Solid State Communications 129 (2004) 765768

www.elsevier.com/locate/ssc

Extended rigidity percolation and chemical thresholds in

Ge Te Pb glasses as revealed by MDSC
P. Zaheerudeen Sahebb, B.H. Sharmilaa, S. Asokana,*, K. Appaji Gowdab
a

Department of Instrumentation, Indian Institute of Science, Bangalore 560012, India

b
Department of Physics, Bangalore University, Bangalore 560056, India

Received 6 October 2003; received in revised form 27 November 2003; accepted 24 December 2003 by A.K. Sood

Abstract
Thermal analysis of Ge20Te802xPbx 2 # x # 8 glasses has been undertaken using modulated differential scanning
calorimetry (MDSC). The compositional dependence of thermal parameters is investigated. The crystallization temperatures
Tc estimated from the total heat flow show detectable changes at compositions x 4; 6.5 and 7.5. Further, the heat capacity
change at the glass transition temperature, measured from the reversible heat flow curve DCpR ; is found to exhibit a maximum
and an inflexion at compositions x 4 and 6.5 and minimum at x 7:5; respectively. Also, the relaxation enthalpy, estimated
from the area under the non-reversing heat flow curve DH NR ; exhibits similar features at the said compositions. From the
observed MDSC results, it has been proposed that the compositions x 4 and x 6:5 denote to the onset and completion of
rigidity percolation and x 7:5 corresponds to the chemical threshold of the system.
q 2004 Elsevier Ltd. All rights reserved.
PACS: 61.43.Fs; 64.70.Pf; 67.80.Gb; 65.40. g; 64.75. g; 72.80.Ng
Keywords: A. Disordered systems; D. Heat capacity; D. Thermodynamic properties

1. Introduction
The differential scanning calorimetry (DSC) is extensively used in studying the thermal events that occur when a
sample is subjected to a temperature regime. The recent
technique of modulated differential scanning calorimetry
(MDSC) uses the deconvolution procedure in which the
total heat flow is resolved into a component that tracks the
temperature modulation leading to the reversing heat flow
and the other which does not track the temperature
modulation giving rise to the non-reversing heat flow.
This information provides unique insights into the structure
of glassy materials [1].
Chalcogenide glasses are known to exhibit two network
topological thresholds namely, the rigidity percolation
* Corresponding author. Tel.: 91-80-3344411; fax: 91-803341683.
E-mail address: sasokan@isu.iisc.ernet.in (S. Asokan).
0038-1098/$ - see front matter q 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ssc.2003.12.043

threshold (RPT) and the chemical threshold (CT). The

former is indicative of a transformation from a floppy
polymeric glass to a rigid amorphous solid [2 8], whereas
the later corresponds to an ordered glass with only
heteropolar bonds [2 5,8]. DSC studies are routinely used
to identify the network topological thresholds in chalcogenide glasses.
The recent MDSC studies have revealed that the rigidity
percolation may span over a range of compositions/average
coordination numbers [9,10], contrary to the earlier understanding that the rigidity percolation is sharp occurring at a
definite composition (RPT). An extended rigidity percolation leads to an intermediate phase existing between the
floppy and the rigid phases. The presence of an intermediate
phase is however, not revealed in many investigations other
than MDSC.
The earlier electrical studies on Ge Te Pb glasses [11]
have revealed the signature of rigidity percolation, though
the occurrence of an intermediate phase has not been

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P. Zaheerudeen Saheb et al. / Solid State Communications 129 (2004) 765768

noticed. In the present work, MDSC measurements have

been carried out to explore the possibility of extended
topological thresholds in Ge20Te802xPbx glasses.

2. Experimental
Bulk Ge20Te802xPbx glasses 2 # x # 8 were prepared
by melt quenching technique. The samples were confirmed
for the amorphous nature by X-ray diffraction. MDSC
studies were undertaken using a TA Instruments MDSCe
(model 2910). The base line correction was done with an
empty pan and the calibration for enthalpy and temperature
was performed using high purity indium. The calibration for
specific heat was achieved with high purity sapphire. All
calibrations were conducted using the same experimental
parameters that were used for the samples. Samples of about
10 16 mg in weight were ground into a powder and were
subsequently transferred to an Al pan and sealed; an empty
pan was taken as a reference. The sample was initially
equilibrated at 30 8C for 2 min with the data storage
capability switched on. The MDSC experiments were
carried out with the heating rate maintained at 5 8C per
min, the modulation amplitude at ^1.00 8C and modulation
period of 60 s. The temperature evolution of the MDSC
signals was deconvoluted from the modulated heat flow into
the total heat flow, reversing heat flow and the non-reversing
heat flow.
The thermal parameters, namely the glass transition
temperature Tg and the crystallization temperature Tc
were estimated from the various MDSC curves; the change
in specific heat was established from the step transition
in the glass transition region from the reversing heat flow
DCpR ; the relaxation enthalpy was calculated by measuring
the area under the non-reversing heat flow curve DH NR :

3. Results and discussion

Fig. 1. Variation with composition/average coordination number of

(a) Crystallization temperature Tc obtained from total heat flow.
(b) Heat capacity jump during glass transition obtained from the
reversible heat flow DCpR : (c) Relaxation enthalpy obtained from
the non-reversing heat flow DH NR :

Fig. 1(a) shows the variation of crystallization temperature Tc of the Ge Te Pb glasses, obtained from the total
heat flow curve, with the composition/average coordination
number krl: Here, for the calculation of krl; the
coordination numbers of Ge and Te are taken to be 4 and
2, respectively. Based on the Kastners proposition that
metal impurities in chalcogenide glasses coordinate tetrahedrally [12], a coordination of 4 has been assumed for Pb.
However, there is no clear experimental evidence for the
actual coordination of Pb in Ge Te Pb glasses. Hence, the
average co-ordinations used here are only suggestive and it
may be more appropriate to use the actual compositions.
It can be seen from Fig. 1(a) that the crystallization
temperature of Ge20Te802xPbx glasses increases with
composition, exhibiting a maximum at x 4 krl 2:48:
The Tc decreases subsequently and a cusp is seen in Tc at

x 6:5 krl 2:53: Beyond this, there is a sharp decrease

in Tc which culminates in a minimum at x 7:5 krl
2:55:
In the recent study by Boolchand et al., [10,13,14] it has
been proposed that the rigidity percolation transition occurs
over a range of mean coordination numbers leading to three
distinct phases namely; floppy, intermediate and rigid. The
occurrence of extended rigidity percolation has been
observed in glasses such as Si Se [10], As Se [14] and
Ge Se [15]. Based on the present results, we propose that
the floppy rigid transition in Ge20Te802xPbx glasses occurs
over a range of average coordination numbers/composition
with the existence of an intermediate phase. Here, the
composition x 4 krl 2:48 corresponds to the onset and
x 6:5 krl 2:53 to the completion of rigidity percolation. The composition x 7:5 krl 2:55 at which a

P. Zaheerudeen Saheb et al. / Solid State Communications 129 (2004) 765768

pronounced minimum is seen in Tc is likely to correspond to

the chemical threshold of the system. The composition
dependence of Tc (at which the material devitrifies) can be
compared with the composition dependence of crystallization pressures PT : The earlier studies have revealed
that PT of many chalcogenide glasses exhibit a sharp
maximum at the rigidity percolation threshold and a
minimum at the chemical threshold [16], which are
consistent with the present observation.
Fig. 1(b) shows the variation of the change in specific
heat capacity during the glass transition, obtained from the
reversing heat flow curve DCpR as a function of
composition/average coordination number. It can be seen
from this figure that a maximum and an inflexion is seen in
DCpR at the onset and the completion of the rigidity
percolation. Further, a minimum is observed at the proposed
chemical threshold of the system.
The change in the specific heat DCp at the glass
transition is the manifestation of the configurational degrees
of freedom of the system characteristic of the liquid state
above the transition [17]. The motions available in the liquid
state, which are locked in below the glass transition are
exclusively configurational and DCp ; which reflects these, is
therefore known as the configurational heat capacity. An
ideal glass is expected to show only small configurational
changes as it is taken through the supercooled liquid
state. When a glass is heated along the transition region, the
liquid like configuration is regained which is registered as
a small change in DCp : Tatsumisago et al., [18] in the
studies on composition dependence of thermal properties of
Ge As Se glasses have interpreted that DCp values could
be related to the ease of glass formation. The smaller DCp is
a characteristic feature of a fragile glass, which has a greater
glass forming ability, whereas higher DCp corresponds to a
strong glass, which has a lesser glass-forming tendency. In
this context it is interesting to compare the composition
dependence of glass forming difficulty (GFD, which is
inverse of glass forming ability) of GexSe1002x glasses. The
GFD of these samples exhibits a minimum around the
rigidity percolation threshold and a maximum at the chemical threshold [5], which is consistent with our conclusion
that the maximum and minimum seen in DCpR is associated
with rigidity percolation and chemical threshold, respectively. It is interesting to note here that earlier studies on
GexSb5Se952x 12:5 # x # 35; GexSb10Se902x, 10 # x #
32:5 and Ge10AsxTe902x 15 # x # 50 glasses [19] have
revealed similar maxima and minima in DCp values at the
rigidity percolation and chemical threshold, respectively. It
is also suggested by Boolchand et al. [20] that a minimum in
DCp indicates the maximization of hetero-polar bonds
occurring near this composition (chemical threshold of the
system).
Enthalpy of relaxation measures the latent heat (configuration energy changes) between the glassy and liquid
states, and it vanishes (or leads to a minimum) when the
network is optimally constrained [21]. Fig. 1(c) shows the

767

compositional dependence of the relaxation enthalpy for

Ge20Te802xPbx glasses obtained from the non-reversing heat
flow curve DH NR ; during a heating scan. It can be seen that
DH NR shows two distinct maxima at x 4 and 6.5, similar
to the crystallization temperature, followed by a global
minimum at x 7:5: The minimum or vanishing of the
DH NR at x 7:5 is usually taken as an evidence for the
absence of network stress [22]; the global minimum seen in
DH NR also confirms that x 7:5 is the chemical threshold
for the present system.

4. Conclusion
Thermal analysis of Ge20Te802xPbx 2 # x # 8 glasses
has been undertaken using modulated differential scanning
calorimetry (MDSC). The crystallization temperatures Tc
estimated from the total heat flow show detectable changes
at compositions x 4; 6.5 and 7.5. Further, the heat
capacity change at the glass transition temperature,
measured from the reversible heat flow curve DCpR ;
exhibits a maximum and an inflexion at compositions x
4 and 6.5 and minimum at x 7:5; respectively. Also, the
relaxation enthalpy, estimated from the area under the nonreversing heat flow curve DH NR ; exhibits similar variations at the said compositions. Based on the present results,
it has been proposed that the composition x 4 and 6.5
denote to the onset and completion of rigidity percolation
and x 7:5 corresponds to the chemical threshold of the
system.

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