Accepted Manuscript

Crystallization kinetics of Sn doped Ge20Te80−xSnx (0 ≤ x ≤ 4) chalcogenide glassy

alloys

Brian Jeevan Fernandes, N. Naresh, K. Ramesh, Kishore Sridharan, N.K.

Udayashankar
PII: S0925-8388(17)32057-1
DOI: 10.1016/j.jallcom.2017.06.070
Reference: JALCOM 42138

To appear in: Journal of Alloys and Compounds

Received Date: 13 December 2016

Revised Date: 26 May 2017
Accepted Date: 5 June 2017

Please cite this article as: B.J. Fernandes, N. Naresh, K. Ramesh, K. Sridharan, N.K. Udayashankar,
Crystallization kinetics of Sn doped Ge20Te80−xSnx (0 ≤ x ≤ 4) chalcogenide glassy alloys, Journal of
Alloys and Compounds (2017), doi: 10.1016/j.jallcom.2017.06.070.

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 ACCEPTED MANUSCRIPT

Crystallization kinetics of Sn doped Ge20Te80-xSnx (0 ≤ x ≤ 4) chalcogenide glassy alloys

Brian Jeevan Fernandes 1, N. Naresh 2, K. Ramesh 2, Kishore Sridharan*, 1 and N. K. Udayashankar *, 1

1
Department of Physics, National Institute of Technology Karnataka, Surathkal, P.O. Srinivasanagar,

Mangaluru, 575025, India

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2
Department of Physics, Indian Institute of Science, C. V. Raman Avenue, Bengaluru 560012, India

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Highlights

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Ge20Te80-xSnx (0 ≤ x ≤ 4) glasses are synthesized through melt quenching technique.

DSC thermograms obtained under non-isothermal conditions are analyzed and discussed.

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Various thermal parameters are calculated based on the variation of Sn content.
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Thermal stability and glass forming ability decrease with increase in Sn content.

Easy devitrifiability of the glasses is useful for phase-change memory applications.

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*
Corresponding authors
Email: kishore@nitk.edu.in, sridharankishore@gmail.com (Kishore Sridharan) and
nkuday_01@yahoo.com (N. K. Udayashankar)

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Abstract

Chalcogenide semiconductors have evolved as multifunctional materials due to their fascinating thermal,

optical, electrical and mechanical properties. In this report, Ge20Te80-xSnx (0 ≤ x ≤ 4) glassy alloys are

systematically studied in order to understand the effect of variation of Sn content on the thermal

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parameters such as glass transition  , onset crystallization  , peak crystallization 
, melting

temperature  , activation energy of glass transition  , and crystallization  . The values of 

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are calculated from the variation of  with the heating rate  , according to Kissinger and Moynihan

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model, while the values of  are calculated from the variation of 
with the heating rate  , according

to Kissinger, Takhor, Augis-Bennett and Ozawa model. Thermal stability and glass forming ability

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(GFA) are discussed for understanding the applicability of the synthesized materials in phase change
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memory (PCM) applications. Thermal parameters are correlated with the electrical switching studies to

get an insight into the phase change mechanism. The results of the calculated thermal parameters reveal
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that the GFA of the synthesized Ge20Te80-xSnx (0 ≤ x ≤ 4) glassy alloys has a synchronous relationship

with their thermal properties studied through differential scanning calorimetry, indicating their potential
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for phase-change memory device applications.

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Keywords: Differential scanning calorimetry, Activation energy, Thermal stability, Crystallization,

Glass forming ability

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1. Introduction

Chalcogenide glasses have received a great deal of attention from a fundamental as well as technological

perspective since their discovery [1-9]. Many of the applications involving chalcogenide glasses require

control over their crystallization, as most promising properties of chalcogenides have been found to

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deteriorate drastically during crystallization. Therefore, understanding the crystallization and its kinetics

is an important aspect [10-14]. Although tellurium (Te) based chalcogenide glasses have been reported to

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exhibit tremendous potential for electrical switching device applications [15-23], fundamental studies are

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still required to understand the thermal stability of different alloy compositions. Various techniques such

as electrical resistivity, X-ray diffraction, electron microscopy and differential scanning calorimetry

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(DSC) have been adopted so far to understand the crystallization of chalcogenide glassy alloys [8].
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However, out of all the above techniques, DSC analysis is found to be the most powerful tool designed to

obtain information about glass structure and its properties over a wide range of length scale and
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applications. DSC can be performed either in isothermal or non-isothermal mode to study the

crystallization kinetics of a material. In isothermal mode, the sample is brought near the crystallization
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temperature very quickly and the changes in the physical quantities are measured as a function of time. In
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case of non-isothermal mode, the sample is heated at a fixed rate and physical parameters are recorded as

a function of temperature. However, DSC measurements in the non-isothermal mode are usually
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preferred, since it is impossible to ensure homogeneous furnace temperature during the injection of the

sample in the isothermal mode [12, 24-26].

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The parameters of crystallization kinetics of a material are generally recorded at the onset

temperature  , temperature  , and

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crystallization glass transition peak crystallization

temperature 
. Molecular motions and the rearrangement of the atoms in the glassy alloys occurring

around the critical transition temperatures reveal its activation energy [27, 28]. Based on the Johnson-

Moynihan-Avarami (JMA) model, several statistical approximations have been deduced to evaluate the

activation energy. The activation energies of chalcogenide glasses at the critical temperatures can be

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illustrated from parameters such as, glass transition activation energy  , onset crystallization

activation energy  and peak crystallization activation energy 

[29-31]. Thermal stability and

glass forming ability (GFA) of a compound describe its relative ability to adopt an amorphous structure.

The GFA criterion ∆ =  −  , also called the thermal stability parameter, was first introduced by

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Dietzel [32], which was later improved by Saad and Poulin (‘S parameter’) [33]. On the other hand,

Hruby developed the GFA criterion  to describe the thermal stability as well as the glass forming

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ability of amorphous materials [34]. These parameters are very useful in understanding the applicability

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of the prepared materials in the field of PCM, optical recording and optical fiber communication.

We herein report the thermal properties of as-synthesized Ge20Te80-xSnx (0 ≤ x ≤ 4) glassy alloys

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through DSC studies. The effect of the addition of Sn (Tin) to the base glass having a composition
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Ge20Te80 on the thermal stability, crystallization behavior and GFA is investigated. Furthermore, a

correlation between the thermal parameters and the previously reported electrical parameters is
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established to validate the results for further understanding of the applications of Ge20Te80-xSnx (0 ≤ x ≤ 4)

glassy alloys in PCM devices [19].

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2. Experimental

2.1. Sample Preparation

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Bulk ternary chalcogenide compounds of composition Ge20Te80-xSnx (0 ≤ x ≤ 4) were prepared by well-

established melt quenching method. Appropriate amounts of Ge, Te, and Sn were weighed accurately and
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transferred to flattened quartz ampoules. The ampoules containing the starting materials were evacuated
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to a pressure of ~10-5 Torr and sealed under vacuum using an oxyacetylene flame burner. The sealed

ampoules were loaded into an indigenously fabricated electric furnace (Indfurr, India) and heated to 1273

K at a heating rate of 100 Kh-1, for a period of 24 h. A continuous rotation of 10 rpm was applied to

ensure homogeneity of the melt. The ampoules were subsequently quenched in an ice water bath mixed

with NaCl. The ampoules were then carefully broken to retrieve the bulk chalcogenide pieces. The

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amorphous nature of the quenched samples was confirmed through X-Ray diffraction using Miniflex 600-

Benchtop XRD (Rigaku, Japan) (Fig. S1, supplementary content). DSC experiments were carried out

using a DSC 8000 Instrument (Perkin Elmer, USA). The samples had mass in the range of 10-20 mg, and

the experiments to record the thermal parameters  ,  and  were performed in the temperature range

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of 323-673 K at a scan rate of 10 Kmin-1. The changes in the specific heat and enthalpy were estimated

and their interdependence was studied as a function of glass composition. Perkin Elmer PyrisTM is a

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compatible software that was employed for calculating parameters like ∆
and ∆ . Surface morphology

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and composition of the prepared and annealed samples were analyzed using a JEM 6380AL model high

resolution scanning electron microscope (JEOL, Japan) equipped with an energy dispersive X-ray

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spectrometer (EDS). To avoid the charging effect during SEM analysis, gold was sputtered onto the
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surface of the samples.
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3. Results and Discussions

3.1. DSC studies – Composition dependence of thermal parameters

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The dependence of the composition on the thermal parameters provides important information regarding
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the crystallization kinetics of the Ge20Te80-xSnx (0 ≤ x ≤ 4) chalcogenide glasses under study and their

suitability for phase-change mechanism. DSC thermograms recorded at a heating rate of 10 K min-1 for
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Ge20Te80-xSnx (0 ≤ x ≤ 4) chalcogenide compounds are shown in Fig. S2 (supplementary content). The

total heat flow curve of one representative Ge20Te78Sn2 glass sample is shown in Fig. 1. First peak
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(endothermic peak) in Fig. 1a denoted as a circle (expanded in Fig. 1b) indicates glass transition
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temperature   representing the glassy nature of the prepared material. Further, the sharp peak

(exothermic peak) appearing at 500 K in Fig. 1a indicates the crystallization  , and the peak appearing

at about 660 K is the characteristic melting temperature  . The variation of characteristic

temperatures,  ,  and  for the studied Ge20Te80-xSnx (0 ≤ x ≤ 4) glasses is tabulated in Table 1.

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Table 1: Characteristic temperatures and specific heat measurements of Ge-Te-Sn Chalcogenides at a

heating rate of 10 Kmin-1.

Glass Glass Onset Crystallization Specific

Sample Transition Melting Crystallization Peak Heat
      

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∆Cp (J/g K)
Ge20Te80 401.24 661.08 487.02 515.8 0.278
Ge20Te79Sn1 415.04 668.31 487.07 502.67 0.238

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Ge20Te78Sn2 414.62 661.26 482.82 503.89 0.286
Ge20Te77Sn3 410.99 659.62 476.8 494.19 0.234

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Ge20Te76Sn4 408.78 644.09 474.3 490.14 0.344

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As observed from the thermograms, single  accompanied by a single  indicates that the prepared
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glasses are homogeneous.  is a very important thermal parameter which is indicative of the connectivity

of the glassy network [35]. The rise in the value of  with the introduction of Sn to the base matrix
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(Ge20Te80) can be attributed to the relatively hard metallic or semi-metallic character of Sn with hydrogen
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like weak bonding in the alloy stoichiometry as reported previously in other chalcogenide glassy alloys

[36, 37]. As a consequence, we have observed rise in activation energies for Ge20Te80-xSnx in comparison
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to pristine Ge20Te80 base matrix. Furthermore, the addition of Sn attributes to the domination of

metallicity factor (more metallic in nature), leading to reduced amorphous network connectivity and
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rigidity [19], which results in the decline in the value of  for Ge20Te80-xSnx. On the other hand, we also

observe a similar trend of decrease in the values of 

and  in Sn doped Ge20Te80 glassy alloys. Lower
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values of  is indicative of the existence of weak homoploar and heteropolar bonds in glassy
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configuration. The observed sharp and continuous crystallization process reported herein for Ge-Te-Sn

chalcogenide alloys exists between  and 

, owing to the continuous breaking of rigid heteropolar

bonds, causing generation of greater amount of heat energy in the specimen [24]. The variation in the 

with respect to the change in composition of Ge20Te80-xSnx (0 ≤ x ≤ 4) is shown in Fig. 2a. It can be seen

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that the  decreases moderately with an increase in Sn concentration, indicating the disruption of the

covalent bonds caused by the decrease in the chain length, owing to the addition of Sn in Ge-Te, resulting

in a reduced structure [38].

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<Fig. 1.>

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The specific heat capacity 
measured at  is an important parameter to characterize a given

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glassy material, since it represents the heat stored in molecular motions [39]. The change of state of a

glassy matrix from a viscous liquid to structurally arrested state is associated with  , wherein it is the

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temperature above which a glassy matrix will attain various structural configurations [25] . Hence, when
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the glass is heated in a DSC furnace, it must exhibit an increase in the specific heat 
value at  . A

change in the specific heat capacity during glass transition ∆

 suggests the occurrence of an extended
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stiffness transition. Liquids that show large changes in ∆

are fragile liquids and those which exhibit
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small changes in ∆
are strong liquids [40]. Based on the obtained values of ∆
listed in Table 1, it is
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clear that the addition of Sn to Ge-Te glasses produces ternary alloys obtained from strong liquids.

Similar results have been reported in the case of Sn doping to Se–Sb glasses, which confirms our
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discussions [25, 26].

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<Fig. 2>
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Generally, the crystallization kinetics of chalcogenide materials are described in terms of the activation

energies of amorphous and crystalline transformation [41]. The dependence of  on heating rate  has

been discussed on the basis of three approaches reported in literature [42-46]. The first empirical

relationship is of the form

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 =  +  1

where A and B are constants for a given glass composition. According to the equation, a useful

assignment of  can be obtained by extrapolating the heating rate to = 1 /"#, i.e.  = .

Additionally, the constant B reflects the rate dependence of configurational changes in super cooled

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liquids [47]. This dependence can provide information on the kinetics of the glass transition [48]. The

values of the constants A and B are obtained by fitting the experimental data to the least squares as shown

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in Fig. 2b. These values are listed in the Table 2.

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Table 2: Lasocka parameters (A and B), Fragility index and the glass transition activation energy

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determined using the Moynihan model and the Kissinger equation.

Activation Energy $  %&/'(

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Lasocka parameters
Fragility
Composition
A(K) Moynihan Model Kissinger Model index (F)
B
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Ge20Te80 371.73 12.59 131.86 123.73 16.10

Ge20Te79Sn1 385.53 12.59 127.21 118.43 14.90

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Ge20Te78Sn2 385.11 12.59 112.07 104.51 13.16

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Ge20Te77Sn3 381.48 12.59 112.07 104.51 13.28

Ge20Te76Sn4 379.27 12.59 108.01 95.94 12.25

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It is useful to compare the values of glass transition activation energy   determined using the
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different models. Evaluation of  using the theory of structural relaxation was first developed by
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Moynihan et al. [46, 49-55], from the heating rate dependence of glass transition temperature given as;


ln = − +  2
+

The plots of ln against 10. / are plotted for various compositions as shown in Fig. 3a and the

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slopes of these plots have been used to calculate the activation energy of glass transition (listed in Table

2).

On the other hand, the Kissinger formulation [45] is also used for the evaluation of the activation

energy for glass transition  . Despite the fact that Kissinger equation is basically used for the

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determination of activation energy in crystallization process, it has been shown that [56-59] the same

equation can be used for the evaluation of glass transition activation energy  , and can be written as;

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1 63
 02 5 = − 72 +  3
34 3

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 is calculated from the slope of the plot of  ⁄4  against 10. / shown in Fig. 3b. The glass

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transition activation energy ( reflects the endothermic energy of the material, which is produced due to
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the unsaturated or hydrogen like bond breaking at the pre crystallization critical temperature [60]. This

mentions that  is associated with the internal energy of the system arising from the relative positions
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and interactions of its parts, which can be changed by transfer of matter or heat or by doing work [10, 61].

From Table 2, it is observed that the activation energy of glass transition ( decreases with the increase
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in Sn content in the samples. Thermal devitrification studies reported herein (section 3.3) suggest that Sn

randomly replaces Ge due to its similar atomic radii and electro-negativity. Commotion of covalent bonds
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of Ge-Te network on further addition of Sn leads to the increase in internal energy of the system, thereby

channeling to the decrease in  values. Similar results on the decrease of  with the addition of metallic
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dopants validate our conclusion [5, 62-64]

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<Fig. 3.>

The fragility is calculated using the following relationship [65]

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:= 4
2.303+

According to Vigils [66], glass forming liquids exhibiting an approximate Arrhenius temperature

dependence of relaxation time are defined as strong liquids and are specified with a low value of (F

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≈16), while the limit for fragile glass-forming liquids is characterized by a high value of (F ≈ 200) [67].

The values of F for all samples have been listed in Table 2. Since the values of F are within the limit of

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16, it is reasonable to state that the prepared Ge20Te80-xSnx (0 ≤ x ≤ 4) glassy alloys are obtained from

strong glass-forming liquids.

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According to the Johnson-Mehl-Avarami (JMA) model, several methods can be used to

deduce  . The first method was suggested by Kissinger [45], and is based on the fact that the

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crystallization rate reaches its maximum value at the peak temperature of crystallization 
. According
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to this approach, the variation of 
with the heating rate  is given by,

 = > = − +  5
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4 +

The second approach is the one which was developed by Takhor [68] by monitoring the variation of
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with respect to heating rate  , and can be written in the form
TE

 = − +  6
+

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The third approach to find the crystallization activation energies is Augis-Bennett [69] approximation

method as given in the following equation.

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 = > = − +  7

+

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Finally, the crystallization activation energies for the studied glasses were also deduced using the

equation, derived by Ozawa [70, 71] as shown below:


ln = − +  8
+

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This equation describes the variation of onset crystallization temperature  with the heating rate ( .

Depending on the equations 5-8, the data for glassy Ge20Te80-xSnx (0 ≤ x ≤ 4) alloys are fitted to linear

functions using the least square fitting function as shown in Fig. 4a-d, respectively, and the activation

energy of the samples are determined from the corresponding slopes as listed in Table 3.

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<Fig. 4.>

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Table 3: Calculated values of crystallization activation energies  using Kissinger, Takhor, Augis-

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Bennett, and Ozawa model.

Activation energy $ (kJ/mol)

Composition
Kissinger
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Takhor Augis-Bennett Ozawa
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Ge20Te80 118.73 127.39 128.62 134.49

Ge20Te79Sn1 117.37 132.38 116.68 149.09

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Ge20Te78Sn2 119.44 132.38 123.88 157.69

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Ge20Te77Sn3 117.35 118.96 114.02 144.02

Ge20Te76Sn4 95.56 110.74 106.61 144.02

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The activation energy for crystallization  is a measure of the potential for crystallization, as it
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indicates the rate of crystallization [72]. The observed values of  calculated through various theoretical

models differ slightly from each other owing to the different approximations used. For example, onset
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crystallization temperature ( ) has been used in Ozawa model where the crystallization just begins, while
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the other three models use peak crystallization temperature 

 at which 62% of crystallization is

complete [73]. However, the variation in the values of  confirms the validity of the studied models as a

means for evaluating  . As observed from Table 3, the activation energy of crystallization  is found

to decrease with respect to increase in Sn content. The decrease in  can be attributed to the decrease in

viscosity of the medium of the studied glasses, which aids crystallization and causes  and 
to occur at

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lower temperatures. The estimated values of  thus indicate why the atoms of the studied glasses require

less energy to switch from amorphous to crystalline form.

3.2. Thermal stability and Glass Forming Ability

The thermal stability ∆ =  −   and glass forming ability are two important parameters that

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determine the utility of chalcogenide alloys as recording materials, since phase change optical recording

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and erasing techniques are based on laser induced thermal amorphization and crystallization of

chalcogenide glasses. Therefore, the origin of thermal stability and glass forming ability is of great

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practical interest. As,  represents the strength or rigidity of a glassy structure, it offers valuable

information on its thermal stability. However, information on the glass forming ability cannot be obtained

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from  alone, owing to which the knowledge of crystallization temperature ( of a glassy material
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becomes essential. It has been reported that unstable glasses show onset crystallization temperature close

to that of the  [32]. Stability towards hot forming processes represents a balance between the need to
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deform the glass without affecting its amorphous nature. A higher value of ∆ indicates a delay in

nucleation process and as the rule of thumb suggests, a minimum value of ∆ of 100 K is needed to
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provide a sufficient temperature window for applications such as fiber drawing [74]. On the other hand,
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lower values of ∆ represent the ability of the glasses to devitrify easily, signifying the suitability of these

materials for PCM devices. The calculated values of ∆ for Ge20Te80-xSnX (0 ≤ x ≤ 4) samples listed in
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Table 4 indicate a consistent decrease with respect to increase in the atomic percentage of Sn, which
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reveals their easy devitrifiable nature suggesting their suitability for PCM applications. Saad and Poulin

[33] suggested another important parameter for thermal stability defined as,
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C = 
−   −  / 9

where 
is the peak crystallization temperature and the difference 
−  is related to the rate of

devitrification transformation of the glassy phases. The value of the S parameter listed in Table 4 shows a

decreasing trend, which is in agreement with the values of ∆ as seen in Fig. 5a.

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<Fig. 5.>

Furthermore, it has been reported that the enthalpy, ∆ , released during the crystallization

process of a glass is associated with its stability, i.e. glasses with the lowest value of ∆ will have a

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maximum value of ∆ [10, 63, 75, 76]. The value of ∆ during the crystallization process has been

estimated by measuring the area under the exothermic peak as,

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η
∆ = 10
"

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where η is an instrumental constant – found to be 1.12; A is the area under the crystallization peak and m

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is the mass of the sample. The obtained values of ∆ for Ge20Te80-xSnx (0 ≤ x ≤ 4) glasses listed in Table
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4 clearly illustrate an increase with increase in Sn content. The degree of disorder in the amorphous

structure is called as entropy ∆C , which can be deduced during the amorphous to crystalline phase
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transitions [77, 78]. Higher values of ∆C are an indicator of a stable glassy state as it possesses a huge

energy unstable atomic configuration. The entropy change during the crystallization process can be
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calculated as [79],
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∆
∆C = 11


As observed from Fig. 5b, the values of ∆ and ∆C exhibit a clearly decreasing trend with respect to the
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increase of Sn content in Ge20Te80-xSnx (0 ≤ x ≤ 4) glasses. From the estimated values of ∆ , ∆C, ∆ and
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S parameter listed in Table 4, it is clear that the thermal stability of Ge-Te-Sn decreases with increasing
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Sn content.

It is well known that thermal stability and glass forming ability (GFA) are related, but they are

independent properties for a given glass. GFA of a glassy alloy correlates to the ease by which the melt

can be cooled while avoiding crystal formation. However, efforts have been made to study and relate the

thermal stability and GFA of chalcogenide glasses with their composition due to their importance in

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determining the utility of chalcogenide alloys for certain applications. Nasciemento et al. suggested that

GFA is related to the rate of crystallization, wherein a high GFA is associated with a small crystallization

rate [80]. The first parameter introduced to estimate the GFA is the reduced glass transformation

temperature,  given as [81],  =  ⁄ , which varies between 0.3 and 0.85 for any glass former and

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is inversely related to the nucleation rate for a variety of materials [82]. Materials with  value larger

than ~ 0.7 feature low nucleation rates and can be quenched into a glassy state without crystallization,

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even during a slow cooling and hence they are called as easy glass formers [82]. On the other hand,

relatively low values of  feature higher nucleation rate, implying their poor glass formability. It should

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be noted that  values are too simplistic for exclusively describing the crystallization kinetics. As seen

from Table 4, the value of  for Ge20Te80-xSnx (0 ≤ x ≤ 4) glasses range from 0.33 to 0.36, which is

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almost constant and is in accordance with literature reports on chalcogenide glasses [25, 26, 28, 82].

Therefore, it can be understood that the values of  have a negligible effect on GFA among various
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compositions of the studied glasses. Hence, it is important to look for another parameter of the GFA that

effectively explains the crystallization kinetics at different compositions of Ge-Te-Sn. Hruby [34] has
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introduced a parameter,  which combines both nucleation and growth aspects of phase transformations
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and is given as,

 − 
 = 12
 − 
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where Tm is the melting temperature. The values of the Hruby number (Hr) obtained for different
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concentrations of Sn at a heating rate of 10 K/min are shown in Table 4. According to Hruby, the

difference ( −  ) is directly proportional to the GFA. The calculated values of  for all compositions
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of Ge-Te-Sn are found to decrease with increasing Sn content, as shown in the Table 4. From the

available data, it is understood that synthesized samples have moderate thermal stability. The orderly

variation in the thermal parameters such as thermal stability and GFA facilitates space to understand the

structural transformation in the studied Ge-Te-Sn chalcogenide glassy alloys. Structural and

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morphological investigations through X-ray diffraction (XRD) and scanning electron microscopy (SEM)

on these materials reported recently [19] clearly indicate a profound change in the structural

transformation with respect to increase in the atomic percentage of Sn. These systematic studies also

advocate how Sn interacts with the host matrix. In order to substantiate the results obtained from DSC

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thermograms, we further carried out thermal crystallization studies to explain the glass formability in the

fabricated Ge-Te-Sn glasses. To identify the crystallized phase, XRD studies were conducted on as-

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synthesized Ge20Te77Sn3 glassy phase and after annealing it at 500 K for 5 h as shown in Fig. 6. The

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diffraction patterns of thermally crystallized Ge20Te77Sn3 sample can be indexed to trigonal Te (JCPDS

card no. 01-089-4899) and hexagonal Ge-Te (JCPDS card no 01-078-3709) phases [83]. In general, when

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a third element is added to a binary glass, it can form its own structural unit in the system. If the newly

formed structural units interact with the parent glass matrix, there will be an increase in the network
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connectivity, owing to which the glass formation in the system will be enhanced. If the added impurity

does not interact with the host matrix, it forms a phase separated network of its own and remains in the
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parent glass matrix as a micro-inclusion [84]. Crystallization in a multicomponent melt is prevented either
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by a competition between the formation of several different types of crystalline structures (with different
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compositions), or simply due to the difficulty in rearranging many different types of atoms to form a

multicomponent crystal. Glass formation in the Ge-Te-Sn system mainly depends on the interaction of Sn
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with the host Ge-Te matrix.

Table 4. Listed values of thermal parameters: Enthalpy, Entropy, Thermal stability, Hruby parameter,
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reduced glass transition.

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Thermal Reduced
Enthalpy Entropy Thermal Hruby
Stability Glass
Sample Released Released Stability parameter
∆ EF
parameter Transition
F
∆Hc (J/g-K) ∆S(J/g-K)
S
Ge20Te80 -44.027 0.20 85.78 6.15 0.78 0.33
Ge20Te79Sn1 -43.293 0.20 71.67 2.70 0.52 0.35
Ge20Te78Sn2 -43.856 0.20 68.2 3.46 0.56 0.36

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Ge20Te77Sn3 -40.451 0.19 65.81 2.78 0.50 0.35

Ge20Te76Sn4 -39.242 0.19 65.52 2.53 0.52 0.36

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<Fig. 6.>

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The devitrification studies on Ge-Te-Sn samples herein give an understanding of the glass

formation which is limited to a narrow range of composition, i.e., 4% of Sn. XRD studies are not able to

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reveal the presence of Sn in Ge–Te matrix. The atomic radii of Ge (1.25 Å) and Sn (1.40 Å) are

comparable and also the electro-negativities of Ge (2.01) and Sn (1.96) are of the same order. Energy

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dispersive X-ray spectroscopy (EDS) studies were carried out to identify the presence of Sn in Ge-Te
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matrix and are shown in Fig. S3-S7 (supplementary content). Structural investigations on four folded

coordinated systems for other chalcogenide systems suggest the possibility of the random replacement of
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Ge by Sn, owing to their similar atomic radii, coordination and electro negativity. This clearly indicates

that Sn does not take active participation in the glassy network formation, owing to which the glass
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formability of Ge-Te-Sn system is restricted to a narrow range of 0 ≤ x ≤ 4 [19, 85, 86].

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3.3. Correlation between electrical switching and thermal properties

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Research focused on glass formation, crystallization and thermal stability of chalcogenide glasses helps in

identifying newer glasses with the potential to be used in phase change memory applications. Since  is
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an indicator of the glassy network connectivity, an increase in TH represents the increase in network
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connectivity. On the other hand, the addition of dopants decreases TH , which has been attributed to nano-

phase separation caused by the segregation of homo-polar bonds [43]. Further, TH is indicative of the

energy required for the phase change from amorphous to crystalline state during memory switching.

Based on a configurational free energy model, an empirical relation between the switching fields and

TH has been suggested in literature as [87],

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EJ4 = CL exp [CQ ∗ kTH − T⁄kT] 13

where EJ is the switching field, CL , and CQ are constants, T is the ambient temperature and k is the

Boltzmann constant. The results of EJ are directly proportional to the variation of TH and herein we notice

the decrease in TH with respect to the stepwise decrease in the switching voltage (VV ), which confirms the

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validity of this relation. In a glassy system, as the network gets more rigid, TW generally increases and

consequentially, VV is expected to increase. Thus the downward trend and the lower values of Tc result in

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the decrease of VV (see Fig. S8, supplementary content). The crystallization temperature and the

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activation energy EW for crystallization, which denote the energy barrier to overcome crystallization are

indicators of the ease of devitrification. As such, a relation between VT and EC for crystallization can be

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expected for memory switching samples. A clear correlation is noticed between the obtained results,

wherein we observe a decrease in the  ,  ,  and X2 [19]. Similar results have been observed in Ge-Te-
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Bi system [88]. Further, a low value of EW could also mean fast crystallization, leading to a good
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switching speed.
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4. Conclusion
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In conclusion, studies on the crystallization mechanisms of melt quenched Ge20Te80-xSnx (0 ≤ x ≤ 4)

chalcogenide glassy alloys were conducted using differential scanning calorimetry and  , , 
,  ,  ,
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 were evaluated. DSC thermograms show that each composition has a single  and single  value.

Various quantitative methods based on Johnson-Mehl-Avarami model were employed to evaluate the
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values of  and  , which are observed to be in close agreement with each other. ∆ and ∆ of the base
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Ge20Te80 glass are found to decrease with the addition of Sn. The glass forming ability of the Ge-Te

decreases with the increase of Sn, resulting in a narrow range of glass forming region. Furthermore, the

obtained thermal parameters of Ge-Te-Sn glasses indicate that the moderate thermal stability and easy

devitrifiability are favorable for phase-change memory device applications. A correlation has been

established with earlier reported electrical switching studies.

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Acknowledgements

The authors are thankful to the Department of Materials and Metallurgical Engineering, NITK Surathkal
for extending the SEM facility. K.S. thanks the Department of Science and Technology, Government of

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India for the DST INSPIRE Faculty award [DST/INSPIRE/04/2015/000001].

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Figures

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Fig. 1. (a) Total heat flow curve of a representative Ge20Te78Sn2 glass sample indicating characteristic
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temperatures such as glass transition temperature   , peak crystallization temperature 

 and melting

temperature  . The enlarged glass transition temperature region in (a) is expanded in (b).

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Fig. 2. Plots showing the (a) dependence of heating rate on the glass transition temperature  and (b)
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glass transition temperature  against  .
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Fig. 3. Plots exhibiting the variation of glass transition with respect to heating rate in Ge20Te80-xSnx (0 ≤ x

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≤ 4) chalcogenide glasses based on (a) Moynihan [ versus 1000⁄ ] and (b) Kissinger [ ⁄4 
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versus 1000⁄ ] models.
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Fig. 4. Plots of (a)  ⁄

4  versus 1000⁄
, (b)  versus 1000⁄
, (c)  ⁄
 versus 1000⁄

and (d)  versus 1000⁄ for Ge20Te80-xSnx (0 ≤ x ≤ 4) chalcogenide glasses corresponding to
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Kissinger, Takhor, Augis-Bennett and Ozawa models for calculation of the crystallization activation
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energy.
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Fig. 5. (a) Variation of thermal stability ∆ Z[ C of Ge20Te80-xSnx glasses with respect to increase in

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Sn content indicates a decreasing trend, signifies the easy devitrifiability of the synthesized glasses. (b)

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Variation of ∆ Z[ ∆C with respect to the composition showing a symmetric decreasing trend indicates
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the presence of disorder in the amorphous system.
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Fig. 6. Comparative XRD patterns of pristine and annealed Ge20Te77Sn3 chalcogenide sample.
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