The chalcogenide glasses have drawn a great attention since last 5 - 6 decades due to their wide range of applications in various fields [1]. These glasses are amorphous semiconductor in nature and transparent to infrared region of electromagnetic wave (radiation) and reveal unique electrical and optical properties. Due to these properties, the chalcogenide glasses are useful for several applications such as threshold switching, memory switching, inorganic photoreceptors and optical wave guide [2,3]. The reversible transformation property of Selenium (Se) based chalcogenide alloys makes these alloys very useful in optical memory devices, X-ray imaging and photonics [4]. But glassy Se has some shortcoming such as low photosensitivity and low thermal stability. The various additives with glassy Se produce binary chalcogenide glassy system e.g., Se-In, Se-Te, Se-Ge, Se-S, Se-Sb and others [5-8]. These are of great interest due to better hardness, better stability, higher sensitivity and change (higher or lower) in crystallization ability. The addition of third element expands the glass forming area and also causes configurationally disorder in the system.

The thermal behavior of the chalcogenide glasses plays an important role in determining the transport mechanism, thermal stability and useful applications. The differential scanning calorimeter (DSC) technique has so for been employed to study the crystallization process in amorphous alloys and proved to be the most effective method for such studies [9]. The DSC can be used eighter in isothermal mode or in non isothermal mode. The drawback of later is that the analysis of non isothermal experiments is generally more complicated than isothermal one [9,10]. However, in isothermal experiments it is impossible to reach a test temperature instantaneously [11]. Iso-Conversional methods are used for non isothermal analysis, in which the transformation rate at a constant crystallized fraction is only a function of temperature as suggested by Vyazovkin et al. [12-15] and other workers [16,17]. IsoConversional techniques make it possible to estimate the activation energy of a process as function of the crystallized fraction α. Analysis of the activation energy dependence on α provides important clues about reaction mechanism. Therefore, the activation energies for such processes can logically not be same and it may vary with degree of conversion [18].

In the present study, we report the crystallization kinetics of Se₈₀In₁₀Pb₁₀ chalcogenide glass. The activation energy was determined using four iso-conversional methods (Kissinger-Akahira-Sunose (KAS), Flynn-WallOzawa (FWO), Tang and Straink). The Avrami exponent also has been determined to study nucleation and growth during crystallization process.

The investigated Se₈₀In₁₀Pb₁₀ chalcogenide glass was prepared from high purity (99.999%) Se, In and Pb elements by melt quenching technique. The desired amounts of constituent elements were weighed according to their atomic weight percentage and put into cleaned quartz ampoule. The ampoule was evacuated and sealed under a vacuum of 10⁻⁵ Torr to exclude reaction of alloying materials with Oxygen at higher temperature. The sealed ampoule was heated in a furnace at rate of 4 - 5 K/min and raised the temperature up to 1100 K and kept it at that temperature for 12 hours. During the melting process the ampoule was frequently rocked to ensure the homogeneity of alloying materials. After the above said period, the ampoule with molten materials was rapidly quenched into ice cooled water. The ingot of glassy material was taken out from ampoule by breaking them. The X-ray diffraction pattern of as prepared material was recorded using Philips PW-1830 Diffractometer with Cu-K_α (λ = 1.54 Å) to confirm the amorphous nature of prepared glass. The XRD pattern of Se₈₀In₁₀Pb₁₀ chalcogenide glass is shown in Figure 1. The absence of sharp structural peak confirms the amorphous nature of Se₈₀In₁₀Pb₁₀ chalcogenide glass. The surface morphology of Se₈₀In₁₀Pb₁₀ chalcogenide glass was done by using Scanning Electron Microscopy (SEM) (Model: Quanta 200). The SEM image is shown in Figure 2(a). This again confirms the amorphous nature of prepared glass. The composition of Se₈₀In₁₀Pb₁₀ chalcogenide glass is also confirmed by using an energy dispersive X-ray analysis (EDAX). The EDAX spectrum of Se₈₀In₁₀Pb₁₀ is shown in Figure 2(b). The crystallization kinetics of prepared chalcogenide glass was studied by using differential scanning calorimeter (DSC) (Model: Shimadzu DSC60) at different heating rates of 5, 10, 15 and 20 K/min. The accuracy of the heat flow in instrument is ±0.01 mW and temperature precision of instrument is ±0.1 K with an average standard error ±1 K in measured values (glass transition, crystallization and melting temperatures). The DSC was calibrated prior to the measurement using high purity standard Indium (In) with well known melting point.

The DSC thermograms of Se₈₀In₁₀Pb₁₀ chalcogenide glass at different heating rates (5, 10, 15 and 20 K/min) are shown in Figure 3. The DSC thermograms at each heating rate shows a well-defined endothermic peak at the glass transition temperature T_g and an exothermic peak at the crystallization temperature T_c. The crystallized fraction α at a given temperature T is given as α = (A_T/A), where A is the total area of the exothermic

peak between the onset temperature (T_i) where crystallization just begins and the temperature (T_f) where the crystallization is completed. A_T is the area between T_i and T. The values of T corresponding to α are listed in Table 1. From Table 1 we observe a systematic shift in T to higher temperature with increasing heating rates. The graph of α versus T at four different heating rates is

Table 1. The values of temperature in crystallization region for different crystallized fraction Se₈₀In₁₀Pb₁₀ chalcogenide glass at different heating rates.

shown in Figure 4. Figure 4 shows the degree of crystallization as a function of temperature at different heating rates.

The kinetics of crystallization in amorphous material can be described by the following rate equation [19]:

where, K is the reaction rate constant usually has Arrhenius temperature dependence, is the reaction model, t is time and α is the crystallized fraction.

But reaction rate constant K is given by following equation:

where, K₀ is pre-exponential factor of rate constant, E is activation energy, T is temperature and R is universal gas constant.

Under non-isothermal condition with a constant heating rate  and using Equation (2), Equa-

tion (1) can be written as:

There is a variety of theoretical models and mathematical equations to explain the estimation of crystallization kinetics. The following four iso-conversional methods have been used in present study to analyze the crystallization kinetics of Se₈₀In₁₀Pb₁₀ chalcogenide glass. All the four methods require the determination of the temperature T_αi at which a fixed fraction α of the total amount is transformed.

1) The activation energy as determined from the four iso-conversional methods was found to be varying in the same way and show a little variation with crystallized fraction and temperature.

2) The Avrami exponent n_α also show a little variation with crystallized fraction and temperature.

3) The transformation from amorphous to crystalline phase in Se₈₀In₁₀Pb₁₀ is a single-step mechanism.

ISR is thankful to the Principal, Dyal Singh College, University of Delhi, New Delhi for sanctioned study leave to carry out research work. We are also thankful to CSIR, New Delhi for providing financial assistance under research project no. 01(2456)/11/EMR-II to carry out research work.