic

database for Ga-In-Te system and experimental
validation: a potential system for thermoelectric
application
Varinder Pal1, Bhupendra Kumar2, Joonphil Choi3, Banty Kumar1, Chandra S. Tiwary1,*,
Manas Paliwal1,*, and Min-Kyu Paek4,*

1
Department of Metallurgical and Materials Engineering, Indian Institute of Technology Kharagpur, Kharagpur, India
2
Research and Development, Tata Steel, Jamshedpur, Jharkhand, India
3
Department of 3D Printing, Korean Institute of Machinery and Materials, Daejeon, South Korea
4
Research Institute of Industrial Science and Technology, RIST, Pohang, South Korea

Received: 6 April 2022 ABSTRACT

Accepted: 22 August 2022 The Ga-In-Te alloy is one of the promising thermoelectric materials and its
Published online: eutectic compositions can be expected to show improved thermoelectric
19 September 2022 behavior. In order to find the possible eutectic compositions in the ternary
system, the thermodynamic modeling approach was considered based on the
Ó The Author(s), under Computer Coupling of Phase Diagrams and Thermochemistry (CALPHAD)
exclusive licence to Springer technique. Thermodynamic optimization and critical evaluation of the ternary
Science+Business Media, LLC, Ga-In-Te system with the sub-binaries were performed using modified quasi-
part of Springer Nature 2022 chemical model (MQM) for the liquid solution and compound energy formalism
(CEF) for the solid solutions, respectively. By integrating the optimized sub-
binaries, thermodynamic properties and phase diagram information in the
ternary Ga-In-Te system were successfully reproduced. The asymmetric ternary
interpolation method was applied to evaluate the Gibbs free energy of the
ternary liquid solution. There were two line compounds of Ga2Te3-In2Te3 as a
complete mutual solubility and InTe with limited solubility of Ga in the ternary
system. The accuracy of the developed database was verified by comparing the
measured phase transition temperatures with predicted phase diagrams and the
microstructural analysis data with equilibrium cooling calculations.

Handling Editor: M. Grant Norton.

Varinder Pal and Bhupendra Kumar equally contributed to this work.

Address correspondence to E-mail: Chandra.tiwary@metal.iitkgp.ac.in; manas.paliwal@metal.iitkgp.ac.in;

minkyupaek@rist.re.kr

https://doi.org/10.1007/s10853-022-07699-3
J Mater Sci (2022) 57:18178–18194 18179

Introduction enhanced phonon scattering [9]. Similarly, Bi2Te3-

In2Te3 eutectic structure reported increased phonon
scattering due to eutectic microstructure that
In the past decade, the tellurides have emerged as an enhanced thermoelectric properties [10]. Although
attractive candidate in designing new materials for various studies reported thermoelectric compositions
optoelectronics, thermoelectric superconductors, in the binary Ga-Te and In-Te systems[7, 9], very little
electrochemical, and electro-catalysts applications. work has been done in the Ga-In-Te ternary system
Among these, the thermoelectric application is of related to the effects of compositions and
wide interest to researchers as it offers a sustainable microstructures on thermoelectric properties. Con-
and cost-effective energy conversion mechanism sidering the fact that eutectic microstructures can
from waste heat to electricity [1]. Various waste heat increase the thermoelectric performance of the
recovery methods are being explored to decrease the material by enhancing the phonon scattering, new
carbon footprint generated by conventional energy eutectic alloy compositions in the Ga-In-Te system
sources [2]. The direct conversion of one form of are investigated in this study. Accordingly, a self-
energy to another can take place in various ways. consistent thermodynamic database for the Ga-In-Te
Thermoelectric being one of them is defined as the system is developed using Computer Coupling of
direct conversion of thermal energy to electrical Phase Diagrams and Thermochemistry (CALPHAD)
energy, which can be used for waste heat recovery technique. The developed database for this ternary
and refrigeration technologies. Thermoelectric per- system is validated by correlating the microstructural
formance of a material is defined by the figure of features of the as-cast alloy with the thermodynamic
merit, zT which is directly proportional to the See- calculations. In addition, thermal analysis of the as-
back coefficient and inversely to the thermal con- cast alloys is also performed, and the phase transition
ductivity of the material [3]. Seeback coefficient is an experimental data is compared with the calculation
intrinsic property of material [3]. One of the best results. Therefore, new eutectic alloy compositions in
ways to improve the figure of merit of a material is by the Ga-In-Te system can be designed using the study
reducing its thermal conductivity. Thermal conduc- that can be expected to exhibit enhanced thermo-
tivity has both electronic and lattice contributions. An electric properties.
electronic contribution is intrinsic to the material Thermodynamic optimization of the In-Te, Ga-In,
whereas thermal conductivity can be reduced by and Ga-In-Te systems is performed in the present
varying lattice thermal conductivity. Phonon scat- study. Our recent modelling result [11] of the Ga-Te
tering is the key mechanism responsible for the system was directly adopted in this study. It is
reduction of lattice thermal conductivity [4]. This observed that liquid solutions in the Ga-Te and In-Te
scattering is enhanced by solid solutions, point systems show strong negative mixing enthalpies,
defects, phonon interactions, grain boundaries, whereas the Ga-In system exhibits positive mixing
alloying, etc. [4, 5]. As the phonon scattering can be enthalpy. Such asymmetric property can be explicitly
tuned using microstructure (eutectic microstructure, described by the Toop-like interpolation method [12]
grain boundaries, etc.), determining the relationship using modified quasichemical model (MQM) [13, 14].
between microstructural features, material composi- Therefore, in order to develop a consistent set of
tions and processing conditions is crucial. database, the same model was used for the descrip-
In2Te3 has a cubic structure (space group: F-43 m tion of liquid Gibbs free energy. The model consis-
(216)) with regular ordered vacancies [6]. Pei et al. tency will be also crucial for the extension of database
has reported reduced lattice thermal conductivity in with Bi- and Sn-containing systems [11, 15]. The
solid solution of In2Te3 and InSb [7]. In2Te3 nano- Gibbs free energies of solid solutions were described
wires developed by thermal chemical vapor deposi- using the compound energy formalism (CEF) [16].
tion show high zT value at room temperature [8]. Among the binary systems, only one solid solution of
In2Te3 has been studied extensively for use in solar the body-centered tetragonal (BCT) phase was
cell detectors due to its good optical and electronic defined in Ga-In system. In the ternary system, two
properties. A low thermal conductivity in Ga2Te3 is line compound phases, GaTe-InTe, and In2Te3-Ga2-
obtained by nano-structuring as well as vacancy Te3 were considered based on our verification
distribution in the microstructure resulted in experiments. Three compositions of ternary alloys
18180 J Mater Sci (2022) 57:18178–18194

   
were chosen, which lie in the GaTe-InTe and Ga2Te3- 1 1 2nii 1 2nij
In2Te3 quasi-binary sections. Microstructure and ¼ þ i ð6Þ
Zi Ziii 2nii þ nij Zij 2nii þ nij
thermal analysis of the as-cast alloys is carried out
using a combination of optical, scanning electron where Zii is the value Zi when all nearest-neighbor
microscopy (SEM), X-ray diffraction (XRD), and dif- atoms of atom i are atoms i, and Zij is the value of Zi
ferential scanning calorimetry (DSC). when all nearest neighbors are j atoms.
Considering all relations through Eq. 1–6, the DgAB
Thermodynamic models can be determined as a function of the pair fraction as
follows:
The thermodynamic properties of liquid solution X X 0j j
 i
were analyzed using the MQM which accounts for DgAB ¼ DgAB þ Dgi0
AB X AA þ DgAB XBB ð7Þ
the short-range ordering (SRO) in terms of the pair i1 j1

approximation as follows: 
where DgAB , Dgi0
0j
AB , and DgAB are the MQM parame-
ðA  A Þ þ ðB  B Þ ¼ 2ðA  B Þ; DgAB ð1Þ ters in the A–B binary liquid solution.
The CEF is used to describe the Gibbs energies of
where (i-j) represents the first-nearest neighbor
solid solution phases such as the BCT structure in the
(FNN) pair between components i and j. DgAB is the
Ga-In binary system and two line compound phases
Gibbs energy change of formation of two moles of (A
of GaTe-InTe and Ga2Te3-In2Te3 in the Ga-In-Te
B) pairs in a binary A-B liquid solution. The Gibbs
ternary system. In the CEF, a solid solution is mod-
energy of the liquid solution can be expressed by the
eled with proper consideration of sublattices [16]. The
following equation:
Gibbs free energy of two sublattice structure,
 
Gsol
L ¼ nA gA þ nB gB  TDS
config
þ ðnAB =2ÞDgAB ð2Þ ðA; BÞn ðC; DÞm can be expressed as:
0 00 0 00 0 00 0 00
where nA , nB; and nAB are the moles of A, B, and (A-B) Gsol
S ¼ yA yC GA:C þ yA yD GA:D þ yB yC GB:C þ yB yD GB:D
þ nRTðy0A ln y0A þ y0B ln y0B Þ þ mRT(y00C lny00C + y00D lny00D Þ
 
pair, respectively. gA and gB are the molar Gibbs
X X
energies of the pure A and B components, which + y0 y0 y00 L + y0 y00 y00 L
i;j;k i j k i;j:k i;j;k k i j k;i:j
were taken from Scientific Group Thermodata Eur-
ope (SGTE) database [17]. ð8Þ
0
DSconfig is the configurational entropy of mixing in where yi and y00i are the site fraction of species i in the
the MQM. As can be seen in Eq. 3, the random dis- corresponding sublattice. Gi:j is the Gibbs free energy
tribution of the (A-A), (B-B), and (A-B) pairs were of an end-member, the Li;j:k and Lk:i;j are the CEF
intrinsically considered based on the ideal entropy of parameters to be determined.
mixing term. FactSage thermochemical software [18] was used to
DSconfig ¼ RðnA lnXA þ nB lnXB Þ determine the model parameters. More detailed
! ! ! notations and correlation of equations in MQM and
XAA XBB XAB
 R nAA ln þ nBB ln þ nAB lnð Þ CEF can be found elsewhere [13, 14, 16]. The self-
Y2A Y2B 2YA YA consistent thermodynamic parameters from the pre-
ð3Þ sent optimization is given in Table 1.

where Xi is the mole fraction of i. Xij and Yi are the

pair fraction of (i  j) pairs and the coordination Materials and methods
equivalent fraction of i, respectively, and defined as
follows: All the metals (Ga, In, and Te) with up to 99% purity
nii were melted in a vacuum induction furnace in argon
Xii ¼ ð4Þ
ðnAA þ nBB þ nAB Þ atmosphere to obtain as-cast alloys. The melting
ZA nA process was performed by keeping the alloy in a
YA ¼ ¼ 1  YB ð5Þ quartz tube. The tube was evacuated in a high vac-
ZA nA þ ZB nB
uum (10–5 bar) followed by argon filing. In addition,
The composition dependent of coordination num- the temperature of melting was kept below 1173 K to
ber, Zi are given as follows: avoid the loss of Te. The target alloy compositions are
J Mater Sci (2022) 57:18178–18194 18181

Table 1 Optimized model parameters of the Ga-In-Te system (All values are in J/mol)

Liquid(a) (Ga, In, Te)

ZIn Ga Te In Ga In Te Ga Te
InIn = ZGaGa = ZTeTe = ZInGa = ZInGa = ZInTe = ZInTe = ZGaTe = 6; ZGaTe = 4;
DgGaIn = 1550 ? 0.5 T
DgInTe = 27000 þ 1:6T þ ð5040 þ 4:08T ÞXInIn þ ð490 þ 1:05T ÞX2InIn þ ð900  12T ÞXTeTe þ ð2500 þ 9TÞX2TeTe
g001
GaInðTeÞ ¼ 0

BCT(b) (Ga, In, Te)(Va)

GGaVa ¼ GSERGa
GInVa ¼ GSER
In
GTe:Va ¼ GSERTe
LGa;In:Va ¼ 9000
Stoichiometric compounds

In4Te3 GIn4 Te3 ¼ 4 GSER  SER
In þ 3 GTe  235500  18:8T

InTe GInTe ¼ GSER  SER
In þ GTe  71200 þ 2:3T

In2Te3 GIn2 Te3 ¼ 2 GIn þ 3 GSER
 SER
Te  190000  19:429T

In2Te5 GIn2 Te5 ¼ 2 GSER  SER
In þ 5 GTe  189300  30:787 T

GaInTe2 GGaInTe2 ¼ GSER  SER  SER
Ga þ GIn þ 2 GTe  152810ð500Þ  6:114T

Line compounds

(Ga,In)2(Te)3 GGa:Te ¼ GGa2 Te3

GIn:Te ¼ GIn2 Te3
L0Ga;In:Te ¼ 4500 þ 12T
L1Ga;In:Te ¼ 1000 - 7 T

(In,Ga)(Te) GInTe ¼ GInTe

GGaTe ¼ GGaTe ?50
L0Ga;In:Te ¼ 6000 þ 18T
L1Ga;In:Te ¼ 2000 þ 15T
a
Modified quasichemical model
b
Compound energy formalism

Table 2 Target alloy compositions and the measured data using SEM–EDS analysis (at%)

Alloy In Ga Te

Nominal compositions
IGT1 25 25 50
IGT2 20 20 60
IGT3 35 15 50
EDS analysis
IGT1 23.64 ± 1.55 26.36 ± 2.04 49.89 ± 2.5
IGT2 18.78 ± 2.17 23.74 ± 2.18 57.48 ± 1.43
IGT3 36 ± 1.5 14.7 ± 2 49.19 ± 1.3

mentioned in Table 2 along with the compositions Leica-DM2500M optical microscope along with SEM
measured using the EDS analysis at the 5X magnifi- Supra 40 equipped with EDS were used for the
cation of all the alloys. More than 20 area analysis microstructure and composition analysis of the
were performed to calculate the average composition. solidified alloys. XRD analysis was performed using
18182 J Mater Sci (2022) 57:18178–18194

Cu-Ka target in Bruker D8 Advance with Lynx 2D

detector. Thermal analysis was performed using a
NETZSCH STA 449 F3 Jupiter system. 20–30 mg of
the starting alloy was placed in Al2O3 crucible and
the analysis was carried out in DSC mode at heating
rate of 10 K/min. All the thermal analysis experi-
ments were done under the purified argon
atmosphere.

Results and discussion

In-Te system

The In-Te system was thermodynamically optimized Figure 1 Calculated phase diagram of In-Te system along with
experimental data and calculated by Oh and Lee [19].
by Oh and Lee [19] using the ionic solution model to
explain the SRO exhibited in the liquid solution.
phase is a superstructure of the b-form with a high
Klemm and Vogel [20] reported a phase diagram of
density of stacking faults. No clear evidence is
the In-Te system for the first time utilizing thermal
reported on stability temperature and composition
and qualitative X-Ray analysis and identified three
range of the disordered phase. Therefore, no phase
compounds In2Te, InTe, and In2Te3. Grochowski et al.
transition in ordered In2Te3 has been considered in
[21] reported four new intermetallic compounds
the present study. The calculated phase diagram is
(In9Te7, In3Te4, In3Te5, and In2Te5) based on DTA,
shown in Fig. 1 along with experimental data and the
metallographic, and XRD analysis along with two
calculated one by Oh and Lee [19].
previously reported intermetallic compounds (InTe
The measured enthalpy of formation of inter-
and In2Te3). Wobst [22] measured the miscibility gap
metallic compounds at 298.15 K is summarized in
of the liquid solution on the In-rich side using DTA.
Table 3 and plotted in Fig. 2 along with the experi-
Glazov and Pavlova [23] measured the liquidus curve
mental data [25, 28–34]. The present optimization
using thermal analysis. Said and Castanet [24]
corresponded very well with all compound phases.
determined the liquidus line using DTA and
However, Oh and Lee [19]’s prediction, shown as
Calorimetry measurements. Zlomanov et al. [25]
dashed line in the figure, has a deviation from the
studied the system to resolve the discrepancies about
experimental data because they considered the dif-
intermetallic compounds. They reported only four
ferent compound phases such as In9Te7, In3Te4, and
intermetallic compounds, In4Te3, InTe, In2Te3, and
In3Te5.
In2Te5 as stable compounds under standard condi-
The calculated mixing enthalpy is shown in
tions based on XRD and calorimetric analysis. The
Fig. 3(a) along with experimental data. The enthalpy
previously reported phases such as In2Te, In9Te7,
of mixing of liquid phase has been measured by
In3Te4, In3Te5, and In4Te7 [20, 21, 26] were not
Maekawa et al. [35] at 753, 843, and 998 K, and Lee
detected by their work. The intermetallic compounds
and Lee [36] at 976 and 891 K using high temperature
of In4Te3, InTe, In2Te3, and In2Te5 confirmed by
calorimetry. They reported the minimum of mixing
Zlomanov et al. [25] were considered in the present
enthalpy around 34–38 kJ/mole-atom at XTe = 0.6.
optimization. Zaslavskii and Sergeeva [27] have
Predel et al. [37] reported a much positive value of
reported two components of In2Te3 phase ordered a-
liquid -22 kJ/mole-atom at XTe = 0.51 using solution
In2Te3 and disordered b-In2Te3 using XRD data.
calorimetry at the temperature 1114 K. Said and
According to Zaslavskii and Sergeeva [27] a-In2Te3
Castanet [38] used the direct reaction calorimetry at
transform to b-In2Te3 at 893 K and is stable in very
987, 1123, and 1340 K. Their data shows the asym-
narrow temperature range. However, electron
metry at 987 K, and the minimum point gradually
microscope study shows two-ordered In2Te3 phase
shifted to near XTe = 0.5 at 1340 K. In order to
(In2Te3-I and In2Te3-II). The first ordered phase is a
reproduce the temperature dependence of symmetry
long period superlattice whereas the second ordered
J Mater Sci (2022) 57:18178–18194 18183

Table 3 Formation enthalpy

Sr. No f: Method Ref
of intermetallic compounds at DH298K (kJ/mole-atom)
298 K
InTe
1 – 48  7 Combustion calorimetry Hahn and Burov 1956 [28]
2 – 35.8  0.5 Solution calorimetry Robinson and Bever 1966 [29]
3 – 35.9 Solution calorimetry Jena et al. 1967 [30]
4 – 35.6  0.2 Bomb calorimetry Lavut et al. 1994 [31]
5 – 35.6  0.2 Synthesis calorimetry Zlomanov et al. [25]
6 – 35.6 Calculated Present study
a– In2Te3
1 – 39.6  2.6 Combustion calorimetry Hahn and Burov 1956 [28]
2 – 38.2  0.6 Solution calorimetry Robinson and Bever 1966 [29]
3 – 42.1  4.2 Synthesis calorimetry Sharifov et al. 1967 [32]
5 – 37.6  0.3 Bomb calorimetry Lavut et al. 1997 [33]
6 – 40 Calculated Present study
In4Te3
1 – 33.6  0.3 Synthesis calorimetry Lavut et al. [34]
2 – 33.6 Calculated Present study
In2Te5
1 – 27.4  0.2 Solution calorimetry Robinson and Bever 1966 [29]
2 – 25  0.4 Synthesis calorimetry Zlomanov et al. [25]
3 – 27.1 Calculated Present study

The activity of In and Te in liquid In-Te is deter-

mined using the EMF method by Naoi et al.[40] at
1073 K, Glazov et al. [41] at 860–1090 K, and Kameda
and Yamaguchi [42] at 1050 K, respectively. Predel
et al. [37] used vapor pressure method for Te activity
in liquid In-Te at 1114 K. The calculated activity at
900 K is shown in Fig. 3(b) along with experimental
data.

Ga-In system

The Ga-In system is a simple eutectic system with

limited In-rich solid solution and negligible In solu-
bility in Ga. The system has been studied well and
assessed critically by various authors [43–48]. Hayes
and Kubachewski [43] reviewed the available exper-
Figure 2 Calculated formation enthalpy of solid phase in In-Te
imental thermodynamic and phase diagram data.
system at 298.15 K along with experimental data [25, 28–34].
Rao and Tiller [44] computed solidus and liquidus
[39], Oh and Lee [19] used ionic model for the liquid curves using linear programming. Ansara et al. [45],
solution with high-order parameters and extremely Rugg and Chart [46], Anderson [47], Reddy and
large value of excess entropy term. On the other Hajra [48] assessed the system using available
hand, the present optimization put more weight on experimental liquidus, enthalpy of mixing, and
the symmetric enthalpy data measured at 1340 K by activity data. Reddy and Hajra [48] described the
considering the correlation with the ternary enthalpy liquid phase in this system using complex parameters
of mixing data as will be discussed in the Ga-In-Te for the Gibbs excess function. Numerous studies have
system. been performed to investigate the Ga-In phase dia-
gram [39, 43, 49–56]. Experimental eutectic
18184 J Mater Sci (2022) 57:18178–18194

Figure 3 Calculated a Enthalpy of mixing of liquid In-Te solution at 1300 K and 980 K, and b Activity at 900 K with respective
experimental data.

temperature (288.35–289.15 K) is under the general calculated activity is shown in Fig. 5b along with
agreement; however, there exists considerable scat- experimental data.
tering in eutectic composition (13.8–16.7 at%In).
Experimentally determined values of eutectic tem- Ga-Te system
perature and compositions are listed in Table 4. As
per the present optimization, the eutectic tempera- Irle et al. [68], Oh and Lee [69] and Liu et al. [70] have
ture and composition are 288.22 K and XIn = 0.16, optimized the Ga-Te binary system. Irle et al. [68]
respectively, which agree with the literature value as used the associate solution model with Ga2Te3 as an
discussed above. The calculated phase diagram in the associate component and obtained a reasonable
present study is shown in Fig. 4 along with experi- agreement with the measured mixing enthalpy
mental values and calculated one by Kulawik et al. [68, 71–73]. Oh and Lee [69] re-evaluated the system
[57]. using a two sub-lattice ionic model for the liquid
The enthalpy of mixing in liquid solution has been phase and considered experimental data that were
measured by Bros et al. [58] at 742 K, Bros at 423 K published after Irle et al. [68]’s work. Later, Liu et al.
[59], Ansara et al. [60] at 995 K, Predel and Stein [52] [70] considered the latest lattice stability parameter of
at 623 K, Girard et al. [61] at 990 K using calorimetry. Te and revised the phase diagram by slight modify-
Mechkovskii and Vecher [62] used thermal analysis ing model parameters. The Ga-Te binary system was
to measure the mixing enthalpy at 443 K. Recently, optimized in our previous study [11] using the MQM
Dominika and Piotr [63] measured the mixing for the liquid phase to keep the thermodynamic
enthalpy along with partial mixing enthalpy of In in consistency for the ternary extension. In addition, the
liquid using high-temperature drop calorimetry at heat capacity of the solid compounds (GaTe, Ga2Te3,
1123, 1273, and 1423 K. The mixing enthalpy of liquid and Ga2Te5) was redefined based on available
data are consistent and agree well with each other experimental data [74–76]. The calculated phase dia-
except Dominika and Piotr [63]. Dominika and Piotr gram along with experimental data [20, 22, 23, 77–79]
[63] reported temperature dependency of mixing and mixing enthalpy of liquid at 1123 K along with
enthalpy between 1123 and 1423 K; however, the rest experimental data [68, 71–73] are shown in Fig. 6a
of the studies do not show such temperature depen- and b, respectively.
dency. The calculated mixing enthalpy is shown in
Fig. 5a along experimental data. The activity in liquid Ga-In-Te system
solution has been measured by Macur et al. [64] using
Kuliev et al. [80] studied the GaTe-InTe section using
Knudsen effusion method, Bergman-Desnuelle [65]
DTA and XRD. Wooley et al. [81] studied Ga2Te3-
using mass spectrometry, Klinedinst et al. [66] and
In2Te3 using thermal and X-ray analysis. According
Pong and Donaghey [67] using the EMF method. The
J Mater Sci (2022) 57:18178–18194 18185

Table 4 Eutectic composition

and temperature XIn T (K) Method Ref

16.1 289.15 Thermograph shape French et al. [39]

16.1 288.85 Thermal analysis Denny et al. [49]
16.7 288.88 Electrical resistance Svirbely and Selis [50]
16.5 288.85 Thermal analysis Huebner and Wincierz [51]
12.5 289.05 Thermal analysis Predel and Stein [52]
14.2 288.95 Calculated Hayes and Kubaschewski [43]
13.8 288.40 Chemical analysis Zakharov [54]
14.2 288.90 Thermal analysis Shurai et al. [55]
13.5 288.35 Vibrational spectroscopy Topchyan et al. [56]

Table 5 Calculated Invariant reactions in Ga-In-Te system

No Invariant reactions Type Composition (at%) Temperature (K)

In Te Ga

1 L ? Ga4Te3 = GaTe ? (Ga,In)2(Te)3 Quasi-peritectic 0.05 0.57 0.38 1030.37

2 L ? GaTe = GaInTe2 ? (Ga,In)2(Te)3 Quasi-peritectic 0.28 0.54 0.18 912.19
3 L ? GaInTe2 = (In,Ga)Te ? (Ga,In)2(Te)3 Quasi -peritectic 0.29 0.54 0.17 907.31
4 L = L2 ? GaInTe2 ? GaTe Ternary monotectic 0.11 0.01 0.88 881.09
5 L = GaTe ? GaInTe2 ? L2 Ternary monotectic 0.33 0.4 0.27 881.09
6 L = GaInTe2 ? (In,Ga)Te ? L2 Ternary monotectic 0.37 0.4 0.23 868.19
7 L = L2 ? GaInTe2 ? (In,Ga)Te Ternary monotectic 0.13 0.01 0.86 868.09
8 L = L2 ? (In,Ga)Te ? In4Te3 Ternary montectic 0.7 0.28 0.02 709.82
9 L = L2 ? (In,Ga)Te ? In4Te3 Ternary montectic 0.86 0.04 0.1 709.82
10 L ? Ga2Te5 = Te ? (Ga,In)2Te3 Quasi-peritectic 0.008 0.898 0.094 693.77
11 L = (Ga,In)2(Te)3 ? Ga2Te5 ? Te Ternary Eutectic 0.094 0.848 0.058 683.2
12 L = In4Te3 ? GaInT2 ? (In,Ga)Te Ternary Eutectic 0.359 0.001 0.64 596.92

also reported similar observation in Ga2Te3-In2Te3

solid solution. Since Ga2Te3 and In2Te3 have the same
crystal structure (defect zinc blende cubic) with the
space group, F-43 m, it was considered as a complete
solid solution in face-centered cubic (FCC) based on
the previously reported study [81, 82]. However, the
crystal structure of the InTe compound (cubic, Fm-
3 m) is different from the GaTe compound (mono-
clinic, C12/m1(12)); thus, the InTe solid solution has
only limited solubility of Ga in the InTe-rich side of
the InTe-GaTe section. R. Blachnik and E. Klose [83]
determined mixing enthalpy in the Ga-In-Te ternary
system at 973, 1073, and 1173 K using heat flow
calorimeter.
Figure 4 Calculated phase diagram of Ga-In binary system along
The optimized thermodynamic parameter for Ga-
with experimental data and calculated one by Kulawik et al. [57].
In and In-Te binary system from the current study
was combined with the already optimized parame-
ters of Ga-Te binary system from our previous study
to Wooley et al. [81], Ga2Te3-In2Te3 is an isomor- [11] to predict the thermodynamic and phase dia-
phous system with complete solid solubility in the gram data in the Ga-In-Te system. ‘‘Toop-like’’
whole composition range. Yamanaka et al. [82] have asymmetric approximation [12] with Te as an
18186 J Mater Sci (2022) 57:18178–18194

Figure 5 Calculated a Mixing enthalpy of Ga-In liquid at 900 K and b Activity of In and Ga in liquid at 1223 K along with respective
experimental data.

Figure 6 Calculated a phase diagram of Ga-Te and b Mixing enthalpy of Ga-Te liquid at 1223 K [11].

asymmetric component was used as a first approxi- enthalpy along the section of Ga0.4In0.6-Te in the
mation of Gibbs free energy of the ternary liquid ternary Ga-In-Te system at 1173 K is shown in Fig. 7c
solution in the Ga-In-Te system. Figure 7a and b together with experimental data [83]. The calculated
shows the calculated pseudo binary sections of InTe- liquidus projection in the Ga-In-Te system is shown
GaTe and In2Te3-Ga2Te3, respectively, along with in Fig. 8 along with the compositions chosen for
experimental data [80, 81]. As shown in Fig. 7a and b, experimental investigation. In addition, the calcu-
the present calculation reproduces well the experi- lated four point intersections or invariant reactions in
mental phase diagram data [80, 81] and the transition the Ga-In-Te are tabulated in Table 5. There are three
temperatures measured in this study. It is noted that monotectic, two eutectic, and four quasi-peritectic
no additional ternary liquid parameter was used for reactions in this ternary system.
the ternary calculations. The calculated mixing
J Mater Sci (2022) 57:18178–18194 18187

Figure 7 Calculated vertical sections of a GaTe-InTe and b In2Te3—Ga2Te3 along with the liquidus and solidus of the investigated alloys,
and c Enthalpy of mixing for the section Ga0.4In0.6-Te at 1173 K along with respective experimental data.

Microstructural analysis Ga28In12Te60 and Ga2In2Te3, respectively. Both com-

positions can be resolved into a solid solutions of
The as-cast microstructure of three alloys investi- Ga2Te3 and In2Te3. The average composition of the
gated in the current study is shown in Fig. 9. As darker region was Ga0.3In0.7Te which corresponds to
shown in Fig. 9a, a bright phase along with the dark the composition of (In,Ga)(Te) with Ga solubility. As
acicular shaped phase was observed in the as-cast shown in Fig. 9e and f, only a single phase was
microstructure of IGT1 alloy. Figure 9b shows the observed in the optical and SEM images of IGT3
magnified image of the same microstructure for IGT1 sample. Although there are tiny visible pores in
alloy. The SEM–EDS analysis reveals the bright phase Fig. 9e, the microstructure exhibits homogenous
as the GaInTe2 compound, whereas the dark acicular composition throughout the sample as confirmed by
shaped phase is found to be the GaTe solid solution. the SEM–EDS point analysis. The average composi-
The as-cast microstructure of IGT2 alloy shows three tion for this phase is determined to be Ga0.3In0.7Te
regions with different contrast in Fig. 9c. Using the which corresponds to the (In,Ga)(Te) with the Ga
SEM–EDS analysis, the primary gray phase and solubility. The average phase compositions deter-
white region in Fig. 9d were characterized as mined using SEM–EDS analysis are shown in Table 6.
18188 J Mater Sci (2022) 57:18178–18194

at 946.48 K, which is indicative of the liquidus tem-

perature of this alloy. The DSC data for IGT1 alloy
also show an adjacent peak, which is suggestive of
the solidus temperatures. The liquidus and solidus
temperature determined from the equilibrium cool-
ing calculations (see Fig. 11b) are found to be 981.52
and 935.89 K, respectively. The phase transition
temperatures (liquidus and solidus) observed in IGT1
alloy are superimposed in the InTe-GaTe quasi-bi-
nary section in Fig. 7a along with the previous phase
diagram data. As seen, the liquidus temperature
determined in this work is lower than the data of
Kuliev et. al [80] who measured the phase transitions
along the whole composition range. Therefore, the
current calculations gave more consideration to
Kuliev’s data which caused the discrepancy between
the phase transition data of IGT1 alloy and thermo-
Figure 8 Calculated ternary liquidus projection in Ga-In-Te dynamic calculations. Nevertheless, equilibrium
ternary system along with compositions investigated. cooling calculations predict the as-cast phases to be
GaTe and GaInTe2 which are in agreement with the
XRD analysis of as-cast IGT1 alloy in Fig. 10 sug- SEM–EDS and the XRD results. The thermal analysis
gests the phases to be GaInTe2 (JCPDF-04-004-0400) data of IGT2 alloy indicates three endothermic peaks:
and GaTe (JCPDF-04-020-8025). The highest intensity peak 1, 2, and 3. Peak 1 at 975.37 K corresponds to the
peaks at 2h value of 29.92 and 33.54° matched with liquidus temperature, whereas the peritectic reaction
GaInTe2 with space group I4/mcm(140) while the between liquid, (In,Ga)(Te) and (Ga,In)2(Te)3 solid
monoclinic GaTe matched with relatively low inten- solutions is manifested as peak 2 at 955.15 K. Clearly,
sity peaks. XRD pattern for the IGT2 reveals the as- the peak temperature at 920.36 K is manifested as
cast microstructural phases to be Ga0.3In0.7Te (JCPDF- solidus temperature of this alloy. As shown in
04-005-3380), In2Te3 (JCPDF- 04–004-6552), and Ga2- Fig. 7b, the experimentally determined phase transi-
Te3 (JCPDF-01–079-2443) phases. In IGT2, there is tion temperatures (liquidus and solidus) of IGT2
slight right shift for Ga2Te3 peaks, which is consistent alloy are superimposed in the In2Te3-Ga2Te3 quasi-
throughout the pattern. Ga0.3In0.7Te is the (In,Ga)(Te) binary section along with the previous phase dia-
solid solution which is shown in Fig. 10. XRD pattern gram data of Wooley et al. [81]. The equilibrium
for IGT3 alloy suggests it be a single Ga0.3In0.7Te cooling calculations of IGT2 alloy (see Fig. 11c) sug-
phase (JCPDF-04-005-3380) with space group-I4/ gests the liquidus and solidus temperature to be
mcm (140). It is noted in all the three as-cast IGT 965.15 and 909.28 K which is in reasonable agreement
alloys, the phase identification using the XRD anal- with the thermal analysis data. Moreover, the equi-
ysis and the SEM–EDS analysis is consistent with librium cooling calculations predicts the as-cast
each other. phases in IGT2 alloys to be (Ga,In)2(Te)3 and
(In,Ga)(Te) solid solution, which is in good agree-
Thermal analysis ment with the SEM–EDS and XRD data. The DSC
data for IGT3 alloy shows only one endothermic peak
The thermal analysis data for the three as-cast alloys
at 961.33 K, which indicates either congruent melting
are summarized in Fig. 11a. In addition, the equilib-
of a phase or an extremely narrow two-phase region
rium cooling calculations from our database for the
(solid ? liquid phase). In the current work, the XRD
In-Ga-Te system are shown in Fig. 11b–d. As shown
and SEM–EDS analysis suggests this phase to be
in Fig. 11a, for the IGT1 alloy, the DSC data upon
Ga0.3In0.7Te. Due to the lack of experimental data, we
heating shows the peak transformation temperature
assumed Ga0.3In0.7Te to be a solid solution of InTe
J Mater Sci (2022) 57:18178–18194 18189

Figure 9 a Bright field optical microstructure of IGT1 at 200X, microstructure of the IGT2 and e Bright field optical
b SEM BSE mode image of the IGT1 at 388X, c Bright field microstructure of IGT3 at 200X, f SEM image of the IGT3 at
optical microstructure of as-cast IGT2 at 200X, d SEM BSE 748X.

Table 6 Compositions of the Ga-In-Te ternary alloys along with phases measured using SEM–EDS

Alloy Nominal alloy composition (at%) Composition of phase (at%) Phase

In Ga Te In Ga Te

IGT1 25 25 50 6.66 ± 4.5 43.07 ± 1.76 50.3 ± 2.62 GaTe

27.16 ± 1.38 22.05 ± 1.48 50.78 ± 2.35 GaInTe2
IGT2 20 20 60 35.87 ± 1.53 15.07 ± 0.896 49.1 ± 0.6 (Ga,In)(Te)
22.4 ± 0.14 20.65 ± 0.35 56.95 ± 0.5 (Ga,In)2(Te)3
15.72 ± 0.39 27.77 ± 0.64 56.6 ± 0.21
IGT3 35 15 50 35.27 ± 0.48 16.45 ± 0.56 48.27 ± 0.38 (In,Ga)(Te)

with limited Ga solubility. The solubility of Ga in the presence of a single phase in as-cast microstructure of
InTe phase is fixed to reproduce the liquidus of IGT3 IGT3 alloy. Hence, more equilibrium phase diagram
(see Fig. 7a). Therefore, the liquidus as per the equi- data is required along the InTe-GaTe section to fix the
librium calculation (943.71 K) shown in Fig. 11d solubility of Ga in InTe phase. The comparison
matches well with the experimentally obtained value between the phase transitions obtained through DSC
(961.33 K). Moreover, equilibrium cooling also pre- data and the thermodynamic calculations is shown in
dicts the formation of GaInTe2 phase. In addition, the Table 7.
SEM–EDS and the XRD analyses suggest the
18190 J Mater Sci (2022) 57:18178–18194

Conclusion

In the current work, we performed the critical eval-

uation and thermodynamic optimization of In-Te,
Ga-In, and Ga-In-Te systems have been performed to
design eutectic alloys for thermoelectric application.
The liquid solution was optimized using modified
quasichemical model. Two ternary solid solutions of
(Ga,In)2(Te)3 and (In,Ga)(Te) were suggested for the
first time and optimized using compound energy
formalism. The newly developed database repro-
duces the phase diagram and thermodynamic prop-
erties reported in the literature of the ternary Ga-In-
Te system within a reasonable error range. The
thermal analysis of investigated alloys is in agree-
Figure 10 XRD patterns for the as-cast IGT1, IGT2, and IGT3
ment with the phase transitions predicted using
using Cu-Ka target.

Figure 11 a DSC curves for the IGT1, IGT2, and IGT3, and equilibrium cooling curves for b IGT1, c IGT2, and d IGT3.
J Mater Sci (2022) 57:18178–18194 18191

Table 7 Comparison of the

thermodynamic and DSC data Thermodynamic calculations DSC results
of the investigated alloys. = Alloys Solidus (K) Liquidus (K) Peaks Tonset (K) TPeak (K) Toffset (K)

IGT1 935.89 981.52 – 926.63 946.48 957.27

IGT2 909.28 965.15 Peak 1 963.41 975.37 984.1
Peak 2 948.11 955.15 963.41
Peak 3 917.08 920.36 924.1
IGT3 933.93 943.71 – 954.05 961.33 963.69

equilibrium cooling calculations. In addition, the as- Mater Res Bull 112:61–65. https://doi.org/10.1016/j.materre
cast microstructural features of investigated alloys in sbull.2018.12.006
the Ga-In-Te system could be explained successfully [9] Kurosaki K, Matsumoto H, Charoenphakdee A et al (2008)
from the equilibrium cooling calculation using the Unexpectedly low thermal conductivity in natural nanos-
current thermal analysis data and literature values. tructured bulk Ga2Te3. Appl Phys Lett 93:012101. https://d
oi.org/10.1063/1.2940591
Declarations [10] Liu D, Drebler C, Seyring M et al (2018) Reduced thermal
conductivity of Bi-In-Te thermoelectric alloys in a eutectic
Conflict of interest The authors declare that they
lamellar structure. J Alloys Compd 748:730–736. https://doi.
have no conflict of interest.
org/10.1016/j.jallcom.2018.03.201
[11] Kumar B, Tiwary CS, Paek M-K, Paliwal M (2021) Ther-
modynamic modelling of the ternary Bi-Ga-Te system for
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