STUDY OF CHALCOGENIDES PROPERTIES AND ITS

APPLICATIONS
TEJASWINI.M.L
Assistant Professor, Don Bosco Institute of Technology, Bangalore-560074, Karnataka, India
mltejaswini238@gmail.com

DR. K.P.LAKSHMI
Associate Professor, BMSCE, Bangalore-560019, Karnataka, India
kpl.ece@bmsce.ac.in

ABSTRACT: Amorphous materials particularly chalcogenide glasses (Se, Te and S alloys) are
promising materials for the fabrication of various solid state devices. The distinctive properties and
functionalities of chalcogenide glasses make them promising materials for photonic applications.
Chalcogenide glasses are transparent from the visible to the near infrared region and can be
moulded into lenses or drawn into fibers. They have useful commercial applications as lenses for
infrared cameras, chalcogenide glass fibers, waveguides, optical switch, as chemical and
temperature sensors and phase change memories. In this paper we present a brief report of the
preparation and application of these materials.

KEYWORDS: Non Crystalline Semiconductors, Chalcogenide, Photonics, photo-induced

phenomena.

INTRODUCTION

Chalcogenides are a well-known group of inorganic glassy materials that include one or more
chalcogen elements: elements of sixteen group of the periodic table such as Sulphur, Selenium and
Tellurium. The chalcogens are usually alloyed with electropositive elements such as Arsenic and
Germanium, and with elements like Phosphor, Antimony, Bismuth, Silicon, Tin, Lead,
Aluminium, Gallium, Silver, Lanthanum, etc to form chalcogenide glasses that exhibit fascinating
properties.

Usual glasses are made of Silicates and quartz, which transmit radiation in the visible range of the
electromagnetic spectra. Several applications in optics, photonic and optoelectronics domain
require glasses that can transmit radiation in infrared range up to a wavelength of approximately
2m. For these applications three categories of special glasses are identified as: Fluoride glasses
such as Zirconium Fluoride (ZrF4) and Hafnium Fluoride (HfF); Chalcogenide Glasses (CG) such
as As-S, As-Se, As-Se-Te, Ge-Se-Te, Ge-As-Se; and Heavy Metal Oxide (HMO) glasses such as
GeO2-Pbo, TeO2-Pbo etc. These glasses transmit both in the middle IR and far IR regions and
have lower values of phonon energies and higher values of refractive indices as compared to SiO2
as shown in Table.1 [1]. Apart from these properties, the other properties of chalcogenide glasses
are as listed below:
 Table 1 Some physical properties of special Glasses
Phonon Transmission Refractive Hardness Thermal Expansion
Type of Glass energy Cm-1 energy m Index Kgf.mm-2 10-7/C
Chalcogenide 330-380 0.5-10.0 2.3-2.7 100-200 240-250
Flouride 440-650 0.25-6.50 1.52 225-250 150-180
HMO 590-850 0.4-7.0 2.65 600 120-180

STRUCTURAL PROPERTIES

A crystalline solid state is characterized by order in the position of atoms even at large atomic
distances. CGs are characterized by Short Range Order (SRO) and partially Intermediate Range
Order (IRO). This means that after changing crystalline state of crystal or non-crystalline state, the
shortest distance between adjacent atoms is almost the same in the crystal, may be with only small
distortion that leads to destroying of the Long Range Order (LRO) [2].

CGs bear some similarity to oxide glasses, since both Oxygen and chalcogen belong to group VI in
the periodic table. A CG can be regarded as a kind of soft semiconductor because its atomic
structure is flexible and viscous and a semiconductor because it possesses a band gap energy (~2
eV) characteristics of semiconductor materials (1-3eV). Accordingly, a CG is classified as a
material in between an oxide glass composed of 3-dimensional networks and an organic polymer
possessing one dimensional chain structure [3].

ELECTRONIC PROPERTIES

CGs posses electrical and optical band gaps of 1-3eV and accordingly regarded as amorphous
semiconductors. Gap decreases in the order of S, Se and Te, reflecting enhanced metallic
character. As a semiconductor, the overall property of CGs can be grasped as the vertical sequence
(Figure 1). That is, the change from organic semiconductors, chalcogenides and hydrogenated
amorphous Si films to crystalline semiconductors, electronic mobility becomes higher and a faster
response is available. The material also becomes rigid.

Figure 1. Characterization and comparison of CGs as glasses and semiconductors with other
materials

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OPTICAL PROPERTIES

CGs are extensively used for photonic applications due to their attractive optical properties such as
high refractive index, high photosensitivity and large optical nonlinearity [4].

Photo-Induced Effects
Several different photo induced phenomena are used to make a variety of physical changes only in
amorphous chalcogenides, but not usually in crystalline chalcogenides. Photo effects are strong
and offer many practical applications for sulphide glasses. There are at-least seven mechanisms
through which this is possible in amorphous chalcogenides that can result in materials that are
having different properties after optical irradiation.

Thus, when samples of a suitable geometry are exposed to light photo crystallization, photo
polymerization, photo decomposition, photo induced morphological changes (i.e. photo-
contraction), photo- vaporization, photo- dissolution of metals and light-induced changes in local
atomic configuration can occur. These changes are accompanied by changes in the optical
constants of the material, in particular in the position of the optical band gap. This is termed photo-
darkening or photo-bleaching depending on the whether the band gap moves to longer or shorter
wavelength. The plenty of processes through which optical changes can be induced in
chalcogenides finds applications in integrated waveguide circuits, diffraction gratings, surface and
potential volume data storage.

Photo-crystallisation
A chalcogenide film is crystallized based on optical irradiation due to a heating effect. This is
predominantly seen in chalcogenides with low glass transition temperature.

Photo-polymerization
Polymerization is the process of two or more molecules combining to form a more complex
continuously bonding molecule. Such processes can be thermally and photo-induced in some
chalcogenides. In the case of the arsenic trisulphide glass, a polymerization model has been
suggested whereby Arsenic Sulfide (As4S4) polymers are created in the material after thermal
annealing at the glass transition temperature.

Photo-dissolution of Metals
A layer of metal in contact with the chalcogenide can be made to melt into it upon irradiation with
light of similar energy as the band-gap of chalcogenide. This process is not easily overturned.

Photo-compaction
This has been reported in Ga:La:S, under light from UV radiation. The nearby compacted region
showed a change in its chemical composition to higher concentrations of Lanthanum and
compaction depths of up to 1.3m were calculated. The densification lead to a changes in
refractive index of n = 10-3 .

Photo-contraction
Photo or radiation compaction has been observed in several chalcogenides. The only difference
with respect to photo compaction is reverse by the use of thermal annealing.

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Photo-darkening
The optical absorption of the chalcogenide increases at a particular wavelength after irradiation, in
part from a shift in the Urbach edge to lesser energies. The effect is major at low temperatures
even as at higher temperature, close to the glass transition; the effect is not calculated since the
glass is annealed as fast as the change is induced. Photo-darkening is sometimes associated with
other structural alterations in the chalcogenide.

Photo-bleaching
Photo-bleaching involves the optical absorption edge shifting to shorter wavelengths. It is a
frequent effect in chalcogenide films and has been observed in Ga:La:S. Like photo-darkening,
bleaching is due to a structural change in the glass network. The direction of the shift in the
absorption edge can be dependent on the film deposition technique and its parameters. For
example, thermally evaporated Arsenic Sulphide based films can be either photo-bleached or
darkened based on the deposition conditions.

Photo-induced Anisotropy
Dichroism and birefringence have been experimentally observed in some amorphous
chalcogenides through illumination by linearly polarized light. Different theoretical models
relating to bond breaking and twisting have been proposed to explain this effect.

Photomechanical Effect
The opto-mechanical effect was first observed by Elliott et al in amorphous chalcogenide films
deposited on clamped STM cantilevers. Here band gap light that is linearly polarized either
parallel or perpendicular to the axis of cantilever, when incident on the chalcogenide film causes
either a contraction or an expansion of the chalcogenide layer. This results in an optically actuated
dislocation of the free end of the clamped cantilever, which is an example of photo-mechanical
effect.

THERMAL PROPERTIES

The thermal properties of CGs are specified by certain characteristic temperatures like:
(i) Glass transition temperature, Tg which is related to the magnitude of cohesive forces within the
network.
(ii) Onset of crystallization temperature, Tx and
(iii) Peak crystallization temperature, TP. These denote the important parameters that are to be
considered for realizing applications using CG. The appropriate values of these parameters are
calculated using (DTA) differential thermal Analysis. A typical DTA trace is as shown in figure 2.
Also important is the softening point, where the glass has a viscosity of ~107.6 poise. At or above
this temperature the glass can be drawn into fiber. The thermal properties of Ga-La-S based
glasses are generally characterized by high transition temperatures relative to other chalcogenide
and halide glasses, provided that improved environmental strength over these materials.

Expansion co-efficient is another thermal property of CGs which gives an idea about the
expansion of the material as a function of temperature. Thermal expansion co-efficient of
chalcogenide glasses are very large compared to those of Oxide glasses. The expansion coefficient
is proportional to the gradient of the curve. In Figure 3 it can be seen that there is a marked
increase in the expansion coefficient after Tg.

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Specific heat, which is the amount of heat, required the temperature of a unit mass of a material by
1 is another important property of CGs. The specific heat of Tellurium based CGs was
determined at temperatures between 373 and 600 K. The values of specific heat increases with
increasing temperature.

Thermal conductivity is a measure of the capability to conduct heat all the way through the body
of that material. The usual values of thermal conductivities of CGs lie in the range 100 and 500 K.

Figure 2. A typical differential thermal analysis trace (DTA) for Ga-La-S glasses illustrating the
characteristic tempeatures, glass transition temperature(Tg), the onset of crystallisation (Tx ) the peak
crystallisation temperature (Tp) and the onset of melting (Tm).

Figure 3. Determination of Tg from the expansion coefficient for a Ga-La-S glass sample.

APPLICATIONS OF CHALCOGENIDE GLASSES

As2S3 was the first commercially developed CG some time during 1950s mainly for Mid IR
applications. A little later, sulphide and selenides glasses were synthesized and used for far IR
applications, Applications of CGs include detection of thermal faults, management of energy,
detection of electronic circuit faults, detection of tumor, identification of finger prints of human
lung cells in different metabolic conditions, monitoring of temperature and night vision [5].

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CGs were developed during 1970s to produce active electronic device components used especially
in photocopying and also for switching. CGs are also being used to fabricate IR fibers with ultra-
low loss for telecommunication signal transmission instead of silica based optical fibers. However,
the theoretical minimum losses of mid IR chalcogenide fibers are found to be greater than
10dB/km. IR optical fibers based on CGs are also used as sensors for the determination of volatile
organic pollutants in ground water.

Optical fibers based on CGs are more compact and suitable for low power transmission. They find
applications in industrial welding and in microsurgery [6].

The photo induced phenomena in CG fibers opens up a wide variety of applications. Using this
property, integrated optic devices like lenses, gratings, optical fibers, multiplexers and de-
multiplexers, optical scanners, heads of printer, logical elements of multiple output and many more
are realized [7].

CGs finds application in optoelectronics. Reversible optoelectronic devices based on CGs have
been developed and used for writing and readout of optical images and also as X-ray solid state
image devices. The new requirements of holographic recording media such as small recording
time, high stability and possibility of recording over large areas are achieved to some extent by
using CG semiconductors. The metal photo dissolution feature of CGs is useful for creation and
storage of image [7].

Phase change materials are based on Chalcogenides and are currently becoming established as the
basis for the next generation of non-volatile memory. In its simplest form, a cell of crystalline or
non-crystalline chalcogenide represents a binary 0 or 1 and by applying energy in the form of
heat into the chalcogenide cell, the preferred phase can be written and information stored. The
state of the cell, that is, whether it is in its crystalline or non-crystalline form can be read in two
ways; optically, wherein the reflectivity of the cell varies depending on its phase, or electrically,
where in the resistivity of a cell can vary by several orders of magnitude between the two phases.
Chalcogenides have been chosen as a memory material as they can be switched between the states
easily and the states are thermally stable. These materials are being considered in the memory
market due to the amazing energy savings and memory density achievable. The chosen materials
for rewritable optical data storage are based on compounds of Tellurium. In recent years, with the
improved scaling to lesser feature sizes, predictable electrical storage technologies, such as Flash,
are expected to be replaced by CG memories commonly called Phase Change RAM (PRAM) [8].

Chalcogenide-based chemical sensors for atmospheric pollution control are becoming a popular
research field for monitoring environmental pollutant gases such as NO2, CO and SO2. A
significant sensitivity has been observed for nitrogen dioxide. The range of NO2 detection is
reported to be 0.95 to1.9 ppm. The response and the recovery time were also observed to be fast
with good reproducibility and high sensibility [9].

CONCLUSIONS

Chalcogenides, which are a class of amorphous semiconductors, are important materials that find
application in electronics and optoelectronics. They exhibit fascinating properties like photo-
induced phenomenon that finds applications in varied fields like fabricating photonic components,

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optical fibers for low loss IR communication, biological and chemical sensing and also in
realizing non volatile memories.

REFERENCES

Populain M, Fluoride Glass Fiber optics, (Academic Press, Inc.,Boston) 1991.

Lucovsky G, optic modes in amorphous As2S3 and As2Se3, physical Rev B, 6 (1972) 1480-1489.
Zallen R, The Physics of Amorphous Solids (John Willey & Sons, New York) 1983.
Zakery and S. R. Elliott, Optical properties and applications of chalcogenide glasses: A review,
Journal of Non-Crystalline Solids, 330:1-12, 2003.
Savage J A, Infrared Optical Materials and their antireflection coatings, (Adam Hilger, Bristol),
1985.
Keirsse J, Boussard-Pledel C, Loreal O, Sire O, Bureau B, Leroyer P, Turlin B & Lucas J,
Chalcogenide glass fibers used as biosensors , J Non-Cryst Solids, 326-327 (2003).
Andriesh A M, Iovu M S & Shutov S D, Chalcogenide non-crystalline Semiconductors in
optoelectronics, J Optoelectron Adv Mater, 4 (2002) 631-647.
K.P. Lakshmi, S. Asokan, Multi-resistance states in the electrical switching behavior of
amorphous Si15Te75Ge10 thin films: Possibility of multi-bit storage, J. Non-Crystalline
Solids, 373-374, 13, 2013.
S. Marian1, D. Tsiulyanu, T. Marian, and H.-D. Liess, Chalcogenide-based chemical sensors for
atmospheric pollution control, IUPAC, Pure and Applied Chemistry 73, 20012004
N.Mehta, Applications of chalcogenide Glasses in Electronics and Optoelectronics: A review,
Journal of scientific & Industrial research, vol.65, October 2006, pp 777-786.
Stanford R. Ovshinsky, Reversible electrical switching phenomena in disordered structures,
Physical Review Letters, 21(20):1450, 1968.
Donald L. Smith, Thin-Film Deposition: Principles and Practice, McGraw Hill, 1995.
A.B. Seddon, Chalcogenide glasses:- a review of their preparation, properties and applications,
Journal of Non-Crystalline Solids 184 (1995) 44-50.
S.R.Elliot, Physics of Amorphous materials, Essex:Longman(1990).

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