Chapter 3.

Experimental techniques

3. Experimental techniques

3.1. Preparation techniques

The disordered state of a liquid which leads to bulk materials or

that of a gas state which yields thin films deposited upon a substrate, it is
necessary to retain at ambient temperature to obtain a glass or an
amorphous solid. The compositional range for which chalcogenide
material can be rendered amorphous depends on the preparation method
used. In the course of this study, bulk samples were produced using a
well known and widely used technique, namely melt quenching. Thin
films can be obtained by using one of several ways of producing
amorphous solids by deposition from a vapour. The technique used in
this study to produce thin films is thermal evaporation (TE).

3.1.1. Melt quenching

The preparing technique of glasses by means of rapid quenching

of a melt is historically the most established and it is still the most
widely used in the preparation of amorphous chalcogenide materials.
The method consists of weighting and mixing the high purity
constituents followed by melting in sealed evacuated quartz ampoules.
The melt is continuously rocked to ensure homogenization.

54
Chapter 3. Experimental techniques

Subsequently, the melt will vitrify when cooled by quenching in ice

water.

Many of factors appear to be important in determining whether or

not a particular material readily vitrifies. The overwhelming
consideration is the avoidance of crystallization in the quenching
process. Thermodynamic aspects relating to the melt can be important. It
is well known that the sham decrease in the liquids temperature
associated with eutectic formation in alloys facilitates glass formation
for compositions straddling the eutectic point. Compositions near the
eutectic favor glass formation since the melting point is depressed and so
the liquid is less supercooled at the glass-transition temperature T g [99],
thereby reducing the possibility of crystallization. However, in
chalcogenide materials, such behavior does not seem to be prevalent;
instead, compound formation and the resulting atomic structure seem to
be the dominant controlling influences. Another important factor which
affects glass-forming ability is the viscosity of the melt. Generally
speaking, the more viscous the melt at a given temperature above the
melting, is the greater the propensity for glass formation.

The rate of quenching is another factor that can influence the glass-
forming ability of chalcogenide materials. In general, the faster the rate
of quenching of the melt, the greater is the likelihood of forming a glass
and not a crystalline product.

55
Chapter 3. Experimental techniques

3.1.2. Bulk samples preparation

High purity (5N) materials of arsenic, selenium and thallium

were used to prepare As20Se80-xTlx for x = 5,10,15,20,25,30 and 35 at %.
The bulk glass was synthesized by weighing out suitable proportions for
the required composition and mixing them in an evacuated sealed silica
-5
tube (vacuum 10 torr.). Alloying the elements was accomplished by
putting the sealed tubes in a furnace with a rocking mechanism (Fig.3.1).

Figure3.1. Rotating mechanism furnace.

1) Ampoule with sample inside.

2) Thermocouple.
3) furnace.
4) Quartz tube.
5) Motor.
6) Temperature controller unit.

56
Chapter 3. Experimental techniques

The rocked motion ensures that a complete mixing of the

materials takes place. To assure complete chemical reactions between the
constituents, the furnace temperature program was adjusted firstly at
3500C for 4 hours secondly at 6500C for 2 hours and at last to 8750C for
16 hours, a schematic thermal program diagram was illustrated in
Fig.3.2.

The selected temperature is higher than the highest melting point

of the elements in the tube (melting point for As = 8170C, Se = 2170C,
Tl = 3070C) [100]. At such high temperature the sealed tube usually
stacks in the oven, therefore, a quartz holder is used to keep the tube far
from the oven walls.

The melt can then be quenched rapidly by dropping the tube

immediately from the oven into a liquid preferably one with a high
thermal conductivity and high latent heat of vaporization so that heat is
conducted away from the sample as fast as possible without the
formation of a thermally insulating vapor layer around the tube. During
this work, an ice-water bath is used for rapid quenching. After
quenching, the material was broken up into small pieces which could be
used as samples.

57
Chapter 3. Experimental techniques

1000

800
Temperature (K)

600

400

200

0
0 5 10 15 20 25
Time (hour)
Figure 3.2. Thermal history program of sample preparation

3.1.3. Thin film samples prepared by thermal

evaporation (TE)

The formation of non-crystalline solids may also be achieved by

depositing one or several components in the vapor state onto a substrate.
There are several techniques based on this process which can yield
amorphous thin films. These techniques can be regarded as having fast
quenching rates and therefore can be used to produce chalcogenide
materials in amorphous form which are difficult to vitrify, or to extend
the compositional range for which a given system can be made
amorphous compared with that attainable using conventional melt-
quenching techniques.
The vapor may be produced by heating a suitable compound and

58
Chapter 3. Experimental techniques

deposit it on a substrate without further modification (no-reactive

deposition), or alternatively (reactive-deposition), in which the vapor'
species are chemically modified with respect to the source material.

Thermal evaporation (TE) technique is perhaps the simplest and

possibly the most widely used method for producing amorphous solids in
thin film forms. TE is normally performed in vacuum and involves
resistive or electron-beam heating of a boat containing the material to be
evaporated, The material is melted then evaporated and finally
condensed onto a cold substrate. This method is suitable for relatively
low melting-point compounds, such as chalcogenides.

The disadvantage of TE as a preparation technique lies in the

variability in purity and composition of the resulting films (in the case of
alloys). There are many experimental variables some of which the
experimentalist can control (and should then specify in a description of
the material preparation), and others which are out of his control, and so
they can change randomly from one preparation to another of ostensibly
the same material. Some of these variables are listed below:
a) Substrate temperature.
b) Substrate-source separation and orientation.
c) Base gas pressure in the chamber.
d) Impurities from the evaporation boat, or disorder gases from the
chamber surface.
e) Boat or filament temperature.

The substrate temperature is important since the higher the

59
Chapter 3. Experimental techniques

temperature, the higher the surface mobility which can lead to a material
with considerably fewer structural defects. However, if the substrate
temperature is too high, the material will crystallize. The relative
orientation of substrate with respect to the source is also of importance
since evaporation at oblique angles of incidence leads to a shadowing
effect and causes a columnar growth morphology to appear with dense
regions approximately parallel to the source-substrate direction. A major
problem with this technique is differential evaporation, in which the
vapor is removed immediately from the vicinity of the molten source,
thereby preventing the establishment of equilibrium. In this case the
element in the source alloy with the highest vapor pressure evaporates
preferentially, depleting the source and leading to composition
inhomogeneities in the deposited film.

The thin films of the As20Se80-xTlx samples were prepared by

thermal evaporation of crushed bulk material. The deposition was
carried out in a coating unit (Model 306A Edwards, England) (Fig.3.3),
under vacuum of about 10-6 torr to reduce contamination. The coating
unit is provided with water cooled vapor, diffusion pump E04, with
pumping speed of 600 L/Sec. Liquid nitrogen trap was located between
the diffusion pump and the high vacuum valve. This trap migrating
diffusion pump vapors. The pumping system is also provided a trap
which eliminates the back-streaming of oil vapors from the rotary pump.

60
Chapter 3. Experimental techniques

Figure 3.3. Vacuum coater

Evaporation is started by passing a low current for a sufficient

period of time in the boat (see Fig.3.5) to heat up the material. The
distance between the boat and the glass substrate was about 15 cm. A
schematic diagram for the evacuation chamber which is used to deposit

61
Chapter 3. Experimental techniques

films for optical and electrical measurements is shown in Fig.3.4.

Figure 3.4. Evaporation chamber schematic diagram which used to

deposit As-Se-Tl thin film samples and electrodes.

The current is gradually and carefully increased, when the material melts
inside the boat the current passing through the boat is increased fairly
quickly. This was done to avoid alloy decomposition. The film thickness
was accurately determined using a quartz crystal monitor , Edward’s
model FTM5. Films of the order of 200 ± 2% nm thick were produced.

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Chapter 3. Experimental techniques

Silica cone

Tungsten
filament

Figure 3.5. Evaporating filament

3.2. Structure examination of As-Se-Tl films

3.2.1. X-ray diffraction spectroscopy (XRD)

The X-Ray spectroscopy technique, allows to check whether the

material is amorphous or crystalline. X-ray investigations of the As-Se-
Tl films deposited on glass substrates were performed with a Philips
diffractometer (type 1710). The patterns were run with Cu as target and
graphite monochromator (  = 0.154178 nm ), at 40 kv and 30mA, with
a scanning speed of 3.76 deg/min. All the diffractograms were carried
out at room temperature.

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Chapter 3. Experimental techniques

3.2.2. Differential scanning calorimetry (DSC)

Thermal studies of the samples under investigation have been

carried out by using the differential scanning calorimetry (DSC)
Schimadzu DSC-50. The crystallization thermograms were recorded as
the temperature of the sample was increased at a uniform rate () 10
k/min. Typically, 15 mg of sample in powder was scanned over a
temperature range from room temperature to about 500oC. The values of
the glass transition temperature, Tg, the crystallization temperature, Tc
and the melting point, Tm [101] were determined with accuracy  0.1 k
by using the microprocessor of the thermal analyzer .

3.2.3. Density determination method

The Archimedes method was used for the measurement of the

density. The weight of a piece of the As-Se-Tl alloy was measured in air
and in water using electronic balance, as w 1 and w2, respectively. The

density of water was measured as  . The density of the As-Se-Tl

water

alloy could be thus determined according to Eq.(3.1), which was :

 = w1/[(w1-w2)/ water]………………(3.1)

The densities of the seven alloys are measured by using Archimdean

technique. The densities of pure As,Se, and Tl used in the mixing rule
calculation were 5.73 g cm-3, 4.82 g cm-3, and 11.85 g cm-3
respectively[32].

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Chapter 3. Experimental techniques

3.2.4. Energy dispersive spectroscopy ( EDS )

Most Scanning Electron Microscopies (SEMs) are equipped with

an energy - dispersive lithium drifted silicon detectors. Energy
Dispersive Spectral (EDS) have the advantage that all quantum energies
with 20 KeV are recorded simultaneously and the specimen is displayed
directly by means of multi-channel analyzer. The characteristic. X-ray
allows quantitative or qualitative analysis of chemical composition.
X-ray detectors are used directly for quantitative analysis by energy
dispersion. Energy dispersion is the process of distinguishing the
characteristic X- ray from the specimen elements according to their
energies rather than their wave lengths. In energy dispersion, the detector
views the specimen directly and measures all the characteristic X-ray
simultaneously.

For quantitative X-ray microanalysis, the number of X-ray

quanta in characteristic lines produced by the specimen and by standard
pure element are counted. The concentration of the element in the
specimen can be calculated from the ratio of these counts. The aim of
quantitative X-ray microanalysis is to measure the atomic fraction or
mass fraction of the element. The counts from the characteristic lines can
be selected in a multi-channel analyzer by setting energy windows at
these lines in order to produce a distribution maps of the corresponding
elements. As the specimen area is scanned, all pulses energy depressive
detector produce dot at the point corresponding to the position of the
beam on the specimen as illustrated in Fig.3.6.

65
Chapter 3. Experimental techniques

The scanning electron microscope(SEM) which are used in this work

model PHILIPS XL 30 attached with EDX unit, which are accelerating
voltage 30 K.V, the sample is coated with carbon.

Figure 3.6. X-ray spectrum of the specimen

3. 3. Optical measurements of As-Se-Tl films

3.3.1. Introduction

Amorphous As-Se-Tl films were prepared by evaporation under

vacuum of 10-6 Torr. Films were deposited on ultrasonically cleaned
glass slides. The freshly prepared films as will as films annealed under
vacuum of 10-3 Torr were examined. The data of the optical Reflectance
and transmittance were obtained utilizing a computerized SHIMADZU
UV-2100 PC double beam spectrophotometer in wavelength range of

66
Chapter 3. Experimental techniques

200 to 1100 nm with 10 nm steps. The optical schematics of (UV-

2100PC) is shown in Fig.3.7.

Figure 3.7. Block diagram of the optical path in

SHIMATZU UV-2100 spectrophotometer.

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 Chapter 3. Experimental techniques

3.3.2. Transmittance, T and reflectance, R measurements

The transmittance of the As-Se-Tl thin films T is simply the ratio

of the signals detected by D2 and D1, as shown in Fig.3.8, where the

reference beam passing through clean glass slide substrate.

Substrate

Reference beam
IoTs
D1

Sample beam
IoTfTs
D2

Film/Substrate

Figure.3.8. Measurement of transmittance of film

where the reference is clean substrate.

If Ift is the intensity of the transmitted light through the (film/glass)

combination, and Iq is that through the glass reference only and then the
measured transmittance of the film is given by
I 
T   ft 1  R q  ……………………………(3.2)
I 
 q 

where Rq is the reflectance of glass substrate.

A specular reflectance accessory was used to measure the reflectance, R,
of the sample under investigation at normally incidence of the

68
Chapter 3. Experimental techniques

monochromatic light. Reflectance of the reference mirror (Al-mirror)

was firstly recorded in the measured range of wavelength. Secondly, the
reflectance of the sample is recorded in the same wavelength range,
where the reference mirror is in front of the sample as shown in
Fig.3.9.

Reference Sample
Almirror Io
Io
IoRs
IoRAl

Figure 3.9. Measurement of reflectance of film where the reference

(Al-mirror) is in front of the sample

If the intensity of light reflected from the front surface of the sample
reaching the detector is Ift from the back surface is Ifr and that reflected
from the aluminum mirror is IAl, then:

I 
R   fr R Al ………………………….(3.3)
 I Al 

where RAl is the reflectance of aluminium reference mirror.

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Chapter 3. Experimental techniques

3. 4. Electrical measurements of As-Se-Tl films

3.4.1. Dc Conductivity measurements

This part deals with the detailed description of the method used
for measuring the conductivity of As-Se-Tl films specimens as a
function of temperature in the temperature range from 175 to 373 K.
A current source consisting of Keithley 240 A power supply (E s) is
connected in series with a known resistor RS, generates a current I
which flows through the sample of thickness 200 ± 2% nm. The
resultant voltage drop across the sample was measured with an
Electrometer Keithley 614 C, and the value of the sample resistance can
be measured. Schematic diagram for the used circuit illustrated in
Fig.3.10.

Figure 3.10. Schematic diagram for dc electrical conductivity, dc

measurement circuit

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Chapter 3. Experimental techniques

The measurement of the electrical properties of thin films were

performed at different temperatures starting from low temperature to
high temperature using liquid nitrogen up to 373K. The measurements
were achieved by using cryostat which is shown in Fig.3.11.
The cryostat consists of an Pyrex body, having two impeded copper-
constantan thermocouple and electrode terminals. The later connected to
the investigated thin film sample through two isolated copper wires
electrically isolated. The cryostat and its isolated cover container its
designed to fit each other so that low vacuum could be achieved. Rubber
insulator protection was supplied to prevent the fraction between the
Pyrex and the container.

The ambient specimen temperature could be decreased by liquid

nitrogen addition to the dewar flask. A Stable constant reading of the
calibrated thermocouple- placed adjacent to the sample- could be
achieved after enough suitable time. This time is the time required to get
the thermal balance between the liquid nitrogen cooling and the ambient
temperature. The electrical conductivity of the thin film samples at this
condition could be measured. The temperature was controlled manually
and measured using digital temperature indicator.

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Chapter 3. Experimental techniques

Figure 3.11. Electrical measurement Cryostat

72
Chapter 3. Experimental techniques

Several film specimen designs were used in the preliminary

experiments included gap, sandwich and comb configurations.
Different metals were examined as electrodes. The results for the
electrical measurements were obtained using gap specimen design and
Cu electrodes. The geometry of the film samples is shown in Fig.3.12.
All samples were deposited on ordinary glass substrate (microscope
slide). A co-planar geometry was used, the inter-electrode gap of 2 mm
width being obtained by using a metal mask. The gap cell geometry has
been used in order to avoid the problem of the contact between the
electrode and the sample, as well as avoiding the surface metal
electrode transmission. Cu evaporation as electrodes was carried out in
the same vacuum chamber used for film deposition at a pressure of 10-5
torr.

73
 Chapter 3. Experimental techniques

2mm

Figure 3.12.a. Top sight view for sample geometry for

electrical conductivity measurements.

Cu electrodes

Thin film sample

Glass substrate

74
 Chapter 3. Experimental techniques

Co-planar Cell Geometry

Figure 3.12.b. Cross-section view of the sample geometry

for electrical conductivity measurements.

1-Cu electrodes
2-Thin film sample
3-Glass substrate

3.4.2. Thermoelectric power measurements

75
Chapter 3. Experimental techniques

For measuring the thermoelectric power, the differential method,

has been used, which based on the eq.(3.4)
T2
E  E1  E 2   ( S 2  S 1 )dT …………………….(3.4)
T 1

where E1 and E2 are the electromotive force (e.m.f) between the film and
contact material (Cu-electrode) at temperatures T1 and T2, respectively
and E is the potential difference between the hot and cold ends of the
thin film. The derivatives of the above equation gives:

E
 S 12 (T2 )  S 2 (T2 )  S 1 (T1 ) ……………………..(3.5)
T

where S1 and S2 are the thermoelectric power between film and contact
material (Cu) at T1 and T2, respectively and S12 is the relative
thermoelectric power. In the differential method, which was used in this
work, a small temperature difference T = T2 – T1 is maintained
between the junctions and the average temperature is varied and the
corresponding e.m.f, E, is measured, then

S12 = E / T ………………………………………..(3.6)

The samples were prepared by thermal deposition of As20Se80-xTlx

films in vacuum of 10-6 torr onto clean glass substrate in the form of
rectangular shape of length 5 cm and width 0.5 cm with the use of sharp
edged mask made up of copper attached to the glass substrate which the
film in thickness range 500 nm. The contacts were printed up onto the
two ends of the thin film by thermal evaporation of pure copper
evaporated from molybdenum boat.

76
Chapter 3. Experimental techniques

For measuring the thermoelectric power of As20Se80-xTlx films,

special holder shown in Fig.3.13 was used. The temperatures (T1, T2) of
the two junctions increased gradually using different high power
resistance (R1, R2) as a heat source and heat sink. The electromotive
force, e.m.f, associated with the temperature gradient along the film was
measured via the two copper contacts using highly internal impedance
electrometer (Keithley 614A), and the temperatures were measured
using Chromel-Alumel thermocouple. Using equation (3.6), the Seebeck
coefficient was measured within the temperature range 290-375 K.

Thermocouple Thermocouple
e.m.f

Insulator
T1 T2
Sample Copper
Small
holder
Heater

Figure 3.13. Holder used for the thermoelectric power

Measurements of As-Se-Tl films samples.

77
 Chapter 3. Experimental techniques

3.4.3. Ac Conductivity measurements

A.c conduction is different from the d.c conduction, where the

electric field frequency is constant during d.c conduction but during a.c
conduction, the electric field frequency is variable.

The effect of the two variable parameters, frequency,  and

temperature, T have been studied. Sample of special design had been
made for measuring the a.c conduction and it’s affected parameters. The
sample sandwiched between two silver electrodes A cross section could
be seen in Fig.3.14.

Ag electrodes Sample

Sample holder

Figure 3.14. Cross section of the sample prepared for a.c conduction.

The a.c conductivity  ac() , dielectric constant, Ɛ 1 and the

dielectric loss tangent Ɛ 2 as a function of frequency,  and temperature,

T for As20Se75Tl5 sample using a programmable automatic RCL meter
(PM 6304 Philips). The ac measurements have been carried out in the
frequency range (1-20 kHz), and in the temperature range (300-373 K).

78