Journal of Non-Crystalline Solids 531 (2020) 119863

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Journal of Non-Crystalline Solids

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

Manifestation of intermediate phase in Cu doped Si-Te glasses T

a b c d b a,⁎
Diptoshi Roy , B. Tanujit , Jagannatha K. B , G. Sreevidya Varma , S. Asokan , Chandasree Das
a
Department of EEE, BMS College of Engineering, Bangalore, Karnataka 560019, India
b
Department of Instrumentation & Applied Physics, Indian Institute of Science, Bangalore, Karnataka 560012, India
c
Department of ECE, BMS Institute of Technology, Bangalore, Karnataka 560064, India
d
Department of Physics, Presidency University, Bangalore, Karnataka 560064, India

A R T I C LE I N FO A B S T R A C T

Keywords: Alternating differential scanning calorimetry (ADSC) analysis has been carried out on bulk Si15Te85-xCux
Chalcogenide glass (1 ≤ x ≤ 10) glasses to examine the thermal properties of the glassy samples in detail. The investigations on the
Boolchand intermediate phase compositional dependence of ΔHNR (non- reversing enthalpy) manifests a trough between the composition
Chemical threshold 2 ≤ x ≤ 6 which stands as the basis of the presence of Boolchand's Intermediate phase in that range.
Additionally, anomalous behavior has been observed at the compositional dependence of various thermal
parameters at x = 9, which stipulates the appearance of chemical threshold at the stated composition. Annealed
bulk samples have been exposed to XRD studies to discern the type of formed crystalline phases. The study has
reported the manifestation of Te, Si1Te2, Si2Te3, Cu3Te2 phases.

1. Introduction reversing heat flow rate (NHF)). The variation of various thermal
parameters with composition such as non-reversing enthalpy change
Chalcogenide glasses being amorphous in nature displays various (ΔHNR), change in specific heat (ΔCp) can be quantified simultaneously
fascinating properties of which some are sizably employed in photonic with enhanced sensitivity.
and electronic devices [1] and stands as a reason for the intense re- Chalcogenides have enticed appreciable attention because of its
search work on the amorphous glasses [2–6]. A considerable change potentiality in PCM application [7]. The PCM works on the basis of
can be incorporated in the structures of the amorphous material by electrical switching [8, 9] which is electro-thermal in nature. Accord-
extrinsic factors like light, heat, radiation of electron or the electric ingly the thermal attributes like glass formability, thermal stability etc.
field, because of the presence of metastable states. The change in the are salient for determining the glass for PCM application.
structure of the material appreciably affects its various thermal prop- Silicon telluride glasses have proved to be competent acoustic optic
erties like glass transition temperature (Tg), crystallization temperature material and are utilized as a memory type switching diode [2, 3].
(Tc) and its rate, optical constants, thermal and electrical conductivity, Incorporation of metal atoms impressively alters the connectivity, ri-
chemical activity, etc. Chalcogenides also manifests unusual deviations gidity and structure of the network which inevitably alters the electrical
in their physical properties at rigidity percolation threshold where the properties namely the switching behavior of the glass [10–12]. The
floppy polymeric glass percolates to rigid amorphous solid, and che- physical attributes of the glass are affected by the network rigidity and
mical threshold. Investigation of the variation of various properties of chemical composition [13]. Different metallic dopant in Si-Te glasses
chalcogenides with respect to the composition helps in identifying the exhibits various properties and hence its study has gained particular
network thresholds on these glasses. interest. In this paper the thermal analysis of various variables such as
The measurement of latent heats and transformation temperatures Tg, thermal stability (ΔT), ΔHNR, ΔCp, with respect to composition for
of diverse thermal transformations has been made easy by alternating the Cu doped Si-Te glasses has been presented.
or modulated Differential Scanning Calorimetry (ADSC or MDSC).
Through ADSC the total heat flow curve (THF) can be deconvoluted 2. Experimental approach
into two parts - one that trails the variation in temperature and hence is
familiar as reversing heat flow rate (RHF) and the other that is in- Bulk Si15Te85-xCux (1 ≤ x ≤ 10) glasses have been prepared by
dependent of the modulation in temperature (referred to as non- quenching the melt from high temperature. Integrant elements of high

⁎
Corresponding author.
E-mail address: [email protected] (C. Das).

https://doi.org/10.1016/j.jnoncrysol.2019.119863
Received 4 October 2019; Received in revised form 6 December 2019; Accepted 14 December 2019
0022-3093/ © 2019 Elsevier B.V. All rights reserved.
D. Roy, et al. Journal of Non-Crystalline Solids 531 (2020) 119863

purity have been taken in quartz ampoules which are evacuated and Si15Te75Cu10 show only two crystalline peaks.
sealed at 10−6 mbar. The horizontal rotary furnace houses the sealed In almost all the chalcogenide systems, it has been seen that the
ampoules and has been programmed to heat the ampoule up to 1100 0C coordination numbers of Si and Te follows the Mott's 8-N theory, where
at the rate of 100 0C/h. The ampoules have been kept in continuous N is the number of electrons in the valence shell. Accordingly in the
rotation in the furnace for 24 h to maintain the homogeneity of the melt present Si-Te-Cu system the coordination number of Si and Te is pre-
and have been eventually quenched in ice-water mixed with NaOH. To sumed to be 4 and 2 respectively. Hypothetically, it is difficult to design
perceive the amorphous nature of as-quenched bulk samples X-ray amorphous semiconductors because of the interatomic associations that
diffraction has been performed using a PANalytical X'Pert3 Powder X- are in turn accountable for short range orders. Authors on the basis of
ray diffractometer with CuKα radiation in the 2θ range from 10° to 80° RDF (Radial Atomic Distribution) studies propose that copper is tetra-
at a rate of 3°/min. hedrally coordinated in chalcogenide glasses. The analysis of the EXAFS
To effectuate thermal studies on Si15Te85-xCux (1 ≤ x ≤ 10) glasses, spectrum reveals the existence of four coordination numbers in copper
ADSC experiment using a Mettler Toledo 822e ADSC instrument has [18], a number which has been observed in the other systems of copper
been performed. The ADSC is graded for tau lag, temperature and heat such as CuFeS [19], Cu3AsS4 [19], and CuAsI [20]. For the current
flow using high purity indium. Two 40 ml aluminum pans are taken work, tetra coordinated copper has been presumed, gaining the re-
wherein one is kept empty and is considered as reference whereas the quisite electrons for the sp3 hybridation of certain tellurium atoms. The
other is sealed with samples of identical thickness. Thermal scans are rigidity percolation model also indicates that the coordination number
consummated in the temperature span of 40 °C to 300 °C at a 3 °C/min of Cu is 4 to explain the increasing glass forming ability [21]. Using
with 1 °C scan amplitude. A modulation period of 1 min is taken for coordination number of 4, 2, 4 for Si, Te and Cu respectively, the
ADSC scan. Argon with a flow rate of 75 ml/min is employed as the average coordination number (<r>) for a specific composition can be
purge gas. THF can be separated into two parts, the RHF and the NHF; deduced using the following formula:
RHF is analogous to the variations in thermodynamic specific heat on
r1Si(15) + r2Te(85 − x) + r3Cu(x)
heating whereas NHF corresponds to the kinetic processes and enthalpy r =
100 (1)
variations that accompanies the structuring in the glassy network [14].
Typical error in the measurement of thermal parameters in within ± 2 In case of Si15Te85-xCux (1 ≤ x ≤ 10) samples the probable bonds
°C. Errors are estimated using the method of standard deviation and the emerged in the system as per the bond energy consideration are Si-Te,
corresponding error bars are included in the figures. Si-Si, Te-Te, Te-Cu and Cu-Cu. The bond energies (D) in KJ/mol in
To discern the thermally crystallized phases that would have ap- decreasing order are D(Si-Te) = 429.2; D(Si-Si) = 310; D(Te-
peared in the as-prepared sample, the later has been kept in sealed Te) = 257.6 ± 4.1; D(Te-Cu) = 230.5 ± 14.6; D(Cu-Cu) = 201 [20].
ampoules and annealed at their respective crystallization temperature The illustration by Bicerano and Ovshinsky [21] on chemical bond
for two hours followed by the diffraction study. Experimental analysis approach explains the formation of structural lattice in chalcogenides.
like EXAFS structural approach, isotopic substitution in neutron dif- Thence, in a chalcogenide network the building of bonds follows the
fraction etc. have divulged that the metal impurities are primarily tri- order of declining bond energies before all the unoccupied valencies are
hedral coordinated in glassy selenides like Ag-As-Se [15], Ge-Se-In [16] filled. Additionally atoms tend to bind more emphatically with atoms of
whereas it has been seen to coordinate tetrahedrally in glassy tellurides dissimilar one rather than of the same type. In Si15Te85 glass, the Si
like Ag-Ge-Te [17]. being 4- fold coordinated pairs with Te atoms which is 2- fold co-
ordinated as the bond energy between Si-Te is highest and thus the
glassy network is embraced by the Si-Te links. After the formation of Si-
3. Results and discussion
Te bonds, the remaining Te atoms combine among themselves to form a
network. A crystallization study on Si20Te80 glasses [22] affirms this
The THF curve of the representative Si15Te85-xCux (1 ≤ x ≤ 10)
conjecture, where the formation of crystalline phases: Te and SiTe2 on
glasses showing the regions of Tg and Tc is shown in Fig. 1. The THF
thermal devitrification has been revealed. Furthermore, a modification
curves of Si15Te85-xCux where x is 2, 4, 6 display one endothermic glass
to the existing network can be expected by the addition of copper atoms
transition peak and three prominent exothermic crystalline peaks sti-
which is 4- fold coordinated to Si15Te85 matrix by replacing Te atoms as
pulates that percolation of stable structural phases of Si-Te-Cu glasses
copper atom can pair with Te atoms and also with Si-Te backbone. The
occurs at different temperatures. However Si15Te77Cu8 and
X-ray diffraction (XRD) of crystallized Si-Te-Cu sample shown in Fig. 2
divulges that the phases which have crystallized out at Tc1, Tc2 and Tc3
are: Hexagonal Te with the unit cell defined by a = b = 4.454 Å,
c = 5.924 Å; tetragonal Cu3Te2 with unit cell of a = b = 3.98 Å and
c = 6.55 Å; hexagonal Si2Te3 with unit cell specified by
a = b = 7.429 Å, c = 13.471 Å and Si1Te2. Thus Cu atoms bond with
Te atoms leading to an intensification in network connectivity in the
system.
Network entropy which is analogous to network connectivity, ri-
gidity etc. is the factor which helps in determining the reason behind
the variation of thermal variables with composition of chalcogenide
glasses. Additionally, the abrupt change in the characteristic of thermal
variables with respect to composition can be related with topological
thresholds.
Fig. 3 shows the variation of Tg with composition for Si15Te85-xCux
(1 ≤ x ≤ 10) glasses. As seen, Tg decreases initially up to the com-
position range of x ≤ 2 and further followed by continuous increase.
The compositional dependence of Tg of glasses is used to ascertain the
network connectivity. An increment in Tg normally signifies strength-
ening of network connection [23] whereas a saturation or decrease in
Tg signals to the phase segmentation because of the separation of
Fig. 1. ADSC THF curves of selected Si15Te85-xCux (1 ≤ x ≤ 10) glasses. homopolar bonds [24]. The initial decline in Tg of Si15Te85-xCux glasses

2
D. Roy, et al. Journal of Non-Crystalline Solids 531 (2020) 119863

Fig. 2. XRD pattern of (a) as-prepared Si15Te84Cu1 glass showing amorphous

nature; (b) Si15Te83Cu2 glass at Tc1; (c) Si15Te83Cu2 glass at Tc2; (d) Si15Te79Cu6
glass at Tc3.

Fig. 4. The compositional dependence of (a) Tc3 and (b) Tc1 of Si15Te85-xCux
(1 ≤ x ≤ 10) glasses. The line connecting the points, is used as a guide to the
Fig. 3. The variation of glass transition temperature (Tg) of Si15Te85-xCux eye.
(1 ≤ x ≤ 10) samples with Cu composition and average coordination number.
The line connecting the points, is used as a guide to the eye.
metallicity of the additive, etc. are some of the factors responsible for
determining the specific nature of peculiarity perceived in a certain
in the composition radius of 1 ≤ x ≤ 2 can be attributed to the se- property at the mechanical threshold.
paration of homopolar Te-Te bonds in Si-Te-Cu network. An increase in A similar trend is discerned in the compositional dependence of first
Tg is marked from x = 2 which indicates that the copper atoms com- crystallization temperature (Tc1) of Si15Te85-xCux (1 ≤ x ≤ 10) system,
bines with the Te-Te matrix in a particular fashion resulting in the as shown in Fig. 4. As can be seen the curve marks a steep increase in
development of Cu-Te network. Tc1 in the range of 2 ≤ x ≤ 6 after which it saturates. Tc3 has the same
An anomaly in different properties normally points out the perco- pattern as Tc1 with insertion of copper. The crystallization of binary and
lation threshold of the glass howbeit the precise feature of variation ternary telluride glasses at Tc1 typically marks the precipitation of Te,
rests on the property under analysis and equally differs with system. resulting in the disintegration of Te-Te chains. As a result of this pro-
Glasses containing tellurium such as Ge–Te [25], Si–Te [26], etc., ex- cedure a glassy residue containing elements of higher coordination is
hibits a minimal value in Tg at the stiffness threshold, while the obtained which is categorized by the higher Tg than the parent glass
amorphous selenides such as Ge–In–Se [27], Ge–Ga–Se [28], etc., ex- [26, 29]. The reduction in the Te-Te bonds of lower energy
hibits a change in slope. It can be noticed from the compositional de- (257.6 ± 4.1 KJ/mol) and the increase in the Si-Te bonds of higher
pendence of Tg (Fig. 3) in Si-Te-Cu system that the stiffness threshold energy (429.2 KJ/mol) makes the precipitation of Te more adverse and
corresponds to a minimum value thus manifesting a congruent behavior inevitably leads to an augmentation in Tc1 with the insertion of Cu.
as in other telluride. Covalency of the constituents, size of the atom, The contrast between Tc and Tg denoted by “ΔT” highlights the

3
D. Roy, et al. Journal of Non-Crystalline Solids 531 (2020) 119863

Fig. 5. The compositional dependence of ΔT = Tc1-Tg of Si15Te85-xCux

(1 ≤ x ≤ 10) glasses. The line connecting the points, is used as a guide to the Fig. 6. Variation of non-reversing heat flow (ΔHNR) of Si15Te85-xCux
eye. (1 ≤ x ≤ 10) glasses with composition (x) and average coordination number.
The line connecting the points, is used as a guide to the eye.

propensity of the system towards crystallization [30]. More the dis-

a fascinating result about the compositional dependence of ΔHNR as
similarity less is the propensity towards crystallization. Moreover, the
glass forming ability (GFA) in chalcogenide systems has been found to shown in Fig. 6, which stipulates that ΔHNR does not vary much in the
composition range of 1 ≤ x ≤ 2. Howbeit a decline is noticed in ΔHNR
have direct proportional relationship with the difference between Tc
and Tg. Fig. 5 shows the glass forming ability also known as thermal at x ≥ 2 followed by the formation of a trough in the compositional
span of 2 ≤ x ≤ 6, and this clearly stipulates the presence of IP in the
stability of the Si15Te85-xCux (1 ≤ x ≤ 10) samples. As seen from the
figure, ΔT increases with copper insertion in the compass of 2 ≤ x ≤ 6, span of 2 ≤ x ≤ 6. Specific group of phase change glasses for instance
Ge-Te-Si, Si-Te-In, etc. [42, 43] exhibits reversibility window in certain
which stipulates that the network connectivity and accordingly the
network rigidity of Si15Te85-xCux increases in the range of 2 ≤ x ≤ 6. composition. Especially Si15Te85-xInx glasses are noticed to have IP in
the average coordination span 〈r〉 = 2.32 to 2.50, wherein the width
The glassy systems which are covalently bonded are seen to be re-
strained by bond stretching and bond bending forces. At an average (Δr) and the centroid of the IP are 0.18 and 2.41 respectively [43];
whereas in Si15Te85-xAgx system the IP is not seen [44]. The structure of
coordination number of 2.40, the glassy system attains a critical point
wherein the constraints per atom and degrees of freedom of the net- the glass is responsible for shaping the compositional width and cen-
troid of the rigidity gradation; the breadth of the IP practically vanishes
work become equal [31, 32]. Rigidity of the network percolates and the
material experiences a change from floppy polymeric glass to rigid in certain networks showcasing a perfect accordance with the extended
constraint theory [45]. IP region, IP width and the centroid of the
amorphous solid at the stiffness threshold. The stiffness threshold is also
synonym as rigidity percolation or mechanical threshold. The stiffness present ternary system (Si15Te85-xCux) has been found to be 2.32 to
2.50, 0.18 and 2.41 respectively which is similar to Si15Te85-xInx
threshold at 〈r〉 = 2.40 is seen in the following binary systems like Si-
glasses.
Te [33], Ge-Se [34] and ternary systems like Al-As-Te [35], Ge-Se-Te
The variation of density with the addition of Cu and also with
[36] etc. Further, Tanaka reported that the systems having medium
average coordination number is displayed in Fig. 7. In spite the atomic
range interactions the stiffness threshold shifts to different average
weight of copper (63.546 amu) is less than Te (127.6 amu), the sub-
coordination number [37]. Prudent research and analysis have revealed
stitution of Te with copper intensifies the density primarily. Howbeit,
that in some glassy systems the stiffness threshold compasses over a
the density increases with the Cu composition along with the plateau
broad composition span [38–40]. These systems are found to transit
seen in the composition range of 3 ≤ x ≤ 6. Literature specifies that
from floppy polymeric phase to an isostatically rigid phase and from an
molar volume manifests a minimum or a maximum is exhibited by
isostatically rigid to a stressed rigid phase or in other words these types
molar density in the region related to Boolchand's IP [46]. The wide
of systems display two stiffness transitions. The intermediate iso-
maximum exhibited by the density versus composition graph of
statically rigid phase are seen to be comprised of the glass composition
Si15Te85−xCux glasses highlights the thermally reversing window in this
which are self-organized, near-ideal and stress-free [38, 39]. Theore-
chalcogenide glass.
tical estimations using techniques such as graph theory, constraint
The change in specific heat (ΔCp) at glass transition with the in-
counting, cluster approximations show the presence of “intermediate
sertion of copper is shown in Fig. 8. As seen ΔCp jumps and exhibits a
phase – IP” (familiar as Boolchand IP) in many chalcogenide systems
minimum at x = 2 (<r> = 2.34). Some glasses when subjected to
[41]. ΔHNR abbreviated for non-reversing enthalpy measures the latent
heat between the glass and its corresponding melt and also quantifies in ADSC have shown a minimum value of ΔCp at the stiffness threshold
[47]. The resilience of the glass structure can be defined in terms of the
the glass transition area, the enthalpy required for composure of the
glass structure. Moreover, the configurational contrast of the glass and specific heat of the glass; a system which shows strong reluctance for
network reformation at Tg can have least value for ΔCp at the rigidity
the liquid is evident from the compositional dependence of ΔHNR. In the
IP it is interesting to find that the ΔHNR of the glasses almost vanishes percolation threshold [30, 31].
Chemically Ordered Random Network (COCRN) model [48] pro-
[38, 39], leading to the conclusion that in the IP both the liquid and the
glass structures look similar and hence are stress free. This study reveals poses that at a certain critical composition (referred as chemical
threshold) of chalcogenide system, the hetero-polar bonds are only seen

4
D. Roy, et al. Journal of Non-Crystalline Solids 531 (2020) 119863

propose a minimum in GFA at the chemical threshold.

An intriguing fact that can be highlighted is that the appearance of
IP in Si15Te85-xCux glass is noticed in the composition versus ΔHNR
characteristic while the variance of Tc and ΔCp with composition
manifests only the effect of rigidity percolation threshold. Customarily,
in glasses the appearance of IP is noticed in the variation of attributes
like thermal diffusivity [51], ΔHNR [52, 39], photo response [53] with
composition, howbeit attributes like electrical switching voltage [54],
Tc [55], etc., manifests solely the effect of rigidity percolation
threshold.

4. Conclusion

The ADSC studies on Si15Te85-xCux (1 ≤ x ≤ 10) glasses stipulate

that the glasses constitute of distinct phases which are stable and per-
colate at different crystallization temperature. The variation of various
thermal parameters like Tg, Tc1, Tc3 with Cu composition indicates an
initial decline in the composition till x ≤ 2 followed by a sustained
increment in the range of 2 ≤ x ≤ 6 indicating a better network
connectivity in this region. The ΔCp at Tg with composition manifests
the presence of rigidity percolation threshold at x = 2. Also the com-
Fig. 7. Variation of density with Cu composition for Si15Te85-xCux (1 ≤ x ≤ 10) positional dependence of thermal stability reveals that the glasses in the
glasses. The line connecting the points, is used as a guide to the eye. span of 2 ≤ x ≤ 6 are thermally more stable. The ΔHNR manifests a
trough between the composition 2 ≤ x ≤ 6, which distinctly stipulates
the existence of intermediate phase in the composition range. The
variation of density with composition shows the signature of mean field
threshold. The anomalous behavior seen in thermal parameters at x = 9
denotes the existence of chemical threshold for these glasses. In short,
the study has helped in revealing the existence of intermediate phase in
the range which is the most stable composition and also the existence of
chemical threshold. These studies will help to correlate and analyze the
results of other studies like electrical switching studies for the other
series of glasses.

Author contribution statement

All the authors have contributed for the research work associated
with this paper in terms of experimentation, documentation, result
analysis, paper writing and communication.

Declaration of Competing Interest

The authors declare that they have no known competing financial

interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Fig. 8. Compositional dependence of specific heat (ΔCp) measured at Tg for
Si15Te85-xCux (1 ≤ x ≤ 10) glasses. The line connecting the points, is used as a Acknowledgements
guide to the eye.
Author Chandasree Das and Diptoshi Roy acknowledge Science and
Engineering Research Board (SERB) India and Technical Education
to exist. At chemical threshold the glass is anticipated to show max-
Quality Improvement Program - II (TEQIP-II) for the financial support
imum chemical organization and is also marked by incongruous var-
to carry out this research work.
iations [34]. Although the chemical threshold is supposed to ensue at
the mean coordination number of 2.67 however it is seen that chemical
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